Publications

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Publications in peer reviewed journals

193 Publications found
  • Analytical strategies to measure gadolinium as a wastewater marker in surface and groundwater systems

    Miguel Angel Marazuela, Martin Stockhausen, Thilo Hofmann
    2023 - MethodsX, 10: in press

    Abstract: 

    The increasing use of gadolinium (Gd)-based contrast agents in magnetic resonance imaging and the recalcitrant behavior of Gd during municipal wastewater treatment have led to increased concentrations of the tracer in aquatic environments. These anthropogenic Gd emissions to wastewater and, subsequently, to surface and groundwater systems can be exploited to calculate groundwater travel times and mixing ratios, identify wastewater inputs, and calibrate groundwater models. However, analytical complexity, costs, and the time needed to directly measure anthropogenic inputs hinder the practical use of Gd. While direct measurements with inductively coupled plasma-mass spectrometry (ICP-MS) are highly efficient and feasible, only total Gd can be detected with this approach. In unknown hydrogeological systems, the differentiation between total, anthropogenic, and geogenic Gd by interpolating rare earth element patterns requires complex sample pre-treatment and pre-concentration. Direct measurements of Gd can be obtained using anion-exchange chromatography coupled to ICP-MS but the limit of quantification will be higher. Here we provide guidelines for selecting the optimal method for the analysis of Gd as a wastewater tracer in surface-groundwater systems.

    • The cost-effectiveness of existing analytical strategies to measure Gd when used as a wastewater tracer in surface-groundwater systems is addressed
    • A novel analytical strategy for direct determination of total Gd is presented

     

  • Seasonal biodegradation of the artificial sweetener acesulfame enhances its use as a transient wastewater tracer

    Miguel Angel Marazuela, Giovanni Formentin, Klaus Erlmeier, Thilo Hofmann
    2023 - Water Research, 232: in press

    Abstract: 

    The persistence of the artificial sweetener acesulfame potassium (ACE) during wastewater treatment and subsequently in the aquatic environment has made it a widely used tracer of wastewater inputs to both surface water and groundwater. However, the recently observed biodegradation of ACE during wastewater treatment has questioned the validity of this application. In this study, we assessed the use of ACE not only as a marker of wastewater, but also as a transient wastewater tracer that allows both the calculation of mixing ratios and travel times through the aquifer as well as the calibration of transient groundwater flow and mass transport models. Our analysis was based on data obtained in a nearly 8-year river water and groundwater sampling campaign along a confirmed wastewater-receiving riverbank filtration site located close to a drinking water supply system. We provide evidence that temperature controls ACE concentration and thus its seasonal oscillation. River water data showed that ACE loads decreased from 1.5–4 mg·s−1 in the cold season (December to June; T<10 °C) to 0–0.5 mg·s−1 in the warm season (July to November; T>10 °C). This seasonal variability of >600% was detectable in the aquifer and preserved >3 km, with ACE concentrations oscillating between <LOQ in the warm season up to 1 μg·L−1 in the cold season. The large seasonal variation in ACE concentrations during wastewater treatment, compared to the other sweeteners (sucralose, cyclamate, and saccharin) and chloride enables its use as a transient tracer of wastewater inflows and riverbank filtration. In addition, the arrival time of the ACE concentration peak can be used to estimate groundwater flow velocity and mixing ratios, thereby demonstrating its potential in the calibration of groundwater numerical models.

  • Small biochar particles hardly disintegrate under cryo-stress

    Gabriel Sigmund, Andrea Schmid, Hans-Peter Schmidt, Nikolas Hagemann, Thomas D. Bucheli, Thilo Hofmann
    2023 - Geoderma, 430: in press

    Abstract: 

    Physical disintegration of biochar has been postulated to determine the persistence and mobility in soil of this recalcitrant carbon pool. Therein, freeze–thaw cycling can induce substantial physical stress to biochars. We here investigated the physical disintegration and subsequent mobilisation of five different biochars under “realistic worst-case scenarios” in a laboratory soil column setup as well as in shaking and sonication batch experiments. The mobilization of carbon from biochar particles (0.25–1 mm) was investigated in the absence of clay at a pH of 6.3 with and without 80 freeze–thaw cycles. The small biochar particles used in this study did not strongly disintegrate after freeze–thaw cycling, possibly because of freezing point depression in biochar micropores. Our results in comparison with findings in literature suggest that freeze–thaw-induced physical disintegration of biochar is a process more pronounced for large biochar particles containing substantial meso- and macropores. Biochars with larger ash fractions disintegrated more, presumably because of the ash-associated formation of unstable cavities within the biochar. Physical stability of biochars produced from the same feedstock at different pyrolysis temperatures decreased with increasing aromaticity, which may be linked to a higher rigidity of more aromatic structures. Moisture content in the soil increased carbon mobilization from biochar more than physical stress such as freeze–thaw cycling. The physical disintegration of biochar and subsequent mobilization of micro-and nanosized carbon should thus be considered of minor relevance and is often not a driving factor for biochar stability in soil.

  • Stromatolitic carbonates from the Middle Miocene of the western Pannonian Basin reflect trace metal availability in microbial habitats during the Badenian Salinity Crisis

    Sebastian Viehmann, Robert Kujawa, Simon V. Hohl, Nathalie Tepe, Alexandra S. Rodler, Thilo Hofmann, Erich Draganits
    2023 - Chemical Geology, 618: in press

    Abstract: 

    Stromatolitic carbonates of the Middle Miocene Oberpullendorf Basin (Austria) provide a great opportunity to study the evolution of microbial habitats under extreme environmental changes during the Badenian (Langhian and early Serravallian) Salinity Crisis. We here present the first geochemical data for Badenian stromatolites and show in a combined approach using major, trace element, and C – O isotope compositions obtained in individual stromatolitic carbonate laminae that short-term variations of palaeo-environmental conditions within the Oberpullendorf Basin coincide with individual microbialite morphologies.

    The studied carbonates were affected by both detrital contamination and post-depositional alteration processes to different degrees. While fluid-mobile elements show clear evidence for post-depositional alteration processes, the rare earth element and yttrium (REY) as well as bio-essential element (Fe, Mn, Co, Zn, Mo, W) compositions of the carbonates remained unaffected. Stromatolitic carbonates that are devoid of detrital contamination (< 300 ppm Al) show typical shale-normalized seawater-like rare earth element and yttrium (REYSN) patterns with positive LaSN, GdSN anomalies, super-chondritic Y/Ho ratios, and heavy over light REYSN enrichments in the lower stromatolite units. These features suggest an open ocean seawater influenced depositional setting at the north-western margin of the Paratethys Sea. Stratigraphically upwards, pure stromatolitic carbonates show suppressed seawater-like REYSN signatures that argue for the development of a (semi)closed lagoon with restricted access to the open sea. Seawater-like REYSN patterns in the uppermost part resemble a reappearance of open marine environmental conditions. Interestingly, geochemical data of the upper part of the section contradict the ambient fossil record, showing the urge for future interdisciplinary approaches targeting the understanding and interplay of geochemistry, palaeontology, and geomicrobiology in modern and ancient microbial habitats. Enrichment factors of bio-essential trace elements that are either used as co-factors in metalloenzymes or metal-activated enzymes in biochemical reactions can be directly linked to the reconstructed environmental conditions: Sufficient element availability is ensured during marine conditions in the lower and uppermost stratigraphic sections; in contrast, continuous decreasing element availability of these elements is directly related to the temporary development of a (semi)closed lagoon.

  • Comparing biochar and hydrochar for reducing the risk of organic contaminants in polluted river sediments used for growing energy crops

    Snežana Maletić, Marijana Kragulj Isakovski, Gabriel Sigmund, Thilo Hofmann, Thorsten Hüffer, Jelena Beljin, Srđan Rončević
    2022 - Science of The Total Environment, 843: in press

    Abstract: 

    In Europe alone, >200 million m3 of river sediments are dredged each year, part of which are contaminated to such an extent that they have to be landfilled. This study compares the use of biochar and hydrochar for the remediation of sediment contaminated with pentachlorobenzene, hexachlorobenzene, lindane, trifluralin, alachlor, simazine, and atrazine with the motivation to make sediments contaminated by such priority substances usable as arable land for growing energy crops. Biochar and hydrochar originating from Miscanthus giganteus and Beta vulgaris shreds were compared for their potential to reduce contaminant associated risk in sediments. Specifically, by investigating the effects of sorbent amendment rate (1, 5, and 10 %) and incubation time (14, 30, and 180 d) on contaminant bioaccessibility, toxicity to the bacteria Vibrio fischeri, as well as toxicity and plant uptake in Zea mays. Biochar reduced contaminant bioaccessibility up to five times more than hydrochar. The bioaccessibility of contaminants decreased up to sevenfold with increasing incubation time, indicating that the performance of carbonaceous sorbents may be underestimated in short-term lab experiments. Biochar reduced contaminants toxicity to Vibrio fischeri, whereas hydrochar was itself toxic to the bacteria. Toxicity to Zea mays was determined by contaminant bioaccessibility but also sorbent feedstock with cellulose rich Beta vulgaris based sorbents exhibiting toxic effects. The plant uptake of all contaminants decreased after sorbent amendment.

  • Effect of Polymer Properties on the Biodegradation of Polyurethane Microplastics

    Patrizia Pfohl, Daniel Bahl, Markus Rückel, Marion Wagner, Lars Meyer, Patrick Bolduan, Glauco Battagliarin, Thorsten Hüffer, Michael Zumstein, Thilo Hofmann, Wendel Wohlleben
    2022 - Environ. Sci. Technol., in press

    Abstract: 

    The release of fragments from plastic products, that is, secondary microplastics, is a major concern in the context of the global plastic pollution. Currently available (thermoplastic) polyurethanes [(T)PU] are not biodegradable and therefore should be recycled. However, the ester bond in (T)PUs might be sufficiently hydrolysable to enable at least partial biodegradation of polyurethane particles. Here, we investigated biodegradation in compost of different types of (T)PU to gain insights into their fragmentation and biodegradation mechanisms. The studied (T)PUs varied regarding the chemistry of their polymer backbone (aromatic/aliphatic), hard phase content, cross-linking degree, and presence of a hydrolysis-stabilizing additive. We developed and validated an efficient and non-destructive polymer particle extraction process for partially biodegraded (T)PUs based on ultrasonication and density separation. Our results showed that biodegradation rates and extents decreased with increasing cross-linking density and hard-segment content. We found that the presence of a hydrolysis stabilizer reduced (T)PU fragmentation while not affecting the conversion of (T)PU carbon into CO2. We propose a biodegradation mechanism for (T)PUs that includes both mother particle shrinkage by surface erosion and fragmentation. The presented results help to understand structure–degradation relationships of (T)PUs and support recycling strategies.

  • Exploring Nanogeochemical Environments: New Insights from Single Particle ICP-TOFMS and AF4-ICPMS

    Manuel D. Montaño, Chad W. Cuss, Haley M. Holliday, Muhammad B. Javed, William Shotyk, Kathryn L. Sobocinski, Thilo Hofmann, Frank von der Kammer, James F. Ranville
    2022 - ACS Earth & Space Chemistry, 6: 943–952

    Abstract: 

    Nanogeochemistry is an emerging focus area recognizing the role of nanoparticles in Earth systems. Engineered nanotechnology has cultivated advanced analytical techniques that are also applicable to nanogeochemistry. Single particle inductively coupled plasma ICP-time-of-flight-mass spectrometry (ICP-TOF-MS) promises a significant step forward, as time-of-flight mass analyzers enable simultaneous quantification of the entire atomic mass spectrum (∼7–250 m/z+). To demonstrate the utility of this approach, samples were collected and analyzed from a large, boreal river, and its surrounding tributaries. These samples provided us with a diversity of particle compositions and morphologies, while their interconnected nature allowed for an examination of the various nanogeochemical processes present in this system. To further expand on this effort, we combined this high-throughput technique with AF4-ICPMS, focusing on major carriers of trace elements. Using spICP-TOF-MS, Al, Si, and Fe were grouped into classes having all combinations of one or more of these elements. Particle-by-particle ICP-TOF-MS analysis found chemically heterogeneous populations, indicating the predominance of diverse mineralogy or heteroaggregates. The importance of suspended Fe and Mn for the speciation of Pb was observed by single particle ICP-TOF-MS and complemented by AF4-ICPMS analysis of dissolved organic matter and nanoparticulate Fe/Mn. Our study exploits the combination of spICP-TOF-MS and AF4-ICP-MS for studying isotopic and elemental ratios (mineralogy) of individual nanoparticles, which opens the door to further explore the mechanisms of colloid facilitated transport of trace elements.

  • Freshwater suspended particulate matter—Key components and processes in floc formation and dynamics

    2022 - Water Research, 220: in press

    Abstract: 

    Freshwater suspended particulate matter (SPM) plays an important role in many biogeochemical cycles and serves multiple ecosystem functions. Most SPM is present as complex floc-like aggregate structures composed of various minerals and organic matter from the molecular to the organism level. Flocs provide habitat for microbes and feed for larger organisms. They constitute microbial bioreactors, with prominent roles in carbon and inorganic nutrient cycles, and transport nutrients as well as pollutants, affecting sediments, inundation zones, and the ocean. Composition, structure, size, and concentration of SPM flocs are subject to high spatiotemporal variability. Floc formation processes and compositional or morphological dynamics can be established around three functional components: phyllosilicates, iron oxides/(oxy)hydroxides (FeOx), and microbial extracellular polymeric substances (EPS). These components and their interactions increase heterogeneity in surface properties, enhancing flocculation. Phyllosilicates exhibit intrinsic heterogeneities in surface charge and hydrophobicity. They are preferential substrates for precipitation or attachment of reactive FeOx. FeOx form patchy coatings on minerals, especially on phyllosilicates, which increase surface charge heterogeneities. Both, phyllosilicates and FeOx strongly adsorb natural organic matter (NOM), preferentially certain EPS. EPS comprise various substances with heterogeneous properties that make them a sticky mixture, enhancing flocculation. Microbial metabolism, and thus EPS release, is supported by the high adsorption capacity and favorable nutrient composition of phyllosilicates, and FeOx supply essential Fe.

  • Generation of Reproducible Model Freshwater Particulate Matter Analogues to Study the Interaction with Particulate Contaminants.

    Helene Walch, Antonia Praetorius, Frank von der Kammer, Thilo Hofmann
    2022 - Water Research, in press

    Abstract: 

    Aquatic fate models and risk assessment require experimental information on the potential of contaminants to interact with riverine suspended particulate matter (SPM). While for dissolved contaminants partition or sorption coefficients are used, the underlying assumption of chemical equilibrium is invalid for particulate contaminants, such as engineered nanomaterials, incidental nanoparticles, micro- or nanoplastics. Their interactions with SPM are governed by physicochemical forces between contaminant-particle and SPM surfaces. The availability of a standard SPM material is thus highly relevant for the development of reproducible test systems to evaluate the fate of particulate contaminants in aquatic systems. Finding suitable SPM analogues, however, is challenging considering the complex composition of natural SPM, which features floc-like structures comprising minerals and organic components from the molecular to the microorganism level. Complex composition comes with a heterogeneity in physicochemical surface properties, that cannot be neglected. We developed a procedure to generate SPM analogue flocs from components selected to represent the most abundant and crucial constituents of natural riverine SPM, and the process-relevant SPM surface characteristics regarding interactions with particulate contaminants. Four components, i.e., illite, hematite, quartz and tryptophan, combined at environmentally realistic mass-ratios, were associated to complex flocs. Flocculation was reproducible regarding floc size and fractal dimension, and multiple tests on floc resilience towards physical impacts (agitation, sedimentation-storage-resuspension, dilution) and hydrochemical changes (pH, electrolytes, dissolved organic matter concentration) confirmed their robustness. These reproducible, ready-to-use SPM analogue flocs will strongly support future research on emerging particulate contaminants.

  • Iron Nitride Nanoparticles for Enhanced Reductive Dechlorination of Trichloroethylene

    Miroslav Brumovský, Jana Oborná, Vesna Micić, Ondřej Malina, Josef Kašlík, Daniel Tunega, Miroslav Kolos, Thilo Hofmann, František Karlický, Jan Filip
    2022 - Environmental Science & Technology, 56: 4425-4436

    Abstract: 

    Nitriding has been used for decades to improve the corrosion resistance of iron and steel materials. Moreover, iron nitrides (FexN) have been shown to give an outstanding catalytic performance in a wide range of applications. We demonstrate that nitriding also substantially enhances the reactivity of zerovalent iron nanoparticles (nZVI) used for groundwater remediation, alongside reducing particle corrosion. Two different types of FexN nanoparticles were synthesized by passing gaseous NH3/N2 mixtures over pristine nZVI at elevated temperatures. The resulting particles were composed mostly of face-centered cubic (γ′-Fe4N) and hexagonal close-packed (ε-Fe2–3N) arrangements. Nitriding was found to increase the particles’ water contact angle and surface availability of iron in reduced forms. The two types of FexN nanoparticles showed a 20- and 5-fold increase in the trichloroethylene (TCE) dechlorination rate, compared to pristine nZVI, and about a 3-fold reduction in the hydrogen evolution rate. This was related to a low energy barrier of 27.0 kJ mol–1 for the first dechlorination step of TCE on the γ′-Fe4N(001) surface, as revealed by density functional theory calculations with an implicit solvation model. TCE dechlorination experiments with aged particles showed that the γ′-Fe4N nanoparticles retained high reactivity even after three months of aging. This combined theoretical-experimental study shows that FexN nanoparticles represent a new and potentially important tool for TCE dechlorination.

  • Mercury Removal from Contaminated Water by Wood-Based Biochar Depends on Natural Organic Matter and Ionic Composition

    Sampriti Chaudhuri, Gabriel Sigmund, Sharon E. Bone, Naresh Kumar, Thilo Hofmann
    2022 - Environ. Sci. Technol., 56: 11354–11362

    Abstract: 

    Biochars can remove potentially toxic elements, such as inorganic mercury [Hg(II)] from contaminated waters. However, their performance in complex water matrices is rarely investigated, and the combined roles of natural organic matter (NOM) and ionic composition in the removal of Hg(II) by biochar remain unclear. Here, we investigate the influence of NOM and major ions such as chloride (Cl-), nitrate (NO3-), calcium (Ca2+), and sodium (Na+) on Hg(II) removal by a wood-based biochar (SWP700). Multiple sorption sites containing sulfur (S) were located within the porous SWP700. In the absence of NOM, Hg(II) removal was driven by these sites. Ca2+ bridging was important in enhancing removal of negatively charged Hg(II)-chloro complexes. In the presence of NOM, formation of soluble Hg-NOM complexes (as seen from speciation calculations), which have limited access to biochar pores, suppressed Hg(II) removal, but Cl- and Ca2+ could still facilitate it. The ability of Ca2+ to aggregate NOM, including Hg-NOM complexes, promoted Hg(II) removal from the dissolved fraction (<0.45 μm). Hg(II) removal in the presence of Cl- followed a stepwise mechanism. Weakly bound oxygen functional groups in NOM were outcompeted by Cl-, forming smaller-sized Hg(II)-chloro complexes, which could access additional intraparticle sorption sites. Therein, Cl- was outcompeted by S, which finally immobilized Hg(II) in SWP700 as confirmed by extended X-ray absorption fine structure spectroscopy. We conclude that in NOM containing oxic waters, with relatively high molar ratios of Cl-: NOM and Ca2+: NOM, Hg(II) removal can still be effective with SWP700.

  • Pharmaceutical pollution of the world’s rivers

    John L. Wilkinson, Alistair B. A. Boxall, Dana W. Kolpin, Kenneth M. Y. Leung, Racliffe W. S. Lai, Cristobal Galban-Malagon, Aiko D. Adell, Julie Mondon, Marc Metian, Robert A. Marchant, Alejandra Bouzas-Monroy, Aida Cuni-Sanchez, Anja Coors, Pedro Carriquiriborde, Macarena Rojo, Chris Gordon, Magdalena Cara, Monique Moermond, Thais Luarte, Vahagn Petrosyan, Yekaterina Perikhanyan, Clare S. Mahon, Christopher J. McGurk, Thilo Hofmann, Tapos Kormoker, Volga Iniguez, Jessica Guzman-Otazo, Jean L. Tavares, Francisco Gildasio De Figueiredo, Maria T. P. Razzolini, Victorien Dougnon, Gildas Gbaguidi, Oumar Traore, Jules M. Blais, Linda E. Kimpe, Michelle Wong, Donald Wong, Romaric Ntchantcho, Jaime Pizarro, Guang-Guo Ying, Chang-Er Chen, Martha Paez, Jina Martinez-Lara, Jean-Paul Otamonga, John Pote, Suspense A. Ifo, Penelope Wilson, Silvia Echeverria-Saenz, Nikolina Udikovic-Kolic, Milena Milakovic, Despo Fatta-Kassinos, Lida Ioannou-Ttofa, Vladimira Belusova, Jan Vymazal, Maria Cardenas-Bustamante, Bayable A. Kas
    2022 - PNAS, 119: e2113947119

    Abstract: 

    Environmental exposure to active pharmaceutical ingredients (APIs) can have negative effects on the health of ecosystems and humans. While numerous studies have monitored APIs in rivers, these employ different analytial methods, measure different APIs, and have ignored many of the countries of the world. This makes it difficult to quantify the scale of the problem from a global perspective. Furthermore, comparison of the existing data, generated for different studies/regions/continents, is challenging due to the vast differences between the analytical methodologies employed. Here, we present a global-scale study of API pollution in 258 of the world’s rivers, representing the environmental influence of 471.4 million people across 137 geographic regions. Samples were obtained from 1,052 locations in 104 countries (representing all continents and 36 countries not previously studied for API contamination) and analyzed for 61 APIs. Highest cumulative API concentrations were observed in sub-Saharan Africa, south Asia, and South America. The most contaminated sites were in low- to middle-income countries and were associated with areas with poor wastewater and waste management infrastructure and pharmaceutical manufacturing. The most frequently detected APIs were carbamazepine, metformin, and caffeine (a compound also arising from lifestyle use), which were detected at over half of the sites monitored. Concentrations of at least one API at 25.7% of the sampling sites were greater than concentrations considered safe for aquatic organisms, or which are of concern in terms of selection for antimicrobial resistance. Therefore, pharmaceutical pollution poses a global threat to environmental and human health, as well as to delivery of the United Nations Sustainable Development Goals.

  • Polyvinyl Chloride Microplastics Leach Phthalates into the Aquatic Environment over Decades

    Charlotte Henkel, Thorsten Hüffer, Thilo Hofmann
    2022 - Environ. Sci. Technol., in press

    Abstract: 

    Phthalic acid esters (phthalates) have been detected everywhere in the environment, but data on leaching kinetics and the governing mass transfer process into aqueous systems remain largely unknown. In this study, we experimentally determined time-dependent leaching curves for three phthalates di(2-ethylhexyl) phthalate, di(2-ethylhexyl) terephthalate, and diisononyl phthalate from polyvinyl chloride (PVC) microplastics and thereby enabled a better understanding of their leaching kinetics. This is essential for exposure assessment and to predict microplastic-bound environmental concentrations of phthalates. Leaching curves were analyzed using models for intraparticle diffusion (IPD) and aqueous boundary layer diffusion (ABLD). We show that ABLD is the governing diffusion process for the continuous leaching of phthalates because phthalates are very hydrophobic (partitioning coefficients between PVC and water log KPVC/W were higher than 8.6), slowing down the diffusion through the ABL. Also, the diffusion coefficient in the polymer DPVC is relatively high (∼8 × 10–14 m2 s–1) and thus enhances IPD. Desorption half-lives of the studied PVC microplastics are greater than 500 years but can be strongly influenced by environmental factors. By combining leaching experiments and modeling, our results reveal that PVC microplastics are a long-term source of phthalates in the environment.

  • Rapid analysis of gunshot residues with single-particle inductively coupled plasma time-of-flight mass spectrometry

    Robert Brünjes, Jan Schüürman, Frank von der Kammer, Thilo Hofmann
    2022 - Forensic Science International, 332: in press

    Abstract: 

    Gunshot residues (GSRs) from different types of ammunition have been characterized using a new method based on single-particle inductively coupled plasma time-of-flight mass spectrometry (sp-ICP-TOF-MS). This method can analyze thousands of particles per minute enabling rapid sample screening for GSR detection with minimal sample preparation. GSR particles are multi-elemental nanoparticles that are mainly defined by the elements lead, barium, and antimony. Sp-ICP-TOF-MS was also used to identify other elements contained in GSR particles while standard particle classification protocols do not consider the complexities of GSR compositions and can therefore miss out on valuable information. The proposed method can be used to support existing GSR detection methods, especially when lead-free, antimony-free, or tagged ammunition has been used; it also provides a possibility for multi-elemental fingerprinting of GSR particles.

  • Sorption and Mobility of Charged Organic Compounds: How to Confront and Overcome Limitations in Their Assessment

    Gabriel Sigmund, Hans Peter H. Arp, Benedikt M. Aumeier, Thomas D. Bucheli, Benny Chefetz, Wei Chen, Steven T. J. Droge, Satoshi Endo, Beate I. Escher, Sarah E. Hale, Thilo Hofmann, Joseph Pignatello, Thorsten Reemtsma, Torsten C. Schmidt, Carina D. Schönsee, Martin Scheringer
    2022 - Environ. Sci. Technol., 56: 4702-2710

    Abstract: 

    Permanently charged and ionizable organic compounds (IOC) are a large and diverse group of compounds belonging to many contaminant classes, including pharmaceuticals, pesticides, industrial chemicals, and natural toxins. Sorption and mobility of IOCs are distinctively different from those of neutral compounds. Due to electrostatic interactions with natural sorbents, existing concepts for describing neutral organic contaminant sorption, and by extension mobility, are inadequate for IOC. Predictive models developed for neutral compounds are based on octanol–water partitioning of compounds (Kow) and organic-carbon content of soil/sediment, which is used to normalize sorption measurements (KOC). We revisit those concepts and their translation to IOC (Dow and DOC) and discuss compound and soil properties determining sorption of IOC under water saturated conditions. Highlighting possible complementary and/or alternative approaches to better assess IOC mobility, we discuss implications on their regulation and risk assessment. The development of better models for IOC mobility needs consistent and reliable sorption measurements at well-defined chemical conditions in natural porewater, better IOC-, as well as sorbent characterization. Such models should be complemented by monitoring data from the natural environment. The state of knowledge presented here may guide urgently needed future investigations in this field for researchers, engineers, and regulators.

  • Stormwater management in urban areas using dry gallery infiltration systems

    Miguel Angel Marazuela, Alejandro García-Gil, Juan C. Santamarta, Samanta Gasco-Cavero, Noelia Cruz-Pérez, Thilo Hofmann
    2022 - Science of The Total Environment, 823: 153705

    Abstract: 

    The increase in the frequency of extreme precipitation events due to climate change, together with the continuous development of cities and surface sealing that hinder water infiltration into the subsoil, is accelerating the search for new facilities to manage stormwater. The Canary Islands (Spain) are taking advantage of the knowledge acquired in the construction of water mines to exploit a novel stormwater management facility, which we have defined as a dry gallery. Dry galleries are constituted by a vertical well connected to a horizontal gallery dug into highly permeable volcanic layers of the vadose zone, from where infiltration takes place. However, the lack of scientific knowledge about these facilities prevents them from being properly dimensioned and managed. In this work, we simulate for the first time the infiltration process and the wetting front propagation from dry galleries based on a 3D unsaturated flow model and provide some recommendations for the installation and sizing of these facilities. The fastest advance of the wetting front takes place during the earliest times of infiltration (<2 h), with plausible propagation velocities and infiltration rates higher than 1000 m∙d−1 and 2 m3∙s−1. As time progresses, the propagation velocity and infiltration rate decrease as a consequence of the hydraulic gradient attenuation between the gallery and the aquifer. Therefore, stormwater infiltration is a highly transient process in which a sizing underestimation of 100% may be committed if unsaturated conditions or geological configuration are neglected.

  • Towards Standardization for Determining Dissolution Kinetics of Nanomaterials in Natural Aquatic Environments: Continuous Flow Dissolution of Ag Nanoparticles

    Lucie Stetten, Aiga Mackevica, Nathalie Tepe, Thilo Hofmann, Frank von der Kammer
    2022 - Nanomaterials, 12: 519

    Abstract: 

    The dissolution of metal-based engineered nanomaterials (ENMs) in aquatic environments is an important mechanism governing the release of toxic dissolved metals. For the registration of ENMs at regulatory bodies such as REACH, their dissolution behavior must therefore be assessed using standardized experimental approaches. To date, there are no standardized procedures for dissolution testing of ENMs in environmentally relevant aquatic media, and the Organisation for Economic Co-operation and Development (OECD) strongly encourages their development into test guidelines. According to a survey of surface water hydrochemistry, we propose to use media with low concentrations of Ca2+ and Mg2+ for a better simulation of the ionic background of surface waters, at pH values representing acidic (5 < pH < 6) and near-neutral/alkaline (7 < pH < 8) waters. We evaluated a continuous flow setup adapted to expose small amounts of ENMs to aqueous media, to mimic ENMs in surface waters. For this purpose, silver nanoparticles (Ag NPs) were used as model for soluble metal-bearing ENMs. Ag NPs were deposited onto a 10 kg.mol−1 membrane through the injection of 500 µL of a 5 mg.L−1 or 20 mg.L−1 Ag NP dispersion, in order to expose only a few micrograms of Ag NPs to the aqueous media. The dissolution rate of Ag NPs in 10 mM NaNO3 was more than two times higher for ~2 µg compared with ~8 µg of Ag NPs deposited onto the membrane, emphasizing the importance of evaluating the dissolution of ENMs at low concentrations in order to keep a realistic scenario. Dissolution rates of Ag NPs in artificial waters (2 mM Ca(NO3)2, 0.5 mM MgSO4, 0–5 mM NaHCO3) were also determined, proving the feasibility of the test using environmentally relevant media. In view of the current lack of harmonized methods, this work encourages the standardization of continuous flow dissolution methods toward OECD guidelines focused on natural aquatic environments, for systematic comparisons of nanomaterials and adapted risk assessments.

  • Uptake, Metabolism, and Accumulation of Tire Wear Particle- Derived Compounds in Lettuce

    Stephanie Castan, Anya Sherman, Ruoting Peng, Michael Zumstein, Wolfgang Wanek, Thorsten Hüffer, Thilo Hofmann
    2022 - Environ. Sci. Technol., in press

    Abstract: 

    Tire wear particle (TWP)-derived compounds may be of high concern to consumers when released in the root zone of edible plants. We exposed lettuce plants to the TWP-derived compounds diphenylguanidine (DPG), hexamethoxymethylmelamine (HMMM), benzothiazole (BTZ), N-phenyl-N′-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), and its quinone transformation product (6PPD-q) at concentrations of 1 mg L–1 in hydroponic solutions over 14 days to analyze if they are taken up and metabolized by the plants. Assuming that TWP may be a long-term source of TWP-derived compounds to plants, we further investigated the effect of leaching from TWP on the concentration of leachate compounds in lettuce leaves by adding constantly leaching TWP to the hydroponic solutions. Concentrations in leaves, roots, and nutrient solution were quantified by triple quadrupole mass spectrometry, and metabolites in the leaves were identified by Orbitrap high resolution mass spectrometry. This study demonstrates that TWP-derived compounds are readily taken up by lettuce with measured maximum leaf concentrations between ∼0.75 (6PPD) and 20 μg g–1 (HMMM). Although these compounds were metabolized in the plant, we identified several transformation products, most of which proved to be more stable in the lettuce leaves than the parent compounds. Furthermore, continuous leaching from TWP led to a resupply and replenishment of the metabolized compounds in the lettuce leaves. The stability of metabolized TWP-derived compounds with largely unknown toxicities is particularly concerning and is an important new aspect for the impact assessment of TWP in the environment.

  • A critical evaluation of short columns for estimating the attachment efficiency of engineered nanomaterials in natural soils

    Knapp Karin Norrfors, Vesna Micić, Olga Borovinskaya, Frank von der Kammer, Thilo Hofmann, Geert Cornelis
    2021 - Environmental Science: Nano, 8: 1801-1814

    Abstract: 

    Short, saturated packed columns are used frequently to estimate the attachment efficiency (α) of engineered nanomaterials (ENMs) in relatively homogeneous porous media, but a combined experimental and theoretical approach to obtain α-values for heterogeneous natural soils has not yet been agreed upon. Accurately determined α-values that can be used to study and predict ENM transport in natural soils should vary with ENM and soil properties, but not with experimental settings. We investigated the effect of experimental conditions, and used different methods to obtain soil parameters, essential to calculate α. We applied 150 different approaches onto 52 transport experiments using short columns with 5 different natural soils and 20 and 80 nm gold- or 27 nm silver sulphide ENMs. The choice of column end-filter material and pore size appeared critical to avoid overestimating α owing to filter – ENM interactions and/or incomplete saturation of the column. Using a low ionic strength (4.4 x 10-5 mol L-1) artificial rain water as an aqueous medium avoided ENM homo- or heteroaggregation in all soils, as confirmed by single-particle inductively coupled plasma - time of flight mass spectrometry. ENM breakthrough curves could be modelled using colloid filtration theory assuming irreversible attachment only. α-values calculated from this model, having the grain size represented by a single average size, accounting for dispersivity and effective porosity based on a prior inert tracer test, explained up to 42 % of the variance in α as revealed by partial least squares analysis. However, column length and dispersivity remained as important experimental parameters, which calls for further standardisation efforts of column tests with ENMs in natural soils, preferably cross-validated with batch tests.

  • Environmentally persistent free radicals are ubiquitous in wildfire charcoals and remain stable for years

    Gabriel Sigmund, Cristina Santín, Marc Pignitter, Nathalie Tepe, Stefan H. Doerr, Thilo Hofmann
    2021 - Communications Earth & Environment, 2: 68

    Abstract: 

    Globally landscape fires produce about 256 Tg of pyrogenic carbon or charcoal each year. The role of charcoal as a source of environmentally persistent free radicals, which are precursors of potentially harmful reactive oxygen species, is poorly constrained. Here, we analyse 60 charcoal samples collected from 10 wildfires, that include crown as well as surface fires in forest, shrubland and grassland spanning different boreal, temperate, subtropical and tropical climate. Using electron spin resonance spectroscopy, we measure high concentrations of environmentally persistent free radicals in charcoal samples, much higher than those found in soils. Concentrations increased with degree of carbonization and woody fuels favoured higher concentrations. Moreover, environmentally persistent free radicals remained stable for an unexpectedly long time of at least 5 years. We suggest that wildfire charcoal is an important global source of environmentally persistent free radicals, and therefore potentially of harmful reactive oxygen species.

  • Methanol-based extraction protocol for insoluble and moderately water-soluble nanoparticles in plants to enable characterization by single particle ICP-MS

    Stephanie Laughton, Adam Laycock, Garret Bland, Frank von der Kammer, Thilo Hofmann, Elizabeth A. Casman, Gregory V. Lowry
    2021 - Analytical and Bioanalytical Chemistry, 413: 299–314

    Abstract: 

    The detection and characterization of soluble metal nanoparticles in plant tissues are an analytical challenge, though a scientific necessity for regulating nano-enabled agrichemicals. The efficacy of two extraction methods to prepare plant samples for analysis by single particle ICP-MS, an analytical method enabling both size determination and quantification of nanoparticles (NP), was assessed. A standard enzyme-based extraction was compared to a newly developed methanol-based approach. Au, CuO, and ZnO NPs were extracted from three different plant leaf materials (lettuce, corn, and kale) selected for their agricultural relevance and differing characteristics. The enzyme-based approach was found to be unsuitable because of changes in the recovered NP size distribution of CuO NP. The MeOH-based extraction allowed reproducible extraction of the particle size distribution (PSD) without major alteration caused by the extraction. The type of leaf tissue did not significantly affect the recovered PSD. Total metal losses during the extraction process were largely due to the filtration step prior to analysis by spICP-MS, though this did not significantly affect PSD recovery. The methanol extraction worked with the three different NPs and plants tested and is suitable for studying the fate of labile metal-based nano-enabled agrichemicals.

  • Microplastic extraction protocols can impact the polymer structure

    Patrizia Pfohl, Christian Roth, Lars Meyer, Ute Heinemeyer, Till Gruendling, Christiane Lang, Nikolaus Nestle, Thilo Hofmann, Wendel Wohlleben, Sarah Jessl
    2021 - Microplastics and Nanoplastics, 1: 8

    Abstract: 

    Although microplastics are ubiquitous in today’s natural environments, our understanding of the materials, quantities, and particle sizes involved remains limited. The recovery of microplastics from different types of environmental matrices requires standardized matrix digestion protocols that allow inter-laboratory comparisons and that have no effect on the polymers themselves. A number of commonly used digestion methods rely on oxidation with concentrated hydrogen peroxide solutions to remove organic matter from the matrix. However, this can alter the nature of polymers through hydrolysis and often does not lead to a complete matrix removal. We have therefore investigated the use of two altered matrix digestion protocols, an acidic (Fenton) protocol and a new alkaline (Basic Piranha) protocol, focusing mainly on the effect on biodegradable polymers (polylactide, polybutylene adipate terephthalate, polybutylene succinate) and polymers with known degradation pathways via hydrolysis (thermoplastic polyurethanes, polyamide). Comparing the initial surface textures, chemical compositions, and particle size distributions with those obtained after digestion revealed that the Fenton protocol left most of the polymers unchanged. The ferrous residue that remains following Fenton digestion had no effect on either the polymer composition or the particle size distribution, but could disturb further analytics (e.g. Raman microscopy due to auto-fluorescence). While increasing the chance of complete matrix removal, the more powerful Basic Piranha protocol is also more likely to affect the polymer properties: Polylactide polymers in particular showed signs of degradation under alkaline digestion (reduced polylactide content, holes in the polymer matrix), indicating the unsuitability of the Basic Piranha protocol in this specific case. Polyamide, however, remained stable during the Basic Piranha treatment, and the surface chemistry, the particle size as well as the molar mass distribution of the investigated thermoplastic polyurethanes were also not affected. Hence, this protocol offers a powerful alternative for microplastic analysis with focus on particle size in more complex environmental matrices (e.g. removal of cellulose in soil), while avoiding ferrous Fenton residue. Unexpectedly, also tire rubber, a frequent target analyte in microplastic monitoring, was found to be susceptible to artefact structures by both oxidation protocols. In summary, controls for the specific combination of polymer and sample preparation protocol are highly recommended to select the most fitting protocol. Here selected suitable combinations are reported.

  • Microplastics and nanoplastics barely enhance contaminant mobility in agricultural soils

    Stephanie Castan, Charlotte Henkel, Thorsten Hüffer, Thilo Hofmann
    2021 - Communications Earth & Environment, 193: 1-9

    Abstract: 

    Farmland soils are prone to contamination with micro- and nanoplastics through a variety of agricultural practices. Concerns are recurrently raised that micro- and nanoplastics act as vector for organic contaminants to deeper soil layers and endanger groundwater resources. Whether and to what extent micro- and nanoplastics facilitate the transport of organic contaminants in soil remains unclear. Here we calculated the ratio between transport and desorption time scales using two diffusion models for micro- and nanoplastics between 100 nm and 1 mm. To identify micro- and nanoplastics bound contaminant transport we evaluated diffusion and partitioning coefficients of prominent agrochemicals and additives and of frequently used polymers e.g., polyethylene and tire material. Our findings suggest that the desorption of most organic contaminants is too fast for micro- and nanoplastics to act as transport facilitators in soil. Contaminant transport enabled by microplastics was found to be relevant only for very hydrophobic contaminants (logKow >5) under preferential flow conditions. While micro- and nanoplastics might be a source of potentially harmful contaminants in farmland soils this study suggests that they do not considerably enhance contaminant mobility.

  • Parameter estimation and uncertainty analysis in hydrological modeling

    Paulo A. Herrera, Miguel Angel Marazuela, Thilo Hofmann
    2021 - WIRES Water, e1569

    Abstract: 

    Nowadays, mathematical models of hydrological systems are used routinely to guide decision making in diverse subjects, such as: environmental and risk assessments, design of remediation strategies for contaminated sites, and evaluation of the impact of climate change on water resources. The correct development and use of them is relevant beyond the realm of hydrology. The continuous improvement in computational power and data collection are leading to the development of increasingly complex models, which integrate multiple coupled physical processes to achieve a better representation of the modeled system. Most of the parameters included in models are difficult to measure directly, so they must be estimated from collected data through a calibration procedure. Furthermore, when models are used to make forecasts about future or hypothetical scenarios, it is important to bound the uncertainty of their results. Therefore, the application of systematic approaches for parameter estimation, sensitivity, and uncertainty analysis to integrate data and models and quantify potential errors, is more necessary now than it was in the past. Even though methodological frameworks for these purposes exist, they have had a slow adoption due to their high computational cost and the required technical knowledge to apply them. We analyze existing methodologies, discuss remaining challenges, and present a survey of emerging trends for the application of parameter estimation and uncertainty analysis in hydrological modeling. Thus, the main objective of this overview article is contributing to improving the quality of models and to their correct use as support tools for decision-making.

  • Wood ash amended biochar for the removal of lead, copper, zinc and cadmium from aqueous solution

    Stuart Cairns, Sampriti Chaudhuri, Gabriel Sigmund, Iain Robertson, Natasha Hawkins, Tom Dunlop, Thilo Hofmann
    2021 - Environmental Technology & Innovation, 24: 1-11

    Abstract: 

    Heavy metals in motorway adjoined aqueous environments have increased at an alarming rate over recent years. This increase has been primarily attributed to anthropogenic activities such as the increase of motor vehicle use. Current remediation techniques, such as balancing ponds have the potential to leave toxic residue with the associated removal costs often proving prohibitive. In this study biochar and wood ash amended biochar were evaluated as remediators of inorganic vehicular pollutants found in motorway runoff, specifically Pb, Cu, Zn and Cd. Biochar from European larch (Larix decidua (L.) Karst.) was produced via fast pyrolysis-gasification (485–530 °C for 90 s) and amended with wood ash post pyrolysis. Pristine larch biochar (BC), larch biochar cold mixed with wood ash (WA) and larch biochar sintered with wood ash (WAS) were studied to evaluate metal immobilisation mechanisms and maximum removal capacities. This study demonstrates that the amendment of biochar with wood ash increases Pb, Cu, Zn, and Cd immobilisation by an order of magnitude compared to BC. The addition of wood ash increases pH whilst adding minerals causing precipitation. Precipitation and ion exchange dominate metal immobilisation and were not correlated to surface area. Sustainability of feedstock, low feedstock/production costs and maximum measured contaminant removal (61.5 mg/g, 38.9 mg/g, 12.1 mg/g and 10.2 mg/g for Pb, Cu, Zn and Cd respectively) indicate that wood ash amended biochar is a viable option to immobilise Pb, Cu, Zn and Cd from motorway runoff.

  • A Large-Scale 3D Study on Transport of Humic Acid-Coated Goethite Nanoparticles for Aquifer Remediation

    Milica Velimirovic, Carlo Bianco, Natalia Ferrantello, Tiziana Tosco, Alessandro Casasso, Rajandrea Sethi, Doris Schmid, Stephan Wagner, Kumiko Miyajima, Norbert Klaas, Rainer U. Meckenstock, Frank von der Kammer, Bert Engelen, Thilo Hofmann
    2020 - Water, 12: 1207

    Abstract: 

    Humic acid-coated goethite nanoparticles (HA-GoeNPs) have been recently proposed as an effective reagent for the in situ nanoremediation of contaminated aquifers. However, the effective dosage of these particles has been studied only at laboratory scale to date. This study investigates the possibility of using HA-GoeNPs in remediation of real field sites by mimicking the injection and transport of HA-GoeNPs under realistic conditions. To this purpose, a three-dimensional (3D) transport experiment was conducted in a large-scale container representing a heterogeneous unconfined aquifer. Monitoring data, including particle size distribution, total iron (Fetot) content and turbidity measurements, revealed a good subsurface mobility of the HA-GoeNP suspension, especially within the higher permeability zones. A radius of influence of 2 m was achieved, proving that HA-GoeNPs delivery is feasible for aquifer restoration. A flow and transport model of the container was built using the numerical code Micro and Nanoparticle transport Model in 3D geometries (MNM3D) to predict the particle behavior during the experiment. The agreement between modeling and experimental results validated the capability of the model to reproduce the HA-GoeNP transport in a 3D heterogeneous aquifer. Such result confirms MNM3D as a valuable tool to support the design of field-scale applications of goethite-based nanoremediation.

  • Accurate quantification of TiO2 nanoparticles in commercial sunscreens using standard materials and orthogonal particle sizing methods for verification

    Milica Velimirovic, Stephan Wagner, Fazel Abdolahpur Monikh, Toni Uusimäki, Ralf Kaegi, Thilo Hofmann, Frank von der Kammer
    2020 - Talanta, 215: 120921

    Abstract: 

    The implementation and enforcement of product labeling obligation as required, for example, by the cosmetic product regulation, needs simple and precise validated analytical methods. This also applies to the analysis of nanoparticles in products such as cosmetics. However, the provision of such methods is often hampered by inaccurate sizing due to unwanted nanoparticle changes, interference of matrix components with sizing and interactions between nanoparticles and analytical instrumentation. It is, therefore, necessary to develop appropriate sample preparation methods that preserve NP properties and reduce or remove matrix compounds that interfere with sizing. Further, accurate particle size analysis of samples containing unknown and possibly multiple nanoparticulate constituents is needed. In this study, we evaluated three sample preparation methods to identify and quantify TiO2 nanoparticles in sunscreens. Specifically, we used a combination of ultracentrifugation and hexane washing, thermal destruction of the matrix, and surfactant assisted particle extraction. The method accuracy was assessed by two internal reference samples: pristine TiO2 nanoparticles (NM104) and similar TiO2 nanoparticles dispersed in a sunscreen matrix. The PSDs were determined using an asymmetrical flow field-flow fractionation hyphenated with multi-angle light scattering and inductively coupled plasma-mass spectroscopy. Particle sizing was based on size calibration of the particle retention time in the AF4. Computation of radius of gyration from MALS data was used as an orthogonal particle sizing approach to verify ideal elution and particle size data from the AF4 calibration. Among the three tested sample preparation methods surfactant assisted particle extraction revealed TiO2 nanoparticle recoveries of above 90% and no increase in particle size due to sample preparation was observed. Finally, the sample preparation methods were applied to two commercial sunscreen samples revealing the existence of TiO2-NP < 100 nm. Conclusively, the surfactant assisted particle extraction method can provide valid data for TiO2-NPs in sunscreen and possibly for cosmetic samples of similar matrix.

  • Carbonates and cherts as archives of seawater chemistry and habitability on a carbonate platform 3.35 Ga ago: Insights from Sm/Nd dating and trace element analysis from the Strelley Pool Formation, Western Australia

    Sebastian Viehmann. Joachim Reitner, NathalieTepe, Simon V. Hohl, Martin Van Kranendonk, Thilo Hofmann, Christian Koeberl, Patrick Meister
    2020 - Precambrian Research, 344: 105742

    Abstract: 

    Carbonates and cherts in the 3.35 billion-year-old Strelley Pool Formation (Fm.; Australia) host stromatolites that are among the oldest remnants of life on Earth. However, it is still not entirely clear whether these mineral phases are authigenic precipitates, and whether they represent reliable geochemical archives of early Earth environments. Here we present major/trace-element and Nd-isotope data of stromatolitic carbonates, associated crystal-fan carbonates, and cherts in the Strelley Pool Fm. (i) to assess the reliability of these chemical sediments as geochemical archives of the fluids from which they precipitated, (ii) to date the time of formation of carbonate and silica phases, and (iii) to trace the sources of elements prevailing in microbial habitats 3.35 Ga ago.

    Stromatolitic carbonates plot together with the stratigraphically underlying Marble Bar cherts on a Sm-Nd regression line yielding 3253 ± 320 Ma. In contrast, associated crystal-fan carbonates together with altered Marble Bar cherts yield 2718 ± 220 Ma, suggesting that their Sm-Nd isotope system was reset after deposition. Both types of carbonates, as well as white cherts, show shale-normalized rare earth element and yttrium patterns (REYSN; with the exception of redox-sensitive Ce and Eu and heavy REYSN to middle REYSN depletion) that are parallel to those of modern seawater, indicating a predominantly seawater-derived origin. Positive EuSN anomalies (2.1–2.4), combined with heterogeneous ɛNd3.35Ga values between −3.2 and +5.8 within individual alternating stromatolite laminae, further support that the dissolved fraction of seawater on the ancient carbonate platform was variably affected by both continental weathering and high-temperature hydrothermal fluids contributing elements of both young mafic or older felsic rocks. In conclusion, trace element and Nd isotope data presented here match well with the depositional environment, as characterized based on lithological, geochemical, and stratigraphic relationships, on an early continent, showing at least episodic emergence above the sea level, supporting microbial life on a shallow marine platform.

     
  • Deep Learning Neural Network Approach for Predicting the Sorption of Ionizable and Polar Organic Pollutants to a Wide Range of Carbonaceous Materials

    Gabriel Sigmund, Mehdi Gharasoo, Thorsten Hüffer, Thilo Hofmann
    2020 - Environmental Science & Technology, 54: 4583-4591

    Abstract: 

    Most contaminants of emerging concern are polar and/or ionizable organic compounds, whose removal from engineered and environmental systems is difficult. Carbonaceous sorbents include activated carbon, biochar, fullerenes, and carbon nanotubes, with applications such as drinking water filtration, wastewater treatment, and contaminant remediation. Tools for predicting sorption of many emerging contaminants to these sorbents are lacking because existing models were developed for neutral compounds. A method to select the appropriate sorbent for a given contaminant based on the ability to predict sorption is required by researchers and practitioners alike. Here, we present a widely applicable deep learning neural network approach that excellently predicted the conventionally used Freundlich isotherm fitting parameters log KF and n (R2 > 0.98 for log KF, and R2 > 0.91 for n). The neural network models are based on parameters generally available for carbonaceous sorbents and/or parameters freely available from online databases. A freely accessible graphical user interface is provided.

  • Groundwater Chemistry Has a Greater Influence on the Mobility of Nanoparticles Used for Remediation than the Chemical Heterogeneity of Aquifer Media

    Vesna Micić, Nathan Bossa, Doris Schmid, Mark R. Wiesner, Thilo Hofmann
    2020 - Environmental Science & Technology, 54: 1250-1257

    Abstract: 

    The application of nanoscale zerovalent iron (nano-ZVI) particles for groundwater remediation has spurred research into the influence of the collector heterogeneity on the  nano-ZVI mobility. The chemical heterogeneity of surfaces within aquifer media affects their surface charge distribution and their affinity for nano-ZVI. The groundwater chemistry affects the properties of both aquifer surfaces and the nano-ZVI particles. Commercial poly(acrylic acid)-coated nano-ZVI (PAA−nano-ZVI) particles were tested in column experiments using two solution chemistries and silica collectors with different degrees of chemical heterogeneity, achieved by ferrihydrite coating. A porous media filtration model was used to determine the attachment efficiency of PAA−nano-ZVI particles, and the Derjaguin−Landau−Verwey−Overbeek (DLVO) theory was used to describe the interactions between PAA−nano-ZVI particles and the aquifer “collectors”. The mobility of PAA−nano-ZVI particles suspended in ultrapure water depended on the extent of ferrihydrite coating on the collector surfaces. The mobility of PAA−nano-ZVI particles under environmentally relevant conditions was independent of the collector chemical heterogeneity. The size of PAA−nano-ZVI aggregates doubled, inducing gravitational sedimentation and possibly straining as mechanisms of particle deposition. There was no repulsive energy barrier between particles and collectors, and the DLVO theory was unable to explain the observed particle attachment. Our results suggest that the groundwater chemistry has a greater influence on the mobility of PAA−nano-ZVI particles than the collector chemical heterogeneity. A better understanding of polymer adsorption to nanoparticles and its conformation under natural groundwater conditions is needed to further elucidate nanoparticle−collector interactions.

  • Intra-laboratory assessment of a method for the detection of TiO2 nanoparticles present in sunscreens based on multi-detector asymmetrical flow field-flow fractionation

    Milica Velimirovic, Stephan Wagner, Robert Koeber, Thilo Hofmann, Frank von der Kammer
    2020 - NanoImpact, 19: 100233

    Abstract: 

    In this study, an intra-laboratory assessment was carried out to establish the effectiveness of a method for the detection of TiO2 engineered nanoparticles (ENPs) present in sunscreen containing nano-scale TiO2 and a higher nanometer-range (approx. 200–500 nm) TiO2, as well as iron oxide particles. Three replicate measurements were performed on five separate days to generate the measurement uncertainties associated with the quantitative asymmetrical flow field-flow fractionation (AF4) measurement of the hydrodynamic radius rh,mode1 (MALS), rh,mode1 (ICP-MS), rh,mode2 (ICP-MS), and calculated mass-based particle size distribution (d10, d50, d90). The validation study demonstrates that the analysis of TiO2 ENPs present in sunscreen by AF4 separation-multi detection produces quantitative data (mass-based particle size distribution) after applying the sample preparation method developed within the NanoDefine project with uncertainties based on the precision (uIP) of 3.9–8.8%. This method can, therefore, be considered as the method with a good precision. Finally, the bias data shows that the trueness of the method (ut = 5.5–52%) can only be taken as a proxy due to the lack of a sunscreen standard containing certified TiO2 ENPs.

  • Quantification and Characterization of Nanoparticulate Zinc in an Urban Watershed

    Shaun Bevers, Manuel David Montano, Laya Rybicki, Thilo Hofmann, Frank von der Kammer, James F. Ranville
    2020 - Frontiers in Environmental Science, 8: 84

    Abstract: 

    The recent expansion in the use of nanomaterials in consumer and industrial applications has led to a growing concern over their behavior, fate, and impacts in environmental systems. However, engineered nanoparticles comprise only a small fraction of the total nanoparticle mass in aquatic systems. Human activities, particularly in urban watersheds, are increasing the population of incidental nanoparticles and are likely  altering the cycling of more abundant natural nanoparticles. Accurate detection, quantification, characterization, and tracking of these different populations is important for assessing both the ecological risks of anthropogenic particles, and their impact on environmental health. The urban portion of the South Platte watershed in Denver, Colorado (United States) was sampled for zinc to identify and quantify different nanomaterial sources. Single particle ICP-QMS was employed, to provide single elemental (Zn) signals arising from particle detection events. Coupling spICP-QMS to sample pre-fractionation (sedimentation, filtration) provided some insights into Zn association with nanoparticulate, colloidal, and suspended sediment phases. Single particle ICP-TOFMS (spICP-TOFMS) provided quantification across a large atomic mass range, yielding an even more detailed characterization (elemental ratios) on a particle-by-particle basis, providing some delineation of multiple sources of particles. Across the watershed, on average, 21% of zinc mass was present as zinc-only particles with a rather uniform mean size of 40.2 nm. Zinc that was detected with one or more other elements, primarily Al, Fe, and Si, is likely to be present as heteroagglomerates or within mineral colloids. Although spICP-TOFMS provides a substantial amount of information, it is still in its early stages as an analytical technique and currently lacks the requisite sensitivity to study the smallest of nanoparticles. As this technique continues to develop, it is anticipated that this methodology can be broadly applied to study sources, behavior and effects of a disparate variety of nanoparticles from both geogenic and anthropogenic origins.

  • Strategies for determining heteroaggregation attachment efficiencies of engineered nanoparticles in aquatic environments

    Antonia Praetorius, Elena Badetti, Andrea Brunelli, Arnaud Clavier, Julián Alberto Gallego-Urrea, Andreas Gondikas, Martin Hassellöv, Thilo Hofmann, Aiga Mackevica, Antonio Marcomini, Willie Peijnenburg, Joris T. K. Quik, Marianne Seijo, Serge Stoll, Nathalie Tepe, Helene Walch, Frank von der Kammer
    2020 - Environmental Science: Nano, 7: 351–367

    Abstract: 

    Heteroaggregation of engineered nanoparticles (ENPs) with suspended particulate matter (SPM) ubiquitous in natural waters often dominates the transport behaviour and overall fate of ENPs in aquatic environments. In order to provide meaningful exposure predictions and support risk assessment for ENPs, environmental fate and transport models require quantitative information about this process, typically in the form of the so-called attachment efficiency for heteroaggregation αhetero. The inherent complexity of heteroaggregation—encompassing at least two different particle populations, various aggregation pathways and several possible attachment efficiencies (α values)—makes its theoretical and experimental determination challenging. In this frontier review we assess the current state of knowledge on heteroaggregation of ENPs with a focus on natural surface waters. A theoretical analysis presents relevant equations, outlines the possible aggregation pathways and highlights different types of α. In a second part, experimental approaches to study heteroaggregation and derive α values are reviewed and three possible strategies are identified: i) monitoring changes in size, ii) monitoring number or mass distribution and iii) studying indirect effects, such as sedimentation. It becomes apparent that the complexity of heteroaggregation creates various challenges and no single best method for its assessment has been developed yet. Nevertheless, many promising strategies have been identified and meaningful data can be derived from carefully designed experiments when accounting for the different concurrent aggregation pathways and clearly stating the type of α reported. For future method development a closer connection between experiments and models is encouraged.

  • Sulfidated nano-scale zerovalent iron is able to effectively reduce in situ hexavalent chromium in a contaminated aquifer

    Miroslav Brumovský, Jana Oborná, Petr Lacina, Michal Hegedüs, Ondra Sracek, Jan Kolařík, Martin Petr, Josef Kašlík, Thilo Hofmann, Jan Filip
    2020 - Journal of Hazardous Materials, 405: 124665

    Abstract: 

    In a number of laboratory studies, sulfidated nanoscale zero-valent iron (S-nZVI) particles showed increased reactivity, reducing capacity, and electron selectivity for Cr(VI) removal from contaminated waters. In our study, core-shell S-nZVI particles were successfully injected into an aquifer contaminated with Cr(VI) at a former chrome plating facility. S-nZVI migrated towards monitoring wells, resulting in a rapid decrease in Cr(VI) and Crtot concentrations and a long-term decrease in groundwater redox potential observed even 35 m downstream the nearest injection well. Characterization of materials recovered from the injection and monitoring wells confirmed the presence of nZVI particles, together with iron corrosion products. Chromium was identified on the surface of the recovered iron particles as Cr(III), and its occurrence was linked to the formation of insoluble chromium-iron (oxyhydr)oxides such as CrxFe(1−x)(OH)3(s). Injected S-nZVI particles formed aggregates, which were slowly transformed into iron (oxyhydr)oxides and carbonate green rust. Elevated contents of Fe0 were detected even several months after injection, indicating good S-nZVI longevity. The sulfide shell was gradually disintegrated and/or dissolved. Geochemical modelling confirmed the overall stability of the resulting Cr(III) phase at field conditions. This study demonstrates the applicability of S-nZVI for the remediation of a Cr(VI)-contaminated aquifer.

  • Technology readiness and overcoming barriers to sustainably implement nanotechnology-enabled plant agriculture

    Thilo Hofmann, Gregory Victor Lowry, Subhasis Ghoshal, Nathalie Tufenkji, Davide Brambilla, John Robert Dutcher, Leanne M. Gilbertson, Juan Pablo Giraldo, Joseph Matthew Kinsella, Markita Patricia Landry, Wess Lovell, Rafik Naccache, Mathews Paret, Joel Alexander Pedersen, Jason Michael Unrine, Jason Christopher White, Kevin James Wilkinson
    2020 - Nature food, 1: 416–425

    Abstract: 

    Nanotechnology offers potential solutions for sustainable agriculture, including increasing nutrient utilization efficiency, improving the efficacy of pest management, mitigating the impacts of climate change, and reducing adverse environmental impacts of agricultural food production. Many promising nanotechnologies have been proposed and evaluated at different scales, but several barriers to implementation must be addressed for technology to be adopted, including efficient delivery at field scale, regulatory and safety concerns, and consumer acceptance. Here we explore these barriers, and rank technology readiness and potential impacts of a wide range of agricultural applications of nanotechnology. We propose pathways to overcome these barriers and develop effective, safe and acceptable nanotechnologies for agriculture.

  • The importance of aromaticity to describe the interactions of organic matter with carbonaceous materials depends on molecular weight and sorbent geometry

    Stephanie Castan, Gabriel Sigmund, Thorsten Hüffer, Nathalie Tepe, Frank von der Kammer, Benny Chefetz, Thilo Hofmann
    2020 - Environmental Science.: Processes & Impacts, 22: 1888-1897

    Abstract: 

    Dissolved organic matter (DOM) is ubiquitous in aquatic environments where it interacts with a variety of particles including carbonaceous materials (CMs). The complexity of both DOM and the CMs makes DOM–CM interactions difficult to predict. In this study we have identified the preferential sorption of specific DOM fractions as being dependent on their aromaticity and molecular weight, as well as on the surface properties of the CMs. This was achieved by conducting sorption batch experiments with three types of DOM (humic acid, Suwannee River natural organic matter, and a compost extract) and three types of CMs (graphite, carbon nanotubes, and biochar) with different geometries and surface complexities. The non-adsorbed DOM fraction was analyzed by size exclusion chromatography and preferentially sorbed molecular weight fractions were analyzed by UV/vis and fluorescence spectroscopy. All three sorbent types were found to preferentially sorb aromatic DOM fractions, but DOM fractionation depended on the particular combination of sorbent and sorbate characteristics. Single-walled carbon nanotubes only sorbed the smaller molecular weight fractions (<1 kDa). The sorption of smaller DOM fractions was not accompanied by a preference for less aromatic compounds, contrary to what was suggested in previous studies. While graphite preferentially sorbed the most aromatic DOM fraction (1–3 kDa), the structural heterogeneity of biochar resulted in reduced selectivity, sorbing all DOM > 1 kDa. The results explain the lack of correlation found in previous studies between the amount of aromatic carbon in a bulk DOM and its sorption coefficient. DOM sorption by CMs was generally controlled by DOM aromaticity but complex sorbent surfaces with high porosity, curvatures and functional groups strongly reduced the importance of aromaticity.

  • The molecular interactions of organic compounds with tire crumb materials differ substantially from those with other microplastics

    2020 - Environmental Science: Processes & Impacts, 22: 121-130

    Abstract: 

    Tire materials are the most commonly found elastomers in the environment and they account for a significant fraction of microplastic pollution. In the discussions on the environmental impact of microplastics tire materials and their sorption properties have been largely overlooked. In this study we used experimental sorption data from six organic probe sorbates sorbing to two tire materials and their major components, styrene butadiene rubber and carbon black, to gain a better understanding of the underlying sorption processes of tire materials. Commonly applied models used to describe non-linear sorption processes were unable to fully explain sorption to tire materials but showed that absorption into the rubber fraction dominated the sorption process. Hydrophobicity was approximated using the hexadecane–water partitioning constant, which correlated very well with the distribution data obtained for styrene rubber, whereas the correlations between hydrophobicity of sorbates and the sorption data to the tire materials were poor. Although hydrophobicity plays an important role in sorption to tire materials, additional interactions must be taken into account. Overall, the processes involved in sorption to tire materials differed significantly from those governing sorption to other microplastics.

  • Biochar particle aggregation in soil pore water: the influence of ionic strength and interactions with pyrene

    Stephanie Castan, Gabriel Sigmund, Thorsten Hüffer, Thilo Hofmann
    2019 - Environmental Science: Processes & Impacts, 21: 1722-1728

    Abstract: 

    The beneficial properties of biochar have led to its increasing application to soils for environmental management. Despite its stability in soil, biochar can physically disintegrate into smaller particles, which can then be relocated from the application area. Biochar transport is strongly dependent on the biochar particle size and aggregation, with the extent of aggregation depending on the chemistry of the soil pore water. Biochar has a strong sorption affinity for polyaromatic hydrocarbons (PAHs) such as pyrene, which can also affect its transport. We therefore investigated biochar particle aggregation in solutions of different ionic strengths (ultrapure water, 0.01 M CaCl2, and 0.1 M CaCl2) with suspensions of biochar particles, and with suspensions of biochar particles loaded with pyrene (0.2 and 3.6 g kg−1). Increasing the pyrene concentration in ultrapure water resulted in an increase in the biochar particle size, an effect that was more pronounced following equilibration for 28 days than following equilibration for only 24 hours. Biochar particle aggregation in solutions containing both pyrene and 0.01 M CaCl2 was greatly enhanced compared to aggregation in similar solutions with no pyrene. However, the influence of pyrene became negligible at high CaCl2 concentrations (0.1 M CaCl2). To determine the fate of biochar in soil, both the presence of PAHs and the influence of the pore water's ionic strength therefore need to be taken into account.

  • Chemosymbiotic bivalves contribute to the nitrogen budget of seagrass ecosystems

    Ulisse Cardini, Marco Bartoli, Sebastian Lücker, Maria Mooshammer, Julia Polzin, Raymond W. Lee, Vesna Micić, Thilo Hofmann, Miriam Weber, Jillian M. Petersen
    2019 - The ISME journal, 3131–3134

    Abstract: 

    In many seagrass sediments, lucinid bivalves and their sulfur-oxidizing symbionts are thought to underpin key ecosystem functions, but little is known about their role in nutrient cycles, particularly nitrogen. We used natural stable isotopes, elemental analyses, and stable isotope probing to study the ecological stoichiometry of a lucinid symbiosis in spring and fall. Chemoautotrophy appeared to dominate in fall, when chemoautotrophic carbon fixation rates were up to one order of magnitude higher as compared with the spring, suggesting a flexible nutritional mutualism. In fall, an isotope pool dilution experiment revealed carbon limitation of the symbiosis and ammonium excretion rates up to tenfold higher compared with fluxes reported for nonsymbiotic marine bivalves. These results provide evidence that lucinid bivalves can contribute substantial amounts of ammonium to the ecosystem. Given the preference of seagrasses for this nitrogen source, lucinid bivalves’ contribution may boost productivity of these important blue carbon ecosystems.
  • Complex-conductivity monitoring to delineate aquifer pore clogging during nanoparticles injection

    Flores Orozco Adrián, Vesna Micić, Matthias Bücker, Jakob Gallistl, Thilo Hofmann, Frederic Nguyen
    2019 - Geophysical Journal International, 3: 1838-1852

    Abstract: 

    Laboratory and field studies have demonstrated the applicability of nanoparticles (NP) for accelerated contaminant degradation. Beside other limitations (e.g. costs, delivery, longevity, non-target specific reactions), concerns of regulators arose regarding toxicity of injected NP and particles delivered off-target (i.e. renegade particles). Renegade particles also significantly reduce the efficiency of the remediation. The delivery of particles off-target is caused, mainly, by unintended fracking, where the fractures act then as preferential flow paths changing the trajectory of the particles. Hence, the real-time monitoring of particle injection is of major importance to verify correct particle delivery and thus help to optimize the remediation strategy. However, to date NP monitoring techniques rely on the analysis of soil and water samples, which cannot provide information about clogging or the formation of fractures away of the sampling points. To overcome these limitations, in this study we investigate the applicability of complex-conductivity imaging (CCI), a geophysical electrical method, to characterize possible pore clogging and fracking during NP injections. We hypothesize that both processes are related to different electrical footprints, considering the loss of porosity during clogging and the accumulation of NP in areas away of the target after fracking. Here, we present CCI results for data collected before and during the injection of Nano-Goethite particles (NGP) applied to enhance biodegradation of a BTEX (benzene, toluene, ethylbenzene and xylene) contaminant plume. Imaging results for background data revealed consistency with the known lithology, while overall high electrical conductivity values and a negligible induced-polarization magnitude correspond with the expected response of a mature hydrocarbon plume. Monitoring images revealed a general increase (∼15 per cent) in the electrical conductivity due to the injected NGP suspension in agreement with geochemical data. Furthermore, abrupt changes in this trend, shortly before daylighting events, show the sensitivity of the method to pore clogging. Such interpretation is in line with the larger variations in CCI resolved in the unsaturated zone, clearly indicating the accumulation of renegade NGP close to the surface due to fracking. Our results demonstrate the applicability of the CCI method for the assessment of pore clogging accompanying particles injection.

  • Emerging contaminants in sediment core from the Iron Gate I reservoir on the Danube River

    Ivana Mati Bujagi, Svetlana Gruji, Mila Lauevi, Thilo Hofmann, Vesna Micić
    2019 - Science of The Total Environment, 77-87

    Abstract: 

    The Iron Gate I Reservoir is the largest impoundment on the Danube River. It retains >50% of the incoming total suspended solids load and the associated organic contaminants. In the sediment core of the Iron Gate I Reservoir we report the presence and fate of four classes of emerging contaminants (pharmaceuticals, pesticides, steroids and perfluorinated compounds), predominantly not covered by the EU monitoring programs, but considered as future candidates. Based on contaminant's partitioning behavior in the water/sediment system and the suspected ecotoxicological potential asserted from the literature data, the risk of recorded concentrations for sediment-dwelling organisms was discussed. The high anticipated risk was associated with antibiotics sulfamethoxazole and erythromycin, and pesticides linuron and carbendazim (banned in the EU, but still approved for use in the investigated area) and malathion. This indicated the need for better control of release of these compounds into the river, and implied their inclusion in future regular monitoring. Higher concentrations of pharmaceuticals and most pesticides and sterols were recorded in the fragment of allochthonous coarser sediment, assumed to have entered the reservoir during a high discharge event. Only one perfluorinated compound was recorded in the upper part of the sediment core. The vertical concentration profiles of pesticides propazine and malathion indicated their uniform source, most likely atmospheric transport and deposition of particles deriving from agricultural land.

  • In situ remediation of subsurface contamination: opportunities and challenges for nanotechnology and advanced materials

    Tong Zhang, Gregory V. Lowry, Natalie L. Capiro, Jianmin Chen, Wei Chen, Yongsheng Chen, Dionysios D. Dionysiou, Daniel W. Elliott, Subhasis Ghoshal, Thilo Hofmann, Heileen Hsu-Kim, Joseph Hughes, Chuanjia Jiang, Guibin Jiang, Chuanyong Jing, Michael Kavanaugh, Qilin Li, Sijin Liu, Jie Ma, Bingcai Pan, Tanapon Phenrat, Xiaolei Qu, Xie Quan, Navid Saleh, Peter J. Vikesland, Qiuquan Wang, Paul Westerhoff, Michael S. Wong, Tian Xia, Baoshan Xing, Bing Yan, Lunliang Zhang, Dongmei Zhouaa, Pedro J. J. Alvarez
    2019 - Environmental Science: Nano, 5: 1283-1302

    Abstract: 

    Complex subsurface contamination domains and limited efficacy of existing treatment approaches pose significant challenges to site remediation and underscore the need for technological innovation to develop cost-effective remedies. Here, we discuss opportunities for nanotechnology-enabled in situ remediation technologies to address soil and groundwater contamination. The discussion covers candidate nanomaterials, applications of nanomaterials to complement existing remediation approaches and address emerging contaminants, as well as the potential barriers for implementation and strategies and research needs to overcome these barriers. Promising nanomaterials in subsurface remediation include multi-functional nanocomposites for synergistic contaminant sequestration and degradation, selective adsorbents and catalysts, nano-tracers for subsurface contaminant delineation, and slow-release reagents enabled by stimuli-responsive nanomaterials. Limitations on mixing and transport of nanomaterials in the subsurface are severe constraints for in situ applications of these materials. Mixing enhancements are needed to overcome transport limitations in laminar flow environments. Reactive nanomaterials may be generated in situ to remediate contamination in low hydraulic conductivity zones. Overall, nano-enabled remediation technologies may improve remediation performance for a broad range of legacy and emerging contaminants. These technologies should continue to be developed and tested to discern theoretical hypotheses from feasible opportunities, and to establish realistic performance expectations for in situ remediation techniques using engineered nanomaterials alone or in combination with other technologies.

  • Legal and practical challenges in classifying nanomaterials according to regulatory definitions

    Martin Miernicki, Thilo Hofmann, Iris Eisenberger, Frank von der Kammer, Antonia Praetorius
    2019 - Nature Nanotechnology, 14: 208–216

    Abstract: 

    The European Union (EU) has adopted nano-specific provisions for cosmetics, food and biocides, among others, which include binding definitions of the term “nanomaterial”. Here we take an interdisciplinary approach to analyse the respective definitions from a legal and practical perspective. Our assessment reveals that the definitions contain several ill-defined terms such as “insoluble” or “characteristic properties” and/or are missing thresholds. Furthermore, the definitions pose major and so far unsolved analytical challenges that, in practice, make it nearly impossible to classify nanomaterials according to EU regulatory requirements. An important purpose of the regulations, the protection of human health and the environment, may remain unfulfilled and the development of innovative applications of nanomaterials may be facing a path full of (legal) uncertainties. Based on our findings, we provide five recommendations for a more coherent and practical approach towards the regulation of nanomaterials.

  • Mineralogy and weathering of realgar-rich tailings at a former As-Sb-Cr mine at Lojane, North Macedonia

    Tamara Dordevic, Uwe Kolitsch, Todor Serafimovski, Goran Tasev, Nathalie Tepe, Michael Stger-Pollach, Thilo Hofmann, Blazo Boev
    2019 - The Canadian Mineralogist, 57: 1-21

    Abstract: 

    In the Lojane area (North Macedonia) ores of Sb (stibnite), As (realgar), and Cr (chromite) were mined and processed in a metallurgical plant until 1979. Over one million tons of flotation tailings containing As, Sb, and other hazardous substances are located in an open dump site for flotation waste created by the mine. The tailings site is completely unprotected, and its orange color reflects a very high concentration of arsenic (fine-grained realgar superficially altered to pararealgar). In order to better understand the weathering behavior of these tailings, which is necessary to evaluate the environmental risks (mainly from the mobilization of As-Sb-Cr), solid waste material was sampled and studied from the chemical and mineralogical point of view. The material was characterized by inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasmaoptical emission spectrometry (ICP-OES), X-ray diffraction analysis (both single crystal and powder), scanning electron microscopy (SEM) with energy-dispersive microanalysis (EDX), Raman spectroscopy, and transmission electron microscopy (TEM) with selected area electron diffraction (SAED), energy-dispersive X-ray analysis (EDX), and electron energy loss spectrometry (EELS). The studied tailings material is comprised mostly of well-crystallized realgar, gypsum, and quartz, and minor amounts of stibnite, pararealgar, chromite, and sulfur. Very minor pyrite is found within quartz aggregates. The most abundant secondary phase, which forms thin coatings around realgar and stibnite grains, is an As-Sb-Fe-Ca-(Ni)-oxide/hydroxide in which the As:Sb ratio varies from ca. 2:1 to 1:2.2 and Fe contents are variable. Antimony-dominant variants of this oxide also form larger homogeneous grains up to 500 lm in size, characterized by broad dehydration cracks suggesting original formation as a gel. Both As-rich and -poor variants were identified as members of the rom´eite group. EELS showed that all the Fe is ferric. Further secondary phases originated from the weathering of realgar, stibnite, and other primary phases are As-bearing sulfur, scorodite (often slightly Sb-bearing, locally common), arsenolite, ‘‘limonite’’, pickeringite (Ni- and Febearing), alunogen, and annabergite. The weathering of primary sulfides in the flotation tailings at Lojane proceeded under mostly oxidizing, acidic, and temporarily wet conditions. Highly acidic conditions on the surface of the tailings dump imply dissolution of arsenolite and scorodite, thus causing contamination of the environment and high mobility of arsenic.

  • NO2 and natural organic matter affect both soot aggregation behavior and sorption of S-metolachlor

    Gabriel Sigmund, Stephanie Castan, Christopher Wabnitz, Rani Bakkour, Thorsten Hüffer, Thilo Hofmann, Martin Elsner
    2019 - Environmental Science: Processes & Impacts, 21: 1729-1735

    Abstract: 

    Soot is an important carbonaceous nanoparticle (CNP) frequently found in natural environments. Its entry into surface waters can occur directly via surface runoff or infiltration, as well as via atmospheric deposition. Pristine soot is likely to rapidly undergo aggregation and subsequent sedimentation in aquatic environments. Further, soot can sorb a variety of organic contaminants, such as S-metolachlor (log KD = 3.25 ± 0.12). During atmospheric transport, soot can be chemically transformed by reactive oxygen species including NO2. The presence of natural organic matter (NOM) in surface waters can further affect the aquatic fate of soot. To better understand the processes driving the fate of soot and its interactions with contaminants, pristine and NO2-transformed model soot suspensions were investigated in the presence and absence of NOM. NO2-oxidized soot showed a smaller particle size, a higher number of particles remaining in suspension, and a decreased sorption of S-metolachlor (log KD = 2.47 ± 0.40). In agreement with findings for other CNPs, soot stability against aggregation was increased for both pristine and NO2 transformed soot in the presence of NOM.

  • Persistence of copper-based nanoparticle-containing foliar sprays in Lactuca sativa (lettuce) characterized by spICP-MS

    Stephanie Laughton, Adam Laycock, Frank von der Kammer, Thilo Hofmann, Elizabeth A. Casman, Sónia M. Rodrigues, Gregory V. Lowry
    2019 - Journal of Nanoparticle Research, 174: in press

    Abstract: 

    Copper oxide and hydroxide nanoparticles (Cu-NPs) are components of some commercial pesticides. When these Cu-NPs dissolve in the environment, their size distribution, efficacy, and toxicity are altered. Since acute toxicity screens typically involve pristine NPs, quantification of the transformation of their size distribution in edible leaf vegetables is necessary for accurate consumer risk assessment. Single particle ICP-MS was used to investigate the persistence of three forms of Cu-NPs following foliar application to live lettuce (Lactuca sativa): CuO NP, Cu(OH)2 NP, and Kocide 3000®. A methanol-based digestion method was used to minimize Cu-NP dissolution during extraction from the leaf tissues. After dosing, the NPs associated with the leaf tissues were characterized over a 9-day period to monitor persistence. Nanoparticle counts and total copper mass concentrations remained constant, though the particle size distributions shifted down over time. Washing the leaves in tap water resulted in removal of total copper while the number of Cu-NPs remaining depended on the form applied. This work indicates that washing of lettuce preferentially removed dissolved Cu over Cu-NPs, and that the amount of residual Cu-NPs remaining is low when applied at the recommended rates for Kocide 3000®.

  • Polyethylene microplastics influence the transport of organic contaminants in soil

    Thorsten Hüffer, Florian Metzelder, Gabriel Sigmund, Sophie Slawek, Torsten C. Schmidt, Thilo Hofmann
    2019 - Science of The Total Environment, 242-247

    Abstract: 

    Plastics are now found in all natural environments including soil. The effects of microplastics in terrestrial systems, however, remain largely unexplored. Polyethylene is one of the mass-manufactured polymers found in terrestrial environments. It is used in many different sectors, for example in agricultural mulches, composite materials, and packaging. The presence of microplastics in soil, including polyethylene, can affect the transport of hydrophobic organic pollutants including pesticides. The objective of this study was to investigate the influence of polyethylene microplastics (<250 μm) on the transport of two selected organic plant-protection agents (atrazine and 4-(2,4-dichlorophenoxy) butyric acid) in soil under different aqueous conditions, using inverse liquid chromatography. The distribution coefficients for the sorbates that were sorbed to pure polyethylene microplastic were found to be significantly smaller than those for the sorbates sorbed to pure soil. The addition of 10% (w/w) polyethylene to the soil therefore led to an overall reduction in sorption, but the sorption trends due to variations in pH and ionic strength were not affected. The results imply that the presence of polyethylene microplastics in soil may therefore increase the mobility of organic contaminants by reducing the sorption capacity of natural soils, which must be validated by further research.

  • Sorption of organic substances to tire wear materials: Similarities and differences with other types of microplastic

    Thorsten Hüffer, Stephan Wagner, Thorsten Reemtsma, Thilo Hofmann
    2019 - Trends in Analytical Chemistry, 113: 392-401

    Abstract: 

    Tire materials are a significant proportion of the (micro)plastics in the environment that until today have been clearly overlooked. These materials are released into the environment, either unintentionally as an abrasion product from tire wear, that reaches the environment via road runoff, or intentionally as, for example, shredded “tire crumble rubber” used as filling material for playgrounds. Although there are a few estimates available the amount of tire-wear material to be found in aquatic environments, investigations on the fate tire materials and especially their interaction with organic substances are missing. Although the sorption processes associated with the complex constituents of tires are an important aspect of any environmental risk assessment for tire-wear materials, they have yet to be thoroughly investigated. In this review we elucidate the sorption properties of the polymeric rubbers and carbon black that form the main components of tires, within the context of current microplastic research.

  • Synthesis and biological evaluation of biotin-conjugated anticancer thiosemicarbazones and their iron(III) and copper(II) complexes

    Sebastian Kallus, Lukas Uhlik, Sushilla van Schoonhoven, Karla Pelivan, Walter Berger, va A. Enyedy, Thilo Hofmann, Petra Heffeter, Christian R. Kowol, Bernhard K. Keppler
    2019 - Journal of Inorganic Biochemistry, 85-97

    Abstract: 

    Triapine, the most prominent anticancer drug candidate from the substance class of thiosemicarbazones, was investigated in >30 clinical phase I and II studies. However, the results were rather disappointing against solid tumors, which can be explained (at least partially) due to inefficient delivery to the tumor site. Hence, we synthesized the first biotin-functionalized thiosemicarbazone derivatives in order to increase tumor specificity and accumulation. Additionally, for Triapine and one biotin conjugate the iron(III) and copper(II) complexes were prepared. Subsequently, the novel compounds were biologically evaluated on a cell line panel with different biotin uptake. The metal-free biotin-conjugated ligands showed comparable activity to the reference compound Triapine. However, astonishingly, the metal complexes of the biotinylated derivative showed strikingly decreased anticancer activity. To further analyze possible differences between the metal complexes, detailed physico- and electrochemical experiments were performed. However, neither lipophilicity or complex solution stability, nor the reduction potential or behavior in the presence of biologically relevant reducing agents showed strong variations between the biotinylated and non-biotinylated derivatives (only some differences in the reduction kinetics were observed). Nonetheless, the metal-free biotin-conjugate of Triapine revealed distinct activity in a colon cancer mouse model upon oral application comparable to Triapine. Therefore, this type of biotin-conjugated thiosemicarbazone is of interest for further synthetic strategies and biological studies.

  • The composition of bacterial communities associated with plastic biofilms differs between different polymers and stages of biofilm succession

    Maria Pinto, Teresa M. Langer, Thorsten Hüffer, Thilo Hofmann, Gerhard J. Herndl
    2019 - PloS one, 14: 1-20

    Abstract: 

    Once in the ocean, plastics are rapidly colonized by complex microbial communities. Factors affecting the development and composition of these communities are still poorly understood. Additionally, whether there are plastic-type specific communities developing on different plastics remains enigmatic. We determined the development and succession of bacterial communities on different plastics under ambient and dim light conditions in the coastal Northern Adriatic over the course of two months using scanning electron microscopy and 16S rRNA gene analyses. Plastics used were low- and high-density polyethylene (LDPE and HDPE, respectively), polypropylene (PP) and polyvinyl chloride with two typical additives (PVC DEHP and PVC DINP). The bacterial communities developing on the plastics clustered in two groups; one group was found on PVC and the other group on all the other plastics and on glass, which was used as an inert control. Specific bacterial taxa were found on specific surfaces in essentially all stages of biofilm development and in both ambient and dim light conditions. Differences in bacterial community composition between the different plastics and light exposures were stronger after an incubation period of one week than at the later stages of the incubation. Under both ambient and dim light conditions, one part of the bacterial community was common on all plastic types, especially in later stages of the biofilm development, with families such as Flavobacteriaceae, Rhodobacteraceae, Planctomycetaceae and Phyllobacteriaceae presenting relatively high relative abundances on all surfaces. Another part of the bacterial community was plastic-type specific. The plastic-type specific fraction was variable among the different plastic types and was more abundant after one week of incubation than at later stages of the succession.

  • The leaching of phthalates from PVC can be determined with an infinite sink approach

    Charlotte Henkel, Thorsten Hüffer, Thilo Hofmann
    2019 - MethodsX, 6: 2729-2734

    Abstract: 

    Polyvinyl chloride (PVC) is the third most used polymer for plastic products in the European Union (+NO/ CH) and contains the highest amounts of additives, especially phthalic acid esters (phthalates). Leaching kinetics of additives from (micro-) plastics into aqueous environments are highly relevant for environmental risk assessment and modelling of the fluxes of plastics and its associated additives. Investigating the leaching of phthalates into aqueous environments in batch experiments is challenging due to their low solubility and high hydrophobicity and there are no standard methods to study release processes. Here we describe an infinite sink method to investigate the leaching of phthalates from PVC into the aqueous phase. Spiking and leaching experiments using bis(2-ethylhexyl)phthalate as a model phthalate enabled the validation and evaluation of the designed infinite sink method. The developed method offers:

    • a low-cost and simple approach to investigate leaching of phthalates from PVC into aqueous environments
    • the use of a high-surface activated carbon powder as an infinite sink
    • a tool to elucidate the transport fluxes of plastics and additives
  • Data on sorption of organic compounds by aged polystyrene microplastic particles

    Thorsten Hüffer, Anne-Katrin Weniger, Thilo Hofmann
    2018 - Data in Brief, 474-479

    Abstract: 

    This article contains data on experimental sorption isotherms of 21 probe sorbates by aged polystyrene microplastics. The polymeric particles were subjected to an UV-induced photo-oxidation procedure using hydrogen peroxide in a custom-made aging chamber. Sorption data were obtained for aged particles. The experimental sorption data was modelled using both single- and poly-parameter linear free-energy relationships. For discussion and interpretation of the presented data, refer to the research article entitled “Sorption of organic compounds by aged polystyrene microplastic particles” (Hüffer et al., 2018) [1].

  • Development of a versatile analytical protocol for the comprehensive determination of the elemental composition of smartphone compartments on the example of printed circuit boards

    B. Bookhagen, W. Obermaier, C. Opper, C. Koeberl, Thilo Hofmann, T. Prohaska J. Irrgeher
    2018 - Analytical Methods, 3: 3864-3871

    Abstract: 

    A versatile approach to determining the elemental content of more than 50 elements in different components of electronic devices on the example of smartphones was developed. The analytical protocol is based on accurate disassembly of smartphones, a single processing microwave-assisted acid digestion followed by ICP-OES and ICP-MS measurements. Method optimization and validation were performed using the certified reference material ERM®-EZ505 electronic scrap. Combined uncertainties revealed measurement uncertainty and sample heterogeneity as main contributors. The contents of up to 57 elements could be quantified in the certified reference material ERM®-EZ505 electronic scrap. The results of the certified elements Au, Be, Cu, In, Ni, Pd, and Pt overlapped within their uncertainties with the certified range and revealed recoveries of 100% ± 16%. Only Ag shows incomplete recoveries (75% ± 35%). The validated method was applied to all metal-containing components of selected smartphones, excluding batteries. The contents of up to 57 elements could be quantified and are presented exemplarily for printed circuit boards, which represent the most complex components in the investigated smartphones and thus limit the capability of the method. The ten most abundant elements in decreasing order are Cu, Fe, Si, Ni, Sn, Zn, Ba, Al, Cr, Ti, which comprise approx. 80% of the weight of the printed circuit boards. The method allows for the determination of metal content in various parts of modern smartphones, providing the basis for the estimation and prediction of future metal usage and thus the comprehensive investigation of recycling and circular economy aspects.

  • Effect of field site hydrogeochemical conditions on the corrosion of milled zerovalent iron particles and their dechlorination efficiency

    Milica Velimirovic, Melanie Auffan, Luca Carniato, Vesna Micić, Doris Schmid, Stephan Wagner, Daniel Borschneck, Olivier Proux, Frank von der Kammer, Thilo Hofmann
    2018 - Science of The Total Environment, 1619-1627

    Abstract: 

    Milled zerovalent iron (milled ZVI) particles have been recognized as a promising agent for groundwater remediation because of (1) their high reactivity with chlorinated aliphatic hydrocarbons, organochlorine pesticides, organic dyes, and a number of inorganic contaminants, and (2) a possible greater persistance than the more extensively investigated nanoscale zerovalent iron. We have used laboratory-scale batch degradation experiments to investigate the effect that hydrogeochemical conditions have on the corrosion of milled ZVI and on its ability to degrade trichloroethene(TCE). The observed pseudo first-order degradation rate constants indicated that the degradation of TCE by milled ZVI is affected by groundwater chemistry. The apparent corrosion rates of milled ZVI particles were of the same order of magnitude for hydrogeochemical conditions representative for two contaminated field sites (133–140 mmol kg− 1 day− 1, indicating a milled ZVI life-time of 128–135 days). Sulfate enhances milled ZVI reactivity by removing passivating iron oxides and hydroxides from the Fe0 surface, thus increasing the number of reactive sites available. The organic matter content of 1.69% in the aquifer material tends to suppress the formation of iron corrosion precipitates. Results from scanning electron microscopy, X-ray diffraction, and iron K-edge X-ray adsorption spectroscopy suggest that the corrosion mechanisms involve the partial dissolution of particles followed by the formation and surface precipitation of magnetite and/or maghemite. Numerical corrosion modeling revealed that fitting iron corrosion rates and hydrogen inhibitory terms to hydrogen and pH measurements in batch reactors can reduce the life-time of milled ZVI particles by a factor of 1.2 to 1.7.

  • Environmental fate of nanopesticides: durability, sorption and photodegradation of nanoformulated clothianidin

    Melanie Kah, Helene Walch, Thilo Hofmann
    2018 - Environmental Science: Nano, 4: 882-889

    Abstract: 

    A lot of research efforts are currently dedicated to the development of nano-enabled agrochemicals. Knowledge about their environmental behaviour is however scarce, which impedes the assessment of the new risk and benefits relative to currently used agrochemicals. With the aim to advance our understanding of the fate of nanopesticides in the environment and support the development of robust exposure assessment procedures, the main objectives of the study were to (i) investigate the extent to which three nanoformulations can affect the photodegradation and sorption of the insecticide clothianidin, and (ii) evaluate various approaches to estimate durability, a key parameter for the exposure assessment of nanopesticides. The nanoformulations increased the photodegradation half-life in water by a maximum of 21% relative to the conventional formulation. Sorption to soil was investigated by two methods and over time, and results show that sorption was increased by up to 51% and 10%, relative to unformulated clothianidin and the commercial formulation, respectively. Our results generally indicate that nanoformulations may have a greater impact on the fate of pesticide active ingredients than commercial formulations. It is important to note however that differences in fate parameters were generally very moderate, including in realistic worst-case conditions (high pesticide concentration and ionic strength). Our results collectively suggest that clothianidin was rapidly released from the nanocarrier systems and that the durability of the three nanoformulations would be short in water as well as in soil environments (including under realistic soil to solution ratio). The durability of nanoformulations after their application in the environment is an essential parameter that needs to be characterised for the development as well as for the evaluation of nano-enabled agrochemicals. This study illustrates how performances of nano-enabled products can be critically benchmarked against existing products to support an objective assessment of new environmental risks and benefits. In this context, the fate of the nanocarrier system is of great interest and should be the topic of further research.

  • Environmental transformation of natural and engineered carbon nanoparticles and implications for the fate of organic contaminants

    Gabriel Sigmund, Chuanjia Jiang, Thilo Hofmann, Wei Chen
    2018 - Environmental Science: Nano, 1: 2500-2518

    Abstract: 

    Environmental transformation of carbon nanoparticles can significantly affect their transport, fate, and effects. The last decade of environmental nano-science has often focused on understanding the behavior of well-defined engineered carbon nanoparticles (eCNPs) in the natural environment. However, more complex pyrogenic/petrogenic carbon nanoparticles (pCNPs), including those derived from soot, fossil coal, wildfire charcoal, and biochar, are more than four orders of magnitude more abundant in the environment. This paper aims to review findings from investigations into eCNPs and to consider their transferability to pCNPs, in order to improve our understanding of pCNPs and identify gaps in our knowledge. Findings from previous investigations into the chemical, physical and biological transformation of larger carbonaceous particles, as well as of eCNPs, can help us to understand the transformation of pCNPs. The transformation of soot during atmospheric transport is relatively well documented, whereas the transformation of pCNPs in soil, sediment, and aqueous systems remains poorly understood. To bridge findings on particulate transport, contaminant binding, and contaminant transformation from eCNPs to pCNPs, the complex compositions of pCNPs need to be taken into account. We therefore suggest that future research on pCNP transformation should focus on changes in intrinsic porosity and on interactions with non-carbonized phases, tar phases, and mineral phases, as well as with organo-mineral complexes in soils, sediments and water bodies.

  • Influence of compost and biochar on microbial communities and the sorption/degradation of PAHs and NSO-substituted PAHs in contaminated soils

    Gabriel Sigmund, Caroline Poyntner, Guadalupe Piñar, Melanie Kah, Thilo Hofmann
    2018 - Journal of Hazardous Materials, 107-113

    Abstract: 

    Diffusely contaminated soils often remain untreated as classical remediation approaches would be disproportionately expensive. Adding compost can accelerate the biodegradation of organic contaminants and adding biochar can immobilize contaminants through sorption. The combined use of compost and biochar to reduce polycyclic aromatic hydrocarbon (PAH) and NSO-substituted PAH contamination has, however, not previously been systematically investigated. We have therefore investigated the processes involved (i) through sorption batch experiments, (ii) by monitoring changes in bacterial, fungal and archaeal communities using denaturing gradient gel electrophoresis, and (iii) through degradation experiments with fluorene, phenanthrene, pyrene, carbazole, dibenzothiophene, and dibenzofuran. Sorption coefficients for organic contaminants in soils increased tenfold following 10% compost addition and up to a hundredfold with further addition of 5% biochar. The rate of PAH and NSO-PAH degradation increased up to twofold following compost addition despite increased sorption, probably due to the introduction of additional microbial species into the autochthonous soil communities. In contrast, degradation of PAHs and NSO-PAHs in soil-compost-biochar mixtures slowed down up to tenfold due to the additional sorption, although some degradation still occurred. The combined use of biochar and compost may therefore provide a strategy for immobilizing PAHs and NSO-PAHs and facilitating degradation of remaining accessible contaminant fractions.

  • Optimising the transport properties and reactivity of microbially-synthesised magnetite for in situ remediation

    Nimisha Joshi, Feixue Liu, Mathew Paul Watts, Heather Williams, Victoria S. Coker, Doris Schmid, Thilo Hofmann, Jonathan R. Lloyd
    2018 - Scientific Reports, 1: in press

    Abstract: 

    Engineered nanoparticles offer the potential for remediation of land and water that has been contaminated by organics and metals. Microbially synthesized nano-scale magnetite, prepared from Fe(III) oxides by subsurface Fe(III)-reducing bacteria, offers a scalable biosynthesis route to such a nano-scale remediation reagent. To underpin delivery of “bionanomagnetite” (BNM) nanomaterial during in situ treatment options, we conducted a range of batch and column experiments to assess and optimise the transport and reactivity of the particles in porous media. Collectively these experiments, which include state of the art gamma imaging of the transport of 99m Tc-labelled BNM in columns, showed that non-toxic, low cost coatings such as guar gum and salts of humic acid can be used to enhance the mobility of the nanomaterial, while maintaining reactivity against target contaminants. Furthermore, BNM reactivity can be enhanced by the addition of surface coatings of nano-Pd, extending the operational lifetime of the BNM, in the presence of a simple electron donor such as hydrogen or formate.

  • Scientific rationale for the development of an OECD test guideline on engineered nanomaterial stability

    Fazel Abdolahpur Monikh, Antonia Praetorius, Andrea Schmid, Philipp Kozin, Boris Meisterjahn, Ekaterina Makarova, Thilo Hofmann, Frank von der Kammer
    2018 - NanoImpact, 42-50

    Abstract: 

    Standardized methods for assessing the behaviour of engineered nanomaterials(ENMs) under relevant environmental conditions are an important part of ENM risk assessment. Existing assays, often developed for traditional chemicals, are frequently not applicable to ENMs, which present special challenges due to their particulate nature and complex intrinsic and extrinsic properties. Here we present the development of the novel OECD test guideline (TG) No. 318 for studying the “dispersion stability of nanomaterials in simulated environmental media”. We discuss the rationalization of the test design and required simplifications to develop a test, which can be executed in standard laboratories on a routine basis at reasonable costs. The relevance of the test for capturing ENM stability in surface waters is ensured by a strategic selection of adequate test media and testing scheme. As an example, we present data of a full test performed according to the new OECD TG using NM 105 as a representative TiO2 ENM. Limitations of the test in terms of scarce kinetic information and a focus on homo- instead of heteroaggregation are discussed. The developed OECD Test No. 318 represents the first standardized assay for ENMs using an operationally defined testing scheme capable of systematically comparing different ENMs in terms of their dispersion stability under environmentally relevant conditions. It will provide crucial data to inform risk assessment and regulation and can be adapted to different types of test media if needed.

  • Sorption of organic compounds by aged polystyrene microplastic particles

    Thorsten Hüffer, Anne-Katrin Weniger, Thilo Hofmann
    2018 - Environmental Pollution, 218-225

    Abstract: 

    Microplastics that are released into the environment undergo aging and interact with other substances such as organic contaminants. Understanding the sorption interactions between aged microplastics and organic contaminants is therefore essential for evaluating the impact of microplastics on the environment. There is little information available on how the aging of microplastics affects their sorption behavior and other properties. We have therefore investigated the effects of an accelerated UV-aging procedure on polystyrene microplastics, which are used in products such as skin cleaners and foams. Physical and chemical particle characterizations showed that aging led to significant surface oxidation and minor localized microcrack formation. Sorption coefficients of organic compounds by polystyrene microplastics following aging were up to one order of magnitude lower than for pristine particles. Sorption isotherms were experimentally determined using a diverse set of probe sorbates covering a variety of substance classes allowing an in-depth evaluation of the poly-parameter linear free-energy relationship (ppLFER) modelling used to investigate the contribution of individual molecular interactions to overall sorption. The ppLFER modelling was validated using internal cross-validation, which confirmed its robustness. This approach therefore yields improved estimates of the interactions between aged polystyrene microplastics and organic contaminants.

  • Sorption of organic substances to tire wear materials: Similarities and differences with other types of microplastic

    Thorsten Hüffer, Stephan Wagner, Thorsten Reemtsma, Thilo Hofmann
    2018 - TrAC Trends in Analytical Chemistry, 392-401

    Abstract: 

    Tire materials are a significant proportion of the (micro)plastics in the environment that until today have been clearly overlooked. These materials are released into the environment, either unintentionally as an abrasion product from tire wear, that reaches the environment via road runoff, or intentionally as, for example, shredded “tire crumble rubber” used as filling material for playgrounds. Although there are a few estimates available the amount of tire-wear material to be found in aquatic environments, investigations on the fate tire materials and especially their interaction with organic substances are missing. Although the sorption processes associated with the complex constituents of tires are an important aspect of any environmental risk assessment for tire-wear materials, they have yet to be thoroughly investigated. In this review we elucidate the sorption properties of the polymeric rubbers and carbon black that form the main components of tires, within the context of current microplastic research.

  • Sorption to soil, biochar and compost: is prediction to multicomponent mixtures possible based on single sorbent measurements?

    Melanie Kah, Gabriel Sigmund, Pedro Luis Manga Chavez, Lucie Bielská, Thilo Hofmann
    2018 - PeerJ, 673 —692

    Abstract: 

    Amendment with biochar and/or compost has been proposed as a strategy to remediate soil contaminated with low levels of polycyclic aromatic hydrocarbons. The strong sorption potential of biochar can help sequestering contaminants while the compost may promote their degradation. An improved understanding of how sorption evolves upon soil amendment is an essential step towards the implementation of the approach. The present study reports on the sorption of pyrene to two soils, four biochars and one compost. Detailed isotherm analyzes across a wide range of concentration confirmed that soil amendments can significantly increase the sorption of pyrene. Comparisons of data obtained by a classical batch and a passive sampling method suggest that dissolved organic matter did not play a significant role on the sorption of pyrene. The addition of 10% compost to soil led to a moderate increase in sorption (<2-fold), which could be well predicted based on measurements of sorption to the individual components. Hence, our result suggest that the sorption of pyrene to soil and compost can be relatively well approximated by an additive process. The addition of 5% biochar to soil (with or without compost) led to a major increase in the sorption of pyrene (2.5–4.7-fold), which was, however, much smaller than that suggested based on the sorption measured on the three individual components. Results suggest that the strong sorption to the biochar was attenuated by up to 80% in the presence of soil and compost, much likely due to surface and pore blockage. Results were very similar in the two soils considered, and collectively suggest that combined amendments with compost and biochar may be a useful approach to remediate soils with low levels of contamination. Further studies carried out in more realistic settings and over longer periods of time are the next step to evaluate the long term viability of remediation approaches based on biochar amendments.

  • Tire wear particles in the aquatic environment - A review on generation, analysis, occurrence, fate and effects

    Wagner S, Thorsten Hüffer, Klöckner P, Wehrhahn M, Thilo Hofmann, Reemtsma T
    2018 - Water Research, 83-100

    Abstract: 

    Tire wear particles (TWP), generated from tire material during use on roads have gained increasing attention as part of organic particulate contaminants, such as microplastic, in aquatic environments. The available information on properties and generation of TWP, analytical techniques to determine TWP, emissions, occurrence and behavior and ecotoxicological effects of TWP are reviewed with a focus on surface water as a potential receptor. TWP emissions are traffic related and contribute 5–30% to non-exhaust emissions from traffic. The mass of TWP generated is estimated at 1,327,000 t/a for the European Union, 1,120,000 t/a for the United States and 133,000 t/a for Germany. For Germany, this is equivalent to four times the amount of pesticides used. The mass of TWP ultimately entering the aquatic environment strongly depends on the extent of collection and treatment of road runoff, which is highly variable. For the German highways it is estimated that up to 11,000 t/a of TWP reach surface waters. Data on TWP concentrations in the environment, including surface waters are fragmentary, which is also due to the lack of suitable analytical methods for their determination. Information on TWP properties such as density and size distribution are missing; this hampers assessing the fate of TWP in the aquatic environment. Effects in the aquatic environment may stem from TWP itself or from compounds released from TWP. It is concluded that reliable knowledge on transport mechanism to surface waters, concentrations in surface waters and sediments, effects of aging, environmental half-lives of TWP as well as effects on aquatic organisms are missing. These aspects need to be addressed to allow for the assessment of risk of TWP in an aquatic environment.

  • Where is the nano? Analytical approaches for the detection and quantification of TiO2 engineered nanoparticles in surface waters

    Andreas Gondikas, Frank von der Kammer, Ralf Kaegi, Olga Borovinskaya, Elisabeth Neubauer, Jana Navratilova, Antonia Praetorius, Geert Cornelis, Thilo Hofmann
    2018 - Environmental Science: Nano, 2: 313-326

    Abstract: 

    Detecting and quantifying engineered nanoparticles (ENPs) in complex environmental matrices requires the distinction between natural nanoparticles (NNPs) and ENPs. The distinction of NNPs and ENPs for regulatory purposes calls for cost-efficient methods, but is hampered by similarities in intrinsic properties, such as particle composition, size, density, surface chemistry, etc. Titanium dioxide (TiO2) ENPs, for instance, are produced in very large quantities but Ti also commonly occurs naturally in nano-scale minerals. In this work, we focus on utilizing particle size and composition to identify ENPs in a system with a significant background concentration of the target metal. We have followed independent approaches involving both conventional and state-of-the-art analytical techniques to detect and quantify TiO2 ENPs released into surface waters from sunscreen products and to distinguish them from Ti-bearing NNPs. To achieve this, we applied single particle inductively coupled plasma mass spectrometry with single-element (spICPMS) and multi-element detection (time-of-flight) spICP-TOFMS, together with transmission electron microscopy (TEM), automated scanning electron microscopy (autoSEM), and bulk elemental analyses. A background concentration of Ti-bearing NPs (approximately 5 × 10particles per ml), possibly of natural origin, was consistently observed outside the bathing season. This concentration increased by up to 40% during the bathing season. Multi-element analysis of individual particles using spICP-TOFMS revealed that Al, Fe, Mn, and Pb are often present in natural Ti-bearing NPs, but no specific multi-element signatures were detected for ENPs. Our data suggests that TiO2 ENPs enter the lake water during bathing activities, eventually agglomerating and sedimenting. We found adhesion of the TiO2 ENPs to the air–water interface for short time periods, depending on wind conditions. This study demonstrates that the use of spICP-TOFMS and spICPMS in combination with other conventional analytical techniques offers significant advantages for discriminating between NNPs and ENPs. The quantitative data produced in this work can be used as input for modeling studies or as a benchmark for analysis protocols and model validations.

  • Bioavailability and toxicity of pyrene in soils upon biochar and compost addition

    Lucie Bielská, Melanie Kah, Gabriel Sigmund, Thilo Hofmann, Sebastian Höss
    2017 - Science of The Total Environment, 132-140

    Abstract: 

    The study investigates the role of biochar and/or compost in mitigating the toxic effects of pyrene in soils using reproduction of nematodes and porewater concentration as measures of pyrene toxicity and bioavailability, respectively. Two soils were spiked with increasing levels of pyrene to achieve a concentration-response relationship for the reproduction of Caenorhabditis elegans. The observed EC50 values (pyrene concentration causing 50% inhibition of reproduction) were 14 mg/kg and 31 mg/kg (dry mass) for these soils, corresponding to equilibrium porewater concentrations of 37 μg/L and 47 μg/L, respectively. Differences in organic carbon content were not sufficient to explain the variability in toxicity between the different soils. Soils causing a significant inhibition of reproduction were further amended with 10%-compost, 5%-biochar, or both, and the effects on reproduction and porewater concentration determined. Combined addition of compost and biochar was identified as the most effective strategy in reducing pyrene concentration in soil porewater, which was also partly reflected in soil toxicity. However, porewater concentrations predicted only 52% of pyrene toxicity to nematodes, pointing to particle-bound or dietary exposure pathways.

    Capsule: Amending pyrene-spiked soil with biochar and compost effectively reduced pyrene porewater concentrations and toxicity to nematodes, which were significantly related.

  • Biochar total surface area and total pore volume determined by N2 and CO2 physisorption are strongly influenced by degassing temperature

    Gabriel Sigmund, Thorsten Hüffer, Thilo Hofmann, Melanie Kah
    2017 - Science of The Total Environment, 770-775

    Abstract: 

    The surface area and pore volume of carbonaceous materials, which are commonly determined by N2 and/or CO2 gas-physisorption, are important parameters when describing environmental processes such as adsorption. Their measurement requires prior degassing of samples, which can change the nature of the material. Current guidelines for biochar characterization recommend different degassing temperatures. To investigate how degassing temperatures affect gas-physisorption we systematically degassed a range of materials (four biochars, carbon nanotubes, and Al2O3 reference material) at different temperatures (105, 150, 200, 250 and 300 °C; for ≥ 14 h each). Degassing temperatures had no effect on Al2O3 or carbon nanotubes but the measured surface areas and pore volumes of biochars increased by up to 300% with degassing temperature. An equation is presented for predicting surface area obtained at different degassing temperatures. Elemental analysis and results from sorption batch experiments suggest that surface area and pore volume may increase as biochar components volatilize during degassing. Our results showed that degassing temperatures change material properties and influence gas-physisorption measurements, and therefore need to be standardized. These results may also apply to the characterization of other complex materials, including carbon nanotubes coated with natural organic matter and fouled activated carbon.

  • Cytotoxicity of Biochar: A Workplace Safety Concern?

    Gabriel Sigmund, Daniela Huber, Thomas D. Bucheli, Martina Baumann, Nicole Borth, Georg M. Guebitz, Thilo Hofmann
    2017 - Environmental Science & Technology Letters, 9: 362-366

    Abstract: 

    Biochar has a number of environmental applications, including soil amendment for agriculture, remediation of contaminated soils and sediments, and climate change mitigation. Dust formed during its production and field application may pose a health risk, but the cytotoxicity of biochar has, to the best of our knowledge, not previously been investigated. Therefore, we measured the concentration-dependent cytotoxicity of biochar on an NIH 3T3 mouse fibroblast cell line. We used a contaminant trap experiment to measure the total and nondesorbable polycyclic aromatic hydrocarbon (PAH) fractions of the biochar. PAH release was found to be negligible because of the biochar’s strong PAH sorption potential. The biochar was nevertheless observed to have a cytotoxic effect on the fibroblast cells; the EC10 values were 49.6 and 18.8 μg/mL after incubation for 24 and 48 h, respectively. This cytotoxic effect is likely to relate to the particulate nature and size distribution of the biochar; the biochar had particles similar in size to atmospheric particulate matter (PM2.5) that bound to the fibroblast cell surface. To minimize the risk of exposure, practitioners should wear respiratory protective equipment during biochar production. During field application, biochar should be applied in slurries and should always be mixed with a soil matrix to avoid secondary dust formation.

  • Effect of ageing on the properties and polycyclic aromatic hydrocarbon composition of biochar

    Gabriel Sigmund, Thomas D. Bucheli, Isabel Hilber, Vesna Micić, Melanie Kah, Thilo Hofmann
    2017 - Environmental Science: Processes & Impacts, 5: 768-774

    Abstract: 

    The influence of ageing on biochar properties has been investigated by comparing three fresh biochars with biochars artificially aged by either H2O2 thermal oxidation or horseradish peroxidase enzymatic oxidation. In addition, a field-aged counterpart for one of the biochars was recovered from an agricultural field site, four years after application. Biochar properties, including surface areas and pore volumes (derived by N2 and CO2 physisorption) and elemental compositions, showed only minor changes following both artificial and field ageing, indicating high biochar stability. Concentrations of the 16 US EPA PAHs were measured in all of the biochars and a contaminant trap was used to investigate the effect of ageing on their bioaccessibility. The concentrations of total and bioaccessible PAHs ranged from 4.4 to 22.6 mg kg−1 and 0.0 to 9.7 mg kg−1, respectively. Concentrations of the 16 US EPA PAHs decreased following field ageing, but the proportion of low molecular weight PAHs increased. The observed changes in PAH composition with field ageing can be explained by uptake from the surrounding soil and intra-biochar transfer processes. To better understand changes in PAH composition with ageing, an additional broad range of alkylated PAHs was also analyzed in selected samples. Our results show that the tested artificial ageing protocols are unable to approximate the changes in PAH composition resulting from field ageing. Nevertheless, total and bioaccessible PAH concentrations decreased for both artificially and field-aged biochars, indicating that biochars release PAHs when they are freshly produced and that the risk of PAH release decreases with ageing.

  • Impact of Sodium Humate Coating on Collector Surfaces on Deposition of Polymer-Coated Nanoiron Particles

    Vesna Micić, Doris Schmid, Nathan Bossa, Andreas Gondikas, Milica Velimirovic, Frank von der Kammer, Mark R. Wiesner, Thilo Hofmann
    2017 - Environmental Science & Technology, 1: 9202-9209

    Abstract: 

    The affinity between nanoscale zerovalent iron (nano-ZVI) and mineral surfaces hinders its mobility, and hence its delivery into contaminated aquifers. We have tested the hypothesis that the attachment of poly(acrylic acid)-coated nano-ZVI (PAA-nano-ZVI) to mineral surfaces could be limited by coating such surfaces with sodium (Na) humate prior to PAA-nano-ZVI injection. Na humate was expected to form a coating over favorable sites for PAA-nano-ZVI attachment and hence reduce the affinity of PAA-nano-ZVI for the collector surfaces through electrosteric repulsion between the two interpenetrating charged polymers. Column experiments demonstrated that a low concentration (10 mg/L) Na humate solution in synthetic water significantly improved the mobility of PAA-nano-ZVI within a standard sand medium. This effect was, however, reduced in more heterogeneous natural collector media from contaminated sites, as not an adequate amount of the collector sites favorable for PAA-nano-ZVI attachment within these media appear to have been screened by the Na humate. Na humate did not interact with the surfaces of acid-washed glass beads or standard Ottawa sand, which presented less surface heterogeneity. Important factors influencing the effectiveness of Na humate application in improving PAA-nano-ZVI mobility include the solution chemistry, the Na humate concentration, and the collector properties.

  • Interactions between aromatic hydrocarbons and functionalized C60 fullerenes insights from experimental data and molecular modelling

    Thorsten Hüffer, Huichao Sun, James D. Kubicki, Thilo Hofmann, Melanie Kah
    2017 - Environmental Science: Nano, 5: 1045-1053

    Abstract: 

    Understanding molecular interactions between organic compounds and carbon-based nanomaterials is crucial to the interpretation of phase transfer processes, both in technical applications and within the environment. There is, however, little information available on the interactions between organic compounds and C60 fullerenes, in particular regarding the effects of functionalization. Experimental sorption isotherms and molecular modelling have therefore been used to systematically investigate how these interactions are affected by functionalization of the sorbate (using one, two and four ring aromatics, with –OH or –NH2functional groups) and the sorbent (i.e., C60 and C60-OH). Functionalization of the sorbent, as well as hydroxyl- and amino-functionalization of the sorbate, had a significant effect on sorption. The enhanced sorption of hydroxyl- and amino-functionalized sorbates by C60 may be due to an increased contribution from π–π electron donor–acceptor interactions. Additional hydrogen bond interactions with C60-OH also appear to play an important role. Our results emphasize that the surface chemistry of C60 is of critical importance to their interactions with organic compounds. The ageing of C60 in technical applications, or in the environment, is therefore likely to significantly affect the molecular interactions, and hence sorption strength, for polar and non-polar organic compounds.

  • Microplastic Exposure Assessment in Aquatic Environments: Learning from Similarities and Differences to Engineered Nanoparticles

    Thorsten Hüffer, Antonia Praetorius, Stephan Wagner, Frank von der Kammer, Thilo Hofmann
    2017 - Environmental Science & Technology, 5: 2499-2507

    Abstract: 

    Microplastics (MPs) have been identified as contaminants of emerging concern in aquatic environments and research into their behavior and fate has been sharply increasing in recent years. Nevertheless, significant gaps remain in our understanding of several crucial aspects of MP exposure and risk assessment, including the quantification of emissions, dominant fate processes, types of analytical tools required for characterization and monitoring, and adequate laboratory protocols for analysis and hazard testing. This Feature aims at identifying transferrable knowledge and experience from engineered nanoparticle (ENP) exposure assessment. This is achieved by comparing ENP and MPs based on their similarities as particulate contaminants, whereas critically discussing specific differences. We also highlight the most pressing research priorities to support an efficient development of tools and methods for MPs environmental risk assessment.

  • Mikroplastik: Lernen aus den Fehlern der Vergangenheit

    2017 - Vom Wasser - das Journal, 115: 1
  • Sensitivity towards the GRP78 inhibitor KP1339/IT-139 is characterized by apoptosis induction via caspase 8 upon disruption of ER homeostasis

    Beatrix Schoenhacker-Alte, Thomas Mohr, Christine Pirker, Kushtrim Kryeziu, Paul-Steffen Kuhn, Alicia Buck, Thilo Hofmann, Christopher Gerner, Gerrit Hermann, Gunda Koellensperger, Bernhard K. Keppler, Walter Berger, Petra Heffeter
    2017 - Cancer Letters, 79-88

    Abstract: 

    The ruthenium drug and GRP78 inhibitor KP1339/IT-139 has already demonstrated promising anticancer activity in a phase I clinical trial. This study aimed to identify mechanisms underlying increased sensitivity to KP1339 treatment. Based on a screen utilizing 23 cell lines, a small panel was selected to compare KP1339-sensitive and low-responsive models. KP1339 sensitivity was neither based on differences in ruthenium accumulation, nor sensitivity to oxidative stress or constituents of KP1339 (ruthenium chloride and indazole). Subsequently, the biochemical response to KP1339 was analyzed using whole genome expression arrays indicating that, while sensitive cell lines were characterized by “response to chemical stimuli” and “regulation of cell death”, low-responsive cells preferentially activated pathways controlling cell cycle, DNA repair, and metabolism. Cell culture experiments confirmed that, while low-responsive cells executed cell cycle arrest in G2 phase, pronounced apoptosis induction via activation of caspase 8 was found in sensitive cells. Cell death induction is based on a unique disruption of the ER homeostasis by depletion of key cellular chaperones including GRP78 in combination with enhanced KP1339-mediated protein damage.

  • Single-particle multi-element fingerprinting (spMEF) using inductively-coupled plasma time-of-flight mass spectrometry (ICP-TOFMS) to identify engineered nanoparticles against the elevated natural background in soils

    Antonia Praetorius, Alexander Gundlach-Graham, Eli Goldberg, Willi Fabienke, Jana Navratilova, Andreas Gondikas, Ralf Kaegi, Detlef Günther, Thilo Hofmann, Frank von der Kammer
    2017 - Environmental Science: Nano, 2: 307-314

    Abstract: 

    The discrimination of engineered nanoparticles (ENPs) from the natural geogenic background is one of the preeminent challenges for assessing their potential implications. At low ENP concentrations, most conventional analytical techniques are not able to take advantage of inherent differences (e.g. in terms of composition, isotopic signatures, element ratios, structure, shape or surface characteristics) between ENPs and naturally occurring nanoscale particles (NNPs) of similar composition. Here, we present a groundbreaking approach to overcome these limitations and enable the discrimination of man-made ENPs from NNPs through simultaneous detection of multiple elements on an individual particle level. This new analytical approach is accessible by an inductively-coupled plasma time-of-flight mass spectrometer (ICP-TOFMS) operated in single-particle mode. Machine learning is employed to classify ENPs and NNPs based on their unique elemental fingerprints and quantify their concentrations. We demonstrate the applicability of this single-particle multi-element fingerprinting (spMEF) method by distinguishing engineered cerium oxide nanoparticles (CeO2 ENPs) from natural Ce-containing nanoparticles (Ce-NNPs) in soils at environmentally relevant ENP concentrations, orders of magnitude below the natural background.

  • Sorption of ionizable and ionic organic compounds to biochar, activated carbon and other carbonaceous materials

    Melanie Kah, Gabriel Sigmund, Feng Xiao, Thilo Hofmann
    2017 - Water Research, 673-692

    Abstract: 

    The sorption of ionic and ionizable organic compounds (IOCs) (e.g., pharmaceuticals and pesticides) on carbonaceous materials plays an important role in governing the fate, transport and bioavailability of IOCs. The paradigms previously established for the sorption of neutral organic compounds do not always apply to IOCs and the importance of accounting for the particular sorption behavior of IOCs is being increasingly recognized. This review presents the current state of knowledge and summarizes the recent advances on the sorption of IOCs to carbonaceous sorbents. A broad range of sorbents were considered to evaluate the possibility to read across between fields of research that are often considered in isolation (e.g., carbon nanotubes, graphene, biochar, and activated carbon). Mechanisms relevant to IOCs sorption on carbonaceous sorbents are discussed and critically evaluated, with special attention being given to emerging sorption mechanisms including low-barrier, charge-assisted hydrogen bonds and cation-π assisted π–π interactions. The key role played by some environmental factors is also discussed, with a particular focus on pH and ionic strength.

    Overall the review reveals significant advances in our understanding of the interactions between IOCs and carbonaceous sorbents. In addition, knowledge gaps are identified and priorities for future research are suggested.

  • TiO2 nanomaterial detection in calcium rich matrices by spICPMS. A matter of resolution and treatment

    Mickaël Tharaud, Andreas P. Gondikas, Marc F. Benedetti, Frank von der Kammer, Thilo Hofmann, Geert Cornelis
    2017 - Journal of Analytical Atomic Spectrometry, 7: 1400-1411

    Abstract: 

    High Ca concentrations in complex matrices such as river waters often hamper the detection of titanium nanomaterials (TiO2 NPs) by single particle inductively coupled plasma mass spectrometry (spICPMS), because of isobaric interference of 48Ca on the most abundant Ti isotope (48Ti). Several approaches were used to reduce this interference while measuring TiO2 in solutions with different Ca concentrations up to 100 mg L−1. ICP-MS/MS was used with ammonia as the reaction cell gas and high resolution (HR) ICP-MS was used under different resolution settings. These approaches were compared by measuring different Ti isotopes (47Ti and 49Ti). spICPMS data were then treated with a deconvolution method to filter out dissolved signals and identify the best approach to detect the lowest possible corresponding spherical size of TiO2 NPs (Dmin). ICP-MS/MS allowed for an important decrease of the theoretical Dmin compared to standard quadrupole ICP-MS, down to 64 nm in ultrapure water; however the sensitivity was reduced by the reaction gas and increasing Ca concentrations also increased the Dmin. The comparably higher sensitivity of HR-ICP-MS allowed for theoretically measuring a Dmin of 10 nm in ultrapure water. Combined with the deconvolution analysis, the highest resolution mode in HR-ICP-MS leads to the lowest Dmin at high Ca concentrations, even though significant broadening of the measured mass distributions occurred for TiO2 NPs at Ca concentrations up to 100 mg L−1.

  • Agar agar-stabilized milled zerovalent iron particles for in situ groundwater remediation

    Milica Velimirovic, Doris Schmid, Stephan Wagner, Vesna Micić, Frank von der Kammer, Thilo Hofmann
    2016 - Science of The Total Environment, 713-723

    Abstract: 

    Submicron-scale milled zerovalent iron (milled ZVI) particles produced by grinding macroscopic raw materials could provide a cost-effective alternative to nanoscale zerovalent iron (nZVI) particles for in situ degradation of chlorinated aliphatic hydrocarbons in groundwater. However, the aggregation and settling of bare milled ZVI particles from suspension presents a significant obstacle to their in situ application for groundwater remediation. In our investigations we reduced the rapid aggregation and settling rate of bare milled ZVI particles from suspension by stabilization with a “green” agar agar polymer. The transport potential of stabilized milled ZVI particle suspensions in a diverse array of natural heterogeneous porous media was evaluated in a series of well-controlled laboratory column experiments. The impact of agar agar on trichloroethene (TCE) removal by milled ZVI particles was assessed in laboratory-scale batch reactors. The use of agar agar significantly enhanced the transport of milled ZVI particles in all of the investigated porous media. Reactivity tests showed that the agar agar-stabilized milled ZVI particles were reactive towards TCE, but that their reactivity was an order of magnitude less than that of bare, non-stabilized milled ZVI particles. Our results suggest that milled ZVI particles could be used as an alternative to nZVI particles as their potential for emplacement into contaminated zone, their reactivity, and expected longevity are beneficial for in situ groundwater remediation.

  • Anthropogenic gadolinium as a transient tracer for investigating river bank filtration

    Robert Brünjes, Andrea Bichler, Philipp Hoehn, Frank Thomas Lange, Heinz-Juergen Brauch, Thilo Hofmann
    2016 - Science of The Total Environment, 1432-1440

    Abstract: 

    The growing use of gadolinium-based contrast agents in magnetic resonance imaging (MRI) leads to an increasing input of anthropogenic gadolinium (Gdanth) into natural environments. Conventional sewage treatment is unable to remove Gdanth and since MRI facilities are mainly used on weekdays the Gdanth inputs to sewage treatment plants are generally higher between Monday and Friday. This transient signal has been traced in both surface water and groundwater through 12-h composite samples collected at high spatial resolutions using depth-discrete rhizon samplers. Propagation of the Gdanth signal from surface water to groundwater was used to calibrate lumped parameter models. Transit time distributions derived for each sampling site revealed mean transit times of between 0.5 and 10 days. Other metrics, such as peak transit time, were shown to correlate better with observed time lags between peak Gdanth concentrations in stream water and groundwater. The relatively stable artificial sweetener acesulfame was investigated as a possible additional sewage indicator, but decreasing concentrations along the flow path indicated its attenuation. We have demonstrated that the ideal tracer Gdanth occurs transiently and can be used to derive groundwater transit times.

  • Combining gas-phase electrophoretic mobility molecular analysis (GEMMA), light scattering, field flow fractionation and cryo electron microscopy in a multidimensional approach to characterize liposomal carrier vesicles

    Carlos Urey, Victor U. Weiss, Andreas Gondikas, Frank von der Kammer, Thilo Hofmann, Martina Marchetti-Deschmann, Günter Allmaier, György Marko-Varga, Roland Andersson
    2016 - International Journal of Pharmaceutics, 1: 309-318

    Abstract: 

    For drug delivery, characterization of liposomes regarding size, particle number concentrations, occurrence of low-sized liposome artefacts and drug encapsulation are of importance to understand their pharmacodynamic properties. In our study, we aimed to demonstrate the applicability of nano Electrospray Gas-Phase Electrophoretic Mobility Molecular Analyser (nES GEMMA) as a suitable technique for analyzing these parameters. We measured number-based particle concentrations, identified differences in size between nominally identical liposomal samples, and detected the presence of low-diameter material which yielded bimodal particle size distributions. Subsequently, we compared these findings to dynamic light scattering(DLS) data and results from light scattering experiments coupled to Asymmetric Flow-Field Flow Fractionation (AF4), the latter improving the detectability of smaller particles in polydisperse samples due to a size separation step prior detection. However, the bimodal size distribution could not be detected due to method inherent limitations. In contrast, cryo transmission electron microscopy corroborated nES GEMMA results. Hence, gas-phase electrophoresis proved to be a versatile tool for liposome characterization as it could analyze both vesicle size and size distribution. Finally, a correlation of nES GEMMA results with cell viability experiments was carried out to demonstrate the importance of liposome batch-to-batch control as low-sized sample components possibly impact cell viability.

  • Impacts of (Nano)formulations on the Fate of an Insecticide in Soil and Consequences for Environmental Exposure Assessment

    Melanie Kah, Anne-Kathrin Weniger, Thilo Hofmann
    2016 - Environmental Science & Technology, 2: 10960-10967

    Abstract: 

    The development of nanopesticides has recently received an increased level of attention. However, there are very few data about the environmental fate of these new products, and it is not known whether nanoformulations can be evaluated within the current pesticide regulatory framework. Sorption and degradation parameters of the insecticide bifenthrin were measured in two soils for (i) the pure active ingredient, (ii) three nanoformulations, and (iii) a commercially available formulation. In most cases, fate parameters derived for the nanopesticides were significantly different from those derived for the pure active ingredient (factors of up to 10 for sorption and 1.8 for degradation), but discrepancies were not easy to relate to the characteristics of the nanocarriers. In some cases, differences were also observed between the commercial formulation and the pure active ingredient (factors of up to 1.4 for sorption and 1.7 for degradation). In the regulatory context, the common assumption that formulations do not influence the environmental fate of pesticide active ingredients after application seems therefore not always adequate. In the absence of direct measurement, an inverse modeling approach was successfully applied to evaluate the durability of the formulations in soil (release half-life ranged between 11 and 74 days). Predicted groundwater concentrations very much depended on the modeling approach adopted but overall suggest that the nanoformulations studied could reduce losses to groundwater.

  • Nano electrospray gas-phase electrophoretic mobility molecular analysis (nES GEMMA) of liposomes: applicability of the technique for nano vesicle batch control

    Victor U. Weiss, Carlos Urey, Andreas Gondikas, Monika Golesne, Gernot Friedbacher, Frank von der Kammer, Thilo Hofmann, Roland Andersson, György Marko-Varga, Martina Marchetti-Deschmann, Günter Allmaier
    2016 - Analyst, 2: 6042-6050

    Abstract: 

    Liposomes are biodegradable nanoparticle vesicles consisting of a lipid bilayer encapsulating an aqueous core. Entrapped cargo material is shielded from the extra-vesicular medium and sustained release of encapsulated material can be achieved. However, application of liposomes as nano-carriers demands their characterization concerning size and size distribution, particle-number concentration, occurrence of vesicle building blocks in solution and determination of the resulting vesicle encapsulation capacity. These questions can be targeted via gas-phase electrophoretic mobility molecular analysis (GEMMA) based on a nano electrospray (nES) charge-reduction source. This instrument separates single-charged nanoparticles in the gas-phase according to size in a high-laminar sheath-flow by means of an orthogonal, tunable electric field. nES GEMMA analysis enables to confirm liposome integrity after passage through the instrument (in combination with atomic force microscopy) as well as to exclude vesicle aggregation. Additionally, nanoparticle diameters at peak apexes and size distribution data are obtained. Differences of hydrodynamic and dry particle diameter values, as well as the effect of number- and mass-based concentration data analysis on obtained liposome diameters are shown. Furthermore, the repeatability of liposome preparation is studied, especially upon incorporation of PEGylated lipids in the bilayer. Finally, the instruments applicability to monitor mechanical stress applied to vesicles is demonstrated.

  • Physicochemical characterization of titanium dioxide pigments using various techniques for size determination and asymmetric flow field flow fractionation hyphenated with inductively coupled plasma mass spectrometry

    Johannes P. F. G. Helsper, Ruud J. B. Peters, Margaretha E. M. van Bemmel, Zahira E. Herrera Rivera, Stephan Wagner, Frank von der Kammer, Peter C. Tromp, Thilo Hofmann, Stefan Weigel
    2016 - Analytical and Bioanalytical Chemistry, 2: 6679-6691

    Abstract: 

    Seven commercial titanium dioxide pigments and two other well-defined TiO2 materials (TiMs) were physicochemically characterised using asymmetric flow field flow fractionation (aF4) for separation, various techniques to determine size distribution and inductively coupled plasma mass spectrometry (ICPMS) for chemical characterization. The aF4-ICPMS conditions were optimised and validated for linearity, limit of detection, recovery, repeatability and reproducibility, all indicating good performance. Multi-element detection with aF4-ICPMS showed that some commercial pigments contained zirconium co-eluting with titanium in aF4. The other two TiMs, NM103 and NM104, contained aluminium as integral part of the titanium peak eluting in aF4. The materials were characterised using various size determination techniques: retention time in aF4, aF4 hyphenated with multi-angle laser light spectrometry (MALS), single particle ICPMS (spICPMS), scanning electron microscopy (SEM) and particle tracking analysis (PTA). PTA appeared inappropriate. For the other techniques, size distribution patterns were quite similar, i.e. high polydispersity with diameters from 20 to >700 nm, a modal peak between 200 and 500 nm and a shoulder at 600 nm. Number-based size distribution techniques as spICPMS and SEM showed smaller modal diameters than aF4-UV, from which mass-based diameters are calculated. With aF4-MALS calculated, light-scattering-based “diameters of gyration” (Øg) are similar to hydrodynamic diameters (Øh) from aF4-UV analyses and diameters observed with SEM, but much larger than with spICPMS. A Øg/Øh ratio of about 1 indicates that the TiMs are oblate spheres or fractal aggregates. SEM observations confirm the latter structure. The rationale for differences in modal peak diameter is discussed.

  • Predicting the Sorption of Aromatic Acids to Noncarbonized and Carbonized Sorbents

    Gabriel Sigmund, Huichao Sun, Thilo Hofmann, Melanie Kah
    2016 - Environmental Science & Technology, 7: 3641-3648

    Abstract: 

    Approaches based on the octanol–water partition coefficient are commonly used to describe sorption of neutral organic compounds in environmental systems, but they are not suitable for organic acids, which can dissociate to form anions. We here investigate the applicability of an alternative approach based on the pH-dependent distribution ratio (DOW) to describe sorption of aromatic acids to sorbents representing different degrees of carbonization. Sorption isotherms for four structurally similar acids ((2,4-dichlorophenoxy)acetic acid (2,4-D), 4-chloro-2-15 methylphenoxy)acetic acid (MCPA), 4-(2,4-dichlorophenoxy)butanoic16 acid (2,4-DB), and 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan)) were measured for 15 sorbents: fresh and carbonized wood shavings, pig manure, sewage sludge, carbon nanotubes, and activated carbon. Dissociation greatly affected the sorption of all acids. Sorption coefficients measured in the high pH range indicated that sorption of the anions ranged over several orders of magnitude and should not be neglected. Sorption trends for all sorbates and carbonized sorbents could be very well described by a single regression equation that included DOW of the sorbate and the specific surface area of the sorbent (R2 > 0.89).

  • Pyrolysis of waste materials: Characterization and prediction of sorption potential across a wide range of mineral contents and pyrolysis temperatures

    Melanie Kah, Huichao Sun, Gabriel Sigmund, Thorsten Hüffer, Thilo Hofmann
    2016 - Bioresource Technology, 225-233

    Abstract: 

    Sewage sludge (50% mineral), manure (29%) and wood (<1%) were pyrolyzed at 200, 350 and 500 °C with the aim to study the characteristics and sorption potential of materials undergoing pyrolysis across a wide range of mineral contents. A commercial plant-derived biochar (41% mineral) was also considered. The materials were extensively characterized and tested for their sorption towards the model sorbates benzene, naphthalene and pyrene. Plant-derived materials, regardless of their mineral content, developed micropores causing size exclusion of pyrene. Changes in properties and sorption behavior upon pyrolysis were generally consistent for the manure and wood series. A single regression equation developed on our data (including the sorbate hydrophobicity and sorbent polarity) provided excellent prediction of previously reported changes in sorption upon pyrolysis across a wide range of mineral content (up to 500 °C). The sewage sludge series, however, followed a particular behavior, possibly due to very high mineral content (up to 67%).

  • Silver and gold nanoparticle separation using asymmetrical flow-field flow fractionation: Influence of run conditions and of particle and membrane charges

    Boris Meisterjahn, Stephan Wagner, Frank von der Kammer, Dieter Hennecke, Thilo Hofmann
    2016 - Journal of Chromatography A, 150-159

    Abstract: 

    Flow-Field Flow Fractionation (Flow-FFF), coupled with online detection systems is one of the most promising tools available for the separation and quantification of engineered nanoparticles (ENPs) in complex matrices. To correctly relate the retention of nanoparticles in the Flow-FFF-channel to the particle size, ideal separation conditions must be met. This requires optimization of the parameters that influence the separation behavior. The aim of this study was therefore to systematically investigate and evaluate the influence of parameters such as the carrier liquid, the cross flow, and the membrane material, on the separation behavior of two metallic ENPs. For this purpose the retention, recovery, and separation efficiency of sterically stabilized silver nanoparticles (AgNPs) and electrostatically stabilized gold nanoparticles (AuNPs), which represent two materials widely used in investigations on environmental fate and ecotoxicology, were investigated against a parameter matrix of three different cross-flow densities, four representative carrier solutions, and two membrane materials.

    The use of a complex mixture of buffers, ionic and non-ionic surfactants (FL-70 solution) together with a medium cross-flow density provided an acceptable compromise in peak quality and recovery for both types of ENPs. However, these separation conditions do not represent a perfect match for both particle types at the same time (maximized recovery at maximized retention).

    It could be shown that the behavior of particles within Flow-FFF channels cannot be predicted or explained purely in terms of electrostatic interactions. Particles were irreversibly lost under conditions where the measured zeta potentials suggested that there should have been sufficient electrostatic repulsion to ensure stabilization of the particles in the Flow-FFF channel resulting in good recoveries.

    The wide variations that we observed in ENP behavior under different conditions, together with the different behavior that has been reported in published literature for the same NPs under similar conditions, indicate a need for improvement in the membrane materials used for Flow-FFF analysis of NPs.

    This research has shown that careful adjustment of separation conditions can result in acceptable, but not ideal, separation conditions for two fundamentally different stabilized materials, and that it may not be possible to separate a set of different particles under ideal conditions for each particle type. This therefore needs to be taking into account in method development and when interpreting FFF results from complex samples.

  • Sorption of non-polar organic compounds by micro-sized plastic particles in aqueous solution

    2016 - Environmental Pollution, 194-201

    Abstract: 

    The presence of microscale polymer particles (i.e., microplastics) in the environment has become a major concern in recent years. Sorption of organic compounds by microplastics may affect the phase distribution within both sediments and aqueous phases. To investigate this process, isotherms were determined for the sorption of seven aliphatic and aromatic organic probe sorbates by four polymers with different physico-chemical properties. Sorption increased in the order polyamide < polyethylene < polyvinylchloride < polystyrene. This order does not reflect the particle sizes of the investigated microplastics within the aqueous dispersions, indicating the influence of additional factors (e.g., π-π-interactions) on the sorption of aromatic compounds by polystyrene. Linear isotherms by polyethylene suggested that sorbate uptake was due to absorption into the bulk polymer. In contrast, non-linear isotherms for sorption by PS, PA, and PVC suggest a predominance of adsorption onto the polymer surface, which is supported by the best fit of these isotherms using the Polanyi-Manes model. A strong relationship between the sorption coefficients of the microplastics and the hydrophobicity of the sorbates suggests that hydrophobic interactions are of major importance.

  • Vulnerability of drinking water supplies to engineered nanoparticles

    Martin Troester, Heinz-Juergen Brauch, Thilo Hofmann
    2016 - Water Research, 255-279

    Abstract: 

    The production and use of engineered nanoparticles (ENPs) inevitably leads to their release into aquatic environments, with the quantities involved expected to increase significantly in the future. Concerns therefore arise over the possibility that ENPs might pose a threat to drinking water supplies. Investigations into the vulnerability of drinking water supplies to ENPs are hampered by the absence of suitable analytical methods that are capable of detecting and quantifiying ENPs in complex aqueous matrices. Analytical data concerning the presence of ENPs in drinking water supplies is therefore scarce. The eventual fate of ENPs in the natural environment and in processes that are important for drinking water production are currently being investigated through laboratory based-experiments and modelling.

    Although the information obtained from these studies may not, as yet, be sufficient to allow comprehensive assessment of the complete life-cycle of ENPs, it does provide a valuable starting point for predicting the significance of ENPs to drinking water supplies.

    This review therefore addresses the vulnerability of drinking water supplies to ENPs. The risk of ENPs entering drinking water is discussed and predicted for drinking water produced from groundwater and from surface water. Our evaluation is based on reviewing published data concerning ENP production amounts and release patterns, the occurrence and behavior of ENPs in aquatic systems relevant for drinking water supply and ENP removability in drinking water purification processes. Quantitative predictions are made based on realistic high-input case scenarios. The results of our synthesis of current knowledge suggest that the risk probability of ENPs being present in surface water resources is generally limited, but that particular local conditions may increase the probability of raw water contamination by ENPs. Drinking water extracted from porous media aquifers are not generally considered to be prone to ENP contamination. In karstic aquifers, however, there is an increased probability that if any ENPs enter the groundwater system they will reach the extraction point of a drinking water treatment plant (DWTP).

    The ability to remove ENPs during water treatment depends on the specific design of the treatment process. In conventional DWTPs with no flocculation step a proportion of ENPs, if present in the raw water, may reach the final drinking water. The use of ultrafiltration techniques improves drinking water safety with respect to ENP contamination.

  • A uniform measurement expression for cross method comparison of nanoparticle aggregate size distributions

    Agnieszka Dudkiewicz, Stephan Wagner, Angela Lehner, Qasim Chaudhry, Stéphane Pietravalle, Karen Tiede, Alistair B. A. Boxall, Guenter Allmaier, Dirk Tiede, Ringo Grombe, Frank von der Kammer, Thilo Hofmann, Kristian Mølhave
    2015 - Analyst, 1: 5257-5267

    Abstract: 

    Available measurement methods for nanomaterials are based on very different measurement principles and hence produce different values when used on aggregated nanoparticle dispersions. This paper provides a solution for relating measurements of nanomaterials comprised of nanoparticle aggregates determined by different techniques using a uniform expression of a mass equivalent diameter (MED). The obtained solution is used to transform into MED the size distributions of the same sample of synthetic amorphous silica (nanomaterial comprising aggregated nanoparticles) measured by six different techniques: scanning electron microscopy in both high vacuum (SEM) and liquid cell setup (Wet-SEM); gas-phase electrophoretic mobility molecular analyzer (GEMMA); centrifugal liquid sedimentation (CLS); nanoparticle tracking analysis (NTA); and asymmetric flow field flow fractionation with inductively coupled plasma mass spectrometry detection (AF4-ICP-MS). Transformed size distributions are then compared between the methods and conclusions drawn on methods’ measurement accuracy, limits of detection and quantification related to the synthetic amorphous silca's size. Two out of the six tested methods (GEMMA and AF4-ICP-MS) cross validate the MED distributions between each other, providing a true measurement. The measurement accuracy of other four techniques is shown to be compromised either by the high limit of detection and quantification (CLS, NTA, Wet-SEM) or the sample preparation that is biased by increased retention of smaller nanomaterials (SEM). This study thereby presents a successful and conclusive cross-method comparison of size distribution measurements of aggregated nanomaterials. The authors recommend the uniform MED size expression for application in nanomaterial risk assessment studies and clarifications in current regulations and definitions concerning nanomaterials.

  • Application of laser-induced breakdown-detection as a sensitive detector for UF membrane surrogate challenge tests

    M. Tröster, P. Lipp, F. Sacher, Thilo Hofmann, H.-J. Brauch
    2015 - Water Supply, 15: 377-383

    Abstract: 

    Characteristics of ultrafiltration membranes with respect to the removal of nanoscale particles can be determined by surrogate challenge tests (SCTs). Key elements of a successful SCT are the selection of a suitable surrogate and a reliable quantification method. A major challenge when using nanoparticles as surrogates is their quantification in the filtrate, since commonly used particle detection methods are often lacking in sensitivity. The applicability of laser-induced breakdown-detection (LIBD) as a monitoring tool for SCTs has therefore been evaluated. The SCTs were carried out using polystyrene (PS) and silicate particles spiked into ultrapure water and into bank filtrate. Nanoparticles were detectable down to 10 nm and, depending on the material, down to a few ng/L. The nominal pore-size of the ultrafiltration membrane could be confirmed during the tests, demonstrating the suitability of LIBD as a highly sensitive monitoring technique for SCTs.

  • Bacterial wax esters in recent fluvial sediments

    Vesna Micić, Jürgen Köster, Michael A. Kruge, Bert Engelen, Thilo Hofmann
    2015 - Organic Geochemistry, 44-55

    Abstract: 

    We investigated the molecular inventory of River Danube sediments and identified wax esters with 28–36 carbons, with C30, C31 and C32 homologs the most abundant. They consist of various combinations of n-, iso- and anteiso-aliphatic acid and alcohol moieties, with different isomer distributions for the esters with odd and even carbon numbers. The short chain length (C28–C36), high proportion of methyl moieties and presence of monounsaturated esters together suggest a bacterial origin for the wax esters. The concentration in surface sediments varied from 0 to 741 μg/kg, being significantly enriched at locations with high nutrient concentration and high primary productivity. Cluster analysis of denaturing gradient gel electrophoresis (DGGE) band patterns revealed different bacterial communities in surface sediments from the stream and surface sediments from the reservoir. The concentration in a 70 cm core of rapidly deposited sediments decreased significantly with depth, following first order kinetics, suggesting a loss of the esters within ca. 3 years following burial and hence a low probability for preservation in the geological record. Wax esters in rivers have rarely been investigated; our results suggest that they represent a bacterial response to enhanced primary production, triggered by higher nutrient supply.

  • Comment on the German Draft Legislation on Hydraulic Fracturing: The Need for an Accurate State of Knowledge and for Independent Scientific Research

    Martin Elsner, Kathrin Schreglmann, Wolfgang Calmano, Axel Bergmann, Andrea Vieth-Hillebrand, Franziska D. H. Wilke, Klaus-Michael Wollin, Anett Georgi, Winfried Schmidt, Thilo Hofmann, Vesna Micić, Avner Vengosh, Bernhard Mayer
    2015 - Environmental Science & Technology, 1: 6367-6369

    Abstract: 

    Exploitation of unconventional gas resources is challenged by societal concerns about environmental risks associated with high volume multistage hydraulic fracturing (HF) in horizontal wells.(1) To regulate HF in Germany, on April first 2015, the German Chancellor’s cabinet signed off on a draft law which is currently under discussion in the parliament and states the following (Figure 1):

    1. HF is prohibited in water protection areas, their catchments and natural habitats by the Water Management Act and the Federal Nature Conservation Act (WHG §13a, Para.1 No. 2, BNatSchG §23 Para. 3, §24 Para. 3, §33 Para.1a). Not regulated are catchments of deeper groundwater horizons or abstraction areas for beverage industries (WHG §9, Para. 2).
    2. Elsewhere, HF and disposal injections of formation water are possible, but subject to Environmental Risk Assessment by Mining Authorities (WHG §9, Para. 2) involving declaration of all chemical additives (WHG § 13b Para. 1).
    3. In shale, coal, clay and marl formations less than 3000 m deep, HF activities are forbidden except for (i) scientific investigations to explore environmental impacts of HF, or (ii) if an accompanying scientific expert panel concludes that HF for commercial purposes is nonproblematic in a given formation (WHG §13a Para. 2, 6, 7).
  • Concentrations and Distributions of Metals Associated with Dissolved Organic Matter from the Suwannee River (GA, USA)

    Keshia M. Kuhn, Elisabeth Neubauer, Thilo Hofmann, Frank von der Kammer, George R. Aiken, Patricia A. Maurice
    2015 - Environmental Engineering Science, 1: 54-65

    Abstract: 

    Concentrations and distributions of metals in Suwannee River (SR) raw filtered surface water (RFSW) and dissolved organic matter (DOM) processed by reverse osmosis (RO), XAD-8 resin (for humic and fulvic acids [FA]), and XAD-4 resin (for “transphilic” acids) were analyzed by asymmetrical flow field-flow fractionation (AsFlFFF). SR samples were compared with DOM samples from Nelson's Creek (NLC), a wetland-draining stream in northern Michigan; previous International Humic Substances Society (IHSS) FA and RO samples from the SR; and an XAD-8 sample from Lake Fryxell (LF), Antarctica. Despite application of cation exchange during sample processing, all XAD and RO samples contained substantial metal concentrations. AsFlFFF fractograms allowed metal distributions to be characterized as a function of DOM component molecular weight (MW). In SR RFSW, Fe, Al, and Cu were primarily associated with intermediate to higher than average MW DOM components. SR RO, XAD-8, and XAD-4 samples from May 2012 showed similar MW trends for Fe and Al but Cu tended to associate more with lower MW DOM. LF DOM had abundant Cu and Zn, perhaps due to amine groups that should be present due to its primarily algal origins. None of the fractograms showed obvious evidence for mineral nanoparticles, although some very small mineral nanoparticles might have been present at trace concentrations. This research suggests that AsFlFFF is important for understanding how metals are distributed in different DOM samples (including IHSS samples), which may be key to metal reactivity and bioavailability.

  • Detection of Engineered Copper Nanoparticles in Soil Using Single Particle ICP-MS

    Jana Navratilova, Antonia Praetorius, Andreas Gondikas, Willi Fabienke, Frank von der Kammer, Thilo Hofmann
    2015 - International Journal of Environmental Research and Public Health, 1: 15756-15768

    Abstract: 

    Regulatory efforts rely on nanometrology for the development and implementation of laws regarding the incorporation of engineered nanomaterials (ENMs) into industrial and consumer products. Copper is currently one of the most common metals used in the constantly developing and expanding sector of nanotechnology. The use of copper nanoparticles in products, such as agricultural biocides, cosmetics and paints, is increasing. Copper based ENMs will eventually be released to the environment through the use and disposal of nano-enabled products, however, the detection of copper ENMs in environmental samples is a challenging task. Single particle inductively coupled plasma mass spectroscopy (spICP-MS) has been suggested as a powerful tool for routine nanometrology efforts. In this work, we apply a spICP-MS method for the detection of engineered copper nanomaterials in colloidal extracts from natural soil samples. Overall, copper nanoparticles were successfully detected in the soil colloidal extracts and the importance of dwell time, background removal, and sample dilution for method optimization and recovery maximization is highlighted.

  • Feasibility of the development of reference materials for the detection of Ag nanoparticles in food: neat dispersions and spiked chicken meat

    Ringo Grombe, Günter Allmaier, Jean Charoud-Got, Agnieszka Dudkiewicz, Håkan Emteborg, Thilo Hofmann, Erik Huusfeldt Larsen, Angela Lehner, Meritxell Llinàs, Katrin Loeschner, Kristian Mølhave, Ruud J. Peters, John Seghers, Conxita Solans, Frank von der Kammer, Stephan Wagner, Stefan Weigel, Thomas P. J. Linsinger
    2015 - Accreditation and Quality Assurance, 1: 3-16

    Abstract: 

    The feasibility of producing colloidal silver nanoparticle reference materials and silver nanoparticle spiked reference matrix materials was investigated. Two concentrations of PVP-coated silver nanoparticle dispersions were evaluated and used to spike chicken meat, with the aim of producing a set of reference materials to support the development of analytical methods for the detection and quantification of nanoparticles in food. Aqueous silver nanoparticle (AgNP) dispersions were evaluated for their homogeneity of mass fraction and particle size and found sufficiently homogeneous to be used as reference materials. Stability studies at 4 °C, 18 °C and 60 °C demonstrated sufficient short- and long-term stability, although particle size decreases in a linear fashion at 60 °C. The AgNP dispersions were characterized for total Ag mass fraction by ICP-OES, dissolved Ag content by ultrafiltration-ICP-MS, as well as AgNP particle size by dynamic light scattering, transmission electron microscopy (TEM) and gas-phase electrophoretic molecular mobility analysis. Chicken breasts were homogenized by cryo-milling and spiked with aqueous AgNP dispersions. Rapid freezing over liquid nitrogen resulted in homogeneous and stable materials. The spiked chicken materials were characterized for their total Ag mass fraction by neutron activation analysis and for the AgNP particle size by TEM and single-particle inductively coupled plasma mass spectrometry. The observed differences in particle sizes between the spiked chicken samples and the original silver dispersions indicate relevant matrix effects. The materials demonstrate that production and characterization of reference materials for the detection and quantification of silver nanoparticles in meat are feasible, but challenges especially in assessing stability and having sufficiently precise methods for assessment of homogeneity and stability remain.

  • First steps towards a generic sample preparation scheme for inorganic engineered nanoparticles in a complex matrix for detection, characterization, and and quantification by asymmetric flow-field flow fractionation coupled to multi-angle light scattering

    S. Wagner, S. Legros, K. Loeschner, J. Liu, J. Navratilova, R. Grombe, T. P. J. Linsinger, E. H. Larsen, Frank von der Kammer, Thilo Hofmann
    2015 - Journal of Analytical Atomic Spectrometry, 6: 1286-1296

    Abstract: 

    The applicability of a multi-step generic procedure to systematically develop sample preparation methods for the detection, characterization, and quantification of inorganic engineered nanoparticles (ENPs) in a complex matrix was successfully demonstrated. The research focused on the optimization of the sample preparation, aiming to achieve a complete separation of ENPs from a complex matrix without altering the ENP size distribution and with minimal loss of ENPs. The separated ENPs were detected and further characterized in terms of particle size distribution and quantified in terms of elemental mass content by asymmetric flow-field flow fractionation coupled to a multi-angle light scattering detector and an inductively coupled plasma mass spectrometer. Following the proposed generic procedure SiO2-ENPs were separated from a tomato soup. Two potential sample preparation methods were tested these being acid digestion and colloidal extraction. With the developed method a complete SiO2-ENPs and matrix separation with a Si mass recovery >90% was achieved by acid digestion. The alteration of the particle size distribution was minimized by particle stabilization. The generic procedure which also provides quality criteria for method development is urgently needed for standardized and systematic development of procedures for separation of ENPs from a complex matrix. The chosen analytical technique was shown to be suitable for detecting SiO2-ENPs in a complex food matrix like tomato soup and may therefore be extended to monitor the existence of ENPs during production and safety control of foodstuffs, food labelling, and compliance with legislative limits.

  • Hydrogeologie und Wasserchemie: So nah und doch so fern

    2015 - Grundwasser, 3: 161-161
  • Measuring the reactivity of commercially available zero-valent iron nanoparticles used for environmental remediation with iopromide

    Doris Schmid, Vesna Micić, Susanne Laumann, Thilo Hofmann
    2015 - Journal of Contaminant Hydrology, 36-45

    Abstract: 

    The high specific surface area and high reactivity of nanoscale zero-valent iron (nZVI) particles have led to much research on their application to environmental remediation. The reactivity of nZVI is affected by both the water chemistry and the properties of the particular type of nZVI particle used. We have investigated the reactivity of three types of commercially available Nanofer particles (from Nanoiron, s.r.o., Czech Republic) that are currently either used in, or proposed for use in full scale environmental remediation projects. The performance of one of these, the air-stable and thus easy-to-handle Nanofer Star particle, has not previously been reported. Experiments were carried out first in batch shaking reactors in order to derive maximum reactivity rates and provide a rapid estimate of the Nanofer particle's reactivity. The experiments were performed under near-natural environmental conditions with respect to the pH value of water and solute concentrations, and results were compared with those obtained using synthetic water. Thereafter, the polyelectrolyte-coated Nanofer 25S particles (having the highest potential for transport within porous media) were chosen for the experiments in column reactors, in order to elucidate nanoparticle reactivity under a more field-site realistic setting.

    Iopromide was rapidly dehalogenated by the investigated nZVI particles, following pseudo-first-order reaction kinetics that was independent of the experimental conditions. The specific surface area normalized reaction rate constant (kSA) value in the batch reactors ranged between 0.12 and 0.53 L m− 2 h− 1; it was highest for the uncoated Nanofer 25 particles, followed by the polyacrylic acid-coated Nanofer 25S and air-stable Nanofer Star particles. In the batch reactors all particles were less reactive in natural water than in synthetic water. The kSA values derived from the column reactor experiments were about 1000 times lower than those from the batch reactors, ranging between 2.6 × 10− 4 and 5.7 × 10− 4 L m− 2 h− 1. Our results revealed that the easy-to-handle and air-stable Nanofer Star particles are the least reactive of all the Nanofer products tested. The reaction kinetics predicted by column experiments were more realistic than those predicted by batch experiments and these should therefore be used when designing a full-scale field application of nanomaterials for environmental remediation.

  • Quantification of river water infiltration in shallow aquifers using acesulfame and anthropogenic gadolinium

    Andrea Bichler, Christian Muellegger, Robert Brünjes, Thilo Hofmann
    2015 - Hydrological Processes, 1: 1742-1756

    Abstract: 

    This study has investigated the use of the artificial sweetener acesulfame and the magnetic resonance imaging contrast agent gadolinium as quantitative tracers for river water infiltration into shallow groundwater. The influence of a river on alluvial groundwater in a subalpine catchment in western Europe has been assessed using the ‘classical’ hydrochemical tracer chloride and the trace contaminants acesulfame and anthropogenic gadolinium. Mixing ratios for riverine bank filtrate with ambient groundwater and the uncertainties associated with the temporal and spatial tracer variability were calculated using acesulfame and gadolinium and compared with those obtained using chloride. The temporal variability of tracer concentrations in river water of gadolinium (standard deviation SD: 63%) and acesulfame (SD: 71%) both exceeded that of chloride (SD: 27%), and this was identified as the main source of uncertainty in the mixing analysis. Similar spatial distributions were detected in the groundwater for chloride and gadolinium, but not for acesulfame. Mixing analyses using acesulfame resulted in calculated mixing ratios that differed from those obtained using gadolinium and chloride by up to 83% and 92%, respectively. At the investigated site, which had oxic conditions and moderate temperatures, acesulfame was found to be a less reliable tracer than either gadolinium or chloride, probably because of natural attenuation and input from other sources. There was no statistically significant difference between the mixing ratios obtained using chloride or gadolinium, the mixing ratios obtained using gadolinium were 40–50% lower than those obtained using chloride. This is mainly due to a bias of the mean gadolinium concentration in river water towards higher values. In view of the uncertainties of the two tracers, neither could be preferred over the other for the quantification of bank filtrate in groundwater. At this specific site gadolinium was able to reliably identify river water infiltration and was a more precise tracer than chloride at low mixing ratios (<20%), because of the exclusive occurrence of gadolinium in river water and its high dynamic range.

  • River-derived humic substances as iron chelators in seawater

    Regina Krachler, Rudolf F. Krachler, Gabriele Wallner, Stephan Hann, Monika Laux, Maria F. Cervantes Recalde, Franz Jirsa, Elisabeth Neubauer, Frank von der Kammer, Thilo Hofmann, Bernhard K. Keppler
    2015 - Marine Chemistry, 85-93

    Abstract: 

    The speciation of iron(III) in oxic seawater is dominated by its hydrolysis and sedimentation of insoluble iron(III)-oxyhydroxide. As a consequence, many oceanic areas have very low iron levels in surface seawater which leads to iron deficiency since phytoplankton require iron as a micronutrient in order to grow. Fortunately, iron solubility is not truly as low as Fe(III) solubility measurements in inorganic seawater would suggest, since oceanic waters contain organic molecules which tend to bind the iron and keep it in solution. Various iron-binding organic ligands which combine to stabilize dissolved iron have been detected and thoroughly investigated in recent years. However, the role of iron-binding ligands from terrestrial sources remains poorly constrained. Blackwater rivers supply large amounts of natural organic material (NOM) to the ocean. This NOM (which consists mainly of vascular plant-derived humic substances) is able to greatly enhance iron bioavailability in estuaries and coastal regions, however, breakdown processes lead to a rapid decrease of river-derived NOM concentrations with increasing distance from land. It has therefore been argued that the influence of river-derived NOM on iron biogeochemistry in offshore seawater does not seem to be significant. Here we used a standard method based on 59Fe as a radiotracer to study the solubility of Fe(III)-oxyhydroxide in seawater in the presence of riverine NOM. We aimed to address the question how effective is freshwater NOM as an iron chelator under open ocean conditions where the concentration of land-derived organic material is about 3 orders of magnitude smaller than in coastal regions, and does this iron chelating ability vary between NOM from different sources and between different size fractions of the river-borne NOM. Our results show that the investigated NOM fractions were able to substantially enhance Fe(III)-oxyhydroxide solubility in seawater at concentrations of the NOM ≥ 5 μg L− 1. Terrigenous NOM concentrations ≥ 5 μg L− 1 are in no way unusual in open ocean surface waters especially of the Arctic and the North Atlantic Oceans. River-derived humic substances could therefore play a greater role as iron carriers in the ocean than previously thought.

  • The Challenge: Carbon nanomaterials in the environment: New threats or wonder materials?

    Melanie Kah, Thilo Hofmann
    2015 - Environmental Toxicology and Chemistry, 5: 954-954
  • A tree-based statistical classification algorithm (CHAID) for identifying variables responsible for the occurrence of faecal indicator bacteria during waterworks operations

    Andrea Bichler, Arnold Neumaier, Thilo Hofmann
    2014 - Journal of Hydrology, 909-917

    Abstract: 

    Microbial contamination of groundwater used for drinking water can affect public health and is of major concern to local water authorities and water suppliers. Potential hazards need to be identified in order to protect raw water resources. We propose a non-parametric data mining technique for exploring the presence of total coliforms (TC) in a groundwater abstraction well and its relationship to readily available, continuous time series of hydrometric monitoring parameters (seven year records of precipitation, river water levels, and groundwater heads). The original monitoring parameters were used to create an extensive generic dataset of explanatory variables by considering different accumulation or averaging periods, as well as temporal offsets of the explanatory variables. A classification tree based on the Chi-Squared Automatic Interaction Detection (CHAID) recursive partitioning algorithm revealed statistically significant relationships between precipitation and the presence of TC in both a production well and a nearby monitoring well. Different secondary explanatory variables were identified for the two wells. Elevated water levels and short-term water table fluctuations in the nearby river were found to be associated with TC in the observation well. The presence of TC in the production well was found to relate to elevated groundwater heads and fluctuations in groundwater levels. The generic variables created proved useful for increasing significance levels. The tree-based model was used to predict the occurrence of TC on the basis of hydrometric variables.

  • Analysing the fate of nanopesticides in soil and the applicability of regulatory protocols using a polymer-based nanoformulation of atrazine

    Melanie Kah, Patrick Machinski, Petra Koerner, Karen Tiede, Renato Grillo, Leonardo Fernandes Fraceto, Thilo Hofmann
    2014 - Environmental Science and Pollution Research, 2: 11699-11707

    Abstract: 

    For the first time, regulatory protocols defined in the OECD guidelines were applied to determine the fate properties of a nanopesticide in two agricultural soils with contrasting characteristics. The nanoformulation studied had no effect on the degradation kinetics of atrazine indicating that (1) the release of atrazine from the polymer nanocarriers occurred rapidly relative to the degradation kinetics (half-lives 36–53 days) and/or that (2) atrazine associated with the nanocarriers was subject to biotic or abiotic degradation. Sorption coefficients, derived from a batch and a centrifugation technique at a realistic soil-to-solution ratio, were higher for the nanoformulated atrazine than for the pure active ingredient. Results indicate that the nanoformulation had an effect on the fate of atrazine. However, since the protocols applied were designed to assess solutes, conclusions about the transport of atrazine loaded onto the nanocarriers should be made extremely cautiously. The centrifugation method applied over time (here over 7 days) appears to be a useful tool to indirectly assess the durability of nanopesticides under realistic soil-to-solution ratios and estimate the period of time during which an influence on the fate of the active ingredient may be expected. More detailed investigations into the bioavailability and durability of nanopesticides are necessary and will require the development of novel methods suitable to address both the “nano” and “organic” characteristics of polymer-based nanopesticides.

  • Asymmetrical flow-field-flow fractionation coupled with inductively coupled plasma mass spectrometry for the analysis of gold nanoparticles in the presence of natural nanoparticles

    Boris Meisterjahn, Elisabeth Neubauer, Frank von der Kammer, Dieter Hennecke, Thilo Hofmann
    2014 - Journal of Chromatography A, 204-211

    Abstract: 

    Flow-Field-Flow Fractionation (Flow-FFF), coupled with online detection systems, is one of the most promising tools available for the analysis and characterization of engineered nanoparticles (ENPs) in complex matrices. In order to demonstrate the applicability of Flow-FFF for the detection, quantification, and characterization of engineered gold nanoparticles (AuNPs), model dispersions were prepared containing AuNPs with diameters of 30 or 100 nm, natural nanoparticles (NNPs) extracted from a soil sample, and different concentrations of natural organic matter (NOM), which were then used to investigate interactions between the AuNPs and the NNPs. It could be shown that light scattering detection can be used to evaluate the fractionation performance of the pure NNPs, but not the fractionation performance of the mixed samples that also contained AuNPs because of specific interactions between the AuNPs and the laser light. A combination of detectors (i.e. light absorbance and inductively coupled plasma mass spectrometry (ICP-MS)) was found to be useful for differentiating between heteroaggregation and homoaggregation of the nanoparticles (NPs). The addition of NOM to samples containing 30 nm AuNPs stabilized the AuNPs without affecting the NP size distribution. However, fractograms for samples with no added NOM showed a change in the size distribution, suggesting interactions between the AuNPs and NNPs. This interpretation was supported by unchanged light absorption wavelengths for the AuNPs. In contrast, results for samples containing 100 nm AuNPs were inconclusive with respect to recovery and size distributions because of problems with the separation system that probably related to the size and high density of these nanoparticles, highlighting the need for extensive method optimization strategies, even for nanoparticles of the same material but different sizes.

  • Finde den Unterschied: synthetische und natürliche Nanopartikel in der Umwelt - Freisetzung, Verhalten und Verbleib

    Stephan Wagner, Andreas Gondikas, Elisabeth Neubauer, Thilo Hofmann, Frank von der Kammer
    2014 - Angewandte Chemie, 4: 12604-12626

    Abstract: 

    Die Produktion und Verwendung von Nanopartikeln haben zur Folge, dass synthetische Nanopartikel in die Umwelt freigesetzt werden, wo sie vielfältige Reaktionen und Wechselwirkungen eingehen können. Für natürlich vorkommende Nanopartikel (1–100 nm) und Kolloide (1–1000 nm) werden solche Reaktionen und das daraus resultierende Verhalten und der Verbleib in der Umwelt seit langem untersucht. Die aus diesen Untersuchungen gewonnenen Erkenntnisse reichen jedoch für die Erstellung genauer Modelle über das Verhalten und den Verbleib synthetischer Nanopartikel in der Umwelt längst nicht aus, bilden aber einen guten Ausgangspunkt für eine Risikobewertung dieser neuen Materialien. Das Ziel dieses Aufsatzes ist der kritische Vergleich zwischen den Prozessen natürlicher und synthetischer Systeme. Auf diese Weise sollen die “nanospezifischen” Eigenschaften der synthetischen Partikel sowie maßgebliche Wissenslücken für eine Risikobewertung von künstlich hergestellten Nanomaterialien in der Umwelt identifiziert werden.

  • Laser-Induced Breakdown-Detection for reliable online monitoring of membrane integrity

    Martin Troester, Pia Lipp, Frank Sacher, Heinz-Juergen Brauch, Thilo Hofmann
    2014 - Journal of Membrane Science, 313-321

    Abstract: 

    The applicability of Laser-Induced Breakdown-Detection (LIBD) as an online membrane integrity monitoring system during ultrafiltration processes has been evaluated by linking a laboratory-scale membrane filtration test system to acoustic LIBD instrumentation. The results demonstrate that LIBD is a sensitive and reliable indirect online system suitable for testing and monitoring membrane integrity in ultrafiltration processes. Particles present in the filtrate can be detected continuously online using a fixed laser pulse energy (continuous mode). The LIBD monitoring system proved to be sensitive to nanoscale particles leaching through breaches in a membrane. In continuous mode 20 nm particles could be detected at concentrations as low as a few ng/L. This is superior in terms of both minimum detectable particle size and minimum concentrations to the turbidity measurement and particle counting methods that are commonly used for continuous online monitoring. Depending on the feed water characteristics and the membrane used, the LIBD system can be adjusted to specific processes by varying the measurement settings. Particle size distributions in the feed and filtrate can also be determined through non-continuous online LIBD measurements by varying the laser pulse energies (non-continuous mode), thus allowing the particle retention characteristics of the membrane to be analyzed.

  • Mobility enhancement of nanoscale zero-valent iron in carbonate porous media through co-injection of polyelectrolytes

    Susanne Laumann, Vesna Micić, Thilo Hofmann
    2014 - Water Research, 70-79

    Abstract: 

    The mobility of nanoscale zero-valent iron (nZVI), which is used for in situ groundwater remediation, is affected by chemical and physical heterogeneities within aquifers. Carbonate minerals in porous aquifers and the presence of divalent cations reduce nZVI mobility. This study assesses the potential for enhancing the mobility of polyacrylic acid coated nZVI (PAA-nZVI) in such aquifers through the co-injection of polyelectrolytes (natural organic matter, humic acid, carboxymethyl cellulose, and lignin sulfonate). When applied at the same concentration, all of the polyelectrolytes produced similar enhancement of PAA-nZVI mobility in carbonate porous media. This increase in mobility was a result of increased repulsion between PAA-nZVI and the carbonate matrix. Lignin sulfonate, an environmentally friendly and inexpensive agent, was identified as the most suitable polyelectrolyte for field applications. The greatest increase in PAA-nZVI mobility was achieved with co-injection of lignin sulfonate at concentrations ≥50 mg L−1; at these concentrations the maximum PAA-nZVI travel distance in carbonate porous media was twice of that in the absence of lignin sulfonate.

  • Nanopesticide research: Current trends and future priorities

    Melanie Kah, Thilo Hofmann
    2014 - Environment International, 224-235

    Abstract: 

    The rapid developments in nanopesticide research over the last two years have motivated a number of international organizations to consider potential issues relating to the use of nanotechnology for crop protection. This analysis of the latest research trends provides a useful basis for identifying research gaps and future priorities.

    Polymer-based formulations have received the greatest attention over the last two years, followed by formulations containing inorganic nanoparticles (e.g., silica, titanium dioxide) and nanoemulsions. Investigations have addressed the lack of information on the efficacy of nanopesticides and a number of products have been demonstrated to have greater efficacy than their commercial counterparts. However, the mechanisms involved remain largely unknown and further research is required before any generalizations can be made.

    There is now increased motivation to develop nanopesticides that are less harmful to the environment than conventional formulations, and future investigations will need to assess whether any promising products developed are able to compete with existing formulations, in terms of both cost and performance.

    Investigations into the environmental fate of nanopesticides remain scarce, and the current state of knowledge does not appear to be sufficient for a reliable assessment to be made of their associated benefits and risks. A great deal of research will therefore be required over the coming years, and will need to include (i) the development of experimental protocols to generate reliable fate properties, (ii) investigations into the bioavailability and durability of nanopesticides, and (iii) evaluation of current environmental risk assessment approaches, and their refinement where appropriate.

  • Production of reference materials for the detection and size determination of silica nanoparticles in tomato soup

    Ringo Grombe, Jean Charoud-Got, Håkan Emteborg, Thomas P. J. Linsinger, John Seghers, Stephan Wagner, Frank von der Kammer, Thilo Hofmann, Agnieszka Dudkiewicz, Meritxell Llinàs, Conxita Solans, Angela Lehner, Günter Allmaier
    2014 - Analytical and Bioanalytical Chemistry, in press

    Abstract: 

    A set of four reference materials for the detection and quantification of silica nanoparticles (NPs) in food was produced as a proof of principle exercise. Neat silica suspensions were ampouled, tested for homogeneity and stability, and characterized for total silica content as well as particle diameter by dynamic light scattering (DLS), electron microscopy (EM), gas-phase electrophoretic molecular mobility analysis (GEMMA), and field-flow fractionation coupled with an inductively coupled mass spectrometer (FFF-ICPMS). Tomato soup was prepared from ingredients free of engineered nanoparticles and was spiked at two concentration levels with the silica NP suspension. Homogeneity of these materials was found sufficient to act as reference materials and the materials are sufficiently stable to allow long-term storage and distribution at ambient temperature, providing proof of principle of the feasibility of producing liquid food reference materials for the detection of nanoparticles. The spiked soups were characterized for particle diameter by EM and FFF-ICPMS (one material only), as well as for the total silica content. Although questions regarding the trueness of the results from EM and FFF-ICPMS procedures remain, the data obtained indicate that even assigning values should eventually be feasible. The materials can therefore be regarded as the first step towards certified reference materials for silica nanoparticles in a food matrix.

  • Release of TiO2 Nanoparticles from Sunscreens into Surface Waters: A One-Year Survey at the Old Danube Recreational Lake

    Andreas P. Gondikas, Frank von der Kammer, Robert B. Reed, Stephan Wagner, James F. Ranville, Thilo Hofmann
    2014 - Environmental Science & Technology, 1: 5415-5422

    Abstract: 

    Monitoring data are necessary for the future production of engineered nanomaterials and the development of regulations for nanomaterials. Therefore, it is necessary to develop methods that reliably detect and quantify nanomaterials in real-world systems at expectedly low concentrations. In this work we tested several methodological approaches to detect titanium dioxide nanomaterials released from sunscreen products into the Old Danube Lake (Vienna, Austria), which is heavily used for recreational activities like bathing and water sports during the summer season. During a 12-month period suspended particulate matter (SPM) was collected from the lake and analyzed using a combination of complementary techniques. By sampling at a location approximately 50 m from the nearest bathing area and at one meter depth from the water surface, we focused on the potentially mobile fraction of the released nanoparticles. We were able to identify titanium dioxide nanoparticles stemming from sunscreens in the suspended matter of the lake using electron microscopy. Bulk analysis of SPM clearly shows an increase of Ti-containing particles during the summer season. These analyses, however, are not able to distinguish sunscreen nanoparticles from natural Ti-bearing nanoparticles. Therefore, Elemental ratios of Ti with Al, V, Ga, Y, Nb, Eu, Ho, Er, Tm, Yb, and Ta as determined by ICPMS and ICPOES, in combination with single particle ICPMS analysis were applied to establish local background values. The observed mild increase of Ti elemental ratios, compared to spring background values indicates that the residence time of released nanomaterials in the water column is rather short. Overall, the advantages and disadvantages of the methods used to detect and characterize the nanomaterials are discussed.

  • Sorption behavior of carbon nanotubes: Changes induced by functionalization, sonication and natural organic matter

    Melanie Kah, Xiaoran Zhang, Thilo Hofmann
    2014 - Science of The Total Environment, 133-138

    Abstract: 

    The effect of functionalization on the sorption behavior of carbon nanotubes (CNTs) remains poorly understood, especially when combined with other factors affecting dispersion. The sorption behavior of a series of functionalized CNTs towards pyrene has therefore been systematically evaluated over a wide range of concentrations and dispersion scenarios. When studied as purchased (in the absence of humic acids and sonication treatment), sorption isotherms showed that OH-, COOH- and NH2-CNTs exhibited significantly different sorption affinity for pyrene. Sonication greatly increased both the sorption affinity and the maximum capacity of all types of functionalized CNTs, to an extent that overwhelmed the differences initially observed (increase of up to 1.5 orders of magnitude lead to log Kdvalues close to 9 L/kg). Results demonstrate that a significant proportion of the CNT surface was unavailable to pyrene prior to sonication. The presence of humic acids enhanced dispersion but decreased sorption, especially when combined with sonication. Sorption affinity, however, remained very high in all cases (log Kd > 7.5 L/kg), suggesting that CNTs can act as strong sorbents under a wide range of conditions.

  • Spot the Difference: Engineered and Natural Nanoparticles in the Environment-Release, Behavior, and Fate

    Stephan Wagner, Andreas Gondikas, Elisabeth Neubauer, Thilo Hofmann, Frank von der Kammer
    2014 - Angewandte Chemie International Edition, in press

    Abstract: 

    The production and use of nanoparticles leads to the emission of manufactured or engineered nanoparticles into the environment. Those particles undergo many possible reactions and interactions in the environment they are exposed to. These reactions and the resulting behavior and fate of nanoparticles in the environment have been studied for decades through naturally occurring nanoparticulate (1–100 nm) and colloidal (1–1000 nm) substances. The knowledge gained from these investigations is nowhere near sufficiently complete to create a detailed model of the behavior and fate of engineered nanoparticles in the environment, but is a valuable starting point for the risk assessment of these novel materials. It is the aim of this Review to critically compare naturally observed processes with those found for engineered systems to identify the “nanospecific” properties of manufactured particles and describe critical knowledge gaps relevant for the risk assessment of manufactured nanomaterials in the environment.

  • Accessibility of Humic-Associated Fe to a Microbial Siderophore: Implications for Bioavailability

    Keshia M. Kuhn, Patricia A. Maurice, Elisabeth Neubauer, Thilo Hofmann, Frank von der Kammer
    2013 - Environmental Science & Technology, 2: 1015-1022

    Abstract: 

    Microorganisms in aerobic, circum-neutral environments are challenged to acquire sufficient nutrient Fe due to low solubilities of Fe oxides. To overcome this challenge, many aerobic microbes produce low molecular weight (MW) organic ligands, or siderophores, with extremely high Fe-binding affinities. This research expands the existing understanding of siderophore-mediated Fe acquisition from minerals by examining the effects of the siderophore desferrioxamine B (DFOB) on Fe removal from aquatic humic substances (XAD-8-isolated) and other organic matter (OM) isolates (reverse osmosis, RO; and “transphilic”, XAD-4) from several rivers including the Suwannee River (GA, USA). Analysis of samples by asymmetrical flow field-flow fractionation (AsFlFFF) with in-line ICP–MS and UV–vis detectors showed that Fe was naturally abundant and primarily associated with intermediate to high MW OM. An excess of DFOB (relative to naturally present Fe) removed ∼75% of Fe and shifted the OM MW distribution to lower MWs, perhaps due to removal of “bridging” Fe, although additional mechanistic study of MW shifts is needed. Removal of other OM-associated metals (e.g., Al, Cu, Zn) by DFOB was minimal for all but a few samples. Fe bound to humic substances and other more “transphilic” organic components therefore should be considered readily bioavailable to aerobic, siderophore-producing microorganisms.

  • Carbonate minerals in porous media decrease mobility of polyacrylic acid modified zero-valent iron nanoparticles used for groundwater remediation

    Susanne Laumann, Vesna Micić, Gregory V. Lowry, Thilo Hofmann
    2013 - Environmental Pollution, 53-60

    Abstract: 

    The limited transport of nanoscale zero-valent iron (nZVI) in porous media is a major obstacle to its widespread application for in situ groundwater remediation. Previous studies on nZVI transport have mainly been carried out in quartz porous media. The effect of carbonate minerals, which often predominate in aquifers, has not been evaluated to date. This study assessed the influence of the carbonate minerals in porous media on the transport of polyacrylic acid modified nZVI (PAA-nZVI). Increasing the proportion of carbonate sand in the porous media resulted in less transport of PAA-nZVI. Predicted travel distances were reduced to a few centimeters in pure carbonate sand compared to approximately 1.6 m in quartz sand. Transport modeling showed that the attachment efficiency and deposition rate coefficient increased linearly with increasing proportion of carbonate sand.

  • Colloid-associated export of arsenic in stream water during stormflow events

    E. Neubauer, Frank von der Kammer, K.-H. Knorr, S. Peiffer, M. Reichert, Thilo Hofmann
    2013 - Chemical Geology, 81-91

    Abstract: 

    Significant correlations between arsenic concentrations and those of iron and natural organic matter (NOM) have been found in run-off from wetlands. This has been suggested to be a result of mobilization of arsenic-NOM colloids. The aim of this study was therefore to elucidate the possible association of iron and arsenic with colloids in surface water from a small, forested catchment area. The impacts that groundwater levels prior to stormflow events and the chemistry of the hydraulically active soil layers have on the release and formation of colloids, such as NOM and iron (oxy)hydroxide colloids, were also investigated.

    At baseflow, the NOM, iron, and arsenic concentrations in the stream water were relatively low (< 650 μmol∙L− 1, < 5.5 μmol∙L− 1, and 8–16 nmol∙L− 1, respectively), and the pH was close to deep groundwater (4.6–5.5). At low groundwater levels prior to stormflow events, the discharging stream water was fed by anoxic groundwater from the deeper layers of the peat, and by deep, oxic groundwater. The iron/DOC ratio in the stream water was high, and iron was present as iron-NOM colloids and precipitated as iron (oxy)hydroxide colloids. Arsenic was dissolved and associated with NOM, and the conditional distribution coefficients of arsenic binding to NOM (logKD values) were relatively high (around 3 L∙mol− 1).

    When initial groundwater table levels were high before stormflow events, the stream was fed by shallow peat layers rich in NOM, iron, and arsenic during the event. The iron/DOC ratios were low and most of the iron was present in iron-NOM colloids in the stream water. The pH of the stream water was also lower under these conditions, and the logKD values of As-NOM associations in the stream water were accordingly lower (< 3 L∙mol− 1). Large quantities of dissolved arsenic (< 1000 g∙mol− 1) were exported under these conditions.

    Our data reveal that the logKD values of As-NOM associations decreased with increasing discharge as a consequence of decreasing pH. The logKD values for arsenic-NOM associations in this study are higher than those reported elsewhere in published literature, which had been derived from laboratory tests with NOM and arsenic. The formation of ternary complexes with ferric iron may therefore have enhanced the binding of arsenic to NOM within the studied stream.

  • Combining spatially resolved hydrochemical data with in-vitro nanoparticle stability testing: Assessing environmental behavior of functionalized gold nanoparticles on a continental scale

    Junfeng Liu, Frank von der Kammer, Boyu Zhang, Samuel Legros, Thilo Hofmann
    2013 - Environment International, 53-62

    Abstract: 

    Many engineered nanoparticles (ENPs) are functionalized with different types of surface coatings to suit specific applications. The functionalization affects the fate and behavior of these ENPs in aquatic environments. In this study, gold nanoparticles (GNPs) coated with either citrate or 11-mercaptoundecanoic acid (MUA) are used as examples of functionalized ENPs. A method has been developed to assess the colloidal stability of functionalized ENPs under complex hydrochemical conditions, using their aggregation rates as indicators. The spatial distributions of stream-water chemistry data from across Europe were combined with the results of in-vitro colloidal stability testing. Aggregation rates were extracted for each stream-water sample and stability maps for Europe were plotted. The tendency of the tested GNPs to be dispersed or aggregated is described for water bodies of the respective region. Natural organic matter was identified as the predominant factor controlling the stability of the GNPs tested. The properties of surface coatings also affect aggregation rates as a result of differences in their hydrochemical parameters. The developed method can be used as a template for a stability assessment, and the results of this study provide a basis for exposure modeling and precautionary decision making.

  • Effect of pH and Stream Order on Iron and Arsenic Speciation in Boreal Catchments

    Elisabeth Neubauer, Stephan J. Köhler, Frank von der Kammer, Hjalmar Laudon, Thilo Hofmann
    2013 - Environmental Science & Technology, 1: 7120-7128

    Abstract: 

    Riverine transport of iron (Fe) and arsenic (As) is affected by their associations with natural organic matter (NOM) and suspended iron (oxy)hydroxides. Speciation has a strong influence on element transport from the headwaters to the ocean because NOM may be transported over longer distances compared to iron (oxy)hydroxides. We show that Fe speciation changes along the flow path of a boreal watercourse, as water moves from NOM-rich, acidic first-order streams with pH as low as 3.9 to less acidic higher-order systems (up to pH 6.4). Analysis by Flow Field-Flow Fractionation and chemical equilibrium modeling revealed that Fe from wetland-dominated headwaters was mainly exported as Fe-NOM complexes; in catchments with a stream order >1 and with higher pH, Fe was present in Fe-NOM complexes and precipitated as nanoparticulate iron(oxy)hydroxides which aggregated as the pH increased, with their size eventually exceeding the membrane filters cutoff (0.2 μm). The measured NOM-bound Fe decreased with increasing pH, from 0.38 to 0.16 mmol Fe·gNOM–1. The high concentrations of NOM-bound Fe emphasize the importance of boreal catchments to Fe export to the oceans. Concentrations of As in the <0.2 μm fraction but larger than what is usually considered “truly dissolved” (<1000 g·mol–1), decreased from 75% to 26% with increasing pH. The As in this size range was mainly associated with NOM but at pH >4.5 became associated with iron(oxy)hydroxides, and its transport thus became more coupled to that of the iron(oxy)hydroxides downstream in the circumneutral streams.

  • How Redox Conditions and Irradiation Affect Sorption of PAHs by Dispersed Fullerenes (nC60)

    Thorsten Hüffer, Melanie Kah, Thilo Hofmann, Torsten C. Schmidt
    2013 - Environmental Science & Technology, 1: 6935-6942

    Abstract: 

    Surface properties, dispersion state, and sorption behavior of carbon-based nanomaterials will change after being released into the environment. To study these processes, five different scenarios were considered to probe the impact of changes in surface properties of dispersed fullerenes (nC60) on their sorption potential due to irradiation and presence of oxygen. Sorption isotherms of pyrene by nC60 were determined at environmentally relevant concentrations applying a passive sampling method. Isotherms of all dispersion scenarios were best fit with the Dubinin–Ashthakov model. Sorption was strongest for nC60 kept under anoxic condition. Both the presence of oxygen and irradiation significantly decreased the sorption capacity of nC60, while commercially available polyhydroxy fullerenes had the smallest sorption. In addition, competition for sorption sites was never observed in multiple sorbate experiments with four polycyclic aromatic hydrocarbons at small concentration. A strong relationship between sorption coefficients and hydrophobic properties of sorbates suggests that hydrophobic interactions are of major importance. The results emphasize that aging of released fullerenes results in a reduced strength of interactions with nonpolar compounds and, thus, reduces the impact on the environmental transport of hydrophobic pollutants.

  • Material flow analysis: An effectiveness assessment tool for in situ thermal remediation

    Susanne Laumann, Vesna Micić, Johann Fellner, David Clement, Thilo Hofmann
    2013 - Vadose Zone Journal, 1: 1-9

    Abstract: 

    The effectiveness of thermal remediation in the vadose zone was assessed by applying material flow analysis. This method enabled evaluation of the remediation performance and the overall contaminant emission into the environment, and provided an overview of contaminant flows in the soil-water-air compartment, both before and during remediation.

    In situ thermal desorption (ISTD) is a remediation technique that increases the effectiveness of soil vapor extraction through the simultaneous application of heat and vacuum. In this study, ISTD was applied to remove a chlorinated solvent source from unsaturated soil beneath an existing aboveground infrastructure. A material flow analysis (MFA) was applied for the first time to assess the effectiveness of ISTD in the vadose zone and to reveal the total emission of chlorinated solvents into the environment before and during remediation. The principle of matter conservation used in MFA enabled the quantification of chlorinated solvent flows in all matrices affected: soil, groundwater, and soil vapor. The MFA results revealed that the mass removed by ISTD was similar to the mean chlorinated solvent mass estimated to have been present in the soil before remediation, indicating high effectiveness in contaminant removal. The remediation target value in soil vapor was achieved after 9 mo of remediation, demonstrating the time efficiency of ISTD for this particular site. The MFA additionally provided an overview of the processes and contaminant transformations occurring in the soil, water, and air compartments during the course of remediation.

  • Nachweis und Charakterisierung von TiO2-Nanomaterial in Oberflächengewässern

    Thilo Hofmann, Andreas Gondikas, Frank von der Kammer, Stephan Wagner
    2013 - Vom Wasser - das Journal, 111: 89-91
  • Nanopesticides: State of knowledge, environmental fate, and exposure modeling

    M. Kah, S. Beulke, K. Tiede, Thilo Hofmann
    2013 - Critical Reviews in Environmental Science and Technology, 1: 1823-1867

    Abstract: 

    Published literature has been reviewed in order to (a) explore the (potential) applications of nanotechnology in pesticide formulation, (b) identify possible impacts on environmental fate, and (c) analyze the suitability of current exposure assessment procedures to account for the novel properties of nanopesticides within the EU regulatory context. The term nanopesticide covers a wide variety of products and cannot be considered to represent a single category. Many nanoformulations combine several surfactants, polymers, and metal nanoparticles in the nanometer size range. The aims of nanoformulations are generally common to other pesticide formulations, these being to increase the apparent solubility of poorly soluble active ingredients, to release the active ingredient in a slow/targeted manner and/or to protect against premature degradation. Nanoformulations are thus expected to (a) have significant impacts on the fate of active ingredients and/or (b) introduce new ingredients for which the environmental fate is still poorly understood (e.g., nanosilver). Therefore, it seems that adaptations of current exposure assessment approaches will be necessary, at least for some nanopesticides. The present analysis provides a useful framework to identify priorities for future research in order to achieve more robust risk assessments of nanopesticides.

  • Natural organic matter and iron export from the Tanner Moor, Austria

    Franz Jirsa, Elisabeth Neubauer, Richard Kittinger, Thilo Hofmann, Regina Krachler, Frank von der Kammer, Bernhard K. Keppler
    2013 - Limnologica, 4: 239-244

    Abstract: 

    Samples from a pristine raised peat bog runoff in Austria, the Tannermoor creek, were analysed for their iron linked to natural organic matter (NOM) content. Dissolved organic carbon < 0.45 μm (DOC) was 41–64 mg L−1, iron 4.4–5.5 mg L−1. Samples were analysed applying asymmetric field flow fractionation (AsFlFFF) coupled to UV–vis absorption, fluorescence and inductively coupled plasma mass spectrometry (ICP-MS). The samples showed an iron peak associated with the NOM peak, one sample exhibiting a second peak of iron independent from the NOM peak. As highland peat bogs with similar climatic conditions and vegetation to the Tanner Moor are found throughout the world, including areas adjacent to the sea, we examined the behaviour of NOM and iron in samples brought to euhaline (35‰) conditions with artificial sea salt. The enhanced ionic strength reduced NOM by 53% and iron by 82%. Size exclusion chromatography (SEC) of the samples at sea-like salinity revealed two major fractions of NOM associated with different iron concentrations. The larger one, eluting sharply after the upper exclusion limits of 4000–5000 g mol−1, seems to be most important for iron chelating. The results outline the global importance of sub-mountainous and mountainous raised peat bogs as a source of iron chelators to the marine environment at sites where such peat bogs release their run-offs into the sea.

  • Natural Organic Matter Concentration and Hydrochemistry Influence Aggregation Kinetics of Functionalized Engineered Nanoparticles

    Junfeng Liu, Samuel Legros, Frank von der Kammer, Thilo Hofmann
    2013 - Environmental Science & Technology, 9: 4113-4120

    Abstract: 

    Understanding the colloidal stability of functionalized engineered nanoparticles (FENPs) in aquatic environments is of paramount importance in order to assess the risk related to FENPs. In this study, gold nanoparticles (GNPs) of 68 and 43 nm diameter, coated with citrate and 11-mercaptoundecanoic acid (MUA) respectively, were used as models of FENPs. Time-resolved dynamic light scattering was employed to investigate the aggregation kinetics of two types of GNPs. The results show that without Suwannee river natural organic matter (SRNOM), MUA coating resulted in greater stability than citrate coating for GNPs. Cations have a destabilizing effect on both GNPs following the order Ca2+ ≈ Mg2+ ≫ Na+; different anions (Cl and SO42–) showed no difference in effects. In the fast aggregation regime, adding SRNOM enhanced the stability of MUA-coated GNPs in both Ca2+ and Mg2+ solutions. However citrate-coated GNPs were only stabilized in Mg2+ solution but enhanced aggregation occurred in high Ca2+ concentration due to interparticle bridging. For the investigated GNPs and in the presence of SRNOM, Ca2+ does not always act as a strong coagulant. This indicates that for the new materials emerging from the application of nanotechnology the well-described aggregation mechanisms of colloids in the environment require a detailed re-examination.

  • Positive and negative impacts of five Austrian gravel pit lakes on groundwater quality

    Christian Muellegger, Andreas Weilhartner, Tom J. Battin, Thilo Hofmann
    2013 - Science of The Total Environment, 14-23

    Abstract: 

    Groundwater-fed gravel pit lakes (GPLs) affect the biological, organic, and inorganic parameters of inflowing groundwater through combined effects of bank filtration at the inflow, reactions within the lake, and bank filtration at the outflow. GPLs result from wet dredging for sand and gravel and may conflict with groundwater protection programs by removing the protective soil cover and exposing groundwater to the atmosphere.

    We have investigated the impact on groundwater of five GPLs with different sizes, ages, and mean residence times, and all having low post-excavation anthropogenic usage. The results revealed highly active biological systems within the lake water, in which primary producers significantly reduced inflowing nitrate concentrations. Decalcification also occurred in lake water, reducing water hardness, which could be beneficial for waterworks in hard groundwater areas. Downgradient groundwater nitrate and calcium concentrations were found to be stable, with only minor seasonal variations. Biological degradation of organic material and organic micropollutants was also observed in the GPLs. For young GPLs adequate sediment deposits may not yet have formed and degradation processes at the outflow may consequently not yet be well established. However, our results showed that within 5 years from the cessation of excavation a protective sediment layer is established that is sufficient to prevent the export of dissolved organic carbon to downgradient groundwater.

    GPLs can improve groundwater quality in anthropogenically (e.g., pesticides and nitrate) or geologically (e.g., hardness) challenging situations. However, post-excavation usage of GPLs is often dominated by human activities such as recreational activities, water sports, or fish farming. These activities will affect lake and groundwater quality and the risks involved are difficult to predict and monitor and can lead to overall negative impacts on groundwater quality.

  • Rückhalt von Titandioxid-Nanopartikeln bei der Mikro- und Ultrafiltration

    Thilo Hofmann, Tröster, M., Happel, O., Sacher, F., Lipp, P., Brauch, H-J
    2013 - Vom Wasser - das Journal, 2: 47-49
  • State of Knowledge on nanopesticides: implications for environmental fate assessment

    Melanie Kah, Sabine Beulke, Karen Tiede, Thilo Hofmann
    2013 - Vom Wasser - das Journal, 111: 38-39
  • The influence of pH on iron speciation in podzol extracts: Iron complexes with natural organic matter, and iron mineral nanoparticles

    Elisabeth Neubauer, Walter D.C. Schenkeveld, Kelly L. Plathe, Christian Rentenberger, Frank von der Kammer, Stephan M. Kraemer, Thilo Hofmann
    2013 - Science of The Total Environment, 108-116

    Abstract: 

    The quantities of natural organic matter (NOM) and associated iron (Fe) in soil extracts are known to increase with increasing extractant pH. However, it was unclear how the extraction pH affects Fe speciation for particles below 30 nm. We used flow field-flow fractionation (FlowFFF) and transmission electron microscopy (TEM) to investigate the association of Fe and trace elements with NOM and nanoparticulate iron (oxy)hydroxides in podzol extracts.

    For extracts prepared at the native soil pH (~ 4), and within a 1–30 nm size range, Fe was associated with NOM. In extracts with a pH ≥ 7 from the E and B soil horizons, Fe was associated with NOM as well as with iron (oxy)hydroxide nanoparticles with a size of approximately 10 nm. The iron (oxy)hydroxide nanoparticles may have either formed within the soil extracts in response to the increase in pH, or they were mobilized from the soil. Additionally, pH shift experiments showed that iron (oxy)hydroxides formed when the native soil pH (~ 4) was increased to 9 following the extraction. The iron (oxy)hydroxide nanoparticles aggregated if the pH was decreased from 9 to 4.

    The speciation of Fe also influenced trace element speciation: lead was partly associated with the iron (oxy)hydroxides (when present), while copper binding to NOM remained unaffected by the presence of iron (oxy)hydroxide nanoparticles. The results of this study are important for interpreting the representativeness of soil extracts prepared at a pH other than the native soil pH, and for understanding the changes in Fe speciation that occur along a pH gradient.

  • The role of nanominerals and mineral nanoparticles in the transport of toxic trace metals: Field-flow fractionation and analytical TEM analyses after nanoparticle isolation and density separation

    Kelly L. Plathe, Frank von der Kammer, Martin Hassellöv, Johnnie N. Moore, Mitsuhiro Murayama, Thilo Hofmann, Michael F. Hochella
    2013 - Geochimica et Cosmochimica Acta, 213-225

    Abstract: 

    Nanominerals and mineral nanoparticles from a mining-contaminated river system were examined to determine their potential to co-transport toxic trace metals. A recent large-scale dam removal project on the Clark Fork River in western Montana (USA) has released reservoir and upstream sediments contaminated with toxic trace metals (Pb, As, Cu and Zn), which had accumulated there as a consequence of more than a century and a half of mining activity proximal to the river’s headwaters near the cities of Butte and Anaconda. To isolate the high-density nanoparticle fractions from riverbed and bank sediments, a density separation with sodium polytungstate (2.8 g/cm3) was employed prior to a standard nanoparticle extraction procedure. The stable, dispersed nanoparticulate fraction was then analyzed by analytical transmission electron microscopy (aTEM) and flow field-flow fractionation (FlFFF) coupled to both multi-angle laser light scattering (MALLS) and high-resolution, inductively coupled plasma mass spectrometry (HR-ICPMS). FlFFF analysis revealed a size distribution in the nano range and that the elution profiles of the trace metals matched most closely to that for Fe and Ti. aTEM confirmed these results as the majority of the Fe and Ti oxides analyzed were associated with one or more of the trace metals of interest. The main mineral phases hosting trace metals are goethite, ferrihydrite and brookite. This demonstrates that they are likely playing a significant role in dictating the transport and distribution of trace metals in this river system, which could affect the bioavailability and toxicity of these metals.

  • Using FLOWFFF and HPSEC to determine trace metalcolloid associations in wetland runoff

    Elisabeth Neubauer, Frank von der Kammer, Thilo Hofmann
    2013 - Water Research, 8: 2757-2769

    Abstract: 

    Natural organic matter (NOM) and iron colloids can coexist in surface water. These colloids might exhibit different affinities to metals and metalloids. Previously it has been shown, that organic and inorganic colloids in the low nanometer range can be fractionated using Flow Field-Flow Fractionation analyzes (FlowFFF), but it is not yet understood how the presence of inorganic colloids influences results obtained by High Performance Size Exclusion Chromatography (HPSEC). Studies that compare the use of these size-separation techniques for the analyzes of organic and inorganic colloids and associated elements are needed in order to interpret results obtained by either of these methods. Therefore, associations between colloids from a small stream draining a wetland area and a selected range of elements (Fe, Al, Ti, Pb, Cu, Ni, As, U, and Rare Earth Elements (REE)) have been investigated. FlowFFF analyzes and HPSEC analyzes were combined with ultrafiltration, functional group titration and arsenic speciation analysis.

    NOM and, in a sample with a pH > 5.2, slightly larger iron organo-mineral colloids, were present in the <0.2 μm fraction in the surface water. Both exhibited notably different affinities for trace elements. Cu, Ni, Al, and the REE all showed similar modes (i.e. peak maxima) and size distributions to the NOM, while Pb and As showed a preferential association with iron organo-mineral colloids. It was not possible to differentiate between NOM and iron-organo mineral colloids with HPSEC. The differences in the results regarding the apparent molecular mass distributions obtained by FlowFFF and HPSEC are discussed.

  • Variations of common riverine contaminants in reservoir sediments

    2013 - Science of The Total Environment, 90-100

    Abstract: 

    Organic molecules in reservoir sediments can be used as tracers of contaminant inputs into rivers. Vertical variations in the molecular records can be ascribed to pre-depositional alteration within the water column, or in situ post-depositional alteration. We report the molecular stratigraphy of four common riverine contaminant groups in sediment of the largest reservoir on the Danube River, the Iron Gate I Reservoir. Sediments were rapidly deposited, with little variation in texture and, as revealed by analytical pyrolysis, in the concentration and composition of natural sedimentary organic matter. However, a detailed molecular inspection did reveal differences in distribution and organic carbon (OC)-normalized concentrations of contaminants.

    The OC-normalized concentrations of nonylphenol increased by one order of magnitude with depth down the 70 cm sediment core. There is a strong correlation between sediment depth and the ratio of nonylphenol to its precursor (nonylphenol monoethoxylate). This indicated that nonylphenol was produced in situ. While the relative proportions of C10–C14 linear alkylbenzenes remained constant with increasing depth, they exhibited variations in isomer distribution. These variations, which are due to different degrees of degradation, appear to have occurred within the water column prior to sedimentation of suspended solids.

    The distribution of 40 polycyclic aromatic hydrocarbons revealed origins from both pyrogenic and petrogenic sources. The differences in their compositions were not depth-related, but rather were associated with variations in the sorption capacities of texturally different sediments. Perylene showed slightly higher concentrations at greater depths, while the OC-normalized concentration of retene systematically increased with sediment depth. This is consistent with formation of retene and perylene via very early diagenetic transformation. The presence of petroleum biomarkers indicated minor contamination by fossil fuels.

  • Bovine Serum Albumin Adsorption to Iron-Oxide Coated Sands Can Change Microsphere Deposition Mechanisms

    Raymond M. Flynn, Xinyao Yang, Thilo Hofmann, Frank von der Kammer
    2012 - Environmental Science & Technology, 5: 2583-2591

    Abstract: 

    Particulate colloids often occur together with proteins in sewage-impacted water. Using Bovine Serum Albumin (BSA) as a surrogate for protein in sewage, column experiments investigating the capacity of iron-oxide coated sands to remove latex microspheres from water revealed that microsphere attenuation mechanisms depended on antecedent BSA coverage. Dual pulse experiment (DPE) results suggested that where all BSA was adsorbed, subsequent multiple pore volume microsphere breakthrough curves reflected progressively reduced colloid deposition rates with increasing adsorbed BSA content. Modeling colloid responses suggested adsorption of 1 μg BSA generated the same response as blockage by between 7.1 × 108 and 2.3 × 109 deposited microspheres. By contrast, microsphere responses in DPEs where BSA coverage of the deposition sites approached/reached saturation revealed the coated sand maintained a finite capacity to attenuate microspheres, even when incapable of further BSA adsorption. Subsequent microsphere breakthrough curves demonstrated the matrix’s colloid attenuation capacity progressively increased with continued microsphere deposition. Experimental findings suggested BSA adsorption on the sand surface approaching/reaching saturation generated attractive deposition sites for colloids, which became progressively more attractive with further colloid deposition (filter ripening). Results demonstrate that adsorption of a single type of protein may either enhance or inhibit colloid mobility in saturated porous media.

  • Comparing the Influence of Two Different Natural Organic Matter Types on Colloid Deposition in Saturated Porous Medium

    Xin Yao Yang, Shi Huai Deng, Fang Min Chen, Raymond Flynn, Frank von der Kammer, Thilo Hofmann
    2012 - Advanced Materials Research, 1324-1329

    Abstract: 

    Humic acid and protein are two major organic matter types encountered in natural and polluted environment, respectively. This study employed Triple Pulse Experiments (TPEs) to investigate and compare the influence of Suwannee River Humic Acid (SRHA) (model humic acid) and Bovine Serum Albumin (BSA) (model protein) on colloid deposition in a column packed with saturated iron oxide-coated quartz sand. Study results suggest that adsorbed SRHA may inhibit colloid deposition by occupying colloid sites on the porous medium. Conversely, BSA may promote colloid deposition by a ‘filter ripening’ mechanism. This study provides insight to understand the complex behavior of colloids in organic matter-presented aquifers and sand filters.

  • Dispersion State and Humic Acids Concentration-Dependent Sorption of Pyrene to Carbon Nanotubes

    Xiaoran Zhang, Melanie Kah, Michiel T. O. Jonker, Thilo Hofmann
    2012 - Environmental Science & Technology, 1: 7166-7173

    Abstract: 

    Sonication and humic acids (HA) are known to disperse carbon nanotube (CNT) suspensions, but potential effects on sorption of chemicals to CNTs remain poorly understood. We applied a passive sampling method to investigate the influence of dispersion/aggregation on sorption of pyrene to CNTs. Sonication broke down CNT aggregates and increased pyrene sorption affinity by up to 1.39 orders of magnitude. Sorption surfaces newly exposed by sonication remained available to pyrene even after reaggregation occurred, suggesting an irreversible effect of sonication. The presence of HA decreased sorption of pyrene to CNTs, but at the highest HA concentration investigated (200 mg/L), sorption affinity was still 1.90 orders of magnitude larger than sorption of pyrene to HA alone. Specific interactions between pyrene and CNTs were thus still taking place, in spite of the presence of a HA coating on the CNTs’ surface. A greater suppression of sorption by CNTs occurred when the HA addition was combined with a sonication pretreatment. Sorption isotherm fitting indicated that the maximum sorption capacity, sorption affinity, and heterogeneity of the CNT surface were all affected by sonication and the presence of HA at a concentration as low as 1 mg/L. The present results contribute to an improved understanding of the sorption behavior of CNTs in both natural and wastewater systems.

  • Entwicklung und Optimierung einer HPLC-MS-Methode zur Detektion und Quantifizierung von Fullerenen

    Thilo Hofmann, Tröster, M., Brauch, H-J.
    2012 - Vom Wasser - das Journal, 3: 76-77
  • Forschung zu Nanopartikeln in Fließgewässern: Kleine Partikel, große Risiken?

    2012 - Politische Ökologie, 130: 116
  • Gravel pit lake ecosystems reduce nitrate and phosphate concentrations in the outflowing groundwater

    Andreas Weilhartner, Christian Muellegger, Martin Kainz, Francine Mathieu, Thilo Hofmann, Tom J. Battin
    2012 - Science of The Total Environment, 222-228

    Abstract: 

    Gravel excavation often bears conflicts with the use of drinking water as under-water-table mining can directly impact groundwater quality downstream of the open gravel pit lake due to exposure of the groundwater aquifer to the atmosphere and to human activities. To assess this potential impact of GPLs on groundwater, we assessed the mass balance for nitrate (NO3) and phosphate (PO4) and whole-ecosystem metabolism of five post-excavation GPLs in Austria. GPLs differed in both age and residence time of lake water. We found that GPLs significantly reduced the concentration of NO3and PO4 as groundwater passes through the lake ecosystem, which in most cases acted as a net sink for these nutrients. Groundwater-derived nutrients enhanced both epilithic and pelagic net primary production in the GPLs, which ultimately leads to biomass accrual. Our data also suggest that this biomass accrual may induce, at least in part, clogging of the GPLs and their successive hydrodynamic isolation from the adjacent groundwater. Despite continuous biomass build-up and elevated concentrations of dissolved organic carbon (DOC) in the lake water compared to the inflowing groundwater, DOC export into the outflowing groundwater remained low. Our data suggest that GPLs could contribute to groundwater amelioration where agricultural land use increases nutrient concentrations in the groundwater given a proper management of these man-made ecosystems.

  • Influence of surface functionalization and particle size on the aggregation kinetics of engineered nanoparticles

    Junfeng Liu, Samuel Legros, Guibin Ma, Jonathan G.C. Veinot, Frank von der Kammer, Thilo Hofmann
    2012 - Chemosphere, 8: 918-924

    Abstract: 

    In an effort to minimize the impact on the environment or improve the properties of choice, most engineered nanoparticles used for commercial applications are surface functionalized. The release of these functionalized engineered nanoparticles (FENPs) into the environment can be either deliberate or accidental. Scientific research to date has tended to focus on evaluating the toxicity of FENPs, with less attention being given to exposure assessments or to the study of their general behavior in natural environments. We have therefore investigated the effects of environmental parameters such as pH, NaCl concentration, and natural organic matter concentration on the aggregation kinetics of FENPs with time resolved dynamic light scattering, using functionalized gold nanoparticles (FAuNPs) as a representative of these particles. We also investigated the effects of average particle size, the type of surface capping agent, and particle concentration on FAuNP aggregation kinetics. Our results show that the physico-chemical properties of the capping agent have a greater influence on the aggregation behavior of FAuNPs than either their core composition or their particle size.

  • Modeling colloid deposition on a protein layer adsorbed to iron-oxide-coated sand

    2012 - Journal of Contaminant Hydrology, 50-62

    Abstract: 

    Our recent study reported that conformation change of granule-associated Bovine Serum Albumin (BSA) may influence the role of the protein controlling colloid deposition in porous media (Flynn et al., 2012). The present study conceptualized the observed phenomena with an ellipsoid morphology model, describing BSA as an ellipsoid taking a side-on or end-on conformation on granular surface, and identified the following processes: (1) at low adsorbed concentrations, BSA exhibited a side-on conformation blocking colloid deposition; (2) at high adsorbed concentrations, BSA adapted to an end-on conformation promoted colloid deposition; and (3) colloid deposition on the BSA layer may progressively generate end-on molecules (sites) by conformation change of side-on BSA, resulting in sustained increasing deposition rates. Generally, the protein layer lowered colloid attenuation by the porous medium, suggesting the overall effect of BSA was inhibitory at the experimental time scale. A mathematical model was developed to interpret the ripening curves. Modeling analysis identified the site generation efficiency of colloid as a control on the ripening rate (declining rate in colloid concentrations), and this efficiency was higher for BSA adsorbed from a more dilute BSA solution.

  • Nanoscale lignin particles as sources of dissolved iron to the ocean

    Regina Krachler, Frank von der Kammer, Franz Jirsa, Altan Süphandag, Rudolf F. Krachler, Christof Plessl, Margret Vogt, Bernhard K. Keppler, Thilo Hofmann
    2012 - Global Biogeochemical Cycles, 3: in press

    Abstract: 

    Primary production in large areas of the open ocean is limited by low iron concentrations. Rivers are potential sources of iron to the ocean, however, riverine iron is prone to intense flocculation and sedimentation in the estuarine mixing zone. Here we report the detection of iron‐rich nanoparticles in a typical peatland‐draining creek which are resistant against salt‐induced flocculation i.e., their behavior is in sharp contrast to the well‐known behavior of Fe colloids in river waters. Sample fractionation by AsFlFFF (Asymmetric Flow Field Flow Fractionation) revealed that these powerful iron carriers are in the size range of only 0.5–3.0 nm hydrodynamic diameter. They were isolated from the water phase using solid phase extraction/gel permeation chromatography, and analyzed by a CuO oxidation/GC‐MS method. Our results suggest that the particles consist mainly of lignin catabolites and that gymnosperm as well as angiosperm tissues are contributors to the seawater‐resistant iron‐bearing DOM. Lignin phenols, which have no autochthonous source in the ocean, have been nevertheless found in low concentrations throughout the entire Arctic, Atlantic, and Pacific oceans. It is therefore tempting to speculate that peatland‐derived iron‐bearing lignin particles may have a sufficiently long half‐life in ocean waters to sustain iron concentration in extended regions of the ocean.

  • The potential of TiO2 nanoparticles as carriers for cadmium uptake in Lumbriculus variegatus and Daphnia magna

    Nanna B. Hartmann, Samuel Legros, Frank von der Kammer, Thilo Hofmann, Anders Baun
    2012 - Aquatic Toxicology, 1-8

    Abstract: 

    The use of engineered nanoparticles (e.g. in industrial applications and consumer products) is increasing. Consequently, these particles will be released into the aquatic environment. Through aggregation/agglomeration and sedimentation, sediments are expected ultimately to be sinks for nanoparticles. Both in the water phase and in the sediments engineered nanoparticles will mix and interact with other environmental pollutants, including metals. In this study the toxicity of cadmium to two freshwater organisms, water column crustacean Daphnia magna and sediment oligochaete Lumbriculus variegatus, was investigated both in the absence and presence of titanium dioxide (TiO2) nanoparticles (P25 Evonic Degussa, d: 30 nm). The uptake of cadmium in sub-lethal concentrations was also studied in the absence and presence of 2 mg/L TiO2 nanoparticles. Formation of larger nanoparticles aggregates/agglomerates was observed and sizes varied depending on media composition (358 ± 13 nm in US EPA moderately hard synthetic freshwater and 1218 ± 7 nm in Elendt M7). TiO2 nanoparticles are potential carriers for cadmium and it was found that 25% and 6% of the total cadmium mass in the test system for L. variegatus and D. magnatests were associated to suspended TiO2 particles, respectively. μXRF (micro X-ray fluorescence) analysis confirmed the uptake of TiO2 in the gut of D. magna. For L. variegatus μXRF analysis indicated attachment of TiO2nanoparticles to the organism surface as well as a discrete distribution within the organisms. Though exact localisation in this organism was more difficult to assess, the uptake seems to be within the coelomic cavity. Results show that the overall body burden and toxicity of cadmium to L. variegatus was unchanged by addition of TiO2 nanoparticles, showing that cadmium adsorption to TiO2 nanoparticles did not affect overall bioavailability. Despite facilitated uptake of cadmium by TiO2 nanoparticles in D. magna, resulting in increased total cadmium body burden, no change in toxicity was observed.

  • Commercial Titanium Dioxide Nanoparticles in Both Natural and Synthetic Water: Comprehensive Multidimensional Testing and Prediction of Aggregation Behavior

    Stephanie Ottofuelling, Frank von der Kammer, Thilo Hofmann
    2011 - Environmental Science & Technology, 2: 10045-10052

    Abstract: 

    Engineered nanoparticles (ENPs) from industrial applications and consumer products are already being released into the environment. Their distribution within the environment is, among other factors, determined by the dispersion state and aggregation behavior of the nanoparticles and, in turn, directly affects the exposure of aquatic organisms to EPNs. The aggregation behavior (or colloidal stability) of these particles is controlled by the water chemistry and, to a large extent, by the surface chemistry of the particles. This paper presents results from extensive colloidal stability tests on commercially relevant titanium dioxide nanoparticles (Evonik P25) in well-controlled synthetic waters covering a wide range of pH values and water chemistries, and also in standard synthetic (EPA) waters and natural waters. The results demonstrate in detail the dependency of TiO2aggregation on the ionic strength of the solution, the presence of relevant monovalent and divalent ions, the presence and copresence of natural organic matter (NOM), and of course the pH of the solution. Specific interactions of both NOM and divalent ions with the TiO2 surfaces modify the chemistry of these surfaces resulting in unexpected behavior. Results from matrix testing in well-controlled batch systems allow predictions to be made on the behavior in the broader natural environment. Our study provides the basis for a testing scheme and data treatment technique to extrapolate and eventually predict nanoparticle behavior in a wide variety of natural waters.

  • Influence of carrier solution ionic strength and injected sample load on retention and recovery of natural nanoparticles using Flow Field-Flow Fractionation

    2011 - Journal of Chromatography A, 3: 6763-6773

    Abstract: 

    Natural nanoparticles, including both natural organic matter (NOM) and inorganic mineral-like phases, have been broadly characterized using Flow Field-Flow Fractionation (FlowFFF). Calibration with polystyrene sulfonate (PSS) standards was generally carried out in order to determine the molecular weight distribution of the NOM, however if the analyzed sample has a different charge density compared to the PSS standards, the resulting molecular weight distribution may become meaningless. The presented study therefore investigates and compares the influences of ionic strength and sample load on the retention time and recovery of both PSS standards and natural nanoparticles from a variety of sources. The minimum ionic strength in the carrier solution and the maximum injected sample load required for satisfactory separation depend on the molecular weight of the PSS standards and on the nature of the NOM. The degree to which results depend on conditions and parameters within the FlowFFF varies significantly between the different natural nanoparticle samples. We found that it may be necessary to calibrate the channel under different conditions from the actual sample runs. Under well controlled and documented conditions this could represent an important move away from the paradigm of “same conditions for standards and sample”. From all conditions tested, the most reliable molecular weight calibrations were obtained at elevated ionic strengths in the carrier solution (>0.04 M) and low injected mass of PSS. However, even under these optimized conditions variations of up to 20% occur in the calculated molecular weights, and the recovery of NOM falls by up to 50% at high ionic strengths. Many applications aim for both correct molecular weight distribution and the measurement of low concentrations of elements bound to natural nanoparticles. We conclude, however, that finding conditions that are equally optimal for both of these analytical tasks is not always feasible.

  • Influence of ionic strength and pH on the limitation of latex microsphere deposition sites on iron-oxide coated sand by humic acid

    2011 - Environmental Pollution, 7: 1896-1904

    Abstract: 

    This study, for the first time, investigates and quantifies the influence of slight changes in solution pH and ionic strength (IS) on colloidal microsphere deposition site coverage by Suwannee River Humic Acid (SRHA) in a column matrix packed with saturated iron-oxide coated sand.

    Triple pulse experimental (TPE) results show adsorbed SRHA enhances microsphere mobility more at higher pH and lower IS and covers more sites than at higher IS and lower pH. Random sequential adsorption (RSA) modelling of experimental data suggests 1 μg of adsorbed SRHA occupied 9.28 ± 0.03 × 109 sites at pH7.6 and IS of 1.6 mMol but covered 2.75 ± 0.2 × 109 sites at pH6.3 and IS of 20 mMol. Experimental responses are suspected to arise from molecular conformation changes whereby SRHA extends more at higher pH and lower ionic strength but is more compact at lower pH and higher IS. Results suggest effects of pH and IS on regulating SRHA conformation were additive.

  • Measuring and Modeling Adsorption of PAHs to Carbon Nanotubes Over a Six Order of Magnitude Wide Concentration Range

    Melanie Kah, Xiaoran Zhang, Michiel T.O. Jonker, Thilo Hofmann
    2011 - Environmental Science & Technology, 1: 6011-6017

    Abstract: 

    Understanding the interactions between organic contaminants and carbon nanomaterials is essential for evaluating the materials’ potential environmental impact and their application as sorbent. Although a great deal of work has been published in the past years, data are still limited in terms of compounds, concentrations, and conditions investigated. We applied a passive sampling method employing polyoxymethylene (POM-SPE) to gain a better understanding of the interactions between polycyclic aromatic hydrocarbons (PAHs) and multiwalled carbon nanotubes (CNTs) over a 6 orders of magnitude wide concentration range. In the low-concentration range (pg-ng L–1), sorption of phenanthrene and pyrene was linear on a nonlogarithmic scale. Here, sorption could thus be described using a single sorption coefficient. Isotherm fits over the entire concentration range showed that (i) monolayer sorption models described the data very well, and (ii) the CNTs sorption capacity was directly related to their surface area. Sorption coefficients for 13 PAHs (11 of which have not been reported to date) were also measured at environmentally relevant low concentrations. No competition seemed to occur in the low-concentration range and sorption affinity was directly related to the solubility of the subcooled liquid of the compounds.

  • Natural, anthropogenic and fossil organic matter in river sediments and suspended particulate matter: A multi-molecular marker approach

    Vesna Micić, M.A. Kruge, J. Köster, Thilo Hofmann
    2011 - Science of The Total Environment, 5: 905-919

    Abstract: 

    Different classes of organic matter (OM) have been systematically investigated in sediments and suspended particulate matter (SPM) along the Danube River in order to understand causes of compositional changes. Analytical pyrolysis revealed the dominance of natural organic matter (NOM) in most of the samples. The predominance of aquatic biomass is evident mainly from the abundance of organonitrogen compounds and phenol distributions. As the river enters a forested gorge, the terrestrial component of the NOM in sediments is more significant. This is reflected in abundant methoxyphenols and a very high carbon preference index. SPM sample from a tributary shows a unique geochemical signature. It contains abundant carboxylic acids, amines, isoprenoids in the pyrolyzate, and is dominated by phytol and 24-methyl-cholesta-5,24(28)-dien-3β-ol in the extract, produced by a diatom bloom. Wax esters with a relatively high proportion of short, methyl-branched alkyl-chains appear together with abundant phytadienes and n-C17 alkane in some samples, suggesting a microbial origin. Anthropogenic OM from runoff and atmospheric deposition was evident from a minor input of polycyclic aromatic hydrocarbons (PAHs) originating from mixed combustion sources. Multivariate analysis using PAH data led us to define simple molecular ratios to distinguish the PAH composition in sand and silty sediments. The newly defined ratios are the alkylated phenanthrenes and anthracenes ratio (APA; C1-C3/C0–C3phenanthrenes and anthracenes) and the PAH ring number ratio (RN; 5–6 ring parent PAHs/all parent PAHs). This demonstrates that alkylated, as well as 5–6 ring PAHs are better preserved in the finer than in coarser grained sediments. A ubiquitous, but minor input of petroleum-related contamination with a uniform composition was evident in all samples as revealed by the analysis of petroleum biomarkers. This study demonstrates that the investigation of different classes of riverine OM requires a detailed molecular analysis, applying a series of analytical techniques and adequate statistical data treatment.

  • Separation and characterization of nanoparticles in complex food and environmental samples by field-flow fractionation

    Frank von der Kammer, Samuel Legros, Thilo Hofmann, Erik H. Larsen, Katrin Loeschner
    2011 - TrAC Trends in Analytical Chemistry, 3: 425-436

    Abstract: 

    The thorough analysis of natural nanoparticles (NPs) and engineered NPs involves the sequence of detection, identification, quantification and, if possible, detailed characterization. In a complex or heterogeneous sample, each step of this sequence is an individual challenge, and, given suitable sample preparation, field-flow fractionation (FFF) is one of the most promising techniques to achieve relevant characterization.

    The objective of this review is to present the current status of FFF as an analytical separation technique for the study of NPs in complex food and environmental samples. FFF has been applied for separation of various types of NP (e.g., organic macromolecules, and carbonaceous or inorganic NPs) in different types of media (e.g., natural waters, soil extracts or food samples).

    FFF can be coupled to different types of detectors that offer additional information and specificity, and the determination of size-dependent properties typically inaccessible to other techniques. The separation conditions need to be carefully adapted to account for specific particle properties, so quantitative analysis of heterogeneous or complex samples is difficult as soon as matrix constituents in the samples require contradictory separation conditions. The potential of FFF analysis should always be evaluated bearing in mind the impact of the necessary sample preparation, the information that can be retrieved from the chosen detection systems and the influence of the chosen separation conditions on all types of NP in the sample. A holistic methodological approach is preferable to a technique-focused one.

  • The lack of microbial degradation of polycyclic aromatic hydrocarbons from coal-rich soils

    Christine Achten, Shubo Cheng, Kristina L. Straub, Thilo Hofmann
    2011 - Environmental Pollution, 2: 623-629

    Abstract: 

    Analytical techniques used to assess the environmental risk of contamination from polycyclic aromatic hydrocarbons (PAHs) typically consider only abiotic sample parameters. Supercritical fluid extraction and sorption enthalpy experiments previously suggested slow desorption rates for PAH compounds in two coal-contaminated floodplain soils. In this study, the actual PAH availability for aerobic soil microorganisms was tested in two series of soil-slurry experiments. The experimental conditions supported microbial degradation of phenanthrene if it was weakly sorbed onto silica gel. Native coals and coal-derived particles in two soils effectively acted as very strong sorbents and prevented microbial PAH degradation. The long history of PAH exposure and degree of coal contamination apparently had no influence on the capability of the microbial soil community to overcome constraints of PAH availability. Within the context of the experimental conditions and the compounds chosen, our results confirm that coal-bound PAHs are not bioavailable and hence of low environmental concern.

  • Variations in concentrations and compositions of polycyclic aromatic hydrocarbons (PAHs) in coals related to the coal rank and origin

    S. Laumann, Vesna Micić, M.A. Kruge, C. Achten, R.F. Sachsenhofer, J. Schwarzbauer, Thilo Hofmann
    2011 - Environmental Pollution, 1: 2690-2697

    Abstract: 

    The release of unburnt coal particles and associated polycyclic aromatic hydrocarbons (PAHs) may cause adverse impacts on the environment. This study assessed variations in the concentration and composition of PAHs in a set of fifty coal samples from eleven coal basins worldwide. The maximum PAH concentrations at high volatile bituminous rank were recorded in samples from a single basin. Considering the entire sample set, the highest PAH concentrations were in fact found outside of this rank range, suggesting that the maceral composition and thus the coal’s origin also influenced PAH concentrations. The examination of the PAH compositions revealed that alkylated 2–3 ring PAHs remain dominant compounds irrespective of coal rank or origin. Multivariate analysis based on PAH and maceral content, bulk and maturity parameters allowed the recognition of seven groups with different rank and origin within the coal sample set.

  • Algal testing of titanium dioxide nanoparticlesTesting considerations, inhibitory effects and modification of cadmium bioavailability

    N.B. Hartmann, Frank von der Kammer, Thilo Hofmann, M. Baalousha, S. Ottofuelling, A. Baun
    2010 - Toxicology, 2: 190-197

    Abstract: 

    The ecotoxicity of three different sizes of titanium dioxide (TiO2) particles (primary particles sizes: 10, 30, and 300 nm) to the freshwater green alga Pseudokirchneriella subcapitata was investigated in this study. Algal growth inhibition was found for all three particle types, but the physiological mode of action is not yet clear. It was possible to establish a concentration/dose–response relationship for the three particle sizes. Reproducibility, however, was affected by concentration-dependent aggregation of the nanoparticles, subsequent sedimentation, and possible attachment to vessel surfaces. It is also believed that heteroaggregation, driven by algal exopolymeric exudates, is occurring and could influence the concentration–response relationship. The ecotoxicity of cadmium to algae was investigated both in the presence and absence of 2 mg/L TiO2. The presence of TiO2 in algal tests reduced the observed toxicity due to decreased bioavailability of cadmium resulting from sorption/complexation of Cd2+ ions to the TiO2 surface. However, for the 30 nm TiO2 nanoparticles, the observed growth inhibition was greater than what could be explained by the concentration of dissolved Cd(II) species, indicating a possible carrier effect, or combined toxic effect of TiO2 nanoparticles and cadmium. These results emphasize the importance of systematic studies of nanoecotoxicological effects of different sizes of nanoparticles and underline the fact that, in addition to particle toxicity, potential interactions with existing environmental contaminants are also of crucial importance in assessing the potential environmental risks of nanoparticles.

  • Assessment of the physico-chemical behavior of titanium dioxide nanoparticles in aquatic environments using multi-dimensional parameter testing

    Frank von der Kammer, Stephanie Ottofuelling, Thilo Hofmann
    2010 - Environmental Pollution, 1: 3472-3481

    Abstract: 

    Assessment of the behavior and fate of engineered nanoparticles (ENPs) in natural aquatic media is crucial for the identification of environmentally critical properties of the ENPs. Here we present a methodology for testing the dispersion stability, ζ-potential and particle size of engineered nanoparticles as a function of pH and water composition. The results obtained from already widely used titanium dioxide nanoparticles (Evonik P25 and Hombikat UV-100) serve as a proof-of-concept for the proposed testing scheme. In most cases the behavior of the particles in the tested settings follows the expectations derived from classical DLVO theory for metal oxide particles with variable charge and an isoelectric point at around pH 5, but deviations also occur. Regardless of a 5-fold difference in BET specific surface area particles composed of the same core material behave in an overall comparable manner. The presented methodology can act as a basis for the development of standardised methods for comparing the behavior of different nanoparticles within aquatic systems.

  • Direct-push profiling of isotopic and hydrochemical vertical gradients

    Thilo Hofmann, Andreas Darsow, Manfred Gröning, Pradeep Aggarwal, Axel Suckow
    2010 - Journal of Hydrology, 1: 84-94

    Abstract: 

    A low-cost and easy to use direct-push method is presented that allows groundwater sampling for isotope and hydrochemical analysis with a depth resolution of 1 m and a final depth in the range of 30 m in unconsolidated sand and gravel aquifers. A trained two-man team can obtain a profile with a dozen different depths within one working day. The technique is demonstrated to provide results for isotope and geochemical studies that are comparable to those from nested multilevel wells, but allow a higher depth resolution and cause smaller hydraulic disturbance of the groundwater system during sampling. The direct-push sampling technique is also shown to give much better results in terms of depth resolution and the identification of geochemical and isotope hydrological gradients than does packer sampling of long-screen wells. Possible applications are the study of geochemical gradients, groundwater age determinations and investigations into recharge processes in unconsolidated aquifers.

  • Importance of the nugget effect in variography on modeling zinc leaching from a contaminated site using simulated annealing

    Thilo Hofmann, Andreas Darsow, Maria-Theresia Schafmeister
    2010 - Journal of Hydrology, 1: 78-89

    Abstract: 

    The spatial heterogeneity of measured data from contaminated sites is a serious problem with regard to uncertainty and risk assessment. Stochastic simulation permits the generation of several realizations of the spatial data distribution without aiming to minimise local error variance (as in kriging, for example), but retaining important statistics such as the histogram, the semivariogram, and the measured data. The nugget-to-sill ratio will, however, influence spatial data interpolation based on geostatistical models. The nugget effect is generally unknown to the investigator and influenced by the sampling density and sampling grid, as well as by complex geological settings, analytical errors, or an unknown small-scale site-specific contaminant input. Using simulated annealing to generate 30 randomly combined input data realizations and a simple transport model, we can show that the modeled zinc discharge is up to 70% higher if the nugget-to-sill ratio is varied by a factor of two times. The variance of zinc discharge was influenced by the nugget-to-sill ratio by a factor of 10 times. By reducing the number of drill holes to one half from the data set at random we have shown that the variance of the reduced data set did not provide a reliable prediction of the data heterogeneity for the complete data set, and the mean zinc discharge was up to 170% higher when only half of the drill holes were considered. Uncertainty analysis based on equal-probability realizations should further be founded by additional variation of nugget-to-sill ratio within a reasonable spectrum.

  • Nanosized Iron Oxide Colloids Strongly Enhance Microbial Iron Reduction

    J. Bosch, K. Heister, Thilo Hofmann, R. U. Meckenstock
    2010 - Applied and environmental microbiology, 1: 184-189

    Abstract: 

    Microbial iron reduction is considered to be a significant subsurface process. The rate-limiting bioavailability of the insoluble iron oxyhydroxides, however, is a topic for debate. Surface area and mineral structure are recognized as crucial parameters for microbial reduction rates of bulk, macroaggregate iron minerals. However, a significant fraction of iron oxide minerals in the subsurface is supposed to be present as nanosized colloids. We therefore studied the role of colloidal iron oxides in microbial iron reduction. In batch growth experiments with Geobacter sulfurreducens, colloids of ferrihydrite (hydrodynamic diameter, 336 nm), hematite (123 nm), goethite (157 nm), and akaganeite (64 nm) were added as electron acceptors. The colloidal iron oxides were reduced up to 2 orders of magnitude more rapidly (up to 1,255 pmol h−1 cell−1) than bulk macroaggregates of the same iron phases (6 to 70 pmol h−1 cell−1). The increased reactivity was not only due to the large surface areas of the colloidal aggregates but also was due to a higher reactivity per unit surface. We hypothesize that this can be attributed to the high bioavailability of the nanosized aggregates and their colloidal suspension. Furthermore, a strong enhancement of reduction rates of bulk ferrihydrite was observed when nanosized ferrihydrite aggregates were added.

    Dissimilatory iron reduction is an important anaerobic respiration process in anoxic subsurface environments. However, the reactivity of ferric iron is mostly limited by the reduction kinetics of the poorly soluble, extracellular iron minerals. Electron transfer from microorganisms to iron oxides can occur via direct contact or by electron shuttling compounds (46). Transport of the electron shuttle between the redox partners is then assumed to occur via diffusion. For example, humic substances can serve as natural electron shuttles that can be reduced by microorganisms and subsequently chemically oxidized by the ferric oxide (18). Shewanella oneidensisexcretes a flavin to stimulate hematite reduction, functioning in a similar manner (27). As another option, formation of conductive pili serving as nanowires was described as a possible way of transferring electrons to the oxide surface (15, 34). Nevertheless, direct attachment has been recognized as a major mode of accessing iron oxides as electron acceptors (12). Direct transfer between microbial outer membrane reductases and the ferric minerals, however, requires close contact of less than 14 Å between the terminal iron reductase on the cell surface and the iron oxide molecule at the mineral surface (19, 25), limiting the rates of electron transfer between cell and mineral.

    Several parameters have been discussed in this context as being decisive for the bioavailability and reactivity of iron oxides, such as, e.g., the mineral surface area (8, 41). Larger surface areas have been shown to be accompanied by higher initial reduction rates. Another parameter that might determine reactivity is the low solubility of ferric iron in water at neutral pH (20). Low solubility entails high crystallinity, which reduces reaction rates (4). Therefore, crystalline bulk iron phases such as goethite or hematite (9) are poorly reducible by microorganisms, in contrast to amorphous ferrihydrite (41). Naturally, well crystalline minerals have lower surface areas, and the effects of surface area and solubility cannot be distinguished sharply. Cell density, initial oxide and substrate concentrations, and ferrous iron adsorbed to the bulk mineral surface were also reported to control microbial reduction rates by exhibiting mutual saturation behavior in Michaelis-Menten-type kinetics (3, 22, 40).

    The latter studies also considered particle sizes, a parameter that has often been overlooked so far. All concepts mentioned above generally assumed a bulk state of the electron-accepting iron oxide. Indeed, iron oxides used in microbiological experiments appear mainly as coarse, flocculating macroaggregates, visible to the naked eye as sludge-like precipitates. In nature, however, nanosized iron oxides are abundant (32, 45) and play a vital role in many biogeochemical processes (2, 16, 28). Such nanoparticles may appear in stable colloidal suspension, even if aggregated as a stable cluster of multiple particles (13). Ferric oxide particles can appear in colloidal suspensions of different aggregate sizes and densities.

    Different particle aggregate sizes might influence the bioavailability of iron oxides in microbial reduction. Nanosized aggregates appearing in colloidal suspensions might be spatially more accessible for microorganisms than large aggregates flocculating as bulk phases. Therefore, the present study aims at assessing the reactivity and putative role of aggregate sizes of iron oxides in dissimilatory iron reduction. A set of ferrihydrite, hematite, goethite, and akaganeite colloids was compared to their respective noncolloidal bulk phases to evaluate this effect.

  • Organic geochemistry of Danube River sediments from Pančevo (Serbia) to the Iron Gate dam (Serbia-Romania)

    Vesna Micić, Michael Kruge, Petra Körner, Nicole Bujalski, Thilo Hofmann
    2010 - Organic Geochemistry, 9: 971-974

    Abstract: 

    The type and source of natural organic matter was investigated in Danube River sediments from the Hungarian Plain near Belgrade to the Carpathian–Balkan Mountains near the Iron Gate dam by means of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). In addition, the input of anthropogenic organic matter to the river was traced using sewage markers (linear alkyl benzenes and alkyl phenolic compounds). The VGI ratio employs the most abundant lignin marker (4-vinylguaiacol) and the most abundant organonitrogen compound (indole) in the sediment pyrolysis products and is proposed as an index of the relative contributions of land plant vs. aquatic biomass to sediments. Sewage marker analysis revealed their enhanced accumulation in sediments close to metropolitan/industrial areas and at the mouth of the Velika Morava tributary, as well as their overall decrease in concentration downstream towards the Iron Gate dam.

  • Quantifying the influence of humic acid adsorption on colloidal microsphere deposition onto iron-oxide-coated sand

    2010 - Environmental Pollution, 1: 3498-3506

    Abstract: 

    This article describes an approach for quantifying microsphere deposition onto iron-oxide-coated sand under the influence of adsorbed Suwannee River Humic Acid (SRHA). The experimental technique involved a triple pulse injection of model latex microspheres (microspheres) in pulses of (1) microspheres, followed by (2) SRHA, and then (3) microspheres, into a column filled with iron-coated quartz sand as a water-saturated porous medium. A random sequential adsorption model (RSA) simulated the gradual rise in the first (microsphere) breakthrough curve (BTC). Using the same model calibration parameters a dramatic increase in concentration at the start of the second particle BTC, generated after SRHA injection, could be simulated by matching microsphere concentrations to extrapolated RSA output. RSA results and microsphere/SRHA recoveries showed that 1 μg of SRHA could block 5.90 ± 0.14 × 109 microsphere deposition sites. This figure was consistent between experiments injecting different SRHA masses, despite contrasting microsphere deposition/release regimes generating the second microsphere BTC.

  • Relevance of peat-draining rivers for the riverine input of dissolved iron into the ocean

    Krachler R, Krachler RF, Frank von der Kammer, Süphandag A, Jirsa F, Ayromlou S, Thilo Hofmann, Keppler BK
    2010 - Science of The Total Environment, 11: 2402-2408

    Abstract: 

    Peat bogs have the ability to produce strong chelate ligands (humic and fulvic acids) which enhance the weathering rates of iron-silicate minerals and greatly increase the solubility of the essential trace metal iron in river water. Fluvial networks link peat bogs with the ocean, and thus terrestrial-derived fulvic-iron complexes fuel the ocean's biological productivity and biological carbon pump, but understanding this role is constrained by inconsistent observations regarding the behaviour of riverine iron in the estuarine mixing zone, where precipitation reactions remove iron from the water column. We applied a characterization of the colloidal iron carriers in peatland-draining rivers in North Scotland, using field-flow fractionation (FFF), in combination with end-member mixing experiments of river water sampled near the river mouth and coastal seawater using a 59Fe radiotracer method. According to our results, the investigated river contributed “truly dissolved” Fe concentrations of about 3300 nmol L− 1 to the ocean which is nearly two orders of magnitude higher than the dissolved iron contribution of the “average world” river (∼ 40 nmol L− 1). Thus we conclude that peatland-draining rivers are important sources of dissolved iron to the ocean margins. We propose highly electrostatic and sterical stabilized iron-organic matter complexes in the size range of < 2 kDa to be responsible for iron transport across the estuarine mixing zone.

  • Tetrachloroferrate containing ionic liquids: Magnetic- and aggregation behavior

    Daniel Kogelnig, Anja Stojanovic, Frank von der Kammer, Peter Terzieff, Markus Galanski, Franz Jirsa, Regina Krachler, Thilo Hofmann, Bernhard K. Keppler
    2010 - Inorganic Chemistry Communications, 1: 1485-1488

    Abstract: 

    The magnetic behavior of a binary salt of tricaprylylmethylammonium tetrachloroferrate and tricaprylylmethylammonium chloride, [A336][FeCl4]0.73[Cl]0.27, was evaluated. With a magnetic susceptibility of 0.011 emu mol− 1 this binary salt exhibited a remarkable response to an external magnetic field. Dynamic light scattering (DLS) measurements allowed to study the aggregation behavior of [A336][FeCl4]0.73[Cl]0.27 as well as of further magnetic ionic liquids [PR6,6,6,14][FeCl4] and (BMIM)[FeCl4] in ethylacetate and ethanol.

  • Themenheft: Hydrogeologie in Österreich

    Steffen Birk, Thilo Hofmann
    2010 - Grundwasser, 1: 3-4
  • Umweltrelevanz von natürlichen polyzyklischen aromatischen Kohlenwasserstoffen aus Steinkohlen – eine Übersicht

    C. Achten, Thilo Hofmann
    2010 - Grundwasser, 1: 5-18

    Abstract: 

    Steinkohlen weisen polyzyklische aromatische Kohlenwasserstoff (PAK)- Konzentrationen bis wenige Hundert mg/kg (16 EPA) und Gesamt-PAK-Gehalte von wenigen Tausend mg/kg auf und sind eine selten beachtete Quelle für diese Substanzen. Die Gehalte variieren international stark und sind von der Reife sowie dem Ausgangsmaterial der Kohle abhängig. Maximale PAK-Gehalte treten im Bereich des Ölfensters auf (niedriger Steinkohlenreifegrad), jedoch liegt in der Regel keine Korrelation vom PAK-Gehalt zur Reife vor. Dies ist nur bei Kohlen aus einer gemeinsamen Herkunft der Fall. Naphthalin und Phenanthren sowie deren alkylierte Derivate stellen die dominierenden Substanzen in Steinkohlen dar. Die Muster der PAK-Einzelsubstanzen verschieben sich mit zunehmender Inkohlung von den noch mit dem Ausgangsmaterial in Verbindung stehenden niedermolekularen, überwiegend alkylierten Substanzen zu den meist höhermolekularen nicht-alkylierten Muttersubstanzen. Erstere sind für petrogene Herkunft typisch, letztere für pyrogene. Derzeit kann mit einfachen diagnostischen Indizes nicht zwischen PAK aus Kohlen und PAK aus Mineralöl und deren Produkten unterschieden werden. Der Kohlepartikelanteil in bergbaubeeinflussten Böden und Sedimenten kann ca. 10–15 % betragen. Wenig ist bisher über die Desorption und die Bioverfügbarkeit von natürlichen (nativen) PAK aus Kohlen bekannt. Bisherige Untersuchungen weisen auf eine geringe Bioverfügbarkeit und eine sehr langsame Desorption hin. Eine systematische Untersuchung der sehr heterogenen Kohlen fehlt bisher. Die Bioverfügbarkeit von PAK aus Kohlepartikeln in Böden und Sedimenten beeinflusst die Gefahrenbeurteilung und sollte in gesetzlichen Regelungen berücksichtigt werden.

  • Using FlFFF and aTEM to determine trace metal - nanoparticle associations in riverbed sediment

    K. L. Plathe, Frank von der Kammer, M. Hassellöv, J. Moore, M. Murayama, Thilo Hofmann, M. F. Hochella
    2010 - Environmental Chemistry, 1: 82

    Abstract: 

    Analytical transmission electron microscopy (aTEM) and flow field flow fractionation (FlFFF) coupled to multi-angle laser light scattering (MALLS) and high-resolution inductively coupled plasma mass spectroscopy (HR-ICPMS) were utilised to elucidate relationships between trace metals and nanoparticles in contaminated sediment. Samples were obtained from the Clark Fork River (Montana, USA), where a large-scale dam removal project has released reservoir sediment contaminated with toxic trace metals (namely Pb, Zn, Cu and As) which had accumulated from a century of mining activities upstream. An aqueous extraction method was used to recover nanoparticles from the sediment for examination; FlFFF results indicate that the toxic metals are held in the nano-size fraction of the sediment and their peak shapes and size distributions correlate best with those for Fe and Ti. TEM data confirms this on a single nanoparticle scale; the toxic metals were found almost exclusively associated with nano-size oxide minerals, most commonly brookite, goethite and lepidocrocite.

  • An ArcGIS approach to include tectonic structures in point data regionalisation

    Andreas Darsow, Maria-Theresia Schafmeister, Thilo Hofmann
    2009 - Ground Water, 4: 591-597

    Abstract: 

    Point data derived from drilling logs must often be regionalized. However, aquifers may show discontinuous surface structures, such as the offset of an aquitard caused by tectonic faults. One main challenge has been to incorporate these structures into the regionalization process of point data. We combined ordinary kriging and inverse distance weighted (IDW) interpolation to account for neotectonic structures in the regionalization process. The study area chosen to test this approach is the largest porous aquifer in Austria. It consists of three basins formed by neotectonic events and delimited by steep faults with a vertical offset of the aquitard up to 70 m within very short distances. First, ordinary kriging was used to incorporate the characteristic spatial variability of the aquitard location by means of a variogram. The tectonic faults could be included into the regionalization process by using breaklines with buffer zones. All data points inside the buffer were deleted. Last, IDW was performed, resulting in an aquitard map representing the discontinuous surface structures. This approach enables one to account for such surfaces using the standard software package ArcGIS®; therefore, it could be adopted in many practical applications.

  • Aqueous accelerated solvent extraction of native polycyclic aromatic hydrocarbons (PAHs) from carbonaceous river floodplain soils

    Yi Yang, Thilo Hofmann
    2009 - Environmental Pollution, 1: 2604-2609

    Abstract: 

    In this study, three river floodplain soils with different compositions of carbonaceous materials and a reference coal sample were extracted with water using the accelerated solvent extraction (ASE) method. The desorption enthalpy values for 2-ring PAHs were highest in the coal sample, with values in the soil samples decreasing with decrease in coal content. The values for the higher condensed PAHs showed that the highest desorption enthalpies were from the samples with the largest amount of coal-derived particles. Elevated desorption enthalpies indicated a strong bonding between PAHs and geosorbents. Moreover, with the application of ASE this study was able to conclude that the PAHs in the samples were preferentially adsorbed to carbonaceous materials with high surface areas.

  • Estimating the relevance of engineered carbonaceous nanoparticle facilitated transport of hydrophobic organic contaminants in porous media

    2009 - Environmental Pollution, 157: 1117-1126

    Abstract: 

    Naturally occurring nanoparticles (NP) enhance the transport of hydrophobic organic contaminants (HOCs) in porous media. In addition, the debate on the environmental impact of engineered nanoparticles (ENP) has become increasingly important. HOC bind strongly to carbonaceous ENP. Thus, carbonaceous ENP may also act as carriers for contaminant transport and might be important when compared to existing transport processes. ENP bound transport is strongly linked to the sorption behavior, and other carbonaceous ENP-specific properties. In our analysis the HOC–ENP sorption mechanism, as well as ENP size and ENP residence time, was of major importance. Our results show that depending on ENP size, sorption kinetics and residence time in the system, the ENP bound transport can be estimated either as (1) negligible, (2) enhancing contaminant transport, or (3) should be assessed by reactive transport modeling. One major challenge to this field is the current lack of data for HOC–ENP desorption kinetics.

  • Kolloide, Nanopartikel und Wasserchemie

    2009 - Vom Wasser - das Journal, 107: 3-3
  • Nanoparticle facilitated transport of organic contaminants

    2009 - Geochmica et Cosmochimica Acta, 73: 545
  • Nanostructured TiO2: Transport Behavior and Effects on Aquatic Microbial Communities under Environmental Conditions

    Tom J. Battin, Frank von der Kammer, Andreas Weilhartner, Stephanie Ottofuelling, Thilo Hofmann
    2009 - Environmental Science & Technology, 2: 8098-8104

    Abstract: 

    Industry has already commenced the large-scale production of some nanomaterials. Evidence for toxic effects of engineered nanoparticles (ENP) on model organisms is increasing. However, in order to assess the consequences of environmental hazards, a better understanding is required of the behavior of ENP in aquatic ecosystems and their impact on complex communities. In this research, through experimenting with different TiO2 nanoparticles in stream microcosms, we have shown that microbial membranes were significantly compromised, even under ambient ultraviolet radiation and nano-TiO2 concentrations predicted for surface waters. Our results suggest adverse effects are not necessarily only attributable to individual particles smaller than 100 nm but also to low concentrations of larger, naturally agglomerating TiO2 nanoparticles. Cell membrane damage was more pronounced in free-living cells than in biofilm cells, indicating the protective role of cell encapsulation against TiO2 nanoparticles. The generation of intracellular reactive oxygen species (ROS) further suggests nano-TiO2-induced effects inside the microbial cells. Our findings indicate a high sensitivity of microbial communities to levels of ENP concentration that are to be expected in the environment, with as yet unknown implications for the functioning and health of ecosystems.

  • Native polycyclic aromatic hydrocarbons (PAH) in coals - A hardly recognized source of environmental contamination

    C. Achten, Thilo Hofmann
    2009 - Science of The Total Environment, 8: 2461-2473

    Abstract: 

    Numerous environmental polycyclic aromatic hydrocarbon (PAH) sources have been reported in literature, however, unburnt hard coal/ bituminous coal is considered only rarely. It can carry native PAH concentrations up to hundreds, in some cases, thousands of mg/kg. The molecular structures of extractable compounds from hard coals consist mostly of 2–6 polyaromatic condensed rings, linked by ether or methylene bridges carrying methyl and phenol side chains. The extractable phase may be released to the aquatic environment, be available to organisms, and thus be an important PAH source. PAH concentrations and patterns in coals depend on the original organic matter type, as well as temperature and pressure conditions during coalification. The environmental impact of native unburnt coal-bound PAH in soils and sediments is not well studied, and an exact source apportionment is hardly possible. In this paper, we review the current state of the art.

  • Occurrence and behaviour of selected hydrophobic alkylphenolic compounds in the Danube River

    2009 - Environmental Pollution, 1: 2759-2768

    Abstract: 

    Six hydrophobic alkylphenolic compounds were investigated for the first time simultaneously in four different matrices in the Danube River. Maximum sediment concentrations were 2.83, 2.10, 0.28, and 0.035 mg kg−1 for nonylphenol, nonylphenol monoethoxylate, nonylphenol diethoxylate and octylphenol. Maximum levels in suspended particulate matter (SPM) were 0.18, 0.12, 0.10, and 0.003 mg kg−1. No correlation between concentrations in SPM and sediments was found. Octylphenol monoethoxylate and octylphenol diethoxylate were recorded only in sediment at one location. In mussels and water only nonylphenol and octylphenol were found. Nonylphenol concentrations in mussels (up to 0.34 mg kg−1) correlate with concentrations found in SPM and indicate a slight bioaccumulation. Concentrations in water were close to the limit of quantification. We assume in situ formation of nonylphenol monoethoxylate and nonylphenol in sediments at some locations. In some cases nonylphenol in sediments exceeded the provisional EU environmental quality standards.

  • Umweltrelevanz von natrlichen polyzyklischen aromatischen Kohlenwasserstoffen aus Steinkohlen eine bersicht

    C. Achten, Thilo Hofmann
    2009 - Grundwasser, 1: 5-18

    Abstract: 

    Steinkohlen weisen polyzyklische aromatische Kohlenwasserstoff (PAK)- Konzentrationen bis wenige Hundert mg/kg (16 EPA) und Gesamt-PAK-Gehalte von wenigen Tausend mg/kg auf und sind eine selten beachtete Quelle für diese Substanzen. Die Gehalte variieren international stark und sind von der Reife sowie dem Ausgangsmaterial der Kohle abhängig. Maximale PAK-Gehalte treten im Bereich des Ölfensters auf (niedriger Steinkohlenreifegrad), jedoch liegt in der Regel keine Korrelation vom PAK-Gehalt zur Reife vor. Dies ist nur bei Kohlen aus einer gemeinsamen Herkunft der Fall. Naphthalin und Phenanthren sowie deren alkylierte Derivate stellen die dominierenden Substanzen in Steinkohlen dar. Die Muster der PAK-Einzelsubstanzen verschieben sich mit zunehmender Inkohlung von den noch mit dem Ausgangsmaterial in Verbindung stehenden niedermolekularen, überwiegend alkylierten Substanzen zu den meist höhermolekularen nicht-alkylierten Muttersubstanzen. Erstere sind für petrogene Herkunft typisch, letztere für pyrogene. Derzeit kann mit einfachen diagnostischen Indizes nicht zwischen PAK aus Kohlen und PAK aus Mineralöl und deren Produkten unterschieden werden. Der Kohlepartikelanteil in bergbaubeeinflussten Böden und Sedimenten kann ca. 10–15 % betragen. Wenig ist bisher über die Desorption und die Bioverfügbarkeit von natürlichen (nativen) PAK aus Kohlen bekannt. Bisherige Untersuchungen weisen auf eine geringe Bioverfügbarkeit und eine sehr langsame Desorption hin. Eine systematische Untersuchung der sehr heterogenen Kohlen fehlt bisher. Die Bioverfügbarkeit von PAK aus Kohlepartikeln in Böden und Sedimenten beeinflusst die Gefahrenbeurteilung und sollte in gesetzlichen Regelungen berücksichtigt werden.

  • Ageing of synthetic and natural schwertmannites at pH 2–8

    S. KUMPULAINEN, M.-L. RÄISÄNEN, Frank von der Kammer, Thilo Hofmann
    2008 - Clay Minerals: journal of the European Clay Groups, 3: 437-448

    Abstract: 

    The transformation of schwertmannite to goethite was studied by ageing one synthetic and five natural schwertmannites in water at room temperature. Additionally, one synthetic and two natural schwertmannites were kept at variable pH (2, 4, 6 and 8). After one year, only the synthetic sample and one natural schwertmannite had transformed to goethite. However, the oxalate solubility of Fe and trace elements in all the samples decreased, whereas the total Fe/S ratios and specific surface areas of all samples increased. Arsenic and organic matter appeared to suppress the schwertmannite-to-goethite phase transformation. At pH 2, synthetic schwertmannite fully-transformed to goethite, but at pH 4–6 only minor transformation occurred. Depending on pH, many trace elements were released into solution during ageing of the natural schwertmannites. In general, Co, Mn, Zn and Si were released to solution, whereas As was enriched in the remaining iron oxide fraction. Al was dissolved at pH <4.

  • Characterization and source identification of polycyclic aromatic hydrocarbons (PAHs) in river bank soils

    Carmen Pies, Burkhard Hoffmann, Jelena Petrowsky, Yi Yang, Thomas A. Ternes, Thilo Hofmann
    2008 - Chemosphere, 1: 1594-1601

    Abstract: 

    Elevated PAH concentrations were detected in bank soils along the Mosel and Saar Rivers in Germany. Information on the identification of PAH sources in this area however remains unclear. This study was able to characterize the PAH sources by application of several approaches, including consideration of the distribution patterns of 45 PAHs (including 16 EPA PAHs and some alkyl PAHs), specific PAH ratios, distribution patterns of n-alkanes and principal component analysis (PCA). In addition, the efficiency of the tested approaches was assessed. The results from the application of the various source identification methods showed that pyrogenic PAHs dominate soil samples collected upstream of the confluence of the Mosel and Saar Rivers, and petrogenic and pyrogenic PAHs dominate samples downstream of the confluence. Based on the analysis of reference materials and organic petrography, the petrogenic input was found to be dominated by coal particles. More detailed information on the petrogenic sources was provided by the n-alkane analyses. The current study concludes that to accurately determine the origin of PAHs, several identification methods must be applied.

  • Humic acid adsorption and surface charge effects on schwertmannite and goethite in acid sulphate waters

    2008 - Water Research, 8: 2051-2060

    Abstract: 

    In acid conditions, as in acid mine drainage waters, iron oxide particles are positively charged, attracting negatively charged organic particles present in surrounding natural waters. Schwertmannite (Fe8O8(OH)6SO4) and goethite (α-FeOOH) are the most typical iron oxide minerals found in mine effluents. We studied schwertmannite formation in the presence of humic acid. Further, surface charge and adsorption of humic acid on synthetic schwertmannite and goethite surfaces in pH 2–9 and in humic acid concentrations of 0.1–100 mg/L C were examined. Schwertmannite did precipitate despite the presence of humic acid, although it contained more sulphate and had higher specific surface area than ordinary schwertmannite. Specific surface area weighted results showed that schwertmannite and goethite had similar humic acid adsorption capacities. Sulphate was released from schwertmannite surfaces with increasing pH, resulting in an increase in specific surface area. Presence of sulphate in solution decreased the surface charge of schwertmannite and goethite similarly, causing coagulation. In acid conditions (pH 2–3.5), according to the zeta potential, schwertmannite is expected to coagulate even in the presence of high concentrations of humic acid (⩽100 mg/L C). However, at high humic acid concentrations (10–100 mg/L C) with moderate acid conditions (pH>3.5), both schwertmannite and goethite surfaces are strongly negatively charged (zeta potential <−30 mV) thus posing a risk for colloid stabilization and colloidal transport.

  • Identification of carbonaceous geosorbents for PAHs by organic petrography in river floodplain soils

    Yi Yang, Bertrand Ligouis, Carmen Pies, Christine Achten, Thilo Hofmann
    2008 - Chemosphere, 1: 2158-2167

    Abstract: 

    Organic petrographic analysis was applied to provide direct information on carbonaceous geosorbents for PAHs in river floodplain soils. The anthropogenic OM group (primarily coal and coal-derived particles) displayed large volume amounts for all the soil samples. Distinct PAH concentrations with similar PAH distribution patterns were determined in grain size and density fractions for each sample. Two-ring PAHs had stronger correlation to organic carbon (OC) than black carbon (BC) contents, while heavier PAHs showed correlation to BC, rather than OC. In this study, we combined grain size and density separation, PAH determinations, TOC and BC measurements, and organic petrographic identification, and concluded that two-ring PAHs in soils were associated to coal particles. Other heavier PAHs could be more controlled by black carbon (BC), which were mostly coal-derived particles from former coal mining and coal industrial activity.

  • Identifying sources of polycyclic aromatic hydrocarbons (PAHs) in soils: distinguishing point and non-point sources using an extended PAH spectrum and n-alkanes

    Carmen Pies, Thomas A. Ternes, Thilo Hofmann
    2008 - Journal of Soils and Sediments, 5: 312-322

    Abstract: 

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants. They are formed during pyrogenic and diagenetic processes and are components of petrogenic materials such as oils and coals. To identify PAH sources, several studies have employed forensic methods, which may be costly to execute. Although a large number of possible forensic methods are available (e.g., total ion chromatograms, PAH ratios, PAH alkyl homologue series, isoalkanes and isoprenoids, steranes and terpanes, stable isotope ratios, n-alkanes), one has to decide which method is the appropriate cost effective screening approach. In this study, three approaches were tested and compared by measuring (1) an extended PAH spectrum (i.e., 45 instead of the common 16 EPA-PAHs), (2) PAH ratios and (3) n-alkanes to determine if point sources are distinguishable from non-point sources, and if an individual source can be distinguished from a multiple source contaminated site in the study area. In addition, the study evaluated whether these methods are sufficient for source identification of selected samples, and if they constitute a sound strategy for source identification prior to the selection of more cost intensive methods.

  • Nanoparticles: structure, properties, preparation and behaviour in environmental media

    P. Christian, Frank von der Kammer, M. Baalousha, Thilo Hofmann
    2008 - Ecotoxicology, 5: 326-343

    Abstract: 

    There is increasing interest and need to develop a deeper understanding of the nature, fate and behaviour of nanoparticles in the environment. This is driven by the increased use of engineered nanoparticles and the increased pressure to commercialise this growing technology. In this review we discuss the key properties of nanoparticles and their preparation and then discuss how these factors can play a role in determining their fate and behaviour in the natural environment. Key focus of the discussion will relate to the surface chemistry of the nanoparticle, which may interact with a range of molecules naturally present in surface waters and sediments. Understanding these factors is a core goal required for understanding the final fate of nanomaterials and predicting which organisms are likely to be exposed to these materials.

  • Occurrence of coal and coal-derived particle-bound polycyclic aromatic hydrocarbons (PAHs) in a river floodplain soil

    Yi Yang, Bertrand Ligouis, Carmen Pies, Peter Grathwohl, Thilo Hofmann
    2008 - Environmental Pollution, 1: 121-129

    Abstract: 

    A PAH contaminated river floodplain soil was separated according to grain size and density. Coal and coal-derived particles from coal mining, coal industry and coal transportation activities were identified by organic petrographic analysis in our samples. Distinct concentrations of PAHs were found in different grain size and density fractions, however, similar distribution patterns of PAHs indicated similar sources. In addition, although light fractions had the mass fraction by weight of less than 5%, they contributed almost 75% of the total PAHs in the soil. PAH concentrations of all sub fractions showed positive correlation with their TOC contents. Altogether, coal and coal-derived particles that were abundant in light fractions could be the dominant geosorbents for PAHs in our samples.

  • PAH desorption from river floodplain soils using supercritical fluid extraction

    Yi Yang, Tomáš Cajthaml, Thilo Hofmann
    2008 - Environmental Pollution, 3: 745-752

    Abstract: 

    Sequential supercritical fluid extraction (SFE) was performed in order to estimate desorption of PAHs from river floodplain soils which contain coal and coal-derived particles. Original soils, soils' light fractions (ρ < 2 g cm−3), and <63 μm fractions were studied for PAHs' desorption kinetics. Desorption data were successfully described using a two-site model. Desorption rate constants were one order of magnitude lower than those of “slow” and “very slow” desorption rates from other studies. This suggests very slow and extremely slow desorption. Estimated time scales releasing 99% of total extractable contaminants ranged from decades for 2–4-ring PAHs and hundreds of years for 5–6-ring PAHs. We demonstrate that, despite high soil PAH concentrations which are due to coal and coal-derived particles, the general environmental risk is reduced by the very slow and extremely slow desorption rates.

  • Sorption of polycyclic aromatic hydrocarbons (PAHs) to carbonaceous materials in a river floodplain soil

    Yi Yang, Thilo Hofmann, Carmen Pies, Peter Grathwohl
    2008 - Environmental Pollution, 3: 1357-1363

    Abstract: 

    We report on sorption isotherm of phenanthrene (Phe) for river floodplain soil associated with carbonaceous materials, with particular attention being devoted to the natural loading of Phe. Our sorption experiments with original soil samples, size, and density sub-fractions showed that the light fraction had the highest sorption capacity comparable to low rank coals. In addition, the light fraction contributed most for the sorption of Phe in total soil samples. Koc values for all fractions were in the same range, thus indicating that coal and coal-derived particles in all samples are responsible for the enhanced sorption for Phe. Sorption was strongly nonlinear and the combined partitioning and pore-filling model gave a better fit than the Freundlich sorption model. In addition, the spiked PAHs did not show the same behavior as the naturally aged ones, therefore the accessibility of indigenous background organic contaminants was reduced when coal and coal-derived particles are associated with the soils.

  • Zn and Pb release of sphalerite (ZnS)-bearing mine waste tailings

    Thilo Hofmann, Nele Schuwirth
    2008 - Journal of Soils and Sediments, 6: 433-441

    Abstract: 

    Contaminated mine drainage water has become a major hydrogeological and geochemical problem. Release of soluble metal contaminants and acidity from mining sites can pose serious chemical risks to surface and groundwater in the surrounding environment, and it is an important socio-economic factor addressed by working groups like SUITMA Morel and Heinrich (J Soils Sediments 8:206–207, 2008). The release of Zn and Pb from sulfide-bearing flotation residues of a small scale mine in Western Germany is investigated with focus on metal transfer to soil solution. Total contents of the soil material as well as soil water sampled with suction cups were analyzed. The influence of pH on leaching behavior was investigated with pHstat tests. Isotopic analyses helped assessing seepage water velocity. The aim of this study was the assessment of the environmental behavior of zinc and lead caused by the weathering of sulfide-bearing mine tailings. Especially, we address in this paper the dissolution of sphalerite (ZnS) in contrast to the well-known dissolution processes of pyrite (FeS2).

  • Colloid facilitated transport of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to the groundwater at Ma Da Area, Vietnam

    Thilo Hofmann, Anke Wendelborn
    2007 - Environmental Science and Pollution Research - International, 4: 223-224

    Abstract: 

    PCDD/Fs are hydrophobic organic substances and strongly sorbing to soil particles. Once adsorbed to soil particles they are believed to be virtually immobile. However, research in the last decades confirmed that strong sorbing contaminants may reach the groundwater via colloid-facilitated transport. This pathway has not been investigated before in Vietnam. Ma Da area, 100 km north of Ho Chi Minh City, was repeatedly sprayed during the Vietnam War (1962–1971) with herbicides like Agent Orange containing, beside others, the teratogenic contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). 11 surface soil samples and 12 water samples were collected in Ma Da area for analysis of PCDD/Fs in solids. Soil TCDD concentrations ranged from 1–41 ppt with a mean of 8.8 ppt and a mean I-TEQ of 9.7 ppt. Two surface water samples showed colloid bound TCDD (7 and 19 ppt). Groundwater samples showed elevated colloid bound PCDD concentrations (mean 770 ng/kg), mainly octachlorodibenzo-p-dioxin. Groundwater colloids separated by filtration did not show any TCDD. The results support that TCDD/Fs can be relocated from the top soil to the groundwater by colloidal pathway. They did not provide evidence that the dioxins bound to groundwater colloids are leftovers from the Second Indochinese War. However, this study reinforces that the colloidal transport pathway has to be included investigating the relocation of strong sorbing organic contaminants.

  • Distribution of polycyclic aromatic hydrocarbons (PAHs) in floodplain soils of the Mosel and Saar River

    Carmen Pies, Yi Yang, Thilo Hofmann
    2007 - Journal of Soils and Sediments, 4: 216-222

    Abstract: 

    Surface soil (0–10 cm) samples from 53 sampling sites including rural and urban areas of Hong Kong were collected and analyzed for 16 EPA priority polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations were in the range of 7.0–410 μg kg−1 (dry wt), with higher concentrations in urban soils than that in rural soils. The three predominant PAHs were Fluoranthene, Naphthalene and Pyrene in rural soils, while Fluoranthene, Naphthalene and Benzo(b + k)fluoranthene dominated the PAHs of urban soils. The values of PAHs isomer indicated that biomass burning might be the major origin of PAHs in rural soils, but vehicular emission around the heavy traffic roads might contribute to the soil PAHs in urban areas. A cluster analysis was performed and grouped the detectable PAHs under 4 clusters, which could be indicative of the PAHs with different origins and PAHs affected by soil organic carbon contents respectively.

  • Elevated polycyclic aromatic hydrocarbons in a river floodplain soil due to coal mining activities

    Thilo Hofmann, C. Pies, Y. Yang
    2007 - Water Science and Technology: Water Supply, 3: 69-74

    Abstract: 

    Elevated PAH concentrations were found in soil samples collected along the Mosel River. These contaminations were associated with the occurrence of coal particles found in the soil. The majority of the PAH contamination in the soils was linked to coal mining activities in the Saar region. Density and grain size separation showed a similar PAH distribution pattern in all of the fractions, indicating a uniform origin of PAHs. Together with coal petrography a good correlation between TOC and PAHs concentration confirmed the impact of former coal mining activity on the PAHs distribution in study area.

  • Implementation of the EU-Waterframework Directive-Hydrochemistry in the Marchfeld region

    Andreas Darsow, Martin Kralik, Thilo Hofmann
    2007 - Geophysical Research Abstracts, 9: in press
  • Native PAHs in hard coal particles as a possible source of increased PAH concentrations in river sediments

    Vesna Micić, C. Achten, J. Schwarzbauer, Thilo Hofmann
    2007 - Geochimica et Cosmochimica Acta, 15: A663
  • Vertical Distribution and Speciation of Trace Metals in Weathering Flotation Residues of a Zinc/Lead Sulfide Mine

    Nele Schuwirth, Andreas Voegelin, Ruben Kretzschmar, Thilo Hofmann
    2007 - Journal of Environment Quality, 1: 61

    Abstract: 

    Sulfide-bearing mine tailings are a serious environmental problem around the world. In this study, the vertical distribution and speciation of Zn and Pb in the fine-grained flotation residues of a former sulfide ore mine in Germany were investigated to assess the inorganic weathering processes that effect the environmental risk arising from this site. Total metal contents were determined by X-ray fluorescence spectroscopy (XRF). Mobilizable fractions of Zn, Pb, Fe, and Mn were quantified by sequential chemical extractions (SCE). Furthermore, the speciation of Zn was analyzed by Zn K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) to identify the residual Zn species. The variations in pH and inorganic C content show an acidification of the topsoil to pH 5.5. EXAFS results confirm that Zn is mainly bound in sphalerite in the subsoil and weathering reactions lead to a redistribution of Zn in the topsoil. A loss of 35% Zn and S from the topsoil compared with the parent material with 10 g kg−1 Zn and neutral pH has been observed. If acidification proceeds it will lead to a significant release of Zn, S, and Pb to the ground water. In contrast to Zn, Pb is enriched in the mobile fraction of the topsoil by more than a factor of two compared with the subsoil which contains a total of 2 g kg−1 Pb. Thus, the high bioavailability of Pb and the potential for Pb uptake by plants and animals currently represent the most severe threat for environmental health.

  • Comparability of and Alternatives to Leaching Tests for the Assessment of the Emission of Inorganic Soil Contamination

    Nele Schuwirth, Thilo Hofmann
    2006 - Journal of Soils and Sediments, 2: 102-112

    Abstract: 

    Goal, Scope and Background

    The suitability of leaching tests for the assessment of soil water concentrations is a controversial issue. The aim of this paper is to review and critically discuss the applicability and comparability of leaching tests in the scope of groundwater risk assessment of inorganic contamination and to discuss soil water sampling methods as alternative.

    Main Features

    First, the theoretical background of leaching tests and the main leaching controlling parameters (pH, redox, ionic strength, reaction kinetics, surface, and speciation) are discussed. Experience with common batch leaching tests (the German DEV S4 test (S4), saturation soil extraction (SSE), ammonia nitrate extraction (ANE), and pHstatic tests) are compiled and an emphasis is set on the comparability of the results of batch leaching tests. Additionally, the comparability between batch tests and column tests is discussed and comparison studies are reviewed. As a feasible alternative, soil water sampling strategies (the suction cup method and centrifugation) are outlined.

    Results and Conclusions

    For an expedient application of leaching tests, it is crucial to identify the main release controlling parameters, which can be both site and contaminant specific. Possible controlling parameters are, for example, pH, redox conditions, specific surface area of the investigated material, liquid to solid-ratio, ionic strength, cation exchange capacity, DOC, speciation, temperature and contact time. It depends on the release process of the contaminant in the investigated material, which parameters are influencing the release predominantly. The following questions have to be answered: Is the release process availability controlled or solubility controlled and are there kinetic limitations? Suction cups are particularly useful for long-term monitoring. In contrast, centrifugation is a fast and simple method to sample soil water also at larger and heterogeneous sites. SSE or similar batch tests for coarse material are suitable if the soil water cannot be investigated directly. Contaminant concentrations of the SSE fit best to contaminant concentrations in soil water compared to other leaching tests. Concentrations measured with S4 tests are usually significantly lower than in real soil water due to the unrealistically high liquid to solid-ratio. The ANE is used for the evaluation of plant uptake. It does not represent realistic soil water concentrations. Cationic contaminants are usually significantly higher concentrated in ANE eluates. pHstatic tests provide an evaluation of the pH dependency of contaminant release and buffer capacity of the investigated material. It provides indications to release processes and often explains deviations in the results of different leaching tests. Previous practical experience and fundamental research studies show that a conversion of leaching test results, as is proposed by the (already withdrawn) DIN V 19735, is impossible. Correlations of results from different methods, regarding different kinds of materials and different sites, are not significant. This is due to different leaching processes.

    Recommendation

    . For short-term risk assessment, soil water should be sampled and investigated directly by suction cups (for monitoring purposes) or centrifugation (for inventory purposes). If this is not possible, the SSE or analogous batch tests for coarse material with a narrow L/S ratio should be applied. A suggestion could be a modified saturation soil extraction where a soil column is saturated and the eluate is removed by suction at the bottom of the column. With this method, an unsaturated column test could follow in the same vessel. In order to assess the long-term leaching behavior, total contents of the investigated material have to be taken into account additionally. Furthermore, it is essential to understand the dominant physical and chemical release processes and to figure out the main leaching controlling parameters. Therefore, the following methods are recommended: pHstatic tests at different pH values provide an insight to leaching processes and possible future leaching scenarios. Batch tests similar to the S4 procedure with different L/S ratios are useful to find out whether the release process is solubility or availability controlled. Additionally, this method allows the determination of maximum solubility and maximum availability, respectively. Furthermore, unsaturated column tests provide an insight into leaching processes and releasable amounts even though they require great experimental effort. Other leaching tests like S4 or ANE are not suitable for the estimation of soil water concentrations.

  • HCHs and DDTs in sediment-dwelling animals from the Yangtze Estuary, China

    Y. Yang, M. Liu, S. Xu, L. Hou, D. Ou, H. Liu, S. Cheng, Thilo Hofmann
    2006 - Chemosphere, 3: 381-389

    Abstract: 

    HCHs and DDTs in sediment-dwelling animals including mollusks and crabs from the Yangtze Estuary were determined by GC-ECD. Levels of t-HCH were in the range of 1.2–5.5 ng g−1 and averaged 3.5 ng g−1 in mollusks, while t-DDT concentrations ranged from 26.0 to 68.8 ng g−1, with a mean of 34.5 ng g−1. In crabs t-HCH concentrations varied from 2.0 to 25.7 ng g−1 and averaged 13.8 ng g−1, whereas the concentrations of t-DDT were in the range of 1.5–24.8 ng g−1 with a mean value of 5.9 ng g−1. The HCHs and DDTs levels depend on geographical position and sources, showing the high levels at fresh water area in the estuary, such as XP, CM and LHK sites, and lower at brackish water area, such as FX site, and little difference between species. Results also indicate there was no significant relationship between t-HCH (t-DDT) concentrations and lipid contents both in mollusks and crabs because of non-equilibrium state under a specific estuarine dynamics; smaller individuals accumulated more HCHs and DDTs than larger individuals of mollusks at LHK site, showing different uptake rate for these pesticides; moreover, HCHs and DDTs levels were lower in female crab bodies than male crab bodies suggesting that the release of spawning. BSAFs (Biota- Sediment Accumulation Factors) from sediment-dwelling animals for HCHs and DDTs show a significant “one high with two low” and “one low with two high” effect in the Yangtze Estuary.

  • Methods of metal release assessment in soil water at anoxic sites

    Nele Schuwirth, Thilo Hofmann
    2006 - Acta hydrochimica et hydrobiologica, 6: 579-586

    Abstract: 

    Metal mobility at contaminated sites can be assessed by soil water investigations or by leaching tests. Leaching tests are usually carried out in open contact with the atmosphere disregarding possible changes of redox conditions. This can affect the original metal speciation and distribution, particularly when anoxic samples are investigated. In this study, the applicability of common leaching tests (the German S4 test (S4), ammonium nitrate extraction (AmmN), and saturation soil extraction (SSE)) is tested for the assessment of zinc release from sulfide‐bearing flotation residues of a former ore mine. Results are compared to soil solution samples obtained by centrifugation and suction cups. The influence of sample storage on S4 leaching test results is investigated in a long‐term study to assess oxidation kinetics. Within the first 200 days the release of zinc increases with a slope of 0.1 mmol kg–1 d–1 or 6.0 mg kg–1 d–1, respectively. Since oxidation of the sulfide‐bearing samples leads to a significant overestimation of metal release, a feasible modification for the conduction of leaching tests for anoxic material is proposed where oxidation is prevented efficiently. The modified SSE is found to be the only of the tested leaching procedures, which can be recommended for the assessment of current soil water concentrations at anoxic sites if direct investigation of the soil water is impossible due to technical reasons.

  • Kolloide: Die vernachlässigten Dimensionen

    2004 - Chemie Unserer Zeit, 24–35

    Abstract: 

    Aquatische Kolloide sind in allen natürlichen Gewässern vorhanden. Sie umfassen anorganische Kolloide wie Tonminerale, organische Kolloide wie Huminstoffe, Mikroorganismen und anthropogen eingetragene Kolloide wie Ruß oder Platin aus Katalysatoren. Kolloide können hydrophobe organische Schadstoffe sorbieren und transportieren oder nachteilig die Wasserqualität beeinflussen (z.B. pathogene Keime). Sie können die Leistung von Brunnen durch Verblockung der Porenräume im Grundwasser mindern. Kolloide können jedoch auch zur Sanierung von Grundwasserschadensfällen eingesetzt (Tenside) oder in der Wasseraufbereitung verwendet werden (Flockungsmittel, Katalysatoren). Kolloide entstehen oder werden mobilisiert durch Verwitterungsprozesse, Umsetzung organischer Substanzen, Auflösungs‐ und Fällungsprozesse sowie hydrochemische und hydraulische Veränderungen. Ihre Stabilität wird maßgeblich von den Oberflächeneigenschaften bestimmt. Viel versprechende neue analytische Techniken wie die Feld‐Fluss‐Fraktionierung, Laserinduzierte Breakdown‐Detektion oder Röntgenmikroskopie werden unser Verständnis von aquatischen Kolloiden in den kommenden Jahren erweitern.

  • Aquatische Kolloide I: Eine Übersichtsarbeit zur Definition, zu Systemen und zur Relevanz

    Thilo Hofmann, Thomas Baumann, Tobias Bundschuh, Frank von der Kammer, Andrew Leis, Daniel Schmitt, Thorsten Schäfer, Jürgen Thieme, Kai-Uwe Totsche, Harald Zänker
    2003 - Grundwasser, 4: 203–212

    Abstract: 

    Kolloide sind Bestandteile aller aquatischen Systeme. Sie umfassen Feststoffe, deren Größe in zumindest einer Dimension zwischen 1 und 1.000 nm liegt. Sie können anorganischer (z. B. Tonteilchen, Karbonate oder Silikate) oder organischer (z. B. Ruß oder höhermolekulare organische Verbindungen wie Huminstoffe) Natur sein. Auch Bakterien, Viren, Sporen und Algen in diesem Größenbereich können zu den Kolloiden gerechnet werden (häufig als “Bio-Kolloide“ bezeichnet). Kolloide können den Transport von (Schad-)stoffen im Untergrund und in Oberflächengewässern beeinflussen, insbesondere von Spurenelementen und hydrophoben organischen Verbindungen, oder zu unerwünschten Effekten wie Porenraumreduktion („Clogging“) führen. Für die Hygiene des Trinkwassers ist das Verhalten von Bakterien, Viren und Sporen (den „Bio-Kolloiden“) von besonderer Bedeutung. Bisher ist das Verhalten von Kolloiden nur unzureichend verstanden. Dieser Artikel soll einen Beitrag zu dem Verständnis des physikalischen Verhaltens der Kolloide, deren Vorkommen in der aquatischen Umwelt sowie Relevanz in Form einer Übersichtsarbeit leisten.

  • Aquatische Kolloide II: Eine bersichtsarbeit zur Probennahme, Probenaufbereitung und Charakterisierung

    Thilo Hofmann, Thomas Baumann, Tobias Bundschuh, Frank von der Kammer, Andrew Leis, Daniel Schmitt, Thorsten Schäfer, Jürgen Thieme, Kai-Uwe Totsche, Harald Zänker
    2003 - Grundwasser, 4: 213-223

    Abstract: 

    Colloids are abundant in all natural aquatic environments; however, the current knowledge on their environmental behaviour, mobilisation, transport, and deposition is considered to be insufficient because of a lack of analytical instrumentation for colloid measurement. Measurement devices are not standard tools, are expensive and in some cases not even available commercially. Furthermore, at present no technique exists to measure simultaneously size distribution over the full colloidal range or concentration, nor which allow for colloid identification at the extremely low concentrations usually found in subsurface aquatic systems. The combination of a range of different techniques is essential if full understanding of aquatic colloids is the objective. Even more challenging is the determination of colloid surface properties. In addition, sampling of colloids is of major concern and standard sampling protocols are not adequate. Special precautions and protocols for colloid sampling have to be applied if natural undisturbed colloids are to be obtained. This paper gives suggestions and protocols for colloid sampling and discusses some of the major techniques from the numerous methods for colloid measurement.

  • Aquatische Kolloide: Kleine Teilchen - große Wirkung

    2001 - Nachrichten aus der Chemie, 49: 1291-1295

    Abstract: 

    Gelöste natürliche und anthropogene (Schad‐)Stoffe verändern die Zusammensetzung eines unserer Hauptnahrungsmittel, des Trinkwassers. Weniger bekannt ist jedoch, dass in jedem aquatischen Milieu auch mobile Feststoffe (Kolloide) die Wasserqualität beeinflussen. Schätzt man den Transport von Bio‐Kolloiden falsch ein, kann dies zu einer unmittelbaren Gefährdung des Trinkwassers führen.

  • The German Water Chemical Society: Actual trends and fields of research in the principle committee "basic research"

    Wolfgang Calmano, Ursula Bilitewski, Hans-Curt Flemming, Thilo Hofmann, Stefan Peiffer, Thomas Ternes, Rolf Dieter Wilken
    2001 - Acta hydrochimica et hydrobiologica, 29: 419-427
  • Behavior of suspended and colloidal particles during artificial groundwater recharge

    Thilo Hofmann, U. Schöttler
    1998 - Colloidal Systems In Environmental Science, 111: 184-188

    Abstract: 

    Transport phenomena in the subsurface environment are often treated on the basis of a two-phase system: an immobile solid phase and a mobile dissolved phase. Many organic and inorganic substances, e.g. PAH, biogen material and heavy metals, have a strong tendency to adsorb readily onto the solid phase, thus, considered to be virtually immobile. However, this solid phase, generally assumed to be immobile, could be mobile as colloidal or suspended particles in the aquifer. These particles can be assumed to be chemically similar to the surface of the aquifer material and hence may have a huge sorption capacity due to their large surface area. Thus, colloidal and suspended particle transport must be taken into consideration in describing and predicting the movement of substances. Particles are abundant in the subsurface environment. Particles are associated with geologic matrices or form due to geochemical reactions. The geochemistry and hydraulic boundary conditions of the aquifer determine the formation, mobilization and transport of particles. They can be mobilized by a hydraulic or geochemical gradient and reach a concentration up to 25 mg/l at the monitored test site “Insel Hengsen” located within the Ruhr valley, Germany.

Book chapters and other publications

7 Publications found
  • Nanoparticle inventory in a sediment core from the Iron Gate I reservoir

    2021 - JDS4 Scientific Report, 501-510

    Abstract: 

    River sediments are a sink for natural and anthropogenic nanoparticles. Given their risk to harm ecosystems and humans the latter are among contaminants of emerging concern. Here we present multi-element single-particle data of a Danube sediment core, aiming to identify anthropogenic nanoparticles and elucidate their occurrence at different sediment depths. A fly ash dump near Kostolac, Serbia, on the right bank of the Danube River is a likely point source of anthropogenic fly ash particles. Kostolac fly ash particles are enriched in elements such as Cu, Ni, and V. The signatures of these elements within nanoparticles of the sediment core reveal four potential events of fly ash release into the Danube.

  • Natürliche Schwebstoffe in Flüssen: Zusammensetzung, Schlüsselkomponenten und Dynamiken

    2021 - Vom Wasser - das Journal, 51-53
  • Comment on Predicting Aqueous Adsorption of Organic Compounds onto Biochars, Carbon Nanotubes, Granular Activated Carbons, And Resins with Machine Learning

    Gabriel Sigmund, Mehdi Gharasoo, Thorsten Hüffer, Thilo Hofmann
    2020 - Environmental Science & Technology, A-B
  • Generalized Guideline for Application of Nanoremediation

    Braun J., Vesna Micić, Thilo Hofmann, et all
    2017 - in press
  • Stability, Mobility, Delivery and Fate of optimized NPs under Field Relevant Conditions

    2016 - in press
  • Alkylphenolic Compounds in the Danube River

    2015 - in The Handbook of Environmental Chemistry: The Danube River Basin. (Igor Liska). Springer-Verlag Berlin Heidelberg

    Abstract: 

    This volume offers a comprehensive review of the chemical, biological and hydromorphological quality of the Danube. The first part examines the chemical pollution of surface waters, focusing on organic compounds (with special emphasis given to EU WFD priority substances and Danube River Basin specific pollutants), heavy metals and nutrients. Attention is also given to pollution of groundwater and drinking water resources by hazardous substances and to radioactivity in the Danube. The second part highlights the biology and hydromorphology of the Danube. It focuses on benthic macroinvertebrates, phytobenthos, macrophytes, fish, phytoplankton as well as microbiology, with chapters dedicated to gaps and uncertainties in the ecological status assessment and to invasive alien species. Further chapters dealing with the hydromorphology, sediment management and isotope hydrology complete the overall picture of the status of the Danube.

  • EU WFD organic priority substances in water, suspended particulate matter, sediments and biota and other organic pollutants

    Manfred Sengl, Vesna Micić, Thilo Hofmann
    2008 - Joint Danube Survey 2 Final Scientific Report, 132-146