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Publications in peer reviewed journals

26 Publications found
  • Antimonite Binding to Natural Organic Matter: Spectroscopic Evidence from a Mine Water Impacted Peatland

    Johannes Besold, Anne Eberle, Vincent Noël, Katharina Kujala, Naresh Kumar, Andreas C. Scheinost, Juan Lezama Pacheco, Scott Fendorf, Britta Planer-Friedrich
    2019 - Environmental Science & Technology, 53: 10792-10802


    Peatlands and other wetlands are sinks for antimony (Sb), and solid natural organic matter (NOM) may play an important role in controlling Sb binding. However, direct evidence of Sb sequestration in natural peat samples is lacking. Here, we analyzed solid phase Sb, iron (Fe), and sulfur (S) as well as aqueous Sb speciation in three profiles up to a depth of 80 cm in a mine water impacted peatland in northern Finland. Linear combination fittings of extended X-ray absorption fine structure spectra showed that Sb binding to Fe phases was of minor importance and observed only in the uppermost layers of the peatland. Instead, the dominant (to almost exclusive) sequestration mechanism was Sb(III) binding to oxygen-containing functional groups, and at greater depths, increasingly Sb(III) binding to thiol groups of NOM. Aqueous Sb speciation was dominated by antimonate, while antimonite concentrations were low, further supporting our findings of much higher reactivity of Sb(III) than Sb(V) toward peat surfaces. Insufficient residence time for efficient reduction of antimonate to antimonite currently hinders higher Sb removal in the studied peatland. Overall, our findings imply that Sb(III) binding to solid NOM acts as an important sequestration mechanism under reducing conditions in peatlands and other high-organic matter environments.

  • Antimonite Complexation with Thiol and Carboxyl/Phenol Groups of Peat Organic Matter

    Johannes Besold, Naresh Kumar, Andreas C. Scheinost, Juan Lezama Pacheco, Scott Fendorf, Britta Planer-Friedrich
    2019 - Environmental Science & Technology, 53: 5005-5015


    Peatlands and other wetlands with abundant natural organic matter (NOM) are important sinks for antimony (Sb). While formation of Sb(III) sulfide phases or Sb(III) binding to NOM are discussed to decrease Sb mobility, the exact binding mechanisms remain elusive. Here, we reacted increasing sulfide concentrations with purified model peat at pH 6, forming reduced organic sulfur species, and subsequently equilibrated the reaction products with 50 μM of antimonite under anoxic conditions. Sulfur solid-phase speciation and the local binding environment of Sb were analyzed using X-ray absorption spectroscopy. We found that 85% of antimonite was sorbed by untreated peat. Sulfide-reacted peat increased sorption to 98%. Shell-by-shell fitting of Sb K-edge X-ray absorption fine structure spectra revealed Sb in untreated peat bound to carboxyl or phenol groups with average Sb–carbon distances of ∼2.90 Å. With increasing content of reduced organic sulfur, Sb was progressively coordinated to S atoms at distances of ∼2.45 Å and Sb–carbon distances of ∼3.33 Å, suggesting increasing Sb–thiol binding. Iterative target factor analysis allowed exclusion of reduced inorganic Sb–sulfur phases with similar Sb–sulfur distances. In conclusion, even when free sulfide concentrations are too low for formation of Sb–sulfur precipitates, peat NOM can sequester Sb in anoxic, sulfur-enriched environments.

  • Are we speaking the same language? Recommendations for a definition and categorisation framework for plastic debris

    Nanna B. Hartmann, Thorsten Hüffer, Richard C. Thompson, Martin Hassellv, Anja Verschoor, Anders E. Daugaard, Sinja Rist, Therese Karlsson, Nicole Brennholt, Matthew Cole, Maria P. Herrling, Maren C. Hess, Natalia P. Ivleva, Amy L. Lusher, Martin Wagner
    2019 - Environmental Science & Technology, 3: 1039-1047


    The accumulation of plastic litter in natural environments is a global issue. Concerns over potential negative impacts on the economy, wildlife, and human health provide strong incentives for improving the sustainable use of plastics. Despite the many voices raised on the issue, we lack a consensus on how to define and categorize plastic debris. This is evident for microplastics, where inconsistent size classes are used and where the materials to be included are under debate. While this is inherent in an emerging research field, an ambiguous terminology results in confusion and miscommunication that may compromise progress in research and mitigation measures. Therefore, we need to be explicit on what exactly we consider plastic debris. Thus, we critically discuss the advantages and disadvantages of a unified terminology, propose a definition and categorization framework, and highlight areas of uncertainty. Going beyond size classes, our framework includes physicochemical properties (polymer composition, solid state, solubility) as defining criteria and size, shape, color, and origin as classifiers for categorization. Acknowledging the rapid evolution of our knowledge on plastic pollution, our framework will promote consensus building within the scientific and regulatory community based on a solid scientific foundation.

  • 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


    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.

  • Characterization of sorption properties of high-density polyethylene using the poly-parameter linearfree-energy relationships

    Tobias H. Uber, Thorsten Hüffer, Sibylle Planitz, Torsten C. Schmidt
    2019 - Environmental Pollution, 312-319


    High-density polyethylene (HDPE) is a known sorbent for non-ionic organic compounds in technical applications. Nevertheless, there is little information available describing sorption to industrial HDPE for a broad range of compounds. With a better understanding of the sorption properties of synthetic polymers, environmental risk assessment would achieve a higher degree of accuracy, especially for microplastic interactions with organic substances. Therefore, a robust methodology for the determination of sorbent properties for non-ionic organic compounds by HDPE is relevant for the understanding of molecular interactions for both technical use and environmental risk assessment.

    In this work, sorption properties of HDPE material used for water pipes were characterized using a poly-parameter linear free-energy relationship (ppLFER) approach. Sorption batch experiments with selected probe sorbates were carried out in a three-phase system (air/HDPE/water) covering an aqueous concentration range of at least three orders of magnitude. Sorption in the concentration range below 10−2 of the aqueous solubility was found to be non-linear and the Freundlich model was used to account for this non-linearity. Multiple regression analysis (MRA) using the determined distribution coefficients and literature-tabulated sorbate descriptors was performed to obtain the ppLFER phase descriptors for HDPE. Sorption properties of HDPE were then derived from the ppLFER model and statistical analysis of its robustness was conducted. The derived ppLFER model described sorption more accurately than commonly used single-parameter predictions, based i.e., on log Ko/w. The ppLFER predicted distribution data with an error 0.5 log units smaller than the spLFERs. The ppLFER was used for a priori prediction of sorption by the characterized sorbent material. The prediction was then compared to experimental data from literature and this work and demonstrated the strength of the ppLFER, based on the training set over several orders of magnitude.

  • 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


    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


    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.

  • Determination of nanoparticle heteroaggregation attachment efficiencies and rates in presence of natural organic matter monomers. Monte Carlo modelling

    Arnaud Clavier, Antonia Praetorius, Serge Stoll
    2019 - Science of The Total Environment, 530-540


    Understanding the transformation and transport of manufactured nanoparticles (NPs) in aquatic systems remains an important issue due to their potential hazard. Once released in aquatic systems, NPs will interact with natural compounds such as suspended inorganic particles and/or natural organic matter (NOM) and heteroaggregation will control their ultimate fate. Unfortunately, systematic experimental methods to study heteroaggregation are not straightforward and still scarce. In addition, the description of heteroaggregation rate constants and attachment efficiencies is still a matter of debate since no clear definition exists.

    In this work, an original cluster-cluster Monte Carlo model is developed to get an insight into heteroaggregation process descriptions. A two-component system composed of NPs and NOM fulvic acid monomers is investigated by considering several water models to cover a range of (relevant) conditions from fresh to marine waters. For that purpose, homo- and hetero- individual attachment efficiencies between NPs and NOM units are adjusted (NP-NP, NOM-NOM and NP-NOM). The influence of NP/NOM ratio, NOM-NOM homoaggregation versus heteroaggregation, and surface coating effects is studied systematically. From a quantitative point of view, aggregation rate constants as well as attachment efficiencies are calculated as a function of physical time so as to characterize the individual influence of each parameter and to allow future comparison with experimental data. Heteroaggregation processes and global attachment efficiencies corresponding to several mechanisms and depending on the evolution of heteroaggregate structures all along the simulations are defined. The calculation of attachment efficiency values is found dependent on NP/NOM concentration ratios via coating effects, by the initial set of elementary attachment efficiencies and influence of homoaggregation.

    Marine water represents a specific case of aggregation where all particle contacts are effective. On the other hand, in “ultrapure” and “fresh waters”, a competition between homo- and heteroaggregation occurs depending on the initial attachment efficiencies therefore indicating that a subtle change in the NP surface properties as well as in the water chemistry have a significant impact on heteroaggregation processes.

  • 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


    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.

  • Improved extraction efficiency of natural nanomaterials in soils to facilitate their characterization using a multimethod approach

    Frédéric Loosli, Zebang Yi, Jingjing Wang, Mohammed Baalousha
    2019 - Science of The Total Environment, 677: 34-46


    Characterization of natural nanomaterial (NNM) physicochemical properties – such as size, size distribution, elemental composition and elemental ratios - is often hindered by lack of methods to disperse NNMs from environmental samples. This study evaluates the effect of extractant composition, pH, and ionic strength on soil NNM extraction in term of recovery and release of primary particles/small aggregate sizes (i.e., <200 nm). The extracted NNMs were characterized for hydrodynamic diameter and zeta potential by dynamic light scattering and laser Doppler electrophoresis, natural organic matter desorption by UV–Vis spectroscopy, element composition by inductively coupled plasma-mass spectroscopy (ICP-MS), size based elemental distribution by field flow fractionation coupled to ICP-MS, and morphology by transmission electron microscopy. The extracted NNM concentrations increased following the order of NaOH ≤ Na2CO3 < Na2C2O4 < Na4P2O7. Na4P2O7 was the most efficient extractant and results in 2–12 folds higher NNM extraction than other extractants. The Na4P2O7 extracted NNMs exhibited narrower size distribution with smaller modal size relative to NaOH, Na2CO3, Na2C2O4 extracted NNMs. Thus, Na4P2O7 enhances the extraction of primary NNMs and/or smaller NNM aggregates (i.e., size <200 nm). Na4P2O7 promote soil microaggregates breakup and release of NNMs by reducing free multivalent cation concentration in soil pore water by forming metal-phosphate complexes and by enhancing NNM surface charge via phosphate sorption on NNM surfaces. Additionally, the extracted NNM concentrations increased with the increase in extractant concentration and pH, except at 100 mM where the high ionic strength might have induced NNM aggregation. The improved NNM-extraction will improve the overall understanding of the physicochemical properties of NNMs in environmental systems. This study presents the key properties of NNMs that can be used as background information to differentiate engineered nanomaterials (ENMs) from NNMs in complex environmental media.

  • 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


    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


    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.

  • Mercury Isotope Fractionation in the Subsurface of a Hg(II) Chloride-Contaminated Industrial Legacy Site

    Flora M. Brocza, Harald Biester, Jan-Helge Richard, Stephan M. Kraemer, Jan G. Wiederhold
    2019 - Environmental Science & Technology, 13: 7296-7305


    To understand the transformations of mercury (Hg) species in the subsurface of a HgCl2-contaminated former industrial site in southwest Germany, Hg isotope analysis was combined with an investigation of Hg forms by a four-step sequential extraction protocol (SEP) and pyrolytic thermodesorption. Data from two soil cores revealed that the initial HgCl2was partly reduced to metallic Hg(0) and that Hg forms of different mobility and oxidation state coexist in the subsurface. The most contaminated sample (K2-8, 802 mg kg–1 Hg) had a bulk δ202Hg value of around −0.43 ± 0.06‰ (2SD), similar to published average values for industrial Hg sources. Other sample signatures varied significantly with depth and between SEP pools. The most Hg-rich samples contained mixtures of Hg(0) and Hg(II) phases, and the water-extractable, mobile Hg pool exhibited heavy δ202Hg values of up to +0.18‰. Sequential water extracts revealed slow dissolution kinetics of mobile Hg pools, continuously releasing isotopically heavy Hg into solution. This was further corroborated by heavy δ202Hg values of groundwater samples. Our results demonstrate that the Hg isotope signature of an industrial contamination source can be significantly altered during the transformations of Hg species in the subsurface, which complicates source tracing applications but offers the possibility of using Hg isotopes as process tracers in contaminated subsurface systems.

  • 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


    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.

  • Models for assessing engineered nanomaterial fate and behaviour in the aquatic environment

    Richard J Williams, Samuel Harrison, Virginie Keller, Jeroen Kuenen, Stephen Lofts, Antonia Praetorius, Claus Svendsen, Lucie C Vermeulen, Jikke van Wijnen
    2019 - Current Opinion in Environmental Sustainability, 105-115


    Engineered nanomaterials (ENMs, material containing particles with at least one dimension less than 100 nm) are present in a range of consumer products and could be released into the environment from these products during their production, use or end-of-life. The high surface to volume ratio of nanomaterials imparts a high reactivity, which is of interest for novel applications but may raise concern for the environment. In the absence of measurement methods, there is a need for modelling to assess likely concentrations and fate arising from current and future releases. To assess the capability that exists to do such modelling, progress in modelling ENM fate since 2011 is reviewed. ENM-specific processes represented in models are mainly limited to aggregation and, in some instances, dissolution. Transformation processes (e.g. sulphidation), the role of the manufactured coatings, particle size distribution and particle form and state are still usually excluded. Progress is also being made in modelling ENMs at larger scales. Currently, models can give a reasonable assessment of the fate of ENMs in the environment, but a full understanding will likely require fuller inclusion of these ENM-specific processes.

  • 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


    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.

  • Opportunities for examining the natural nanogeochemical environment using recent advances in nanoparticle analysis

    Manuel D. Montaño, Frank von der Kammer, Chad W. Cuss, James F. Ranville
    2019 - Journal of Analytical Atomic Spectrometry, 34: 1768-1772


    The characterization of engineered nanoparticles (ENPs) has been a main pillar in the advancement of nanotechnology in recent decades. Because the properties of ENPs are closely linked to their size, shape, morphology, and surface coatings, development of nanoanalysis methods capable of assessing these parameters was necessary. Many advanced instruments and data analysis tools have now been established for analysis of ENPs in complex matrices, providing a comprehensive assessment of not only their intended virtues, but also the unintended consequences of their manufacture, use, and disposal. Current generation electron microscopy enables atom-scale imaging. Hyphenated (FFF-ICP-MS), and single particle (spICP-MS) techniques now possess the requisite sensitivity and elemental selectivity to quantify and characterize inorganic ENPs. These tools also provide a means to examine processes involving naturally-occurring nanoparticles (NNPs) to a degree not previously attainable. Though colloids and nanominerals have been investigated for decades, modern nanoanalysis offers a wealth of opportunities to improve our understanding of the natural nanogeochemical environment. Applying nanoanalysis on a single particle basis may lead to a more mechanistic understanding of particle formation and reactivity, global biogeochemical cycling, quantifying nanoparticle transport and impacts as they relate to hydrochemical and geochemical factors, and possibly differentiating ENPs from NNPs.

  • 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


    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


    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 non-ionic organic compounds by polystyrene in water

    Tobias H. Uber, Thorsten Hüffer, Sibylle Planitz, Thorsten C. Schmidt
    2019 - Science of The Total Environment, 682: 348-355


    Polystyrene (PS) is a plastic material that is well known for its use in many different applications, e.g. as shock sensitive packaging.With its prevalence across society, PS contributes significantly to the overall plastic load in aqueous systems. Sorption of organic compounds by the plastics, especiallymicrometer-sized particles, in the environment has become a concern in the past years. The aim of this study was to improve the understanding of sorption properties of PS, one of the major plastic pollutants in the aqueous environment. Batch experiments with PS film (29 μmthickness)were performed for 4 days using a diverse set of 24 sorbates to account for varying molecular properties like polarity or molecular volume. Isotherms were evaluated using different sorption models to elucidate the sorption process of PS. Sorption to PS film was non-linear and absorption into the bulk materialwas the dominant sorption mode. A clear discrimination between the specific and non-specific interactions in the aqueous environment could be shown. The non-linear sorption to PS was shown to be controlled by themolar volume but also by the polarizability/dipolarity parameter (S) of the ppLFER model. The latter is influenced
    by the aromaticπ-π-interactions of PSwith the sorbate. Similar to other plastics like polyethylene, sorption to PS is driven by hydrophobic interactions but phase descriptors of pristine PS were significantly different than descriptors for other environmental relevant plastics.

  • 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


    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


    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 Carbon-Isotope Record of the Sub-Seafloor Biosphere

    Patrick Meister, Carolina Reyes
    2019 - Geosciences, 9: 507


    Sub-seafloor microbial environments exhibit large carbon-isotope fractionation effects as a result of microbial enzymatic reactions. Isotopically light, dissolved inorganic carbon (DIC) derived from organic carbon is commonly released into the interstitial water due to microbial dissimilatory processes prevailing in the sub-surface biosphere. Much stronger carbon-isotope fractionation occurs, however, during methanogenesis, whereby methane is depleted in 13C and, by mass balance, DIC is enriched in 13C, such that isotopic distributions are predominantly influenced by microbial metabolisms involving methane. Methane metabolisms are essentially mediated through a single enzymatic pathway in both Archaea and Bacteria, the Wood–Ljungdahl (WL) pathway, but it remains unclear where in the pathway carbon-isotope fractionation occurs. While it is generally assumed that fractionation arises from kinetic effects of enzymatic reactions, it has recently been suggested that partial carbon-isotope equilibration occurs within the pathway of anaerobic methane oxidation. Equilibrium fractionation might also occur during methanogenesis, as the isotopic difference between DIC and methane is commonly on the order of 75‰, which is near the thermodynamic equilibrium. The isotopic signature in DIC and methane highly varies in marine porewaters, reflecting the distribution of different microbial metabolisms contributing to DIC. If carbon isotopes are preserved in diagenetic carbonates, they may provide a powerful biosignature for the conditions in the deep biosphere, specifically in proximity to the sulphate–methane transition zone. Large variations in isotopic signatures in diagenetic archives have been found that document dramatic changes in sub-seafloor biosphere activity over geological time scales. We present a brief overview on carbon isotopes, including microbial fractionation mechanisms, transport effects, preservation in diagenetic carbonate archives, and their implications for the past sub-seafloor biosphere and its role in the global carbon cycle. We discuss open questions and future potentials of carbon isotopes as archives to trace the deep biosphere through time.

  • 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


    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 Effect of pH and biogenic ligands on the weathering of chrysotile asbestos: The pivotal role of tetrahedral Fe in dissolution kinetics and radical formation

    Martin Walter, Walter D. C. Schenkeveld, Michael Reissner, Lars Gille, Stephan M. Kraemer
    2019 - Chemistry A European Journal, 13: 3286-3300


    Chrysotile asbestos is a soil pollutant in many countries. It is a carcinogenic mineral, partly due to its surface chemistry. In chrysotile, FeII and FeIII substitute Mg octahedra (Fe[6]), and FeIII substitutes Si tetrahedra (Fe[4]). Fe on fiber surfaces can generate hydroxyl radicals (HO.) in Fenton reactions, which damage biomolecules. To better understand chrysotile weathering in soils, net Mg and Si dissolution rates over the pH range 3.0–11.5 were determined in the presence and absence of biogenic ligands. Also, HO. generation and Fe bulk speciation of pristine and weathered fibers were examined by EPR and Mössbauer spectroscopy. Dissolution rates were increased by ligands and inversely related to pH with complete inhibition at cement pH (11.5). Surface‐exposed Mg layers readily dissolved at low pH, but only after days at neutral pH. On longer timescales, the slow dissolution of Si layers became rate‐determining. In the absence of ligands, Fe[6] precipitated as Fenton‐inactive Fe phases, whereas Fe[4] (7 % of bulk Fe) remained redox‐active throughout two‐week experiments and at pH 7.5 generated 50±10 % of the HO. yield of Fe[6] at pristine fiber surfaces. Ligand‐promoted dissolution of Fe[4] (and potentially Al[4]) labilized exposed Si layers. This increased Si and Mg dissolution rates and lowered HO. generation to near‐background level. It is concluded that Fe[4] surface species control long‐term HO. generation and dissolution rates of chrysotile at natural soil pH.

  • 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


    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

Book chapters and other publications

1 Publication found
  • Response to the Letter to the Editor Regarding Our Feature “Are We Speaking the Same Language? Recommendations for a Definition and Categorization Framework for Plastic Debris”

    Nanna B. Hartmann, Thorsten Hüffer, Richard C. Thompson, Martin Hassellöv, Anja Verschoor, Anders E. Daugaard, Sinja Rist, Therese Karlsson, Nicole Brennholt, Matthew Cole, Maria P. Herrling, Maren C. Hess, Natalia P. Ivleva, Amy L. Lusher, Martin Wagner
    2019 - Environmental Science & Technology, 53: 4678−4679