Publications

Engineered and incidental nanomaterials are emerging contaminants of environmental concern. In aquatic systems, their transport, fate, and bioavailability strongly depend on heteroagglomeration with natural suspended particulate matter (SPM). Since particulate contaminants underlie different mechanisms than dissolved contaminants, harmonized, particle-specific test systems and protocols are needed for environmental risk assessment and for the comparability of environmental fate studies. The heteroagglomeration attachment efficiency (α_het) can parametrize heteroagglomeration in fate models which inform exposure assessment. It describes the attachment probability upon nanomaterial-SPM collision and reflects the physicochemical affinity between their surfaces. This work introduces a new versatile test system to determine α_het under environmentally relevant conditions. The test matrix combines model SPM analogs and an adjustable model hydrochemistry, both designed to represent the process-relevant characteristics of natural freshwater systems, while being standardizable and reproducible. We developed a stirred-batch method that addresses shortcomings of existing strategies for α_het determination and conducted heteroagglomeration experiments with CeO2 (<25 nm) as a model nanomaterial. Single-particle ICP-MS allowed working at environmentally relevant concentrations and determination of α_het values by following the decrease of non-reacted nanomaterial over time. The α_het values received for the model freshwater test matrix were evaluated against a natural river-water sample. Almost identical α_het values show that the model test system adequately reflects the natural system, and the experimental setup proved to be robust and in line with the theoretical concept for α_het determination. Combinations of natural SPM in model water and model SPM in natural water allowed further insight into their respective impacts. The α_het values determined for nano-CeO2 in the natural river water sample (0.0044-0.0051) translate to a travel distance of 143-373 km downstream until 50% is heteroagglomerated, assuming an average flow velocity of 5 km h^-1 and an SPM concentration of 20-45 mg L^-1. These half-lives illustrate the importance of heteroagglomeration kinetics.

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.

This study describes an interlaboratory comparison (ILC) among nine (9) laboratories to evaluate and validate
the standard operation procedure (SOP) for single-particle (sp) ICP-TOFMS developed within the
context of the Horizon 2020 project ACEnano. The ILC was based on the characterization of two different Pt
nanoparticle (NP) suspensions in terms of particle mass, particle number concentration, and isotopic composition.
The two Pt NP suspensions were measured using icpTOF instruments (TOFWERK AG, Switzerland). Two Pt NP samples were characterized and mass equivalent spherical sizes (MESSs) of 40.4 ± 7 nm and 58.8 ± 8 nm were obtained, respectively. MESSs showed <16% relative standard deviation (RSD) among all participating labs and <4% RSD after exclusion of the two outliers. A good agreement was achieved between the different participating laboratories regarding particle mass, but the particle number concentration results were more scattered, with <53% RSD among all laboratories, which is consistent with results from previous ILC studies conducted using ICP-MS instrumentation equipped with a sequential mass spectrometer. Additionally, the capabilities of sp-ICP-TOFMS to determine masses on a particle basis are discussed with respect to the potential for particle density determination. Finally, because quasi-simultaneous multi-isotope and multielement determinations are a strength of ICP-TOFMS instrumentation, the precision and trueness of isotope ratio determinations were assessed. The average of 1000 measured particles yielded a precision of below ±1% for intensity ratios of the most abundant Pt isotopes, i.e. 194Pt and 195Pt, while the accuracy of isotope ratios with the lower abundant isotopes was limited by counting statistics.

Over the recent years, EU chemicals legislation, guidance and test guidelines have been developed or adapted for nanomaterials to facilitate safe use of nanomaterials. This paper provides an overview of the information requirements across different EU regulatory areas. For each information requirement, a group of 22 experts identified potential needs for further action to accommodate guidance and test guidelines to nanomaterials. Eleven different needs for action were identified, capturing twenty-two information requirements that are specific to nanomaterials and relevant to multiple regulatory areas. These were further reduced to three overarching issues: 1) resolve issues around nanomaterial dispersion stability and dosing in toxicity testing, in particular for human health endpoints, 2) further develop tests or guidance on degradation and transformation of organic nanomaterials or nanomaterials with organic components, and 3) further develop tests and guidance to measure (a)cellular reactivity of nanomaterials. Efforts towards addressing these issues will result in better fit-for-purpose test methods for (EU) regulatory compliance. Moreover, it secures validity of hazard and risk assessments of nanomaterials. The results of the study accentuate the need for a structural process of identification of information needs and knowledge generation, preferably as part of risk governance and closely connected to technological innovation policy.

The environmental mobility of Cu and therefore its potential toxicity are closely linked to its attachment to natural organic matter (NOM). Geochemical models assume full lability of metals bound to NOM, especially under strong oxidizing conditions, which often leads to an overestimation of the lability of soil metals. Stable isotope dilution (SID) has been successfully applied to estimate the labile (isotopically exchangeable) pool of soil metals. However, its application to study the lability of NOM-Cu required development of a robust separation and detection approach so that free Cu ions can be discriminated from (the also soluble) NOM-Cu. We developed a SID protocol (with enriched ⁶⁵Cu) to quantify the labile pool of NOM-Cu using size exclusion chromatography coupled to a UV detector (for the identification of different NOM molecular weights) and ICP-MS (for ⁶⁵Cu/⁶³Cu ratio measurement). The Cu isotopic-exchange technique was first characterized and verified using standard NOM (SR-NOM) before applying the developed technique to an “organic-rich” podzol soil extract. The developed protocol indicated that, in contrast to the common knowledge, significant proportions of SR-NOM-Cu (25%) and soil organic-Cu (55%) were not labile, i.e., permanently locked into inaccessible organic structures. These findings need to be considered in defining Cu interactions with the reactive pool of NOM using geochemical models and risk evaluation protocols in which complexed Cu has always been implicitly assumed to be fully labile and exchangeable with free Cu ions.

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 (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.

Particulate emissions from vehicle exhaust catalysts are the primary contributors to platinum group elements (PGEs) being released into roadside environments, especially platinum (Pt) particles. With increasing traffic density, it is essential to quantify the emission, accumulation, and potential health effects of traffic-emitted Pt particles. In this study, three procedures were investigated to extract Pt nanoparticles (NPs) from sediments and characterize them by single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOF-MS). For this purpose, a reference sediment sample was spiked with manufactured Pt NPs. Pt NPs’ extraction recoveries reached from 50% up to 102%, depending on the extraction procedure and whether the particle mass or number was used as the metric. Between 17% and 35% of the Pt NPs were found as unassociated Pt NPs and between 31% and 78% as Pt NPs hetero-aggregated with other sediment particles. Multi-elemental analysis of Pt-containing NPs in the pristine sediment revealed frequently co-occurring elements such as Au, Bi, and Ir, which can be used to determine a natural background baseline. Our results demonstrated that spICP-TOF-MS elemental characterization allows for distinguishing anthropogenic Pt NPs from the natural background. In the future, this could enable the sensitive monitoring of PGE release from anthropogenic sources such as vehicle exhausts.

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.

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.

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.

Foraminifera are unicellular organisms and play a pivotal role in the marine material cycles. Past observations have shown that the species Elphidium excavatum is the most common foraminifera in the Baltic Sea. Feeding experiments showed that the food uptake and thus the turnover of organic matter are influenced by changes of physical parameters (e.g., temperature, salinity). Since many areas of the Baltic Sea are strongly affected by anthropogenic activity and are strongly contaminated by heavy elements from shipping in the past, this study examined the effect of heavy elements pollution on the food uptake of the most common foraminiferal species of the Baltic Sea, E. excavatum which was a subject of several previous studies. Therefore, Baltic Sea seawater was enriched with metals at various levels above normal seawater levels and the uptake of ¹³C- and ¹⁵N-labelled phytodetritus was measured by isotope ratio mass spectrometry. For each combination of metal type, concentration and time point 20 individuals of E. excavatum (three replicates) were fed with the green algae Dunaliella tertiolecta. The effect of dose parameters was measured in a two-way analysis of variance. Significant differences of food uptake were observable at different types and levels of heavy elements in sea water. Even a 557-fold increase in the Pb concentration did not affect food uptake, whereas strong negative effects were found for higher levels of Zn (144 and 1044-fold) and especially for Cu (5.6 and 24.3-fold). In summary it can be stated, that an increase in the heavy elements pollution in the Kiel Fjord will lead to a significant reduction in the turnover of organic matter by foraminifera such as E. excavatum.

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.

A systematic study on the colloidal behavior of uncoated and polyvinylpyrrolidone (PVP) coated TiO₂ engineered nanomaterials (ENMs) in simulated aqueous media is herein reported, in which conditions representative for natural waters (pH, presence of divalent electrolytes (i.e. Ca²⁺/Mg²⁺ and SO₄²⁻), of natural organic matter (NOM) and of suspended particulate matter (SPM)) were systematically varied. The colloidal stability of the different dispersions was investigated by means of Dynamic and Electrophoretic Light Scattering (DLS and ELS) and Centrifugal Separation Analysis (CSA), and a global stability index based on these three techniques was developed. The index allows to quantitatively classify the nano-based dispersions according to their colloidal stability affected by the different parameters studied. This multimethod approach clearly identifies inorganic SPM followed by divalent electrolytes as the main natural components destabilizing TiO₂ ENMs upon entering in simulated natural waters, while it highlights a moderate stabilization induced by NOM, depending mainly on pH. Moreover, the PVP coating was found to attenuate the influence of these parameters on the colloidal stability. The obtained results show how the global stability index developed is influenced by the complexity of the system, suggesting the importance of combining the information gathered from all the techniques employed to better elucidate the fate and behavior of ENMs in natural surface waters.

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 (Fe_tot) 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.

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.

The chemical composition and properties of environmental media determine nanomaterial (NM) transport, fate, biouptake, and organism response. To compare and interpret experimental data, it is essential that sufficient context be provided for describing the physical and chemical characteristics of the setting in which a nanomaterial may be present. While the nanomaterial environmental, health and safety (NanoEHS) field has begun harmonization to allow data comparison and re-use (e.g. using standardized materials, defining a minimum set of required material characterizations), there is limited guidance for standardizing test media. Since most of the NM properties driving environmental behaviour and toxicity are medium-dependent, harmonization of media is critical. A workshop in March 2016 at Duke University identified five categories of test media: aquatic testing media, soil and sediment testing media, biological testing media, engineered systems testing media and product matrix testing media. For each category of test media, a minimum set of medium characteristics to report in all NM tests is recommended. Definitions and detail level of the recommendations for specific standardized media vary across these media categories. This reflects the variation in the maturity of their use as a test medium and associated measurement techniques, variation in utility and relevance of standardizing medium properties, ability to simplify standardizing reporting requirements, and in the availability of established standard reference media. Adoption of these media harmonization recommendations will facilitate the generation of integrated comparable datasets on NM fate and effects. This will in turn allow testing of the predictive utility of functional assay measurements on NMs in relevant media, support investigation of first principles approaches to understand behavioral mechanisms, and support categorization strategies to guide research, commercial development, and policy.

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.

Nanotechnology is identified as a key enabling technology due to its potential to contribute to economic growth and societal well-being across industrial sectors. Sustainable nanotechnology requires a scientifically based and proportionate risk governance structure to support innovation, including a robust framework for environmental risk assessment (ERA) that ideally builds on methods established for conventional chemicals to ensure alignment and avoid duplication. Exposure assessment developed as a tiered approach is equally beneficial to nano-specific ERA as for other classes of chemicals. Here we present the developing knowledge, practical considerations and key principles need to support exposure assessment for engineered nanomaterials for regulatory and research applications.

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.

Emissions of Ce from anthropogenic activities (anthropogenic Ce) into urban wastewater systems and the environment result from its widespread industrial use (abrasives, catalysts, nanotechnology). Because Ce in sewage sludge can also be of geogenic origin, the quantification of anthropogenic Ce in sewage sludge remains elusive. In this study, we evaluated the suitability of Ce oxidation state and rare earth element (REE) patterns for the quantification of anthropogenic Ce fractions in sewage sludge. A diverse set of soil samples served to gain baseline information on geogenic Ce. Geogenic Ce in the soils was characterized by high Ce(III) fractions (≥70%) and their REE patterns were comparable to the REE patterns of the upper continental crust. The sewage sludges contained on average ∼80% Ce(IV) (range 18–108%), pointing to the importance of anthropogenic inputs of Ce(IV). The quantification of the anthropogenic Ce fraction based on Ce oxidation state, however, was associated with considerable uncertainty because geogenic and anthropogenic Ce cannot exclusively be assigned to Ce(III) and Ce(IV), respectively. The REE patterns of most sewage sludges indicated a clear enrichment of Ce compared to heavier REE. Based on the assumption that the industrially used Ce is free of (most) other REE, we estimated the fraction of anthropogenic Ce in the sludges based on individual Ce/REE ratios. For the individual sludges the anthropogenic contributions were very variable (10–100%) but consistent fractions were obtained for individual sludges when calculated based on Ce/Dy (dysprosium), Ce/Er (erbium) and Ce/Eu (europium) ratios. Electron microscopy analysis of sludges dominated by anthropogenic Ce revealed that the Ce was mostly contained in nanoscale particles devoid of elements characteristic of Ce-bearing minerals. Thus, anthropogenic Ce contents derived from REE patterns may be used to validate current mass flow models for engineered CeO₂ nanoparticles.

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.

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.

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.

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®.

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.

Nanoenabled products (NEPs) have numerous outdoor uses in construction, transportation or consumer scenarios, and there is evidence that their fragments are released in the environment at low rates. We hypothesized that the lower surface availability of NEPs fragment reduced their environmental effects with respect to pristine nanomaterials. This hypothesis was explored by testing fragments generated by intentional micronisation (“the SUN approach”; Nowack et al. Meeting the Needs for Released Nanomaterials Required for Further Testing: The SUN Approach. Environmental Science & Technology, 2016 (50), 2747). The NEPs were composed of four matrices (epoxy, polyolefin, polyoxymethylene, and cement) with up to 5% content of three nanomaterials (carbon nanotubes, iron oxide, and organic pigment). Regardless of the type of nanomaterial or matrix used, it was observed that nanomaterials were only partially exposed at the NEP fragment surface, indicating that mostly the intrinsic and extrinsic properties of the matrix drove the NEP fragment toxicity. Ecotoxicity in multiple assays was done covering relevant media from terrestrial to aquatic, including sewage treatment plant (biological activity), soil worms (Enchytraeus crypticus), and fish (zebrafish embryo and larvae and trout cell lines). We designed the studies to explore the possible modulation of ecotoxicity by nanomaterial additives in plastics/polymer/cement, finding none. The results support NEPs grouping by the matrix material regarding ecotoxicological effect during the use phase. Furthermore, control results on nanomaterial-free polymer fragments representing microplastic had no significant adverse effects up to the highest concentration tested.

Titanium dioxide (TiO₂) based nanomaterials (NMs) are among the most produced NMs worldwide. When irradiated with light, particularly UV, TiO₂ is photoactive, a property that is explored for several purposes. There are an increasing number of reports on the negative effects of photoactivated TiO₂ on non-target organisms. We have here studied the effect of a suite of reference type TiO₂ NMs (i.e. NM103, NM104, and NM105 and compared these to the bulk) with and without UV radiation to the oligochaete Enchytraeus crypticus. High-throughput gene expression was used to assess the molecular mechanisms, while also anchoring it to the known effects at the organism level (i.e., reproduction). Results showed that the photoactivity of TiO₂ (UV exposed) played a major role in enhancing TiO₂ toxicity, activating the transcription of oxidative stress, lysosome damage and apoptosis mechanisms. For non-UV activated TiO₂, where toxicity at the organism level (reproduction) was lower, results showed potential for long-term effects (i.e., mutagenic and epigenetic). NM specific mechanisms were identified: NM103 affected transcription and translation, NM104_UV negatively affected the reproductive system/organs, and NM105_UV activated superoxide anion response. Results provided mechanistic information on UV-related phototoxicity of TiO₂ materials and evidence for the potential long-term effects.

The scientific community has invested effort into standardising methodologies for the regulatory ecotoxicity testing of engineered nanomaterials (ENMs), but the practical requirements for bioaccumulation testing of ENMs have been given less attention. A strategy for a tiered approach to bioaccumulation testing of ENMs using fish is proposed, with recommendations for its implementation by regulatory agencies. The strategy recognises that testing the many shapes, sizes and chemistries of ENMs as new substances in vivo would be an unrealistic workload. The approach therefore includes grouping/read-across methods and tools to screen out ENMs of negligible/low bioaccumulation potential. The strategy proposes reductions of animal use for in vivo testing and with greater consideration of in vitro methods. The first tier uses dissolution in water or lipids and particle settling rates as environmental chemistry triggers for ‘ENMs of concern’. The first tier also involves a weight of evidence from these tests, plus using existing data sets from selected literature that meet data quality criteria for ENMs. Tier 2 involves new data generation using in silico models now being validated for ENMs, including QSARs and systems biology tools. Tier 2 also includes using existing experimental data, and an option to collect new data. These data can be on soils/sediments, microbial degradation, and bioaccumulation studies on invertebrates or fish cell lines. In tier 3, an in chemico digestibility assay simulating the gut lumen of fish is proposed to identify the bioaccessible fractions from an oral exposure to ENMs. If the digestibility assay is positive, then in vitro gut sacs from rainbow trout can be used to confirm accumulation by the gut mucosa. Only if both these tests in tier 3 are positive would the work proceed to the final in vivo test (tier 4) which is essentially the OECD TG 305 method for dietary bioaccumulation testing using fish, with some caveats and recommendations for ENMs. These include considerations of terminology, how to prepare contaminated food for dietary exposures, the additional controls and endpoints for ENMs, measuring ENMs in food and tissues to confirm the exposure, and the limitations of any subsequent calculation of the bioaccumulation potential.

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.

Here we compare the standard European benchmark of wood treatment by molecularly dissolved copper amine (Cu–amine), also referred to as aqueous copper amine (ACA), against two nanoenabled formulations: copper(II)oxide nanoparticles (CuO NPs) in an acrylic paint to concentrate Cu as a barrier on the wood surface, and a suspension of micronized basic copper carbonate (CuCO₃·Cu(OH)₂) for wood pressure treatment. After characterizing the properties of the (nano)materials and their formulations, we assessed their effects in vitro against three fungal species: Coniophora puteana, Gloeophyllum trabeum, and Trametes versicolor, finding them to be mediated only partially by ionic transformation. To assess the use phase, we quantify both release rate and form. Cu leaching rates for the two types of impregnated wood (conventional and nanoenabled) are not significantly different at 172 ± 6 mg/m², with Cu being released predominantly in ionic form. Various simulations of outdoor aging with release sampling by runoff, during condensation, by different levels of mechanical shear, all resulted in comparable form and rate of release from the nanoenabled or the molecular impregnated woods. Because of dissolving transformations, the nanoenabled impregnation does not introduce additional concern over and above that associated with the traditional impregnation. In contrast, Cu released from wood coated with the CuO acrylate contained particles, but the rate was at least 100-fold lower. In the same ranking, the effectiveness to protect against the wood-decaying basidiomycete Coniophora puteana was significant with both impregnation technologies but remained insignificant for untreated wood and wood coated by the acrylic CuO. Accordingly, a lifecycle-based sustainability analysis indicates that the CuO acrylic coating is less sustainable than the technological alternatives, and should not be developed into a commercial product.

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 × 10³ particles 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.

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.

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.

The life cycle of nanoscale pigments in plastics may cause environmental or human exposure by various release scenarios. We investigated spontaneous and induced release with mechanical stress during/after simulated sunlight and rain degradation of polyethylene (PE) with organic and inorganic pigments. Additionally, primary leaching in food contact and secondary leaching from nanocomposite fragments with an increased surface into environmental media was examined. Standardized protocols/methods for release sampling, detection, and characterization of release rate and form were applied: Transformation of the bulk material was analyzed by Scanning Electron Microscopy (SEM), X-ray-tomography and Fourier-Transform Infrared spectroscopy (FTIR); releases were quantified by Inductively Coupled Plasma Mass Spectrometry (ICP-MS), single-particle-ICP-MS (sp-ICP-MS), Transmission Electron Microscopy (TEM), Analytical Ultracentrifugation (AUC), and UV/Vis spectroscopy. In all scenarios, the detectable particulate releases were attributed primarily to contaminations from handling and machining of the plastics, and were not identified with the pigments, although the contamination of 4 mg/kg (Fe) was dwarfed by the intentional content of 5800 mg/kg (Fe as Fe₂O₃ pigment). We observed modulations (which were at least partially preventable by UV stabilizers) when comparing as-produced and aged nanocomposites, but no significant increase of releases. Release of pigments was negligible within the experimental error for all investigated scenarios, with upper limits of 10 mg/m² or 1600 particles/mL. This is the first holistic confirmation that pigment nanomaterials remain strongly contained in a plastic that has low diffusion and high persistence such as the polyolefin High Density Polyethylene (HDPE).

A large fraction of engineered nanomaterials (ENM) will be deposited in landfills and it is assumed that ENM are securely locked in landfill sites and cannot leach into the environment (e.g. surface waters). However, experimental evidence supporting this assumption is lacking, as current production volumes of ENM are still too small and/or analytical techniques not sensitive enough to allow for the detection and quantification of ENM in landfill leachates. TiO2 particles are currently used in large quantities, for example in construction materials such as paints and renders as white pigments and their sizes extend into the nano-size range. We, therefore, selected TiO₂ particles as a surrogate to assess the potential release of ENM from construction and demolition (C&D) landfill sites. We collected leachate samples from a landfill over one year and used complementary analytical techniques, including inductively coupled plasma (ICP) – optical emission spectroscopy (OES), automated scanning electron microscopy (auto SEM), transmission electron microscopy (TEM) and single particle ICP - mass spectrometry (spICPMS) to quantify TiO2 particles in landfill leachates. Total elemental Ti contents were mostly around a few tens of μg L^− 1 and were strongly correlated with total suspended solids. Based on the volumetric discharge of the landfill leachate water from the landfill, we estimate a total amount of ~ 0.5 kg of TiO₂ particles that are released annually from the landfill. Ti concentrations derived from ICP-OES measurements were in good agreement with quantifications based on TiO₂ particles detected by auto SEM analyses. spICPMS measurements indicated a number concentration of Ti-containing particles in the order of 10⁵ mL^− 1 and TEM analyses dominantly revealed nanoscale TiO₂ particles with a spherical shape typically observed for TiO₂ particles used as white pigments. In addition, angular TiO₂ particles with a well-defined crystal habitus were detected, suggesting that also natural TiO₂ particles of comparable sizes are present in the landfill leachates.

The results from this study indicate that (nanoscale) TiO₂ particles are released from C&D landfill sites (~ 5 g/year). Although the amount of TiO₂ particles released from C&D landfill sites may still be rather low, these particles may serve as proxy for assessing the future release of ENM from C&D landfill sites, which may become relevant as an increasing use of ENM is predicted for construction materials in general.

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.

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 (D_min). ICP-MS/MS allowed for an important decrease of the theoretical D_min 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 D_min. The comparably higher sensitivity of HR-ICP-MS allowed for theoretically measuring a D_min of 10 nm in ultrapure water. Combined with the deconvolution analysis, the highest resolution mode in HR-ICP-MS leads to the lowest D_min 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.

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.

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.

The analysis of the potential risks of engineered nanomaterials (ENM) has so far been almost exclusively focused on the pristine, as-produced particles. However, when considering a life-cycle perspective, it is clear that ENM released from genuine products during manufacturing, use, and disposal is far more relevant. Research on the release of materials from nanoproducts is growing and the next necessary step is to investigate the behavior and effects of these released materials in the environment and on humans. Therefore, sufficient amounts of released materials need to be available for further testing. In addition, ENM-free reference materials are needed since many processes not only release ENM but also nanosized fragments from the ENM-containing matrix that may interfere with further tests. The SUN consortium (Project on “Sustainable Nanotechnologies”, EU seventh Framework funding) uses methods to characterize and quantify nanomaterials released from composite samples that are exposed to environmental stressors. Here we describe an approach to provide materials in hundreds of gram quantities mimicking actual released materials from coatings and polymer nanocomposites by producing what is called “fragmented products” (FP). These FP can further be exposed to environmental conditions (e.g., humidity, light) to produce “weathered fragmented products” (WFP) or can be subjected to a further size fractionation to isolate “sieved fragmented products” (SFP) that are representative for inhalation studies. In this perspective we describe the approach, and the used methods to obtain released materials in amounts large enough to be suitable for further fate and (eco)toxicity testing. We present a case study (nanoparticulate organic pigment in polypropylene) to show exemplarily the procedures used to produce the FP. We present some characterization data of the FP and discuss critically the further potential and the usefulness of the approach we developed.

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.

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.

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.

Proper understanding of the basic processes and specific properties of engineered nanomaterials (NMs) that modify the fate and effects of NMs is crucial for NM-tailored risk assessment. This in turn requires developers of NMs and for regulators to consider the most important parameters governing the properties, behavior and toxicity of NMs. As fate and effect studies are commonly performed in laboratory settings, mimicking to a varying extent realistic exposure conditions, it is important to be able to extrapolate results of fate and effect studies in synthetic media to realistic environmental conditions. This requires detailed understanding of the processes controlling the fate and behavior of NMs in terrestrial and aquatic media, as dependent on the composition of the medium. It is the aim of this contribution to provide background reading to the NM and media specific properties and processes that affect the fate and behavior of NMs in aquatic environments, focusing on the specific properties of NMs that modulate the interactions in the aquatic environment. A general introduction on the dominant fate determining processes of NMs is supplemented by case studies on specific classes of NMs: metal NMs, stable oxides, iron oxides, and carbon nanotubes. Based on the synthesis of the current knowledge base toward essential data and information needs, the review provides a description of the particle specific properties and the water characteristics that need monitoring in order to allow for future quantification and extrapolation of fate and behavior properties of NMs in freshwater compartments of varying composition.

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.

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.

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.

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.

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.

Environmental exposure modeling has been used extensively in the last years to obtain estimates of environmental concentrations of engineered nanomaterials (ENMs). In this perspective piece, we explore the issues when aiming to validate modeled environmental concentrations and propose options for both modelers and analytical chemists on how to proceed in the future to better compliment one another's efforts. In this context, validation means to determine the degree to which the simulation results from a model are accurate representations of the real world by comparison with analytical data. Therefore, for such a model validation procedure, analytical methods need to be available which provide information in the same subject area. Currently, a major issue with nanometrology is that a multitude of nanomaterials are present in natural systems but only some are ENMs; various other particles of natural origin are abundant in the same systems. The analytical tools available are not yet capable to distinguish the natural from engineered nanomaterials at the low ENM concentrations expected in complex environmental matrices. However, both modeling and analytical studies are able to provide an orthogonal view on nanomaterials: modeling is able to yield estimates of the presence of ENMs in various environmental compartments while analytics can provide physical characterization of ENMs in these systems with hints towards the total nanomaterial concentration. While we need to make strides to improve the two approaches separately, using the resulting data together in a mutually supportive way will advance the field of ENM risk assessment.

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.

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.

The increasing manufacture and implementation of engineered nanomaterials (ENMs) will continue to lead to the release of these materials into the environment. Reliably assessing the environmental exposure risk of ENMs will depend highly on the ability to quantify and characterise these materials in environmental samples. However, performing these measurements is obstructed by the complexity of environmental sample matrices, physiochemical processes altering the state of the ENM and the high background of naturally occurring nanoparticles (NNPs), which may be similar in size, shape and composition to their engineered analogues. Current analytical techniques can be implemented to overcome some of these obstacles, but the ubiquity of NNPs presents a unique challenge requiring the exploitation of properties that discriminate engineered and natural nanomaterials. To this end, new techniques are being developed that take advantage of the nature of ENMs to discern them from naturally occurring analogues. This paper reviews the current techniques utilised in the detection and characterisation of ENMs in environmental samples as well as discusses promising new approaches to overcome the high backgrounds of NNPs. Despite their occurrence in the atmosphere and soil, this review will be limited to a discussion of aqueous-based samples containing ENMs, as this environment will serve as a principal medium for the environmental dispersion of ENMs.

Increased use of nanomaterials in everyday products leads to their environmental release and therefore, the information need on their fate and behaviour. Nanomaterials have to be suspended with high repeatability and comparability for studies on environmental effects. They also have to be well characterised with a focus on the state of agglomeration and particle size distribution. Dynamic light-scattering (DLS) is a common technique used for these measurements. If suspensions are prepared in different laboratories, then concern has risen about the comparability of the measured results, especially when different DLS instruments are used. Therefore, for quality assurance, a round-robin test was conducted to assess the comparability of different DLS instruments and a dispersion protocol in ten independent laboratories. Polystyrene and TiO₂ were chosen as test (nano)materials. For the comparability of the DLS instruments, the average sizes of the PSL and a stabilised TiO₂ suspension were measured. The measured average hydrodynamic diameter shows an overall good inter-laboratory comparability. For the PSL suspension, an average hydrodynamic diameter of 201 ± 13 nm and for the TiO₂ suspension an average diameter of 224 ± 24 nm were detected. For the TiO₂ suspension that was prepared at each laboratory following an established suspension preparation protocol, an average hydrodynamic diameter of 211 ± 11 nm was detected. The measured average particle size (mode) increased up to 284 nm with a high standard deviation of 119 nm if the preparation protocol could not established and different procedures or different equipment were employed. This study shows that no significant differences between the employed DLS instrument types were determined. It was also shown that comparable measurements and suspension preparation could be achieved if well-defined suspension preparation protocols and comparable equipment can be used.

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.

The increasing use of engineered nanoparticles in industrial and consumer products leads to a release of the anthropogenic contaminants to the aquatic environment. To obtain a better understanding of the environmental effects of these particles, the nematode Caenorhabditis elegans was used to investigate the organism‐level effects and in vivo molecular responses. Toxicity of bulk‐scale (∼160 nm) and nanoscale (21 nm) titanium dioxide (TiO₂) was tested under dark and light conditions, following ISO 10872. The expression of sod‐3, a mitochondrial superoxide dismutase, was quantified as an indicator for oxidative stress induced by the photocatalytically active material. Particle sizes were estimated using dynamic light scattering and scanning electron microscopy. Although both materials agglomerated to a comparable secondary particle size of 300 nm to 1500 nm and were ingested into the intestine, only nanoscale‐TiO₂ significantly inhibited reproduction (lowest‐observed‐effect‐concentration [LOEC]: 10 mg/L). Light exposure induced the production of reactive oxygen species (ROS) by nanoscale‐TiO₂ and increased toxicity of the nanomaterial from a median effect concentration of more than 100 mg/L to 53 mg/L. No evidence was found for inner cellular photocatalytic activity of nanoscale‐TiO₂. Therefore, oxidative damage of the membranes of intestinal cells is suggested as a potential mode of action. Results highlight the importance of primary particle size and environmental parameters on the toxicity of TiO₂.

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.

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.

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.

Adequate fate descriptors are crucial input parameters in models used to predict the behaviour and transport of a contaminant in the environment and determine predicted environmental concentrations for risk assessment. When new fate models are being developed for emerging contaminants, such as engineered nanoparticles (ENPs), special care has to be applied in adjusting conventional approaches and fate descriptors to a new set of substances. The aim of this paper is to clarify misconceptions about the applicability of equilibrium partition coefficients, such as the octanol–water partition coefficient (K_ow) or the soil–water distribution coefficient (K_d), whose application in the context of ENP fate assessment is frequently suggested despite lacking scientific justification. ENPs are present in the environment as thermodynamically unstable suspensions and their behaviour must be represented by kinetically controlled attachment and deposition processes as has been established by colloid science. Here, we illustrate the underlying theories of equilibrium partitioning and kinetically controlled attachment and discuss why the use of any coefficient based on equilibrium partitioning is inadequate for ENPs and can lead to significant errors in ENP fate predictions and risk assessment.

The European COoperation in Science and Technology (COST) Action ES1205 on the transfer of Engineered Nano materials from wastewater Treatment and stormwatEr to Rivers (ENTER) aims to create and to maintain a trans European network among scientists. This perspective article delivers a brief overview on the status quo at the beginning of the project by addressing the following aspects on engineered nano materials (ENMs) in the urban systems: (1) ENMs that need to be considered on a European level; (2) uncertainties on production-volume estimations; (3) fate of selected ENMs during waste water transport and treatment; (4) analytical strategies for ENM analysis; (5) ecotoxicity of ENMs, and (6) future needs. These six step stones deliver the derivation of the position of the ES1205 network at the beginning of the projects runtime, by defining six fundamental aspects that should be considered in future discussions on risk evaluation of ENMs in urban water systems.

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.

This study addressed the relative importance of particle coating, sewage sludge amendment, and aging on aggregation and dissolution of manufactured Ag nanoparticles (Ag MNPs) in soil pore water. Ag MNPs with citrate (CIT) or polyvinylpyrrolidone (PVP) coatings were incubated with soil or municipal sewage sludge which was then amended to soil (1% or 3% sludge (w/w)). Pore waters were extracted after 1 week and 2 and 6 months and analyzed for chemical speciation, aggregation state and dissolution. Ag MNP coating had profound effects on aggregation state and partitioning to pore water in the absence of sewage sludge, but pre-incubation with sewage sludge negated these effects. This suggests that Ag MNP coating does not need to be taken into account to understand fate of AgMNPs applied to soil through biosolids amendment. Aging of soil also had profound effects that depended on Ag MNP coating and sludge amendment.

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 (logK_D 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 logK_D 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 logK_D values of As-NOM associations decreased with increasing discharge as a consequence of decreasing pH. The logK_D 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.

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.

Bringing together topic-related European Union (EU)-funded projects, the so-called “NanoSafety Cluster” aims at identifying key areas for further research on risk assessment procedures for nanomaterials (NM). The outcome of NanoSafety Cluster Working Group 10, this commentary presents a vision for concern-driven integrated approaches for the (eco-)toxicological testing and assessment (IATA) of NM. Such approaches should start out by determining concerns, i.e., specific information needs for a given NM based on realistic exposure scenarios. Recognised concerns can be addressed in a set of tiers using standardised protocols for NM preparation and testing. Tier 1 includes determining physico-chemical properties, non-testing (e.g., structure–activity relationships) and evaluating existing data. In tier 2, a limited set of in vitro and in vivo tests are performed that can either indicate that the risk of the specific concern is sufficiently known or indicate the need for further testing, including details for such testing. Ecotoxicological testing begins with representative test organisms followed by complex test systems. After each tier, it is evaluated whether the information gained permits assessing the safety of the NM so that further testing can be waived. By effectively exploiting all available information, IATA allow accelerating the risk assessment process and reducing testing costs and animal use (in line with the 3Rs principle implemented in EU Directive 2010/63/EU). Combining material properties, exposure, biokinetics and hazard data, information gained with IATA can be used to recognise groups of NM based upon similar modes of action. Grouping of substances in return should form integral part of the IATA themselves.

A method of analysis of silver nanoparticles (AgNPs) in chicken meat was developed. The homogenized chicken meat sample, which was spiked with AgNPs, was subjected to enzymolysis by Proteinase K for 40 min at 37 °C. Transmission electron microscopy and inductively coupled plasma mass spectrometry (ICP-MS) in single particle mode were used to characterize the number-based size distribution of AgNPs in the meat digestate. Because similar size distributions were found in the meat digestate and in the aqueous suspension of AgNPs used for spiking the meat, it was shown that no detectable dissolution of the AgNPs took place during the sample preparation stage. The digestate was injected into the asymmetric flow field flow fractionation (AF⁴) -ICP-MS system, which enabled fractionation of nanoparticles from the remaining meat matrix, and resulted in one large peak in the fractograms as well as two smaller peaks eluting close to the void volume. The recovery of silver contained in the large AgNP peak was around 80 %. Size determination of AgNPs in the meat matrix, based on external size calibration of the AF⁴ channel, was hampered by non-ideal (early elution) behavior of the AgNPs. Single particle ICP-MS was applied for determination of the number-based particle size distribution of AgNPs in collected fractions. The presented work describes for the first time the coupling of AF⁴ and ICP-MS for AgNP separation in a food matrix.

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·g_NOM^–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.

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.

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 SO₄^2–) 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.

Asymmetric flow field-flow fractionation (AF⁴) in combination with on-line optical detection and mass spectrometry is one of the most promising methods for separation and quantification of nanoparticles (NPs) in complex matrices including food. However, to obtain meaningful results regarding especially the NP size distribution a number of parameters influencing the separation need to be optimized. This paper describes the development of a separation method for polyvinylpyrrolidone-stabilized silver nanoparticles (AgNPs) in aqueous suspension. Carrier liquid composition, membrane material, cross flow rate and spacer height were shown to have a significant influence on the recoveries and retention times of the nanoparticles. Focus time and focus flow rate were optimized with regard to minimum elution of AgNPs in the void volume. The developed method was successfully tested for injected masses of AgNPs from 0.2 to 5.0 μg. The on-line combination of AF⁴ with detection methods including ICP-MS, light absorbance and light scattering was helpful because each detector provided different types of information about the eluting NP fraction. Differences in the time-resolved appearance of the signals obtained by the three detection methods were explained based on the physical origin of the signal. Two different approaches for conversion of retention times of AgNPs to their corresponding sizes and size distributions were tested and compared, namely size calibration with polystyrene nanoparticles (PSNPs) and calculations of size based on AF⁴ theory. Fraction collection followed by transmission electron microscopy was performed to confirm the obtained size distributions and to obtain further information regarding the AgNP shape. Characteristics of the absorbance spectra were used to confirm the presence of non-spherical AgNP.

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.

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.

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.

The potential impact of nanomaterials on the environment and on human health has already triggered legislation requiring labelling of products containing nanoparticles. However, so far, no validated analytical methods for the implementation of this legislation exist. This paper outlines a generic approach for the validation of methods for detection and quantification of nanoparticles in food samples. It proposes validation of identity, selectivity, precision, working range, limit of detection and robustness, bearing in mind that each “result” must include information about the chemical identity, particle size and mass or particle number concentration. This has an impact on testing for selectivity and trueness, which also must take these aspects into consideration. Selectivity must not only be tested against matrix constituents and other nanoparticles, but it shall also be tested whether the methods apply equally well to particles of different suppliers. In trueness testing, information whether the particle size distribution has changed during analysis is required. Results are largely expected to follow normal distributions due to the expected high number of particles. An approach of estimating measurement uncertainties from the validation data is given.

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.

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.

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.

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.

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 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.

Advances in the study of the environmental fate, transport, and ecotoxicological effects of engineered nanomaterials (ENMs) have been hampered by a lack of adequate techniques for the detection and quantification of ENMs at environmentally relevant concentrations in complex media. Analysis of ENMs differs from traditional chemical analysis because both chemical and physical forms must be considered. Because ENMs are present as colloidal systems, their physicochemical properties are dependent on their surroundings. Therefore, the simple act of trying to isolate, observe, and quantify ENMs may change their physicochemical properties, making analysis extremely susceptible to artifacts. Many analytical techniques applied in materials science and other chemical/biological/physical disciplines may be applied to ENM analysis as well; however, environmental and biological studies may require that methods be adapted to work at low concentrations in complex matrices. The most pressing research needs are the development of techniques for extraction, cleanup, separation, and sample storage that introduce minimal artifacts to increase the speed, sensitivity, and specificity of analytical techniques, as well as the development of techniques that can differentiate between abundant, naturally occurring particles, and manufactured nanoparticles.

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.

Interest in nanoparticles (NPs) has increased explosively over the past two decades. Using NPs, high loadings of vitamins and health-benefit actives can be achieved in food, and stable flavors as well as natural food-coloring dispersions can be developed. Detection and characterization of NPs are essential in understanding the benefits as well as the potential risks of the application of such materials in food. While many such applications are described in the literature, methods for detection and characterization of such particles are lacking. Organic NPs suitable for application in food are lipid-, protein- or polysaccharide-based particles, and this review describes current analytical techniques that are used, or could be used, for identification and characterization of such particles in food products. We divide the analytical approaches into four sections: sample preparation; separation; imaging; and, characterization.

We discuss techniques and reported applications for NPs or otherwise related particle compounds. The results of this investigation show that, for a successful characterization of NPs in food, at least some kind of sample preparation will be required. While a simple sample preparation may be satisfactory for imaging techniques for known analytes, for other techniques, a further separation using chromatography, field-flow fractionation or ion-mobility separation is necessary. Subsequently, photon-correlation spectroscopy and especially mass spectrometry techniques as matrix-assisted laser desorption/ionization combined with time-of-flight mass spectrometry, seem suitable techniques for characterizing a wide variety of organic NPs.

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.

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.

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 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 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.

Field-Flow Fractionation (FFF) is now recognised as a versatile pool of techniques allowing particle size or molar mass to be obtained in a wide variety of samples covering numerous applications in the fields of environment, materials or biology. In the same time, Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) has an indisputable place in the field of elemental detectors and the coupling between FFF and ICP-MS can be considered as an emerging technique capable to reach relevant physico-chemical information at sub-micrometre scale and trace element concentration level. This paper gives some key elements of FFF-based fractionation linking theory and practical analytical aspects, from injection and preconcentration to analysis. The different components of the coupling are described. Summary tables of the main operating conditions of FFF-ICP-MS coupling are presented and operating conditions such as carrier composition, flow and nebulizers are discussed. Special attention is given to the FFF-ICP-MS interface. Qualitative and quantitative analysis is also discussed. Applications in the fields of environment, bioanalysis and nanoparticles are presented in order to illustrate the potentialities of such coupling.

NanoImpactNet is a European Commission Framework Programme 7 (FP7) funded project that provides a forum for the discussion of current opinions on nanomaterials in relation to human and environmental issues. In September 2008, in Zurich, a NanoImpactNet environmental workshop focused on three key questions:

1. What properties should be characterised for nanomaterials used in environmental and ecotoxicology studies?
2. What reference materials should be developed for use in environmental and ecotoxicological studies?
3. Is it possible to group different nanomaterials into categories for consideration in environmental studies?

Such questions have been, at least partially, addressed by other projects/workshops especially in relation to human health effects. Such projects provide a useful basis on which this workshop was based, but in this particular case these questions were reformulated in order to focus specifically on environmental studies. The workshop participants, through a series of discussion and reflection sessions, generated the conclusions listed below.

The physicochemical characterisation information identified as important for environmental studies included measures of aggregation/agglomeration/dispersability, size, dissolution (solubility), surface area, surface charge, surface chemistry/composition, with the assumption that chemical composition would already be known.

There is a need to have test materials for ecotoxicology, and several substances are potentially useful, including TiO₂ nanoparticles, polystyrene beads labelled with fluorescent dyes, and silver nanoparticles. Some of these test materials could then be developed into certified reference materials over time.

No clear consensus was reached regarding the classification of nanomaterials into categories to aid environmental studies, except that a chemistry-based classification system was a reasonable starting point, with some modifications. It was suggested, that additional work may be required to derive criteria that can be used to generate such categories, that would also include aspects of the material structure and physical behaviour.

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.

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.

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 [PR_6,6,6,14][FeCl₄] and (BMIM)[FeCl₄] in ethylacetate and ethanol.

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.

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.

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.

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.

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.

Topsoils are often contaminated by trace metals, and it is important to understand how different processes govern the transport of such metals to fresh and marine waters. This paper presents measurements of natural nanoparticles and colloidal organic matter in soil and river samples from Germany and Sweden. In our analytical approach, a nanoparticle separation technique is combined with multielement detection and applied to soil and river samples to link the macroscale field observations with detailed molecular studies in the laboratory. It was determined that lead is associated with iron oxide colloids, which are ubiquitous nanoparticles that can be efficiently transported. Eventually both iron oxides and lead are removed by flocculation under conditions of estuarine mixing. Iron-rich nanoparticles compete efficiently with natural organic matter (NOM) complexation for lead binding in both the soil and river systems studied.

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.

The fractionation of natural nanoparticles by Asymmetrical Flow Field Flow Fractionation (As-Fl-FFF) was optimised by considering the following operating conditions: ionic strength, surfactant concentration and crossflow rate. The method performances such as fractionation recovery and fractionation efficiency were evaluated on a stable solution of colloidal-size natural inorganic particles. The online multi-detection by ultraviolet/visible spectrophotometer (UV) and multi-angle laser light scattering (MALLS) provided the monitoring of the sample during the separation and the evaluation of the fractionation efficiency. The lowest ionic strength and surfactant concentrations (i.e. 10⁻³ mol L⁻¹ NH₄NO₃ and 3 × 10⁻⁴ mol L⁻¹ SDS) allowed to obtain the highest sample recovery and lowest loss of the largest particles. The crossflow rate was investigated in order to avoid significant membrane–sample interaction. The applicability of the fractionation in optimised conditions was evaluated on a natural soil leachate, which was filtrated with different filter cut-offs. Filtration efficiency was stressed by the decrease of the large unfractionated particle influence in the void volume. For the first time, robust operating conditions were proposed to well size-fractionate and characterize soil nanoparticles within a single multi-detection analysis.

The emerging literature on the ecotoxicity of nanoparticles and nanomaterials is summarised, then the fundamental physico-chemistry that governs particle behaviour is explained in an ecotoxicological context. Techniques for measuring nanoparticles in various biological and chemical matrices are also outlined. The emerging ecotoxicological literature shows toxic effects on fish and invertebrates, often at low mg l⁻¹ concentrations of nanoparticles. However, data on bacteria, plants, and terrestrial species are particularly lacking at present. Initial data suggest that at least some manufactured nanoparticles may interact with other contaminants, influencing their ecotoxicity. Particle behaviour is influenced by particle size, shape, surface charge, and the presence of other materials in the environment. Nanoparticles tend to aggregate in hard water and seawater, and are greatly influenced by the specific type of organic matter or other natural particles (colloids) present in freshwater. The state of dispersion will alter ecotoxicity, but many abiotic factors that influence this, such as pH, salinity, and the presence of organic matter remain to be systematically investigated as part of ecotoxicological studies. Concentrations of manufactured nanoparticles have rarely been measured in the environment to date. Various techniques are available to characterise nanoparticles for exposure and dosimetry, although each of these methods has advantages and disadvantages for the ecotoxicologist. We conclude with a consideration of implications for environmental risk assessment of manufactured nanoparticles.

Flow-field flow fractionation (FlFFF) coupled to multi-angle laser light scattering (MALLS) was evaluated for size and shape determination of standard spherical and arbitrarily shaped natural colloids. Different fitting methods for light scattering data retrieved from MALLS were evaluated to determine the particle size of spherical standards and natural colloids. In addition, FlFFF was optimized for best fractionation in connection to MALLS, minimal colloids-membrane interaction, and minimal sample losses. FlFFF, calibrated with standard particles, was used to determine hydrodynamic diameter, or radius (D_h or R_h), of the fractionated colloids, whereas the MALLS was used to determine root mean square radius of gyration (R_g) for fractionated colloids. Combining both results, by calculating the R_g/R_h ratio, allows an estimation of colloid deviation from the shape of homogeneous sphere. Accordingly, this study demonstrates that, FlFFF–MALLS is a valuable technique for characterizing heterogeneous and arbitrarily shaped natural colloidal particles in terms of size and shape. To check the usefulness of FlFFF–MALLS in natural colloid studies, the technique was used to investigate the sedimentation behavior of extracted soil colloidal particles. Results illustrate that, in a silty till sample, carbonates function as cement between the colloidal particles, and consequently, change their sedimentation behavior. On the other hand, carbonate dissolution generates a more homogeneous colloidal sample.

Flow field flow fractionation (FlFFF), inductively coupled plasma-mass spectroscopy (ICP-MS), and transmission electron microscopy (TEM) coupled to X-ray energy dispersive spectrometry (X-EDS) are used in series for the first time to characterize colloids. Results demonstrate the utility of FlFFF−ICP-MS−TEM/X-EDS to relate physical properties (size) of colloids to their chemical properties (chemical composition, surface chemical composition, and colloids−trace elements association). Results suggest that the major part of natural organic matter (NOM) is concentrated in the fraction <0.01 μm (C2). Aluminum, iron, and manganese are the main colloidal components in the fraction 0.01−0.45 μm (C1). Aluminum occurs as aluminum oxides or aluminosilicates in the whole size range, while iron and manganese occur as individual oxyhydroxides in the size range <0.20 μm. Within the C2 fraction, Al, Mn, Cu, and Ni elements are complexed to NOM (e.g., humic substances). Iron is complexed to NOM in some samples and probably free in other samples. Lead is totally free in all samples. Within the C1 fraction, Cu and Pb are mostly associated to Fe and Mn oxyhydroxides. Consequently, NOM with Fe and Mn oxyhydroxides are the main colloidal carriers of trace elements in the Loire watershed system.

Understanding the role of colloids in the environment needs a more complete characterization of their size and shape than the usually used hydrodynamic diameter. A novel methodology to determine three dimensional description of colloids has been successfully experimented in this work by coupling Flow-Field Flow Fractionation (FlFFF) to Multi Angle Laser Light Scattering (MALLS), and Transmission Electron Microscope (TEM). This methodology was evaluated for a soil colloidal sample. Results show that, the particles surface areas determined by FlFFF-MALLS-TEM, are 3–4 times greater than those calculated using the hydrodynamic diameter determined by FlFFF. Further, results indicated that, the surface area/volume values are 3–5 times greater than those calculated based on the hydrodynamic diameter. Therefore, a correction factor must be applied when the particle surface area is calculated from the hydrodynamic diameter determined by FlFFF.

A new operation mode for HPLC-type fluorescence detectors is presented and evaluated using synthetic and environmental particles in the colloidal size range. By applying identical wavelengths for excitation and emission a nephelometric turbidity or single angle light scattering detector is created which can be easily coupled to flow or sedimentation Field-Flow Fractionation (Flow FFF or Sed FFF) for the analysis of colloidal dispersions. The results are compared with standard UV–vis detection methods. Signals obtained are given as a function of particle size and selected detection wavelength. Conclusions can be drawn which affect the current practice of FFF but also for other techniques as groundwater sampling and laboratory column experiments when turbidity is measured in nephelometric mode and in small sample volumes or at low flow rates.

The water quality of the river Elbe near Magdeburg represents the pollution situation of the middle course of the river Elbe under normal discharge conditions. In order to identify critical changes in the water quality caused by the century flood in August 2002, numerous measurement programs were launched accompanying the flood wave. This paper compares and discusses results based on different sampling strategies and analytical methods of three institutions mainly using the example of trace metals.

Results from the analysis of natural colloid with a coupling of field-flow fractionation (FFF) with multi-angle laser light scattering photometers (MALLS) are presented. The results indicate that after FFF of natural colloids MALLS is applicable to retrieve independent and absolute particle sizes (RMS radius or radius of gyration) for the colloids fractionated. For the analysed samples of soil colloids the appropriate data processing in MALLS is the linear or second order ZIMM fitting method for particle sizes up to 500 nm in diameter. This is in contrast to the MALLS analysis of latex beads, where the ZIMM fitting method produces reliable results only below ∼100 nm in diameter. The reason for the good results for the soil colloids can be found in the behaviour of the particle form factor P(θ) which was found to be linear function when plotted as Kc/R(θ) over sin²(θ/2).

Two flow field flow fractionation (FlFFF) systems: symmetrical (SFlFFF) and asymmetrical (ASFlFFF) were evaluated to fractionate river colloids. Samples stability during storage and colloids concentration are the main challenges limiting their fractionation and characterization by FlFFF. A pre-fractionation (<0.45 μm) and addition of a bactericide such as NaN₃ into river colloidal samples allowed obtaining stable samples without inducing any modification to their size. Stirred cell ultra-filtration allowed colloidal concentration enrichment of 25-folds. Scanning electron microscope (SEM) micrographs confirmed the gentle pre-concentration of river samples using the ultra-filtration stirred cell. Additionally, larger sample injection volume in the case of SFlFFF and on channel concentration in the case of ASFlFFF were applied to minimize the required pre-concentration. Multi angle laser light scattering (MALLS), and transmission electron microscope (TEM) techniques are used to evaluate FlFFF fractionation behavior and the possible artifacts during fractionation process. This study demonstrates that, FlFFF–MALLS–TEM coupling is a valuable method to fractionate and characterize colloids. Results prove an ideal fractionation behavior in case of Brugeilles sample and steric effect influencing the elution mode in case of Cézerat and Chatillon. Furthermore, comparison of SFlFFF and ASFlFFF fractograms for the same sample shows small differences in particle size distributions.

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.

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.

The retention of lead in zeolite-supported sand-filter columns has been tested with focus on the effect of potentially mobile natural nanophases (natural colloids, humic substances). It could be shown that interaction of lead with natural nanophases enhanced the mobility of the contaminant. In the presence of iron oxide particles (goethite) a normal breakthrough of lead was observed. Humic substance can act as a carrier for lead itself and can enhance the mobility of lead bound to inorganic nanophases, because of the increased mobility of the nanophases in the presence of humic substances.