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Environmental context The effects of the presence of polymer additives and polymeric structure on sorption of xenobiotics to microplastics remain unclear. Our results combined data from experimental sorption batch experiments using three environmentally relevant model sorbates with confocal microscopy. This provides clear evidence that both factors play a major role in sorption strength and the underlying sorption process, affecting sorption onto the particle surface and partitioning into the bulk polymer. Abstract Microplastics are particulate contaminants of global concern. Interactions of microplastics with organic contaminants are frequently studied with commercially available polymer materials as surrogates. The influence of the polymer structure (i.e. internal 3D polymer geometry and monomer chain length) and the presence of additives on their interactions with xenobiotics remains unclear. This work investigates sorption of three sorbates of environmental concern to two polyamide (PA) and two polyvinyl chloride (PVC) sorbents of different molecular composition and additive content, respectively. Sorption was studied using complementary data from sorption isotherms and confocal laser-scanning microscopy. The additives in PVC increased sorption affinity owing to an increased sorbent hydrophobicity and a higher void volume within the polymer. Surface area normalisation indicated surface adsorption for unplasticised PVC and absorption for 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH)-plasticised PVC, which were confirmed using confocal laser-scanning microscopy. The strong sorption to PA was mainly driven by hydrogen-bond interactions. The contribution depended on the molecular features of the sorbent and the sorbate. Confocal laser-scanning microscopy showed that PA6 was taking up more sorbate into its bulk polymer matrix than PA12, the two being different in their chemical composition. This difference could be attributed to the higher swelling capability of PA6. The results emphasise that the molecular structure of the polymer and the presence of additives have to be taken into consideration when sorption of organic substances to plastics is investigated.

A potential risk from human uptake of microplastics is the release of plastics-associated xenobiotics, but the key physicochemical properties of microplastics controlling this process are elusive. Here, we show that the gastrointestinal bioaccessibility, assessed using an in vitro digestive model, of two model xenobiotics (pyrene, at 391-624 mg/kg, and 4-nonylphenol, at 3054-8117 mg/kg) bound to 18 microplastics (including pristine polystyrene, polyvinyl chloride, polyethylene terephthalate, polypropylene, thermoplastic polyurethane, and polyethylene, and two artificially aged samples of each polymer) covered wide ranges: 16.1-77.4% and 26.4-83.8%, respectively. Sorption/desorption experiments conducted in simulated gastric fluid indicated that structural rigidity of polymers was an important factor controlling bioaccessibility of the nonpolar, nonionic pyrene, likely by inducing physical entrapment of pyrene in porous domains, whereas polarity of microplastics controlled bioaccessibility of 4-nonylphenol, by regulating polar interactions. The changes of bioaccessibility induced by microplastics aging corroborated the important roles of polymeric structures and surface polarity in dictating sorption affinity and degree of desorption hysteresis, and consequently, gastrointestinal bioaccessibility. Variance-based global sensitivity analysis using a deep learning neural network approach further revealed that micropore volume was the most important microplastics property controlling bioaccessibility of pyrene, whereas the O/C ratio played a key role in dictating the bioaccessibility of 4-nonylphenol in the gastric tract.

Dissolved organic matter (DOM) is ubiquitous in aquatic environments where it interacts with a variety of particles including carbonaceous materials (CMs). The complexity of both DOM and the CMs makes DOM-CM interactions difficult to predict. In this study we have identified the preferential sorption of specific DOM fractions as being dependent on their aromaticity and molecular weight, as well as on the surface properties of the CMs. This was achieved by conducting sorption batch experiments with three types of DOM (humic acid, Suwannee River natural organic matter, and a compost extract) and three types of CMs (graphite, carbon nanotubes, and biochar) with different geometries and surface complexities. The non-adsorbed DOM fraction was analyzed by size exclusion chromatography and preferentially sorbed molecular weight fractions were analyzed by UV/vis and fluorescence spectroscopy. All three sorbent types were found to preferentially sorb aromatic DOM fractions, but DOM fractionation depended on the particular combination of sorbent and sorbate characteristics. Single-walled carbon nanotubes only sorbed the smaller molecular weight fractions (1 kDa). The sorption of smaller DOM fractions was not accompanied by a preference for less aromatic compounds, contrary to what was suggested in previous studies. While graphite preferentially sorbed the most aromatic DOM fraction (1-3 kDa), the structural heterogeneity of biochar resulted in reduced selectivity, sorbing all DOM1 kDa. The results explain the lack of correlation found in previous studies between the amount of aromatic carbon in a bulk DOM and its sorption coefficient. DOM sorption by CMs was generally controlled by DOM aromaticity but complex sorbent surfaces with high porosity, curvatures and functional groups strongly reduced the importance of aromaticity.

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

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

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

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

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

Short, saturated packed columns are used frequently to estimate the attachment efficiency (alpha) of engineered nanomaterials (ENMs) in relatively homogeneous porous media, but a combined experimental and theoretical approach to obtain alpha-values for heterogeneous natural soils has not yet been agreed upon. Accurately determined alpha-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 alpha. We applied 150 different approaches to determine alpha-values from 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 alpha 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. alpha-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 alpha 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.

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

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.

The increasing use of gadolinium-based contrast agents (GBCAs) for magnetic resonance imaging is leading to widespread contamination of freshwater and drinking water systems. Contrary to previous assumptions that GBCAs are stable throughout the water cycle, they can degrade. The stability of GBCAs depends largely on their organic ligands, but also on the physicochemical conditions. There is specific concern regarding UV end-of-pipe water treatments, which may degrade GBCAs. Degradation products in drinking water supplies can increase the risk of adverse health effects. This is of particular relevance where the raw water for drinking water production has a higher proportion of recycled wastewater. GBCAs concentrations in aquatic systems, often referred to as anthropogenic gadolinium, are determined using a variety of calculation methods. Where anthropogenic gadolinium concentrations are low, the inconsistent use of these methods results in high discrepancies and high levels of uncertainty. The current COVID-19 crisis will, in the short-term, drastically decrease the input of GBCAs to freshwater systems. Temporal variations in anthropogenic gadolinium concentrations in river water can be used to better understand river-aquifer interactions and groundwater flow velocities. Collecting urine from all patients following MRI examinations could be a way forward to halt the generally increasing concentrations of Gd in drinking water systems and recover this technologically critical element., Graphical abstract Image 1, Highlights • Rising concentration of gadolinium-based contrast agents (GBCAs) in drinking water. • Stability of GBCAs is determined by their organic ligands. • UV end-of-pipe treatment may enhance the risks posed by GBCAs in drinking water. • Inconsistent use of methods to calculate Gd anomalies and anthropogenic Gd. • Temporal Gd patterns in rivers can improve understanding of subsurface systems.

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 alpha(hetero). The inherent complexity of heteroaggregation-encompassing at least two different particle populations, various aggregation pathways and several possible attachment efficiencies (alpha 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 alpha. In a second part, experimental approaches to study heteroaggregation and derive alpha 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 alpha reported. For future method development a closer connection between experiments and models is encouraged.

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

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.

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

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

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

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

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

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

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

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

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

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

Sewage sludge (50% mineral), manure (29%) and wood (

The production and use of engineered nanoparticles (ENPs) inevitably leads to their release into aquatic environments, with the quantities involved expected to increase significantly in the future. Concerns therefore arise over the possibility that ENPs might pose a threat to drinking water supplies. Investigations into the vulnerability of drinking water supplies to ENPs are hampered by the absence of suitable analytical methods that are capable of detecting and quantifiying ENPs in complex aqueous matrices. Analytical data concerning the presence of ENPs in drinking water supplies is therefore scarce. The eventual fate of ENPs in the natural environment and in processes that are important for drinking water production are currently being investigated through laboratory based-experiments and modelling. Although the information obtained from these studies may not, as yet, be sufficient to allow comprehensive assessment of the complete life-cycle of ENPs, it does provide a valuable starting point for predicting the significance of ENPs to drinking water supplies. This review therefore addresses the vulnerability of drinking water supplies to ENPs. The risk of ENPs entering drinking water is discussed and predicted for drinking water produced from groundwater and from surface water. Our evaluation is based on reviewing published data concerning ENP production amounts and release patterns, the occurrence and behavior of ENPs in aquatic systems relevant for drinking water supply and ENP removability in drinking water purification processes. Quantitative predictions are made based on realistic high-input case scenarios. The results of our synthesis of current knowledge suggest that the risk probability of ENPs being present in surface water resources is generally limited, but that particular local conditions may increase the probability of raw water contamination by ENPs. Drinking water extracted from porous media aquifers are not generally considered to be prone to ENP contamination. In karstic aquifers, however, there is an increased probability that if any ENPs enter the groundwater system they will reach the extraction point of a drinking water treatment plant (DWTP). The ability to remove ENPs during water treatment depends on the specific design of the treatment process. In conventional DWTPs with no flocculation step a proportion of ENPs, if present in the raw water, may reach the final drinking water. The use of ultrafiltration techniques improves drinking water safety with respect to ENP contamination.

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.

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

Carbonates and cherts in the 3.35 billion-year-old Strelley Pool Formation (Fm.; Australia) host stromatolites that are among the oldest remnants of life on Earth. However, it is still not entirely clear whether these mineral phases are authigenic precipitates, and whether they represent reliable geochemical archives of early Earth environments. Here we present major/trace-element and Nd-isotope data of stromatolitic carbonates, associated crystal-fan carbonates, and cherts in the Strelley Pool Fm. (i) to assess the reliability of these chemical sediments as geochemical archives of the fluids from which they precipitated, (ii) to date the time of formation of carbonate and silica phases, and (iii) to trace the sources of elements prevailing in microbial habitats 3.35 Ga ago. Stromatolitic carbonates plot together with the stratigraphically underlying Marble Bar cherts on a Sm-Nd regression line yielding 3253 ±320 Ma. In contrast, associated crystal-fan carbonates together with altered Marble Bar cherts yield 2718 ±220 Ma, suggesting that their Sm-Nd isotope system was reset after deposition. Both types of carbonates, as well as white cherts, show shale-normalized rare earth element and yttrium patterns (REYSN; with the exception of redox-sensitive Ce and Eu and heavy REYSN to middle REYSN depletion) that are parallel to those of modern seawater, indicating a predominantly seawater-derived origin. Positive EuSN anomalies (2.1 - 2.4), combined with heterogeneous ɛNd3.35Ga values between -3.2 and +5.8 within individual alternating stromatolite laminae, further support that the dissolved fraction of seawater on the ancient carbonate platform was variably affected by both continental weathering and high-temperature hydrothermal fluids contributing elements of both young mafic or older felsic rocks. In conclusion, trace element and Nd isotope data presented here match well with the depositional environment, as characterized based on lithological, geochemical, and stratigraphic relationships, on an early continent, showing at least episodic emergence above the sea level, supporting microbial life on a shallow marine platform.

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) Ti02, 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 r(h, mode1) (MALS), rh,,odei (ICP-MS), r(h, mode2) (ICP-MS), and calculated mass-based particle size distribution (d(10), d(50), d(90)). 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 (u(IP)) 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 (u(t) = 5.5-52%) can only be taken as a proxy due to the lack of a sunscreen standard containing certified TiO2 ENPs.

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

Amendment with biochar and/or compost has been proposed as a strategy to remediate soil contaminated with low levels of polycyclic aromatic hydrocarbons. The strong sorption potential of biochar can help sequestering contaminants while the compost may promote their degradation. An improved understanding of how sorption evolves upon soil amendment is an essential step towards the implementation of the approach. The present study reports on the sorption of pyrene to two soils, four biochars and one compost. Detailed isotherm analyzes across a wide range of concentration confirmed that soil amendments can significantly increase the sorption of pyrene. Comparisons of data obtained by a classical batch and a passive sampling method suggest that dissolved organic matter did not play a significant role on the sorption of pyrene. The addition of 10% compost to soil led to a moderate increase in sorption (

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

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

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

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

International audience; 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.

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.

Understanding molecular interactions between organic compounds and carbon-based nanomaterials is crucial to the interpretation of phase transfer processes, both in technical applications and within the environment. There is, however, little information available on the interactions between organic compounds and C60 fullerenes, in particular regarding the effects of functionalization. Experimental sorption isotherms and molecular modelling have therefore been used to systematically investigate how these interactions are affected by functionalization of the sorbate (using one, two and four ring aromatics, with –OH or –NH2 functional groups) and the sorbent (i.e., C60 and C60-OH). Functionalization of the sorbent, as well as hydroxyl- and amino-functionalization of the sorbate, had a significant effect on sorption. The enhanced sorption of hydroxyl- and amino-functionalized sorbates by C60 may be due to an increased contribution from π–π electron donor–acceptor interactions. Additional hydrogen bond interactions with C60-OH also appear to play an important role. Our results emphasize that the surface chemistry of C60 is of critical importance to their interactions with organic compounds. The ageing of C60 in technical applications, or in the environment, is therefore likely to significantly affect the molecular interactions, and hence sorption strength, for polar and non-polar organic compounds.

International audience; 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 Ca-48 on the most abundant Ti isotope (Ti-48). 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 (Ti-47 and Ti-49). 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,in). 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

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

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

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.

The presence of microscale polymer particles (i.e., microplastics) in the environment has become a major concern in recent years. Sorption of organic compounds by microplastics may affect the phase distribution within both sediments and aqueous phases. To investigate this process, isotherms were determined for the sorption of seven aliphatic and aromatic organic probe sorbates by four polymers with different physico-chemical properties. Sorption increased in the order polyamide

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

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 (alpha-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 (or = 100 mg/L C). However, at high humic acid concentrations (10-100 mg/L C) with moderate acid conditions (pH3.5), both schwertmannite and goethite surfaces are strongly negatively charged (zeta potential-30 mV) thus posing a risk for colloid stabilization and colloidal transport.

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.