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Determining the potential for accumulation of Ag from Ag2S NPs as an environmentally relevant form of AgNPs in different terrestrial organisms is an essential component of a realistic risk assessment of AgNP emissions to soils. The objectives of this study were first to determine the uptake kinetics of Ag in mealworms (Tenebrio molitor) and woodlice (Porcellio scaber) exposed to Ag2S NPs in a mesocosm test, and second, to check if the obtained toxicokinetics could be predicted by single-species bioaccumulation tests. In the mesocosms, mealworms and woodlice were exposed together with plants and earthworms in soil columns spiked with 10 μg Ag g−1 dry soil as Ag2S NPs or AgNO3. The total Ag concentrations in the biota were measured after 7, 14, and 28 days of exposure. A one-compartment model was used to calculate the Ag uptake and elimination rate constants. Ag from Ag2S NPs appeared to be taken up by the mealworms with significantly different uptake rate constants in the mesocosm compared to single-species tests (K1 = 0.056 and 1.66 g dry soil g−1 dry body weight day−1, respectively), and a significant difference was found for the Ag bioaccumulation factor (BAFk = 0.79 and 0.15 g dry soil g−1 dry body weight, respectively). Woodlice did not accumulate Ag from Ag2S NPs in both tests, but uptake from AgNO3 was significantly slower in mesocosm than in single-species tests (K1 = 0.037 and 0.26 g dry soil g−1 dry body weight day−1, respectively). Our results are of high significance because they show that single-species tests may not be a good predictor for the Ag uptake in mealworms and woodlice in exposure systems having greater levels of biological complexity. Nevertheless, single-species tests could be used as a fast screening approach to assess the potential of a substance to accumulate in biota before more complex tests are conducted.

Silver nanoparticles (AgNPs) are highly produced in developed countries for a variety of products. Consequently, AgNPs end up being introduced in aquatic systems all over the world, and usually deposited in riverine sediments, from where they can be taken up by aquatic organisms and transferred along the food chain. The analysis of AgNPs in natural samples is not an easy task, because of their low presence and complicated reactions, which can change their speciation. The objective of this work is to help in this challenge, developing a method applicable to analyse sediment samples from any place around the world where AgNPs are suspected to be present. Firstly, four methods for the synthesis of AgNPs were investigated by Ultraviolet–visible (UV–VIS) spectroscopy and particle size analysis. The methods differed in the reducing agent used and in the concentration of the stabilising agent applied. The method including NaBH4 and SDS (sodium dodecyl sulphate) resulted to be more adequate as the Surface Plasmon Resonance (SPR) band position and width indicated. This conclusion was corroborated considering the hydrodynamic diameters and polydispersity indices of the synthesised AgNPs. The Z-average hydrodynamic diameter and the UV–VIS spectrum of AgNPs synthesised using this method indicated that the AgNPs remained kinetically stable for at least 10 days. Finally, ten potential extraction solutions were investigated, in terms of maximal extraction efficiency, but minimal effects on AgNP dissolution and aggregation. The candidate solutions ranged from deionized water and salts to strong acids and bases. The intensity of the SPR band concluded that using NaOH media the synthesised AgNPs was kinetically stable. Moreover, TEM (Transmission Electron Microscopy) images showed that the AgNPs in NaOH retained their shape and size after 10 days. Therefore, NaOH media turned out to be the best potential extractant for the analysis of sediment samples.

Microplastic pollution of the terrestrial environment and its potential impact on ecosystem services are gaining increasing public and scientific attention. Although the number of investigations on microplastic presence in soil under different management systems is growing, knowledge on the potential mobility of microplastics and their spatial distribution within soil is still lacking. In particular, microplastic fibres are often considered less mobile in soil due to their elongated shape and the resulting potential entanglement in pore structures or aggregated soil particles. While these processes may affect their water-driven transport, biologically-driven transport may still occur unimpeded because particles may be ingested by macrofauna such as earthworms. Micro- and nanoplastic transport by earthworms has been previously observed, however, the effect of particle shape on the transport dynamics is still elusive.For understanding microplastic fibre transport in soil from a mechanistic perspective, we performed a series of process-studies with deep-burrowing earthworms, i.e. Lumbricus terrestris, in microcosms. We utilized metal-doped fibrous polyethylene terephthalate (PET) microplastics (1.27±0.66 mm) for a facilitated detection through acid extraction and subsequent analysis via inductively-coupled plasma mass-spectrometry. Fibres were spiked into the top of the soil columns of the microcosms, which were sampled according to specific depth segments every 7 days for four weeks. As a result, we were able to quantify fibre transport in soil profiles with a temporal resolution. Earthworms were important drivers of vertical transport of microplastic fibres in the soil, with fibres visibly incorporated into burrow walls. Thus, despite their elongated shape and relative larger size, microplastic fibres are not necessarily immobilized by interactions with soil particles, but continuously affected by burrowing soil organisms. Understanding these transport dynamics and the potential spatial distribution of microplastics of different shapes and sizes in the field is crucial in order to support appropriate sampling schemes for monitoring and for obtaining accurate mass estimates of microplastic pollution of terrestrial ecosystems.

The advancement of analytical methods for nanoparticle measurements is critical both for the growing industrial exploitation of engineered nanoparticles and for developing robust strategies to understand and control the concentration of nanomaterials in humans and the environment. For high value nanoparticles, the measurement of nanoparticle number concentration in a liquid directly impacts the ability to assess the scale and reproducibility of the production process, it allows optimisation of efficiency and supports regulatory compliance. This measurement is also useful to monitor and control the intentional or accidental release of engineered nanoparticles into the environment at the production plant, as well as by end-users., peer-reviewed

Plastic pollution is increasingly perceived as an emerging threat to terrestrial environments, but the spatial and temporal dimension of plastic exposure in soils is poorly understood. Bioturbation displaces microplastics (>1 μm) in soils and likely also nanoplastics (, Risk assessment of nanoplastics in soils should consider bioturbation that causes significant downward displacement and nanoplastic hotspots along burrow walls.

A novel method to directly quantify nanoparticles (NPs) in a soil matrix by laser ablation single particle inductively coupled plasma mass spectrometry (LA-sp-ICPMS) was developed. Different concentrations of 60, 100, or 250 nm diameter gold NPs (AuNP) were deposited directly on polyether sulfone (PES) ultrafiltration membranes or immersed in soil. The ICPMS sensitivity was calibrated using aqueous dissolved Au standards and an aqueous AuNP size standard dispersion was used to calculate the transmission efficiency. In the case of the soil samples, sizing proved to be more accurate when calibration occurred while ablating a non-spiked soil. A linear relation was found between the spiked AuNP number concentrations and the particle event frequencies measured in the ablated area. Particle recovery on PES filters ranged only between 29 to 42% and recovery of soil-spiked AuNP on thin tape was between 15 and 60% and increased with size. However, 70–85% mass recovery in the ablated area was obtained when the soil sample was deposited on a thicker, opaque double sided tape suggesting that the substrate material is instrumental in absorbing excess laser energy thus enhancing recovery. The rate of soil ablation and mass transfer into the plasma was quantified to calculate the recovery using the same soils spiked with indium. The presented method thus has significant potential to be used for routine quantification of the particle size distributions of engineered or natural NPs in soil and possibly other powder samples with significantly fewer artifacts than extraction followed by aqueous analysis.

Sewage sludge contains Ag2S-NPs causing NP exposure of soil fauna when sludge is applied as soil amendment. Earthworm bioturbation is an important process affecting many soil functions. Bioturbation may be affected by the presence of Ag2S-NPs, but the earthworm activity itself may also influence the displacement of these NPs that otherwise show little transport in the soil. The aim of this study was to determine effects of Ag2S-NPs on earthworm bioturbation and effect of this bioturbation on the vertical distribution of Ag2S-NPs. Columns (12 cm) of a sandy loamy soil with and without Lumbricus rubellus were prepared with and without 10 mg Ag kg−1, applied as Ag2S-NPs in the top 2 cm of the soil, while artificial rainwater was applied at ∼1.2 mm day−1. The soil columns were sampled at three depths weekly for 28 days and leachate collected from the bottom. Total Ag measurements showed more displacement of Ag to deeper soil layers in the columns with earthworms. The application of rain only did not significantly affect Ag transport in the soil. No Ag was detected in column leachates. X-ray tomography showed that changes in macro porosity and pore size distribution as a result of bioturbation were not different between columns with and without Ag2S-NPs. Earthworm activity was therefore not affected by Ag2S-NPs at the used exposure concentration. Ag concentrations along the columns and the earthworm density allowed the calculation of the bioturbation rate. The effect on the Ag transport in the soil shows that earthworm burrowing activity is a relevant process that must be taken into account when studying the fate of nanoparticles in soils. Earthworm bioturbation plays a more important role than rainfall in the vertical transport of Ag2S-NPs in soil.

Research in environmental risk assessment (ERA) of nanomaterials (NMs) has been an important incentive to develop analytical approaches to better understand and quantify fate and ecotoxicity of these materials in standard media and field environmental samples. This chapter presents and overview of the most recent insights in fate and ecotoxicity of NMs to steer analytical chemists to the most pressing analytical needs to further ERA of NMs thus avoid making it overly conservative. Sensitive analysis is required to quantify and characterize NMs at generally low expected concentrations (μg L− 1 to ng L− 1 range). Moreover, analysis of the core NM composition is required because many NMs are subject to transformation reactions in the environment, which in turn affects their fate and ecotoxicity. At the very minimum, dissolution of the NMs should be quantified, especially during standard ecotoxicity assays, while mesocosm-scale experiments have revealed unexpected NM behaviour that otherwise does not appear from standard tests. Finally, databases of relevant fate descriptors need development to aid NM fate prediction, similarly to soluble contaminants.

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.

A novel off-lattice three-dimensional coarse-grained Monte Carlo model is developed to study engineered nanoparticle (ENP) behavior in porous media. Based on individual particle tracking and on the assumption that different physicochemical processes may occur with different probabilities, our model is used to independently evaluate the influence of homoaggregation, attachment and detachment processes on ENP transport and retention inside porous media made of colloidal collectors. The possibility of straining, i.e. trapping of ENPs or aggregates that are too large to pass pore necks, is also included in the model. The overall probability of ENP retention as a function of the above mentioned processes is quantified using functional tests in the form of a alpha(global)(t(ref)) retention parameter. High alpha(global)(t(ref)) values were obtained for moderate probabilities of homoaggregation between ENPs (alpha(ENP-ENP)) and very small probabilities of attachment between ENPs and collectors (alpha(att)), thus indicating the important role of homoaggregation and attachment in ENP retention. Moreover, attaching ENPs and large aggregates was found to cause pore neck enclosure and thus largely contributed to the straining of unbound ENPs. An analysis of depth distribution of retained ENPs revealed that, depending on the dominating conditions, the number of ENPs was decreasing monotonously or exponentially with depth. The introduction of the ENP detachment probability (alpha(det)) from collectors resulted in an increased ENP occurrence at the porous media matrix outlet. It was also found that different sets of alpha(det) and alpha(att) values, reflecting different ENPs and collector physicochemical properties and inter-particle forces, lead to identical alpha(global)(t(ref)) values. This constitutes an important outcome indicating that alpha(global)(t(ref)) values determined from functional tests are not mechanistic but operationally defined parameters and thus cannot be deemed predictive beyond these tests.

Engineered nanomaterials (ENMs), i.e., man-made particles having at least one dimension smaller than 100 nm, have found their way into the environment. Parallel to the efforts to elucidate the possible harmful effects of ENMs, techniques have been developed to monitor environmental ENM concentrations. This chapter discusses the techniques that can currently distinguish ENMs from naturally occurring particles at realistic concentration detection limits without a tedious sample pretreatment procedure. For inorganic ENMs, the most promising approach is based on single particle ICP-MS, and this technique has been developed in recent years to measure solid samples in addition to aquatic samples and distinguish the many different forms of occurrence of ENMs in realistic samples from naturally occurring particles. The detection capabilities for C-based particles are lagging and will likely be the focus of analytical developments in the coming years.

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.

Quantification of the uptake and elimination of nanomaterials (NMs) by organisms is key in assessing the environmental risks of NMs. For this, uptake models for conventional solutes may be used, although no consensus exists on their applicability for NMs. In this critical review therefore, conventional modelling approaches are scrutinised for their applicability for NMs. Statically derived accumulation factors, like BCF or BAF based on measured concentrations, are considered to be flawed because NMs are thermodynamically not stable, an important assumption for this approach. Dynamically derived accumulation factors, based on kinetic exposure experiments, may be applicable because no equilibrium between the organism and exposure medium is needed. Currently there is no full understanding of the passive uptake of NMs, which hampers assessment of the applicability of biotic ligand models. Passive uptake, however, is generally considered to be very limited, which would imply a limited applicability of BLMs for NMs. Physiologically based pharmacokinetic (PBPK) models, or biodynamic models, have successfully been applied in uptake studies with NMs. Their underlying assumptions can be met in experiments addressing NMs and case studies presented in this review demonstrate their applicability to model NM-form specific kinetics, integrated with environmental fate models, including relevant physiological processes. Their application requires the a priori definition of the major mechanisms driving the uptake kinetics and the quantification of the associated kinetic rate constants. This limits their application to those mechanisms for which the kinetic rate constants can actually be quantified. Within these limitations, PBPK models have been shown to be applicable and provide a promising general approach to improve modelling of NM-accumulation in organisms.

Despite the consensus about the importance of chemical speciation in controlling the bioavailability and ecotoxicity of trace elements, detailed speciation studies during laboratory ecotoxicity testing remain scarce, contributing to uncertainty when extrapolating laboratory findings to real field situations in risk assessment. We characterized the speciation and ecotoxicological effects of chromium (CrIII and CrVI ) in the International Organization for Standardization (ISO) medium for algal ecotoxicity testing. Total and dissolved (< 0.22 μm) Cr concentrations showed little variability in media spiked with CrVI , whereas dissolved Cr concentration decreased by as much as 80% over a 72-h time period in medium amended with CrIII . Analyses by ion chromatography inductively coupled plasma mass spectrometry (IC-ICP-MS) highlighted the absence of redox interconversion between CrIII or CrVI both in the presence and absence of algal cells (Raphidocelis subcapitata). Furthermore, the concentration of ionic CrIII dropped below detection limits in less than 2 h with the corresponding formation of carbonate complexes and Cr hydroxides. Precipitation of CrIII in the form of colloidal particles of variable diameters was confirmed by nanoparticle (NP) tracking analysis, single particle ICP-MS, and single particle counting. In terms of time-weighted dissolved (< 0.22 μm) Cr concentration, CrIII was 4 to 10 times more toxic than CrVI . However, CrIII ecotoxicity could arise from interactions between free ionic CrIII and algae at the beginning of the test, from the presence of Cr-bearing NPs, or from a combination of the 2. Future ecotoxicological studies must pay more attention to Cr speciation to reliably compare the ecotoxicity of CrIII and CrVI . Environ Toxicol Chem 2018;37:983-992. © 2017 SETAC.

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.

Soils overlying buried gold (Au) and platinum (Pt) deposits are often Au/Pt-anomalous, widening exploration footprints. This may be a result of the dispersion of (bio)geochemically formed Au/Pt nanoparticles and their sorption/deposition by solid soil phases. However, the influence of soil properties on nanoparticle dispersion, sorption and partitioning are little understood. To assess the partitioning and sorption behaviour of Au- and Pt nanoparticles, soils were spiked with spherical, citrate-stabilized Au- and Pt nanoparticles (diameter: 10–12 nm, final concentration 100 μg kg− 1). Soil slurries (1:10, w:w, soil:deionized water) were incubated at 22 °C on an end-over-end shaker for 28 days. Gold/Pt concentrations were measured in 0.45 μm and 1 kDa filtered solutions using inductively coupled plasma-mass spectrometry. Neither Pt nor Au were detected in 1 kDa filtrates. Between 10.3 and 98.7 wt% of Au/Pt was sorbed to solid soil phases. Clay, Corg, Mg, Mn, Fe and Ca contents of soils were significant predictors of Au/Pt-nanoparticle sorption, with clay content explaining > 80% of variation within the Au sorption dataset. Partitioning of sorbed nanoparticles between solid phases was assessed using selective sequential extractions. In all soils 1–20 wt% of Au/Pt was detected in watery extracts. A further 1–25 wt% were associated with the easily remobilizable fraction. The majority of sorbed Au/Pt nanoparticles were sorbed to the organic matter (OM, 53–77 wt% for Pt and 14–80 wt% for Au) and the Fe/Mn-oxides (up to 42 wt%). These results show that: i) Au- and Pt nanoparticles are stable and can remain highly mobile/dispersible in soil solutions, and ii) elevated clay, Corg and Fe/Mn-oxide contents decrease, whereas elevated sand contents and pH increase their mobility. Across all soils, OM and clays were the most important sorbent of Au/Pt nanoparticles, suggesting that the separation of clays and OM, and analyses of their Au/Pt-contents may enhance the contrast of geochemical footprints.

Biogeochemical processes are known to drive the cycling of gold via dissolution/re-precipitation reactions that result in the transformation of gold grain in near-surface environments. In this study, placer gold grains were collected from West Coast Creek, Queensland, Australia and characterized using high-resolution electron microscopy. The outer surface of grains contains 98.1 mol% Au and 1.9 mol% Ag. Crevices occur on the surface of grains and are filled with organics and clay minerals in which nanometer-size gold colloids and micrometer-sized octahedral gold platelets are embedded. The formation of these secondary gold structures is attributed to gold precipitation by the availability of reducing agents such as microbiota, residual organics and clays. Bacterioform gold contains 74.7 mol% Au and 25.3 mol% Ag and is also embedded in clay minerals within crevices. From sonicated gold grains, grain surfaces beneath the clay minerals are striated and contain 68.5 mol% Au and 31.5 mol% Ag. This data suggests that dissolution processes occur at the gold grain interface. Varying sizes of gold colloids on the grains suggest that five ‘episodes’ of gold dissolution/re-precipitation processes occurred; each episode was estimated to be 7.64 ± 4.1 years. Therefore, these grains represent 17.9–58.5 years of gold cycling and mobilization within this subtropical environment. Furthermore, laboratory experiments involving colloidal gold dispersion demonstrated that iron-oxides and organic material from West Coast Creek sediment adsorbed 94.5% of suspended gold colloids. In conclusion, this study highlights the value of nanophase gold characterization for the interpretation of biogeochemical processes affecting gold grain transformation and mobility in near-surface environments. Importantly, this study is the first to estimate the kinetics of biogeochemical gold cycling with regards to colloidal gold dispersion and re-concentration.

Sewage sludge contains Ag

Iron oxyhydroxide nanoparticles (Fe-NPs) are natural vectors of phosphate (PO4) in the environment. Their mobility is determined by colloidal stability, which is affected by surface composition. This might be manipulated in engineered NPs for environmental or agricultural applications. Here, the stability of PO4-Fe-NPs (HFO/goethite) was determined across contrasting environmental conditions (pH, Ca concentration) and by using fulvates (FA) and polyphosphates (poly-P’s) as coatings. The PO4-Fe-NPs are unstable at Ca concentrations above 0.1 mM. Addition of FA and some poly-P’s significantly improved stability. Zeta potential explained colloidal stability across treatments; surface charge was calculated with surface complexation models and explained for phytic acid (PA) and hexametaphosphate (HMP) by a partial (1–4 of the 6 PO4 units) adsorption to the surface, while the remaining PO4 units stayed in solution. This study suggests that Ca concentration mainly affects the mobility of natural or engineered PO4-Fe-NPs and that HMP is a promising agent for increasing colloidal stability. ispartof: Journal of Agricultural and Food Chemistry vol:64 issue:45 pages:8465-8473 ispartof: location:United States status: published

Gold nanoparticles (AuNP) possess unique characteristics that render them adequate for applications and also to be used as a model NP to evaluate the fate and behavior at low NP concentrations due to the ease of detection by modern analytical techniques. Moreover, AuNP may result in some negative effects in the environment and there is a necessity to predict their aquatic environmental concentrations by parameterizing the underlying transport and transformation processes. This study investigated the coagulation and sedimentation of 30 nm citrate-coated AuNP under enviro-mimicking conditions, i.e. model natural freshwaters (MNW) covering the range of European water chemistries relevant for colloids and NP (major ions, pH and dissolved organic matter) and artificial seawater (ASW). Firstly, the coagulation rates of AuNP at mg/L concentrations were evaluated using time-resolved dynamic light scattering which showed a decreased rate upon addition of Suwannee river natural organic matter (SRNOM) at low ionic strength (IS) but remained relatively high at high IS. Contrastingly, AuNP approaching environmental realistic concentrations (80 μg/L) in quiescent microcosms showed slow decline rates in all MNW and ASW regardless of the presence of SRNOM, as measured by nanoparticle tracking analysis and elemental Au spectrometry. When illite was added as model natural colloid the rates of decline of AuNP remained low as well. This is owing to limited collisions at low particle number concentrations. The results show that besides IS, pH, NOM concentration and type and the intrinsic surface charge of the particles, the particle number concentration and size distribution of both AuNP and natural colloids determine the extent of the large-scale fate of NP in aquatic environments.

International audience; 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.

Laboratory-based leaching tests are frequently used for in situ risk assessments of contaminant leaching to groundwater and surface waters. This study evaluated the ability of three standardised leaching tests to assess leaching of lead (Pb), zinc (Zn), arsenic (As) and antimony (Sb) from four intact soil profiles, by considering particulate (0.45-8 μm; percolation test), colloidal (10 kDa-0.45 μm) and truly dissolved (10 kDa) fractions of these elements. Deionised water was used as the percolation test leachant, while either deionised water or 1 mM CaCl

This chapter covers how engineered nanomaterials (ENMs) may enter soils, how they behave in soils, the exposure dynamics this presents to soil organisms, and resulting issues for uptake and food-chain transfer. Special attention is given to summarizing the main issues and the current state of the art for the most important elements of how ENMs act as pollutants in soil, namely: The routes and consequent forms of entry of ENMs from nanoenabled products into soils; the fate and transformations ENMs undergo in soil systems; ENM bioavailability to and interactions with soil biology, including exposure and hazard assessment, toxicokinetics, and trophic transfer.

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.

Despite the consensus about the importance of chemical speciation in controlling the bioavailability and ecotoxicity of trace elements, detailed speciation studies during laboratory ecotoxicity testing remain scarce, contributing to uncertainty when extrapolating laboratory findings to real field situations in risk assessment. We characterized the speciation and ecotoxicological effects of chromium (Cr

Chromium is a common soil contaminant and, although it has been studied widely, questions about its speciation and dissolutions kinetics remain unanswered. We combined information from an irrigation experiment performed with intact soil columns with data from batch experiments to evaluate solubility and mobilization mechanisms of Cr(III) in a historically contaminated soil (65 years). Particulate and colloidal Cr(III) forms dominated transport in this soil, but their concentrations were independent of irrigation intensity (2-20 mm h

The quantities of engineered nanoparticles (NP) released to the environment are often influenced by their fate in waste water treatment plants (WWTP). Here, 40 nm silver NP (AgNP) were spiked into a mesocosm simulating the process used at a major municipal WWTP. The evolution of the mass distributions and number concentrations were followed by fast acquisition speed technique single particle inductively coupled mass spectrometry (FAST spICP-MS) using a high-resolution ICP-MS. It was thus possible to detect smaller Ag containing NP than hitherto possible in similar studies. These small particles (ca. 5–10 nm in corresponding metallic Ag equivalent spherical diameter) were possibly dissolved Ag+ precipitated as Ag2S particles. They were detected immediately upon spiking and were stable with respect to aggregation and thus much less removed by the WWTP process compared to the 40 nm AgNP. The results also suggested that any transformation of the latter AgNP occurred without dissolution. Most of these larger AgNP were probably removed by aggregation with large floc particles and subsequent sedimentation with the suspended particulate matter in the simulated WWTP process. The results have implications for differentiating the fate of nanoparticles as a function of size and demonstrate how spICP-MS can reveal such size-dependent fate dynamics.

Correction for ‘Measurement of number concentrations and sizes of Au nano-particles spiked into soil by laser ablation single particle ICPMS’ by Jani Tuoriniemi et al., J. Anal. At. Spectrom., 2020, 35, 1678–1686, DOI: 10.1039/D0JA00243G

Single particle ICP-MS (spICP-MS) analysis of inorganic nanoparticles (NPs) cannot accurately distinguish dissolved ion signals and signals from relatively small NPs, although these particles are often more reactive than their larger counterparts. A signal deconvolution method was developed for spICP-MS analysis using gold (Au) NPs of nominally 10, 15 or 30 nm diameter. The signal distributions of dissolved Au standards were parameterised as a function of concentration using a mixed Polyagaussian probability mass function. Dissolved curves were fitted using this parameterisation to the low-intensity signals of samples containing NPs to subtract and deconvolute the dissolved signals from the particle signals. The dissolved signals were quantified in this process. The accuracy of the deconvolution method was confirmed for all NP suspensions studied when comparing the size and number concentration obtained with the deconvolution method with values based on transmission electron microscopy. This method thus allows analysis of NP suspensions with spICP-MS where it was hitherto not possible. The applicability domain lies predominantly with relatively small NPs and/or when a relatively high concentration of dissolved ions of the element of interest is present, where overlapping between dissolved and particulate signals occurs.

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

Wastewater treatment (WWT) is generally efficient in removing nanoparticles (NPs) from sewage effluent, but the variety in removal rates has not yet been explained. WWT parameters such as the activated sludge (AS) concentration, shear rate and ionic strength were varied in kinetic batch attachment and sedimentation studies using silver NPs having nominal 20 or 80 nm sizes and citrate or PEG coatings. The fitted attachment and detachment rate constants and the resulting distribution ratios at steady state varied with WWT process parameters, but most notably with the NP size, which was also found to influence the settling rates most. The NP coating molecules had a limited or no effect. A meta-analysis of literature distribution ratios (attached/detached concentration) of NPs composed of Ag and other materials showed the NP (aggregate) size as the only significant parameter. However, while the distribution ratio of silver NPs to AS increased linearly with AS concentration, the final effect of NP effluent concentrations is partly offset by decreased sedimentation rates. The results thus confirm that a WWT process is efficient in removing NPs from wastewater, but relatively small (

Iron oxyhydroxide nanoparticles (Fe-NPs) are natural vectors of phosphate (PO

Developing methods to measure interactions of carbon nanotubes (CNTs) with soils and sediments and understanding the impact of soil and sediment properties on CNT deposition are essential for assessing CNT environmental risks. In this study, we utilized functionalized carbon-14 labeled nanotubes to systematically investigate retention of multiwall CNTs (MWCNTs) by 3 humic acids, 3 natural biopolymers, and 10 model solid-phase polymers, collectively termed macromolecules. Surface properties, rather than bulk properties of macromolecules, greatly influenced MWCNT retention. As shown via multiple linear regression analysis and path analysis, aromaticity and surface polarity were the two most positive factors for retention, suggesting retention was regulated by π-π stacking and hydrogen bonding interactions. Moreover, MWCNT deposition was irreversible. These observations may explain the high retention of MWCNT in natural soils. Moreover, our findings on the relative contribution of each macromolecule property on CNT retention provide information on macromolecule selection for removal of MWCNTs from wastewater and provide a method for measuring CNT interactions with organic macromolecules.

Article history:Received 20 September 2011Accepted 21 June 2012Keywords:Adsorption (C)Stability (C)Carbonation (C)Monosulphate (D)Waste management (E) Antimonate (Sb(OH) 6 ) leaching in hydrated cement pastes (HCP) was investigated by adsorption isothermswith cement minerals, EXAFS, geochemical modelling and by synthesising the antimonate AFm end-member,Ca 4 Al 2 [Sb(OH) 6 ] 2 (OH) 12 ·3H 2 O. Antimonate forms inner-sphere complexes with portlandite and ettringitesurfaces. Much stronger interaction of antimonate with monosulphate was most likely AFm solid solutionformation, whereas the mechanism of strong sorption by C S H was unclear. Modelling Sb leaching fromHCP containingca.1000 mg kg 1 Sb and EXAFS analysis suggested the variable structure of calcium antimo-nate may explain the Sb leaching increase at decreasing pH or extended carbonation times. In HCP with lowerSb concentrations (ca.300 mg kg 1 ) leaching is lower probably because it is controlled by a combination ofAFm solid solution and/or C S H adsorption that can ensure long-term stabilisation, whereas calcium anti-monate precipitation appears sensitive to weathering reactions such as carbonation.© 2012 Elsevier Ltd. All rights reserved.

The solubility of Zn in Zn fertilizers plays an important role in the agronomic effectiveness of the fertilizer. On the basis of thermodynamics, zinc oxide (ZnO) nanoparticles (NPs) should dissolve faster and to a greater extent than bulk ZnO particles (equivalent spherical diameter >100 nm). These novel solubility features of ZnO NPs might be exploited to improve the efficiency of Zn fertilizers. In this study, we compared the Zn solubility and dissolution kinetics of ZnO nanoparticles and bulk ZnO particles coated onto two selected granular macronutrient fertilizers, urea and monoammonium phosphate (MAP). The main Zn species on coated MAP and urea granules were zinc ammonium phosphate and ZnO, respectively. Coated MAP granules showed greater Zn solubility and faster dissolution rates in sand columns compared to coated urea granules, which may be related to pH differences in the solution surrounding the fertilizer granules. The kinetics of Zn dissolution was not affected by the size of the ZnO particles applied for coating of either fertilizer type, possibly because solubility was controlled by formation of the same compounds irrespective of the size of the original ZnO particles used for coating.

The technical properties of cement mortars containing natural fine aggregate that is replaced by lead blast furnace slag at 25 and 35% level were assessed at fixed water-to-cement (W/C) ratio and at fixed flow table value. The leachabilities of some toxic elements from the cement mortars were also assessed to test the environmental suitability of the slag for use in preparation of cement mortar. At fixed W/C ratio, the strength of the mortar decreased with increase of the slag content. On the other hand, at fixed consistency, strength increased with increasing slag content in the mortar composition. The concentrations of some toxic elements in the leachates collected from the mortars containing slag were slightly higher than for the control mortar, but the concentrations in the leachates remained within the regulatory limits for recycling in construction applications. For most elements, leaching from a mortar containing 35% of slag was similar to that from a mortar containing 25% of slag. Therefore, 35% of natural sand can be beneficially replaced with Pb slag to produce cement mortar without affecting the mechanical and leaching properties studied in this work.

The detection capabilities of single particle inductively coupled plasma-mass spectrometry (spICPMS) with respect to particle size and number concentrations are investigated for the case of silver nanoparticles (ca. 20-80 nm). An iterative algorithm was developed where particle measurement events were distinguished as outliers from the more continuous dissolved ion signal if the measured intensity was more than five times the standard deviation of the whole data set. The optimal dwell time for 40-80 nm particles, limiting both incomplete and multiple particle events, was 5 ms. The smallest detectable particle size (ca. 20 nm) is mainly limited by the overlap of particle events and dissolved signal that increases with noise on both signals. The lowest measurable number concentration is limited by the relative frequency of erroneously identified particle events, a limit that can be reduced by acquiring more data points. Finally, the potential of spICPMS for environmental detection of nanoparticles is demonstrated for a wastewater treatment plant effluent sample.

Ecotoxicology research is using many methods for engineered nanomaterials (ENMs), but the collective experience from researchers has not been documented. This paper reports the practical issues for working with ENMs and suggests nano-specific modifications to protocols. The review considers generic practical issues, as well as specific issues for aquatic tests, marine grazers, soil organisms, and bioaccumulation studies. Current procedures for cleaning glassware are adequate, but electrodes are problematic. The maintenance of exposure concentration is challenging, but can be achieved with some ENMs. The need to characterize the media during experiments is identified, but rapid analytical methods are not available to do this. The use of sonication and natural/synthetic dispersants are discussed. Nano-specific biological endpoints may be developed for a tiered monitoring scheme to diagnose ENM exposure or effect. A case study of the algal growth test highlights many small deviations in current regulatory test protocols that are allowed (shaking, lighting, mixing methods), but these should be standardized for ENMs. Invertebrate (Daphnia) tests should account for mechanical toxicity of ENMs. Fish tests should consider semistatic exposure to minimize wastewater and animal husbandry. The inclusion of a benthic test is recommended for the base set of ecotoxicity tests with ENMs. The sensitivity of soil tests needs to be increased for ENMs and shortened for logistics reasons; improvements include using Caenorhabditis elegans, aquatic media, and metabolism endpoints in the plant growth tests. The existing bioaccumulation tests are conceptually flawed and require considerable modification, or a new test, to work for ENMs. Overall, most methodologies need some amendments, and recommendations are made to assist researchers.

The stability of pyrochlores as a function of solution composition is relevant in the context of hazardous waste immobilisation as this mineral family comprises minerals that can control actinide solubility in ceramic formulations as well as romeites or calcium antimonates that possibly control the solubility of Sb in cement pastes. However, to date, no thermodynamic model exists that can be used for long-term risk assessment of pyrochlores as stabilising minerals. In this work synthetic romeites were precipitated at pH 6.5 and pH 12 and at varying molar Ca:Sb ratio and analysed by XRD and Rietveld refinement which showed that, like naturally occurring romeites, synthesized romeites have a Ca1+xSb2O6OH2−2x structure with less vacancies and a higher Ca-content as pH and Ca-availability were higher during synthesis. These romeites dissolve incongruently with preferential Ca leaching and antimonate is less soluble from romeites synthesized in alkaline conditions. Batch extractions of romeite in equilibrium with increasing Ca(NO3)2 additions up to 1 mol L−1 showed a minimum equilibrium Sb concentration at [Ca] = 0.01 mol L−1 that could only be explained by assuming the formation of a CaSb ( OH ) 6 + complex. Increasing the Ca concentration in romeite suspensions also resulted in a pH decline in the equilibrium solution, which may be explained by the increasing concomitant uptake of Ca2+ and OH− in the romeite structure as a function of increasing Ca(NO3)2 additions. Thermodynamic modelling supported these assumptions that may explain the incongruent dissolution behaviour of romeite, but the fitting of two equilibrium constants was required. Although the validity of these constants needs more experimental confirmation, this study suggests that despite possible CaSb ( OH ) 6 + formation, the solubility of Ca antimonate in alkaline conditions can be responsible for lower equilibrium Sb concentrations than previously assumed.

Geochemical modelling of leaching of oxyanion forming elements such as arsenic (As) and selenium (Se) is frequently not successful. A consistent thermodynamic dataset of As and Se was therefore composed, not only including precipitation, but also adsorption and solid solution, and was applied to the pH-dependent leaching behaviour of As and Se in an alkaline residue with a pH 11.1 from the lime treatment of sulphuric acid wastewaters from the production of non-ferrous metals. The As and Se content ranged up to 6.7 wt% and 0.29 wt%, respectively and speciation analysis showed that 96.3% of As occured as arsenate whereas Se speciation comprised 79% selenate and 21.0% selenite. XRD and SEM/EDX analysis showed that arsenate occurred as rauenthalite (Ca 3 (AsO 4 ) 2 ·10H 2 O), associated with gypsum, the most important mineral. Arsenate and arsenite concentrations were only slightly below equilibrium with rauenthalite and calciumarsenite (CaHAsO 3 ), respectively and consideration of adsorption and solid solution only marginally improved model predictions. Selenate (Se VI ) and selenite (Se IV ), on the other hand, were far from equilibrium with their corresponding calcium metalate. The application of solid solutions and adsorption of Se VI and Se IV oxyanions with gypsum, calcite and ettringite significantly improved model predictions but missing thermodynamic data and especially the lack of a comprehensive model for solid solution and surface exchange with calcite and ettringite still hampered efficient modelling.

An overview is presented on possible mechanisms that control the leaching behaviour of the oxyanion forming elements As, Cr, Mo, Sb, Se, V and W in cementituous systems and alkaline solid wastes, such as municipal solid waste incinerator bottom ash, fly ash and air pollution control residues, coal fly ash and metallurgical slags. Although the leachability of these elements generally depends on their redox state, speciation measurements are not common. Therefore, experimental observations available in the literature are combined with a summary of the thermal behaviour of these elements to assess possible redox states in freshly produced alkaline wastes, given their origin at high temperature. Possible redox reactions occurring at room temperature, on the other hand, are reviewed because these may alter the initial redox state in alkaline wastes and their leachates. In many cases, precipitation of oxyanions as a pure metalate cannot provide a satisfactory explanation for their leaching behaviour. It is therefore highly likely that adsorption and solid solution formation with common minerals in alkaline waste and cement reduce the leachate concentration of oxyanions below pure-phase solubility.

Exposure assessment of engineered nanoparticles (ENPs) in soil and sediment is severely hampered by a lack of understanding of the underlying processes and of the impact of matrix constituents on the fate of ENPs in natural systems, including porewater properties like pH, ionic strength, and presence of naturally occurring (nano)particles. Additional issues such as lack of proper methods for in-situ assessment of ENP speciation, ENP ageing, and agglomeration state, hinder proper exposure assessment. Let alone that the lack does not allow for development of predictive methods for endpoints like transformation and agglomeration potential. This paper discusses current approaches for fate assessment of ENPs in solids dominated media and addresses the most prominent knowledge gaps and how these may be addressed. It is concluded that the key issue to be dealt with, are the attachment and deposition processes that are characteristic for ENPs as opposed to equilibrium-driven partitioning processes of non-particulate organic and inorganic contaminants.

Modeling the environmental fate of nanomaterials (NMs) and their uptake by cells and organisms in the environment is essential to underpin experimental research, develop overarching theories, improve our fundamental understanding of NM exposure and hazard, and thus enable risk assessment of NMs. Here, we critically review the state-of-the-art of the available models that can be applied/adapted to quantify/predict NM fate and uptake in aquatic and terrestrial systems and make recommendations regarding future directions for model development. Fate models have evolved from substance flow analysis models that lack nano-specific processes to more advanced mechanistic models that (at least partially) take nano-specific (typically non-equilibrium, dynamic) processes into account, with a focus on key fate processes such as agglomeration, sedimentation and dissolution. Similarly, NM uptake by organisms is driven by dynamic processes rather than by equilibrium partitioning. Hence, biokinetic models are more suited to model NM uptake, compared with the simple bioaccumulation factors used for organic compounds. Additionally, biokinetic models take speciation processes (e.g. particulate versus ionic uptake) into account, although identifying essential environment-specific processes to include in models remains a challenge. The models developed so far require parameterization, calibration and validation with available data, e.g. field data (if available), or experimental data (e.g. aquatic and terrestrial mesocosms), rather than extension to more complex and sophisticated models that include all possible transformation processes. Collaborative efforts between experimentalists and modelers to generate appropriate ground-truth data would advance the field most rapidly.

Porosity is possibly an important parameter with respect to leaching of constituents from cement monoliths. During its lifetime, the pore structure of cementitious matrices changes due to carbonation and leaching. This paper discusses the effects of both accelerated carbonation and continuous leaching on the porosity, and, conversely, how porosity affects leaching properties. Two sample types are investigated: a mortar with MSWI-bottom ash substituting the sand fraction and a cement paste with 30 wt% of the cement substituted by a flue gas cleaning residue. The samples have been intensively carbonated in a 20% CO2 atmosphere for up to 60 days and were subsequently leached. The porosity was investigated by mercury intrusion porosimetry. Accelerated carbonation decreases total porosity by 12% in the case of 60 days of treatment of bottom ash mortars, whereas continuous leaching during 225 days increases it by 16%. Both carbonation and leaching decrease the amount of smaller capillary pores. Carbonation decreases both porosity and pH. Decreasing porosity diminishes leaching of sodium and potassium, while the decrease in pH increases leaching. However, the former process dominates the latter, resulting in a net decreasing effect of carbonation on the release of sodium and potassium from these cement matrices.

Environmental reporting with quantitative indicators is becoming popular worldwide. However, environmental response indicators, which describe the reaction of societal actors to environmental problems and to government policy, still remain under investigation. This paper describes the collection of potential response indicators for the industry and energy sectors in Flanders, the quality assessment, and the identification of a core set of suitable response indicators. The selected core set consists of four indicators: eco-efficiency (a mainstream indicator for decades), the presence of an environmental management system, the amount of environmental expenditures and the use of sustainable energy. This core set is applied to the Flemish situation in order to assess the environmental performance of the industry and energy sectors. The core set allows identification of areas where the industry and energy sectors are performing better than other sectors, as well as areas where additional efforts are needed.

The leaching of Sb from waste-to-energy (WtE) bottom ash (BA) often exceeds the Dutch limit value of 0.32mgkg(-1) for recycling of BA in open construction applications. From the immobilization mechanisms described in the literature, it could be concluded that both Ca and Fe play an important role in the immobilization of Sb in WtE BA. Therefore, Ca and Fe containing compounds were added to the samples of the sand fraction of WtE BA, which in contrast to the granulate fraction is not recyclable to date, and the effect on the Sb leaching was studied by means of batch leaching tests. Results showed that addition of 0.5 and 2.5% CaO, 5% CaCl2, 2.5% Fe2(SO4)3 and 1% FeCl3 decreased the Sb leaching from 0.62±0.02mgkgDM(-1) to 0.20±0.02, 0.083±0.044, 0.25±0.01, 0.27±0.002 and 0.29±0.02mgkgDM(-1), respectively. Due to the increase in pH from 11.41 to 12.53 when 2.5% CaO was added, Pb and Zn leaching increased and exceeded the respective leaching limits. Addition of 5% CaCO3 had almost no effect on the Sb leaching, as evidenced by the resulting 0.53mgkgDM(-1) leaching concentration. This paper shows a complementary enhancement of the effect of Ca and Fe, by comparing the aforementioned Sb leaching results with those of WtE BA with combined addition of 2.5% CaO or 5% CaCl2 with 2.5% Fe2(SO4)3 or 1% FeCl3. These lab scale results suggest that formation of romeites with a high Ca content and formation of iron antimonate (tripuhyite) with a very low solubility are the main immobilization mechanisms of Sb in WtE BA. Besides the pure compounds and their mixtures, also addition of 10% of two Ca and Fe containing residues of the steel industry, hereafter referred to as R1 and R2, was effective in decreasing the Sb leaching from WtE BA below the Dutch limit value for reuse in open construction applications. To evaluate the long term effect of the additives, pilot plots of WtE BA with 10% of R1 and 5% and 10% of R2 were built and samples were submitted to leaching tests at regular intervals over time. The Sb leaching from untreated WtE BA was just below or above the Dutch limit value. The Sb leaching from the pilot plots of BA with additives first remained stable around 0.13mgkg(-1) but had a tendency to slightly increase after 6months, indicating the need for further research on the effect of weathering, and more specifically of carbonation, on Sb leaching from WtE BA. publisher: Elsevier articletitle: Immobilization of antimony in waste-to-energy bottom ash by addition of calcium and iron containing additives journaltitle: Waste Management articlelink: http://dx.doi.org/10.1016/j.wasman.2016.05.007 content_type: article copyright: © 2016 Elsevier Ltd. All rights reserved. ispartof: Waste Management vol:54 pages:162-168 ispartof: location:United States status: published

The recycling potential of municipal solid waste incinerator (MSWI) bottom ash may be limited by the leaching of antimony (Sb). Therefore, treatment methodologies need to be developed. The pH-dependent leaching behaviour of this oxyanion-forming element in fresh and weathered bottom ash is, however, not understood. Sb leaching was investigated in a wide range of both pH and extent of carbonation. Sb came close to equilibrium with calcium antimonate (Ca[Sb(OH)(6)](2)) at acid and neutral pH. Therefore, adsorption experiments with synthetic calcite (CaCO(3)), ettringite (Ca(6)Al(2)(SO(4))(3)(OH)(12) x 26H(2)O), gypsum (CaSO(4) x 2H(2)O), and portlandite (Ca(OH)(2)) and adsorption modelling to hydrous ferric oxides (HFO) and amorphous aluminium minerals (AAM) were conducted to investigate which minerals decrease Sb leaching below equilibrium with calcium antimonate. At pH12, calcium antimonate comes into solution due to portlandite formation, but the subsequent increase in Sb leaching is reduced due to strong interaction of Sb with portlandite and ettringite. Ettringite appears to be an important host mineral for Sb at the natural pH of mildly weathered bottom ash (11.8) because a minimum in leaching is observed. When pH is decreased below 10.5, ettringite dissolves and Sb comes into solution, approaching equilibrium with calcium antimonate near pH 9. Gypsum showed no affinity for Sb. The interaction of calcite with Sb was not clear. Adsorption modelling suggested that HFO, rather than AAM, control Sb leaching when pH9. During carbonation, Sb leaching first increased, most likely due to dissolution of ettringite. Then, Sb leaching decreased, since the pH became low enough to allow sorption by HFO.

DOI 10.1002/aic.10662Published online September 19, 2005 in Wiley InterScience (www.interscience.wiley.com).Contradictory leaching results from carbonated cement-bound wastes have been re-ported in various investigations. However, the degree of carbonation of the examinedsamples is rarely considered as an important parameter in leaching results. This articlefocuses on the effect of progressive carbonation on leaching properties of cement-boundwaste (bottom ash or flue gas cleaning residue), including uncarbonated, partiallycarbonated, and almost completely carbonated samples. Leaching is investigated aftercarbonation by means of semi-dynamic leaching of monoliths, supported by batch solu-bility and release measurements on particle-size reduced material. For partially carbon-ated samples, leaching of metals is in most cases less than observed from uncarbonatedsamples, resulting from the conversion of hydroxides to carbonates. For completelycarbonated samples, increased leaching of most metals was observed in comparison topartially carbonated samples, resulting from leachate induced transformation of carbon-ate into more soluble bicarbonate speciation.