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Abstract Microbial mats and microbialites are essential tools for reconstructing early life and its environments. To better understand microbial trace element cycling, a microbial mat was collected from the sinkhole systems of the western shores of the Dead Sea, a dynamic environment exhibiting diverse extreme environments. Intense arsenic enrichment was measured (up to 6.5 million times higher than current concentrations in water, and 400 times the bulk concentration in the mat). Arsenic was found predominantly as As(V) in organic molecules, as shown by XANES spectra and high‐resolution elemental mapping. Arsenic cycling genes obtained from metagenomic analysis were associated with arsenic detoxification, supporting an active mechanism of As(V) uptake, As(III) efflux and organoarsenic accumulation in the extracellular polymeric substances (EPS) of the mat. Thus, we propose that such localized As enrichment can be attributed to a transient increase in As(V) concentrations in the circulating subsurface water of the Dead Sea shore and its subsequent incorporation into organoarsenic molecules through microbial detoxification processes. Our data set supports the possibility of metalloid enrichment recorded in very localized facies due to rapid geogenic fluctuations in the chemistry of the water flowing over a biofilm. In this context, this example calls for caution in interpreting metal(loid) enrichment in organic matter‐rich layers and microbialites of Paleoproterozoic origin. Arsenic signatures in Precambrian organic matter and carbonate rocks may host biosignatures, including evidence for extracellular polymeric substances, As‐binding and detoxification processes, without supporting arsenotrophy. However, they provide clues to better assess the paleoenvironmental conditions at the time of microbial mat formation.

Unicellular algae play important roles in the biogeochemical cycles of numerous elements, particularly through the biomineralization capacity of certain species (e.g., coccolithophores greatly contributing to the organic carbon pump of the oceans), and unidentified actors of these cycles are still being discovered. This is the case of the unicellular alga Tetraselmis cordiformis (Chlorophyta) that was recently discovered to form intracellular mineral inclusions, called micropearls, which had been previously overlooked. These intracellular inclusions of hydrated amorphous calcium carbonates (ACCs) were first described in Lake Geneva (Switzerland) and are the result of a novel biomineralization process. The genus Tetraselmis includes more than 30 species that have been widely studied since the description of the type species in 1878.The present study shows that many other Tetraselmis species share this biomineralization capacity: 10 species out of the 12 tested contained micropearls, including T. chui, T. convolutae, T. levis, T. subcordiformis, T. suecica and T. tetrathele. Our results indicate that micropearls are not randomly distributed inside the Tetraselmis cells but are located preferentially under the plasma membrane and seem to form a definite pattern, which differs among species. In Tetraselmis cells, the biomineralization process seems to systematically start with a rod-shaped nucleus and results in an enrichment of the micropearls in Sr over Ca (the Sr∕Ca ratio is more than 200 times higher in the micropearls than in the surrounding water or growth medium). This concentrating capacity varies among species and may be of interest for possible bioremediation techniques regarding radioactive 90Sr water pollution.The Tetraselmis species forming micropearls live in various habitats, indicating that this novel biomineralization process takes place in different environments (marine, brackish and freshwater) and is therefore a widespread phenomenon.

Macrolitter, especially macroplastics, (> 0.5 cm) negatively impact freshwater ecosystems, where they can be retained along lake shores, riverbanks, floodplains or bed sediments. Long-term and large-scale assessments of macrolitter on riverbanks and lake shores provide an understanding of litter abundance, composition, and origin in freshwater systems. Combining macrolitter quantification with hydrometeorological variables allows further study of leakage, transport, and accumulation characteristics. Several studies have explored the role of hydrometeorological factors in influencing macrolitter distribution and found that river discharge, runoff, and wind only partially explains its distribution. Other factors, such as land-use features, have not yet been thoroughly investigated. In this study, we provide a country-scale assessment of land-use influence on macrolitter abundance in freshwater systems. We analyzed the composition of the most commonly found macrolitter items (referred to as 'top items', n = 42,565) sampled across lake shores and riverbanks in Switzerland between April 2020 and May 2021. We explored the relationship between eleven land-use features and macrolitter abundance at survey locations (n = 143). The land-use features included buildings, city centers, public infrastructure, recreational areas, forests, marshlands, vineyards, orchards, other land, and rivers and canals. The majority of top items are significantly and positively correlated with land-use features related to urban coverage, notably roads and buildings. Over 60% of top items were found to be correlated with either roads or buildings. Notably, tobacco, food and beverage-related products, as well as packaging and sanitary products, showed strong associations with these urban land-use features. Other types of items, however, did not exhibit a relationship with land-use features, such as industry and construction-related items. Ultimately, this highlights the need to combine measures at the local and regional/national scales for effective litter reduction., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Strontium-90 ( 90 Sr) is an artificial radioisotope produced by nuclear fission, with a relatively long half-life of 29 years. This radionuclide is released into the environment in the event of a nuclear incident, posing a serious risk to human and ecosystem health. There is a need to develop new efficient methods for the remediation of 90 Sr, as current techniques for its removal have significant technical limitations and involve high energy and economic costs. Recently, several species of green microalgae within the class Chlorodendrophyceae have been found to form intracellular mineral inclusions of amorphous calcium carbonate (ACC), which can be highly enriched in natural (non-radiogenic) Sr. As bioremediation techniques are an attractive option to address radioactive pollution, we investigated the capacity of the unicellular alga Tetraselmis chui (class Chlorodendrophyceae) to sequester 90 Sr. The 90 Sr uptake capacity of T. chui cells was assessed in laboratory cultures by monitoring the time course of radioactivity in the culture medium using liquid scintillation counting (LSC). T. chui was shown to effectively sequester 90 Sr, reducing the initial radioactivity of the culture medium by up to 50%. Thus, this study demonstrates the potential of the microalga T. chui to be used as a bioremediation agent against 90 Sr pollution.

The formation constants of about 100 different complexes of Ge(IV) with some 50 organic, low-molecular-weight ligands, principally bidentate oxygen and/or nitrogen donors, are determined by potentiometric titrations at 25 °C and an ionic strength of 0.1 mol L -1 (KNO 3 ). In the few cases for which literature data are available, these older data are critically discussed and completed in light of our new experimental data. The overall picture emerging from our work is that such complexes are comparatively weak, except when a chelate effect comes into play, as is observed with aminopolyols, α-hydroxocarboxylic acids, and carbohydrate derivatives, where even quantitative chelation of Ge is possible. No binding to amino acids or peptides is detected. An important finding is our evidence for the existence of a bridged dinuclear germanium(IV) tartrate complex in the aqueous phase, whose occurrence in solids was confirmed by X-ray diffraction beforehand. Our work has implications for the general understanding of the aqueous coordination chemistry of Ge, its geochemical cycling, and its behavior in environmental and biological systems. Potentiometric raw data for use by other researchers are publicly accessible in the repository Zenodo at CERN.

We identified the antimony species present in a wide variety of plastic samples by X ray absorption spectroscopy (XAS) at the Sb L 3 -edge. The samples contained different concentrations of antimony (Sb), ranging from PET bottles in which Sb compounds are used as catalysts, with concentrations around 300 mg/kg, to electrical equipment in which the element is used as a flame retardant, with concentrations of several tens of thousands of mg/kg. Although the shape of the spectra at the L 3 -edge is quite similar for all Sb reference materials, we were able to identify antimony glycolate or acetate in PET bottles, bound organic Sb in c-PET trays and senarmontite in electrical materials as the main Sb components. In samples with high Ca content (e.g., electrical objects, some c-PET food trays and textiles) the Ca K a emission line interferes with the Sb L a line by introducing a high background which reduces the signal-to-noise ratio in the Sb XAS spectrum, resulting in noisy and distorted spectra. The element-resolved map on a PET bottle sample revealed both Sb and Ca hot spots of around 10-20 microns in size, with no correlation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Because of their convenience, the demand for decorative plastic plants has been increasing over recent years. However, no information exists on the origin or nature of the polymers employed or the type of additives used in order to understand potential environmental impacts and inform safe and sustainable disposal or recycling practices. In this study, 203 parts or offcuts from 175 plastic plants acquired from European shops and venues have been analysed by X-ray fluorescence spectrometry to determine elemental content, while a selection has been analysed by infrared spectrometry to establish polymer type. The (usually green) moulded components (n = 159) were commonly constructed of polyethylene or polypropylene, while leaves and colourful petals (n = 40) were generally made of polyethylene terephthalate fabric that had been glued to the moulded component. However, both components also exhibited evidence of being coated with a resin or adhesive for support, protection or appearance. Barium, Fe, Ti and Zn-based additives were commonly encountered but more important from an environmental and health perspective were variable concentrations of potentially hazardous elements in the moulded parts: namely, Br (6.1 to 108,000 mg kg -1 ; n = 78), Pb (7.6 to 17,400 mg kg -1 ; n = 53) and Sb (58.6 to 70,800 mg kg -1 ; n = 17). These observations suggest that many of the moulded components are derived from recyclates that are contaminated by waste electronic and electrical plastic, introducing brominated flame retardants, the flame retardant synergist, Sb 2 O 3 , and Pb into the final product. There are no standards for these chemicals in plastic plants, but regulations for electronic plastic, toy safety and packaging are frequently exceeded or potentially exceeded. Widespread contamination of plastic plants may impose constraints on their recycling and disposal., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Aluminium, gallium, and indium are group 13 metals with similar chemical and physical properties. While aluminium is one of the most abundant elements in the Earth's crust, gallium and indium are present only in trace amounts. However, the increased use of the latter metals in novel technologies may result in increased human and environmental exposure. There is mounting evidence that these metals are toxic, but the underlying mechanisms remain poorly understood. Likewise, little is known about how cells protect themselves from these metals. Aluminium, gallium, and indium are relatively insoluble at neutral pH, and here we show that they precipitate in yeast culture medium at acidic pH as metal-phosphate species. Despite this, the dissolved metal concentrations are sufficient to induce toxicity in the yeast Saccharomyces cerevisiae. By chemical-genomic profiling of the S. cerevisiae gene deletion collection, we identified genes that maintain growth in the presence of the three metals. We found both shared and metal-specific genes that confer resistance. The shared gene products included functions related to calcium metabolism and Ire1/Hac1-mediated protection. Metal-specific gene products included functions in vesicle-mediated transport and autophagy for aluminium, protein folding and phospholipid metabolism for gallium, and chorismate metabolic processes for indium. Many of the identified yeast genes have human orthologues involved in disease processes. Thus, similar protective mechanisms may act in yeast and humans. The protective functions identified in this study provide a basis for further investigations into toxicity and resistance mechanisms in yeast, plants, and humans., (© The Author(s) 2023. Published by Oxford University Press.)

The interaction of V(IV) and V(V) with succinic acid was investigated by affinity capillary electrophoresis (ACE) in aqueous acid solutions at pH values 1.5, 2.0 and 2.4, and different ligand concentrations. V(IV) and V(V) form protonated complexes with succinic acid ligand at this pH range. The logarithms of the stability constants, measured at 0.1 mol L -1 (NaClO 4 /HClO 4 ) ionic strength and 25 °C, are logβ 111 =7.4 ± 0.2 and logβ 122 =14.1 ± 0.5 for V(IV), and logβ 111 =7.3 ± 0.1 for V(V), respectively. The stability constant values, extrapolated to zero ionic strength with the Davies equation, are logβ° 111 =8.3 ± 0.2 and logβ° 122 =15.6 ± 0.5 for V(IV) and logβ° 111 =7.9 ± 0.1 for V(V). The application of ACE to the simultaneous equilibria of V(IV) and V(V) (injection of two analytes) was also attempted. When the results were compared with those obtained when introducing only one analyte in the capillary, using the traditional version of the method, similar stability constants and precision are obtained. The possibility of studying two analytes simultaneously decreases the time needed for the determination of the constants; this feature is especially valuable when working with hazardous materials or when only small quantities of ligand are available., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Arsenic speciation was followed monthly along the spring productivity period (January-June 2021) in the Petit Lac (76 m deep) and in April and June 2021 in the Grand Lac (309.7 m deep) of Lake Geneva (Switzerland/France). Lake Geneva is presently an oligo-mesotrophic lake, and As-unpolluted. The water column never becomes anoxic but the oxygen saturation at the bottom of the Grand Lac is now below 30% owing to lack of water column mixing since 2012. Thus, this lake offers excellent conditions to study As behaviour in an unpolluted, oxic freshwater body. The following 'dissolved' As species: iAs(III), iAs(III + V), MA(III), MA(III + V), DMA(III + V), and TMAO were analysed by HG-CT-ICP-MS/MS. Water column measurements were complemented with occasional sampling in the main rivers feeding the lake and in the interstitial waters of a sediment core. The presence of MA(III) and TMAO and the predominance of iAs(V) in lake and river samples has been confirmed as well as the key role of algae in the formation of organic species. While the total 'dissolved' As concentrations showed nearly vertical profiles in the Petit Lac, As concentrations steadily increase at deeper depths in the Grand Lac due to the lack of mixing and build up in bottom waters. The evaluation of 25 years of monthly data of 'dissolved' As concentrations showed no significant temporal trends between 1997 and 2021. The observed seasonal character of the 'dissolved' As along this period coincides with a lack of seasonality in As mass inventories, pointing to a seasonal internal cycling of As species in the water column with exchanges between the 'dissolved' and 'particulate' ( i.e. , algae) fractions.

Although titanium dioxide (TiO 2 ) is the most widely used pigment in plastics, there is limited quantitative information available for consumer goods and environmental samples. Moreover, and despite its photocatalytic activity, the potential impacts of TiO 2 on the behaviour and fate of environmental plastics has received little attention. This paper compiles measurements of Ti in plastic samples from aquatic environments and in consumer goods that are known to make important contributions to environmental pollution. These data, along with a critical evaluation of experimental studies using TiO 2 -pigmented plastics, are used to formulate an understanding of how the pigment modifies the properties and persistence of environmental plastics. Titanium is heterogeneously distributed amongst different categories and sources of plastic, with concentrations ranging from <1 mg kg -1 in transparent-translucent materials to over 50,000 mg kg -1 in brightly coloured samples. Concentrations towards the higher end are sufficient to change positively buoyant polyolefins into negatively buoyant plastics, suggesting that environmental fractionation based on Ti content might occur. Accelerated leaching of TiO 2 from aged plastic has been demonstrated empirically, and while mobilised particles are reported within a size range greater than biotically-active titania nanoparticles, modelling studies suggest that the latter could be derived from TiO 2 pigments in the environment. Although rutile appears to be the most important polymorph of TiO 2 in non-fibrous plastics, the degree and type of engineered surface modification in consumer and environmental plastics are generally unknown. Surface modification is likely to have a significant impact on the photo-oxidative degradation of plastics and the mobilisation of fine (and, possibly, nano-sized) TiO 2 particles and requires further research., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Strontium-rich micropearls (intracellular inclusions of amorphous calcium carbonate) have been observed in several species of green microalgae within the class Chlorodendrophyceae, suggesting the potential use of these organisms for 90 Sr bioremediation purposes. However, very little is known about the micropearl formation process and the Ca and Sr uptake dynamics of these microalgae. To better understand this phenomenon, we investigated, through laboratory cultures, the behaviour of two species within the class Chorodendrophyceae: Tetraselmis chui, forming micropearls, and T. marina, not forming micropearls. We show that T. chui growth and micropearl formation requires available Ca in the culture medium, and that the addition of dissolved Sr can partially replace the function of Ca in cells. On the other hand, T. marina can grow without added Ca and Sr, probably due to its inability to form micropearls. T. chui cells show a high Ca and Sr uptake, significantly decreasing the concentration of both elements in the culture medium. Strontium is incorporated in micropearls in a short period of time, suggesting that micropearl formation is, most likely, a fast process that only takes a few hours. In addition, we show that micropearls equally distribute between daughter cells during cell division., (© 2022 The Authors. Environmental Microbiology Reports published by Society for Applied Microbiology and John Wiley & Sons Ltd.)

Once emitted into the environment, macro- (MaP), micro- (MP) and nanoplastics (NP) are exposed to environmental weathering. Yet, the effects of biogeochemical weathering factors occurring in the soil environment are unknown. As the transport, fate, and toxicity of MP and NP depend directly on their surface properties, it is crucial to characterize their transformation in soils to better predict their impact and interactions in this environment. Here, we used scanning transmission x-ray micro spectroscopy to characterize depth profiles of the surface alteration of environmental plastic debris retrieved from soil samples. Controlled weathering experiments in soil and with UV radiation were also performed to investigate the individual effect of these weathering factors on polymer surface alteration. The results revealed a weathered surface on a depth varying between 1 µm and 100 nm in PS, PET and PP environmental plastic fragments naturally weathered in soil. Moreover, the initial step of surface fragmentation was observed on a PS fragment, providing an insight on the factors and processes leading to the release of MP and NP in soils. The comparison of environmental, soil incubated (for 1 year) and UV weathered samples showed that the treatments led to different surface chemical modifications. While the environmental samples showed evidence of alteration involving oxidation processes, the UV weathered samples did not reveal oxidation signs at the surface but only decrease in peak intensities (indicating decrease of the number of chemical C bonds). After a one-year incubation of samples in soil no clear aging effects were observed, indicating that the aging of polymers can be slow in soils., Supplementary Information: The online version contains supplementary material available at 10.1186/s43591-023-00066-2., Competing Interests: Competing interestsThe authors declare no competing interests., (© Springer Nature Switzerland AG 2023.)

Lead chromate was commonly employed as a pigment in coloured road markings until restrictions led to the development of safer alternatives. In this study, the presence and concentrations of Pb and Cr have been determined in 236 road paints of various colours sampled from streets, highways, footways and carparks from eleven European countries. According to energy-dispersive X-ray fluorescence spectrometry, Pb was detected (>10 mg kg -1 ) in 148 samples at concentrations up to 17.2% by weight, and above 1000 mg kg -1 yellow was the dominant paint colour. Lead concentrations on an area basis varied from 0.02 to 8.46 mg cm -2 and the metal was located at different depths amongst the samples, suggesting that formulations had been painted both recently and historically (and overpainted). Chromium was detected (>5 to 50 mg kg -1 ) in 81 samples at concentrations between 20 and 20,000 mg kg -1 and most often in yellow paints, and concentrations co-varied with those of Pb. These observations, and results of scanning electron microscopy coupled with energy-dispersive X-ray spectrometry, suggested that heterogeneously dispersed PbCrO 4 was the dominant, but not the only, Pb-based pigment in the samples. Although there were significant international differences in frequency of Pb detection and median Pb concentrations, overall, and despite various, albeit complex, regulations, recent or extant road paint pigmented with Pb and Cr remains a pervasive environmental problem and a potential health risk in many European countries., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Although potentially hazardous chemical elements (e.g., Cu, Cr, Pb, Sb, Ti, Zn) have been studied in clothing textiles, their presence in cleaning textiles is unknown. In this study, 48 cleaning cloth products (consisting of 81 individual samples) purchased in Europe, and consisting of synthetic (petroleum-based), semi-synthetic or natural fibres or combinations of these different types, have been analysed for 16 chemical elements by X-ray fluorescence (XRF) spectrometry. Titanium was detected in most cases (median and maximum concentrations ~3700 and 12,400 mg kg -1 , respectively) and Raman microspectroscopy revealed that TiO 2 was present as anatase. Barium, Br, Cr, Cu, Fe and Zn were frequently detected over a range of concentrations, reflecting the presence of various additives, and Sb was present at concentrations up to about 200 mg kg -1 in samples containing polyester as catalytic residue from the polymerisation process. Lead was detected as a contaminant in four samples and at concentrations below 10 mg kg -1 . Overall, the range of the chemical element profiles and concentrations was similar to those for clothing materials published in the literature, suggesting that broadly the same additives, materials and processes are employed to manufacture cloths and clothing textiles. The mechanisms by which potentially hazardous chemical elements are released into the environment with microfibres or mobilised into soluble or nano-particulate forms remain to be explored., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

We have investigated the biomineralisation of barite ‒a useful proxy for reconstructing paleoproductivity‒ in a freshwater alga, Spirogyra, by combining in vitro and in vivo approaches to unveil the nature of its barite microcrystals. Scanning electron microscope (SEM) and energy-dispersive X-ray spectroscopy (EDXS) observations on simply dried samples revealed that the number and size of barite crystals were related to the barium concentration in the media. Additionally, their morphology showed a crystallographic face (011), which is not normally observed, suggesting the influence of organic molecules on the growth kinetics. The critical point drying method was used to preserve the internal and external structures of Spirogyra cells for SEM imaging. Crystals were found adjacent to the cytoplasmic membrane, near chloroplasts and fibrillary network. In vivo optical microscopy and Raman tweezer microspectroscopy in living cells showed that barite microcrystals are optically visible and follow cytoplasmic streaming. These results led us to propose that barite formation in Spirogyra occurs in the cytoplasm where barium and sulphate are both available: barium supplied non-selectively through the active transport of the divalent cations needed for actin polymerisation, and sulphate because necessary for amino acid biosynthesis in chloroplasts., (Copyright © 2022 The Authors. Published by Elsevier GmbH.. All rights reserved.)

Nanoplastics (NP) are of environmental and human health concern. We tested a novel NP extraction method and scanning transmission X-ray spectro-microscopy (STXM) in combination with near-edge X-ray absorption fine-structure spectroscopy (NEXAFS) to image and identify individual NP in environmental and food matrices. We (1) discussed the potential of STXM compared to other methods potentially suitable for NP analysis, (2) applied the method on NP suspensions of eight of the most common polymers, (3) analyzed environmental water and soil samples spiked with NP and (4) characterized NP in tea water infused in plastic teabags and unspiked soil samples. Here we show that STXM has methodological advantages and that polymers give characteristic spectra, which allows NP identification in environmental and food matrices. For soils we deliver a visual and spectroscopic characterization of NP, proving their presence and highlighting their diversity. Thus, STXM, can be used for the detection and characterisation of NP in different types of matrices., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

An unsuspected biomineralization process, which produces intracellular inclusions of amorphous calcium carbonate (ACC), was recently discovered in unicellular eukaryotes. These mineral inclusions, called micropearls, can be highly enriched with other alkaline-earth metals (AEM) such as Sr and Ba. Similar intracellular inclusions of ACC have also been observed in prokaryotic organisms. These comparable biomineralization processes involving phylogenetically distant microorganisms are not entirely understood yet. This review gives a broad vision of the topic in order to establish a basis for discussion on the possible molecular processes behind the formation of the inclusions, their physiological role, the impact of these microorganisms on the geochemical cycles of AEM and their evolutionary relationship. Finally, some insights are provided to guide future research., (© 2021 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.)

Historically, many additives and catalysts used in plastics were based on compounds of toxic metals (and metalloids), like arsenic, cadmium, chromium(VI), and lead. Despite subsequent restrictions, hazardous additives remain in plastics in societal circulation because of the pervasiveness of many products and the more general contamination of recycled goods. However, little is understood about their presence and impacts in the environment, with most studies focusing on the role of plastics in acquiring metals from their surroundings through, for example, adsorption. Accordingly, this paper provides a review of the uses of hazardous, metal-based additives in plastics, the relevant European regulations that have been introduced to restrict or prohibit usage in various sectors, and the likely environmental impacts of hazardous additives once plastics are lost in nature. Examination of the literature reveals widespread occurrence of hazardous metals in environmental plastics, with impacts ranging from contamination of the waste stream to increasing the density and settling rates of material in aquatic systems. A potential concern from an ecotoxicological perspective is the diffusion of metals from the matrix of micro- and nanoplastics under certain physico-chemical conditions, and especially favorable here are the acidic environments encountered in the digestive tract of many animals (birds, fish, mammals) that inadvertently consume plastics. For instance, in vitro studies have shown that the mobilization of Cd and Pb from historical microplastics can greatly exceed concentrations deemed to be safe according to migration limits specified by the current European Toy Safety Directive (17 mg kg -1 and 23 mg kg -1 , respectively). When compared with concentrations of metals typically adsorbed to plastics from the environment, the risks from pervasive, historical additives are far more significant., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Plastics (n = 3880) have been sampled from 39 beaches of ten Swiss lakes of varying sizes, hydrodynamics, and catchments, with a selection (n = 598) analysed for potentially hazardous (and regulated) chemical elements (As, Ba, Br, Cd, Cr, Hg, Pb, Sb, Se) by X-ray fluorescence spectrometry. Plastic objects and fragments with identifiable or unidentifiable origins were present on all beaches surveyed, and were often most abundant in proximity to major riverine inputs. Chemical elements were detected in between two (Hg) and 340 (Ba) samples with maximum concentrations exceeding 2% by weight for Ba, Cd, Cr, Pb, and Sb. Inter-element relationships and characteristics of the samples suggest that elements are largely present as various additives, including pigments (e.g., Cd 2 SSe, PbCrO 4 ), stabilizers (in polyvinyl chloride), and flame retardants (Br). Observations are similar to, and complement, those previously reported in Switzerland's largest lake (Lake Geneva). Comparison of concentrations of targeted chemical elements in beached plastic with currently used plastics illustrate the interest of these types of measurements in providing an insight into the persistence of plastics in standing stocks and in lakes. This information could help to introduce management schemes that consider whether plastic pollution is new or old and act accordingly., (© 2021. The Author(s).)

Polyvinyl chloride (PVC) is one of the most widely used thermoplastics but is also a material of concern because of the generation and release of harmful chemicals during its life cycle. Amongst the chemicals added to PVC are metal-based stabilisers and Sb-based halogenated flame retardant synergists. However, very little quantitative information exists on these additives, and in particular in PVC lost to the environment. In this study, the distribution of PVC amongst consumer plastics in societal circulation and plastics retrieved from marine and lacustrine beaches and agricultural soils are compared, along with the presence and concentrations of Ba, Cd, Pb, Sb, Sn and Zn as proxies for common metal-based additives and determined by X-ray fluorescence spectrometry. About 10% of consumer plastics and 2% of environmental plastics were constructed of PVC, with the discrepancy attributed to the long service lives and managed disposal of PVC used in the construction sector and the propensity of the plastic to sink in aquatic systems and evade detection. Metal-based additives, defined as having a metal concentration >1000 mg kg -1 , were present in about 75% of consumer and environmental PVC, with Ba and Pb most abundant and Cd and Zn least abundant in both types of sample, and median concentrations statistically different only for Ba. Metals also appeared to be present as contaminants (defined as concentrations <1000 mg kg -1 ) arising from manufacturing or recycling. Metals in PVC are believed to pose little risk when the material is in use, but experimental evidence in the literature suggests that significant mobilisation and exposure may occur from PVC microplastics when ingested by wildlife.

A method for the speciation analysis of the three main species of germanium in environmental waters, namely inorganic germanium (iGe), monomethyl germanium (MMGe) and dimethyl germanium (DMGe), has been developed. Germanium species were volatilized by hydride generation (HG) prior to their preconcentration/separation in a semi-automated cryogenic trap (cryotrapping, CT) and detection by ICP-MS/MS. A procedure to minimize the iGe blanks from the chemicals and water is reported. One mL of water can be analyzed without any pretreatment. After application of this procedure, and the careful optimization of all experimental variables, limits of detection (LOD) of 0.015, 0.005 and 0.003 ng L -1 have been obtained for iGe, MMGe and DMGe, respectively. Standard addition experiments did not show any significant matrix effect, and, therefore, external calibration was used for sample analysis. In the Tris-HCl + L-Cysteine reaction media, additional experiments did not reveal any significant demethylation of MMGe to iGe in the process of HG-CT, which could affect the accuracy of the analysis in seawater. The method has been applied to the analysis of iGe, MMGe and DMGe in certified reference materials of unspiked natural waters: CASS-4, CASS-5 and CASS-6 (nearshore seawater); NASS-5 and NASS-7 (seawater); SLRS-4, SLRS-5 and SLRS-6 (river water)., (Copyright © 2020 Elsevier B.V. All rights reserved.)

X-ray fluorescence spectrometry has been employed to measure Pb in a wide range of consumer and environmental plastics, including food-packaging material, household goods, electronic casings, beach litter and agricultural waste. Results reveal high concentrations of Pb (>1000 mg kg -1 ) in historical items that are still in use or circulation (e.g. toys, construction plastics, wiring insulation) and variable, but generally lower concentrations in more recently manufactured articles. Analysis of Br, Cl and Cr, proxies for brominated flame retardants, polyvinyl chloride (PVC) and chromate pigments, respectively, suggests that as historical material is recycled, Pb from electronic plastics and pigments, but not PVC, is dispersed into a variety of newer products. Although most cases in the consumer sector comply with relevant EU Directives, some products that are non-compliant highlight shortfalls in regulations where recycling is involved and potential problems arising from the direct fashioning of industrial plastics into new consumer goods through attempts to be environmentally positive. The uncontrolled loss of historical and recycled plastics has also resulted in Pb contamination of the environment. Here, it is proposed that litter can be classified as hazardous depending on its Pb content and according to existing regulations that embrace consumer plastics., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Polyester fibres are usually contaminated by antimony because of its use as a catalyst in the production of polyethylene terephthalate and as a flame retardant synergist in a variety of new and recycled polymers. The present study determined the release of antimony (at total concentrations ranging from about 125 to 470 μg g -1 ) from polyester textile samples designed to be in contact with human skin using standard artificial sweat solutions (ISO 105-E04 and EN 1811). The study also examined the role of different experimental parameters on the release of the metalloid. Overall, and using the default parameters, between about 0.05 and 2% of total antimony (or 0.1-1 μg g -1 ) was mobilized into artificial sweat. A reduction in time (from 24 to 12 h) and temperature (from 37 to 20 or 4 °C) and an increase in pH (from 5.5 to 7) resulted in a decline in antimony mobilization from textiles, while altering textile mass to solution volume and the presence of lactate had little impact on the results. Removal of a filtration step increased antimony mobilization but this was attributed to artefacts associated with release from microfibres during extract storage and analysis. In general, antimony mobilization was sufficiently repeatable using either EN 1811 or ISO 105-E04 but the latter is recommended for an assessment of antimony mobilization and potential exposure because its pH is closer to that of human sweat. Since the first fraction of either extractions mobilized the greatest quantity of antimony, exposure can be minimized by washing articles before use., (Copyright © 2020 The Author(s). Published by Elsevier Inc. All rights reserved.)

Over the last 30 years, bottled water has gained in popularity reaching high sales world-wide. Most of this water is sold in polyethylene terephthalate (PET) bottles. About 15 years ago, the presence of antimony in water in those PET bottles raised concerns and studies on the subject have been regularly published since then. This review aims to evaluate whether the use of good analytical practices and the correct design of these studies support the accepted facts (i.e., PET is the origin of antimony presence in bottled waters, antimony concentrations are usually below regulated values, temperature increasing favours antimony leaching). The detailed analysis of published data has confirmed these facts but has also revealed frequency of faulty analytical practices and a lack of well-designed studies. A better understanding of the structure of PET polymer in the bottles, coupled with statistically-robust antimony release experiments, is required to progress in the field., Competing Interests: Declaration of competing interest The author declares that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2020 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Several species of the genus Tetraselmis (Chlorodendrophyceae, Chlorophyta) were recently discovered to possess unsuspected biomineralization capacities: they produce multiple intracellular inclusions of amorphous calcium carbonate (ACC), called micropearls. Early light-microscopists had spotted rows of refractive granules in some species, although without identifying their mineral nature. Scanning electron microscope (SEM) observations showed that the distribution of the micropearls in the cell forms a pattern, which appears to be characteristic for a given species. The present study shows that this pattern correlates with the shape of the chloroplast, which differs between Tetraselmis species, because micropearls align themselves along the incisions between chloroplast lobes. This was observed both by SEM and in live cells by light microscopy (LM) using Nomarski differential interference contrast. Additionally, molecular phylogenetic analyses, of rbcL and ITS2 gene sequences from diverse strains of Chlorodendrophyceae, corroborated the morphological observations by identifying two groups among nominal Tetraselmis spp. that differ in chloroplast morphology, micropearl arrangement, and ITS2 RNA secondary structure., (Copyright © 2020 The Authors. Published by Elsevier GmbH.. All rights reserved.)

With an inherent density marginally below that of seawater, polyolefins (polyethylene-polypropylene) are predicted to float or undergo beaching in the marine environment. Polyolefins commonly observed on the seabed, therefore, require additional considerations that are usually based around increasing density through fouling or packaging into sinking faecal matter. Here, however, we propose that the presence of additives is of least equal significance to the behaviour of such plastics in marine systems. We compared barium, present largely as the filler, BaSO 4 (density = 4.5 g cm -3 ), in consumer and beached plastics and established that the metal was more abundant and occurred at higher concentrations in the former samples, consistent with the environmental fractionation of plastics based on additive content. Significantly, the Ba content of polyolefins required to confer a density above seawater is about 13,000 mg kg -1 , a value that was exceeded in many consumer plastics but never observed in beached samples., (Copyright © 2020 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Kohl is an eye cosmetic that was traditionally used in many Asian and African countries but that is now more widely available. Ingredients of kohl reported in previous studies seem to be rather variable but mention is frequently made of minerals based on Pb whose use in cosmetic products is prohibited in Europe. We purchased 23 products of kohl from retail outlets in five different European countries and over the internet and analysed their chemical composition by XRF and SEM-EDXS. The majority of the products (n = 17) did not conform with European legislation based on the presence of Pb (often as galena), whose concentrations ranged from a few mg kg -1 to over 400000 mg kg -1 . Cadmium, another element prohibited in cosmetic products in Europe, was also present as a contaminant in 13 products at concentrations up to a few hundred mg kg -1 . In addition to heavy metals, minerals of other metals (e.g. Fe and Zn) appeared to be present in the nano-size range and might represent an additional health hazard. Clearly, the lack of quality control in the manufacture of kohl results in the widespread occurrence of toxic and unwanted elements and the trade of illegal products in Europe. In principle, shop sales would be relatively straightforward to prevent, but products traded through internet are more difficult to regulate., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

TCEs stands for technology-critical elements, a group of chemical elements for which imbalances between supply and demand exist or are deemed probable. This article challenges the scientific usefulness of such a classification when dealing with environmental and toxicological issues. Criticality is an economic conceptualization that is not well suited to guiding environmental chemistry research efforts. The classification is even counterproductive because it does not foster collaborative research with the countries directly touched by the environmental problems which are directly linked to the production of the elements.

Antimony (Sb) is a technology critical element whose presence is ubiquitous in manufactured products, and in particular in plastics where it is used extensively as a flame retardant synergist for brominated compounds, as a catalyst for polyethylene terephthalate production, and as a pigment for colour. This study reviews the usage, regulations and fate of Sb in plastics by examining primary data on its production, applications, contents in and migration from manufactured objects, and presence in and release from waste, including the disposal and recycling routes for this material (i.e., non-controlled disposal, incineration, landfilling and recycling). Consumption of Sb and the relative apportioning of the metalloid between different uses in plastics change continuously and are largely driven by dynamic economic factors; accordingly, reference to secondary data or sources can be misleading. Since Sb is not recovered from plastics, its fate is entirely linked to the fate of plastics themselves which, as far as disposal and recycling are concerned, might be dictated by the presence of co-associated regulated substances such as brominated flame retardants. Significantly, because of the high leachability of Sb from bottom incineration ashes, the EU considers the metalloid as the most problematic substance regarding the potential reuse of this material., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Concentrations of antimony have been determined for paints and enamels that are available to the consumer or accessible to the public by x-ray fluorescence spectrometry. The metalloid was only present in consumer paints of a speciality (e.g. artistic) nature, but was common in old household paints as an anti-chalking agent and in brightly-coloured contemporary exterior paints (on roads, street furniture and playground equipment, for example) as a colour fastener with concentrations ranging from a few hundred to about 25,000 μg g - 1 . Antimony was also found in contemporary container glass and ceramic products as an additive or opacifier and as a colour fastener in enamels at concentrations up to a few thousand μg g - 1 . Overall, the yellow pigment, lead antimonate, was only evident in two ceramic products analysed, with Sb concentrations exceeding 62,800 μg g - 1 . Available data in the literature suggests that, while Sb concentrations up to 30 μg g - 1 are bioaccessible in exterior paints and that concentrations of up to 20 mg L - 1 are migratable in some ceramicware, no relevant regulations are currently in place. Given our lack of understanding of the health impacts of Sb, more studies on its toxicity and mobility from commonly encountered products are called for., Competing Interests: Declaration of competing interest We declare that we have no conflicts of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A crucial part of any equilibrium modelling calculation is the selection of equilibrium constants that quantify the strength of interactions between metals and ligands. For researchers new to the field of solution chemistry, locating suitable equilibrium constants that lead to reliable model results can be problematic. Numerous large compilations of equilibrium constant values have been published each having their own limitations, coverage and availability. This work surveys eleven major compilations of equilibrium constants including those from authoritative groups such as IUPAC, NIST, and NEA. For each compilation surveyed, details are given related to the historical background and underlying project, scope of the database with respect to range of included metals and ligands, and the present-day availability of publications or computer databases resulting from the project. The various methods employed by different data compilers in their critical assessment for each compilation are also discussed., (Copyright © 2019 Elsevier B.V. All rights reserved.)

A completely selective method for electrochemical determination of very low concentrations (ngL -1 ) of niobium is presented. The method relies on the cathodic reduction of the pyrogallol red‑niobium complex at pH3. Virtually no sample preparation (apart from cation exchange) is required. The method is both free from interferences (particularly from Ta) and affordable. Time consuming preconcentration and separation procedures as well as the use of hydrofluoric acid, fluorides or problematic solvents are avoided. The applicability of the method is illustrated through analysis of mineral waters containing niobium concentrations ranging from 1 to several hundred ngL -1 ., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The plastics of waste of electric and electronic equipment (WEEE) are improved for fire safety by flame retardants, and particularly brominated flame retardants (BFR). As waste, the management of these plastic fractions must comply with the update of the regulation of waste hazard classification (2014, 2017), the publication of a technical standard on management of WEEE (2015), and a restriction of use for decabromodiphenylether in the product regulation (2017). Data of bromine (n=4283) and BFR concentrations (n=98) in plastics from electric and electronic equipment (EEE), and from WEEE processing facilities before and after sorting for bromine in four sites in France have been studied for chemical composition and for regulatory classification. The WEEE was analysed by handheld X-ray fluorescence, and the waste was sorted after shredding, by on-line X-ray transmission for total bromine content (< or > 2000 mg/kg) in small household appliances (SHA), cathode ray tubes (CRT) and flat screens plastics. In equipment (n=347), 15% of the equipment items have no bromine, while 46% have at least one part with bromine, and 39% have all parts brominated. The bromine concentration in plastics is very heterogeneous, found in high concentrations in large household appliance (LHA) plastics, and also found in unexpected product categories, as observed by other authors. Clearly, an unwanted global loop of brominated substances occurs via the international recycling of plastic scrap. In waste (n=65), polybromobiphenyls, polybromodiphenylethers (PBDE), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane were analysed. The most concentrated BFRs are decaBDE (3000 mg/kg) and TBBPA (8000 mg/kg). The bromine concentration of regulated brominated substances was identified in 2014 and 2015 to be up to 86% of total bromine in "old" waste (SHA, CRT), 30-50% in "younger" waste (Flat screens), and a mean of only 8% in recent products (2009-2013). Regulated substances are a minority of all the brominated substances and the only practical way to sort is to measure total bromine on-line. The sorting reduces the mean bromine concentration in the "Low Br" fraction in all sites, and reduces the decaBDE concentration to levels below the restricted use limit. After sorting, the concentration in the "High Br" fractions exceeds all present or future regulatory limits. In conclusion, sorting of small household appliances, cathode ray tubes and flat screen plastics is necessary to avoid uncontrolled dispersion of regulated substances in recycled raw material. Other categories (large household appliances, electric and electronic tools, lighting equipment) should also be considered, since their total bromine content (unweighted mean concentration) is high for some of these products. A European campaign consisting of 7 countries and 35 sites will begin in 2017, directed by WEEE Forum, the European association speaking for thirty-one not-for-profit e-waste producer responsibility organisations, to assess the mean bromine content of plastics from large household appliances after shredding., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

A range of plastic consumer products and components thereof have been analysed by x-ray fluorescence (XRF) spectrometry in a low density mode for Br as a surrogate for brominated flame retardant (BFR) content. Bromine was detected in about 42% of 267 analyses performed on electronic (and electrical) samples and 18% of 789 analyses performed on non-electronic samples, with respective concentrations ranging from 1.8 to 171,000μgg -1 and 2.6 to 28,500μgg -1 . Amongst the electronic items, the highest concentrations of Br were encountered in relatively small appliances, many of which predated 2005 (e.g. a fan heater, boiler thermostat and smoke detector, and various rechargers, light bulb collars and printed circuit boards), and usually in association with Sb, a component of antimony oxide flame retardant synergists, and Pb, a heavy metal additive and contaminant. Amongst the non-electronic samples, Br concentrations were highest in items of jewellery, a coffee stirrer, a child's puzzle, a picture frame, and various clothes hangers, Christmas decorations and thermos cup lids, and were often associated with the presence of Sb and Pb. These observations, coupled with the presence of Br at concentrations below those required for flame-retardancy in a wider range of electronic and non-electronic items, are consistent with the widespread recycling of electronic plastic waste. That most Br-contaminated items were black suggests the current and recent demand for black plastics in particular is met, at least partially, through this route. Given many Br-contaminated items would evade the attention of the end-user and recycler, their disposal by conventional municipal means affords a course of BFR entry into the environment and, for food-contact items, a means of exposure to humans., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The possible environmental impact of the recent increase in use of a group of technology-critical elements (Nb, Ta, Ga, In, Ge and Te) is analysed by reviewing published concentration profiles in environmental archives (ice cores, ombrotrophic peat bogs, freshwater sediments and moss surveys) and evaluating temporal trends in surface waters. No increase has so far been recorded. The low potential direct emissions of these elements, resulting from their absolute low production levels, make it unlikely that the increasing use of these elements in modern technology has any noticeable effect on their environmental concentrations on a global scale. This holds particularly true for those of these elements that are probably emitted in relatively high amounts from other human activities (i.e., coal combustion and non-ferrous smelting), such as In, the most studied element of the group., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Very little systematic information exists on the occurrence and concentrations of antimony (Sb) in consumer products. In this study, a Niton XL3t field-portable-X-ray fluorescence (FP-XRF) spectrometer was deployed in situ and in the laboratory to provide quantitative information on Sb dissipated in plastic items and fixtures (including rubber, textile and foamed materials) from the domestic, school, vehicular and office settings. The metalloid was detected in 18% of over 800 measurements performed, with concentrations ranging from about 60 to 60,000μgg -1 . The highest concentrations were encountered in white, electronic casings and in association with similar concentrations of Br, consistent with the use of antimony oxides (e.g. Sb 2 O 3 ) as synergistic flame retardants. Concentrations above 1000μgg -1 , and with or without Br, were also encountered in paints, piping and hosing, adhesives, whiteboards, Christmas decorations, Lego blocks, document carriers, garden furniture, upholstered products and interior panels of private motor vehicles. Lower concentrations of Sb were encountered in a wide variety of items but its presence (without Br) in food tray packaging, single-use drinks bottles, straws and small toys were of greatest concern from a human health perspective. While the latter observations are consistent with the use of antimony compounds as catalysts in the production of polyethylene terephthalate, co-association of Sb and Br in many products not requiring flame retardancy suggests that electronic casings are widely recycled. Further research is required into the mobility of Sb when dissipated in new, recycled and aged polymeric materials., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The use of alkyl lead derivatives as antiknock agents in gasoline can be considered as one of the main pollution disasters of the 20th century because of both the global character of the pollution emitted and the seriousness of the impact on human health. Alkyl lead derivatives in themselves cannot be considered to be persistent pollutants because they readily degrade either before being released from the tailpipes or soon afterwards in the atmosphere. However, the inorganic lead they produced has been deposited in soils all over the planet, largely, but not exclusively in urban areas and along motorways, since the direct emission of lead into the atmosphere favored its dispersal over great distances: The signal of the massive use of alkyl lead derivatives has been found all over the world, including in remote sites such as polar areas. The short residence time of lead in the atmosphere implies that this compartment is highly responsive to changes in emissions. This was demonstrated when leaded gasoline was phased-out and is in striking contrast to the very long permanence of inorganic lead in soils, where resuspension is a permanent source of toxic lead.

Until now, descriptions of intracellular biomineralization of amorphous inclusions involving alkaline-earth metal (AEM) carbonates other than calcium have been confined exclusively to cyanobacteria (Couradeau et al., 2012). Here, we report the first evidence of the presence of intracellular amorphous granules of AEM carbonates (calcium, strontium, and barium) in unicellular eukaryotes. These inclusions, which we have named micropearls, show concentric and oscillatory zoning on a nanometric scale. They are widespread in certain eukaryote phytoplankters of Lake Geneva (Switzerland) and represent a previously unknown type of non-skeletal biomineralization, revealing an unexpected pathway in the geochemical cycle of AEMs. We have identified Tetraselmis cf. cordiformis (Chlorophyta, Prasinophyceae) as being responsible for the formation of one micropearl type containing strontium ([Ca,Sr]CO 3 ), which we also found in a cultured strain of Tetraselmis cordiformis. A different flagellated eukaryotic cell forms barium-rich micropearls [(Ca,Ba)CO 3 ]. The strontium and barium concentrations of both micropearl types are extremely high compared with the undersaturated water of Lake Geneva (the Ba/Ca ratio of the micropearls is up to 800,000 times higher than in the water). This can only be explained by a high biological pre-concentration of these elements. The particular characteristics of the micropearls, along with the presence of organic sulfur-containing compounds-associated with and surrounding the micropearls-strongly suggest the existence of a yet-unreported intracellular biomineralization pathway in eukaryotic micro-organisms., (© 2016 John Wiley & Sons Ltd.)

The toxicity of Cd being well established and that of Te suspected, the bulk, surface-normalized steady-state dissolution rates of two industrially important binary tellurides-polycrystalline cadmium and bismuth tellurides- were studied over the pH range 3-11, at various temperatures (25-70 °C) and dissolved oxygen concentrations (0-100% O2 in the gas phase). The behavior of both tellurides is strikingly different. The dissolution rates of CdTe monotonically decreased with increasing pH, the trend becoming more pronounced with increasing temperature. Activation energies were of the order of magnitude associated with surface controlled processes; they decreased with decreasing acidity. At pH 7, the CdTe dissolution rate increased linearly with dissolved oxygen. In anoxic solution, CdTe dissolved at a finite rate. In contrast, the dissolution rate of Bi2Te3 passed through a minimum at pH 5.3. The activation energy had a maximum in the rate minimum at pH 5.3 and fell below the threshold for diffusion control at pH 11. No oxygen dependence was detected. Bi2Te3 dissolves much more slowly than CdTe; from one to more than 3.5 orders of magnitude in the Bi2Te3 rate minimum. Both will readily dissolve under long-term landfill deposition conditions but comparatively slowly.

Tellurium is one of the elements recently identified as technologically critical and is becoming a new emergent contaminant. No reliable method exists for its determination in environmental samples such as natural waters. This gap is filled by the method described here; it allows the rapid detection of trace concentrations of Te(IV) and Te(VI) in surface waters by differential pulse cathodic stripping voltammetry. It is based on the proton reduction catalysed by the absorption of Te(IV) on the mercury electrode. Under our conditions (0.1 mol L(-1) HCl) a detection limit of about 5 ng L(-1) for a deposition time of 300 s is achieved. Organic matter does not represent a problem at low concentrations; higher concentrations are eliminated by adsorptive purification. Tellurium occurs primarily as Te(IV) and Te(VI) in natural waters. Thus, determining total Te requires the reduction of Te(VI) that it is not electroactive. A number of reduction procedures have been carefully evaluated and a method based on the addition of TiCl3 to the acidified samples has been proven to reduce Te(VI) at the trace level to Te(IV) reliably and quantitatively. Therefore, the procedure described allows the direct determination of total Te and its redox speciation. It is flexible, reliable and cost effective compared to any possible alternative method based on the common preconcentration-ICPMS approach. It is readily implementable as a routine method and can be deployed in the field with relative ease., (Copyright © 2015 Elsevier B.V. All rights reserved.)