Stability Constants of Tetravalent Germanium Complexes in Aqueous Solution: Small Organic Oxygen and Nitrogen Donor Ligands.

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 (KNO3). 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.

Micropearls and other intracellular inclusions of amorphous calcium carbonate: an unsuspected biomineralization capacity shared by diverse microorganisms.

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.

Antimony release from polyester textiles by artificial sweat solutions: A call for a standardized procedure.

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.

What the presence of regulated chemical elements in beached lacustrine plastics can tell us: the case of Swiss lakes.

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., Cd2SSe, PbCrO4), 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.

Kohl containing lead (and other toxic elements) is widely available in Europe.

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.

Bulk Dissolution Rates of Cadmium and Bismuth Tellurides As a Function of pH, Temperature and Dissolved Oxygen.

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.

Strontium-90 pollution can be bioremediated with the green microalga Tetraselmis chui.

Strontium-90 (90Sr) 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 90Sr, 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 90Sr. The 90Sr 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 90Sr, 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 90Sr pollution.

Natural organic matter quantification in the waters of a semiarid freshwater wetland (Tablas de Daimiel, Spain).

Dissolved organic matter (DOM) concentrations have been measured in the waters of a semiarid freshwater wetland, the Tablas de Daimiel, Spain, when the system-characterised by variable hydroperiodicity conditions, was completely flooded (February 2011). Fluxes of DOM from the wetland soils to the overlying waters were measured by using a passive diffusion sampler (peeper). Not only dissolved organic carbon (DOC) concentrations were measured but refractory organic matter (ROM, usually known as humic substances) was also quantified using a novel voltammetric method. Fluorescence spectra were recorded to help in selecting the appropriate standard for ROM quantification, test the homogeneity of DOM in the waters and get an indication of their source. The results obtained show a 7-fold increase in measured ROM concentrations from the Gigüela River to the outlet, which points to a net exportation of ROM from the wetland and to the existence of an internal source of ROM in the system, probably diffusion from the wetland soils. This hypothesis is confirmed by the flux of ROM from the soils to the water column measured with the peeper and by the common fluorescence characteristics of column and interstitial waters. The smaller increase in DOC concentrations along the wetland, in spite of the higher DOC fluxes from soils, suggests that there is significant turnover of organic carbon (OC) in the water column. The system acts as a major carbon sink but, when flooded, exports OC as DOM.

Chemical characteristics of artificial plastic plants and the presence of hazardous elements from the recycling of electrical and electronic waste.

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, Sb2O3, 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.

Lead and chromium in European road paints.

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 PbCrO4 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.

The role of titanium dioxide on the behaviour and fate of plastics in the aquatic environment.

Although titanium dioxide (TiO2) 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 TiO2 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 TiO2-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 TiO2 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 TiO2 pigments in the environment. Although rutile appears to be the most important polymorph of TiO2 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) TiO2 particles and requires further research.

High calcium and strontium uptake by the green microalga Tetraselmis chui is related to micropearl formation and cell growth.

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.

After the sun: a nanoscale comparison of the surface chemical composition of UV and soil weathered plastics.

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.

Vanadium(IV) and vanadium(V) complexation by succinic acid studied by affinity capillary electrophoresis. Simultaneous injection of two analytes in equilibrium studies.

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 (NaClO4/HClO4) ionic strength and 25 °C, are logß111=7.4 ± 0.2 and logß122=14.1 ± 0.5 for V(IV), and logß111=7.3 ± 0.1 for V(V), respectively. The stability constant values, extrapolated to zero ionic strength with the Davies equation, are logß°111=8.3 ± 0.2 and logß°122=15.6 ± 0.5 for V(IV) and logß°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.

Arsenic in Lake Geneva (Switzerland, France): long term monitoring, and redox and methylation speciation in an As unpolluted, oligo-mesotrophic lake.

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.

Chemical-genomic profiling identifies genes that protect yeast from aluminium, gallium, and indium toxicity.

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.