A detailed understanding of the formation of the potent neurotoxic methylmercury is needed to explain the large observed variability in methylmercury levels in aquatic systems. While it is known that ...organic matter interacts strongly with mercury, the role of organic matter composition in the formation of methylmercury in aquatic systems remains poorly understood. Here we show that phytoplankton-derived organic compounds enhance mercury methylation rates in boreal lake sediments through an overall increase of bacterial activity. Accordingly, in situ mercury methylation defines methylmercury levels in lake sediments strongly influenced by planktonic blooms. In contrast, sediments dominated by terrigenous organic matter inputs have far lower methylation rates but higher concentrations of methylmercury, suggesting that methylmercury was formed in the catchment and imported into lakes. Our findings demonstrate that the origin and molecular composition of organic matter are critical parameters to understand and predict methylmercury formation and accumulation in boreal lake sediments.
Dietary deficiency of selenium is a global health threat related to low selenium concentrations in crops. Despite the chemical similarity of selenium to the two more abundantly studied elements ...sulfur and arsenic, the understanding of its accumulation in soils and availability for plants is limited. The lack of understanding of soil selenium cycling is largely due to the unavailability of methods to characterize selenium species in soils, especially the organic ones. Here we develop a size-resolved multi-elemental method using liquid chromatography and elemental mass spectrometry, which enables an advanced characterization of selenium, sulfur, and arsenic species in soil extracts. We apply the analytical approach to soils sampled along the Kohala rainfall gradient on Big Island (Hawaii), which cover a large range of organic carbon and (oxy)hydroxides contents. Similarly to sulfur but contrarily to arsenic, a large fraction of selenium is found associated with organic matter in these soils. However, while sulfur and arsenic are predominantly found as oxyanions in water extracts, selenium mainly exists as small hydrophilic organic compounds. Combining Kohala soil speciation data with concentrations in parent rock and plants further suggests that selenium association with organic matter limits its mobility in soils and availability for plants.
Les cérémonies des Jeux olympiques se structurent autour d’un unique rite commun à toute l’humanité. Cette singularité, exceptionnelle, doit beaucoup à son créateur, Pierre de Coubertin, qui saisit ...d’emblée l’enjeu qu’elles constituent pour son œuvre olympique. Sur un peu plus d’un siècle d’existence, les cérémonies olympiques, pérennes par leur rituel symbolique, reflètent cependant bien d’autres enjeux, en fonction des époques et selon que l’on se place du point de vue du cio ou du pays organisateur. Paris 2024 ne fait pas exception, avec des enjeux, inédits, qui s’entrechoquent comme jamais aux contraintes géopolitiques .
Selenium 0 (Se
) is a powerful anti-proliferative agent in cancer research. We investigated the impact of sub-toxic concentrations of Se
functionalized nanoparticles (SeNPs) on prostate cancer PC-3 ...cells and determined their intracellular localization and fate. An in-depth characterization of functionalized selenium nanoparticles composition is proposed to certify that no chemical bias relative to synthesis issues might have impacted the study. Selenium is an extremely diluted element in the biological environment and therefore requires high-performance techniques with a very low detection limit and high spatial resolution for intracellular imaging. This was explored with state-of-the-art techniques, but also with cryopreparation to preserve the chemical and structural integrity of the cells for spatially resolved and speciation techniques. Monodisperse solutions of SeNPs capped with bovine serum albumin (BSA) were shown to slow down the migration capacity of aggressive prostate cancer cells compared to polydisperse solutions of SeNPs capped with chitosan. BSA coating could prevent interactions between the reactive surface of the nanoparticles and the plasma membrane, mitigating the generation of reactive oxygen species. The intracellular localization showed interaction with mitochondria and also a localization in the lysosome-related organelle. The SeNPs-BSA localization in mitochondria constitute a possible explanation for our result showing a very significant dampening of the PC-3 cell proliferation capabilities. The purpose of the use of sublethal compound concentrations was to limit adverse effects resulting from high cell death to best evaluate some cellular changes and the fate of these SeNPs on PC-3. Our findings provide new insight to further study the various mechanisms of cytotoxicity of SeNPs.
In shallow aquatic environments, sediment is a significant source of monomethylmercury (MMHg) for surface water (SW). High-altitude aquatic ecosystems are characterized by extreme hydro-climatic ...constraints (e.g., low oxygen and high UV radiation). We studied, during two seasons, the diel cycles of MMHg in SW and sediment porewaters (PW) of Lake Uru Uru (3686 m a.s.l, Bolivia) contaminated by urban and mining activities. Our results show that diel changes in SW MMHg concentrations (up to 1.8 ng L−1) overwhelm seasonal ones, with higher MMHg accumulation during the night-time and the dry season. The calculation of MMHg diffusive fluxes demonstrates that the sediment compartment was the primary source of MMHg to the SW. Most MMHg efflux occurred during the dry season (35.7 ± 17.4 ng m−2 day−1), when the lake was relatively shallow, more eutrophicated, and with the redoxcline located above the sediment–water interface (SWI). Changes in MMHg accumulation in the PWs were attributed to diel redox oscillations around the SWI driving both the bacterial sulfate reduction and bio-methylation. Finally, we highlight that although MMHg loading from the PW to the SW is large, MMHg photodegradation and demethylation by microorganisms control the net MMHg accumulation in the water column.
Stable Hg isotope analyses are nowadays widely employed to discriminate Hg sources and understand its biogeochemical cycle. Until now, total Hg isotopic compositions have been mainly used but Hg ...compound-specific isotopic analysis (CSIA) methodologies are emerging. Online Hg-CSIA were limited to samples containing high concentrations, but in this work we overcome this limitation for the measurement of inorganic (IHg) and monomethylmercury (MMHg) by gas chromatography hyphenated to multicollector-inductively coupled plasma mass spectrometry (GC/MC-ICPMS) through the use of an automated online preconcentration strategy, allowing injection volumes up to 100 times larger than usual. The preconcentration of Hg species and subsequent transfer to the column were achieved by a programmed temperature vaporization (PTV) injector fitted with a packed liner. The PTV parameters were first optimized using a quadrupole ICPMS, and then its suitability for Hg-CSIA was evaluated with long-term replicate analysis of various standards and reference materials (RMs). The large preconcentration capability enables analyses with Hg concentrations in the organic solvent 2 orders of magnitude lower than the previous conventional GC/MC-ICPMS method, but a compound specific standard bracketing procedure was required for MMHg in order to correct for the differential behavior of Hg species in the liner. The external reproducibility of the method ranged from 0.19 to 0.39 ‰ for Δ199Hg and δ202Hg (as 2 SD, n = 143–167) depending on the species. The analysis of various RMs demonstrated the applicability to environmental samples with species concentrations down to about 150 ng g–1. This new methodology opens the way for a much wider range of online Hg-CSIA measurements that will improve our understanding of the Hg biogeochemical cycle.
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Under anoxic conditions, the interactions between As-bearing ferrihydrite (Fh) and As(V)-reducing bacteria are known to cause Fh transformations and As mobilization. However, the impact of different ...types of organic matter (OM) on microbial As/Fe transformation in As-bearing Fh-organic associations remains unclear. In our study, we therefore exposed arsenate-adsorbed ferrihydrite, ferrihydrite-PGA (polygalacturonic acid), and ferrihydrite-HA (humic acid) complexes to two typical Fe(III)- and As(V)-reducing bacteria, and followed the fate of Fe and As in the solid and aqueous phases. Results show that PGA and HA promoted the reductive dissolution of Fh, resulting in 0.7–1.6 and 0.8–1.9 times more As release than in the OM-free Fh, respectively. This was achieved by higher cell numbers in the presence of PGA, and through Fe-reduction via electron-shuttling facilitated by HA. Arsenic-XAS results showed that the solid-phase arsenite fraction in Fh-PGA and Fh-HA was 15–19% and 27–28% higher than in pure Fh, respectively. The solid-associated arsenite fraction likely increased because PGA promoted cell growth and As(V) reduction, while HA provided electron shuttling compounds for direct microbial As(V)-reduction. Collectively, our findings demonstrate that As speciation and partitioning during microbial reduction of Fh-organic associations are strongly influenced by PGA and HA, as well as the strains’ abilities to utilize electron-shuttling compounds.
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Oxides of silicon (Si), manganese (Mn), and zinc (Zn) have been used as soil amendments to reduce As mobility and uptake in paddy soil systems. However, these amendments are hypothesized to be ...affected differently depending on the soil pH and their effect on As speciation in rice paddy systems is not fully understood. Herein, we used a microcosm experiment to investigate the effects of natural Si-rich fly ash and synthetic Mn and Zn oxides on the temporal development of porewater chemistry, including aqueous As speciation (As(III), As(V), MMA, DMA, and DMMTA) and solid-phase As solubility, in a naturally calcareous soil with or without soil acidification (with sulfuric acid) during 28 days of flooding and subsequent 14 days of drainage. We found that soil acidification to pH 4.5 considerably increased the solubility of Si, Fe, Mn, and Zn compared to the non-acidified soil. Additions of Mn and Zn oxides decreased the concentrations of dissolved arsenite and arsenate in the non-acidified soil whereas additions of Zn oxide and combined Si–Zn oxides increased them in the acidified soil. The Si-rich fly ash did not increase dissolved Si and As in the acidified and non-acidified soils. Dimethylated monothioarsenate (DMMTA) was mainly observed in the acidified soil during the later stage of soil flooding. The initial 28 days of soil flooding decreased the levels of soluble and exchangeable As and increased As associated with Mn oxides, whereas the subsequent 14 days of soil drainage reversed the trend. This study highlighted that soil acidification considerably controlled the solubilization of Ca and Fe, thus influencing the soil pH-Eh buffering capacity, the solubility of Si, Mn, and Zn oxides, and the mobility of different As species in carbonate-rich and acidic soils under redox fluctuations.
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•Solubilities of Si, Mn, and Zn oxides differed in acidified and non-acidified soils.•Soil acidification greatly impacted As, Si, Mn, and Zn solubility in paddy soils.•Mn and Zn oxides decreased arsenite and arsenate in non-acidified soil.•Zn oxide increased dissolved arsenite and arsenate in acidified soil.•Soil acidification and reaeration synergistically increased H4SiO4-to-H3AsO3 ratio.
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•On-line preconcentration for Hg, Sn and Pb species analysis by GC-ICP-MS was developed.•A Programmed Temperature Vaporization (PTV) injector with a packed liner was used.•Methodological Detection ...Limits are in the pg L−1 range, reaching legislation levels.•Validation through analyses of pristine river samples.
The current EU legislation lays down Environmental Quality Standards (EQS) for 45 priority substances in surface waters; among them levels for (organo)metallic species of Hg, Sn and Pb are set between ng L−1 (for Hg and Sn) and μg L−1 (for Pb). To date, only a few analytical methods can reach these very restrictive limits and there is thus a need for comprehensive methods able to analyze these species down to these levels in natural waters. The aim of this work was to develop an online automated pre-concentration method using large volume injections with a Programmed Temperature Vaporization (PTV) injector fitted with a sorbent packed liner coupled to GC-ICP-MS to further improve the detection limits associated to this well-established method. The influence of several parameters such as the PTV transfer temperature and time, carrier gas flow rate and amount of packing material was investigated. Finally, the maximum volume injected through single or multiple injection modes was optimized to obtain the best compromise between chromatographic resolution and sensitivity. After optimization, very satisfactory results in terms of absolute and methodological detection limits were achieved, down to the pg L−1 level for all species studied. The potential of the method was exemplified by determining the concentrations of organometallic compounds in unpolluted river waters samples from the Adour river basin (SW France) and results were compared with conventional (splitless) GC-ICP-MS. The strength of this analytical method lies in the low detection limits reached for the simultaneous analysis of a wide group of organometallic compounds, and the potential to transfer this method to other gas chromatographic applications with inherent lower sensitivity.
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•DOM is mainly present as acidic and neutral hydrophobic compounds.•Metals are primarily found within the acidic hydrophobic and hydrophilic fractions.•Most metals are associated with high molecular ...weight DOM (40–100kDa).•Few metals exist as “free” ions or complexed by low molecular weight DOM.•Reference FA bind many metals while reference HA bind only a few.
We investigated the concentration levels, fractionation and molecular weight distribution (MWD) of dissolved organic matter (DOM) and metals (V, Cr, Co, Ni, Cu, Zn, As, Cd, Sn, Ba, Hg and Pb) in a polluted groundwater from an industrial area in Northern Sweden. DOM was mainly recovered in the hydrophobic acidic and hydrophobic neutral sub-fractions (45 and 35%, respectively) while most metals were found in the acidic sub-fractions (46–93%) except for V, Fe and As, which were predominant in the basic sub-fractions (74–93%) and Cd in the neutral ones (50%). DOM exhibited a broad MWD in groundwaters, usually from 5 to 200kDa and was dominated by high molecular weight hydrophobic acids, low molecular weight hydrophilic acids and hydrophilic neutral compounds. Most of the studied metals (Fe, Cr, Co, Sn, Ba, Hg) were associated with the high molecular weight DOM fraction (ca. 40–100kDa). Cu, Pb, Zn, Cd and Ni interacted with a broad range of DOM size fractions but were still most abundant in the high molecular weight fraction. Few metal/metalloids (As, V and Cr in some cases) presented a very weak affinity for DOM and presumably existed predominantly as “free” inorganic ions in solution.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
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