Reactions of hypobromous acid with dimethyl selenide, dimethyl diselenide and other organic selenium compounds: kinetics and product formation.

Selenium (Se) is an essential micronutrient for many living organisms particularly due to its unique redox properties. We recently found that the sulfur (S) analog for dimethyl selenide (DMSe), i.e. dimethyl sulfide (DMS), reacts fast with the marine oxidant hypobromous acid (HOBr) which likely serves as a sink of marine DMS. Here we investigated the reactivity of HOBr with dimethyl selenide and dimethyl diselenide (DMDSe), which are the main volatile Se compounds biogenically produced in marine waters. In addition, the reactivity of HOBr with further organic Se compounds was tested, i.e., SeMet (as N-acetylated-SeMet), and selenocystine (SeCys2 as N-acetylated-SeCys2), as well as the phenyl-analogs of DMSe and DMDSe, respectively, diphenyl selenide (DPSe) and diphenyl diselenide (DPDSe). Apparent second-order rate constants at pH 8 for the reactions of HOBr with the studied Se compounds were (7.1 ± 0.7) × 107 M-1 s-1 for DMSe, (4.3 ± 0.4) × 107 M-1 s-1 for DMDSe, (2.8 ± 0.3) × 108 M-1 s-1 for SeMet, (3.8 ± 0.2) × 107 M-1 s-1 for SeCys2, (3.5 ± 0.1) × 107 M-1 s-1 for DPSe, and (8.0 ± 0.4) × 106 M-1 s-1 for DPDSe, indicating a very high reactivity of all selected Se compounds with HOBr. The reactivity between HOBr and DMSe is lower than for DMS and therefore this reaction is likely not relevant for marine DMSe abatement. However, the high reactivity of SeMet with HOBr suggests that SeMet may act as a relevant quencher of HOBr.

Sensitive analysis of selenium speciation in natural seawater by isotope-dilution and large volume injection using PTV-GC-ICP-MS.

Although oceans play a key role in the global selenium (Se) cycle, there is currently very little quantitative information available on the distribution of Se concentrations and Se speciation in marine environments. In general, determining Se concentration and speciation in seawater is highly challenging due to very low Se levels ((sub)ng⋅L-1), whereas matrix elements interfering Se pre-concentration and detection are up to the g⋅L-1 levels. In this study, we established a sensitive method for the determination of the various Se chemical fractions present in natural seawater, i.e. selenite (SeIV), selenate (SeVI), organic Se-II + Se0 and total Se, using species-specific isotope dilution gas chromatography coupled to inductively coupled plasma mass spectrometry (ID-GC-ICP-MS). We compared different derivatization reagents and optimized specific pre-treatment protocols, including a microwave assisted oxidation protocol for the determination of total Se and organic Se-II + Se0 using H2O2. To increase sensitivity, we developed an online pre-concentration method based on large volume injection (LVI) using a programmed temperature vaporization (PTV) inlet. Eventually, the developed method achieved low absolute and methodological detection limits, i.e., respectively, 0.1-0.3 pg and 0.9-3.1 ng.L-1 for the different fractions. The accuracy of our method was of 2% for a certified reference material (CRM) diluted in artificial seawater while the precision was better than 4% for a freshwater CRM in artificial seawater matrix as well as two common seawater CRMs certified for trace elements excluding Se. As a proof-of-concept, we quantified the various Se fractions in a large number of natural water samples from the Baltic and North Seas, encompassing a wide range of salinity (7-35 psu), which shows that its detection limits are sufficient to determine total Se, SeIV, SeVI and organic Se-II + Se0 concentrations in brackish and marine systems.

Holocene variations in Lake Titicaca water level and their implications for sociopolitical developments in the central Andes.

Holocene climate in the high tropical Andes was characterized by both gradual and abrupt changes, which disrupted the hydrological cycle and impacted landscapes and societies. High-resolution paleoenvironmental records are essential to contextualize archaeological data and to evaluate the sociopolitical response of ancient societies to environmental variability. Middle-to-Late Holocene water levels in Lake Titicaca were reevaluated through a transfer function model based on measurements of organic carbon stable isotopes, combined with high-resolution profiles of other geochemical variables and paleoshoreline indicators. Our reconstruction indicates that following a prolonged low stand during the Middle Holocene (4000 to 2400 BCE), lake level rose rapidly ~15 m by 1800 BCE, and then increased another 3 to 6 m in a series of steps, attaining the highest values after ~1600 CE. The largest lake-level increases coincided with major sociopolitical changes reported by archaeologists. In particular, at the end of the Formative Period (500 CE), a major lake-level rise inundated large shoreline areas and forced populations to migrate to higher elevation, likely contributing to the emergence of the Tiwanaku culture.

Understanding soil selenium accumulation and bioavailability through size resolved and elemental characterization of soil extracts.

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.

Long-term preservation of biomolecules in lake sediments: potential importance of physical shielding by recalcitrant cell walls.

Even though lake sediments are globally important organic carbon (OC) sinks, the controls on long-term OC storage in these sediments are unclear. Using a multiproxy approach, we investigate changes in diatom, green algae, and vascular plant biomolecules in sedimentary records from the past centuries across five temperate lakes with different trophic histories. Despite past increases in the input and burial of OC in sediments of eutrophic lakes, biomolecule quantities in sediments of all lakes are primarily controlled by postburial microbial degradation over the time scales studied. We, moreover, observe major differences in biomolecule degradation patterns across diatoms, green algae, and vascular plants. Degradation rates of labile diatom DNA exceed those of chemically more resistant diatom lipids, suggesting that chemical reactivity mainly controls diatom biomolecule degradation rates in the lakes studied. By contrast, degradation rates of green algal and vascular plant DNA are significantly lower than those of diatom DNA, and in a similar range as corresponding, much less reactive lipid biomarkers and structural macromolecules, including lignin. We propose that physical shielding by degradation-resistant cell wall components, such as algaenan in green algae and lignin in vascular plants, contributes to the long-term preservation of labile biomolecules in both groups and significantly influences the long-term burial of OC in lake sediments.

Photochemical Production of Sulfate and Methanesulfonic Acid from Dissolved Organic Sulfur.

Photodegradation processes play an important role in releasing elements tied up in biologically refractory forms in the environment, and are increasingly being recognized as important contributors to biogeochemical cycles. While complete photo-oxidation of dissolved organic carbon (to CO2) and dissolved organic phosphorous (to PO43-) has been documented, the analogous photoproduction of sulfate from dissolved organic sulfur (DOS) has not yet been reported. Recent high-resolution mass spectrometry studies showed a selective loss of organic sulfur during photodegradation of dissolved organic matter, which was hypothesized to result in the production of sulfate. Here, we provide evidence of ubiquitous production of sulfate, methanesulfonic acid (MSA), and methanesulfinic acid (MSIA) during photodegradation of DOM samples from a wide range of natural terrestrial environments. We show that photochemical production of sulfate is generally more efficient than the production of MSA and MSIA, as well as volatile S-containing compounds such as CS2 and COS. We also identify possible molecular precursors for sulfate and MSA, and we demonstrate that a wide range of relevant classes of DOS compounds (in terms of S oxidation state and molecular structure) can liberate sulfate upon photosensitized degradation. This work suggests that photochemistry may play a more significant role in the aquatic and atmospheric fate of DOS than currently believed.

Methanogens and Iron-Reducing Bacteria: the Overlooked Members of Mercury-Methylating Microbial Communities in Boreal Lakes.

Methylmercury is a potent human neurotoxin which biomagnifies in aquatic food webs. Although anaerobic microorganisms containing the hgcA gene potentially mediate the formation of methylmercury in natural environments, the diversity of these mercury-methylating microbial communities remains largely unexplored. Previous studies have implicated sulfate-reducing bacteria as the main mercury methylators in aquatic ecosystems. In the present study, we characterized the diversity of mercury-methylating microbial communities of boreal lake sediments using high-throughput sequencing of 16S rRNA and hgcA genes. Our results show that in the lake sediments, Methanomicrobiales and Geobacteraceae also represent abundant members of the mercury-methylating communities. In fact, incubation experiments with a mercury isotopic tracer and molybdate revealed that only between 38% and 45% of mercury methylation was attributed to sulfate reduction. These results suggest that methanogens and iron-reducing bacteria may contribute to more than half of the mercury methylation in boreal lakes.IMPORTANCE Despite the global awareness that mercury, and methylmercury in particular, is a neurotoxin to which millions of people continue to be exposed, there are sizable gaps in the understanding of the processes and organisms involved in methylmercury formation in aquatic ecosystems. In the present study, we shed light on the diversity of the microorganisms responsible for methylmercury formation in boreal lake sediments. All the microorganisms identified are associated with the processing of organic matter in aquatic systems. Moreover, our results show that the well-known mercury-methylating sulfate-reducing bacteria constituted only a minor portion of the potential mercury methylators. In contrast, methanogens and iron-reducing bacteria were important contributors to methylmercury formation, highlighting their role in mercury cycling in the environment.

Molecular composition of organic matter controls methylmercury formation in boreal lakes.

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.

High-throughput characterization of sediment organic matter by pyrolysis-gas chromatography/mass spectrometry and multivariate curve resolution: A promising analytical tool in (paleo)limnology.

Molecular-level chemical information about organic matter (OM) in sediments helps to establish the sources of OM and the prevalent degradation/diagenetic processes, both essential for understanding the cycling of carbon (C) and of the elements associated with OM (toxic trace metals and nutrients) in lake ecosystems. Ideally, analytical methods for characterizing OM should allow high sample throughput, consume small amounts of sample and yield relevant chemical information, which are essential for multidisciplinary, high-temporal resolution and/or large spatial scale investigations. We have developed a high-throughput analytical method based on pyrolysis-gas chromatography/mass spectrometry and automated data processing to characterize sedimentary OM in sediments. Our method consumes 200 µg of freeze-dried and ground sediment sample. Pyrolysis was performed at 450°C, which was found to avoid degradation of specific biomarkers (e.g., lignin compounds, fresh carbohydrates/cellulose) compared to 650°C, which is in the range of temperatures commonly applied for environmental samples. The optimization was conducted using the top ten sediment samples of an annually resolved sediment record (containing 16-18% and 1.3-1.9% of total carbon and nitrogen, respectively). Several hundred pyrolytic compound peaks were detected of which over 200 were identified, which represent different classes of organic compounds (i.e., n-alkanes, n-alkenes, 2-ketones, carboxylic acids, carbohydrates, proteins, other N compounds, (methoxy)phenols, (poly)aromatics, chlorophyll and steroids/hopanoids). Technical reproducibility measured as relative standard deviation of the identified peaks in triplicate analyses was 5.5±4.3%, with 90% of the RSD values within 10% and 98% within 15%. Finally, a multivariate calibration model was calculated between the pyrolytic degradation compounds and the sediment depth (i.e., sediment age), which is a function of degradation processes and changes in OM source type. This allowed validation of the Py-GC/MS dataset against fundamental processes involved in OM cycling in aquatic ecosystems.

Early land use and centennial scale changes in lake-water organic carbon prior to contemporary monitoring.

Organic carbon concentrations have increased in surface waters across parts of Europe and North America during the past decades, but the main drivers causing this phenomenon are still debated. A lack of observations beyond the last few decades inhibits a better mechanistic understanding of this process and thus a reliable prediction of future changes. Here we present past lake-water organic carbon trends inferred from sediment records across central Sweden that allow us to assess the observed increase on a centennial to millennial time scale. Our data show the recent increase in lake-water carbon but also that this increase was preceded by a landscape-wide, long-term decrease beginning already A.D. 1450-1600. Geochemical and biological proxies reveal that these dynamics coincided with an intensification of human catchment disturbance that decreased over the past century. Catchment disturbance was driven by the expansion and later cessation of widespread summer forest grazing and farming across central Scandinavia. Our findings demonstrate that early land use strongly affected past organic carbon dynamics and suggest that the influence of historical landscape utilization on contemporary changes in lake-water carbon levels has thus far been underestimated. We propose that past changes in land use are also a strong contributing factor in ongoing organic carbon trends in other regions that underwent similar comprehensive changes due to early cultivation and grazing over centuries to millennia.

Downwash of atmospherically deposited trace metals in peat and the influence of rainfall intensity: an experimental test.

Accumulation records of pollutant metals in peat have been frequently used to reconstruct past atmospheric deposition rates. While there is good support for peat as a record of relative changes in metal deposition over time, questions remain whether peat archives represent a quantitative or a qualitative record. Several processes can potentially influence the quantitative record of which downwashing is particularly pertinent as it would have a direct influence on how and where atmospherically deposited metals are accumulated in peat. The aim of our study was two-fold: first, to compare and contrast the retention of dissolved Pb, Cu, Zn and Ni in peat cores; and second, to test the influence of different precipitation intensities on the potential downwashing of metals. We applied four 'rainfall' treatments to 13 peat cores over a 3-week period, including both daily (2 or 5.3 mm day(-1)) and event-based additions (37 mm day(-1), added over 1h or over a 10h rain event). Two main trends were apparent: 1) there was a difference in retention of the added dissolved metals in the surface layer (0-2 cm): 21-85% for Pb, 18-63% for Cu, 10-25% for Zn and 10-20% for Ni. 2) For all metals and both peat types (sphagnum lawn and fen), the addition treatments resulted in different downwashing depths, i.e., as the precipitation-addition increased so did the depth at which added metals could be detected. Although the largest fraction of Pb and Cu was retained in the surface layer and the remainder effectively immobilized in the upper peat (≤ 10 cm), there was a smearing effect on the overall retention, where precipitation intensity exerts an influence on the vertical distribution of added trace metals. These results indicate that the relative position of a deposition signal in peat records would be preserved, but it would be quantitatively attenuated.

Distribution and speciation of ambient selenium in contrasted soils, from mineral to organic rich.

Selenium adsorption onto oxy-hydroxides mainly controls its mobility in volcanic soils, red earths and soils poor in organic matter (OM) while the influence of OM was emphasized in podzol and peat soils. This work aims at deciphering how those solid phases influence ambient Se mobility and speciation under less contrasted conditions in 26 soils spanning extensive ranges of OM (1-32%), Fe/Al oxy-hydroxides (0.3-6.1%) contents and pH (4.0-8.3). The soil collection included agriculture, meadow and forest soils to assess the influence of OM quality as well. Trace concentrations of six ambient Se species (Se(IV), Se(VI) and 4 organo-Se compounds) were analyzed by HPLC-ICP-MS in three extractants (ultrapure water, phosphate and sodium hydroxide) targeting Se associated to different soil phases. The Kd values determined from ultrapure water extraction were higher than those reported in commonly used short-term experiments after Se-spiking. Correlations of ambient Se content and distribution with soil parameters explained this difference by an involvement of slow processes in Se retention in soils. The 26 Kd values determined here for a wide variety of soils thus represent a relevant database for long-term prediction of Se mobility. For soils containing less than 20% OM, ambient Se solubility is primarily controlled by its adsorption onto crystalline oxy-hydroxides. However, OM plays an important role in Se mobility by forming organo-mineral associations that may protect adsorbed Se from leaching and/or create anoxic zones (aggregates) where Se is immobilized after its reduction. Although for the first time, inorganic Se(IV), Se(VI) and organo-Se compounds were simultaneously investigated in a large soil collection, high Se proportions remain unidentified in each soil extract, most probably due to Se incorporation and/or binding to colloidal-sized OM. Variations of environmental factors regulating the extent of OM-mineral associations/aggregation may thus lead to changes in Se mobility and bio-availability.

A new methodology involving stable isotope tracer to compare simultaneously short- and long-term selenium mobility in soils.

A better understanding of Se fate in soils is required for different environmental issues, such as radioactive waste management or soil fertilization procedures. In these contexts, the mobility and speciation of Se have to be studied at both short and long terms after Se inputs. Here, we present a new methodology to monitor simultaneously the reactivity of added (isotopic enriched tracers) and ambient Se at trace level in soils by high-performance liquid chromatography inductively coupled plasma mass spectrometry (ICP-MS) following specific extractions. To do so, the collision/reaction cell of the ICP-MS instrument and the interference corrections were optimized to measure reliably the four major Se isotopes. To exemplify the method capabilities, the behaviors of added (77)Se(IV) and ambient Se were followed up in two soils submitted to an ageing process during 3 months. The solid/liquid distribution of added Se reached a steady state after 1 month while its speciation and distribution among soil solid phases were still changing after 3 months. The results clearly demonstrate that slow processes are involved in Se retention and transformation in soils. The usual short-term experiments (<1 month) performed after Se addition are thus not suitable for long-term risk assessment. Interestingly, the behavior of added Se tended to that of ambient Se, suggesting that ambient Se would be useful to infer the fate of Se input over long time scales.

Selenium speciation analysis at trace level in soils.

This paper describes the development of an analytical methodology to determine speciation of selenium present in soils at trace level (µg kg(-1)). The methodology was based on parallel single extractions and high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICPMS). Two complementary chromatographic separations were used to confirm Se species identity. Different extractants, selected on the basis of sequential extraction schemes, were compared. Ultrapure water, 0.1 molL(-1) phosphate buffer (KH(2)PO(4)/K(2)HPO(4)) at pH 7 and 0.1 molL(-1) sodium hydroxide extractants were finally chosen owing to their efficiency in extracting Se and compatibility with Se species stability. These extractants allow also assessing respectively water-soluble Se (i.e. the most mobile Se fraction), exchangeable Se (i.e. sorbed onto soil component surface) and Se bound to soil organic matter. This methodology gives thus information on Se mobility related to its distribution in soil with preservation of original Se speciation. Detection limits range from 3 to 29ng(Se)L(-1) and from 0.1 to 10 µg(Se)kg(-1), allowing determination of Se species concentrations in extracts from soils containing native Se at trace level. The methodology was applied to three soils with total Se concentrations between 210 and 1560 µg(Se)kg(-1).