Sensitive and High-Throughput Analysis of Volatile Organic Species of S, Se, Br, and I at Trace Levels in Water and Atmospheric Samples by Thermal Desorption Coupled to Gas Chromatography and Inductively Coupled Plasma Mass Spectrometry.

Emissions of volatile organic sulfur (S), selenium (Se), bromine (Br), and iodine (I) species from aquatic ecosystems represent an important source of these elements into the atmosphere. Available methods to measure these species are either not sensitive enough or not automated, which hinder a full understanding of species distribution and production mechanisms. Here, we present a sensitive and high-throughput method for the simultaneous and comprehensive quantification of S, Se, Br, and I volatile organic species in atmospheric and aqueous samples using a preconcentration step onto sorbent tubes and subsequent analysis by thermal desorption coupled to gas chromatography and inductively coupled plasma mass spectrometry (TD-GC-ICP-MS). Selected commercially available sorbent tubes, consisting of mixed porous polymer and graphitized black carbon, offered the highest trapping capacity and lowest loss of species when stored at -20 °C for 28 days after sampling. After optimization of the TD-GC-ICP-MS method, absolute detection limits were better than 3.8 pg, 9.1 fg, 313 fg, and 50 fg, respectively, for S, Se, Br, and I species. As a proof of concept, the concentrations of target species were determined in aqueous and continuously collected atmospheric samples during a cruise in the Baltic and North Seas. Moreover, unknown S, Br, and I volatile species were detected in both aqueous and atmospheric samples demonstrating the full potential of the method.

Geochemical Soil Atlas of Switzerland - Distribution of Toxic Elements.

Chemical elements such as copper and molybdenum are essential for animal and human health but may become toxic at elevated concentrations depending on the exposure and intake rate. Other elements such as mercury pose a threat to human health at already low concentrations. The soil acts as the main source of these elements for plant uptake and is thus driving accumulation along the food chain. However, in Switzerland, no nationwide information on elemental distributions in soils has existed up to now. The geochemical soil atlas of Switzerland will fill this gap by presenting the concentration ranges and the spatial distribution of 20 elements in the topsoil. In this summary, we present the methodological approaches and some main findings of the atlas with a focus on toxic elements as well as elements that can be or are toxic at higher concentrations.

Reaction of DMS and HOBr as a Sink for Marine DMS and an Inhibitor of Bromoform Formation.

Recently, we suggested that hypobromous acid (HOBr) is a sink for the marine volatile organic sulfur compound dimethyl sulfide (DMS). However, HOBr is also known to react with reactive moieties of dissolved organic matter (DOM) such as phenolic compounds to form bromoform (CHBr3) and other brominated compounds. The reaction between HOBr and DMS may thus compete with the reaction between HOBr and DOM. To study this potential competition, kinetic batch and diffusion-reactor experiments with DMS, HOBr, and DOM were performed. Based on the reaction kinetics, we modeled concentrations of DMS, HOBr, and CHBr3 during typical algal bloom fluxes of DMS and HOBr (10-13 to 10-9 M s-1). For an intermediate to high HOBr flux (≥10-11 M s-1) and a DMS flux ≤10-11 M s-1, the model shows that the DMS degradation by HOBr was higher than for photochemical oxidation, biological consumption, and sea-air gas exchange combined. For HOBr fluxes ≤10-11 M s-1 and a DMS flux of 10-11 M s-1, our model shows that CHBr3 decreases by 86% compared to a lower DMS flux of 10-12 M s-1. Therefore, the reaction between HOBr and DMS likely not only presents a sink for DMS but also may lead to suppressed CHBr3 formation.

Constraining Atmospheric Selenium Emissions Using Observations, Global Modeling, and Bayesian Inference.

Selenium (Se) is an essential dietary element for humans and animals, and the atmosphere is an important source of Se to soils. However, estimates of global atmospheric Se fluxes are highly uncertain. To constrain these uncertainties, we use a global model of atmospheric Se cycling and a database of more than 600 sites where Se in aerosol has been measured. Applying Bayesian inference techniques, we determine the probability distributions of global Se emissions from the four major sources: anthropogenic activities, volcanoes, marine biosphere, and terrestrial biosphere. Between 29 and 36 Gg of Se are emitted to the atmosphere every year, doubling previous estimates of emissions. Using emission parameters optimized by aerosol network measurements, our model shows good agreement with the aerosol Se observations (R2 = 0.66), as well as with independent aerosol (0.59) and wet deposition measurements (0.57). Both model and measurements show a decline in Se over North America in the last two decades because of changes in technology and energy policy. Our results highlight the role of the ocean as a net atmospheric Se sink, with around 7 Gg yr-1 of Se transferred from land through the atmosphere. The constrained Se emissions represent a substantial step forward in understanding the global Se cycle.

Selenium deficiency risk predicted to increase under future climate change.

Deficiencies of micronutrients, including essential trace elements, affect up to 3 billion people worldwide. The dietary availability of trace elements is determined largely by their soil concentrations. Until now, the mechanisms governing soil concentrations have been evaluated in small-scale studies, which identify soil physicochemical properties as governing variables. However, global concentrations of trace elements and the factors controlling their distributions are virtually unknown. We used 33,241 soil data points to model recent (1980-1999) global distributions of Selenium (Se), an essential trace element that is required for humans. Worldwide, up to one in seven people have been estimated to have low dietary Se intake. Contrary to small-scale studies, soil Se concentrations were dominated by climate-soil interactions. Using moderate climate-change scenarios for 2080-2099, we predicted that changes in climate and soil organic carbon content will lead to overall decreased soil Se concentrations, particularly in agricultural areas; these decreases could increase the prevalence of Se deficiency. The importance of climate-soil interactions to Se distributions suggests that other trace elements with similar retention mechanisms will be similarly affected by climate change.

Arsenic and Other Geogenic Contaminants in Groundwater - A Global Challenge.

Groundwater is a much safer and more dependable source of drinking water than surface water. However, natural (geogenic) hazardous elements can contaminate groundwater and lead to severe health problems in consumers. Arsenic concentrations exceeding the WHO drinking water guideline of 10 µg/L globally affect over 220 million people and can cause arsenicosis (skin lesions and cancers). Fluoride, while preventing caries at low concentrations, has detrimental effects when above the WHO drinking water guideline of 1.5 mg/L and puts several hundred million people at risk of dental and skeletal fluorosis. In this article, we report on the geochemistry and occurrence of arsenic and fluoride in groundwater and on the development of global and regional risk maps that help alert governments and water providers to take appropriate mitigation measures for the provision of safe drinking water. We then summarize research on the removal of arsenic and fluoride from drinking water, focusing on adapted technologies for water treatment. Finally, we discuss the applicability of various measures in a larger context and future challenges in reaching the goal of access to safe drinking water for all.

Marine versus Continental Sources of Iodine and Selenium in Rainfall at Two European High-Altitude Locations.

The essential elements selenium (Se) and iodine (I) are often present in low levels in terrestrial diets, leading to potential deficiencies. Marine I and Se emissions and subsequent atmospheric wet deposition has been suggested to be an important source of I and Se to soils and terrestrial food chains. However, the contribution of recycled moisture of continental origin to I and Se to precipitation has never been analyzed. Here we report concentrations and speciation of I and Se, as well as of bromine (Br), sulfur (S), and DOC-δ13C signatures for weekly collected precipitation samples (in the period of April 2015 to September 2016) at two high altitude sites, i.e., Jungfraujoch (JFJ; Switzerland) and Pic du Midi (PDM; France). Analysis of precipitation chemistry and moisture sources indicate combined marine and continental sources of precipitation and Se, I, Br, and S at both sites. At JFJ, concentrations of I and Se were highest when continental moisture sources were dominant, indicating important terrestrial sources for these elements. Furthermore, correlations between investigated elements and DOC-δ13C, particularly when continental moisture source contributions were high, indicate a link between these elements and the source of dissolved organic matter, especially for I (JFJ and PDM) and Se (JFJ).

Hypobromous Acid as an Unaccounted Sink for Marine Dimethyl Sulfide?

Marine emissions of dimethyl sulfide (DMS) to the atmosphere play a fundamental role in the global sulfur (S) cycle and have important consequences for the Earth's radiative balance. In the ocean, DMS is mainly produced by marine algae and bacteria via cleavage of the precursor compound dimethylsulfoniopropionate (DMSP). Here, we studied the reaction between DMS and the strong oxidant hypobromous acid (HOBr), which is also produced by marine algae. Further, reactions between DMS oxidation products and HOBr were studied. The second-order rate constants were determined in competition kinetic experiments using sulfite as a competitor. In addition, we developed a new HPLC-ICP-MS/MS method to identify and quantify the oxidation products of DMS and related compounds. We found that HOBr reacts very fast with DMS to dimethyl sulfoxide (DMSO), with a second-order rate constant of 1.6 × 109 M-1 s-1, while the subsequent oxidation of DMSO to dimethyl sulfone (DMSO2) is much slower (0.4 M-1 s-1). Concentrations of DMSP, DMSO2, and methanesulfonic acid (MSA) did not decrease when exposed to excess concentrations of HOBr, implying that these S-containing compounds are not or only slightly reactive toward HOBr. A quantitative comparison of known DMS sinks shows that HOBr may be an important, hitherto neglected sink for marine DMS that needs to be considered in ocean-atmosphere chemistry models.

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.

Marine Primary Productivity as a Potential Indirect Source of Selenium and Other Trace Elements in Atmospheric Deposition.

Atmospheric processes play an important role in the supply of the trace element selenium (Se) as well as other essential trace elements to terrestrial environments, mainly via wet deposition. Here we investigate whether the marine biosphere can be identified as a source of Se and of other trace elements in precipitation samples. We used artificial neural network (ANN) modeling and other statistical methods to analyze relationships between a high-resolution atmospheric deposition chemistry time series (March 2007-January 2009) from Plynlimon (UK) and exposure of air masses to marine chlorophyll a and to other source proxies. Using ANN sensitivity analyses, we found that higher air mass exposure to marine productivity leads to higher concentrations of dissolved organic carbon (DOC) in rainfall. Furthermore, marine productivity was found to be an important but indirect factor in controlling Se as well as vanadium (V), cobalt (Co), nickel (Ni), zinc (Zn), and aluminum (Al) concentrations in atmospheric deposition, likely via scavenging by organic compounds derived from marine organisms. Marine organisms may thus play an indirect but important role in the delivery of trace elements to terrestrial environments and food chains.

Quantification of Element Fluxes in Wastewaters: A Nationwide Survey in Switzerland.

The number and quantities of trace elements used in industry, (high-tech) consumer products, and medicine are rapidly increasing, but the resulting emissions and waste streams are largely unknown. We assessed the concentrations of 69 elements in digested sewage sludge and effluent samples from 64 municipal wastewater treatment plants as well as in major rivers in Switzerland. This data set, representative of an entire industrialized country, presents a reference point for current element concentrations, average per-capita fluxes, loads discharged to surface waters, and economic waste-stream values. The spatial distribution of many individual elements could be attributed either to predominant geogenic or to anthropogenic inputs. Per-capita element fluxes ranged from <10 µg day-1 (e.g., Au, In, and Lu) to >1 mg day-1 (e.g., Zn, Sc, Y, Nb, and Gd) and >1 g day-1 (e.g., for P, Fe, and S). Effluent loads of some elements contributed significantly to riverine budgets (e.g., 24% for Zn, 50% for P, and 83% for Gd), indicating large anthropogenic inputs via the wastewater stream. At various locations, precious metal concentrations in sludge were similar to those in profitable mining ores, with total flux values of up to 6.8 USD per capita per year or 15 USD per metric ton of dry sludge.

Selenium Uptake and Methylation by the Microalga Chlamydomonas reinhardtii.

Biogenic selenium (Se) emissions play a major role in the biogeochemical cycle of this essential micronutrient. Microalgae may be responsible for a large portion of these emissions via production of methylated Se compounds that volatilize into the atmosphere. However, the biochemical mechanisms underlying Se methylation in microalgae are poorly understood. Here, we study Se methylation by Chlamydomonas reinhardtii, a model freshwater alga, as a function of uptake and intracellular Se concentrations and present a biochemical model that quantitatively describes Se uptake and methylation. Both selenite and selenate, two major inorganic forms of Se, are readily internalized by C. reinhardtii, but selenite is accumulated around ten times more efficiently than selenate due to different membrane transporters. With either selenite or selenate as substrates, Se methylation was highly efficient (up to 89% of intracellular Se) and directly coupled to intracellular Se levels (R(2) > 0.92) over an intracellular concentration range exceeding an order of magnitude. At intracellular concentrations exceeding 10 mM, intracellular zerovalent Se was formed. The relationship between uptake, intracellular accumulation, and methylation was used by the biochemical model to successfully predict measured concentrations of methylated Se in natural waters. Therefore, biological Se methylation by microalgae could significantly contribute to environmental Se cycling.

Predicting geogenic arsenic contamination in shallow groundwater of south Louisiana, United States.

Groundwater contaminated with arsenic (As) threatens the health of more than 140 million people worldwide. Previous studies indicate that geology and sedimentary depositional environments are important factors controlling groundwater As contamination. The Mississippi River delta has broadly similar geology and sedimentary depositional environments to the large deltas in South and Southeast Asia, which are severely affected by geogenic As contamination and therefore may also be vulnerable to groundwater As contamination. In this study, logistic regression is used to develop a probability model based on surface hydrology, soil properties, geology, and sedimentary depositional environments. The model is calibrated using 3286 aggregated and binary-coded groundwater As concentration measurements from Bangladesh and verified using 78 As measurements from south Louisiana. The model's predictions are in good agreement with the known spatial distribution of groundwater As contamination of Bangladesh, and the predictions also indicate high risk of As contamination in shallow groundwater from Holocene sediments of south Louisiana. Furthermore, the model correctly predicted 79% of the existing shallow groundwater As measurements in the study region, indicating good performance of the model in predicting groundwater As contamination in shallow aquifers of south Louisiana.

Arsenic pollution of groundwater in Vietnam exacerbated by deep aquifer exploitation for more than a century.

Arsenic contamination of shallow groundwater is among the biggest health threats in the developing world. Targeting uncontaminated deep aquifers is a popular mitigation option although its long-term impact remains unknown. Here we present the alarming results of a large-scale groundwater survey covering the entire Red River Delta and a unique probability model based on three-dimensional Quaternary geology. Our unprecedented dataset reveals that ∼7 million delta inhabitants use groundwater contaminated with toxic elements, including manganese, selenium, and barium. Depth-resolved probabilities and arsenic concentrations indicate drawdown of arsenic-enriched waters from Holocene aquifers to naturally uncontaminated Pleistocene aquifers as a result of > 100 years of groundwater abstraction. Vertical arsenic migration induced by large-scale pumping from deep aquifers has been discussed to occur elsewhere, but has never been shown to occur at the scale seen here. The present situation in the Red River Delta is a warning for other As-affected regions where groundwater is extensively pumped from uncontaminated aquifers underlying high arsenic aquifers or zones.

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.

Emerging investigator series: predicted losses of sulfur and selenium in european soils using machine learning: a call for prudent model interrogation and selection.

Reductions in sulfur (S) atmospheric deposition in recent decades have been attributed to S deficiencies in crops. Similarly, global soil selenium (Se) concentrations were predicted to drop, particularly in Europe, due to increases in leaching attributed to increases in aridity. Given its international importance in agriculture, reductions of essential elements, including S and Se, in European soils could have important impacts on nutrition and human health. Our objectives were to model current soil S and Se levels in Europe and predict concentration changes for the 21st century. We interrogated four machine-learning (ML) techniques, but after critical evaluation, only outputs for linear support vector regression (Lin-SVR) models for S and Se and the multilayer perceptron model (MLP) for Se were consistent with known mechanisms reported in literature. Other models exhibited overfitting even when differences in training and testing performance were low or non-existent. Furthermore, our results highlight that similarly performing models based on RMSE or R2 can lead to drastically different predictions and conclusions, thus highlighting the need to interrogate machine learning models and to ensure they are consistent with known mechanisms reported in the literature. Both elements exhibited similar spatial patterns with predicted gains in Scandinavia versus losses in the central and Mediterranean regions of Europe, respectively, by the end of the 21st century for an extreme climate scenario. The median change was -5.5% for S (Lin-SVR) and -3.5% (MLP) and -4.0% (Lin-SVR) for Se. For both elements, modeled losses were driven by decreases in soil organic carbon, S and Se atmospheric deposition, and gains were driven by increases in evapotranspiration.

Colloidal properties of nanoparticular biogenic selenium govern environmental fate and bioremediation effectiveness.

Microbial selenium (Se) bioremediation is based on conversion of water soluble, toxic Se oxyanions to water insoluble, elemental Se. Formed biogenic elemental Se is of nanometer size, hampering straightforward separation from the aqueous phase. This study represents the first systematic investigation on colloidal properties of pure biogenic Se suspensions, linking electrophoretic mobility (ζ-potential) to column settling behavior. It was demonstrated that circumneutral pH, commonly applied in bioremediation, is not appropriate for gravitational separation due to the negative ζ-potential preventing agglomeration. Mono/di/trivalent counter cations and acidity (protons) were used to screen efficiently the intrinsic negative charge of biogenic Se suspensions at circumneutral pH. Fast settling was induced by La(3+) addition in the micromolar range (86.2 ± 3.5% within 0.5 h), whereas considerably higher concentrations were needed when Ca(2+) or Na(+) was used. Colloidal stability was furthermore studied in different model waters. It was demonstrated that surface waters as such represent a fragile system regarding colloidal stability of biogenic Se suspensions (ζ-potential ∼ -30 mV), whereas dissolved organic matter increases colloidal stability. In marine waters, biogenic Se is colloidally destabilized and is thus expected to settle, representing a potential sink for Se during transport in the aquatic environment.

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.

Online preconcentration-IC-ICP-MS for selenium quantification and speciation at ultratraces.

Selenium (Se) is of key importance to human health with a very narrow concentration range of optimal dietary intake. Due to the inherent analytical challenge linked with the low natural abundance, information on precise and accurate Se speciation in deficient environments is hardly existent. This study presents a novel approach to determine Se species-specifically at ultratraces, by online coupling of a preconcentration (trap) column to an ion chromatography inductively coupled plasma mass spectrometry (IC-ICP-MS) system. It is demonstrated that with this robust and work/time efficient method, the predominant selenium oxyanions, selenite (Se(IV)) and selenate (Se(VI)), can be quantified down to 7.3 and 8.3 picogram total Se, respectively, in an overall analytical time of 420 s, only. The applicability for environmental samples was proven on pristine volcanic ashes collected from seven different volcanoes. The high sensitivity of the novel approach allowed to determine speciation in samples that were strongly depleted in total selenium (<0.05 mg kg(-1) Se) with only minor fractions of Se mobilized (i.e., less than 10% of the total selenium was leached in 10 out of 12 samples). The studied samples showed considerate differences in selenium speciation, with selenite and selenate co-occurring in most samples. The fact that the studied sample leachates had a wide range of pH (3.78-9.55) and major anion/cation composition underlines the versatility and wide potential application range of the method presented.

Environmental selenium research: from microscopic processes to global understanding.

Selenium is a natural trace element that is of fundamental importance to human health. The extreme geographical variation in selenium concentrations in soils and food crops has resulted in significant health problems related to deficient or excess levels of selenium in the environment. To deal with these kinds of problems in the future it is essential to get a better understanding of the processes that control the global distribution of selenium. The recent development of analytical techniques and methods enables accurate selenium measurements of environmental concentrations, which will lead to a better understanding of biogeochemical processes. This improved understanding may enable us to predict the distribution of selenium in areas where this is currently unknown. These predictions are essential to prevent future Se health hazards in a world that is increasingly affected by human activities.