Species-specific second-order rate constants for the reactions of eight model sulfoxides with hypochlorous acid (k_HOCl) were determined to be in the range of 2.7 M⁻¹ s⁻¹ to 5.8 × 10³M⁻¹ s⁻¹. A quantitative structure–activity relationships (QSAR) with Taft σ* constants was developed based on eight measured k_HOCl-values, showing a good linear correlation (R² = 0.89) with a negative slope ρ = -1.5 typical for electrophilic reactions. The reaction is mainly controlled by HOCl, with a minor contribution of OCl^–. The contributions of other reactive chlorine species (e.g., Cl₂ and Cl₂O) to the overall kinetics are only 7 % for Cl₂O and 5 % for Cl₂ under typical drinking water treatment conditions. A combination of several analytical methods (HPLC-MS/MS, HPLC-ICP-MS/MS, and NMR) was applied for the identification of transformation products. Major transformation products from the reactions of chlorine with sulfoxides are sulfones, Cl-substituted sulfoxides, aldehydes, and sulfonic acids potentially formed via a transient chlorosulfonium cation. In general, sulfoxides react more readily with chlorine compared to bromine. This might be caused by a partial positive charge on the sulfur which leads to a stronger interaction with Cl in HOCl having a smaller partial positive charge than Br in HOBr. The ratios of the species-specific second-order rate constants for the reactions of the selected sulfoxides with chlorine or bromine (k_HOCl/k_HOBr) range from 6 to 480. For sulfoxide compounds with strong electron-withdrawing substituents the reaction occurs most likely via a carbanion intermediate for which the reaction with HOBr is preferred, resulting in a k_HOCl/k_HOBr = 0.8.

Arsenic, a toxic element from both anthropogenic and natural sources, reaches surface environments through atmospheric cycling and dry and wet deposition. Biomethylation volatilizes arsenic into the atmosphere and deposition cycles it back to the surface, affecting soil-plant systems. Chemical speciation of deposited arsenic is important for understanding further processing in soils and bioavailability. However, the range of atmospheric transport and source signature of arsenic species remain understudied. Here we report significant levels of methylated arsenic in precipitation, cloud water and aerosols collected under free tropospheric conditions at Pic du Midi Observatory (France) indicating long-range transport, which is crucial for atmospheric budgets. Through chemical analyses and moisture source diagnostics, we identify terrestrial and marine sources for distinct arsenic species. Estimated atmospheric deposition fluxes of methylated arsenic are similar to reported methylation rates in soils, highlighting atmospheric deposition as a significant, overlooked source of potentially bioavailable methylated arsenic species impacting plant uptake in soils.

The organic matter composition of lake sediments influences important in-lake biogeochemical processes and stores information on environmental changes. Extracting this information is notoriously difficult because of the complexity of the organic matter matrix, which routinely imposes trade-offs between high temporal and analytical detail in the selection of methods of analysis. Here, we demonstrate the potential of diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) for achieving both of these objectives using untreated bulk samples from two Holocene lake-sediment cores from central Sweden. We develop quantitative models for sediment total organic carbon (TOC) with the same predictive abilities as models based on samples diluted with KBr and qualitatively characterize the organic matter using a spectra processing-pipeline combined with principal component analysis. In the qualitative analysis we identified four organic matter sub-fractions and the interpretation of these is supported and further advanced with molecular data from pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Within these organic fractions, compound groups such as aromatics, lignin, aliphatics, proteins and polysaccharides were identified by means of DRIFTS and the analyses and processes outlined here enables rapid and detailed quantitative and qualitative analysis of sediment organic matter. The DRIFTS approach can be used as stand-alone method for OM characterization with high temporal resolution in Holocene sediment records. It may also function as a screening process for more specific analyses of sample subsets, such as when coupled with pyrolysis-GC/MS to further tease apart the OM composition, identify sources and determine degradation status.

Atmospheric deposition is an important source of the micronutrient selenium for terrestrial ecosystems and food chains. However, the factors determining the total concentrations and chemical forms (speciation) of selenium in atmospheric deposition remain poorly understood. Here, aerosol samples were collected weekly over 5 years at Pic du Midi Observatory (French Pyrenees), alongside highly temporally resolved samples of aerosols, precipitation, and cloud water taken during a 2-month campaign. Firstly, measurements of selenium, other elements, and water isotopes were combined with sophisticated modelling approaches (aerosol-chemistry-climate SOCOL-AERv2 model and air parcel backward trajectories and Lagrangian moisture source analyses). Aerosol selenium measurements agreed well with SOCOL-AERv2-predicted values, and interestingly, higher fluxes of selenium and other elements were associated with deep convective activity during thunderstorms, highlighting the importance of local cloud dynamics in high deposition fluxes. Our results further indicate the coupling of element and water cycles from source to cloud formation, with decoupling during precipitation due to below-cloud scavenging. Secondly, selenium speciation was investigated in relation to sulfur speciation, organic composition, and moisture sources. While in the 5-year aerosol series, selenite (SeIV) was linked to anthropogenic source factors, in wet deposition it was related to pH and Atlantic moisture sources. We also report an organic selenium fraction, tracing it back to a marine biogenic source in both aerosols and wet deposition. With a comprehensive set of observations and model diagnostics, our study underscores the role of weather system dynamics alongside source contributions in explaining the atmospheric supply of trace elements to surface environments.

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.

Arsenic (As) and mercury (Hg) are highly toxic contaminants whereas selenium (Se) is both an essential trace element and potentially harmful at higher concentrations. The hyper-saline lakes of southern Bolivian Altiplano, which are ecological niches for endemic species, are also expected to be enriched in these toxic trace elements. The biogeochemistry of As, Hg, and Se in such high-altitude extreme environments (e.g., high UV radiation and salt content) remains poorly understood. In this study, we investigated the concentrations and chemical forms (speciation) of As, Hg, and Se in sediment, water, and air samples of Lagunas Colorada (LC), Verde (LV), and Blanca (LB) in the South Lipez region (>4200 m a.s.l.). We compared them with the repartition of biodiversity (invertebrates, algae, and bacteria). Extreme As concentrations were found in water (up to 82 mg L⁻¹), and the main As species was inorganic As(V), with neither biogenic methylated As nor volatile As forms being detected in water and air, respectively. Se concentrations in water were of 0.1 to 1.4 μg L⁻¹, and Se existed under different redox states, i.e., Se(IV), Se(VI), and reduced Se (0, -II), including biogenic methylated Se(-II) (trimethyl selenonium). Volatile Se compounds (e.g., dimethyl selenide) were detected in water and air samples. Hg was enriched in the surface water (6 to 30 ng L⁻¹) compared to other regional water bodies, and a significant amount of methyl-Hg and gaseous Hg(0) was detected. The drastic disparity between As, Se and Hg concentrations and speciation between lakes has important implications for their cycling in these extreme aquatic systems. While As mostly accumulated in its oxidized and non-volatile form, Hg and Se concentrations can be controlled by significant conversion to reduced and methylated forms, allowing efficient evasion to the atmosphere. Finally, the salinity, including major ions, and high levels of As were among the main drivers of biodiversity repartition between lakes.

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 (Se^IV), selenate (Se^VI), 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, Se^IV, Se^VI and organic Se^-II + Se⁰ concentrations in brackish and marine systems.

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.

Carbohydrates serve as structural materials, energy storage compounds, and energy carriers in organisms and provide insights into the dominant sources and the degradation state of organic matter (OM). Several studies have analyzed dissolved and/or particulate carbohydrates in the environment, often with the aim of studying particular carbohydrate groups of interest. These studies have often employed different acids and hydrolytic conditions, making comparisons across studies a challenge. Here, we introduce a sequential acid hydrolysis protocol for the comprehensive extraction, quantification and compositional investigation of carbohydrates in sediment samples. This protocol has four acid hydrolysis steps that sequentially increase in extraction strength, where each subsequent hydrolysis step is performed on the unextracted remains previously hydrolyzed. The four hydrolysis steps consist of 1 M HCl for 2 h at (1) room temperature, (2) 50 °C, and (3) 105 °C, followed by incubation for 8 h using (4) 6 M HCl and 105 °C. Based on tests using diverse carbohydrate standard compounds, the protocol recovers most di- and oligosaccharides and soluble polysaccharides during the initial hydrolysis steps, whereas the recovery of most insoluble polysaccharides is highest during the final extraction step. Applying this protocol to different sediment types shows that recoveries of neutral sugars, amino sugars and sugar alcohols are on average ~60% higher than with a reference one-step extraction method using only hydrolysis with hot 6 M HCl. This sequential extraction protocol thus provides an important new tool for the quantitative and compositional analysis of carbohydrates in aquatic sediments.

Photodegradation processes play an important role in releasing elements tied up in biologically refractory forms in the environment, and are increasingly recognized as important contributors to biogeochemical cycles. While complete photooxidation of dissolved organic carbon (to CO₂), and dissolved organic phosphorous (to PO₄^3-) 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 (i.e., 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.