Bas Vriens

Selenium Cycling Across Soil-Plant-Atmosphere Interfaces: A Critical Review

Selenium (Se) is an essential element for humans and animals, which occurs ubiquitously in the environment. It is present in trace amounts in both organic and inorganic forms in marine and freshwater systems, soils, biomass and in the atmosphere. Low Se levels in certain terrestrial environments have resulted in Se deficiency in humans, while elevated Se levels in waters and soils can be toxic and result in the death of aquatic wildlife and other animals. Human dietary Se intake is largely governed by Se concentrations in plants, which are controlled by root uptake of Se as a function of soil Se concentrations, speciation and bioavailability. In addition, plants and microorganisms can biomethylate Se, which can result in a loss of Se to the atmosphere. The mobilization of Se across soil-plant-atmosphere interfaces is thus of crucial importance for human Se status. This review gives an overview of current knowledge on Se cycling with a specific focus on soil-plant-atmosphere interfaces. Sources, speciation and mobility of Se in soils and plants will be discussed as well as Se hyperaccumulation by plants, biofortification and biomethylation. Future research on Se cycling in the environment is essential to minimize the adverse health effects associated with unsafe environmental Se levels.

Natural wetland emissions of methylated trace elements

Natural wetlands are well known for their significant methane emissions. However, trace element emissions via biomethylation and subsequent volatilization from pristine wetlands are virtually unstudied, even though wetlands constitute large reservoirs for trace elements. Here we show that the average volatile fluxes of selenium (<0.12 μg m(-2) day(-1)), sulphur (<37 μg m(-2) day(-1)) and arsenic (<0.54 μg m(-2) day(-1)) from a pristine peatland are considerable and consistent over two summers. We compare these fluxes with the total concentrations in the peat and show that selenium is up to 40 times more efficiently volatilized than arsenic, and over 100 times more efficiently volatilized than sulphur. We further show that the volatilization of selenium and arsenic increases with temperature, implying that emissions of these health-relevant trace elements will increase with global warming. We suggest that biomethylation and volatilization in wetlands play a crucial role in the mobilization and global biogeochemical cycling of trace elements.

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.

Quantification of methylated selenium, sulfur, and arsenic in the environment.

Biomethylation and volatilization of trace elements may contribute to their redistribution in the environment. However, quantification of volatile, methylated species in the environment is complicated by a lack of straightforward and field-deployable air sampling methods that preserve element speciation. This paper presents a robust and versatile gas trapping method for the simultaneous preconcentration of volatile selenium (Se), sulfur (S), and arsenic (As) species. Using HPLC-HR-ICP-MS and ESI-MS/MS analyses, we demonstrate that volatile Se and S species efficiently transform into specific non-volatile compounds during trapping, which enables the deduction of the original gaseous speciation. With minor adaptations, the presented HPLC-HR-ICP-MS method also allows for the quantification of 13 non-volatile methylated species and oxyanions of Se, S, and As in natural waters. Application of these methods in a peatland indicated that, at the selected sites, fluxes varied between 190–210 ng Se·m−2·d−1, 90–270 ng As·m−2·d−1, and 4–14 µg S·m−2·d−1, and contained at least 70% methylated Se and S species. In the surface water, methylated species were particularly abundant for As (>50% of total As). Our results indicate that methylation plays a significant role in the biogeochemical cycles of these elements.

Quantification of volatile-alkylated selenium and sulfur in complex aqueous media using solid-phase microextraction

Biologically produced volatile-alkylated Se and S compounds play an important role in the global biogeochemical Se and S cycles, are important constituents of odorous industrial emissions, and contribute to (off-)flavors in food and beverages. This study presents a fully automated direct-immersion solid-phase microextraction (DI-SPME) method coupled with capillary gas chromatography-mass spectrometry (GC/MS) for the simultaneous quantification of 10 volatile-alkylated Se and S compounds in complex aqueous media. Instrumental parameters of the SPME procedure were optimized to yield extraction efficiencies of up to 96% from complex aqueous matrices. The effects of sample matrix composition and analyte transformation during sample storage were critically assessed. With the use of internal standards and procedural calibrations, the DI-SPME-GC/MS method allows for trace-level quantification of volatile Se and S compounds in the ng/L range (e.g. down to 30 ng/L dimethyl sulfide and 75 ng/L dimethyl selenide). The applicability and robustness of the presented method demonstrate that the method may be used to quantify volatile Se and S compounds in complex aqueous samples, such as industrial effluents or food and beverage samples.

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.

Studying selenium and sulfur volatilisation by marine algae Emiliania huxleyi and Thalassiosira oceanica in culture

Environmental context Volatile selenium compounds from the oceans may ultimately be an important selenium source for agricultural soils. It has been hypothesised that marine algae are responsible for volatile selenium emissions, but in laboratory experiments, we observed minimal volatile selenium production by two marine algae known to produce large amounts of volatile sulfur. Instead, we found hints that bacterial processes may be important in the production of volatile selenium in the oceans. Abstract Volatile methylated selenium compounds, especially dimethylselenide, are thought to comprise the majority of marine selenium emissions. Despite their potential importance for the global redistribution of this trace element, which is essential for human health, little is known about the algal production of volatile organic selenium compounds. Previous studies have found correlations between dissolved dimethylselenide concentrations, dimethylsulfide concentrations (the sulfur analogue of dimethylselenide) and proxies for algal activity, most notably during a bloom of the coccolithophorid Emiliania huxleyi. In culturing studies, we investigated the ability of three globally important marine algal species, E. huxleyi, Phaeocystis globosa and the diatom Thalassiosira oceanica, to produce dimethylselenide. Despite substantial uptake of selenium and the production of volatile sulfur, E. huxleyi and T. oceanica produced negligible volatile selenium (<2nM). P. globosa produced low amounts of volatile selenium (~8nM), but grew poorly in our laboratory. However, cultures of marine bacteria and mixed bacterial–algal cultures showed that substantial amounts of volatile selenium can be produced in the presence of marine bacteria. In addition, a culture of marine bacteria alone produced ~50nM volatile selenium, far more than axenic cultures of E. huxleyi when exposed to equivalent selenite concentrations. Our results hint that marine algae may be of minor importance in the direct production of volatile selenium in the oceans, and suggest that the production of these compounds in the marine biosphere may instead be controlled by bacterial activity.