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The fungi Aureobasidium pullulans, Mortierella humilis, Trichoderma harzianum and Phoma glomerata were used to investigate the formation of selenium- and tellurium-containing nanoparticles during growth on selenium- and tellurium-containing media. Most organisms were able to grow on both selenium- and tellurium-containing media at concentrations of 1 mM resulting in extensive precipitation of elemental selenium and tellurium on fungal surfaces as observed by the red and black colour changes. Red or black deposits were confirmed as elemental selenium and tellurium, respectively. Selenium oxide and tellurium oxide were also found after growth of Trichoderma harzianum with 1 mM selenite and tellurite as well as the formation of elemental selenium and tellurium. The hyphal matrix provided nucleation sites for metalloid deposition with extracellular protein and extracellular polymeric substances localizing the resultant Se or Te nanoparticles. These findings are relevant to remedial treatments for selenium and tellurium and to novel approaches for selenium and tellurium biorecovery.

Three month old Thunbergia alata were exposed for 13 days to 10 μM selenite to determine the biotransformation of selenite in their roots. Selenium in formic acid extracts (80 ± 3%) was present as selenopeptides with Se-S bonds and selenium-PC complexes (selenocysteinyl-2-3-dihydroxypropionyl-glutathione, seleno-phytochelatin2, seleno-di-glutathione). An analytical method using HPLC-ICPMS to detect and quantify elemental selenium in roots of T. alata plants using sodium sulfite to quantitatively transform elemental selenium to selenosulfate was also developed. Elemental selenium was determined as 18 ± 4% of the total selenium in the roots which was equivalent to the selenium not extracted using formic acid extraction. The results are in an agreement with the XAS measurements of the exposed roots which showed no occurrence of selenite or selenate but a mixture of selenocysteine and elemental selenium.

Quantification and speciation of volatile selenium (Se) fluxes in remote areas has not been feasible previously, due to the absence of a simple and easily transportable trapping technique that preserves speciation. This paper presents a chemo-trapping method with nitric acid (HNO3) for volatile Se species, which preserves speciation of trapped compounds. The recovery and speciation of dimethylselenide (DMSe) and dimethyl diselenide (DMDSe) entrained through both concentrated nitric acid and hydrogen peroxide (H2O2) were compared by HPLC-ICP-MS and HPLC-HG-AFS analyses. It was demonstrated that trap reproducibility was better for nitric acid and a recovery of 65.2 +/- 1.9% for DMSe and 81.3 +/- 3.9% for DMDSe was found in nitric acid traps. HPLC-ES-MS identified dimethyl selenoxide (DMSeO) as the trapped product of DMSe. Methylseleninic acid (MSA) was identified to be the single product of DMDSe trapping. These oxidized derivatives have a high stability and low volatility, which makes nitric acid a highly attractive trapping liquid for volatile Se species and enables reconstruction of the speciation of those species. The presented trapping method is simple, quantifiable, reproducible, and robust and can potentially be applied to qualitatively and quantitatively study Se volatilization in a wide range of natural environments.

Standard mode and collision/reaction cell mass spectroscopy methods have been utilized in order to overcome spectral interferences and provide ultra‐low quantification of selenium (Se) and tellurium (Te) in British Carboniferous coals for the first time. The accurate detection of Se and Te in coals is becoming increasingly important, as coals and pyrite have been identified as potentially significant trace element sources. The mean Se concentration of British coals bear comparison to that of world coals, with anomalous Se content (concentrations above 4 mg/kg) across westerly exposures, often coinciding with high sulphur (S) content and visible pyrite. New Te data for British coals gives a mean concentration of 0.02 mg/kg, with anomalous Te in Ayrshire. There is a positive correlation in the Te/Se ratio across the sample set. The close relationship between Se and Te, as well as Se–Te with both early syngenetic and later cleat‐filling pyrite, confirms an important role for sulphides in Se and Te sequestration in British coals. The high Se‐Bowland Shale and/or Ordovician volcanics may have provided the trace element source for British coals of similar or younger age. Regional intrusive activity (shallow tabular intrusions or more extensive plutons) and episodes of intense deformation can alter the thermal maturity of coals and may have driven the movement of trace element‐rich fluids through strata, locally enriching coals in Se and Te. [ABSTRACT FROM AUTHOR]

A method for ultra-trace determination of Se and Te in coal by inductively coupled plasma mass spectrometry (ICP-MS) was developed. Samples (up to 500 mg) were prepared by microwave-induced combustion (MIC) in a closed system pressurized with 20 bar of oxygen. Inorganic acids or their mixtures were evaluated as absorbing solution. Using HNO3 + HCl (1 + 1), results obtained for Se and Te after sample preparation by MIC agreed with those obtained by reference methods, microwave-assisted wet digestion (MAWD) using concentrated HNO3 and HF, and solid sampling electrothermal vaporization inductively coupled plasma mass spectrometry (SS-ETV-ICP-MS), and also with a certified reference material of coal (NIST 1632c) for Se. Very low limits of quantification (LOQ) were obtained: 0.002 and 0.007 mg kg−1 for Se and Te, respectively. Major elements were determined in final solutions obtained by MAWD and MIC, and their concentration in solutions of MIC was negligible (<10 μg L−1), minimizing the risk of interference in ICP-MS analysis. The proposed method was applied to samples of coal from the United Kingdom, with a wide range of inorganic composition (from 3 to 41% ash content), showing its robustness and feasibility for routine analysis. Se concentration ranged from 0.291 to 11.5 mg kg−1, and Te was mainly found at ultra-trace levels (<0.007 to 0.11 mg kg−1). The proposed method presents several advantages over the reference methods, such as the use of a higher sample mass, low LOQs and, an important aspect, no need of using HF. [ABSTRACT FROM AUTHOR]

Mid-Jurassic pyritic coals exposed at the village of Brora, northern Scotland, UK, contain a marked enrichment of tellurium (Te) relative to crustal mean, average world coal compositions and British Isles Carboniferous coals. The Te content of Brora coal pyrite is more than one order of magnitude higher than in sampled pyrite of Carboniferous coals. The Te enrichment coincides with selenium (Se) and mercury (Hg) enrichment in the rims of pyrite, and Se/Te is much lower than in pyrites of Carboniferous coals. Initial pyrite formation is attributed to early burial (syn-diagenesis), with incorporation of Te, Se, Hg and lead (Pb) during later pyrite formation. The source of Te may have been a local hydrothermal system which was responsible for alluvial gold (Au) in the region, with some Au in Brora headwaters occurring as tellurides. Anomalous Te is not ubiquitous in coal, but may occur locally, and is detectable by laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS). [ABSTRACT FROM AUTHOR]

The Parys Mountain copper mining district (Anglesey, North Wales) hosts exposed pyritic bedrock, solid mine waste spoil heaps, and acid drainage (ochre sediment) deposits. Both natural and waste deposits show elevated trace element concentrations, including selenium (Se), at abundances of both economic and environmental consideration. Elevated concentrations of semi-metals such as Se in waste smelts highlight the potential for economic reserves in this and similar base metal mining sites. Selenium is sourced from the pyritic bedrock and concentrations are retained in red weathering smelt soils, but lost in bedrock-weathered soils and clays. Selenium correlates with Te, Au, Bi, Cd, Hg, Pb, S, and Sb across bedrock and weathered deposits. Man-made mine waste deposits show enrichment of As, Bi, Cu, Sb, and Te, with Fe oxide-rich smelt materials containing high Pb, up to 1.5 wt %, and Au contents, up to 1.2 ppm. The trace elements As, Co, Cu, and Pb are retained from bedrock to all sediments, including high Cu content in Fe oxide-rich ochre sediments. The high abundance and mobility of trace elements in sediments and waters should be considered as potential pollutants to the area, and also as a source for economic reserves of previously extracted and new strategic commodities. [ABSTRACT FROM AUTHOR]

The essential trace metals iron, zinc, and copper have a significant physiological role in healthy brain development and function. Especially zinc is important for neurogenesis, synaptogenesis, synaptic transmission and plasticity, and neurite outgrowth. Given the key role of trace metals in many cellular processes, it is important to maintain adequate levels in the brain. However, the physiological concentration of trace metals, and in particular zinc, in the human and animal brain is not well described so far. For example, little is known about the trace metal content of the brain of animals outside the class of mammals. Here, we report the concentration of iron, zinc, and copper in fresh brain tissue of different model-species of the phyla Chordata (vertebrates (mammals, fish)), Annelida, Arthropoda (insects), and Mollusca (snails), using inductively coupled plasma mass-spectrometry (ICP-MS). Our results show that the trace metals are present in the nervous system of all species and that significant differences can be detected between species of different phyla. We further show that a region-specific distribution of metals within the nervous system already exists in earthworms, hinting at a tightly controlled metal distribution. In line with this, the trace metal content of the brain of different species does not simply correlate with brain size. We conclude that although the functional consequences of the controlled metal homeostasis within the brain of many species remains elusive, trace metal biology may not only play an important role in the nervous system of mammals but across the whole animal kingdom. [ABSTRACT FROM AUTHOR]

The exploration for selenium (Se) and tellurium (Te) will become intensified as the technological demand for these elements grows. It is known that they are enriched in organic-rich sedimentary rocks over crustal mean values. LA-ICP-MS measurement of pyrite in two biodegraded palaeo-oil reservoirs in central England shows that Se and Te are enriched in them, but not in other sulfide samples from the region and elsewhere. The Carboniferous source rock shales in the region are Se-rich, implying that this enrichment was conferred to the oil generated from them. The Se and Te are located in pyrite precipitated in the palaeo-reservoirs by microbial activity. Exhumed oil reservoirs merit further investigation for concentrations of these elements. [ABSTRACT FROM AUTHOR]

The former mining site at Kisgruva near Kongsberg, Norway, is primarily composed of worked sulphide ore deposits, of hydrothermal origin, which occur within Precambrian metamorphic basement. Though the original targets at the Kisgruva mine site were extraction of copper (Cu), sulphur (S) and iron (Fe), the sulphide ore also contains exceptionally high concentrations of selenium (Se) and tellurium (Te), hosted within selenides (clausthalite and minor naumannite) and tellurides (hessite and minor altaite and tellurobismuthite). Both Se and Te are also present within the sulphide ore in pyrite and chalcopyrite, which contain exceptionally high concentrations of up to 688 ppm Se and 81 ppm Te. Additionally, oxidative weathering of the exposed bedrock has resulted in the accumulation of hyper-enriched, unconsolidated weathered crust deposits at surface (Se up to 1590 ppm; Te up to 63 ppm), containing selenite (SeO 3 2− ) and tellurite (TeO 3 2− ) ions. Concentrations of Se and Te are subsequently higher in the weathering products than in the sulphide ore, due to fixation on to organic matter (∼0.4% in weathered ore crusts), jarosite (formed from oxidation of sulphides from the primary ore), ferric oxide and hydroxide phases (goethite and haematite). Increasing demand for Se and Te to use in green technologies has led to the reassessment of these orebodies and their associated weathered ore crust deposits. Though these elements are currently considered mining contaminants, this and similar sites may be of future economic importance, particularly as demand for Se and Te continues to rise. [ABSTRACT FROM AUTHOR]

The Carboniferous Lower and Middle Coal Measures coals of the Northumberland Coalfield are anomalously rich in selenium (Se) content (up to 62 ppm) compared to the averages for the common UK and worldwide coals. As well as posing an environmental toxicity threat, Se is now regarded as an important resource for alloys, photovoltaic products and nanotechnologies, and high Se coals in North East England offer an opportunity to assess the Se means of occurrence, origins, transport mechanisms and enrichment in coals. At least two generations of pyrite host high Se in the sampled coal seams: microbial-formed disseminated pyrite (both cubic and framboidal in habit) and later cleat-filling pyrite, identified by petrographic observations, laser ablation methods and sulphur isotope compositions. There is a notable Se enrichment of up to 250 ppm in later formed cleat-filling pyrite. Trace element enrichment may have been sourced and influenced by seawater distribution during diagenesis, and localised dykes and deformation may have acted as an enrichment mechanism for sampled seams in the region. The high Se coals in Northumberland may provide a potential E tech element source and should be considered and carefully managed as coal mining and production are reduced in the area. The study also highlights the nature of Se enrichment in pyritic coals affected by cleat formation and multiple episodes of mineralisation, important as critical element demand continues to increase worldwide. [ABSTRACT FROM AUTHOR]

A method is proposed for the determination of selenium at low concentration in coal by collision/reaction cell technology inductively coupled plasma mass spectrometry (CRC-ICP-MS). Samples were decomposed by high pressure microwave-assisted wet digestion (MAWD) using 250 mg of coal, a mixture of 5 mL of 14.4 mol L −1 HNO 3 and 1 mL of 40% HF and 70 min of heating program (200 °C and 40 bar). Hydrogen gas used in the collision/reaction cell was investigated to minimize the argon-based interferences at m/z 77, 78 and 80. The rejection parameter (RPq) and the H 2 gas flow rate were set to 0.45 and 4.8 mL min −1 , respectively. The use of H 2 in the cell resulted in other polyatomic interferences, such as 76 Ge 1 H + , 79 Br 1 H + and 81 Br 1 H + , which impaired Se determination using 77 Se, 80 Se and 82 Se isotopes, thus Se determination was carried out by monitoring only 78 Se isotope. Selenium was determined in certified reference materials of coal (NIST 1635 and SARM 20) and an agreement better than 95% was observed between the results obtained by CRC-ICP-MS and the certified values. Under optimized conditions, the instrumental limit of detection was 0.01 μg L −1 and the method limit of detection was 0.01 μg g −1 , which was suitable for Se determination at very low concentration in coal. [ABSTRACT FROM AUTHOR]

We investigated the role of glutathione (GSH) and phytochelatins (PCs) on the detoxification of selenite using Arabidopsis thaliana . The wild-type (WT) of Arabidopsis thaliana and its mutants (glutathione deficient Cad 2–1 and phytochelatins deficient Cad 1–3) were separately exposed to varying concentrations of selenite and arsenate and jointly to both toxicants to determine their sensitivities. The results of the study revealed that, the mutants were about 20-fold more sensitive to arsenate than the WT, an indication that the GSH and PCs affect arsenate detoxification. On the contrary, the WT and both mutants showed a similar level of sensitivity to selenite, an indication that the GSH and PCs do not significantly affect selenite detoxification. However, the WT is about 8 times more sensitive to selenite than to arsenate, and the mutants were more resistant to selenite than arsenate by a factor of 2. This could not be explained by the accumulation of both elements in roots and shoots in exposure experiments. The co-exposure of the WT indicates a synergistic effect with regards to toxicity since selenite did not induce PCs but arsenic and selenium compete in their PC binding as revealed by speciation analysis of the root extracts using HPLC–ICP–MS/ESI–MS. In the absence of PCs an antagonistic effect has been detected which might suggest indirectly that the formation of Se glutathione complex prevent the formation of detrimental selenopeptides. This study, therefore, revealed that PC and GSH have only a subordinate role in the detoxification of selenite. [ABSTRACT FROM AUTHOR]