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Selenium species, particularly the oxyanions selenite (SeO3 (2-)) and selenate (SeO4 (2-)), are significant pollutants in the environment that leach from rocks and are released by anthropogenic activities. Selenium is also an essential micronutrient for organisms across the tree of life, including microorganisms and human beings, particularly because of its presence in the 21st genetically encoded amino acid, selenocysteine. Environmental microorganisms are known to be capable of a range of transformations of selenium species, including reduction, methylation, oxidation, and demethylation. Assimilatory reduction of selenium species is necessary for the synthesis of selenoproteins. Dissimilatory reduction of selenate is known to support the anaerobic respiration of a number of microorganisms, and the dissimilatory reduction of soluble selenate and selenite to nanoparticulate elemental selenium greatly reduces the toxicity and bioavailability of selenium and has a major role in bioremediation and potentially in the production of selenium nanospheres for technological applications. Also, microbial methylation after reduction of Se oxyanions is another potentially effective detoxification process if limitations with low reaction rates and capture of the volatile methylated selenium species can be overcome. This review discusses microbial transformations of different forms of Se in an environmental context, with special emphasis on bioremediation of Se pollution., (Copyright © 2016, American Society for Microbiology. All Rights Reserved.)

This study provides background levels for five arsenic species in urine, based on urinary data obtained from 95 nonoccupationally exposed volunteers based in the UK. Using a novel, sensitive, robust and reliable speciation methodology, five species of arsenic (arsenobetaine [AB], arsenite [As(3+)], arsenate [As(5+)], monomethylarsonic acid [MMA(5+)] and dimethylarsinic acid [DMA(5+)]) were determined in urine samples collected from 95 adults. The analytical instrumentation used to analyze the urine samples was a hyphenated micro liquid chromatography (μLC) system coupled to an inductively coupled plasma mass spectrometry (ICP-MS). Separation was achieved using an anion exchange micro-sized column. The results presented give the 95th percentile of concentrations, both uncorrected for creatinine (µg/L) and creatinine corrected (µmol/mol) in urine for the 95 volunteers. Statistical analysis was performed on the dataset using a Bayesian model to determine and quantify effects of gender, smoking and diet. The statistical results show that the consumption of fish, shellfish and red wine has a significant elevating effect on AB, DMA and MMA urinary concentrations; however, no significant effect was observed for smoking. The regression model results indicate that creatinine correction was effective for arsenic species As(3+), MMA, DMA and AB. The background levels established here can be used as reference values to help aid interpretation of arsenic speciation results and better assess exposure.

Methane-oxidizing bacteria are ubiquitous in the environment and are globally important in oxidizing the potent greenhouse gas methane. It is also well recognized that they have wide potential for bioremediation of organic and chlorinated organic pollutants, thanks to the wide substrate ranges of the methane monooxygenase enzymes that they produce. Here we have demonstrated that the well characterized model methanotroph Methylococcus capsulatus (Bath) is able to bioremediate chromium(VI) pollution over a wide range of concentrations (1.4-1000 mg L(-1) of Cr(6+)), thus extending the bioremediation potential of this major group of microorganisms to include an important heavy-metal pollutant. The chromium(VI) reduction reaction was dependent on the availability of reducing equivalents from the growth substrate methane and was partially inhibited by the metabolic poison sodium azide. X-ray spectroscopy showed that the cell-associated chromium was predominantly in the +3 oxidation state and associated with cell- or medium-derived moieties that were most likely phosphate groups. The genome sequence of Mc. capsulatus (Bath) suggests at least five candidate genes for the chromium(VI) reductase activity in this organism.

Some of the main biochemical features of selenium have emerged only in the last five years, although it has been known to be an essential element for nearly 40 years. The investigations into selenoproteome gene expression and a better understanding of the selenocysteine synthetic pathway have undoubtedly provided the evidence that underpins the biochemical roles of the element. To date, 25 selenium-containing proteins have been identified in humans but the functions of a number of these have yet to be elucidated. The roles of the selenium-containing enyzmes (glutathione peroxidases, thioredoxin reductases and iodothyronine deiodinases) are well established, the first two being linked with antioxidant activity, and the latter involved with thyroid hormone metabolism. Recently, the interaction between sulphur, in the same periodic group and therefore chemically similar, and selenium has been investigated in a bid to understand the role of both elements in disease. There is renewed interest in the anticancer properties of selenium-containing compounds as evidence of their effectiveness in animal models has been demonstrated. Herein, selenium metabolism, gene expression, interaction with sulphur, and role in cancer are reviewed.

We report the synthesis and structural characterisation of a new family of stable phosphonioalkylthiosulfate zwitterions, R3P+ (CH2)nS2O3- (R = Ph or Bu, n = 3,4,6, 8 or 10) which behave as cationic masked thiolate ligands with applications in the functionalisation of gold nanoparticles, having potential as new diagnostic biorecognition systems. The ligands were prepared by treatment of omega-bromoalkylphosphonium salts with sodium thiosulfate. The crystal and molecular structures of the zwitterions (R = Ph, n = 3) and (R = Bu, n = 3) were determined. A series of phosphonioalkanethiolate-capped gold nanoparticles dispersed in water was prepared by borohydride reduction of potassium tetrachloroaurate in the presence of the zwitterions in a dichloromethane-water system. UV-visible spectroscopy and scanning transmission electron-microscopy indicated that capped nanoparticles of ca. 5 nm diameter were present.

In biosciences and biotechnology, the expanding application of physicochemical approaches using modern instrumental techniques is an efficient strategy to obtain valuable and often unique information at the molecular level. In this work, we applied a combination of vibrational (Fourier transform infrared (FTIR), FT-Raman) spectroscopic techniques, useful in overall structural and compositional analysis of bacterial cells of the rhizobacterium Azospirillum brasilense, with 57Co emission Mössbauer spectroscopy (EMS) used for sensitive monitoring of metal binding and further transformations in live bacterial cells. The information obtained, together with ICP-MS analyses for metals taken up by the bacteria, is useful in analysing the impact of the environmental conditions (heavy metal stress) on the bacterial metabolism and some differences in the heavy metal stress-induced behaviour of non-endophytic (Sp7) and facultatively endophytic (Sp245) strains. The results show that, while both strains Sp7 and Sp245 take up noticeable and comparable amounts of heavy metals from the medium (0.12 and 0.13 mg Co, 0.48 and 0.44 mg Cu or 4.2 and 2.1 mg Zn per gram of dry biomass, respectively, at a metal concentration of 0.2 mM in the medium), their metabolic responses differ essentially. Whereas for strain Sp7 the FTIR measurements showed significant accumulation of polyhydroxyalkanoates as storage materials involved in stress endurance, strain Sp245 did not show any major changes in cellular composition. Nevertheless, EMS measurements showed rapid binding of cobalt(II) by live bacterial cells (chemically similar to metal binding by dead bacteria) and its further transformation in the live cells within an hour.

The plant-associated nitrogen-fixing rhizobacterium Azospirillum brasilense attracts world-wide attention owing to its plant growth-promoting activities. Among hundreds of its strains known up to date, wild-type strain Sp245 has been proved to be capable of colonising both the plant-root interior and exterior (i.e. a facultative endophyte), whereas others are non-endophytes colonising the root surface only. Thus, the different ecological niches occupied by these strains in the rhizosphere suggest that their responses to environmental conditions might differ as well. In this study, responses of A. brasilense strains Sp245 and Sp7 to several heavy metals (Co2+, Cu2+, Zn2+), present in the medium at tolerable concentrations (up to 0.2 mmol/l) and taken up by the bacteria, were compared. Fourier transform infrared (FTIR) spectroscopy was used for controlling the compositional features of whole cells. The results obtained show that in strain Sp7 (non-endophyte) the heavy metals induced an enhanced accumulation of polyester compounds (poly-3-hydroxybutyrate; PHB). In contrast, the response of the endophytic strain Sp245 to heavy metal uptake was found to be much less pronounced. These dissimilarities in their behaviour may be caused by different adaptation abilities of these strains to stress conditions owing to their different ecological status. It was also found that adding 0.2 mmol/l Cu2+ or Cd2+ in the culture medium resulted in noticeably reducing the levels of indole-3-acetic acid (IAA, auxin) produced by both the strains of the bacterium. This can directly affect the efficiency of associative plant-bacterial symbioses involving A. brasilense in heavy-metal-contaminated soil.

Modern analytical techniques have been applied to investigate the nature of lead pipe corrosion products formed in pH adjusted, orthophosphate-treated, low alkalinity water, under supply conditions. Depth profiling and surface analysis have been carried out on pipe samples obtained from the water distribution system in Glasgow, Scotland, UK. X-ray diffraction spectrometry identified basic lead carbonate, lead oxide and lead phosphate as the principal components. Scanning electron microscopy/energy-dispersive x-ray spectrometry revealed the crystalline structure within the corrosion product and also showed spatial correlations existed between calcium, iron, lead, oxygen and phosphorus. Elemental profiling, conducted by means of secondary ion mass spectrometry (SIMS) and secondary neutrals mass spectrometry (SNMS) indicated that the corrosion product was not uniform with depth. However, no clear stratification was apparent. Indeed, counts obtained for carbonate, phosphate and oxide were well correlated within the depth range probed by SIMS. SNMS showed relationships existed between carbon, calcium, iron, and phosphorus within the bulk of the scale, as well as at the surface. SIMS imaging confirmed the relationship between calcium and lead and suggested there might also be an association between chloride and phosphorus.

Gold biosorption by dealginated seaweed waste has been studied to elucidate the mechanisms of metal uptake from solution. Dealginated seaweed was able to retain up to 1 mmol g(-1) of Au from solution at pH 3. FT-IR showed the presence of carboxylate groups on the surface of the biosorbent; however, the changes observed for the Au-bound samples suggested very little sorption to the carboxyl moieties. Colloidal Au formed on the surface of dealginated seaweed by reduction of Au(III) to Au(0) was observed using ESEM and four different types of particles were clearly identified. The Au distribution matched closely that obtained for S atoms indicating a possible link between these elements. EXAFS measurements showed that colloidal Au is present on the surface of the biosorbent. Evidence of gold reduction from Au(III) to Au(I) and Au(0) was also confirmed by the measured bond distances characteristic of the metal. The coordination number obtained by EXAFS indicated that approximately 75% of the Au on the sample was present in the colloidal form and the remaining Au was bound to S as nearest neighbor. The proposed mechanisms for Au removal from solution are reduction of Au species by components on the surface of the biosorbent to form colloidal metal followed by retention of the ionic Au(I) species at the sulfur containing sites. The results show that dealginated seaweed can be used for the cleanup of gold-containing effluents.

The ability of dealginated seaweed waste, a waste material derived from the commercial processing of seaweed for alginate production, to remove cadmium from solution was determined. Cadmium sorption was found to be rapid (91% removal within 5 min), achieving a residual concentration of 0.8 mg L-1 after 1-h contact time from an initial solution concentration of 10 mg L-1. The binding of cadmium by dealginate was found to be pH dependent, optimal sorption occurring at around pH 6-8. The mechanism of cadmium ion binding by dealginate was investigated by a number of techniques. Potentiometric titration of the dealginate revealed two distinct pKa values, the first having a value similar to carboxyl groups and the second comparable with that of saturated thiols and amines. Esterification of the dealginate resulted in the subsequent reduction in cadmium sorption (95% to 17%), indicating that carboxyl groups are largely responsible for sorption. Evidence from FT-IR spectra confirmed the presence of carboxyl groups in untreated dealginate, while the number of carboxyl groups was markedly reduced in the esterified sample. Furthermore, the FT-IR spectrum for dealginate was found to be similar to that previously reported for mannuronic acid-rich calcium alginate. Determination of a molar ratio in the displacement of calcium by cadmium on dealginate further supported the presence of an ion-exchange relationship. The ion-exchange constant was calculated to be 0.329 x 10(-6). The speciation of cadmium in solution both before and after sorption was determined by an ion-selective electrode (ISE) technique. The findings of this study suggest that the sorption of cadmium by dealginate is mainly due to an ion-exchange mechanism.

The biological roles of selenium and its mode of action have only recently begun to be revealed. To date, the major functions of selenium can be attributed to its antioxidative properties and its role in the regulation of thyroid hormone metabolism, cell growth and eicosanoid biosynthesis. The unusual feature of selenoprotein synthesis is that selenocysteine insertion is specified by the stop UGA codon. A number of selenocysteine-specific gene products and a stem-loop structure in the 3' untranslated region are required for selenocysteine biosynthesis and the decoding of UGA codons in the open reading frame of the mRNA. The major biological functions of selenium are achieved through its redox activity when present as selenocysteine at the active sites of selenoproteins and these proteins are selenium-dependent since replacement with the sulphur analogue cysteine causes loss of enzyme activity. Both organic and inorganic forms of selenium may be utilised by the body, with the selenoamino acids showing greatest bioavailability. Knowledge of the biochemistry of the element coupled with appropriate techniques for the study of the distribution of selenium species in health and disease could help to identify sensitive markers of selenium status.

An optimized method for the simultaneous determination of Cr(III) and Cr(VI) in aqueous solutions using ion chromatography with chemiluminescence detection is described. Excellent resolution of the two chromium species was obtained using a single mixed-bed ion-exchange column with continuous elution. After postcolumn reduction of Cr(VI) to Cr(III), the light emitted during the Cr(III)-catalyzed oxidation of luminol with hydrogen peroxide was measured. Parameters affecting the postcolumn reactions such as reductant concentration, reductant mixing, point of luminol introduction, and luminol flow rate were optimized. The calibration curves in the range tested (0.01-50 μg L(-)(1)) were linear, and detection limits of 0.002 μg L(-)(1) for both Cr(III) and Cr(VI) were obtained. The results of the analyses of the water reference materials LGC CRM6010 and NIST SRM1643d with certified chromium values of 49 ± 4 and 18.53 ± 0.20 μg L(-)(1) and found to contain only Cr(III) were 49.2 ± 1.8 and 19.0 ± 1.5 μg L(-)(1), respectively. Values of 10.6 ± 0.5 and 10.1 ± 0.5 μg L(-)(1) were obtained when a simulated water sample containing 10 μg L(-)(1) Cr(III) and Cr(VI) was analyzed.

A method is described for the direct determination of selenium in serum or plasma by electrothermal atomic absorption spectrometry with deuterium-arc background correction. Samples are diluted (1 + 2) with a modifier containing palladium nitrate and Triton X-100. Samples are atomised from a L'vov platform in a pyrolytically-coated electrographite tube and peak area signals are measured. Direct determination is possible by using selenium standards matched to the physiological concentrations of sodium chloride, calcium and phosphate. The detection limit is 6 micrograms/L in the original sample. Precision at a selenium concentration of 97 micrograms/L was 2.2% RSD within batch and 3.0% RSD between batch. Accuracy is shown by (i) analysis of a Seronorm reference serum (value obtained 97 +/- 3 micrograms/L; recommended value 96 micrograms/L); (ii) recovery of added selenium (93.3 +/- 6.7% and 98.2 +/- 3.3% at additions of 30 and 60 micrograms/L, respectively) and (iii) comparison of results with mean of all laboratories in an external quality assessment scheme.

The identification and characterisation of the various species of a trace element in a system could provide important clues as to its biochemical role(s). In order that the results of experiments reflect the true situation in the system under study at the time the sample was taken, chemical and physical changes that can affect the distribution profile of a given element have to be understood and controlled. A number of factors that can influence the nature and form of chemical species before, during and after sampling of biological systems have been identified and discussed. Precautions that could help in limiting such changes are recommended.