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Tellurium is one of the elements recently identified as technologically critical and is becoming a new emergent contaminant. No reliable method exists for its determination in environmental samples such as natural waters. This gap is filled by the method described here; it allows the rapid detection of trace concentrations of Te(IV) and Te(VI) in surface waters by differential pulse cathodic stripping voltammetry. It is based on the proton reduction catalysed by the absorption of Te(IV) on the mercury electrode. Under our conditions (0.1 mol L(-1) HCl) a detection limit of about 5 ng L(-1) for a deposition time of 300 s is achieved. Organic matter does not represent a problem at low concentrations; higher concentrations are eliminated by adsorptive purification. Tellurium occurs primarily as Te(IV) and Te(VI) in natural waters. Thus, determining total Te requires the reduction of Te(VI) that it is not electroactive. A number of reduction procedures have been carefully evaluated and a method based on the addition of TiCl3 to the acidified samples has been proven to reduce Te(VI) at the trace level to Te(IV) reliably and quantitatively. Therefore, the procedure described allows the direct determination of total Te and its redox speciation. It is flexible, reliable and cost effective compared to any possible alternative method based on the common preconcentration-ICPMS approach. It is readily implementable as a routine method and can be deployed in the field with relative ease., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Although reduced sulphur substances, such as thiol compounds, contain extremely reactive functional groups in the cell, and influence metal speciation and solubility, very few techniques have been developed to quantify such substances in natural waters. In this paper we present a novel method that allows for the simultaneous identification and quantification of glutathione (GSH), thioacetamide-like compounds (TA), and refractory organic matter (ROM) by differential pulse cathodic stripping voltammetry (DP-CSV). Organic compounds are initially deposited on a mercury drop electrode at 0.000 V, pH 1.95, in the presence of ~200 nmol L(-1) Mo(VI), and then stripped, creating reduction peak currents at specific potentials. Using a 60-s deposition time, limits of detection (LODs) are 1 nmol L(-1), 81 nmol L(-1) and 14 μg C L(-1) for GSH, TA and ROM, respectively. By increasing the deposition time to 300 s, LOD is decreased to 0.2 nmol L(-1), 22 nmol L(-1) and 2 μg C L(-1), respectively. This method has a number of advantages in terms of its rapidity, low cost, and relative simplicity (due to the lack of derivatization and pre-concentration steps) and is also an effective method for simultaneously analysing GSH, TA and ROM in water. When not mixed in solution, GSH, L-cysteine and N-acetyl-L-cysteine, as well as TA-like compounds and thiourea, can be detected and identified by measuring their peak potential and standard addition, due to the acidic pH, which also allows for a longer preservation of the filtered sample. The new method described in this paper was tested along an entire river-seawater gradient of the Aulne Estuary (Brittany, France) to assess its capability in terms of determining these natural organic compounds in various surface waters., (© 2013 Elsevier B.V. All rights reserved.)

The processes leading to the attenuation of the antimony concentration in the water draining from the abandoned antimony mine in Goesdorf, Luxembourg, have been studied. Antimony has been mined in Goesdorf since Roman times from a stibnite-rich mesothermal vein system hosted in metasedimentary schist. The draining waters have pH values between 7 and 8 because the mineralization itself contains calcite and dolomite. This study combines the identification of minerals in the supergene zone with the application of bulk techniques (e.g., measurement of antimony in the waters of the adit and the creek draining the mine, sediment sequential extractions) over a period of five years. Antimony concentrations in the water that leaves the supergene zone are controlled by the dissolution of stibnite and the subsequent formation of Sb(III) oxides and sulphates. The relative proportions of the main secondary minerals can be qualitatively estimated as follows: 70% valentinite, 15% senarmontite and 12% sulphates (coquandite, klebelsbergite and peretaite). Further antimony attenuation along the adit and the creek that drain the mine waters is due partly to dilution, through mixing with waters that have not been in contact with the ore, and partly to sorption onto amorphous iron and manganese oxides present in the colluvial sediments.

Knowledge of antimony redox kinetics is crucial in understanding the impact and fate of antimony in the environment. The oxidation of Sb(III) with iodate was measured in 0.5 mol L(-1) NaCl solutions as a function of pH at environmentally significant concentrations of antimony and iodate. The oxidation of Sb(III) with iodate is pH dependent: no measurable oxidation is observed below pH 9. The undissociated Sb(OH)3 does not react with iodate and the formation of significant amounts of Sb(OH)4- is needed for the reaction to take place. It is thus unlikely that iodate oxidizes Sb(III) in seawater. Our results support that the observed presence of the thermodynamically unstable Sb(III) in oxic waters can be due to the kinetic stabilization of the trivalent state vis-à-vis some common abiotic oxidants at natural pH values. However, caution must be exercised because the presence of iodate in seawater favours fast oxidation of Sb(III) if water samples are acidified, as is the case in many analytical procedures.