Arsenic oxidation state determinations, method

Since crushed basalt has been recommended as a major backfill component (1), experiments were completed to evaluate the rate of dissolved oxygen consumption and the redox conditions that develop in basalt-water systems under conditions similar to those expected in the near-field environment of a waste package. Two approaches to this problem were used in this study (l)the As(III)/As(V) redox couple as an indirect method of monitoring Eh and (2) the measurement of dissolved oxygen levels in solutions from hydrothermal experiments as a function of time. The first approach involves oxidation state determinations on trace levels of arsenic in solution (4-5) and provides an estimate of redox conditions over restricted intervals of time, depending on reaction rates and sensitivities of the analyses. The arsenic oxidation state approach also provides data at conditions that are more reducing than in solutions with detectable levels of dissolved oxygen. 

Molybdenum blue method. When arsenic, as arsenate, is treated with ammonium molybdate solution and the resulting heteropolymolybdoarsenate (arseno-molybdate) is reduced with hydrazinium sulphate or with tin(II) chloride, a blue soluble complex molybdenum blue is formed. The constitution is uncertain, but it is evident that the molybdenum is present in a lower oxidation state. The stable blue colour has a maximum absorption at about 840 nm and shows no appreciable change in 24 hours. Various techniques for carrying out the determination are available, but only one can be given here. Phosphate reacts in the same manner as arsenate (and with about the same sensitivity) and must be absent. 

Johnson and Pilson [229] have described a spectrophotometric molybdenum blue method for the determination of phosphate, arsenate, and arsenite in estuary water and sea water. A reducing reagent is used to lower the oxidation state of any arsenic present to +3, which eliminates any absorbance caused by molybdoarsenate, since arsenite will not form the molybdenum complex. This results in an absorbance value for phosphate only. 

The optimal reaction conditions for the generation of the hydrides can be quite different for the various elements. The type of acid and its concentration in the sample solution often have a marked effect on sensitivity. Additional complications arise because many of the hydrideforming elements exist in two oxidation states which are not equally amenable to borohydride reduction. For example, potassium iodide is often used to pre-reduce AsV and SbV to the 3+ oxidation state for maximum sensitivity, but this can also cause reduction of Se IV to elemental selenium from which no hydride is formed. For this and other reasons Thompson et al. [132] found it necessary to develop a separate procedure for the determination of selenium in soils and sediments although arsenic, antimony and bismuth could be determined simultaneously [133]. A method for simultaneous determination of As III, Sb III and Se IV has been reported in which the problem of reduction of Se IV to Se O by potassium iodide was circumvented by adding the potassium iodide after the addition of sodium borohydride [134], Goulden et al. [123] have reported the simultaneous determination of arsenic, antimony, selenium, tin and bismuth, but it appears that in this case the generation of arsine and stibene occurs from the 5+ oxidation state. 

These workers showed that dissolved arsenic and antimony in natural waters can exist in die trivalent and pentavalent oxidation states, and the biochemical and geochemical reactivities of these elements are dependent upon their chemical forms. They developed a method for the simultaneous determination of arsenic (III)+antimony (III+V)+ antimony (III+V) that uses selective hydride generation, liquid nitrogen cooled trapping, and gas chromatography-photoionisation detection. The detection limit for arsenic is lOpmol L 1 while that for antimony is 3.3pmol L 1 precision (as relative standard deviation) for both elements is better than 3%. 

Solid-phase speciation has been measured both by wet chemical extraction and, for arsenic, by instrumental methods principally X-ray absorption near edge structure spectroscopy (XANES) (Brown et al., 1999). La Force et al. (2000) used XANES and selective extractions to determine the likely speciation of arsenic in a wetland affected by mine wastes. They identified seasonal effects with As(El) and As(V) thought to be associated with carbonates in the summer, iron oxides in the autumn and winter, and silicates in the spring. Extended X-ray absorption fine stmcture spectroscopy (EXAES) has been used to determine the oxidation state of arsenic in arsenic-rich Californian mine wastes (Eoster et al., 1998b). Typical concentrations of arsenic in sods and sediments (arsenic <20 mg kg ) are often too low for EXAFS measurements, but as more powerful photon beams become available, the use of such techniques should increase. 

Pre-treatment to destroy organic matter. Organic selenium species are more widespread in the environment than comparable arsenic species. The determination of total selenium by most analytical methods requires samples to be pre-treated to remove organic matter, release selenium, and change its oxidation state. 

Anodic stripping voltammetry was in use already in 1972 to determine Bi in plasma [120]. Bismuth is one of the elements most easily determined with this method. It can be deposited on electrodes at potentials at which most other elements ate in solution. Glassy carbon electrodes coated with films of mercury [100,121-124], but also of gold [101,125], are used. As reference served calomel or silver/silver chloride electrodes [121]. Platinum foils or wires were used as counterelectrodes. At -0.7 V carbon electrodes are precoated with mercury from acid Hg(II) or gold from acid Au(III) solutions. To deposit Bi on the electrode -0.2 to -0.3 V is a sufficient potential for preelectrolysis, but mostly higher voltages are chosen to determine other metals as well. Bi is stripped fiom the electrode at potentials of about -0.10 to -0.16 V. Only some elements interfere with Bi, such as arsenic, mercury, copper, and antimony. Copper interferes at high concentrations and is separated by extraction [101]. Arsenic or antimony in urine are oxidized to their pentavalent states [125]. 

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