Methodologies for the environmental analysis of total antimony and aqueous chemical speciation are critically reviewed, including preparation techniques for aqueous and solid matrices and the determination of solid state partitioning and recommendations are given for future research directions. Concentrations of total antimony commonly present in aqueous and solid environmental samples are readily determined using present day analytical techniques. This has resulted primarily from technological advances in microwave digestion for solid matrices and the development of plasma based analyte detection systems. ICP-AES and ICP-MS techniques are both utilised for the environmental analysis of total antimony concentrations. However, ICP-MS is increasingly favoured as a result of reduced spectral interferences and the potential for analyte detection in the pg mL(-1) range. Determination of aqueous antimony speciation presents a number of complex analytical challenges and highly selective separation and identification techniques are required prior to detection. The majority of published techniques including common applications of hydride generation are insufficiently selective for the determination of intrinsic chemical speciation and often only oxidation state data are obtained. The recent in-line applications of HPLC-ICP-MS offer the potential for highly selective separations of aqueous antimony species and determination of detailed chemical speciation data. However, considerable development work is required to optimise chromatographic separations and identify uncharacterised species resident in environmental systems. Analytical techniques to aid the determination of antimony's associations with solid environmental matrices include the application of chemical extraction procedures and leaching experiments. To date, this area of analytical research has received little attention and further studies are required to elucidate this aspect of antimony's environmental chemistry.
Concentrations of trace and major elements are examined in several soil profiles from national parks and wildlife reserves in Kenya. Broad variations in soil trace element concentrations between locations are largely attributable to differences in parent material and variations in soil pH are related to sodium and calcium concentrations. However, element concentrations and distributions are also influenced by soil forming processes. The process of sodication in alkaline solonetz soils in Lake Nakuru National Park appears to have lowered the concentrations of copper, cobalt and nickel in the surface horizon. At Amboseli National Park, a marked accumulation of molybdenum, sodium, potassium, calcium and magnesium in the surface horizon of an alkaline solonchak is probably due to salinization processes. Apparent mobilization of copper, cobalt and nickel down the profile of a humic nitisol in the Aberdares Salient is associated with eluviation and leaching processes. In two andosols and an ando-humic nitisol, copper, cobalt and nickel tend to accumulate in the surface horizon in association with organic matter. In vertisols from Amboseli National Park and Lewa Downs Wildlife Reserve, the relatively constant trace element concentrations in the A and B horizons are linked to the self-swallowing processes that characterize this soil type. The elevated pH in the solonetz and solonchak soils at Lake Nakuru and Amboseli National Parks results in enhanced uptake of molybdenum in the grass species Sporobulus spicatus . At Lake Nakuru National Park, high molybdenum concentrations in this and other plant species are associated with low copper status of impala. The implications of soil geochemistry for the trace element nutrition of wild animals in small conservation areas are discussed.
The vertical migration of metals through soils and rocks was investigated at five historical lead smelting sites ranging in age between 220 and 1900 years. Core samples were taken through metal-contaminated soils and the underlying strata. Concentration profiles of lead and zinc are presented from which values for the distances and rates of migration have been derived. Slag-rich soil horizons contain highly elevated metal concentrations and some contamination of underlying strata has occurred at all sites. However, the amounts of lead and zinc that have migrated from soils and been retained at greater depths are comparatively low. This low metal mobility in contaminated soils is partly attributed to the elevation of soil pH by the presence of calcium and carbonate originating from slag wastes and perhaps gangue minerals. Distances and rates of vertical migration were higher at those sites with soils underlain by sandstone than at those with soils underlain by clay. For sites with the same parent material, metal mobility appears to be increased at lower soil pH. The mean migration rates for lead and zinc reach maxima of 0.75 and 0.46 cm yr(-1) respectively in sandstone at Bole A where the elements have moved mean distances of 4.3 and 2.6 m respectively. There is some evidence that metal transport in the sandstone underlying Bole A and Cupola B occurs preferentially along rock fractures. The migration of lead and zinc is attenuated by subsurface clays leading to relatively low mean migration rates which range from 0.03 to 0.31 cm yr(-1) with many values typical of migration solely by diffusion. However, enhanced metal migration in clays at Cupola A suggest a preferential transport mechanism possibly in cracks or biopores.
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