Speciation of arsenic in sulfidic waters

Formation constants for thioarsenite species have been determined in dilute solutions at 25°C, ΣH(2)S from 10(-7.5 )to 10(-3.0 )M, ΣAs from 10(-5.6 )to 10(-4.8 )M, and pH 7 and 10. The principal inorganic arsenic species in anoxic aquatic systems are arsenite, As(OH)(3)(0), and a mononuclear thioarsenite with an S/As ratio of 3:1. Thioarsenic species with S/As ratios of 1 : 1,2 : 1, and 4 : 1 are lesser components in sulfidic solutions that might be encountered in natural aquatic environments. Thioarsenites dominate arsenic speciation at sulfide concentrations > 10(-4.3 )M at neutral pH. Conversion from neutral As(OH)(3)(0 )to anionic thioarsenite species may regulate the transport and fate of arsenic in sulfate-reducing environments by governing sorption and mineral precipitation reactions

The History, Relevance, and Applications of the Periodic System in Geochemistry

Geochemistry is a discipline in the earth sciences concerned with understanding the chemistry of the Earth and what that chemistry tells us about the processes that control the formation and evolution of Earth materials and the planet itself. The periodic table and the periodic system, as developed by Mendeleev and others in the nineteenth century, are as important in geochemistry as in other areas of chemistry. In fact, systemisation of the myriad of observations that geochemists make is perhaps even more important in this branch of chemistry, given the huge variability in the nature of Earth materials – from the Fe-rich core, through the silicate-dominated mantle and crust, to the volatile-rich ocean and atmosphere. This systemisation started in the eighteenth century, when geochemistry did not yet exist as a separate pursuit in itself. Mineralogy, one of the disciplines that eventually became geochemistry, was central to the discovery of the elements, and nineteenth-century mineralogists played a key role in this endeavour. Early “geochemists” continued this systemisation effort into the twentieth century, particularly highlighted in the career of V.M. Goldschmidt. The focus of the modern discipline of geochemistry has moved well beyond classification, in order to invert the information held in the properties of elements across the periodic table and their distribution across Earth and planetary materials, to learn about the physicochemical processes that shaped the Earth and other planets, on all scales. We illustrate this approach with key examples, those rooted in the patterns inherent in the periodic law as well as those that exploit concepts that only became familiar after Mendeleev, such as stable and radiogenic isotopes

Picritic Glasses from Hawaii

ESTIMATES of the MgO content of primary Hawaiian tholeiitic melts range from 8wt% to as high as 25wt% (refs 1, 2). In general, these estimates are derived from analysis of the whole-rock composition of lavas, coupled with the compositions of the most magnesian olivine phenocrysts observed. But the best estimate of magma composition comes from volcanic glass, as it represents the liquid composition at the time of quenching; minimal changes occur during the quenching process. Here we report the discovery of tholeiitic basalt glasses, recovered offshore of Kilauea volcano, that contain up to 15.0 wt% MgO. To our knowledge, these are the most magnesian glasses, and have the highest eruption temperatures (∼ 1,316°C), yet found. The existence of these picritic (high-MgO) liquids provides constraints on the temperature structure of the upper mantle, magma transport and the material and thermal budgets of the Hawaiian volcanoes. Furthermore, picritic melts are affected little by magma-reservoir processes, and it is therefore relatively straightforward to extrapolate back to the composition of the primary melt and its volatile contents