Geochemical concentration

Figs. 3-6. Gold and trace element geochemical concentrations with depth In DDH-WB-08-04. Values are not corrected for mass loss or gains. Higher values of Cu, Zn and As exist In the mudstones underlying the rhyolites In hole WB-08-04. 

Sulfate concentration in streams and changes over time are discussed later in this article as one of the principal indices of human influences on stream water composition. Also, it will be shown that differences and similarities ia sulfate yields help in attaining a reasonable perspective on the importance of various hydrologic and geochemical characteristics of individual drainage systems. 

In reality, many other chemical and photochemical processes take place leading to a sort of steady-state concentration of O3 which is a sensitive function of height. To be accurate, it is necessary to include the reactions of nitrogen oxides, chlorine- and hydrogen-containing free radicals (molecules containing an unpaired electron). However, occurrence of a layer due to the altitude dependence of the photochemical processes is of fundamental geochemical importance and can be demonstrated simply by the approach of Chapman (1930). 

Fig. 9-8 Histogram of dissolved solids of samples from the Orinoco and Amazon River basins and corresponding denudation rates for morpho-tectonic regions in the humid tropics of South America (Stal-lard, 1985). The approximate denudation scale is calculated as the product of dissolved solids concentrations, mean armual runoff (1 m/yr), and a correction factor to account for large ratios of suspended load in rivers that drain mountain belts and for the greater than average annual precipitation in the lowlands close to the equator. The correction factor was treated as a linear function of dissolved solids and ranged from 2 for the most dilute rivers (dissolved solids less than lOmg/L) to 4 for the most concentrated rivers (dissolved solids more than 1000 mg/L). Bedrock density is assumed to be 2.65 g/cm. (Reproduced with permission from R. F. Stallard (1988). Weathering and erosion in the humid tropics. In A. Lerman and M. Meybeck, Physical and Chemical Weathering in Geochemical Cycles," pp. 225-246, Kluwer Academic Publishers, Dordrecht, The Netherlands.)...

While these calculations provide information about the ultimate equilibrium conditions, redox reactions are often slow on human time scales, and sometimes even on geological time scales. Furthermore, the reactions in natural systems are complex and may be catalyzed or inhibited by the solids or trace constituents present. There is a dearth of information on the kinetics of redox reactions in such systems, but it is clear that many chemical species commonly found in environmental samples would not be present if equilibrium were attained. Furthermore, the conditions at equilibrium depend on the concentration of other species in the system, many of which are difficult or impossible to determine analytically. Morgan and Stone (1985) reviewed the kinetics of many environmentally important reactions and pointed out that determination of whether an equilibrium model is appropriate in a given situation depends on the relative time constants of the chemical reactions of interest and the physical processes governing the movement of material through the system. This point is discussed in some detail in Section 15.3.8. In the absence of detailed information with which to evaluate these time constants, chemical analysis for metals in each of their oxidation states, rather than equilibrium calculations, must be conducted to evaluate the current state of a system and the biological or geochemical importance of the metals it contains. 

One of the most complex separation schemes utilizes flash liquid chromatography and PLC to obtain petropophyrins both from geochemical samples or those synthesized and used subsequently as standards [110]. Ocampo and Repeta [111] described the scheme of petroporphyrins isolation in which at the first step the sediment extract is fractionated into ten fractions on silica gel using dichlo-romethane (fractions 1 to 4), a mixture of dichloromethane-acetone with increasing acetone concentrations (for fractions 5 to 9), and, at last, dichlo-romethane methanol (4 1) (fraction 10). Next, the fifth fraction was separated on silica PLC plates using dichloromethane-acetone (97.5 2.5 v v v) as a developer. Two purple bands (with Rj 0.53 and 0.50) were recovered from silica and purified further on a silica gel column with dichloromethane-acetone (97.5 2.5, v v v) as an eluent. The emiched fraction was then separated by PLC with the same solvent mixture, and the purple bands containing two bacteriopheophytin allomers were recovered with acetone. 

As already noted in section 1.4.3, geochemical features of ore fluids responsible for base-metal and gold-silver types of deposits are distinct. They are summarized in Table 1.22. The differences in metals concentrated to the deposits and geochemical fectures of ore fluids responsible for both types of deposits are interpreted in terms of HSAB (hard, soft, acids and bases) principle by Pearson (1963, 1968) below. 

These correlations mean that the HSAB principle could be a useful approach to evaluate the geochemical behavior of metals and ligands in ore fluids responsible for the formation of the epithermal vein-type deposits. Among the ligands in the ore fluids, HS" and H2S are the most likely to form complexes with the metals concentrated in the gold-silver deposits (e.g., Au, Ag, Cu, Hg, Tl, Cd), whereas Cl prefers to form complexes with the metals concentrated in the base-metal deposits (e.g., Pb, Zn, Mn, Fe, Cu, and Sn) (Crerar et al., 1985). 

Seki, Y. (1990) Gas concentration in aquifer fluid prior to boiling in the Oku-aizu geothermal system, Fukushima, Japan. Geochem. J., 24, 105-121. 

The As (arsenic) concentration of seawater is controlled by input of rivers, sedimentation on the seafloor, weathering of the seafloor, exchange between atmosphere and seawater, volcanic gas input, and hydrothermal input. Previous studies on the geochemical cycle of As have not taken into account the hydrothermal flux of As. Therefore, hydrothermal flux of As from back-arc, island arc and midoceanic ridges to ocean is considered below. 

Today it has become clear that the effect of trace elements in living systems, in food, and in the environment depends on the chemical form in which the element enters the system and the final form in which it is present. The form, or species, clearly governs its biochemical and geochemical behaviour. lUPAC (the International Union for Pure and Applied Chemistry) has recently set guidelines for terms related to chemical speciation of trace elements (Templeton et al. 2000). Speciation, or the analytical activity of measuring the chemical species, is a relatively new scientific field. The procedures usually consist of two consecutive steps (i) the separation of the species, and (2) their measurement An evident handicap in speciation analysis is that the concentration of the individual species is far lower than the total elemental concentration so that an enrichment step is indispensable in many cases. Such a proliferation of steps in analytical procedure not only increases the danger of losses due to incomplete recovery, chemical instability of the species and adsorption to laboratory ware, but may also enhance the risk of contamination from reagents and equipment. 

Gladney ES, Perrin DR, Owens JW, and Knab D (1979) Elemental concentrations in the United States Geological Survey s geochemical exploration reference samples - a review. Anal Chem 51 1557-1569. 

Modern geochemical studies use data for a much larger suite of elements, determined at much lower concentrations, to model the tectonic movements of continental plates, and to understand the sources of magma generated in that process (e.g. Lightfoot 1993 Sutcliffe 1993). The key elemental suites include the incompatible ... 

Boron concentrations and isotopes are also useful geochemical tracers of contamination in MORB. Boron concentrations are low (<2 ppm) in unaltered ocean floor basalt but high in altered basalts (>8 ppm B) (Spivack and Edmond 1987 Ryan and Langmuir 1993). Goldstein et al. (1989) measured B concentrations in their samples and found them to be less than 1.6 ppm, inconsistent with contamination. More recently, B isotopes have been used to assess contamination since large differences in 5 B are known to exist between seawater, sediments, and unaltered MORB. Sims et al. (2002) reported that 6 B for their 9°N EPR samples were inconsistent with incorporation of any seawater or seawater-derived material. 

Anderson RF (1987) Redox behavior of uranium in an anoxic marine basin. Uranium 3 145-164 Anderson RF, Fleisher MQ, LeHuray AP (1989) Concentration, oxidation state, and particulate flux of uranium in the Black Sea. Geochim Cosmochim Acta 53 2215-2224 Back W, Hanshaw BB, Pyler TE, Plummer LN, Weiede AE (1979) Geochemical significance of groundwater discharge in Caleta Xel Ha, Quintana Roo, Mexico. Water Res 15 1521-1535 Barnes CE, Cochran JK (1990) Uranium removal in oceanic sediments and the oceanic U balance. Earth. Planet. Sci. Lett 97 94-101... 

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