Seawater evolution

The advances in instrumentation and particularly the arrival of the multicollector inductively coupled plasma mass spectrometers (MC-ICPMS) opened a window for a number of new tracers that were difficult to tackle with the old instrumentation. A pattern for seawater evolution is thus emerging for isotopes of boron and calcium. 

Silver reduces the oxygen evolution potential at the anode, which reduces the rate of corrosion and decreases lead contamination of the cathode. Lead—antimony—silver alloy anodes are used for the production of thin copper foil for use in electronics. Lead—silver (2 wt %), lead—silver (1 wt %)—tin (1 wt %), and lead—antimony (6 wt %)—silver (1—2 wt %) alloys ate used as anodes in cathodic protection of steel pipes and stmctures in fresh, brackish, or seawater. The lead dioxide layer is not only conductive, but also resists decomposition in chloride environments. Silver-free alloys rapidly become passivated and scale badly in seawater. Silver is also added to the positive grids of lead—acid batteries in small amounts (0.005—0.05 wt %) to reduce the rate of corrosion. 

In oxygen-free seawater, the J(U) curves, together with the Tafel straight lines for hydrogen evolution, correspond to Eq. (2-19) (see Fig. 2-2lb). A limiting current density occurs with COj flushing for which the reaction ... 

Zsolnay and Kiel [26] have used flow calorimetry to determine total hydrocarbons in seawater. In this method the seawater (1 litre) was extracted with trichlorotrifluoroethane (10 ml) and the extract was concentrated, first in a vacuum desiccator, then with a stream of nitrogen to 10 pi A 50 pi portion of this solution was injected into a stainless steel column (5 cm x 1.8 mm) packed with silica gel (0.063-0.2 mm) deactivated with 10% of water. Elution was effected, under pressure of helium, with trichlorotrifluoroethane at 5.2 ml per hour and the eluate passed through the calorimeter. In this the solution flowed over a reference thermistor and thence over a detector thermistor. The latter was embedded in porous glass beads on which the solutes were adsorbed with evolution of heat. The difference in temperature between the two thermistors was recorded. The area of the desorption peak was proportional to the amount of solute present. 

The results are shown in Figures 6-5 and 6-6. Figure 6-5 depicts how the system evolves from its initial conditions to a repeatable oscillation about annual average conditions. This evolution is clearest for the calcium ion concentration, which rises toward twice the seawater value. Calcium does not quite reach twice the seawater value because it is removed from the system by the precipitation of calcium carbonate. The rise in calcium is a consequence of the evaporative concentration of the water s dissolved constituents. 

The radiocarbon ratio also evolves very rapidly from its initial value of -50 to an average value of about -8 per mil. This evolution is not a consequence of evaporative concentration but, instead, of an approach to equilibrium with atmospheric carbon dioxide. Average surface seawater contains significantly less radiocarbon than does the atmosphere because its isotopic composition is affected by exchange with the deep ocean as... 

Fig. 6-5. The evolution of the lagoon s waters in response to oscillations in biological productivity. The results show the adjustment of the system from an initial composition equal to that of seawater. This figure shows isotope ratios, calcium concentration, the saturation index, and productivity.

Figure 8-10 shows the first 200 years of evolution of the concentrations at the same depths as plotted in Figure 8-9. The concentrations of both total carbon and calcium at a 500-centimeter depth decrease at first and then increase. This decrease occurs because I used starting values equal to seawater values. The waters were initially supersaturated and started out by precipitating calcium carbonate. This initial precipitation was overwhelmed at the shallower depths by the rapid addition of carbon as a result of respiration.

The evolution of the isotope ratio at various depths is shown in Figure 8-11 for the first 200 years of the calculation. The shallowest depths depart little from the seawater value because they are diffusively coupled to open water. Respiration at somewhat greater depths drives the isotope ratio... 

The evolution of the profiles of the isotope ratio is shown in Figure 8-12, which plots the profiles at various times in the calculation. Early in the calculation, isotope ratios at shallow depths have been driven more negative by the release of isotopically light respiration carbon, but little change has occurred at greater depths. As the evolution proceeds, the ratios at shallow depths become more positive as the result of the dissolution and diffusion of heavier carbon from both above and below. In the final steady state, after some 15,000 years, the isotope ratio is nearly constant at about -0.6 per mil at depths below 100 centimeters, rising rapidly to the seawater value, +2 per mil in the top 100 centimeters. The final values reflect a balance between the release of isotopically light carbon by respiration and the release of isotopically heavy carbon by dissolution, with the additional influence of the diffusion of isotopically heavy seawater carbon. 

Ca and SO4 contents in surface waters from the Ebro Basin also show large variations (both between 0.5 and 7 mmol L-1) and plot below the seawater dilution line in an SO4 versus Ca diagram (Fig. 8). There is a clear evolution of the Ca and S04 contents along the Ebro from up to downstream, with decreasing Ca/S04 molar ratios mean values from 2.19 0.70 in Mendavia to 1.28 0.49 in Sastago and finally a slight increase (1.40 0.33) in Tortosa. In the middle part of the basin, for... 

To model the chemical effects of evaporation, we construct a reaction path in which H2O is removed from a solution, thereby progressively concentrating the solutes. We also must account in the model for the exchange of gases such as CO2 and O2 between fluid and atmosphere. In this chapter we construct simulations of this sort, modeling the chemical evolution of water from saline alkaline lakes and the reactions that occur as seawater evaporates to desiccation. 

Since the experimental studies of van t Hoff at the turn of the century, geochemists have sought a quantitative basis for describing the chemical evolution of seawater and other complex natural waters, including the minerals that precipitate from them, as they evaporate. The interest has stemmed in large part from a desire to understand the origins of ancient deposits of evaporite minerals, a goal that remains mostly unfulfilled (Hardie, 1991). 

Fig. 24.8. Evolution of fluid chemistry during the simulated evaporation of seawater as an equilibrium system at 25 °C, calculated using the Harvie-Mpller-Weare activity model. Upper figures show variation in salinity, water activity (aw), and ionic strength (/) over the reaction path in Figure 24.7 bottom figure shows how the fluid s bulk composition varies.

Grustal reservoirs are also variable in Gl-isotope compositions (Figs. 1-6) due to fractionation of the Gl-isotope compositions inherited from their mantle source through fluid-mineral reactions, incorporation of G1 derived from the oceans and fractionation within fluid reservoirs by diffusion (see below). For example, the oceanic crust is enriched in Gl (and pore fluids depleted in Gl) through reaction of seawater with basaltic crust derived from the depleted mantle (Fig. 1 Magenheim et al. 1995). Undoubtedly, future investigations of Gl-isotopes in whole rocks and mineral separates will address the Gl-isotope compositions of these reservoirs and their evolution. 

Deniel D, Vidal P, Fernandez A, LeFort P, Peucat JJ (1987) Isotopic study of the Manaslu granite (Himalaya, Nepal) inference on the age and source of Himalayan leucogranites. Contrib Mineral Petrol 96 78-92 DePaolo DJ (1986) Detailed record of the Neogene Sr isotopic evolution of seawater from DSDP Site 590B. Geology 14 103-106... 

Horita J, Zimmermann H, Holland HD (2002) Chemical evolution of seawater during the Phanerozoic implications from the record of marine evaporates. Geochim Cosmochim Acta 66 3733—3756 Inghram MG, Brown H, Patterson C, Hess DC (1950) The branching ratio of K-40 radioactive decay. Phys Rev 80 916-917... 

Most of the water on Earth s surfece is in the ocean relatively little is present in the atmosphere or on land. Because of its chemical and physical properties, this water has had a great influence on the continuing biogeochemical evolution of our planet. Most notably, water is an excellent solvent. As such, the oceans contain at least a little bit of almost every substance present on this planet. Reaction probability is enhanced if the reactants are in dissolved fitrm as compared with their gaseous or solid phases. Many of the chemical changes that occur in seawater and the sediments are mediated by marine organisms. In some cases, marine organisms have developed unique biosynthetic pathways to help them survive the environmental conditions fitimd only in the oceans. Some of their metabolic products have proven useful to humans as pharmaceuticals, nutraceuticals, food additives, and cosmeceuticals. 

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