Water rock interactions

The most important conclusion derived from the isotopic studies mentioned above is that isotopic characteristics of Kuroko ore fluids were caused dominantly by seawater-volcanic rock interaction at elevated temperature and by the mixing of seawater with small portions of igneous water or the hydrothermal solution whose chemical and isotopic compositions are controlled by water-rock interaction under the rock-dominated condition and also small proportion of mixing of meteoric water. 

The variations in Fe and Mg contents of the 14 A Fe-chlorite-14 A Mg-chlorite solid solution are considered here. However, structural formulae for chlorite are not as simple as those considered here. As mentioned by Walshe and Solomon (1981), Stoesell (1984), Cathelineau and Nieva (1985) and Walshe (1986), chlorite solid solution may be represented by six components, and accurate thermochemical data on each end-member component at the hydrothermal conditions of concern are necessary to provide a far more rigorous calculation of the equilibrium between chlorite and hydrothermal solution. However, the above argument demonstrates that the composition of chlorite is a highly useful indicator of physicochemical conditions of hydrothermal solution and extent of water-rock interaction. 

Hydrothermal alteration is reflected by the changes in many variables (temperature, water/rock ratio, extent of water-rock interaction (reaction progress), reaction rate, flow rate of fluids etc.) (Fujimoto, 1987). Theoretical and experimental works on hydrothermal alteration were reviewed by Meyer and Hemley (1967), and Rose and Burt (1979). 

In the last two decades, great progress has been made in the field of hydrothemal alteration studies, mainly from computation works on water-rock interactions at elevated temperatures (e.g., Wolery, 1978 Reed, 1983, 1997 Takeno, 1989). These studies revealed the relationship between the changes in chemical composition of hydrothermal solution and the relative abundance of minerals in the rocks. 

Giggenbach (1984) calculated the effect of temperature on the chemical composition of fluids buffered by alteration minerals. The causes for the hydrothermal alteration considered below are mainly based on the works by Shikazono (1978a) and Giggenbach (1984). The effect of the extent of water-rock interaction is not taken into account. 

Bence, A.E. (1983) Volcanogenic massive sulfides rtx k/water interactions in ba.saltic systems and their effects on the distribution of the rare earth elements and selected first. series transition elements (abst.). 4th International Symposium on Water-Rock interaction, Mi.sasa, Japan, 48. 

D Amore, F. and Gianelli, G. (1983) Oxygen and sulphur fugacity buffering in geothermal systems. Extended Abstracts, 4th Int. Symp. Water-Rock Interaction, pp. 103-107. 

Gamo, T. (1995) Wide variation of chemical characteristic of submarine hydrothermal fluids due to secondary modification processes after high temperature water-rock interaction, a review. In Sakai, H. and Nozaki, Y. (eds.), Biogeochemical Processes and Ocean Flux in the Western Pacific, Terra Sci. Publ., pp. 425-451. 

Maruyama, S., Liou, J.G. and Cho, M. (1983) Experimental investigation of heulandite-laumontite equilibrium. Ext. Abstr., 4th Int. Symp. on Water-Rock Interaction, Misasa, pp. 305-308. 

Shikazono, N. (1985c) Water-rock interaction and Kuroko genesis. DMRDC/GSJ, Kuroko Workshop, p. 9. 

Chemical compositions of major elements (alkali, alkali earth elements. Si) in back-arc and midoceanic ridge hydrothermal solutions are not so different (Table 2.15). This is thought to be due to the effect of water-rock interaction. For example, Berndt et al. (1989) have shown that mQ i+ of midoceanic ridge hydrothermal fluids is controlled by anorthite-epidote equilibrium (Fig. 2.37). Figure 2.37 shows that /Mca2+/m + of back-arc hydrothermal fluids is also controlled by this equilibrium. 

These differences are considered to be attributed to the dilferences in compositions of rocks and alteration minerals interacted with circulating seawater or modified seawater at elevated temperatures. For example, high K and Li concentrations in the hydrothermal solution in the Mid-Okinawa Trough baek-arc basin (Jade site) are due to the interaction of hydrothermal solution with acidic volcanic rocks (Sakai et al., 1990). It is evident that the chemical compositions of hydrothermal solution are largely alfected by water-rock interaction at elevated temperatures. 

The pH of hydrothermal solution of white smoker from which anhydrite is precipitating shows very low 2 for Lau Basin Vail Lili fluid. This low pH cannot be explained only by water-rock interaction process. One likely explanation is decreasing of pH due to precipitation of sulfides. The pH decreases by the following reaction,... 

Ellis, A.J. and Mahon, W.A.J. (1967) Natural hydrothermal. systems and experimental hot water/rock interactions. Geochim. Cosmochim. Acta, 28, 1323-1357. 

The ore fluids responsible for epithermal base-metal vein-type deposits were generated predominantly by meteoric water-rock interaction at elevated temperatures (200-350°C). Fossil seawater in marine sediments was also involved in the ore fluids responsible for this type of deposits. Epithermal precious metal ore fluids were generated by meteoric water-rock interaction at 150-250°C. Small amounts of seawater sulfate were involved in the ore fluids responsible for epithermal precious metal vein-type deposits occurring in Green tuff region (submarine volcanic and sedimentary rocks). 

Processes controlling nuclide distributions. The general equations for onedimensional advective transport along a groundwater flow path of groundwater constituents, and the incorporation of water/rock interactions, are given in such texts as Freeze and Cherry (1979). The equations can be applied to the distribution in groundwater of each isotope I with a molar concentration Iw and parent with Pw to obtain... 

There are four naturally occurring isotopes of Ra " " Ra (ti/2 = 5.8 a) and " Ra (3.7 d) in the Th series, (1600 a) in the series, and Ra (11.7 d) in the series (Table 1). The data for Ra are more limited, since it is generally present in low concentrations due to the low abundance of The differences in half lives and the connections across the different decay series have been used to infer a variety of groundwater and water-rock interaction features. For the short-lived Ra isotopes, the dominant input term to groundwater is recoil, rather than weathering, and steady state concentrations are often achieved (see Section 2.2). 

While it is expected that the source rocks for the radionuclides of interest in many environments were deposited more than a million years ago and that the isotopes of uranium would be in a state of radioactive equilibrium, physical fractionation of " U from U during water-rock interaction results in disequilibrium conditions in the fluid phase. This is a result of (1) preferential leaching of " U from damaged sites of the crystal lattice upon alpha decay of U, (2) oxidation of insoluble tetravalent " U to soluble hexavalent " U during alpha decay, and (3) alpha recoil of " Th (and its daughter " U) into the solute phase. If initial ( " U/ U).4 in the waters can be reasonably estimated a priori, the following relationship can be used to establish the time T since deposition,... 

Figure 20. Secular variation in 5 U(0) for Bahamas flowstone sequence. Changes in 5 U(0) are related to uranium-series disequilibrium conditions in host limestone, periodic addition of new material with elevated (marine) 5 U(0), alpha recoil effects and variation in recharge, and hence water-rock interaction times (see text for details).

Patterson CG, Runnells DD. 1992. Dissolved gases in groundwater as indicators of redox conditions. Water-Rock Interaction, Proc Int Symp, 7th 1 517-520. 

KharakaY.K., Cole D.R., et al. Gas-water-rock interactions in Frio formation follow-ing C02 injection implication for the storage of greenhouse gase in sedimentary basins. 2006 Geology 34 577-580. 

Fig. 2.11. Configurations of reactive transport models of water-rock interaction in a system open to groundwater flow (a) linear domain in one dimension, (b) radial domain in one dimension, and (c) linear domain in two dimensions. Domains are divided into nodal blocks, within each of which the model solves for the distribution of chemical mass as it changes over time, in response to transport by the flowing groundwater. In each case, unreacted fluid enters the domain and reacted fluid leaves it.

---