Precipitation minerals

Sato (1973) and Ohmoto et al. (1983) calculated the amounts of sulfides precipitated due to the mixing of ascending hydrothermal solution and cold seawater. Their calculations showed that the calculated ratios of the amounts of minerals precipitated are generally consistent with those in Kuroko ore deposits. 

Drummond, S.E. Jr. (1981) Boiling and mixing of hydrothermal fluids Chemical effects on mineral precipitation. Ph.D. Thesis, Pennsylvania State U. 

Nagayama, T. (1993b) Pressure loss, boiling and vein formation An example model for the mineral precipitation in the Hishikari vein deposits. Resource Geology Special Issue, 14, 29-36. 

Barite and sphalerite tend to precipitate at lower temperature from the hydrothermal solution mixed with a large amount of cold seawater (but mixing ratio (seawater/hydrothermal solution) may be less than 0.2). These minerals precipitate on the seafloor and/or at very shallow subsurface environment. However, chalcopyrite tends to precipitate from high temperature solutions in ore bodies and/or at the sub-seafloor sediments. Usually shale which is relatively impermeable overlies the Besshi-type ore bodies. This suggests that hydrothermal solution could not issue from the seafloor and... 

Injection wells and/or infiltration galleries may become plugged by microbial growth or mineral precipitation. 

Biofouling or mineral precipitation in extraction wells or treatment processes can reduce system performance. 

Mass transfer can be described in more sophisticated ways. By taking in the previous example to represent time, the rate at which feldspar dissolves and product minerals precipitate can be set using kinetic rate laws, as discussed in Chapter 16. The model calculates the actual rates of mass transfer at each step of the reaction progress from the rate constants, as measured in laboratory experiments, and the fluid s degree of undersaturation or supersaturation. 

Thirteen minerals appear supersaturated in the first block of results produced by the chemical model (Table 6.6). These results, therefore, represent an equilibrium achieved internally within the fluid but metastable with respect to mineral precipitation. It is quite common in modeling natural waters, especially when working at low temperature, to find one or more minerals listed as supersaturated. Unfortunately, the error sources in geochemical modeling are large enough that it can be difficult to determine whether or not a water is in fact supersaturated. 

Many natural waters are supersaturated at low temperature, primarily because less stable minerals dissolve more quickly than more stable minerals precipitate. Relatively unstable silica phases such as chalcedony or amorphous silica, for example, may control a fluid s SiC>2 concentration because quartz, the most stable silica mineral, precipitates slowly. 

Finally, common ion effects link many mineral precipitation reactions, so the reactions do not operate independently. In the seawater example, dolomite precipitation consumed magnesium and produced hydrogen ions, significantly altering the saturation states of the other supersaturated minerals. 

Here, we set a vanishingly small free mass for each mineral so that only negligible amounts can dissolve during the calculation s second step, when supersaturated minerals precipitate from the fluid. 

Because little mass can precipitate from it, the brine, if related to deposition of the metalliferous muds, is likely to be a residuum of the original ore fluid. As it discharged into the deep, the ore fluid was richer in metals than in reduced sulfur. Mineral precipitation depleted the fluid of nearly all of its reduced sulfur without exhausting the metals, leaving the metal-rich brine observed in the deep. 

In this chapter we consider how to construct reactions paths that account for the effects of simple reactants, a name given to reactants that are added to or removed from a system at constant rates. We take on other types of mass transfer in later chapters. Chapter 14 treats the mass transfer implicit in setting a species activity or gas fugacity over a reaction path. In Chapter 16 we develop reaction models in which the rates of mineral precipitation and dissolution are governed by kinetic rate laws. 

We might, for example, study the rate at which the ferrous ion Fe++ oxidizes by reaction with O2 to produce the ferric species Fe+++. Since the reaction occurs within a single phase, it is termed homogeneous. Reactions involving more than one phase (including the reactions by which minerals precipitate and dissolve and those involving a catalyst) are called heterogeneous. 

Despite the authority apparent in its name, no single rate law describes how quickly a mineral precipitates or dissolves. The mass action equation, which describes the equilibrium point of a mineral s dissolution reaction, is independent of reaction mechanism. A rate law, on the other hand, reflects our idea of how a reaction proceeds on a molecular scale. Rate laws, in fact, quantify the slowest or rate-limiting step in a hypothesized reaction mechanism. 

Comparing the development here to the accounting for the kinetics of mineral precipitation and dissolution presented in the previous chapter (Chapter 16), we see the mass transfer coefficients v and so on serve a function parallel to the coefficients v , etc., in Reaction 16.1. The rates of change in the mole number of each basis entry, accounting for the effect of each kinetic redox reaction carried in the simulation, for example,... 

In the calculation results (Fig. 24.1), amorphous silica, calcite (CaCCF), and sepiolite precipitate as water is removed from the system. The fluid s pH and ionic strength increase with evaporation as the water evolves toward an Na-C03 brine (Fig. 24.2). The concentrations of the components Na+, K+, Cl-, and SO4- rise monotonically (Fig. 24.2), since they are not consumed by mineral precipitation. The HCO3 and Si02(aq) concentrations increase sharply but less regularly, since they are taken up in forming the minerals. The components Ca++ and Mg++ are largely consumed by the precipitation of calcite and sepiolite. Their concentrations, after a small initial rise, decrease with evaporation. 

In a first calculation, we specify that the fluid maintains equilibrium with whatever minerals precipitate. Minerals that form, therefore, can redissolve into the brine as evaporation proceeds. In react, we set the Harvie-Moilcr-Weare model and specify that our initial system contains seawater... 

Fig. 24.7. Volumes of minerals precipitated during a reaction model simulating the evaporation of seawater as an equilibrium system at 25 °C, calculated using the Harvie-Mpller-Weare activity model. Abbreviations Ep = Epsomite, Hx = Hexahydrite.

Fig. 25.1. Mineralogical consequences of mixing the two fluids shown in Table 25.1 at 60 °C in the presence of microcline, muscovite, quartz, and dolomite. Results shown as the volume change for each mineral (precipitation is positive, dissolution negative), expressed per kg of pore water.

In calculating most of the reaction paths in this book, we have measured reaction progress with respect to the dimensionless variable . We showed in Chapter 16, however, that by incorporating kinetic rate laws into a reaction model, we can trace reaction paths describing mineral precipitation and dissolution using time as the reaction coordinate. 

Fig. 30.1. Volumes of minerals precipitated during a reaction model simulating the mixing at reservoir temperature of seawater into formation fluids from the Miller, Forties, and Amethyst oil fields in the North Sea. The reservoir temperatures and compositions of the formation fluids are given in Table 30.1. The initial extent of the system in each case is 1 kg of solvent water. Not shown for the Amethyst results are small volumes of strontianite, barite, and dolomite that form during mixing.

Sulfate, halide, and carbonate minerals form in mine waste as a result of chemical weathering reactions and as a by-product of mineral processing. The formation of carbonate minerals is of particular interest for its potential in offsetting greenhouse gas emissions associated with mining. We have documented secondary carbonate mineral precipitation at the Mount Keith Nickel Mine (Western Australia) and the... 

The negative sign refers to mineral precipitation instead of dissolution. Such computations are done with PHREEQC (Parkhurst Appelo 1999). An inescapable conclusion of mass balances is that during the weathering of pyritiferous hydrothermally altered rock, iron and silica are precipitated. 

Almost nothing is known about the uppermost 4 km of the Banyu Pahit stream due to difficult field access, although differences in stream composition across this interval have been reported, van Hinsberg (2001) suggested three potential explanations for the observed changes 1) dilution by another fluid source, 2) fluid-rock interaction, and 3) mineral precipitation. 

Geochemical simulations (not shown) of water quality suggest that Ni is soluble in the test conditions, eliminating secondary mineral precipitation as an explanation for the absence of Ni in leachates. These observations could be explained by the metal retention potential of the Lac Tio waste rock being still active in the humidity cell tests. Consequently, the Ni produced in the humidity cell tests will continue to be retained by the fresh waste rock until saturation of the retention sites. 

Olivine is assumed to be the only mineral precipitating and the fa and fo subscripts refer to pure fayalite and forsterite. Upon crystallization of the incremental amount dM i of cumulate, the incremental amount dMfa of fayalite is precipitated, and, since the iron content of fayalite is constant... 

No assumption on constant parameters has been made so far. If the amount of mineral precipitated is proportional to the amount of assimilated material, e.g., if latent heat is conserved, then r is constant. For the initial liquid state F = 1, C iq = C0 as in Section 9.3.1... 

A significant amount of seawater is trapped in the open spaces that exist between the particles in marine sediments. This fluid is termed pore water or interstitial water. Marine sediments are the site of many chemical reactions, such as sulfate reduction, as well as mineral precipitation and dissolution. These sedimentary reactions can alter the major ion ratios. As a result, the chemical composition of pore water is usually quite different from that of seawater. The chemistry of marine sediments is the subject of Part 111. 

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