18 6. DISPERSION PROCESSES. 6.1. General The chemical, mechanical and biochemical processes involved in the movement of material between different locations in the natural environment result in geochemical Mispersion. Purely mechanical processes, apart from alluvial sorting, usually involve mixing, but not differentiation. In contrast, chemical and biochemical processes commonly create fractions of widely differing chemical composition due to the enhanced mobility of specific elements. In both primary and secondary (i.e. surficial) environments geochemical dispersion is often reflected by distinct geochemical patterns. The fact that the dispersion patterns associated with mineral deposits are commonly far more extensive than the actual deposits provides the justification for most geochemical exploration techniques. The response of an element to geochemical dispersion processes is governed by its mobility in the prevailing environment. This in turn is influenced by the physical and chemical characteristics of the element in question. In geochemical exploration, environments are normally categorized as primary (i.e. deep-seated) or surficial. The majority of geochemical exploration programs are concerned with the collection and analysis of samples from the surficial environment. Therefore the processes controlling geochemical dispersion in the surficial environment will be discussed in some detail. 6.2. Primary Environment. In deep-seated magmatic environments geochemical dispersion may result from exclusively mechanical agencies such as magma injection. More often dispersion results from a combination of chemical and mechanical processes as for example as a result of partitioning during crystallization and the separation of mobile aqueous solutions. The Mobility of components (H,O, CO,, H,S, SO,, F, Cl, B, and sometimes also Cu, Pb, Zn, Au, etc.), which enter the aqueous solutions, ere significantly enhanced and are more likely to undergo significant dispersion Metamorphic environments differ from magmatic in that most reactions occur in the solid state. No actual melting is involved in metamorphism except at the very highest temperatures. However, pore fluids rich in water furnish mobile phases into which some rock constituents may be extracted and dispersed by mineral solution or exchange. Again both chemical and mechanical processes are important factors in the development of geochemical dispersion patterns. A wide range of chemical and physical changes occur in sediments during and after burial; changes which alter solid mineral phases and interstitial fluids by a complex series of so-called diagenetic processes. Some of these processes may occur over extended periods of time, but the diagenetic history of a sedimentary mass may by19 punctuated by episodic events, such as loss of fluid and dissolved material that may occur during tectonism. In conjunction with normal basinal fluid migration these processes obviously have a major influence on geochemical dispersion in sedimentary rocks. It is also of course necessary to emphasize that faults, fractures, and intergranular openings provide channelways for dispersion of materials in aqueous solution in a wide variety of bedrock environments, especially at shallow to moderate depths. 6.3. Surficial Environment On exposure to the surficial environment as a result of uplift and erosion, dispersion patterns created at depth are modified and new patterns formed by surficial processes. The surficial environment is characterized by low temperature and pressure, and high concentrations of water, free oxygen and carbon dioxide. Most of the minerals formed under deep-seated conditions are not stable in this environment (Rose, et al., 1979). In surficial environments chemical, mechanical, and biological processes alll play major roles in geochemical dispersion. Although these processes often operate simultaneously, their relative importance depends on the local environment. Thus in arid, arctic _and mountainous terrain mechanical processes tend to dominate, whilst in the humid tropics chemical processes generally become more important. 6.3.1. Chemical Dispersion Chemical dispersion in the surficial environment is dominated by aqueous solution geochemistry. The behavior of trace metals in natural aqueous systems is highly complex due to the large numbers of possible interactions with ill-defined dissolved and particulate compounds, and non-equilibrium conditions (Salomons and Forstner, 1984). However, extensive observations of element mobility in the surficial aqueous ‘environment have permitted development of certain generalizations. (Table 6.1). These demonstrate the strong influence of pH (hydrogen ion concentration) and Eh (oxidation-reduction (redox) potential) on chemical dispersion in the secondary environment. As the Eh and pH conditions in natural surficial environments can be estimated (Figs. 6.1 and 6.2) or, better still, measured, published Eh-pH diagrams (Figs. 6.3. and 6.4) permit some prediction of solution chemistry. However, these predictions must be treated with extreme caution. Natural conditions are generally far more complex and influenced by a far greater number of factors than the controlled laboratory experiments and theoretical calculations used to construct the Eh-pH diagrams. This is well illustrated in the case of gold, where practical experience suggests greater mobility than might be expected from published theoretical solution chemistry studies (Figs. 6.5 and 6.6). The phase diagrams indicate some gold transport is possible under very acidic oxidizing20 — | se se dba Cu.cownitawng.Au | u,Co.NLMg.Ag Au as.ce Pb,LLRD.Ba.Be 81/Se.Ge.c8,71 TABLE 6.1 Relative mobilities of elements i (Modified after Andrew-Jones, 1968) the surficial environment.FIG 64 ‘Approximate position of some natural environments as characterized by Eh and pH. (Rose, Hawkes, & Webb; 1979) os 06 Z o- & o2 ° -02| ° FIG 6.2 Eh and pH values of mine waters. (x) oxidized ore zone; (@) primary ore zone. (Rose, Hawkes & Webb, 1979) at22 FIG 6.3 system Enh-pH diagram for part of the system Zn-O-H-S-C. The assumed activities for dissolved species are: Zn=10"*, C=10°, S=10". (Brookins, 1988) FIG 6.4 Fields of stability of solids and predominant dissolved zinc species in system Zn + CO, + $ + H,O at 25°C and 1 atm pressure in relation to Eh and pH. Dissolved zinc activity, 10° moles/\; dissolved carbon dioxide and sulfer species, 10° moles/I. (Hem, 1972) conditions in the presence of dissolved chlorine. At Summitville, Colorado observations ‘Suggest that gold can in fact also be locally mobilized in acidic, low-chloride environments (Stoffregen, 1986) as a result of the transient formation of gold-thiosulfate complexes. Mobile gold-thiosulfate complexes can also form under the neutral to basic, moderately oxidizing conditions found in the vicinity of weathering carbonate veins (Webster and Mann, 1984). Baker (1978) showed that humic acids can play an important role in the dissolution of gold in the supergene environment, whilst Ong and Swanson (1969) provided experimental evidence that these acids can stabilize gold colloids in solutions and thereby enhance their mobility.23 Auch i Pawel eveten aacon 25°C, 1 bar -CI-0-H 250, 1 bar 302 | i | > ] a = ; -0.6 -0.6 | 708 2 4 6 a 1 12 ta 70.85 2 + 6 e FIG. 6.5 Eh-pH diagram for part of the system FIG 6.6 —_Eh-pH diagram for part of the system Au-CI-O-H. The assumed activities for ‘Au-CLO-H. The assumed activitles for dissolved species are: Au = 10%", Cl dissolved species are: Au = 10°, = 10°*°. (Brookins, 1988) Cl = 10". (Brookins, 1988) Mercury is another element whose behavior in the surficial environment differs substantially from that indicated by theoretical solution chemistry calculations (and in this case also vapor phase chemistry). Theoretical solution chemistry takes no account of adsorption by iron and manganese oxides and chemical bonding which can restrict mercury mobility in many situations (Carr, et al., 1986). The mobility of many trace elements in the surficial environment is in fact strongly influenced by adsorption by and ion exchange onto colloidal particles, especially those of iron and manganese oxides and hydroxides, organic matter, clays and silica. Typically, adsorption onto metal oxides and organic substances increases dramatically with fairly small increases in pH (Fig. 6.7). Initially, ions adsorbed on surfaces are in active equilibrium with the host solutions and therefore readily desorp if pH conditions decrease. However, with time they may move into crystal lattice sites and become less effected by changes in local environmental conditions. Experiments have shown that when an absorbent material (i.e. manganese24 PERCENT METAL ADSORBED 100 - fam = Fe(OH), (1410°M) sol. eo} 20h 9 510330 9/1) aos on Fractional adsorption of metals of various oxide substrates (Fig. a: amorphous Fe(OH) ; Fig b: -T-AlO,; Fig. c: a-SiO,) and effects of adsorbate concentrations. (Salomon & Forstner, 1984)25 s "e 3 2 FIG6.8 —_Absorption-desorption results with changing BH for Mn-oxide exposed to solutions of 10°M Co. (Rose, Hawkes & Webb, 1979) oxide) is exposed to a more dilute solution, only a proportion of the expected amount of adsorped ions are in fact released (Fig. 6.8). 6.3.2. Mechanical Dispersion Mechanical processes play a major role in the dispersion of solid weathering products in geochemical exploration. The principal force responsible for mechanical dispersion is of course gravity, acting directly or indirectly (i.e. through water or ice movement) on solid surficial materials. Even on gentle slopes, rock debris and soil continually move downhill under the influence of gravity. The presence of moisture acts as a lubricant and helps accelerate this movement, sometimes with catastrophic results. Surface water runoff in the form of sheetwash and stream flow is also responsible for the dispersion of large amounts of solid material. Sheetwash mainly involves the selective erosion and transport of soil fines, especially clay size materials, Streams, depending on flow and source materials, can transport a far wider range of material from boulders on down. Groundwater movement, under the influence of gravity or hydrostatic head, generally involves dissolved ions rather than the solid particulate products of weathering. Large areas, especially at the higher latitudes, have been subject to periods of intensive glaciation in recent geologic time. The resulting erosion and deposition has involved a variety of processes which are reflected by extensive glacially derived surficial cover obscuring bedrock. A proportion of this cover is lodgement till formed at the base26 of continental ice sheets from crushed and pulverized transported material plucked from bedrock by the ice. Ablation till, deposited by surficial melting of the ice, commonly overlies the lodgement til. A variety of water-deposited sediments form within (e.g. gskers) and along the margins (e.g. kames) of glaciers. The large streams flowing out Of glaciers often cover extensive areas with glaciofluvial deposits (outwash). The glaciers themselves can disrupt local drainage systems. Fine stratified sediments are often deposited in the resultant lakes. Erosion and transport by wind action is most important in arid and semi-arid areas where there is little or no protective vegetation cover. In desert terrain this can result in sand cover over large areas, whilst in the vicinity of some arid desert and glaciated areas, loess deposits are common. Wind is also responsible for the dispersion of man made contaminants from industrial sites. ‘Substantial amounts of sub-surface weathered material are transported to surface by many burrowing animal species, especially worms and termites. This is particularly important in deeply leached areas where transport of mineralized fragments to surface can significantly enhance surface geochemical response. 6.3.3. Biological Dispersion Uptake of inorganic matter by plant root systems results in the redistribution of this matter throughout the remainder of the plant (which is the basis of the biogeochemical exploration method). During subsequent plant decay the more insoluble components are Concentrated in the upper part of the soil profile, whilst the more mobile tend to be removed by ground and surface waters (biogeo-chemical cycle). Microorganisms (bacteria, algae, fungi, etc.) are also important factors in metal dispersion as they are intimately involved in many redox reactions. (The influence of redox conditions on element mobility has been discussed above.) Microorganisms also often appear to capable of assimilating and concentrating certain metals.