Colombia is one of the largest gold producer in Latinamerica. Low technology processes are used in the mining and mineral processing of gold, and as consequence these activities have a negative impact on the environment. The main objetive of this study is research about the geochemical behavior of Cu, Pb, Zn, Cd, Ag, As, Hg, Sb, and Bi, metals which are predominantly released by the mining activities in the Marmato Area (Gold District vein type), and in addition to consider their impact to the environment The main sources of these elements are Acid Mine Drainages (AMD), tailings, and erosion of waste rock deposits. These metals are entering the streams in the area in dissolved form and as particulate matter. A sampling programme (summer and winter seasons) was carried out. Surface waters, sediments and suspended particulate matter were collected in streams (Aguas Claras, Cascabel, Pantanos, Marmato, Arguía, Chirapotó), mine drainages and processing effluents from Marmato, and in the Cauca river. Aguas Claras was used as a reference stream, since it is still in a pristine state. Temperature, pH, conductivity, turbidity, sulfides and flow were determined in situ. Cyanides (total and free), COD, TOC, TS, DS, NH3, chlorides, cations (Na+, K+, Ca2+, Mg2+), and dissolved metais (Cu, Pb, Zn, Cd, Ag, As, Hg, Sb and Cd) were determined in waters. Heavy metals (total and bioavailable fraction) were analyzed in sediments and suspended particulate matter. The distribution of the metals over the various phases was studied with selective extraction methods (speciation). In this way it was possible to distinguish between geochemically reactive and inert fractions. The Aguas Claras stream is the reference stream and it shows the lowest values of TS (199 mgl-1) and conductivity (259 Scm-1), and the lowest concentration of heavy metals in its waters and sediments. Its pH (7.5) is biased towards basic range, which could be explained by reported carbonate rocks in this area. The mobile fraction for Bi, Zn, Cd, Pb, Ag and Cu is higher than 30%, a fact that shows their high bioavailability in spite of their lower concentrations. In active mines, oxidation of sulfide minerals takes place and produces AMD (pH 2,9-3,5 and pH 4,4) which are partially neutralized by effluents of milling and processing (pH4,4-8,7 and pH 6,4-8,3). These effluents are biased towards basic range, due to natural carbonates, lime and organic additives of processing. The Marmato stream that receives the whole drainage from the mining area and flows into the Cauca river, has neutral pH, showing that neutralization processes must be taking place. The discharge of tailings and increased erosion in the area are reflected in the high TS contents of the streams. COD and NH3 show positive correlation with cyanides which could mean that these parameters reflect the decay of cyanides in the system. Heavy metals are in high concentrations in sediments and particulate suspended matter from the Marmato Arca. Their levels range from 129-619ppm for Cu; 330ppm-2,28% for Pb; 1365ppm-1,18% for Zn; 7,6-200ppm for Ag; 218-1850ppm for As; 6,8-56ppm for Sb; 28-240ppm for Cd; 95-370ppb for Hg and 4-306ppm for Bi. The Marmato stream has the highest concentrations while Arguia and Chirapoto streams have lower values. These values reflect the mining activities in their drainage area, and reveal the contribution of sulfide minerais from the ore body (pyrite, sphalerite cadmian, galena bismuthian, chalcopyrite, arsenopyrite, argentopyrite, pyrrhotite, pyrargyrite and the non sulfide ore siderite). The mobile fraction in suspended matter is greater than in sediments. In this way the heavy metals could be dispersed long distances and end up in other environment compartments. In Marmato the highest mobility is for Bi, Pb and As, whilst in Arguia the highest bioavailability is for Ag, Cd, Zn, and Cu. In Marmato and Arguía streams, Sb and Hg do not show evidente of bioavailability (0% mobile fraction). Copper is mainly associated to the residual fraction (56-90%) and in lower percentages to carbonates (4-25%) and to organics and sulfides (4-25%), confirming its low mobility and its source in sulfides. Lead is associated with reducible (13-75%) and residual (16-82%) species, and in lower percentages to carbonates, sulfides and to the exchangeable fraction; showing its association with hydrous iron oxides generated by sulfides weathering. Zinc is mainly associated with the organic and sulfide fraction (13-64%) and in lower proportion with residual (9-47%) and reducible (10-33%) forms. Exchangeable or loosely-held Zn is noticeable (up to 6%). These associations reflect high bioavailability for Zn. Cadmiun is associated with the residual fraction (31-61%), with organics and sulfides (14-34%) and with the exchangeable fraction (4-14%). Antimony is mainly associated with the residual fraction (39-86%), and in lower levels with carbonates (14-40%); showing its character as not mobile metal and revealing its lithologic source. Bismuth is associated with reducible fraction (18-73%) and with carbonates (13-50%), but also there are appreciable levels of mobile Bi in Aguas Claras, Marmato, Pantanos and Cascabei. The Cauca river shows the lowest values of metals, in levels that reflect the contents of its tributaries; its solid load (TS 208-234 mgr), turbidity (40,80-62,7 NTU) and pH (7,2-7,4) are in agreement to values for other natural rivers that carry loads of erosive materials and have neutral waters. Eito the Cauca river, Sb, Hg and Bi do not show mobile fraction, whilst Cu and Pb present higher bioavailability in suspended matter than in sediments. Copper shows higher mobility in the Cauca tiver than in Marmato, due to the contribution of other anthropogenic sources, for instance wastes of herbicides and fertilizers. Lead presents higher mobility and bioavailability in the Cauca river. In spite of the fact that Pb is main!), associated with the reducible fraction (80-92%), and to a lesser extension with sulfides and organics, it shows higher exchangeable or loosely-held fraction (1,3-6,5%), reflecting the inputs of gasoline emissions in this area (automobile use). The heavy metal levels in sediments, suspended matter and waters become greater in the Cauca river after receiving Marmato and Arguía loads. The concentration of heavy metals in sediments of the Cauca decrease few kilometers downstream of the mining zone, due to dilution processes (flow 605,3-641,8 m3s-1), and additionally because of the metals are quickly carried as ions and as suspended particles; facts that are accelerated due to the fast rate flow of the river in this zone (steep gradient). In conclusion could be said that the Marmato ecosystern is strongly impacted by natural and anthropogenic inputs originated in the mining zone. In the waters fiam Marmato some number quality criteria are exceeded (U.S.E,P.A., 1976, 1982; 0.P.S., 1985, 1987), making them unsuitable for drinking water, agriculture irrigation, aquatic life or industrial use (Cyanides 0,13-3,8 mgl-1; TS 9422-39952 mgl-1). Heavy metals in sediments and suspended matter of Marmato are highly enriched in comparison to earth's crust averages, to Aguas Claras concentrations, (local background), and to Arguía (less mining activities), and Chirapotó levels (regional background). In Marmato and Arguia, the chemical speciation shows that Cd, Zn, Pb and Bi have the highest bioavailability and could be transferred from sediments and suspended matter towards other compartments, specially to the biota and also should be incorporated into the food chain. On the other hand, the waters and sediments of the Cauca river in this region, are not greatly polluted by heavy metals coming from the mining zone of Marmato. The ecosystem of the Cauca river in this area, has diluted and assimilated the inputs of the mining area up to now. Differing from Marmato, its physical - chemical parameters in waters, and the levels and standards of speciation for Cu, Pb, Sb, Bi, Ag and Hg in its sediments and suspended matter, obey the standards for other natural and not polluted river systems.
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