Geochemical patterns of active stream sediments: An artificial neural networks approach

Juan Lacassie Servicio Nacional de Geologa y Minera, SERNAGEOMIN, Chile Javier RuizDel Solar Advanced Mining Technology Centre, Universidad de Chile Alejandro Daz Empresa Nacional de Minera, ENAMI, Chile Leonardo Baeza and Felipe Astudillo Department of Geology, Universidad de Chile

ABSTRACT
A new methodology has been applied for the study of four impacted and nonimpacted mine related fluvial systems in central and northern Chile: the Rapel, Lluta, Huasco and Limar fluvial systems. The method involves chemical compositional data of the < 180m fraction of active stream sediments samples collected along these fluvial systems. The chemical data has been analysed as a whole by using an advanced statistical technique based on dynamic growing self organising maps. This technique enables the visualisation of major and secondary chemical patterns along specific parts of these fluvial systems. The results show that, for each fluvial system, the data can be separated into a limited number of groups with distinguishing geochemical characteristics, which are restricted to specific segments of the rivers. In particular, this technique enables the recognition of, in the first place, metal contamination (Cu, Mo, Sb, Co, As and Zn) along the Cachapoal river, a highly populated area of the Rapel fluvial system, which could be due to downstream remobilisation of miningderived material from the El Teniente CuMo mine; and in the second place, recognition of specific chemical signatures associated with prospective and/or mineralised areas in the Lluta, Huasco and Limar fluvial systems. The results show that this method presents a high potential for: first, the assessment of possible mineassociated river contamination and second, the identification of prospective areas and their characteristic geochemical signatures. Moreover, this technique uses the linear and nonlinear information contained in the chemical data. Therefore, it highlights higher order correlations and allows visual perception of subtle inter relations between the chemical variables, which may have not been previously recognised by other conventional linear statistical techniques.

INTRODUCTION
The chemical composition of stream sediments have been used extensively to monitor river quality, to determine the influence of bedrock geology and to assess the impact on the fluvial systems of anthropogenic factors such as mining activities, industry and urbanisation. The study of stream sediments is an issue of environmental and human health concern, especially since sediments are a sink for environmental contaminants and may function as a source of heavymetal exposure to aquatic organisms. In turn, geochemical surveys based on analysis of stream sediments, has shown to be a robust method for identifying areas of high mineral potential. Concordantly, during the last five decades, worldwide systematic collection of stream sediment has been carried out [1] and the volume of the associated geochemical grows continuously. The manner in which these data are interpreted and visualised provides competitive advantages and exploration opportunities [2]. Therefore advanced multivariate statistical procedures are required. In particular, SelfOrganising Maps (SOM) [3] provides a nonlinear, nonparametric, rapid and robust tool for analysing multivariate data. In this contribution we use Growing Cell Structures (GCS) [4], an extension of SOM, both for clustering fluvial geochemical data and for finding visual representations of geochemical data that simplify the analysis and yet allow all relevant information to be preserved. The method has been tested with geochemical analyses of active stream sediments collected from the Lluta, Limar, Huasco and Rapel fluvial systems, in Chile. These fluvial systems, respectively supply water to catchments with relatively large populations, whose main economic activities are agriculture and mining. In particular, in the upper reaches of the Rapel catchment, is located the El Teniente porphyry CuMo deposit, the worlds largest underground copper mine (Figure 1). In turn, in the upper reaches of the Huasco catchment, is located the PascuaLama mining project, a large gold openpit mine which is planned to start operating in the coming future (Figure 2).

METHODOLOGY Sampling, sample treatment and chemical analysis

Respectively, a total of 109, 126, 131 and 90 stream sediment samples were collected along the Lluta, Limar, Huasco and Rapel fluvial systems. Each sample corresponds to a composite of stream sediment subsamples, taken over a channel length of 2050 m, collected using a plastic scoop, and then combined and stored as single samples in plastic bags. At the laboratory of Sernageomin, the samples were ovendried (60C for 48h), cooled to room temperature (25C), and subsequently sieved using stainless steel mesh sieves in order to separate the fraction finer than 180m (< 180m fraction) which was grounded in an automatic agate mill. The element concentration of the grounded material was determined at ACME Labs with an ICPAES (Lluta and Limar samples) and at Sernageomin, with an ICPAES (Rapel samples) and with an XRay Fluorescence Spectrometer (Huasco samples). Additionally, the Hg and Au concentration of the Huasco samples were determined at Sernageomin by Atomic Absorption Spectrometry.

Geochemical datasets
The four geochemical datasets (Lluta, Limar, Huasco and Rapel datasets) comprise the geochemical data of the < 180m fraction of the collected stream sediment samples. Each sample includes information concerning the concentrations of major oxides and trace elements (Table 1). In

order to examine the influence of the geographical variation of the bedrock in the geochemical composition of the sediment samples, the EastUTM coordinate of each sample was also included as an extra input variable.

Table 1 List of chemical elements included in the geochemical datasets

Dataset Lluta and Limar Huasco Major Oxides (wt%) SiO2, TiO2, Al2O3, K2O, Na2O, CaO, Fe2O3, MgO, MnO, Cr2O3, P2O5. SiO2, TiO2, Al2O3, K2O, Na2O, CaO, Fe2O3, MgO, MnO, P2O5. SiO2, TiO2, Al2O3, K2O, CaO, Fe2O3, MgO, MnO, P2O5. Trace elements (ppm) Ba, Be, Co, Cs, Ga, Hf, Nb, Rb, Sc, Sn, Sr, Ta, Th, U, V, W, Zr, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mo, Cu, Pb, Zn, Ni, As, Cd, Sb, Bi, Ag, Hg, Tl, Se. Ag, As, Ba, Bi, Ce, Co, Cr, Cu, Hg, La, Ni, Pb, Sb, Sr, V, Y, Zn, Zr. As, B, Ba, Ce, Co, Cr, Cu, La, Mo, Ni, Pb, Sb, Sr, V, Y, Zn. Trace elements (ppb) Au.

Au.

Rapel

Multidimensional analysis
Prior to the multidimensional analysis, each dataset was standardised, so that the mean and variance of each variable equals to 0 and 1, respectively. Each dataset was analysed separately using the GCS algorithm. Starting from a three unit GCS map, the coupled GCS learning and network growing process continued until the insertion of a new unit, do not involved relevant geochemical discrimination between the units of the GCS map. After the GCS map size is selected, in this case using expert criteria, the average values for individual input variables are then displayed on colour maps and overlain on the final GCS map structure, allowing simple visual comparisons.

RESULTS
For each dataset, the GCS analysis of resulted in a neural map composed of interconnected nodes, each node representing a group of sediment samples with similar geochemical characteristics (Figures 1 to 4). Each node groups samples with similar geochemical features that are broadly restricted to specific segments of the corresponding fluvial system. In each fluvial system, the resulting geographical distribution of the samplenode associations shows that there is a close relationship between the geographical position and the geochemical signature of the studied stream sediments.

Rapel fluvial system

The GCS analysis of the Rapel dataset resulted in a neural map composed of eight interconnected nodes, each associated with a group of sediment samples that presents similar geochemical characteristics (Figure 1). The geographical distribution of the samplenode associations shows that, in the upper part of the catchment, it is possible to distinguish three geochemical segments (Figure 1). In particular, the upper to middle reaches of the Cachapoal river are characterised by the 28 node

association. Thus the corresponding stream sediments present typical high concentrations of Cu, B, Mo, Sb, Co, As, Zn and CaO (Figure 1). This chemical signature of elevated CuMoAsSb concentrations is typical of mine affected fluvial systems. Thus, it likely reflects downstream remobilisation of material associated with the El Teniente CuMo mine. Downstream, the sediments of the lower reaches of the Cachapoal river, are almost completely associated with node 6 (Figure 1). This chemical change occurs broadly downstream the confluence with the Claro river. Thus, it reflects a dilution effect, as indicated by the lower Cu, B, Mo, Sb, Co, As, Zn, Pb and CaO concentrations of the associated sediments. In the southern part of the catchment, the Tinguiririca river is dominated by node 1, which is characterised by conspicuously high P2O5, Ba and Sr concentrations (Figure 1). In particular, the high P2O5 concentrations reflect an extensive use of phosphates in the floodplain of this river.

Figure 1 (a) Samplenode distribution in the upper catchment of the Rapel fluvial system (modified from [5]). Insert shows the GCS neural Map. Only the nodes relevant for this part of the catchment are coloured. The samples present the same colour of the node to which they are associated. Their samplenumber (samplecode) is also indicated. Geology modified from the Geological map of Chile [6]. ET: El Teniente CuMo mine (white star symbol). TD13: main tailing dams. LL: Los Leones creek. Crc: Claro river creek. (b) Visualization of the distributions of each input variable. Scales at right indicate whole rock concentrations (wt%) for the major oxides and parts per million (ppm) for the trace elements.

Huasco fluvial system

The analysis of the Huasco dataset resulted in a neural map composed of nine interconnected nodes (Figure. 2). The geographical distribution of the samplenode associations shows that, in geochemical terms, it is possible to distinguish different segments along this fluvial system (Figure. 2). In the upper part of the catchment, the Estrecho and Chollay rivers are respectively characterised by node 1 and node 9 associated samples. This indicates that: 1) the Estrecho river presents a conspicuous geochemical signature of high concentrations of Au, Hg, As, Sb, Pb, Ba, La, Ce, SiO2, K2O and Sr; 2) the same signature, although diluted, characterises the Chollay river (Figure. 2). In particular, the AuHgAsSbPbBa anomaly of the Estrecho and, to a lesser extent, of the Chollay river, fits well with the mineralisation and alteration paragenesis described for the PacuaLama deposit. This includes native gold, tellurides, calomel (Hg2Cl2), arsenolite, enargite, stibnite, galena, anglesite and barite [7]. Therefore, the geochemical signature of the sediments of Estrecho and Chollay rivers, corresponds to a natural signature that reflects the presence of an important mineralised area in the upper reaches of their catchment. This area corresponds to the alteration zone where the PascuaLama mining project is located (Figure. 2). In turn, the Del Trnsito river, located downstream, is dominated by a node 64 association (Figure 2). In particular, the geographic distribution of the node 6associated samples, which present typical high values of Cu, Ni and Zn, broadly coincides with restricted outcrops of Palaeozoic basement (Figure 2). This suggests that these outcrops are potential exploration targets for CuNiZn mineralisation. The node 3association also characterises the upper reaches of this catchment. It is typicall of the Potrerillo, Tres quebradas, Chollay and Conay rivers. The associated samples present high concentrations of SiO2, K2O, Sr and La (Figure 2). This can be interpreted as a background chemical signature that reflects detritus from sources with hydrothermal alteration located in those areas [8]. In this context, both the chemistry and geographic distribution of the node8 associated samples suggest that they reflect a dilution of the node3 signature downstream the Del Carmen river (node 8). However, in the middle reaches of this last river, several node5 associated samples with characteristic high values of Ag, Cr, Bi Y and Sb (not shown in figure 2), suggest the presence of Ag mineralised areas. Concordantly this part of the catchment coincides with historical Ag mining, located mainly in the Graben de la Plata (Graben of Silver) area [8].

Lluta fluvial system

The analysis of the Lluta dataset resulted in a neural map composed of eight interconnected nodes (Figure 3). As for the previous fluvial systems, along the Lluta fluvial system it is possible to distinguish different nodeassociations. In particular, the 156 node association is restricted to a specific area located in the upper reaches of the catchment, which coincides with the Putre Vilauumani hydrotermal alteration zone (Figure 3). The associated sediments present a conspicuous geochemical signature of high concentrations of AuHgAsMoSBiSeWBa (node 1), URbK2OBe (node 5) and BeCsAsAl2O3HREE (node 6). These results suggest that the Putre Vilauumani hydrotermal alteration zone corresponds to one of the most important prospective areas of the upper catchment of the Lluta fluvial system. The study of Baeza [9] has shown that it is common to find primary Ubearing minerals in the stream sediments of this area. Therefore, this part of the catchment could be a good candidate for being the source of the sedimentary Udeposits located downstream this catchment [9].

Figure 2 (a) Samplenode distribution in the upper catchment of the Huasco fluvial system. Insert shows the GCS neural Map. The samples present the same colour of the node to which they are associated. Geology modified from the Geological Map of Chile [6]. (b) Visualisation of the distributions of each input variable. Scales at right indicate whole rock concentrations (wt%) for major oxides and part per million (ppm) for trace elements.

Figure 3 (a) Samplenode distribution in the upper catchment of the Lluta fluvial system (modified from [9]). Insert shows the GCS neural Map. Only the nodes relevant for this part of the catchment are coloured. The samples present the same colour of the node to which they are associated. Satellite image from Google Earth. (b) Visualisation of the distributions of each input variable. Scales at right indicate whole rock concentrations (wt%) for major oxides and part per million (ppm) for trace elements.

Figure 4 (a) Samplenode distribution in the Limar fluvial system. Insert shows the GCS neural Map. The samples present the same colour and symbol of the node to which they are associated. Geology modified from the Geological Map of Chile (Sernageomin, 2004). (b) Visualisation of the distributions of each input variable. Scales at right indicate whole rock concentrations (ppm).

Limar fluvial system

The analysis of the Limar dataset resulted in a neural map composed of eight interconnected nodes (Figure 4). As for the Lluta fluvial system, in the Limar fluvial system it is also possible to distinguish a very conspicuous area. This corresponds to the upper reaches of the Hurtado river, which is characterised by the 82 node association (Figure 4). The sediments of this area present typical high values of CuMoNiCoZnAsBeBiCdMnUSn, coupled with high concentrations of REE (not shown in figure 4). This geochemical signature suggests the presence of an important altered/mineralised area at the upper reaches of the Hurtado river. In agreement with the suggestions of previous studies [10], this area most probably coincides with the alteration zone associated with the Coipita prospect.

CONCLUSIONS
The proposed methodology, based on dynamic growing self organising maps, was successful in distinguishing the geochemical characteristics of specific segments of the studied fluvial systems. In particular, it enables the recognition of the impact of mine and agroindustrial activities, downstream the Rapel fluvial system. The method also shows a considerable potential for revealing the relevant geochemical characteristics of prospective areas, located in the upper reaches of the Lluta, Limar and Huasco fluvial systems. Those chemical signatures can be used as mineral exploration guidelines based on geochemical data of active stream sediment.

REFERENCES
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