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Felipe Leo, Marcio A. Kronbauer, Marcos L.S. Oliveira, Csar M. N. L. Cutruneo, Luis F. O. Silva
University Center La Salle, Master in Environmental Impact Assessment in Mining, Av. Victor Barreto, 2288, Canoas-RS, Brazil E-mail:

Acid drainage from coal mines and metal mining is a major source of underground and surface water contamination in the world. The coal mining acid drainage (CMAD) from mine contains large amount of solids in suspension and a high content of sulphate and dissolved metals (Al, Mn, Zn, Cu, Pb, Fe, etc.) that finally are deposited in the rivers. Since this problem can persist for centuries after mine abandonment, it is necessary to apply multidisciplinary methods to determine the potential risk in a determinate area. These multidisciplinary methods must include molecular and elemental analysis and finally all information must be studied statistically. This methodology was used in the case of coal mining acid drainage from the Tubarao River (Santa Catarina, Brazil). During molecular analysis, Raman Spectroscopy, electron bean, and X-ray diffraction (XRD) have been proven very useful for the study of minerals present in sediment rivers near this CMAD. The obtained spectra allow the precise identification of the minerals as jarosite, quartz, clays, etc. The elemental analysis (Al, As, Fe, K, Na, Ba, Mg, Mn, Ti, V, Zn, Ag, Co, Li, Mo, Ni, Se, Sn, W, B, Cr, Cu, Pb and Sr) was realized by inductively coupled plasma mass spectrometry (ICP-MS). Statistical analysis (Principal Component Analysis) of these dates of concentration reveals the existence of different groups of samples with specific pollution profiles in different areas of the Tubarao River. KEYWORDS: Sediment; Coal acid mine drainage; Environmental impacts; Stability minerals; Drainage evolution.

1. INTRODUCTION Coal is the major fuel used for the generation of electricity worldwide while the process of coal mining involves the discharge of huge amount of effluent into the surface water (Mishra et al., 2008). Mining operations involving sulphide minerals generally result in the excavation of large quantities of rock from the anoxic subsurface and its transport to the surface oxic environment (Hochella et al., 2005). Unfortunately, there are few Brazilian studies on the partitioning behavior and geo-chemistry of trace elements during the coal cleaning and subsequent discharge in the river courses, although this is basic for understanding their environmental impact (Silva et al., 2011a,b,c,d). Such sediment drainages cover all the particulate materials (coal residues from the dump storage mountains and soil) released by rain flows as well as those new mineral phases formed as reprecipitated compounds when saturation from dissolved cationanion pairs is attained. One of the most common approaches to waste rock stack construction is to encapsulate the most pyrite-rich rocks in the core of a waste rock stack (Bussiere et al., 2004). This potential acid-forming rock is surrounded and/or capped by waste rockswith lower potential for generating acid, or even some acid neutralisation capacity (Lottermoser, 2003). A key part of this process is detailed knowledge of the relative acid generation potentials of waste rocks during the coal mining process, so that each truckload of waste rock stacks (Hughes et al., 2007). Hence, it is desirable to be able to characterize waste rocks at the out-crop or truckload scale in a rapid and cost-effective manner.

Acid drainage from coal mines and metal mining results from a group of chemical, electrochemical and microbiological reactions that are triggered by the exposure of sulphide geological materials to atmospheric water and oxygen. The rivers of Santa Catarina State (Tubaro, Urussanga, and Ararangu) receive the effluents generated from the coalmines. Contamination of the water resources is due to coal drainage from 134 strip mine sites covering a total area of 2964 ha, 115 waste deposit areas on a total of 2734 hectares, 77 sites on 58 hectares with acidic pools, and hundreds of underground mines (ABMC, 2011). However, the production and circulation of acidic streams in dump areas create a problem for land reclamation as it impedes the establishment of vegetation and even causes the disappearance of already well-established vegetation (SIECESC, 2011). The environmental problems are the result of 130 years of mining activity and other pollution sources (Silva et al., 2011a,b,c; Oliveira et al., 2012a,b; Quispe et al., 2012). In 1980, the Santa Catarina Coal Region (Fig. 1) was designated a Critical National Area for Pollution Control and Environmental Conservation. Due to this grave situation, the Federal Attorney General filed suit in 1993 against the federal and state governments and coal companies, seeking environmental recovery of the areas affected by coal mining in addition to termination of the environmental degradation by the active mines. In 2000, a federal judge in Cricima, Santa Catarina, ordered the government-run companies to establish a recovery project within 6 months that would be implemented over 3 years and encompass the damage caused by coal mining activities in the entire coal region in the southern part of the state (SIECESC, 2011). Before this area can be effectively remediated, a sound geochemical model and improved phase characterization is required. The standard methods of sediment contaminant analysis (both mineralogical and elemental) involve scanning electron microscopy (SEM) and X-ray diffraction (XRD). Prior studies of samples collected from this area using SEM have revealed that the mineralogical relationships present within the fluvial sub-environments are extremely complex (Silva et al., 2011d; Silva and DaBoit, 2011). In addition, determining the mineralogy of contaminated samples is critical since the stability/mobility of the elements in different geological environments is dependent not only on the environmental chemistry of the system but also on the crystallinity and chemistry of the metal (loid)-bearing phases (Ribeiro et al., 2010; Quispe et al., 2012; Cerqueira et al., 2012). Her is describe field occurrences and mineralogical data for minerals associated with oxidative weathering of minerals in sediment rivers from coal mining acid drainage (CMAD) by Micro-Raman Spectroscopy, XRD, FE-SEM and HR-TEM at several localities in the Santa Catarina State, Brazil, and also the elemental concentrations present in this sediment with the aim to identify the different pollution areas using Principal Component Analysis (PCA) as a tool. 1.1 Coal mining acid drainage Iron sulphide minerals, especially pyrite (FeS2) and pyrrhotite (Fe1xS), contribute the most to the formation of acid mining drainageAMD (Ros et al., 2008; Oliveira et al., 2012a,b). The pyrite oxidation is controlled by bacterial species that have definite pH growth range and pH growth optimum (Kuhn, 2005). The conversion of Fe 2+ to Fe 3+ in the overall pyrite reaction sequence has been described as the rate determining step, which can be greatly accelerated by bacterial action (Ros et al., 2008). The most common pyrite-oxidising bacterium is Acidithiobacillus ferro oxidans, which is of great practical importance due to the extensive acid and metal pollution generated when this species releases metals from acid mine waters (Prescott et al., 1999). Once pyrite oxidation and acid production have begun, conditions are favorable for bacteria to further accelerate the reaction rate. At pH values of about 6 and above, bacterial activity is thought to be insignificant or comparable to abiotic reaction rates. The knowledge of the mineralogical processes occurs during the atmospheric oxidation of pyrite and other sulphide minerals in the presence of oxidizing bacteria and any other product generated as a consequence of oxidation reactions (e.g., heavy metals solubilised by acid solutions) is very useful in both the prediction of CMAD

and its treatment. Ligands that form complexes with Fe(II), e.g., SO4 2, are known to decrease the oxidation rate (Stumm and Morgan, 1981). Trace amounts of Cu(II) are on the other hand known to catalyze the oxidation (Stumm and Morgan, 1981). Natural organic matter (NOM) can significantly influence the oxidation rate at low partial pressure of O2, possibly by changing the reaction pathway (Liang et al., 1993), though little effect of NOM is seen at atmospheric partial pressure. 2. SAMPLING AND ANALYTICAL METHODOLOGY A map of the area with the location (five regions in Santa Catarina State; Lauro Muller, Treviso, Urusanga, Criciuma and Capiravi de Baixo) and images of the sampling points of sediment rivers (11 samples) all near washing plants of coal process can be seen in Fig. 1. The sediment samples from different rivers of the Tubaro basin were directly stored in 500 mLpolyethylene bottles, while the ochre-ous, colloidal precipitates were taken with 250 mL-syringes and/or by filtering acid water using a manual suction kit. The sampling protocol was developed by Smith et al. (2000) as a statistically based, cost-effective sampling strategy for screening and prioritizing mine waste piles for remediation on a regional or a watershed scale. Use of theb2 mm fraction reduces sampling error and sample size, and provides an estimate of the worst-case scenario for metal leachability (Hammarstrom et al., 2003). Sediments were air-dried, theb80 mesh (b0.177 mm) fraction was sieved out, subsampled, pulverized, and approximately 100 g ofb150 mesh material was submitted for chemical analysis (Hammarstrom et al., 2003). In the extraction method, 0.5 g of dried sediment was transferred to an extraction vessel with 20 mL of HNO3/HCl (Tracepur, Meck) acid mix. Ultrasound energy was applied for 6 min. by means of a HD2070 Sonopuls Ultrasonic Homogenizer (Bandelin), equipped with a 6 mm glass probe. The extract was filtered through a0.45 m filter and diluted in water. The HNO3concentration in the samples was adjusted to 1%. Chemical analysis for trace element determination of Al, As, Fe, K, Na, Ba, Mg, Mn, Ti, V, Zn, Ag, Co, Li, Mo Ni, Se, Sn, W, B, Cr, Cu, Pb and Sr was performed by inductively coupled plasma/mass spectrometry (ICP-MSElan9000 from PerkinElmer, Ontario, Canada) using the external calibration method. Before analysis by ICP/MS, internal standards Be 9, Sc 45 , In 115 and Bi 209 (10gL 1 each) were added to the diluted samples (S. Fdez-Ortiz de Vallejuelo et al. 2008). Blanks were processed in a similar way. All the aliquots were stored at 4 C until analysis. The ICP-MS provided with Ryton cross-flow nebulizer, scott-type double pass spray chamber and standard nickel cones. Data were acquired using Elan 3.4. Common isobaric interferences are preprogrammed and corrections are automatically applied (Carrero et al., 2010). All measurements were run in triplicate. The acquisition masses and integration times provided more than sufficient sensitivity to meet all certified values. Preparation of calibrants and analysis of samples were done inside a clean room(class 100). Argon (99.999%, Praxair, Spain) was used as carrier gas in the ICP/MS measurements. The accuracy of the analytical procedure was verified analyzing the certified reference materials PACS-2 (harbour sediment, National Research Council of Canada, Ottawa, Canada), NIST 1944 (New York/New Jersey waterway sediment, National Institute of Standards and Technology, Gaithersburg, USA), NIST 1646a (estuarine sediment, National Institute of Standards and Technology, Gaithersburg, USA) and SGR-1 (River Shale, US Geological Survey, Denver, USA) with satisfactory results. For quality assurance purposes the certified reference materials PACS-2, NIST 1646a and a freshwater SRM 1640 containing trace elements (Natural Water, National Institute of Standards and Technology, Gaithersburg, USA) were routinely analyzed in each sample batch. 3. CONCLUSIONS

The field investigation carried out showed that sediments in the middle of the Tubaro River and in the Capivari River present the high metal concentration levels. They range between (0.00525) As mgkg 1, (0.557) Pb mgkg 1, (0.00115) Cr mgkg 1, (0.423) Cu mgkg 1or (2984) Zn mgkg 1 for the elements considered as the most hazardous. According to the results, apart from carbon polymorph remains, the sediment drainages were mainly composed by quartz, iron oxides (hematite, goethite and magnetite) and also were identified rutile, and different aluminium-silicates such as amazonite, kaolinite or microcline. Calcite and some sulphates (gypsum, calcium hemihydrates and barite) were occasionally detected in the drainages of certain area studied. The acidity of researched coal mine drainages also depends on Fe 3+ and Al content; the hydrolysis of these substances results in important increases in acidity and provokes the buffering of the AMD systems. These results confirm that the application simultaneity of molecular and elemental analysis may be used to determine the potential risk in a determinate area where coal mining acid drainage is presented. Our results demonstrate that selective management of spoil sites is the restoration practice that offers the best protection against contamination of surface and subsurface waters, providing a suitable procedure to apply in the future construction of dump surfaces. Because improvement in the quality of drainage systems using this practice can significantly reduce the cost of treatment in the purification plant prior to effluents being discharged to the receiving catchment zone.


Figure 1

Figure 1 - Geographical location of the Santa Catarina State (Southern Brazil). and the location of the sampling stations of sediments from drainages acids: SD1 and SD2 (Carbonfera Caratarinese, Lauro Muller), SD3 (Lngua do Drago, Treviso), SD4 (Rio do Rastro, Lauro Muller), SD5 and SD6 (mine of Urussanga), SD7 (Mina of So Geraldo), SD8 (Carbonfera of COMIN, Criciuma) and SD9, SD10 and SD11 (Capivari de Baixo). Figure 2

Figure 2 - Projection of the scores on the space formed by the first, second and third PCs, obtained after Principal Component Analysis (PCA) of the data of trace element concentration in sediments from acid mine drainage from the Tubarao River.

Figure 3

Figure 3 - Minerals in sediments from acid drainages: SEM images and XRD of jarosites, TEM images and TEM/EDS of nanojarosites.

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