Environmental Pollution xxx (2011) 1e6 Contents lists available at ScienceDirect Environmental Pollution journal homepage: www.elsevier.com/locate/envpol Indoor metallic pollution related to mining activity in the Bolivian Altiplano Francisco E Fontúrbel a, *, Enio Barbieri b, Cristian Herbas c, Flavia L Barbieri b, d, Jacques Gardon b, d a Departamento de Ciencias Ecológicas, Facultad de Ciencias, Universidad de Chile, Santiago, Chile IRD-HSM (Institut de Recherche pour le Développement), La Paz, Bolivia c Universidad Mayor de San Andrés, IGEMA Institute (Instituto de Investigaciones Geológicas y del Medio Ambiente), La Paz, Bolivia d Universidad Mayor de San Andrés, SELADIS Institute (Instituto de Servicios de Laboratorio para el Diagnóstico e Investigación en Salud), La Paz, Bolivia b a r t i c l e i n f o a b s t r a c t Article history: Received 31 December 2010 Received in revised form 26 April 2011 Accepted 29 April 2011 The environmental pollution associated with mining and metallurgical activities reaches its greatest extent in several Andean cities and villages. Many locations in this area have accumulated through centuries a large amount of mining wastes, often disregarding the magnitude of this situation. However, in these naturally mineralized regions, there is little information available stating the exact role of mining and metallurgical industries in urban pollution. In this study, we demonstrated that the various metallic elements present in indoor dust (As, Cd, Cu, Pb, Sb, Sn, Zn) had a common origin and this contamination was increased by the proximity to the mines. Lead dust concentration was found at concerning levels for public health. In addition, wrong behaviors such as carrying mining workwear home contributed to this indoor dust pollution. Consequently, the constant exposure of the population could represent a potential health hazard for vulnerable groups, especially children. Ó 2011 Elsevier Ltd. All rights reserved. Keywords: Geostatistical analysis Household dust Human exposure Metallic trace element Mining pollution 1. Introduction Altiplanic regions in South America are naturally rich in polymetallic deposits (Clark et al., 1990), which is why mining and metallurgical activities play a fundamental role in the economy of these populations. In the Bolivian Altiplano mining has been an essential activity since pre-Colonial times (Abbott and Wolfe, 2003) and many villages, towns and even cities were developed in close proximity to the mines and smelters. In the last years, in spite of the strong variations in the trading value of base metals, the global demand still stands. As a consequence, extractive activities are currently intense even at several formerly abandoned mines. For economic, political, and social reasons, there is little or no control over the consequent contamination. The mining wastes create a permanent source of pollution (Miller et al., 2004; Reif et al., 1989; Smolders et al., 2003), especially in these arid and windy regions where metallic elements deposited in soils can be easily dispersed through air. In the Oruro mining district, where numerous mines and large smelters are currently in activity, the environmental contamination by a complex cocktail of Pb, Sn, Sb, As, Cd, and other elements is known (Díaz-Barriga et al., 1997a, 1997b; PPO, 1997). The consequences of chronic exposure to these metallic elements are potentially dangerous for children and women of childbearing age (Calderón et al., 2001; Díaz-Barriga et al., 1997a; Koller et al., 2004; * Corresponding author. E-mail address: [email protected] (F.E. Fontúrbel). Landrigan et al., 2004; Lidsky and Schneider, 2003). Handto-mouth dust ingestion constitutes an important pathway of exposure especially for toddlers and young children. As a consequence, metallic element concentration in indoor dust is crucial in describing the risk of exposure. Our study aimed to verify the existence of a significantly higher household contamination in a Bolivian mining town, comparing indoor dust trace element concentrations obtained from the mining district and from a peripheral district, relatively far from mining or metallurgical activities. 2. Material and methods 2.1. Study area The city of Oruro (17.97 Se67.10 W; Fig. 1) is located in the central Bolivian Altiplanic region, at 3700 m of altitude above sea level. Oruro city has 220,000 inhabitants (w2.4% of the Bolivian population, according to the National 2001 Census: INE, 2001), mainly dedicated to mining and metallurgical activities and trading (Langer, 2009; Montes de Oca, 1997). Because of its location at the topmost of the Altiplano, Oruro is a windy city. According to the Bolivian Meteorological Service, the average of daily maximum wind speeds was w15 km/h in 2006 (SENAMHI, 2011), reaching annual maximum wind speeds around w37 km/h from 2001 to 2010. The total annual precipitation for the same decade was w400 mm, with a remarkable difference between the rainy season (w250 mm from December to February) and the dry season (w11 mm from May to July). In the arid environment of the Altiplano, the vegetation coverage of the soil is rather scarce. Additionally, its location near several mining centers (which usually do not properly cover residual materials, storage facilities, and trucks) and sand dunes makes Oruro a dusty city. Those are risk factors for the metallic elements widespread. 0269-7491/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.envpol.2011.04.039 Please cite this article in press as: Fontúrbel, F.E., et al., Indoor metallic pollution related to mining activity in the Bolivian Altiplano, Environmental Pollution (2011), doi:10.1016/j.envpol.2011.04.039 2 F.E. Fontúrbel et al. / Environmental Pollution xxx (2011) 1e6 Fig. 1. Sampling sites location in the urban area of Oruro. 2.2. Samples and data collection We sampled two locations in Oruro; the first was San José (17.95 Se67.12 W; hereafter mining district) chosen due to its proximity to two important mines of Oruro: San José and La Colorada. The second location sampled was Villa Challacollo (18.01 Se67.14 W; hereafter peripheral district), located at the southern periphery of the city, approximately at 3.5 km from the nearest mine. We sampled a total of 98 households, 57 at the mining district and 41 at the peripheral district. We collected samples of around 1 g of dust from the top surfaces of furniture or windowsills using a 1.5” brush previously treated with deionized and ultrafiltered water. We kept the samples in sealed polyethylene bags to avoid contamination and delivered them directly to the laboratory. We georeferenced each house, using a GPS (Global Positioning System). We also conducted a questionnaire on several socioeconomic factors, focusing on the working habits of each family, especially regarding mining activities. We specifically inquired whether someone in the family worked at the mine or not; if so, we inquired if they carried home their work clothes or tools. 2.3. Sample preparation and analysis We analyzed dust samples at the Geological and Environmental Research Institute (IGEMA) of the Universidad Mayor de San Andrés in La Paz, Bolivia. We determined metallic elements concentrations using ICPeOES (Inductively Coupled PlasmaeOptical Emission Spectrometer). Considering the health impact of the potential human exposure, we chose to measure Pb, As, Cd, Sb and Sn as nonessential (or potentially toxic) elements, as well as Cu and Zn as essential elements. Each sample was previously homogenized; a sub-sample of 0.5 0.0001 g was transferred to a 50 mL digestion tube with 6 mL of HCl and 2 mL of HNO3, and digested in a microwave oven for 45 min. Samples were degasified, cooled, and transferred to a 100 mL flask in order to extract some remaining insoluble silicate particles. Standard solutions were prepared and the samples were analyzed at the ICPeOES spectrometer. We used two types of reference materials, the first set was provided by Canadian Association for Environmental Analytical Laboratories (CAEAL), and the second set was provided by the National Research Council of Canada; reference standards of the first were: C17 (metals in soils), C17e3 (low range), C17e4 (high range); and for the second set: HISS-1 (low range, marine sediment reference materials for trace elements and other constituents), MESS-3 (mid range), and PACS-2 (high range). 2.4. Data analysis We checked data for normality with the KolmogoroveSmirnov test and used logarithmic or BoxeCox transformations to normalize data distributions, when necessary. To assess differences in metal concentrations between the mining and peripheral districts, we performed a one-way Multivariate Analysis of Variance (MANOVA), operating the seven metallic concentration variables as a single Please cite this article in press as: Fontúrbel, F.E., et al., Indoor metallic pollution related to mining activity in the Bolivian Altiplano, Environmental Pollution (2011), doi:10.1016/j.envpol.2011.04.039 F.E. Fontúrbel et al. / Environmental Pollution xxx (2011) 1e6 Table 1 Theoretical semivariogram models of prediction and data transformations. Metal Method Semivariogram model Nugget/sill Transformation As Cd Cu Pb Sb Sn Zn Ordinary Kriging Ordinary Kriging Ordinary Kriging Ordinary Kriging Simple Kriging Ordinary Kriging Ordinary Kriging Spherical Circular Rational quadratic Rational quadratic Rational quadratic Exponential Exponential 0.776 0.761 1.506 0.939 1.699 0.997 0.956 Log BoxeCox Log Log Log Log Log 3 At the mining district, having at least one family member working in a mine significantly increased the polymetallic indoor dust concentrations (Wilks’ lambda ¼ 4.85, hypothesis df ¼ 7, error df ¼ 49, p < 0.001). Regarding people’s habits, carrying work tools home had no significant effect on indoor polymetallic concentrations (Wilks’ lambda ¼ 0.76, hypothesis df ¼ 7, error df ¼ 20, p ¼ 0. 62), but these significantly increased when work clothes were carried home (Wilks’ lambda ¼ 3.06, hypothesis df ¼ 7, error df ¼ 20, p ¼ 0.02). 3.2. Geostatistical analysis and spatial distribution response vector. Then, we performed additional MANOVA tests only for the mining district data (because there were no miner workers at the peripheral district), in order to test effects of: (1) having at least one person working at the mine, (2) if work clothes were carried home, and (3) if work tools were carried home. We did not test interactions because the statistic power was <0.85 for those tests. We chose Spearman correlation to construct correlation matrix separately for each district (based on the untransformed data), because the normalizations of trace element distributions were not obtained with the same transformation. For each test, equality of variances was checked through a Levene test (Sokal and Rohlf, 1995). All analyses were conducted using PASW Statistics 18 (SPSS Inc., 2009). 2.5. Geostatistical analysis based on GIS We estimated the distances from each sampling point to the mines using ArcGIS v.9.1 (ESRI Co., Redlands CA). We employed spatial interpolation and GIS mapping techniques to generate prediction maps with the spatial distributions of the seven assessed metallic elements. All procedures were conducted using the Geostatistical Analyst module of ArcGIS, following Shi et al. (2008). We used a Kriging interpolation, with data transformations when necessary to ensure the normality of residuals (Table 1). Theoretical semivariogram models were used to build the prediction maps, a nugget/sill ratio criterion was used to optimize data sets reducing the spatial autocorrelation (Shi et al., 2008). Using only the mining district points (n ¼ 57), we have estimated critical distances for each metallic element. As there are no maximum tolerable limit values published for domestic dust, for all the elements assessed here, we defined the critical concentration area as the maximum radius of the highest concentration contour on the prediction maps, which is calculated from the largest distance vector, derived from the semivariogram model. Consequently, ranges with the highest metal concentration were: 364e636 ppm for As, 48e101 for Cd, 382e617 for Cu, 4036e8413 for Pb, 2712e6199 for Sb, 638e1172 for Sn, and 1310e2295 for Zn. We repeated this analysis using only the Pb Kriging, since it is the most health-risky element and the only one with a maximum tolerable limit in dust published by the EPA (2001). Then, we estimated the risky area of Oruro, as the area comprised in all contours, which Pb content in dust was above 400 ppm. 3. Results 3.1. Metallic trace element concentrations For all metallic elements assessed, concentrations were higher and more variable at the mining than at the peripheral district (Table 2). Metal concentrations were strong and significantly correlated at the mining district (Table 3), and varied significantly between the mining and the peripheral districts (Wilks’ lambda ¼ 13.11, hypothesis df ¼ 7, error df ¼ 90, p < 0.001; Fig. 2). Prediction maps showed a differential spatial distribution among the seven assessed metals in Oruro (Fig. 3). Concentrations at the mining district were critical for As, Cu, Pb, and Zn, whereas Sb and Sn showed a more homogeneous spatial distribution, despite also being higher at the mining district. From the mining district data, we estimated a high-metallic concentration distance of 1113 184 m (mean 1SE), based on the higher concentration contour of each element. When considering only Pb content in dust, and the 400-ppm limit defined by EPA for Pb contents in soil, we estimated a high exposure area of 1305 ha, above the permitted limits. With such approach, this area is not limited to the mining district, but also comprises downtown and the some peripheral area southward. 4. Discussion The present results allowed us to assess the general situation of indoor metallic trace elements contamination in the city of Oruro. It showed us effectively which elements were present in the household dust and, consequently, in direct contact with the people from the two selected districts. As seen on the prediction maps, the spatial distribution of the metallic elements in dust is not homogeneous. We found a considerable difference in the metallic elements concentrations between the two districts, being consistently higher in the Mining district. The most remarkable case is in the concentrations of Pb and Sb, which were four times higher in the Mining district than in the Peripheral district. There was a strong correlation among most metallic trace elements (Table 3), suggesting a common origin for the polymetallic contents in household dust. This correlation was consistent in both districts. Likewise, our prediction maps show that, in spite of slight differences in the different metallic elements’ spatial distribution, there is an identifiable pattern common to all of them. The areas with the highest concentrations were very similar for all the elements, significantly higher near around the Mining district. Cases reporting metallic elements exposure emitted from workplaces can be found in the literature (Abdul-Wahab and Yaghi, 2004; Maharachpong et al., 2006). Previous studies have demonstrated Table 2 Metal concentrations (ppm) determined in domestic dust in Oruro. Metallic element As Cd Cu Pb Sb Sn Zn Mining district Peripheral district Arithmetic mean (Standard error) Geometric mean MineMax value Arithmetic mean (Standard error) Geometric mean MineMax value 143.38 15.96 114.30 1289.78 494.44 114.13 583.75 90.28 11.48 88.97 619.11 152.91 76.39 442.91 12.90e635.55 4.60e101.34 30.30e471.25 66.60e8413.45 21.50e6199.35 19.60e1172.35 119.30e2295.22 42.50 6.05 77.02 221.43 46.43 36.21 252.06 41.68 5.94 56.56 133.66 39.23 33.90 228.34 30.19e68.75 4.19e10.31 23.90e617.20 48.51e2415.25 18.11e203.65 19.49e76.87 132.00e843.38 (19.33) (2.49) (12.43) (235.36) (138.50) (21.73) (64.69) (1.40) (0.20) (15.27) (60.59) (5.93) (2.16) (21.00) Please cite this article in press as: Fontúrbel, F.E., et al., Indoor metallic pollution related to mining activity in the Bolivian Altiplano, Environmental Pollution (2011), doi:10.1016/j.envpol.2011.04.039 4 F.E. Fontúrbel et al. / Environmental Pollution xxx (2011) 1e6 Table 3 Spearman correlation coefficients of metal concentrations, values above the diagonal correspond to the mining district (n ¼ 57), and values below the diagonal correspond to the peripheral district (n ¼ 41). As Cd Cu Pb Sb Sn Zn As Cd Cu Pb Sb Sn Zn 1.000 0.689** 0.674** 0.304 0.407* 0.666** 0.456* 0.882** 1.000 0.610** 0.332* 0.418* 0.690** 0.478* 0.806** 0.791** 1.000 0.324* 0.373* 0.673** 0.607** 0.880** 0.894** 0.766** 1.000 0.807** 0.403* 0.523** 0.785** 0.820** 0.795** 0.834** 1.000 0.505** 0.423* 0.839** 0.761** 0.783** 0.766** 0.761** 1.000 0.551** 0.734** 0.710** 0.532** 0.683** 0.523** 0.694** 1.000 * Significant at p < 0.05. ** Significant at p < 0.001. Italic values stand for rank correlation above 0.6 and bold values above 0.8. that when a stationary metal source exists nearby the city, there are usually high metal concentrations in soils (Gallagher et al., 2008; Madrid et al., 2008; Shi et al., 2008), which are usually correlated with the dust concentrations (Louekari et al., 2004; Murgueytio et al., 1998; Thornton et al., 1990; von Lindern et al., 2003). As a matter of fact, the most significant factor in our study was the distance between the household and the mines. Our geostatistical analyses showed a high-exposure radius (ranging from 543 m to 1.8 km) around the mines and mineral processing facilities, in the Mining district. The San José district and its surroundings were not intended to be a residential area (in fact, it was designed to be a mining camp), but it gradually went populated by miners and their families, due to its proximity to the work place. Later on, non-miners families also contributed to the population of these mining areas, bringing also commercial activities, a hospital, a school, etc. However, metallic elements concentrations not only depended on the distance to the mines. In the particular case of the miners, the habits of carrying their workwear home contributed to increase dust indoor metal concentrations, by means of carrying every day metal particles into the household. This kind of relationship was Fig. 2. Metallic elements profile by district. Z-score represents standardized data after a log10 transformation (to smooth outliers). All mining-peripheral district pairwise comparisons were significantly different (p < 0.05, after a ManneWhitney test), except for Zn. previously observed in other studies (Maharachpong et al., 2006; Sutton et al., 1995). Metal particles present in dust will no self-degrade or naturally diminish in the environment, residing for a long time (Stigliani et al., 1991). Consequently, they will accumulate as long as dust is not removed, which is why the indoor dust metal concentrations will increase proportionally according to the amount of dust. This contaminated dust can be easily dispersed through wind (Fields, 2003; Louekari et al., 2004), and deposited as dust in houses, schools, and streets. For many physiological and behavioral reasons, children are a vulnerable group for this particular scenario (Landrigan et al., 2004). Furthermore, they are more likely to spend time doing sports and other outdoors activities. This can increase their exposure, not only by airborne particles inhalation, but most importantly dust ingestion (Díaz-Barriga et al., 1997a; Landrigan and Todd, 1994; Mielke et al., 1997). Taking Pb as a major concern, the concentration in dust was significantly higher at the mining district than in peripheral district (see Pb bars on Fig. 2), being the mining district concentrations considerably above the EPA (2001) reference levels for soil. Based on EPA (2001), ATSDR (2005), and Díaz-Barriga et al. (1997a) criteria, Pb ingestion in the mining district children might be up to six times higher than those from the peripheral district, and also up to five times higher than the Tolerable Daily Intake (TDI) values recommended by FAO and WHO (Table 4). Certain particular characteristics in the city of Oruro might increase dust accumulation and the subsequent human exposure to the metallic elements, such as the dry weather with strong winds, lack of vegetation and dust roads. Besides, in the studied districts the housing conditions are representative of a difficult socioeconomic situation (Table 5). Many houses lack ceiling or wall coating, and around half of them have precarious floors, being considerably unprotected against the wind and dust. A recently published study assessed children exposure using a biomarker in the city of Oruro (Barbieri et al., 2011). The authors sampled hair from school-age children from different districts of Oruro, including the mining district and the peripheral district, aiming to compare the general situation of metallic trace element exposure. The houses sampled in our study corresponded to the same children who participated in the study by Barbieri et al. (2011). Consistently, in their study the children from the mining and the metallurgical district showed significantly higher metallic concentrations in hair, compared to the children from the other districts, being the peripheral district the one with the lowest hair metallic levels in Oruro. Those results corroborated our assumption that the children from the mining district were more exposed to metallic elements, considering that the sampled dust from their houses also showed the highest metallic concentrations. Please cite this article in press as: Fontúrbel, F.E., et al., Indoor metallic pollution related to mining activity in the Bolivian Altiplano, Environmental Pollution (2011), doi:10.1016/j.envpol.2011.04.039 F.E. Fontúrbel et al. / Environmental Pollution xxx (2011) 1e6 5 Fig. 3. Prediction maps of metal distribution in domestic dust in Oruro. Dotted polygons indicate the study locations and the dots indicate the sampling points. Table 4 Pb daily intake (mg/day) for children according to location and for different dust ingestion scenarios using geometric mean (GM) and 75th percentile (P75) of lead concentrations in household dust. Location EPAa GM e P75 ATSDRb GM e P75 Díaz-Barriga et al. (1997a),c GM e P75 TDId Mining district Peripheral district 53e99 11e17 62e117 13e20 217e408 47e69 87.5 Dust ingestion criteria: a EPA: 85 mg of dust a day for a 6 years old child (2001). b ATSDR: 100 mg of dust a day (2005). c Díaz-Barriga et al.: 350 mg of dust a day (1997a). d Tolerable Daily Intake Values are based on FAO/WHO guidelines (UNEP, 2006), and calculated with a mean weight of 25 kg. 5. Conclusions There is a clear situation of metallic trace elements contamination in the city of Oruro, much higher in the surroundings of the mines and mineral processing facilities. This constant exposure of the population, especially children, could represent a significant risk. We can only theorize about the potentially harmful impact on human health and children development, but so far no health impact studies have been published in this particular region. Either way, considering the toxic potential of these elements, measures could be undertaken to minimize children contact with contaminated dust, including some important changes in the population’s habits. It would be suitable, in this mining city, to reconsider the Please cite this article in press as: Fontúrbel, F.E., et al., Indoor metallic pollution related to mining activity in the Bolivian Altiplano, Environmental Pollution (2011), doi:10.1016/j.envpol.2011.04.039 6 F.E. Fontúrbel et al. / Environmental Pollution xxx (2011) 1e6 Table 5 General characteristics of the households in the city of Oruro, by district. Household characteristics Roof without ceiling Wall without coating* Precarious floor House without essential services Miner in the household They bring home their clothes** They bring home their tools They bring home both their clothes and their tools Mining district (n ¼ 57) 12 39 30 33 28 21 24 18 (21.05%) (69.64%) (52.63%) (57.89%) (49.12%) (75.00%) (85.71%) (64.29%) Peripheral district (n ¼ 41) 12 (29.27%) 20 (48.78%) 19 (46.34%) 30 (73.17%) None *Significant difference at p ¼ 0.04. **Significant difference at p ¼ 0.02. general organization of their land use planning, in order to keep a healthy distance between their mining/metallurgical areas and their urban areas. Acknowledgments We thank all the house owners who allowed us to take samples in their homes. S. Ignacio helped with the questionnaire surveys. E. Silva helped with the statistical analyses. R. Llano collaborated with a map. FEF was supported by a doctoral fellowship of the Chilean Foundation for Science (CONICYT). 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