Anda di halaman 1dari 10

Science of the Total Environment 449 (2013) 363372

Contents lists available at SciVerse ScienceDirect

Science of the Total Environment


journal homepage: www.elsevier.com/locate/scitotenv

Contribution of mine wastes to atmospheric metal deposition in the surrounding area of an abandoned heavily polluted mining district (Rio Tinto mines, Spain)
Sonia Castillo a,, Jess D. de la Rosa a, b, Ana M. Snchez de la Campa a, Yolanda Gonzlez-Castanedo a, Juan C. Fernndez-Caliani a, b, Isabel Gonzalez c, Antonio Romero c
a Associate Unit CSIC-University of Huelva Atmospheric Pollution, Centre for Research in Sustainable Chemistry (CIQSO), Campus of Excellence CeiA3, University of Huelva, E27071 Huelva, Spain b Department of Geology, Faculty of Experimental Sciences, University of Huelva, E21071 Huelva, Spain c Department of Crystallography, Mineralogy and Agricultural Chemistry, Faculty of Chemistry, University of Seville, 41071 Seville, Spain

H I G H L I G H T S Metal dust appears in areas exposed to dust-bearing winds owing from Rio Tinto mine. PM deposited is characterized by enrichment in potentially toxic metals/metalloids. Mine waste source made up of elements such as Cu, Zn, As, Sb, Ba, Pb, Sn, Cd and Bi. A decrease in deposition uxes is observed as we move away from the waste deposits. Particle grain segregation is observed during metal dust transport from mine waste.

a r t i c l e

i n f o

a b s t r a c t
The present study seeks to estimate the impact of abandoned mine wastes on the levels and chemical prole of total atmospheric deposition in one of the oldest and largest mining districts in Europe (Rio Tinto mines, Iberian Pyrite Belt), on the basis of a complete geochemical characterization of particulate matter samples periodically collected in ve sampling stations located around the mining district between March 2009 and February 2011. The annual levels of total bulk deposition (soluble and insoluble fractions) registered in the Rio Tinto Mining District ranged between 18 and 43 g/m2 depending on the distance from the sampling station with regard to the mine waste deposits. As a general pattern in the area, high mass levels of Zn and Cu were deposited in a range of 962 mg/m2 not only in the insoluble but also in the soluble fraction. Other potentially toxic trace elements such as As, Sb, Ba, Pb, Sn and Bi showed greater deposition uxes in the locations closest to the mine waste deposits. A principal component analysis with a Multilinear Regression Analysis certies the presence of two common sources in the mining area: 1) a mineral factor composed mainly of elements derived from silicate minerals + 2 , SO4 , NO3 ) within (Al, Ca, Sr, Ti, Li, Mg, Mn, K, Na and Fe), mixed with other anthropogenic species (NH4 2 the village closest to the mine; and 2) a marine factor composed of Na, Cl, Mg, SO4 and Sr. In addition, a mine waste factor made up of toxic elements (Cu, Zn, Ga, As, Sb, Ba, Pb, Sn, Cd and Bi) has been recognized in the sampling sites exposed to dust-bearing winds downwind of the mining area, suggesting that mine wastes are a relevant source of heavy-mineral particles with potentially adverse environmental effects to surrounding soils, plants and humans. 2013 Elsevier B.V. All rights reserved.

Article history: Received 20 October 2012 Received in revised form 24 January 2013 Accepted 25 January 2013 Available online 26 February 2013 Keywords: Atmospheric deposition Mine wastes Metals Insoluble fraction Soluble fraction Rio Tinto mines

1. Introduction In ancient mining districts with long histories of mining and metallurgical activity, mine wastes represent one of the main sources of pollution to soils, water, air and biota (Hudson-Edwards et al., 2011;

Corresponding author. Tel.: +34 959219821. E-mail address: sonia.castle@gmail.com (S. Castillo). 0048-9697/$ see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.scitotenv.2013.01.076

Csavina et al., 2011, 2012). Oxidation of sulphide minerals in mine wastes (Nordstrom, 2011) generates acid water loaded with dissolved iron, sulphates and potentially toxic elements (As, Se, Cu, Zn, Cd, Hg, and more), which are discharged into proximal uvial and estuarine systems adversely affecting water and soil quality (Galn et al., 2003). However, this is not the only possible cause of water and soil contamination. The atmospheric dispersion of particulate matter (PM) by air is also a signicant contributor of contaminants to the environment. Particle resuspension from open-cast mining, metallurgical activities

364

S. Castillo et al. / Science of the Total Environment 449 (2013) 363372

and mine waste dumps are important mechanisms whereby the contaminants can be redistributed in the environment, mainly the metallic species (Ghose and Majee, 2000; Zota et al., 2009; Brotons et al., 2010; Taylor et al., 2010; Pumlee and Morman, 2011; Csavina et al., 2011). Unlike water, soil and biota, air masses are not conned to an extension with topographic boundaries or barriers, thereby preventing their transportation (McGechan and Lewis, 2002; Mulligan and Yong, 2004; Braune et al., 2005). In addition, air masses have the greatest potential to transport contaminants rapidly (from hours to days) through the environment due to the fact that they move faster than water and soil particles. This contamination not only occurs when the mines are in operation, but the resuspension of metalbearing particles from abandoned mine waste deposits could also be an important source of pollutants to air and may have a signicant impact on the surrounding environment (Chopin et al., 2003; Ekosse et al., 2004; Chopin and Alloway, 2007; Lehndorff and Schwark, 2008; Lpez et al., 2008). Resuspension of large quantities of PM from mine waste deposits, whether active or abandoned, and mainly associated to wind events, may have adverse health effects for people living nearby through different intake pathways, such as inhalation, ingestion and/or dermal contact (Pumlee and Morman, 2011). Metal coarse particles resulting from mine waste resuspension can be deposited in the upper respiratory system, swallowed and go through the digestive system where contaminants may be absorbed, depending on their bioavailability (Krombach et al., 1997; Park and Wexler, 2008; Valiulis et al., 2008). Not only the metallic particles have a direct impact on human health, but some studies have found negative effects from metals and metalloids on plant matter also (Chardonnens et al., 1999; Ernst and Nelissen, 2000; Alonso et al., 2002; Kim et al., 2003; Youse et al., 2011). Although living organisms generally need trace amounts of elements (including metals) for good health, it has been shown that large amount of these elements may cause chronic or acute toxicity (Trepka et al., 1997; Benin et al., 1999; Kpper et al., 2002). At the Rio Tinto Mining District (RTMD), in SW Spain, there is strong evidence of soil pollution by heavy metals (Fernndez-Caliani and Galn, 1996; Chopin et al., 2003; Gonzlez et al., 2004; Chopin and Alloway, 2007; Lpez et al., 2008; Fernndez-Caliani et al., 2009). Recently, Snchez de la Campa et al. (2011) have described and quantied the composition and concentration of respirable atmospheric particulate matter (PM10) in RTMD by measuring the windmobilized material from the mine wastes, and a preliminary study by Fernndez-Caliani et al. (2010) showed that atmospheric deposition of heavy-mineral particles (mainly pyrite and chalcopyrite) could have potential effects on soils and plants around the mining area. In fact, Gonzlez et al. (2008) and Romero et al. (2012) found high levels of As, Cd, Co, Ni and Zn in the leaves of the citrus trees surrounding the mines, and they identied a direct correlation between the metal concentration range of the plants and the distance to the mine wastes, principally in the prevailing wind direction NWSE. In this paper, a complete chemical characterization and quantication of the deposition uxes, and identication and quantication of the emission sources based on receptor modelling tools were made in order to determine the contribution of mine wastes to levels and chemical prole of atmospheric PM deposited in the RTMD.

base metals (Zn, Cu, Pb) and a variety of associated trace elements (As, Cd, Tl, Sn, Hg, Ag and Au, among others). The Rio Tinto orebodies have been exploited since pre-roman times for their valuable copper, gold and silver deposits, although the most intensive period of mining operations occurred between the end of the 19th century and the middle of the 20th century when pyrite was the main raw material used for sulphuric acid production by the European chemical industry. The mining, mineral processing and smelting activities have generated huge amounts of hazardous mine waste (ore stockpiles, slag deposits, spoil heaps, mine tailings and waste rock piles) deposited over extensive areas (Fig. 2). These deposits are affected not only by water run-off and leaching, but also by wind erosion. The most widespread waste rocks are composed mainly of primary minerals such as quartz, feldspars and micas, but they also contain metal-bearing phases the principal being pyrite with minor chalcopyrite, sphalerite, galena and arsenopyrite, and their secondary weathering products such as hematite, goethite, jarosite and sulphate eforescences. Therefore, these materials have the potential for releasing potentially toxic and environmentally harmful trace elements, such as As, Cu, Pb and Zn, into the environment (Lottermoser, 2007; Romero et al., 2006; Chopin and Alloway, 2007; Lpez et al., 2008; FernndezCaliani et al., 2009). This region is characterized by a dry Mediterranean climate modied somewhat by Atlantic inuences with long dry summers, and short mild winters. According to historic climate data (18871987) recorded by the Rio Tinto Co. Ltd., the mean annual precipitation is 742 mm and the mean annual temperature is 18 C. In summer, evaporation of acid sulphate waters causes precipitation of eforescent iron sulphate minerals on the surface of the waste piles and along the banks of streams (Lottermoser, 2007). During the study period the prevailing wind direction in the area was NWNNW and SESSE (Fig. 1).

3. Methodology 3.1. Sampling A total of ve deposition collectors were placed in the mining area (Fig. 1). One of them (Cementerio, CEM) was placed in the immediate vicinity of the biggest abandoned mine waste deposit. Another collector (Rio Tinto Fruit, RTF) was situated in a citrus exploitation near the mine waste deposits where high levels of heavy metals in the leaves of the citrus trees were found. Another two collectors were placed in the village of Nerva, one (Ayuntamiento, AYU) on the Town Hall terrace, and another (Centro de Transportes, CTRA) near the truck-transfer station and the main road of the village. The village of Nerva, with a population of 6000 inhabitants, is the most potentially affected area by mining activities and their consequences were once abandoned. AYU and CTRA stations along with CEM were placed in the prevailing wind direction NWSE (Fig. 1). The last sampling site, Las Delgadas (LD), was located further from the rest, at 6 km SSSW from the waste deposits (Fig. 1). This sampling site was selected as a background station. Sampling was performed from March 2009 to February 2011 in AYU, CEM, CTRA and RTF and from October 2009 to February 2011 in LD, at a rate of 1 sample/15 days in an open bulk deposition collector MCV-PS model (placed 1.5 m above the ground). This model consists of a 30.5 cm diameter collector connected to a 10 l polyethylene bottle. In the case of samples in absence of precipitation, the collector was cleaned with 200 ml of MilliQ grade distilled water. In the presence of precipitation the rainwater was collected and then the collector was cleaned with distilled water. In each sampling, the polyethylene bottle was retrieved and replaced by one cleaned in the laboratory (washed with 1% HNO3 solution and MilliQ grade distilled water). Blanks of MilliQ grade distilled water were analyzed with the samples to ensure that there was no contamination between samples.

2. The study area Rio Tinto is one of the oldest and best-known mining districts in the Iberian Pyrite Belt (IPB, Fig. 1), a vast mineralised zone that extends along the south-western margin of the Iberian Peninsula, hosting a large number of volcanogenic massive sulphide deposits (Leistel et al., 1998). The ore deposits are mineralogically composed mainly of pyrite (FeS2), with minor amounts of sphalerite (ZnS), chalcopyrite (CuFeS2) and galena (PbS), and so they are characterized by an abundance of

S. Castillo et al. / Science of the Total Environment 449 (2013) 363372

365

-6.60o
-8 42 40 38 36 -4 0 4

-6.58o

-6.56o

-6.54o 37.74o

Rio Tinto mining district

37.72o

37.70o

37.68o

NNW N NNE NE NW WNW W WSW SW SSW S SSE ENE E ESE SE

N
500 m

37.66o

Fig. 1. Map of the Rio Tinto Mining District showing the wind rose diagram for the period March 2009 to February 2010.

3.2. Chemical analysis Upon sampling, pH, conductivity and alkalinity were measured in unltered samples. Later, the samples were ltered through 0.45 m quartz microber lters Munktell (47 mm of diameter), to separate the soluble and insoluble fractions. A) Soluble fraction To determine the deposition levels of soluble material the samples were ltered. An aliquot of each ltered sample was acidied with 1% HNO3 for the analysis of major elements by ICP-OES. An unaltered 2 aliquot was used for the analysis of soluble anions (SO4 , NO3 and + Cl ) and ammonium (NH4 ) by Ion Chromatography. The quality of data was veried by the ionic balance method in all the soluble fraction samples. The ionic balance in a solution is represented by the cation/anion ratio, which should approach 1 (number of cations is equal to number of anions). In experimental chemistry this ratio ranges between 0.8 and 1.2 due to the occurrence of species such as certain organic acids that are not represented in the alkalinity measure in precipitation. B) Insoluble fraction The insoluble fraction was measured in the solid residue deposited in the lters. To determine the major and trace element concentrations we used the procedure developed by Querol et al. (2001). A half of each lter was digested in closed PFA (peruoroalkoxy) reactors with HNO3:HF:HClO4 (1:2:1) at 90 C. Subsequently, the acidic solution was cooled and dried on a hot plate at 200 C. The dry residue

was re-dissolved in 1.25 ml of HNO3 and MiliQ grade distilled water, and subsequently made up to the volume of 25 ml. Finally, we obtain a 5% acidied solution. The contents of major and trace elements were determined by means of ICP-OES and ICP-MS. Blank values corresponding to blank Munktell lters were subtracted from measured concentrations. Certied reference materials (SRM 1633b, y ash) were run throughout the analyses. Total carbon content was measured using a LECO analyzer. For most elements, average precision and accuracy are lower than the typical analytical errors (35% and 10% for ICP-OES and ICP-MS, respectively). Indirect concentrations of some compounds were calculated. The silica and carbonate contents were estimated by stoichiometry from the content of Ca, Mg and Al, on the basis of former experimental equations 2 by Querol et al. (2001): 3Al2O3 = SiO2; 1.5Ca + 2.5 Mg= CO3 . The levels of C non-mineral (organic plus elemental carbon) were estimated by subtracting the C carbonate from the direct C total determinations. 3.3. Source apportionment Receptor modelling techniques were applied to identify sources and to quantify their contribution to the PM deposited. A varimax rotated Factor Analysis (FA-PCA) followed by a Multilinear Regression Analysis (PCA-MLRA) was performed to identify the main sources affecting the aerosol composition (Thurston and Spengler, 1985). This technique was chosen because of its simplicity and suitability for this type of data (Harrison and Pio, 1983; Henry et al., 1984). In PCA-MLRA, given that the data are normalized during the PCA analysis, factors with

366

S. Castillo et al. / Science of the Total Environment 449 (2013) 363372

Fig. 2. Panoramic view of the abandoned mine wastes of Cerro Colorado, taken from the southern side of the mining district of Rio Tinto.

eigenvalues greater than 1 are retained, as they account for more variance than the original variables. The components with higher loadings in each factor were interpreted as ngerprints of the emission sources in order to identify the actual emission sources in accordance with the chemical emission proles. The quantitative contribution of each factor was then derived by MLRA using the bulk mass concentration deposited values as the dependent variable, and absolute factor scores (as dened by Thurston and Spengler, 1985) as independent variables (Harrison et al., 1997). The main limitations of FA are: (a) that it is unable to produce a ne resolution of the sources, and (b) that it provides no information on their geographical location (Henry et al., 1984). FA-PCA results were only accepted when the sum of the principal components accounted for more than 70% of the total variance of the dataset, and the PCA-MLRA results were only accepted when the R2 between the modelled and the gravimetric results was greater than 0.85. 4. Results and discussion 4.1. Total deposition During the study period (from March 2009 to February 2011), the acidity of the bulk deposition showed a marked seasonality in the RTMD (Fig. 3A). In summer, the deposition was more alkaline than in winter. This marked seasonal variation in pH values matches with the tendency registered in Spain (Castillo, 2006) responding to the geochemical aerosol conduct in the Mediterranean area (including the Atlantic zone of the Iberian Peninsula). Due to the aridity of the surface (causing greater soil resuspension), the low precipitation levels (causing greater residence time in aerosols in atmosphere) and the greater afuence of African dust intrusion episodes registered during the warm season in the Mediterranean area (Rodrguez et al., 2001; Escudero et al., 2005), the presence of cations in atmosphere, in suspension and deposition (Ca2+, K+, Mg2+, P3+, Ti2+), was bigger than in the cold season. The levels of acids in atmosphere (H2SO4, SO2, HNO3, NO2) in the study area were similar throughout the year, whereas the cations presented greater levels in the warm season. For this reason, there is a

predominance of cations in atmosphere and deposition in the Mediterranean area (Castillo, 2006). The annual uxes of total bulk deposition (soluble and insoluble fractions) registered in the RTMD surface area were between 18 and 43 g/m2 depending on the distance to the mine waste deposits from the sampling site (Table 1). The locations that registered greater annual deposition uxes were CEM, AYU and CTRA with 24.842.7 g/m2 from March 2009 to February 2010, and 29.640.7 g/m2 from March 2010 to February 2011 (Table 1). Such sampling sites were oriented to the prevailing wind direction (NW) and, therefore, exposed to dust-bearing winds downwind of the mine wastes (Fig. 1). Of the three locations mentioned above, it was in CEM (in close proximity to the biggest mine waste deposit) where a greater mass deposition was registered (42.7 and 33.8 g/m 2 for the rst and the second study year, respectively). The RTF and LD sampling stations registered apparently lower deposition levels, although RTF (34.5 g/m2) registered greater levels than AYU (29.6 g/m2) in the period March 2009 to February 2010. It must be noted that RTF, like CEM, is situated near the biggest mine waste deposit but, however, not exposed to the prevailing winds (Fig. 1). Finally, LD (the farthest location from the mining district) registered similar levels to AYU (approximately 30 g/m2 in both sites). In comparison to the annual deposition levels of this mining area with other rural areas in Spain (around 2030 g/m2; Castillo, 2006), the deposition levels registered in RTMD were high. The mass distribution observed between the soluble and insoluble fractions reects the predominance of the latter in the PM deposition in the study area, where 6784% of the bulk mass is derived from this fraction. The distribution of the mass in atmospheric deposition depends directly on precipitation. Precipitation was concentrated in the cold season whereas throughout the summer it was almost absent. During winter the deposition levels in the soluble fraction were higher than in summer where notably, the insoluble fraction predominated (Fig. 3B and C). With an annual precipitation volume of 500800 l/m2 from March 2009 to February 2010, the levels registered in the soluble fraction oscillated between 5.8 and 10.3 g/m 2 in RTF and AYU, respectively (Table 1). In this rst sampling year, AYU shows higher mass deposition levels in the soluble fraction than the rest (6.9, 6.5 and 5.8 g/m2 in CEM, CTRA

S. Castillo et al. / Science of the Total Environment 449 (2013) 363372

367
precip

10 8 6 4 2 7500 6000 4500 3000 1500 0

A)

pH

AYU CEM CTRA RTF LD

mg/m2

B)

soluble fraction

300

precip. l/m2

200 100 0

7500 6000 4500 3000 1500 0 jan-09

mg/m2

C)

19813

8900

8500

insoluble fraction

300

precip. l/m2

200 100 0 jan-12

jan-10

jan-11

Fig. 3. Seasonal evolution of pH values (A), and monthly deposition uxes in the soluble (B) and insoluble (C) fractions (mg/m2) versus precipitation from March 2009 to February 2011.

and RTF, respectively). In contrast, in the insoluble fraction CEM registered greater annual deposition levels (35.8 g/m 2) than the rest (21.3, 18.3 and 12.6 g/m2 in AYU, CTRA and RTF, respectively). The second sampling year shows several differences. First, the annual precipitation

volume was double with 9501050 l/m 2. This caused higher deposition levels in the soluble fraction (between 1 and 2 g/m2 more, except in AYU where they are similar, Table 1). The levels in the insoluble fraction present more differences, whereas in AYU and CEM the annual levels

Table 1 Annual deposition uxes (mg/m2) of total deposition and major ions (soluble and insoluble fractions), annual precipitation volume (P), electrical conductivity (EC) and pH values, in the ve sampling locations during the periods March 2009February 2010 and March 2010February 2011. CEM m09f10 P (l/m2) pH EC (S) 793 6.6 47 m10f11 1004 6.7 37 AYU m09f10 595 6.9 51 m10f11 1055 7.1 118 CTRA m09f10 794 6.5 45 m10f11 1057 6.6 46 RTF m09f10 766 6.0 46 m10f11 972 6.3 38 LD m09f10 m10f11 961 6.3 38

Total uxes deposited (mg/m2) Soluble 6944 Insoluble 35,784 Total 42,728 Major soluble ions (mg/m2) HCO3 694 Al 1.3 Ca 1137 Fe 3.4 K 220 Mg 154 Mn 1.1 Na 846 P 62 S2 97 2 SO4 1007 NO3 528 Cl 1748 + NH4 415 Major insoluble ions (mg/m2) C 2062 SiO2 2146 2 CO3 397 Al2O3 1349 Ca 114 Fe 512 K 206 Mg 90 Mn 5.4 Na 53 P 15 Ti 72 2 S 36 2 SO4 107

7360 26,397 33,757

10,358 21,344 31,702

9452 20,147 29,600

6540 18,279 24,820

8825 31,890 40,716

5780 12,631 18,410

7827 26,664 34,490

7460 22,477 29,940

1081 1.7 1517 4.9 95 199 0.4 1029 52 74 1002 336 1731 197

1479 3.7 2443 3.7 135 150 2.7 844 28 84 3235 1110 1864 1118

2307 0.8 3266 1.5 361 184 0.2 1002 31 21 1411 631 1767 55

519 3.9 958 1.2 127 168 1.7 951 64 57 1071 597 1615 359

1001 0.003 2015 5.4 212 220 3.1 1058 22 53 1191 690 2029 248

209 7.1 458 0.9 300 113 4.4 797 186 51 869 571 1384 391

556 0.3 1476 4.7 320 151 7.3 1020 135 44 1157 519 1734 140

567 0.02 1266 0.3 56 157 1.3 1030 30 43 799 1455 1695 152

1594 1264 314 795 78 422 144 79 4.7 47 42 48 53 160

1468 1428 333 898 96 201 132 76 5.7 47 17 44 18 53

1329 1176 553 740 223 387 153 87 5.6 45 71 46 27 81

1656 1496 322 941 96 211 146 71 9.1 75 8.6 39 7.5 22

1660 2031 568 1278 161 679 273 131 15 144 43 65 45 134

1638 768 150 483 36 112 78 38 9.0 22 5.2 19 12 34

2066 1029 338 647 83 343 150 85 22 46 46 33 41 122

1126 1267 495 797 141 418 156 113 6.2 85 29 34 21 64

368

S. Castillo et al. / Science of the Total Environment 449 (2013) 363372

fall, in CTRA and RTF they rise markedly (Table 1). These results show the elevated concentration of highly insoluble species in atmosphere in this area at a rate of 2.1 to 5.6 times higher than the concentration of the soluble species (Fig. 3B and C). 4.2. Chemistry The results of the chemical prole of the total atmospheric deposition in the RTMD are summarized in Tables 1 and 2. The annual mass deposited for major ions (Table 1) differs depending on the weather conditions and the species solubility. As expected, ionic species with high solubility such as HCO3 , Ca2+, Mg2+, Na+, Cl, 2 + SO4 , NO3 and NH4 , were deposited predominantly in the soluble fraction. Thus, for instance, Ca2+ registered an annual mass deposited in the soluble fraction within the range 4583266 mg/m 2 ahead of 36223 mg/m2 in the insoluble fraction, AYU being the sampling station that registered the highest Ca 2 + levels deposited (> 2400 mg/m 2). Carbonate displays a similar behaviour, showing a range of 209 2307 mg/m 2 in the soluble fraction, ahead of 150568 mg/m2 in the insoluble fraction, with greater deposition uxes measured in AYU. Sul phate, similar to Ca 2+ and HCO3 , was deposited mainly in the soluble fraction in a range of 7993235 mg/m2, whereas deposition levels as

low as 22160 mg/m 2 were recorded in the insoluble one. These results are in accordance with studies carried out in Spain by vila and Rod (2002) and Castillo (2006), who reported high atmospheric deposition uxes of Ca 2+ and HCO3 in the soluble fraction as a result of the incorporation of mineral dust from the Sahara desert and the high rate of soil resuspension. The most stable species in the study area were Na + and Cl , both typically marine in origin, and both mainly in the soluble fraction. The annual deposited mass ranged between 797 and 1058 mg/m 2 for Na + and 16152029 mg/m 2 for Cl, showing similar trends in all the stations (Table 1). The high contribution of particles with marine origin registered in the RTMD is similar to other places located in Atlantic areas of Spain (Castillo, 2006). On the other hand, major metallic species such as Fe, Mn and Ti registered the largest mass deposition levels in the insoluble fraction. The Fe annual mass deposited in the RTMD ranged between 201 and 679 mg/m 2 in the insoluble fraction and 0.35.4 mg/m 2 in the soluble one. The locations presenting the greatest deposited Fe levels were CEM and RTF, the stations close to the abandoned mine waste deposits. Ti was only detected in the insoluble fraction (1972 mg/m 2) because of its very low solubility. Finally, Mn ranged between 0.2 and 7.3 and 5.422 mg/m2 in the soluble and insoluble fractions, respectively.

Table 2 Annual deposition uxes (mg/m2) of trace elements (soluble and insoluble fractions) in the ve sampling locations during the periods March 2009February 2010 and March 2010February 2011. CEM m09f10 m10f11 AYU m09f10 0.6 1.0 3.8 9.2 4.3 6.3 m10f11 0.5 1.7 1.9 25 3.1 3.5 CTRA m09f10 7.0 0.3 0.3 33 2.0 5.2 m10f11 8.0 2.1 3.6 61 2.6 2.8 RTF m09f10 41 0.3 68 28 1.4 3.0 m10f11 16 1.6 207 62 1.7 1.6 LD m09f10 m10f11 9.2 1.2 7.1 35 1.6 0.7

Trace elements in the soluble fraction (mg/m2) H+ 1.4 3.0 Ni 0.4 4.2 Cu 2.2 1.6 Zn 16 24 Sr 1.7 1.8 Ba 9.1 6.7 Trace elements in the insoluble fraction (mg/m2) Li 0.5 0.3 Sc 0.2 0.1 V 1.0 0.7 Cr 1.1 0.6 Co 0.6 0.4 Ni 0.8 0.3 Cu 8.0 5.4 Zn 14 9.2 Ga 0.5 3.4 Ge 0.1 0.1 As 4.4 2.1 Se 0.8 0.04 Rb 1.0 0.6 Sr 1.2 0.7 Y 0.3 0.2 Zr 1.4 1.1 Nb 0.2 0.1 Mo 0.4 0.3 Cd 0.3 0.03 Sn 0.5 0.3 Sb 3.4 0.6 Cs 0.4 0.03 Ba 67 12 LREEa 3.3 1.3 HREEb 2.1 0.2 Hf 0.3 0.03 Ta 0.4 0.4 W 0.1 0.02 Tl 0.2 0.02 Pb 16 5.2 Bi 0.8 0.2 Th 0.2 0.1 U 0.1 0.03
a b

0.4 0.2 0.7 0.7 1.2 0.4 3.7 9.1 0.2 0.02 0.7 0.2 0.6 0.7 0.2 1.0 0.2 0.3 0.04 0.2 0.3 0.2 4.3 1.3 1.1 0.03 0.2 0.03 0.03 3.6 0.04 0.1 0.03

0.4 0.1 1.0 1.2 0.8 0.5 3.8 12 1.1 0.05 0.5 0.03 0.7 0.8 0.2 1.1 0.1 0.3 0.04 0.2 0.1 0.1 4.0 1.3 0.2 0.03 0.1 0.02 0.01 2.4 0.1 0.1 0.03

0.3 0.1 1.0 2.0 0.3 1.1 4.1 33 0.2 0.03 0.7 0.04 0.7 0.7 0.2 0.9 0.1 0.1 0.1 0.3 0.2 0.03 4.3 1.2 0.1 0.03 0.01 0.03 0.02 7.2 0.1 0.1 0.02

0.4 0.2 1.5 3.9 0.8 1.8 7.4 59 1.5 0.1 1.0 0.1 1.0 1.0 0.4 1.6 0.2 0.3 0.6 0.9 0.3 0.1 5.1 2.0 0.2 0.1 0.02 0.05 0.01 13 0.2 0.1 0.04

0.2 0.05 0.5 0.5 0.1 0.3 2.8 14 0.1 0.01 0.3 0.1 0.4 0.4 0.1 0.6 0.1 0.03 0.01 0.1 0.1 0.02 3.6 0.7 0.1 0.02 b 0.01 0.01 0.01 1.2 0.03 0.05 0.01

0.3 0.1 0.8 0.8 0.5 0.5 16 22 1.4 0.1 0.4 0.03 0.7 0.8 0.2 1.0 0.1 0.4 0.02 0.1 0.1 0.04 5.3 1.3 0.1 0.03 0.01 0.01 0.01 2.1 0.03 0.1 0.03

0.3 0.1 1.2 1.0 0.3 0.4 3.1 14 1.1 0.05 0.3 0.03 0.7 0.9 0.2 1.0 0.1 0.2 0.02 0.2 0.1 0.04 4.6 1.2 0.1 0.03 b 0.01 b 0.01 b 0.01 2.2 0.03 0.1 0.03

LREE La, Ce, Pr, Nd, and Sm. HREE Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

S. Castillo et al. / Science of the Total Environment 449 (2013) 363372

369

m09-f10
100 50 0 20 10 0 5 2,5 0 2 1 0 1 0,5 0

m10-f11

Zn

100 50 0 5 2,5 0 4 2 0

Ba

Cu

As

Cr

Sb

Ni

1 0,5 0

Se

Sn

1 0,5 0

Cd

mg/m2

20 10 0 CEM
*

Pb

1 0,5 0

Bi

AYU *

CTRA *

RTF

LD

CEM

AYU

CTRA *

RTF

LD

Close to the waste deposits


* Prevailing wind direction NW

Away from the waste deposits

Fig. 4. Annual deposition uxes (mg/m2) of Zn, Cu, Cr, Ni, Sn, Pb, Se, Cd and Bi from March 2009 to February 2010 and March 2010 to February 2011, in the sampling stations sorted by the distance to the mine waste location.

The annual mass deposited for trace elements both in the soluble and insoluble fractions is given in Table 2 with the aim of assessing the inuence of the abandoned mine wastes on the sampling locations (mainly in the insoluble fraction). The results showed high deposition levels of Cu and Zn in the study area as a general pattern. The levels of Cu varied widely from 0.3 to 207 mg/m2 in the soluble fraction, and only from 2.8 to 16 mg/m2 in the insoluble one, whereas Zn showed a similar variation range (9 to 62 mg/m2) in both fractions. The high mass deposition levels of Cu in the soluble fraction in the RTF station are noteworthy, reaching up to 207 mg/m2 between March 2010 and February 2011, whereas in the insoluble fraction the Cu levels were similar to those of the rest of stations. This anomaly may be due to the fact that the RTF collector was placed in a citrus exploitation that was treated with copper sulphate (Cu2SO4) for insect control during the spring period (February, March and April). Nevertheless, CEM was the station most affected by the mine wastes (Table 2, Fig. 4), as noted by the high deposition uxes of mining-related trace elements in the insoluble fraction, such as Cu (85.4 mg/m2), Zn (149.2 mg/m 2), As (4.42.1 mg/m 2), Sb (3.40.6 mg/m 2), Pb (165.2 mg/m 2) and Bi (0.80.2 mg/m 2) for the periods March 09 February 10 and March 10February 11, respectively. This suite of potentially pollutant elements along with Fe could represent the chemical prole of the atmospheric PM inuenced by the mining source, although the CTRA station also showed high annual deposition levels of Cu (up to 7.4 mg/m2), Zn (up to 59 mg/m2) and Pb (up to 13 mg/m2). Besides this, the relative abundance of Cr (up to 3.9 mg/m2) and Ni (up to 1.8 mg/m2) in the insoluble fraction suggests another source of atmospheric PM. In this sampling site, located farthest from the mine waste deposits and near the main road of the village of Nerva and the truck-transfer station, it was usual to nd high deposition levels of certain elements coming from trafc activity (Zn, Cu, Pb, Cr, Ni, As, La Co, Sn, Sb and Bi, Fig. 3). The LD sampling site can be regarded as a rural station with high deposition levels of Cu and Zn in both the soluble

and insoluble fractions that are similar to those of the other stations, but with a more softened chemical prole (Tables 1 and 2 and Fig. 4). Comparing the average deposition uxes of some trace elements at RTMD to other ones measured in a heavily polluted industrial area such as the Tokyo Bay (Sakata et al., 2008), elements such as As, Cd, Cu and Pb have been found principally in similar levels in CEM station (the nearest to the waste deposits) and minor in RTF and CTRA (the latest probably with the inuence of the trafc activity). Considering that the industrial areas emit metals to the atmosphere continuously, the levels of some metals found in RTMD note the impact of the metal dust from the abandoned mine waste deposits from mines, this being an abandoned activity. When the results are sorted by proximity to the emission source (Fig. 4) a decrease in the deposition uxes is observed as we move away from the mine waste deposits, particularly for some anthropogenic toxic elements. This decrease was more pronounced in the period March09February10, during which PM resuspension was more effective due to the prolonged dry weather conditions throughout this year. Since the CTRA station was affected by direct anthropogenic sources (trafc and road dust) that did not affected the rest of the locations, the deposition uxes for elements associated with these anthropogenic sources (Pb, Zn, Cr, Ni and Sn) were greater than the uxes, for the same elements, registered in the stations closest to the mine wastes (CEM and AYU). In the second period, March10February11, the decrease was not as high probably due to the prolonged wet weather conditions inhibiting PM resuspension. Despite the different meteorological conditions in the two years, elements such as Ba, Bi, Se, Sb and As continue to decrease as we move away from the waste deposits. 4.3. Source apportionment Principal component analysis carried out with the chemical data reveals two common factors in the RTMD (Table 3): A mineral factor,

370

S. Castillo et al. / Science of the Total Environment 449 (2013) 363372


2 of the same elements in the soluble fraction (Na, Cl, Mg, Ca, SO4 and minor Zn and Sr) in all the sampling stations. A factor composed mainly of trace elements such as Ba, Sb, Bi, Sn, Pb, LREE (La, Ce, Pr, Nd and Sm), Ni, Cu, Zn, Cd and HREE (Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) appears in CEM and AYU (which are placed in the prevailing wind direction and nearest to the abandoned mine lands). This factor was only composed of trace elements because they are derived from the wastes of the sulphides used in the metal extraction processes when the mine was in use. In this metal extraction, the major elements have been eliminated during the process. Resuspension events derived from the wind action raise a metal dust from the mine waste deposits that are registered in such stations. However, this mine waste factor does not appear as a single factor in the rest of stations. In the stations outside the prevailing winds, RTF and LD, it was observed that the trace elements that composed the mineral factor (Ni, Sn, Pb, Ba, Bi, LREE, HREE, As, Sb, Ni and Cd) had the same chemical prole as the mine waste source found in CEM and AYU. This may be explained by the fact that dust resuspended from the mine wastes has a direct impact in areas along the prevailing wind direction line, such as the village of Nerva, and an indirect impact in areas outside this line, mixed with the dominant mineral source. It is signicant that in CTRA, the last location placed in the prevailing wind direction farthest from the waste deposits, and near the main road and the truck-transfer station of the village, the source mineral factor showed a mixture of heavy metals probably derived from trafc, road dust and metal dust from the mine wastes together with geogenic species such as silicates and carbonates. In this sampling site a factor with + minor load composed of K, Ca, NO3 and NH4 appears to be derived from trafc (mainly truck trafc) and road dust emission characteristic of areas with these kinds of activities (Amato et al., 2009). A local mineral factor appears in AYU, RTF and LD. This factor presents a different composition depending on the dominant land use where the station was situated. For example, in LD this factor is com+ 3 posed of NH4 (s), PO4 (s), K(s), C and P, linked to particles derived from agricultural soils with compost additions. In RTF the local mineral factor is mainly composed of Mg, Ca, Al, Na, Fe, Ti and K resulting from the resuspension of the nearby slaty soils devoted to citrus culture. In 4 AYU, this factor is composed of Ca, Fe, Sr, K(s), PO3 (s), and P originates from a mixture of the surrounding soils. Fig. 5 shows the contribution of each source to the total mass deposited by means of Multilinear Regression Analysis. It can be observed that the contribution to the bulk atmospheric deposition did not change notably throughout the study period, except for minor differences taking into account that the volume of precipitation registered for each year was signicantly different (600700 l/m 2 from March 2009 to February 2010 and 9001000 l/m 2 from March 2010 to February 2011). The contribution of the mineral source (mineral + local emissions in AYU) was dominant in the area. Between 18 and 32 g/m 2 was deposited in a year, accounting for between 59 and 79% of the total atmospheric deposition. The marine source was present in the entire area contributing to the mass deposited between 3.6 and 7.8 g/m2, except in RTF where the contribution fell to 12 g/m2. In RTF, the local mineral factor registered the greatest contribution with 7.1 and 12.4 g/m2 for each study year, which accounted for 34 and 36%, of the total mass deposited, respectively. The contribution of the local mineral factor in AYU (3.5 and 6.7 g/m2, respectively, 9 and 19%) and LD (2.4 g/m 2, 8%) was lower than that in RTF. The factor derived from trafc and road dust, which only appears in CTRA, had a stable contribution accumulating 3.5 and 4.7 g/m 2 for the rst and second study years, respectively (accounting for 14 and 11%, respectively). Finally, the greatest contribution from the mine waste source was found in CEM (i.e. the station closest to the mine wastes), registering 8.8 and 2.6 g/m2 in the two study years (19 and 8%, respectively). This difference in the annual bulk mass deposition can be explained by the different meteorological conditions in the study years. As explained above, resuspension of metal dust

Table 3 Results of the factor analysis carried out with the mass deposition levels. Elements are presented in decreasing order of their factor loads. (s) soluble fraction; the rest means insoluble fraction. * typical mine waste elements mixed in other sources. Site Factor Source Factor Mineral 1 CEM Sr, Ni, V, Ti, Li, Mg, Mo, Ca, Mn, As, K, Al, Sn, C, Na, Cd, Zn, Fe, Cu, Se
+ NH4 (s), 2 SO4 (s), Na, Cu, S, NO3 (s), Ti, Al, Zn, K, Mg, Mn Mg (s), Na (s), Cl (s), Ca (s), Zn (s), Sr (s)

AYU

CTRA Mn, Fe, Zn, Sn, Al, V, Pb, K, Cu, LREE, Na, Sb, P, S, As, Mg, Ti, Mo, Cd, C, Ca, Zn

RTF Ni*, Sn*, Pb*, Ba*, Bi*, HREE*, LREE*, Sb*, Zn*, V*, As*, Cd*, P, S, Li, Mo, K, Mn, Sr, Fe, Ti, Al, Na

LD Si, Al, LREE, V, Na, Mg, Fe, As*, K, Sn*, Pb*, Cd*, Sb*, Ti*, Zn*, HREE*, Ca, Ni, Mn, P, Bi*

Factor Mineral + local 1 emissions

Factor Marine 2

Factor Mine waste 3

Cl (s), Mg (s), Na (s), Ca (s), 2 SO4 (s),S2 (s) Ba, Sb, Bi, LREE, + Pb, NH4 (s), K (s), Fe, Cu, Zn

Mg (s), Cl (s), Na 2 (s), SO4 (s)

Mg (s), Na (s), Cl (s), 2 SO4 (s), Ca (s), Sr (s)

Na (s), Mg (s), Cl (s), 2 SO4 (s), Ca (s)

Pb, Sn, As, HREE, Se, Sb, Mo, Li, LREE, Ba, Cd, Ni, V K (s), Ca (s), NO3 + (s), NH4 (s) Ca, Fe, Sr, K (s), P, 4 PO3 (s)
+ Mg, Ca, Al, NH4 (s), 3 Na, Fe, Ti, K PO4 (s), K (s), C, P

Factor Trafc + road 4 dust

Factor Local mineral 5

which is more or less mixed depending of the collector position; and a marine factor, which is very marked and has the same composition in all locations. In addition, a mine waste factor was present in two ways: First, as a separate factor, in the locations placed in the prevailing wind direction, which are exposed to the direct metal dust resuspension from the mine wastes; and mixed with the mineral factor as we move away from the mining area. Finally, a local mineral factor was also observed in some sampling locations. The mineral factor has been identied in all the sampling stations as being the dominant source. This factor presents a general prole composed by Sr, Ti, Li, Mg, Ca, Mn, K, Al, C, Na and Fe, mainly derived from soil minerals, and others such as Zn, Cu, Pb, As, Cd, Se, Mo, Sb, Bi and Sn derived mainly from sulphide minerals. One variation of this factor was found in AYU, where it also contains other additional + 2 anthropogenic species (NH4 , SO4 and NO3 ). This fact may be due to the station being placed in the middle of the village of Nerva and was also affected by domestic and trafc emissions from the village. To differentiate this mixed source we have called it mineral + local emissions. In air, in PM10, Snchez de la Campa et al. (2011) found this source separately but with similar composition to that in deposition. As for other sources found in RTMD, the marine factor is composed

S. Castillo et al. / Science of the Total Environment 449 (2013) 363372

371

F5; 7,1; 34%


F2; 1,5; 7%

RTF
F3; 8,8; 19%

F1; 12,5; 59%

March2009February2010
F2; 1,2; 3%

F5; 12,4; 36%

RTF
F3; 2,6; 8%

F1; 21,0; 61%

March2010February2011

F2; 7,9; 18%

CEM

F1; 28,7; 63% F3; 0,2; 2% F5; 3,5; 9%

F2; 7,8; 26%

CEM
F3; 0,2; 2%

F1; 20,0; 66%

F2; 5,0; 13%

AYU

F1'; 29,5; 76%

F5; 6,7; 19%

F4; 3,7; 14%


F2; 3,6; 14%

F2; 7,0; 20% F1; 18,5; 72%

AYU

F1'; 20,6; 59%


F4; 4,7; 11%

CTRA

F2; 3,9; 10%

CTRA

F1; 32,5; 79%

F1 Mineral F1 Mineral+local emissions

F2 Marine F3 Mine waste F4 Traffic+road dust F5 Local mineral


NNW N NNE NE NW WNW ENE W E WSW ESE SW SE SSW S SSE

F2; 6,0; 21%

F5; 2,4; 8%

LD

F1; 20,3; 71%

N
500 m

Fig. 5. Annual mass contribution (mg/m2; %) of the different sources to the bulk mass deposited in the Rio Tinto Mining District during the study periods (left: March 2009February 2010; and right: March 2010February 2011).

from mine wastes needs the action of the wind and dry conditions (minor precipitation), thus favouring looser particles than in wet conditions. In the second study year the volume of precipitation was double, so the conditions for particle resuspension were less favourable than the rst study year. No annual difference was observed in AYU where the mine waste factor was 0.2 g/m2 (2%) for the two study years. This contribution is indicative of the dominant coarse size distribution of the metal dust derived from the abandoned mine lands. In the vicinity of the mine wastes, the contribution can be a few grams per square metre, while as we move away from the mining area, particle segregation occurs during transport which signicantly reduces the size of the PM deposited.

5. Conclusions The chemical prole of the atmospheric PM deposited in RTMD is characterized by an enrichment of potentially toxic metals and metalloids such as Cu, Zn, As, Sb, Ba, Pb, Cd and Bi mainly in the insoluble fraction and Ni, Zn and Ba in the soluble fraction, with greater deposition uxes in areas close to the mine waste deposits. Two regional sources (mineral and marine factors) and three local sources (local mineral, trafc +road dust and mine waste factors) have been identied in the mining district. Mineral source is the predominant source in the area, displaying a natural chemical prole (Sr, Al, Mg, K, Ti, Ca) in the rural sampling stations, and mixed with other secondary + 2 species (NH4 , SO4 ,Cu, Zn, NO3 and Mn) in the sampling sites located inside the village of Nerva. This mineral + local emission factor comprises a mixture of species caused by both natural origin (soil particle resuspension) and anthropogenic origin (trafc, domestic emissions principally). In both cases this factor (mineral in rural areas and mineral+ local emissions inside the village) was the major factor that contributed to the bulk mass deposition in RTMD. The marine source 2 showed a stable chemical prole (Na, Cl, Mg, Ca, SO4 ) in the area throughout the study period. A local mineral factor appears only in

three sampling sites presenting different compositions depending on the soil composition around the location. The mine waste factor is evident in the sampling sites exposed to dust-bearing winds downwind of the mining area, suggesting that mine wastes are the source of heavy metal particles (e.g. pyrite, chalcopyrite, sphalerite, galena and arsenopyrite) giving rise to a typical suite of hazardous trace elements (Zn, Cu, Sb, Bi, Pb, As, Sn, Mo, Fe, Ni, Cd, LREE and HREE) with potentially adverse environmental effects to surrounding soils and plants, and the vicinity of Nerva village located in the direction of the prevailing winds. Particle grain segregation was observed during the transport of this metal dust from the mine wastes, registering a difference of between 3 and 8 g/m 2 of PM deposited along the prevailing wind direction. This segregation may occur during wind events resulting in resuspension of coarse particles from the mine wastes. Once the coarse particles are deposited (within meters of the mine waste deposits), the ne fraction of this metal dust may be transported to long distances by winds causing a direct impact on the population of Nerva and on the agricultural crops around RTMD. Besides this direct impact, the chemical prole of the sampling locations outside the prevailing wind direction also contains the same toxic elements as the areas inside the prevailing wind line, implying that the metal dust derived from the mine waste deposits has a certain inuence in the entire mining district. Acknowledgments This study was supported by the Spanish Ministry of Science and Innovation (Projects CRACCIE-CSD2007-0067 and CGL2008-06270-C0202/CLI), the Department of the Environment and the Department of Innovation, Science and Enterprise (Project RNM2007-02729 and RNM2009-5163M) of the Andalusian Autonomous Government. The authors wish to thank the environmental ofcers at the Nerva Council, the staff of the Rio Tinto Fruit Company, and the residents of Las Delgadas village for their assistance with the sampling. The authors would like to give special thanks to Christine Price for her support in the revision tasks.

372

S. Castillo et al. / Science of the Total Environment 449 (2013) 363372 Harrison RM, Smith DJT, Pio CA, Castro LM. Comparative receptor modeling study of airbone particulate pollutants in Birmingham. Atmos Environ 1997;31(20):330921. Henry RC, Lewis CH, Hopke PK, Williamson HJ. Review of receptor models fundamentals. Atmos Environ 1984;18:150715. Hudson-Edwards KA, Jamieson HE, Lottermoser BG. Mine wastes: past, present, future. Elements 2011;7:37580. Kim CG, Bell JNB, Power SA. Effects of soil cadmium on Pinus sylvestris L. seedlings. Plant Soil 2003;257:4439. Krombach F, Munzing S, Allmeling AM, Gerlach JT, Behr J, Dorger M. Cell size of alveolar macrophages: an interspecies comparison. Environ Health Perspect 1997;105: 12613. Kpper H, Setlk I, Spiller M, Kpper FC, PrSil O. Heavy metal-induced inhibition of photosynthesis: targets of in vivo heavy metal chlorophyll formation. J Phycol 2002;38:42941. Lehndorff E, Schwark L. Accumulation histories of major and trace elements on pine needles in the Cologne Conurbation as function of air quality. Atmos Environ 2008;42:83345. Leistel JM, Marcoux E, Thieblemont D, Quesada C, Sanchez A, Almodovar GR, et al. The volcanic-hosted massive sulphide deposits of the Iberian Pyrite Belt. Miner Deposita 1998;33:2-30. Lpez M, Gonzlez I, Romero A. Trace elements contamination of agricultural soils affected by sulphide exploitation (Iberian Pyrite Belt, SW Spain). Environ Geol 2008;54: 80518. Lottermoser BG. Mine wastes. Characterization, treatment, environmental impacts. 2nd ed. Berlin Heidelberg: Springer-Verlag; 2007. McGechan M, Lewis D. Transport of particulate and colloid-sorbed contaminants through soil, Part 1: general principles. Biosyst Eng 2002;83:25573. Mulligan CN, Yong RN. Natural attenuation of contaminated soils. Environ Int 2004;30: 587601. Nordstrom DK. Hydrogeochemical processes governing the origin, transport and fate of major and trace elements from mine wastes and mineralized rock to surface waters. Appl Geochem 2011;26:177791. Park SS, Wexler AS. Size-dependent deposition of particles in the human lung at steadystate breathing. J Aerosol Sci 2008;39:26676. Pumlee GS, Morman SA. Mine wastes and human health. Elements 2011;7:399404. Querol X, Alastuey A, Rodrguez S, Plana F, Ruiz CR, Cots N, et al. PM10 and PM2.5 source apportionment in the Barcelona Metropolitan Area, Catalonia, Spain. Atmos Environ 2001;35:640719. Rodrguez S, Querol X, Alastuey A, Kallos G, Kakaliagou O. Saharan dust contributions to PM10 and TSP levels in Southern and E. Spain. Atmos Environ 2001;35:243347. Romero A, Gonzlez I, Galn E. Estimation of potential pollution of waste mining dumps at Pea del Hierro (Pyrite Belt, SW Spain) as a base for future mitigation actions. Appl Geochem 2006;21:1093108. Romero A, Gonzlez I, Galn E. Trace elements absorption by citrus in a heavily polluted mining site. J Geochem Explor 2012;113:7685. Sakata M, Tani Y, Takagi T. Wet and dry deposition uxes of trace elements in Tokyo Bay. Atmos Environ 2008;42:591322. Snchez de la Campa AM, de la Rosa J, Fernndez-Caliani JC, Gonzlez-Castanedo Y. Impact of abandoned mine waste on atmospheric respirable particulate matter in the historic mining district of Rio Tinto (Iberian Pyrite Belt). Environ Res 2011;111:101823. Taylor MP, Mackay AK, Hudson-Edwards KA, Holz E. Soil Cd, Cu, Pb and Zn contaminants around Mount Isa city, Queensland, Australia: potential sources and risks to human health. Appl Geochem 2010;25:84155. Thurston GD, Spengler JD. A quantitative assessment of source contribution to inhalable particulate matter pollution in Metropolitan Boston. Atmos Environ 1985;19:9-25. Trepka MJ, Heinrich J, Krause C, Schulz C, Lippold U, Meyer E, et al. The internal burden of lead among children in a smelter towna small area analysis. Environ Res 1997;72: 11830. Valiulis D, Sakalys J, Plauskaite K. Heavy metal penetration into the human respiratory tract in Vilnius. Lithuanian J Phys 2008;48:34955. Youse N, Chehregani A, Malayeri B, Lorestani B, Cheraghi M. Investigating the effect of heavy metals on developmental stages of anther and pollen in Chenopodium botrys L. (Chenopodiaceae). Biol Trace Elem Res 2011;140:36876. Zota A, Willis R, Jim R, Norris GA, Shine JP, Duvall RM, et al. Impact of mine waste on airborne respirable particulates in northeastern Oklahoma, United States. J Air Waste Manage Assoc 2009;59:134757.

References
Alonso ML, Benedito JL, Miranda M, Castillo C, Hernandez J, Shore RF. Interactions between toxic and essential trace metals in cattle from a region with low levels of pollution. Arch Environ Contam Toxicol 2002;42:16572. Amato F, Pandol M, Viana M, Querol X, Alastuey A, Moreno T. Spatial and chemical patterns of PM10 in road dust deposited in urban environment. Atmos Environ 2009;43: 16509. vila A, Rod F. Assessing decadal changes in rainwater alkalinity at a rural Mediterranean site in the Montseny Mountains (NE Spain). Atmos Environ 2002;36:288190. Benin AL, Sargent JD, Dalton M, Roda S. High concentrations of heavy metals in neighborhoods near ore smelters in northern Mexico. Environ Health Perspect 1999;107: 27984. Braune B, Outridge P, Fisk A, Muir D, Helm P, Hobbs K, et al. Persistent organic pollutants and mercury in marine biota of the Canadian Arctic: an overview of spatial and temporal trends. Sci Total Environ 2005;351352:4-56. Brotons JM, Diaz AR, Sarria FA, Serrato FB. Wind erosion on mining waste in southeast Spain. Land Degrad Dev 2010;21:196209. Castillo S. Impacto de las masas de aire africano sobre los niveles y composicin del material particulado atmosfrico en Canarias y el NE de la Pennsula Ibrica. Doctoral Thesis, Technical University of Catalonia, Spain, 2006. Chardonnens AN, Bookum WM, Vellinga S, Schat H, Verkleij JAC, Ernst WHO. Allocation patterns of zinc and cadmium in heavy metal tolerant and sensitive Silene vulgaris. J Plant Physiol 1999;155:77887. Chopin EIB, Alloway BJ. Trace element partitioning and soil particle characterisation around mining and smelting areas at Tharsis, Riotinto and Huelva, SW Spain. Sci Total Environ 2007;373:488500. Chopin EIB, Black S, Hodson ME, Coleman ML, Alloway BJ. A preliminary investigation into mining and smelting impacts on trace element concentrations in the soils and vegetation around Tharsis, SW Spain. Mineral Mag 2003;67:27988. Csavina J, Landzuri A, Wonaschtz A, Rine K, Rheinheimer P, Barbaris B, et al. Metal and metalloid contaminants in atmospheric aerosols from mining operations. Water Air Soil Pollut 2011;221:14557. Csavina J, Field J, Taylor MP, Gao S, Landzuri A, Betterton EA, et al. A review on the importance of metals and metalloids in atmospheric dust and aerosol from mining operations. Sci Total Environ 2012;433:5873. Ekosse G, van den Heever DJ, de Lager L, Totolo O. Environmental chemistry and mineralogy of particulate air matter around Selebi Phikwe nickelcopper plant, Botswana. Miner Eng 2004;17:34953. Ernst WHO, Nelissen HJM. Life-cycle phases of a zinc- and cadmium-resistant ecotype of Silene vulgaris in risk assessment of polymetallic mine soils. Environ Pollut 2000;107: 32938. Escudero M, Castillo S, Querol X, Avila A, Alarcn M, Viana MM, et al. Wet and dry African dust episodes over Eastern Spain. J Geophys Res 2005;110(D18S08):10.1029. Fernndez-Caliani JC, Galn E. Impacto ambiental de la minera en el devenir histrico de la comarca de Riotinto (Huelva). Geogaceta 1996;20:11689. Fernndez-Caliani JC, Barba-Brioso C, Gonzalez I, Galan E. Heavy metal pollution in soils around the abandoned mine sites of the Iberian Pyrite Belt (Southwest Spain). Water Air Soil Pollut 2009;200:21126. Fernndez-Caliani JC, De la Rosa J, Snchez de la Campa AM, Gonzlez-Castanedo Y, Gonzlez I, Romero A, et al. Datos qumicos y mineralgicos preliminares de las partculas atmosfricas sedimentables en la Cuenca Minera de Riotinto (Huelva). Macla 2010;13:7980. Galn E, Gmez-Ariza JL, Gonzlez I, Fernndez-Caliani JC, Morales E, Girldez I. Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt. Appl Geochem 2003;18:40921. Ghose MK, Majee SR. Assessment of the impact on the air environment due to opencast coal miningan Indian case study. Atmos Environ 2000;34:27916. Gonzlez I, Romero A, Galn E. Environmental aspects of waste dumps at the Pea de Hierro Mine (Iberian Pyrite Belt SW Spain). In: Pecchio M, Andrade FR, D'Agostino LZ, Kahn H, Sant Agostino LM, Tasinari MI, editors. Applied mineralogy: developments in science and technology, vol. I. ; 2004. p. 41922. Gonzlez I, Lpez M, Romero A. Problemtica de los suelos afectados por la explotacin de sulfuros. Macla 2008;10:6175. Harrison RM, Pio CA. Size differentiated composition of inorganic aerosol of both marine and polluted continental origin. Atmos Environ 1983;17:17338.