Dec. 2010, Volume 4, No.12 (Serial No.

37) Journal of Environmental Science and Engineering, ISSN 1934-8932, USA

Characterization of Topsoil Samples and Analysis of the Distribution of Heavy Metals in Parral Chihuahua, Mexico
L. Rodrguez Vzquez1, H. Ferman vila1, E. Torres Carrillo1, L. Senz Macas1, J. Luna Carrete1, E. Herrera2, G. Gonzlez2, D. Aranda Caro2, J. Carrillo2 and L. Lozoya2
1. Instituto Tecnolgico de Parral, Avenida Tecnolgico # 57, 33860 Parral Chihuahua, Mxico 2. Centro de Investigacin en Materiales Avanzados (CIMAV), Miguel de Cervantes # 120, 31109 Complejo Industrial Chihuahua, Chihuahua, Chihuahua Mxico Received: September 7, 2010 / Accepted: October 14, 2010 / Published: December 20, 2010. Abstract: During the 17th Century, Parral City in the Chihuahua State in Mexico was one of the most important miner zones in the whole world. After more than three centuries important amounts of residuals, known as tailings, with high contents of heavy metals were generated. These residuals are a potential risk for the environment and human health. Given to that, it decided to carry out the analysis of the concentrations of cadmium, lead, chromium, zinc and arsenics, in topsoil samples susceptible of airborne transport and accumulation in risky zones (populated areas). A 120 km2 area was selected, this include Parral City and its surroundings. From this area 30 samples were obtained. For this purpose, Atomic Absorption Spectroscopy technique was used, expecting high concentrations of heavy metals, above the permit limits, since several studies carried out in the same region, as in San Francisco del Oro Chihuahua, show that the concentrations of all the elements sampled, in topsoil, were above the limits. The analysis in the space distribution of the heavy metal detected will allow us to set the points with the highest susceptibility to the accumulation of those pollutants and to propose mitigation measures and control. Key words: Heavy metals, mining activity, topsoil.

1. Introduction
The study of the activities and processes developed by humans, that may represent a potentially damaging change to alter the environment, has taken on greater significance in recent decades due to the impact that these cause to the health of human beings and their environment. Parral Chihuahua is located at 26.9324-North latitude and -105.6661-West longitude in the southern
Corresponding author: L. Rodrguez Vzquez (1980- ), male, Ph.D., research fields: environmental science, air quality and atmospheric simulation. E-mail: miguel.rodriguez@cimav. edu.mx. E. Herrera (1953- ), male, Ph.D., research fields: environmental science and radiological monitoring, air quality, climate change and atmospheric simulation. E-mail: eduardo.herrera@ cimav.edu.mx.

part of the Chihuahua State, at the north of the Mexican Republic (Figs. 1 and 2). The climate of the entity is classified as semi-humid and warm with temperatures ranging between 32 and -12 with a rainfall of 450 mm per year on average. The climate of the entity is classified as semi-humid and temperate, with temperatures ranging between 32 and -12 with an amount of rainfall per year 450 mm on average. Vegetation ranges from grasslands in the valleys to various conifer species in the higher elevations [1]. Being the mining, one of the most important natural resources of the municipality, this was one of the main drivers of the economy in the region, reaching to place

Characterization of Topsoil Samples and Analysis of the Distribution of Heavy Metals in Parral Chihuahua, Mexico

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The environmental protection agency of the United States (USEPA) includes the following elements: arsenic, chromium, cobalt, nickel, copper, zinc, silver, cadmium, mercury, titanium, selenium and lead, as part of the elements that can pose a health risk to certain concentrations or in combination with other elements or environmental factors [5]. Heavy metals are regarded as a representation trace element with less than 0.1% in the crust but a high toxicity, and half-life also high, reaching periods between 1000 and 3000 years half-life in medium climates [6]. These metals tend to accumulate in the soil surface
Fig. 1 Localization of the City of Parral in the Chihuahua State.

being accessible to the consumption of crops roots [7]. Plants grown in contaminated soils generally absorb more trace elements and the concentration of these in plant tissues is often directly related to their abundance in soil, specifically in wet solution [8]. Excessive concentrations of metals in the soil could impact the quality of food, security of crop production and environmental quality [9]. Metals accumulated in the soil surface are slowly reduced by leaching, consumption by plants, and erosion [10], the processes by which can lead to groundwater pollution, risks to human health by consuming contaminated food and decreasing of air quality, the presence of heavy metals detached from the site by wind and airborne towed to different locations outside the site of original accumulation, which may overstate the problem by having a larger impact area. In a mine site the main routes of exposure may be particulated matter in air, soil contaminated (dust generated from a mine, by material from the tailings or the deposition of particles from the air), dust contaminated and even, depending on the geographic area, the pollution of water bodies by washing polluted tailings or soil. Consequently, the mining sites should be considered as potentially hazardous to human health [11]. Given the problems described is intended to analyze

Fig. 2 Limits and boundaries of the town of Parral.

the entity during the years of C XVII between one of the most important worldwide mining regions [2]. Derivatives of this flourishing and booming economic and industrial activity are subsequently generated significant amounts of waste, own the process, with high levels of heavy metals. In a mine site, there are two main sources of pollution: the primary process of metal treatment, and generation of mining waste tailings. The tailings are toxic to living organisms and are inhibitors of the ecological factors affecting plant growth and development of life on general [3]. Until recent years mining generated about 65% of industrial waste produced in Mxico [4].

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Characterization of Topsoil Samples and Analysis of the Distribution of Heavy Metals in Parral Chihuahua, Mexico

the current state of the quality of soil, related to the content of heavy metals Cd (cadmium), Pb (lead), Zn (zinc) and As (arsenic) of the city of Hidalgo del Parral Chihuahua and its surroundings as well as the possible impact of those factors, to be airlifted to other areas.

The sample collection was performed by a sweep of the surface around each of the preset points to collect around 1 kg of topsoil which was placed in plastic bags after removing coarse particles by a pre sieving. The screening of the samples was made based on the standard method ASTM C-136 which is a mechanical process of dry sieving. The dichotomy used for the screening process was performed with standard sieves No. 20, No. 40, No. 100, No. 140, No. 200, until the silt fraction less than 75 m. 2.3 Analysis by Atomic Absorption Spectrophotometry of Samples Collected Silt samples collected from the screening process were analyzed by atomic absorption technique based on the methods 3010 and 7000A of the SW 846, from EPA 2007, for the determination of heavy metal content in each of them. 2.4 Spatial Analysis of the Distribution of Heavy Metals in the Area in Process of the Study We used an auxiliary program for three-

2. Methods
2.1 Localizations of Monitory Sites Taking as a reference the center point of the city was selected an approximated area of 120 km2 in which one include near to the 100% of the urban area, and a part of surroundings. Thirty random sites, located at the same distance between them (2 km), were selected. Additionally, 13 points were selected in order to give more coverage to the urban area, for a total of 43 points. The Fig. 3 shows de localization of monitory sites in the area in process of study. 2.2 Monitoring and Preparation of Samples Prior to Analysis Topsoil collection in each of the points previously established was conducted. The samples were subjected to a screening process to a smaller particle size of 75 m for subsequent analysis by atomic absorption technique, in order to determine the content of heavy metals such as arsenic, cadmium, chromium, lead and Zinc.

dimensional graphic display of the concentrations of heavy metals detected in the samples analyzed.

3. Results and Discussion

The low efficiency of benefit processes in the material extraction in the mining of the City of Hida-lgo del Parral during the years of C XVII, and due to the ignorance of the potential dangers of the waste generated by this activity, resulted in the accumulation of large quantities of lead, zinc and arsenic mainly during the gold and silver production in the region. Although not with the same intensity, the generation of heavy metals remains up to these days. Being Parral in a period of time a worldwide major silver-producing area, it was highly possible the detection of lead in soil surface, resulting from scattering by wind drag of the main sources of emissions in the city, in this case four of the largest

Fig. 3 Monitory sites.

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tailings deposits in the area are located one in the southwestern part of the city, generated by the La Esmeralda Mina, two more further west, generated by the Posadeo Mine and Palmilla Mine, and the largest of the four in the northeast part of the area of analysis, owned by the company which once was named Mina La Prieta, and today it is managed as tourist attraction in the city. The concentration of heavy metals like lead, zinc and arsenic found in topsoil samples clearly confirm the problem, which initially was raised as a hypothesis about heavy metals pollution of the area in process of study. From the samples collected in the monitoring campaign of topsoil designed for this analysis, 43 in total, was possible to analyze only near to 70% of these samples, 28 samples in total. However, it is enough information to establish criteria on the contents dispersal patterns and the areas most susceptible to be affected by these pollutants. Table 1 shows information obtained from 28 topsoil samples taken in urban areas and surroundings of the City of Parral in Chihuahua State, Mexico. From the five pollutants analyzed, As, Pb, Cd, Cr and Zn, concentrations of consideration were only detected for As, Pb and Zn. The concentrations of Cd and Cr are below detection limit. The three-dimensional graphics show the distribution of each heavy metal in the City of Parral. According to the results shown in Table 1, the concentration levels of arsenic in the monitoring sites are considered as normal levels by the Environmental Protection Agency norm, EPA 2001, establishing as maximum allowed limit for topsoil of 100 ppm, to be considered as an excessive phitotoxic. However, IHOBE considers as a limit, 35 ppm of arsenic as a tolerable risk for the protection of ecosystems. Taking into consideration a half point between the criteria established by the EPA and the IHOBE regulations, we consider that there is no risk of damage to human health by arsenic contamination. However,

Table 1 Localization of sample sites and level concentration of arsenic, lead and zinc in soil samples. SITE Longitud PA1 PA2 PA3 PA4 PA5 PA6 PA7 PA8 PA9 Conc As Conc Pb Conc Zn (ppm) (ppm) (ppm) -105.72504 26.94922 21.24 314.41 356.05 Latititud 105.704817 26.94922 56.56 105.684583 26.94922 -105.66436 26.94922 65.32 -105.72504 26.931055 24.67 105.704806 26.931055 65.83 105.684583 26.931055 -105.66436 26.931055 51.12 105.644137 26.931055 71.62 571.63 443.48 288.67 23.51 135.67 896.65 693.95 795.30 777.65 116.04 45.91 232.16 54.55 240.86 876.41 104.64 631.48 325.27 129.14 227.20 39.66 95.22 162.21 153.80 205.59 104.13 81.62 796.23 892.69 527.37 99.07 806.89 1160.89 1126.77 793.27 788.72 266.72 119.63 493.66 114.89 389.85 965.00 270.68 1162.22 440.16 284.77 342.96 138.82 177.49 1021.54 387.55 658.72 230.92 233.92

PA10 -105.72504 26.912891 48.57 PA11 -105.704806 26.912891 40.80 PA12 -105.684583 26.912891 28.82 PA13 -105.644137 26.912891 53.53 P10 P11 P14 P15 P16 P17 P18 P19 P20 P21 P22 P23 P24 P26 P27 -105.674482 26.958302 35.96 -105.65426 26.958302 51.58 -105.714928 26.940137 46.47 -105.694705 26.940137 23.92 -105.674482 26.940137 73.92 -105.654260 26.940137 38.96 -105.634036 26.940137 33.88 -105.735151 26.921973 78.57 -105.714928 26.921973 11.78 -105.694705 26.921973 17.93 -105.674482 26.921973 -105.654260 26.921973 21.66 -105.634036 26.921973 29.54 -105.714928 26.903809 42.73 -105.694705 26.903809 38.82

since the study region is surrounded by farmland, the limits set by the IHOBE make latent risk in the surrounding ecosystem and result in potential damage to human health by ingestion of contaminated crops. Both concentrations of lead, such as zinc, are attributed to the generated process to obtain gold and silver, therefore, it was possible to find them in substantial amounts in the samples collected. The concentrations shown in Table 1 confirm the hypothesis stated in the beginning of the investigation. Most of the sampled sites contain values above 400 parts per million of lead, which is the maximum limit

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Characterization of Topsoil Samples and Analysis of the Distribution of Heavy Metals in Parral Chihuahua, Mexico

allowed by the EPA in relation to playgrounds sites or recreational facilities. IHOBE establishes a level of 330 ppm maximum tolerable risk value for ecosystem protection. The risk to the environment is evident. Although the maximum allowed levels of lead, established by the EPA for common use areas, is 1,200 ppm, we should not forget that the source of emission of charged particles containing heavy metals is latent, and continue carrying out exploration work and exploitation of other mineral deposits in the area, so it is extremely important to address this problem and consider the region as a risk area for lead contamination. For zinc, the EPA sets the maximum allowed limits, values between 200 and 400 ppm, whereas the sites with concentrations in that range, as excessively phitotoxic. Moreover, IHOBE establishes 840 ppm of zinc as maximum tolerable risk for the protection of the environment. Taking into consideration both criteria, we can conclude that the content of zinc in the study area is a potential risk to both human health and its environment. As shown in Figs. 4 to 6, the highest concentrations are recorded in the northern part of the city and following a uniform dispersion pattern, which is influenced by the prevailing winds that circulate in NE for the first months of the year in the area in the

process of study. It confirms the finding of a cleaner area for heavy metals in this environment is in the south area of the city, as well as the southeast.

4. Summary
The results shown confirm the hypothesis that residues from the mining industry in the city contaminate the soil with high levels of heavy metals, mainly lead and zinc, and taking into consideration the IHOBE criteria can include arsenic, which represents a potential risk for human health. It becomes necessary to cover other means such as air and water, for a more comprehensive and objective assessment of potential harm to human health and the environment by heavy metals contamination in the area in process of study. Maximum concentrations were found: 78.57 ppm for arsenic in the P19 site, 896.65 ppm lead in the PA7 site, and zinc, 1160 ppm and 1162 ppm in PA7 and P16 points respectively; concentrations that show a potential health risk for humans and their environment. The area, which can be considered within the maximum allowed limits set by various international organizations, is the south and southwest regions of the City of Parral Chihuahua, Mexico, such as shown in Figs. 4 to 6.

Fig. 4 Distributions of the arsenic concentrations in silts.

Characterization of Topsoil Samples and Analysis of the Distribution of Heavy Metals in Parral Chihuahua, Mexico

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Fig. 5 Distributions of the lead concentrations in silts.

Fig. 6 Distributions of the zinc concentrations in silts.

Acknowledgments
CONACYT (Consejo Nacional de Ciencia y Tecnologa), for the financial support to develop this work; CIMAV (Centro de Investigaci[on en Materiales Avanzados), for your hospitality and technical and scientific support, and Professor of English, Sergio Valles Aros, for your help.

[4]

References
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J. Geochim. Explor. (1995) 5-23. SEDESOL, Informe de la situacin general en materia de equilibrio ecolgico y proteccin al ambiente 1991-1992. Secretara de desarrollo Social, Mxico, 1993. [5] INE, 2009: Investigacin sobre Sustancias Qumicas y Riesgos Eco toxicolgicos; Metales Pesados [6] Informacin Minera y Ambiental, 2008: Metales Pesados. [7] C. Baird, Environmental Chemistry, 2nd ed., W.H.Freman & Company, 1999. [8] A. Kabata-Pendias, H. Pendias, Trace Elements in Soils and Plants CRC, Press, Florida, 2001. [9] B.L. Gulson, K.J. Mizon, M.J. Korsch, D. Howarth, Non-orebody sources are significant contributors to blood lead of some children with low to moderate lead exposure in a mayor mining community, The Science of the Total Environment 181 (1996) 223-230. [10] S. Puga, Contaminacin por Metales Pesados en Suelo Provocada por la Industria Minera, 2006. [11] S.L. Miliarium Aureum, Contaminacin por metales pesados, 2004.