REDUCTION OF Cr(VI) TO Cr (III) BY ASCORBIC ACID IN AN HEAVELY CONTAMINATED SOIL Luz Alicia Galeana Corrales , Jorge Javier Ramrez

Garca(1), Lzaro Raymundo Reyes Gutirrez(2), Elizabeth Teresita Romero Guzmn(3) 1) Universidad Autnoma del Estado de Mxico. Facultad de Qumica, Laboratorio de Anlisis Instrumental. Paseo Coln esquina Paseo Tollocan; Colonia. Residencial Coln. Toluca, Estado de Mxico. C.P. 50180. Tel: +52 (722) 2 17 51 09 Ext. 113, Fax: +52 (722) 2 17 38 90. e-mail: jjramirezg@uaemex.mx 2) Instituto Potosino de Investigacin Cientfica y Tecnolgica. Divisin de Geociencias Aplicadas, Camino a la Presa San Jos 2055, Col. Lomas 4a. seccin C.P. 78216, San Luis Potos, San Luis Potos, Mxico 3) Instituto Nacional de Investigaciones Nucleares. Departamento de Qumica, Carretera Mxico-Toluca Km. 36.5, AP 18-1027. C.P. 52750, Salazar, Estado de Mxico, Mxico Abbreviations: XPS, X-ray photoelectron spectroscopy XRD, X-ray diffraction HPLC, high performance liquid chromatography SEM, Scanning electron microscopy EDS, X-ray energy dispersive spectrometry CCr(VI), chromium VI concentration t, time kobs, observed second-order rate constant T, reaction temperature A, pre-exponential factor R, universal constant of gases Ea, activation energy Abstract This study was conducted to evaluate the reduction of Cr(VI) to Cr(III) by ascorbic acid in samples of a Cr(VI) contaminated soil. The characterization of contaminated soil shows a concentration of 5886.2 mg/kg of Cr(VI) determined by the diphenylcarbazide method, the XPS analysis indicates the presence of Cr(VI) as chromate, and XRD analysis indicate that the mineral species is CaCrO4. We obtained the reduction of Cr(VI) to 100% in a ratio of Cr(VI): ascorbic acid concentration in units of mg/kg 1:5. The characterization of the soil after remediation process shows the reduction of the Cr(VI). In the XPS analysis the signals detected, only correspond to related species to Cr(III), and the signal of CaCrO4 is not detected in the XRD analysis. In the soluble fraction was possible to observe the reaction progress by HPLC with the formation of dehydroascorbic acid and Cr(III), and the decline and subsequent disappearance of the signals corresponding to the Cr(VI) and ascorbic acid. Keywords. XPS 1 Introduction The presence of heavy metals such as chromium in soils can be geogenic or anthropogenic origin. The anthropogenic source refers to the hazardous materials from industrial, agricultural, mining, and urban solid waste. (Galan and Romero 2008). It is said that a soil is contaminated when one or more pollutants exceed the maximum permissible level, these level are defined as concentrations which above them, undesirable effects are shown in the environment and/or in the surrounding living organisms. Unlike other environmental compartments (atmosphere and water) the pollutants present in soil have long residence periods. The
(1)

decontamination of the ground could represent a social problem due to the importance of protecting the environment, human health and because of its economic relevance. It is clear the need to find techniques for soil remediation that offer the proper and correct elimination and disposal of the pollutants. The potential effects of chromium on health depend on a variety of factors, such as the chemical state in which is found, the amount, exposure time and the way chromium is incorporated to the organism (ingestion, inhalation and absorption through skin). Although the Cr(III) (in low doses) is an essential trace element in animals (Schwartz and Mertz 1959; Mertz 1975), Cr(VI) is not, and it is considered to be carcinogen (ATSDR 2000; U.S. EPA 1984, 1990, 1998; IARC 1990; OMS 1988). The main human activities that increase Cr(VI) concentrations are steel, chromite processing industry, leather and textile manufacturing, pigments, electroplating and other industrial applications of Cr(VI). It is common that many of these residues remain in, or around the sites of factories, especially in the case of wastes and foundry salts, whose toxicity, generally low, tends to increase along the time (Palmer and Wittbrodt 1991). In soils, Cr(III) is relatively static due to its high adsorption capacity, particularly for iron and manganese oxides, clay minerals and sand (Santone 2009). Cr(III) as hydroxides, once again sedimented this compounds are hardly moved, because the oxidation of Cr(III) compounds to form Cr(VI) compounds practically does not occur naturally (Lee and Hering 2005; Unceta 2010). Cr(VI), has great mobility in the subsurface due to its high solubility, and even in relatively low concentrations is toxic, being pH of the soil a determinant factor (Palmer and Wittbrodt 1991). The technologies that incorporate sorption mechanisms have demonstrated a limited sorption capacity of Cr(VI) and to increase those values it is required to generate an acid environment (Carro Navarro et al. 1995; Gupta and Babu 2006; Devaprasath et al. 2007; Otiniano et al. 2007; Popuri et al. 2007; Acosta et al. 2008). Also it is need to remark that if migration of Cr(VI) is not consider from those adsorbents materials to the environment, only the speed of advection of Cr(VI) will be retard.(Palmer and Wittbrodt 1991). Chemical treatment is the main aim of reducing the bioavailability/mobility of pollutants through reactions with specific reagents, it is the case for chromium in which redox reactions are aimed at reducing the Cr(VI) to Cr(III), which is less toxic and mobile. Bioremediation of soils contaminated by Cr(VI) studies show that the reduction of Cr(VI) by microorganisms is possible when the concentration of Cr(VI) is low and in anaerobic conditions, however, for highly contaminated soils (>4000 mg/kg) reduction is inhibited, possibly because the amount of chromium is toxic for microorganisms and generate low population (Tseng and Bielefeldt 2002; Tokunaga et al. 2003). Studies of reduction by chemical agents as Fe(II), C6H6FeNO6, C12H22O11, H3PO3, C4H6O6 and TiO2 have shown extreme conditions of acidity (< 1 - 3) and in some cases a radiation source so the reduction is carried out at an appropriate level (Batchelor et al. 1998; Wang et al. 1999; Tzou et al. 2003; Khan et al. 2006; Abida et al. 2010; Wang et al. 2010). Research involving standard solutions of K2Cr2O7 indicates that the reduction of Cr(VI) to Cr(III) by vitamin C (ascorbic acid) occur both under the irradiation and in the dark, present low reaction time, in a wide range of temperature and pH, with the added bonus that the reaction product, dehydroascorbic acid, can be degraded

by microorganisms in groundwater or soil (Xu et al. 2004; Xu et al. 2005; Liu et al. 2005). Its applicability to environmental conditions has not yet been explored. The present research shows the evaluation of the reduction of Cr(VI) by ascorbic acid in an heavily contaminated soil, the samples were collected from an industrial landfill located in the field of Qumica Central, a company engaged in the manufacture and marketing of chemical products derived from chromium, located in the State of Guanajuato, Mexico. The company is located adjacent to the highway and to the railroad Len-San Francisco del Rincn, and to the river Los Gmez-Len-Turbio and the northwestern edges of the San Germn dam. Also, the lands of Qumica Central are located very close to the urban nucleus of Buenavista. The areas situated to the east, northeast and southeast are used for agriculture purposes, mainly sorghum and lucerne (Reyes-Gutierrez et al. 2009). The specific objectives of this study were: a) to evaluate the kinetic of the reduction in samples taken from the chromium-contaminated soil at different temperatures, b) to characterize morphological and mineralogical the soil before and after treatment, c) to identify the chemical species in the solid and soluble fraction of each sample in order to evaluate the reduction method of Cr(VI) by using ascorbic acid. 2 Materials and Methods 2.1 Sampling Four points were selected for sampling in the Qumica Central landfill (Fig. 1): an unaltered area of 1 m2 was cleaned and a one meter deep hole was drilled. In the vadose zone, a fine to medium texture sediment was collected. Soil profiles, respectively 30, 60 and 100 cm deep were investigated to assess Cr content. Samples of 2 kg were collected into polyethylene bags, transported in an ice pail to the laboratory and stored in a refrigerator at 4 C in an in situ moisture condition (0 to ~ 0.1 kPa of water potential). The samples were air dried to retard the activity of Cr(VI) (U.S. EPA, 1996, method 3060A). Besides, a composite sample was prepared by mixing several of the collected samples (100 g), and passing them through a No. 40 polyethylene mesh to obtain a subsample with a relatively homogeneous particle size; this sample was used in the experiments (Reyes-Gutierrez et al. 2009). 2.2 Cr(VI) sample determination and effect of the [Cr(VI)]:[ascorbic acid] mg/kg ratio on soil treatment 1 g of sample was weighted and transferred to a 100 mL volumetric flask, dissolved with distilled water and kept in agitation for 24 hours. The concentration of Cr(VI) was determined by the diphenylcarbazide method. The samples were analyzed in a UV-Vis spectrophotometer PERKIN-ELMER model Lambda 25. All reagents used for the quantification of Cr(VI) in samples were reactive grade. Once determined the concentration of Cr(VI) in the sample, a reduction test was performed by duplicate in 1 g of soil by direct contact at room temperature, for 24 hours to determine the concentration of ascorbic acid that carries out 100% of reduction, in assessing concentrations Cr(VI) - ascorbic acid 1: 1, 2, 3, 4, 5 and 6 in mg/kg. 2.3 Kinetic analysis

Reduction kinetics was carried out by duplicate, using the batch equilibrium technique which consists to in direct contact ascorbic acid solution with contaminated soil during specific periods of time (1, 3, 5, 10, 20,30, 45, 60, 90, 120 y 180 min). Experiments took place without adjustment of pH and at temperatures of 10, 20, 25, 30, 40 y 50 C. Fermont A.C.S. ascorbic acid standard solution was used for the reduction tests. 2.4 Physicochemical characterization The morphology and elemental chemical analysis of samples was performed by SEM: scanning electron microscope model JSM-6510LV JEOL brand, a device coupled with energy dispersive spectroscopy X-ray (EDS) model X3 Incapet Oxford brand. To determine XRD mineralogical species was used: an X-ray diffractometer Bruker D8 Advance, Cu lamp with a tube voltage and current of 30 kV and 25 mA respectively, continuously in a range of 5 to 80 2 and a step size of 0.03 2 for 40 min. Speciation of chromium in the soil surface by XPS. The XPS wide and narrow spectra was aquired using a JEOL JPS-9200, eqquiped with a Mg X-ray source (1253.6 eV) at 200 W, the area of analysis was 1mm, and the vacuum was in the order of 10-8 Torr for all samples. The spectra was analyzed using the specsurfTM software included with the instrument, all spectra was charge corrected by means of the adventitious carbon signal (C1s) at 284.5 eV. The Shirley method was used for the background substraction, whereas for the curve fitting the GaussLorentz method was used. For speciation of chromium in the soluble fraction was used a HPLC technique with RP18 column Lichospher Metachem 5 m 250 x 4.0 mm, 25 mM potassium phosphate monobasic pH 3.0, detection wavelength dual Waters 2487, Waters 1515 isocratic pump and Breeze software for data processing. The analysis of the present species in samples was made by comparing obtained signals (retention time) with standard solutions of Cr(VI), Cr(III), ascorbic acid and dehydroascorbic acid. 3 Results and Discussion 3.1 Cr(VI) sample determination and effect of the [Cr(VI)]:[ascorbic acid] mg/kg ratio on soil treatment The content of Cr(VI) was determined in 50 parts of the sample obtained by the method of diphenylcarbazide, yielding an average concentration of 5886.2 mg/kg of dry soil with a coefficient of variation of 9.6% (Table 1), this concentration exceeds the limit establish by the NOM-147-SEMARNAT-SSA1-2004 for industrial land use (510 mg/kg). From the evidence of reduction at 24 h with different Cr(VI): ascorbic acid ratios in mg/kg, it was observed that at 1:5 ratio, 100% of the initial Cr(VI) were reduced at natural pH and room temperature (Table 2). 3.2 Kinetic analysis The efficiency and rate in the reduction of Cr(VI) increase as the reaction temperature increases as is shown in Fig. 2. In 180 min 100 % of reduction is reached at 40 and 50 C, at the other hand, 89 % of reduction is reached at 10 C. The initial pH was 8.2 0.5, while treated soil pH was 7.1 0.2 during all experiments; no acidification of the ground is generated. The experimental results have not demonstrated a first order dependence as reported in studies with potassium dichromate solution (Xu et al. 2004, Xu et al. 2005, Liu et al. 2005). The experimental data satisfies second order kinetics:

dC Cr (VI ) dt

2 = k obs CCr (VI )

(1)

The kobs values calculated by equation (1) are listed in Table 3 (0.973 < r 2 < 0.997). The coefficients of determination values indicate that the reduction follows second order kinetics model during the first hour of the reaction. Assumming that kobs has Arrhenius behavior, the activation energy (Ea) can be calculated from the relation below:

k obs (T ) = A e

Ea RT

(2)

Where A is the pre-exponential factor, R is the universal constant of gases (8.314 J/molK), and T is the reaction temperature (K). According to that, the minimum energy required for the reduction of Cr(VI) by ascorbic acid in the contaminated soil is 104.1 kJ/mol (Fig. 3). 3.3 Physicochemical characterization The transition elements are characterized for their capacity to change color when they are reduced. This was observed in the reduction test by ascorbic acid. The yellow color presented in Cr(VI) contaminated sample turns to green, indicating the presence of Cr(III) compounds in soil. The obtained micrographs by SEM of the Cr(VI) contaminated soil and treated soil show a heterogeneous soil, as well as, small aggregates adhered to particles of major size, indicating that the material is a heterogeneous powder. The size of discrete soil particles ranges from 250 m to less than 1 m (Fig. 4). Elemental chemical analysis by energy dispersive spectroscopy X-ray (EDS), Table 4 shows the results from content in weight % of each element present in the sample, both contaminated and treated soils show the usual composition of aluminosilicates (Si, Al, O, Na and Ca) and indicate that the main constituents of the soils are O, Si and C. Cr represents 0.75% by weight in the treated samples, similar to the Cr content in the contaminated sample (0.66%). There is no decreasing in the amount of Cr, due to the process only reduce the oxidation state of Cr(VI) to Cr(III), and not imply a remotion process. The treated and contaminated soil samples were analyzed by XRD, the diffractogram of the contaminated soil (Fig. 5a) shows that the principal minerals found are quartz, SiO2 (JCPDS card 33-1161), albite (Na, Ca)(Si, Al)4O8 (JCPDS card 20-0554), and chromatite CaCrO4 (JCPDS card 08-0458); as they were previously reported by Reyes-Gutirrez et al. 2009. The chromatite evidence the presence of Cr(VI). Fig. 5b shows the diffractogram of the soil after remediation process. These samples have a mineralogical composition of quartz, SiO2 (JCPDS card 33-1161) and albite (Na, Ca)(Si, Al)4O8 (JCPDS card 20-0554). It should be noted that no chromatite was identified by XRD in this sample. The XPS surface analysis was used to determine the oxidation state of chromium present in the polluted and treated soil. The narrow scan of Cr 2p3/2 from the contaminated and treated soil samples are shown in Fig. 6.

From the deconvolution of chromium, it is obtained that the contaminated soil present two peaks at binding energies of 578.7 eV and 577.4 eV corresponding to Cr(VI) probably as CrO 3 (70.5 %) and Cr(III) as Cr(OH)3 (29.5 %) respectively, while in the soil after remediation process only shows signals corresponding to compounds of Cr(III), at 575.6 eV and 577.1 eV as Cr2O3 and Cr(OH)3 respectively. It is clear from the intensity of the peaks in Fig. 5, that ascorbic acid reduced Cr(VI) to Cr (III) at 100% Speciation of the chromium in the soluble fraction of contaminated and treated soil, was carried out by HPLC at 230 nm, this technique allows following the progress of the reaction:

Cr 2 O72 + 3C 6 H 8 O6 + 8H + 2Cr 3+ + 3C 6 H 6 O6 + 7 H 2 O
2005)

(Liu et al.

Fig. 7a, presents the chromatogram for the contaminated soil showing the signal of Cr(VI) at 2.4 min, the chromatogram for the soil after remediation process shows only the signal corresponding to Cr(III) at 2.0 min (Fig. 7b). The chromatogram of the soil treated with an excess of ascorbic acid, shows signals of Cr(III) at 2.0 min, dehydroascorbic acid at 2.8 min, and ascorbic acid at 3.2 min (Fig. 8a). The chromatogram obtained from the soil sample treated at 10 C, shows Cr(III) and Cr(VI) signals, where 10 % of Cr(VI) was not reduced (Fig. 8b). In this way it was possible to observe the reaction progress by HPLC with the formation of dehydroascorbic acid and Cr(III), and the decline and subsequent disappearance of the signals corresponding to the Cr(VI) and ascorbic acid. 4 Conclusions The concentration of Cr(VI) in the soil sample was 5886.2 mg/kg. The ascorbic acid in a 1:5 ([Cr(VI)]: [ascorbic acid], mg/kg) ratio reduces the Cr(VI) at 100 % in 24 hours at temperatures of 20-50 C. The reduction in the soil follows a second order kinetic reaction in the first 60 minutes and the activation energy is 104.1 kJ/mol. The XPS and HPLC analysis verify the reduction of Cr(VI) to Cr(III) by ascorbic acid, identified in treated soil only species corresponding to Cr(III). On the basis of the results present in this study, it can be concluded that the ascorbic acid treatment could be an efficient method as a part of a global strategy of remediation of heavily contaminated soils. However in addition to the results obtained in this study, numerical techniques must be applied to take into account the processes affecting the migration of Cr(VI) as well as the reducing agent on the ground including groundwater situ. Acknowledgments flow, diffusion-controlled mass transfer across heterogeneous boundaries, dissolution/precipitation, and adsorption/desorption, to predict the rate and percentage of Cr(VI) reduction in

In first place to Qumica Central de Mxico for the technical support, to the Universidad Autnoma del Estado de Mxico (UAEM) for the financial support through proyects 2049/2005 y 2566/2007U, and also to the Centro Conjunto de Investigacin en Qumica Sustentable UAEM-UNAM for the analytical support. References Abida, O., Mailhot, G., Mestankova, H., Litter, M., & Bolte, M. (2010). Photoinduced reduction of chromium (VI) by iron aminopolycarboxylate complex (FeNTA). Photochem. Photobiol. Sci., 9, 823-829. Acosta, I., Crdenas, J. F., Alvarado-Hernandez, D., et al. (2008). Remocin de Cromo(VI) en Solucin Acuosa por la Biomasa Celular de Paecilomyces sp. Inf. Tecnol., 19(1), 69-74. ATSDR Agency for Toxic Substances and Disease Registry. (2000). Toxicological Profile for Chromium. Atlanta, GA: Department of Health and Human Services. UU., Public Health Service. Batchelor, B., Schlautman, M., Hwang, I., & Wang, R. (1998). Kinetics of chromium(VI) reduction by ferrous ion, ANRCP-1998-13, Amarillo National Resource Center for Plutonium, U.S. DOE: Amarillo, TX. Carro Navarro, B., Moctezuma, M. De G., & Acosta, I. (1995). Remocin de cromo(VI) por la biomasa celular de la levadura capsulada Cryptococcus neoformans. Centro de Investigacin y de Estudios de Posgrado, Facultad de Ciencias Qumicas. Universidad Autnoma de San Luis Potos. Editorial Universitaria Potosina. 179-182. Devaprasath, P.M., Solomon, J.S. & Thomas, B.V. (2007). Removal of Cr(VI) from aqueous solution using natural plant material. J. ASES, 2(3), 77-83. Galan, E., & Romero, A. (2008). Contaminacin de suelos por metales pesados. MACLA 10, 48-60. Gupta, S., & Babu, B.V. (2006). Adsorption of chromium(VI) by a low-cost adsorbent prepared from tamarind seeds. In: Proceedings of International Symposium & 59th Annual Session of IIChE in association with International Partners (CHEMCON-2006), GNFC Complex, Bharuch, December 2730. IARC International Agency for Research on Cancer. (1990). Chromium, nickel, and welding. Monographs on the Evaluation of Carcinogenic Risks to Humans 49. Khan, Z., Hashmi, A. A., & Din, K. (1998). Reduction of chromium(VI) by phosponic acid. Transit Metal Chem, 23(2), 147-150. Lee, G., & Hering, J.G. (2005) Oxidative dissolution of chromium(III) hydroxide at pH 9, 3, and 2 with product inhibition at pH 2. Environ Sci Technol, 39, 4921-4928. Liu, Y., Xu, X.-H., & He, P. (2005). Remediation of Cr(VI) in solution using vitamin C. J Zhejiang Univ Sci, 6B(6), 540-542. Mertz, W. (1975). Effects and metabolism of glucose tolerance factor. Nutr Rev, 33, 129-135 Norma Oficial Mexicana. (2004). NOM-147-SEMARNAT-SSA1-2004, Criterios para determinar las concentraciones de remediacin de suelos contaminados por arsnico, bario, berilio, cadmio, cromo hexavalente, mercurio, nquel, plata, plomo, selenio, talio y/o vanadio. Mxico, Secretara de Medio Ambiente y Recursos Naturales.

Otiniano M., Tuesta L., Robles H., Lujn M., & Chavez M. (2007). Biorremediacin de cromo(VI) de aguas residuales de curtiembres por Pseudomonas sp y su efecto sobre el ciclo celular de Allium cepa. Rev. Med. Vallejiana, 4(1), 32-42. Palmer, C. D., & Wittbrodt P. R. (1991). Processes Affecting the Remediation of Chromium-Contaminated Sites. Environ Health Persp, 92, 25-40. Popuri, S.R., Jammala, A., Reddy, K.V.N.S., & Abburi, K. (2007). Biosorption of hexavalent chromium using Tamarind (Tamarindus indica) fruit shell-a comparative study. Electron J Biotechn, doi: 10.2225/vol10issue3-fulltext-11 Reyes-Gutirrez, L. R., Romero Guzmn, E. T., Olmos Salinas, M. G., & Rodrguez Castillo, R. (2009). Chemical Species of Chromatite of an Industrial Landfill in the Leon Valley, Guanajuato, Mexico. Rev Mex Cienc Geol. 26(1) :104-116 Santonen T. (2009). Inorganic chromium(III) compounds. World Health Organization, United Nations Environment Programme, International Labour Organisation, Inter-Organization Programme for the Sound Management of Chemicals, International Program on Chemical Safety. World Health Organization, 2009 Science pp. 88 Schwarz, K., & Mertz, W. (1959). Chromium III and the glucose tolerance factor. Arch Biochem Biophys 85, 292-295 Tokunaga, T.K., Wam, J., et.al. (2003). In situ reduction of chromium(VI) in heavily contaminated soils through organic carbon amendment. J Environ Qual, 32(5), 1641-1649. Tseng, J.K., & Bielefeldt, A.R. (2002). Low-temperature chromium(VI) biotransformation in soil with varying electron acceptors. J Environ Qual, 31, 1831-1841. Tzou, Y.M., Loeppert, R.H., & Wang, M.K. (2003). Light-Catalyzed Chromium(VI) reduction by organic compounds and soil minerals. J Environ Qual, 32, 2076-2084. Unceta, N., Seby, F., Malherbe, J., & Donard, O.F.X. (2009). Chromium speciation in solid matrices and regulation: a review. Anal Bioanal Chem, 397(3), 1097-1111, doi: 10.1007/s00216-009-3417-1 U.S. EPA United States Environmental Protection Agency. (1984). Health assessment document for chromium (final report). Research Triangle Park, NC: U.S. Environmental Protection Agency. U.S. EPA United States Environmental Protection Agency. (1990). Noncarcinogenic effects of chromium: Update to health assessment document. Research Triangle Park, NC: U.S. Environmental Protection Agency. U.S. EPA United States Environmental Protection Agency. (1996), Soil Screening Guidance: Users Guide: Washington, DC, United States Environmental Protection Agency Office of Solid Waste and Emergency Response, EPA/540/R-96/0180, 178. U.S. EPA United States Environmental Protection Agency. (1998). Toxicological profile update on hexavalent chromium. Integrated Risk Information System (IRIS). Cincinnati: U.S. Environmental Protection Agency. Wang, C., Martin, D.F., & Martin, B.B. (1999). Reaction of Chromium(VI) Wastes with Sugars. Fla. Sci., 62(1), 4857.

Wang, N., Zhu, L., Deng, K., She, Y., Yu, Y., & Hang H. 2010. Visible light photocatalytic reduction of Cr(VI) on TiO2 in situ modified with small molecular weight organic acids. Appl Catal B-Environ, 25( 3-4), 400-407. World Health Organization. (1988). Environmental health criteria 61: chromium. Geneva: WHO. Xu, X.-R., Li H.-B., Li X.-Y. & Gu J.-D. (2004). Reduction of hexavalent chromium by ascorbic acid in aqueous solutions. Chemospere, 57,609-613. Xu, X.-R., Li H.-B., Gu J.-D. & Li X.-Y. (2005). Kinetics of the reduction of chromium(VI) by vitamin C. Environ Toxicol Chem, 24(6), 1310-1314

FIGURE CAPTIONS Fig. 1 Map of study area, Buenavista, Len Guanajuato, Mxico. The location of the sampling sites at the industrial landfill of the chromium wastes in the facilities of the Qumica Central chromate factory is shown. (Reyes-Gutirrez, et al., 2009) Fig. 2 Effects of temperature on the Cr(VI) reduction efficiency Fig. 3 Plot of ln(kobs) versus 1/T under different temperatures. Reactions were performed at natural pH of the soil sample Fig. 4 Scanning Electron Microscope (SEM) micrographs. a soil contaminated with Cr(VI). b soil after remediation process Fig. 5 X-ray diffraction (XRD) patterns that show the intensity of diffracted X-rays from various planes as a function of 2 value for a soil contaminated with Cr(VI). b soil after remediation process. Q: quartz, A: albite, and C: chromatite Fig. 6 X-ray photoelectron spectroscopy (XPS) spectrums for a soil contaminated with Cr(VI). b soil after remediation process. The binding energy peaks are assigned to various valence states of chromium Fig. 7 Chromatograms obtained using High Performance Liquid Chromatography (HPLC) at 230 nm for the soluble fraction from a soil contaminated with Cr(VI). b soil after remediation process Fig. 8 The typical chromatograms of chromium species obtained from real samples a with an excess of ascorbic acid. b an incomplete Cr(VI) reduction