Chemical Speciation and Bioavailability (2011), 23(3)

183

Evaluation of the chromium bioavailability in tanned leather shavings using the SM&T sequential extractions scheme
Llian Irene Dias da Silva, Fernanda Veronesi Marinho Pontes, Manuel Castro Carneiro, Maria Ines Couto Monteiro*, Marcelo Dominguez de Almeida and Arnaldo Alcover Neto
Coordenacao de Analises Minerais, Centro de Tecnologia Mineral CETEM, Av. Pedro Calmon 900, Cidade Universitaria, CEP 21941-908, Rio de Janeiro, RJ, Brazil *E-mail: mmonteiro@cetem.gov.br ABSTRACT Tanned leather shavings from Brazilian tanneries were analysed in order to assess the chromium extractability and bioavailability, and consequently its potential release into other environmental compartments when the shavings are deposited on landll sites. The conventional SM&T (Standard, Measurement and Testing Programme) sequential extractions scheme was applied. Also, Cr(VI) and Cr(III) concentrations in the oxidizable fraction were determined. The results indicated high total chromium concentrations (1.04, 1.46 and 2.74%) in the samples A, B and C, respectively. A signicant quantity of chromium (about 6 11% of total chromium) was easily released in slightly acidic conditions (step 1). This fraction is the most labile, and therefore the most dangerous and bioavailable for the surrounding environment. Less chromium (1 3% of total chromium) was released in reducing conditions (step 2), whereas about 0.5 3% of total chromium was strongly associated to the leather shaving structure (residual fraction step 4), and therefore, its release under environmental conditions would be unlikely. Most of chromium (about 83 92% of the total chromium) was bound to the organic matter, as expected, since it was released in oxidizing condition (step 3). Part of chromium released in this fraction was also converted into Cr(VI), which is more labile and toxic than Cr(III). Considering the chromium concentrations, the sequentially extracted fractions may be ordered as follows: oxidizable4exchangeable4reducible4residual. Keywords: chromium speciation, availability, extraction, tanned leather shavings

1. INTRODUCTION The major leather production centres in the world are found in Mexico, Brazil, Japan, South Korea, China, India and Pakistan. Whereas Korea, Japan and Italy import hides from countries which have a large meat production industry, the South American countries, such as Argentina and Brazil process their own hides. The leather industry is prevalent in Brazil, especially in the South, in the Rio Grande do Sul State, where more than 50% of Brazilian leather is produced (Basegio et al., 2002). In the tanning industry, raw skin is transformed into leather by means of a series of chemical and mechanical processes (Alvarez-Bernal et al., 2006; Basegio et al., 2002). Skin in tanning process, which is the main process that protects the leather against some environmental effects such as microbial degradation, heat, sweat or moisture, is

stabilized by using a tannage material such as some mineral and vegetable-based substances and aldehyde (Erdem and Ozverdi, 2008). Trivalent chromium salts (in particular chromium sulfate) are the most widely used tanning substances today. About 90% of all hides are tanned with Cr(III) salts. Hides that have been tanned with chromium salts have a good mechanical resistance, an extraordinary dyeing suitability and a better hydrothermal resistance in comparison with hides treated with vegetable substances. Chromium salts also have a high rate of penetration into the interbrillar spaces of the skins. This results in a saving in terms of production time and a better control of the process (Basegio et al., 2002; Berry et al., 2002). The tanning industry generates substantial quantities of waste. One tonne of wet hide yields only 200 kg of leather, whereas over 600 kg of solid waste or by-product are

doi: 10.3184/095422911X13027118597382

www.chemspecbio.co.uk

184

Chromium bioavailability in tanned leather shavings extraction tests, i.e., toxicity characteristic leaching procedures, single extraction procedure and ASTM methods to extract metals (Cd, Cr, Cu, Ni, Pb and Zn) in various matrices including leather debris. The use of the SM&T (Standard, Measurement and Testing Programme) sequential extractions scheme as well the chromium speciation in the oxidizable fraction has not been reported for tanned leather shavings. The aim of the present work was to study the chromium concentration potentially bioavailable in tanned leather shavings. The SM&T sequential extractions scheme was applied for leather shaving samples collected in different Brazilian tanneries. Also, chromium species concentrations in the oxidizable fractions were investigated. 2. EXPERIMENTAL 2.1 Apparatus and operating conditions The Cr extraction was performed by using a heated waterbath model 572 (Fisatom Equipamentos Cientcos Ltda (Sa o Paulo, SP, Brazil), a centrifuge model CT-6000 (Cientec Equipamentos para Laboratorios, Piracicaba, SP, Brazil) with 3200 rpm of speed and an orbital shaker Marconi model MA141 (Piracicaba, SP, Brazil). A heated plate Marconi model MA 239 (Piracicaba, SP, Brazil) was used to digest the samples for total chromium determination. A ame atomic absorption spectrometer model SpectrAA 50 B from Varian Inc. (Palo Alto, CA, USA) was operated under the conditions recommended by the manufacturer. Acetylene (Linde, RJ, Brazil) and nitrous oxide (White Martins, RJ, Brazil) with purities of 99.7% and 99% were used, respectively. The chromium hollow cathode lamp was operated at 7 mA; the absorbance measurements were made at the 357.9 nm wavelength and a slit width of 0.2 nm was used. Absorbance measurements for determination of Cr(VI) were performed on a spectrophotometer HACH model DR 5000 (Loveland, Colorado, USA), using 1 cm quartz cuvettes and 540 nm of wavelength. 2.2 Reagents and samples All solutions were prepared with analytical grade reagents and ultra-pure water, obtained from a reverse osmosis system model Elix 5 coupled to a Milli-Q Gradient model, from Millipore (Barueri, SP, Brazil). All glassware vessels were soaked in 12% (vyv) HNO3 for 24 h and rinsed thoroughly with distilled water and, nally, rinsed for the last time with ultra-pure water. Standard stock solutions containing 1000 mg L 1 Cr(VI) as K2CrO4, was prepared from Fixanal concentrate (Riedel-de-Hae n, Seelze, Germany). Intermediate low concentration solutions were prepared daily by dilution of the corresponding stock solution with water. Glacial acetic acid 99.7%, hydroxylamine hydrochloride, ammonium acetate, hydrogen peroxide 30% myv, nitric acid 65%, sulfuric acid 98%, diphenilcarbazide and acetone were supplied by Vetec Qumica Fina (Duque de Caxias, RJ, Brazil). Three tanned leather shaving samples were collected in different Brazilian tanneries.

generated. Leather shavings constitute 75% of the solid wastes containing chromium in the tanning process (Erdem, 2006). In the literature, there are many studies which convert tannery wastes to useful products (Basegio et al., 2002; Dettmer et al., 2010; Erdem, 2006; Oliveira et al., 2007; Trezza and Scian, 2007; Yilmaz et al., 2007). However, chromium-tanned leather, consisting mainly of shavings and nished parts, is normally disposed on landll sites (Ferreira et al., 2010; Yilmaz et al., 2007), especially in developing countries, because of its low investment and operational costs (Xiaoli, 2007). Therefore, solid wastes from tannery industry deposited on landll sites require special attention because of the large amount produced, toxic and hazardous effects and legislative restrictions (Basegio et al., 2002; Berry et al., 2002; Trezza and Scian, 2007; Yilmaz et al., 2007). The potential hazard of the wastes deposited on landll based on the total metal content is not enough to evaluate the environmental impact because the chemical state in which the metals are bound to wastes must be known to evaluate their mobility and bioavailability (Perez-Lopez et al., 2008). Trace metals in wastes may exist in different chemical forms or ways of binding. The environmental behavior of chromium depends on its oxidation state. Whereas Cr(III) compounds tend to form relatively inert precipitates at near-neutral pH, Cr(VI) compounds are strong oxidizers and highly soluble, and therefore more toxic than Cr(III) compounds (Kotas and Stasicka, 2000; Losi et al., 1994). Single and sequential extractions schemes (SES) were designed in the 1980s in order to assess the retentionyrelease of metals in soil and sediment samples (Quevauviller, 2002; Rauret et al., 2000; Prusty et al., 2009). Later, these procedures were applied to other matrices. Gupta and Sinha (2006) have studied the chemical fractionation and heavy metal accumulation in a plant grown on soil amended with tannery sludge using single extractants. Recently, Rao et al. (2008) have reviewed extraction procedures applied for soil, industrially contaminated soil, sludge amended soil, sewage sludge, waste and road dust and run-off. Sequential extractions procedures are the most used for the determination of different forms of metals in wastes, such as mining wastes (Clevenger, 1990; Margu et al., 2004; Perez-Lopez et al., 2008), coal ash (Landsberger et al., 1995), municipal solid wastes (Xiaoli et al., 2007) and untreated industrial wastewater sludge (Kazi et al., 2005). Only two works have been found for wastes from the tannery industry. Raju and Tandon (1999) have applied the Stovers SES for tannery sludges in order to determine the distribution of chromium into exchangeable, adsorbed, organic, carbonate and sulde forms. The sequence of reagents, extraction time and solution : solid ratio were as follows: (i) 1 mol L 1 KNO3, 16 h, 50 : 1; (ii) 0.5 mol L 1 KF, 16 h, 80 : 1; (iii) 0.1 mol L 1 Na4P2O7, 16 h, 80 : 1; (iv) 0.1 mol L 1 EDTA, 16 h, 80 : 1; (v) and 1 mol L 1 HNO3, 16 h, 50 : 1. Chang et al. (2001) have evaluated three

Llian Irene Dias da Silva et al.

185

Table 1 Total chromium concentrations and chromium concentrations in the SM&T sequential extraction scheme fractions for tanned leather shaving samples (n 3) Sample SM&T sequential extraction scheme fractions Exchangeable (mg kg 1) A B C 667 + 33 1102 + 21 2980 + 100 Reducible (mg kg 1) 118 + 11 164 + 37 849 + 12 Oxidizable (%) 0.96 + 0.03 1.33 + 0.04 2.28 + 0.02 Residual (mg kg 1) 56 + 8 75 + 18 802 + 103 1.04 + 0.03 1.46 + 0.01 2.74 + 0.03 1.07 + 0.02 1.45 + 0.04 2.79 + 0.05 Total Cr (sum) (%) Total Cr found (%)

2.3 Procedures The conventional SM&T (Standard, Measurement and Testing Programme) sequential extraction scheme (Filgueiras et al., 2002) is described as follows: step 1 (acid-soluble and exchangeable fraction) 20 mL of 0.11 mol L 1 acetic acid was added to 0.5 g of sample without previous treatment in a 50 mL polypropylene centrifuge tube, and shaken for 16 h at room temperature. The phases were separated by centrifugation for 30 min, and the supernatant was separated for chromium determination. About 10 mL of water was added to the residue, shaken for 15 min and centrifuged for 30 min. The washing was discarded, and the residue was separated for the next step; step 2 (reducible fraction) 20 mL of 0.1 mol L 1 hydroxylamine hydrochoride (adjusted to pH of about 2 by adding nitric acid) was added to the residue from step 1, and shaken for 16 h at room temperature. The phases were separated by centrifugation for 30 min, and the supernatant was separated for chromium determination. The residue was washed with water as described in step 1; step 3 (oxidizable fraction) 5 mL of 30% (myv) hydrogen peroxide was added to the residue from step 2, and occasionally and manually shaken for 1 h at room temperature. After that, the mixture was heated in a water-bath for 1 h at 85 C, and then evaporated to almost dryness at 100 C. Then, 5 mL of 30% (myv) hydrogen peroxide were added, and the mixture was heated in a water-bath for 1 h at 85 C, and then evaporated to almost dryness at 100 C. After that, 25 mL of 1 mol L 1 ammonium acetate were added, and shaken for 16 h at room temperature. The phases were separated by centrifugation for 30 min, and the supernatant was separated for chromium determination. The residue was washed with water as described in step 1; step 4 (residual fraction) the residue from step 3 was transferred to a glass beaker with the aid of 20 mL of nitric acid 1 : 1. Then, the beaker was heated until the residue was dissolved. The solution was let to cool at room temperature, transferred to 25 mL volumetric ask, and the ask was lled to the mark with water. This solution was used for chromium determination. To evaluate the validity of the SM&T (Standard, Measurement and Testing Programme) sequential extractions scheme for Cr in each tanned leather shaving sample, we compared the sum of the chromium concentrations found in each step with the value of total chromium concentration. The total chromium concentration was deter-

mined by using the procedure described in step 4, except that about 2 g of sample and a 50 mL volumetric ask were used. The following procedure was used for chromium(VI) determination in the oxidizable fraction: aliquots of 0.1 mL (samples A and B) and 5 mL (sample C) of extracted oxidizable fraction were transferred to a 50 mL volumetric ask. The pH values were adjusted by adding 200 mL (for samples A and B) and 600 mL (for sample C) of concentrated H2SO4. Then, 1 mL of diphenilcarbazide 0.5% myv (0.25 g of diphenilcarbazide in 50 mL of acetone) was added, and the ask was lled to the mark with water. The solution was homogenized and let stand for 5 min for colour development. The Cr(III) concentration was calculated by difference. 3. RESULTS AND DISCUSSION The extractable chromium concentrations in each sequential extraction step and total chromium concentrations in tanned leather shaving samples are shown in Table 1. The results indicated high total chromium concentrations (1.04, 1.46 and 2.74%) in samples A, B and C, respectively. The sums of the Cr concentrations found in each step for all samples were similar to the values of total chromium concentrations (t-test, condence level of 95%), validating the SM&T scheme. The extracted chromium percent values with respect to the sum of the four fractions are depicted in Figure 1. A meaningful quantity of chromium (about 6 11% of total chromium) was easily released in slightly acidic condition. A lower chromium fraction (1 3% of total chromium) was released in reducing condition. The most of chromium (about 83 92% of total chromium) was released in oxidizing condition, whereas about 0.5 3% of total chromium was strongly associated with the leather shaving structure (residual fraction), and therefore its release under environmental conditions would be unlikely. Considering the chromium concentrations, the sequentially extracted fractions may be ordered as follows: oxidizable4exchangeable4reducible4residual. Table 2 shows the chromium species concentrations in the oxidizable fraction, whereas the chromium species relative concentrations in this fraction are depicted in Figure 2. About 48, 5 and 0.9% of chromium of the oxidizable fractions of the samples A, B and C were

186

Chromium bioavailability in tanned leather shavings

Table 2 Concentrations of Cr(VI) found and of Cr(III) calculated in the oxidizable fraction of the SM&T sequential extraction scheme for tanned leather shaving samples (n 3) Sample Concentration (%) Cr(VI) found A B C 0.46 + 0.06 0.18 + 0.06 0.02 + 0.01 Cr(III) calculated 0.50 + 0.07 1.15 + 0.06 2.26 + 0.03

Figure 1 Chromium fractionation patterns obtained by using the SM&T sequential extractions scheme applied for tanned leather shaving samples (n 3).

converted into Cr(VI), respectively. The relative chromium species concentrations in the oxidizable fractions varied with the chromium concentrations in these fractions. This fact probably occurred because the addition of the oxidative reagent was constant and not enough to oxidize all the organic matter and Cr(III), specially in samples with higher chromium concentrations. The evidence of conversion of Cr(III) into Cr(VI) in step 3 showed the risk of the disposal of this type of waste in the environment under oxidative conditions.

potential mobility and the possible transfer of chromium to the surrounding environment indicated that a signicant amount of chromium (about 6 11% of total chromium) was easily released in slightly acidic condition (step 1). This fraction is the most labile, and therefore the most dangerous and potentially bioavailable for the surrounding environment. A lower chromium fraction (1 3% of total chromium) was released in reducing condition (step 2), whereas about 0.5 3% of total chromium was strongly associated to the leather shaving structure (residual fraction step 4), and therefore, its releasing under environmental conditions would be unlikely. Most of chromium (about 83 92% of the total chromium) was bound to the organic matter, as expected, since it was released in oxidizing condition (step 3). Part of chromium released in this fraction was also converted into Cr(VI), which is more labile and toxic than Cr(III). Considering the chromium concentrations, the sequentially extracted fractions may be ordered as follows: oxidizable4exchangeable4reducible4residual.

4. CONCLUSION High total chromium concentrations (1.04, 1.46 and 2.74%) in samples A, B and C were found, respectively. The SM&S (Standard, Measurement and Testing Programme) sequential extractions scheme applied to evaluate the REFERENCES
Alvarez-Bernal, D., Contreras-Ramos, S.M., Trujillo-Tapia, N., Olalde-Portugal, V., Frias-Hernandez, J.T. and Dendooven, L. (2006) Effects of tanneries wastewater on chemical and biological soil characteristics. Appl. Soil. Ecol., 33, 269 277. Basegio, T., Berutti, F., Bernardes, A. and Bergmann, C.P. (2002) Environmental and technical aspects of the utilization of tannery sludge as a raw material for clay products. J. Eur. Ceram. S., 22, 2251 2259. Berry, F.J., Costantini, N. and Smart, L.E. (2002) Synthesis of chromium-containing pigments from chromium recovered from leather waste. Waste Manag., 22, 761 772. Chang, E.E., Chiang, P.C., Lu, P.H. and Ko, Y.W. (2001) Comparisons of metal leachability for various wastes by extraction and leaching methods. Chemosphere, 45, 91 99. Clevenger, T.E. (1990) Use of sequential extraction to evaluate the heavy metals in mining wastes. Water Air Soil Pollut., 50, 241 254. Dettmer, A., Nunes, K.G.P., Gutterres, M. and Marcilio, N.R. (2010) Production of basic chromium sulfate by using recovered chromium from ashes of thermally treated leather. J. Hazard. Mater., 176, 710 714. Erdem, M. (2006) Chromium recovery from chrome shaving generated in tanning process. J. Hazard. Mater., 129, 143 146.

Figure 2 Chromium species fractionation patterns in the oxidizable fraction obtained by using the SM&T sequential extractions scheme applied for tanned leather shaving samples (n 3).

Llian Irene Dias da Silva et al.

Erdem, M. and Ozverdi, A. (2008) Leaching behavior of chromium in chrome shaving generated in tanning process and its stabilization. J. Hazard. Mater., 156, 51 55. Ferreira, M.J., Almeida, M.F., Pinho, S.C. and Santos, I.C. (2010) Finished leather waste chromium acid extraction and anaerobic biodegradation of the products. Waste Manag., 30, 1091 1100. Filgueiras, A.V., Lavilla, I. and Bendicho, C. (2002) Comparison of the standard SM&T sequential extraction method with smallscale ultrasound-assisted single extractions for metal partitioning in sediments. Anal. Bioanal. Chem., 374, 103 108. Gupta, A.K. and Sinha, S. (2006) Chemical fractionation and heavy metal accumulation in the plant of Sesamum indicum (L.) var. T55 grown on soil amended with tannery sludge: selection of single extractants. Chemosphere, 64, 161 173. Kazi, T.G., Jamali, M.K., Kazi, G.H., Arain, M.B., Afridi, H.I. and Siddiqui, A. (2005) Evaluating the mobility of toxic metals in untreated industrial wastewater sludge using a BCR sequential extraction procedure and a leaching test. Anal. Bioanal. Chem., 383, 297 304. Kotas, J. and Stasicka, Z. (2000) Chromium occurrence in the environment and methods of its speciation. Environ. Pollut., 107, 263 283. Landsberger, S., Cerbus, J.F. and Larson, S. (1995) Elemental characterization of coal ash and its leachates using sequential extraction techniques. J. Radioanalyt. Nucl. Chem., 192, 265 274. Losi, M.E., Amrhein, C. and Frankenberger, W.T. Jr. (1994) Environmental biochemistry of chromium. Rev. Environ. Contam. Toxicol., 136, 91 121. Margu, E., Salvado, V., Queralt, I. and Hidalgo, M. (2004) Comparison of three-stage sequential extraction and toxicity characteristic leaching tests to evaluate metal mobility in mining wastes. Anal. Chim. Acta, 524, 151 159. Oliveira, L.C.A., Goncalves, M., Oliveira, D.Q.L., Guerreiro, M.C., Guilherme, L.R.G. and Dallago, R.M. (2007) Solid waste from leather industry as adsorbent of organic dyes in aqueous-medium. J. Hazard. Mater., 141, 344 347.

187

Perez-Lopez, R., Alvarez-Valero, A.M., Nieto, J.M., Saez, R. and Matos, J.X. (2008) Use of sequential extraction procedure for assessing the environmental impact at regional scale of the Sao Domingos Mine (Iberian Pyrite Belt). Appl. Geochem., 23, 3452 3463. Prusty, B.A.K., Chandra, R. and Azeez, P.A. (2009) Chem. Spec. Bioavail., 21(3), 141 151. Quevauviller, Ph. (2002) Operationally-dened extraction procedures for soil and sediment analysis. Part 3: New CRMs for trace-element extractable contents. Trends Anal. Chem., 21, 774 785. Raju, M. and Tandon, S.N. (1999) Operationally determined speciation of chromium in tannery sludges. Chem. Spec. Bioavail., 11, 67 70. Rao, C.R.M., Sahuquillo, A. and Sanchez, J.F.L. (2008) A review of the different methods applied in environmental geochemistry for single and sequential extraction of trace elements in soils and related materials. Water Air Soil Pollut., 189, 291 333. Rauret, G., Lopez-Sanchez, J-F., Sahuquillo, A., Barahona, E., Lachica, M., Ure, A.M., Davidson, C.M., Gomez, A., Luck, D., Bacon, J., Yli-Halla, M., Muntau, H. and Quevauviller, Ph. (2000) Application of a modied BCR sequential extraction (three-step) procedure for the determination of extractable trace metal contents in a sewage sludge amended soil reference material (CRM 483), complemented by a three-year stability study of acetic acid and ECTA extractable metal content. J. Environ. Monit., 2, 228 233. Trezza, M.A. and Scian, A.N. (2007) Waste with chrome in the Portland cement clinker production. J. Hazard. Mater., 147, 188 196. Xiaoli, C., Shimaoka, T., Xianyan, C., Qiang, G. and Youcai, Z. (2007) Characteristics and mobility of heavy metals in an MSW landll: Implications in risk assessment and reclamation. J. Hazard. Mater., 144, 485 491. Yilmaz, O., Kantarli, I.C., Yuksel, M., Saglam, M. and Yanik, J. (2007) Conversion of leather wastes to useful products. Resour. Conserv. Recy., 49, 436 448.