Continental J. Environmental Sciences 3: 13 - 18, 2009 Wilolud Online Journals, 2009.

CHROMIUM IN SOILS: A REVIEW OF ITS DISTRIBUTION AND IMPACTS Yahaya Ahmed Iyaka Department of Chemistry, Federal University of Technology, P.M.B. 65, Minna. ABSTRACT Generally, the parent material determines the levels of chromium in soils, and typical soil chromium concentrations vary widely with elevated contents been associated with anthropogenic contamination. The less toxic, less mobile and naturally abundant trivalent chromium is mainly found bound to organic matter in soils, but chromium compounds in the hexavalent state are toxic, rare and usually associated with industrial pollution. Soil-plant barrier system limits the chromium impact on the food chain, due to the immobility of the soil-chromium, however, at the elevated levels chromium in soils may influence chromium uptake by plants, as well as ingestion by children through touching and eating contaminated soil. KEY WORDS: Chromium, trace metal, soil, environmental impact. INTRODUCTION Chromium was discovered by the French Chemist Louis Nicolas Vanquelin in 1797, who prepared the metal from the Siberian red lead ore (crocoite; PbCrO4)in 1798(Berloux,1999). It is the tenth most abundant metal in the earths crust (Bartlett and James, 1996), and belongs to the first five in commercial importance. The natural or major sources of chromium in the earths crust are in the trivalent state, but naturally occurring chromium compounds in the hexavalent state are rare and mostly man-made products (WHO, 1988).Chromium (III) is less toxic, less mobile and is mainly found bound to organic matter in soils (Becquer et al., 2003), while Chromium (VI) is the most toxic form of chromium, that usually occurs in association with oxygen as chromate or dichromate. Table 1 shows the occupational sources associated with chromium exposure. Physical and Chemical properties Chromium is brittle, hard, lustrous and silver-gray metal. It is more difficult to shape than most other metals. It has a melting point 1907oC, boiling point 2672oC and density of 7.19gcm-3 at 20 oC. Chromium is a transition metal of atomic number 24 with relative atomic mass 51.996 belonging to Group VI of the Periodic Table. Chromium may theoretically occur in any oxidation state from -2 to +6; however, it is most often common in 0, +2, +3, and +6. Elemental chromium (0) is inert in biological materials and not naturally present in the earths crust. Divalent chromium (Cr+2) is not also available in the biological system, but gets readily oxidized when in contact with air, hence, a strong reductant. Trivalent chromium (Cr+3) is the most stable oxidation state in which chromium is found in biological materials. Chromium (III) is soluble in acidic solutions, forming hexahedral complexes with ligands such as oxalate and sulphate ions. The second most stable oxidation state is the hexavalent chromium ((Cr+6), with strong oxidizing potential, particularly in acidic media (Garrett, 1982; EVM, 2002; Pechova and Pavlata, 2007). Applications Chromium is most useful in combination with other metals, either as an ingredient in alloys or as an electroplated coating. It is highly valued due to its ability to impart corrosion resistance, heat resistance and increased strength to other metals (Garrett, 1982). Major applications of chromium that impact significantly in the environment are in stainless steel, industrial liquors and urban sewage; electroplating baths as waste chromates, tanning processes as trade effluents and heat exchange systems as corrosion inhibitors(Cabrera- Vique et al., 1997), as well as leather manufacturing wastes. Chromium is also used widely as a catalyst and in giving glass an emerald green colour. Chromium contents, inputs and distribution in soils The common chromium mineral is chromite, and the chromium content of acid igneous and sedimentary rocks ranges from 5-120ppm (Kabata-Pendias and Pendias, 1992). Generally, the parent material determines the levels of chromium in soil, and typical soil chromium contents range from 20-65ppm (Kabata-Pendias and Pendias, 1984). However, Langard (1980), has identified the elevated levels of chromium with anthropogenic contamination mainly through industrial processes. Alloway and Ayres(1997) have reported an average concentration of 100ppm for chromium in earths crust, and natural chromium content in surface soils has been

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Yahaya Ahmed Iyaka: Continental J. Environmental Sciences 3: 13 - 18, 2009

estimated to range from 5-1100ppm, with a mean value of 60ppm(Ward,1995). Furthermore, Kabata-Pendias and Pendias (1992) have reported the mean chromium content for world sandy soils to be 47ppm. Table 2 shows various chromium concentrations in soils from different sources. Table 1 Occupational sources associated with chromium exposure (with chemical forms of interest given in bracket) Sources

Stainless steel welding [chromium (VI)] Chromate production [chromium (VI)] Chrome plating [chromium (VI)] Ferrochrome industry [chromium (III) and chromium (VI)] Chrome pigments [chromium (III) and chromium (VI)] Leather tanning [mostly chromium (III)] Battery makers [chromium (VI)] Candle makers [chromium (III) and chromium (VI)] Cement makers [chromium (III) and chromium (VI)] Dye makers [chromium (III)] Painters [chromium (III) and chromium (VI)] Printers [chromium (III) and chromium (VI)] Rubber makers [chromium (III) and chromium (VI)] Workers involved in the handling of copying machines [chromium (VI)]

Source: Public Health Statement for Chromium (2008).

Table 2 Chromium contents in soils from different sources

Source
Natural soils

Content ppm
5-1000 5-1500 5-3000 30-300 100-300 (mean 200) 10-150 (mean 40) 100-5000 (mean 43) 87 (mean) 25-85 (mean 37) 57 (mean) 74 (mean)

World soils Canadian soils Japanese soils U. S. soils Swedish soils

Adapted from Shanker et al., 2005; Discarded manufactured products and coal ashes constitute the major sources of anthropogenic chromium inputs into soils, and the total worldwide inputs of chromium into soils is estimated to be 898 x 103 tonnes per year(Nriagu,1990). Values representing the maximum allowable limits (MAL) of chromium contents in soils for many countries have also been documented by Kabata-Pendias (1995); Great Britain (50ppm), Canada (75ppm), Austria and Poland (100ppm), as well as 200ppm for Germany. Chromium of environmental concern is the waste chromium, which has the characteristic spinel structure, FeO.Cr2O3; whose trivalent chromium can be converted to hexavalent chromium after an alkaline roasting process (Bartlett and James, 1996), leaving them as residuals that become waste forms of chromium in soil-water system.

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Yahaya Ahmed Iyaka: Continental J. Environmental Sciences 3: 13 - 18, 2009 Generally, very little chromium is leached from soil due its presence as an insoluble Cr2O3. xH2O (Fishbein, 1981). However, mobility and toxicity of chromium depend on its oxidation state; trivalent chromium is relatively immobile, often bound to both organic and inorganic ligands in soils, more stable and extremely less toxic than hexavalent chromium (Ross et al., 1981), which is a peculiar industrial pollutant. Furthermore, the biological reduction of toxic and more mobile hexavalent chromium to trivalent chromium by organic matter occurs in soils (Barlett and Kimble, 1976), and this is responsible for the low chromium availability to plants. The major processes by which the trivalent chromium is transported from soil include aerial and surface water transport through aerosol formation and runoff respectively (U.S.EPA, 1984) Transmission through the food chain Soil-plant barrier helps in protecting the food chain, because of the immobility of the soil-chromium. However, in animals, chromium introduction into feeds could lead to its bioaccumulation in meat byproducts such as skin, bone and meat meals, and consequently into soils and crops fertilized with animal manure (Gallo and Serpe, 1997), and finally into humans through the food chain. Chromium in Plants Generally, chromium is not considered as an essential element for plant growth and development, however, Bonet et al.,(1991) have reported that low concentrations of chromium stimulates plant growth. Chromium is toxic for agronomic plants at a content range of about 5.0 to 100ppm of available chromium in soil (Hossner et al., 1998), but Davies et al., (2002) reported that chromium is toxic to higher plants at 100M kg-1. Moreover, hexavalent chromium compounds due to their high solubility (James, 1996), easy permeability through biological membranes and subsequent interaction with protein components and nucleic acids inside the cell (Basu et al., 1997) are comparatively more toxic than trivalent chromium. Chromium distribution in crops has a stable character that is independent of the soil properties and content of the element; usually the major concentration of the contaminant element is always found in roots with minimum levels present in the vegetative and reproductive organs (Golovatyj et al., 1999). The high chromium accumulation in the roots could be due to immobilization of chromium in the vacuoles of the root cells, thereby rendering it less toxic, probably because of the natural toxicity response of the plant (Shanker et al., 2004a).However, effects of chromium toxicity on plant growth and development include reduction in seed germination (Rout et al., 2000; Peralta et al., 2001), decrease in root growth (Samantaray et al., 1999; Chen et al., 2001; Prasad et al., 2001),and reduction in plant height and shoot growth due to adverse effects of chromium has also been reported by various researchers(Sharma and Sharma,1993; Joseph et al.,1995; Barton et al.,2000). Furthermore, various authors have reported different adverse effects of chromium on leaves depending on the concentration of the applied chromium and plant type (Karunyal et al., 1994; Jain et al., 2000; Singh, 2001), hence, Tripathi et al.,(1999) observed that leaf growth traits could serve in the choice of suitable bioindicators and resistant species. Chromium in animals and humans The primary sources of chromium exposure are by breathing air, drinking water, eating food containing chromium or through skin contact with chromium or chromium compounds. For the general population, the most likely route of exposure to trivalent chromium is by eating foods that contain chromium, and trivalent chromium is identified as a natural essential nutrient for humans in many fresh vegetables, fruits, grain, meat and yeast (Public Health Statement for Chromium, 2008). 50-200g/d has been identified as an estimated safe and adequate daily dietary intake (ESADDI) for chromium (NRC, 1989), which corresponds to 0.71-2.9g/kg/day for a 70-kg adult. Reference Daily Intake for chromium of 120 g/d has also been selected by FDA (DHHS, 1995). However, hexavalent chromium is more easily absorbed by the body than trivalent chromium, but once inside the body system, hexavalent chromium is changed to trivalent chromium (DeFlora et al., 1987; Debetto and Luciani, 1988), that is essential for animals and humans (EPA, 1998), because it facilitates interaction of insulin with its receptor site, influencing metabolism of glucose, lipid and protein in its biologically active form. Chromium deficiency has been associated with atherosclerorsis, cataract, growth failure, hyperglycaemia, and neuropathy (Saner et al., 1980) as well as with diabetes in human body due its vital role in metabolism of carbohydrates (Jamal et al.,1986). Furthermore, effects such as acute tubular necrosis, kidney failure, and metabolic acidosis and in some cases death have been identified with accidental poisoning through hexavalent chromium compounds such as chromic acid and potassium tetrachromate (Saryan and Reedy, 1988).

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Yahaya Ahmed Iyaka: Continental J. Environmental Sciences 3: 13 - 18, 2009 Municipal waste water which may contain <0.7mgl-1 chromium in hexavalent chromium form, mainly represents the major route of chromium toxic intake by marine species, algae and microorganisms. Moreover, Alloway and Ayres (1997) observed that in the presence of organic matter reduction of chromate (VI) to chromite (III) which appears to be more toxic to fish, especially salmon, often occurs, and the toxic contents for several species of fish ranged from 0.2 5.0 mgl-1. The bioconcentration factor (BCF) has been estimated to be <1.0 for hexavalent chromium in fish, but values of as high as 125 and 192 have been reported for oyster and blue mussel respectively (U.S.EPA, 1980). CONCLUSION The natural and abundant trivalent chromium is less toxic, less mobile and is mainly found bound to organic matter in soils, but chromium compounds in the hexavalent state are toxic, rare and usually associated with industrial pollution. Soil-plant barrier system limits the chromium impact on the food chain, because of the immobility of the soil-chromium, however, elevated levels of chromium in soils through anthropogenic contamination may influence chromium uptake by plants, as well as ingestion by children through touching and eating contaminated soil. Furthermore, chromium deficiency has also been identified to have adverse effects on the growth and development of animals and humans, particularly in children. Hence, to predict a comprehensive impact of chromium in soil and its consequence on the environment through the food chain, the model requires knowledge of soil chromium, reaction and mobility of chromium in soil as well as levels of atmospheric chromium especially in industrial areas, since soil is an ultimate sink for heavy metal deposition. REFERENCES Alloway,B. J. and D.C. Ayres. 1997. Chemical Principles of Environmental Pollution. Blackie Academic and Professional, London. Bartlett, R. J. and J. M. Kimble. 1976. Behviour of chromium in soils II. Hexavalent forms. J. Environ. Qual. 5: 383-386. Barton, L. L., G.V. Johnson, A.G. ONan, and B.M. Wagener. 2000.Inhibition of ferric chelate reductase in alfalfa roots by cobalt, nickel, chromium and copper. J. Plant Nutr. 23: 1833-1845. Basu, M., S. Bhattacharya and A. K. Paul. 1997. Isolation and characterization of chromium- resistant bacteria from tannery effluents. Bulletin of Environmental Contamination and Toxicology. 58(4): 535-542 Batlett, R. J. and B.R. James. 1996. Chromium. Pp 683-701. In: J.M. Bigham (ed). Methods of Soil Analysis. Part 3. Chemical Methods. Soil Sc. Society of America Inc ., USA Becquer, T., C.Quatin, M. Sicot and J. P. Boudot. 2003. Chromium availability in ultramafic Soils from New Caledonia. Sci. Total Environ. 301: 251-261. Berceloux, D. G. 1999. Chromium. Clinical Toxicology, 37: 173-194. Bonet, A., C. Poschenrieder, J. Barcelo. 1991. Chromium III- iron interaction in Fe- deficient and Fesufficient bean plants. I. Growth and nutrient content. J. plant Nutr. 14: 403- 414. Cabrera- Vique, C., P. Teissedre, M. Cabanis and J. Cabanis. 1997. Determination and levels of Chromium French wine and Grapes by Graphite Furnace Atomic Absorption Spectrometry. J. Agric. Food Chem. 45: 1808-1811 Chen, N. C., S. Kanazawa, T. Horiguchi and N.C. Chen. 2001. Effects of chromium on some enzyme activities in the wheat rhizosphere. Soil Microorg. 55: 3-10 Davies, F. T., J. D. Puryear, R.J. Newton, J.N. Egila and J. A. S. Grossi. 2002. Mycorrhizal fungi increase chromium uptake by sun flower plants: Influence on tissue mineral concentration, growth, and gas exchange. J. Plant Nutr. 25: 2389-2407. Debetto, P. and S. Luciani. 1988. Toxic effect of chromium on cellular metabolism. Sci. Total Environ. 71:365-377.

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Yahaya Ahmed Iyaka: Continental J. Environmental Sciences 3: 13 - 18, 2009 DeFlora, S., G. S. Badolati, D. Serra, et al. 1987. Circadian reduction of chromium in the gastric environment. Mutat Res. 192: 169-174 Department of Health and Human Services (DHHS). 1995. Food and Drug Administration. Food Labelling: Reference Daily Intakes, Final Rule.21 CFR Part 101. Federal Register. 60(249):67164-67175 U.S. Environmental Protection Agency (EPA). 1998.Toxicological Review of Hexavalent Chromium. In Support of Summary Information on the Integrated Risk Information System (IRIS). Washington, D.C. EVM. 2002. Expert Group on Vitamins and Minerals. Review of Chromium. Fishbein, L. 1981. Source, transport and alterations of metal compounds: An Overview. In: Arsenic, Beryllium, Cadmium, Chromium and Nickel. Environ. Health Perspect. 40: 43-64. Garrett, A. B. 1982. Zinc. Pp116-117. In : W.D. Halsey, and E. Friedman(Eds). Merit Students Encyclopedia. Macmillan Educational Company, New York. Golovatyj, S. E., E.N. Bogatyreva, S.E. Golovatyi. 1999. Effects of levels of chromium content in a soil on its distribution in organs of corn plants. Soil Res. Fert. 197-204 Hossner, L. R., R.H. Loeppert, R. J. Newton, P.J. Szaniszlo and Jr., Moses Attrep. 1998. Literature review: Phytoaccumulation of chromium, uranium, and plutonium in plant systems. Amarillo National Resource Center for Plutonium. Report ANRCP Jain, R., S. Srivastava, V.K. Madan and R. Jain. 2000. Influence of chromium on growth and cell division of sugarcane. Indian J. Plant physiol. 5:228-231. Jamal, H., H. Raza, K. M. Janua and M.K. Bhatty. 1986. Effect of minor minerals containing chromium on human health. Pak. J. Sci. Ind. Res. 29:45-47 James, B. R. 1996. The challenge of remediating chromium- contaminated soil. Environ. Sci. 30(6): 248-251 Joseph, G.W., R.A. Merrilee and E. Raymond. 1995. Comparative toxicities of six heavy metals using root elongation and shoot growth in three plant species. The symposium on environmental toxicology and risk assessment, Atlanta, G.A, U.S.A. pp26-29 Kabata-Pendias, A. 1995. Agricultural Problems related to excessive Trace Metal Contents of Soil. Pp3-18. In: W. Salomons, U. Forstner, and P. Mader(Ed). Heavy Metals (Problems and Solutions). Springer Verlag, London. Kabata-Pendias, A. and H. Pendias. 1984. Trace Elements in Soils and Plants. CRC Press Inc., Boca Raton, Florida. Kabata-Pendias, A. and H. Pendias. 1992. Trace Elements in Soils and Plants. CRC Press, London. Karunyal,S., G. Renuga and K. Paliwal. 1994. Effects of tannery effluent on seed germination, leaf area, biomass and mineral content of some plants. Bioresour Technol. 47: 215-218. Langard, S. 1980. Chromium. Pp 111-132. In: Waldron(Ed). Metals in the Environment. Academy Press Inc., New York. National Research Council (NRC). 1989. Recommended dietary allowances. 10th Ed. Washington, D.C. National Academy of Sciences. pp241-243 Nriagu, J.O. 1990. Global Metal Pollution poisoning the Biosphere? Environment. 32: 7-32. Pechova, A. and L. Pavlata. 2007. Chromium as an essential nutrient: A Review. Veterinarni Medicina. 52(1): 1-18

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Peralta, J. R., J.L. Gardea Torresdey, K.J. Tiemann, E. Gomez, S. Arteaga, Rascon, E., et al. 2001. Uptake and effects of five heavy metals on seed germination and plant growth in alfalfa (Medicago sativa)L.B. Environ. Contam. Toxicol. 66(6): 727-734. Prasad, M.N.V., M. Greger and T. Landberg. 2001. Acacia nilotica L. bark removes toxic elements from solution: Corroboration from toxicity bioassay using Salix viminalis L. in hydroponic system. Int. J. Phytoremed 3: 289-300 Public Health Statement for Chromium. 2008. In: S. Draggan(Ed). Agency for Toxic Substances and Disease Registry and National Center for Environmental Health. Ross, D. S., R. E. Sjogren, and R. J. Bartlett. 1981. Behavior of chromium in soils IV. Toxicity to microorganisms. J. Environ. Qual. 10: 145-148. Rout, G.R., S. Sanghamitra and P. Das. 2000. Effects of chromium and nickel on germination and growth in tolerant and non-tolerant populations of Echinochloa colona L. Chemosphere. 40:855-859. Samantaray,S., G.R. Rout, and P. Das. 1999. Studies on differential tolerance of mungbean cultivars to metalliferous minewastes. Agribiol. Res. 52: 193-201 Saner, G., T. Yuksel and C. T. Gurson. 1980. Effect of chromium on insulin secretion and glucose removal rate in the new born. Am. J. Clin. Nutr. 33: 232-235 Saryan,L.A. and M. Reedy. 1988. Chromium determinations in a case of chromic acid ingestion. J. Anal. Toxicol. 12: 162-164 Shanker,A.K., M.Djanaguiraman, R.Sudhagar, C.N.Chandrashekar and G. Pathmanabhan. 2004a. Differential antioxidative response of ascorbate glutathione pathway enzymes and metabolites to chromium speciation stress in green gram ( vigna radiata L. R. Wilczek,cv CO 4) roots. Plant Sci. 166: 1035-1043. Shanker, A. K., C. Cervantes, H. Loza-Tavera and S. Avudainayagam. 2005. Chromium toxicity in plants. Environment International. 31:739-753. Sharma, D. C, and C.P. Sharma.1993. Chromium uptake and its effects on growth biological yield of wheat. Cereal Res. Commun. 21: 317-321. Singh,A. K. 2001.Effect of trivalent and hexavalent chromium on spinach(Spinacea oleracea L.). Environ. Ecol. 19: 807-810 Tripathi, A.K., S. Tripathi, and S. Tripathi. 1999. Changes in some physiological and biochemical characters in Albizia lebbek as bioindicators of heavy metal toxicity. J. Environ. Biol. 20: 93-98. U.S.EPA, 1984 Ward, N.I. 1995. Trace Elements. Pp321-351. In : Fifield, F. W. and H. R. J. Blackie(Ed). Environmental Analytical Chemistry. Academic and Professional,Glasgow. WHO. 1988. International Programme on Chemical Safety, Environmental Health Criteria 61. World Health Organisation, Geneva. Received for Publication: 07/11/2008 Accepted for Publication: 24/03/2009 Corresponding Author: Email: iyaka7@yahoo.com

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