N 4 - December 1997

chromium tanned leather and its environmental impact. prepared by Vincent Van den Bossche, Grard Gavend and Marie-Jolle Brun (CTC - Centre Technique Cuir Chaussure Maroquinerie), Lyon France. Introduction Trivalent chromium salts are the most widely used tanning agent in the world for the transformation of hides and skins into leather. Chromium tanned leather has been used for almost a century for the manufacture of consumer products such as clothing, gloves, footwear, furniture, automobile upholstery, as well as a variety of personal leather goods. The leather manufacturing process generates liquid and solid wastes containing chromium (III). This manufacturing activity and the resulting by-products prompt questions concerning their impact upon the environment and mankind. This article summarises the current state of knowledge on this subject. The transformation of hide into leather The use of leather goes back to prehistoric times. Archaeological evidence shows that the material was widely used in antiquity. The raw material is mammalian skin, which today is derived principally from animals which are butchered for the food industry, and to a lesser extent, skins from reptiles, fish and birds(1). The tannery operations consist of transforming the raw hide, a highly putrescible material, into leather, a stable product which can be conserved indefinitely and which has a significant commercial value. These operations follow a sequence of organised chemical reactions (using reactive products) and mechanical processes using specialised machinery. Amongst these, tanning is the fundamental stage which confers to leather its stability and essential characteristics. Tanning Tanning is the most important step in the production of leather and it is carried out in an aqueous environment with water in rotating drums(2). Its objective is to process the skins which arrive from the abattoirs in a dried, salted state, to a condition which will facilitate the chemical operation of tanning. During this operation, collagen, the principal protein of the skin, will fix the tanning agent to its reactive sites, thus stopping the putrefaction phenomenon(3). The products which are capable of being fixed to skin to achieve tanning are many and varied. They can be vegetable type mineral tannins classified tannins (chromium, into three (mimosa, chestnut, iron, zirconium, in groups : quebracho) salt form)

- other organic tannins (formaldehyde, synthetic tannins, fish oil ...) The most widely used today are chromium salts. The process which was invented at the turn of the century uses chromium (III) hydroxysulfate salts in powder form, on skins which have been previously prepared following methods which were derived from work carried out in 1959(4). Regarding chromium tanning, only chromium (III) sulphate possesses tanning properties with respect to skin collagen. This tanning agent is produced from a natural product found in the form of chromite. To obtain good quality leather, it is necessary to use a quantity of chromium salts representing 2 to 2.5 % (calculated as Cr2O3) of the mass of skins to be tanned. This implies the use of 8 to 10 % of commercial product containing on average 25 % of Cr2O3(5). This procedure has thus replaced all the techniques based upon the use of chromium (VI) which, in the past, necessitated the reduction to a valency of (III) in the tannery, before tanning.After tanning, the leather is stored for several days which allows the consolidation of the chromium/collagen bonds. The resulting product can resist temperatures as high as 120C whilst collagen is denatured at 50C(6).In order to be transformed into a commercial product, the leather needs to be split and shaved to an even thickness, then superficially retanned with low quantities of tanning agents such as chromium, aluminium salts or vegetable/synthetic tannins, dyed with colouring agents, then fat liquored with natural or synthetic fats in order to render the product flexible. After drying, it is embellished with a film of more or less pigmented products on its outer surface in order to attain the appearance and degree of protection required for its final use. The last stages are called leather finishing(7). The advantages and applications of chromium tanned leather Chromium tanning is preferred because the process is quick, simple, reproducible and is very cost effective. It yields a material with a high mechanical and thermal resistance and a pronounced capacity for dyeing, so that a wide range of colours, rich or pastel shades are possible. The collagen chromium bond is actually the strongest known today amongst the various alternatives, including vegetable and synthetic tannins. By virtue of their quality and mechanical characteristics, chromium tanned leathers are well suited to a wide range of applications : gloves, footwear, leather goods, luggage and upholstery. Despite extensive investigation in laboratories around the world, no fully satisfactory alternative to chrome tanning has been found or is likely to be found in the foreseeable future. Health risks for tannery staff For many years the health risk associated with the use of chromium salts in the tanning industry has been questioned. Unlike chromium (VI), chromium (III) salts of the type used for tanning are less likely to penetrate and sensitize the skin (8). Further to the low risk of allergies due to chromium (III)(8), it was feared that leather dust could have an adverse effect on the nose, throat and lungs. Dust is produced during several operations, notably by the buffing of the outer surface during finishing, which produces particles of which 50 % have a diameter < 5 m(9). The International Agency for Research on Cancer (IARC) evaluated studies(9, 10) dealing with the incidence of nasal cancer in tannery workers and has not reported significant findings(11). The results of analyses carried out on air from tanneries(9), have revealed chromium (III) contents ranging from 5.5 to 8.0 g/m3 which is far below the French or American-ACGIH Time Weighted Average (TWA) values, which are 0.5 mg/m3(12, 13). From an epidemiological point of view, an American study (14)related to a period from 1940 to 1982 in two tanneries in Minnesota and Wisconsin concerning 9,365

workers, did not show higher death rates from nasal or lung cancer than that observed in the general population. An English study(15) related to a period from 1939 to 1982 concerning 833 tannery workers of which 573 were concerned with vegetable tanning and 260 with chromium tanning, did not reveal a higher incidence of death from cancer (of the stomach, large intestine, lung, rectum or prostate) compared to the general population. IARC concluded in its monograph that the only study specific to tanning failed to reveal a statistically significant risk(9). Impacts on the environment Chromium salts which are not fixed to the collagen during the tanning process are discharged as effluents to the environment, notably water and the ground. Water - It has been estimated that, with traditional tanning methods, from 4 to 9.5 kg of chromium (calculated as Cr2O3) per ton of skins are not chemically fixed during processing if it is not carried out with a suitable high exhaustion tanning system (16). Two thirds are rejected in the liquid effluent at the tanning stage(17). According to a Canadian scientific bibliography, in an aqueous medium of neutral pH, chromium (III) compounds form oxides, hydroxides and highly insoluble phosphates, which bind themselves to solids in suspension. This is why soluble chromium (III) compounds are rapidly eliminated from surface water into sediment. This chromium complex is relatively stable and slightly biologically available(18). This aptitude for precipitation was confirmed in a study carried out in Costa Rica on a river polluted by several tanneries (19). Work was carried out by the CTC on activated sludge in an effluent treatment plant. Using the respirometry method, the purpose was to measure the toxicity of chromium. It was shown that whilst chromium is maintained in an insoluble form (pH neutral or alkaline), its toxicity on activated sludge cannot be detected(20). World wide regulatory limits fixing the chromium (III) content of water which can be discharged into surface waters, vary from 0.5 to 15 mg/l (21). Widely practised efficient treatment of effluent combined with clean technologies (which we will mention later and which are increasingly being adopted by tanneries), enable tanners to comply with these strict regulations. To measure the effect of chromium (III) compounds, studies were carried out on living species in water. They showed that because of its low solubility (experimental conditions pH 7), chromium (III) did not prove to be toxic to bacteria, seaweed or fish. Only daphnia showed a marked sensitivity to concentrations in the order of 6 to 9 mg/l(20). Ground - The manufacture of chromium tanned leather also generates solid wastes or scrap resulting from mechanical operations of which the chromium (III) content (calculated as Cr2O3) is, on average, between 2 and 5.5 %(22). In Europe, these are not listed as hazardous waste(23) and in the USA they are specifically exempt from Federal hazardous waste regulations(24,25). The US Environmental Protection Agency (EPA) has conducted an extensive risk evaluation of chromium (III) in sludge used for agricultural land application and could find no adverse effect for any pathway of exposure (26). Therefore, chromium limits for land applied sludge have been eliminated(27,28). The Organisation for Economic Cooperation and Development (OECD) considers that solid wastes produced by tanneries are to be included on the green list, which signifies that they only need to conform to commercial requirements with respect to their transboundary transport. On the other hand, leather dust and sludge are included on the amber list which signifies that the tanner and recipient of the goods are required to inform their local or national environment administration concerning the commercial transaction (29). In the USA, one publicly-owned waste water treatment plant receives 95 % of its input from a tannery. Since 1977, it has been dumping on land sludge containing 34 g of chromium (III)/kg. For the past ten years,

the town has been monitoring ground water immediately below the landfill at down gradient wells. It reported that the chromium level in ground water was below the detection limit of 0.01 mg/l(30). When chrome containing sludge is mixed with earth, the appearance of chromium (VI) could theoretically occur at redox potentials typically found in well aerated soils(31). However, in practice, the oxidation of chromium (III) to chromium (VI) does not occur in earth even under experimental conditions combining maximum aeration and high pH(32, 33, 34). Ground life and micro-organisms - On micro organisms(35), the inhibitory effects of chromium (III) (concentrations up to 1,000 ppm) were noticed on short term exposure but were no longer evident after a period of six weeks. However, 10,000 ppm of chromium (III) completely blocked nitrogen transformation. Earthworms could survive even with a chromium (III) concentration in their stomachs of 100 ppm(36). With higher concentrations, toxic effects were noticed : the individuals were less numerous and their size decreased. However, after extensive risk evaluation, the US EPA has established guidance cleanup for chromium (III) at land disposal sites of 78,000 mg/kg(37). This limit value is related to the most relevant pathway risk which, concerning chromium (III) and according to the US EPA, is ingestion of contaminated soil. Over this limit value, the site owner can be asked to perform a site specific risk evaluation and even to clean up the site. As a conclusion, care should be taken to avoid high accumulation which could produce harmful effects. Vegetables and animals - Many studies have been carried out to determine the impact of chromium (III) compounds on different crops : chicory, wheat, peas, tomatoes, fennel, etc., particularly with respect to the spreading of sludge onto agricultural ground (38, 39, 40, 41). These studies concluded that chromium (III) compounds can be considered as non-toxic in concentrations up to 500 mg/kg(38). Once again care should be taken to avoid an accumulation of chromium (III) compounds in the ground. No toxic effect was detected on rats consuming water containing 25 mg/l of chromium (III) over a 6-month period(39). Impact on the consumer The consumer, the end-user of articles made from chromium tanned leather has a right to ask whether the use of such leather constitutes a health risk. As we have already indicated(8), unlike chromium (VI), chromium (III) compounds are only weakly allergenic. The question, however, is whether there is a risk of the appearance of chromium (VI) in leather articles. A French study has demonstrated that under specific conditions of humidity, ultraviolet-C light and pH, there is a possibility of transforming chromium (III) compounds into chromium (VI) compounds which could migrate from the leather (40). The values found were in the order of not detectable to 17 mg of chromium (VI) per kg of dried degreased leather. As a precautionary measure, the German authorities require (41) that chromium (VI) content which could be leached should be below the limits of detection and reproducibility of the analytical methods available to industry , that is to say of the order of 2 to 3 mg/kg of leather(42). Furthermore, based on a similar precautionary principle, the European standard for safety gloves, EN 420(43) specifies a maximum limit for leachable chromium (VI) compounds, as being 2 mg/kg of leather. However research is still needed to better understand the transformation mechanism of chromium (III) to (VI) in finished leather as well as the potential toxic effects to man at this very low range of values. The development of clean technologies The aforementioned studies did show some harmful effects on species living in the ground. Accumulation into the environment should therefore be avoided. Motivated by this objective

and in order to economise chemicals and water, tanners have developed manufacturing methods whose aim is to reduce chromium emissions into the environment. These efforts are often based upon methods for the optimisation of the use of chromium, through the exhaustion of tanning baths and the re-use of residual water, developed by research institutes and manufacturers of chromium salts(44, 45). The chromium exhaustion ratio in tanning floats, traditionally 70-80 % can attain 97 % with the new processes(17). Effluent treatment plants are increasingly being installed throughout the world in order to purify liquid waste, often providing a common treatment service in highly concentrated tannery zones. In parallel, work is being carried out concerning the recovery of chromium (III) compounds from tanned waste and tannery sludge(46, 47). Conclusion Chromium (III) salts in the hydroxysulfate form, remain an irreplaceable tanning agent due to their ease of use and the quality that they confer to leather. Studies known today conclude that chromium (III) tanned leather produces no toxic effect on the consumer. On the other hand, regarding fauna and flora, high accumulation in the environment is to be avoided. This is why tanners are concentrating their efforts on the application of clean technologies and processes for the recycling of effluent and solid waste containing chromium (III). References 1. JULLIEN I., PREVOT J., GAVEND G., La peau matire premire de la tannerie mgisserie, Lyon : CTC, 1989. 2. JULLIEN I., Le travail de rivire, Lyon : CTC, 1983. 3. HEIDEMANN E., Vergleich zwischen Chrom und Vegetabilgerbung, abgeleitet aus den Bindepositionen am Kollagen, Das Leder, 5, 1997, 99-104. 4. SPAHRKS H., SCHMIDT H., Das Leder, 10, 1959, 145-147. 5. JULLIEN I., Le tannage au chrome, Lyon : CTC, 1981. 6. HEIDEMANN E., Fundamentals of leather manufacturing, Darmstadt : Eduard Roether KG, 1993. 7. JULLIEN I., GAVEND G., Le cuir, origine et fabrication (also in English), 4th ed., Lyon : CTC, 1990. 8. BARUTHIO F., Toxic effects of Chromium and its compounds, Biological Trace Element Research, v. 32, 1992, 145-153. 9. IARC monographs on the evaluation of the carcinogenic risk of chemicals to humans : wood, leather and some associated industries, v. 25, Lyon : International Agency for Research on Cancer (IARC), February 1981. 10. LANGERWERF JSA., Mutagenicity of Cr : Physico-chemical aspects of the genotoxicological behaviour of tri and hexavalent Cr compounds, International symposium on chemical and toxicological aspects of environmental quality, 23-25 November 1983. 11. BERNAL X, BORSA J., LOPEZ F., TURUGUET D., Compuestos Qumicos en la industria de curtidos y acabados : aproximacin al problema en Catalunya, XXI International Union of Leather Technologists and Chemists Societies Congress, Barcelona-Spain, 25-29 September 1991. 12. Ministre franais du travail, Valeurs admises indicatives des concentrations dans latmosphre des lieux de travail, Ciculaire du 19 juillet 1982 modifie par circ. n 96-8, August 1996. 13. ACGIH, 1996 Threshold limit values (TLVs) for chemical substances and physical agents and biological exposure indices (BEI), ACGIH Cincinnati USA, 1996. 14. STERN FB., BEAUMONT JJ., HALPERIN WE., MURTHY LI., HILLS BW., FAJEN JM.,

Mortality of chrome leather tannery workers and chemical exposures in tanneries, Scand J. Work Environ. Health 13, 1987, 108-117. 15. PIPPARD E.C., ACHESON E.D., WINTER P.D., Mortality of tanners, British Journal of Industrial Medicine, 42, 1985, 285-287. 16. International Environment Commission (IUE), Typical pollution values related to conventional tannery processes, World leather, v. 9, 7, 1996, 13. 17. LUCK W., WEHLING B., Cr Tanning process with high exhaustion bath, Lecture at 33rd annual congress of Asociacin Quimica Espaola de la Industria del Cuero, 30 April 1984. 18. Gouvernement du Canada, Loi canadienne sur la protection de lenvironnement ; liste des substances dintrt prioritaire ; rapport dvaluation ; le Cr et ses composs (also in English), ref. En40-215/39F, 1994. 19. FULLER CC., DAVIS JA., LAMOTHE PJ., FRIES TL., FERNANDEZ G., VARGAS JA., MURILLO MM., Distribution and transport of sediment-bound metal contaminants in the Rio grande de Tarcoles, Costa Rica, Wat. Res. v. 24, 7, 1990, 805-812. 20. CARRE M.C., VULLIERMET A., VULLIERMET B., Tannerie et environnement (also in English), Lyon : CTC, 1983. 21. BULJAN J., Pollution limits for discharge of tannery effluents into water bodies and sewers, World Leather, v. 9, 7, 1996, 65-68. 22. COVINGTON A.D., Chromium in the leather industry, Chromium Review, 5, 1985, 2-9. 23. European Council Decision of 22 December 1994 (OJEC of 31 December 1994) and European Commission Decision of 20 December 1993 (OJEC of 7 January 1994). 24. RUTLAND F.H., Tanneries and the environment, a look into the nineties. The Leather Manufacturer, v. 108, 5, 1990, 18-22. 25. Title 40, US Code of Federal Regulations, Section 261.4 (b) (6). 26. US EPA, Technical support document for the surface disposal of severage sludge, November 1992. 27. US Federal Register, vol 60, page 54764. 28. RUTLAND F.H., An environmental renaissance, a review of development in the United States over the past year, World Leather, v. 9, 7, 1996, 10-12. 29. OECD, Le systme de contrle OCDE pour les mouvements transfrontires de dchets destins des oprations de valorisation. Manuel dapplication - Monographie sur lenvironnement n 96, Paris : OECD, 1995. 30. DAVY S., The leather industry fights back, Leather, 3, 1995, 37-40. 31. SHIVAS S.A.J., The field disposal of tannery sludge, The Journal of the American Leather Chemists Association, 74, 3, 1979, 70-81. 32. BARTLETT R.J., KIMBLE J.M., Behaviour of chromium in soils - I - Trivalent forms J. Environ. Qual., 5, 4, 1976, 379-383. 33. LOLLAR R.M., Cr III or Cr VI : bases for delisting solid wastes containing trivalent chromium, The Leather Manufacturer, 100, 11, 1982, 16-22. 34. BLOMFIELD C., PRUDEN G., The behaviour of chrome VI in soil under aerobic conditions, Environ. Pollut., 23, 2 A., 1980, 103-114. 35. SHIVAS S.A.J., The environmental effects of chromium in tannery effluents, The Journal of the American Leather Chemists Association, 73, 8, 1978, 370-377. 36. SHIVAS S.A.J, The effects of trivalent chromium from tannery wastes on earthworms, The Journal of the American Leather Chemists Association, 75, 1980, 300-304. 37. US EPA, Soil screening guidance : technical background document, report N EPA/540/R-95/128, 1996. 38. SYKES R.L., CORNING D.R., EARL N.J., The effect of soil chromium III on the growth and chromium absorption of various plants, The Journal of the American Leather Chemists Association, 76, 3, 1981, 102-125. 39. KATZ S.A., SALEM H., The toxicology of chromium with respect to its chemical speciation : a review, J. Appl. Toxicol., v. 13, 1993, 217-224. 40. MARTINETTI R., Thse Contribution la labellisation 'coproduit' de cuirs tanns aux

sels de Chrome : tude de la mobilit du Chrome, Lyon-France : CTC, 27 October 1994. 41. NICKOLAUS G., Does leather contain chromium (VI) ?, XXII International Union of Leather Technologists and Chemists Societies congress, Freidrichshafen-Germany, 15-20 May 1995. 42. International Union of Leather Technologists and Chemists Societies, IUC18 standard : leather determination of chromium (VI) content, September 1994. 43. CEN, EN 420 Protective gloves : general requirements, September 1994. 44. GREGORI J., MARSAL A., MANICH A.M., COT J., Optimizacin del proceso de curticin al cromo : influencia del comportamiento de tres tipos de agentes complejantes, XXI International Union of Leather Technologists and Chemists Societies Congress, BarcelonaSpain, 25-29 September 1991. 45. DAVIS M.H., SCROGGIE J.G., Theory and practice of direct chrome liquor recycling, XVI International Union of Leather Technologists and Chemists Societies Congress, VersaillesFrance, 4-6 September 1979, v. II. 46. TAYLOR M.M., DIEFENDORF E.J., THOMSON C.J., BROWN E.M., MARMER W.N., CABEZA i FABRA L.F., Extraction of value added by-products from the treatment of chromium containing collagenous waste generated in the leather industry, Bol. Tec. AQEIC, 3, 1996, 124-150. 47. HARRIS T., Practical experience in chromium recovery, World leather, v. 9, 7, 1996, 2932.

International Chromium Development Association 45 rue de Lisbonne, 75008 Paris, France. Tel: 33 01 40 76 06 89 Fax: 33 01 40 76 06 87 International Chromium Development Association 1997

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