Abstract
In recent years, the extensive use of chromium in industrial processes has led to the promotion of several directives and recommendations by the European Union, that try to limit and regulate the presence of Cr(VI) in the environment and to protect industrial workers using chromium and end-users of manufactured products. As a consequence, new standard methods and analytical procedures have been published at the EU level for Cr(VI) determination in soil, sludge, sediment, and similar waste materials, workplace atmospheres, cement, packaging materials, industrially produced samples, and corrosion-protection layers on some components of vehicles and electrical and electronic equipment. The objective of this article is to summarize the different directives and recommendations and to critically review the currently existing standard methods and the methods published in the literature for chromium speciation in the above mentioned solid matrices, putting the emphasis on the different extraction procedures which have been developed for each matrix. Particular attention has been paid to Cr(III) and Cr(VI) inter-conversions that can occur during extraction and efforts to minimize these unwanted reactions. Although the use of NaOH-Na2CO3 solutions with hot plate extraction seems to be the more widespread procedure, species transformation can still occur and several studies suggest that speciated isotope-dilution mass spectrometry (SIDMS) could be a suitable tool for correction of these interconversions. Besides, recent studies have proved the role of Cr(III) in chromium toxicology. As a consequence, the authors suggest an update of standard methods in the near future.
Similar content being viewed by others
References
Hansen MB, Johansen JD, Menne T (2003) Contact Dermatitis 49:206–212
Eastmond DA, MacGregor JT, Slesinski RS (2008) Crit Rev Toxicol 38:173–190
Agency for Toxic Substances and Disease Registry (ATSDR) (1998) Toxicological Profile for Chromium, US Department of Hearth and Human Services, Public Health Service, Atlanta, GA, USA
USEPA (1998) Toxicological Review of Hexavalent Chromium. U.S. Government Printing Office, Washington
IARC (1990) Monographs on the Evaluation of Carcinogenic Risks to Humans, vol 49. Chromium, Nickel and Welding, International Agency for Cancer Research, Lyon
Kotas J, Stasicka Z (2000) Environ Pollut 107:263–283
Eary LE, Rai D (1987) Environ Sci Technol 21:1178–1184
Pettine M, Capri S (2005) Anal Chim Acta 540:231–238
Richard FC, Bourg ACM (1991) Water Res 25:807–816
James BR, Petura JC, Vitale RJ, Mussoline GR (1995) Environ Sci Technol 29:2377–2381
USEPA (1995) Chromium, Hexavalent (Colorimetric), Method 7196A, in Test Methods for Evaluating Solid Waste-Physical/Chemical Methods, SW-846, update 3. U.S. Government Printing Office, Washington
USEPA (1996) Determination of hexavalent chromium in drinking water, groundwater and industrial wastewater effluents by ion-chromatography, Method 7199A, in Test Methods for Evaluating Solid Waste-Physical/Chemical Methods, SW-846, update 3. U.S. Government Printing Office, Washington
Tirez K, Scharf H, Calzolari D, Cleven R, Kisser M, Luck D (2007) J Environ Monit 9:749–759
Grabarczyk M, Korolczuk M, Tyszczuk K (2006) Anal Bioanal Chem 386:357–362
Grabarczyk M (2008) Anal Bioanal Chem 390:979–986
Grabarczyk M (2008) J Hazard Mater 158:491–498
Grabarczyk M (2008) Electroanalysis 20:1857–1862
Khmiri A, Samet B (2009) Adv Cem Res 21:39–44
Ndung’u K, Djane N-K, Malcus F, Mathiasson L (1999) Analyst 124:1367–1372
Milacic R, Scancar J (2000) Analyst 125:1938–1942
Scancar J, Milacic R (2002) Analyst 127:629–633
Potgieter SS, Panichev N, Potgieter JH, Panicheva S (2003) Cem Concr Res 2364
Panichev N, Mandiwana K, Foukaridis G (2003) Anal Chim Acta 491:81–89
Scancar J, Milacic R, Séby F, Donard OFX (2005) J Anal At Spectrom 20:871–875
Goldoni M, Caglieri A, Poli D, Vettori MV, Corradi M, Apostoli P, Mutti A (2006) Anal Chim Acta 562:229–235
Mandiwana KL, Panichev N, Resane T (2006) J Hazard Mater 136:379–382
Long X, Miro M, Hansen EH (2006) Analyst 131:132–140
Mandiwana KL, Panichev N, Kataeva M, Siebert S (2007) J Hazard Mater 147:540–545
Scancar J, Zupancic M, Milacic R (2007) Water Air, Soil Pollut 185:121–129
Mandiwana KL (2008) Talanta 74:736–740
Narukawa T, Riley KW, French DH, Chiba K (2007) Talanta 73:178–184
Marques MJ, Salvador A, Morales-Rubio A, de la Guardia M (2000) Fresenius J Anal Chem 367:601–613
Cornelis R, Caruso J, Heumann KG (2003) Handbook of elemental speciation: techniques and methodology. Wiley, Chichester
Barnowski C, Jakubowski N, Stuewer D, Broekaert JAC (1997) J Anal At Spectrom 12:1155–1161
Tirez K, Brusten W, Cluyts A, Patyn J, De Brucker N (2003) J Anal At Spectrom 18:922–932
Rahman GMM, Kingston HMS, Towns TG, Vitale RJ, Clay KR (2005) Anal Bioanal Chem 382:1111–1120
Vassileva E (2001) Analusis 28:878–884
Séby F, Charles S, Gagean M, Garraud H, Donard OFX (2003) J Anal At Spectrom 18:1386–1390
Andrle CM, Jakubowski N, Broekaert JAC (1997) Spectrochim Acta Part B 52B:189–200
Vanhaecke F, Saverwyns S, De Wannemacker G, Moens L, Dams R (2000) Anal Chim Acta 419:55–64
Hagendorfer H, Goessler W (2008) Talanta 76:656–661
Huo D, Lu Y, Kingston HM (1998) Environ Sci Technol 32:3418–3423
Huo D, Kingston HM (2000) Anal Chem 72:5047–5054
Coedo AG, Dorado T, Padilla I, Alguacil FJ (2000) J Anal At Spectrom 15:1564–1568
Dermatas D, Moon D (2006) Environ Eng Sci 23:77–87
Zachara J, Ainsworth C, Brown G, Catalano J, McKinley J, Qafoku O, Smith S, Szecsody J, Traina S, Warner J (2004) Geochim Cosmochim Ac 68:13–30
Anandan C, William Grips V, Rajam K, Jayaram V, Bera P (2002) Appl Surf Sci 191:254–260
Jeffcoate C, Isaacs H, Aldykiewicz A, Ryan M (2000) J Electrochem Soc 147:540–547
Pappert E, Flock J, Broeckaert JA (1999) Spectrochim Acta Part B 54:299–310
Aubriet F, Maunit B, Muller J (2001) Int J Mass Spectrom 209:5–21
Aubriet F, Maunit B, Courrier B, Muller J (1997) Rapid Commun Mass Spectrom 11:1596–1601
Aubriet F, Poleunis C, Bertrand P (2001) J Mass Spectrom 36:641–651
Robertson-Honecker J, Zhang N, Pavkovich A, King F (2008) J Anal At Spectrom 23:1508–1517
Matsumoto K, Matsunami A, Oyama H, Kitagawa K (2005) Microchem J j81:195–200
Malherbe J, Fernandez B, Martinez H, Panjan P, Donard O (2008) J Anal At Spectrom 23:1378–1387
Asteman H, Norling R, Svensson J, Nylund A, Nyborg L (2002) Surf Interface Anal 34:234–238
Zhang X, Sloof W, Hovestad A, Van Westing E, Terryn H, de Wit J (2005) Surf Coat Tech 197:168–176
Escobar Galindo R, Forniès E, Gago R, Albella J (2007) J Anal At Spectrom 22:1512–1516
Kikuchi S, Yagishita T (2005) Anal Sci 21:197–198
Swedish Environmental Protection Agency (2002) Guidelines for polluted soils. Stockholm, Sweden
Ministero dell’Ambiente della Republica Italiana (1999) Decreto Ministeriale n. 471, Gazzeta Ufficiale Supplemento Ordinario N. 293, Rome, Italy
Luque-Garcia JL, Luque de Castro MD (2002) Analyst 127:1115–1120
Morales-Munoz S, Luque-Garcia JL, Luque de Castro MD (2004) Anal Chim Acta 515:343–348
USEPA (1995) Alkaline Digestion of Hexavalent Chromium, Method 3060A, in Test Methods for Evaluating Solid Waste - Physical/Chemical Methods, SW-846, update 3. Government Printing Office, Washington
EN15192 (2006) Characterization of waste and soil. Determination of Chromium(VI) in solid material by alkaline digestion and ion chromatography with spectrophotometric detection
Kingston HM, Huo D, Lu Y, Chalk S (1998) Spectrochim Acta, Part B 53B:299–309
Ashley K, Howe AM, Demange M, Nygren O (2003) J Environ Monit 5:707–716
Occupational Safety and Health Administration (OSHA) (1998) Analytical methods manual, method ID-215. Hexavalent chromium in workplace atmospheres. OSHA, Salt Lake City
National Institute for Occupational Safety and Health (NIOSH) (1994) Manual of Analytical Methods Method No. 7604, Chromium, Hexavalent, NIOSH, Cincinnati, OH, USA
American Conference of Governmental Industrial Hygienists (ACGIH) (2008) Threshold limit values for chemical substances and physical agents & biological exposure indices. ACGIH, Cincinnati
Vahčič M, Milačič R, Mladenovič A, Murko S, Zuliani T, Zupančič M, Ščančar J (2008) Waste Manag 28:2667–2674
ISO (2005) ISO 16740, Workplace air - Determination of Hexavalent Chromium in Airborne Particulate Matter - Method by Ion Chromatography and Spectrophotometric Measurement using Diphenylcarbazide. ISO, Geneva
National Institute for Occupational Safety and Health (NIOSH) (2003) Manual of Analytical Methods Method No. 7605, Hexavalent Chromium by Ion Chromatography, NIOSH, Cincinnati, OH, USA
National Institute for Occupational Safety and Health (NIOSH) (2003) Manual of Analytical Methods Method No. 7703, Hexavalent Chromium by Field-Portable Spectrophotometry, NIOSH, Cincinnati, OH, USA
Kingston HM, Cain R, Huo D, Rahman GMM (2005) J Environ Monit 7:899–905
Milacic R, Scancar J, Tusek J (2002) Anal Bioanal Chem 372:549–553
Ashley K, Applegate GT, Marcy AD, Drake PL, Pierce PA, Carabin N, Demange M (2009) J Environ Monit 11:318–325
The Council of the European Union (2003) European Directive 2003/53/EC amending for the 26th time Council Directive 76/769/EEC relating to restrictions on the marketing and use of certain dangerous substances and preparations (nonylphenol, nonylphenol ethoxylate and cement), No. L178/24, Aberdeen, UK
Federal Institute for Occupational Safety and Health of Germany (2002) Industrial regulations for hazardous materials TRGS-613. Dortmund, Germany
European Committee for Standardization (CEN) (2006) EN196-10 Methods of testing cement - Part 10: Determination of the water soluble chromium (VI) content of cement. CEN, Brussels
The Council of the European Union (1994) European Directive 1994/62/EC on Packaging and Packaging waste. Official Journal of European Communities No. L365, Aberdeen
ICG/TC2 (2001) Glass Technol 42:148–152
Kim KC, Park YB, Lee MJ, Kim JB, Huh JW, Kim DH, Lee JB, Kim JC (2008) Food Res Int 41:411–418
The Council of the European Union (2002) European Directive 2002/95/EC on the restriction of the use of certain hazardous substances in electrical and electronic equipment. Official Journal of European Communities, Aberdeen
The Council of the European Union (2000) European Directive 2000/53/EC on end-of life vehicles. Official Journal of European Communities, Aberdeen
Zentral Verband Oberlächentechik ZVO (German Suppliers Association). Qualitative Cr (VI) Determination of chromated coatings on structural units using spot test. ZVO-0102-QUA-02e Status 02
European Committee for Standardization (CEN) (2006) EN 15205 Determination of hexavalent chromium in corrosion protection layers — Qualitative analysis. CEN, Brussels
ISO (1995) EN ISO 3613 Chromate conversion coatings on zinc and cadmium. Test methods. ISO, Geneva
Séby F, Castetbon A, Ortega R, Guimon C, Niveau F, Barrois-Oudin N, Garraud H, Donard OFX (2008) Anal Bioanal Chem 391:587–597
Hua L, Chan YC, Wu YP, Wu BY (2009) J Hazard Mater 163:1360–1368
Pourbaix M (1964) Atlas d’équilibres électrochimiques à 25 °C, Paris (France)
Bartlett RJ (1991) Environ Health Perspect 92:17–24
European Committee for Standardization (CEN) (2006) EN 15192 Determination of Chromium(VI) in solid material by alkaline digestion and ion chromatography with spectrophotometric detection. CEN, Brussels
British Standard Institution (2003) PD CEN/TR 14589:2003. Characterization of waste. State of the art document. Chromium VI specification in solid matrices, Bristol, England
Wang J, Ashley K, Marlow D, England EC, Carlton G (1999) Anal Chem 71:1027–1032
Metze D, Herzog H, Gosciniak B, Gladtke D, Jakubowski N (2004) Anal Bioanal Chem 378:123–128
Samanta G, Boring CB, Dasgupta PK (2001) Anal Chem 73:2034–2040
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Unceta, N., Séby, F., Malherbe, J. et al. Chromium speciation in solid matrices and regulation: a review. Anal Bioanal Chem 397, 1097–1111 (2010). https://doi.org/10.1007/s00216-009-3417-1
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-009-3417-1