Abstract
The European Union’s as well as India’s reduction of hazardous materials (RoHS) directives state that producers of certain categories of electrical and electronic equipments will not be able to offer for sale any product that contains any of hazardous substances: Cd, Pb, Hg, Cr6+, polybrominated biphenyls (PBB), polybrominated diphenyl ethers (PBDE), bis(2-ethylhexyl) phthalate (DEHP), butyl benzyl phthalate (BBP), dibutyl phthalate (DBP) and diisobutyl phthalate (DIBP) beyond the specified limits. Allowable concentration levels in any homogeneous material contained within a product are extremely low: 0.01% for Cd and 0.1% for other substances by weight. These substances when present in quantities in excess of the permissible limits are considered hazardous and damaging to the environment and human health. With the introduction of the RoHS Directive many manufacturing companies in the world are pursuing chemical testing as a means to identify and quantify these hazardous substances. This article presents various testing methods that are currently available to the manufacturing firms who need to generate data to prove that their products are compliant to the RoHS directive. The utility of portable X-ray fluorescence spectrometer (XRF) and also the potential of laser-induced breakdown spectrometer (LIBS) for rapid screening applications is described. For quantitative determination of Pb, Cd, Hg and Cr, the role of instrumental analytical techniques such as atomic absorption spectrometry, XRF, instrumental neutron activation analysis, inductively coupled plasma optical emission spectrometry, the inductively coupled plasma mass spectrometry (ICP-MS), LIBS and the potential of the new analytical technique, microwave plasma atomic emission spectrometry is discussed. Applicability of hyphenated techniques such as HPLC-ICP-MS for Cr6+, GC–MS for the determination of PBB, PBDE and phthalates, and the importance of certified reference materials, challenges and future trends are presented.
Similar content being viewed by others
References
V. Kuntz, White paper on European Union RoHS directive: understanding exemptions, Assent, Canada, (2015) 1–14.
S. Chatterjee, India’s readiness on ROHS directives: a strategic analysis, Glob. J. Sci. Frontier Res. Interdiscip., 12(1) (2012) 1–13.
U. Rambabu, V. Balaram, R. Ratheesh, S. Chatterjee, M.K. Babu and N.R. Munirathnam, Assessment of hazardous substances in electrical cables: implementation of RoHS regulations in India, J. Test. Eval., 46(5) (2018). https://doi.org/10.1520/JTE20160645. ISSN 0090-3973.
https://www.revolvy.com/main/index.php?s=Restriction%20of%20Hazardous%20Substances%20Directive.
T.W. Dahl, M. Ruhl, E.U. Hammarlund, D.E. Canfield, M.T. Rosing and C. J. Bjerrum, Tracing euxinia by molybdenum concentrations in sediments using handheld X-ray fluorescence spectroscopy (HHXRF), Chem. Geol., 360–361 (2013) 241–251.
G.E.M. Hall, M.B. McClenaghan and L. Pagé, Application of portable XRF to the direct analysis of till samples from various deposit types in Canada, Geochem. Explor. Environ. Anal., 16 (2015) 62–84.
V. Balaram, Field-portable instruments in mineral exploration: past, present and future, J. Appl. Geochem., 19(4) (2017) 382–399.
N.H. Nilsson, B. Malmgren-Hansen and I. Christensen, Development and use of screening methods to determine chromium (VI) and brominated flame retardants in electrical and electronic equipment, Danish Ministry of the Environment (2009) pp. 1–35.
K.Ting, M. Gill and O. Garbin, GC/MS screening method for phthalate esters in children’s toys, J. AOAC Int., 92(3) (2009) 951–958.
A. E. Harvey Jr., J.A. Smart and E.S. Amis, Simultaneous spectrophotometric determination of iron(ii) and total iron with 1,10-phenanthroline, Anal. Chem., 27(1) (1955) 26–29.
L. Hua, Y.C. Chan, Y.P. Wu and B.Y. Wu, Determination of hexavalent chromium (Cr6+) in electronic and electrical components and products to comply with RoHS regulations, J Hazard. Mater., 163(2–3) (2008) 1360–1368.
S.K. Pradhan and P.K. Tarafder, Scheme for performance evaluations of UV–visible spectrophotometer by standard procedures including certified reference materials for the analysis of geological samples, MAPAN-J. Metrol. Soc. India, 31(4) (2017) 275–281.
V. Balaram, R. Mathur, M. Satyanarayanan, S.S. Sawant, P. Roy, K.S.V. Subramanyam, C.T. Kamala, K.V. Anjaiah, S.L. Ramesh and B. Dasaram, A rapid method for the determination of gold in rocks, ores and other geological materials by F-AAS and GF-AAS after separation and preconcentration by DIBK extraction for prospecting studies. MAPAN-J. Metrol. Soc. India, 27(2) (2012) 87–95.
A.M.G. Alegria, M.G. Canez-Carrasco, M. Serna-Felix and A. Gomez-Alverez, Estimation of uncertainty in the determination of serum electrolytes (Na, K, Ca, Mg) by flame atomic absorption spectroscopy, MAPAN-J. Metrol. Soc. India, (2018), https://doi.org/10.1007/s12647-017-0244-2.
A. Walsh, The application of atomic absorption spectra to chemical analysis, Spectrochim. Acta 7 (1955) 108–117.
L. Boris, Recent advances in absolute analysis by graphite furnace atomic absorption spectrometry, Spectrochim. Acta Part B At. Spectrosc., 45 (1990) 633–655.
A.T. Duarte, M.B. Dessuy, M.M. Silva, M.G.R Vale and B. Welz, Determination of cadmium and lead in plastic material from waste electronic equipment using solid sampling graphite furnace atomic absorption spectrometry, Microchem. J., 96 (2010) 102–107.
A.T. Duarte, M.B. Dessuy, M.G.R. Vale and B. Welz, Determination of chromium and antimony in polymers from electrical and electronic equipment using high resolution continuum source graphite furnace atomic absorption spectrometry, Anal. Methods, 24 (2013) 6941–6946.
R. Mathur, V. Balaram and S. Babu, Determination of mercury in geological samples by cold vapor atomic absorption spectrometric technique, Indian J. Chem., 44A (2005) 1619–1624.
A. Hioki, M. Ohata, S. Matsuyama and S. Kinugasa, Development of plastic certified reference materials (CRMs) to cope with restrictions on hazardous substances—CRMs for analysis of heavy metals and brominated flame retardants regulated by RoHS directive, Synthesiol. Engl. Ed., 8(1) (2015) 29–42.
R. Glocker and H. Schreiber, Quantitative Röntgenspektralanalyse mit Kalterregung des Spektrums, Ann. Physik., 85 (1928) 1089–1102.
P.J. Potts and C. Webb, X-ray fluorescence spectrometry, J. Geochem. Explor., 44(1–3) (1992) 251–296.
E.L. Hoffman, Instrumental neutron activation in geoanalysis, J. Geochem. Explor., 44(1–3) (1992) 297–319.
A. El-Taher, Elemental analysis of granite by instrumental neutron activation analysis (INAA) and X-ray fluorescence analysis (XRF), Appl. Radiat. Isot., 70(1) (2012) 350–354.
R.A. Nadkarni and G.H. Morrison, Multielement analysis of sludge samples by instrumental neutron activation analysis, Environ. Lett., 6(4) (1974) 273–285.
K. Park and N. Kang, Instrumental neutron activation analysis of mass fractions of toxic metals in plastic, Talanta, 73 (2007) 791–794.
M. Tsutomu, O. Ryo, I. Yuto, S. Shun, T. Koichi and O. Masaki, Precise determination of bromine in PP resin pellet by instrumental neutron activation analysis using internal standardization, J. Radioanal. Nucl. Chem., 303(2) (2015) 1417–1420.
N. Ismail, and J. Yoo, Determination of Lead (Pb) concentration level in solder finished product using Laser Induced Breakdown Spectroscopy (LIBS), Proceedings on 12th electronics packaging technology conference, Singapore, (2010) pp. 456–461.
A.A. Bol’shakov, J.H. Yoo, C. Liu, J.R. Plumer and R.E. Russo, Laser-induced breakdown spectroscopy in industrial and security applications, Appl. Opt., 49(13) (2010) C133–C142.
S. Greenfield, I.L.I. Jones and C.T. Berry, High pressure plasmas as spectroscopic emission sources, Analyst, 89 (1964) 713–720.
R.H. Wendt and V. Fassel, Inductively-coupled plasma spectrometric excitation source, Anal. Chem., 37 (1965) 920–922.
V. Balaram, K.V. Anjaiah and M.R.P. Reddy, A comparative study on the trace and rare earth element analysis of an Indian polymetallic nodule reface sample by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry, Analyst, 120 (1995) 1401–1406.
H.J. Cho and S.W. Myung, Determination of cadmium, chromium and lead in polymers by ICP-OES using a high pressure asher (HPA), Bull. Korean Chem. Soc., 32(2) (2011) 489–497.
R.S. Houk, V.A. Fassel, G.D. Flesch, H.J. Svec, A.L. Gray and C.E. Taylor, Inductively coupled argon plasma as an ion source for mass spectrometric determination of trace elements, Anal. Chem., 52 (1980) 2283–2289.
V. Balaram, Recent trends in the instrumental analysis of rare earth elements in geological and industrial materials, Trends Anal. Chem., 15 (1996) 475–486.
V. Balaram, M. Satyanarayanan, P.K. Murthy, C. Mohapatra and K.L. Prasad, Quantitative multi-element analysis of cobalt crust from Afanasy-Nikitin seamount in the north central Indian Ocean by inductively coupled plasma time-of-flight mass spectrometry, MAPAN-J. Metrol. Soc. India, 28(2) (2013) 63–77.
M. Satyanarayanan, V. Balaram, S.S. Sawant, K.S.V. Subramanyam, V. Krishna, B. Dasaram, and C. Manikyamba, Rapid determination of REE, PGE and other trace elements in geological and environmental materials by HR-ICP-MS, At. Spectrosc., 39(1) (2018) 1–15.
M.C. Santos, J.A. Nóbregab and S. Cadorea, Determination of Cd, Cr, Hg and Pb in plastics from waste electrical and electronic equipment by inductively coupled plasma mass spectrometry with collision–reaction interface technology, J. Hazard. Mater., 190 (2011) 833–839.
F. Kyoko and C. Atsushi, Determination of trace amounts of mercury, lead, and cadmium in steel and iron ore, JFE GIHO, 13 (2006) 35–41.
C. Mans, D. Alber, M. Radtke, S. Hanning, A. Buhler and M. Kreyenschmidt, New polymeric candidate reference materials for XRF and LA-ICP-MS—development and preliminary characterization, X-ray Spectrom., 38 (2009) 52–57.
H. Osterlund, L. Rodushkin, K. Ylinenjarvi and D.C. Baxter, Determination of total chlorine and bromine in solid wastes by sintering and inductively coupled plasma-sector field mass spectrometry, Waste Manage., 29(4) (2008) 1258–1264.
B. Novotnik, T. Zuliani, J. Scancar and R. Milacic, The determination of Cr(VI) in corrosion protection coatings by speciated isotope dilution, ICP-MS.J. Anal. At. Spectrom., 27 (2012) 1484–1493.
M.R. Hammer, A magnetically excited microwave plasma source for atomic emission spectroscopy with performance approaching that of the inductively coupled plasma, Spectrochim. Acta Part B, 63 (2008) 456–464.
V. Balaram, V. Dharmendra, P. Roy, C. Taylor, P. Kar, A.K. Raju and A. Krishnaiah, Determination of precious metals in rocks and ores by microwave plasma-atomic emission spectrometry (MP-AES) for geochemical prospecting, Curr. Sci., 104(9) (2013) 1207–1215.
C.T. Kamala, V. Balaram, V. Dharmendra, P. Roy, M. Satyanarayanan, K.S.V. Subramanyam, Application of microwave plasma atomic emission spectrometry (MP-AES) for environmental monitoring of industrially contaminated sites in Hyderabad city, Environ. Monit. Assess. 186 (2014) 7097–7113.
V. Sreenivasulu, V. Dharmendra, V. Balaram, C.N. Rao A. Krishnaiah, H. Zhengxu and Z. Zhen, Determination of B, P and Mo in bio-sludge samples by microwave plasma atomic emission spectrometry (MP-AES), Appl. Sci., 7 (2017) 264–273.
L.D. George, S.A. Renata, D. Schiavo, A.N. Joaquim, Determination of Cr, Ni, Pb and V in gasoline and ethanol fuel by microwave plasma optical emission spectrometry, J. Anal. At. Spectrom., 28 (2013) 755–759.
D. Pfeil, Measurement techniques for mercury: which approach is right for you?, Spectroscopy, 26(9) (2011) 40–43.
Z. Grosser, L. Thompson and L. Davidowski, Inorganic analysis for environmental RoHS compliance, American Laboratory, October (2007) pp. 1–4.
G.M.M. Rahman, H.M.S. Kingston, T.G. Towns, R.J. Vitale and K.R. Clay, Determination of hexavalent chromium by using speciated isotope-dilution mass spectrometry after microwave speciated extraction of environmental and other solid materials, Anal. Bioanal. Chem., 382 (2005) 1111–1120.
S. Yue-Feng, W. Feng, B. Li-Ying, X. Bin and C. Shi, Determination and factor analysis of trace hexavalent chromium in plastics for RoHS directive, Acta Chim. Sin., 66(6) (2008) 662–668.
L. Hua, Y.C. Chan, Y.P. Wu and B.Y. Wu, The determination of hexavalent chromium (Cr6+) in electronic and electrical components and products to comply with RoHS regulations, J. Hazard. Mater., 163 (2009) 1360–1368.
J.S. Kim, Y.R. Choi, Y.S. Kim, Y.J. Lee, Y.H. Ko, S.Y. Kwon and S.B. Heo, Determination of hexavalent chromium (Cr(VI)) in plastics using organic-assisted alkaline extraction, Anal. Chim. Acta, 690(2) (2011) 182–189.
E. Hoh, L. Zhu, R.A. Hites, Novel flame retardants, 1,2-bis(2,4,6-tribromophenoxy) ethane and 2,3,4,5,6-pentabromoethylbenzene, in United States’ environmental samples, Environ. Sci. Technol., 39 (2005) 2472–2477.
J.H. Christensen, M. Glasius, M. Pécseli, J. Platz, G. Pritz, Polybrominated diphenyl ethers (PBDEs) in marine fish and blue mussels from southern Greenland, Chemosphere, 47(6) (2002) 631–638.
E. Eljarrat and D. Barceló, Priority lists for persistent organic pollutants and emerging contaminants based on their relative toxic potency in environmental samples, Trends Anal. Chem., 22(10) (2003) 655–665.
L.G. Costa and G. Giordano, Developmental neurotoxicity of polybrominated diphenyl ether (PBDE) flame retardants, Neurotoxicology, 28(6) (2007)1047–1067.
M. Riess and R. Eldi, Identification of brominated flame retardants in polymeric materials by reversed-phase liquid chromatography with ultraviolet detection, J. Chromatogr. A, 827 (1998) 65–71.
B. Kolarik, C. Bornehag, K. Naydenov, J. Sundell, P. Stavova and O.F. Nielsen, Concentrations of phthalates in settled dust in Bulgarian homes in relation to building characteristic and cleaning habits in the family, Atmos. Environ., 42(37) (2008) 8553–8559.
H. Shen, Simultaneous screening and determination eight phthalates in plastic products for food use by sonication-assisted extraction/GC–MS methods, Talanta, 66(3) (2005) 734–739.
C.K. Wei, L.C. Fung and M. Pang, Determination of six phthalates in polypropylene consumer products by sonification assisted extraction-GC–MS method, Malaysian J. Anal. Sci., 15(2) (2011) 167–174.
S. G. Aggarwal, Recent developments in aerosol measurement techniques and the metrological issues, MAPAN-J. Metrol. Soc. India, 25(3) (2010) 165–189.
M. Schlummer, F. Brandl, A. Mäurer and R. van Eldik, Analysis of flame retardant additives in polymer fractions of waste of electric and electronic equipment (WEEE) by means of HPLC-UV/MS and GPC-HPLC-UV. J Chromatogr. A, 1064(1) (2005) 39–51.
Y. Chen, J. Li, L. Chen, S. Chen and W. Diao, Brominated flame retardants (BFRs) in waste electrical and electronic equipment (WEEE) plastics and printed circuit boards (PCBs), Procedia Environ. Sci., 16 (2012) 552–559.
M. Pöhlein, B. Müller, M. Wolf and R. van Eldik, GIT Labor-Fachzeitschrift, 48 (2004) 754 (in German language).
M. Shao, J. Jiang, M. Li, L. Wu and M. Hu, Recent developments in the analysis of polybrominated diphenyl ethers and polybrominated biphenyls in plastic, Rev. Anal. Chem., 35(3) (2016) 133–143.
M.S. Qureshi, A.R.M. Yusoff, M.D.H. Wirzal, Sirajuddin, J. Barek, H.I. Afridi and Z. Ustundag, Methods for the determination of endocrine-disrupting phthalate esters, Crit. Rev. Anal. Chem., 46(2) (2016) 146–159.
H. Vasakova, A powerful tool for material identification: Raman Spectroscopy, Int. J. Math. Models Methods Appl. Sci., 7(5) (2011) 1205–1212.
R. Taurino, M. Cannio, T. Mafredini and P. Pozzi, An efficient and fast analytical procedure for the bromine determination in waste electrical and electronic equipment plastics, Environ. Technol., 35(21–24) (2014) 3147–3152.
S. Kikuchi, K. Kawauchi, S. Ooki, M. Kurosawa, H. Honjho and T. Yagishita, Non-destructive rapid analysis of brominated flame retardants in electrical and electronic equipment using Raman Spectroscopy, Anal. Sci., 20 (2004) 1111–1112.
J.E. Martin, L.L.A. Smith, G. Adjei-Bekoe and R. Thomas, Comparison of different sample preparation procedures for the determination of RoHS/WEEE-regulated elements in printed circuit boards and electrical components by EDXRF, Spectroscopy 25(4) (2010) 40–47.
V. Balaram, Microwave dissolution techniques for the analysis of geological materials by ICP-MS, Curr. Sci., 73 (1997) 1019–1023.
F. Vilaplana, A. Ribes-Greus and S. Karlsson, Microwave-assisted extraction for qualitative and quantitative determination of brominated flame retardants in styrenic plastic fractions from waste electrical and electronic equipment (WEEE), Talanta, 78(1) (2009) 33–39.
USGS (2017) https://pubs.usgs.gov/gip/0167/gip167.pdf.
RoHS FAQ Guidance document (2016) http://ec.europa.eu/environment/waste/rohs_eee/pdf/faq.pdf.
K.S.V. Subramanyam, V. Balaram, U.V.B. Reddy, M. Satyanarayanan, P. Roy and S.S. Sawant. Problems involved in using improper calibration CRMs in geochemical analyses: a case study on mafic rocks of Boggulakonda Pluton, East of Cuddapah Basin, India, MAPAN-J. Metrol. Soc. India, 28(1) (2013) 1–9.
V. Balaram, M.L. Patil, A.K. Agrawal, D.V.S. Rao, S.N. Charan, M. Satyanarayanan, R. Mathur, K. Kapilavastu, D.S. Sarma, M.S. Gowda, S.L. Ramesh, P. Sangurmath, K.V. Anjaiah, B. Dasaram, R.K. Saxena and Z. Begum, Preparation and certification of high-grade gold geochemical reference material, Accred. Qual. Assur., 11 (2006) 329–335.
M. Pöhlein, R.U. Bertran, M. Wolf, R. van Eldik, Preparation of reference materials for the determination of RoHS-relevant flame retardants in styrenic polymers, Anal. Bioanal. Chem., 394 (2009) 583–595.
NMIJ 2008 CRM 8108-a http://www.seishinsyoji.co.jp/Standard/2007.11Plastic%20Reference%20Material.pdf.
M. Ohata and A. Hioki, Development of PVC and PP resin pellet certified reference materials for heavy metal analysis with respect to the RoHS directive, Anal. Sci., 29 (2013) 239–246.
C. Bergh, G. Luongo, S. Wise and C. Östman, Organophosphate and phthalate esters in standard reference material 2585 organic contaminants in house dust, Anal. Bioanal. Chem., 402(1) (2012) 51–59.
G. Flora, D. Gupta and A. Tiwari, Toxicity of lead: a review with recent updates, Interdiscip. Toxicol., 5(2) (2012) 47–58.
B.F. Azevedo, L.B. Furieri, F.M. Peçanha, G.A. Wiggers, P.F. Vassallo, M.R. Simões, J. Fiorim, P.R. Batista, M. Fioresi, L. Rossoni, I. Stefanon, M.J. Alonso, M. Salaices and D.V. Vassallo, Toxic effects of mercury on the cardiovascular and central nervous systems, J. Biomed. Biotechnol., Article ID 949048, (2012) 1–11, https://doi.org/10.1155/2012/949048.
U.S. Department of Health and Human Services, Public Health Service, Agency for toxic Substances and Disease Registry (ATSDR), Toxicological Profile for Cadmium (2012).
U.S. Department of Labor, Health effects of hexavalent chromium, Occupational Safety and Health Administration (2006).
M.A. Siddiqi, R.H. Laessig and K.D. Reed, Polybrominated diphenyl ethers (PBDEs): new pollutants-old diseases, Clin. Med. Res., 1(4) (2003) 281–290.
A. Covaci, S. Voorspoels, L. Ramos, H. Neels and R. Blust, Recent developments in the analysis of brominated flame retardants and brominated natural compounds, J. Chromatogr. A, 1153 (2007) 145–171.
C.F. Wilkinson and J.C. Lamb IV, The potential health effects of phthalate esters in children’s toys: a review and risk assessment, Regul. Toxicol. Pharmacol., 30(2) (1999) 140–155.
L. Randall, V. Wal, T.M. Ticich, J.R. West and A. Paul, Trace metal detection by laser-induced breakdown spectroscopy, Appl. Spectrosc., 53(10) (1999) 1226–1236.
V. Balaram, V. Dharmendra, P. Roy, C. Taylor, C.T. Kamala, M. Satyanarayanan, P. Kar, K.S.V. Subramanyam, A.K. Raju, A. Krishnaiah, Analysis of geochemical samples by microwave plasma-AES, At. Spectrosc., 35(2) (2014) 65–78.
B. Welz, Atomic absorption spectroscopy, 2nd edn., VCH, Weinheim and Deerfield Beach, FL (1985) p. 506.
X. Hou and B.T. Jones, Inductively coupled plasma/optical emission spectrometry. In: Encyclopedia of analytical chemistry, R.A. Meyers (Ed.) John Wiley & Sons Ltd, Chichester (2000) pp. 9468–9485
V. Balaram and T.G. Rao, Rapid determination of REE and other trace elements in geological samples by microwave acid digestion and ICP-MS, At. Spectrosc., 24(6) (2003) 206–212.
B. Passariello, M. Barbaro, S. Quaresima, A.A. Marabini, Determination of mercury by inductively coupled plasma-mass spectrometry, Microchemical J., 54(4) (1996) 348–354.
V.R. Bellotto and N. Miekeley, Improvements in calibration procedures for the quantitative determination of trace elements in carbonate material (mussel shells) by laser ablation ICP-MS, Fresenius J. Anal. Chem., 367(2000) 635–640.
R. Van Grieken and J. Injuk, Current applications of XRF and micro-XRF techniques in environmental and industrial fields (1999) (unpublished work).
B. Binici, M. Bilsel, M. Karakas, I. Koyuncu and A.C. Goren, An efficient GC-IDMS method for determination of PBDEs and PBB in plastic materials, Talanta, 116 (2013) 417–426.
N. Boley, Development of a procedure for the determination of selected brominated flame retardants (PBB, PBDE) in plastics by HPLC-ICP-MS. National Measurement Office, Teddington, (2010) pp. 1–41.
Acknowledgements
One of the authors (VB) would like to express sincere thanks to the Ministry of Electronics and Information Technology (MeitY), Government of India, New Delhi and the Director, C-MET, Hyderabad for appointing him as the Chairman of the Monitoring Committee for the RoHS Project at C-MET, Hyderabad during 2012–2017.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Balaram, V., Rambabu, U., Reddy, M.R.P. et al. RoHS Regulation: Challenges in the Measurement of Substances of Concern in Industrial Products by Different Analytical Techniques. MAPAN 33, 329–346 (2018). https://doi.org/10.1007/s12647-018-0263-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12647-018-0263-7