Analytical Method for Restricted Substances in Industrial Products Regulated by EU

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1 Analytical Method for Restricted Substances in Industrial Products Regulated by EU Sumika Chemical Analysis Service, Ltd. Ehime Laboratory Masayuki ONISHI In recent years, advanced regulations concerning restrictions on the use of hazardous substances have been enforced in the European Union (EU) as environmental pollution control acts. Subsequent to the RoHS (Restriction of the use of certain Hazardous Substances in electrical and electronic equipment) directive for electric and electronic equipment, restrictions on the use of hazardous substances are being examined in the field of all industrial products, where REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) regulations have been enforced. The use of fifteen substances of very high concern has been restricted by the REACH regulations. The European Commission (EC) has submitted proposals to amend the RoHS directive and one proposal is to consider adding four substances to the list of restricted substances. The importance of hazardous substances management in industrial products is increasing more and more from such a background. This paper describes testing methods for restricted substances in industrial products regulated by the EU EU RoHS Restriction of the use of certain Hazardous Substances in electrical and electronic equipment RoHS REACH Registration, Evaluation, Authorization and Restriction of Chemicals PIC Prior Informed Consent

2 1) RoHS Restriction of the use of certain Hazardous Substances in electrical and electronic equipment RoHS EU RoHS RoHS RoHS RoHS RoHS 1), 2) REACH Registration, Evaluation, Authorization and Restriction of Chemicals EU RoHS REACH EU EU REACH REACH ; Carcinogens Mutagens toxic to Reproduction PBT; Persistent Bioaccumulative Toxic Table Substances of very high concern in REACH regulation Substances name Anthracene 4,4 -Diaminodiphenylmethane Dibutyl phtalate Cobalt dichloride Diarsenic pentaoxide Diarsenic trioxide Sodium dichromate dihydrate Musk xylene Bis(2-ethyl(hexyl)phthalate Hexabromocyclododecane Alakanes, C1 ~ 13, Chloro (Short Chain Chlorinated Paraffines) Bis(tributyltin)oxide Lead hydrogen arsenate Triethyl arsenate Benzyl butyl phthalate * : Persistent, Bioaccumulative, Toxic ** : Carcinogens, Mutagens, toxic to Reproduction *** : very Persistent, very Bioaccumulative Reason for proposing PBT* vpvb*** PBT* PBT* vpvb; very Persistent very Bioaccumulative 28 1 Table 1 1 Table Table 2 Potential substances of very high concern in REACH regulation Reason for Substances name proposing Anthracene oil PBT Anthracene oil, anthracene, paste, distin. lights PBT Antracene oil, anthracene, paste, antracene fraction PBT Anthracene oil, antracene-low PBT Anthracene oil, anthracene paste PBT Coal tar pitch, high temperature PBT and Acrylamide Aluminosilicate, refractory ceramic fibres Zirconia aluminiosilicate, refractory ceramic fibres 2,4-Dinitrotoluene Diisobutyl phthalate Lead chromate Lead chromate molybdate sulphate red (C.I. Pigment Red) Lead chromate yellow(c.i. Pigment Yellow34) Tris(2-chloroethyl)phosphate PBT and are same meaning as Table 1 29-

12 13 1 Substances of very high concern in REACH regulation Substances name Anthracene 4,4 -Diaminodiphenylmethane Dibutyl phtalate Cobalt dichloride Diarsenic pentaoxide Diarsenic trioxide Sodium

3 REACH REACH REACH RoHS RoHS A29 2 REACH / GC-MS 2-4, ,4-1 1 GC-MS GC-MSFig. 1 Fig. 2.1 SCAN Fig. 2 2 ABS 19 Table 3.1 Table 3 Result of determination of substances of very high concern in industrial product (wt. %) Product No. material Anthracene Musk xylene Tris 2,4- (2-chloroethyl) Dinitrotoluene phosphate 4,4 - Hexabromo Diaminodipheny cyclododecane lmethane Dibutyl phthalate Benzyl butyl phthalate Bis (2-ethylhexyl) phthalate Diisobutyl Phthalate Polystyrene Polystylene PET PET ABS ABS ABS PVC PVC Polyester and Polyethylene.2 18 Stylene acrylonitrile

material Anthracene Musk xylene Tris 2,4- (2-chloroethyl) Dinitrotoluene phosphate 4,4 - Hexabromo Diaminodipheny cyclododecane lmethane Dibutyl phthalate

4 ,4-Dinitrotoluene Tris(2-chloroethyl)phosphate Anthracene Musk xylene Diisobutyl phthalate Dibutyl phthalate 4,4-Diaminodiphenylmethane Benzyl butyl phthalate Bis(2-ethylhexyl)phthalate Hexabromocyclododecane Fig. 1 Typical TIC chromatogram of substances of very high concern by GC-MS Anthracene Musk xylene ,4 -Diaminodiphenylmethane Diisobutyl Phthalate Benzyl butyl phthalate Hexabromocyclododecane Bis(2-ethylhexyl)phthalate Dibutyl phthalate ,4-Dinitrotoluene Tris(2-chloroethyl) phosphate Fig. 2 Mass spectrums of substances of very high concern 29-

2,4-Dinitrotoluene Tris(2-chloroethyl)phosphate Anthracene Musk xylene Diisobutyl phthalate Dibutyl phthalate 4,4-Diaminodiphenylmethane Benzyl butyl phthalate Bis(2-ethylhexyl)phthalate

5 OA 3) RoHSPBB PBDE HBCDD A TBBPA PBB,PBDE 2 HBCDD REACH1RoHS TBBPA RoHS HBCDDTBBPA 1 4), ) PBB, PBDE HBCDDTBBPA 6) 2 GC-MS HBCDD TBBPA GC-MS HBCDD TBBPA TMS TBBPATMS HBCDD TBBPA HBCDDFig. 3 Recovery of HBCDD/% Amount of TMS reagent/µl Fig. 3 Recovery of HBCDD with TMS reagent GC-MS /LC-MS/ MS 6), 7) LC-MS/MS LC-MS/MS LC-MS/MS Table 4Fig. 4 LC-MS/MS HBCDD α, β, γ ng/ml 1ng/mL 3 HBCDDTBBPA 29-

3 Recovery of HBCDD/% 8 6 4 2 1 2 3 4 Amount of TMS reagent/µl Fig.

6 Table 4 LC system MS/MS system Column Mobile phase A B Gradient Time/min A conc./% B conc./% Flow rate Column temp. Injection volume Ionization method Mode Polarity Monitoring time Analytical condition for determination of HBCDD and TBBPA ACQUITY UPLC system(waters) Qtrap32(Applied Biosystems) SUMIPAX ODS D-21MS µm(2mmi.d. cm) Acetonitrile water mL/min 4 C µl ESI MRM(Multiple Reaction Monitoring) Negative 4min REACH PIC 8) 9) Intensity, cps Intensity, cps 1.e 1.4e 1.3e 1.2e 1.1e 1.e 9.e4 8.e4 7.e4 6.e4.e4 4.e4 3.e4 2.e4 1.e4. 3.8e 3.6e 3.4e 3.2e 3.e 2.8e 2.6e 2.4e 2.2e 2.e 1.8e 1.6e 1.4e 1.2e 1.e 8.e4 6.e4 4.e4 2.e4. Fig. 4 (a) (b) Time, min α -HBCDD B -HBCDD γ -HBCDD TBBPA Typical MRM chromatograms of HBCDD and TBBPA by LC-MS/MS (a)hbcdd, (b)tbbpa HBCDDTBBPA9 1 9) / ) Mizuishi 11) / / Fig. 3mL 3mL GC-MS 29-

µm(2mmi.d. cm) Acetonitrile water 9 2 9 3 1.2mL/min 4 C µl ESI MRM(Multiple Reaction Monitoring) Negative 4min 4 1 1 1. REACH 29 2 1 PIC 8) 9) Intensity, cps Intensity, cps 1.e 1.4e 1.3e 1.2e 1.1e 1.

7 Recovery/% Fraction/mL TBT LC-MS/MS ng/ml 1ng/mL 3 9 Fig. Elution pattern of TBT from column chromatography LC-MS/MS LC-MS/MS Fig. 6 TBT N=N EN Table Joint Industry Guide JIG Intensity, cps Intensity, cps Fig. 6 (a) (b) Time, min TBT-d Time, min 2.6 Typical MRM chromatograms of TBT compound by LC-MS/MS (a)tbt, (b)tbt-d27 Table Specific aromatic amines in EN362 Specific aromatic amines 4-Aminodiphenyl Benzidine 4-Chloro-o-toluidine 2-Naphthylamine o-aminoazotoluene 2-Amino-4-nitrotoluene p-chloroaniline 2,4-Diaminoanisole 4,4 -Methylenedianiline 3,3 -Dichlorobenzidine 3,3 -Dimethoxybenzidine 3,3 -Dimethylbenzidine 4,4 -Methylenedi-o-toluidine p-cresidine 4,4 -Methylenebis(2-chloroaniline) 4,4 -Oxydianiline 4,4 -Thiodianiline o-toluidine 4-Methyl-m-phenylenediamine 2,4,-Trimethylaniline o-anisidine 4-Amino azo benzene 29-

6 Typical MRM chromatograms of TBT compound by LC-MS/MS (a)tbt, (b)tbt-d27 Table 1 2 3 4 6 7 8 9 1 11 12 13 1 16 17 18 19 2 21 22 Specific aromatic amines in EN362 Specific aromatic amines

8 2-A 1 EN ) EN ,4-4- -m- 4-1,4- EN Fig. 73 1,4- EN362-1 Gowda 13) Peak Area aminobiphenyl benzidine Fig chloro-o-toluidine 2-naphthylamine o-aminoazotoluene 2-amino-4-nitrotoluene 4-chloroaniline 2,4-diaminoanisole 4,4 -methylenedianiline 3,3 -dichlorobenzidine 3,3 -dimethoxybenzidine Reaction time/min 3,3 -dimethylbenzidine 4,4 -methylenedi-o-toluidine p-cresidine 4,4 -methylenebis(2-chloroaniline) 4,4 -oxydianiline 4,4 -thiodianiline o-toluidine 4-methyl-m-phenylenediamine 2,4,-trimethylaniline o-anisidine 4-aminoazobenzene Effect of reaction time in derivatived reaction of specific aromatic amines 2 Fig. 8 EN362-1 Table 6 EN EN362-1GC-MS LC- MS/MS ng/ml 1ng/mL 29-

-dimethoxybenzidine Reaction time/min 3,3 -dimethylbenzidine 4,4 -methylenedi-o-toluidine p-cresidine 4,4 -methylenebis(2-chloroaniline) 4,4 -oxydianiline 4,4 -thiodianiline

9 Fig. 8 Table 6 Recovery/% aminobiphenyl benzidine 4-chloro-o-toluidine Inhouse method EN362-1method 2-naphthylamine o-aminoazotoluene 2-amino-4-nitrotoluene 4-chloroaniline 2,4-diaminoanisole 4,4 -methylenedianiline 3,3 -dichlorobenzidine 3,3 -dimethoxybenzidine 3,3 -dimethylbenzidine 4,4 -methylenedi-o-toluidine p-cresidine 4,4 -methylenebis(2-chloroaniline) 4,4 -oxydianiline 4,4 -thiodianiline o-toluidine 4-methyl-m-phenylenediamine Comparison of recovery of between Inhouse and EN362-1 method Recovery of specific aromatic amines from azo dyes Table 8 2,4,-trimethylaniline o-anisidine 4-aminoazobenzene aniline 1,4-phenylenediamine Recovery of specific aromatic amines from azo pigments in polystylene Azo dye Direct Red 28 (Congo Red) Direct Blue1 Direct Blue2 Bismarck Brown R Ponceau 3R Sudan R Sudan III Table 7 Specific aromatic amine derived from azo dye Benzidine 3,3 -Dimethoxybenzidine 3,3 -Dimethylbenzidine 4-Methyl-m-phenylenediamine 2,4,-Trimethylaniline o-anisidine Aniline 1,4-Phenylenediamine Recovery/% Inhouse EN Recovery of specific aromatic amines from azo dyes in polystylene Azo pigment EN36-1 Specific aromatic amine derived from azo pigments Benzidine Yellow 3,3 -Dichlorobenzidine (Pigment Yellow) 4 Pigment Red (Pigment Red1) Pigment Red4 Pigment Yellow 1 1,4-Phenylenediamine 2-Chloro-1,4-phenylenediamine 4-Methyl-o-phenylenediamine Recovery/% Inhouse EN362 Azo dye Direct Red 28 (Congo Red) Direct Blue1 Direct Blue2 Sudan IV Bismarck Brown R Ponceau 3R Sudan R Sudan III Specific aromatic amine derived from azo dye Benzidine 3,3 -Dimethoxybenzidine 3,3 -Diethylbenzidine o-toluizine 4-Methyl-m-phenylenediamine 2,4,-Trimethylamine o-anisidine Aniline 1,4-Phenylendiamine Recovery/% Inhouse EN362 REACH 3 Table 7 Table 8 1),, (28). 2),,, 16, 28 (29). 3) (FRCJ) ( 29-

-oxydianiline 4,4 -thiodianiline o-toluidine 4-methyl-m-phenylenediamine Comparison of recovery of between Inhouse and EN362-1 method Recovery of specific aromatic amines from azo dyes Table 8

10 4),, MATERIAL STAGE, 4 (1), 79 (24). ),,,, 44 (26). 6) M. Frederiksen, K. Vorkamp, R. Bossi, F. Riget, M. Dam and B. Sevensmark, Intern. J. Environ. Anal. Chem., 87 (1), 19 (27). 7),,,, 18, 24 (29). 8),,,,, 41, 246 (2). 9),,,,,, 43, 28 (22). 1) Xiupin Wnag, Haiyan Jin, Lan Ding, Huarong Zhang, Hanqi Zhang, Cheling Qu and Aimin Yu, Talanta, 7, 6 (28). 11) K. Mizuishi, M.Takeuchi and T. Hobo, Analyst, 123, 329 (1998). 12) EN362-1 (23). 13) S. Gowda, K. Abiraj and D. Channe Gowda, Tetrahedron Letters, 43, 1329 (22). PROFILE Masayuki ONISHI 29-

1) Xiupin Wnag, Haiyan Jin, Lan Ding, Huarong Zhang, Hanqi Zhang, Cheling Qu and Aimin Yu, Talanta, 7, 6 (28). 11) K. Mizuishi, M.

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