Migration of Parabens, Bisphenols, Benzophenone-Type UV filters, Triclosan, and Triclocarban from Teethers and Its Implications for Infant Exposure Alexandros G. Asimakopoulos a,, Madhavan Elangovan a,, Kurunthachalam Kannan a,b* a Wadsworth Center, New York State Department of Health, and Department of Environmental Health Sciences, School of Public Health, State University of New York at Albany, Empire State Plaza, P.O. Box 509, Albany, New York 12201-0509, United States. b Biochemistry Department, Faculty of Science and Bioactive Natural Products Research Group, King Abdulaziz University, Jeddah, Saudi Arabia. *Corresponding author: K. Kannan Wadsworth Center Empire State Plaza, P.O. Box 509 Albany, NY 12201-0509 Tel: +1-518-474-0015 Fax: +1-518-473-2895 E-mail: kurunthachalam.kannan@health.ny.gov For submission to: Environmental Science & Technology These authors contributed equally. Number of pages: 12 Number of figures: 4 Number of tables: 7 Supporting Information S1
Fig. 1S. Migration trial with Milli-Q water. S2
Fig. 2S. Migration trial with methanol. S3
Fig. 3S. Differences between the median of the gel-filled teethers with the water-filled and solid teethers for MeP, EtP, PrP, and BuP. S4
% Total Exctracted Amount 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% Water Methanol Fig. 4S. Migration profiles of parabens, bisphenols, benzophenones and antimicrobial agents from baby teethers into water and methanol extracts; Values in Y-axis refers to % of the total extraction. Values in X-axis refer to methyl- [MeP], ethyl- [EtP], propyl- [PrP], butyl- [BuP], benzyl- [BezP] heptyl- [HeP] parabens, 4-hydroxy benzoic acid [4-HB], 3,4-dihydroxy benzoic acid [3,4-DHB], methyl-protocatechuic acid [OH-MeP] and ethyl-protocatechuic acid [OH-EtP], 2,2-bis(4-hydroxyphenyl)propane [BPA], 4,4 - (hexafluoroisopropylidene)-diphenol [BPAF], 4,4 -(1-phenylethylidene) bisphenol [BPAP], 4,4 -sulfonyldiphenol [BPS], 4,4 - dihydroxydiphenylmethane [BPF], 4,4 -(1,4-phenylenediisopropylidene) bisphenol [BPP], 4,4 -cyclo-hexylidenebisphenol [BPZ], 2,2-bis(4-hydroxyphenyl)butane [BPB], and 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene [BPM], 2-hydroxy-4 - methoxybenzophenone [BP-3], 2,4-dihydroxybenzophenone [BP-1], 2,2,4,4-tetrahydroxybenzophenone [BP-2], and 4- hydroxybenzophenone [4-OH-BP], triclosan [TCS], and triclocarban [TCC]. S5
Table S1. Tandem MS transitions of the target analytes and internal standards Compound Precursor ions (m/z) Product ions (m/z) BPA 227 212 BPB 241 212 BPS 249 108 BPAF 335 265 BPAP 289 274 BPF 199 93 BPZ 267 173 BPP 345 330 BPM 345 132.8 13 C 12 -BPA 239 224 13 C 12 -BPS 261 114 13 C 12 -BPAF 346.8 276.9 MeP 151 92 EtP 165 92 PrP 179 92 BuP 193 92 BezP 227 92 HeP 235 92 4-HB 137 93 3,4-DHB 153 109 OH-MeP 167 108 OH-EtP 181 108 TCS 287 35 TCC 313 160 13 C 6 -MeP 157 98 13 C 6 -EtP 171 98 13 C 6 -PrP 185 98 13 C 6 -BuP 199 98 2 D 4 -BzP 231 96 2 D 4 -HeP 239 96 13 C 6-4-HB 143 99 13 C 6 -TCC 319 160 BP1 213 91 BP2 245 91 BP3 227 211 BP8 243 93 4-OH-BP 197 92 13 C 6 -BP3 233 217 S6
Table S2. Limits of Detection (LODs) and limits of quantification (LOQs) Target Chemicals LODs (ng/ml) LOQs (ng/ml) BPA 0.20 0.66 BPAF 0.20 0.66 BPAP 0.050 0.17 BPS 0.020 0.07 BPF 0.50 1.65 BPP 0.20 0.66 BPZ 0.030 0.10 BPB 0.10 0.33 BPM 1.00 3.33 MeP 0.17 0.50 EtP 0.17 0.50 PrP 0.050 0.15 BuP 0.040 0.11 BezP 0.010 0.03 HeP 0.005 0.015 4-HB 0.81 2.44 3,4-DHB 0.39 1.16 OH-MeP 0.21 0.52 OH-EtP 0.13 0.39 BP-3 0.20 0.66 BP-1 0.40 1.32 BP-8 0.40 1.32 BP-2 0.30 0.99 4-OH-BP 0.40 1.32 TCS 0.040 0.11 TCC 0.040 0.13 S7
Table S3. Reagent blank amounts (ng) Target Chemicals Mean (SD; N=9) ng Milli-Q water trial Mean (SD; N=9) ng Methanol trial BPA 0.42 (0.21) 0.68 (0.21) BPAF 0.023 (0.010) 0.026 (0.022) BPAP 0.031 (0.042) 0.024 (0.030) BPS 0.12 (0.064) 0.18 (0.18) BPF 0.74 (0.67) 0.46 (0.32) BPP - - BPZ 0.019 (0.023) 0.035 (0.033) BPB 0.015 (0.017) 0.025 (0.038) BPM 0.051 (0.054) 0.12 (0.16) MeP 0.70 (0.82) 0.40 (0.40) EtP 0.14 (0.21) 0.11 (0.11) PrP 0.20 (0.88) 0.14 (0.067) BuP 0.011 (0.008) 0.017 (0.005) BezP - - HeP - - 4-HB 3.20 (6.8) 1.91 (0.55) 3,4-DHB 0.47 (1.42) 0.36 (0.25) OH-MeP 0.093 (0.064) 0.057 (0.026) OH-EtP 0.013 (0.016) 0.015 (0.014) BP-3 0.051 (0.13) 0.40 (0.23) BP-1 0.094 (0.11) - BP-8 0.24 (0.14) - BP-2 0.053 (0.096) 0.14 (0.12) 4-OH-BP 0.085 (0.075) 0.13 (0.14) TCS 0.084 (0.12) 0.076 (0.12) TCC 0.009 (0.007) 0.008 (0.010) S8
Table S4. Mean absolute and relative recoveries (N=7, 50 ng/ml) of the target analytes Compound (internal standard used for calculating the relative recoveries and quantification) Absolute recovery % from Milli-Q water/methanol solution Relative recovery % from Milli-Q water/methanol solution BPA ( 13 C 12 -BPA) 49.6/81.9 67.7/80.3 BPB ( 13 C 12 -BPA) 70.5/135.3 94.8/110.1 BPS ( 13 C 12 -BPS) 56.5/59.3 103.7/110.1 BPAF ( 13 C 12 -BPAF) 68.0/84.8 93.7/95.0 BPAP ( 13 C 12 -BPA) 149.5/76.9 122.5/75.7 BPF ( 13 C 12 -BPA) 61.8/75.7 82.3/74.3 BPZ ( 13 C 12 -BPAF) 67.0/72.9 95.3/75.8 BPP ( 13 C 12 -BPA) 33.0/44.3 69.4/68.9 BPM ( 13 C 12 -BPA) 75.8/79.8 99.1/82.4 MeP ( 13 C 6 -MeP) 94.6/81.0 78.7/75.2 EtP ( 13 C 6 -EtP) 104.1/71.8 64.2/72.4 PrP ( 13 C 6 -PrP) 100.5/83.6 68.9/76.9 BuP ( 13 C 6 -BuP) 110.8/75.9 67.5/78.6 BezP ( 2 D 4 -BezP) 120.8/72.9 75.3/81.7 HeP ( 2 D 4 -HeP) 113.0/68.1 79.4/87.1 4-HB ( 13 C 6-4-HB) 68.0/69.2 113.6/80.5 3,4-DHB ( 13 C 6-4-HB) 41.7/51.1 68.0/74.2 OH-MeP ( 13 C 6 -MeP) 81.6/89.5 96.5/98.0 OH-EtP ( 13 C 6 -EtP) 84.7/92.6 98.5/99.0 TCS ( 13 C 12 -TCC) 53.5/57.8 54.1/72.8 TCC ( 13 C 6 -TCC) 70.9/64.9 76.0/74.4 BP-1 ( 13 C 6 -BP-3) 51.1/58.4 78.9/129.5 BP-2 ( 13 C 6 -BP-3) 60.0/31.9 70.3/68.9 BP-3 ( 13 C 6 -BP-3) 68.2/56.3 82.0/73.0 BP-8 ( 13 C 6 -BP-3) 58.5/58.4 69.4/76.6 4-OH-BP ( 13 C 6 -BP3) 88.8/125.2 52.1/132.7 S9
Table S5. Amounts of methyl- (MeP), ethyl- (EtP), propyl- (PrP), butyl- (BuP), benzyl- (BzP) parabens, 4-hydroxy benzoic acid [4- HB], 3,4-dihydroxy benzoic acid [3,4-DHB], methyl-protocatechuic acid [OH-MeP], and ethyl-protocatechuic acid [OH-EtP] leached from baby teethers into water and methanol extracts. Parabens MeP EtP PrP BuP BezP Migration to water/methanol/total* W M T W M T W M T W M T W M T Detected samples (out of 59) 43 53 55 51 50 58 55 59 59 48 53 54 13 30 34 Average (ng) 18.9 47.4 60.5 6.58 22.2 24.9 10.6 41.7 51.6 1.03 23.9 24.4 0.004 0.020 0.019 Median (ng) 7.07 13.4 15.8 0.82 1.38 2.42 0.88 2.85 3.57 0.070 0.18 0.24 0.003 0.011 0.011 Max. Detected (ng) 129 395 425 76.2 366 371 89.9 884 974 30.9 1223 1254 0.008 0.004 0.003 Min. Detected (ng) 0.52 1.47 0.65 0.053 0.18 0.14 0.069 0.13 0.23 0.012 0.039 0.030 0.003 0.072 0.072 Parabens HeP 4-HB 3,4-DHB OH-MeP OH-EtP Migration to water/methanol/total* W M T W M T W M T W M T W M T Detected samples (out of 59) 23 28 40 36 51 58 41 39 53 39 38 50 21 22 32 Average (ng) 0.008 0.017 0.016 27.7 12.8 28.0 2.59 1.40 3.03 5.09 7.58 9.73 8.96 18.9 18.9 Median (ng) 0.002 0.005 0.005 9.75 5.18 8.36 1.98 0.82 2.27 0.22 0.47 0.42 0.41 0.14 0.16 Max. Detected (ng) 0.069 0.070 0.11 214 200 331 17.3 6.85 17.9 143 139 260 138 226 364 Min. Detected (ng) 0.002 0.005 0.002 0.26 0.86 0.86 0.12 0.41 0.21 0.055 0.18 0.055 0.041 0.14 0.041 *total (T): Sum of amounts from water and methanol migration trials; W=Water extract; M=methanol extract. S10
Table S6. Amounts of 2,2-bis(4-hydroxyphenyl)propane [BPA], 4,4 -(hexafluoroisopropylidene)-diphenol [BPAF], 4,4 -(1- phenylethylidene) bisphenol [BPAP], 4,4 -sulfonyldiphenol [BPS], 4,4 -dihydroxydiphenylmethane [BPF], 4,4 -(1,4- phenylenediisopropylidene) bisphenol [BPP], 4,4 -cyclo-hexylidenebisphenol [BPZ], 2,2-bis(4-hydroxyphenyl)butane [BPB], and 1,3- bis(2-(4-hydroxyphenyl)-2-propyl)benzene [BPM] leached from baby teethers into water and methanol extracts. Bisphenol derivatives BPA BPS BPF BPB Migration to water/methanol/total* W M T W M T W M T W M T Detected samples (out of 59) 58 55 59 55 57 59 23 32 44 14 3 15 Average (ng) 4.84 13.7 17.5 7.23 3.83 10.4 4.49 1.42 3.38 0.084 1.21 0.32 Median (ng) 2.28 8.41 10.9 2.32 3.10 5.48 4.66 1.17 2.26 0.035 0.79 0.035 Max. Detected (ng) 53.4 169 192 104 10.9 115 12.6 4.17 12.6 0.32 2.36 2.36 Min. Detected (ng) 0.071 0.24 0.36 0.074 0.29 0.15 0.18 0.58 0.39 0.035 0.47 0.035 Bisphenol derivatives BPZ BPAP BPAF BPP BPM Migration to water/methanol/total* W M T W M T W M T W M T W M T Detected samples (out of 59) 14 2 14 8 2 9 14 6 18 1 0 1 3 2 5 Average (ng) 0.31 0.11 0.32 0.23 0.23 0.26 0.63 0.95 0.81 0.60-0.60 0.35 2.35 1.15 Median (ng) 0.13 0.11 0.15 0.10 0.23 0.22 0.071 0.57 0.14 0.60-0.60 0.35 2.35 0.35 Max. Detected (ng) 1.79 0.14 1.79 0.85 0.24 0.85 7.13 3.03 8.20 0.60-0.60 0.35 2.35 2.35 Min. Detected (ng) 0.045 0.080 0.045 0.062 0.22 0.062 0.071 0.24 0.071 0.60-0.60 0.35 2.35 0.35 *total (T): Sum of amounts from water and methanol migration trials; W=Water extract; M=methanol extract. S11
Table S7. Amounts of 2-hydroxy-4-methoxybenzophenone [BP-3], 2,4-dihydroxybenzophenone [BP-1], 2,2-dihydroxy-4- methoxybenzophenone [BP-8], 2,2,4,4-tetrahydroxybenzophenone [BP-2], 4-hydroxybenzophenone [4-OH-BP], triclosan [TCS], and triclocarban [TCC] leached from baby teethers into water and methanol extracts. Benzophenones BP-3 BP-1 BP-2 BP-8 4-OH-BP Migration to water/methanol/total* W M T W M T W M T W M T W M T Detected samples (out of 59) 28 54 58 29 1 29 23 37 44 0 0 0 39 16 42 Average (ng) 0.71 11.2 10.8 2.04 2.92 2.14 0.24 0.97 0.95 - - - 3.01 2.78 3.86 Median (ng) 0.28 2.69 2.54 0.23 2.92 0.23 0.11 0.59 0.59 - - - 0.37 1.83 0.61 Max. Detected (ng) 5.46 269 295 33.7 2.92 36.6 1.13 6.56 6.67 - - - 27.8 12.4 30.6 Min. Detected (ng) 0.070 0.23 0.070 0.11 2.92 0.11 0.11 0.35 0.11 - - - 0.14 0.47 0.14 Antimicrobials TCS TCC Migration to water/methanol/total* W M T W M T Detected samples (out of 59) 31 48 54 38 54 55 Average (ng) 0.44 1.30 1.41 0.12 0.26 0.34 Median (ng) 0.18 0.32 0.36 0.028 0.092 0.11 Max. Detected (ng) 8.39 25.7 25.9 2.91 2.07 4.98 Min. Detected (ng) 0.012 0.039 0.023 0.014 0.046 0.014 *total (T): Sum of amounts from water and methanol migration trials; W=Water extract; M=methanol extract. S12