Occurrence and Risk Assessment of Selected Phthalates in Finished Drinking Water of China

Supplementary Information

Occurrence and Risk Assessment of Selected Phthalates in Finished Drinking Water of China

Xiaowei Liu1, Jianghong Shi1,*, Ting Bo1,Huiyuan Li1, John C. Crittenden2

1State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875, P. R. China

2Brook Byers Institute of Sustainable Systems, School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States

* Corresponding author. Tel./fax: +86 10 58802846.

E-mail address: (J. Shi)

Fig. S1 Sampling regions of finished drinking water samples in China. Northeast China (NEC), North China (NC), Northwest China (NWC), Southwest China (SWC), South China (SC), East China (EC) and Central China (CC)

Table S1 Information of the investigated drinking water treatment plants

Sampling date / Geographical zones / Water source type / Sediment tank / Flocculant / Disinfector / Sample number
12/02/2009 / NC / river / MA / PAFC / liquid chlorine，O3，KMnO4，H2O2 / 1(214)
12/02/2009 / NC / lake and reservoir / HF / PAFC / liquid Cl2 / 2(212)
12/02/2009 / NC / river / - / - / - / 3
12/02/2009 / NC / groundwater / - / - / ClO2 / 4(215)
12/02/2009 / NC / groundwater / - / - / ClO2 / 5(216)
4/1/2010 / NC / groundwater / - / - / liquid chlorine / 11(204)
4/1/2010 / NC / river / HF / PAC / liquid chlorine / 12(205)
4/1/2010 / NC / groundwater / - / - / liquid chlorine / 13(203
4/8/2010 / NC / groundwater / - / - / liquid chlorine / 14(241)
4/8/2010 / NC / river / - / - / liquid chlorine / 15(242)
4/8/2010 / NC / lake and reservoir / - / - / liquid chlorine / 16(243)
7/21/2010 / NC / lake and reservoir / - / - / liquid chlorine / 38(209)
7/21/2010 / NC / groundwater / - / - / liquid chlorine / 39(211)
7/21/2010 / NC / lake and reservoir / - / - / - / 40(210)
7/25/2010 / NC / groundwater / HF / - / liquid chlorine / 41(206)
7/25/2010 / NC / groundwater / HF / - / liquid chlorine / 42(207)
7/25/2010 / NC / lake and reservoir / RT / PAC / chlorine / 43(208)
7/30/2010 / NC / lake and reservoir / HF / - / liquid chlorine / 44(235)
7/30/2010 / NC / lake and reservoir / HF / - / liquid chlorine / 45(236)
7/30/2010 / NC / lake and reservoir / HF / PAC / liquid chlorine / 46(237)
3/16/2011 / NC / lake and reservoir / HF / PAC / liquid chlorine / 123(219)
3/16/2011 / NC / river / HF / PAC / liquid chlorine / 124(217)
2/27/2012 / NC / groundwater / - / - / liquid chlorine / 13(203)
2/27/2012 / NC / groundwater / - / - / liquid chlorine / 11(204)
2/27/2012 / NC / river / HF / PAC / liquid chlorine / 205(12)
3/2/2012 / NC / groundwater / HF / - / liquid chlorine / 206(41)
3/2/2012 / NC / groundwater / HF / - / liquid chlorine / 207(42)
3/2/2012 / NC / lake and reservoir / RT / PAC / chlorine / 208(43)
3/5/2012 / NC / lake and reservoir / - / - / liquid chlorine / 209(38)
3/5/2012 / NC / lake and reservoir / - / - / - / 210(40)
3/5/2012 / NC / lake and reservoir / - / - / liquid chlorine / 211(39)
3/9/2012 / NC / lake and reservoir / HF / - / liquid chlorine / 212(7)
3/9/2012 / NC / lake and reservoir / MA / PAFC / liquid Cl2，O3，KMnO4 and H2O2 / 214(6)
3/9/2012 / NC / groundwater / - / - / ClO2 / 215(9)
3/9/2012 / NC / lake and reservoir / - / - / ClO2 / 216(10)
3/13/2012 / NC / river / HF / PAC / liquid chlorine / 218
3/13/2012 / NC / lake and reservoir / HF / PAC / liquid chlorine / 219(123)
5/24/2012 / NC / lake and reservoir / HF / - / liquid chlorine / 235(44)
5/24/2012 / NC / lake and reservoir / HF / - / liquid chlorine / 236(45)
5/24/2012 / NC / lake and reservoir / HF / PAC / liquid chlorine / 237(46)
5/31/2012 / NC / groundwater / HF / - / liquid chlorine / 241(14)
5/31/2012 / NC / reservoir / - / - / liquid chlorine / 242(15)
5/31/2012 / NC / reservoir / - / - / liquid chlorine / 243(16)
3/2/2010 / NEC / lake and reservoir / RPL / PAC / liquid chlorine / 6(234)
3/2/2010 / NEC / river / - / - / - / 7
3/2/2010 / NEC / river / - / - / - / 8
8/1/2010 / NEC / lake and reservoir / HF / PAC / liquid chlorine / 48(225)
8/1/2010 / NEC / lake and reservoir / HF-RPL / PAC/PAM / liquid chlorine / 49(226)
8/1/2010 / NEC / lake and reservoir / HF / PAC/PAM / liquid chlorine / 50(227)
8/1/2010 / NEC / lake and reservoir / HF-RPL / PAC / liquid chlorine / 51(228)
8/3/2010 / NEC / groundwater / CWT / - / liquid chlorine / 54(238)
8/3/2010 / NEC / groundwater / CWT / liquid chlorine / 55(239)
8/3/2010 / NEC / groundwater / RT / PAC / liquid chlorine / 56(240)
8/6/2010 / NEC / lake and reservoir / - / - / liquid chlorine / 58(231)
8/6/2010 / NEC / lake and reservoir / RPI / PAC / liquid chlorine / 58(232)
8/6/2010 / NEC / lake and reservoir / RPL / - / liquid chlorine / 59(233)
5/15/2012 / NEC / lake and reservoir / HF / PAC / liquid chlorine / 225(48)
5/15/2012 / NEC / lake and reservoir / HF-RPI / PAC/PAM / liquid chlorine / 226(49)
5/15/2012 / NEC / lake and reservoir / double-
deck HF / PAC/PAM / liquid chlorine / 227(50)
5/15/2012 / NEC / lake and reservoir / HF-RPI / PAC / liquid chlorine / 228(51)
5/18/2012 / NEC / lake and reservoir / - / - / liquid chlorine / 231(57)
5/21/2012 / NEC / lake and reservoir / RPI / PAC / liquid chlorine / 232(58)
5/24/2012 / NEC / lake and reservoir / RPL / - / liquid chlorine / 233(59)
5/24/2012 / NEC / lake and reservoir / RPI / PAC / liquid chlorine / 234(3)
5/25/2012 / NEC / groundwater / CWT / - / liquid chlorine / 238(54)
5/31/2012 / NEC / groundwater / CWT / - / liquid chlorine / 239(55)
5/31/2012 / NEC / groundwater / RPI / PAC / liquid chlorine / 240(56）
6/2/2010 / SWC / river / HF-RPI / PAC / liquid chlorine / 15(169)
6/2/2010 / SWC / lake and reservoir / RPL / PAC / ClO2 / 16(170)
6/14/2010 / SWC / river / HF / PAC / liquid chlorine / 26(166)
6/14/2010 / SWC / river / HF / PAC / liquid chlorine / 27(167)
6/14/2010 / SWC / river / HF / PAC / liquid chlorine / 28(168)
6/14/2010 / SWC / river / - / - / - / 29
7/17/2010 / SWC / river / - / - / - / 30
7/17/2010 / SWC / river / - / - / - / 31
7/17/2010 / SWC / river / - / - / - / 32
7/17/2010 / SWC / river / - / - / - / 33
7/20/2010 / SWC / lake and reservoir / - / - / - / 34
7/20/2010 / SWC / lake and reservoir / - / - / - / 35
7/20/2010 / SWC / lake and reservoir / - / - / - / 36
7/20/2010 / SWC / lake and reservoir / - / - / - / 37
11/29/2010 / SWC / river / HF / PAC/PAM / chlorine / 99(178)
11/29/2010 / SWC / river / HF / PAC / chlorine / 100(179)
11/29/2010 / SWC / river / RPI / PAC / liquid chlorine / 101(180)
11/29/2010 / SWC / river / MA / PAC / liquid chlorine / 1012(181)
12/3/2010 / SWC / river / HF / PAFCS / liquid chlorine / 103(175)
12/3/2010 / SWC / river / HF / PAFCS / liquid chlorine / 104(176)
12/3/2010 / SWC / river / MA / PAFCS / chlorine / 105(177)
10/25/2011 / SWC / river / HF / PAC / liquid chlorine / 166(26)
10/25/2011 / SWC / river / HF / PAC / liquid chlorine / 167(27)
10/25/2011 / SWC / river / HF / PAC / liquid chlorine / 168(28)
10/28/2011 / SWC / river / HF-RPI / PAC / liquid chlorine / 169(1)
10/28/2011 / SWC / lake and reservoir / RPL / PAC / chlorinedioxide / 170(2)
11/2/2011 / SWC / lake and reservoir / HF / PAC / liquid chlorine / 171
11/2/2011 / SWC / lake and reservoir / HF-RPI / PAC / liquid chlorine / 172
11/2/2011 / SWC / lake and reservoir / Grid-RPI / PAC / chlorine / 173
11/22/2011 / SWC / river / HF / PAFCS / liquid chlorine / 175(103)
11/22/2011 / SWC / river / HF / PAFCS / liquid chlorine / 176(104)
11/23/2011 / SWC / river / - / - / - / 176
11/24/2011 / SWC / river / MA / PAFCS / chlorine / 177(105)
11/24/2011 / SWC / reservoir / HF / PAC/PAM / chlorine / 178(99)
11/24/2011 / SWC / river / HF / PAC / chlorine / 179(100)
11/24/2011 / SWC / river / RPI / PAC / liquid chlorine / 180(101)
11/24/2011 / SWC / river / MA / PAC / liquid chlorine / 181(102)
4/25/2010 / EC / river / HP / PAC / liquid chlorine / 17(189)
4/25/2010 / EC / river / HF / Al2(SO4)3 / NaClO / 18(188)
4/25/2010 / EC / river / HF / Al2(SO4)3 / NaClO / 20(190
4/25/2010 / EC / river / - / - / - / 21
11/21/2010 / EC / lake and reservoir / HF / PAC / liquid chlorine / 96(182-1)
11/21/2010 / EC / lake and reservoir / HF / PAC / liquid chlorine / 97(183)
11/21/2010 / EC / lake and reservoir / HF / PAC / liquid chlorine / 98(184)
12/8/2010 / EC / river / HF / PAC / liquid chlorine / 106(185)
12/8/2010 / EC / river / HF / PAC / liquid chlorine / 107(186)
12/8/2010 / EC / river / HF / PAC / liquid chlorine / 108(187)
12/13/2010 / EC / river / HF / PAC / liquid chlorine / 109(191)
12/13/2010 / EC / river / HF-RPL / PAC / liquid chlorine / 110(192)
12/13/2010 / EC / river / RPL / PAC / liquid chlorine / 111(193)
11/28/2011 / EC / reservoir / HF / PAC / liquid chlorine / 182-001
11/28/2011 / EC / reservoir / - / - / - / 182-004
11/29/2011 / EC / reservoir / HF / PAC / liquid chlorine / 183(97)
11/29/2011 / EC / reservoir / HF / PAC / liquid chlorine / 184(98)
12/5/2011 / EC / river and reservoir / HF / PAC / liquid chlorine / 185(106)
12/5/2011 / EC / river and reservoir / HF / PAC / liquid chlorine / 186(107)
12/5/2011 / EC / river / HF / PAC / liquid chlorine / 187(108)
12/8/2011 / EC / river / HF / Al2(SO4)3 / NaClO / 188(18)
12/8/2011 / EC / river / 188-004
12/8/2011 / EC / river / HP / PAC / liquid chlorine / 189(17)
12/8/2011 / EC / reservoir / HF / Al2(SO4)3 / NaClO / 190(20)
12/13/2011 / EC / river / HF / PAC / liquid chlorine / 191(109)
12/13/2011 / EC / river / HF-RPL / PAC / liquid chlorine / 192(110)
12/13/2011 / EC / river / RPL / PAC / liquid chlorine / 193(111)
9/3/2010 / NWC / groundwater / - / - / liquid chlorine / 60(143)
9/3/2010 / NWC / groundwater / - / - / liquid chlorine / 61(144)
9/3/2010 / NWC / groundwater / - / - / liquid chlorine / 62(145)
9/3/2010 / NWC / groundwater / - / - / liquid chlorine / 63(146)
9/3/2010 / NWC / river / - / - / liquid chlorine / 64(147)
9/20/2010 / NWC / lake and reservoir / HF / PAC / liquid chlorine / 65(130)
9/20/2010 / NWC / river / HP-RPI / PAC / chlorine / 66(131)
9/20/2010 / NWC / river / - / - / - / 67
9/20/2010 / NWC / groundwater / - / - / chlorine / 68(133)
9/26/2010 / NWC / river / RaF-HF / HCA,PAC,PFAC / liquid chlorine / 69(134)
9/26/2010 / NWC / river / - / - / liquid chlorine / 70(135)
9/26/2010 / NWC / river / - / - / liquid chlorine / 71(136)
9/26/2010 / NWC / lake and reservoir / SRF / PAC / liquid chlorine / 72(140)
10/16/2010 / NWC / groundwater / - / - / liquid chlorine / 73(141)
10/16/2010 / NWC / groundwater / - / - / liquid chlorine / 74(142)
10/16/2010 / NWC / groundwater / HF / - / liquid chlorine / 75(137)
10/16/2010 / NWC / groundwater / HF / - / liquid chlorine / 76(138)
10/16/2010 / NWC / groundwater / HF / - / liquid chlorine / 77(139)
8/17/2011 / NWC / reservoir / HF / PAC / liquid chlorine / 130(65)
8/17/2011 / NWC / reservoir / HF-RPI / PAC / chlorine / 131(66)
8/17/2011 / NWC / groundwater / - / - / chlorine / 133(68)
8/19/2011 / NWC / river / HP-HF / HCA,PAC,PFAC / liquid chlorine / 134(69)
8/19/2011 / NWC / groundwater / - / - / liquid chlorine / 135(70)
8/19/2011 / NWC / groundwater / - / - / liquid chlorine / 136(71)
8/23/2011 / NWC / groundwater / HF / - / liquid chlorine / 137(75)
8/23/2011 / NWC / groundwater / HF / - / liquid chlorine / 138(76)
8/23/2011 / NWC / groundwater / HF / - / liquid chlorine / 139(77)
8/25/2011 / NWC / river / SRF / PAC / liquid chlorine / 140(72)
8/25/2011 / NWC / groundwater / - / - / liquid chlorine / 141(73)
8/25/2011 / NWC / groundwater / - / - / liquid chlorine / 142(74)
8/25/2011 / NWC / groundwater / - / - / liquid chlorine / 143(60)
8/25/2011 / NWC / groundwater / - / - / liquid chlorine / 144(61)
8/25/2011 / NWC / groundwater / - / - / liquid chlorine / 145(62)
8/25/2011 / NWC / groundwater / - / - / liquid chlorine / 146(63)
8/25/2011 / NWC / reservoir / - / - / liquid chlorine / 147(64)
5/8/2012 / NWC / reservoir / CP / PAC / liquid chlorine / 222
5/8/2012 / NWC / groundwater / HF / PAC / liquid chlorine / 223
5/8/2012 / NWC / reservoir and groundwater / RoF / - / liquid chlorine / 224
10/12/2010 / SWC / river / HF / PAC / liquid chlorine / 78(151)
10/12/2010 / SWC / river / RPI / PAC / liquid chlorine / 79(152)
10/12/2010 / SWC / river / - / - / - / 80(153)
10/12/2010 / SWC / river / RPI / PAC / liquid chlorine / 81(154)
10/12/2010 / SWC / river / RPI / PAC / liquid chlorine / 82(155)
10/16/2010 / SWC / river / HF-RPI / PAC / liquid chlorine / 83(148)
10/16/2010 / SWC / river / RPI / PAC / liquid chlorine and NaClO / 84(149)
10/16/2010 / SWC / river / HF-RPI / PAC / liquid chlorine and sodium hypochlorite / 85(150)
10/24/2010 / SWC / lake and reservoir / HF / PAC / liquid chlorine / 85-1(156)
10/24/2010 / SWC / lake and reservoir / RPI / PAC / liquid chlorine / 86(157)
10/24/2010 / SWC / lake and reservoir / HF / PAC / chlorine / 87(158)
10/24/2010 / SWC / lake and reservoir / RPI / PAC / liquid chlorine / 88(159)
10/24/2010 / SWC / lake and reservoir / - / - / - / 89
10/28/2010 / SWC / lake and reservoir / HF / PAC / liquid chlorine / 90(160)
10/28/2010 / SWC / lake and reservoir / AF / PAC / liquid chlorine / 91(161)
10/28/2010 / SWC / river / HF / PAC / liquid chlorine / 92(162)
11/7/2010 / SWC / river / HF / PAC / liquid chlorine / 93(163)
11/7/2010 / SWC / river / RPI / PAC / ClO2 / 94(164)
11/7/2010 / SWC / river / HF / PAC / liquid chlorine / 95(165)
9/14/2011 / SWC / river / HF-RPI / PAC / liquid chlorine / 148(83）
9/14/2011 / SWC / river / RPI / PAC / liquid chlorine and NaClO / 149(84)
9/14/2011 / SWC / river / HF-RPI / PAC / liquid chlorine and NaClO / 150(85)
9/16/2011 / SWC / river / HF / PAC / liquid chlorine / 151(78)
9/16/2011 / SWC / river / RPI / PAC / liquidchlorine / 152(79)
9/16/2011 / SWC / river / RPI / PAC / liquid chlorine / 154(81)
9/16/2011 / SWC / river / RPI / PAC / liquid chlorine / 155(82)
9/20/2011 / SWC / lake and reservoir / HF / PAC / liquid chlorine / 156(85-1)
9/20/2011 / SWC / groundwater / RPI / PAC / liquid chlorine / 157(86)
9/20/2011 / SWC / reservoir / HF / PAC / chlorine / 158(87)
9/20/2011 / SWC / reservoir / RPI / PAC / liquid chlorine / 159(88)
10/10/2011 / SWC / reservoir / HF / PAC / liquid chlorine / 160(90)
10/10/2011 / SWC / reservoir / AF / PAC / liquid chlorine / 161(91)
10/14/2011 / SWC / river / HF / PAC / liquid chlorine / 162(92)
10/14/2011 / SWC / river / HF / PAC / liquid chlorine / 163(93)
10/14/2011 / SWC / river / RPI / PAC / ClO2 / 164(94)
10/14/2011 / SWC / river / HF / PAC / liquid chlorine / 165(95)
12/16/2010 / CC / lake and reservoir / HF / PAC / liquid chlorine / 112(195)
12/16/2010 / CC / lake and reservoir / - / - / - / 113
12/16/2010 / CC / lake and reservoir / HF / PAC / liquid chlorine / 114(194)
12/19/2010 / CC / river / RPL / PAC / chlorine / 115(221)
12/19/2010 / CC / river / HF / PAC / chlorine / 116(220)
12/19/2010 / CC / river / HF / KAl(SO4)2 / liquid chlorine / 117(197)
12/24/2010 / CC / lake and reservoir / HF / PAC / liquid chlorine / 118(198)
12/24/2010 / CC / river / HF / KAl(SO4)2 / liquid chlorine and ozone / 119(199)
12/24/2010 / CC / river / HF / PAC / liquid chlorine / 120(200)
12/24/2010 / CC / river / HF / PAC / liquid chlorine / 121(201)
12/24/2010 / CC / river / HF / PAC / liquid chlorine / 122(202)
12/21/2011 / CC / reservoir / HF / PAFC / liquid chlorine / 194(114)
12/21/2011 / CC / reservoir / HF / PAFC / liquid chlorine / 195(112)
12/30/2011 / CC / reservoir / HF / KAl(SO4)2 / liquid chlorine / 197(117)
12/30/2011 / CC / river / HF / PAC / liquid chlorine / 198(118)
12/30/2011 / CC / river / HF / KAl(SO4)2 / liquid chlorine and ozone / 199(119)
1/5/2012 / CC / river / HF / PAC / liquid chlorine / 200(120)
1/5/2012 / CC / river / HF / PAC / liquid chlorine / 201(121)
1/5/2012 / CC / river / HF / PAC / liquid chlorine / 202(122)
4/24/2012 / CC / reservoir / RPL / PAC / chlorine / 221(115)

NEC:Northeast China; NC: North China; NWC: Northwest China; SWC: Southwest China; SC: South China; EC: East China; CC: Central China; MA: mechanical agitation; HF: horizontal flow; RPL: rampplate; RPI: ramppipe; HP: hippedplate; RaF: radialflow; CWT: clear-water tank; SRF: sludge return flow; AF: air floatation; CP: Central-positioned type; RoF: rotational-flow type; PAFC: poly-aluminum ferrous chloride; PAC: poly-aluminum chloride

Fig.S2 Location of the sampling of drinking water from 35 main cities in mainland China.

Fig. S3Comparisons of target phthalates in duplicate sample

Table S2Procedure blanks analysis for controlling background contamination

Test / Step 1 / Step 2 / Step 3 / Step 4 / Step 5 / Step 6 / Objective
Test 1 / To determine the background contamination of the whole pretreatment process including the contributions of Milli-Q water, HLB, elution reagent, air and reconstituted reagent.
Test2 / To determine the background contamination of the whole pretreatment process including the contributions of Milli-Q water, HLB, elution reagentand reconstituted reagent, excluding air contamination.
Test 3 / To determine the background contamination of HLB, elution reagent, air and reconstituted reagent, excluding Milli-Q water.
Test4 / To determine the background contamination of elution reagent, air and reconstituted reagent, excluding Milli-Q water and HLB.
Test 5 / To determine the background contamination of reconstituted reagent, excluding Milli-Q water, HLB, air and elution reagent.

Step 1: HLB cartridge was preconditioned with 5 mL of methanol/diethyl ether (5/95, v/v), 5 mL of methanol and 10 mL of Milli-Q water; Step 2: 1 L water sample (Milli-Q water)waspassed through the HLB cartridge; Step 3:The cartridge was then eluted with 6 mL of methanol/diethyl ether (5/95, v/v); Step 4: The cartridge was dried under vacuum; Step 5: The cartridge was dried under a flow of nitrogen; Step 6: The extract was reconstituted with l mL of n-hexane. The steps with highlighted with gray were performed in this step.

Table S3Concentration levels (Mean ± SD) of the six phthalates in the experimental procedure detected by GC-MS (μg/L) (n=4)

Experimental materials / DMP / DEP / DBP / BBP / DEHP / DnOP
Reconstituted reagent / 0.017
(±0.003) / 0.014 (±0.002) / 0.021 (±0.002) / 0.010 (±0.003) / 0.024 (±0.002) / 0.024 (±0.002)
Elution reagent, air and reconstituted reagent / 0.014 (±0.004) / 0.014 (±0.003) / 0.022 (0.003) / 0.016 (±0.002) / 0.032 (±0.002) / 0.029 (±0.004)
HLB, elution reagent, air and reconstituted reagent / 0.019 (±0.003) / 0.015 (±0.001) / 0.025 (±0.002) / 0.017 (±0.004) / 0.039 (±0.005) / 0.031 (±0.003)
Milli-Q water (1L), HLB, elution reagent, air and reconstituted reagent / 0.017 (±0.003) / 0.016 (±0.002) / 0.030 (±0.004) / 0.020 (±0.003) / 0.042 (±0.003) / 0.029 (±0.003)
Milli-Q water (1L), HLB, elution reagent, nitrogen and reconstituted reagent / 0.015 (±0.003) / 0.014 (±0.001) / 0.026 (±0.003) / 0.022 (±0.002) / 0.034 (±0.001) / 0.025 (±0.002)

Elution reagent: methanol/diethyl ether (5/95, v/v); reconstituted reagent: n-hexane.

Table S4Contribution of phthalates in every tested material to real sample (μg/L)

Experimental materials / DMP / DEP / DBP / BBP / DEHP / DnOP
Reconstituted reagent / 0.017 / 0.014 / 0.021 / 0.010 / 0.024 / 0.024
Elution reagent / -0.003 / 0 / 0.001 / 0.006 / 0.008 / 0.005
HLB / 0.005 / 0.001 / 0.003 / 0.001 / 0.007 / 0.002
Milli-Q water (1L) / -0.002 / 0.001 / 0.005 / 0.003 / 0.003 / -0.002
Air / 0.002 / 0.002 / 0.004 / -0.002 / 0.008 / 0.004

The contributions of phthalates in every tested material to real sample were calculated in terms of Table S3.

Table S5Recoveries and method detection limits (MDLs) of the six phthalates in source waters (n=6)

Compounds / Recovery (mean ± RSD, %) / MDLs (μg/L)
DMP / 64.5 (±7.6) / 0.002
DEP / 71.3 (±8.2) / 0.005
DBP / 84.1 (±10.5) / 0.010
BBP / 60.2 (±5.3) / 0.002
DEHP / 76.9 (±7.3) / 0.010
DnOP / 72.7 (±10.1) / 0.002

RSD: relative standard deviation

Estimation of phthalate concentration in vapor phase of bathroom

For inhalation intake, the concentration of phthalate in vapor phase of bathroom can be estimatedbased on the methodas follows (Moya et al. 1999; Wang et al. 2007):

whereCair is the concentration of chemical in vapor phase(μg/L);YS(t) is the initial concentration in shower room (assumed as 0 μg/L); YSi is concentration of chemical in shower room at time t (min); t is time in bathroom with 7 min (MEPC 2014); N is a dimensionless coefficient that calculated from KOL; QL is water flow rate with5 L/min;3QG is air flow rate with 50 L/min (Little 1992); VS is bathroom volume with 8 m3; CW is concentration of chemical in water phase, μg/L; H is dimensionless Henry's law constants; KOL is Overall mass transfer coefficient , L/min. The KOL of chemical was calculated based on the method reported by Moya et al. (1999): 1/KOL=1/(H*Dl)+1/(Dg), where H is the Henry's constant andDgand Dl represent the gas- and liquid-film mass transfer coefficient for each chemical, which are presented in Table S6.

Table S6Parameters for estimating overall mass transfer coefficients of the target compounds

Compound / Abbreviation / CAS / Boiling point (°C)* / Henry constant** / Dl (cm2/s) / Dg (cm2/s)
Diethyl phthalate / DEP / 84-66-2 / 298 / 3.13×10-5 / 6.40×10-6 / 0.0537
Di-n-butyl phthalate / DBP / 84-74-2 / 340 / 1.55×10-7 / 5.40×10-6 / 0.0464
Bis(2-ethylhexyl) phthalate / DEHP / 117-81-7 / 385 / 6.99×10-6 / 4.26×10-6 / 0.0376
Dimethyl phthalate / DMP / 131-11-3 / 285 / - / 7.13×10-6 / 0.0588
Di-n-octyl phthalate / DnOP / 117-84-0 / 390 / 5.26×10-3 / 4.26×10-6 / 0.0376
Butylbenzyl phthalate / BBP / 85-68-7 / 370 / 9.33×10-5 / 5.10×10-6 / 0.0433

* ACC, 2011; ** Dl and Dgare diffusion coefficients in water and air, respectively, which were estimated using USEPA On-line Tools ( The temperature for the physical properties is 30°C.

Table S7Exposure factors for population in different regions in China (MEPC 2013).

Region / IRw
(L/day) / SA
(cm2) / ET
(hour/day) / ED
(years) / IRair*
(L/hour) / BW
(kg) / DAIR
(m3/d)
NWC / 1.125 / 16000 / 0.07 / 74.8 / 498 / 61.5 / 15.8
NEC / 1.000 / 17000 / 0.10 / 74.8 / 510 / 64.0 / 16.2
NC / 1.250 / 17000 / 0.08 / 74.8 / 498 / 64.3 / 15.9
EC / 1.225 / 16000 / 0.15 / 74.8 / 492 / 61.0 / 15.6
SC / 1.125 / 16000 / 0.17 / 74.8 / 486 / 57.3 / 15.4
SWC / 1.000 / 16000 / 0.08 / 74.8 / 480 / 57.1 / 15.3
CC / 1.125 / 16000 / 0.08 / 74.8 / 498 / 61.0 / 15.8
China / 1.125 / 16000 / 0.12 / 74.8 / 492 / 60.6 / 15.7

IRw is ingestion rate of tap water; SA is the skin surface area available for contact;ET is exposure time during bathing or showering; ED is exposure duration for lifetime; IRair is inhalation rate during bathing or showering. BW is average body weight of a Chinese adult; DAIR is inhalation rate for adult. *Due to the inhalation rates for Chinese population being unavailable, the inhalation rates for people with low-intensity activity were used.

Table S8Chemical-specific parameters for exposure and risk assessments

Parameters / Chemicals / value / Data source
Adult
Kp(cm/hr) / DEP / 0.0039 / (U.S.EPA 2004)
DBP / 0.024
DEHP / 0.025
DnOP* / 2.149 / Estimated value
BBP* / 0.030
RfDo (μg /kg/day) / DEP / 800 / (U.S.EPA 2014a)
DBP / 100 / (U.S.EPA 2014b)
DEHP / 20 / (U.S.EPA2014c)
DnOP / 10 / (U.S.EPA 2014d)
DMP / Not available
BBP / 200 / (U.S.EPA 2014e)
SFo (μg/kg/day)-1 / DEHP / 1.4×10-5 / (U.S.EPA 2014b)
ABSgi (unitless) / 1 / (U.S. EPA 2014f)
IUR (μg/m3)-1 / DEHP / 2.4×10-6 / (U.S. EPA 2014g)

Kp is dermal permeability coefficient; CF is a volumetric conversion factor; DAIR is inhalation rate for adult;RfDo is reference dose for oral ingestion; SFo is slope factor; ABSgi is the fraction of chemical absorbed in the gastrointestinal tract; IUR is inhalation unit risk. *The permeability coefficients for DnOP and BBP were estimated using an empirical predictive correlation for organic permeability coefficients, which is described in the following part (Benotti et al. 2008; WHO, 2011; U.S.EPA 2004).

Empirical predictive correlation for permeability coefficient of organics

The permeability coefficient of BBP can be estimated using the empirical predictive correlation for permeability coefficient of organics (U.S.EPA 2004):

whereKp is dermal permeability coefficient of compounds in water (cm/hr); Kow is octanol/water partition coefficient of the non-ionized species (dimensionless); MW is molecular weight (g/mole).

Fig.S4 Detection frequencies of phthalates in finished drinking water of China

Table S9Statistical test report for DEP

Table S10Statistical test report for DBP

Table S11Statistical test report for DEHP

Table S12Report of statistical test for DnOP

Table S13Report of statistical test for DMP

Table S14Report of statistical test for BBP

References:

ACC (American Chemistry Council) (2001) High Production Volume Chemical Challenge Program for the Phthalate Ester Category.ExxonMobil Biomedical Sciences, Inc.

Benotti MJ, Trenholm RA, Vanderford BJ, Holady J C, Stanford BD, Snyder SA (2008) Pharmaceuticals and rndocrine disrupting compounds in U.S. drinking Water. Environ. Sci. Technol. 43(3):597-603

Little JC (1992)Applying the two-resistance theory to contaminant volatilization in showers.Environ. Sci. Technol.26(7):1341-1349.

MEPC (Ministry of Environmental Protection, China) (2013) Exposure Factors Handbook of Chinese Population. China Environmental Science Press,Beijing

Moya J, Howard-Reed C,Corsi RL (1999)Volatilization of Chemicals from Tap Water to Indoor Air from Contaminated Water Used for Showering. Environ. Sci. Technol.33(14):2321-2327.

U.S.EPA (2004) Guidance for Superfund Volume I- Human Heatlh Evaluation Manual (Part E, Supplemental Guidance for Dermal Risk Assessment). Office of Superfund Remediation and Technology Innovation , Washington, DC

U.S.EPA (2014a) Diethyl phthalate (DEP) (CASRN 84-66-2). Integrated Risk Information System. 10 May 2014

U.S.EPA (2014b)Dibutyl phthalate (DBP).Integrated Risk Information System. Accessed 10 May 2014

U.S.EPA (2014c) Di(2-ethylhexyl) phthalate (DEHP) (CASRN 117-81-7).Integrated Risk Information System. 10 May 2014

U.S.EPA (2014d) Provisional Peer Reviewed Toxicity Values for Superfund (PPRTV): PPRTV Assessments Electronic Library. Accessed 12 May 2014

U.S.EPA (2014e) Butyl phthalate (BBP). Integrated Risk Information System. 10 May 2014

U.S.EPA (2014f) Regional Screening Levels for Chemical Contaminants at Superfund Sites. Accessed 20 May 2014

U.S.EPA (2014g) Mid-AtlanticRisk Assessment: standard default factor. 21 May 2014

Wang GS, Deng YC, Lin TF (2007) Cancer risk assessment from trihalomethanes in drinking water.Sci. Total Environ. 387 (1–3):86-95

WHO2011 Guidelines for drinking-water quality-4th ed. WHO Press, Geneva