Supporting Information s6

Supporting Information

Occurrence and fate of PPCPs and correlations with water quality parameters in urban riverine waters of the Pear River Delta, South China

Xin Yang, Feng Chen, Fangang Meng, Yuanyu Xie, Hui Chen, Wangxing Luo, Tingjin Ye, Wenjie Fu

X. Yang ( ) ∙ Fangang Meng ( ) ∙ Yuanyu Xie ∙ Hui Chen ∙ Wenjie Fu

Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Guangzhou, 510275, China

SYSU-HKUST Research Center for Innovative Environmental Technology (SHRCIET), School of Environmental Science and Engineering, Sun Yat-sen University, Guangzhou, 510275, China

Email: [email protected] (X. Yang); [email protected] (F.G. Meng)

F. Chen ∙ W.X. Luo ∙ T.J. Ye

Foshan Water Group, Foshan, 52800, China

K. Young

Department of Environmental Engineering, University of Wisconsin – Madison, WI, USA Text S1.

EEM spectra were operationally divided into five regions as shown in Figure 2. Calculations were

preformed using the method developed by Chen et al. (2003). The volume (Fi) beneath region “i”

of the EEM can be calculated with i  I (exem )dex dem . For discrete data, it can be ex em

  I(  )  calculated with i   ex em ex em , in which ex is the excitation wavelength ex em

interval (taken as 5 nm), em is the emission wavelength interval (taken as 5 nm), and I(exem) is the fluorescence intensity at each excitation-emission wavelength pair. The cumulative volume

beneath the EEM (FT) was calculated as FT = SFi.

Table S1. Precursor ion, product ions, and optimal collision voltage for targeted analytes.

Compound Precursor ion Major Collision Minor Collision (m/z) product ion energy product ion energy (m/z) (eV) (m/z) (eV) Trimethoprim 291 230 22 123 23 Caffeine 195 138 17 13 C3-Caffeine 198 140 17 DEET 192 119 13 91 24 Sulfamethoxazole 254 156 19 108.1 23

Erithromycin-H2O 716.4 522 13 Carbamazepine 237 194 17 192 23 Ciprofloxacin 332 314 12 288 14 Acetaminophen 151.9 110 15 x10 5 +ESI TIC MRM CID@** (** -> **) Sample_017.d 1 0.460 0.633 1 2 2 1.405 1.519 1.629 1.813 2.057 0 x10 4 +ESI MRM Frag=135.0V [email protected] (716.4 -> 158.0) Sample_017.d 2 1 0.510 1 2 2

0 x10 3 +ESI MRM Frag=135.0V [email protected] (716.4 -> 522.0) Sample_017.d Erythromycin 1 0.468 1 2 2

0 x10 4 +ESI MRM Frag=135.0V [email protected] (332.0 -> 288.0) Sample_017.d 1 0.457 1 2 2

0.707 0.829 0.956 1.116 1.336 0 Ciprofloxacin x10 3 +ESI MRM Frag=135.0V [email protected] (332.0 -> 314.0) Sample_017.d 1 0.461 1 2 2 x10 4 +ESI MRM Frag=135.0V [email protected] (332.0 -> 288.0) Sample_017.d

1 0.457 0.597 0.705 0.816 1.196 1 2 2 0 5 0.707 0.829 0.956 1.116 1.336 x10 0 +ESI MRM Frag=135.0V [email protected] (291.1 -> 123.0) Sample_017.d 1 0.461 1 2 2 x10 3 +ESI MRM Frag=135.0V [email protected] (332.0 -> 314.0) Sample_017.d 0.461 Trimethoprim 1 0.615 1 2 2 0 1.196 5 0.597 0.705 0.816 x10 0 +ESI MRM Frag=135.0V [email protected] (291.1 -> 230.0) Sample_017.d 1 0.461 1 2 2 x10 5 +ESI MRM Frag=135.0V [email protected] (291.1 -> 123.0) Sample_017.d 1 0.461 1 2 2 0 4 +ESI MRM Frag=135.0V [email protected] (254.2 -> 108.1)0.615 Sample_017.d x10 0 1 0.519 1 2 2 x10 5 +ESI MRM Frag=135.0V [email protected] (291.1 -> 230.0) Sample_017.d 1 0.461 Sulfamethoxazole 1 2 2 0 4 +ESI MRM Frag=135.0V [email protected] (254.2 -> 156.1) Sample_017.d x10 0 1 0.520 1 2 2 4 +ESI MRM Frag=135.0V [email protected] (254.2 -> 108.1) Sample_017.d x10x10 6 +ESI TIC MRM Frag=135.0V CID@** (** -> **) Sample_006.d 2 1 1 1.8 1 0.519 1 2 2 1.6 1.40

1.2 x10 14 +ESI MRM Frag=135.0V [email protected] (237.0 -> 192.0) Sample_017.d 0.80 Carbamazepine 0.6 0.45 1 0.637 1 2 2 x100.24 +ESI MRM Frag=135.0V [email protected] (254.2 -> 156.1) Sample_017.d 0

x10 6 +ESI MRM Frag=135.0V [email protected] (192.2 -> 91.0) Sample_006.d 1 1 0.520 1 1 0.372 0.831 1 2 2 0.90 0.8 0.7 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 0.6 0.50 计数与采集时间 (分钟) 0.4 0.34 x100.2 +ESI MRM Frag=135.0V [email protected] (237.0 -> 192.0) Sample_017.d 0.1 1.241 05 1 0.637 1 2 2 x10 6 +ESI MRM Frag=135.0V [email protected] (192.2 -> 118.9) Sample_006.d 1 1 1 0.376 0.9 0.8 0.831 DEET 0.70 0.6 0.5 x100.45 +ESI MRM Frag=135.0V [email protected] (237.0 -> 193.9) Sample_017.d 0.3 0.22 0.1 1 0.637 1 2 2 0.961 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1 1.05 1.1 1.15 1.2 1.25 计数与采集时间 (分钟 ) 0.818 0

x10 4 +ESI MRM Frag=135.0V [email protected] (195.0 -> 137.8) Sample_017.d 1 0.480 Caffeine 1 2 2

0.637 0

x10 4 +ESI MRM Frag=135.0V [email protected] (151.9 -> 110.0) Sample_017.d 5 1 0.467 Acetaminophen 1 2 2

0.684 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 计数与采集时间 (分钟)

Figure S1. LC/MS/MS chromatograph of a standard mix solution of PPCPs. Figure S2. EEM spectra of water samples collected in Zhujiang River in August 2011. 1e+5 I (a) II III 8e+4 IV V

e 6e+4 m u l o V

E 4e+4 E

0 S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 Sampling sites

1e+5 I (b) II III 8e+4 IV V

e 6e+4 m u l o V

E 4e+4 E

0 S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 Sampling sites Figure S3. The fluorescence EEM volume in each sampling sites along the Zhujiang river. (a) first sampling (b) second sampling. Figure S4. EEM spectra of water samples collected in Beijiang River. 500

200 Caffeine Acetaminophen 100 Ciprofloxacin

0 Sulfamethoxazole S1 S2 S3 S6 S7 S8 S9 S10 S11 S12 S13 S14

Figure S5. Concentrations of sulfamethoxazole, ciprofloxacin, acetaminophen and caffeine along the Zhujiang River in second sampling campaign.