Jiao Tang,A,C Taicheng An,A,Bjukun Xiong,A,Bguiying Lib,*

Supplementary Data:

The evolution of pollution profile and health risk assessment for three groups SVOCs pollutants along with Beijiang River, China

Jiao Tang,a,c Taicheng An,a,bJukun Xiong,a,bGuiying Lib,*

a State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China

bGuangzhou Key Laboratory of Environmental Catalysis and Pollution Control, School of Environmental Science and Engineering, Institute of Environmental Health and Pollution Control, Guangdong University of Technology, Guangzhou, 510006, China

c University of Chinese Academy of Sciences, Beijing 100049, China

* Corresponding author: Prof. Guiying Li

Tel: +86-20-39322298

E-mail:

Experiential

Materials

The 16 PAHs standards contain naphthalene (Nap), acenaphthylene (Ace), acenaphthene (Dih), fluorene (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene (Flua), pyrene (Pyr), benzo[a]anthracene (BaA), chrysene (Chry), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd]pyrene (IncdP), dibenz[a,h]anthracene (DiB), and benzo[g,h,i]perylene (BghiP).Surrogate standards for PAHs consist of five deuterated PAHs including naphthalene-d8, acenaphthylene-d10, phenanthrene-d10, chrysene-d12, and perylene-d12. The 20 OCPs standards were α-, β-, γ-, δ-HCH, p,p′-DDD, p,p′-DDE, p,p′-DDT, α-chlordane, γ-chlordane, heptachlor (Heptach), heptachlor epoxide (Hepch epo), α-endosulfan, β-endosulfan, endosulfan sulfate, aldrin, dieldrin, endrin, endrin aldehyde, endrin ketone, and methoxychlor. Surrogate standards for OCPs were 2,4,5,6-tetrachloro-m-xylene (TMX) and 2,2′,3,3′,4,4′,5,5′,6,6′-decachlorobiphenyl (PCB209). The 15 PAEs standards were dimethyl phthalate (DMP), diethylphthalate (DEP), diisobutyl phthalate (DiBP), dibutylphthalate (DnBP), bis(4-methyl-2-pentyl)phthalate (BMPP), bis(2-ethoxyethyl) phthalate (BEEP), diamylphthalate (DAP), dihexyl phthalate (DHP), butylbenzyl phthalate(BBP), bis(2-methoxyethyl)phthalate (BMEP), bis(2-butoxyethyl) phthalate (BBEP), dicyclohexyl phthalate(DCHP), di(2-ethylhexyl) phthalate (DEHP), dinonylphthalate (DnNP), and dioctyl phthalate (DnOP). Surrogate standard for PAEs was only Diphenylphthalate (DphP).Hexamethylbenzene (HMB) was used as internal standard of PAHs and PAEs, while pentachloronitrobenzene (PCNB) was used for OCPs.

Sixteen PAHsstandard coupling withfivedeuterated PAHs surrogate standards in a mixture solution of 200 and 4000µgmL-1; twenty OCP standards(1000µg mL-1), their two surrogate standards of 2,4,5,6-tetrachloro-m-xylene (TMX)(1000µg mL-1) and2,2’,3,3’,4,4’,5,5’,6,6’-decachlorobiphenyl (PCB209)(500µg mL-1), as well as oneinternalstandard pentachloronitrobenzene (PCNB)(2000µg mL-1)were all purchased from Supelco (Bellefonte, PA, USA).Fifteen PAEs standard (1000µg mL-1) and one surrogate standards of di-phenyl phthalate (DphP) (500µg mL-1) were obtained from AccuStandard (New Haven, USA). Hexamethylbenzene (HMB)(2000µg mL-1) as internal standard for PAHs and PAEs were purchasedfrom Dr. Ehrenstorfer GmbH (Augsburg, Germany).

HPLC-gradient grade acetone, methanol and residual grade n-Hexane, dichloromethane were purchased from CNW Technologies GmbH (Germany) and used for sample analysis.Glassfiber filters (GFF, 142mm,Whatman,England) were baked at 450ºCfor 5 hand then weighed after constant weight for 24h. XAD-2 resins (Supelco, Bellefonate, USA) were Soxhlet extracted with methanol, DCM and methanolfor 24 h, respectively. Neutral alumina (100-200 mesh, Shanghai, China) and neutral silica gel (80-100 mesh, Qingdao, China) were Soxhlet extracted with DCM for 72 h, then dried and stored in the jar.Afterward, alumina and silica gel were activated by heating at 250ºC and 180ºC for 12 h, respectively, and then deactivated with 3% deionized water after balance for 12 h, and saturated in n-hexane until use. Anhydrous sodium sulfate (Tianjin, China) was pre-cleansed at 450ºC for 5 hto remove impuritybefore the use. Glassware was rinsed with hot K2CrO7/H2SO4solution and baked at 450ºC for at least 4h.

Sample pretreatment

Sample extraction and purifying were performed as described in our previous study (Sun et al., 2014). The water samples were filtered through prebaked glass microfiber filters (GF/Fs, 142 mm in diameter, Whatman, England) to separate suspend particulate. The filters were stored at -20oC fridges until use for suspend particulate analysis. The filtrate were added three categories surrogate standards, and pass through the pretreated XAD-2 columns (Supelco, Bellefonte, USA) to enrich the target compounds. Then, the target compounds were eluted in turn using 50 mL menthol for one time, 40 mL methanol/dichloromethane (DCM)=4:1 for two times, and finally 50 mL of methanol/DCM=1:1 for two times. After the elution, the XAD-2 resins were extracted gradually with 90 mL and 50 mL (2 times) of methanol/DCM=1:1 with ultra-sonication for 15 min each time. The mixture of eluent and ultrasonic solution were extracted using liquid-liquid extraction with a mixture of DCM, saturation salt water and deionized water. The DCM fractions were then collected and concentrated to approximately 5-10 mL using rotary evaporation. The concentrated samples were exchanged with n-hexane and continuously concentrated to 1 mL for cleansing with a silica gel-alumina column(8 mm inner diameter) filled with 12 cm silica, 6 cm gel-alumina and 1 cm anhydrous sodium sulfate from the bottom to top. The column was in turn eluted with 10 mL n-hexane, 70 mL n-hexane/DCM (7:3) and 60 mL n-hexane/acetone (8:2). The PAHs and OCPs were in the second fraction and PAEs were in the last fraction. Finally, the separated fractions were concentrated to approximately 2 mL using rotary evaporation and sequentially concentrated to 200 µL under a gentle stream of high-purity nitrogen. The filters containing suspend particulate were freeze-dried and weighed after constant weight for 24 h and spiked surrogate standards, and then extracted using soxhlet extractor with 200 mL DCM for 72 h. The following steps were as same as the water sample treatments, except that the fraction parts were concentrated to 500 µL under a gentle stream of high-purity nitrogen. Finally, known concentrations of internal standard were spiked for the later instrumental analysis.

Instrument analysis

All the samples were quantified using a 7890A gas chromatography (GC) coupled with a 5975C mass spectrometer detector (Agilent Technologies, USA) equipped with a HP-5MS silica fused capillary column (30 m×250 μm×0.25 μm). For PAHs, the column temperature was programmed from 80oC to 280oC at a rate of 3 oC min-1 and to 300oC at 10 oCmin-1, then held there for 10 min. For OCPs, the temperature held at 80oC for 1 min and programmed to 140 oC at a rate of 15 oC min-1 and further to 280oC at 4 oC min-1, and finally at 10 oC min-1 to 300oC for 10 min. For PAEs, the temperature was programed as follow: initial 80oC held 1 min, increased to 180oC at 10 oC min-1 and held there for 1 min, and then to 260oC at 2 oC min-1, and finally to 300oC at 10 oC min-1 and held there for 10 min. In three processes, 290oC, 250oC, 300oC were selected for the injector temperature of PAHs, OCPs and PAEs, respectively.The mass spectrometer was performed in the selective ion monitoring (SIM) mode using positive ion electron impact ionization (EI).An aliquot sample (1 µL) was injected in the splitless mode and high-purity helium was served as the carrier gas (1.0 mL min-1). The individual compound were determined by comparing the GC retention time and the compound m/z referring to the exactly standard compound m/z by using scan ion monitoring (Scan) mode.

Table S1Sampling sites with basic parameters from Beijiang River

TableS2Recoveries of surrogate standards in the water and suspend particulate

TableS3Essential parameter using for non-cariogenic risk and cancer risk assessment

E=Environmental Criteria and Assessment Office; P=PPRT

Table S4The value for risk assessment from USEPA

a(USEPA 1989d),b(UAEPA 2014)

TableS5The concentrations of PAHs in the dissolved and particulate phase

Nd: not detected.

TableS6Comparison of PAHs levels with the other rivers studies

TableS7The concentrations of OCPs in dissolved and particulate phase

Nd: not detected.

TableS8Comparison of OCPs levels with others studies

Nd: not detected.N: numbers of PAHs

Table S9Concentrations of PAEs in the dissolved and particulate phase

Nd: not detected.

Table S10Comparison of PAEs levels with the others studies

N: numbers of PAHs

Table S11 Pearson’s correlation coefficientsbetween PAHs, OCPs and PAEs with each other in dissolved phase (a) and particulate phase (b)

Fig. S1 The sampling sites of Beijiang River

Fig. S2 PAHs, OCPs and PAEs concentrations in particulate phase in Beijiang River

Fig. S3Sources analysis of PAHs in the dissolved phase in Beijiang River

Fig. S4Sources analysis of PAHs in the particulate phase in Beijiang River

Fig. S5Composition of OCPs in the dissolved (a) and particulate phase(b) in Beijiang River

Fig. S6 Sources identification of DDTs in dissolved (a) and the particulate phase(b) in Beijiang River

Fig.S7Hazard quotient of PAHs through ingestion absorption in dissolved phase (a) and particulate phase (b)

Fig.S8Lifetime cancer risk of PAHs of ingestion absorption in dissolved phase (a) and particulate phase (b)

Fig.S9 Hazard quotient of PAHs through dermal absorption in dissolved phase (a) and particulate phase (b)

Fig.S10Lifetime cancer risk of PAHs through dermal absorption inin dissolved phase (a) and particulate phase (b)

Fig.S11Hazard quotient of OCPs through ingestion absorption in dissolved phase (a) and particulate phase (b)

Fig.S12Lifetime cancer risk of OCPs through ingestion absorption in dissolved phase (a) and particulate phase (b)

Fig.S13 Hazard quotient of OCPs through dermal absorption in dissolved phase (a) and particulate phase (b)

Fig.S14Lifetime cancer risk of OCPs through dermal absorption in dissolved phase (a) and particulate phase (b)

Fig.S15Hazard quotient of PAEs through ingestion absorption in dissolved phase (a) and particulate phase (b)

Fig.S16Lifetimecancer risk of PAEs through ingestion absorptionin dissolved phase (a) and particulate phase (b)

Fig. S17Hazard quotient of PAEs through dermal absorption in dissolved phase (a) and particulate phase (b)

Fig.S18Lifetimecancer risk of PAEs through dermal absorption in dissolvedphase (a) and particulate phase (b)

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