| Pharmaceuticals and personal care products(PPCPs)as the emerging pollutants comprise a lot of chemical substances,including pharmaceuticals,antibacterial agent,antibiotics,personal care products and estrogenic hormone.In this study,non-antibiotics(N-APs),sulfonamides(SAs),tetracyclines(TCs),macrolides(MCs),quinolones(QNs)and estrogens were selected as target compounds,considering that they are the most commonly used pharmaceuticals in Haihe River basin of China.Occurrence and behavior of PPCPs in typical water body of Haihe River basin such as Baiyangdian lake,Guanting Reservoir and its upstream rivers,urban rivers in Beijing,water source in Haihe River basin and groundwater in typical city of Haihe River basin were researched in this study.Also,the Risk assessment was undertaken using calculated risk quotients(RQ).This work was the first investigation about PPCPs in Guanting Reservoir,water source and underground water in typical city of Haihe River basin.This work filled the gaps in the field about PPCPs,and this will provided important data for decision makes in this region.The simultaneous analysis method for multiple classes of PPCPs in water samples via solid phase extraction and sediment samples via ultrasonic extraction and ultra-high performance liquid coupled with chromatography-tandem mass spectrometry(UPLC-MS/MS)were established and optimized.The limit of detection and the limit of quantitation of target PPCP compounds in water were at the range of 0.2-2.0 ng/L and 0.6-6.0 ng/L,respectively.The limit of detection and limit of quantitation of target PPCP compounds in sediments were at the range of 0.2-0.8 ng/g and 0.6-2.5 ng/g,respectively.The recoveries of target PPCPs in water samples and in sediment samples were 73.8-112%and 65.3-123.5%,respectively.The relative standard deviation was less than 20%in water and sediment samples.The analytical method which we established and optimized in this study was applied for the detection of PPCPs in Baiyangdian Lake,Guanting Reservoir(GTR)and its upstream rivers,the rivers in Beijing,drinking water source,and groundwater in Haihe River basin.(1)In Baiyangdian Lake,eighteen selected PPCPs,consisting of five non-antibiotic pharmaceuticals(N-APs),four sulfonamides(SAs),four tetracyclines(TCs),four macrolides(MCs),and one quinolone(QN)were detected in water,pore water,and sediment samples from Baiyangdian Lake,China.The total concentrations of the different classes of PPCPs followed the order:N-APs(53.26%)>MCs(25.39)>SAs(10.06%)>TCs(7.64%)>QNs(3.64%)in surface water;N-APs(42.70%)>MCs(25.43%)>TCs(14.69%)>SAs(13.90%)>QNs(3.24%)in sediment samples,and MCs(42.12%)>N-APs(34.80%)>SAs(11.71%)>TCs(7.48%)>QNs(3.88%)in pore water samples.An environmental risk assessment for the upper quartile concentration was undertaken using calculated risk quotients,and indicated a low or medium high risk from target PPCPs in Baiyangdian Lake.While the risk quotients of some selected PPCPs of this study in sediments from Baiyangdian Lake and its upstream rivers were above 1.0,which showed the high risks in Baiyangdian Lake and its upstream rivers.(2)In GTR and its upstream rivers,acetaminophen,caffeine,chlorotetracycline,and ofloxacin were detected with 100%frequency in surface water from the reservoir’s upstream rivers.Acetaminophen and caffeine were detected with 100%frequency in sediment from GTR and its upstream rivers,while high concentrations of ofloxacin in GTR,and carbamazepine,tetracycline,and chlortetracycline in upstream rivers were also detected in 100%of samples.Five N-APs,especially acetaminophen and caffeine,were prominent pollutants.The mean concentrations of acetaminophen were 155 and 302 ng/L in surface water and 529 and 202 ng/g in sediments from GTR and upstream rivers,respectively.The mean concentrations of caffeine were 208 and 338 ng/L in surface water samples and 1430 and 1020 ng/g in sediments from GTR and upstream rivers,respectively.An environmental risk assessment for the worst-case scenario was undertaken using calculated risk quotients,which indicated a medium from erythromycin in GTR and a high risk in its upstream rivers.While the risk quotients of some selected PPCPs of this study in sediments from GTR and its upstream rivers were above 1.0,which showed high risks in GTR and its upstream rivers.(3)In urban rivers of Beijing,ten selected PPCPs were detected.The range of geometric mean values were at N.D.-655 and N.D.-252 ng/L in water samples from urban rivers and lakes,respectively.The range of detection ratio were N.D.-100%of 10 PPCPs in river water samples,caffeine was the dominant pollution in water samples and the detection ratio was 100%in river samples.The detection ratio of acetaminophen,lincomycin,caffeine and azithromycin were 100%in lake water samples.The range of mean values was N.D.-510.2 and N.D.-161.8 ng/g in sediment samples from urban rivers and lakes.The range of detection ratio was N.D.-100%and N.D.-100%of 10 PPCPs in river and lake sediment samples,respectively.The RQ values of most PPCPs which selected in water samples from Beijing water-body were not much high,but acetaminophen,caffeine,lincomycin and azithromycin in sediments from Beijing water-body showed high risks.(4)In drinking water source of Haihe River basin,10 out of 28 PPCPs were detected.The concentrations of 10 PPCPs in different drinking water source were larger difference.The concentration of 28 PPCPs in YCSK was highest and WKSK was lowest in 33 drinking water sources.The concentration of ACE was highest in ten PPCPs which were detected in dirking sources of Haihe River basin.The RQ values of most PPCPs in drinking water source from Haihe River basin were below 0.01,which showed no risk.The RQ values of ERY in YCSK、XHHSK.XFSK and XHSK were between 0.1 to 1.0,which showed medium risk.(5)In groundwater of Zhangjiakou and Qinhuangdao from Haihe River basin,10 out of 28 PPCPs were detected.The detection rate of ten PPCPs was 6.67-46.7%;the detection rate and concentration of chlorotetracycline were 46.7%and 4.16 ng/L,respectively.Compared with the groundwater in Qiqihaer of Song-Liao basin,the concentration of PPCPs in Haihe River basin was lower than Song-Liao basin.Compared with the groundwater of the world,the concentration of PPCPs in Haihe River basin were much lower. |
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