Characteristics And Ecological Risk Assessment Of PPCPs' Pollution In The Urban And Offshore Waterbody Of Haikou City

Pharmaceuticals and personal care products(PPCPs)are typical emerging pollutants.Because of the large amount of usage,strong biological activity and pseudocapacitive,and potential risk to aquatic organisms,it has attracted wide attention by environmental scientists and even the public in the past ten years.In recent years under the support of national policies,Haikou has become the free trade pilot port of China,the national "Belt and Road" strategic fulcrum city,the national ecological civilization demonstration area,led to a fast development with a rapid increase of population,logistics and urbanization.Therefore,the pollution load in urban rivers and lakes which have ecological environment and social service function and in coastal bay is increasing.It seriously affects the quality and safety of ecological water environment in Haikou.Currently,as to PPCPs there are no environmental discharge standards and safety limits in China,and no relevant research has been carried out in Haikou.Therefore it is very important to investigate PPCPs pollution situation in Haikou water environment.In this study,surface waters in Haikou and coastal seawater in Haikou bay were selected as the research area.PPCPs in waters,sediment and aquatic organisms were indentified and quantified using non-target screening technology and target screening analysis.The pollution sources were analyzed,and the ecological risk of target PPCPs in waters and sediments were evaluated by Risk quotient(RQ)method.High-risk PPCPs and ecologically sensitive areas in water environment of Haikou were identified.The results would provide theoretical guidance for water pollution control,coastal management in Haikou.The main results are as follows:(1)There were 75 kinds of PPCPs identified and quantified in Haikou.Total ?PPCPs concentrations in surface waters was up to 8527.48 ng/L,in seawater samples reached5033.03 ng/L.Caffeine,ofloxacin,sulfamethoxazole,roxithromycin,erythromycin,tetracycline,paracetamol,methylparaben,mosquito repellent,climbazole,ibuprofen are the dominant pollutants.The most serious polluted area of surface water is Longkun channel(L8)with ?PPCPs of 1860.54 ng/L,namely 21.8 % of the total ?PPCPs of surface waters;the concentration in turn is Jinniuling Lake(L9)378.10 ng/L > Hongcheng Lake(L10)271.03 ng/L > Dongxi Lake(L13)198.84 ng/L.In the rivers,the pollution in Wuyuan River is the highest,followed by Meishe River,and the pollution in Nandu River is relatively low.As to seawater the most polluted area is Longzhu Bay(S8),its ?PPCPs reaches 3172.89 ng/L,accounting for 63.04 % of total ?PPCPs of seawater.In the West Coast of Haikou(S2,S3,S4,S5),PPCPs pollution is relatively low,due to low population,wide sea surface and strong water flow exchange,therefore.The ratio of paracetamol to carbamazepine is above 10 with 34.4 % of surface water and seawater samples in Haikou,indicating that the sewage treatment rate in Haikou is not good enough.There may be some serious leakage in sewage pipe network,and direct discharge occured.It is suggested that the sewage pipe network has to be checked carefully,improve source control and pollution interception.(2)Total ?PPCPs was up to 33422.21 ng/g in the sediments of surface waters.The total concentration of 41 detected antibiotics was 25452.73 ng/g,accounting for 76.2 % of the total ?PPCPs,and the ?PPCPs of biocides was 7951.76 ng/g(23.8 %).The antibiotics concentration in turn is ofloxacin > oxytetracycline > norfloxacin > tetracyclin >doxycycline > ciprofloxacin > pefloxacin > erythromycin,the total concentration of these 8antibiotics reached 24723.14 ng/g,accounting for 97.1 % of the total antibiotics in the sediments of surface waters,which is the dominant pollutants in the surface water sediments,especially ofloxacin accounting for 39.5 %.Disinfectants and fungicides are the major pollutants of biocides,while triclosan and triclaban are dominant biocides in the surface water sediments.Total ?PPCPs content in marine sediments is 9389.46 ng/g.The dominant pollutant is biocides with a total content of 7087.16 ng/g,accounting for 75.5 %of the total ?PPCPs of marine sediments,especially the combined concentration of triclosan and triclacaban as disinfectants is 6721.7 ng/g,accounting for 71.6 % of the total?PPCPs.The pollution level of rivers and lakes in the main area of the city is higher than that of the coastal sewage ditch.?PPCPs in Dongxi Lake > Hongcheng Lake > Jinnuling Lake,while in Meishe River > Haidian River > Wuyuan River > Nandujiang River.The ?PPCPs concentrations of coastal sewage ditch in Xiuying sewage ditch(L5)and the west end of Yawei River(L16)is higher.?PPCPs of coastal sediments is higher than that offshore 2km;The area from Hengda Haikou Bay to Century Bridge is a serious polluted area in the northern sea area of Haikou.Longzhu Bay(S8)is the most polluted sites in marine sediments.In addition to biocide pollution,tetracycline and quinolones antibiotics pollution is also serious in this area.(3)There were 48 kinds of PPCPs detected in biological samples with the contents ranging from nd-1435.36 ng/g ww.?PPCPs in different tissues of orgamisms shows fish eggs > liver > muscle.Different kinds of PPCPs have different accumulation characteristics in different tissues.The average ?antibiotics content is liver > egg > muscle;the average ?antifouling agent content is egg > muscle > liver.Fungicides accumulated more in liver and fish eggs.The accumulation of PPCPs in different organisms are also different with fish > crab.The average content of antifouling agent and mosquito repellent in fish muscle is higher than that in crab muscle,but the content of disinfectant,preservative and antifungal agent in crab muscle is higher than that in fish muscle.The contents of climbazole,DCOIT,DEET,triclosan,narasin,itraconazole,clotrimazole were higher,indicating dominant pollutants in biological samples.PPCPs residuals in tilapia in different waters were different.The residues of antibiotics in fish tissues in Hongcheng Lake,Meishe River and Haidian River are relatively high,while in Jinniuling Lake and Dongxi Lake are relatively low.The PPCPs residual level in Wuyuan River is higher than that in Nandu River.The contents of biocides in fish tissues from the lower reaches of Nandu River and Wuyuan River were relatively high.The average Log BAF of PPCPs in biological tissues was in a range of-0.10-6.36L/kg.There were 19 kinds of PPCPs showing bioaccumulation effect in fish tissues.DCOIT had the highest bioaccumulation effect,and could have also bioaccumulation effect in liver,muscle and fish eggs.Fluoroquinolones antibiotics,zolium antifungal agents and disinfectants have significant bioaccumulation effect.(4)The RQ evaluation shows that the potential ecological risk of PPCPs to aquatic organisms in the waters and sediments is algae > invertebrates > fish,and in surface waters is greater than that in seawater.High potential risks were found for triclosan,triclaban,DCOIT,sulfamethoxazole,ofloxacin and clindbazole in the aqueous phase,and for ofloxacin,norfloxacin,ciprofloxacin,tetracycline,oxytetracycline,triclosan and triclacaban in the sediments.They are the main emerging pollutants with high ecological risk in the water environment of Haikou,and is worthy of great attention.This study is the first time to systematically study the pollution types,levels and ecological risks of PPCPs pollutants in waters,sediments and organisms in Haikou and the northern coastal waters.It found the dominant pollutants and fragile sites from ecological environment view.It would be a consideration for Haikou sewage collection,chemical management,coastal zone pollution prevention and control,management and development of decision-making,and the sustainable utilization of marine resources in Haikou Bay.