Residual Levels And Health Risk Assessment Of Phthalate Esters In Marine Organisms From Coastal Areas Of Guangdong Province

Phthalate esters, due to its excellent comprehensive performance, are widely usedas additives in a broad spectrum of industrial and commercial products includingplastic products, textiles, household goods and building materials, especially used asplasticizers for plastics. With the development of plastic industry, PAEs are ubiquitouspollutants in environment. PAEs are now beeoming the focus due to its frequentdetection, high concentrations found in the environment and its harmful effects onanimals or human. Guangdong province is the place where plastic industries are mostprosperous in China, leading to a higher PAEs content in various environment media ofGuangdong province than the rest areas of China.To investigate the pollution status ofPAEs in marine organisms, firstly,we established a method for detecting the15kindsof phthalate esters in marine organisms by gas chromatography-mass spectrometry（GC-MS）.Then we analysed the phthalate esters contents in150samples of85species marine organisms (included fish, shrimp, shellfish and crabs) from the coastalwaters of Guangdong province, Guangxi province and from Nansha islands of SouthChina Sea. We compiled and analysed the residues and the composition characteric ofPAEs congeners in all marine organisms’ samples, and also probed into the distributionof PAEs in various tissues of Sharks. Human health risk assessment on PAEs pollutedmarine organisms from study waters also carried out according to the PAEs intake ofresidents of Guangdong urban areas. Results are as following:1. A robust and efficient method for determination of the15kinds of phthalateesters in marine organisms was established with the optimized conditions is thatsample extracted by ultrasonic DCM: hexane (1:1,v/v), cleanedup by neutral alumina column Chromatography with a series of polarity gradually increased mixture reagents as eluent,and followed by gas chromatography-massspectrometry.Under the optimized conditions,the linear ranges of15phthalate esterswere in the range of0.05~1.0mg/L with correlation coefficients(r)not less than0.9991.The average recoveries range of15phthalate esters in different kinds of marineorganisms samples at three spiked levels were in the range of81%~123%,with relativestandard deviations(RSDs,n=3)less than15%.The limits of detection (LOD,S/N=3) andquantitation（LOQ, S/N=10）are0.04~1.18g/kg,0.20~4.00g/kg respectively.Themethod we established is with of many advantages, such as easy to operation, highaccuraty and precision, high sensitivity and repeatability.It is proved that this method issuitable for detecting the15phthalate esters in marine biota simultaneously.2. PAEs contents in marine organisms are describled as following:①The total concentrations of15kinds of phthalate esters (15PAEs) in marineorganisms collected from nine coastal waters of Guangdong province and Guangxiprovince ranged from48.9g/kg to2136g/kg, with the mean and median of15PAEsare311g/kg and263g/kg respectively. The highest and the lowest concentrationsare in penaeus penicillatus from Daya Bay and platycephalus indicus (Linnaeus) fromShenzhen Bay respectively. The average of the total PAEs concentrations in marineorganisms is different among the nine coastal waters. Which exhibited decreasing orderas Daya Bay(1107g/kg)>Nan’ao Bay (407g/kg)>Wanshan islands of Pearl RiverEstuary (398g/kg)>Bohe Harbor (354g/kg)>KaozhouyangBay(315g/kg)>Qinzhou Bay(256g/kg)> Zhan jiang Harbor (219g/kg)>DapengBay (189g/kg)>Shenzhen Bay(163g/kg). The residues of PAEs in marine organismscollected from different coastal waters are different, and the differences among somecoastal waters are statistically significant (P<0.05).②The total concentrations of15kinds of phthalate esters (15PAEs) in19marineorganisms samples collected from Nansha islands of South China Sea ranged from5.47g/kg to196g/kg, the mean of15PAEs is78.4g/kg. The total concentrationrange (mean)of15kinds of PAEs in fish, crustaceans, shellfish and cephalopods are5.47~196μg/kg (84.4μg/kg),64.5～84.0μg/kg（75.7μg/kg）,58.3μg/kg and23.6μg/kgrespectively.Overall, PAEs residues in organisms from Xisha, Zhongsha, Nanshaislands waters are lower than the organisms from Guangdong coastal waters1.4to16.7times. ③The average of PAEs content in tissues of shallow sea thresher（Alopiaspelagicus） is higher than the corresponding tissues of deep-sea thresher(Alopiassuperciliosus). The total concentration ranges (means) of PAEs in tissues of shallowsea thresher, deep-sea thresher (Ⅰ) anddeep-sea thresher (Ⅱ) are69.4~212(139)μg/kg, lower than the limits of detection (ND)~297(61.4) μg/kg,9.26~165(72.5) μg/kgrespectively. The PAEs contents in tissues of sharks have no obvious regularity,suggesting that bioaccumulation of PAEs in sharks’ tissues is species specific andtissues specific.④Lipid contents, ability of metabolization, habitats of organisms, the growth andreproductive cycle of marine organisms and PAEs concentrations in the habitatenvironment may be responsible for the bioaccumulation of PAEs.⑤Compared with aquatic organisms from other waters around the world,concentrations of PAEs in marine organisms from the research waters are at mediunlevel and downwards.3. The composition of PAEs in organisms from the research waters as following:To some degree, all the15kinds of phthalate esters were detected in marineorganisms samples collected from the research waters. The six kinds of PAEs listed as“priority pollutants” together with DIBP are the dominant congers of PAEs residues,among those DIBP, DBP and DEHP are predominant chimicals, with the percentagerange is54.9%~99.6%. There are still some subtle differences of the percentage ofDIBP, DBP and DEHP as an individual compound, and the differences manily manifestas the order of DIBP, DBP and DEHP concentration.4. we assessed the health risk posed by PAEs through dieting aquatic productsfrom the research areas.The assessment of health risk according to the residues ofPAEs in marine organisms from the research waters has shown that the cancer riskaroused by DEHP are less than the maxium acceptable risk level(1×10-4) recommendedby US EPA.However，in most of the samples the cancer risk index always fall into1×10-6to1×10-5, indicating that there are some potential cancer risk，therefore,somespecial attentions should be paid to the marine organisms with high DEHP residues.Inall samples the PAEs individual congeners’s non-cancer risk is much less than one.Thetotal non-cancer risk is less than one too,with DEHP makes a remarkable contributionto the total non-cancer risks. Both the cancer risk and non-cancer risk posed by PAEs residue in organisms from the research waters to adults are slightly higher thanchildren. According to the detected marine organisms’ samples, we argue that thehealth risks posed by PAEs in marine organisms from our studied waters are negligible.