Investigation of the distribution of alkylphenol and alkylphenol polyethoxylates in main rivers and harbor areas of Kaohsiung city by LC-MS/MS
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Abstract Hou-Chin stream, Love river, and Chien-Chen river, the three main rivers in Kaohsiung city, flow through the populous residential and industrial areas. A large portion of sewage from domestic and industrial sources are discharged into these rivers, then the Love river and Chien-Chen river pour into the harbor area. In order to understand the pollution of alkylphenol polyethoxylates in these areas, water and sediment samples in Hou-Chin stream, Love river, Chien-Chen river and harbor area in Kaohsiung city were collected and the contents of alkylphenol and corresponding polyethoxylates were analyzed in this study. LC/MS/MS was used as the analytical instrument which is relatively time-saving in comparison with other instruments. It is also more convenient due to the facts that no derivation or colorization are needed in sample pretreatment. The detection limit can reach to 0.03 ng/ml and recovery can be around 83.6~91.6%. It can analyze alkylphenols combinded with long ethoxylate chain with improved sensitivity and selectivity. In the four sampling areas, the concentration of NPs in water were between 7.4~241.8ng/ml, and OPs were between 0.66~64.2ng/ml. The most contaminated water samples were found at Chih-Ping Bridge on the mainstream of Love river and Pau-Chu-Kou Dam Station and Min-Tsu Bridge on the tributary of Love river where the concentrations of NPs were greater than 200ng/ml, OPs were greater than 30ng/ml. We found that the main pollution sources were from Lung-Hsin Bridge, Tzu-Yu Bridge, Lung -Hua Bridge, and Pau-Chu-Kou Dam Station. The pollution sources of the Chien-Chen river were mainly from Chung-An Bridge and Chen-Chuan Bridge. Concentration of NPs in upper sediments were between 633.1~2113.8ng/g, OPs were between 50.3~287.9ng/g. The highest concentration of NPs was at Ho-Ti Bridge on the mainstream of Love river, and the lowest concentration of NPs was at Chung-An Bridge on Chien-Chen river. The highest concentration of OPs was at Chen-Chuan Bridge in Chien-Chen river, and the lowest concentration of OPs was IV
Min-Tsu Bridge on the tributary of Love river. The concentration of NPs in deeper sediments were between 523.9~1919.5ng/g, OPs were between 39.9~322.0ng/g. The highest concentration of NPs was at Chung-Hua Bridge on the tributary of Lover river, and the lowest concentration of NPs was at Chung-An Bridge on Chien-Chen river. The highest concentration of OPs was at Chi-Chin Fishing Port, and the lowest concentration of OPs was at Min-Tsu Bridge on the tributary of Love river. The salinity of water samples and the total organic carbon in sediment sample will influence the distribution coefficient of alkylphenol polyethoxylates with different length of ethoxylate chains, their distribution coefficients were between 0.48~2.67. In comparison with foreign studies, the concentrations of alkylphenol polyethoxylates of water and sediments amples in this study were between the highest and lowest values reported. However, the observed concentrations of alkylphenols in these study areas were higher then other rivers in Taiwan. These values were higher than the Probable No Effect Concentrations ( PNEC) of NP risk assessed by European Union. It can be concluded that the pollution of alkylphenol polyethoxylates of water and sediment is getting more serious in Hou-Chin stream, Love river, Chien-Chen river and harbor area in Kaohsiung city. V
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(NP) (Estradiol) IX
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C 9 H 19 O-(CH2-CH2-O)n-CH2-CH2-OH n=0-18 Nonylphenol polyethoxylates(npneo) C9H19 OH Nonylphenol(NP) C8H17 OH Octylphenol(OP) 2
3 C 9 H 19 - - OH C 8 H 17 - ----- - OH
1,1-dichloro-2,2-bis (p-chlorophenyl) ethylene 4
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HO (Nonylphenol) OH HO (17 Estradiol) (NP) (Estradiol) 6
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Ahel, M. and Giger, W. 1993. 9
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Nimrod and Benson, 1996 11
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Blackburn and Waldock, 1995; Thiele et al., 1997; Harries et al.,1997; Ying et al., 2002 13
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Ding, et al., 1999; Ding and Wu, 2000;, 2001 15
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107 a. Reference 26 b. Reference 27
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140 442.50 6.85 313.50 5.36 415.00 3.66 71.75 5.33 27.65 5.21 92.35 5.23 63.45 3.98 556.00 3.54 7.04 2.31 303.50 8.94 137.00 4.51 269.50 4.31 555.00 11.59 647.50 4.33 522.00 4.88 66.90 6.40 2815.00 5.98 105.00 2.89 24.00 2.36 2760.00 6.53 75.35 5.87 130.50 5.99 85.70 4.39 215.00 7.25 679.00 8.76 630.00 7.21 219.00 5.30 106.00 7.51 52.40 5.14 205.50 5.10 225.00 5.40 682.00 3.95 1045.00 6.44 988.00 3.64 4670.00 10.07 324.50 3.65
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