探討高屏地區主要河川及河口中烷酚類化合物之流布與底質吸附潛勢之研究

A study of alkylphenols distribution and its sorption potential to sediment in rivers and estuaries of Kaoping area

柯冠宇(Guan-Yew Ku)

指導教授 ： 邱春惠 ； 黃益助

國立屏東科技大學/工學院/環境工程與科學系所/碩士(2012年)

https://doi.org/10.6346/NPUST.2012.00268

摘要

本研究於2011年10月至2012年4月份間，沿屏東縣萬年溪和東港溪及高雄市二仁溪所設置之19個取樣站合計攜回之51件河水及21件底質(sediment)樣本。利用固相萃取法(solid phase extraction, SPE)進行液態樣本前處理後，再以高效液相層析儀搭配螢光偵測器(high-performance liquid chromatography with fluorescence detector, HPLC/FLD)進行分析，探討雙酚A (bisphenol A, BPA)、辛基酚(octylphenol, OP)及壬基酚 (nonylphenol, NP)濃度受時間、空間及水文、水質與底質等理化性質之影響，並瞭解萬年溪、東港溪與二仁溪水體與底質中，酚類化合物之流布及其分配係數(distribution coefficient, Kd)，以及藉由Kd及Koc (soil-water partition coefficient normalized to organic carbon)探討酚類化合物在水體和底質之分配特性和相關性。
結果顯示，萬年溪水體樣本OP、NP及BPA之平均檢出率分別為100%、92%及85%。OP、NP及BPA濃度分別為21.8 - 230.4、ND (MDL = 8.9) - 240.1及 ND (MDL = 8.7) - 107.5 ng L-1。OP及NP濃度與溫度呈負相關性，即水溫愈高則濃度愈低。底質中三種化合物的平均檢出率皆為100%，OP、NP及BPA濃度分別為10.0-87.6、7.0-64.0及21.0-42.7 ng g-1；以2011年而言，儘管在水樣中BPA濃度較OP及NP兩者低，但於底質中BPA濃度和OP及NP相當。2012年1及2月份，東港溪水體22件樣本中OP、NP及BPA濃度範圍(平均值)分別為ND (MDL = 8.4) - 544.6 (245.3)、ND (MDL = 8.9) - 240 (110.0)和34.0 - 320.0 (117.4) ng L-1，其中以OP濃度為最高；底質中OP、NP及BPA濃度範圍（平均值）分別為14.2 - 489.7 (152.0)、13.0 - 300.3 (95.6) 及9.0 - 69.3 (31.5) ng g-1，其中以OP濃度為最高。OP、NP及BPA之平均log Kd分別為2.80、2.90與2.40。底質總有機碳(total organic carbon, TOC)與目標化合物之log Kd呈正相關性，相關係數(R)分別為OP = 0.823、NP = 0.746和BPA = 0.636。計算目標烷酚類化合物之log Koc (soil-water partition coefficient normalized to organic carbon, Koc)皆落於99%的信賴區間，即OP、NP和BPA之log Koc分別介於3.81 ± 0.66、4.14 ± 0.66和3.09 ± 0.67。OP、NP及BPA濃度於液、固相基質(matrix)間均呈正相關性(R皆大於0.742)。底質TOC濃度亦與OP、NP及BPA呈正相關性；R分別為0.504、0.589及0.615。2012年4月份，二仁溪水體樣本中之OP、NP及BPA濃度範圍（平均值）分別為49.1 - 146.3 (103.0) 、53.3 - 470.9 (268.2)和91.8 - 1,080 (484.7) ng L-1，其中NP於部分河段，其濃度值已超出歐盟之預估無顯著影響濃度(330 ng L-1)；底質中OP、NP及BPA濃度範圍（平均值）分別為83.4 - 105.3 (83.1)、291.9 - 585.9 (497.7)和34.3 - 194.5 (90.4) ng g-1。目標化合物濃度於液、固相基質(matrix)間亦均呈正相關性(R皆大於0.806)。底質TOC亦與其目標化合物濃度呈正相關性，R皆大於0.837。計算目標烷酚類化合物之log Koc皆落於99%的信賴區間。整體而言，東港溪與二仁溪流域於不同月份呈現底質TOC與目標化合物間相關性，以BPA為最低，可能與BPA之疏水性較低有關。本研究烷酚類化合物之分配係數成果可了解其在河川水體及底質間之流布，可作為主管機關擬定烷酚類化合物管制和整治策略之參考。

關鍵字

雙酚A ； 辛基酚 ； 壬基酚 ； 固相萃取法 ； 總有機碳 ； 分布係數

並列摘要

From October 2011 to April 2012, 51 water and 21 sediment samples were collected from 19 sampling stations along the Wan-Nian River as well as Tung-Kang River in Ping-Tung County and the Erh-Jen River in Kaohsiung City. Water samples were pretreated with solid phase extraction method and then quantified for bisphenol A (BPA), octylphenol (OP), and nonylphenol (NP) by a high-performance liquid chromatography coupled with fluorescence detection (HPLC/FLD) to investigate their concentration variations with temporal, spatial, and hydrological parameters as well as water quality and sediment physicochemical properties. The correlation and distribution characteristics of alkylphenol compounds between water and sediments were also explored via distribution coefficient (Kd) and soil-water partition coefficient normalized to organic carbon (Koc).
The results showed that the average detection ratios of OP, NP, and BPA were 100%, 92%, and 85% in the water samples of Wan-Nian River, respectively. The concentration ranges of OP, NP, and BPA were 21.8 - 230.4, ND (MDL = 8.9) - 240.1, and ND (MDL = 8.7) - 107.5 ng L-1, respectively. The OP and NP concentrations were negatively correlated with water temperature, i.e. the higher the water temperature was, the lower the OP and NP concentration. The average detection ratios of the three alkylphenol compounds in the sediment are all 100%. The OP, NP, and BPA content ranges were 10.0 - 87.6, 7.0 - 64.0, and 21.0 - 42.7 ng g-1, respectively. In the case of samples collected in 2011, concentrations of BPA were lower than those of both OP and NP in water samples. However, the contents of the three alkylphenol compounds were similar in sediments.
For the 22 water samples collected from the Tung-Kang River in January 13 and February 11, 2012, the BPA, OP, and NP concentrations (average) in water were ND (MDL = 8.4) - 544.6 (245.3), ND (MDL = 8.9) - 240 (110.0), and 34.0 - 320.0 (117.4) ng L-1, respectively, with the highest OP concentration. The NP, OP, and BPA contents (average) in sediments were 14.2 - 489.37 (152.0), 13.0 - 300.3 (95.6), and 9.0 - 69.3 (31.5) ng g-1, respectively, also with the highest OP contents. The average values of log Kd of OP, NP, and BPA were 2.80, 2.90, and 2.40, respectively. Total organic carbon (TOC) in sediments was positively correlated with the target compounds with correlation coefficients (R) of 0.82 for OP, 0.75 for NP, and 0.64 for BPA. The calculated log Koc with log Kd divided by TOC (foc) fell within 99% confidence interval. The log Koc values of OP, NP, and BPA were 3.81 ± 0.66, 4.14 ± 0.66, and 3.09 ± 0.67, respectively. The concentrations of three alkylphenol compounds in water were positively correlated with their contents in sediments with all R greater than 0.74. TOC contents in sediments were positively correlated with BPA, OP and NP with respective R of 0.50, 0.59, and 0.62.
The water samples collected from the Erh-Jen River on 22 of April, 2012, BPA, the concentration ranges (average) of OP, NP, and BPA were 49.1 - 146.3 (103.0), 53.3 - 470.9 (268.2), and 91.8 - 1,080 (484.7) ng L-1, respectively. Some NP concentrations sampled from the Erh-Jen River exceeded the no observation effect concentration (NOEC) of 330 ng L-1 regulated by European Union (EU). The NP, OP, and BPA contents (average) in sediments were 83.4 - 105.3 (83.1), 291.9 - 585.9 (497.7), and 34.3 - 194.5 (90.4) ng g-1, respectively. The concentrations of target compounds in water were also positively correlated with those in sediments with R all greater than 0.81. Total organic carbon (TOC) in sediments was also positively correlated with the target compounds with R all larger than 0.84. The calculated log Koc with log Kd divided by TOC (foc) also fell within 99% confidence interval. Overall, the correlation between TOC in sediments and BPA was less than that of OP and NP for the Tung-Kang and Erh-Jen River. That may be due to the less hydrophobic properties of BPA. The Kd values of alkylphenol compounds obtained from the present study are useful to better understand their transport and distribution between water and sediments and to frame the control and remediation strategies of concerned alkylphenol compounds for the authorities.

並列關鍵字

bisphenol A (BPA) ； 4-tert-octylphenol (OP) ； 4-n-nonylphenol (NP) ； solid phase extraction (SPE) ； total organic carbon (TOC) ； distribution coefficient (Kd)

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