污水廠廢水溶解性有機質特性及結合雌激性化合物探討

Characterization of Dissolved Organic Matters in Various Wastewaters and Estrogenic Compounds Sorption Behavior

許峻瑋(Chun-Wei Hsu)

指導教授 ： 陳庭堅

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.2012.00237

摘要

溶解性有機物質(Dissolved Organic Matter, DOM)的來源廣泛且具多樣性，並會影響有機污染物之分配、吸附、傳輸及生物毒性，以及扮演生物化學循環的關鍵角色。密集式動物飼養業(Concentrated Animal Feedlot Operations, CAFOs)產生的廢棄物富含大量的DOM，本研究探討養豬場污水中的DOM，經過污水處理單元後其性質的改變，以及對類雌激素化合物的吸附性，並比較生活污水廠(以下簡稱為D、F、L廠)與養豬場(以下簡稱P1、P2、P3)放流水之吸附性。
本研究利用紫外光/可見光分光光度計與螢光光譜儀分析廢水中的DOM，再以UV光學指標與螢光光學指標做更進一步探討，結果顯示大型養豬場廢水的DOM，隨著處理單元的增加，其腐植化程度與分子量均明顯變高。生活污水廠放流水D廠之腐植化程度較高，F與L廠波峰均呈現藍光位移，代表腐植化程度較差。養豬場放流水，P3之腐植化程度最好，P2次佳，P1最差。
水樣分離成大分子溶液(0.45 μm-1 kDa)與小分子溶液(1 kDa以下)後，其DOM性質與吸附特性。大型養豬場不同處理單元，原水、厭氧與好氧後之分離液，均顯示大分子溶液腐植化程度高於小分子溶液，而放流水的結果卻成相反情形。不同污水廠放流水的比較，D廠、L廠與三間養豬場之放流水，大分子溶液的波長與螢光強度均大於小分子溶液。
利用螢光衰減法探討壬基苯酚(Nonylphenol, NP)、辛基苯酚(Octylphenol, OP)、雙酚A(Bisphenol A, BPA)與DOM之吸附性，動物源之污水，大分子溶液之吸附效果均優於小分子溶液。生活污水廠分離液的吸附效果，均為小分子溶液優於大分子溶液。利用螢光衰減法計算之log Kdoc值，BPA為3.46~5.58之間、OP為3.87~5.73之間、NP為2.26~5.83之間。
養豬場不同處理單元樣本之FT-IR圖譜，五個樣本均有OH基團、羧基的O-H鍵結、烯烴之C=C鍵結、烷基、醚類、醇類和碳水化合物的C-O鍵結、芳香環的C-H鍵結。分離大小分子後的FT-IR圖譜，呈現之鍵結並無較大之改變，而小分子樣本鍵結之訊號大多大於大分子樣本。
相關性分析，發現Bio/Geo(Biochemical index/Geochemical index)、R4/R5(螢光區域積分法第IV區/螢光區域積分法第V區)、R3/R5(螢光區域積分法第III區/螢光區域積分法第V區)、A250(波長250 nm-450 nm吸光值的總和)與SUVA254(波長254 nm處的吸光值/溶解性有機碳濃度)指標有良好的相關性，尤其是A250指標未來可做為SUVA254之替代參數。

關鍵字

溶解性有機質 ； 雌激性化合物 ； 螢光光譜儀 ； 紫外光/可見光分光光度計 ； 螢光衰減法

並列摘要

Dissolved organic matter (DOM) originates from widely diverse sources, which affect the distribution, sorption, transport, and biological toxicity of persistent organic pollutants, and play a key role in biogeochemical cycles. Wastes generated by concentrated animal feedlot operations (CAFOs) are rich in DOM. This study investigated the change in pig farm wastewater DOM following different wastewater treatments. The binding capacity to estrogen-like compounds was also studied. In addition, the binding capacity and properties were compared with the different sources of wastewater treatment plant effluent.
In this study, optical indices of UV/Vis and fluorescence spectra were used to characterize the properties of DOM in different wastewater treatment units. The results showed that the humification degree and molecular weight increased in DOM following wastewater treatment. Three municipal and three pig farm effluents were studied. Regarding municipal wastewater treatment plant effluents, the plant “D” municipal effluent had a higher degree of humification than two other plants, plants “F” and “L”. Fluorescence peaks showed a blue shift, which represented a smaller degree of humification. Considering the humification degree of the pig farm effluent, plant “P3” had higher degree humification than plants “P2” and “P1”.
The DOMs were separated into high and low molecular weight solutions (HMWOM and LMWOM, respectively). The HMWOM had a higher degree of humification than the LMWOM in treatment processes that included raw water, an anaerobic process, and an aerobic process but the effluent had different properties in a large pig farm wastewater treatment plant. Different effluent DOMs in a wastewater treatment plant (EfOM), the “D” and “L” plants, and three pig farm effluents, had a higher wavelength and intensity in the HMWOM fluorescence peak than LMWOM.
The investigation of nonylphenol (NP), octylphenol (OP), and bisphenol A (BPA) sorption capacity to DOM with a fluorescence quenching method shows that HMWOM had a better sorption capacity than LMWOM but there were conflicting results in the municipal wastewater effluents. The log Kdoc values ranged from 3.46 to 5.58 for BPA, from 3.87 to 5.73 for OP, and from 2.26 to 5.83 for NP.
FT-IR spectra of the DOM samples in pig farm wastewater in different treatment units showed five samples had a hydroxyl group (OH), a carboxyl bond (O-H), olefins bond (C=C), alkyl, ethers, alcohols and carbohydrates bonds (C-O), and an aromatic bond (C-H). The FT-IR spectra in HMWOM and LMWOM had a similar bonding signal but the LMWOM had a stronger signal than the HMWOM. The correlation analysis showed that indices of Bio/Geo, sum of fluorescence intensity in region IV divided to sum of fluorescence intensity in region V (R4/R5), sum of fluorescence intensity in region III divided to sum of fluorescence intensity in region V (R3/R5), and absorbance integral area from 250 nm to 450 nm (A250) had good correlation with specific ultraviolet absorbance at 254 nm divided DOM carbon concentration (SUVA254). Especially the index of A250; it can be used as alternative parameters of SUVA254, and had a significantly positive correlation with SUVA254, which is a well-established humification index.

並列關鍵字

Dissolved organic matter ； Estrogen-like compounds ； Fluorescence spectra ； UV/Vis spectra ； Fluorescence quenching method

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