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Title: | 淨水場處理流程對於鄰苯二甲酸酯類之去除效率探討 Investigation on the Removal Efficiency of Phthalate Esters in Drinking Water Treatment Process |
Authors: | Yi-Lun Hsieh 謝依倫 |
Advisor: | 王根樹(Gen-Shuh Wang) |
Keyword: | 鄰苯二甲酸酯類,淨水廠,固相微萃取,加氯消毒,混凝/沉澱,過濾, phthalate esters,drinking water treatment plants,solid-phase microextraction,chlorination,coagulation/sedimentation,filtration, |
Publication Year : | 2013 |
Degree: | 碩士 |
Abstract: | 鄰苯二甲酸酯類(phthalate esters, PAEs)為工業常用之塑化劑原料,其功用為軟化塑膠或橡膠等製品,並使其具有延展性。2011年台灣發生鄰苯二甲酸酯類被不當作為食品添加劑,於食品及飲料中皆有檢驗出其成分,使得民眾對於鄰苯二甲酸酯類產生恐慌事件。鄰苯二甲酸酯類被認為是一種荷爾蒙干擾物質(endocrine disrupting compounds),對於人體可能會造成生殖或生長的不良影響,此外可能增加肝癌的發生,其潛在危害不容忽視。雖然透過攝入食品與飲料為暴露鄰苯二甲酸酯類之主要途徑,然而透過飲用水的攝入途徑仍不可忽視,因為飲用水為人類每天必須攝取的資源,因此本研究針對台灣地區淨水廠進行實廠調查與模擬分析,評估處理流程對於鄰苯二甲酸酯類之去除效率。
本研究所探討之鄰苯二甲酸酯類包含:鄰苯二甲酸二甲酯 (DMP)、鄰苯二甲酸二乙酯 (DEP)、鄰苯二甲酸二丁酯 (DBP)、鄰苯二甲酸甲苯基丁酯 (BBP)、鄰苯二酸二(2-乙基己基)酯 (DEHP)及鄰苯二甲酸二辛酯 (DOP)。研究架構包括三部份:(1) 鄰苯二甲酸酯類分析方法之建立與改善。(2) 台灣淨水廠之全流程處理單元採樣分析。(3) 單一處理單元/全流程處理單元之淨水處理程序模擬。針對液相-液相萃取(liquid- liquid extraction, LLE)及固相微萃取(solid-phase microextraction, SPME)對鄰苯二甲酸酯類之萃取與定量效果比較,透過SPME處理之檢量線之線性效果較佳,尤其是針對DEHP (R2=0.9985) 和 DOP (R2=0.9965)。因此後續水樣分析使用SPME萃取搭配氣相層析串聯質譜儀(gas chromatography tendon mass spectrometry, GC/MS)分析。pH值之測試條件顯示,中性pH值之水樣有較佳的回收率,且中性pH值較不易破壞SPME之萃取纖維,使其使用壽命得以延長。由於硫代硫酸鈉之主要功能為中止含氯消毒劑之反應,於9 mL水樣中添加0.01 g 硫代硫酸鈉已足以中止反應,不致於因為加入鹽類導致萃取誤差。針對淨水廠之採樣結果顯示DEP, DBP和DEHP存在於原水水體之中,然而經過傳統淨水程序後,其濃度皆有下降的趨勢;較值得一提的是新山水廠原水中DEHP之濃度為3.3 ng mL-1,經過處理後之清水濃度仍有2 ng mL-1。配置100 ng mL-1鄰苯二甲酸酯類模擬原水進行全流程淨水處理流程之結果顯示,除了以新山水廠之原水為模擬基質之DMP (42%)和DEP (41%)之外,傳統處理對六種鄰苯二甲酸酯類皆有70%以上之總去除效率。傳統處理對DMP與DEP之去除效果不佳,不同基質樣品經處理後最終濃度約20~60 ng mL-1,但其餘四種鄰苯二甲酸酯類之去除效率約90%以上,最終濃度約1~7 ng mL-1。由全流程淨水模擬之結果可發現加氯消毒以及過濾程序可能是主要鄰苯二甲酸酯類之去除機制,混凝沉澱流程的去除效率與水體濁度相關,濁度高者之去除效率較佳。雖然不同模擬基質之組成不盡相同,且鄰苯二甲酸酯類在各單元間的去除效果也不相同,但實驗結果顯示三種不同模擬基質之總去除效率卻有相似的結果。 本研究使用較新且較環保之固相微萃取做為樣本前處理之方法,以減少有機溶劑之使用量,且評估效果顯示固相微萃取之定量效果較佳。由實場採樣結果發現,新山淨水廠之清水中檢測出DEHP之濃度約2 ng mL-1,雖然低於法規標準值(6 μg L-1),但仍需要定期檢測淨水場中清水之鄰苯二甲酸酯類濃度,以避免污染事件造成飲用水對人體健康之疑慮。 In Taiwan, the phthalate esters (PAEs) were used as substitute of clouding agent in the food and drink products which caused the crisis of PAEs in 2011. In addition to the food and drinks, the possible pathway from consumption of drinking water should also be concerned. The purpose of this study is to investigate and compare the removal efficiency of PAEs in full scale drinking water treatment plants (DWTPs) and simulated drinking water treatment process. Since PAEs are not chemically but only physically bound to the plastic structure, they may be easily released into environment. In addition to their ubiquitous presence, the PAEs are considered as endocrine disrupting compounds, and they may cause potential adverse health effects for human. In this study, six commonly used PAEs were included as the target chemicals: dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), di(2-ethylhexyl) phthalate (DEHP) and dioctyl phthalate (DOP). The purposes of this study were to clarify the removal efficiency of PAEs with conventional drinking water treatment process and the specific purposes include: (I) Selection and modification of analytical method for PAEs; (II) Evaluations of treatment efficiencies for PAEs removals based on samples obtained from full scale DWTPs in Taiwan; (III) Assessment of PAEs treatment efficiencies based on laboratory simulated treatment process. The results of comparisons of extraction methods showed that solid-phase microextraction (SPME) provides better linear ranges (R2 > 0.995) than liquid- liquid extraction (LLE), thus SPME was adopted for extraction of PAEs from water. The results also showed that neutral pH gives better extraction and prolong the life of SPME fiber. The addition of 0.01 g sodium thiosulfate effectively suppressed the chlorine without causing apparent interference during extraction. Although DEP, DBP and DEHP can be detected in the treated water from Changhxing DWTP and Shinshan DWTPs, the concentrations of those compounds were decreased with the water treatment units. The noteworthy point was the concentration of DEHP, which was detected at 3.3 ng mL-1 in the raw water of Shinshan DWTP, decreased to 2 ng mL-1 after water treatment process. The overall treatment efficiencies of simulation study with three water matrices showed similar removal rates which were higher than 70% for all PAEs, except DMP (42%) and DEP (41%) with Shinshan DWTP water. The final concentrations of DMP and DEP after complete treatment process were 20~60 ng mL-1 within different matrices; the final concentration of other PAEs were ranged 1~7 ng mL-1, and the overall removal efficiency was above 90%. The chlorination and filtration were noticed to be the main treatment units for removal of PAEs in conventional treatment process. The removal efficiency in sedimentation unit was based on the turbidity of water; and the matrix with higher turbidity gave better removal for PAEs during sedimentation. The different composition of water matrix might influence the treatment efficiency with PAEs; however, the total removal rates were seemed similar for all target compounds. In this study, SPME was shown to be a proper extraction method because of its advantage of less solvent requirement, and the quantification ability was better than conventional LLE. Although the concentration of PAEs in finished water was lower than the water quality standard (6 μg L-1), routine monitoring is recommended to avoid the potential adverse health effects. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/60269 |
Fulltext Rights: | 有償授權 |
Appears in Collections: | 環境衛生研究所 |
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