工業放流水中潛在性毒性物質的溯源和追蹤

Tracing and Tracking of Potential Toxic Substances in Industrial Discharge Water

顏嘉良(Chia-Liang Yen)

指導教授 ： 凌永健

國立清華大學/理學院/化學系所/博士(2018年)

摘要

本研究主要針對工業放流水為目標，區分工業園區廠商放流水（潛在性）化學物質評估、生物急毒性模式生物檢測方法建立、工業放流水毒性鑑定方法建立及污水處理廠放流水（潛在性毒物）的環境宿命等5大研究主軸。
工業放流水評估：重金屬選擇硫酸銅、硫酸鋅、硫酸鎘、硫酸鎵、硫酸銦、硝酸銅、硝酸鎘、硝酸鉛、三氧化鉬等金屬鹽類代表放流水主要毒物，作為參考毒物對水蚤、羅漢魚、斑馬魚胚胎等進行生物毒性試驗。結果顯示硝酸銅的生物毒性最嚴重。有機污染物（四甲基氫氧化銨及4-氯酚）及重金屬污染物（硫酸銅），製備具生物毒性之人工水樣，三種毒物對水蚤及羅漢魚毒性大小依序為：硫酸銅 ＞ 4-氯酚 ＞ 氫氧化四甲基銨。分別用（1）氫氧化四甲基銨/ 4-氯酚、（2）氫氧化四甲基銨/ 硫酸銅、（3）4-氯酚 / 硫酸銅、及（4）氫氧化四甲基銨 / 4-氯酚 / 硫酸銅等進行毒物混合毒性試驗。對水蚤及羅漢魚，皆以4-氯酚 / 硫酸銅之毒性為最強，且出現協同效應。含氧化物（次氯酸鈉、過氧化氫）對水蚤及羅漢魚之毒性高低依序為：次氯酸鈉＞過氧化氫；水蚤及羅漢魚的耐酸鹼範圍分別為pH 5.4~10.2及pH 4.2~10.8；二物種對二氧化矽及氟化鈣產生之濁度，皆具有極高的耐受性（＞18000 NTU）。
模式生物檢測方法建立研究：（1）建立斑馬魚胚胎毒性檢測方法；（2） 建立細菌螢光急毒性檢測方法；（3）建立短角異劍水蚤無脊椎海水生物急毒性檢測方法；（4） 建立日本青鱂魚淡水及海水水質生物急毒性檢測方法。後續進行參考毒物試驗及實際放流水檢測，結果顯示具有好的生物毒性檢測反應。
工業放流水毒性鑑定方法建立研究：我們參考國外研究建立適用於台灣工業放流水毒性鑑定程序。表明運用於水體毒性成因鑑定及評估的潛力。結果證實利用化學分析及生物毒性分析水樣，雙向評估鑑定毒化物之可行性，可改善及彌補台灣現在的工業廢水毒性鑑定方法及生物輔助檢測方式，並強化管制河川放流水監測機制。
放流水（潛在性毒物）的環境宿命研究：利用毒性鑑定評估程序與歐盟毒性效應導向分析方法結合，並以斑馬魚胚胎毒性檢測方法為輔助，有效鑑定及評估水體及沉積物中潛藏毒化物。
最後建議：（1）慎選生物毒性試驗測試生物，靈敏度須有所差異。（2）研發結合毒性鑑定評估流程及效應導向分析方法，鑑定工業廢水生物毒性及毒物。（3）研發自動化和智慧化的生物毒性方法，包括急毒性和慢毒性，以持續提升方法績效和數據品質。（4）研發生物化學和細胞基礎的高通量快篩測試方法及建置相關核心技術。（5）研發計算毒理技術及建置相關軟體設備，朝向預測和預防毒理學目標邁進。

關鍵字

工業放流水 ； 水蚤 ； 羅漢魚 ； 斑馬魚胚胎 ； 費氏弧菌 ； 短角異劍水蚤 ； 青鱂魚 ； 毒性鑑定評估 ； 效應導向分析

並列摘要

This study is aimed at industrial wastewater, and distinguishes industrial park manufacturers' discharge water（potential chemical substances）assessment, Establishment of model bioassay method, industrial discharge water toxicity identification, and environmental fate of sewage treatment plant discharge water （potential poisons）. 5 major research spindles.
Industrial discharge water evaluation: heavy metal selection of copper sulfate, zinc sulfate, cadmium sulfate, gallium sulfate, indium sulfate, copper nitrate, cadmium nitrate, lead nitrate, molybdenum trioxide and other metal salts represent the main poison of the discharged water, as a reference poison to the water Biotoxicity tests were carried out on D.magna and Pseudorasbora parva and zebrafish embryos. The results show that copper nitrate is the most serious biological toxicity. Organic pollutants （tetramethylammonium hydroxide and 4-chlorophenol）and heavy metal pollutants （copper sulfate）to prepare bio-toxic artificial water samples. The toxicity of three poisons to D.magna and Pseudorasbora parva is: copper sulfate > 4-Chlorophenol > Tetramethylammonium hydroxide. Use（1）tetramethylammonium hydroxide / 4-chlorophenol,（2）tetramethylammonium hydroxide / copper sulfate,（3）4-chlorophenol / copper sulfate, and（4）tetramethylammonium hydroxide / 4-Chlorophenol / copper sulfate for mixed toxicity test. For D.magna and Pseudorasbora parva , the toxicity of 4-chlorophenol/copper sulfate is the strongest and synergistic effect occurs. The toxicity of sulphur（sodium hypochlorite, hydrogen peroxide）to D.magna and Pseudorasbora parva is: sodium hypochlorite > hydrogen peroxide; the acid and alkali resistance of D.magna and Pseudorasbora parva are pH 5.4 ~ 10.2 and pH 4.2 ~ 10.8, respectively. Both species have extremely high tolerance（>18000 NTU）for the turbidity produced by Silicon dioxide and calcium fluoride.
Establishment of model bioassay method:（1）Zebrafish embryo toxicity detection method;（2）Bacterial fluorescence acute toxicity detection method;（3）Apocyclops royi invertebrates marine acute toxicity detection method;（4）Method for detecting acute toxicity of freshwater and seawater in medaka. Subsequent reference poison tests and real industrial drain water tests showed good biotoxicity detection reactions.
Study on the method for the identification of industrial discharge water toxicity: We have established a procedure for the identification of industrial discharge water toxicity in Taiwan. Indicates the potential for identification and assessment of the cause of water toxicity. The results confirmed that chemical analysis and biological toxicity analysis of water samples, two-way evaluation of the feasibility of identifying poisons, can improve and make up for Taiwan's industrial wastewater toxicity identification methods and biological detection methods, and control the river discharge water monitoring mechanism.
Environmental fate study of released water（potential poisons）: The toxicity assessment procedure is combined with the Effect-Directed Analysis method, and the zebrafish embryo toxicity test method is used as a supplement to effectively identify and evaluate potential poisons in water bodies and sediments.
Final recommendations:（1）Careful selection of biological toxicity test test organisms, sensitivity must be different.（2）Research and development combined with toxicity identification evaluation process and effect-oriented analysis method to identify industrial wastewater biological toxicity and poison.（3）Automation and intelligent biotoxic methods, including acute toxicity and chronic toxicity, to continuously improve method performance and data quality.（4）Research and development of biochemical and cell-based high-throughput fast screening test methods and related core technologies.（5）Research and development of toxicology technology and the establishment of related software equipment, towards the goal of predicting and preventing toxicology.

並列關鍵字

Industrial Discharge Water ； Daphnia magna ； Pseudorasbora parva ； Zebrafish embryos ； Aliivibrio fischeri ； Apocyclops royi ； Oryzias latipes ； Toxicity Identification Evaluation ； Effect-Directed Analysis

參考文獻

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