巴拉刈工廠4,4'-雙吡啶原料及其廢水之分析

Analysis of Components of Waste Water and Raw Materials from Three Paraquat Manufacturing Factories

郭憲文(Hsien-Wen Kuo) ； 王榮德(Jung-Der Wang)

《中華民國公共衛生學會雜誌》 11卷4期 (1992/12) Pp. 269-276

https://doi.org/10.6288/JNPHARC1992-11-04-01

摘要

台灣地區自民國七十二年發生部份巴拉刈作業員工罹患皮膚癌前期症狀以來，此種致皮膚癌因子是否爲4,4'-雙吡啶及其異構物，或者范狀不純物至今尚無定論，而巴拉刈工人經常所接觸之合成原料及排放廢水之物質，是否含有這些物質，一直缺乏分析測量資料。故本研究旨在分析巴拉刈工廠所使用之原料及其排放之廢水，以作爲未來研究巴拉刈工人致癌因子之參考。
本研究係利用高效率液相層析法(HPLC)，分析4,4'-雙吡啶及其異構物，其適當分析條件流動相爲15/85氰甲烷／30mM磷酸銨溶淤二次去離子水，以磷酸調整酸鹼值爲4.6，流速1.0ml/min，管柱爲Inertial ODS-2。分析廢水之結果得知含有4,4'-雙吡啶爲147.6μg/ml吡啶爲0.90μg/ml及2,3-雙吡啶爲14.56μg/ml，2,4-雙吡啶爲43.6μg/ml，另外有少量疑似皮膚致癌物的奎諾林之衍生物(Quinoline derivatives)，此物已經由氣相層析／質譜儀鑑定證實。至於國內自行合成之4,4'-雙吡啶，其產品內容物與廢水大致類同，而國外進口之4,4'-雙吡啶原料中，並未含有奎諾林之衍生物及2,4-雙吡啶，且其純度較前者低。由於僅從事國外進口之4,4'-雙吡啶相關作業者，其工人亦有輕微之皮膚黑斑症狀，類似致癌之最初期變化；故我們推測從前廢水中仍有奎諾林之衍生物，但皮膚變化卻不能單由它來解釋；可能至少也需有雙吡啶之參與。

關鍵字

4,4'-雙吡啶 ； 巴拉刈工廠 ； 原料 ； 廢水

並列摘要

The procedure of high performance liquid chromatography (HPLC) for the determination of bipyridyl derivatives in waste water and raw materials of paraquat manufacturing factories is described. Samples were collected from three paraquat factories in Taiwan. One of the three factories (factory A) produces self-synthesized paraquat products by the high temperature sodium process, while the others directly imported 4, 4'-bipyridine from the ICI Corp, and then formulated paraquat products with methyl chloride. Samples were extracted with methanol and then purified by passing them through a SEP-PARK(superscript ®) C18 cartridge (Waters Associates). Reverse phase HPLC with an ultraviolet detector was developed to analyze the above material by comparing it with a mixture of standard solutions of six bipyridyl derivatives. All samples were further verified by a GC/MS (Gas Chromatography/Mass Spectrometry) instrument. The results indicate that the waste water taken from Factory A contained 4,4'-bipyridine, pyridine, 2, 3-, 2,4-bipyridine and a quinoline derivative. Their concentrations in the waste water were 147.6 mg/mL, 0.90 mg/mL, 14.5 mg/mL, 43.6 mg/mL and 12.4 mg/mL, respectively. The raw materials imported by the other two factories also contained 4,4'-bipyridine, pyridine, and 2,3-bipyridine, but did not contained the quinoline derivative or 2,4-bipyrid- me. Although quinoline is a known carcinogen, two workers who were only exposed to imported 4,4'-bipyridine still developed freckles, we conclude that the quinoline derivative alone may not be responsible for the development of skin lesions among workers, but rather, 4,4'-or 2,4-bipyridine, or a combination of all of them may be the cause.

並列關鍵字

4,4'-bipyridine ； paraquat factory ； waste water ； quinoline derivative