(I)應用幾丁聚醣結合SPME來處理及分析水中有機氯殺蟲劑(II)使用HFM-SPME分析牛奶中有機氯殺蟲劑

(I)Application of chitosan beads combined with SPME for the determination and treatment of organochlorine pesticides in water(II)Using hollow fiber membrane-protected SPME to determine the of organochlorine pesticides in bovine milk

王成一(Chang-I Wang)

指導教授 ： 薛文發

淡江大學/理學院/化學學系碩士班/碩士(2009年)

https://doi.org/10.6846/TKU.2009.00306

摘要

第一部分：
本研究使用固相微萃取法(簡稱SPME)結合蟹殼(Crab shell)與幾丁聚醣(Chitosan)來分析及處理水中之有機氯殺蟲劑(Organochlorine pesticides)。二次大戰後，有機氯殺蟲劑成為防治病蟲害與消滅傳染病的對最大利器，但不易分解之特性，卻是造成今日生態環境殘留問題的主因。現有針對有機氯殺蟲劑的處理與去除，多採用物理吸附及生物轉化、分解等方式。本研究則利用具多孔性之生物高分子蟹殼與幾丁聚醣，來處理水樣中有機氯殺蟲劑之殘留。所使用之有機氯殺蟲劑包含α-HCH、β-HCH、γ-HCH、δ-HCH、Heptachlor、Aldrin、Heptachlor epoxide isomer B、α-Endosulfan、4,4'-DDE、Dieldrin、Endrin、β-Endosulfan、4,4'-DDD、Endrin aldehyde、Endosulfan sulfate、4,4'- DDT、Endrin ketone與Methoxychlor等十八種。
將經蟹殼與幾丁聚醣處理後之水樣，利用65 μm PDMS/DVB纖維針，以頂空(Headspace)與直接浸入(Direct immersion)兩種方式對同一樣品採樣，並以氣相層析儀(GC)搭配電子捕獲偵測器(ECD)進行分析與偵測。實驗結果發現，含有機氯殺蟲劑(2.8 ng)之水樣經蟹殼處理後，其中十七種殺蟲劑之去除率可達100％；含有機氯殺蟲劑(2.8 ng)的水樣經幾丁聚醣處理後，其中十六種殺蟲劑之去除率可達100％，另外一種達99.3％。因此，蟹殼、幾丁聚醣對於水中有機氯殺蟲劑之處理，不僅效果顯著且兼具多樣性，亦因蟹殼成本低廉、取得容易，就環保觀點來說，確實可以加以應用與開發；而結合固相微萃取法不同的採樣方式，對於分析揮發性相對較低的有機氯殺蟲劑，更能夠提供完整的結果。

第二部分：
本研究使用中空纖維薄膜保護式固相微萃取法(Hollow fiber membrane-protected SPME，簡稱HFM-SPME)來分析牛奶中之有機氯殺蟲劑(Organochlorine pesticides)。有機氯殺蟲劑雖已禁用多年，但不易分解與親脂性之特性，於生物體之脂肪、血液、尿液、糞便、精液和母奶仍能發現其蹤跡。本研究將利用65 μm PDMS/DVB纖維針，以HFM-SPME方式對牛奶樣品採樣，並結合氣相層析儀(GC)搭配電子捕獲偵測器(ECD)進行分析與偵測，來建立一套精確且有效的分析方法。實驗中所使用之有機氯殺蟲劑包含α-HCH、β-HCH、γ-HCH、δ-HCH、Heptachlor、Aldrin、Heptachlor epoxide isomer B、α-Endosulfan、4,4'-DDE、Dieldrin、Endrin、β-Endosulfan、4,4'-DDD、Endrin aldehyde、Endosulfan sulfate、4,4'- DDT、Endrin ketone與Methoxychlor等十八種。
HFM-SPME最佳化條件之測試，包括萃取溫度、萃取時間、鹽類濃度與pH值。實驗結果發現，最佳化之萃取溫度為100℃、萃取時間為60分鐘、鹽類濃度為1%(w/v)、pH值則為6.6。而在此條件下，採樣含有機氯殺蟲劑之零脂牛奶，可萃取到16種；採樣含有機氯殺蟲劑之全脂牛奶，則可萃取到11種。由此可知，中空纖維薄膜與SPME的搭配使用，不僅達到對含複雜基質的樣品萃取，更能保護萃取纖維針，延長使用時間。

關鍵字

固相微萃取法 ； 有機氯殺蟲劑 ； 頂空採樣 ； 直接浸入採樣 ； 中空纖維薄膜 ； 蟹殼 ； 幾丁聚醣 ； 牛奶

並列摘要

Part. I
A new method for analyzing and treatment of organochlorine pesticides (OCPs) in water by solid-phase microextraction (SPME) combined with crab shell and chitosan as an adsorbent is described. The OCPs can effectively control almost all kinds of pests including insect, fungi, rodent, etc. However, they continue to be detected in both biological and environmental samples worldwide because of their persistent and bioaccumulative properties. The present study is the first to use porous biopolymer crab shell and chitosan as an adsorbent for removal of the 18 kinds of OCPs remaining in the water samples. The OCPs standards in the study, including α-HCH、β-HCH、γ-HCH、δ-HCH、Heptachlor、Aldrin、Heptachlor epoxide isomer B、α-Endosulfan、4,4'-DDE、Dieldrin、Endrin、β-Endosulfan、4,4'-DDD、Endrin aldehyde、Endosulfan sulfate、4,4'- DDT、Endrin ketone and Methoxychlor.
We use the 65μm PDMS/DVB fibers and two ways sampling, headspace mode and direct immersion mode, to extract the OCPs from the treatment water samples. Finally, we inject the sample to the GC/ECD for analysis. According to experiments, the water samples after crab shell treatment, we find that seventeen kinds of OCPs can be effectively treatment to 100 % (2.8 ng). The water samples after chitosan treatment, we also find that sixteen kinds of OCPs can be effectively treatment to 100 % (2.8 ng), and the other one is 99.3 %. In this study, we present here the use of crab shell and chitosan have good result and multiplicity concurrently for the removal of OCPs present in water samples. It is easy for the crab shell to obtain and cheap cost, from the environmental protection view, can really use and develop.

Part. II
A method for analyzing of organochlorine pesticides (OCPs) in bovine milk by hollow fiber membrane-protected solid-phase microextraction (HFM-SPME) is described. Although most of OCPs have been banished from use for many years, they are still detected in organism adipose tissue, blood, urine, feces, sperm and breast milk because of their great chemical stability and lipid solubility. In this study, we use the 65μm PDMS/DVB SPME fibers and hollow fiber membrane-protected mode to extract the OCPs from bovine milk samples. After the sampling, then inject the sample to the GC/ECD for analysis. There are 18 kinds of OCPs standards in the study, including α-HCH、β-HCH、γ-HCH、δ-HCH、Heptachlor、Aldrin、Heptachlor epoxide isomer B、α-Endosulfan、4,4'-DDE、Dieldrin、Endrin、β-Endosulfan、4,4'-DDD、Endrin aldehyde、Endosulfan sulfate、4,4'- DDT、Endrin ketone and Methoxychlor.
HFM-SPME experimental parameters such as extraction temperature, extraction time, salt concentration and pH values were investigated and optimized. According to experiments, we choose that 100 ℃extraction temperature, 60 min extraction time, 1 %(w/v) salt concentration and pH 6.6 for the best response in HFM extraction mode. In this optimal parameters, we find that sixteen kinds of OCPs can be effectively extracted in skim milk samples and eleven kinds of OCPs in whole milk samples. We present here that HFM-SPME was an efficient pretreatment method and have good results for complex matrices samples.

並列關鍵字

Solid phase microextraction(SPME) ； Organochlorine pesticides ； Headspace mode ； Direct immersion mode ； Hollow fiber membrane-protected ； Crab shell ； Chitosan ； Milk

參考文獻

19.行政院環境保護署，毒性化學物質運送管理辦法修訂，2007年1月

91.洪東巽, 應用固相微萃取法配合蟹殼與幾丁聚醣來分析及處理水中有機氯殺蟲劑, 碩士論文, 淡江大學化研所, 2007

96.何美儀, (I)利用高效能液相層析法建立山藥及山楂的化學指紋圖譜(II)應用固相微萃取法配合幾丁聚醣來分析及處理水中的有機氯殺蟲劑, 碩士論文, 淡江大學化研所, 2006

39.Awasthi, N.; Singh, A. K.; Jain, R. K.; Khangarot, B. S.; Kumar, A. Appl. Microbiol. Biotechnol. 2003, 62, 279-283

9.Chao, H. R.; Wang, S. L.; Lin, T. C.; Chung, X. H. Chemosphere 2006, 62, 1774-1785