水產品中多種農藥殘留同時檢測新技術的開發及水產品取食風險評估

Abstract

本研究的目的有二：1.利用固相萃取(solid phase extraction)技術，建立各種水產品中，包括貝類(bivalve)、甲殼類(crustacean)、魚類(fish)及頭足類(cuttlefish)，多種農藥殘留同時檢測的技術。檢測藥劑包括胺基甲酸鹽類(carbamate)、有機氯類(organochlorine)、有機磷類(organophosphate)及合成除蟲菊類(synthetic pyrethroids)等4大類共91種的農藥，以簡化水產品中農藥殘留檢測的工作。2.利用所建立的水產品中多種農藥殘留檢測技術，針對市售各類水產品進行農藥殘留檢測，以評估殘留藥劑對消費者的健康風險。 在所建立的方法中，甲殼類及魚類樣品均質化時使用的溶劑為乙腈(acetonitrile)。貝類樣品則以水、丙酮(acetone)及乙腈組成的混合溶劑進行均質處理；頭足類樣品則須先添加水份打碎後，再以乙腈進行均質化。後兩者樣品，由於添加水份，在後續的萃取過程中，必須加入鹽析(salting out)步驟。每種方法的萃取液，均利用串聯的C18 及aminopropyl層析匣進行樣品的淨化，並以乙腈為唯一的淋洗溶液。最後，再以氣相層析儀(gas chromatography, GC)附電子捕擭式檢出器(electron capture detector, ECD)及火焰光度檢出器(flame photometric detector, FPD)、及液相層析儀(high performance liquid chromatography, HPLC) 附螢光檢出器(Fluorescence detector)進行分析。各類水產品農藥殘留分析方法適用性的確認，是評估樣品添加3種不同濃度之標準劑後的回收率。根據回收試驗結果，所有檢測藥劑中，除了1-naphthol、3-hydroxy carbofuran、aldicarb sulfoxide、heptachlor、trifuralin、acephate、dichlorvs、methamidophos、monocrotophos及omethoate共10個藥劑外，餘各藥劑在4類水產品中的回收率均在60-120%間，回收變異係數(coefficients of variation, CV) < 20%。本研究中所描述的水產品中農藥殘留的萃取和樣品淨化技術，有利於藥物殘留監測計畫中，農藥殘留的快速篩檢工作。 為探討水產品受農藥污染的情形及評估殘留農藥對人體健康危害風險，本研究進一步地，利用前述建立的水產品中多種農藥殘留同時檢測技術，針對市售水產品進行農藥殘留檢測及取食風險評估，樣品採集時間為2001至2003年，樣品種類涵蓋國人取食的5大類水產品，包括魚類、蝦類、貝類、蟹類及頭足類，進行4類共91種農藥殘留檢測。結果顯示，在魚類、貝類、甲殼類及頭足類樣品中，分別有65.40%、93.55% 、84.92% 及98.33%的樣品未測得有農藥的殘留(即檢出值低於檢測極限)。所有樣品中，雖然僅檢出有機磷及有機氯類藥劑的殘留，檢出藥劑僅有DDT及其代謝產物、dieldrin、chlorpyrifos、fenitrotion、fenthion及prothion等6種藥劑，但已證實消費者取食水產品確實有暴露於殘留農藥的風險存在。然而，與世界糧農組織所訂定的各藥劑的每人每日可攝取量(acceptable daily intakes, ADIs)相較，國人經由取食水產品暴露於殘留農藥的量，仍低於ADI值，其中以男性暴露於dieldrin的風險為最高，佔ADI值的93.56%。本研究亦建議，除了例行性地魚體中有機氯類藥劑殘留監測外，魚體中有機磷類藥劑殘留監測工作，亦值得重視。

In order to simplify the survey of pesticide (including carbamate, organochlorine, organophosphate and synthetic pyrethroid pesticides) residues in fishery products (including bivalve, crustacean, fish and cuttlefish), multiresidue determination methods were developed through a solid phase extraction (SPE) technique. In the present procedures, samples were extracted with acetonitrile except for bivalve and cuttlefish samples. Mixed solvent of water, acetone and acetonitrile was added to bivalve prior to homogenization, whereas water was needed in cuttlefish samples for blending. For both kinds of sample, an additional procedure of salting-out was needed during extraction. Tandem SPE cartridges of C18 and aminopropyl, using acetonitrile as the only solvent, were used to clean up extracts from either method. A total of 91 pesticides in four major pesticide groups were tested in this study. Gas chromatography (GC, equipped with electron capture detector and flame photometric detector) and high-performance liquid-chromatography (HPLC) equipped with fluorescence detector were used for analysis. The validation of the method was evaluated for each fishery product using samples spiked with all pesticide standards at three concentration levels. The results indicated percentage of recovery ranged from 60% - 120% and coefficients of variation < 20% for all but 10 of the pesticides analyzed (including 1-naphthol, 3-hydroxy carbofuran, aldicarb sulfoxide, heptachlor, trifuralin, acephate, dichlorvs, methamidophos, monocrotophos and omethoate). Residue extraction techniques described in this report are rapid and suitable for screening of pesticide residues in monitoring programs. For assessment of consumer’s exposure to pesticide residues in fisheries products, the methos described above were used. The fisheries products in this study comprise fish, bivalve, crustacean and cephalopod collected from different types of market in Taiwan between the years of 2001-2003. A total of ninety-one pesticide residues belonging to four major pesticide groups were tested and analyzed. The test results show that 65.40% of fish, 93.55% of shellfish, 84.92% of crustacean and 98.33% of cephalopod samples contain no detectable residues. There are only two kinds (organochlorine and organophosphate) of totally six pesticides (DDTs, dieldrin, chlorpyrifos, fenitrotion, fenthion and prothion) that have been detected from the fisheries products in this study. For there were pesticides present in the fish products, consumption of fisheries product there was no zero risk. But the exposure of consumer did not exceed the acceptable daily intakes (ADI). For male, there was the highest risk in exposure to dieldrin, which the percentage of ADI was 93.56%. This study also suggests that a yearly monitoring program for organophosphate pesticide residues in fish is necessity.