以極致液相層析/串聯式質譜術定量食品中之有機污染物

人類可能藉由食物的攝取暴露於各種食物生產過程中的污染物，例如殺蟲劑與工業污染物，進而產生危害。因此，為了確保消費者的安全，全面的食物安全檢測極為重要。非標的性分析和標的性定量分析的整合被描述為一種可以快速篩檢和定量食品中出現的環境污染物。先前的研究以超高效能液相層析搭配四極桿-飛行時間串聯式質譜儀(UHPLC-QTOF-MS) 進行對食物中化學污染物殘留之篩查。該研究也針對篩查出之化學物質，以其各種資料做為參考依據，建置了優先化學品清單。先前的研究僅限於非標的性分析；因此，本研究旨在延續之前的研究，使用了極致液相層析/串聯式質譜儀(UPLC-QqQ-MS) 定量先前研究已優先化之物質，以確定食物中關注化學物質的濃度。先前已優先化之物質包括11種農藥，10種人類與動物用藥，4種食物添加劑，3種蒽醌類物質，2種有機磷系阻燃劑，1種黴菌毒素，1種塑化劑及1種工業化學物，共33種化學物質。本研究個別從台北市區、彰化縣大二林地區及連江縣南竿鎮採集了23項食材(7種蔬菜、7種海鮮、3種肉類、豬肝、蛋、奶、米、麵粉、黃豆)。三地區個別採集一次，採集了共127個樣本進行食物中化學污染物殘留之定量分析。為了與先前非標的性分析研究之定性結果做比較，彰化縣與連江縣之食物樣本的採樣管道皆與之前相同，並在此基礎上增加了台北市之採樣。採買時間分別為2022年2月至2022年3月。為了達到與先前研究的一致性，本研究應用了先前優化之樣本萃取及淨化方法。食物樣本以QuEChERS方法萃取，PRiME HLB cartridge淨化後，使用了Waters I-Class PLUS極致液相層析(ultra-performance liquid chromatography, UPLC)搭配Waters Xevo TQ-XS串聯式質譜儀，以 ESI+ 與 ESI- 游離對該33個優先化合物進行定量分析。其UPLC 和 MS 參數經過優化後，使用了 Waters CORTECS (30 × 2.1 mm, 1.6 μm)層析液相管柱，有機動相為甲醇，水性動相為5-mM醋酸銨溶液 (pH 6.44)，梯度流析流速0.4 mL/min。檢量線的線性範圍為 0.1 至 500 ng/mL。本研究也針對先前研究之 QuEChERS 方法進行方法確效，27中待測物在食物中的基質效應大致為60–140%，萃取效率為40–70%。大部分物質之同日和異日回收率在80–120%，且變異係數 (CV%)低於20%。對於真實樣本分析為藉由通過與標準品比對在食物中測的化學物質之2個離子對 (2個產物離子) 和層析波峰的滯留時間來確認，且滯留時間的漂移容忍度為 0.1分鐘。實際樣本分析結果顯示，農藥是殘留於蔬菜中的主要環境污染物，但殘留濃度普遍低於2 ng/g。在蔬菜中檢測到含量最高的農藥是賓克隆（在白菜中殘留量為 367 ng/g）。工業化學物、飼料添加劑和人類與動物用藥是海鮮產品中的主要污染物。此研究也32 個海鮮樣本中7個樣本中檢測出松香酸（檢測濃度為 23.0 - 88.8 ng/g）。除此之外，在40%的鮭魚樣品中檢測到衣索金，平均濃度為 14.8 ng/g。對於穀物和塊根作物樣本，此研究分別在 17 個樣本中的 5 個樣本和 8 個樣品中檢測出蒽醌類物質和有機磷系阻燃劑。工業化學品，例如松香酸和己二酸二(2-乙基己基) (DEHA) 酯遍存在於畜禽產品中。 6個豬肝樣本中的5個樣本被檢測出松香酸，平均濃度為 410 ng/g，31個的畜禽產品樣本中的23個被檢測出 DEHA，濃度範圍為0.42 到 38.7 ng/g。本研究結果發現大部分食物樣本含有被先前研究排序優先之化學物，證明了非標的性篩查在食物中應用的可行性。此外，大部分農藥殘留皆符合最大殘留容許量標準 (MRL)，表明了日常生活食物中的污染物暴露風險較低。綜合上述結果證明了非標的性篩查與標的性定量分析的整合適用於分析食物中多重污染物殘留。

關鍵字

有機污染物；食品； PRiME HLB ；極致液相層析/串聯式質譜儀；定量分析

並列摘要

Humans may be exposed to different contaminants, including pesticides and industrial chemicals, through food consumption due to contamination in various stages of food production. As a result, a comprehensive protocol for monitoring chemical substances in food is required to ensure consumer safety. The combination of non-target screening and target analysis was described as a strategic approach that consists of identifying and quantifying emerging environmental pollutants in food. The workflow of suspect screening of organic contaminants in food using ultra-high performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS) was developed in the previous study. The chemicals identified by the suspect screening were ranked and prioritized by taking empirical data and external information of the chemicals into consideration. The scope of the previous study was limited to non-target analysis. Therefore, this study aimed to continue from previous work by quantifying the previous prioritized chemicals using ultra-performance liquid chromatography/tandem mass spectrometry (UPLC-QqQ-MS) in food. The 33 previous prioritized chemicals included 11 pesticides, 10 human and veterinary medicines, four food additives, three fungal anthraquinones, two organophosphate flame retardants, one mycotoxin, one plasticizer, and one industrial chemical. A total of three batches of food samples (127 samples) were collected in Taipei, Changhua, and Matsu from February 2022 to March 2022. Twenty-three types of food were obtained in the above three areas, including seven vegetables, seven seafood, three types of meat, pork liver, egg, milk, rice, flour, and soybean. Sampling sites and vendors were the same as in the previous study of qualification analysis (Changhua County, Lienchiang County), with the addition of Taipei City in this study. The sample preparation method optimized in the previous study was applied in this study to quantify the 33 prioritized compounds. The homogenized samples were extracted with QuEChERS and cleaned up with PRiME HLB, then according to the results of previous results, 33 compounds were selected for further targeted quantitative analysis. The analytes were measured using Waters UPLC I-Class PLUS coupled with a Waters Xevo TQ-XS tandem mass spectrometer (UPLC-MS/MS) at positive electrospray ionization (ESI+) and negative electrospray ionization (ESI-). UPLC and MS parameters were fully optimized and Waters CORTECS C18 column (30 × 2.1, 1.6 μm) with mobile phases of (A) 5-mM ammonium acetate(aq) (pH 6.44) and (B) methanol were used at a flow rate of 0.4 mL/min. The linear ranges of calibration curves were from 0.1 to 500 ng/mL, with the correlation of determination (r2) greater than 0.990. The optimized QuEChERS methods were validated for matrix effects, extraction efficiencies, intra-day, inter-day accuracy and precision. The general matrix effects and extraction efficiencies of the 27 analytes ranged from 60 to 140% and 40 to 70%, respectively. Most analytes have recoveries of inter- and intra-day of 80-120% and coefficient of variation (CV%) below 20%. For real sample analysis, the identity of the analytes was confirmed by two MS/MS transitions (2 product ions of precursor ion), and the difference of retention time between the detected analytes and standard substances must not exceed the tolerance limit of 0.1 min. For real sample analysis, pesticides were the major types of environmental pollutants detected in vegetables, and the concentrations were generally lower than 2 ng/g. The highest level of pesticides detected in vegetables was pencycuron (367 ng/g in bokchoy). Industrial chemicals, feed additives, and human and veterinary drugs were the main pollutants in seafood products. Abietic acid was detected in 7 out of 32 seafood samples (ranged from 23.0 to 88.8 ng/g), and ethoxyquin was detected in 40% of salmon samples with an average concentration of 14.8 ng/g. For grains and root crops, fungal anthraquinones and OPFRS were detected in 5 samples out of 17 samples and 8 samples out of 17 samples, respectively. Industrial chemicals, abietic acid, and DEHA were prevalent in livestock and poultry products. 5 out of 6 pork liver samples have detected abietic acid with an average concentration of 410 ng/g, and 23 out of 31 of all livestock and poultry products have detected DEHA, ranged from 0.42 to 38.7 ng/g. All samples have been discovered with substantial concentrations of contaminants, and compounds flagged as prioritized chemicals previously were generally found to have residue in food samples in this study. This result indicates that suspect screening is a feasible approach to facilitate the detection of organic contaminants in food by reducing the time and money spent on identifying all potential organic contaminants in food. Furthermore, most of the pesticide residuals in food commodities in this study complied with the MRL requirements, suggesting that the exposure risks of these contaminants were low in our daily life. All the above findings proved that the combination of suspect screening and target quantification analysis was fit to evaluate a variety of organic compounds in food samples.

並列關鍵字

Organic contaminants ； food ； PRiME HLB ； UPLC-QqQ-MS ； target analysis ； quantification

參考文獻

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