EPA-102-1604-02-03

102

2,200 千元

2013/04/22

2013/12/31

陳家揚

環檢所

趙春美

國立臺灣大學

環境監測及檢測

液相層析串聯式質譜儀;土壤;底泥

LC-MS/MS;soil;sediment

龍世俊

陳家揚

02-33668101#

dbms@ntu.edu.tw

農藥、酚類（尤其是氯酚）、塑化劑、有機錫等之廣泛施用，可經由雨水沖刷或空氣沈降至河川、地下水及土壤等環境中。多環芳香烴亦能經由交通污染或燃燒源透過空氣散佈至他處，沉積於底泥或土壤。上述化合物在處於土壤或底泥的厭氧環境中，可能導致其於環境之持久性，因而土壤與底泥中之化合物殘留，較適合代表環境中較為長期之污染趨勢。 本研究開發以極致液相層析-質譜/質譜儀(UPLC-MS/MS)偵測土壤與底泥中有機磷類(11種)、氨基甲酸鹽類(5種)、合成除蟲菊精類(7種)、酚類(16種)、塑化劑(8種)、多環芳香烴(24種，包含16個環保署優先多環芳香烴)、有機錫(8種)等共79個重要環境污染物之方法。土壤與底泥先經由QuEChERS前處理後，於液相層析搭配串聯式質譜儀以電灑游離（ESI）或大氣壓力光游離法（APPI）分析;農藥和塑化劑於ESI+ 選用Phenomenex Kinetex PFP 管柱 (2.6 μm, 50 × 2.1 mm)， 酚類於ESI- 選用Waters Cortecs UPLC C18 管柱 (1.6 μm, 30 × 2.1 mm) ，以及多環芳香烴於 APPI+ 選用Restek Pinnacle DB PAH UHPLC管柱 (1.9 μm，50 × 2.1mm) 進行層析分離。有機錫類待測物雖可於質譜儀在ESI+及APPI+中被偵測到，但接上液相層析後則只有Fenbutatin oxide (芬佈賜) 和 Triphenyltin (三苯基錫) 能在不同濃度標準品下會出現進樣量與訊號強度的正相關。因有機錫類的待測物易黏附在質譜儀進樣錐 (cone) 上面，使得進行分析時需常清洗cone，恐有損儀器;建議未來有機錫之分析改採其他層析方式，例如衍生後由氣相層析/質譜儀分析。 本研究亦進行比較傳統之超音波萃取與新開發之QuEChERS用於土壤與底泥之萃取效率。QuEChERS萃取回收率較超音波萃取佳，尤其對於多環芳香烴類。各待測物土壤和底泥 (溼重) 之方法偵測極限範圍為20 - 120 ng/g和 30 - 180 ng/g; 大部分待測物檢量線的範圍皆能達r2=0.990以上。大部分待測物之基質效應因子約為45-88%，但利用穩定同位素標定內標準品校正可使大部分待測物的達良好的回收率。為驗證分析方法之適用性，本研究分析11個底泥、2個民生污水廠污泥、9個土壤樣本等共22件實際樣本，以瞭解71種重要環境污染物於土壤和底泥之背景殘留;底泥及土壤中塑化劑與多環芳香烴類檢出濃度及檢出率較高;農藥中護粒松 (Edifenphos)及加保利(Carbaryl)有檢出。除了自行添加之樣本外，本研究也使用認證參考樣本進行方法驗證。本研究建立IPR (Initial precision and recovery) 和檢測方法草案，供計畫委託單位參考。

液相層析串聯式質譜儀;土壤;底泥

EPA-102-1604-02-03.pdf

3MB

期末報告定稿本

2014/2/1 上午 12:00:00

Pesticides, phenols (e.g. chlorophenols), phthalates, and organotins are heavily used, and polycyclic aromatic hydrocarbons (PAHs) are emitted ubiquitously from transportation and combustion sources. The above chemicals may run off or via wet or dry deposition to the river, ground water, sediment, and soil. Since most conditions in soil and sediment are anaerobic, the above compounds may exist in the environment persistently; consequently, the residue level in soil or sediment may represent a long term trend of pollution. This study developed a method for detecting 79 important environmental pollutants, including 11 organophosphates, 5 carbamates, 7 pyrethroids, 16 phenols, 8 phthalates, 24 PAHs (containing the 16 EPA priority PAHs), and 8 organotins, in soil and sediment, using ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). Soils and sediments samples were treated with QuEChERS and the extracts were analyzed using UPLC-MS/MS with electrospray ionization (ESI) or atmospheric pressure photoionization (APPI). Pesticides and phthalates were separated with a Phenomenex Kinetex PFP column (2.6 μm, 50 × 2.1 mm) at ESI positive mode; phenols were separated with a Waters Cortecs UPLC C18 column (1.6 μm, 30 × 2.1 mm) at ESI negative mode, and PAHs were separated with a Restek Pinnacle DB PAH UHPLC column (1.9 μm，50 × 2.1mm) at APPI positive mode. The organotins could be detected at ESI and APPI positive modes, while the linearity of calibration cureves of organotins were not so good except for fenbutatin oxide and triphenyltin. Furthermore, the organotins tend to accumulate on the cone of the MS ionization probe, resulting in a need of fragment clean up on the cone; this may damage the instrument. Other detection methods, such as the use of GC-MS with chemical derivatization, were suggested for the analysis of organotins. This study compared the extraction efficiency of QuEChERS and sonication extraction in soil and sediment, and the former was better than the latter. The limits of detection of soil and sediment ranged from 20 to 120 ng/g (wet weight) and 30 to 180 ng/g (wet weight),respectively. The square of regression coefficients (r2) of calibration curves were higher than 0.990. The matrix effect factors of analytes were between 45-88%, and the use of isotope-labeled internal standards can cancel out the effects on quantitation resulting from matrix effects or variations of extraction efficiency, then reached good recoveries. Spiked samples and certified reference materials were used for method validation; 22 real samples, including 11 sediments, two sludge from a water treatment plant, and 9 soils, were also analyzed for method validation. Phthaltes and PAHs were in higher positive rates and the pesticide Edifenphos and Carbaryls were detected in the real samples.The results of this study can be used to establish the initial precision and recovery (IPR) and a draft of standard analytical procedure for the National Institute of Enviromental Analysis.

LC-MS/MS;soil;sediment