A reliable, sensitive, and efficient method was developed for routine analysis of perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) in various edible crop matrices including cereal (grain), root vegetable (carrot), leafy vegetable (lettuce), and melon vegetable (pumpkin). The target analytes were extracted by ion-pair approach followed by solid-phase extraction clean-up and HPLC-MS/MS. The type of extraction solvent, clean-up cartridge, and the usage of Supelclean graphitized carbon were evaluated to reach an optimized pretreatment procedure. The matrix-matched standard calibrations relative to the isotope-labeled internal standard were used in the developed method to obtain more reliable quantitative results. The average recoveries at four spiked levels (0.5, 10, 25, 50 ng/g) in the diverse matrices ranged from 70.9 to 114.6% with relative standard deviations (RSD) lower than 11.5%. The matrix-dependent method detection limits using the common equipment (HPLC-MS/MS) were between 0.020 and 0.140 ng/g (dw), equivalent to the 3–130 pg/g (fw), corresponding to the sensitivity of superior equipment (e.g., UPLC-MS/MS and HPLC-QTOF-HRMS). Furthermore, the developed method was conferred with the practicality through determination of the analytes in actual crops sampled from several farms in China’s Pearl River Delta.
This is a preview of subscription content, log in to check access
Compliance with Ethical Standards
The manuscript has not been published previously (partly or in full). The manuscript has not been submitted to more than one journal for simultaneous consideration. Consent to submit has been received explicitly from all co-authors, as well as from the institute/organization where the work has been carried out, before the work is submitted. Authors whose names appear on the submission have contributed sufficiently to the scientific work and therefore share collective responsibility and accountability for the results.
This work was funded by the National Natural Science Foundation of China (41573093), the NSFC-Guangdong Joint Fund (U1501233), the Research Team Project of the Natural Science Foundation of Guangdong Province (2016A030312009), the project on the Integration of Industry, Education and Research of Guangdong Province (2015B090903070 and 2013B0906001), the Program of the Guangdong Science and Technology Department (2016B020242005 and 2015B020235008), and Guangdong college student’s research fund (pdjh 2016a0052).
Conflict of Interest
Lei Xiang declares that he has no conflict of interest. Teng-Fei Sun declares that she has no conflict of interest. Lei Chen declares that he has no conflict of interest. Tao Xiao declares that he has no conflict of interest. Quan-Ying Cai declares that she has no conflict of interest. Hui Li declares that she has no conflict of interest. De-Chun He declares that he has no conflict of interest. Ming-Hung Wong declares that he has no conflict of interest. Yan-Wen Li declares that she has no conflict of interest. Ce-Hui Mo declares that he has no conflict of interest.
This article does not contain any studies with human participants or animals performed by any of the authors.
Informed consent is not applicable.
Ballesteros-Gómez A, Rubio S, van Leeuwen S (2010) Tetrahydrofuran–water extraction, in-line clean-up and selective liquid chromatography/tandem mass spectrometry for the quantitation of perfluorinated compounds in food at the low picogram per gram level. J Chromatogr A 1217:5913–5921CrossRefGoogle Scholar
Blaine AC, Rich CD, Hundal LS, Lau C, Mills MA, Harris KM, Higgins CP (2013) Uptake of perfluoroalkyl acids into edible crops via land applied biosolids: field and greenhouse studies. Environ Sci Technol 47:14062–14069CrossRefGoogle Scholar
Ciccotelli V, Abete MC, Squadrone S (2016) PFOS and PFOA in cereals and fish: development and validation of a high performance liquid chromatography-tandem mass spectrometry method. Food Control 59:46–52CrossRefGoogle Scholar
de Voogt P, Sáez M (2006) Analytical chemistry of perfluoroalkylated substances. TrAC Trend Anal Chem 25:326–342CrossRefGoogle Scholar
Ericson I, Domingo JL, Nadal M, Bigas E, Llebaria X, van Bavel B, Lindström G (2009) Levels of perfluorinated chemicals in municipal drinking water from Catalonia, Spain. Arch Environ Con Tox 57:631–638CrossRefGoogle Scholar
Felizeter S, McLachlan MS, De Voogt P (2014) Root uptake and translocation of perfluorinated alkyl acids by three hydroponically grown crops. J Agri Food Chem 62:3334–3342CrossRefGoogle Scholar
Haug LS, Thomsen C, Brantsaeter AL, Kvalem HE, Haugen M, Becher G, Alexandera J, Meltzera HM, Knutsena HK (2010) Diet and particularly seafood are major sources of perfluorinated compounds in humans. Environ Int 36:772–778CrossRefGoogle Scholar
Herzke D, Olsson E, Posner S (2012) Perfluoroalkyl and polyfluoroalkyl substances (PFASs) in consumer products in Norway—a pilot study. Chemosphere 88:980–987CrossRefGoogle Scholar
Houde M, De Silva AO, Muir DCG, Letcher R (2011) Monitoring of perfluorinated compounds in aquatic biota: an updated review. Environ Sci Technol 45:7962–7973CrossRefGoogle Scholar
Lacina O, Hradkova P, Pulkrabova J, Hajslova J (2011) Simple, high throughput ultra-high performance liquid chromatography/tandem mass spectrometry trace analysis of perfluorinated alkylated substances in food of animal origin: milk and fish. J Chromatogr A 1218:4312–4321CrossRefGoogle Scholar
Lechner M, Knapp H (2011) Carryover of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) from soil to plant and distribution to the different plant compartments studied in cultures of carrots (Daucus carota ssp. sativus), potatoes (Solanum tuberosum), and cucumbers (Cucumis sativus). J Agri Food Chem 59:11011–11018CrossRefGoogle Scholar
Li YW, Zhan XJ, Xiang L, Deng ZS, Huang BH, Wen HF, Sun TF, Cai QY, Li H, Mo CH (2014) Analysis of trace microcystins in vegetables using solid-phase extraction followed by high performance liquid chromatography triple-quadrupole mass spectrometry. J Agri Food Chem 62:11831–11839CrossRefGoogle Scholar
Llorca M, Farré M, Picó Y, Barceló D (2009) Development and validation of a pressurized liquid extraction liquid chromatography–tandem mass spectrometry method for perfluorinated compounds determination in fish. J Chromatogr A 1216:7195–7204CrossRefGoogle Scholar
Lu Z, Song L, Zhao Z, Ma Y, Wang J, Yang HZ, Ma HM, Cai MH, Codling G, Ebinghaus R, Xie ZY, Giesye JP (2015) Occurrence and trends in concentrations of perfluoroalkyl substances (PFASs) in surface waters of eastern China. Chemosphere 119:820–827CrossRefGoogle Scholar
Martínez-Moral MP, Tena MT (2013) Focused ultrasound solid–liquid extraction of perfluorinated compounds from sewage sludge. Talanta 109:197–202CrossRefGoogle Scholar
Picó Y, Farré M, Llorca M, Barceló D (2011) Perfluorinated compounds in food: a global perspective. Crit Rev Food Sci 51:605–625CrossRefGoogle Scholar
Poothong S, Boontanon SK, Boontanon N (2012) Determination of perfluorooctane sulfonate and perfluorooctanoic acid in food packaging using liquid chromatography coupled with tandem mass spectrometry. J Hazard Mater 205:139–143CrossRefGoogle Scholar
Powley CR, George SW, Ryan TW, Buck RC (2005) Matrix effect-free analytical methods for determination of perfluorinated carboxylic acids in environmental matrixes. Anal Chem 77:6353–6358CrossRefGoogle Scholar
Richardson SD (2011) Environmental mass spectrometry: emerging contaminants and current issues. Anal Chem 84:747–778CrossRefGoogle Scholar
Stahl T, Heyn J, Thiele H, Hüther J, Failing K, Georgii S, Brunn H (2009) Carryover of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) from soil to plants. Arch Environ Con Tox 57:289–298CrossRefGoogle Scholar
Taniyasu S, Kannan K, So MK, Gulkowska A, Sinclair E, Okazawa T, Yamashita N (2005) Analysis of fluorotelomer alcohols, fluorotelomer acids, and short-and long-chain perfluorinated acids in water and biota. J Chromatogr A 1093:89–97CrossRefGoogle Scholar
Ullah S, Alsberg T, Vestergren R, Berger U (2012) Determination of perfluoroalkyl carboxylic, sulfonic, and phosphonic acids in food. Anal Bioanal Chem 404:2193–2201CrossRefGoogle Scholar
Vestergren R, Ullah S, Cousins IT, Berger U (2012) A matrix effect-free method for reliable quantification of perfluoroalkyl carboxylic acids and perfluoroalkane sulfonic acids at low parts per trillion levels in dietary samples. J Chromatogr A 1237:64–71CrossRefGoogle Scholar
Xiang L, Wang XK, Li YW, Huang XP, Wu XL, Zhao HM, Li H, Cai QY, Mo CH (2015) Analysis of trace quaternary ammonium compounds (QACs) in vegetables using ultrasonic-assisted extraction and gas chromatography–mass spectrometry. J Agri Food Chem 63:6689–6697CrossRefGoogle Scholar
Yang L, Jin F, Zhang P, Zhang Y, Wang J, Shao H, Jin MJ, Wang SS, Zheng LF, Wang J (2015) Simultaneous determination of perfluorinated compounds in edible oil by gel-permeation chromatography combined with dispersive solid-phase extraction and liquid chromatography-tandem mass spectrometry. J Agri Food Chem 63:8364–8371CrossRefGoogle Scholar
Yang SW, Xu FF, Wu FC, Wang SR, Zheng BH (2014) Development of PFOS and PFOA criteria for the protection of freshwater aquatic life in China. Sci Total Environ 470:677–683CrossRefGoogle Scholar
Yoo H, Washington JW, Jenkins TM, Ellington JJ (2011) Quantitative determination of perfluorochemicals and fluorotelomer alcohols in plants from biosolid-amended fields using LC/MS/MS and GC/MS. Environ Sci Technol 45:7985–7990CrossRefGoogle Scholar
Young WM, South P, Begley TH, Noonan GO (2013) Determination of perfluorochemicals in fish and shellfish using liquid chromatography-tandem mass spectrometry. J Agri Food Chem 61:11166–11172CrossRefGoogle Scholar
Zabaleta I, Bizkarguenaga E, Iparragirre A, Navarro P, Prieto A, Fernández LÁ, Zuloaga O (2014) Focused ultrasound solid–liquid extraction for the determination of perfluorinated compounds in fish, vegetables and amended soil. J Chromatogr A 1331:27–37CrossRefGoogle Scholar
Zhang K, Wan Y, Giesy JP, Lam MHW, Wiseman S, Jones PD, Hu HY (2010) Tissue concentration of polybrominated compounds in Chinese sturgeon (Acipenser sinensis): origin, hepatic sequestration, and maternal transfer. Environ Sci Technol 44:5781–5786CrossRefGoogle Scholar