Determination of organophosphate flame retardants in soil and fish using ultrasound‐assisted extraction,solid‐phase clean‐up,and liquid chromatography with tandem mass spectrometry

A solid–liquid extraction method in combination with high‐performance liquid chromatography and tandem mass spectrometry was developed and optimized for extraction and analysis of organophosphorus flame retardants in soil and fish. Methanol was chosen as the optimum extraction solvent, not only in terms of extraction efficiency, but also for its broader analyte coverage. The subsequent clean‐up by solid‐phase extraction is required to eliminate matrix coextractives and reduce matrix effects. Recoveries of the optimized method were 50–121% for soil and 47–123% for biota, both with high precision (RSDs <12% in soil and <23% in biota). The method limits of detection ranged from 0.06 to 0.20 ng/g dry weight and between 0.02 and 0.30 ng/g wet weight for soil and biota samples, respectively. However, samples with a high lipid content produce several problems as solid‐phase extraction cartridge clogging that increase variability and analysis time. The method was successfully applied for the determination of organophosphorus flame retardants in soil and fish from L'Albufera Natural Park (Valencia, Spain). Target compounds were detected in all soil and fish samples with values varying from 13.8 to 89.7 ng/g dry weight and from 3.3 to 53.0 ng/g wet weight, respectively.     

Analysis of paroxetine, fluoxetine and norfluoxetine in fish tissues using pressurized liquid extraction, mixed mode solid phase extraction cleanup and liquid chromatography-tandem mass spectrometry

Recent studies have shown that selective serotonin reuptake inhibitors (SSRIs) such as fluoxetine are accumulated in the tissues of fish as a result of discharges of pharmaceuticals into surface waters from municipal wastewater treatment plants. In this study, an analytical method based on liquid chromatography with atmospheric pressure chemical ionization and tandem mass spectrometry (LC-APCI-MS/MS) was developed and validated for the determination of residues of paroxetine, fluoxetine and its active metabolite, norfluoxetine, in fish tissue. The procedure for sample preparation includes extraction of tissue by pressurized liquid extraction (PLE), followed by cleanup on a mixed-mode solid phase extraction (SPE) cartridge, Oasis MCX. With the optimized method, matrix interferences were reduced and recoveries >85% were obtained. The limits of quantitation (LOQ) determined by analysis of spiked fish tissue were 0.24, 0.07, and 0.14 ng/g wet weight for paroxetine, fluoxetine and norfluoxetine, respectively. This method was successfully applied to the analysis of samples of fish collected from Hamilton Harbour in Ontario, Canada, which is an urbanized and industrialized embayment of Lake Ontario. These analyses showed that the three analytes were present in fish tissues at concentrations up to approximately 1 microg/kg wet weight.     

The determination of 5 anticoccidial drugs (nicarbazin,lasalocid, monensin,salinomycin and narasin) in animal livers and eggs by liquid chromatography linked with tandem mass spectrometry (LC-MS-MS)

A method has been developed for the simultaneous extraction and determination of five of the most commonly used anticoccidial drugs (nicarbazin, lasalocid, monensin, narasin and salinomycin) from livers and eggs by LC-MS-MS. Results show good repeatability, with mean spiked recoveries for nicarbazin, lasalocid, monensin, narasin and salinomycin in poultry livers in the average range of 92-118%, and 86-110% in eggs. The detection limit is at 1 ng ml(-1) for all the named compounds and a quantitation level of 2.5 ng g(-1) has been achieved. A high throughput of samples is achievable using this method which allows the analysis of up to 40 samples by one analyst in a day.     

Evaluating polymer monolith in-tube solid-phase microextraction coupled to liquid chromatography/quadrupole time-of-flight mass spectrometry for reliable quantification and confirmation of quinolone antibacterials in edible animal food

A simple, rapid, and sensitive method is presented to determine seven trace quinolone antibacterials simultaneously in milk, egg, chicken and fish. This method is based on the combination of polymer monolith in-tube solid-phase microextraction with liquid chromatography and electrospray ionization quadrupole time-of-flight mass spectrometry (LC/ESI-QTOF-MS). LC/ESI-QTOF-MS offers the capability of unequivocal identification of target compounds from complex matrices, as well as the possibility of quantitation at low-level concentrations in real samples. The extraction was performed with a poly(methacrylic acid-ethylene glycol dimethacrylate) monolithic column. Under the optimized extraction conditions, good extraction efficiencies for the targets were obtained with no matrix interference in the subsequent LC/ESI-QTOF-MS. Good linearities were obtained for seven quinolones with the correlation coefficients (R) above 0.9951. The limits of detection (S/N = 3) for seven quinolones were found to be 0.3–1.2 ng/g in egg, 0.2–3.0 ng/mL in milk, 0.2–0.7 ng/g in chicken and 0.2–1.0 ng/g in fish. The recoveries of quinolones spiked in four different matrices ranged from 80.2 to 115.0%, with relative standard deviations less than 14.5%. The developed method was applied for the determination of quinolone residues in animal-producing food, and the positive samples were confirmed with high number of identification points (IPs) according to the IP system defined by the European Union (Commission Decision 2002/657/EC).     

Efficient and sensitive screening and confirmation of residues of selected polyether ionophore antibiotics in liver and eggs by liquid chromatography-electrospray tandem mass spectrometry.

A method using liquid chromatography tandem mass spectrometry (LC-MS-MS) with electrospray (ES) for the determination of traces of narasin, monensin and salinomycin in chicken liver and eggs was developed, validated and used for routine surveillance. The essence of this paper is to demonstrate that one single method can serve very well for two entirely different purposes, i.e., screening and confirmation. Highly reliable confirmation of the identity at low concentrations was demonstrated when residues of narasin were detected and quantified (0.2 to 11 ng g(-1)) in 50% of the Swedish eggs analysed in 1999. Four daughter ions were detected with ion ratios meeting suggested confirmation criteria for the European Union, even at 0.2 ng g(-1). The method was found to be highly cost-effective since both screening and confirmation of 98 liver samples were performed in only two analytical runs (the Swedish national surveillance scheme of 1999, report level 5 ng g(-1)). The high performance of the method for the different applications was possible due to a combination of the power of ES-LC-MS-MS, a procedure involving screening of pooled samples, and method optimisation of the work-up (automated solid phase extraction), LC and MS parameters. Validation data for narasin (0.5 to 20 ng g(-1)) in eggs are presented (accuracy 94 to 108%, relative standard deviation 4 to 10%, limit of detection 0.026 ng g(-1)). The time for an LC-MS-MS run was 4 min, corresponding to 48 s per sample in a pool.     

Liquid chromatography-electrospray ionization tandem mass spectrometry and liquid chromatography with fluorescence detection for determination of octylphenol and nonylphenol in municipal wastewater at trace levels

Summary Reversed-phase liquid chromatography with fluorescence detection (RPLC-FD) and with electrospray ionization (ESI) tandem mass spectrometric detection (RPLC-ESI-MS-MS), both coupled with automated solid-phase sample extraction, have been used for trace enrichment and analysis of octylphenol and nonylphenol (NP) in municipal wastewater. Quality data calculated for the methods were detection limits (LOD), quantitation limits, linearity, precision, and accuracy. For LC-ESI-MS-MS theLOD were below 0.08 μg L⁻¹. Unequivocal detection of NP in wastewater samples was achieved by use of LC-ESI-MS and LC-ESI-MS-MS. In particular, application of the LC methods to wastewater samples revealed that the selectivity of LC-MS-MS was more than that of LC-FD for qualitative and quantitative analysis of complex matrices.     

Enantiomeric specific determination of hexabromocyclododecane by liquid chromatography-quadrupole linear ion trap mass spectrometry in sediment samples

This paper describes the determination and quantitation of hexabromocyclododecane (HBCD) enantiomers by liquid chromatography-quadrupole linear ion trap mass spectrometry (LC-QqLIT-MS). The method is based on the use of a chiral chromatographic column Nucleodex beta-PM (200 mm x 4.0 mm, 5 microm), which allows a good separation between HBCD enantiomers [(+/-)alpha, (+/-)beta and (+/-)gamma] in less than 15 min and the detection is performed by a Q-Trap instrument. Linearity was checked between 0.05 and 25 injected ng. Limits of detection (LODs) were in the range of 0.3-1.5 pg, limits of quantification (LOQs) were between 1 and 6 pg, and both values are lower than those published in the literature applying LC-MS-MS methods. The method was applied to sediment samples collected along the Cinca River, a tributary of the Ebro River (northeast of Spain). Samples were extracted and purified following a pressurized liquid extraction method. LODs of the method were between 0.12 and 5.61 ng/g and LOQs, from 0.38 to 1.87 ng/g. Total HBCD levels in these sediments ranged from not detected to 2660 ng/g dry weight. Enantiomeric fractions (EFs) were calculated and compared with EF obtained from standard injections. It is important to note that calculated EFs were corrected using (2)H(18)-labeled HBCD standards, in order to compensate matrix effect. EFs obtained in sediment samples suggested a higher presence of (+)alpha-HBCD and (+)gamma-HBCD in technical mixture, this suggests that it is not a racemic mixture.     

Monitoring Farmed Fish Welfare by Measurement of Cortisol as a Stress Marker in Fish Feces by Liquid Chromatography Coupled with Tandem Mass Spectrometry

The aquaculture industry has become a sustainable source of food for humans. Remaining challenges include disease issues and ethical concerns for the discomfort and stress of farmed fish. There is a need for reliable biomarkers to monitor welfare in fish, and the stress hormone cortisol has been suggested as a good candidate. This study presents a novel method for measurement of cortisol in fish feces based on enzymatic hydrolysis, liquid–liquid extraction, derivatization, and finally instrumental analysis by liquid chromatography coupled with tandem mass spectrometry. Hydrolysis and extraction conditions were optimized. Cortisol appeared to be mostly conjugated to sulfate and less conjugated to glucuronic acid in the studied samples of feces from farmed Atlantic salmon. The method was suitable for quantification of cortisol after enzymatic deconjugation by either combined glucuronidase and sulfatase activity, or by glucuronidase activity alone. The limit of detection was 0.15 ng/g, the limit of quantification was 0.34 ng/g, and the method was linear (R² > 0.997) up to 380 ng/g, for measurement of cortisol in wet feces. Method repeatability and intermediate precision were acceptable, both with a coefficient of variation (CV) of 11%. Stress level was high in fish released into seawater, and significantly reduced after eight days.     

Analysis of perfluorooctanesulfonate and related fluorochemicals in water and biological tissue samples by liquid chromatography-ion trap mass spectrometry

A method for the determination of perfluorinated compounds (PFCs) in various water and biological tissue samples was developed and validated. The contents of selected PFCs (i.e., perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA) and perfluorodecanoate (PFDA)) in water samples were extracted by the C(18) solid-phase extraction (SPE). The biological tissue samples (frozen-dried fish and oysters) were simply extracted by liquid-solid extraction with MTBE and adding tetrabutylammonium hydrogensulfate (TBA) as an ion-pairing reagent. The analytes were then identified and quantitated by liquid chromatography-ion trap negative electrospray mass spectrometry (LC-ESI ion-trap-MS). Limits of quantitation (LOQ) were established between 0.5 and 6 ng/l in 250 ml of water sample, while 5-50 ng/g (dry weight) for biological tissue sample. Intrabatch and interbatch precision with their accuracy at two concentration levels were also investigated. Precision for these three PFCs, as indicated by RSD, proved to be less than 11 and 17%, respectively. The total contents of PFOA, PFOS and PFDA were detected in concentrations of up to 400 ng/l in various water samples, while up to 1,100 ng/g in fish and oyster samples. PFOA and PFDA was the major PFCs detected in water samples and biological tissue samples, respectively.     

A rapid method for the determination of lasalocid in animal tissues and eggs by high performance liquid chromatography with fluorescence detection and confirmation by LC-MS-MS

A simple and rapid method has been developed for the extraction of lasalocid from chicken muscle, eggs and liver and kidney from chicken, pig, sheep and calf. This method allows the screening of a large number of samples, i.e. 30-40 within a working day, and has an overall analysis time of 90 min. Lasalocid standard solution can be detected at 1 ng ml-1 by both HPLC-fluorescence (HPLC-F) and LC-MS-MS; the limit of quantification in fortified samples by the described method is 1 ng g-1. Results show good repeatability and mean 'spiked' recoveries by HPLC-F in the range of 10 to 200 ng g-1 (ppb) of 103, 87, 107, 97, 97, 103, 93, 109 and 100% in chicken muscle, chicken liver, egg, pig liver, pig kidney, sheep liver, sheep kidney, calf liver and calf kidney, respectively. For concentrations between 1 and 6 ng g-1 of spiked lasalocid in eggs and chicken liver by LC-MS-MS, the average recoveries were 76 and 59%, respectively.     

Determination of ranolazine in human plasma by liquid chromatographic-tandem mass spectrometric assay

A highly sensitive liquid chromatographic-tandem mass spectrometric method (LC-MS-MS) is developed to quantitate ranolazine in human plasma. The analyte and internal standard tramadol are extracted from plasma by liquid-liquid extraction using diethyl ether-dichloromethane (60:40 v/v), and separated on a Zorbax extend C(18) column using methanol-10mM ammonium acetate (60:40 v/v, pH 4.0) at a flow of 1.0 mL/min. Detection is carried out by multiple reaction monitoring on a QtrapTM LC-MS-MS system with an electrospray ionization interface. The assay is linear over the range 10-5000 ng/mL with a limit of quantitation of 10 ng/mL and a lower limit of detection (S/N > 3) of 1 ng/mL. Intra- and inter-day precision are < 3.1% and < 2.8%, respectively, and the accuracy is in the range 96.7-101.6%. The validated method is successfully used to analyze the drug in samples of human plasma for pharmacokinetic studies.     

气相色谱-三重四极杆质谱同位素内标法测定鱼样中20种多氯联苯

建立了一种气相色谱-三重四极杆质谱结合双稳定性同位素内标检测鱼样中多氯联苯的方法。采用自动索氏提取器提取样品中的多氯联苯,经一根复合净化柱净化后,采用质谱多反应监测模式检测,选取两个独立的离子对。分析了20种多氯联苯,包含7种指示性多氯联苯,从三氯联苯到八氯联苯每族3个化合物,九氯联苯和十氯联苯各一个,每族使用一个相同氯代程度的¹³C₁₂标记多氯联苯作为定量内标、2种回收内标。20种多氯联苯在33 min内流出,分离良好,线性范围为0.05~10 μg/L,相关系数r均在0.99以上,低、中、高3种水平的加标回收率均在80.3%~117.6%之间,相对标准偏差（RSD,n=6）在5.09%~18.5%之间,方法检出限为0.01~0.02 μg/kg。20种多氯联苯总量在1.2~8.8 μg/kg（湿重）范围内,7个指示性多氯联苯总量在0.68~6.4 μg/kg（湿重）范围内。该方法缩短了分析时间,减少了有机溶剂的使用量,适合鱼样中多氯联苯的测定。     

Gas chromatography/tandem mass spectrometry method for the simultaneous analysis of 19 brominated compounds in environmental and biological samples

A methodology for the simultaneous analysis of eight polybrominated diphenyl ethers (PBDEs); eight methoxylated PBDEs (MeO-PBDEs); and three emerging flame retardants, hexabromobenzene (HBB), pentabromoethyl benzene (PBEB), and decabromodiphenyl ethane (DBDPE) by gas chromatography coupled to tandem mass spectrometry (GC-MS-MS) was developed for two environmental matrices (sediment and sludge) and three biological matrices (fish, dolphin blubber, and bird eggs). The use of selective reaction monitoring (SRM) allows a high selectivity, which is critical in the analysis of complex samples like blubber. Analytical parameters such as linearity, reproducibility, or accuracy were evaluated. Method limits of detection and quantification were evaluated and compared with GC-EI-MS and GC-NCI-MS. Method detection limits were valid for the environmental analysis in all cases, with values between 0.01 and 1.65 ng/g dw for sediment, 0.05 and 2.78 ng/g dw for sludge, 0.04 and 10.6 ng/g lw for fish, 0.01 and 1.11 ng/g lw for dolphin blubber, and 0.03 and 3.20 ng/g lw for bird eggs. The developed method was applied to five samples of each matrix. PBDEs were detected in all samples, while MeO-PBDEs were only detected in dolphin blubber. DBDPE was detected in sediment and sludge.     

Determination of perfluorochemicals in biological, environmental and food samples by an automated on-line solid phase extraction ultra high performance liquid chromatography tandem mass spectrometry method

A rapid on-line solid phase extraction ultra high performance liquid chromatography tandem mass spectrometry method was developed for the identification and quantitation of nine perfluorinated compounds in matrices of environmental, biological and food interest. Pre-treatment, solid phase extraction, chromatographic and mass detection conditions were optimised, in order to apply the whole methodology to the analysis of different matrices. Particular attention was devoted to the evaluation of matrix effect and the correlated phenomena of ion enhancement or suppression in mass spectrometry detection. LOD and LOQ range from 3 to 15ngL(-1) and from 10 to 50ngL(-1), respectively. Method detection limits (MDLs) were also calculated for each kind of matrix. The recovery, evaluated for each analyte, does not depend on analyte concentration in the explored concentration range: average Rˉ% values are always greater than 82.9%. In the whole, the results obtained for samples of river waters, blood serum, blood plasma, and fish confirm the ubiquitous presence of perfluorinated compounds, as recently denounced by many sources.     

Determination of perfluorinated chemicals in food and drinking water using high-flow solid-phase extraction and ultra-high performance liquid chromatography/tandem mass spectrometry

For this study, we developed methods of determining ten perfluorinated chemicals in drinking water, milk, fish, beef, and pig liver using high-flow automated solid-phase extraction (SPE) and ultra-high performance liquid chromatography/tandem mass spectrometry. The analytes were separated on a core-shell Kinetex C18 column. The mobile phase was composed of methanol and 10-mM N-methylmorpholine. Milk was digested with 0.5 N potassium hydroxide in Milli-Q water, and was extracted with an Atlantic HLB disk to perform automated SPE at a flow rate ranged from 70 to 86 mL/min. Drinking water was directly extracted by the SPE. Solid food samples were digested in alkaline methanol and their supernatants were diluted and also processed by SPE. The disks were washed with 40% methanol/60% water and then eluted with 0.1% ammonium hydroxide in methanol. Suppression of signal intensity of most analytes by matrixes was lower than 50%; it was generally lower in fish and drinking water but higher in liver. Most quantitative biases and relative standard deviations were lower than 15%. The limits of detection for most analytes were sub-nanograms per liter for drinking water and sub-nanograms per gram for solid food samples. This method greatly shortened the time and labor needed for digestion, SPE, and liquid chromatography. This method has been applied to analyze 14 types of food samples. Perfluorooctanoic acid was found to be the highest among the analytes (median at 3.2-64 ng/g wet weight), followed by perfluorodecanoic acid (0.7-25 ng/g) and perfluorododecanoic acid (0.6-15 ng/g).     

Determination of Carbon‐based Engineered Nanoparticles in Marketed Fish by Microwave‐assisted Extraction and Liquid Chromatography‐atmospheric Pressure Photoionization‐tandem Mass Spectrometry

An optimized method for the determination of two major carbon‐based engineered nanoparticles (C₆₀ and C₇₀) in marketed fish samples is described. The method involves the use of microwave‐assisted extraction (MAE) coupled with liquid chromatography ‐ tandem mass spectrometry with atmospheric pressure photoionization (LC‐APPI‐MS/MS). Factors affecting the extraction efficiency of the analytes from fish samples were optimized by a central composite design method. The optimal extraction temperature and time for MAE were found to be 233 °C for 22 min, and the extraction solution was composed of toluene and acetone in a ratio of 4.64:1. The limits of quantitation (LOQs) were 0.1 and 0.05 ng/g for C₆₀ and C₇₀, respectively. The precision for these analytes at two spiked levels, as indicated by relative standard deviations (RSDs), were less than 10% for both intra‐ and inter‐day analysis. Accuracy, expressed as the mean extraction recovery, was between 85 and 98%. The method was further validated based on EU Commission Decision 2002/657/EC, including a decision limit (CCα) and detection capability (CCβ) for marketed fish samples.     

Analysis of sub μg/kg lincomycin in honey, muscle, milk, and eggs using fast liquid chromatography-tandem mass spectrometry

A fast liquid chromatography-tandem mass spectrometry (LC-MS-MS) method is developed to determine lincomycin (LM) in honey, muscle, milk, and egg. Samples are cleaned-up at pH 4.7 using Strata-X-C mixed-mode polymeric strong cation exchange solid-phase extraction (SPE) cartridges, which could selectively adsorb the lincomycin from matrices under the acidic condition. LM is separated on the recently introduced Kinetex XB core-shell type HPLC column using isocratic elution mode with a mobile phase containing 0.1% formic acid in water/acetonitrile (93/7, v/v, pH 2.6) at a flow rate of 0.7 mL/min. The subsequent MS/MS detection has decreased ion effect, which allows the limit of detection (LOD) of LM for honey to be 0.05 μg/kg for honey and 0.5 μg/kg for muscle, milk, and egg. These LODs are much lower than those reported previously. The other main advantage of the developed method is the analysis time of only 3.5 min, which is about three times shorter than other reported LC-MS-MS methods. Recoveries varies between 94.2% and 125.2% and in-house reproducibility ranges from 3.7% to 28.7%. The developed method is validated according to European Union (EU) Commission Decision 2002/657/EC using a matrix-comprehensive validation strategy. All studied analytical parameters fulfills the EU guidelines.     

A validated method for the determination of traces of UV filters in fish using LC–MS/MS

An analytical method for the determination of UV filter substances in fish tissue has been developed and validated using benzophenone-3, 3-(4-methylbenzylidene)-camphor, 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate and 2-ethylhexyl 3-(methoxyphenyl)-2-propenoate as target analytes. The fish fillets were homogenised and extracted by Soxhlet extraction. The extracts were run through a clean-up process including gel permeation chromatography followed by solid-phase extraction. Quantification of the compounds was performed using liquid chromatography with tandem mass spectrometric detection. Blank fish as well as spiked blank fish were analysed to validate the analytical method. The analytical method developed has the multiple advantages of enabling separation, simultaneous identification and quantification of each of the four selected compounds in a single run. Contamination of blank samples and abnormally high concentrations in spiked samples were avoided by taking extensive precautions during the fish preparation procedure. The method was validated in accordance with internationally accepted criteria, such as specificity, accuracy and repeatability. The combination of LC with tandem mass spectrometry ensures a high level of specificity. The accuracy of the method was reported as the mean recovery rate for the analytes in the sample matrix. Mean recoveries were in the range 86–108%. The precision is expressed as the relative standard deviation, and in all but one of the cases was 20% or below. The accuracy of the method allows residue analyses to be performed on biological matrices at ng/g levels. The determined limit of quantification for each analyte was 8 ng/g fish. For all spiking levels ≥8 ng/g, relative standard deviations were ≤ 20%.     

Simultaneous analysis of select pharmaceuticals and personal care products in fish tissue using pressurized liquid extraction combined with silica gel cleanup

Analytical improvements were developed and validated for measuring select personal care products (PCPs) and two pharmaceuticals in fish tissue. The method was validated using fortified fillet tissue for twelve PCPs including fragrance materials, alkylphenols, photo initiators, and triclosan as well as two pharmaceuticals including carbamazepine (anti-seizure) and diazepam (anti-convulsant). The analytical method utilized pressurized liquid extraction (PLE) combined with silica gel cleanup, gel permeation chromatography, and gas chromatography ion-trap tandem mass spectrometry. Silica gel cleanup was combined with the PLE to produce one automated extraction/cleanup technique. This analytical improvement served to reduce the incurred cost, time, and loss of potential target analytes associated with independent cleanup steps. The combined extraction/cleanup technique resulted in an average increase of 10% in analyte recoveries. Average triplicate recoveries and relative standard deviations for the entire method, using 2.5 g of fish fillet tissue, were 92 ± 9% (recoveries ranged from 64 to 131%). The sensitivity of the analytical methods was improved by optimizing the resonant collision induced dissociation energy to the hundredths place (0.01 V). Improvements in ion production range from 24 to 122% for six of the 12 PCPs. Statistically derived method detection limits (MDLs) were also lowered on average by a factor of 8 and ranged from 1.2 to 38 ng/g wet weight. MDLs for carbamazepine and diazepam were 18 and 3.7 ng/g wet weight, respectively. Galaxolide and tonalide were measured in an environmental sample at concentrations of 81 and 5.5 ng/g wet weight, respectively.     

Development of extraction methods for the analysis of perfluorinated compounds in human hair and nail by high performance liquid chromatography tandem mass spectrometry

Perfluorinated compounds (PFCs) are ubiquitous in the environment and are becoming a public health concern. It is desirable to develop sensitive and accurate methods to measure PFCs in non-invasive matrices such as hair and nail for biomonitoring of body burden. Different extraction methods coupled with solid phase extraction were investigated for extraction efficiency. The extracts were separated, identified and quantified by liquid chromatography-tandem mass spectrometry. Extraction with acetonitrile proved to be the most efficient extraction method for human hair sample, while extraction by methanol with alkaline digestion performed best for human nail sample. The matrix recoveries of the optimized methods ranged from 78% to 116% for hair and from 87% to 126% for nail sample. The ranges of the limit of detection (LOD) were 0.026–0.069 ng/g and 0.023–0.094 ng/g for hair and nail, respectively. These methods were validated by evaluating LOD, accuracy and precision and were proven to be useful for measuring paired human hair and nail samples collected from the general population.