Identification of novel fluorochemicals in aqueous film-forming foams used by the US military

Aqueous film-forming foams (AFFFs) are a vital tool to fight large hydrocarbon fires and can be used by public, commercial, and military firefighting organizations. In order to possess these superior firefighting capabilities, AFFFs contain fluorochemical surfactants, of which many of the chemical identities are listed as proprietary. Large-scale controlled (e.g., training activities) and uncontrolled releases of AFFF have resulted in contamination of groundwater. Information on the composition of AFFF formulations is needed to fully define the extent of groundwater contamination, and the first step is to fully define the fluorochemical composition of AFFFs used by the US military. Fast atom bombardment mass spectrometry (FAB-MS) and high resolution quadrupole-time-of-flight mass spectrometry (QTOF-MS) were combined to elucidate chemical formulas for the fluorochemicals in AFFF mixtures, and, along with patent-based information, structures were assigned. Sample collection and analysis was focused on AFFFs that have been designated as certified for US military use. Ten different fluorochemical classes were identified in the seven military-certified AFFF formulations and include anionic, cationic, and zwitterionic surfactants with perfluoroalkyl chain lengths ranging from 4 to 12. The environmental implications are discussed, and research needs are identified.     

Quantitative determination of perfluorochemicals and fluorotelomer alcohols in plants from biosolid-amended fields using LC/MS/MS and GC/MS

Analytical methods for determining perfluorochemicals (PFCs) and fluorotelomer alcohols (FTOHs) in plants using liquid chromatography/tandem mass spectrometry (LC/MS/MS) and gas chromatography/mass spectrometry (GC/MS) were developed, and applied to quantify a suite of analytes in plants from biosolid-amended fields. Dichloromethane-methanol and ethylacetate were chosen as extracting solutions for PFCs and FTOHs, respectively. Nine perfluorocarboxylic acids (PFCAs), three perfluorosulfonic acids (PFSAs), and ten FTOHs were monitored. Most PFCAs and perfluorooctanesulfonate (PFOS) were quantifiable in plants grown in contaminated soils, whereas PFCs went undetected in plants from two background fields. Perfluorooctanoic acid (PFOA) was a major homologue (～10-200 ng/g dry wt), followed by perfluorodecanoic acid (～3-170 ng/g). [PFOS] in plants (1-20 ng/g) generally was less than or equal to most [PFCAs]. The site-specific grass/soil accumulation factor (GSAF = [PFC](Grass)/[PFC](Soil)) was calculated to assess transfer potentials from soils. Perfluorohexanoic acid had the highest GSAF (= 3.8), but the GSAF decreased considerably with increasing PFCA chain length. Log-transformed GSAF was significantly correlated with the PFCA carbon-length (p < 0.05). Of the measured alcohols, 8:2nFTOH was the dominant species (≤1.5 ng/g), but generally was present at ≥10× lower concentrations than PFOA.     

Fluorotelomer carboxylic acids and PFOS in rainwater from an urban center in Canada

A method based on LC/MS/MS analysis of fluorotelomer carboxylic acids (FTCAs: CnF2n+1CH2COOH, n = 6, 8, and 10) and fluorotelomer unsaturated carboxylic acids (FTUCAs: CnF2nCHCOOH, n = 6, 8, and 10) in rainwater using negative ionization electrospray multiple reaction monitoring conditions is described. These compounds are thought to be oxidative products of atmospherically transported fluorotelomer alcohols (FTOHs: CnF2n+1CH2CH2CH2OH). Preconcentration from rainwater samples collected in Winnipeg, Manitoba, Canada, was achieved using solid-phase extraction on C18 sorbent. Low parts per trillion levels of the C10- and C12-FTCAs and FTUCAs were detected, suggesting that one possible pathway of removing FTOHs from the atmosphere is through oxidation and wet deposition. Perfluorocarboxylic acids (PFCAs) and perfluorooctane sulfonate (PFOS) were simultaneously analyzed in the rainwater samples using established LC/MS/MS methods. PFOS was deposited in rainwater with a concentration of 0.59 ng/L while PFCAs were not detected above their respective method detection limits.     

Use of liquid chromatography/tandem mass spectrometry to detect distinctive indicators of in situ RDX transformation in contaminated groundwater

An important element of monitored natural attenuation is the detection in groundwater of distinctive products of pollutant degradation or transformation. In this study, three distinctive products of the explosive RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) were detected in contaminated groundwater from the Iowa Army Ammunition Plant; the products were MNX (hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine), DNX (hexahydro-1,3-dinitroso-5-nitro-1,3,5-triazine), and TNX (hexahydro-1,3,5-trinitroso-1,3,5-triazine). These compounds are powerful indicators of RDX transformation for several reasons: (a) they have unique chemical features that reveal their origin as RDX daughter products, (b) they have no known commercial, industrial, or natural sources, and (c) they are well documented as anaerobic RDX metabolites in laboratory studies. The products were analyzed by LC/MS/MS (liquid chromatography/mass spectrometry/mass spectrometry) with selected reaction monitoring and internal standard quantification using [ring-U-15N]RDX. Validation tests showed the novel LC/MS/MS method to be of favorable sensitivity (detection limits ca. 0.1 microg/L), accuracy, and precision. The products, which were detected in all groundwater samples with RDX concentrations of > ca. 1 microg/L (25 out of 55 samples analyzed), were present at concentrations ranging from near the detection limit to 430 microg/L. MNX was the typically the most abundant of the three nitroso-substituted products; concentrations of the products seldom exceeded 4 mol % of the RDX concentration, although they ranged as high as 26 mol % (TNX). Geographic and temporal distributions of RDX, MNX, DNX, and TNX were assessed. A degradation product resulting from RDX ring cleavage, methylenedinitramine, was not detected by LC/MS/MS in any sample (detection limit ca. 0.6-4 microg/L). This extensive field characterization of MNX, DNX, and TNX distributions in groundwater by a highly selective analytical method (LC/MS/MS) is significant because very little is known about the occurrence of intrinsic RDX transformation in contaminated aquifers.     

Analytical method for carbamate pesticides in processed foods by LC/MS/MS

A rapid analytical method for the simultaneous determination of carbamate pesticides in processed foods was established by liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). The pesticides were extracted from samples with acetonitrile using accelerated solvent extract equipment, except for the fine powder type spices, which were extracted in an ultrasonic bath. The crude extract was cleaned up with a multi-solvent GPC column (Shodex Asahipak GF-310 HQ) using acetonitrile as a mobile phase. The eluent from the column at the retention time between 13 to 18 min was concentrated under nitrogen gas and dissolved in a mixture of acetonitrile-water-0.2 mol/L ammonium formate buffer pH 6.0 (10 : 9 : 1). An aliquot was injected into the LC/MS/MS using electrospray ionization (ESI) with acquisition in the positive mode.The recoveries of 29 kinds of pesticide from dried fruits (raisin, prune and mango) and spices (turmeric, masala, sage, thyme and red pepper) fortified at levels of 0.1 and 0.01 microg/g were mostly in the range of 50 to 150% and those from soybean paste and soy sauce fortified at 0.01 microg/g were 46.9 to 122.6% (C.V. 3.8 to 37.6%), except for 4 kinds of pesticide. The determination limits (S/N> or =10) corresponded to 0.001 to 0.05 mug/g of the pesticides in red pepper.     

Simultaneous determination of pesticides in agricultural products by LC/MS/MS using clean-up with ultrafiltration

A method for simultaneous determination of multiple pesticide residues in agricultural products was developed by using a pretreatment with ultrafiltration, followed by liquid chromatography-tandem mass spectrometry (LC/MS/MS). The pretreatment process (extraction of pesticides from agricultural products with methanol, dilution of the extract with water, and ultrafiltration) gave recoveries in the range of 50-150% for 63 of 83 pesticides spiked at 0.25 microg/ g into 6 agricultural products. The detection limits of pesticides by LC/MS/MS were below 0.0005-0.05 micro/g. This method is useful for screening purposes and for multiresidue analysis of pesticides in agricultural products. Pesticide residues in 50 domestic crops were investigated by this method, and residues of 14 pesticides were detected in 30 crops.     

Determination of mepiquat chloride in grape, wine and juice by liquid chromatography with electrospray tandem mass spectrometry

A simple and rapid method was developed for the analysis of mepiquat chloride in grape, wine and juice by high-performance liquid chromatography with electrospray tandem mass spectrometry (LC/MS/MS). Mepiquat chloride was extracted with water-methanol (1:1). Extracted solution was adjusted to pH 10 with ammonia solution. A part of the extracted solution was cleaned up on a styrenedivinylbenzene (SDVB) cartridge for LC/MS/MS. The LC separation was performed on a C18 column (50 mm x 2 mm i.d.) using 0.1% IPCC-MS7-methanol (60:40) as the mobile phase at a flow rate of 0.2 mL/min. The mass spectral acquisition was done in the positive ion mode by applying selected reaction monitoring (SRM). The recoveries of mepiquat chloride from fresh grape, wine and juice fortified at 5 microg/kg and 50 microg/kg were 84.5-96.1%. The lower limit of quantification was 1 microg/kg. Fourteen fresh grape samples, 14 wines (white), 36 wines (red) and 11 juice samples were analyzed by this method. Mepiquat chloride was detected in 5 fresh grape samples, 3 wines (white) and 1 wine (red) at the level of 12.8-199 microg/kg, 5.7-47.7 microg/kg and 24.1 microg/kg, respectively.     

Fluorochemical mass flows in a municipal wastewater treatment facility

Fluorochemicals have widespread applications and are released into municipal wastewater treatment plants via domestic wastewater. A field study was conducted at a full-scale municipal wastewater treatment plant to determine the mass flows of selected fluorochemicals. Flow-proportional, 24 h samples of raw influent, primary effluent, trickling filter effluent, secondary effluent, and final effluent and grab samples of primary, thickened, activated, and anaerobically digested sludge were collected over 10 days and analyzed by liquid chromatography electrospray-ionization tandem mass spectrometry. Significant decreases in the mass flows of perfluorohexane sulfonate and perfluorodecanoate occurred during trickling filtration and primary clarification, while activated sludge treatment decreased the mass flow of perfluorohexanoate. Mass flows of the 6:2 fluorotelomer sulfonate and perfluorooctanoate were unchanged as a result of wastewater treatment, which indicates that conventional wastewater treatment is not effective for removal of these compounds. A net increase in the mass flows for perfluorooctane and perfluorodecane sulfonates occurred from trickling filtration and activated sludge treatment. Mass flows for perfluoroalkylsulfonamides and perfluorononanoate also increased during activated sludge treatment and are attributed to degradation of precursor molecules.     

Multiresidue method for determination of pesticides in fruits and vegetables by GC/MS (SCAN) and LC/MS (SIM)

A rapid multiresidue method has been developed for determination of many pesticides in fruits and vegetables using GC/MS and LC/MS. The method of analysis was the same as that reported by Kakimoto et al. in 2003 except for the use of LC/MS. Good recoveries in the range of 70-120% were obtained for 70 (32 by GC/MS, 38 by LC/MS) of 113 pesticides spiked at 0.1 microg/g into fruits and vegetables. For screening purposes, the method could be appiled to 82 pesticides. Considering the report by Kakimoto et al. in 2004, 177 pesticides were suitable for screening by this method. The limits of detection were 0.001-0.015 microg/g (by GC/MS) and < 0.001-0.010 microg/g (by LC/MS). The calibration curves were linear for most pesticides, with correlation coefficients of 0.976-1.000 (by GC/MS) and 0.968-1.000 (by LC/MS). The values obtained for fruits and vegetables naturally contaminated with pesticides by this method were nearly equal to those by the official method.     

Analysis of benzylsuccinates in groundwater by liquid chromatography/tandem mass spectrometry and its use for monitoring in situ BTEX biodegradaton

Benzylsuccinic acid (BS) and methylbenzylsuccinic acid (MeBS) isomers have been proposed as distinctive indicators of anaerobic toluene and xylene metabolism in fuel-contaminated aquifers; however, labor-intensive analytical procedures have limited their analysis at field sites. In this article, a rapid electrospray LC/MS/MS (liquid chromatography/mass spectrometry/mass spectrometry) method for benzylsuccinates is described that involves selected reaction monitoring, internal standard quantification with [ring-2H5]BS, small sample size (<1 mL), and no extraction/concentration steps. The highly selective LC/MS/ MS method was shown to be sensitive (detection limits ca. 0.3 microg/L), accurate, and precise. The method was used to characterize geographic and temporal distributions of BS and MeBS isomers in an anaerobic, hydrocarbon-contaminated aquifer. BS was never detected, and MeBS isomers were detected in the three wells with the highest concentrations of BTEX (benzene, toluene, ethylbenzene, and xylenes); MeBS concentrations ranged from <0.3 to 205 microg/L. A strong linear correlation (r2 = 0.94; n = 12) was found between concentrations of total MeBS isomers and their parent compounds, xylenes, which suggests that anaerobic xylene metabolism at this site was probably first-order rather than zero-order. The novel LC/MS/MS method for BS and MeBS isomers is a promising technique for rapid and reliable monitoring of in situ bioremediation of gasoline-contaminated groundwater.     

Simultaneous determination of ochratoxin A, B and citrinin in foods by HPLC-FL and LC/MS/MS

Methods using high-performance liquid chromatography with fluorescence detection (HPLC-FL) and using liquid chromatography with tandem mass spectrometry (LC/MS/MS) were developed for simultaneous determination of ochratoxin A (OTA), ochratoxin B (OTB) and citrinin (CIT) in cereal, fruit, and coffee products. The samples were extracted with ethyl acetate under an acidic condition, and then cleaned up with liquid-liquid separation. The test solutions were analyzed by reverse-phase HPLC-FL and LC/MS/MS. Mass spectral acquisition was performed in positive ion mode by applying multiple reaction monitoring. The performances of both detectors were almost equivalent. The recoveries of OTA and OTB were 87-111%, and that of CIT were 70-88%. The limits of quantification (S/N> or =10) of OTA, OTB and CIT was 0.1 mug/kg or less. These methods were considered to be useful for the determination of the three mycotoxins at low levels (0.1 microg/kg).     

Determination of tetrodotoxin in puffer-fish tissues, and in serum and urine of intoxicated humans by liquid chromatography with tandem mass spectrometry

A simple and rapid method was developed for the analysis of tetrodotoxin in puffer-fish tissues, and in serum and urine of humans poisoned after consuming puffer-fish, by means of high-performance liquid chromatography with tandem mass spectrometry (LC/MS/MS). Tetrodotoxin was extracted with 2% acetic acid. The extracted solution from puffer-fish tissues was diluted with water, and the extracted solution from human serum and urine was cleaned up by LC/MS/MS with a methacrylate-styrenedivinylbenzene cartridge. The LC separation was performed on a C18 column (50 mm x 2.1 mm i.d.) using 10 mmol/L IPCC-MS7-methanol (65 : 35) as the mobile phase at a flow rate of 0.2 mL/min. The mass spectral acquisition was done in the positive ion mode by applying selected reaction monitoring (SRM). The recoveries of tetrodotoxin were 79-90% from puffer-fish tissues fortified at 0.1 microg/g and 1 microg/g, and 93-101% from human serum and urine fortified at 0.5 ng/mL and 5 ng/mL. The detection limits of tetrodotoxin were 0.01 microg/g in puffer-fish tissues and 0.1 ng/mL in human serum and urine. Thirty samples of puffer-fish from wholesale markets, and 7 serum and 5 urine samples of humans poisoned after consuming puffer-fish were analyzed by this method. Tetrodotoxin was detected in all puffer-fish tissues, and all serum and urine samples at the levels of 0.04-140 microg/g, 0.9-1.8 ng/mL and 15-150 ng/mL, respectively.     

Chemical profiling of Punica granatum peels from Jordan using LC–MS/MS and study on their biological activities

A paucity of local information concerning the chemical profiles and biological activities of extracts obtained from less-studied P. granatum peel of Jordanian origin was considered in this study for the first time. Fractionation of the crude ethanol extracts was performed because of their higher phenolic and flavonoid contents compared to the water and acetone extracts. The chemical compositions of the respective samples, that is, extracts/fractions were identified by LC–MS/MS, and the elemental content of the raw materials was also analysed using atomic absorption spectrometry. Antioxidant activities of extracts and fractions were evaluated against DPPH and ABTS radical scavenging assays, and the antibacterial activities were investigated by disc diffusion method and MIC (Minimum Inhibitory Concentration). The LC–MS/MS results correlated strongly with the total phenolic and flavonoid contents, where ethanol displayed higher efficacy for extracting bioactive ingredients. Overall, a total of 19 phenolics were detected in the ethanolic peel extract of P. granatum. All of the analysed extracts showed strong antioxidant activities. Fractionation of ethanolic extracts resulted in fractions with almost similar chemical LC–MS/MS profiles, but the relative proportion of constituents was different. All fractions showed lower intensities of antioxidant capacities than crude extracts, highlighting the superiority of some components, either individually or combined, as well as their relative proportion on the biological activity of each fraction. The results of the present study emphasise the need to further explore the effect of putative interactions among plant bioactive ingredients and focus on possible interactions with drugs along with foods.     

Applicability of GC, GC/MS and liquid chromatography with tandem mass spectrometry to screening for 140 pesticides in agricultural products

The applicability of GC, GC/MS and liquid chromatography with tandem mass spectrometry (LC/MS/MS) to screening for 140 pesticides in agricultural products was examined. Validation of multi-residue screening methods for the determination of 88 pesticides in 12 crops (asparagus, cauliflower, burdock, carrot, broccoli, spinach, matsutake mushroom, orange, soybean, sesame, millet and tea) was done by GC and GC/MS. Of the 88 pesticides, 63 were obtained with recoveries in the range from 50 to 150% at the 0.1 microg/g level in the 12 crops. Applicability of the official methods in Japan to 74 pesticides, including 22 pesticides with low recovery (< 50%) by GC or GC/MS analysis, was also examined by LC/MS/MS. LC/MS/MS acquisition parameters were established for 67 pesticides in positive and negative electrospray ionization (ESI) modes. Of 67 pesticides validated in 7 crops using LC/MS/MS at the 0.1 microg/g level, 44 showed recoveries in the range from 50 to 150%. The occurrence of matrix interference in LC/MS/MS can lead to false-positive detection of MCPA in spinach, cabbage and orange and false-negative detection of four pesticides in orange, spinach, apple and unpolished rice. Good linearity was observed in the studied ranges by GC, GC/MS (r > 0.990) and LC/MS/MS (r > 0.995). Of the total of 140 pesticides validated by GC, GC/MS and LC/MS/MS, 107 were newly recognized as suitable subjects for screening.     

Citrinin Determination in Red Fermented Rice Products by Optimized Extraction Method Coupled to Liquid Chromatography Tandem Mass Spectrometry (LC‐MS/MS)

A rapid and sensitive method was developed and validated for citrinin determination in red fermented rice products by liquid chromatography tandem mass spectrometry (LC‐MS/MS) under the selected reaction monitoring mode. Sample preparation was especially focused, and the quantitative methods of LC‐MS/MS and high‐performance liquid chromatography with fluorescence detection (HPLC‐FLD) were compared. In red fermented rice samples, the limit of detection was 1.0 μg/kg for LC‐MS/MS compared to 250 μg/kg for HPLC‐FLD, the limit of quantification was 3.0 μg/kg for LC‐MS/MS compared to 825 μg/kg for HPLC‐FLD. High correlation coefficient was obtained (R² = 0.999) within the linear range (0.1 to 100 μg/L) in the MS method. The recoveries ranging from 80.9% to 106.5% were obtained in different spiking concentrations. The average intra‐ and inter‐day accuracy ranged from 75.4% to 103.1%, and the intra‐ and inter‐day precisions were from 3.3% to 7.9%. The developed method was applied to 12 commercial red fermented rice products, and citrinin was found in 10 samples ranging from 0.14 to 44.24 mg/kg. Compared to traditional qualitative and quantitative methods, the newly developed LC‐MS/MS method for citrinin determination includes the merits of using a small amount of extraction solvent, simple preparation steps, and high sensitivity.     

Analysis of tetracyclines in honey and royal jelly by LC/MS/MS

A simple and accurate method using liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS) was developed for the determination of tetracyclines (TCs), i.e., oxytetracycline (OTC), chlortetracycline (CTC) and tetracycline (TC), in honey and royal jelly. Mass spectral acquisition was performed in the positive mode. In LC separation, L-column ODS and 0.01% formic acid-acetonitrile were used as the column and mobile phase, respectively. TCs in a honey sample were diluted with water, while TCs in royal jelly were extracted with 2% metaphosphoric acid-methanol (6:4). They were cleaned up with Oasis HLB and Sep Pak C18 cartridges, respectively. The quantification limits of TC, OTC, and CTC were 5, 5, and 10 ng/g, respectively, while those in royal jelly were 25, 25, and 50 ng/g, respectively. The recoveries of TCs from both honey and royal jelly were 75-120%.     

Comparative study of low- versus high-resolution liquid chromatography-mass spectrometric strategies for measuring perfluorinated contaminants in fish

Perfluorinated compounds (PFCs) are usually monitored by high-performance liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) on triple quadrupole instruments. Although not yet widely implemented in the field, high-resolution mass spectrometry (HRMS) today appears as a valuable alternative for these halogenated chemicals due to their significant mass defect. Indeed, this second approach offers a way to cope with particular matrix effects caused by co-eluting and isobaric interferences affecting the measurement of some PFCs in fish. The present study compares three different LC-MS-related instruments and various signal acquisition modes, from low-resolution full-scan and selected ion-monitoring (SIM) mode on a triple quadrupole (QqQ) instrument to high-resolution full-scan or product ion-scan mode on orbital trap (LTQ-Orbitrap) or quadrupole-time-of-flight (Q-TOF) devices. Performances are compared for seven model compounds belonging to seven PFCs subclasses: perfluoralkylsulfonate, perfluoroalkylcarboxylate, perfluoroalkylsulfinate, perfluoroalkyl-sulfonamide, fluorotelomer saturated acid, fluorotelomer unsaturated acid and perfluoroalkylphosphonic acid. Low-resolution MS/MS was found to be unsurprisingly reliable for extended multi-residue monitoring. However, the high stability of PFCs leads to a relatively poor and non-specific fragmentation pathway in MS/MS. In addition, biliary acid-interfering compounds (e.g. taurochenodeoxycholic acid), which where encountered in the present case in fish samples but that may be present in other biological samples, were found particularly disturbing in low-resolution MS/MS. Indeed, these interferences presented the same retention time and diagnostic signals as PFOS, leading to a possible overestimation of the PFOS quantification in LC-MS/MS. On the other hand, high-resolution MS and MS/MS (LTQ-Orbitrap and Q-TOF) provided better results in terms of signal specificity and sensitivity. For instance, the estimated limits of detection (LOD) reached for PFOS on QqQ, Q-TOF and LTQ-Orbitrap instruments were 3.8, 0.7 and 0.5 pg injected, respectively.     

LC FT-ICR MS精确分析卵清蛋白在真空干燥过程中的糖基化修饰

研究了卵清蛋白与葡萄糖混合物在真空干燥的过程中,卵清蛋白的糖基化修饰情况。首次采用胃蛋白酶和液相-傅立叶变换离子回旋共振(LC-FT-ICR)精确质谱分析技术对卵清蛋白的糖基化修饰位点进行研究,其蛋白质覆盖率可以达到100%,研究发现在真空干燥过程中,卵清蛋白中的赖氨酸会与还原糖发生美拉德初级反应,形成糖基化修饰,主要发生在卵清蛋白的K47,56,62,182,190,323和370的赖氨酸氨基上,而卵清蛋白中的精氨酸和氮末端氨基未发现被糖基化修饰;同时,采用离子碰撞诱导解离三级质谱CID-MS3验证m/z7863+的离子峰为m/z7323+的离子峰上添加一个162Da。本论文的研究为精确分析蛋白质修饰的一级结构变化提供了重要的研究方法,为真空干燥在实验分析中的应用提供重要参考。     

Simultaneous determination of sedecamycin and terdecamycin in livestock products by LC/MS

A simple and rapid LC/MS method for simultaneous determination of sedecamyin (SCM) and terdecamycin (TDM) in livestock products has been developed. SCM and TDM were extracted with acetonitrile. The extract was washed with n-hexane and then evaporated to dryness. The residue was dissolved in methanol, and injected into the LC/MS. The mass spectrometer was operated in the positive electrospray ionization (ESI) mode. LC separation was performed on a high-pH-resistant C18 column with 10 mmol/L carbonic acid-ammonia buffer (pH 10.0)-acetonitrile as a mobile pahse. The recoveries from swine muscle and liver fortified at the levels of 0.01 and 0.05 microg/g were 77-88%, and those from poultry muscle and liver fortified at the levels of 0.01 and 0.3 microg/g were 51-93%. The quantitation limits of SCM and TDM were 0.008 microg/g and 0.005 microg/g, respectively.     

Rapid determination of residues of 4 tetracyclines in meat by a microbiological screening, HPLC and LC/MS/MS

A rapid and precise determination residues of 4 tetracyclines (TCs) (oxytetracycline (OTC), tetracycline (TC), chlortetracycline (CTC) and doxycycline (DOXY)) in meat was developed by employing three analyses; a microbiological screening, HPLC and LC/MS/MS. TCs were extracted with pH 4.0 McIlvaine buffer containing 0.01 mol/L EDTA from a meat sample, and then purified using a mixed mode, reversed-phase and cation-exchange cartridge. The mean recoveries (n=5) of 0.2 microg/g OTC, TC and CTC, 0.05 microg/g DOXY spiked in meat samples were 76.6-99.0% (C.V. 1.6-5.4%). In 13 meat samples in which the microbiological screening indicated the presence of TCs, CTC (9 samples) and DOXY (4 samples) were identified with HPLC and LC/MS/MS.