Determination of perfluoroalkyl carboxylic, sulfonic, and phosphonic acids in food

A sensitive and accurate method was developed and validated for simultaneous analysis of perfluoroalkyl carboxylic acids, sulfonic acids, and phosphonic acids (PFPAs) at low picograms per gram concentrations in a variety of food matrices. The method employed extraction with acetonitrile/water and cleanup on a mixed-mode co-polymeric sorbent (C8?+?quaternary amine) using solid-phase extraction. High-performance liquid chromatographic separation was achieved on a C18 column using a mobile phase gradient containing 5?mM 1-methyl piperidine for optimal chromatographic resolution of PFPAs. A quadrupole time-of-flight high-resolution mass spectrometer operating in negative ion mode was used as detector. Method detection limits were in the range of 0.002 to 0.02?ng?g^?1 for all analytes. Sample preparation (extraction and cleanup) recoveries at a spiking level of 0.1?ng?g^?1 to a baby food composite were in the range of 59 to 98?%. A strong matrix effect was observed in the analysis of PFPAs in food extracts, which was tentatively assigned to sorption of PFPAs to the injection vial in the solvent-based calibration standard. The method was successfully applied to a range of different food matrices including duplicate diet samples, vegetables, meat, and fish samples.

An on-line solid phase extraction-liquid chromatography tandem mass spectrometry method for the determination of perfluoroalkyl substances in the Antarctic ice core samples

An on-line solid phase extraction-high performance liquid chromatography-tandemmass spectrometry method for the analysis of perfluoroalkyl substances (PFASs) in water samples was developed. The optimal analytical conditions were obtained through the optimization of the extraction efficiency of online solid phase extraction column, sample loading rate and loading volume, and the concentration of ammonium acetate in mobile phase. Under the optimal condition, the analytical method displayed good linearity (r² > 0.99) for 12 PFASs (C5-C14 perfluoroalkyl carboxylic acids and C6/C8 perfluoroalkyl sulfonic acids) over a concentration range of 0.5-100 ng/L. The limits of quantitation for samples were between 0.025 ng/L and 0.5 ng/L and the relative standard deviations (RSD) of five consecutive analyses were less than 10% for 1 ng/L standard solution. Satisfactory results were obtained using this analytical method for the analysis of perfluoroalkyl substances in Antarctic ice core samples. The recoveries of all perfluoroalkyl substances were in a range of 73%-117% when the sampleswere spiked with standards at the concentrations of 2.5 ng/L and 25 ng/L.     

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

The present study documents development and validation of a novel approach for determination of 23 perfluorinated alkylated substances (PFASs) in food of animal origin represented by milk and fish. The list of target analytes comprises four classes of PFASs, both ionic and non-ionic: 11 perfluorocarboxylic acids (PFCAs), 4 perfluorosulphonic acids (PFSAs), 5 perfluorosulphonamides (FOSAs) and 3 perfluorophosphonic acids (PFPAs). Fast sample preparation procedure is based on an extraction of target analytes with acetonitrile (MeCN) and their transfer (supported by inorganic salts and acidification) into the organic phase. Removing of matrix co-extracts by a simple dispersive solid phase extraction (SPE) employing ENVI-Carb and C18 sorbents is followed by an efficient sample pre-concentration performed by acetonitrile evaporation and subsequent dilution of residue in a small volume of methanol (matrix equivalent in the final extracts was 16 and 8 g mL(-1), for milk and fish respectively). Using modern instrumentation consisting of ultra-high performance liquid chromatography (UHPLC) hyphenated with a tandem mass spectrometer (MS/MS), limits of quantification (LOQs) as low as 0.001-0.006 μg kg(-1) for milk and 0.002-0.013 μg kg(-1) for fish can be achieved. Under these conditions, a wide spectrum of PFASs, including minor representatives, can be determined which enables collecting data required for human exposure studies. The pilot study employing the new method for examination of milk and canned fish samples was realized. Whereas in majority of canned fish products a wide spectrum of PFCAs, perfluorooctanesulphonic acid (PFOS) and perfluoro-1-octanesulphonamide (PFOSA) was detected, only in a few milk samples very low concentrations (LOQ levels) of PFOS and perfluorooctansulphonic acid (PFDS) were found.     

Determination of fluorotelomer alcohols by liquid chromatography/tandem mass spectrometry in water

Fluorotelomer alcohols (FTOHs) are important polyfluorinated raw materials that belong to the general category of perfluoroalkyl substances (PFAS). PFAS, including perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates, have recently attracted considerable attention because they are persistent and found globally in the environment. FTOHs are precursors that may degrade in the environment to PFCAs. The development of analytical methods for determination FTOHs in environmental samples is necessary to determine the environmental presence of FTOHs. This work presents the development and validation of a liquid chromatography/tandem mass spectrometry (LC/MS/MS) method for the determination of FTOHs (6-2, 8-2, 10-2) in aqueous samples. Chromatographic conditions were optimized in order to obtain focused FTOH chromatographic peaks. The mobile phase and mass spectrometric conditions were optimized to enable formation of deprotonated FTOH molecules in the negative ion electrospray mode. Two extraction methods were investigated using acetonitrile and methyl tert-butyl ether (MTBE). These methods were validated for a range of environmental water samples fortified with FTOHs at three different levels. Both extraction methods resulted in recoveries from 70 to 120%. Detection limits of FTOHs were estimated to be approximately 0.09 ng/mL for LC/MS/MS detection. An LC/MS method was also developed for FTOH determination with an estimated 1.2 ng/mL limit of detection. Various sample storage scenarios were investigated. It was determined that the aqueous samples of FTOHs are best preserved by storing them frozen in sealed vials with aluminum foil lined septa.     

混合无机酸消解-固相萃取-高效液相色谱-串联质谱法分析贝类壳体中的3种全氟磺酸化合物

建立了采用混合无机酸消解-固相萃取(SPE)-高效液相色谱-电喷雾电离串联质谱(HPLC-ESI-MS/MS)分析贝类壳体中的3种全氟磺酸化合物的方法。将贝壳粉经硝酸/盐酸混合酸消解,用氢氧化钠调节消解液的pH值至6后采用Oasis WAX固相萃取柱富集净化,然后采用内标法通过HPLC-ESI-MS/MS在分时段选择反应监测模式下分析上述全氟磺酸化合物。结果表明,该方法对于贝壳中全氟丁烷磺酸、全氟己烷磺酸和全氟辛烷磺酸的检出限(LOD)分别为0.28, 0.42和0.43 ng/g,加标回收率为94.88%～96.24%。采用此方法对渤海湾两种双壳贝类壳体进行的采样分析也表明,贝壳中3种目标污染物的含量范围为＜LOD～0.70 ng/g,比其在贝类软组织中的含量低约1个数量级。实验结果表明混合酸消解-SPE提取是检测贝类壳体中此类污染物的有效前处理方法。     

Selective Determination of Se4+ and Se6+ Using SPME and GC/MS

A method for the selective determination of Se⁴⁺ and Se⁶⁺ using solid phase microextraction (SPME) and GC/MS analysis is presented. Se⁴⁺ is selectively derivatized by reaction with 4,5-dichloro-1,2-phenylenediamine to form the corresponding piazselenolo complex, extracted by the SPME fiber, and determined by GC/MS. The RSD at a 5 μg/L concentration was 9.88% and the theoretical detection limit 6 ng/L. The method was employed to test real matrices; tap and river water were analyzed before and after spiking giving a recovery rate of 102% in river water and 97% in tap water.     

Headspace solid phase microextraction in-situ supercritical fluid extraction coupled to gas chromatography-tandem mass spectrometry for simultaneous determination of perfluorocarboxylic acids in sediments

Headspace solid phase microextraction (HS-SPME) in-situ supercritical fluid extraction (SFE) was investigated for the determination of trace amounts of perfluorocarboxylic acids (PFCAs) in sediments. Quantitation was performed by using gas chromatography coupled to negative chemical ionization-tandem mass spectrometry (GC-NCI-MS/MS). The optimum conditions of HS-SPME following SFE were obtained using 500 μL n-butanol as a derivatization reagent in supercritical carbon dioxide with static extraction for 10 min, then dynamic extraction for 20 min at 30 MPa and 70 °C and simultaneous collected with 100 μm film thickness PDMS fiber. The linear range of proposed method was from 5 to 5000 ng g(-1), with limit of detection ranging from 0.39 to 0.54 ng g(-1) and limit of quantitation ranging from 1.30 to 1.80 ng g(-1). The developed method was successfully applied to analyze PFCAs in sediments from rivers and beach near industrial areas. The concentrations of PFCAs determined are from 282 to 4473 ng g(-1).     

Direct screening of water samples for benzene hydrocarbon compounds by headspace liquid-phase microextraction-gas chromatography

The applicability of headspace liquid-phase microextraction and gas chromatography is evaluated for the expeditious and reliable screening of tap and drinking water samples for selected volatile organic compounds (viz., benzene, toluene, ethylbenzene, and xylene isomers, BTEX). The method uses 3.5 microL of n-hexadecane as extraction solvent, 10 min extraction time with stirring at 1250 rpm, at 20 degrees C and 0.38 g/mL salt addition. The enrichment factors of this method are from 135 to 213. Limits of detection are in the range of 4.1-23.5 ng/L. The relative standard deviations at 0.05, 50, 200, and 400 microg/L of spiking levels are in the range of 0.61%-4.01%. Recoveries of six BTEX from drinking water at these spiking levels are between 95.4% and 104.4%.     

Determination of some organophosphorus and azole group pesticides in water samples by dispersive liquid-liquid microextraction coupled with GC/MS

A dispersive liquid-liquid microextraction (DLLME) procedure coupled with GC/MS detection is described for preconcentration and determination of some organophosphorus and azole group pesticides from water samples. Experimental conditions affecting the DLLME procedure were optimized by means of an experimental design. A mixture of 60 microL chlorobenzene (extraction solvent) and 750 microL acetonitrile (disperser solvent), 3.5 min extraction time, and 7.5 mL aqueous sample volume were chosen for the best recovery by DLLME. The linear range was 1.6-32 microg/L. The LOD ranged from 48.8 to 68.7 ng/L. The RSD values for organophosphorus and azole group pesticides at spiking levels of 3, 6, and 9 microg/L in water samples were in the range of 1.1-12.8%. The applicability and accuracy of the developed method were determined by analysis of spiked water samples, and the recoveries of the analyzed pesticides from artesian, stream, and tap waters at spiking levels of 3, 6, and 9 microg/L were 89.3-105.6, 89.5-103.0, and 92.0-111.3%, respectively.     

Determination of polyfluoroalkyl phosphoric acid diesters, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, perfluoroalkyl carboxylic acids, and perfluoroalkane sulfonic acids in lake trout from the Great Lakes region

A comprehensive method to extract perfluoroalkyl carboxylic acids, perfluoroalkane sulfonic acids, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, and polyfluoroalkyl phosphoric acid diesters simultaneously from fish samples has been developed. The recoveries of target compounds ranged from 78?% to 121?%. The new method was used to analyze lake trout (Salvelinus namaycush) from the Great Lakes region. The results showed that the total perfluoroalkane sulfonate concentrations ranged from 0.1 to 145?ng/g (wet weight) with perfluorooctane sulfonate (PFOS) as the dominant contaminant. Concentrations in fish between lakes were in the order of Lakes Ontario ≈ Erie > Huron > Superior ≈ Nipigon. The total perfluoroalkyl carboxylic acid concentrations ranged from 0.2 to 18.2?ng/g wet weight. The aggregate mean perfluorooctanoic acid (PFOA) concentration in fish across all lakes was 0.045?±?0.023?ng/g. Mean concentrations of PFOA were not significantly different (p?>?0.1) among the five lakes. Perfluoroalkyl phosphinic acids were detected in lake trout from Lake Ontario, Lake Erie, and Lake Huron with concentration ranging from non-detect (ND) to 0.032?ng/g. Polyfluoroalkyl phosphoric acid diesters were detected only in lake trout from Lake Huron, at levels similar to perfluorooctanoic acid.     

顶空固相微萃取-气相色谱-质谱联用测定饮用水中的2-甲基异莰醇和土臭素

2-甲基异莰醇(2-methylisoborneol, 2-MIB)和土臭素(geosmin, GSM)在水源水中大量分泌排放是造成饮用水土霉异味突发事件、引发居民用水恐慌的重用因素之一。使用顶空固相微萃取(HS-SPME)与气相色谱-质谱联用技术(GC-MS)建立了水库水、水库附近土壤、居民自来水中2-MIB和GSM的测定方法。结合正交分析优化了加盐量、萃取温度、萃取时间条件,在电子轰击(EI)-选择离子扫描(SIM)模式下进行了目标物的定性定量分析。结果表明:在5~1000 ng/L范围内,2-MIB和GSM的色谱峰面积与其质量浓度的线性关系良好(r²≥0.998), 2-MIB与GSM的检出限分别为0.72 ng/L和0.34 ng/L,定量限分别为2.40 ng/L和1.13 ng/L;目标物加标水平为10~600 ng/L时,平均回收率为93.6%~107.7%,相对标准偏差(RSD)≤6.1%(n=6)。基于上述方法,对辽宁省某地区水库水、水库附近土壤、居民自来水中的目标物进行检测,结果表明:水库水目标物质量浓度范围为3.0~3.6 ng/L,水库附近土壤中提取的2-MIB为8.1 ng/L、提取的GSM为17.8 ng/L,居民自来水中的目标物未检出。该方法操作简便、准确可靠,灵敏度高,无需有机溶剂,适合于饮用水中2-MIB和GSM的分析检测。     

Simultaneous determination of benzotriazoles and ultraviolet filters in ground water, effluent and biosolid samples using gas chromatography-tandem mass spectrometry

A new method using gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed for the determination of four benzotriazoles, i.e. benzotriazole (BT), 5-methylbenzotriazole (5-TTri), 5-chlorobenzotriazole (CBT), 5,6-dimethylbenzotriazole (XTri), and six UV filters, i.e. benzophenone-3 (BP-3), 3-(4-methylbenzylidene)camphor (4-MBC), octyl 4-methoxycinnamate (OMC), 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chloro benzotriazole (UV-326), 2-(2'-hydroxy-5'-octylphenyl)-benzotriazole (UV-329), and octocrylene (OC) in ground water, effluent and biosolid samples. Solid phase extraction (SPE) and pressurized liquid extraction (PLE) were applied as the preconcentration method for water samples (ground water and effluent) and biosolid samples, respectively. The optimized method allowed us to quantify all target compounds with the method detection limits ranging from 0.29 to 11.02 ng/L, 0.5 to 14.1 ng/L and 0.33 to 8.23 ng/g in tap water, effluent and biosolid samples, respectively. The recoveries of the target analytes in tap water, effluent and biosolid samples were 70-150%, 82-127% and 81-133%, respectively. The developed analytical method was applied in the determination of these target compounds in ground water, effluent and biosolid samples collected from Bolivar sewage treatment plants in South Australia. In effluent samples, the target compounds BT, 5-TTri, CBT, XTri and BP-3 tested were detected with the maximum concentration up to 2.2 μg/L for BT. In biosolid samples, eight out of ten compounds tested were found to be present at the concentrations ranging between 18.7 ng/g (5-TTri) and 250 ng/g (4-MBC).     

固相萃取液相色谱-质谱/质谱联用测定河水中大环内酯类抗生素

应用固相萃取（SPE）及LC—MS／MS技术,建立了水中痕量大环内酯类抗生素即红霉素、脱水红霉素、罗红霉素的分析方法,优化了固相萃取、液相色谱-质谱／质谱等相关条件。水样经HLB固相萃取柱富集净化,以多反应检测方式（MRM）对待测物进行定性和定量分析。3种抗生素在10-2000ng／L范围内具有良好的线性。其定量下限为5ng／L（S／N〉10）。加标纯水和实际水样的回收率在71％-111％之间,相对标准偏差（RSD）在3．7％-8．6％之间。该方法灵敏度高、选择性好、准确度高,适合实际水样中痕量大环内酯类药物的检测。使用该方法测得珠江广州河段某水样中红霉素、脱水红霉素和罗红霉素质量浓度分别为164、291和134ng／L。     

Fast screening of perfluorooctane sulfonate in water using vortex-assisted liquid-liquid microextraction coupled to liquid chromatography-mass spectrometry

Fast screening of trace amounts of the perfluorooctane sulfonate anion (PFOS) in water samples was performed following a simple, fast and efficient sample preparation procedure based on vortex-assisted liquid-liquid microextraction (VALLME) prior to liquid chromatography-mass spectrometry. VALLME initially uses vortex agitation, a mild emulsification procedure to disperse microvolumes of octanol, a low density extractant solvent, in the aqueous sample. Microextraction under equilibrium conditions is thus achieved within few minutes. Subsequently, centrifugation separates the two phases and restores the initial microdrop shape of the octanol acceptor phase, which can be collected and used for liquid chromatography-single quadrupole mass spectrometry analysis. Several experimental parameters were controlled and the optimum conditions found were: 50 μL of octanol as the extractant phase; 20 mL aqueous donor samples (pH=2); a 2 min vortex extraction time with the vortex agitator set at a 2500 rpm rotational speed; no ionic strength adjustment. Centrifugation for 2 min at 3500 rpm yielded separation of the two phases throughout this study. Enhanced extraction efficiencies were observed at low pH which was likely due to enhanced electrostatic interaction between the negatively PFOS molecules and the positively charged octanol/water interface. The effect of pH was reduced in the presence of sodium chloride, likely due to electrical double layer compression. The linear response range for PFOS was from 5 to 500 ng L(-1) (coefficient of determination, r(2), 0.997) and the relative standard deviation for aqueous solutions containing 10 and 500 ng L(-1) PFOS were 7.4% and 6.5%, respectively. The limit of detection was 1.6 ng L(-1) with an enrichment factor of approximately 250. Analysis of spiked tap, river and well water samples revealed that matrix did not affect extraction.     

Simultaneous determination of macrolides, sulfonamides, and other pharmaceuticals in water samples by solid-phase extraction and LC-(ESI) MS

This paper describes a method for determining 11 pharmaceuticals in various water sources by SPE followed by LC-(ESI) MS. SPE was carried out with Oasis HLB and the recoveries were 33-67% for 250 and 100 mL sewage water, 55-77% for 500 mL river water and 72-98% for 1 L tap water, with the exception of sulfamethoxazole and omeprazole which showed lower recoveries in all kinds of sample. The LODs in river water were of 5 ng/L for sulfadiazine, trimethoprim, sulfamethazine, sulfamethoxazole, and ranitidine and 10 ng/L for the other compounds. The highest concentrations found in river waters were for sulfamethoxazole (50 ng/L). In influent sewage waters, ranitidine was the most commonly detected compound with a maximum value of 0.24 microg/L.     

Trace analysis of diethylstilbestrol, dienestrol and hexestrol in environmental water by Nylon 6 nanofibers mat-based solid-phase extraction coupled with liquid chromatography-mass spectrometry

A simple, rapid and sensitive method for the determination of diethylstilbestrol (DES), dienestrol (DE) and hexestrol (HEX) was developed by using the Nylon 6 nanofibers mat-based solid-phase extraction (SPE) coupled with liquid chromatography-tandem mass spectrometry (LC-MS). These estrogens were separated within 8 min by LC using an ODS column and methanol/water (80/20, v/v) at a flow rate of 1.0 mL min(-1). Electrospray ionization conditions in the negative ion mode were optimized for MS detection of the estrogens. Under the optimum SPE conditions, all target analytes in 50 mL environmental water samples can be completely extracted by 1.5 mg Nylon 6 nanofibers mat at flow rate of 3.0 mL min(-1) and easily eluted by passage of 500 μL mobile phase. By using the novel SPE-LC/MS method, good linearity of the calibration curve (r(2) ≥ 0.9992) was obtained in the concentration range from 0.10 ng L(-1) to 1.0 mg L(-1) (except for DE which was 0.20 ng L(-1) to 1.0 mg L(-1)) for all analytes examined. The limits of detection (S/N = 3) of the three estrogens ranged from 0.05 ng L(-1) to 0.10 ng L(-1). This method was applied successfully to the analysis of environmental water samples without any other pretreatment and interference peaks. Several water samples were collected from Jinchuan River and Xuanwu Lake, and in Jinchuan River water DES was detected at 0.13 ng L(-1). The recoveries of estrogens spiked into tap water were above 98.2%, and the relative standard deviations were below 4.78%.     

A fully automated system with on-line micro solid-phase extraction combined with capillary liquid chromatography-tandem mass spectrometry for high throughput analysis of microcystins and nodularin-R in tap water and lake water

Microcystins and nodularins are cyclic peptide hepatotoxins and tumour promoters from cyanobacteria. The present study describes the development, validation and practical application of a fully automated analytical method based on on-line micro solid-phase extraction-capillary liquid chromatography-tandem mass spectrometry for the simultaneous determination of seven microcystins and nodularin-R in tap water and lake water. Aliquots of just 100 μL of water samples are sufficient for the detection and quantification of all eight toxins. Selected reaction monitoring was used to obtain the highest sensitivity. Good linear calibrations were obtained for microcystins (50-2000ng/L) and nodularin-R (25-1000 ng/L) in spiked tap water and lake water samples. Excellent interday and intraday repeatability were achieved for eight toxins with relative standard deviation less than 15.7% in three different concentrations. Acceptable recoveries were achieved in the three concentrations with both tap water matrix and lake water matrix and no significant matrix effect was found in tap water and lake water except for microcystin-RR. The limits of detection (signal to noise ratio=3) of toxins were lower than 56.6 ng/L which is far below the 1 μg/L defined by the World Health Organization provisional guideline for microcystin-LR. Finally, this method was successfully applied to lake water samples from Tai lake and proved to be useful for water quality monitoring.     

Analysis of perfluoroalkyl anion fragmentation pathways for perfluoroalkyl carboxylates and sulfonates during liquid chromatography/tandem mass spectrometry: evidence for fluorine migration prior to secondary and tertiary fragmentation

It is known that under liquid chromatography/electrospray tandem mass spectrometry (LC/ES-MS/MS) conditions, the perfluorocarboxylate anion [R(F)CO(2)](-) first loses CO(2) to give a perfluoroalkyl anion R(F)(-), [(M-H)-CO(2)](-), which can subsequently fragment to give inter alia lower mass carbanions. It has been suggested in a previous study that such secondary fragmentation involves cleavage of C(n)F(2n) segments. Our study of the LC/ES-MS/MS of a series of (13)C-labeled perfluoroalkyl carboxylic acids (PFCAs) indicates that fragmentation of the R(F)(-) anion does not involve simple 'unzipping' of a primary perfluoroalkyl anion of the type F(3)C(CF(2))(x)CF(2)(-). For example, we have discovered that the secondary transition for the mass-labeled PFOA, perfluoro-1,2,3,4-(13)C(4)-octanoic acid (MPFOA), gives two signals of equal intensity at m/z 169 and 172. We propose a mechanism of fragmentation that involves rapid fluorine shifts, after the initial decarboxylation, which generate a series of new anions prior to secondary and tertiary fragmentation.     

Validated dispersive liquid-liquid microextraction for analysis of organophosphorous pesticides in water

Dispersive liquid-liquid microextraction (DLLME) combined with gas chromatography and mass spectrometry (GC-MS) was applied to the determination of six organophosphorous pesticides (OPPs) in water samples. The analytes included in this study were prophos, diazinon, chlorpyrifos methyl, methyl parathion, fenchlorphos and chlorpyrifos. Several extraction and dispersion solvents were tested for dispersive liquid-liquid microextraction of these analytes and the best results were obtained using chloroform as extraction solvent and 2-propanol as dispersion solvent. Calibration curves of the analytes in water samples were constructed in the concentration range from 100 to 1100 ng/L for prophos, diazinon and methyl parathion and in the range from 100 to 1000 ng/L for chlorpyrifos methyl, fenchlorphos and chlorpyrifos. Limits of detection (LODs) were in the range of 1.5-9.1 ng/L and limits of quantification (LOQs) were in the range of 5.1-30.3 ng/L, below the maximum admissible level for drinking water. Relative standard deviations (RSDs) were between 6.5 and 10.1% in the concentration range of 100-1000 ng/L. The relative recoveries (%RRs) of tap, well and irrigation water samples fortified at 800 ng/L were in the range of 46.1-129.4%, with a larger matrix effect being detected in tap water.     

固相萃取-超高压液相色谱-串联质谱同时分析环境水样中四环素类和喹诺酮类抗生素

应用固相萃取及超高压液相色谱-质谱联用技术,建立了环境水样中4种四环素类和6种喹诺酮类抗生素的同时分析方法。样品经HLB固相萃取柱富集、净化后用甲醇洗脱,以超高压液相色谱-串联质谱仪多反应监测(MRM)离子模式定性、定量分析。以河水和海水为基质,卡巴氧为替代物进行回收率评价,4种四环素类抗生素在加标质量浓度分别为20.0 ng/L和100.0 ng/L时的回收率为94.0%～117.0%,相对标准偏差为2.0%～9.7%(n=4),方法的检出限均为20.0 ng/L;6种喹诺酮类抗生素在加标质量浓度分别为5.0 ng/L和20.0 ng/L时的回收率为63.6%～93.9%,相对标准偏差为1.6%～8.1%(n=4),方法的检出限为0.4 ng/L。结果表明,所建立的方法可成功地应用于近岸海域表层环境水样中目标抗生素残留的分析。