Determination of bromophenols as dioxin precursors in combustion gases of fire retarded extruded polystyrene by sorptive sampling-capillary gas chromatography-mass spectrometry

Extruded polystyrene (XPS) is often treated with hexabromocyclododecane (HBCD) as fire retardant (FR). Because of its aliphatic structure, HBCD is not suspected to cause formation of polybrominated dioxins upon combustion. Precursors of polybrominated dioxins, namely bromophenols, were detected during tubular furnace combustion experiments of FR-XPS in combination with sorptive enrichment on polydimethylsiloxane followed by on-line thermal desorption-capillary GC/MS. The highest concentration of mono- and tribromophenols detected were 85.9 and 3.7 mg kg(-1), respectively, at a temperature of 700 degrees C, while a temperature of 500 degrees C yielded the highest concentration of dibromophenols namely 10.4 mg kg(-1). At a combustion temperature of 900 degrees C no bromophenols were detected.     

Development and Comprehensive SPE-UHPLC-MS/MS Analysis Optimization,Comparison, and Evaluation of 2,4-Epibrassinolide in Different Plant Tissues

A determination method for trace 24-epibrassinolide (EBL) in plant tissues was developed using ultra-high-performance liquid chromatography–tandem mass spectrometry (UPLC-MS/MS). The plant tissue samples were extracted using a methanol–formic acid solution, and the corresponding supernatant was purified with ODS C18 solid-phase extraction column. The extracts were separated using a Zorbax Eclipse Plus C18 (2.1 mm × 50 mm, 1.8 μm) column with methanol and 0.1% formic acid as the mobile phase. The ion source for the mass spectrometry was an electrospray ionization source with positive ion mode detection. The linear range of the target compound was 0.7~104 μg/kg, the limit of detection (LOD) was 0.11~0.37 μg/kg, the limit of quantification (LOQ) was 0.36~1.22 μg/kg, the recovery rate was 84.0~116.3%, and the relative standard deviation (RSD%) was 0.8~10.5. The samples of maize plumule, brassica rapeseed flower, and marigold leaf were detected using the external standard method. The optimization of the extraction method and detection method of EBL improved the detection sensitivity, laid a foundation for the artificial synthesis of EBL, improved the extraction rate of EBL, and provided a theoretical basis for the study of EBL in many plants.     

顶空衍生化固相微萃取法测定酱油中3-氯-1,2丙二醇

建立顶空衍生化固相微萃取测定酱油中3-氯-1,2丙二醇(3-MCPD)的方法。聚乙二醇-二乙烯基苯(CW-DVB)萃取纤维先顶空吸附苯基硼酸,然后同时萃取和衍生化样品顶空气体中的3-MCPD和内标物d5-3-MCPD,衍生化产物在进样口热解吸,GC-MS检测,内标法定量,特征离子为m/z196、201。结果表明,样品中3-MCPD质量浓度为0.01~1mg/kg时,工作曲线的线性良好(r=0.9994),添加回收率为89%~104%,检出限为0.01mg/kg。     

固相萃取-气相色谱/质谱法分析水果和蔬菜中残留的嘧菌酯

建立了多种水果和蔬菜中嘧菌酯残留的气相色谱/质谱分析方法。首先用乙酸乙酯-环己烷(体积比为1∶1)对样品中的嘧菌酯进行超声波提取,经硅胶固相萃取小柱对样品提取液进行净化、富集,采用气相色谱/质谱法以选择离子监测模式(m/z 344,372,388,403定性,m/z 344定量)进行检测。实验结果表明,嘧菌酯在0.01～1.0 mg/kg浓度范围内呈线性,其相关系数r>0.99。在低、中、高3个添加水平,嘧菌酯的回收率为85.2%～98.2%,相对标准偏差为5.8%～21.5%。方法的检测限不大于0.01 mg/kg,定量限不大于0.05 mg/kg。     

固相萃取–气相色谱–负化学源质谱法检测水果和蔬菜中的毒杀芬

采用改进的分散固相萃取(QuEchERs)法对样品进行前处理,建立水果和蔬菜中毒杀芬残留的气相色谱–负化学电离源质谱(GC–NCI–MS)检测方法。样品中的毒杀芬由正己烷提取,经吸附剂PSA+GCB净化,在GC–NCI–MS的选择离子扫描模式下进样分析。毒杀芬的色谱保留时间在12.5~18.0 min区间内,采用面积归一化法积分,外标法定量。毒杀芬质量浓度在0.050~2.000 mg/L范围内与色谱峰面积呈良好的线性关系,相关系数r=0.999 1。分别以蓝莓、黄桃、菠菜为基质,在0.025,0.050 mg/kg添加水平下,毒杀芬的回收率为107.2%~118.1%,测定结果的相对标准偏差为5.5%~8.8%(n=6),定量限为0.025 mg/kg。该方法检测快速,适用于水果和蔬菜中毒杀芬残留的日常检测。     

气相色谱-质谱法测定涂料中的六溴环十二烷

提出了用气相色谱-质谱法测定涂料中六溴环十二烷含量的方法。样品用二氯甲烷-丙酮(1+1)混合溶剂超声提取,提取液经硅胶固相萃取小柱净化、平行蒸发定量浓缩后,用DB-5MS毛细管柱进行分离,全扫描模式和选择离子监测模式测定。六溴环十二烷的质量浓度在1～50mg·L-1范围内与其峰面积呈线性关系,测定下限(10S/N)为10 mg·kg-1。添加5,20,50mg·L-1 3个浓度水平进行加标回收试验,回收率在82.0%～106%之间,测定值的相对标准偏差(n=8)在2.8%～5.3%之间。     

Rapid identification of brominated flame retardants by using direct exposure probe mass spectrometry

A rapid method for analyzing brominated flame retardants (BFRs) was developed using direct exposure probe/mass spectrometry (DEP/MS). The BFRs used in this study included 1,2-bis(pentabromophenyl)ethane (EBP), tetrabromobisphenol A (TBBPA), and hexabromocyclododecane (HBCD), which are included in the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment (RoHS).Quantitative analysis was conducted using octabromodiphenyl ether (octa-BDE), nonabromodiphenyl ether (nona-BDE), and decabromodiphenyl ether (deca-BDE). The samples were extracted by ultrasonication, following which the diluted sample solutions were analyzed by DEP/MS. Finally, the characteristic ions in the mass spectra of BFRs were identified.The limit of detection (LOD) and limit of quantification (LOQ) for deca-BDE were 0.163 and 0.495 mg/kg, respectively. The calibration curve showed a linearity (R² = 0.9984) within 0.5-16 μg/mL. The relative standard deviation ranged from 2.78% to 6.76%. The octa-BDE and nona-BDE samples showed similar results. Finally, the certified reference material (CRM, NMIJ CRM 8108-a, Japan) for the deca-BDE analysis was used, and the recovery was 96.4%.     

Determination of hexabromocyclododecane isomers in sewage sludge by LC‐MS/MS

A method has been developed to determine α, β and γ diastereoisomers of hexabromocyclododecane (HBCD), a brominated flame retardant, in sewage sludge, based on the ultrasonic‐assisted extraction (UAE) of samples with dichloromethane–ACN (1:1) and the subsequent clean‐up of extracts by dispersive solid phase extraction with primary–secondary amine. Levels of HBCD diastereoisomers were determined by LC coupled with ESI MS/MS. Evaluation of the matrix effect showed a high ion suppression for all the diastereoisomers studied, which was counteracted by using a mixture of labelled HBCD diastereoisomers as internal standards. This method yielded recoveries in the range of 79.6–112.5% with SDs equal or lower than 9.1 The limits of detection were 0.3 ng/g for α‐ and β‐HBCD and 0.2 ng/g for γ‐HBCD. The developed method was successfully applied to 19 sludge samples collected from the province of Madrid (Spain). In most of the samples, β‐HBCD was below the method detection limit, whereas α‐ and γ‐HBCD were quantified in all of the sludge samples, and γ‐HBCD was the predominant diastereoisomer in 63% of the analyzed samples and α‐HBCD predominated in the rest.     

超高效液相色谱-串联四极杆质谱法检测小型家电外壳中的六溴环十二烷

建立了加热回流萃取-超高效液相色谱-串联四极杆质谱检测小型家用电器中六溴环十二烷( Hexabromocyclododecane,HBCD)的方法.实验优化了电子电器类产品的前处理方法,以甲苯-甲醇(10∶1,V/V)为萃取剂,加热回流4h.萃取出的溶液经N2吹干,初始流动相复溶,涡旋、离心、过膜,经ACQUITYTMUPLC BEH C18色谱柱分离;以甲醇-乙腈(4∶1,V/V)-10 mmol/L醋酸铵为流动相,质谱的多反应监测模式(MRM)进行检测,HBCD的3种同分异构体在3 min内完全分开.该物质的检山限为0.014 mg/L:定量限为0.068 mg/L;标准曲线的线性范围为1.6～ 32.4 mg/L,线性相关系数大于0.996,萃取回收率为68.0％～75.2％.通过外标法定量,并将本方法应用于实际样品(电视机外壳、电子相框、电磁炉外壳等)的检测.     

Multi-Class Procedure for Analysis of 50 Antibacterial Compounds in Eggshells Using Ultra-High-Performance Liquid Chromatography–Tandem Mass Spectrometry

In this work, for the first time, Ultra-High-Performance Liquid Chromatography–Tandem Mass Spectrometry (UHPLC–MS/MS) method was developed for qualitative and quantitative analysis of veterinary antibiotics (cephalosporins, diaminopyrimidines, fluoro(quinolones), lincosamides, macrolides, penicillins, pleuromutilins, sulfonamides, tetracyclines, and sulfones) in hen eggshells. The sample preparation method is based on a liquid–liquid extraction with a mixture of metaphosphoric acid, ascorbic acid, EDTA disodium salt dihydrate, and acetonitrile. The chromatographic separation was performed on Luna^® Omega Polar C18 10 column in gradient elution mode and quantitated in an 8 min run. Validation such as linearity, selectivity, precision, recovery, matrix effect, limit of quantification (LOQ), and limit of detection (LOD) was found to be within the acceptance criteria of the validation guidelines of the Commission Decision 2002/657/EC and EUR 28099 EN. Average recoveries ranged from 81–120%. The calculated LOQ values ranged from 1 to 10 µg/kg, the LOD values ranged from 0.3 to 4.0 µg/kg, depending on analyte. The developed method has been successfully applied to the determination of antibacterial compounds in hen eggshell samples obtained from different sources. The results revealed that enrofloxacin, lincomycin, doxycycline, and oxytetracycline were detected in hen eggshell samples.     

Refinements to the diastereoisomer-specific method for the analysis of hexabromocyclododecane

The emergence of hexabromocyclododecane (HBCD) as a bromine-based flame retardant of concern is partly attributable to recent measurements on the environmental occurrence of the individual diastereoisomers (alpha, beta and gamma). These measurements were fuelled by a newly developed liquid chromatography/tandem mass spectrometric (LC/MS/MS)-based analytical method. However, in the course of our recent studies on the environmental fate and behaviour of the diastereoisomers of HBCD, some interesting features of the LC/MS/MS method became apparent. For example, the ion signal of the native ions was found to be dependent on the final extract volume. This was true for both biotic and sediment samples and was found to arise from the suppression of the ion signal due to endogenous material in the extracts that escape clean-up. We have also found differences in the stability of the diastereoisomers in different solvents. If left unaccounted for, both factors can compromise analytical measurement data. By way of a series of controlled experiments conducted at our two laboratories [Department of Fisheries & Oceans Canada (DFO) and Environment Canada (EC)], we illustrate these features and demonstrate that use of newly synthesized labelled HBCD isomers [(13-carbon (13C) and deuterium (d18)] can minimize and often circumvent matrix-related effects.     

Determination of Methylene Blue and Its Metabolite Residues in Aquatic Products by High-Performance Liquid Chromatography–Tandem Mass Spectrometry

A sensitive and reliable method was developed to determine methylene blue (MB) and its metabolite residues, including azure A (AZA), azure B (AZB), and azure C (AZC) in aquatic products by HPLC–MS/MS. The samples were extracted by acetonitrile and cleaned up by alumina-neutral (ALN) cartridges. The analytes were separated on a Sunfire C18 column (150 mm × 2.1 mm, 5 µm). The method was validated according to the European criteria of Commission Decision 2002/657/CE. Good linearity between 1–500 µg/L was obtained with correlation coefficients (R²) greater than 0.99. The limit of quantification (LOQ) was 1.0 µg/kg. The average recoveries at three levels of each compound (1, 5, and 10 µg/kg) were demonstrated to be in the range of 71.8–97.5%, with relative standard deviations (RSDs) from 1.05% to 8.63%. This method was suitable for the detection of methylene blue and its metabolite residues in aquatic products.     

Simultaneous quantitative determination of amphetamines, ketamine, opiates and metabolites in human hair by gas chromatography/mass spectrometry

A gas chromatography/mass spectrometry (GC/MS) method was developed and validated for the determination of common drugs of abuse in Asia. The method was able to simultaneously quantify amphetamines (amphetamine; AP, methamphetamine; MA, methylenedioxy amphetamine; MDA, methylenedioxymeth mphetamine; MDMA, methylenedioxy ethylamphetamine; MDEA), ketamine (ketamine; K, norketamine; NK), and opiates (morphine; MOR, codeine; COD, 6-acetylmorphine; 6-AM) in human hair. Hair samples (25 mg) were washed, cut, and incubated overnight at 25 degrees C in methanol/trifluoroacetic acid (methanol/TFA). The samples were extracted by solid-phase extraction (SPE), derivatized using heptafluorobutyric acid anhydride (HFBA) at 70 degrees C for 30 min, and the derivatives were analyzed by electron ionization (EI) GC/MS in selected ion monitoring mode. Confirmation was accomplished by comparing retention times and the relative abundances of selected ions with those of standards. Deuterated analogs of the analytes were used as internal standards for quantification. Calibration curves for ten analytes were established in the concentration range 0.1-10 ng/mg with high correlation coefficients (r2 > 0.999). The intra-day and inter-day precisions were within 12.1% and 15.8%, respectively. The intra-day and inter-day accuracies were between -8.7% and 10.7%, and between -5.9% and 13.8%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) obtained were 0.03 and 0.05 ng/mg for AP, MA, MDA, MDMA and MDEA; 0.05 and 0.08 ng/mg for K, NK, MOR and COD; and 0.08 and 0.1 ng/mg for 6-AM. The recoveries were above 88.6% for all the compounds, except K and NK which were in the range of 71.7-72.7%. Eight hair samples from known polydrug abusers were examined by this method. These results show that the method is suitable for broad-spectrum drug testing in a single hair specimen.     

Simultaneous Analysis for Quality Control of Traditional Herbal Medicine,Gungha-Tang,Using Liquid Chromatography–Tandem Mass Spectrometry

Gungha-tang (GHT), a traditional herbal medicine, consists of nine medicinal herbs (Cnidii Rhizoma, Pinelliae Tuber, Poria Sclerotium, Citri Unshius Pericarpium, Citri Unshius Pericarpium Immaturus, Aurantii Fructus Immaturus, Atracylodis Rhizoma Alba, Glycyrrhizae Radix et Rhizoma, and Zingiberis Rhizoma Recens). It has been used for various diseases caused by phlegm. This study aimed to develop and verify the simultaneous liquid chromatography–tandem mass spectrometry (LC–MS/MS) analysis method, using nine marker components (liquiritin apioside, neoeriocitrin, narirutin, naringin, hesperidin, neohesperidin, liquiritigenin, glycyrrhizin, and 6-shogaol) for quality control of GHT. LC–MS/MS analysis was conducted using a Waters TQ-XS system. All marker analytes were separated on a Waters Acquity UPLC BEH C₁₈ column (2.1 × 100 mm, 1.7 μm) using gradient elution with a distilled water solution (containing 5 mM ammonium formate and 0.1% [v/v] formic acid)–acetonitrile mobile phase. LC–MS/MS multiple reaction monitoring (MRM) analysis was carried out in negative and positive ion modes of an electrospray ionization source. The developed LC–MS/MS MRM method was validated by examining the linearity, limits of detection and quantification, recovery, and precision. LOD and LOQ values of nine markers were calculated as 0.02–8.33 ng/mL and 0.05–25.00 ng/mL. The recovery was determined to be 89.00–118.08% and precision was assessed with a coefficient of variation value of 1.74–8.64%. In the established LC–MS/MS MRM method, all markers in GHT samples were detected at 0.003–16.157 mg/g. Information gathered during the development and verification of the LC–MS/MS method will be useful for the quality assessment of GHT and other herbal medicines.     

Determination of pesticides in aqueous samples by solid-phase microextraction in-line coupled to gas chromatography—mass spectrometry

A multiresidue method was developed for the determination of nitrogen- and phosphorous-containing pesticides (amines, anilides, phosphorothioates, and triazines) by solid-phase microextraction (SPME) in-line coupled to gas chromatography—mass spectrometry (GC/MS). The 85-µm polyacrylate fiber was first dipped into the aqueous sample for a given time and then directly introduced into the heated injector of the gas chromatography—mass spectrometer, where the analytes are thermally desorbed. The method was evaluated with respect to the limit of detection, linearity, and precision. The limit of detection [selected ion monitoring (SIM) mode] depends on the compound and varies from 5 to 90 ng/L. The method is linear over at least 3 orders of magnitude with coefficients of correlation usually ≥0.996. In general, the coefficient of variation (precision) is <10%. The partitioning of the analyte between the aqueous phase and the polymeric phase depends on the hydrophobicity of the compound as expressed by the octanol—water partitioning coefficient P _ow. The addition of sodium chloride has a strong effect on the extraction efficiency. This effect increases with decreasing hydrophobicity (increasing polarity) of the compound. The triazines atrazine, simazine, and terbuthylazine were first identified and quantified in water samples from the effluent of sewage plants by SPME-gas chromatography—nitrogen—phosphorus detection (GC/NPD). For such a complex matrix GC/NPD is not sufficiently selective for an unambiguous identification at low levels (<1 ppb) of pesticides. Selectivity may be enhanced by using SMPE-GC/MS in the SIM mode with three characteristic ions for each pesticide. This method allows an unequivocal identification and quantification at low levels of pesticides in environmental samples. At a target limit of detection below 100 ng/L, SPME-GC/MS represents a very simple, fast, selective, and solvent-free multimethod for the extraction and determination of these nitrogen- and phosphorous-containing pesticides from aqueous samples.     

Evaluation of Dissipation Behavior,Residues, and Dietary Risk Assessment of Fludioxonil in Cherry via QuEChERS Using HPLC-MS/MS Technique

The chemical fungicide fludioxonil is widely used to control post-harvest fungal disease in cherries. This study was implemented to investigate the dissipation behaviours and residues of fludioxonil on cherries. A reliable and efficient analytical method was established. Cherry samples from four product areas were analyzed by QuEChERS and HPLC-MS/MS methods with acceptable linearity (R² > 0.99), accuracy (recoveries of 81–94%), and precision (relative standard deviation of 2.5–11.9%). The limits of quantification (LOQs) and limits of detection (LODs) of cherries were 0.01 mg/kg and 0.005 mg/kg. The dissipation of fludioxonil on cherries followed first order kinetics with half-lives of 33.7–44.7 days. The terminal residues of fludioxonil were all lower than 5.00 mg/kg, which is the MRL recommended by the European Commission. According to Chinese dietary patterns and terminal residue distributions, the risk quotient (RQs) of fludioxonil was 0.61%, revealing that the evaluated cherries exhibited an acceptably low dietary risk to consumers.     

单分散键合型含铕聚苯乙烯微球的制备与荧光传感性能

制备了一种可定性定量检测水溶液中三价铁离子的含铕聚苯乙烯微球, 分别用固体核磁碳谱(¹³C CP/MAS NMR)、 傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 元素分析、 粒度分析和ζ电位分析等对其化学组成和结构形貌进行表征. 当铕配合物单体用量低于2.5%时, 可以得到稳定的单分散键合型含铕聚苯乙烯微球. 用紫外光激发时, 该含铕聚苯乙烯微球发射铕离子的特征红光. Fe³⁺能猝灭该微球的荧光, 酸根离子和其它金属离子对其干扰较少; 猝灭效率与Fe³⁺浓度在0~300 μmol/L浓度范围内均呈线性关系; 随着铕配合物单体用量的增加, 微球的荧光增强, 其在检测Fe³⁺的荧光时, 猝灭常数(K_SV)增加, 检测限(LOD)下降. 调节铕配合物单体的用量, 可获得热性能优异、 红光发射强度高且稳定性好的单分散聚苯乙烯荧光微球, 对Fe³⁺荧光检测显示出较高的选择性, 在生物检测和环境保护等领域具有较高的应用价值.     

Application of tandem mass spectrometry combined with gas chromatography to the routine analysis of ethyl carbamate in stone-fruit spirits

Gas chromatography (GC) coupled to mass spectrometry (MS) operated in selected ion monitoring (SIM) mode is currently the method of choice for the determination of the toxic contaminant ethyl carbamate in alcoholic beverages. However, even after extensive sample cleanup over diatomaceous earth columns, the identity of ethyl carbamate often cannot be ascertained with confidence, due to inconsistent ratios of the SIM ions m/z 62, 74 and 44 because the qualifier ions are highly susceptible to interferences. Therefore, a new method combining GC and tandem MS using a triple-quadrupole instrument is introduced to determine ethyl carbamate in stone-fruit spirits. For quantitative analysis the characteristic transitions of m/z 74 --> 44 and m/z 62 --> 44 for ethyl carbamate as well as m/z 64 --> 44 for the deuterated internal standard ethyl carbamate-d5 were monitored in the multiple reaction monitoring (MRM) mode. In the validation studies, ethyl carbamate exhibited good linearity with a regression coefficient of 1.000. The limits of detection and quantitation were 0.01 and 0.04 mg/L. The recovery of the method was 100.4 +/- 9.4%. The precision never exceeded 7.8% (intraday) and 10.1% (interday) and the trueness never exceeded 11.3% (intraday) and 12.2% (interday) at any of the concentrations examined, indicating good assay accuracy. A good agreement of analytical results between a previously developed GC/MS SIM method and the GC/MS/MS MRM procedure was found (R=0.987). Regarding the validation data, the procedure is sensitive, selective and reproducible. The applicability of the developed method was demonstrated by the investigation of 70 stone-fruit spirits from commercial trade. The ethyl carbamate concentration of the samples ranged between 0.07 and 7.70 mg/L (mean 1.21 mg/L). The main advantage of the developed GC/MS/MS method is the reliability of the results without the need for time-consuming confirmatory analyses.     

High-throughput GC/MS and HPLC/MS/MS techniques for the multiclass, multiresidue determination of 653 pesticides and chemical pollutants in tea

An efficient and sensitive method has been established for simultaneous determination of 653 pesticides in teas by GC/MS and HPLC/MS/MS. The method involved extraction with acetonitrile followed by cleanup using Cleanert-TPT SPE and subsequent identification and quantitation of 490 pesticides by GC/MS and 448 pesticides by HPLC/MS/ MS. The LODs for pesticides determined by GC/MS were between 1.0 and 500 microg/kg, and those determined by HPLC/MS/MS were between 0.03 and 4820 microg/kg. At the low fortification levels of 0.01-100 microg/kg, the average recoveries of 94% of the pesticides determined by GC/MS were between 60 and 120%, 77% of which had an RSD below 20%. For 91% of pesticides determined by HPLC/MS/MS, the average recoveries were between 60 and 120%, 76% of which had an RSD below 20%. The paper also reports a novel SPE column, Cleanert TPT, which comprised graphitized carbon black (PestiCarb), polyamine silica, and amide polystyrene for purifying the tea samples. The results indicated good repeatiblity and reproducibility.     

Gas chromatography/mass spectrometry determination of amphetamine-related drugs and ephedrines in plasma, urine and hair samples after derivatization with 2,2,2-trichloroethyl chloroformate

A new analytical approach, based on derivatization with 2,2,2-trichloroethyl chloroformate and gas chromatography/mass spectrometry (GC/MS), was investigated for qualitative and quantitative analyses of a large range of amphetamine-related drugs and ephedrines in plasma, urine and hair samples. Sample preparation involved alkaline extraction of analytes from biological samples using Extrelut columns, after addition of the internal standard 3,4-methylenedioxypropylamphetamine (MDPA), and subsequent derivatization to produce 2,2,2-trichloroethylcarbamates. GC/MS analyses, in splitless mode using a slightly polar 30-m capillary column, were performed with quadrupole or ion trap instruments. MS acquisition modes were electron ionization (EI) in full-scan or selected ion monitoring (SIM) modes (quadrupole), and full-scan MS or MS/MS modes with chemical ionization (CI) conditions (ion trap). EI spectra of 2,2,2-trichloroethylcarbamates showed variably abundant molecular ions as well as abundant diagnostic fragment ions, both characterized by ion clusters reflecting the isotope distribution of three chlorine atoms in the derivatized molecules. CI spectra showed abundant protonated molecules. Quantitative studies using EI SIM conditions gave recoveries in the range 74-89%, linear response over ranges of 10-2000 ng/mL (plasma and urine) and 0.20-20 ng/mg (hair), with corresponding limits of detection in the ranges 2-5 ng/mL and 0.1-0.2 ng/mg. Potential applications (following full method validation) include clinical and forensic toxicology, as well as doping control.