A multi-residue method for the determination of 203 pesticides in rice paddies using gas chromatography/mass spectrometry

This work reports a rapid, specific and sensitive multi-residue method based on the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) sample preparation method and gas chromatography with mass spectrometric detection in the selected ion monitoring mode (GC-MS-SIM) using one quantification ion and two identification ions for the routine analysis of 203 pesticides in rice paddies. Analyses of fortified rice paddy samples were performed at different levels (0.05, 0.20 and 0.50 mg kg⁻¹). Mean recoveries from five replicates ranged from 75% to 115%, with coefficients of variation lower than 17%. The limit of quantification was in the range of 0.002-0.05 mg kg⁻¹ for the pesticides. 1040 rice paddy samples were analyzed for method application.     

Microwave-assisted silylation followed by gas chromatography/mass spectrometry for rapid determination of ergosterol in cigarettes

Ergosterol is one of the important precursors of tumorigenic polynuclear aromatic hydrocarbons. To the best of our knowledge, a large amount of ergosterol is present in moldy cigarettes, which derives from fungal contaminations. Thus, the development of a simple, fast, and efficient method for the analysis of ergosterol is in great demand. In this paper, GC/MS following microwave-assisted silylation (MAS) was developed for the rapid quantitative analysis of ergosterol in cigarettes for the first time. In our work, total ergosterol in cigarettes after NaOH saponification was extracted with hexane, and then was fast derivatized with bis(trimethylsilyl)trifluoroacetamide (BSTFA) under microwave irradiation. Finally, the ergosterol trimethylsilyl derivative was analyzed by GC/MS. Derivatization conditions including microwave reaction solvent, irradiation time, and power were investigated. Method validations (linear range, LOD, precision, and recovery) were also studied. The results showed that the proposed method provided a fast, simple, and sensitive approach for the determination of ergosterol in cigarettes. Finally it was successfully applied to the analysis of ergosterol in normal and mildewy cigarettes.     

Microwave-assisted solvent extraction and gas chromatography ion trap mass spectrometry procedure for the determination of persistent organochlorine pesticides (POPs) in marine sediment

Microwave-assisted solvent extraction of persistent organochlorine pesticides (POPs) in marine sediment was developed and optimized by means of two-level factorial designs. Six variables (microwave power, extraction time and temperature, amount of sample, solvent volume, and sample moisture) were considered as factors in the optimization process. The results show that the amount of sample to be extracted and solvent volume are statistically significant for the overall recovery of the studied pesticides, although compromise conditions have to be established with the object of avoiding overpressure in closed vessels. After extraction, a clean up step including the use of a silica cartridge was performed prior to chromatographic determination in order to remove interferences. The optimized procedure was compared to conventional Soxhlet extraction. The MS-MS ion preparation mode was applied to improve the sensitivity and selectivity of the chromatographic technique.     

Fatty acid profiling of blood cell membranes by gas chromatography with mass spectrometry

Fatty acids, which are well‐known for their influence on human metabolism and signal transduction, are also a substantial component of cellular membranes and regulate the basic properties and functions of membranes. Owing to their multiple functions, fatty acid profiles of cell membranes are of great interest to those who are studying the relationship between membrane biochemical compositions and functions. A HCl‐catalyzed derivation method and a gas chromatography with mass spectrometry analysis method were developed to accurately profile the fatty acids in cell membranes of erythrocytes, leukocytes, and platelets. The detection limits of all 35 fatty acids ranged from 0.58 to 22 ng/mL and the limits of quantitation were between 2.1 and 72 ng/mL. Finally, the established method was used to profile the membrane fatty acids of 44 healthy volunteers from the north and south of China. Results revealed significant differences in the fatty acid profiles from the two regions, particularly those of the erythrocytes. This technique may be applied to cell membrane studies to generate new biological hypotheses concerning fatty acid composition and membrane functions as well as to construct related disease profiles.     

Pressurized solvent extraction followed by gas chromatography tandem mass spectrometry for the determination of benzotriazole light stabilizers in indoor dust

A novel and sensitive method for the determination of five benzotriazole compounds (commonly used as light stabilizers) in indoor dust is presented. Pressurized liquid extraction (PLE) and gas chromatography followed by tandem in time mass spectrometry (GC–MS/MS) were used as sample preparation and determination techniques, respectively. Extraction and clean-up were integrated on-line and, after an evaporative concentration step, the extract provided by the PLE instrument was injected directly in the GC–MS/MS system. Parameters affecting the performance of the sample preparation process were evaluated using experimental factorial designs. Under optimized conditions, analytes were recovered from 0.5 g samples in 3 static extraction cycles of 10 min, using a hexane:dichloromethane (7:3) mixture, at 90 °C. Silica (1 g) was placed in the bottom of the extraction cells as clean-up sorbent. The recoveries of the method varied from 82 to 122%, with standard deviations below 13. The inter-day precision ranged from 9 to 12%, and the limits of quantification (LOQs) remained below 10 ng g⁻¹ for all species. For the first time, four of the five investigated species were found in dust from indoor environments. Their mean concentrations ranged from 71 to 780 ng g⁻¹.     

固相萃取-气相色谱-质谱联用法测定水中的硝基苯类有机污染物的分析方法研究

建立了固相萃取、毛细柱气相色谱-质谱、内标标准曲线法使用选择离子(SIM)监测采集数据定量分析水中硝基苯类有机化合物的分析方法.通过对固相萃取柱的选择、固相萃取条件(样品溶液的pH、上样速率、上样体积、洗脱液选择及配比)的优化,得出了最佳实验条件.始漏体积达1.5 L.回收率大于80%.检出限为0.015～0.045 μg/L.RSD在1.1%～5.9%之间.     

Determination of gaseous carbonyl compounds by their pentafluorophenyl hydrazones with gas chromatography/mass spectrometry

A sensitive and reliable method has been developed for the simultaneous determination of 20 airborne carbonyl compounds in the C₁-C₁₀ range. The carbonyls were collected onto solid sorbent coated with pentafluorophenyl hydrazine (PFPH), followed by solvent extraction and gas chromatographic (GC)/mass spectrometric (MS) analysis of the PFPH derivatives. The sorbent is packed into two separate sections in a glass sampling tube. The two-section design allows convenient checking of collection efficiency and breakthrough. The sampling tube, with a coating amount of 971 nmol PFPH per 100 mg Tenax TA and operated at a sampling flow rate of 80 mL min⁻¹, collects the 20 carbonyls with efficiencies above 95%. Hexane extracts the collected carbonyls in their PFPH derivatives in the sampling tube with better than 95% extraction efficiency. It is necessary to let the sampling tube sit at ambient temperature for 3 days before solvent extraction to ensure complete derivatization of the carbonyls. The limits of detection (LODs) of the tested carbonyls are in the range of 3.7-11.6 ng per sample. The method has been field-tested both in ambient environment and in an indoor environment from burning mosquito-repellent incense. Eighteen carbonyls were detected in the ambient air samples with the exception of o-tolualdehyde and m-tolualdehyde, while all the 20 target carbonyls were found in the incense smoke. Compare field test with classical DNPH-HPLC/UV method, good agreement exited between the two methods for lower molecular carbonyls but PFPH method is found to be a better analytical method for determination of high molecular weight carbonyls.     

Gas chromatography-mass spectrometry and high-performance liquid chromatography-tandem mass spectrometry in quantifying fatty acids

This critical overview covers current analytical methods and future developments in quantitative determination of fatty acids (FAs), emphasizing sample extraction, derivatization and instrumental analysis with gas chromatography/mass spectrometry (GC/MS) and high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS²). We compare the benefits and the drawbacks of these two analytical techniques.We consider the well-established GC/MS method with pre-derivatization to be a traditional technique in terms of highly standardized sample-preparation procedures, affordability and readily available library searching for compound identification. However, the complicated derivatization steps required prior to instrumental analysis with GC/MS take a long time, with loss and transformation of FAs, low recovery and poor reproducibility.HPLC/MS² without derivatization shows the benefits of simple, mild sample-processing conditions, satisfactory recovery, short running time and high selectivity and sensitivity, which may allow it to become a viable alternative to GC/MS for the analysis of FAs in the years ahead.     

气相色谱/质谱法分析孔石莼中的脂肪酸

建立了孔石莼脂肪酸的气相色谱/质谱(GC/MS)测定方法。使用Folch法提取了孔石莼中的总脂,经过2 mol/L HCl-甲醇溶液的甲酯化处理后,采用GC/MS法对其脂肪酸组成进行了分离分析,同时结合有机质谱学规律,分别对饱和脂肪酸甲酯、单不饱和脂肪酸甲酯和多不饱和脂肪酸甲酯的裂解规律和质谱特征进行了分析归纳。通过质谱数据库检索和标准品对照,鉴定出孔石莼中的24种脂肪酸,其中9,12,15-十八碳三烯酸、4,7,10,13-十六碳四烯酸和6,9,2,15-十八碳四烯酸3种主要多不饱和脂肪酸占总脂肪酸含量的45.14%。通过对孔石莼中脂肪酸的分析,表明特征离子在脂肪酸甲酯尤其是多不饱和脂肪酸甲酯的定性方面具有很好的应用价值。     

Measurement of oleic acid in human plasma by isotope dilution mass spectrometry

Summary A method for the quantitative determination of oleic acid in human plasma by isotope-dilution mass spectrometric technique is described. For the measurement of the fatty acid concentration (1-¹³C) oleic acid is added to the plasma sample. The fatty acids are extracted with n-hexane. Portions of the extract are esterified by the boron trifluoridemethanol method or stable isotope methylation. The methyl ester derivatives of the fatty acids are separated and detected by GC-MS with the mass spectrometer set to m/z 296 and 297. For the measurement of oleic acid after stable isotope methylation the m/z 299 and m/z 300 are monitored. The amounts of oleic acid in the plasma are calculated from the isotope ratios measured by selected ion monitoring. The recovery of the methylation step and the precision and accuracy of the GC-MS method are presented and discussed.     

Combination of liquid chromatography/tandem mass spectrometry and gas chromatography/mass spectrometry for the detection of 21 anabolic steroid residues in bovine urine

For the detection of anabolic steroid residues in bovine urine, a highly sensitive liquid chromatographic/electrospray ionization tandem mass spectrometric (LC/ESI-MS/MS) method was developed using both positive and negative ionization. For four compounds the ESI mode was not sensitive enough and gas chromatographic/mass spectrometric GC/MS detection was therefore still necessary as a complementary method. The sample clean-up consisted of solid-phase extraction (SPE) on a C(18) column followed by enzymatic hydrolysis and a second solid-phase extraction on a combination of a C(18) and a NH(2) column. After this last SPE clean-up, the eluate was split into two equal aliquots. One aliquot was further purified and after derivatization used for GC/MS analysis. The other aliquot was analyzed with LC/MS/MS in both ESI+ and ESI- modes. The method was validated according to the European Commission Decision 2002/657/EC. Decision limits (CCalpha) were between 0.16 and 1 ng ml(-1) for the compounds detected with the LC/MS/MS method. The developed method is used in routine analysis in our laboratory.     

Capillary gas chromatography/mass spectrometry of aza-arenes isolated from crude coal tar

Summary The basic fraction of crude coal tar was isolated in a two-step partition process. Its constituents, mostly azaarenes up to four-ring structures, were resolved on a Superox-coated glass capillary column and tentatively identified by combined gas chromatography/mass spectrometry.     

Determination of nitrosamines in water by gas chromatography/chemical ionization/selective ion trapping mass spectrometry

A gas chromatography/mass spectrometry (GC/MS) method for determination of nine N-nitrosamines (NAs) in water is described. Two ionization modes, electron impact (EI) and chemical ionization (CI) with methanol, as well as different ion analysis techniques, i.e. full scan, selected ion storage (SIS) and tandem mass spectrometry (MS/MS) were tested. Chemical ionization followed by SIS resulted the mass spectrometric method of choice, with detection limits in the range of 1-2ng/L. Solid Phase Extraction (SPE) with coconut charcoal cartridges was applied to extract NAs from real samples, according EPA Method 521. Drinking water samples were collected from seven surface- and two groundwater treatment plants. Three surface water treatment plants were sampled before and after addition of O(3)/ClO(2) to observe the effect of disinfection on NAs' formation. N-nitrosodiethylamine (NDEA), n-nitrosodipropylamine (NDPA), n-nitrosomorpholine (NMOR) and n-nitrosodibutylamine (NDBA) were found up to concentrations exceeding three times the risk level of 10ng/L set by the California Department of Public Health. Because dermal adsorption has been recently indicated as a new contamination route of exposure to NAs for people who practice swimming activity, water samples from five swimming pools in the Bologna (Italy) area were collected. N-nitrosopyrrolidine (NPYR) was detected in all samples at concentrations larger than 50ng/L, likely as a disinfection by-product from the amino acid precursor proline, a main constituent of skin collagen.     

Simultaneous determination of 18 pyrethroids in indoor air by gas chromatography/mass spectrometry

An analytical method was developed for the simultaneous measurement of 18 pyrethroids (allethrin, bifenthrin, cyfluthrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, fenpropathrin, furamethrin, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, resmethrin, tetramethrin and transfluthrin) in indoor air. The pyrethroids were collected for 24 h using a combination of adsorbents (quartz fiber filter disk and Empore C18 disk), with protection from light, and then extracted with acetone, concentrated, and analyzed by GC/MS. They could be determined accurately and precisely (detection limits: ca. 1 ng/m³). The collected pyrethroid samples could be stored for up to one month at 4 °C in a refrigerator.     

杂色鲍脂肪酸及烯醚键基团的气相色谱/质谱分析

研究了简便快速分析杂色鲍中脂肪酸及烯醚键基团的方法.杂色鲍经F0lch法提取总脂,以10%浓硫酸.甲醇溶液为衍生试剂,于60℃水浴衍生15 min,采用气相色谱/质谱联用技术进行分析,共鉴定出31个化合物,包括25种脂肪酸和6种脂肪醛二甲基缩醛.杂色鲍脂肪酸以C16:0、C20:4(n-6)、C20:5(n-3)、C1...     

土壤中64种痕量半挥发性有机污染物的分析方法研究

利用超声提取技术将土壤中的半挥发性有机污染物(SVOC)提取出来, 经旋转蒸发浓缩至一定体积后, 用ODSC18柱净化, 再用氮吹浓缩后, 取1.0 μL注入气相色谱中, 用DB-5 ms柱分离, 用气相色谱质谱仪(GC-MS)进行定性定量分析. 本方法研究土壤中64种半挥发性有机污染物, 其中包括苯系物、苯酚类、苯胺类、硝基芳香烃类、氯代芳烃类、多环芳烃类和酞酸酯类等物质的提取、净化方法以及回收率、精密度和检测限的测定. 该方法回收率为52.5%～105%.     

Comparison of solvent mixtures for pressurized solvent extraction of soil fatty acid biomarkers

The extraction and transesterification of soil lipids into fatty acid methyl esters (FAMEs) is a useful technique for studying soil microbial communities. The objective of this study was to find the best solvent mixture to extract soil lipids with a pressurized solvent extractor system. Four solvent mixtures were selected for testing: chloroform:methanol:phosphate buffer (1:2:0.8, v/v/v), chloroform:methanol (1:2, v/v), hexane:2-propanol (3:2, v/v) and acetone. Soils were from agricultural fields and had a wide range of clay, organic matter and microbial biomass contents. Total lipid fatty acid methyl esters (TL-FAMEs) were the extractable soil lipids identified and quantified with gas chromatography and flame ionization detection. Concentrations of TL-FAMEs ranged from 57.3 to 542.2 n mole g⁻¹ soil (dry weight basis). The highest concentrations of TL-FAMEs were extracted with chloroform:methanol:buffer or chloroform:methanol mixtures than with the hexane:2-propanol or acetone solvents. The concentrations of TL-FAMEs in chemical groups, including saturated, branched, mono- and poly-unsaturated and hydroxy fatty acids were assessed, and biological groups (soil bacteria, mycorrhizal fungi, saprophytic fungi and higher plants) was distinguished. The extraction efficiency for the chemical and biological groups followed the general trend of: chloroform:methanol:buffer ≥ chloroform:methanol > hexane:2-propanol = acetone. Discriminant analysis revealed differences in TL-FAME profiles based on the solvent mixture and the soil type. Although solvent mixtures containing chloroform and methanol were the most efficient for extracting lipids from the agricultural soils in this study, soil properties and the lipid groups to be studied should be considered when selecting a solvent mixture. According to our knowledge, this is the first report of soil lipid extraction with hexane:2-propanol or acetone in a pressurized solvent extraction system.     

Accelerated solvent extraction combined with dispersive liquid–liquid microextraction before gas chromatography with mass spectrometry for the sensitive determination of phenols in soil samples

A method combining accelerated solvent extraction with dispersive liquid–liquid microextraction was developed for the first time as a sample pretreatment for the rapid analysis of phenols (including phenol, m‐cresol, 2,4‐dichlorophenol, and 2,4,6‐trichlorophenol) in soil samples. In the accelerated solvent extraction procedure, water was used as an extraction solvent, and phenols were extracted from soil samples into water. The dispersive liquid–liquid microextraction technique was then performed on the obtained aqueous solution. Important accelerated solvent extraction and dispersive liquid–liquid microextraction parameters were investigated and optimized. Under optimized conditions, the new method provided wide linearity (6.1–3080 ng/g), low limits of detection (0.06–1.83 ng/g), and excellent reproducibility (<10%) for phenols. Four real soil samples were analyzed by the proposed method to assess its applicability. Experimental results showed that the soil samples were free of our target compounds, and average recoveries were in the range of 87.9–110%. These findings indicate that accelerated solvent extraction with dispersive liquid–liquid microextraction as a sample pretreatment procedure coupled with gas chromatography and mass spectrometry is an excellent method for the rapid analysis of trace levels of phenols in environmental soil samples.     

Determination of fatty acids in soil samples by gas chromatography with mass spectrometry coupled with headspace solid‐phase microextraction using a homemade sol–gel fiber†

Through the use of a homemade sol–gel‐derived fiber, a headspace solid‐phase microextraction technique coupled to gas chromatography with mass spectrometry was developed for the determination of fatty acids with long, even‐numbered carbon chains (C₁₂–C₂₄) in soil samples. The experimental parameters such as reaction time, temperature, and ionic strength that might affect derivatization, extraction, and desorption were investigated. Under the optimized conditions, the linearity of the method ranged from 0.1 to 100 mg/L with a correlation coefficient >0.997. The limit of detection values based on a signal‐to‐noise ratio of 3:1 were determined with the concentration from 0.39 to 39.4 μg/L. The recoveries of the method for the soil samples were from 91.15 to 108.1%. This developed method using a homemade fiber showed a higher sensitivity than that using a commercial polydimethylsiloxane fiber and was also for the analysis of real soil samples from the Paomaling geological park of China.     

Measurement of bisphenol A in human serum by gas chromatography/mass spectrometry

The purpose of this study is to establish an easy and accurate method for the determination of bisphenol A (BPA) in the human serum. The samples were applied to the C₁₈ solid phase extraction (SPE) column for clean up of samples. The BPA is conjugated with tetrabutylammonium hydrogen sulfate as the counter ion in alkali solution. The ion paired BPA is moves from the aqueous phase to the organic phase as an ion paired extraction. BPA extracted from human serum were derivatized with pentafluorobenzyl bromide (PFBBr). The derivative was analyzed by gas chromatography (GC)/mass spectrometry (MS) using negative chemical ionization (NCI). The instrumental detection limit of BPA was 5 pg/ml (10 fg). The instrumental response between 0.01 and 100 pg/ml of BPA standards was linear (r²=0.998). The recovery of BPA spiked into human serum was 101.0±4.63 (1 pg/ml) and 100.9±3.75 (10 pg/ml), respectively. The concentration of BPA in the human serum from 20 individuals was 0.54 pg/ml.