Automation of the GC/MS analysis of mineral oil contaminations in water

An automation of the sample preparation and analysis of mineral oil contaminations in water was developed. The automated sample preparation was carried out according to ISO/DIS 9377-4 [1]. The standard is applicable to the determination of hydrocarbons in the boiling range of n-decane (n-C10) up to n-tetracontane (n-C40) by GC. Extraction of the sample and clean-up of the extract were performed by an autosampler with a movable head which is capable of carrying different syringes for gas and liquid handling. A GC/MS-system with a programmed temperature vaporizing (PTV) injector including the possibility of large volume injections (LVI) was employed for the analysis. The recovery of analytes was 101.8%, the repeatability 2.9% relative standard deviation (RSD). The linear range covered 0.3 to 40 mg/L oil but may be larger since no higher concentrations were measured. With an FID, being the detector of choice mentioned in the standard, it should be possible to achieve at least four orders of magnitude in the linear range. The limit of determination was found to be 0.3-0.4 mg/L, the limit of detection 0.1-0.2 mg/L [2]. Measurements of spiked deionized, bidistilled water and spiked water from a lake confirmed the accuracy of the analysis. Due to automation and miniaturization of the analysis it is possible to economize time and chemicals without loss of precision and accuracy.     

Automation of the GC/MS analysis of mineral oil contaminations in water

An automation of the sample preparation and analysis of mineral oil contaminations in water was developed. The automated sample preparation was carried out according to ISO/DIS 9377–4 [1]. The standard is applicable to the determination of hydrocarbons in the boiling range of n-decane (n-C10) up to n-tetracontane (n-C40) by GC. Extraction of the sample and clean-up of the extract were performed by an autosampler with a movable head which is capable of carrying different syringes for gas and liquid handling. A GC/MS-system with a programmed temperature vaporizing (PTV) injector including the possibility of large volume injections (LVI) was employed for the analysis. The recovery of analytes was 101.8%, the repeatability 2.9% relative standard deviation (RSD). The linear range covered 0.3 to 40 mg/L oil but may be larger since no higher concentrations were measured. With an FID, being the detector of choice mentioned in the standard, it should be possible to achieve at least four orders of magnitude in the linear range. The limit of determination was found to be 0.3–0.4 mg/L, the limit of detection 0.1–0.2 mg/L [2]. Measurements of spiked deionized, bidistilled water and spiked water from a lake confirmed the accuracy of the analysis. Due to automation and miniaturization of the analysis it is possible to economize time and chemicals without loss of precision and accuracy. Received: 6 October 1999 / Revised: 6 December 1999 / Accepted: 10 December 1999     

Application of gas chromatography–tandem mass spectrometry (GC/MS/MS) for the analysis of deuterium enrichment of water

Incorporation of deuterium from deuterium oxide (²H₂O) into biological components is a commonly used approach in metabolic studies. Determining the dilution of deuterium in the body water (BW) pool can be used to estimate body composition. We describe three sensitive GC/MS/MS methods to measure water enrichment in BW. Samples were reacted with NaOH and U‐¹³C₃‐acetone in an autosampler vial to promote deuterium exchange with U‐¹³C₃‐acetone hydrogens. Headspace injections were made of U‐¹³C₃‐acetone‐saturated air onto a 30‐m DB‐1MS column in electron impact‐mode. Subjects ingested 30 ml ²H₂O, and plasma samples were collected. BW was determined by standard equation. Dual‐energy X‐ray absorptiometry scans were performed to calculate body mass, body volume and bone mineral content. A four‐compartmental model was used to estimate body composition (fat and fat free mass). Full‐scan experiments generated an m/z 45 peak and to a lesser extent an m/z 61 peak. Product fragment ions further monitored included 45 and 46 using selected ion monitoring (Method1), the 61 > 45 and 62 > 46 transition using multiple reaction monitoring (MRM; Method2) and the neutral loss, 62 > 45, transition (Method3). MRM methods were optimized for collision energy (CE) and collision‐induced dissociation (CID) argon gas pressure with 6 eV CE and 1.5 mTorr CID gas being optimal. Method2 was used for final determination of ²H₂O enrichment of subjects because of lower natural background. We have developed a sensitive method to determine ²H₂O enrichment in BW to enable measurement of FM and FFM. Copyright © 2015 John Wiley & Sons, Ltd.     

Identification of Dinocap in water using GC/IR and GC/MS

The determination of Dinocap, one of the most often used acaricides and contact fungicides, is complicated by the fact that it consists of several isomeric alkyldinitro-phenyl-crotonates. In a first step, GC/IR and GC/MS has been used to separate the mixture, to determine the chromatographic behaviour and to fully characterize the six different isomeric compounds. The structures of additional impurities in the commerical preparation were shown to be the correlating phenols. An extraction/preconcentration method has been devised based on Carbopack B, yielding recoveries between 75 and 98%. A qualified estimation of the total Dinocap content of drinking water can be made by this approach for concentrations well below the limits set by the European drinking water regulations. The development of a complete analytical procedure based on these results appears to be feasible.Dedicated to Professor Dr. Dr. h.c. mult J. F. K. Huber on the occasion of his 70th birthday     

High-temperature (GC)2/MS investigations

The analysis of low volatile compounds by (GC)²/MS using high-temperature stable glass-capillary columns and a commercially available GC/quadrupole MS instrument is described. It will be shown that no special modifications or procedures are required in analyzing organic compounds exceeding carbon numbers of 50. The application to industrially and naturally occuring high boiling mixtures will be discussed.     

GC/MS方法分析豇豆中水胺硫磷等37种农药残留

建立了GC/MS法同时测定豇豆中水胺硫磷等37种农药残留的方法.农药经过乙腈提取,NH2/CARBON复合固相萃取小柱净化,HP-5MS(30 m×0.25 mm×0.25 μm)弹性石英毛细管柱分离后,用GC/MS选择离子模式进行测定.农药在0.020～0.500 mg/L时与峰面积有良好的线性关系(r2>0.990...     

Development of a simultaneous analysis method for carbofuran and its three derivative pesticides in water by GC/MS with temperature programmable inlet on-column injection.

A simultaneous analytical method was examined for carbofuran and its derivative pesticides in water. Since carbofuran derivatives are hydrolyzed to carbofuran in water, the liquid-liquid extraction method was used to obtain an accurate concentration value. Moreover, since these compounds are easily decomposed at the GC/MS injection port, temperature programmable inlet on-column injection was used. By combining the two methods, a sensitive analytical method was established without hydrolysis and thermal decomposition. As a result of recovery experiments using distilled water, river water and tap water, acceptable recovery rates and favorable reproducibility were obtained. This method was used in a field investigation to determine carbofuran and its derivative pesticides in river water taken from three points of the Y river over a period of one year. Carbofuran, benfuracarb, and carbosulfan were detected and corresponded to the period when these pesticides were used in the area. Although benfuracarb and carbosulfan using traditional methods are believed to easily hydrolyze and thermally decompose during the analytical process, by using our method they can be detected.     

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.     

Biodegradation of the (aliphatic + aromatic) fraction of Oural crude oil. Biomarker identification using GC/MS SIM and GC/MS/MS

A simplified fraction of the Oural crude oil (aliphatic and aromatic hydrocarbons) was incubated in the presence of an hydrocarbonoclastic bacterial community isolated from a marine sediment highly contaminated by petroleum residue. The biodegradation has been carried out under aerobic conditions for 5 weeks and followed by FTIR, UV synchronous luminescence and GC/FID. Disappearance of the n-alkanes (2nd week), an important attack of the isopreno?d compounds (5th week) and preferential alteration of monomethylated polyaromatics were observed. Concerning the biomarkers, the bicyclic alkanes and pentacyclic terpanes have been comparatively elucidated using GC/MS data. The identification of C(26) to C(29) steranes has required a most selective method, namely GC/MS/MS. Many molecular ratios based on GC/MS abundances were calculated, which showed good stability. Consequently, they can be used to determine the origin of a petroleum even one altered by biodegradation.     

A combination atmospheric pressure LC/MS:GC/MS ion source: Advantages of dual AP-LC/MS:GC/MS instrumentation

Modification of commercial LC/MS instrumentation to allow both atmospheric pressure (AP) LC/MS and GC/MS is described. Advantages of this additional capability versus LC/MS alone include higher chromatographic resolution in the GC versus LC mode, greater peak capacity for complex mixture analysis, higher sensitivity for a variety of volatile compounds, and the ability to observe compounds of low polarity that are not readily observed in LC/MS. Advantages over conventional GC/MS include the ability to use higher carrier gas flow and shorter columns for passing less volatile materials through the gas chromatograph, selective ionization, and rapid switching between positive and negative ion modes. Other advantages include application of the enhanced capabilities of LC/MS instrumentation to GC/MS analyses such as cone voltage fragmentation, MS(n), high mass resolution, and accurate mass measurement. Limitations of APGC/MS include the inability to observe saturated hydrocarbon and certain other highly nonpolar compounds and less odd-electron fragmentation for computer aided library searching. For some analyses, the limitation related to ionization of highly nonpolar compounds is advantageous, as is the simplified mass spectrum and easy molecular weight identification that results from less fragmentation observed in the AP ionization mode.     

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.     

Simultaneous analysis of carbamate pesticides in tap and raw water by LC/ESI/MS.

Ten carbamate pesticides including four suspected endocrine disruptors, methomyl, benomyl (carbendazim), aldicarb and carbaryl, were simultaneously analyzed by LC/ESI/MS. The influence of the matrix on the variation of the ion signal intensities of (M + H)+ and adduct ions was investigated. Although the intensities of three oxamyl ions changed depending on the matrix, the variation in the concentration calculation of oxamyl was reduced by using the sum total of the area value of two ions. The limits of the quantitation of ten pesticides without a concentration procedure were from 0.4 - 30 microg/l. The solid-phase recovery rates of ten pesticides spiked into tap water and raw water were in the range of 69-111%. Using this method, the concentrations of the pesticides in tap and raw water sampled at 14 monitoring points in Hyogo Prefecture were determined. Carbendazim in three raw water samples and carbofuran in one of these three samples were detected at low concentrations (less than 0.32 microg/l).