Gas Chromatography-mass Selective Detection Research Articles

Preparation of reference material for organochlorine pesticides in a herbal matrix

The development of reference material for four organochlorine pesticides, namely hexachlorobenzene and three isomers of hexachlorocyclohexane (alpha-hexachlorocyclohexane, beta-hexachlorocyclohexane and gamma-hexachlorocyclohexane), in a ginseng root sample is presented. Raw materials (Panax ginseng) were purchased from a local market and confirmed to contain certain levels of incurred organochlorine pesticide residues by a validated gas chromatography-mass selective detection method. A total of more than 300 bottles each containing 25 g of samples were prepared after the materials had been freeze-dried, milled and thoroughly mixed. The homogeneity and stability of samples from randomly selected bottles were verified and the reference values were characterized using a highly precise isotope dilution gas chromatography-mass spectrometry (ID-GCMS) method that was recently developed by our laboratory. The purity of standard organochlorine chemicals was determined against certified reference materials to establish the accuracy of the ID-GCMS analysis. The concentrations (+/- expanded uncertainty) of hexachlorobenzene, alpha-hexachlorocyclohexane, beta-hexachlorocyclohexane and gamma-hexachlorocyclohexane in the reference material were 0.198 +/- 0.015, 0.450 +/- 0.022, 0.213 +/- 0.011 and 0.370 +/- 0.032 mg kg(-1), respectively. A portion (70 bottles) of the samples was also used in a proficiency testing (PT) scheme for assessing the testing capabilities of field laboratories. The consensus mean values of the PT obtained from the 70 participants were on the same order but deviated by -2.7 to -14.1% from those of the assigned reference values. Because of the wide spread of participants' data (relative standard deviation ranging from 44 to 56%), the PT results were not included in the calculation of the assigned values of the reference materials. The materials served as suitable reference materials to ascertain the quality control and validation processes for the determination of organochlorine pesticides in herbal matrices.

Exposure to volatile organic compounds (VOC) in public buses of Pamplona, Northern Spain

This study examines the exposure level of passengers and drivers to VOC in public buses in a medium-size metropolitan area (Northern Spain). In-vehicle monitoring was performed on different routes, on peak and non-peak hours, during January and February 2007. A total of 112 air samples were collected onto adsorbent tubes and analysed by thermal desorption (TD) and gas chromatography/mass selective detector (GC/MSD) technique. Statistical differences were found among route to route concentrations, with those routes with major prevalence in the commercial area of the city displaying higher values; differences between peak and non-peak hours were also observed. A decrease in VOC concentrations was also registered during the weekend. BTEX ratios were estimated and found to be related to traffic emissions and similar for all the surveyed routes. Correlations confirmed traffic as the main emission source for BTEX and trimethylbenzene, their concentrations being highly associated to changes in meteorological conditions.

Gas chromatography-mass spectrometry (GC-MS) method for the determination of 16 European priority polycyclic aromatic hydrocarbons in smoked meat products and edible oils

A gas chromatography-mass spectrometry (GC-MS) method was developed for the analysis of 15 polycyclic aromatic hydrocarbons (PAHs) highlighted as carcinogenic by the Scientific Committee on Food (SCF) plus benzo[c]fluorine (recommended to be analysed by the Joint FAO/WHO Expert Committee on Food Additives (JECFA)) in fat-containing foods such as edible oils and smoked meat products. This method includes accelerated solvent extraction (ASE) and the highly automated clean-up steps gel permeation chromatography (GPC) and solid-phase extraction (SPE). Using a VF-17ms GC column, a good separation of benzo[b]fluoranthene, benzo[j]fluoranthene and benzo[k]fluoranthene was achieved. Furthermore, the six methylchrysene isomers and the PAH compounds with a molecular weight of 302 Daltons in fat-containing foods attained a better chromatographic separation in comparison with a 5-ms column. The reliability of the analytical method for edible oils was demonstrated by the results from a proficiency test. Measurements with GC-high-resolution mass spectroscopy (HRMS) and gas chromatography-mass selective detection (GC-MSD) led to comparable results. A survey of the 16 PAHs in 22 smoked meat products showed concentrations in the range <0.01–19 µg kg−1. The median concentration for benzo[a]pyrene was below 0.15 µg kg−1.

Housing Characteristics and Indoor Concentrations of Selected Volatile Organic Compounds (VOCs) in Quebec City, Canada

Concentrations of 26 volatile organic compounds (VOCs) were measured continuously for 7 days during winter in 96 homes in Quebec City, Canada. Characteristics of the houses and activities of the occupants were documented through detailed questionnaires filled out by one adult per household. VOCs were sampled using passive monitors and analyzed by gas chromatography-mass selective detector (GC-MSD). Results indicate contributions to indoor levels of some VOCs from combustion sources and recent renovation activities. Negative associations were seen between certain VOCs and the presence of carpets and furniture. In general, higher VOCs concentrations were found in newer houses. No association was found between individual VOCs and air change rate. Results suggest that multiple indoor sources contribute to occupants' exposure to VOCs during winter in Quebec City homes.

Relationship Between Cholinesterase Inhibitor Insecticides In Human Blood And Insecticides Residues In Drinking Water In Mansoura City- Egypt

Pesticides are classified into four major groups; insecticides, herbicides, rodenticides and fungicides. Insecticides poisoning is one of the most common poisoning affecting our population. The study investigates the relationship between cholinesterase inhibitor insecticides in human blood and insecticides residues in drinking water in Mansoura city. Sixty patients suffering from insecticides poisoning admitted to Emergency Hospital Mansoura University- Egypt in March 2005, were included in this study. Blood samples were collected from these patients. The studied patients and their relatives were asked to obtain water samples of their drinking water from the localities where they live. Thirty drinking water samples were collected. Blood and water samples were extracted using Liquid-liquid extraction technique (LLE) and analyzed for pesticides using Gas Chromatography-Mass Selective Detector (GC-MSD). In addition, blood samples were analyzed for plasma pseudo-cholinesterase level (PChE) and red blood cells acetyl cholinesterase activity (AChE). The analysis of drinking water and blood samples revealed organophosphorous (Mevinphos) and organochlorine (Aldrin) insecticides. Moderate insecticides poisoning was more common among the studied groups (65.0%) compared to mild and severe poisoning. The peak incidence of poisoning was in the age group from 20-30 years (46.67%), followed by the age group from 10-20 years (43.33%). There was a female sex predominance among the poisoned patients (56.67%). There was a negative correlation between the severity of poisoning and each of PChE levels and AChE activity % being lowest (p<0.001) in severe poisoning compared to moderate and mild poisoning.

The effect of strain rate on polycyclic aromatic hydrocarbon (PAH) formation in acetylene diffusion flames

Acetylene is a ubiquitous combustion intermediate that is also believed to be the major precursor for aromatic, polycyclic aromatic hydrocarbon (PAH), and soot formation in both hydrocarbon and halogenated hydrocarbon flames. However, in spite of its important role as a flame intermediate, the detailed chemical structures of acetylene diffusion flames have not been studied in the past. Here the detailed chemical structures of counterflow diffusion flames of acetylene at strain rates of 37.7 and 50.3 s −1 are presented. Both flames possessed the same carbon density of 0.37 g/L corresponding to an acetylene mole fraction of 0.375 in argon on the fuel side, and an oxygen mole fraction of 0.22 in argon on the oxidizer side. Concentration profiles of a large number of major, minor, and trace species, including a wide spectrum of aromatics and PAH, have been determined by direct sampling from flames using a heated quartz microprobe coupled to an online gas chromatograph/mass selective detector (GC/MSD). Temperature profiles were made using a thermocouple and the rapid insertion technique. Although the major species concentrations were nearly the same in the two flames, the mole fraction profiles of trace combustion by-products were significantly lower in the higher-strain-rate flame, by nearly two orders of magnitude for PAH. These comparative results provide new information on the trace chemistries of acetylene flames and should be useful for the development and validation of detailed chemical kinetic mechanisms describing the formation of toxic by-products in the combustion of hydrocarbons and halogenated hydrocarbons.

Stigmastane and hopanes as conserved biomarkers for estimating oil biodegradation in a former refinery plant-contaminated soil

In the last decade, a refinery plant located in Lido Adriano, East Ravenna (Italy) has been subject to mineral oil contamination. The mineral crude oil, extracted from the offshore in Adriatic sea, consisted of 78% aliphatics, cyclic alkanes and saturated polycyclic hydrocarbons, 9% aromatics, polycyclic aromatic hydrocarbons (PAHs) and alkylated derivatives, and 13% of tars/asphaltenes. Analysis of soil after 10 years of natural attenuation revealed a complete depletion of linear (n-C(9)-C(24)), light aromatics (C1-C3/benzenes) and PAHs (C2/naphthalene, C1/phenanthrene); besides a substantial degradation of isoprenoids prystane and phytane, branched and cyclic alkanes. The remaining contaminants which withstood to natural degradation was saturated polycyclic hydrocarbons (perhydro-PAH derivatives), unsaturated polycyclic hydrocarbons (tetrahydro, dihydro-PAH derivatives), terpanes, steranes and unidentified compounds. Such residues resulted in 80% reduction of its concentration after two months of laboratory treatment. Samples were extracted by organic solvents, separated by silica/alumina gel column chromatography and analyzed by gas chromatography-mass selective detector (GC-MSD). Identification and quantification of aliphatic, cyclic alkanes, typical PAHs, terpanes and steranes were carried out to chromatograms of M/Z=85, 83, individual M/Zs, M/Z=191 and 217, respectively. The present work shows that, among numerous biomarkers present in the source oil, stigmastane and two isomers of hopane showed invariable concentrations after laboratory experiments that mimic natural biodegradation in the field, so they can be used as conserved internal biomarkers. These are very useful tools to assess alterations in less stable classes of saturated compounds contained in petroleum. Marked degradation of perhydro, tetrahydro, dihydro-PAH derivatives in the laboratory treatment has been evidenced.

Chemical Characteristics and Source Implications of Petroleum Hydrocarbon Contaminants in the Sediments near Major Drainage Outfalls along the Coastal of Laizhou Bay, Bohai Sea, China

The associated industrial and urban developments are located to a large extent along the Laizhou Bay, Bohai Sea coastal and raw sewage is often discharged into near shore waters with little treatment. To find out chemical characteristics and pollution source of the petroleum related contaminations in sediments near the major drainage outfalls located in the coastal, in this study, 10 surface sediment samples were collected during June. Sediment samples were extracted by organic solvents, separated by silica gel column chromatography and the concentrations and the profiles of n-alkane, biomarker and PAH in sediments were analyzed by gas chromatography-mass selective detector (GC-MSD). The use of several molecular markers and related indexes derived for n-alkane and PAHs has been proposed for assessing the relative contributions to the environment of hydrocarbon sources. As a result, n-alkanes reflect that the sea area of paper mill (Station ZZ08) is dominated by vascular plant. DY petroleum oil field and outer shore of the paper mill (Station ZZ02) have some degrees of petroleum related hydrocarbon contamination. Whereas the contamination of the sea area of TH River may be ascribed to different sources such as territorial non-point pollution source, domestic sewages, and stormwater runoff. Judged by their PAH ratios, the sediments near the paper mill (Station ZZ02) and the outer station of the oil field (Staion TH2) were pyrolytic. The estuary of Tiao River including the inner Station THX, TH10 and TH05 are petrogenic. The marine sediment near DY drainage outfall may have a mixture source of PAH both pyrolytic and petrogenic.

Spatial and temporal trends of volatile organic compounds (VOC) in a rural area of northern Spain

Ambient concentrations of volatile organic compounds (VOCs) were measured at 40 rural sampling points in Navarre (northern Spain). Air samples were collected by means of sorbent passive sampling and analyzed by thermal desorption (TD) and gas chromatography/mass-selective detector (GC/MSD). A total of 140 VOCs were identified during the study, which was carried out between May to October 2004 for a total of a 10 biweekly sampling campaigns. Concentrations of benzene, toluene, ethylbenzene, m/p-xylenes, o-xylene (BTEX) and 1,3,5-trimethylbenzene were determined in order to investigate their temporal and spatial distributions. Geostatistical analysis pointed to traffic as the main emission source of these compounds. Supporting this idea, BTEX and nitrogen oxides concentrations were found to be highly significantly correlated (r=0.495, P=0.001), whereas a strong negative correlation between BTEX and ozone was also observed (r=−0.355, P=0.025). The concentrations for the BTEX group were similar to the values that have been previously reported for other rural areas.

Occurrence of nitro-polycyclic aromatic hydrocarbons in urban particulate matter PM10

Ambient measurements of nitro-polycyclic aromatic hydrocarbons (nitro-PAHs) were carried out during July 2000 and September–October 2000 in Santiago de Chile City. Fifteen samples of 24 h were collected at two sampling sites whose characteristics were representative of the prevailing conditions of the area. These compounds were characterized and quantified by gas chromatography mass selective detection. Atmospheric concentrations of nitro-PAHs are of interest because these compound classes include potent mutagens and carcinogens. The compounds analyzed in the samples included 1-nitropyrene, 2-nitrofluorene and 3-nitrofluoranthene. The concentration found ranged from below the detection limit in all cases to 1.8 ng m − 3 for 1-nitropyrene, to 1.12 ng m − 3 for 2-nitrofluorene and to 3.9 ng m − 3 for 3-nitrofluoranthene. This study respresents evidence of nitroaromatics in urban air particles from Santiago de Chile.

An assessment of the bioavailability of persistent organic pollutants from contaminated soil

A procedure to assess the bioavailability of persistent organic pollutants (POPs) from soil samples has been developed. The procedure is based on the use of simulated in vitro gastrointestinal extraction to remove POPs from soil matrices. The level of recovery, using this approach, is assessed following liquid-liquid extraction (LLE) and analysis by gas chromatography-mass selective detection (GC-MSD). The remaining soil residue is then extracted using pressurised fluid extraction (PFE) followed by GC-MSD analysis to assess the residual fraction. The residual fraction is monitored to determine the unavailable fraction i.e. not available for absorption in the gastrointestinal tract of humans. The procedure was applied to four soil samples i.e. an aged, spiked soil and three certified reference materials (CRMs) contaminated with POPs. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II), phenols (cresol, TCP and PCP), and base neutral compounds (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from aged, spiked soil following extraction with gastric fluid ranged from 0.8 to 8.3% while following intestinal extraction ranged from 5.5 to 13.5%, irrespective of POP. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II) from CRM 805-050 following extraction with gastric fluid were below the limit of detection while following intestinal extraction ranged from 5.3 to 12.8%. Recoveries of phenols (cresol, TCP and PCP) from CRM 401-225 following extraction with gastric fluid ranged from 1.6 to 2.0% while following intestinal extraction ranged from 4.1 to 5.4%. Recoveries of base neutral acid analytes (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from CRM 107-100 following extraction with gastric fluid ranged from 1.4 to 4.0% while following intestinal extraction ranged from 6.6 to 12.7%. It has been found that the majority of POPs present i.e. >75%, would be excreted if consumed and not be absorbed in the gastrointestinal tract of humans.

Determination of 266 pesticide residues in apple juice by matrix solid-phase dispersion and gas chromatography–mass selective detection

A macro matrix solid-phase dispersion (MSPD) method was developed to extract 266 pesticides from apple juice samples prior to gas chromatography-mass selective detection (GC-MSD) determination. A 10 g samples was mixed with 20 g diatomaceous earth. The mixture was transferred into a glass column. Pesticide residues were leached with a 160 mL hexane-dichloromethane (1:1) at 5 mL/min. Two hundred and sixty-six pesticides were divided into three groups and detected by GC-MSD under selective ion monitoring. The proposed method takes advantage of both liquid-liquid extraction and conventional MSPD methods. Application was illustrated by the analysis of 236 apple juice samples produced in Shaanxi province China mainland this year.

Aplicação da técnica de dispersão da matriz em fase sólida (DMFS) na análise de pesticidas em quiabo por CG-EM

A matrix solid phase dispersion and gas chromatography-mass selective detection method for the simultaneous determination of monocrotophos, methyl parathion, cypermethrin and deltamethrin in okra is described. Analyses of 2 g of fortified okra (0.05-0.75 mg kg-1) showed an average recovery of 96.2% (71.4-128.4%) and average relative standard deviation of 11.7% (1.4-37.1%). The cypermethrin recovery at the lower level was above 130%. The limit of detection ranged from 0.02 to 0.15 mg kg-1. The procedure was applied to the okra samples and has found 0.56 mg kg-1 of cypermethrin-cis, 0.75 mg kg-1 of cypermethrin-trans and 2.71 mg kg-1 of deltamethrin.

Determination of Multiclass Pesticide Residues in Apple Juice by Gas Chromatography-Mass Selective Detection after Extraction by Matrix Solid-Phase Dispersion

A multiresidue method is described for the analysis of 106 multiclass pesticides (organochlorine, organophosphate, carbamate, pyrethroid, and triazine classes) in apple juice in a single injection. The determination procedure was based on matrix solid-phase dispersion of juice on diatomaceous earth in a glass column and subsequent extraction with a mixture of hexane-dichloromethane (1 + 1) at a flow rate of 5 mL/min. The analytes were determined by capillary gas chromatography with mass spectrometric detection and confirmed by their retention times and ion ratios. The coefficients of variation for analysis of samples fortified over the range of 0.01-0.2 mg/kg were 1.62 to 18.4%, and the recoveries for all analytes were between 70 and 110%.

Tetraglyme Trap for the Determination of Volatile Organic Compounds in Urban Air. Projects for Undergraduate Analytical Chemistry

Volatile organic compounds (VOCs), including benzene and its derivatives, contribute significantly to the pollution of urban air; at low altitudes, VOCs enhance ozone production. Monitoring VOCs in urban air has important health implications, especially since asthma and other lung diseases in inner-city communities are above the national average. Present methods for the determination of VOCs in ambient air are expensive and complex; the search is on for simpler methods. Students at Medgar Evers College use tetraglyme (tetraethylene glycol dimethyl ether) to scrub a variety of VOCs from ambient air. The chilled tetraglyme traps VOCs as the air is bubbled through it. The VOCs are then dispersed in water, from which they are analyzed by purge-and-trap, followed by GC-MSD (gas chromatography-mass selective detector). This method has been used for a number of projects for the quantitative analysis course. Students are also introduced to the practical features of 23-factorial design of experiments to optimize the method; they monitor three variables (location, volume of tetraglyme, and sampling rate) simultaneously. This method is simple, low-cost, and appropriate for undergraduate students to monitor a number of compounds in ambient and indoor air.

Petroleum hydrocarbons and polycyclic aromatic hydrocarbons in the surficial sediments of Xiamen Harbour and Yuan Dan Lake, China

Surficial sediments were sampled from nine stations in Xiamen Harbour and two stations in Yuan Dan Lake during April 2002. Sediment samples were extracted by organic solvents, separated by silica gel column chromatography and analyzed by gas chromatography–mass selective detector (GC–MSD). Selected ion monitoring was at M/Z=57 for petroleum hydrocarbons (PHCs) and individual M/Zs for each of the 15 typical polycyclic aromatic hydrocarbons (PAHs) and nine alkylated PAHs. The results showed that concentrations of PHCs and total PAHs in the sediments of Yuan Dan Lake were 1397 μg g −1 (dry weight, dw) and 1377 ng g −1 (dw), respectively. The ranges for PHCs and total PAHs in the sediments from Xiamen Harbour were 133–943 μg g −1 (dw) and 98–309 ng g −1 (dw), respectively. Shipping activities, industrial wastewater discharges, fuel oil spillage from ships and vehicles were the main sources of PHCs and PAHs in the Harbour. In addition, the widespread use of coal for industrial processes and domestic consumption accounted for the second largest source of PAHs in the sediments, while atmospheric transport and deposition of PAHs are also important.

Identification of homoserine lactone derivatives using the methionine functionalized solid phase synthesis by gas chromatography/mass spectrometry.

Combinatorial homoserine lactone mixtures and individual products were obtained from the methionine-functionalized resin in solid-phase synthesis. The four-step process consisting of a coupling step of an N-Fmoc-L-methionine, deprotection of N-Fmoc group, N-coupling with a carboxylic acid, and cleavage reaction through a polymer supported strategy is described. Gas chromatography-mass selective detector (GC-MSD) techniques provide the most powerful methods for identifying both the combinatorial mixtures and individual products.

A study of polycyclic aromatic hydrocarbons in airborne particulate matter in central Taiwan

Two sampling sites in central Taiwan, at Hungkuang University (HKU) and Tunghai University (THU), were chosen to contrast the content of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere from November 2000 to April 2001. PAHs that arise from incomplete combustion of organic materials, especially fossil fuels, are the major toxic pollutants in central Taiwan. This study aimed to analyse PAHs, by using a PS-1 sampler and a gas chromatograph/mass selective detector (GC/MSD), and to identify the major sources of PAHs. At the HKU sampling site, the primary emission sources are probably vehicles and coal burning, and vehicular emissions are the primary contributor at the THU sampling site.

Preliminary measurements of aromatic VOCs in public transportation modes in Guangzhou, China

This study examined the exposure level of aromatic volatile organic compounds (VOCs) in public transportation modes in Guangzhou, China. A total of 40 VOC samples were conducted in four popular public commuting modes (subway, taxis, non-air-conditioned buses and air-conditioned buses) while traversing in urban areas of Guangzhou. Traffic-related VOCs (benzene, toluene, ethylbenzene, m/ p-xylene and o-xylene) were collected on adsorbent tubes and analyzed by thermal desorption (TD) and gas chromatography/mass-selective detector (GC/MSD) technique. The results indicate that commuter exposure to VOCs is greatly influenced by the choice of public transport. For the benzene measured, the mean exposure level in taxis (33.6 μg/m 3) was the highest and was followed by air-conditioned buses (13.5 μg/m 3) and non-air-conditioned buses (11.3 μg/m 3). The exposure level in the subway (7.6 μg/m 3) is clearly lower than that in roadway transports. The inter-microenvironment variations of other target compounds were similar to that of benzene. The target VOCs were well correlated to each other in all the measured transports. The concentration profile of the measured transport was also investigated and was found to be similar to each other. Based on the experiment results, the average B/T/E/X found in this study was about (1.0/4.3/0.7/1.4). In this study, the VOC levels measured in evening peak hours were only slightly higher than those in afternoon non-peak hours. This is due to the insignificant change of traffic volume on the measured routes between these two set times. The out-dated vehicle emission controls and slow-moving traffic conditions may be the major reasons leading elevated in-vehicle exposure level in some public commuting journeys.

The effect of wet film thickness on VOC emissions from a finishing varnish

Finishing varnishes, a typical type of oil-based varnishes, are widely used to shine metal, wood trim and cabinet surfaces in Hong Kong. The influence of wet film thickness on volatile organic compound (VOC) emissions from a finishing varnish was studied in an environmental test chamber. The varnish was applied on an aluminium foil with three different wet film thickness (35.2, 69.9 and 107.3 μm). The experimental conditions were 25.0 °C, 50.0% relative humidity (RH) with an air exchange rate of 0.5 h −1. The concentrations of the major VOCs were monitored for the first 10 h. The air samples were collected by canisters and analysed by gas chromatography/mass selective detector (GC/MSD). Six major VOCs including toluene, chlorobenzene, ethylbenzene, m, p-xylene, o-xylene and 1,3,5-trimethylbenzene were identified and quantified. Marked differences were observed for three different film thicknesses. VOC concentrations increased rapidly during the first few hours and then decreased as the emission rates declined. The thicker the wet film, the higher the VOC emissions. A model expression included an exponentially decreasing emission rate of varnish film. The concentration and time data measured in the chamber were used to determine the parameters of empirical emission rate model. The present work confirmed that the film thickness of varnish influenced markedly the concentrations and emissions of VOCs.