Determination of indicator polychlorinated biphenyls (PCBs) by gas chromatography–electron capture detector

An effective method for determination of indicator polychlorinated biphenyls (PCBs) has been validated using gas chromatography (GC) equipped with electron capture detector (ECD). The GC–ECD method was validated by determining the linear range (working range) for determination of the compounds, minimum detectable quantities (MDQ), the precision and accuracy of the method for the analysis of the compounds. MDQ obtained for the compounds ranges from 0.0005 to 0.002 ng. Indeed the method was found to be more sensitive as the number of chlorine atoms attached to the biphenyl increases. The precision and accuracy of the GC method validated ranges from 2.4% to 14.5% and −7.0% to 14.6% respectively. Coefficient of variation associated with the repeatability of the retention times and corresponding peak areas was found to be 0.0001–0.0007 for the retention times and 0.0014–0.059 for the peak areas. Percentage recoveries for the compounds were in the range of 95.7–101.0%. The validated method was then applied to determine levels of indicator PCBs in sediments sampled from eleven sampling points along the Lake Bosuntwi in Ghana and the highest PCB load of 19.17 ng g⁻¹ was recorded at Pipie No. 2. PCB 52 and PCB 101 were found to be the most ubiquitous indicator PCBs in the study area, both with 90.91% occurrence.     

Analysis of nitrated polynuclear aromatic hydrocarbons

A derivatization-gas chromatography/electron capture detector (GC/ECD) method has been developed for the measurement of trace nitrated polynuclear aromatic hydrocarbons (NPAHs) in air. The method involves first the derivatization of parent nitro-PAHs to their corresponding fluorinated derivatives, followed by GC/ECD analysis. The sensitivity of the method is an order of magnitude higher than those of direct GC/ECD analysis of NPAHs themselves. The method is simple and robust and thus ideally suited for the routine monitoring of NPAHs in air samples. The sensitivity and reproducibility of GC/negative ion chemical ionization MS (NICIMS) for the measurement of NPAHs after derivatization has been evaluated. The method has sensitivity comparable to GC/ECD, but is less reproducible in quantification. The method is therefore suitable for method validation and NPAHs peak confirmation rather than routine operations.     

Agricultural reuse of reclaimed water and uptake of organic compounds: pilot study at Mutah University wastewater treatment plant, Jordan

The residues of polynuclear aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlorinated benzenes (CBs) and phenols were investigated for soil, wastewater, groundwater and plants. The uptake concentration of these compounds was comparatively determined using various plant types: Zea mays L., Helianthus annus L., Capsicum annum L., Abelmoschus esculentus L., Solanum melongena L. and Lycopersicon esculentum L. which were grown in a pilot site established at Mutah University wastewater treatment plant, Jordan. Soil, wastewater, groundwater and various plant parts (roots, leaves and fruits) samples were extracted in duplicate, cleaned up by open-column chromatography and analyzed by a multi-residue analytical methods using gas chromatography equipped with either mass selective detector (GC/MS), electron capture detector (GC/ECD), or flame ionization detector (FID). Environmentally relevant concentrations of targeted compounds were detected for wastewater much higher than for groundwater. The overall distribution profiles of PAHs and PCBs appeared similar for groundwater and wastewater indicating common potential pollution sources. The concentrations of PAHs, PCBs and phenols for different soils ranged from 169.34 to 673.20 microg kg(-1), 0.04 to 73.86 microg kg(-1) and 73.83 to 8724.42 microg kg(-1), respectively. However, much lower concentrations were detected for reference soil. CBs were detected in very low concentrations. Furthermore, it was found that different plants have different uptake and translocation behavior. As a consequence, there are some difficulties in evaluating the translocation of PAHs, CBs, PCBs and phenols from soil-roots-plant system. The uptake concentrations of various compounds from soil, in which plants grown, were dependent on plant variety and plant part, and they showed different uptake concentrations. Among the different plant parts, roots were found to be the most contaminated and fruits the least contaminated.     

Online hourly determination of 62 VOCs in ambient air: system evaluation and comparison with another two analytical techniques

This paper presents results of the processing and validation of data collected by an automatic gas chromatograph (AGC). This system was used to monitor 62 volatile organic compounds (VOCs) in urban air in the Basque Country, Spain. The nonpolar compounds (C2-C10) identified-paraffins, olefins, aromatics, and chlorinated compounds-accounted for 88% of the mass of total non-methane hydrocarbons (TNMHCs) in ambient air. The evaluation of linearity, precision, detection limits (DLs), and stability of retention times (RTs) indicates that the equipment is suitable for measuring ambient air automatically for prolonged periods (6 months). The calibration of the equipment using response factors calculated on the basis of the effective carbon number (ECN) showed variations of over 10% for acetylene, isoprene, and n-hexane. The results provided by the automatic chromatograph correlated significantly with simultaneous results from other widely used techniques for determining VOCs in ambient air: (1) portable GC, equipped with photoionization detector (PID), and (2) active adsorption on Tenax-TA followed by thermal desorption and chromatographic analysis.     

Dissipation,half-lives,and mass spectrometric identification of chlorpyrifos and its two metabolites on field-grown collard and kale

The persistence and fate of chlorpyrifos and its two metabolites, chlorpyrifos-oxon and the 3, 5, 6-trichloro-2-pyridinol (TCP) break-down product were investigated on kale and collard leaves under field conditions. A simultaneous extraction and quantification procedure was developed for chrorpyrifos and its two main metabolites. Residues of chlorpyrifos, chlorpyrifos oxon, and TCP were determined using a gas chromatograph (GC) equipped with an electron capture detector (GC/ECD). Chlorpyrifos metabolites were detectable up to 23 days following application. Residues were confirmed using a GC equipped with a mass selective detector (GC/MSD) in total ion mode. Initial residues of chlorpyrifos were greater on collard (14.5 µg g^?1) than kale (8.2 µg g^?1) corresponding to half-lives (T_1/2) values of 7.4 and 2.2 days, respectively. TCP, the hydrolysis product, was more persistent on collards with an estimated T_1/2 of 6.5 days compared to kale (T_1/2 of 1.9 days).     

Structure and origin of the natural halogenated monoterpene MHC-1 and its concentrations in marine mammals and fish

The halogenated natural product previously named mixed-halogenated compound 1 (MHC-1) was isolated from the red seaweed Plocamium cartilagineum harvested in Helgoland, Germany. A total of 1.9mg of pure MHC-1 was obtained from 1g air-dried seaweed. The (1)H and (13)C NMR data matched those reported for a natural monoterpene isolated from this species. Thus, the structure of MHC-1 was established to be (1R,2S,4R,5R,1'E)-2-bromo-1-bromomethyl-1,4-dichloro-5-(2'-chloroethenyl)-5-methylcyclohexane. Moreover, the isolated monoterpene proved to be identical with the compound previously detected in marine mammals and fish from different locations. In addition we examined two samples of P. cartilagineum from Ireland and from the Antarctic; however MHC-1 was only present at low levels. Not only the concentrations were lower but also the pattern of polybrominated compounds differed from MHC-1. A calibrated solution of MHC-1 was used to determine correct concentrations from samples where previously only estimates existed relative to the gas chromatography-electron capture detector (GC/ECD) response of trans-chlordane, which underrated the MHC-1 concentrations by more than factor 2. The highest MHC-1 concentration determined to date in marine mammals is 0.14mgkg(-1) blubber. Significantly higher MHC-1 concentrations were determined in farmed fish with up to 2.2mgkg(-1) lipids. The samples with high concentrations of MHC-1 have in common that they were collected in proximity of the natural habitats of P. cartilagineum.     

Determination of Q1, an unknown organochlorine contaminant, in human milk, Antarctic air, and further environmental samples

Q1, an organochlorine component with the molecular formula C(9)H(3)Cl(7)N(2) and of unknown origin was recently identified in seal blubber samples from the Namibian coast (southwest of Africa) and the Antarctic. In these samples, Q1 was more abundant than PCBs and on the level of DDT residues. Furthermore, Q1 was more abundant in seals from the Antarctic than the Arctic. To prove this assumption, gas chromatography-electron-capture negative ion mass spectrometry (GC/ECNI-MS), which is sensitive and selective for Q1, allowed for screening of traces of Q1 even in samples with particularly high levels of other organochlorine contaminants. Q1 was isolated by high-performance liquid chromatography (HPLC) from a skua liver sample. A 1:1 mixture with trans-nonachlor in electron-capture detectors (ECDs) was used to determine the relative response factor with ECNI-MS. The ECNI-MS response of Q1 turned out to be 4.5 times higher than that of trans-nonachlor in an ECD. With GC/ECNI-MS in the selected ion-monitoring mode, four Antarctic and four Arctic air samples were investigated for the presence of Q1. In the Antarctic air samples, Q1 levels ranged from 0.7 to 0.9 fg/m(3). In Arctic air samples, however, Q1 was below the detection limit (<0.06 fg/m(3) or 60 ag/m(3)). We also report on high Q1 levels in selected human milk samples (12-230 microg/kg lipid) and, therefore, suggested that the unknown Q1 is an environmental compound whose origin and distribution should be investigated in detail. Our data confirm that Q1 is a bioaccumulative natural organochlorine product. Detection of a highly chlorinated natural organochlorine compound in air and human milk is novel.     

GC × GC--A New Analytical Tool For Environmental Forensics

Comprehensive two-dimensional gas chromatography, GC 2 GC, is a new analytical tool with a tremendous capability to separate and identify organic compounds in complex environmental samples. GC 2 GC uses two different chromatography columns coupled serially by a modulator to produce a volatility by polarity separation and distribute compound peaks across a two-dimensional retention time plane. The two-dimensional separation produces an order of magnitude more resolved peaks than traditional GC methods. The grouping or ordering of the peaks in the GC 2 GC chromatogram facilitates the identification of unknown compounds and the comparison of complex environmental samples. When a mass spectrometer detector is used, each resolved GC 2 GC peak yields a single-component, interference-free mass spectrum that leads to accurate matching with mass spectral libraries. GC 2 GC examination of marine sediment extracts identified a wide variety of chemical contaminants including polychlorinated biphenyls, p -nonylphenol isomers, polycyclic aromatic hydrocarbons, benzotriazoles, and the alkane, cycloalkane, alkylbenzene, alkylnaphthalene, and biomarker fractions of petroleum. The two-dimensional GC 2 GC chromatogram image permits rapid screening of the sediment extracts for these and other unknown contaminants.     

Determination of chemical warfare agents in soil and material samples

A gas Chromatographic method for the determination of phenylarsenic compounds (sternutators) and their metabolites in soil and material samples is described. The chemical warfare agents (CWA), but not their hydrolysis and oxidation products, can be detected with GC/ECD. After derivatization with thiols or dithiols, the sum of diphenylarsenic and phenylarsenic compounds can be determined with GC/ECD. The comparison of the analytical results with and without derivatization shows that the sternutators in the investigated samples are metabolized in part.     

Application of the QuEChERS method for the determination of organochlorine pesticide residues in Brazilian fruit pulps by GC-ECD

The Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method was applied to the extraction of 14 organochlorine pesticides (OCPs) residues from commercial fruit pulps available in supermarkets in Fortaleza, Northeastern Brazil. The analyses were carried out by gas chromatography (GC), coupled to an electron-capture detector (ECD), and were confirmed by GC-tandem mass spectrometry (MS). The parameters of the analytical method, such as accuracy, precision, linear range, limits of detection and quantification, were determined for each pesticide. The results showed good linearity (R² ≥ 0.9916) and the overall average recoveries were considered satisfactory obtaining values between 69 and 110%, RSD of 2–15 %, except for hexachlorobenzene (HCB) in açai, acerola and guava pulp samples. The OCPs were detected in guava (α–HCH; lindane) and soursop (α, β–HCH isomers) samples. The QuEChERS method and GC–ECD were successfully used to analyze OCPs in commercially available Brazilian fruit pulps and can be applied in routine analytical laboratories.     

改进GC/FID法连续观测大气中CO浓度

改进装配有氢火焰离子化检测器(即FID)的气相色谱仪(GC),可连续监测大气中痕量气体CO浓度.本系统采用单阀双柱反吹进样技术,优选前置柱能更有效地剔除杂质,提高了分析柱效率,保持色谱基线平稳,提高分辨率和定量分析的准确率.优化后的气路设计与色谱柱的改进,使GC/FID对CO的最低检出限达到10×10-9、精密度误差小于2%,准确度在±2%之内.将气相色谱与动态气体稀释仪耦合使系统能够自动进行工作曲线校准,系统自动采样、分析和标定,无需人员职守.对北京大气CO连续观测结果表明,北京大气CO浓度变化受气象要素与排放源双重控制.     

Air and groundwater pollution in an agricultural region of the Turkish Mediterranean coast

Air pollution and groundwater pollution in conjunction with agricultural activity were investigated in Antayla province on the Turkish Mediterranean coast. The air pollution was investigated in terms of gas-phase nitric acid (HNO3), sulfur dioxide (SO2), ammonia (NH3), and particulate matter for a 6-month period in the atmosphere using a "filter pack" system, which was developed and optimized in our laboratory. Ozone was measured by using an automated analyzer. Among all of the gas-phase pollutants, HNO3 had the lowest concentration (0.42 microg x m(-3)) followed by NH3. Agricultural activities seem to be the major source of observed NH3 in the air. The current state of water pollution was investigated in terms of organochlorine and organophosphorus pesticides around the greenhouses, in which mainly tomato, pepper, and eggplant are cultivated. Water samples were collected from 40 points, 28 of which were wells and 12 of which were surface water. The pesticide concentrations in water samples were determined by means of solid-phase extraction (SPE) followed by a gas chromatography (GC)-electron capture detector (ECD)/nitrogen phosphorus detector (NPD) system. In general, surface water samples were more polluted by the pesticides than groundwater samples. The most frequently observed pesticides were chlorpyriphos (57%) and aldrin (79%) in groundwater, and chlorpyriphos (75%), aldrin, and endosulfan sulfate (83%) in surface water samples. The highest concentrations were observed for fenamiphos (394.8 ng/L) and aldrin (68.51 ng/L) in groundwater, and dichlorvos (322.2 ng/L) and endosulfan sulfate (89.5 ng/L) in surface water samples. At least one pesticide had a concentration above the health limit in 38% of all the water samples analyzed.     

An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Abstract

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO₂) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography‐electron capture detector (GC‐ECD) indicated that the herbicide trifluralin (2,6‐dinitro‐N,N‐dipropyl‐4‐trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid‐phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low‐cost home‐made system that did not require the use of organic solvents.     

Organochlorine compounds,nitro musks and perfluorinated substances in breast milk – Results from Bavarian Monitoring of Breast Milk 2007/8

The aim of the Bavarian Monitoring of Breast Milk (BAMBI) project was to examine 10 organochlorine pesticides (OPs), 3 nitro musks, 6 indicator polychlorinated biphenyls (PCBs), 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), 12 dioxin-like PCBs (dl-PCBs) and several perfluorinated alkyl compounds in breast milk samples. A total of 516 breast milk samples were collected from seven regions in Bavaria and were analyzed by means of GC/ECD, GC/HRMS, and LC/MS-MS.     

Arizona Hazardous Air Pollutants Monitoring Program

ABSTRACT

In order to evaluate the existing risk to public health in Arizona related to hazardous air pollution, ambient air monitoring for selected hazardous air pollutants (HAPs) was carried out in 1994-1996 in several representative urban and rural areas of Arizona. A wide range of organic HAPs was monitored, requiring a variety of sampling and analysis methods. Stainless steel SUMMA canisters were used for collection of volatile hydrocarbons and halocarbons, which were analyzed by capillary gas chromatography with flame ionization and electron capture detection (GC-FID/ECD). Carbonyl compounds were collected using 2,4-dinitrophenylhydrazine-impregnated cartridges and analyzed by high performance liquid chromatog-raphy with ultraviolet detection. Semi-volatile and non-volatile polycyclic aromatic compounds were collected using a sampling train consisting of a filter followed by a PUF/XAD-4/PUF sandwich cartridge. Following extraction, samples were analyzed by capillary GC with mass spectrometric detection (GC-MS). Database software was developed for data processing and reporting functions. This paper describes the sampling strategy and the sampling and analysis methods employed in the monitoring program and presents a summary of all the results obtained during the duration of the sampling program.     

Method development for determination of fluroxypyr in soil

Four methods were developed for the analysis of fluroxypyr in soil samples from oil palm plantations. The first method involved the extraction of the herbicide with 0.05 M NaOH in methanol followed by purification using acid base partition. The concentrated material was subjected to derivatization and then cleaning process using a florisil column and finally analyzed by gas chromatography (GC) equipped with electron capture detector (ECD). By this method, the recovery of fluroxypyr from the spiked soil ranged from 70 to 104% with the minimum detection limit at 5 microg/kg. The second method involved solid liquid extraction of fluroxypyr using a horizontal shaker followed by quantification using high performance liquid chromatography (HPLC) equipped with UV detector. The recovery of fluroxypyr using this method, ranged from 80 to 120% when the soil was spiked with fluroxypyr at 0.1-0.2 microg/g soil. In the third method, the recovery of fluroxypyr was determined by solid liquid extraction using an ultrasonic bath. The recovery of fluroxypyr at spiking levels of 4-50 microg/L ranged from 88 to 98% with relative standard deviations of 3.0-5.8% with a minimum detection limit of 4 microg/kg. In the fourth method, fluroxypyr was extracted using the solid liquid extraction method followed by the cleaning up step with OASIS HLB (polyvinyl dibenzene). The recovery of fluroxypyr was between 91 and 95% with relative standard deviations of 4.2-6.2%, respectively. The limit of detection in method 4 was further improved to 1 pg/kg. When the weight of soil used was increased 4 fold, the recovery of fluroxypyr at spiking level of 1-50 microg/kg ranged from 82-107% with relative standard deviations of 0.5-4.7%.     

Residue evaluation of famoxadone and trifloxystrobin in cultivated mushrooms

Dissipation of the fungicides famoxadone and trifloxystrobin in basidiocarps of Agaricus bisporus was studied in mushroom growing rooms. The mushroom samples taken at all three consecutive production flushes following single or split applications of the fungicides were extracted with solvents and the residues were determined by using a gas chromatograph equipped with an electron capture detector (GC-ECD). Recoveries from the fortified control samples ranged from 87 to 105%. Following drench applications at 0.1-1 g/m2 of culture bed area, the highest famoxadone residue determined in basidiocarps was 0.1447 mg/kg. Analysis of trifloxystrobin revealed a quantitative relationship between the application rate (0.8-1.8 g/m2) and the residue levels of both the parent compound and its acid metabolite. The maximal combined residues of trifloxystrobin and its metabolite were 0.1313 mg/kg. Short- and long-term dietary risk assessment for both fungicides was carried out using consumption data from World Health Organization and the UK Pesticide Safety Directorate's Ten Consumer Model. The potential acute and chronic residue intakes via mushroom consumption were below toxicologically significant indicators.     

河南境内黄河流域集中式城市饮用水源水有机污染特性研究

摘要为探查和研究与公众生命健康关系密切的饮用水有机污染现状,采用GC／MS、HPLC、GC／ECD等多种分析技术,对河南省黄河流域部分饮用水水源地分平、丰、枯三期进行了有机物监测和研究。12个点位三期共检出599种有机物．根据毒性资料筛选出62种主要污染物。主要有毒化合物的浓度水平绝大多数远低于我国新颁布的“集中式生活饮用水地表水源地特定项目标准限值”．个别点位的极个别化合物如苯并(a)芘有超标现象．显示出明显的潜在危害作用。     

Occurrence and distribution of hexachlorocyclohexane isomers in vegetation samples from a contaminated area

The occurrence and distribution of four major hexachlorocyclohexane (HCH) isomers (alpha-, beta-, gamma- and delta-) were studied in vegetation samples of a highly contaminated area close to a small-scale industrial belt in Lucknow (North India). Eight species of plants were collected at different points of the contaminated area and different parts of the plants were separated in order to study the difference in uptake and accumulation. The samples were extracted by matrix solid-phase dispersion (MSPD) extraction and finally determined by a gas-chromatograph equipped with (63)Ni electron capture detector (ECD). HCH isomers were present in almost all samples and the concentration of total HCH in the plant sample analyzed varied between 13 and 44 mg kg(-1), being the main isomer of beta-HCH (8-22 mg kg(-1)). Lindane (gamma-HCH) was present in all samples (1-9 mg kg(-1)). Solanum torvum Sw., and Erianthus munja shows the highest and lowest capacity for accumulation of HCH, respectively with a significant difference at p<0.01 level. The highest concentration of HCH residue in root samples indicates the most likely mechanism of HCH accumulation in these plants was sorption of soil HCH on roots. Solanum torvum Sw., and Withania somnifera (L.) Dunal could accumulate considerable levels of HCH isomers (44 and 34 mg kg(-1), respectively). The results reflect the importance of plants in monitoring purposes and their potential for phytoremediation of HCH contaminated soils.     

A Continuous Quantitative Detection Method for Total Mercaptans,Organic Sulphides,H2S,and CS2 for Odouriferous Emissions

A monitoring system enabling detection and determination of the nature of odour nuisance caused by industrial emissions of volatile organic sulphur compounds is presented. The system consists of two continuous, highly sensitive detectors for sulphur compounds at the ppb-level. One of the detectors is equipped with a SO_x-scrubber and measures the total amount of non-S0₂ sulphur compounds. By the use of a newly developed scrubber retaining S0₂, H₂S and CS₂ the second detector monitors the presence of odorous mercaptans and organic sulphides in ambient air. Both these continuous detection signals are fed to a data processor which triggers air collection for the determination of the individual compounds by gas chromatographic analysis in the laboratory. The concept and operation, as well as the practical possibilities and applications of the system are explained