Evaluation of a high-resolution time-of-flight mass spectrometer for the gas chromatographic determination of selected environmental contaminants

A benchtop high-resolution time-of-flight mass spectrometer (TOF MS) was evaluated for the determination of key organic microcontaminants. The major advantage of the TOF MS proved to be the high mass resolution of about 0.002 Da (10 ppm). Consequently, the detectability of polar pesticides, polynuclear aromatic hydrocarbons and polychlorinated biphenyls is excellent, and detection limits are in the order of 1–4 pg injected mass. Best mass spectral resolution was obtained for medium-scale peaks. It is a disadvantage that the calibration range is rather limited, viz. to about two orders of magnitude. The high mass spectral resolution was especially useful to improve the selectivity and sensitivity when analyzing target compounds in complex samples and to prevent false-positive identifications.     

An analytical multi-residue approach for the determination of semi-volatile organic pollutants in pine needles

Vegetation (and pine needles in particular) has been widely used as an alternative to other conventional sampling devices to assess the atmospheric presence of semi-volatile organic contaminants (SVOCs). While most analytical procedures developed focus only on one or two chemical classes, this this work intends to establish a multi-component protocol to quantify brominated flame-retardants (BFRs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polynuclear aromatic hydrocarbons (PAHs) and one class of contaminant of emerging concern, the synthetic musks fragrances (SMCs). Pine needles extracts were obtained by ultrasonic solvents extraction (USE), and different cleanup approaches using solid-phase extraction (SPE) employing combinations of sorbents and solvents as well as gel permeation chromatography (GPC) were tested. SPE with alumina followed by GCP yielded the best results, with average recoveries over 80%.     

Characterization of polychlorinated aromatic hydrocarbons by reversed-phase liquid chromatography with ultraviolet absorbance and mass spectrometric detection

Ten polychlorinated aromatic hydrocarbons (PCAHs), perchlorobenzene (I), perchlorobiphenyl (II), perchlorobenzo[f]inden-1-one (III), perchloronaphthalene (IV), perchloropenta[def]phenanthren-4-one (V), 6H-1,2,4,5,7,8,9,10,11-nonachlorobenzo[cd]pyrene-3-one (VI), perchloroacenaphthylene (VII), 6-(p-tolyl)-6H-1,2,3,4,5,7,8,9,10,11-decachlorobenzo[cd]pyrene (VIII), perchlorofluoranthene (IX) and 6-(p-tolyl)-6H-1,11-dihydroxy-2,3,4,5,7,8,9,10-octachlorobenzo[cd]pyrene (X) have been separated with reversed-phase liquid chromatography (RPLC) by using two gradient eluents (toluene/methanol and cyclohexane/methanol), and were detected by ultraviolet (UV) and mass spectrometry (MS). The separation and detection of half of these ten compounds, which are of extremely high molecular weights, is an improvement over the chromatographic analysis of PCAHs. When the procedure was applied to the analysis of PCAHs of the products from the combustion of chlorobenzene and carbon tetrachloride, I, II, IV, VIII and X could be detected.     

Development of an improved analytical method for the determination of carcinogenic polycyclic aromatic hydrocarbons in transformer oil

Polynuclear aromatic hydrocarbons (PAHs) are natural constituents of transformer oils and are essential in prolonging transformer in-service lifetime. Issues concerning PAH carcinogenicity demand methods that provide qualitative and quantitative information on the PAH composition of new and in-service oils to allow informed operational decisions to be made. However, current analytical methods focus on PAH fingerprinting, as opposed to quantitative analysis and are also cumbersome, relying on the use of large (>100 ml) volumes of organic solvents, some of which are hazardous. This paper reports a method for the improved quantification of carcinogenic PAHs in transformer oils that is both simple and repeatable. The method uses commercially available solid-phase extraction columns and millilitre volumes of relatively non-hazardous solvents. Extraction efficiencies of > or =74% were obtained for the Environmental Protection Agency priority PAHs. The method has potential for automation and high-throughput analysis and thus is of interest to industries that use transformer oils.     

Micellar microwave-assisted extraction combined with solid-phase microextraction for the determination of polycyclic aromatic hydrocarbons in a certified marine sediment

A method for the determination of polycyclic aromatic hydrocarbons (PAHs) in marine sediments using microwave-assisted extraction with a micellar medium combined with solid-phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS) has been developed. Two kinds of SPME fibers (100 μm polydimethylsiloxane and 85 μm polyacrylate) and different micellar media were compared for the extraction efficiency of the 16 EPA priority PAHs. The polyacrylate fiber with a micellar medium of polyoxyethylene-10-laurylether provides the highest extraction efficiency. The method is remarkable for presenting lower equilibrium times and considerably higher reproducibilities than the obtained in aqueous medium. The LODs obtained ranged between 0.28 ng/ml for fluorene and 7.66 ng/ml for indeno[1,2,3-cd]pyrene. The method has been applied to the determination of PAHs in a certified marine sediment (SRM 1941a), obtaining recoveries between 58.6 and 111.5% for three- to five-ring PAHs with precision close to or lower than the certified values.     

Gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons formed during the pyrolysis of phenylalanine

The formation of polycyclic aromatic hydrocarbons (PAHs) during pyrolysis process of phenylalanine had been studied. Ten PAHs, including fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[k]fluoranthene, benzo[e]pyrene, and benzo[a]pyrene were analyzed by gas chromatography-mass spectrometry using selective ion monitoring mode. This technique offers the capability to analyze trace amounts of PAHs in phenylalanine pyrolyzates. The pyrolysis was carried out in a micro-furnace with quartz furnace liner. The injection was conducted with glass pelletizer syringe to avoid metal contamination. Qualitative results were obtained at 900 degrees C and quantitative analysis of 10 PAHs was done for 700 and 900 degrees C.     

Comparison of five extraction methods for measuring PCBs,PBDEs, organochlorine pesticides,and lipid content in serum

An increasing number of studies use blood obtained noninvasively to monitor organohalogen contaminants; however, blood can be difficult to analyze because of its aqueous nature and high protein content. We compared five methods for extracting polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), organochlorine pesticides, and lipids from serum using National Institute of Standards and Technology Standard Reference Material 1589a PCBs, Pesticides, PBDEs, and Dioxins/Furans in Human Serum. Liquid:liquid (LLE), cavity-dispersed microwave-assisted (MAE), focused microwave-assisted (FME), solid-phase (SPE), and pressurized fluid (PFE) extraction techniques were compared. FME extraction yielded the optimal recovery of internal standards (IS). All methods resulted in similar contaminant concentrations that also agreed with the certified values for SRM 1589a, except for only a few compounds measured by methods other than FME. Based on these findings, the FME method was determined to be the best overall extraction method. One procedural factor was found to affect contaminant concentrations; use of IS carrier solvents that were immiscible with serum (or when the serum was not directly physically mixed with IS) resulted in a 30% underestimation of organohalogen concentrations. This study offers valid, novel extraction alternatives beyond traditional methods (e.g., LLE) for blood contaminant measurements. Figure       

Factors affecting the retention of polycyclic aromatic hydrocarbons in gas chromatography

Summary The retention index of a planar polynuclear aromatic hydrocarbon on the GC phases OV-101, SE-52, and OV-17 is strictly related only to the boiling point, and less closely to the relative molecular mass. The very approximates relation with connectivity index ins only a consequence of the latter. On a nematic lqiuid crystal phase, a variation of activity coefficient, expressed in terms of a shape factor, also influences the retention of PAH.     

A relationship between the retention indices on nematic and isotropic phases and the shape of polycyclic aromatic hydrocarbons

Summary An equation has been derived allowing to predict retention index values on nematic phases from computable parameters and sizes of the molecules of polycyclic aromatic hydrocarbons. Another equation, which has also been derived, allows to determine the shape parameter of a molecule from chromatographic data.     

Headspace solvent microextraction and gas chromatographic determination of some polycyclic aromatic hydrocarbons in water samples

Headspace solvent microextraction (HSME) was shown to be an efficient preconcentration method for extraction of some polycyclic aromatic hydrocarbons (PAHs) from aqueous sample solutions. A microdrop of 1-butanol (as extracting solvent) containing biphenyl (as internal standard) was used in this investigation. Extraction occurred by suspending a 3 μl drop of 1-butanol from the tip of a microsyringe fixed above the surface of solution in a sealed vial. After extraction for a preset time, the microdrop was retracted back into the syringe and injected directly into a GC injection port. The effects of nature of extracting solvent, microdrop and sample temperatures, stirring rate, microdrop and sample volumes, ionic strength and extraction time on HSME efficiency were investigated and optimized. Finally, the enrichment factor, dynamic linear range (DLR), limit of detection (LOD) and precision of the method were evaluated by water samples spiked with PAHs. The optimized procedure was successfully applied to the extraction and determination of PAHs in different water samples.     

Extraction of polycyclic aromatic hydrocarbons and organochlorine pesticides from soils: a comparison between Soxhlet extraction, microwave-assisted extraction and accelerated solvent extraction techniques

The methods of simultaneous extraction of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) from soils using Soxhlet extraction, microwave-assisted extraction (MAE) and accelerated solvent extraction (ASE) were established, and the extraction efficiencies using the three methods were systemically compared from procedural blank, limits of detection and quantification, method recovery and reproducibility, method chromatogram and other factors. In addition, soils with different total organic carbon contents were used to test the extraction efficiencies of the three methods. The results showed that the values obtained in this study were comparable with the values reported by other studies. In some respects such as method recovery and reproducibility, there were no significant differences among the three methods for the extraction of PAHs and OCPs. In some respects such as procedural blank and limits of detection and quantification, there were significant differences among the three methods. Overall, ASE had the best extraction efficiency compared to MAE and Soxhlet extraction, and the extraction efficiencies of MAE and Soxhlet extraction were comparable to each other depending on the property such as TOC content of the studied soil. Considering other factors such as solvent consumption and extraction time, ASE and MAE are preferable to Soxhlet extraction.     

Simultaneous microwave-assisted extraction of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, phthalate esters and nonylphenols in sediments

A new method was developed for the simultaneous extraction of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalate esters (PEs), nonylphenols (NPs) and nonylphenol mono- and diethoxylates (NP1EOs and NP2EOs, respectively) in sediment samples by means of a closed microwave system. The extractions were carried out at 21 psi and 80% of microwave power and 15 ml of acetone were used as the common extraction solvent. The filtered extract was further fractionated in two groups using Florisil cartridges: PAHs and PCBs were eluted with n-hexane:toluene (4:1) and the PEs, NPs and ethoxylates were eluted with ethyl acetate. All the compounds were analysed by gas chromatography-mass spectrometry (GC-MS). In case of PAHs and PCBs, the developed method was validated by comparison of the results obtained for the certified reference material NIST 1944 with the certified values. In the absence of a reference material for phthalate esters and nonylphenols, one sediment sample was extracted twice under the optimal conditions in order to check than an exhaustive extraction of the analytes occurred. This method is currently used in the study of the distribution of those organic contaminants in the estuaries of the Bay of Biscay (Spain).     

Fast isolation of hydrophobic organic environmental contaminants from exposed semipermeable membrane devices (SPMDs) prior to GC analysis

Semipermeable membrane devices (SPMD) represent a passive sampling technology that is becoming widely used for monitoring of surface waters pollution. While "classic" procedures employ dialysis to recover target compounds from exposed SPMDs, in the present study analytes were isolated from cut membrane together with sequestering medium (triolein) using hexane as an extraction solvent. This approach allowed us to reduce the time needed for accomplishment of isolation step from 48 h to only 1 h. Automated gel permeation chromatography (GPC) clean-up is employed in the following step to separate triolein from analytes fraction. Musk compounds (MCs), polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs) and several other persistent organochlorine compounds (OCs) were determined in the respective fraction by GC method employing selective detectors (MSD, ECD). As shown in a series of analyses of SPMDs deployed in various aquatic ecosystems, high recoveries and good repeatability of results together with a possibility to obtain the information on the pollution of sampling site at the day of sample arrival to laboratory make this newly implemented procedure an interesting alternative to time consuming dialysis.     

Calibration bias in the determination of polynuclear aromatic hydrocarbons in water

 We present the results of an investigative interlaboratory test to determine the reasons for poor agreement between data from different laboratories for the determination of polynuclear aromatic hydrocarbons in water. Received: 2 July 1998 · Accepted: 1 August 1998     

Retention behavior of polycyclic aromatic hydrocarbons in supercritical fluid chromatography on a chemically bonded stationary phases based upon liquid-crystalline polymer

Summary The retention behavior of a set of polycyclic aromatic hydrocarbons in supercritical fluid chromatography have been studied on a chemically bonded stationary phase based upon a side chain liquid crystalline polymer (LCP) with carbon dioxide-based mobile phase. The effects of the mobile phase pressure, column temperature and amount of mobile phase organic modifier have been investigated in order to detect a possible structural change in the liquid crystal polymer linked to the silica support. The influence of these factors on the selectivity coefficients has also been studied. Two distinctive behaviors with temperature are noted at low pressure on the one hand and at higher pressure on the other. This change in behavior is based on the density of the supercritical CO₂ and the PAH volatility rather than on any specific stationary phase structural change. Both lower mobile phase pressure and amount of mobile phase modifier are required to obtain better selectivities. Better planarity recognition is observed in SFC than in HPLC with these new bonded liquid crystal stationary phases. The bonded liquid crystal phase is only weakly affected by the addition of organic modifier in the supercritical CO₂.     

Determination of trace amounts of polycyclic aromatic hydrocarbons in soil

A method for monitoring the contamination of soil with polycyclic aromatic hydrocarbons (PAHs) is introduced. Drying at elevated temperature is omitted to avoid losses of the more volatile constituents (primarily naphthalene). The soil sample, including its natural water content, is extracted with 2-methoxyethanol and cleaned up using a disposable C₈ cartridge and the PAHs are eluted with pentane, concentrated and measured by capillary gas chromatography with flame ionization detection. Determination limits between 15 and 35μg kg^?1 are obtained and the recovery is 80–90% measured at the 125 μg kg^?1 spike level, except for naphthalene (66%). Special attention is given to the design of the spiking technique, which simulates natural incorporation as far as possible, takes account of evaporation losses and therefore allows “real” recovery rates to be determined.     

Methods for determination of polybrominated diphenyl ethers in environmental samples - review

Polybrominated diphenyl ethers (PBDEs) are a group of persistent organic pollutants. They are used as flame retardants in plastics, paints, varnishes and textile materials. PBDEs pose great risk to the environment because of their high persistence and ability to get into the environment easily due to the lack of chemical bonds with the matrix of materials, to which they are added. Global research studies confirmed the occurrence of those compounds in the majority of elements of water and land environment. Analysis of PBDEs in environmental samples is one of the specific analytical methods of criteria that comprise low detection limits and high selectivity. The analysis of PBDEs in environmental samples is one of the specific analytical methods, in which the main criteria are low detection limits and high selectivity. In this article, a literature review of methods for environmental sample preparation and analysis of the PBDE content was presented. The article discusses the potential of modern extraction techniques such as: solid-phase microextraction, single-drop microextraction, dispersive liquid-liquid microextraction, microwave-assisted extraction, cloud point extraction, hollow fibre-liquid phase microextraction and others for the separation of PBDEs from environmental samples with a complex matrix. Among the methods for qualitative and quantitative determination of PBDEs, a particular focus was put on gas chromatography/mass spectrometry with various injection techniques and different types of sample ionisation.     

A review of techniques for the determination of polycyclic aromatic hydrocarbons in air

We provide an extensive review of the common methodologies employed in the analysis of airborne polycyclic aromatic hydrocarbons (PAHs). The review focuses on gas-chromatography-based approaches, in the light of their universal application with excellent separation, resolution, and sensitivity.We first describe collection methods for airborne PAHs in the gas and particle phases. We then evaluate the efficiency of extraction techniques employed for separating target PAHs from sampling media, using conventional solvent-based and emerging thermal-desorption approaches.We also describe commonly employed analytical methods with respect to their applicability to PAHs in gas and particle phases, collected from diverse environmental settings. As an essential part of basic quality assurance, we examine each method with special emphasis on key parameters (e.g., limit of detection and reproducibility).Finally, we address the likely directions of methodological developments, their limitations, and the future prospects for PAH analysis.     

Clean-up and analysis of carbazole and acridine type polycyclic aromatic nitrogen heterocyclics in complex sample matrices

A HPLC method for the analysis of polycyclic aromatic nitrogen heterocyclics (PANHs) in complex sample matrices is presented. It isolated and separated carbazole and acridine type PANHs with an absolute recovery of between 79–98%. Open column chromatography is used as an initial step to isolate a PANH fraction. By applying normal-phase liquid chromatography using a dimethylaminopropyl silica stationary phase and utilising back-flush technique it was possible to separate the PANH fraction into two fractions containing acridine type and carbazole type PANHs, respectively. The method applied on a sample of solvent refined coal heavy distillate (SRC II HD). A number of 3–5 ring acridines and carbazoles were identified with GC–electron impact MS and quantified with GC–nitrogen–phosphorous detection. Polycyclic aromatic hydrocarbons (PAHs) were determined in the SRC II HD sample by automated on-line clean-up and analysis of the obtained PAH fraction with coupled LC–GC–flame ionization detection. There was no overlap between the PANH and the PAH fractions with this method, and carbazoles and acridines were efficiently separated.     

Development of an improved method for the determination of polycyclic aromatic hydrocarbons in mainstream tobacco smoke

A gas chromatograph/mass-selective detection (GC/MS) method has been developed and validated for the quantitation of 16 polycyclic aromatic hydrocarbons found in mainstream tobacco smoke condensate. The utilization of two types of solid-phase extraction media combined with capillary column technology removed matrix interferences, afforded a significant reduction in analysis run time, and increased accuracy. Also, the addition of a chilled impinger was used to trap semi-volatile polycyclic aromatic hydrocarbons and to provide more accurate data. This was done without sacrificing the repeatability, reproducibility, and precision obtained in previously published methods. The development and validation studies discussed in this paper resulted in an improved, robust analytical method capable of increasing laboratory capacity and reducing sample reporting time.