Characterization and classification of complex PAH samples using GC-qMS and GC-TOFMS

The aim of this study was to compare the polycyclic aromatic hydrocarbon (PAH) contents in a number of complex samples, including soil samples from industrial sites, anti-skid sand, urban dust and ash samples from municipal solid waste incinerators. The samples were characterized by routine analysis of PAHs (gas chromatography–quadrupole mass spectrometry) and gas chromatography–time of flight mass spectrometry (GC–TOFMS). Classification of the samples by principal component analysis (PCA) according to their composition of PAHs revealed that samples associated with traffic and the municipal incinerator formed homogeneous clusters, while the PAH-contaminated soils clustered in separate groups. Using spectral data to resolve co-eluting chromatographic peaks, 962 peaks could be identified in the GC–TOFMS analysis of a pooled sample and 123–527 peaks in the individual samples. Many of the studied extracts included a unique set of chemicals, indicating that they had a much more diverse contamination profile than their PAH contents suggested. Compared to routine analysis, GC–TOFMS provided more detailed information about each sample and in this study a large number of alkylated PAHs were found to be associated with the corresponding unsubstituted PAHs. The possibility to filter peaks according to different criteria (e.g. to include only peaks that were detected in the analysis of another sample) was explored and used to identify unique as well as common compounds within samples. This procedure could prove to be valuable for obtaining relevant chemical data for use in conjunction with results from various biological test systems.     

Development of molecular marker source profiles for emissions from on-road gasoline and diesel vehicle fleets

As part of the Gasoline/Diesel PM Split Study, relatively large fleets of gasoline vehicles and diesel vehicles were tested on a chassis dynamometer to develop chemical source profiles for source attribution of atmospheric particulate matter in California's South Coast Air Basin. Gasoline vehicles were tested in cold-start and warm-start conditions, and diesel vehicles were tested through several driving cycles. Tailpipe emissions of particulate matter were analyzed for organic tracer compounds, including hopanes, steranes, and polycyclic aromatic hydrocarbons. Large intervehicle variation was seen in emission rate and composition, and results were averaged to examine the impacts of vehicle ages, weight classes, and driving cycles on the variation. Average profiles, weighted by mass emission rate, had much lower uncertainty than that associated with intervehicle variation. Mass emission rates and elemental carbon/organic carbon (EC/OC) ratios for gasoline vehicle age classes were influenced most by use of cold-start or warm-start driving cycle (factor of 2-7). Individual smoker vehicles had a large range of mass and EC/OC (factors of 40 and 625, respectively). Gasoline vehicle age averages, data on vehicle ages and miles traveled in the area, and several assumptions about smoker contributions were used to create emissions profiles representative of on-road vehicle fleets in the Los Angeles area in 2001. In the representative gasoline fleet profiles, variation was further reduced, with cold-start or warm-start and the representation of smoker vehicles making a difference of approximately a factor of two in mass emission rate and EC/OC. Diesel vehicle profiles were created on the basis of vehicle age, weight class, and driving cycle. Mass emission rate and EC/OC for diesel averages were influenced by vehicle age (factor of 2-5), weight class (factor of 2-7), and driving cycle (factor of 10-20). Absolute and relative emissions of molecular marker compounds showed levels of variation similar to those of mass and EC/OC.     

Determination of dimethyl fumarate (DMFu) in silica gel pouches using gas chromatography coupled ion trap mass spectrometry

A simple method for the determination of dimethyl fumarate (DMFu) in silica gel pouches has been developed. The gas chromatographic behaviour of DMFu was investigated; the instrumental method, based on EI mass spectrometry coupled with an Ion Trap Detector operating whether in full scan mode or in MS/MS mode was also investigated. Several factors have been evaluated and optimized during the development process: solvent and temperature of extraction, type of stationary phase in capillary column. The analytical procedure consists of two steps as follows: (a) the sample preparation using 10 g of sample extracted with acetonitrile in an ultrasonic, heated bath and (b) the determination by gas chromatography-ion trap mass spectrometry. Mass spectrometry in conjunction with chromatographic separation is a very powerful combination for identification of an analyte in the extract in spite of selective detectors employed with GC, such as ECD, FPD and NPD, that offer only limited specificity. Blank samples show no interfering peaks in the areas of interest, so the specificity of the method was assured under the investigated GC/MS conditions. The method has been validated in terms of recovery, repeatability, linearity, detection limits and measurement uncertainty. The results obtained meet both the method validation criteria and requirements of the European/National legislation. The method was verified to be accurate with 97 % mean recoveries at 0.05 mg/kg and 1.00 mg/kg levels; the repeatability (expressed as RSD %) was found to be better than 15 %. Good linearity was found in the range between 0.05 μg/mL and 5.0 μg/mL and a value of R2 > 0.9998 was calculated. The procedure ensures high specificity and a good sensitivity with detection limit (ld) of 0.02 mg/kg and quantification limit (LOQ) of 0.05 mg/kg. This procedure has been successfully applied for the analysis of several hundred of real samples collected during a monitoring control plan started last year in our country. All samples exceeding the maximum allowed level of DMFu (0, 1 mg/kg) were confirmed by GC/MS/MS (ITD) for a higher degree of confidence in identification. The main advantages of this method include: rapidity, simplicity (few, simple steps), reliability, cheapness, no need for long and difficult clean-up and evaporation steps, high specificity by using GC/MS and GC/MS/MS, availability for routine monitoring.     

Characterization of humic substances of different origin by means of mass spectrometry and neural networks

Mass spectrometry fingerprinting of humic acids extracted from different soils has been carried out using laser desorption/ionization mass spectrometry (LDI-TOF MS). LDI-TOF MS provides characteristic mass spectra fingerprints for the humic acids of different origin. The information given in the fingerprints was evaluated for natural grouping trends in the samples by neural networks computing tools, such as self-organizing feature map (SOFM). This approach is efficient for recognizing patterns in the humic acids samples independently of their characteristic variability; variability characterizing natural products such as humic substances. The use of multi-layer perceptron artificial neural networks gave a successful classification of the samples.     

Application of automated mass spectrometry deconvolution and identification software for pesticide analysis in surface waters

A new approach to surface water analysis has been investigated in order to enhance the detection of different organic contaminants in Nathan Creek, British Columbia. Water samples from Nathan Creek were prepared by liquid/liquid extraction using dichloromethane (DCM) as an extraction solvent and analyzed by gas chromatography mass spectrometry method in scan mode (GC-MS scan). To increase sensitivity for pesticides detection, acquired scan data were further analyzed by Automated Mass Spectrometry Deconvolution and Identification Software (AMDIS) incorporated into the Agilent Deconvolution Reporting Software (DRS), which also includes mass spectral libraries for 567 pesticides. Extracts were reanalyzed by gas chromatography mass spectrometry single ion monitoring (GC-MS-SIM) to confirm and quantitate detected pesticides. Pesticides: atrazine, dimethoate, diazinone, metalaxyl, myclobutanil, napropamide, oxadiazon, propazine and simazine were detected at three sampling sites on the mainstream of the Nathan Creek. Results of the study are further discussed in terms of detectivity and identification level for each pesticide found. The proposed approach of monitoring pesticides in surface waters enables their detection and identification at trace levels.     

Time-resolved mass concentration,composition and sources of aerosol particles in a metropolitan underground railway station

Aerosol samples were collected using a stacked filter unit (SFU) for PM10-2.0 and PM2.0 size fractions on the platform of a metropolitan underground railway station in downtown Budapest. Temporal variations in the PM10 mass concentration and wind speed and direction were determined with time resolutions of 30 and 4 s using a tapered-element oscillating microbalance (TEOM) and a wind monitor, respectively. Sample analysis involved gravimetry for particulate mass, and particle-induced X-ray emission spectrometry (PIXE) for elemental composition. Diurnal variation of the PM10 mass concentration exhibited two peaks, one at approximately 07:00 h and the other at approximately 17:00 h. The mean±SD PM10 mass concentration for working hours was 155±55 μg m⁻³. Iron, Mn, Ni, Cu, and Cr concentrations were higher than in outdoor air by factors between 5 and 20, showing substantial enrichment compared to both the average crustal rock composition and the average outdoor aerosol composition. Iron accounted for 40% and 46% of the PM10-2.0 and PM2.0 masses, respectively, and 72% of the PM10 mass was associated with the PM10-2.0 size fraction. The aerosol composition in the metro station (in particular the abundance of the metals mentioned above) is quite different from the average outdoor downtown composition. Mechanical wear and friction of electric conducting rails and bow sliding collectors, ordinary rails and wheels, as well as resuspension, were identified as the primary sources. Possible health implications based on comparison to various limit values and to data available for other underground railways are discussed.     

Application of Automated Mass Spectrometry Deconvolution and Identification Software for Pesticide Analysis in Surface Waters

A new approach to surface water analysis has been investigated in order to enhance the detection of different organic contaminants in Nathan Creek, British Columbia. Water samples from Nathan Creek were prepared by liquid/liquid extraction using dichloromethane (DCM) as an extraction solvent and analyzed by gas chromatography mass spectrometry method in scan mode (GC-MS scan). To increase sensitivity for pesticides detection, acquired scan data were further analyzed by Automated Mass Spectrometry Deconvolution and Identification Software (AMDIS) incorporated into the Agilent Deconvolution Reporting Software (DRS), which also includes mass spectral libraries for 567 pesticides. Extracts were reanalyzed by gas chromatography mass spectrometry single ion monitoring (GC-MS-SIM) to confirm and quantitate detected pesticides. Pesticides: atrazine, dimethoate, diazinone, metalaxyl, myclobutanil, napropamide, oxadiazon, propazine and simazine were detected at three sampling sites on the mainstream of the Nathan Creek. Results of the study are further discussed in terms of detectivity and identification level for each pesticide found. The proposed approach of monitoring pesticides in surface waters enables their detection and identification at trace levels.     

A morphological investigation of soot produced by the detonation of munitions

The morphology of three different detonation soot samples along with other common soot materials such as carbon black, diesel soot and chimney soot was studied by elemental and proximate analysis, X-ray diffraction and electron microscopy. The goal of this study was to better define the morphology of the detonation soot in order to better assess the interactions of this type of soot with explosive residues. The detonation soot samples were obtained by the detonation of artillery 155mm projectiles filled with either pure TNT (2,4,6-trinitrotoluene) or composition B, a military explosive based on a mixture of TNT and RDX (trimethylentrinitramine). The carbon content of the soot samples varied considerably depending on the feedstock composition. Detonation soot contains less carbon and more nitrogen than the other carbonaceous samples studied, due to the molecular structure of the energetic materials detonated such as TNT and RDX. The ash concentration was higher for detonation soot samples due to the high metal content coming from the projectiles shell and to the soil contamination which occurred during the detonation. By X-ray diffraction, diamond and graphite were found to be the major crystalline carbon forms in the detonation soot. Two electron microscopy techniques were used in this study to visualise the primary particles and to try to explain the formation mechanism of detonation soot samples.     

The determination of toxaphene in environmental samples by negative ion electron capture high resolution mass spectrometry

A method is described for the analysis of toxaphene in environmental samples by high resolution gas chromatography high resolution mass spectrometry in selected ion electron capture negative ion mode. Toxaphene is detected by monitoring [M-Cl]- fragments ions of chlorobornanes (Cl6-Cl10) and chlorobornenes (Cl6-Cl7) using formal ion ratio criteria. The method shows high sensitivity and excellent specificity for the detection of chlorobornanes with negligible interference from of a wide range of common environmental organochlorines including chlordanes, PCBs and PCB-oxygen adducts. The analytical scheme is applicable to sediment and biological tissue samples and typically provide sample detection limits of less than 0.2 ng/g technical toxaphene for a 10 g sample.     

Enantiomer fractions of polychlorinated biphenyls in three selected Standard Reference Materials

The enantiomer composition of six chiral polychlorinated biphenyls (PCBs) were measured in three different certified Standard Reference Materials (SRMs) from the US National Institute of Standards and Technology (NIST): SRM 1946 (Lake Superior fish tissue), SRM 1939a (PCB Congeners in Hudson River Sediment), and SRM 2978 (organic contaminants in mussel tissue--Raritan Bay, New Jersey) to aid in quality assurance/quality control methodologies in the study of chiral pollutants in sediments and biota. Enantiomer fractions (EFs) of PCBs 91, 95, 136, 149, 174, and 183 were measured using a suite of chiral columns by gas chromatography/mass spectrometry. Concentrations of target analytes were in agreement with certified values. Target analyte EFs in reference materials were measured precisely (<2% relative standard deviation), indicating the utility of SRM in quality assurance/control methodologies for analyses of chiral compounds in environmental samples. Measured EFs were also in agreement with previously published analyses of similar samples, indicating that similar enantioselective processes were taking place in these environmental matrices.     

Sensitivity of source apportionment of urban particulate matter to uncertainty in motor vehicle emissions profiles

A sensitivity analysis was conducted to characterize sources of uncertainty in results of a molecular marker source apportionment model of ambient particulate matter using mobile source emissions profiles obtained as part of the Gasoline/Diesel PM Split Study. A chemical mass balance (CMB) model was used to determine source contributions to samples of fine particulate matter (PM2.5) collected over 3 weeks at two sites in the Los Angeles area in July 2001. The ambient samples were composited for organic compound analysis by the day of the week to investigate weekly trends in source contributions. The sensitivity analysis specifically examined the impact of the uncertainty in mobile source emissions profiles on the CMB model results. The key parameter impacting model sensitivity was the source profile for gasoline smoker vehicles. High-emitting gasoline smoker vehicles with visible plumes were seen to be a significant source of PM in the area, but use of different measured profiles for smoker vehicles in the model gave very different results for apportionment of gasoline, diesel, and smoker vehicle tailpipe emissions. In addition, the contributions of gasoline and diesel emissions to total ambient PM varied as a function of the site and the day of the week.     

The stable carbon isotope composition of atmospheric PAHs

A method for compound-specific stable carbon isotope analysis of atmospheric polycyclic aromatic hydrocarbons (PAHs) in carbonaceous aerosols is described. Atmospheric aerosol samples containing PAHs (C-10 to C-20) were collected on filters using a high-volume sampling technique, solvent extracted, taken through a cleanup procedure, separated by gas chromatography, oxidized to CO₂ on-line, and introduced into an isotope ratio mass spectrometer for analysis. The method can be used to determine the isotope composition of a few nanograms of PAHs. This technique was used to analyse and compare the isotope composition of atmospheric PAHs from standards, as well as two samples from urban and rural locations. Isotopic variability in atmospheric PAHs is greater than measurement uncertainties which makes this a potentially useful technique for source identification when used together with concentration measurements.     

Characterization of organic aerosol in Big Bend National Park,Texas

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study was conducted in Big Bend National Park, Texas, July through October 1999. Daily PM_2.5 organic aerosol samples were collected on pre-fired quartz fiber filters. Daily concentrations were too low for detailed organic analysis by gas chromatography-mass spectrometry (GC-MS) and were grouped based on their air mass trajectories. A total of 12 composites, each containing 3–10 daily samples, were analyzed. Alkane carbon preference indices suggest primary biogenic emissions were small contributors to primary PM_2.5 organic matter (OM) during the first 3 months, while in October air masses advecting from the north and south were more strongly influenced by biogenic sources. A series of trace organic compounds previously shown to serve as particle phase tracers for various carbonaceous aerosol source types were examined. Molecular tracer species were generally at or below detection limits, except for the wood smoke tracer levoglucosan in one composite, so maximum possible source influences were calculated using the detection limit as an upper bound to the tracer concentration. Wood smoke was found not to contribute significantly to PM_2.5 OM, with contributions for most samples at <1% of the total organic particulate matter. Vehicular exhaust also appeared to make only minor contributions, with maximum possible influences calculated to be 1–4% of PM_2.5 OM. Several factors indicate that secondary organic aerosol formation was important throughout the study, and may have significantly altered the molecular composition of the aerosol during transport.     

Sensitivity of Source Apportionment of Urban Particulate Matter to Uncertainty in Motor Vehicle Emissions Profiles

Abstract

A sensitivity analysis was conducted to characterize sources of uncertainty in results of a molecular marker source apportionment model of ambient particulate matter using mobile source emissions profiles obtained as part of the Gasoline/Diesel PM Split Study. A chemical mass balance (CMB) model was used to determine source contributions to samples of fine particulate matter (PM_2.5) collected over 3 weeks at two sites in the Los Angeles area in July 2001. The ambient samples were composited for organic compound analysis by the day of the week to investigate weekly trends in source contributions. The sensitivity analysis specifically examined the impact of the uncertainty in mobile source emissions profiles on the CMB model results. The key parameter impacting model sensitivity was the source profile for gasoline smoker vehicles. High-emitting gasoline smoker vehicles with visible plumes were seen to be a significant source of PM in the area, but use of different measured profiles for smoker vehicles in the model gave very different results for apportionment of gasoline, diesel, and smoker vehicle tailpipe emissions. In addition, the contributions of gasoline and diesel emissions to total ambient PM varied as a function of the site and the day of the week.     

Preliminary characterization and source assessment of PAHs in tributary sediments of the Athabasca River,Canada

The Athabasca Oil Sands are one of four natural oil sands deposits in Northern Alberta, Canada. As a number of new mines are planned in the area, there is a need to establish background levels of natural hydrocarbon release prior to these developments. To this end, various environmental samples were taken from selected tributaries in the oil sands region of the Athabasca River Basin and analysed by gas chromatography/mass spectrometry (GC/MS) for polycyclic aromatic hydrocarbons (PAHs) and their alkylated analogues. Samples were collected over 3 years (1998-2000) to provide an increased understanding of the spatial distribution, nature and extent of natural hydrocarbon release to the environment. Results indicated that levels of total PAHs were elevated in the tributaries (up to 34.7 µg/g) compared to the main stem Athabasca River (<2 µg/g). As expected, samples from the oil sands deposits contained the greatest amounts of PAHs and alkylated PAHs. Profiles of the alkylated PAM distributions were very similar, indicating that all the samples tested were from a common petrogenic source.     

Quantification of airborne fossil and biomass carbonylic carbon by combined radiocarbon and liquid chromatography mass spectrometry

Airborne carbonyl compounds have been sampled at three European semi-remote to semi-urban test sites for radiocarbon (¹⁴C) analysis. The used methodology included collection on 2,4-dinitrophenylhydrazine coated silica gel cartridges, chromatographic isolation of the formed hydrazones, combustion into CO₂, reduction into graphite followed by accelerator mass spectrometry. In combination with this, liquid chromatography coupled to atmospheric pressure chemical ionisation mass spectrometry was used for chemical speciation of the collected carbonyls.At all sites the carbonyls were found to be of a mixed biogenic/anthropogenic origin. The determining factor for the proportion of fossil (anthropogenic) carbon in the samples was the vicinity of urban sources for carbonyls and their photochemical precursors. At meteorological conditions, which gave the test sites semi-rural/semi-remote characteristics the samples contained an average of 24% (range: 10–34%) of fossil carbonylic carbon. When air masses were transported from urban areas to the test-sites significantly higher proportions of fossil carbonylic carbon were determined with a maximum of 61%. Principal component analysis on this limited data set indicated that a low fossil proportion of carbonylic carbon is associated with high proportions of acetaldehyde, acetone, pentanone and acrolein. Until further radicarbon studies are carried out the conclusion remains that for the carbonyl compounds measured European background levels are of a predominant biogenic origin.     

Polycyclic aromatic hydrocarbons in cigarette sidestream smoke particulates from a Taiwanese brand and their carcinogenic relevance

Polycyclic aromatic hydrocarbons (PAHs) adsorbed on cigarette sidestream smoke particulates (CSSPs) have been regarded as important contributors to lung carcinogenesis in never smokers. However, limited information is available on PAH levels in cigarette sidestream smoke. Here we determine the concentrations of 22 PAHs, including 16 US EPA priority PAHs, in CSSPs generated from a high market-share domestic brand in Taiwan. Five of the 22 PAHs are undetectable. The remaining 17 PAHs constitute about 0.022% of the total mass of CSSPs. Near one fifth of the PAH mass come from IARC group 1 and group 2 carcinogens. Carcinogenic potency is equivalent to 144 ng benzo[a]pyrene per cigarette converted according to potency equivalency factors (PEFs). The CSSP condensate could activate AhR activity and induce AhR target gene expression. High concentrations of CSSPs also exhibited AhR-independent cytotoxicity. However, mixing the 17 PAHs as the composition in the CSSP condensate could not reconstitute either capacity. Since AhR activation and cytotoxicity are important mechanisms underlying carcinogenic potency, the results suggest that other component compounds play a more active role in carcinogenesis. The approach of individual PAH profiling plus PEF conversion commonly used in risk assessment is likely to underestimate the risk caused by environmental cigarette smoke exposure.     

Development and applications of a mass spectrometry/mass spectrometry method for the quantification of polychlorinated dibenzo-p-dioxins and dibenzofurans

Mass spectrometry/mass spectrometry (MS/MS) has been demonstrated to be a valuable technique in the analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs, PCDFs). In this study, we demonstrate both the value and limitations of high-resolution mass spectrometry (HRMS) and MS/MS in the analysis of PCDDs and PCDFs. We have found that in certain cases, MS/MS can solve analytical problems that cannot be solved by high-resolution mass spectrometry and we demonstrate the reliability and reproducibility of MS/MS in the analysis of PCDDs and PCDFs in environmental matrices.     

Environmental tobacco smoke particles in multizone indoor environments

Environmental tobacco smoke (ETS) is a major source of human exposure to airborne particles. To better understand the factors that affect exposure, and to investigate the potential effectiveness of technical control measures, a series of experiments was conducted in a two-room test facility. Particle concentrations, size distributions, and airflow rates were measured during and after combustion of a cigarette. Experiments were varied to obtain information about the effects on exposure of smoker segregation, ventilation modification, and air filtration. The experimental data were used to test the performance of an analytical model of the two-zone environment and a numerical multizone aerosol dynamics model. A respiratory tract particle deposition model was also applied to the results to estimate the mass of ETS particles that would be deposited in the lungs of a nonsmoker exposed in either the smoking or nonsmoking room. Comparisons between the experimental data and model predictions showed good agreement. For time-averaged particle mass concentration, the average bias between model and experiments was less than 10%. The average absolute error was typically 35%, probably because of variability in particle emission rates from cigarettes. For the conditions tested, the use of a portable air filtration unit yielded 65–90% reductions in predicted lung deposition relative to the baseline scenario. The use of exhaust ventilation in the smoking room reduced predicted lung deposition in the nonsmoking room by more than 80%, as did segregating the smoker from nonsmokers with a closed door.     

Interpretation of Meteorological Pollutant Roses in Areas Subject to Nocturnal Drainage Winds

The composition of aerosol particle products formed from the photochemical reaction of terpenes with NO_x and the chemical reaction of terpenes with ozone was determined using direct insertion probe/high resolution mass spectrometry. Samples of the aerosol particles generated from these gas phase reactions were collected on stainless steel disks using a specially-designed impactor. The samples were analyzed using computer-controlled high resolution mass spectrometry. The photochemical reaction of limonene with NO_x produced more than 30 reaction products in the aerosol phase. The major products identified included aldehydes, alcohols, acids, peroxides, and nitrate esters of alcohols, acids, and peroxides. In addition, there was evidence of dimeric and possibly trimeric reaction products. The composition of aerosol particle products formed from the dark reaction of ozone with limonene was determined and found similar to those products generated in the photochemical reaction, excluding the nitrated species. Aerosol concentrations were monitored using nephelometry which indicated a conversion of terpene to aerosol of 50% or greater for both the limonene and terpinolene reaction systems. The results show that direct insertion probe high resolution mass spectrometric technique has the capability for determining the composition of very polar and high molecular weight materials in aerosol particles. The composition of terpene aerosol particle products and the mass spectral data obtained from their analysis can be used in further studies to determine the importance of terpene aerosol particle formation in ambient air.