Identification, characterization and quantitation of pyrogenic polycylic aromatic hydrocarbons and other organic compounds in tire fire products

On 15 August 2001, a tire fire took place at the Pneu Lavoie Facility in Gatineau, Quebec, in which 4000 to 6000 new and recycled tires were stored along with other potentially hazardous materials. Comprehensive gas chromatography-mass spectrometry (GC-MS) analyses were performed on the tire fire samples to facilitate detailed chemical composition characterization of toxic polycyclic aromatic hydrocarbons (PAHs) and other organic compounds in samples. It is found that significant amounts of PAHs, particularly the high-ring-number PAHs, were generated during the fire. In total, 165 PAH compounds including 13 isomers of molecular weight (MW) 302, 10 isomers of MW 278, 10 isomers of MW 276, 7 isomers of MW 252, 7 isomers of MW 228, and 8 isomers of MW 216 PAHs were positively identified in the tire fire wipe samples for the first time. Numerous S-, O-, and N-containing PAH compounds were also detected. The identification and characterization of the PAH isomers was mainly based on: (1) a positive match of mass spectral data of the PAH isomers with the NIST authentic mass spectra database; (2) a positive match of the GC retention indices (I) of PAHs with authentic standards and with those reported in the literature; (3) agreement of the PAH elution order with the NIST (US National Institute of Standards and Technology) Standard Reference Material 1597 for complex mixture of PAHs from coal tar; (4) a positive match of the distribution patterns of PAH isomers in the SIM mode between the tire fire samples and the NIST Standard Reference Materials and well-characterized reference oils. Quantitation of target PAHs was done on the GC-MS in the selected ion monitoring (SIM) mode using the internal standard method. The relative response factors (RRF) for target PAHs were obtained from analyses of authentic PAH standard compounds. Alkylated PAH homologues were quantitated using straight baseline integration of each level of alkylation.     

Role of methyl radicals in the growth of PAHs

The role of methyl radicals in the networking of sp² carbons has been explored through kinetic analysis of mass spectra of the gas-phase products of the pyrolysis of toluene and toluene/acetone mixtures. Pyrolytic reactions were performed in a flow tube reactor at temperatures of 1140–1320 K and a constant total pressure of 10.38 Torr with a residence time of 0.585 s. On addition of acetone, methyl substituted products and their derivatives were enhanced. Mass peaks were observed in several sequences at an interval of 14 mass units; these ions correspond to methyl substituted products formed as a result of hydrogen abstraction (−H) followed by methyl radical addition (+CH₃). Each major peak was usually preceded by a peak at two mass units lower, which was likely produced through dehydrogenation/dehydrocyclization (−H₂) of methyl substituted products. Detected species include a large number of alkyl, cyclotetrafused (CT), cyclopentafused (CP) mono-, di-, and polycyclic aromatic hydrocarbons (PAHs) along with primary PAHs. The analysis showed that MAC (methyl addition/cyclization) has a unique capacity to induce the sequential growth of hexagonal networks of sp² carbons from all fusing sites [1] of a PAH. Moreover, MAC was found capable of answering an important question in PAH growth, which is expansion of the CT → CP → hexagonal network for which other reported mechanisms are inefficient.     

Comparison of immunoassay and gas chromatography-mass spectrometry for measurement of polycyclic aromatic hydrocarbons in contaminated soil

Polycyclic aromatic hydrocarbons (PAHs) are frequently encountered in the environment and may pose health concerns due to their carcinogenicity. A commercial enzyme-linked immunosorbent assay (ELISA), was evaluated as a screening method for monitoring PAHs at contaminated sites. The ELISA was a carcinogenic PAH (C-PAH) RaPID assay testing kit that cross-reacts with several PAHs and utilizes benzo[a]pyrene (BaP) as a calibrator. Soil samples were extracted with 50% acetone in dichloromethane (DCM) for analysis by ELISA and gas chromatography-mass spectrometry (GC-MS). The overall method precision was within ±30% for ELISA and within ±20% for GC-MS. Recovery data for spiked soils ranged from 46 to 140% for BaP as determined by ELISA. Recoveries data of the GC-MS surrogate standards, 2-fluorobiphenyl and chrysene, were greater than 70%. The GC-MS procedure detected a total of 19 priority PAHs (2-6-ring PAHs) including seven probable human carcinogens (4-6-ring B2-PAHs). The ELISA results were compared to GC-MS summation results for the total 19 target PAHs as well as for the subset of the seven B2-PAH compounds. For all soil samples, the PAH concentrations derived from ELISA were greater than the sum of B2-PAH concentrations obtained by GC-MS. ELISA determinations were also frequently greater than the results obtained by GC-MS for the total 19 PAH compounds. This discrepancy can be expected, since the ELISA is a screening assay for the detection of several related PAHs while the GC-MS procedure detects priority PAH compounds. Thus, only a subset of PAHs (e.g. 19 PAHs) in the soil samples were measured by GC-MS while additional PAHs, including alkylated PAHs, and PAH derivatives have been demonstrated to be cross-reactive in the C-PAH ELISA. Results of paired tests show that the PAH data from ELISA and GC-MS methods are significantly different (P<0.001), but highly correlated. The ELISA data had a strong positive relationship with the GC-MS summation data for the B2-PAHs as well as for the 19 PAHs targeted by the GC-MS method. Results indicate that the ELISA may be useful as a broad screen for monitoring PAHs in environmental samples.     

Initial applications of phospholipid-coated mercury electrodes to the determination of polynuclear aromatic hydrocarbons and other organic micropollutants in aqueous systems

Mercury electrodes coated with di-oleoyl lecithin are described for the determination of polynuclear aromatic hydrocarbons (PAHs) and other micropollutants in aqueous solutions. The coated electrodes give a characteristic response in the capacitance/voltage curve to three-, four- and five- ring PAHs. The extent of the negative potential shift in the reversible capacitance peaks (and thus sensitivity) is related to the number of aromatic rings and substituents on the PAH. The capacitance/voltage curves were recorded by phase-sensitive a.c. voltammetry. The response is quantitatively related to the concentration of PAH in solution. Detection limits are about 0.4 μg l^?1 and the reproducibility (RSD) for separate samples is 7%. Intercalibration of the method with fluorescence spectrophotometry of pyrene-spiked sea-water samples, showed recoveries of 80%. The analytical system is useful for sea water and tap water. Bovine serum albumin (1 mg l^?1) enhances the sensitivity to pyrene. The monolayer is sensitive to oil-contaminated waters ( > 40 μg l^?1). The capacitance peaks respond selectively to other groups of compounds and to individual compounds within a group. The monolayer appears highly sensitive to the solution behaviour of PAHs because only soluble unbound PAHs penetrate the monolayer. Humic acid added to the solution decreases the response to PAH presumably by binding a fraction of PAH in the solution.     

Annulative π-Extension by Rhodium(III)-Catalyzed Ketone-Directed C−H Activation: Rapid Access to Pyrenes and Related Polycyclic Aromatic Hydrocarbons (PAHs)

Annulative π-extension (APEX) reaction has become a powerful tool for the precise synthesis of well-defined polycyclic aromatic hydrocarbons (PAHs) such as nanographene, graphene, and other PAHs possessing unique structure. Herein, an APEX reaction has been realized at the masked bay-region for the efficient and rapid synthesis of valuable PAH, pyrene, bearing substitutions at the most challenging K-region. Rh^III-catalyzed ketone-directed C−H activation at the peri-position of a naphthyl-derived ketone, alkyne-insertion, intramolecular nucleophilic attack at the carbonyl-group, dehydration, and aromatization steps occurred in one-pot to effectuate the protocol. Employing this strategy, a two-fold APEX reaction on enantiopure BINOL-derived ketones provided access to axially-chiral bipyrene derivatives. The detailed DFT study to support proposed mechanism, and synthesis of helical PAHs like dipyrenothiophene and dipyrenofuran are other highlights of the present study.     

Source apportionment of polycyclic aromatic hydrocarbons in surface sediments of Izmit Bay (Turkey)

Thirty-five surface sediment samples were collected from the northeastern coast of the Izmit Bay to apportion the sources of polycyclic aromatic hydrocarbons (PAH) entering the Bay. Samples were collected in February and June, 2002 and they were analyzed for 16 PAH compounds using HPLC-UV. Total PAHs ranged from 1.1 to 68.4?μg?g^?1-dry wt. Both the factor analysis and the factor analysis-absolute factor score multiple linear regression analysis were applied to the results of 11 PAH compounds which were observed in more than 80% of the samples. From the factor analysis, two factors explaining 91.3% of the total variance were identified. The first factor was petrogenic and explained 76% of the variance. Except for the Anthracene, 57 to 85% of the lower molecular mass PAH compounds (from Fluorene to Chrysene) were contributed by this factor.     

Direct LD-FTMS detection of mineral-associated PAHs and their influence on the detection of co-existing amino acids

Polycyclic aromatic hydrocarbon (PAH) compounds and amino acids (AAs) are both ubiquitous throughout the universe and can be co-located in mineral matrices (e.g., meteorites); therefore, co-detection of PAHs and AAs associated with terrestrial and extra-terrestrial minerals is of interest. Nine PAH compounds representing four chemical classes of PAH (unsubstituted, acetyl-, amino-, and nitro-substituted) were applied onto the surface of quartz, plagioclase, olivine, and ilmenite mineral standards and analyzed using laser desorption/ionization Fourier transform mass spectrometry (LD-FTMS). Mass-to-charge peaks derived from PAH compounds were detected from the surfaces of all minerals evaluated. All PAH compounds were detected in the positive ion mode, whereas only nitro-substituted PAH compounds were detected in negative ion mode. In this and earlier studies, the ability to directly detect mineral-associated AAs by LD-FTMS was dependent on the mineral geomatrix. On iron-bearing minerals AAs appeared as highly fragmented ions in the spectra or were not detectable; however, the addition of the PAH chrysene enabled the ionization and detection of AAs threonine and histidine by LD-FTMS. Thus, for mineral systems such as meteorites, interstellar dust particles, soils, and sediments, the co-detection of AAs associated with PAHs by LD-FTMS is feasible.     

Analysis of alkyl and 2-6-ringed polycyclic aromatic hydrocarbons by isotope dilution gas chromatography/mass spectrometry. Quality assurance and determination in Spanish river sediments

An accurate, precise and sensitive method is described for the analysis of 29 polycyclic aromatic hydrocarbons (PAHs), including 19 2-6-ringed PAHs and 10 alkyl-PAHs. The method is based on an isotope dilution technique using gas chromatography/mass spectrometry (GC/MS) and available labeled PAHs as internal standards. Quality parameters were calculated with satisfactory results and 36 Spanish river sediments were analysed. Results were evaluated regarding to the sediment quality guidelines (SQGs) based on the effects range-low (ERL) and the effects range-median (ERM) values. Most analysed sediments showed a good quality, since only 7 of them exceeded ERL values, including one sample surpassing ERM values. PAH profiles were studied in order to identify PAH sources as mainly petrogenic or pyrogenic. Most samples showed petrogenic-type fingerprints, although 6 of the 11 sediments with the highest PAH concentrations (> 1000 ng/g) were classified as pyrogenic, including 4 of the 7 samples exceeding ERL values. Quality assurance was carried out by the triplicate analysis of one preanalysed river sediment without PAHs subsequently spiked at a medium (500 ng/g) and a low concentration level (10 ng/g) of each analyte. Main quality requirements for methods based on isotope dilution were accomplished. Method accuracy was 80-120% for most PAHs, method precision was <15% for all the analysed compounds and method detection limits (MDLs) were 1-3 ng/g.     

Light-dependent isomeric effects of polycyclic aromatic hydrocarbons on the predication of DNA cleavage factor efficiency

PAHs, short for polycyclic aromatic hydrocarbons, are a ubiquitous group of chemically related, environmentally persistent organic compounds having diverse structures and varied toxicity. They have been shown to cause mutagenic and carcinogenic effects on organisms and are quite immunosuppressive. Time-dependent density functional theory (TD-DFT) offers a practical means of understanding the behavior of excitation energies for PAHs. Here, we examined the performance of the long-range corrected Coulomb-attenuating functional (CAM-B3LYP) in relation to four different basis sets, determining which basis set compliments the functional better in identifying the most reactive atomic site on six isomeric PAH compounds. Condensed Fukui function indices were used to compare the performance of applied basis sets in identifying the most reactive atomic site on six isomeric PAHs compounds, assessing which basis set would be more appropriate in determining the site where free-radical formation would occur after light irradiation. Dunning’s correlation consistent triple-zeta (cc-pVTZ) basis set was determined to have the best PAH characterization performance, concluding the need for application of a higher-level basis set with the long-range corrected Coulomb-attenuating functional. Although each compound was a structural isomer of the other, the reactive atomic sites varied for each molecule with the use of an applied basis set. It was concluded that structural shape has some influence on the calculation of PAH characteristics. Lastly, in order to predict DNA single-stranded cleavage factor for the compounds proposed here, we have used the quantitative structure-activity relationship (QSAR). The cleavage factor values for the set of aromatic molecules with similar structures have been collected from the literature for a total number of 22 compounds.     

An experimental design approach to optimise the determination of polycyclic aromatic hydrocarbons from rainfall water using stir bar sorptive extraction and high performance liquid chromatography-fluorescence detection

Stir bar sorptive extraction (SBSE) followed by HPLC-fluorescence detection (FLD) was optimised for analysing 15 polycyclic aromatic hydrocarbons (PAHs) from water samples, especially rainfall water with low PAH content. The literature data described widely different experimental conditions for the extraction of PAHs by SBSE. A chemometric approach was therefore used to evaluate the statistically influential and/or interacting factors, among those described in the literature, and to find the best extraction and desorption conditions. Among six factors studied in a 2(6-2) fractional factorial design, only sample volume, extraction time and the interaction between both of them had significant effects on the PAH extraction recoveries. Optimal sample volume of 10 mL and extraction time of 140 min were obtained with a response surface design. For the desorption conditions, a Box-Behnken design showed that desorption time, temperature and PAH concentrations had significant effects. The best conditions were two successive desorptions with 100 microL of acetonitrile for 25 min at 50 degrees C. The optimised method was repeatable (RSD< or =5.3% for 50 ng L(-1) spiked water and < or =12.8% for 5 ng L(-1) spiked water), linear (R(2)> or =0.9956), with quantitative absolute recoveries (> or =87.8% for 50 ng L(-1) spiked water), and with the LOD between 0.2 and 1.5 ng L(-1). The optimised method was successfully applied to six-rainfall water samples collected in a suburban area. The total PAHs concentrations studied ranged from 31 to 105.1 ng L(-1). Seasonal variation was observed and on average three PAHs were at the highest concentrations (phenanthrene, fluoranthene and pyrene).     

Differentiation of isomeric polyaromatic hydrocarbons by electrospray Ag(I) cationization mass spectrometry

Abundant Ag(I)-cationized complexes of 13 polyaromatic hydrocarbons (PAHs), [Ag+PAH](+) and [Ag+2(PAH)](+), were readily generated by electrospray ionization (ESI). In-source collision-induced dissociation (CID) of the [Ag+2(PAH)](+) complex yielded the monomer complex [Ag+PAH](+), which fragmented further to yield the radical molecular ion [PAH](+.). Based on significant differences in relative intensities of [Ag+2(PAH)](+), [Ag+PAH](+) and [PAH](+.), isomeric PAHs can be differentiated. The [PAH](+.)/[Ag+PAH](+) ion intensity ratio was found to increase with decreasing ionization potentials (IPs) of PAHs. The ratio was significantly different for the isomeric PAHs studied over a wide range of PAH concentrations (1.6-100 nmol/mL), and showed good measurement reproducibility; the coefficient of variation of inter-day measurements was in the range 3-12% for four representative PAHs (n = 5). Detection limits for phenanthrene, pyrene, chrysene and benzo[a]pyrene, in the form of the monomer complexes [(107)Ag+PAH](+) and measured in the selected-ion monitoring (SIM) mode, were 0.31, 0.63, 0.16 and 1.25 pmol/5 microl injection, respectively (S/N ratio approximately 2-3).     

Determination of polycyclic aromatic hydrocarbons in water by solid-phase microextraction and liquid chromatography.

This study describes the determination of polycyclic aromatic hydrocarbons (PAHs) in water using high-performance liquid chromatography (HPLC) coupled with fluorescence detection (FLD). Because individual PAHs are generally present in water only at trace levels, a sensitive and accurate determination technique is essential. The separation and detection of five PAHs were run completely within 25 min by the HPLC/FLD system with an analytical C18 column, a fluorescence detection, and acetonitrile-water gradient elution. Calibration graphs were linear with very good correlation coefficients (r > 0.9998), and the detection limits were in the range of 2-6 ng/l for five PAHs. Solid phase microextraction (SPME) was performed for sample pretreatment prior to HPLC-FLD determination, and the governing parameters were investigated. Compared to conventional methods, SPME has high recovery, saves considerable time, and reduces solvents waste. The extraction efficiencies of five PAHs were above 88% and the extraction times were 35 min in one pretreatment procedure. One particular discovery is that 1.5 M sodium monochloroactate (ClCH2COONa) can improve the extraction yield of PAH compounds more than other inorganic salts. The SPME-HPLC-FLD technique provides a relatively simple, convenient, practical procedure, which was here successfully applied to determine five PAHs in water from authentic water samples.     

Behaviour of polycyclic aromatic hydrocarbons in dissolved,colloidal, and particulate phases in sedimentary cores

Solid-phase microextraction (SPME) has been successfully used for extracting polycyclic aromatic hydrocarbons (PAHs) from porewater samples from the Mersey Estuary, UK. The majority of the PAHs in porewater samples are associated with colloids due to the high DOC concentrations. The truly dissolved PAH concentrations varied from 66 to 1050?ng?L^?1 in core 2 and from 95 to 740?ng?L^?1 in core 3, and were dominated by naphthalene, fluoranthene, and pyrene. Although absent in the dissolved phase, the high-molecular-mass compounds were found in the colloid-associated fraction of porewater. PAHs in sediments arose from a range of compounds with 4- and 5-ring PAHs dominating. The partitioning of PAHs between sediment and porewater shows that PAHs are enriched in the sediment phase. When the soot carbon content was considered, predictions of the partition behaviour were found to agree more closely with the observed distribution. The results reiterate the importance of evaluating the speciation of organic pollutants in both porewater and sediments in order to accurately predict their environmental fate and potential toxicity.     

Capillary GC analysis of diesel fuels using simultaneous parallel triple detection

Diesel fuels from different parts of the UK have been analyzed for polycyclic aromatic hydrocarbons (PAH), nitrogen-containing PAH, and sulfur-containing PAH using capillary column GC with simultaneous parallel triple detection. The concentrations of polyaromatic compounds (PAC) were high and showed considerable variability amongst the fuels. The PAH are mainly naphthalene, fluorene, and phenanthrene and their alkylated homologs; the PANH are mainly carbazole and its methyl derivatives; the PASH are mainly dibenzothiophene and its methyl derivatives.     

Application of direct thermal desorption gas chromatography and comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry for analysis of organic compounds in ambient aerosol particles

Semivolatile organic compounds (SVOC) associated with ambient particles smaller than 2.5 microm (PM2.5) were determined in the city of Augsburg, Germany. Daily samples were collected at a central monitoring station from late summer 2002 to spring 2005. SVOC were analysed by direct thermal desorption (DTD)-GC and comprehensive 2-D GC coupled to TOF MS (DTD-GC-TOF MS and DTD-GC x GC-TOF MS). Two hundred compounds were quantified and 'semi-quantified' on a daily basis by DTD-GC-TOF MS. n-Alkanes, n-alkan-2-ones, n-alkanoic acid methyl esters, acetic acid esters, n-alkanoic acid amides, nitriles, linear alkylbenzenes and 2-alkyl-toluenes, hopanes, PAH, alkylated PAH and oxidised PAH, and several compounds that are not-grouped in homologous rows or compound classes were determined. Changes in concentration and pattern of several target compounds as well as methodological advantages and restrictions of DTD-GC-TOF MS are briefly discussed. DTD-GC-TOF MS analysis provided data particularly suited for source receptor modelling and epidemiological time series studies on the health effects of ambient PM. GC x GC enhances chromatographic resolution of PM samples and therefore amplifies the peak identification capabilities of the TOF MS.     

Crystal Structures of trans-Tetrahydrotetrols of Benzo[a]pyrene and Chrysene: A Possible Structure-Activity Relationship in Quasi-Planar Bay-Region Polycyclic Aromatic Hydrocarbons

The molecular structures of two racemic trans-tetrahydrotetrols formed by hydrolysis of the (±)anti-7,8-dihydroxy-9,10-epoxy-7,8,9,10-tetrahydro derivatives of the strong carcinogen benzo[a]pyrene and the weak carcinogen chrysene have been determined by X-ray crystallographic methods.³ Focusing on the (+)isomers, the stereochemical features of the two tetrols are discussed in detail to determine structural differences, which can be related to the different biological activity of their parent hydrocarbons, since they provide a model for the hydrocarbon moiety in the major PAH-DNA adduct. As a result of this study, a tentative correlation can be stated between biological activity of quasi-planar bay-region PAHs and the presence of structural features, which can decrease the steric hindrance of the aromatic skeleton and the other hydroxy groups on the pseudo-axial O4, which mimics the position of the covalent bond to DNA. The significant structural features seem to be an out-of-plane distortion with a negative torsion angle at the bay region and a half chair conformation of the saturated ring distorted toward the envelope with C8 at the tip as in BPT, in addition to the axial and pseudo-axial conformations of the hydroxy groups at C9 and C10 due to the near bay region. They may be considered generated by trans-opening of the oxirane ring in an anti-diol epoxide biologically active because it is highly strained. The strains, derived from the activation of bay-region PAHs with a negative torsion angle, seem greater in an anti-diol epoxide relative to the syn-isomer. Thus, when the strains are released, the derived trans-tetrol occurs with structural features, which seem to better fit the target. As a consequence, the presence of a methyl group at a bay region should increase the biological activity of a PAH, imposing greater strains to the structure of the anti-diol epoxide.     

Rapid method for the determination of polycyclic aromatic hydrocarbons in agricultural soils by sonication-assisted extraction in small columns

A rapid method has been developed for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in soil based on their sonication-assisted extraction in small columns (SAESC) with a low volume of ethyl acetate and subsequent quantitation and identification by GC with electron impact mass spectrometric detection in the SIM mode (GC-MS-SIM). Spiked blank soil extracts were used as standards to counteract the matrix effect observed in the chromatographic determination. PAHs were confirmed at trace level by their retention times, their qualifier and target ions, and their qualifier/target abundance ratios. Recovery studies were performed at 0.5, 1.0, 5.0, and 10 microg/kg fortification levels for each PAH, and the recoveries obtained ranged from 91.2 to 99.8% with RSDs between 0.4 and 9.3%. The detection limits of the method ranged from 0.03 to 0.3 microg/kg for the different PAHs studied. The developed method is linear over the range assayed, 1-100 microg/L with determination coefficients higher than 0.996. PAH levels were determined using this method in soil samples taken from different agricultural areas of Spain. In general, PAH concentrations were low and the most frequently occurring PAHs were naphthalene, pyrene, phenanthrene, and fluoranthene.     

Which Hydrogen Atom of Toluene Protonates PAH molecules in (+)-Mode APPI MS Analysis?

A previous study (Ahmed, A. et al., Anal. Chem. 84, 1146–1151( 2012) reported that toluene used as a solvent was the proton source for polyaromatic hydrocarbon compounds (PAHs) that were subjected to (+)-mode atmospheric-pressure photoionization. In the current study, the exact position of the hydrogen atom in the toluene molecule (either a methyl hydrogen or an aromatic ring hydrogen) involved in the formation of protonated PAH ions was investigated. Experimental analyses of benzene and anisole demonstrated that although the aromatic hydrogen atom of toluene did not contribute to the formation of protonated anthracene, it did contribute to the formation of protonated acridine. Thermochemical data and quantum mechanical calculations showed that the protonation of anthracene by an aromatic ring hydrogen atom of toluene is endothermic, while protonation by a methyl hydrogen atom is exothermic. However, protonation of acridine by either an aromatic ring hydrogen or a methyl hydrogen atom of toluene is exothermic. The different behavior of acridine and anthracene was attributed to differences in gas-phase basicity. It was concluded that both types of hydrogen in toluene can be used for protonation of PAH compounds, but a methyl hydrogen atom is preferred, especially for non-basic compounds.      

Decomposition of Chlorobenzene by Thermal Plasma Processing

Decomposition of chlorobenzene as a model molecule of aromatic chlorinated compounds was studied in radiofrequency thermal plasma both in neutral and oxidative conditions. Optical emission spectroscopy was applied for the evaluation of the plasma excitation and molecular rotational-vibrational temperature. Atomic (C, H, O) and molecular (CH, OH, C₂) radicals were identified, while the morphology of the formed soot was characterized by electron microscopy. Organic compounds adsorbed on the surface of the soot after plasma processing were comprised of various polycyclic aromatic hydrocarbons (PAH) and chlorinated PAH molecules. Their amount was greatly affected by experimental conditions, especially the oxygen content and plate power. The higher input power reduced the ring number of the PAH molecules. Addition of oxygen significantly reduced the amount of both PAHs chlorinated PAH molecules but enhanced the formation of polychlorinated benzene compounds.     

Determination of Polycyclic Aromatic Hydrocarbons in Mangrove Sediments: Comparison of Two Internal Standard Surrogate Methods and Quality-Control Procedures

Two internal standard surrogate (ISS) methods, ISS-I (with m-terphenyl as a single ISS) and ISS-2 (using five deuterated PAHs as a multi-ISS), for the determination of polycyclic aromatic hydrocarbons (PAHs) in mangrove sediments were compared. The recovery percentages of 16 PAHs except naphthalene in HS-6 (a certified reference material) were high, ranging from 69.3 to 111.8% for ISS-1 and from 71.8 to 120.3% for the ISS-2 method. Similarly, the PAH recovery percentages in spiked mangrove sediments and clean sand were lower for ISS-I than for ISS-2, but both methods met the accurate acceptance criteria for PAH recoveries. The reproducibility (i.e. the method precision) between the two ISS methods was also comparable and satisfactory, with relative standard deviation values in most cases within 20% of the data variability. These results indicate that both ISS methods were acceptable for the determination of PAHs in mangrove sediments, despite the fact that the matrix of mangrove sediments may interfere with the PAH recovery efficiency.