Extensive chemical and bioassay analysis of polycyclic aromatic compounds in a creosote-contaminated superfund soil following steam enhanced extraction.

Polycyclic aromatic compounds (PACs) are organic compounds commonly found in contaminated soil. Previous studies have shown the removal of polycyclic aromatic hydrocarbons (PAHs) in creosote-contaminated soils during steam enhanced extraction (SEE). However, less is known about the removal of alkyl-PAHs and heterocyclic compounds, such as azaarenes, and oxygen- and sulfur-heterocyclic PACs (OPACs and PASHs, respectively). Further, the impact of SEE on the freely dissolved concentration of PACs in soil as well as the soil bioactivity pre- and post-SEE have yet to be addressed. To fulfil these research gaps, chemical and bioanalytical analysis of a creosote-contaminated soil, collected from a U.S. Superfund site, pre- and post-SEE were performed. The decrease of 64 PACs (5-100%) and increase in the concentrations of nine oxygenated-PAHs (OPAHs) (150%) during SEE, some of which are known to be toxic and can potentially contaminate ground water, were observed. The freely dissolved concentrations of PACs in soil were assessed using polyoxymethylene (POM) strips and the concentrations of 66 PACs decreased post-SEE (1-100%). Three in vitro reporter gene bioassays (DR-CALUX®, ERα-CALUX® and anti-AR CALUX®) were used to measure soil bioactivities pre- and post-SEE and all reporter gene bioassays measured soil bioactivity decreases post-SEE. Mass defect suspect screening tentatively identified 27 unique isomers of azaarenes and OPAC in the soil. As a remediation technique, SEE was found to remove alkyl-PAHs and heterocyclic PACs, reduce the concentrations of freely dissolved PACs, and decrease soil bioactivities.

Assessing the oxidative potential of PAHs in ambient PM2.5 using the DTT consumption assay.

The oxidative potential (OP) of atmospheric fine particulate matter (PM2.5) has been linked to organic content, which includes polycyclic aromatic hydrocarbons (PAHs). The OP of 135 individual PAHs (including six subclasses) was measured using the dithiolthreitol (DTT) consumption assay. The DTT assay results were used to compute the concentration of each PAH needed to consume 50% of the DTT concentration in the assay (DTT50), and the reduction potential of the PAHs (ΔGrxn). Computed reduction potential results were found to match literature reduction potential values (r2 = 0.97), while DTT50 results had no correlations with the computed ΔGrxn values (r2 < 0.1). The GINI equality index was used to assess the electron distribution across the surface of unreacted and reacted PAHs. GINI values correlated with ΔGrxn in UPAH, HPAH, and OHPAH subclasses, as well as with all 135 PAHs in this study but did not correlate with DTT50, indicating that electron dispersion is linked to thermodynamic reactions and structural differences in PAHs, but not linked to the OP of PAHs. Three ambient PM2.5 filters extracts were measured in the DTT assay, alongside mixtures of analytical standards prepared to match PAH concentrations in the filter extracts to test if the OP follows an additive model of toxicity. The additive prediction model did not accurately predict the DTT consumption in the assay for any of the prepared standard mixtures or ambient PM2.5 filter extracts, indicating a much more complex model of toxicity for the OP of PAHs in ambient PM2.5. This study combined computed molecular properties with toxicologically relevant assay results to probe the OP of anthropogenically driven portions of ambient PM2.5, and results in a better understanding of the complexity of ambient PM2.5 OP.

Time-Related Alteration of Aqueous-Phase Anthracene and Phenanthrene Photoproducts in the Presence of TiO2 Nanoparticles.

Polycyclic aromatic hydrocarbons (PAHs) and titanium dioxide (TiO2) nanoparticles (NPs) are photoactive environmental pollutants that can contaminate aquatic environments. Aqueous-phase interactions between PAHs and TiO2-NPs are of interest due to their emerging environmental relevance, particularly with the deliberate application of TiO2-NPs to remediate pollution events (e.g., oil spills). Our objective was to investigate anthracene (ANT) and phenanthrene (PHE) photoproduct formation and transformation following ultraviolet A (UVA) irradiation in the presence and absence of TiO2-NPs. ANT and PHE solutions were prepared alone or in combination with TiO2-NPs, UVA-irradiated, and either exposed to larval zebrafish or collected for chemical analyses of diverse hydroxylated PAHs (OHPAHs) and oxygenated PAHs (OPAHs). The expression profiles of genes encoding for enzymes involved in PAH metabolism showed PAH-specific and time-dependent inductions that demonstrated changes in PAH and photoproduct bioavailability in the presence of TiO2-NPs. Chemical analyses of PAH/NP solutions in the absence of zebrafish larvae identified diverse photoproducts of differing size and ring arrangements, which suggested photodissociation, recombination, and ring re-arrangements of PAHs occurred either during or following UVA irradiation. Both ANT and PHE solutions showed heightened oxidative potential following irradiation, but TiO2-NP-related increases in oxidative potential were PAH-specific. The exploitation of multiple analytical methods provided novel insights into distinct PAH photoactivity, TiO2-NP influence on photoproduct formation in a PAH-specific manner, and the significant role time plays in photochemical processes.

Workflow for Comparison of Chemical and Biological Metrics of Filter Collected PM2.5.

There is limited understanding of adverse health effect associations with chemical constituents of fine particulate matter (PM2.5) as well as the underlying mechanisms. We outlined a workflow to assess metrics, beyond concentration, using household and personal PM2.5 filter samples collected in India as a proof of concept for future large-scale studies. Oxidative potential, chemical composition (polycyclic aromatic hydrocarbons and elements), and bioactivity (developmental exposures in zebrafish) were determined. Significant differences were observed in all metrics between personal and household PM2.5 samples. This work established methods to characterize multiple metrics of PM2.5 to ultimately support the identification of more health-relevant metrics than concentration.

Impact of local and regional sources of PAHs on tribal reservation air quality in the U.S. Pacific Northwest.

Atmospheric fine particulate matter (PM2.5) transports polycyclic aromatic hydrocarbons (PAHs) regionally and globally, influencing the air quality of communities around the planet. Concentrations of 130 PAHs extracted from PM2.5, collected on a Native American Tribal Reservation in the Northern Puget Sound region of the American Pacific Northwest, were used to assess the air quality impacts of regional and local PAH sources, atmospheric transport, and human health implications. Wind coming from the southeast of the sampling locations increased the overall PAH concentration of the PM2.5, while winds from the southwest decreased the PAH concentration. Concentrations of PAH subclasses increased or decreased independently at the two sampling locations with different changes in wind patterns, changing the excess lifetime cancer risk significantly. No long-range transport was measured, but emissions from local and regional PAH sources were measured. Samples collected during regional wildfires showed increased PAH concentrations. Samples collected during predicted weather inversions resulted in the highest PAH concentrations, and up to a ten-fold increase in excess lifetime cancer risk over the normal days.

Formation of Polycyclic Aromatic Hydrocarbon Oxidation Products in α-Pinene Secondary Organic Aerosol Particles Formed through Ozonolysis.

Accurate long-range atmospheric transport (LRAT) modeling of polycyclic aromatic hydrocarbons (PAHs) and PAH oxidation products (PAH-OPs) in secondary organic aerosol (SOA) particles relies on the known chemical composition of the particles. Four PAHs, phenanthrene (PHE), dibenzothiophene (DBT), pyrene (PYR), and benz(a)anthracene (BaA), were studied individually to identify and quantify PAH-OPs produced and incorporated into SOA particles formed by ozonolysis of α-pinene in the presence of PAH vapor. SOA particles were characterized using real-time in situ instrumentation, and collected on quartz fiber filters for offline analysis of PAHs and PAH-OPs. PAH-OPs were measured in all PAH experiments at equal or greater concentrations than the individual PAHs they were produced from. The total mass of PAH and PAH-OPs, relative to the total SOA mass, varied for different experiments on individual parent PAHs: PHE and 6 quantified PHE-OPs (3.0%), DBT and dibenzothiophene sulfone (4.9%), PYR and 3 quantified PYR-OPs (3.1%), and BaA and benz(a)anthracene-7,12-dione (0.26%). Further exposure of PAH-SOA to ozone generally increased the concentration ratio of PAH-OPs to PAH, suggesting longer atmospheric lifetimes for PAH-OPs, relative to PAHs. These data indicate that PAH-OPs are formed during SOA particle formation and growth.

PM2.5 Filter Extraction Methods: Implications for Chemical and Toxicological Analyses.

Toxicology research into the global public health burden of fine particulate matter (PM2.5) exposures frequently requires extraction of PM2.5 from filters. A standardized method for these extractions does not exist, leading to inaccurate interlaboratory comparisons. It is largely unknown how different filter extraction methods might impact the composition and bioactivity of the resulting samples. We characterized the variation in these metrics by using equal portions of a single PM2.5 filter, with each portion undergoing a different extraction method. Significant differences were observed between extraction methods for concentrations of elements and polycyclic aromatic hydrocarbons (PAHs) for the PM2.5 tested following its preparation for biological response studies. Importantly, the chemical profiles differed from those observed when we used standard protocols for chemical characterization of the ambient sample, demonstrating that extraction can alter both chemical component amounts and species profiles of the extracts. The impact of these chemical differences on sensitive end points of zebrafish development was investigated. Significant differences in the percent incidence and timing of mortality were associated with the PM2.5 extraction method. This research highlights the importance of and rationale for considering the extraction method when interlaboratory comparisons of PM2.5 toxicology research are made.

Evaluating Computational and Structural Approaches to Predict Transformation Products of Polycyclic Aromatic Hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) undergo transformation reactions with atmospheric photochemical oxidants, such as hydroxyl radicals (OH•), nitrogen oxides (NOx), and ozone (O3). The most common PAH-transformation products (PAH-TPs) are nitrated, oxygenated, and hydroxylated PAHs (NPAHs, OPAHs, and OHPAHs, respectively), some of which are known to pose potential human health concerns. We sampled four theoretical approaches for predicting the location of reactive sites on PAHs (i.e., the carbon where atmospheric oxidants attack), and hence the chemoselectivity of the PAHs. All computed results are based on density functional theory (B3LYP/6-31G(d) optimized structures and energies). The four approaches are (1) Clar's prediction of aromatic resonance structures, (2) thermodynamic stability of all OHPAH adduct intermediates, (3) computed atomic charges (Natural Bond order, ChelpG, and Mulliken) at each carbon on the PAH, and (4) average local ionization energy (ALIE) at atom or bond sites. To evaluate the accuracy of these approaches, the predicted PAH-TPs were compared to published laboratory observations of major NPAH, OPAH, and OHPAH products in both gas and particle phases. We found that the Clar's resonance structures were able to predict the least stable rings on the PAHs but did not offer insights in terms of which individual carbon is most reactive. The OHPAH adduct thermodynamics and the ALIE approaches were the most accurate when compared to laboratory data, showing great potential for predicting the formation of previously unstudied PAH-TPs that are likely to form in the atmosphere.

In-Vial Extraction Large Volume Gas Chromatography Mass Spectrometry for Analysis of Volatile PFASs on Papers and Textiles.

Volatile per- and polyfluorinated alkyl substances (PFASs) are found in consumer goods that contribute to human exposure to PFASs. Volatile PFAS precursors transform to perfluorinated carboxylates (PFCAs) and sulfonates (PFSAs) in both humans and the environment. Established methods for volatile PFASs in consumer goods exist, but higher sample throughput and greener sample preparation methods are needed to minimize analyte loss, while maintaining sensitivity. New analytical methodology was developed where a 1.5 × 1.5 cm piece of paper or textile is placed into an autosampler vial with solvent and mass-labeled internal standards, sonicated for 30 min, and directly injected without removal of material from the autosampler vial. Large volume injection (20 µL) gas chromatography mass spectrometry was applied for the quantification for 21 individual PFASs from five classes: fluorotelomer alcohols (FTOHs), fluorinated sulfonamides (N-MeFASA, N-EtFASA), and fluorinated sulfonamidoethanols (N-MeFASE, N-EtFASE). Nontargeted analysis revealed additional C2-C7 homologues of N-MeFASE and N-EtFASE, which accounted for 14-18% of the total volatile PFASs on three textiles. Overlooking short-chain (≤C7) N-MeFASE, N-EtFASE, and long-chained (10:2-14:2) FTOHs on older textiles from the 1980s leads to an underestimation of human and environmental exposure to volatile PFAS.

Comparative developmental toxicity of a comprehensive suite of polycyclic aromatic hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants that occur in complex mixtures. Several PAHs are known or suspected mutagens and/or carcinogens, but developmental toxicity data is lacking for PAHs, particularly their oxygenated and nitrated derivatives. Such data are necessary to understand and predict the toxicity of environmental mixtures. 123 PAHs were assessed for morphological and neurobehavioral effects for a range of concentrations between 0.1 and 50 µM, using a high throughput early-life stage zebrafish assay, including 33 parent, 22 nitrated, 17 oxygenated, 19 hydroxylated, 14 methylated, 16 heterocyclic, and 2 aminated PAHs. Additionally, each PAH was evaluated for AHR activation, by assessing CYP1A protein expression using whole animal immunohistochemistry (IHC). Responses to PAHs varied in a structurally dependent manner. High-molecular weight PAHs were significantly more developmentally toxic than the low-molecular weight PAHs, and CYP1A expression was detected in five distinct tissues, including vasculature, liver, skin, neuromasts and yolk.

Investigating the application of a nitroreductase-expressing transgenic zebrafish line for high-throughput toxicity testing.

Nitroreductase enzymes are responsible for the reduction of nitro functional groups to amino functional groups, and are found in a range of animal models, zebrafish (Danio rerio) excluded. Transgenic zebrafish models have been developed for tissue-specific cell ablation, which use nitroreductase to ablate specific tissues or cell types following exposure to the non-toxic pro-drug metronidazole (MTZ). When metabolized by nitroreductase, MTZ produces a potent cytotoxin, which specifically ablates the tissue in which metabolism occurs. Uses, beyond tissue-specific cell ablation, are possible for the hepatocyte-specific Tg(l-fabp:CFP-NTR)s891 zebrafish line, including investigations of the role of nitroreductase in the toxicity of nitrated compounds. The hepatic ablation characteristics of this transgenic line were explored, in order to expand its potential uses. Embryos were exposed at 48, 72, or 96 hours post fertilization (hpf) to a range of MTZ concentrations, and the ablation profiles were compared. Ablation occurred at a 10-fold lower concentration than previously reported. Embryos were exposed to a selection of other compounds, with and without MTZ, in order to investigate alternative uses for this transgenic line. Test compounds were selected based on: their ability to undergo nitroreduction, known importance of hepatic metabolism to toxicity, and known pharmaceutical hepatotoxins. Selected compounds included nitrated polycyclic aromatic hydrocarbons (nitro-PAHs), the PAHs retene and benzo[a]pyrene, and the pharmaceuticals acetaminophen and flutamide. The results suggest a range of potential roles of the liver in the toxicity of these compounds, and highlight the additional uses of this transgenic model in toxicity testing.

The effect of gas-phase polycyclic aromatic hydrocarbons on the formation and properties of biogenic secondary organic aerosol particles.

When secondary organic aerosol (SOA) particles are formed by ozonolysis in the presence of gas-phase polycyclic aromatic hydrocarbons (PAHs), their formation and properties are significantly different from SOA particles formed without PAHs. For all SOA precursors and all PAHs, discussed in this study, the presence of the gas-phase PAHs during SOA formation significantly affects particle mass loadings, composition, growth, evaporation kinetics, and viscosity. SOA particles formed in the presence of PAHs have, as part of their compositions, trapped unreacted PAHs and products of heterogeneous reactions between PAHs and ozone. Compared to 'pure' SOA particles, these particles exhibit slower evaporation kinetics, have higher fractions of non-volatile components, like oligomers, and higher viscosities, assuring their longer atmospheric lifetimes. In turn, the increased viscosity and decreased volatility provide a shield that protects PAHs from chemical degradation and evaporation, allowing for the long-range transport of these toxic pollutants. The magnitude of the effect of PAHs on SOA formation is surprisingly large. The presence of PAHs during SOA formation increases mass loadings by factors of two to five, and particle number concentrations, in some cases, by more than a factor of 100. Increases in SOA mass, particle number concentrations, and lifetime have important implications to many atmospheric processes related to climate, weather, visibility, and human health, all of which relate to the interactions between biogenic SOA and anthropogenic PAHs. The synergistic relationship between SOA and PAHs presented here are clearly complex and call for future research to elucidate further the underlying processes and their exact atmospheric implications.

Identification of polar transformation products and high molecular weight polycyclic aromatic hydrocarbons (PAHs) in contaminated soil following bioremediation.

Bioremediation is a technique commonly used to reduce the toxicity associated with polycyclic aromatic hydrocarbons (PAHs) in contaminated soils. However, the efficacy of bioremedial applications is evaluated based on the removal of a subset of parent (or unsubstituted) PAHs and does not incorporate toxic polar transformation products or the more mutagenic high molecular weight PAHs (MW≥302amu or MW302-PAHs). Previously, an effects-directed analysis approach was used to assess the effect of bioremediation on the toxicity of a coal tar-contaminated soil. Increased genotoxicity and developmental toxicity was measured postbioremedation in the more polar soil extract fractions, as compared to the less polar fractions where the targeted PAHs eluted, and could not be attributed to the 88 target PAHs analyzed for (including selected oxygen-containing PAHs). In this study, comprehensive two-dimensional gas chromatography time-of-flight and liquid chromatography quadrupole time-of-flight mass spectrometry were used to characterize transformation products in the soil extract fractions identified as toxic, previously. Additionally, the degradation of 12MW302-PAHs, picene (MW=278) and coronene (MW=300) were evaluated following bioremediation. Non-targeted analysis resulted in the tentative identification of 10 peaks with increased intensity postbioremediation (based on mass spectral library matching and fragmentation patterns from >5000 candidate peaks in the soil extracts). Several of these compounds contained oxygen, suggesting they would be relatively polar. MW302-PAHs were not significantly degraded during bioremediation, suggesting that the carcinogenic potential associated with these PAHs might remain unchanged. The results of this study suggest that polar transformation products, and MW302-PAHs, should be considered for realistic risk assessment of bioremediated soils.

Trophic magnification of Dechlorane Plus in the marine food webs of Fildes Peninsula in Antarctica.

The food web composition, assimilation efficiency of Dechlorane Plus (DP) in food web components, and even extrinsic conditions can affect the trophic biomagnification potentials of DP isomers in food webs. Antarctica ecological system is characterized by the presence of few consumers and simple trophic levels (TLs), which are crucial in discussing the behavior of contaminants. To assess the biomagnification potential of DP in the Antarctic food web, nine representative species were sampled and analyzed from the Fildes Peninsula. Results showed the DP concentrations ranged from 0.25ngg-1 to 6.81ngg-1 lipid weight in Antarctic biota and the concentrations of anti-DP and syn-DP showed significantly positive correlations with TLs (p<0.05, ra=0.85; rs=0.81, respectively), suggesting that syn-DP and anti-DP underwent biomagnification and the biomagnification ability of anti-DP was higher than that of syn-DP. The anti-DP fraction (anti-DP/∑DP) (ƒanti=0.23-0.53) of the organisms was lower than that of commercial products (ƒanti=0.68), demonstrating ƒanti was changed during long-range atmospheric transport or stereoselection enrichment through the food web. Furthermore, based on food web magnification factors (FWMF) comparison between DP and polychlorinated biphenyls (PCBs), the biomagnification potential of DP was found to be similar to that of highly chlorinated PCBs.

Mechanistic Investigations Into the Developmental Toxicity of Nitrated and Heterocyclic PAHs.

Nitrated polycyclic aromatic hydrocarbons (NPAHs) and heterocyclic PAHs (HPAHs) are recognized environmental pollutants. However, the health risks of NPAHs and HPAHs to humans and environmental systems are not well-studied. The developmental zebrafish (Danio rerio) model was used to evaluate the toxicity of a structurally diverse set of 27 NPAHs and 10 HPAHs. The individual activity of each compound towards the aryl hydrocarbon receptor (AHR), including the role of the AHR in observed toxicity, and genetic markers of oxidative stress and cardiac toxicity were evaluated. Zebrafish embryos were exposed from 6 to 120 hours post fertilization (hpf), to a broad concentration range of individual compounds, and evaluated for 22 developmental endpoints. The potential role of AHR was determined using the transgenic Tg(cyp1a:nls-egfp) reporter zebrafish line. All compounds were screened computationally through molecular docking using a previously developed AHR models of zebrafish isoforms 1A, 1B, and 2. Some compounds did not induce observable developmental toxic responses, whereas others produced statistically significant concentration-dependent toxicity. The tested compounds also exhibited a range of predicted AHR binding and cyp1a/GFP induction patterns, including cyp1a expression in the liver, vasculature, skin, and yolk, which we determined to be due to distinct isoforms of the AHR, using morpholino oligonucleotide knockdown. Furthermore, we investigated mRNA expression of oxidative and cardiac stress genes at 48 and 120 hpf, which indicated several potential mechanisms-of-action for NPAHs. Overall, we observed a range of developmental toxicities, cyp1a/GFP expression patterns, and gene expression profiles, suggestive of several potential mechanisms of action.

Global long-range transport and lung cancer risk from polycyclic aromatic hydrocarbons shielded by coatings of organic aerosol.

Polycyclic aromatic hydrocarbons (PAHs) have toxic impacts on humans and ecosystems. One of the most carcinogenic PAHs, benzo(a)pyrene (BaP), is efficiently bound to and transported with atmospheric particles. Laboratory measurements show that particle-bound BaP degrades in a few hours by heterogeneous reaction with ozone, yet field observations indicate BaP persists much longer in the atmosphere, and some previous chemical transport modeling studies have ignored heterogeneous oxidation of BaP to bring model predictions into better agreement with field observations. We attribute this unexplained discrepancy to the shielding of BaP from oxidation by coatings of viscous organic aerosol (OA). Accounting for this OA viscosity-dependent shielding, which varies with temperature and humidity, in a global climate/chemistry model brings model predictions into much better agreement with BaP measurements, and demonstrates stronger long-range transport, greater deposition fluxes, and substantially elevated lung cancer risk from PAHs. Model results indicate that the OA coating is more effective in shielding BaP in the middle/high latitudes compared with the tropics because of differences in OA properties (semisolid when cool/dry vs. liquid-like when warm/humid). Faster chemical degradation of BaP in the tropics leads to higher concentrations of BaP oxidation products over the tropics compared with higher latitudes. This study has profound implications demonstrating that OA strongly modulates the atmospheric persistence of PAHs and their cancer risks.

Integrated Framework for Identifying Toxic Transformation Products in Complex Environmental Mixtures.

Complex environmental mixtures consist of hundreds to thousands of unknown and unregulated organic compounds that may have toxicological relevance, including transformation products (TPs) of anthropogenic organic pollutants. Non-targeted analysis and suspect screening analysis offer analytical approaches for potentially identifying these toxic transformation products. However, additional tools and strategies are needed in order to reduce the number of chemicals of interest and focus analytical efforts on chemicals that may pose risks to humans and the environment. This brief review highlights recent developments in this field and suggests an integrated framework that incorporates complementary instrumental techniques, computational chemistry, and toxicity analysis, for prioritizing and identifying toxic TPs in the environment.

Organic contaminants in western pond turtles in remote habitat in California.

Remote aquatic ecosystems are exposed to an assortment of semivolatile organic compounds (SOCs) originating from current and historic uses, of local and global origin. Here, a representative suite of 57 current- and historic-use pesticides, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons were surveyed in the plasma of the western pond turtle (Emys marmorata) and their potential prey items and habitat. California study sites included Sequoia National Park, Whiskeytown National Recreation Area, and Six Rivers National Forest. Each was downstream of undeveloped watersheds and varied in distance from agricultural and urban pollution sources. SOCs were detected frequently in all sites with more found in turtle plasma and aquatic macroinvertebrates in the two sites closest to agricultural and urban sources. Summed PCBs were highest in Whiskeytown National Recreation Area turtle plasma (mean; 1.56 ng/g ww) compared to plasma from Sequoia National Park (0.16 ng/g ww; p = 0.002) and Six Rivers National Forest (0.07 ng/g ww; p = 0.001). While no current-use pesticides were detected in turtle plasma at any site, both current- and historic-use pesticides were found prominently in sediment and macroinvertebrates at the Sequoia National Park site, which is immediately downwind of Central Valley agriculture. SOC classes associated with urban and industrial pollution were found more often and at higher concentrations at Whiskeytown National Recreation Area. These findings demonstrate a range of SOC exposure in a turtle species with current and proposed conservation status and shed additional light on the fate of environmental contaminants in remote watersheds.

Metabolism and excretion rates of parent and hydroxy-PAHs in urine collected after consumption of traditionally smoked salmon for Native American volunteers.

Few studies have been published on the excretion rates of parent polycyclic aromatic hydrocarbons (PAHs) and hydroxy-polycyclic aromatic hydrocarbons (OH-PAHs) following oral exposure. This study investigated the metabolism and excretion rates of 4 parent PAHs and 10 OH-PAHs after the consumption of smoked salmon. Nine members of the Confederated Tribes of the Umatilla Indian Reservation consumed 50 g of traditionally smoked salmon with breakfast and five urine samples were collected during the following 24 h. The concentrations of OH-PAHs increased from 43.9 µg/g creatinine for 2-OH-Nap to 349 ng/g creatinine for 1-OH-Pyr, 3 to 6 h post-consumption. Despite volunteers following a restricted diet, there appeared to be a secondary source of naphthalene and fluorene, which led to excretion efficiencies greater than 100%. For the parent PAHs that were detected in urine, the excretion efficiencies ranged from 13% for phenanthrene (and its metabolite) to 240% for naphthalene (and its metabolites). The half-lives for PAHs ranged from 1.4 h for retene to 3.3h for pyrene. The half-lives for OH-PAHs were higher and ranged from 1.7 h for 9-OH-fluorene to 7.0 h for 3-OH-fluorene. The concentrations of most parent PAHs, and their metabolites, returned to the background levels 24 h post-consumption.

Determination of parent and hydroxy PAHs in personal PM2.5 and urine samples collected during Native American fish smoking activities.

A method was developed for the measurement of 19 parent PAHs (PAHs) and 34 hydroxylated PAHs (OH-PAHs) in urine and personal air samples of particulate matter less than 2.5 µm in diameter (PM2.5) using GC-MS and validated using NIST SRM 3672 (Organic Contaminants in Smoker's Urine) and SRM 3673 (Organic Contaminants in Nonsmoker's Urine). The method was used to measure PAHs and OH-PAHs in urine and personal PM2.5 samples collected from the operators of two different fish smoking facilities (tipi and smoke shed) burning two different wood types (alder and apple) on the Confederated Tribes of Umatilla Indian Reservation (CTUIR) while they smoked salmon. Urine samples were spiked with ß-glucuronidase/arylsulfatase to hydrolyze the conjugates of OH-PAHs and the PAHs and OH-PAHs were extracted using Plexa and C18 solid phases, in series. The 34 OH-PAHs were derivatized using MTBSTFA, and the mixture was measured by GC-MS. The personal PM2.5 samples were extracted using pressurized liquid extraction, derivatized with MTBSTFA and analyzed by GC-MS for PAHs and OH-PAHs. Fourteen isotopically labeled surrogates were added to accurately quantify PAHs and OH-PAHs in the urine and PM2.5 samples and three isotopically labeled internal standards were used to calculate the recovery of the surrogates. Estimated detection limits in urine ranged from 6.0 to 181 pg/ml for OH-PAHs and from 3.0 to 90 pg/ml for PAHs, and, in PM2.5, they ranged from 5.2 to 155 pg/m(3) for OH-PAHs and from 2.5 to 77 pg/m(3) for PAHs. The results showed an increase in OH-PAH concentrations in urine after 6h of fish smoking and an increase in PAH concentrations in air within each smoking facility. In general, the PAH exposure in the smoke shed was higher than in the tipi and the PAH exposure from burning apple wood was higher than burning alder.