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Interactions between polycyclic aromatic hydrocarbons (PAHs) and titanium dioxide (TiO 2 ) nanoparticles (NPs) can produce unforeseen photoproducts in the aqueous phase. Both PAHs and TiO 2 -NPs are well-studied and highly persistent environmental pollutants, but the consequences of PAH-TiO 2 -NP interactions are rarely explored. We investigated PAH photoproduct formation over time for benzo[a]pyrene (BaP), fluoranthene (FLT), and pyrene (PYR) in the presence of ultraviolet A (UVA) using a combination of analytical and computational methods including, identification of PAH photoproducts, assessment of expression profiles for gene indicators of PAH metabolism, and computational evaluation of the reaction mechanisms through which certain photoproducts might be formed. Chemical analyses identified diverse photoproducts, but all PAHs shared a primary photoproduct, 9,10-phenanthraquinone (9,10-PQ), regardless of TiO 2 -NP presence. The computed reaction mechanisms revealed the roles photodissociation and singlet oxygen chemistry likely play in PAH mediated photochemical processes that result in the congruent production of 9,10-PQ within this study. Our investigation of PAH photoproduct formation has provided substantial evidence of the many, diverse and congruent, photoproducts formed from physicochemically distinct PAHs and how TiO 2 -NPs influence bioavailability and time-related formation of PAH photoproducts., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The oxidative potential (OP) of atmospheric fine particulate matter (PM 2.5 ) 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 (DTT 50 ), and the reduction potential of the PAHs (ΔG rxn ). Computed reduction potential results were found to match literature reduction potential values (r 2  = 0.97), while DTT 50 results had no correlations with the computed ΔG rxn values (r 2  < 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 ΔG rxn in UPAH, HPAH, and OHPAH subclasses, as well as with all 135 PAHs in this study but did not correlate with DTT 50 , indicating that electron dispersion is linked to thermodynamic reactions and structural differences in PAHs, but not linked to the OP of PAHs. Three ambient PM 2.5 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 PM 2.5 filter extracts, indicating a much more complex model of toxicity for the OP of PAHs in ambient PM 2.5 . This study combined computed molecular properties with toxicologically relevant assay results to probe the OP of anthropogenically driven portions of ambient PM 2.5 , and results in a better understanding of the complexity of ambient PM 2.5 OP., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Polycyclic aromatic hydrocarbons (PAHs) and titanium dioxide (TiO 2 ) nanoparticles (NPs) are photoactive environmental pollutants that can contaminate aquatic environments. Aqueous-phase interactions between PAHs and TiO 2 -NPs are of interest due to their emerging environmental relevance, particularly with the deliberate application of TiO 2 -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 TiO 2 -NPs. ANT and PHE solutions were prepared alone or in combination with TiO 2 -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 TiO 2 -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 TiO 2 -NP-related increases in oxidative potential were PAH-specific. The exploitation of multiple analytical methods provided novel insights into distinct PAH photoactivity, TiO 2 -NP influence on photoproduct formation in a PAH-specific manner, and the significant role time plays in photochemical processes.

There is limited understanding of adverse health effect associations with chemical constituents of fine particulate matter (PM 2.5 ) as well as the underlying mechanisms. We outlined a workflow to assess metrics, beyond concentration, using household and personal PM 2.5 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 PM 2.5 samples. This work established methods to characterize multiple metrics of PM 2.5 to ultimately support the identification of more health-relevant metrics than concentration., Competing Interests: Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:

Atmospheric fine particulate matter (PM 2.5 ) transports polycyclic aromatic hydrocarbons (PAHs) regionally and globally, influencing the air quality of communities around the planet. Concentrations of 130 PAHs extracted from PM 2.5 , 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 PM 2.5 , 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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.

Polycyclic aromatic hydrocarbons (PAHs) undergo transformation reactions with atmospheric photochemical oxidants, such as hydroxyl radicals (OH • ), nitrogen oxides (NOx), and ozone (O 3 ). 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.

Toxicology research into the global public health burden of fine particulate matter (PM 2.5 ) exposures frequently requires extraction of PM 2.5 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 PM 2.5 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 PM 2.5 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 PM 2.5 extraction method. This research highlights the importance of and rationale for considering the extraction method when interlaboratory comparisons of PM 2.5 toxicology research are made.

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 C 2 -C 7 homologues of N-MeFASE and N-EtFASE, which accounted for 14-18% of the total volatile PFASs on three textiles. Overlooking short-chain (≤C 7 ) 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.

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.

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., (Copyright © 2017 Elsevier B.V. All rights reserved.)

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.

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., (© The Author 2017. Published by Oxford University Press on behalf of the Society of Toxicology.)

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, r a =0.85; r s =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) (ƒ anti =0.23-0.53) of the organisms was lower than that of commercial products (ƒ anti =0.68), demonstrating ƒ anti 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., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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., Competing Interests: The authors declare no competing financial interest.

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., Competing Interests: The authors declare no conflict of interest.

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., Competing Interests: The authors declare no conflicts of interest.

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., (Published by Elsevier Ltd.)

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., (Copyright © 2015 Elsevier B.V. All rights reserved.)

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 β-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., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Anthropogenic semivolatile organic compounds (SOCs) that persist in the environment, bioaccumulate, are toxic at low concentrations, and undergo long-range atmospheric transport (LRT) were identified and quantified in the atmosphere of a Saharan dust source region (Mali) and during Saharan dust incursions at downwind sites in the eastern Caribbean (U.S. Virgin Islands, Trinidad and Tobago) and Cape Verde. More organochlorine and organophosphate pesticides (OCPPs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyl (PCB) congeners were detected in the Saharan dust region than at downwind sites. Seven of the 13 OCPPs detected occurred at all sites: chlordanes, chlorpyrifos, dacthal, dieldrin, endosulfans, hexachlorobenzene (HCB), and trifluralin. Total SOCs ranged from 1.9-126 ng/m(3) (mean = 25 ± 34) at source and 0.05-0.71 ng/m(3) (mean = 0.24 ± 0.18) at downwind sites during dust conditions. Most SOC concentrations were 1-3 orders of magnitude higher in source than downwind sites. A Saharan source was confirmed for sampled air masses at downwind sites based on dust particle elemental composition and rare earth ratios, atmospheric back trajectory models, and field observations. SOC concentrations were considerably below existing occupational and/or regulatory limits; however, few regulatory limits exist for these persistent organic compounds. Long-term effects of chronic exposure to low concentrations of SOCs are unknown, as are possible additive or synergistic effects of mixtures of SOCs, biologically active trace metals, and mineral dust particles transported together in Saharan dust air masses., (© 2013.)

The heterogeneous reactions of benzo[a]pyrene-d12 (BaP-d12), benzo[k]fluoranthene-d12 (BkF-d12), benzo[ghi]perylene-d12 (BghiP-d12), dibenzo[a,i]pyrene-d14 (DaiP-d14), and dibenzo[a,l]pyrene (DalP) with NO2, NO3/N2O5, and OH radicals were investigated at room temperature and atmospheric pressure in an indoor Teflon chamber and novel mono-NO2-DaiP and mono-NO2-DalP products were identified. Quartz fiber filters (QFF) were used as a reaction surface and the filter extracts were analyzed by GC/MS for nitrated-PAHs (NPAHs) and tested in the Salmonella mutagenicity assay, using Salmonella typhimurium strain TA98 (with and without metabolic activation). In parallel to the laboratory experiments, a theoretical study was conducted to rationalize the formation of NPAH isomers based on the thermodynamic stability of OH-PAH intermediates, formed from OH-radical-initiated reactions. NO2 and NO3/N2O5 were effective oxidizing agents in transforming PAHs to NPAHs, with BaP-d12 being the most readily nitrated. Reaction of BaP-d12, BkF-d12, and BghiP-d12 with NO2 and NO3/N2O5 resulted in the formation of more than one mononitro isomer product, while the reaction of DaiP-d14 and DalP resulted in the formation of only one mononitro isomer product. The direct-acting mutagenicity increased the most after NO3/N2O5 exposure, particularly for BkF-d12 in which di-NO2-BkF-d10 isomers were measured. The deuterium isotope effect study suggested that substitution of deuterium for hydrogen lowered both the direct and indirect acting mutagenicity of NPAHs and may result in an underestimation of the mutagencity of the novel NPAHs identified in this study.

Reactions of ambient particles collected from four sites within the Los Angeles, CA air basin and Beijing, China with a mixture of N2O5, NO2, and NO3 radicals were studied in an environmental chamber at ambient pressure and temperature. Exposures in the chamber system resulted in the degradation of particle-bound PAHs and formation of molecular weight (mw) 247 nitropyrenes (NPYs) and nitrofluoranthenes (NFLs), mw 273 nitrotriphenylenes (NTPs), nitrobenz[a]anthracenes (NBaAs), nitrochrysene (NCHR), and mw 297 nitrobenzo[a]pyrene (NBaP). The distinct isomer distributions resulting from exposure of filter-adsorbed deuterated fluoranthene to N2O5/NO3/NO2 and that collected from the chamber gas-phase suggest that formation of NFLs in ambient particles did not occur by NO3 radical-initiated reaction but from reaction of N2O5, presumably subsequent to its surface adsorption. Accordingly, isomers known to result from gas-phase radical-initiated reactions of parent PAHs, such as 2-NFL and 2- and 4-NPY, were not enhanced from the exposure of ambient particulate matter to N2O5/NO3/NO2. The reactivity of ambient particles toward nitration by N2O5/NO3/NO2, defined by relative 1-NPY formation, varied significantly, with the relative amounts of freshly emitted particles versus aged particles (particles that had undergone atmospheric chemical processing) affecting the reactivity of particle-bound PAHs toward heterogeneous nitration. Analyses of unexposed ambient samples suggested that, in nighttime samples where NO3 radical-initiated chemistry had occurred, heterogeneous formation of 1-NPY on ambient particles may have contributed to the ambient 1-NPY concentrations at downwind receptor sites. These results, together with observations that 2-NFL is consistently the dominant particle-bound nitro-PAH measured in ambient atmospheres, suggest that for PAHs that exist in both the gas- and particle-phase, the heterogeneous formation of particle-bound nitro-PAHs is a minor formation route compared to gas-phase formation.

The objective of this research was to investigate the relationship between lung cancer mortality rates, carcinogenic polycyclic aromatic hydrocarbon (PAH) emissions, and smoking on a global scale, as well as for different socioeconomic country groups. The estimated lung cancer deaths per 100,000 people (ED100000) and age standardized lung cancer death rate per 100,000 people (ASDR100000) in 2004 were regressed on PAH emissions in benzo[a]pyrene equivalence (BaPeq), smoking prevalence, cigarette price, gross domestic product per capita, percentage of people with diabetes, and average body mass index using simple and multiple linear regression for 136 countries. Using stepwise multiple linear regression, a statistically significant positive linear relationship was found between loge(ED100000) and loge(BaPeq) emissions for high (p-value <0.01) and for the combination of upper-middle and high (p-value <0.05) socioeconomic country groups. A similar relationship was found between loge(ASDR100000) and loge(BaPeq) emissions for the combination of upper-middle and high (p-value <0.01) socioeconomic country groups. Conversely, for loge(ED100000) and loge(ASDR100000), smoking prevalence was the only significant independent variable in the low socioeconomic country group (p-value <0.001). These results suggest that reducing BaPeq emissions in the U.S., Canada, Australia, France, Germany, Brazil, South Africa, Poland, Mexico, and Malaysia could reduce ED100000, while reducing smoking prevalence in Democratic People's Republic of Korea, Nepal, Mongolia, Cambodia, and Bangladesh could significantly reduce the ED100000 and ASDR100000.

Contaminants used at low elevation, such as pesticides on crops, can be transported tens of kilometers and deposited in adjacent mountains in many parts of the world. Atmospherically deposited organic contaminants in the Sierra Nevada Mountains of California, USA, have exceeded some thresholds of concern, but the spatial and temporal distributions of contaminants in the mountains are not well known. The authors sampled shallow-water sediment and tadpoles (Pseudacris sierra) for pesticides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls in four high-elevation sites in Yosemite National Park in the central Sierra Nevada twice during the summers of 2006, 2007, and 2008. Both historic- and current-use pesticides showed a striking pattern of lower concentrations in both sediment and tadpoles in Yosemite than was observed previously in Sequoia-Kings Canyon National Parks in the southern Sierra Nevada. By contrast, PAH concentrations in sediment were generally greater in Yosemite than in Sequoia-Kings Canyon. The authors suggest that pesticide concentrations tend to be greater in Sequoia-Kings Canyon because of a longer air flow path over agricultural lands for this park along with greater pesticide use near this park. Concentrations for DDT-related compounds in some sediment samples exceeded guidelines or critical thresholds in both parks. A general pattern of difference between Yosemite and Sequoia-Kings Canyon was not evident for total tadpole cholinesterase activity, an indicator of harmful exposure to organophosphorus and carbamate pesticides. Variability of chemical concentrations among sites, between sampling periods within each year, and among years, contributed significantly to total variation, although the relative contributions differed between sediment and tadpoles., (Copyright © 2013 SETAC.)

The enantiomer fractions (EFs) of alpha-hexachlorocyclohexane (α-HCH), cis-, trans-, and oxychlordane, and heptachlor epoxide were measured in 73 snow, fish, and sediment samples collected from remote lake catchments, over a wide range of latitudes, in seven western U.S. National Parks/Preserves to investigate their sources, fate, accumulation and biotransformation in these ecosystems. The present study is novel because these lakes had no inflow or outflow, and the measurement of chiral organochlorine pesticides (OCPs) EFs in snowpack from these lake catchments provided a better understanding of the OCP sources in the western United States, whereas their measurement in fish and sediment provided a better understanding of their biotic transformations within the lake catchments. Nonracemic α-HCH was measured in seasonal snowpack collected from continental U.S. National Parks, and racemic α-HCH was measured in seasonal snowpack collected from the Alaskan parks, suggesting the influence of regional sources to the continental U.S. parks and long-range sources to the Alaskan parks. The α-HCH EFs measured in trout collected from the lake catchments were similar to the α-HCH EFs measured in seasonal snowpack collected from the same lake catchments, suggesting that these fish did not biotransform α-HCH enantioselectively. Racemic cis-chlordane was measured in seasonal snowpack and sediment collected from Sequoia, indicating that it had not undergone significant enantioselective biotransformation in urban soils since its use as a termiticide in the surrounding urban areas. However, nonracemic cis-chlordane was measured in seasonal snowpack and sediments from the Rocky Mountains, suggesting that cis-chlordane does undergo enantioselective biotransformation in agricultural soils. The trout from these lakes showed preferential biotransformation of the (+)-enantiomer of cis-chlordane and the (-)-enantiomer of trans-chlordane., (Copyright © 2011 SETAC.)

Bulk deposition samples were collected in remote, rural village and urban areas of Beijing-Tianjin region, North China in spring, summer, fall and winter from 2007 to 2008. The annually averaged PAHs concentration and deposition flux were 11.81±4.61 μg/g and 5.2±3.89 μg/m2/day respectively. PHE and FLA had the highest deposition flux, accounting for 35.3% and 20.7% of total deposition flux, respectively. More exposure risk from deposition existed in the fall for the local inhabitants. In addition, the PAHs deposition flux in rural villages (3.91 μg/m2/day) and urban areas (8.28 μg/m2/day) was 3.8 and 9.1 times higher than in background area (0.82 μg/m2/day), respectively. This spatial variation of deposition fluxes of PAHs was related to the PAHs emission sources, local population density and air concentration of PAHs, and the PAHs emission sources alone can explain 36%, 49%, 21% and 30% of the spatial variation in spring, summer, fall and winter, respectively., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

The concentrations, profiles, sources and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) were determined in 40 surface soil samples collected from Beijing, Tianjin and surrounding areas, North China in 2007, and all sampling sites were far from industrial areas, roadsides and other pollution sources, and across a range of soil types in remote, rural villages and urban areas. The total concentrations of 16 PAHs ranged from 31.6 to 1475.0 ng/g, with an arithmetic average of 336.4 ng/g. The highest PAH concentrations were measured in urban soils, followed by rural village soils and soils from remote locations. The remote-rural village-urban PAH concentration gradient was related to population density, gross domestic product (GDP), long-range atmospheric transport and different types of land use. In addition, the PAH concentration was well correlated with the total organic carbon (TOC) concentration of the soil. The PAH profile suggested that coal combustion and biomass burning were primary PAH sources., (Copyright 2010 Elsevier Ltd. All rights reserved.)

A model was used to predict the photodebromination of the BDE-203, 197, 196, and 153, the major components of the octa-polybrominated diphenyl ether (PBDE) technical mixture, as well as BDE-47, and the predicted results were compared to the experimental results. The predicted reaction time profiles of the photodebromination products correlate well with the experimental results. In addition, the slope of the linear regression between the measured product concentrations of the first step of the photodebromination products and their enthalpies of formation was found to be close to their theoretical value. The photodebromination results of the octa-BDE technical mixture were compared with anaerobic microbial debromination results and were found to be the same in both experiments. The debromination pathways of technical octa-BDE mixture were identified and BDE-154, 99, 47, and 31 were found to be the most abundant hexa-, penta-, tetra-, and tri-BDE debromination products, respectively. In addition to photodebromination and anaerobic biodebromination, the model prediction was also compared to the zero-valent iron reduction of BDE-209, 100, and 47 and the same debromination products were observed. Good correlation was observed between the photodebromination rate constants of fifteen PBDE congeners and their calculated lowest unoccupied molecular orbital (LUMO) energies, indicating that PBDE photodebromination is caused by electron transfer. Furthermore, the rate constants for the three different PBDE debromination processes are controlled by C-Br bond dissociation energy. With the model from the present study, the major debromination products for any PBDE congener released into the environment can be predicted., ((c) 2010 SETAC.)

With the phaseout of the manufacture of some polybrominated diphenyl ether (PBDE) formulations, namely penta-brominated diphenyl ether (BDE) and octa-BDE, and the continued use of the deca-BDE formulation, it is important to be able to predict the photodegradation of the more highly brominated congeners. A model was developed and validated to predict the products and their relative concentrations from the photodegradation of PBDEs. The enthalpies of formation of the 209 PBDE congeners were calculated, and the relative reaction rate constants were obtained. The predicted reaction rate constants for PBDEs show linear correlation with previous experimental results. Because of their large volume use, their presence in the environment, and/or importance in the photodegradation of the deca-BDE formulation, BDE-209, BDE-184, BDE-100, and BDE-99 were chosen for further ultraviolet photodegradation experiments in isooctane. The photodegradation model successfully predicted the products of the photochemical reactions of PBDEs in experimental studies. A gas chromatography retention time model for PBDEs was developed using a multiple linear regression analysis and, together with the photodegradation model and additional PBDE standards, provided a way to identify unknown products from PBDE photodegradation experiments. Based on the results of the photodegradation experiments, as well as the model predictions, it appears that the photodegradation of PBDEs is a first-order reaction and, further, that the rate-determining step is the stepwise loss of bromine. Our results suggest that, based on photodegradation, over time, BDE-99 will remain the most abundant penta-BDE, while BDE-49 and BDE-66 will increase greatly and will be comparable in abundance to BDE-47.