Although human exposure to polycyclic aromatic hydrocarbons (PAH) has been associated with in vivo oxidative damage, and hydroxyPAH metabolites have been used as biomarkers to assess PAH-induced oxidative stress, few studies have looked at the likely causative compounds for oxidative stress in humans - PAH quinones. We developed a method using pre-column derivatization - liquid chromatography-heated electrospray ionization-tandem mass spectrometry (LC-HESI-MS/MS) to analyze ortho-phenanthrene quinones (PheQs) in human urine. 1,2-PheQ and 3,4-PheQ were identified and quantified in 3 mL of human urine; their total concentrations were higher in cigarette smokers (0.79 ± 0.98 nmol/6h urine) than in nonsmokers (0.20 ± 0.98 nmol/6h urine) (p < 0.01). The total of 1,2-PheQ and 3,4-PheQ were more strongly correlated with urinary (Z)-7-[1R,2R,3R,5S)-3,5-dihydroxy-2-[(E,3S)-3-hydroxyoct-1-enyl]cyclopentyl]hept-5-enoic acid (8-iso-PGF₂α), a biomarker of lipid peroxidation (R² = 0.53, p < 0.001), than the other phenanthrene metabolites including phenanthrene tetraol (PheT), phenanthrene-1,2-dihydrodiol (1,2-PheD), and total phenanthrene phenols (OHPhe), consistent with the concept that PheQs and likely other PAH quinones play a causal role in the generation of reactive oxygen species (ROS) in humans. Thus, PheQs may be suitable as biomarkers to assess human exposure to oxygenated PAH and the subsequent oxidative damage. This study provides unique support, by analysis of human urinary metabolites, for the PAH quinone mediated oxidative damage hypothesis of PAH carcinogenesis.

Whereas non-extractable residue (NER) formation is recognized as an important process affecting the ecological risk of organic contaminants in soils, it is commonly neglected in regional-scale multi-media models assessing chemical environmental fate and risk. We used a combined field and modeling study to elucidate the relative importance of NER formation to the reduction in available organic contaminants compared with fate processes commonly considered in risk assessment models (volatilization, leaching, and biodegradation). Specifically, four polycyclic aromatic hydrocarbons (PAHs), i.e., phenanthrene (Phe), pyrene (Pyr), benzo[a]pyrene (BaP), and benzo[ghi]perylene (BghiP), were spiked and measured in a one-year field pot experiment at four sites with diverse environmental conditions on the eastern Tibetan Plateau. The rate of NER formation was derived as the difference between the overall rate of decline in total-extractable PAH concentrations, obtained by fitting a biphasic first-order model to the measured concentrations, and the sum of the calculated rates of volatilization, leaching, and biodegradation. Our work shows that the total-extractable PAH concentration undergoes a rapid decline and a slow decline, with shorter overall half-lives (especially for BaP and BghiP) than those observed in earlier studies. Generally, NER formation was assessed to be the dominant contributor (64 ± 33%) to the overall decline of PAHs, followed by biodegradation (35 ± 32%); volatilization and leaching were the smallest contributors. In particular, heavier PAHs (i.e. BaP and BghiP) tend to have shorter half-lives in the rapid and the overall decline phase, indicating that the erroneous estimation of environmental fate and risks might be more pronounced for organic contaminants with a large molecular size. The trend of overall decline rates of PAHs displayed a combined effect of NER formation and biodegradation. This work indicates the need to consider NER formation as a process in multi-media models of chemical fate and risk.

Black carbon (BC) exerts a large impact on climate radiative forcing and public health, and such impacts depend strongly on chemical composition and mixing state. Here a single particle aerosol mass spectrometry (SPA-MS) along with an aerosol chemical speciation monitor was employed to characterize the composition and mixing state of BC-containing particles in summer and winter in Beijing. Approximately 2 million BC-containing particles were chemically analyzed, and the particles were classified into nine and eight different types in summer and winter, respectively, according to mass spectral signatures and composition. The BC-containing particles in summer were dominated by the type of nitrate-related BC (BC-N, 56.7%), while in winter the BC mixed with organic carbon (OC) and sulfate (BCOC-S), and OC and nitrate (BCOC-N) were two dominant types accounting for 44.9% and 16.6%, respectively. The number fractions of BC-N in summer, and BCOC-N and BC-SN in winter increased largely during periods with severe air pollution, suggesting the enhanced secondary formation on BC-containing particles. We also found that the primary emissions of the biomass burning and coal combustion can affect BC mixing state substaintially as indicated by the considerable fraction of BC mixed with levoglucosan and polycyclic aromatic hydrocarbons in winter. Bivariate polar plots and back trajectory analysis indicated that the sulfate-associated BC-containing particles were mostly from regional transport while the nitrate-related type was more from local production. The optical parameter of absorbing Ångström exponents (AAE) of BC was 1.2 and 1.5 in summer and winter, respectively, and the AAE dependence of BC mixing state was also different in the two seasons. While higher fractions of BC-N were observed during lower AAE periods in summer, the variations of dominant OC-related BC-containing particles in winter were fairly stable as a function of AAE.

Coal mining activities may increase residential exposure to polycyclic aromatic hydrocarbons (PAHs), but personal PAH exposures have not been studied in mining areas. We used silicone wristbands as passive personal samplers to estimate PAH exposures in coal mining communities in Central Appalachia in the United States. Adults (N = 101) wore wristbands for one week; 51 resided in communities within approximately three miles of surface mining sites, and 50 resided 10 or more miles from mining sites. Passive indoor polyurethane foam (PUF) sampling was conducted in residents’ homes, and a sample of 16 outdoor PUF samples were also collected. Nine PAH congeners were commonly detected in wristbands (mean ± standard deviation), including phenanthrene (50.2 ± 68.7 ng/g), benz[a]anthracene (20.2 ± 58.2 ng/g), fluoranthene (19.4 ± 24.1 ng/g) and pyrene (15.2 ± 18.2 ng/g). Controlling for participant characteristics and season, participants living closer to mining sites had significantly higher levels of phenanthrene, fluorene, fluoranthene, pyrene and ∑PAHs in wristbands compared to participants living farther from mining. Indoor air showed no significant group differences except for pyrene, but outdoor air showed significant or marginally significant differences for phenanthrene, fluorene, pyrene and ∑PAHs. The results suggest that mining community residents face exposure to outdoor mining-related pollutants, and demonstrate that personal silicone wristbands can be deployed as effective passive sampling devices.

Polycyclic aromatic hydrocarbons containing at least 24 carbon atoms (≥C₂₄-PAH) are often associated with pyrogenic processes such as combustion of fuel, wood or coal, and occur in the environment in diesel particulate matter, black carbon and coal tar. Some of the ≥C₂₄-PAH, particularly the group of dibenzopyrenes (five isomers, six aromatic rings) are known to show high mutagenic and carcinogenic activita.Gas chromatography – mass spectrometry is a well-established method for the analysis of lower molecular weight PAH but is not optimally suited for the analysis of ≥C₂₄-PAH due to their low vapor pressures. Also, hundreds of ≥C₂₄-PAH isomers are possible but only a few compounds are commercially available as reference standards. Therefore, in this study, a combination of multidimensional liquid chromatography, UV–Vis diode array detection, PAH selective and highly sensitive atmospheric pressure laser ionization – mass spectrometry is used to detect and unequivocally identify PAH. For identification of PAH in two bituminous coals and one petrol coke sample, unique and compound specific UV–Vis spectra were acquired. It was possible to identify ten compounds (naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[e,ghi]perylene, dibenzo[cd,lm]perylene, benzo[a]coronene, phenanthrol[5,4,3,2-abcde]perylene, benzo[ghi]naphtho[8,1,2-bcd]perylene, benzo[pqr]naphtho[8,1,2-bcd]perylene, naphtho[8,1,2-abc]coronene and tribenzo[e,ghi,k]perylene) by comparison of acquired spectra with spectra from literature. Additionally, it was possible to detect similar distribution patterns in different samples and signals related to alkylated naphthopyrenes, naphthofluoranthenes or dibenzopyrenes. Subsequent effect-directed analysis of a bituminous coal sample using the microEROD (ethoxyresorufin-O-deethylase) bioassay showed high suitability and revealed lower EROD induction for the ≥C₂₄-PAH (TEQ range 0.67–10.07 ng/g) than for the allover < C₂₄-PAH containing fraction (TEQ 84.00 ng/g). Nevertheless, the toxicity of ≥C₂₄-PAH has a significant impact compared with <C₂₄-PAH and must be considered for risk assessment. The LC-DAD-APLI-MS method, presented in this study, is a powerful tool for the unequivocal identification of these ≥ C₂₄-PAH.

Burial in sediments is a crucial way to reduce mobilization and risks of hydrophobic organic contaminants (HOCs), but ability of sediments to bury HOCs may be altered if the environment is changed. Whether the ability of sediments to bury HOCs has been affected by climate change remains largely unclear. We excluded the impacts of anthropogenic emissions and eutrophication from that of climate change, and for the first time found that not only the rising surface air temperature but also the declining wind speed and the reducing days with precipitation had weakened the ability of Chinese lakes to bury 16 polycyclic aromatic hydrocarbon (PAHs) by 69.2% ± 9.4%–85.7% ± 3.6% from 1951 to 2017. The relative contributions of the climatic variables to the reduced burial ability depended on the properties of the PAHs, and lakes. Burial ability of the PAHs responded differently to climate change, and was correlated to their volatilization and aqueous solubility, and lake area, catchment area/lake area ratio, and water depth. Our study suggests that not only the rising surface air temperature but also the declining wind speed and the reducing days with precipitation can undermine global efforts to reduce environmental and human exposure to PAHs.

Epidemiological studies have demonstrated association between the total mass of fine particulate matter (PM2.5) exposures and inflammation. There are few studies exploring the associations between PM2.5 constituents and the biomarkers of inflammation in older adults and the underlying biological mechanisms are not exact. In this study, we examined the associations between PM2.5 and its constituents (organic carbon (OC), elemental carbon (EC), total carbon (TC), polycyclic aromatic hydrocarbons (PAHs) and complement three factor (C3), an important biomarker of inflammation in a repeated panel of 175 older adults in Beijing, China. We have constructed three different linear mixed effect models (single-pollutant model, constituent-PM2.5 joint model, and constituent-residual model) to evaluate the association of PM2.5 and its constituents and complement C3, controlling for concentration of high sensitive C-reactive protein (hs-CRP), day of week, mean temperature, relative humidity, location and potential individual confounders. We found robust positive associations of OC, EC, TC, PAHs and PM2.5 mass concentration with complement C3 at different lag patterns. The cumulative effects of pollutants increased across average of 2–5 days. Individuals aged 65 and above, or with diabetes, or BMI ≥30, or with no-cardiopathy, or with hypertension also exhibited positive associations between PM2.5 and complement C3. The results revealed that short-term exposure to PM2.5 and its constituents could result in a significant increase in serum level of complement C3. These findings suggested a possible involvement of complement C3 in the effect of PM2.5 on inflammatory reaction.

In this study, nine congeners of polybrominated diphenyl ethers (PBDEs) and sixteen congeners of polycyclic aromatic hydrocarbons (PAHs) were measured in water samples to elucidate their spatial distribution, congener profiles, sources and ecological risks in the Guanlan River during both the dry season (DS) and the wet season (WS). The concentration of Σ9PBDE ranged from 58.40 to 186.35 ng/L with an average of 115.72 ng/L in the DS, and from 8.20 to 37.80 ng/L with an average of 22.15 ng/L in the WS. Meanwhile, the concentration of Σ16PAHs was ranged from 121.80 to 8371.70 ng/L with an average of 3271.18 ng/L in the DS and from 1.85 to 7124.25 ng/L with an average of 908.11 ng/L in the WS. The concentrations of PBDEs and PAHs in the DS were significantly higher than those in the WS, probably due to the dilution of the river during the rainy season. Moreover, the spatial distribution of pollutants revealed decreasing trend in the concentration from upstream to downstream and almost identical pattern was observed during both seasons. The source apportionment suggested that penta-BDE and to some extent octa-BDE commercial products were major sources of PBDEs in the study area. However, the sources of PAHs were mainly comprised of fossil fuels and biomass burning, followed by the petroleum products and their mixtures. The results of the ecological risk assessment indicated PBDEs contamination posed high ecological risks, while PAHs exhibited low or no ecological risks in the study area. Consistent with the environmental levels, the ecological risks of pollutants were relatively lower in the WS, compared to that in the DS. The results from this study would provide valuable baseline data and technical support for policy makers to protect the ecological environment of the Guanlan River.

Muzzle emissions from firing an M4 carbine rifle in a semi-enclosed chamber were characterized for an array of compounds to provide quantitative data for future studies on potential inhalation exposure and rangeland contamination. Air emissions were characterized for particulate matter (PM) size distribution, composition, and morphology; carbon monoxide (CO); carbon dioxide (CO₂); energetics; metals; polycyclic aromatic hydrocarbons; and methane. Three types of ammunition were used: a “Legacy” (Vietnam-era) round, the common M855 round (no longer fielded), and its variant, an M855 round with added potassium (K)-based salts to reduce muzzle flash. Average CO concentrations up to 1500 ppm significantly exceeded CO₂ concentrations. Emitted particles were in the respirable size range with mass median diameters between 0.33 and 0.58 μm. PM emissions were highest from the M855 salt-added ammunition, likely due to incomplete secondary combustion in the muzzle blast caused by scavenging of combustion radicals by the K salt. Copper (Cu) had the highest emitted metal concentration for all three round formulations, likely originating from the Cu jacket on the bullet. Based on a mass balance analysis of each round's formulation, lead (Pb) was completely emitted for all three round types. This work demonstrated methods for characterizing emissions from gun firing which can distinguish between round-specific effects and can be used to initiate studies of inhalation risk and environmental deposition.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants with a number of them being carcinogenic. One of the approaches to assess human exposure to PAHs is to measure their urinary metabolites, monohydroxyl polycyclic aromatic hydrocarbons (OH-PAHs), with a method allowing for high throughput and short turn-around time. We developed a method to quantify nine urinary OH-PAHs by using supported liquid phase extraction (SLE) and isotope dilution gas chromatography tandem mass spectrometry (GC-MS/MS). SLE demonstrated advantages over the traditionally used liquid-liquid extraction techniques. The target analytes with spiked deuterated and ¹³C-labeled internal standards were extracted from urine by SLE after enzymatic cleavage of the glucuronide and sulfate conjugates. The extracted analytes were then derivatized with N-Methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA), and analyzed by GC-MS/MS. Six solvent mixtures were evaluated as the SLE extraction solvent, and pentane:chloroform (7:3, v/v) was selected due to its best overall analytical performance. Method detection limits for the 9 analytes ranged from 2.3 to 13.8 pg/mL. Precision and accuracy were satisfactory. SLE and internal isotope labeled standard combination reduced matrix effect effectively. This new method using SLE sample preparation techniques coupled with GC-MS/MS proves applicable to urinary measurements for PAH exposure studies for general population.