Polycyclic Aromatic Hydrocarbons Mixtures Research Articles

Particle size-resolved emission characteristics of complex polycyclic aromatic hydrocarbon (PAH) mixtures from various combustion sources

Combustion of domestic solid fuels is a significant source of polycyclic aromatic hydrocarbons (PAHs). Some oxygenated PAHs (o-PAHs) and PAHs with molecular weight of 302 (MW302 PAHs) are more toxic than the traditional 16 priority PAHs, whereas their emissions were much less elucidated. This study characterized the size-dependent emissions of parent PAHs (p-PAHs), o-PAHs, and MW302 PAHs from various combustion sources. The estimated emission factors (eEFs) from biomass burning sources were highest for most of the PAHs (391–8928 μg/kg), much higher than that of anthracite coal combustion (43.0–145 μg/kg), both which were operated in an indoor stove. Cigarette smoking had a high eEF of o-PAHs (240 ng/g). MW302 PAHs were not found in the emissions of smoking, cooking, and vehicular exhausts. Particle-size distributions of PAHs were compound- and source-dependent, and the tendency to associate with smaller particles was observed especially in biomass burning and cigarette smoking sources. Furthermore, the inter-source differences in PAH eEFs were associated with their dominance in fine particles. PAH composition profiles also varied with the particle size, showing increasing contributions of large-molecule PAHs with decreasing sizes in most cases. The size distributions of p-PAHs are much more significantly dependent on their n-octanol/air partition coefficients and vapor pressures than those of o-PAHs, suggesting differences in mechanisms governing their distributions. Several molecular diagnostic ratios (MDRs), including two based on MW302 PAHs, specific to these combustion scenarios were identified. However, the MDRs within some sources are also strongly size-dependent, providing a new explanation for the uncertainty in their application for source identification of PAHs. This work also highlights the necessity for understanding the size-resolved atmospheric behaviors and fate of PAHs after their emission.

Competitive Metabolism of Polycyclic Aromatic Hydrocarbons (PAHs): An Assessment Using In Vitro Metabolism and Physiologically Based Pharmacokinetic (PBPK) Modeling.

Humans are routinely exposed to complex mixtures such as polycyclic aromatic hydrocarbons (PAHs) rather than to single compounds, as are often assessed for hazards. Cytochrome P450 enzymes (CYPs) metabolize PAHs, and multiple PAHs found in mixtures can compete as substrates for individual CYPs (e.g., CYP1A1, CYP1B1, etc.). The objective of this study was to assess competitive inhibition of metabolism of PAH mixtures in humans and evaluate a key assumption of the Relative Potency Factor approach that common human exposures will not cause interactions among mixture components. To test this objective, we co-incubated binary mixtures of benzo[a]pyrene (BaP) and dibenzo[def,p]chrysene (DBC) in human hepatic microsomes and measured rates of enzymatic BaP and DBC disappearance. We observed competitive inhibition of BaP and DBC metabolism and measured inhibition coefficients (Ki), observing that BaP inhibited DBC metabolism more potently than DBC inhibited BaP metabolism (0.061 vs. 0.44 µM Ki, respectively). We developed a physiologically based pharmacokinetic (PBPK) interaction model by integrating PBPK models of DBC and BaP and incorporating measured metabolism inhibition coefficients. The PBPK model predicts significant increases in BaP and DBC concentrations in blood AUCs following high oral doses of PAHs (≥100 mg), five orders of magnitude higher than typical human exposures. We also measured inhibition coefficients of Supermix-10, a mixture of the most abundant PAHs measured at the Portland Harbor Superfund Site, on BaP and DBC metabolism. We observed similar potencies of inhibition coefficients of Supermix-10 compared to BaP and DBC. Overall, results of this study demonstrate that these PAHs compete for the same enzymes and, at high doses, inhibit metabolism and alter internal dosimetry of exposed PAHs. This approach predicts that BaP and DBC exposures required to observe metabolic interaction are much higher than typical human exposures, consistent with assumptions used when applying the Relative Potency Factor approach for PAH mixture risk assessment.

Aryl hydrocarbon receptor activation-mediated vascular toxicity of ambient fine particulate matter: contribution of polycyclic aromatic hydrocarbons and osteopontin as a biomarker

BackgroundExposure to ambient fine particulate matter (PM2.5) is associated with vascular diseases. Polycyclic aromatic hydrocarbons (PAHs) in PM2.5 are highly hazardous; however, the contribution of PM2.5-bound PAHs to PM2.5-associated vascular diseases remains unclear. The ToxCast high-throughput in vitro screening database indicates that some PM2.5-bound PAHs activate the aryl hydrocarbon receptor (AhR). The present study investigated whether the AhR pathway is involved in the mechanism of PM2.5-induced vascular toxicity, identified the PAH in PM2.5 that was the major contributor of AhR activation, and identified a biomarker for vascular toxicity of PM2.5-bound PAHs.ResultsTreatment of vascular smooth muscle cells (VMSCs) with an AhR antagonist inhibited the PM2.5-induced increase in the cell migration ability; NF-κB activity; and expression of cytochrome P450 1A1 (CYP1A1), 1B1 (CYP1B1), interleukin-6 (IL-6), and osteopontin (OPN). Most PM2.5-bound PAHs were extracted into the organic fraction, which drastically enhanced VSMC migration and increased mRNA levels of CYP1A1, CYP1B1, IL-6, and OPN. However, the inorganic fraction of PM2.5 moderately enhanced VSMC migration and only increased IL-6 mRNA levels. PM2.5 increased IL-6 secretion through NF-κB activation; however, PM2.5 and its organic extract increased OPN secretion in a CYP1B1-dependent manner. Inhibiting CYP1B1 activity and silencing OPN expression prevented the increase in VSMC migration ability caused by PM2.5 and its organic extract. The AhR activation potencies of seven PM2.5-bound PAHs, reported in the ToxCast database, were strongly correlated with their capabilities of enhancing the migration ability of VSMCs. Benzo(k)fluoranthene (BkF) contributed the most to the AhR agonistic activity of ambient PM2.5-bound PAHs. The association between PM2.5-induced vascular toxicity, AhR activity, and OPN secretion was further verified in mice; PM2.5-induced intimal hyperplasia in pulmonary small arteries and OPN secretion were alleviated in mice with low AhR affinity. Finally, urinary concentrations of 1-hydroxypyrene, a major PAH metabolite, were positively correlated with plasma OPN levels in healthy humans.ConclusionsThe present study offers in vitro, animal, and human evidences supporting the importance of AhR activation for PM2.5-induced vascular toxicities and that BkF was the major contributor of AhR activation. OPN is an AhR-dependent biomarker of PM2.5-induced vascular toxicity. The AhR activation potency may be applied in the risk assessment of vascular toxicity in PAH mixtures.

Urinary concentrations of polycyclic aromatic hydrocarbon and phthalate metabolite mixtures in relation to semen quality among men attending an infertility clinic.

Previous studies have reported that exposure to phthalates and polycyclic aromatic hydrocarbons (PAHs) is individually associated with altered semen quality, but no human studies have evaluated their joint effects of exposure mixtures, a more real-world scenario. We aimed to explore urinary metabolite mixtures of phthalates and PAHs in associations with semen quality. Repeated spot-urine samples gathered from 695 men attending a fertility clinic were analyzed for urinary metabolites of eight phthalates and ten monohydroxylated-PAHs (OH-PAHs). Principal component analysis (PCA)-multivariable linear regression (MLR) model, quantile g-computation (qg-comp), and Bayesian kernel machine regression (BKMR) were applied to estimate the associations of urinary mixtures of phthalate and OH-PAH metabolites with semen quality. The overall effects of urinary mixtures of phthalate and PAH metabolites on semen quality were not statistically significant. However, hydroxynaphthalene (OHNa) factor identified from PCA was monotonically associated with decreased total sperm count and sperm concentration, whereas di(2-ethylhexyl) phthalate (DEHP) factor was non-monotonically related to increased progressive sperm motility and total sperm motility. Qg-comp and BKMR models confirmed these findings and identified 2-OHNa and 2-OHFlu as the primary negative contributors, whereas MEOHP and MEHP as the primary positive contributors. Our findings suggest that exposure to mixtures of naphthalene and DEHP is associated with altered semen quality. The finding is warranted to confirm in further well-designed epidemiological studies.

Ecological risk assessment of priority PAHs pollutants in crude oil contaminated soil and its impacts on soil biological properties

Polycyclic aromatic hydrocarbons (PAHs) are one of the major toxic constituents of crude oil and therefore, an understanding on PAHs associated risks and their relationship with soil biological parameters are necessary for adopting effective risk-based and site specific remediation strategies in the contaminated soil. Here, risks evaluation of eight detected PAHs in terms of toxic equivalent concentration (TEQC), benzo(a)pyrene equivalent (BaPeq), contamination factor (CF), pollution load index (PLI), hazard quotient (HQ), hazard index (HI), toxic unit for individual PAHs (TU) and PAHs mixture (TUm) have been evaluated. Besides, the effect of PAHs contamination on soil biological properties has also been investigated and correlated with PAHs concentrations. The TEQc of eight PAHs was recorded in the range of 0.06–5.0 mg kg−1 soil, whereas the BaPeq value was 25.3 mg kg−1 soil which exceed the permissible limit. Similarly, CF (85.5–1668.2), PLI (322.8), HQ (311.7–8340.9), HI (26,443.8), TU (227.9–3821.6) and TUm(7916.2) also exceed the permissible values for non-toxic conditions indicating carcinogenic risk for humans. Besides, activities of soil dehydrogenase, urease, alkaline-phosphatase, catalase, amylase and cellulase were decreased by 1.5–2.3 folds in the contaminated soil than control. The results of Pearson’s correlation matrix also established negative impact of PAHs on the soil's biological properties.

Associations of urinary polycyclic aromatic hydrocarbon metabolites and blood pressure with the mediating role of cytokines: A panel study among children

Little was known regarding the relations of polycyclic aromatic hydrocarbon (PAH) mixture with children's blood pressure (BP) and its potential mechanism. We conducted a panel study with up to 3 visits across 3 seasons in 2017-2018 among 103 children aged 4-13 years. Urinary PAH metabolites (OH-PAHs) were measured by gas chromatograph-tandem triple quadrupole mass spectrometer, and serum cytokines were detected by Bio-Rad 48-Plex Screening Panel. We employed linear mixed-effects models to assess the relations of each urinary OH-PAH with BP, least absolute shrinkage and selection operator (LASSO), and weighted quantile sum (WQS) regression to evaluate associations of OH-PAHs mixture with BP, and mediation analyses for the role of serum cytokines. We found the consistently positive associations of 1-hydroxynaphthalene and 9-hydroxyphenanthrene (9-OHPh) with systolic BP (SBP), 4-OHPh, and 9-OHPh with diastolic BP (DBP) and mean arterial pressure (MAP) in a dose-responsive manner. For instance, each 1-fold increment of 9-OHPh was related with increase of 0.92% (95% confidence interval (CI): 0.25%, 1.60%) in SBP, 1.32% (95%CI: 0.25%, 2.39%) in DBP, and 1.15% (95%CI: 0.40%, 1.88%) in MAP. Meanwhile, based on LASSO and WQS regression, OH-PAHs mixture was linked with increased DBP and MAP, to which 9-OHPh and 4-OHPh were the major contributors. Such relationships were modified by passive smoking status and 3-4 times stronger in passive smokers than non-passive smokers. A 1-fold increase in 9-OHPh was associated with an elevation of 3.51% in SBP among passive smokers while that of 0.55% in SBP among non-passive smokers. Furthermore, 4-OHPh and 9-OHPh were related to multiple cytokines elevation, of which platelet-derived growth factor (PDGF) mediated 9.99% and 12.57% in 4-OHPh-related DBP and MAP elevation, respectively. Accordingly, urinary OH-PAHs dominated by 9-OHPh and 4-OHPh were dose-responsively associated with elevated BP whereby a mechanism partly involving PDGF among children.

Prenatal exposure to a mixture of PAHs causes the dysfunction of islet cells in adult male mice: Association with type 1 diabetes mellitus

Polycyclic aromatic hydrocarbons (PAHs) have been detected throughout the human body. Whether exposure to PAHs is associated with the incidence of type 1 diabetes mellitus should be investigated. To this end, pregnant mice were exposed to mixed PAHs (5, 50, or 500 μg/kg) once every other day during gestation. The adult male offspring displayed impaired glucose tolerance and reduced serum levels of glucagon and insulin. Immunohistochemical staining revealed increased numbers of apoptotic β-cells and a reduced β-cell mass in these males. The downregulated expression of pancreatic estrogen receptor α, androgen receptor, and transcription factor PDX1 was responsible for impacting β-cell development. The relatively reduced α-cell area was associated with downregulated ARX expression. The transcription of Isn2 and Gcg in pancreatic tissue was downregulated, which indicated that the function of β-cells and α-cells was impaired. Methylation levels in the Isn2 promotor were significantly elevated in mice prenatally exposed to 500 µg/kg PAHs, which was consistent with the change in its mRNA levels. The number of macrophages infiltrating islets was significantly increased, indicating that prenatal PAH exposure might reduce islet cell numbers in an autoimmune manner. This study shows that prenatal exposure to PAHs may promote the pathogenesis of type 1 diabetes mellitus.

Catalytic cracking of three-ring polycyclic aromatic hydrocarbons in the presence of hydrogen donors

Catalytic cracking of three-ring polycyclic aromatic hydrocarbons (PAHs) in the residue fluid catalytic cracking (RFCC) process was investigated. Catalytic cracking of mixtures of three-ring PAHs and various model hydrocarbons was carried out using RFCC equilibrium catalysts. Most of the three-ring PAHs were converted to coke in the absence of hydrogen donors, whereas coke formation was suppressed and decomposition of three-ring PAHs was promoted in the presence of aliphatic hydrocarbons, saturated rings, and aromatic ring side chains. Three-ring PAHs were first converted to noncondensed two-ring PAHs and subsequently decomposed to monocyclic aromatic hydrocarbons and condensed two-ring PAHs. This reaction can be depicted by partial hydrogenation of three-ring PAHs by hydrogen transfer reaction with coexisting hydrogen donors and sequential cracking of saturated rings. When a hydrogen donor was sufficiently present, cracking of saturated rings was the rate-determining step, and the reaction can be accelerated by increasing the reaction temperature or using a catalyst with a high acid content. These results are expected to lead to the effective utilization of heavy oil by promoting PAH cracking in the RFCC process.

Methods and limitations of stable isotope measurements via direct elution of chromatographic peaks using gas chromotography-Orbitrap mass spectrometry

The Thermo Scientific™ QExactive Orbitrap™ mass spectrometer combined with a Thermo Scientific™ Trace™ 1310 GC enables high-mass-resolution measurements of molecular isotopic structure (e.g., molecular-average, position-specific, and multiple substitution measurements), but thus far has employed non-traditional, slow sample introduction methods and long integrations lasting minutes or tens of minutes to optimize measurement precision. This study examines the performance of the Orbitrap for isotope ratio measurements of analytes eluting directly from the gas chromatograph (GC) as traditional GC peaks — i.e. eluting over a period of seconds and with rapidly varying signal intensities. Such a measurement holds potential for simultaneous compound identification and isotope ratio measurement of numerous analytes separated by GC within a single acquisition. We applied this “direct elution” measurement strategy to molecular and fragment ions of para-xylene, serine, and a mixture of polycyclic aromatic hydrocarbons (PAHs) at natural isotope abundances. We built a mathematical model and used a Monte Carlo simulation to evaluate how variations in data processing decisions and GC peak characteristics (e.g., peak shape and elution timing) affect the accuracy of the resulting absolute isotope ratios and sample-standard comparisons (δ values). These case studies inform our recommendations for applying direct elution measurements. The method is appropriate for systems with large position-specific, molecular, or multiply-substituted isotopic anomalies (e.g., isotopically labelled or extraterrestrial compounds), and for compounds that produce strong molecular ions. Precisions improve when experiments are designed to (1) target ions with relatively high mass spectral intensities, (2) optimize the number of ions and range of masses admitted into the Orbitrap, and (3) minimize the nominal resolution settings while still separating relevant isobars.

Formation of organic sulfur compounds through SO<sub>2</sub>-initiated photochemistry of PAHs and dimethylsulfoxide at the air-water interface

Abstract. The presence of organic sulfur compounds (OS) at the water surface acting as organic surfactants, may influence the air-water interaction and contribute to new particle formation in the atmosphere. However, the impact of ubiquitous anthropogenic pollutant emissions, such as SO2 and polycyclic aromatic hydrocarbons (PAHs) on the formation of OS at the air-water interface still remains unknown. Here, we observe large amounts of OS formation in the presence of SO2, upon irradiation of aqueous solutions containing typical PAHs, such as pyrene (PYR), fluoranthene (FLA), and phenanthrene (PHE) as well as dimethylsulfoxide (DMSO). We observe rapid formation of several gaseous OSs from light-induced heterogeneous reactions of SO2 with either DMSO or a mixture of PAHs and DMSO (PAHs/DMSO), and some of these OSs (e.g. methanesulfonic acid) are well established secondary organic aerosol (SOA) precursors. A myriad of OSs and unsaturated compounds are produced and detected in the aqueous phase. The tentative reaction pathways are supported by theoretical calculations of the Gibbs energy of reactions. Our findings provide new insights into potential sources and formation pathways of OSs occurring at the water (sea, lake, river) surface, that should be considered in future model studies for a better representation of the air-water interaction and SOA formation processes.

Risk-Based Prioritization of Organic Chemicals and Locations of Ecological Concern in Sediment From Great Lakes Tributaries.

With improved analytical techniques, environmental monitoring studies are increasingly able to report the occurrence of tens or hundreds of chemicals per site, making it difficult to identify the most relevant chemicals from a biological standpoint. For the present study, organic chemical occurrence was examined, individually and as mixtures, in the context of potential biological effects. Sediment was collected at 71 Great Lakes (USA/Canada) tributary sites and analyzed for 87 chemicals. Multiple risk‐based lines of evidence were used to prioritize chemicals and locations, including comparing sediment concentrations and estimated porewater concentrations with established whole‐organism benchmarks (i.e., sediment and water quality criteria and screening values) and with high‐throughput toxicity screening data from the US Environmental Protection Agency's ToxCast database, estimating additive effects of chemical mixtures on common ToxCast endpoints, and estimating toxic equivalencies for mixtures of alkylphenols and polycyclic aromatic hydrocarbons (PAHs). This multiple‐lines‐of‐evidence approach enabled the screening of more chemicals, mitigated the uncertainties of individual approaches, and strengthened common conclusions. Collectively, at least one benchmark/screening value was exceeded for 54 of the 87 chemicals, with exceedances observed at all 71 of the monitoring sites. Chemicals with the greatest potential for biological effects, both individually and as mixture components, were bisphenol A, 4‐nonylphenol, indole, carbazole, and several PAHs. Potential adverse outcomes based on ToxCast gene targets and putative adverse outcome pathways relevant to individual chemicals and chemical mixtures included tumors, skewed sex ratios, reproductive dysfunction, hepatic steatosis, and early mortality, among others. The results provide a screening‐level prioritization of chemicals with the greatest potential for adverse biological effects and an indication of sites where they are most likely to occur. Environ Toxicol Chem 2022;41:1016–1041. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Synergistic toxicity to the toxigenic Microcystis and enhanced microcystin release exposed to polycyclic aromatic hydrocarbon mixtures

With the continued influx and accumulation of polycyclic aromatic hydrocarbons (PAHs) in eutrophic waters, the effects of PAHs on cyanobacteria bloom need to be clarified. PAHs usually existed as mixtures in aquatic environments, but the combined toxicity of PAH mixtures to toxigenic cyanobacteria remained unknown. This study investigated the effects of phenanthrene (Phe) and benzo [a]pyrene (BaP), alone or in combination, on the growth and physiology of Microcystis aeruginosa. The results showed that a hormesis effect on growth at low doses of the single Phe (≤1 mg/L) or PAH mixtures (≤0.279 mg/L) was observed, whereas the single BaP induced significant growth inhibitions at all concentrations (≥0.2 mg/L). The median effective concentrations (96 h) for Phe, BaP and their mixtures were 4.29, 1.29 and 1.07 mg/L, respectively. Mixture toxicity models showed that Phe and BaP elicited a synergistic interaction on M. aeruginosa. The synergy may be ascribed to the excessive oxidative stress induced by PAH mixtures, which further led to membrane structure damages, photosynthesis inhibitions and decreased metabolic activity. Moreover, the microcystins (MCs) release significantly increased by 25.3% and 31.9% upon exposure to 0.558 and 1.116 mg/L of PAH mixtures. In all, this study suggested that the enhanced release of MCs by PAH mixtures might exacerbate potential risks to the aquatic environment.

Intelligent Detection and Analysis of Polycyclic Aromatic Hydrocarbons Based on Surface-Enhanced Raman Scattering Spectroscopy.

Cycloaromatic hydrocarbons are a type of potentially hazardous chemicals that are widely present in the environment and pose a serious threat to human health. However, the traditional research methods for their detection process are cumbersome, the detection cycle is long, and the sensitivity is low. In response to the above problems, this article combines the molecular fingerprint information characteristics of surface-enhanced Raman scattering technology to simulate the four polycyclic aromatic hydrocarbons of pyrene, anthracene, phenanthrene, and trichenium and quantitative detection of cyclic aromatic hydrocarbons and four kinds of polycyclic aromatic hydrocarbon mixtures. The experimental results show that the PAHs based on SERS have the advantages of higher sensitivity and high selectivity, which verifies the accuracy and feasibility of the method in this article.

Quantitative analysis of polycyclic aromatic hydrocarbons using high‐performance liquid chromatography‐photodiode array‐high‐resolution mass spectrometric detection platform coupled to electrospray and atmospheric pressure photoionization sources By Anusha Priyadarshani Silva Hettiyadura and Alexander Laskin

Polycyclic aromatic hydrocarbons (PAHs) are organic environmental pollutants of primary concern because of their strong toxicological effects. They decrease immune function and can be linked to many health disorders. PAHs are mainly emitted during incomplete combustion of fossil fuel and biomass. Once they are emitted to the atmosphere, they are transported long distances by air plumes and then removed by wet and dry deposition. While airborne, they undergo atmospheric photo degradation and various oxidation reactions. The major pathway of human exposure to PAHs is through inhalation of polluted air and the health effects of the individual PAHs depend on the length and route of the exposure, relative toxicity, and the concentration levels of exposure. In this tutorial special feature, Alexander Laskin and co-workers present a methodical framework for quantitative analysis of multicomponent PAH mixtures using HPLC-PDA-HRMS, including molecular identification, quantitation and light absorbing properties of individual components. Alexander Laskin is Professor of Chemistry at Purdue University. His research interests are centered on the analytical and physical chemistry of atmospheric aerosols.

Structural Selectivity of PAH Removal Processes in Soil, and the Effect of Metal Co-Contaminants

Polycyclic aromatic hydrocarbons (PAHs) form a convenient structural series of molecules with which to examine the selectivity exerted on their removal by soil microbiota. It is known that there is an inverse relationship between PAH molecular size and degradation rates in soil. In this paper, we look at how the magnitude of the slope for this relationship, m, can be used as an indicator of the effect of metal co-contaminants on degradation rates across a range of PAH molecular weights. The analysis utilises data collected from our previous microcosm study (Deary, M.E.; Ekumankama, C.C.; Cummings, S.P. Development of a novel kinetic model for the analysis of PAH biodegradation in the presence of lead and cadmium co-contaminants. Journal of Hazard Materials 2016, 307, 240–252) in which we followed the degradation of the 16 US EPA PAHs over 40 weeks in soil microcosms taken from a high organic matter content woodland soil. The soil was amended with a PAH mixture (total concentration of 2166 mg kg−1) and with a range of metal co-contaminant concentrations (lead, up to 782 mg kg−1; cadmium up to 620 mg kg−1; and mercury up to 1150 mg kg−1). It was found that the magnitude of m increases in relation to the applied concentration of metal co-contaminant, indicating a more adverse effect on microbial communities that participate in the removal of higher molecular weight PAHs. We conclude that m is a useful parameter by which we might measure the differential effects of environmental contaminants on the PAH removal. Such information will be useful in planning and implementing remediation strategies.

The Carcinogenic Properties of Overlooked yet Prevalent Polycyclic Aromatic Hydrocarbons in Human Lung Epithelial Cells.

The WHO classified air pollution as a human lung carcinogen and polycyclic aromatic hydrocarbons (PAHs) are components of both indoor (e.g., tobacco smoke and cookstoves) and outdoor (e.g., wildfires and industrial and vehicle emissions) air pollution, thus a human health concern. However, few studies have evaluated the adverse effects of low molecular weight (LMW) PAHs, the most abundant PAHs in the environment. We hypothesized that LMW PAHs combined with the carcinogenic PAH benzo[a]pyrene (B[a]P) act as co-carcinogens in human lung epithelial cell lines (BEAS-2B and A549). Therefore, in this paper, we evaluate several endpoints, such as micronuclei, gap junctional intercellular communication (GJIC) activity, cell cycle analysis, anti-BPDE-DNA adduct formation, and cytotoxicity after mixed exposures of LMW PAHs with B[a]P. The individual PAH doses used for each endpoint did not elicit cytotoxicity nor cell death and were relevant to human exposures. The addition of a binary mixture of LMW PAHs (fluoranthene and 1-methylanthracene) to B[a]P treated cells resulted in significant increases in micronuclei formation, dysregulation of GJIC, and changes in cell cycle as compared to cells treated with either B[a]P or the binary mixture alone. In addition, anti-BPDE-DNA adducts were significantly increased in human lung cells treated with B[a]P combined with the binary mixture of LMW PAHs as compared to cells treated with B[a]P alone, further supporting the increased co-carcinogenic potential by LMW PAHs. Collectively, these novel studies using LMW PAHs provide evidence of adverse pulmonary effects that should warrant further investigation.

Prenatal urinary metabolites of polycyclic aromatic hydrocarbons and toddler cognition, language, and behavior.

Animal and epidemiological studies suggest that prenatal exposure to polycyclic aromatic hydrocarbons (PAHs) may negatively impact toddler neurodevelopment. We investigated this association in 835 mother-child pairs from CANDLE, a diverse pregnancy cohort in the mid-South region of the U.S. PAH metabolite concentrations were measured in mid-pregnancy maternal urine. Cognitive and Language composite scores at ages 2 and 3years were derived from the Bayley Scales of Infant and Toddler Development, 3rd edition (Bayley-3). Behavior Problem and Competence scores at age 2 were derived from the Brief Infant and Toddler Social Emotional Assessment (BITSEA). We used multivariate linear or Poisson regression to estimate associations with continuous scores and relative risks (RR) of neurodevelopment delay or behavior problems per 2-fold increase in PAH, adjusted for maternal health, nutrition, and socioeconomic status. Secondary analyses investigated associations with PAH mixture using Weighted Quantile Sum Regression (WQS) with a permutation test extension. 1- hydroxypyrene was associated with elevated relative risk for Neurodevelopmental Delay at age 2 (RR=1.20, 95% CI: 1.03,1.39). Contrary to hypotheses, 1-hydroxynaphthalene was associated with lower risk for Behavior Problems at age 2 (RR=0.90, 95% CI: 0.83,0.98), and combined 1- and 9-hydroxyphenanthrene was associated with 0.52-point higher (95% CI: 0.11,0.93) Cognitive score at age 3. For PAH mixtures, a quintile increase in hydroxy-PAH mixture was associated with lower Language score at age 2 (βwqs=-1.59; 95% CI: -2.84, -0.34; ppermutation=0.07) and higher Cognitive score at age 3 (βwqs=0.96; 95% CI: 0.11, 1.82; ppermutation=0.05). All other estimates were consistent with null associations. In this large southern U.S. population we observed some support for adverse associations between PAHs and neurodevelopment.

Tobacco-specific and combustion pollutants in settled house dust in Malta.

Aim:Most of the carcinogenic pollutants coming from tobacco smoking or other combustion processes tend to accumulate in settled house dust (SHD) over time. This study evaluated the load of these pollutants in smokers and non-smokers’ houses from relatively fresh SHD collected in five different districts on the island of Malta.Methods:An improved, efficient extraction method to obtain three fractions from a 200 mg of SHD was developed. It was validated for the analysis of nicotine and polycyclic aromatic hydrocarbons (PAH) by GC-MS/MS and nicotelline and TSNA by LC-MS/MS. Kruskal-Wallis H tests were used to evaluate differences across districts, while a Mann-Whitney U test was used to check differences between smokers and non-smokers’ houses. Diagnostic ratios were used to evaluate the carcinogenicity of PAH in SHD in Malta.Results:For all analytes, no statistical difference was observed across different districts, but, in smokers’ houses, 97.9% of the total concentration of all target analytes found in SHD is nicotine, 0.1% is TSNA, and 2.0% is PAH. In non-smokers’ houses, nicotine represents 16.8% of the load, while 0.4% and 82.8% are TSNA and PAH, respectively. The carcinogenicity of the PAH mixture in Maltese SHD, expressed as the mean benzo(a)pyrene equivalent (BaPeq) is 371 ng/g.Conclusion:Indoor activities, ventilation practices, and infiltration of outdoor pollutants contribute to a complex SHD composition. Although the BaPeq is on the lower end of carcinogenicity, the effects of a mixture including tobacco-related potent carcinogens in SHD are largely unknown. In view of indoor, continuous exposure to SHD through several pathways, further research is warranted.

New insights into denitrification and phosphorus removal with degradation of polycyclic aromatic hydrocarbons in two-sludge system

Polycyclic aromatic hydrocarbons (PAHs) have led to failure of waste water treatment plant operations. In this study, a two-sludge system was used to solve this problem of simultaneously removing phosphorus, nitrogen, and PAHs. The results showed that increasing the maximum PAHs concentration to 15 mg/L did not have any negative effect on the removal rates of total nitrogen (79.68%) and chemical oxygen demand (75.94%); however, the phosphorus removal efficiency decreased to 61.16%. The system exhibited a stronger degradation ability for phenanthrene. Thauera, Hydrogenophaga, and Hyphomicrobium were enriched, which resulted in good denitrification, and contributed to PAHs removal. PAHs mixture promoted PAHs functional genes but restrained denitrification functional genes. However, single naphthalene enhanced denitrification functional genes, which confirmed the feasibility of denitrification coupled with PAHs degradation. In conclusion, for the removal of pollutants from sewage treatment, nitrogen and phosphorus removal coupled with PAHs could be maintained by selecting a two-sludge system.

Environmental dose of 16 priority-controlled PAHs mixture induce damages of vascular endothelial cells involved in oxidative stress and inflammation

Epidemiological studies have shown that cardiovascular diseases caused by PM2.5 pollution account for the second death rate in China. Polycyclic aromatic hydrocarbons (PAHs) are one important group of persistent organic pollutants absorbed on PM2.5. Though individual PAH is related to vascular disease, the relationship between environmental PAHs exposure and vascular damages is still unclear. To explore the effect of PAHs on blood vessel, human umbilical vein endothelial cells (HUVECs) are treated with 16 priority–controlled PAHs at various concentrations to study their cytotoxicity and morphological alteration. Results showed that, after 48 h treatment, PAHs mixture generally attenuated the ability of wound healing, transwell migration and tube formation of HUVECs (p < 0.01) except for 1 × PAHs in transwell migration. Moreover, PAHs increased the levels of ROS and 8-hydroxy-2′-deoxyguanosine (p < 0.05), indicating that it exceeded the scavenging ability of superoxide dismutase activity. However, PAHs mixture did not increase apoptosis rate, which may be attribute to the difference of PAH concentration and composition between this study and previous reports. Downstream signaling cascades significantly and generally upregulated the relative expression of proteins in Nrf2/HO-1 and NF-ƙB/TNF-α pathway with the activation of oxidative stress, including HO-, TNF-α and Nrf2. In summary, this study suggests that environmental mixture of 16 priority-controlled PAHs can induce the damages of vascular endothelial cells involved in cellular oxidative stress and inflammation.