The management of digested sludge derived from treatment water plants is a problem worldwide due to the possible transfer of contamination from sludge to amended soil and, in turn, to humans. Within this work, through a chemometric experimental design, a robust GC-MS method for the simultaneous determination of two classes of micropollutants of concern (polycyclic aromatic hydrocarbons-PAHs-and polychlorinated biphenyls-PCBs-including dioxin-like compounds) was developed using microwave-assisted extraction (MAE). The method, which showed interesting greenness features in compliance with the 12 principles of Green Chemistry, allowed PCB and PAH extraction with recoveries higher than 75% (RSD < 14%) with method detection limits between 4.6 and 11.5 µg kg-1 (PAHs) and between 6.9 and 13.7 µg kg-1 (PCBs), without preconcentration. The matrix effect was below 20%. The validated protocol allowed the characterization of two digested sludges sampled in an urban and a peri-urban district, representative models of two scenarios of different anthropic impacts. This study highlighted higher contamination for the sludge derived from the urban area, accounted for by the 4-ring PAHs. In addition, since carcinogenic PAHs were detected, the environmental risk (by mean of the comparison of predicted vs predicted no-effect concentrations) and the carcinogenic human risk from dermal contact (through the calculation of the adsorbed lifetime average daily dose) were assessed in the case of soils amended with the sludges considered, pointing out that the measured concentrations do not pose a risk.

OBJECTIVE: Polycyclic aromatic hydrocarbons (PAHs), present in air and food, generated during energy production and waste incineration, are known for health toxicity. PAHs may activate the aryl hydrocarbon receptor, which could in turn modify estrogen-dependent inflammatory pathways in endometriosis. The possible role of PAHs in the pathogenesis of endometriosis remains unclear. The study aimed to evaluate the potential link between exposure to PAHs and the occurrence of peritoneal and ovarian endometriosis.
METHODS: A prospective case-control tertiary-center study included 46 women aged 22-45 undergoing laparoscopy due to pelvic endometriosis (n ​= ​32; arm 1) and idiopathic infertility (n ​= ​14; arm 2). A sample of the greater omentum was collected intraoperatively for detection of 16 standard PAHs by gas chromatography-isotope dilution mass spectrometry method. PAHs concentrations were compared in both study arms. The associations between PAHs concentrations and selected variables were investigated.
RESULTS: There were no significant differences between both arms in terms of reference PAHs concentrations, nor correlations between PAHs concentrations and the stage of endometriosis. However, notable differences were observed in specific PAHs concentrations related to certain conditions. The concentrations of acenaphthene (p ​= ​0.016) and fluorene (p ​= ​0.013) were significantly lower in women with peritoneal adhesions, while the concentrations of benz[a]anthracene, benzo[k]fluoranthene and indeno[1,2,3-cd]pyrene [ng/g] were higher in cigarette smokers.
CONCLUSIONS: The study showed no differences in exposure to PAHs between women with and without pelvic endometriosis. Determining the toxicity of PAHs in endometriosis requires further research.

Chemical and microlitter (ML) pollution in three Estonian coastal areas (Baltic Sea) was investigated using mussels (Mytilus trossulus). Polycyclic aromatic hydrocarbons (PAH) in mussel tissues were observed in moderate levels with high bioaccumulation factors for the more hydrophilic and low molecular weight PAH (LMW PAH), namely anthracene and fluorene. Tissue concentrations of polybrominated diphenyl ethers (PBDE) and cadmium within mussel populations exceeded the Good Environmental Status thresholds by more than 200% and 60%, respectively. Multiple contamination at the Muuga Harbour site by tributyltin, high molecular weight PAH, including the highly toxic benzo[c]fluorene and PBDE, coincided with the inhibition of acetylcholinesterase activity and a lower condition index of the mussels. The metabolization and removal of bioaccumulated LMW PAH, reflected in the dominance of oxy-PAH such as anthracene-9,10-dione, is likely associated with the increased activity of glutathione S-transferase in caged mussels. Only a few microplastic particles were observed among the ML in mussel tissues, with coloured cellulose-based microfibers being the most prevalent. The average concentration of ML in mussels was significantly higher at the harbour area than at other sites. The integrated biomarker response index values allowed for the differentiation of pollution levels across studied locations representing high, intermediate, and low pollution levels within the studied area.

There is considerable inconsistency in results pertaining to the biomagnification of PAHs in aquatic systems. Zooplankton specifically play an important role controlling the fate and distribution of organic contaminants up the food chain, particularly in large plateau reservoirs. However, it remains largely unknown how secondary factors affect the magnification of organic compounds in zooplankton. The present study assessed plankton species and nutrients affecting the trophic transfer of PAHs through the micro-food chain in plateau reservoirs, Guizhou Province China. Results show soluble ∑PAHs range from 99.9 - 147.3 ng L-1, and concentrations of ∑PAHs in zooplankton range from 1003.2 - 22441.3, with a mean of 4460.7 ng g-1 dw. Trophic magnification factors (TMFs) > 1 show biomagnifications of PAHs from phytoplankton to zooplankton. The main mechanisms for trophic magnification > 1 are 1) small Copepoda, Cladocera and Rotifera are prey for larger N. schmackeri and P. tunguidus, and 2) the δ15N and TLs of zooplankton are increasing with the increasing nutrients TN, NO3- and CODMn. As a result, log PAHs concentrations in zooplankton are positively correlated with the trophic levels (TLs) of zooplankton, and log BAFs of the PAHs in zooplankton are increasing with increasing TLs and log Kow. Temperature further enhances TMFs and biomagnifications of PAHs as noted by temperature related reductions in δ15N. There are also available soluble PAHs in the water column which are assimilated with increasing phytoplankton biomass within the taxa groups, diatoms, dinoflagellates and chlorophytes. Notable TMFs of PAHs in zooplankton in Guizhou plateau reservoirs are not significantly affected by phytoplankton and zooplankton biomass dilutions. The present study demonstrates the important roles of species selection, nutrients and temperature in the environmental fate of PAHs in freshwaters.

Infrared (IR) emission bands by interstellar polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic nitrogen heterocycles (PANHs) are observed towards a large variety of interstellar objects and offer detailed insights into the chemistry and physics of the interstellar medium. The analysis of the emission bands, and thus the interpretation of the molecular characteristics of the carriers, heavily relies on the use of density functional theory (DFT) calculated IR spectra. However, there are significant challenges in accurately predicting the experimental IR band positions, particularly for PANH emission vibrational modes around 6 μm. In this work, we present gas-phase mid-infrared (mid-IR) spectra of cationic 3-azafluoranthene (3AF⋅+) and protonated 3-azafluoranthene (3AFH+) to investigate their experimental IR band positions in relation to DFT calculated bands. The experimental spectra are compared to DFT simulated spectra, where different approaches were followed to correct for anharmonicities. The best agreement is achieved by scaling frequencies of modes with large nitrogen displacements with a different factor. Even though our findings might be limited to a small number of PANH structures, they indicate, that nitrogen atom incorporation needs to be accounted for by carefully adjusting the corresponding scaling factors while computing IR spectra of PANHs on DFT level.

OBJECTIVE: Polycyclic aromatic hydrocarbons (PAHs) represent a class of ubiquitous pollutants recognized as established human carcinogens and endocrine-disrupting chemicals. PAHs have seldom been modeled at the population-level in epidemiological studies. Fluoranthene is a prevalent PAH in urban settings and correlates with the occurrence of other PAHs. The purpose of this study was to evaluate associations between long-term residential exposure to ambient PAHs and breast cancer risk, both pre- and post-menopausal, in Canada.
METHODS: Using the National Enhanced Cancer Surveillance System (NECSS), a national-scale Canadian population-based case-control study, annual fluoranthene exposures were estimated using the GEM-MACH-PAH chemical transport model on the basis of geocoded residential histories throughout a 20-year exposure window. Odds ratios (ORs) and 95% confidence intervals (CIs) controlling for potential confounders were estimated using logistic regression. Separate analyses were conducted for Ontario and national samples given a finer-resolution exposure surface and additional risk factor information available for Ontario.
RESULTS: Positive associations were observed between fluoranthene exposure and premenopausal breast cancer, with inconsistent findings for postmenopausal breast cancer. For premenopausal breast cancer, adjusted ORs of 2.48 (95% CI: 1.29, 4.77) and 1.59 (95% CI: 1.11, 2.29) were observed when comparing the second highest category of exposure to the lowest, among the Ontario and national samples, respectively. For postmenopausal breast cancer, adjusted ORs were 1.10 (95% CI: 0.67, 1.80) and 1.33 (95% CI: 1.02, 1.73). Associations for the highest level of exposure, across both samples and menopausal strata, were non-significant.
CONCLUSIONS: This study provides support for the hypothesis that ambient PAH exposures increase the risk of premenopausal breast cancer.

Birds are excellent bioindicators of environmental pollution, and blood provides information on contaminant exposure, although its analysis is challenging because of the low volumes that can be sampled. The objective of the present study was to optimize and validate a miniaturized and functional extraction and analytical method based on gas chromatography coupled to Orbitrap mass spectrometry (GCOrbitrap-MS) for the trace analysis of contaminants in avian blood. Studied compounds included 25 organochlorine pesticides (OCPs), 6 polychlorinated biphenyls (PCBs), 8 polybrominated diphenyl ethers (PBDEs) and 15 polycyclic aromatic hydrocarbons (PAHs). Four extraction and clean-up conditions were optimized and compared in terms of efficiency, accuracy, and uncertainty assessment. Extraction with hexane:dichloromethane and miniaturized Florisil pipette clean-up was the most adequate considering precision and accuracy, time, and costs, and was thereafter used to analyse 20 blood samples of a pelagic seabird, namely the Bermuda petrel (Pterodroma cahow). This species, endemic to the Northwest Atlantic, is among the most endangered seabirds of the region that in the \'60 faced a decrease in the breeding success likely linked to a consistent exposure to dichloro-diphenyl-trichloroethane (DDT). Indeed, p,p\'-DDE, the main DDT metabolite, was detected in all samples and ranged bewteen 1.13 and 6.87 ng/g wet weight. Other ubiquitous compounds were PCBs (ranging from 0.13 to 6.76 ng/g ww), hexachlorobenzene, and mirex, while PAHs were sporadically detected at low concentrations, and PBDEs were not present. Overall, the extraction method herein proposed allowed analysing very small blood volumes (∼ 100 µL), thus respecting ethical principles prioritising the application of less-invasive sampling protocols, fundamental when studying threatened avian species.

This study addresses the sources of aliphatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) in the surface sediments of the northwestern Persian Gulf and the muscle tissues of Jinga shrimp (Metapenaeus affinis), a commercially important aquatic species. In November 2018, 28 Jinga shrimp samples were systematically collected from four key fishing areas in Behrgan and Khormusi: Imam Khomeini Port (S1), Mahshahr Port (S2), Sejafi (S3), and Behrgan Wharf (S4). Additionally, sediment samples were collected from these locations, and AHs and PAHs concentrations were analyzed using gas chromatography-mass spectrometry (GC-MS). The average aliphatic concentration in Jinga shrimp was 4800.32 (μg g-1 DW), exceeding the sediment samples\' 2496.69 (μg g-1 DW) estimate. Hydrocarbon component analysis revealed EPA priority list (PAH-16) and measured PAHs (PAH-29) concentrations in Jinga shrimp ranging from 1095.8 to 2698.3 (ng g-1 DW) and in sediments from 653.6 to 1019.5 (ng g-1 DW). Elevated AHs and PAHs in Jinga shrimp, compared to sediments, suggest a petrogenic source, notably at station S4 near Behrgansar and Nowruz oil fields. Low molecular weight (LMW) compounds dominated in both shrimp and sediment PAHs. Aliphatic composition profiles in shrimps closely mirrored sediment profiles, illustrating an even-to-odd carbon dominance gradient. Diagnostic ratio examinations of hydrocarbons indicated pervasive petroleum derivatives in the environment. This study establishes a direct correlation between hydrocarbon concentrations in shrimp and sediment samples and the corresponding aliphatic groups, PAH-16, and PAH-29. The findings underscore the potential of Jinga shrimp as a reliable indicator of hydrocarbon pollution in the northwestern Persian Gulf.

XRCC1 is involved in repair of single-strand breaks generated by mutagenic exposure. Polymorphisms within XRCC1 affect its ability to efficiently repair DNA damage. Polycyclic aromatic hydrocarbons or PAHs are genotoxic compounds which form bulky DNA adducts that are linked with infertility. Few reports suggest combined role of XRCC1 polymorphisms and PAHs in infertility. Present study investigates association of three XRCC1 polymorphisms (p.Arg194Trp, p.Arg280His, p.Arg399Gln) with male and female infertility in a North-West Indian population using case-control approach. Additionally, in silico approach has been used to predict whether XRCC1 polymorphisms effect interaction of XRCC1 with different PAHs. For case-control study, XRCC1 polymorphisms were screened in peripheral blood samples of age- and gender-matched 201 infertile cases (♂-100, ♀-101) and 201 fertile controls (♂-100, ♀-101) using PCR-RFLP method. For in silico study, AutoDock v4.2.6 was used for molecular docking of B[a]P, BPDE-I, ( ±)-anti-BPDE, DB[a,l]P, 1-N, 2-N, 1-OHP, 2-OHF with XRCC1 and assess effect of XRCC1 polymorphisms on their interaction. In case-control study, statistical analysis showed association of XRCC1 p.Arg280His GA genotype (p = 0.027), A allele (p = 0.019) with reduced risk of male infertility. XRCC1 p.Arg399Gln AA genotype (p = 0.021), A allele (p = 0.014) were associated with reduced risk for female primary infertility. XRCC1 p.Arg194Trp T allele was associated with increased risk for female infertility (p = 0.035). In silico analysis showed XRCC1-PAH interaction with non-significant effect of XRCC1 polymorphisms on predicted binding. Therefore, present study concludes that XRCC1 polymorphism-modified risk for male and female infertility in North-West Indians without significant effect on predicted XRCC1-PAH interactions. This is the first report on XRCC1 in female infertility.

Increasing use of chemical dispersants for oil spills highlights the need to understand their adverse effects on marine microalgae and nutrient assimilation because the toxic components of crude oil can be more bioavailable. We employed the crude oil water-accommodated fraction (WAF) and chemically enhanced WAF (CEWAF) to compare different responses in marine microalgae (Phaeodactylum tricornutum) coupled with stable isotopic signatures. The concentration and proportion of high-molecular-weight polycyclic aromatic hydrocarbons (HMW PAHs), which are key toxic components in crude oil, increased after dispersant addition. CEWAF exposure caused higher percent growth inhibition and a lower chlorophyll-a level of microalgae than those after WAF exposure. Compared with WAF exposure, CEWAF led to an enhancement in the self-defense mechanism of P. tricornutum, accompanied by an increased content of extracellular polymeric substances. 13C-depletion and carbon assimilation were altered in P. tricornutum, suggesting more HMW PAHs could be utilized as carbon sources by microalgae under CEWAF. CEWAF had no significant effects on the isotopic fractionation or assimilation of nitrogen in P. tricornutum. Our study unveiled the impact on the growth, physiological response, and nutrient assimilation of microalgae upon WAF and CEWAF exposures. Our data provide new insights into the ecological effects of dispersant applications for coastal oil spills.