Chlorinated and brominated polycyclic aromatic hydrocarbons (Cl/Br-PAHs) are persistent organic pollutants with potential carcinogenic toxicities that are even higher than those of their parent PAH congeners. Current knowledge of Cl/Br-PAH sources and emission characteristics is lacking. Electric arc furnace (EAF) steelmaking is a potential source for Cl/Br-PAHs, considering that preheating of raw materials before they enter the EAF could produce suitable conditions for Cl/Br-PAHs formation. In this field study, we identified EAFs as an important source of Cl/Br-PAHs and clarified their emission concentrations, fingerprints by gas chromatography coupled with high-resolution magnetic mass spectrometry. Potential formation mechanisms of Cl/Br-PAHs were also proposed. The mass concentration ranges for Σ₁₈Cl-PAHs and Σ₁₈Br-PAHs in stack gas were 25.85–4191 ng Nm⁻³ and 1.02–341 ng Nm⁻³, respectively. The variation of concentration indicated that the steel scrap composition greatly affected the production of Cl/Br-PAHs. The congener ratios including 6-chlorobenzo [a]pyrene/3-chlorofluoranthene and 1-chloroanthracene/1-chloropyrene could be used to estimate the influence of industrial sources on Cl-PAH occurrences in the air. Ring structure growth was the dominant formation pathway for Cl/Br-PAHs, distinctly different from dioxin formation mechanisms dominated by precursor dimerization and chlorination.

Nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are receiving attention because of their high toxicity compared with parent PAHs. However, the experimental data of their physicochemical properties has been limited. This study proposed the gas chromatographic retention time (GC-RT) technique as an effective alternative one to determine octanol-air partition coefficients (KOA) and sub-cooled liquid vapor pressures (PL) for 11 NPAHs, 10 OPAHs, and 19 parent PAHs. The slopes and intercepts of the linear regressions between temperature versus KOA and PL were provided and can be used to estimate KOA and PL for the 40 targeted compounds at any temperature. The internal energies of phase transfer (ΔUOA) and enthalpies of vaporization (ΔHL) for all targeted compounds were also calculated using the GC-RT technique. High-molecular-weight compounds may release or absorb higher heat energy to transform between different phases. NPAHs and OPAHs had a non-ideal solution behavior with activity in octanol (γₒcₜ) in the range of 19–53 and 18–1,078, respectively, which is larger than the unity threshold. A comparison among four groups of PAH derivatives showed that a functional group (nitro-, oxygen-, chloro-, and bromo-) in PAH derivatives increased γₒcₜ for corresponding parent PAHs by tens (mono-group) to hundreds of times (di-group). This study suggests that the GC-RT method is applicable for indirectly measuring the physicochemical properties of various groups of organic compounds.

The association of co-exposure to polycyclic aromatic hydrocarbons (PAHs) and phthalates (PAEs) with blood cell-based inflammatory biomarkers is largely unknown. We conducted a panel study of 144 children aged 4–12 years, with up to 3 repeated visits across 3 seasons. For each visit, we collected the first-morning urine for 4 consecutive days and fasting blood on the day of physical examination. We developed a gas chromatography/tandem mass spectrometry method to detect the metabolites of 10 PAHs (OH-PAHs) and 10 PAEs (mPAEs) in urine samples. We employed linear mixed-effects models to evaluate the individual associations of each OH-PAH and mPAE with blood cell-based inflammatory biomarkers over different lag times. Bayesian kernel machine regression (BKMR) and quantile g-computation were used to evaluate the overall associations of OH-PAHs and mPAEs mixtures with blood cell-based inflammatory biomarkers. After multiple adjustments, we found positive associations of summed hydroxylphenanthrene (∑OHPHE), summed OH-PAHs, and mono-n-butyl phthalate with inflammatory biomarkers such as neutrophil count, neutrophil-to-lymphocyte ratio, platelet-to-lymphocyte ratio, and the systemic immune-inflammation index (SII) at lag 0 (the day of physical examination). Each 1% increase in ∑OHPHE was related to a 0.18% (95% confidence interval: 0.10%, 0.25%) increase in SII, which was the strongest among the above associations. The results of BKMR and quantile g-computation suggested that co-exposure to PAHs and PAEs mixture was associated with an elevated white blood cell count, neutrophil count, neutrophil-to-lymphocyte ratio, platelet-to-lymphocyte ratio, and SII, to which ∑OHPHE and 1-hydroxypyrene (1-OHPYR) might be the major contributors. In addition, gender and age modified the associations of ∑OHPHE and 1-OHPYR with inflammatory biomarkers, where girls and younger children were more susceptible. In conclusion, co-exposure to PAHs and PAEs was associated with elevated inflammation in children, in which ∑OHPHE and 1-OHPYR might play important roles.

The endocrine-disrupting effects of human exposure to polybrominated diphenyl ethers (PBDEs) have been studied, but their associations with menstrual status were not clearly clarified. This study was to evaluate the associations between PBDE levels in adipose tissues and the menstrual cycle and menstrual bleeding duration alteration. A total of 298 female cases undergoing surgery were recruited from two hospitals in Shantou, China. Demographic, clinical, and pathological information were collected, and adipose tissues were obtained during mammary or abdominal surgery. Gas chromatography with mass spectrometry was used to analyze 14 PBDE congeners in the adipose samples. The associations between PBDE levels and menstrual cycle (MC) and menstrual duration (MD) were analyzed by logistic regression models, estimating odds ratios (ORs) and 95% confidence intervals (CIs). BDE-153 had the highest level in the adipose samples, followed by BDE-209, BDE-183 and BDE-47. Compared with referents, median levels of BDE-47, -71, −153, −183 were higher in women with MC > 30 days (all P < 0.05); BDE-47, -153, −183, −209 were also higher in women with MD > 5.5 days (all P < 0.05). After adjusted for age and parity, BDE-47, -71, −153, −183 were associated with prolonged MC (OR = 1.20, 1.15, 1.12, 1.11, respectively, all P < 0.05) in the logistic regression models; and BDE-47, -153, −183, −209 were associated with the prolonged MD (OR = 1.13, 1.09, 1.10, 1.11, respectively, all P < 0.05). Several individual PBDE congeners in female adipose were found associated with prolonged menstrual cycle and menstrual duration. PBDEs may influence reproductive health of women by altering menstrual status.

Concentrations of polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) in the atmosphere of Ny-Ålesund, Svalbard, were investigated. Passive air samples were collected for eight consecutive one-year periods from August 2011 to August 2019 at seven Arctic sampling sites. High-resolution gas chromatography coupled with high-resolution mass spectrometry (HRGC-HRMS) and gas chromatography coupled with election capture negative ionization mass spectrometry (GC-NCI-MS) were employed for PBDE and NBFR analysis, respectively. The median concentrations of Ʃ₁₁PBDEs and Ʃ₆NBFRs were 0.6 pg/m³ and 4.0 pg/m³, respectively. Hexabromobenzene and BDE-47 were the most abundant NBFR and PBDE congeners in the atmosphere, accounting for 31% and 24% of ƩNBFR and ƩPBDE concentrations, respectively. ƩNBFR concentration was approximately six times higher than that of ƩPBDEs in the same samples. Among NBFRs, the concentrations of 1,2,3,4,5-pentabromobenzene, 2,3,4,5,6-pentabromobenzene, and 2,3-dibromopropyl-2,4,6-tribromophenyl ether showed increasing temporal variations, with estimated doubling times of 3.0, 3.3, and 2.8 years, respectively. The concentrations of almost all PBDE congeners showed a decreasing variation, with halving times ranging from 2.1 to 9.5 years.

Organic matter from salmon farms has been shown to be assimilated by soft sediment and rocky reef communities within the ecological footprint of salmon farms. Given these findings, another question arises – What other chemicals in salmon feed may be assimilated into wild communities via organic waste from salmon farms? Here we measured a suite of organic contaminants in salmon feed, in organisms used in a controlled feeding experiment, and in reef species collected within the depositional footprint of salmon farms. Gas Chromatography-Tandem Mass Spectrometry was used to quantify trace concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and current-use (CPUs) and historic-use pesticides (HUPs) in salmon feed imported to New Zealand. The effect of assimilation of farm-derived organic matter on contaminant profiles differed among species during the controlled feeding experiment and demonstrated that migration of individuals to a farm-associated site has the potential to increase or decrease organic contaminant concentrations. Concentrations of PCBs in Parapercis colias (blue cod), a highly resident, long-lived fish, were significantly higher at farm sites than at reference sites. While these concentrations were relatively low in a global context, this result presents blue cod as an important candidate for future monitoring of organic contaminants around point sources. PCBs and PBDEs measured in wild marine species were all below limits set by the European Union, whereas concentrations of certain HUPs, specifically dichlorodiphenyltrichloroethane (DDT) and its degradation products and endosulfan, may be of concern as a consequence of alternative anthropogenic activities. Overall, feed imported to New Zealand had relatively low levels of most organic contaminants that, at current levels, are unlikely to result in significant ecological effects to wild communities in adjacent habitats.

Clothes may contain a large range of chemical additives and other toxic substances, which may eventually pose a significant risk to human health. Since they are associated with pigments, polychlorinated biphenyls (PCBs) may be especially relevant. On the other hand, infants are very sensitive to chemical exposure and they may wear some contact and colored textiles for a prolonged time. Consequently, a specific human health risk assessment is required. This preliminary study was aimed at analyzing the concentrations of PCBs in ten bodysuits purchased in on-line stores and local retailers. The concentrations of 12 dioxin-like and 8 non-dioxin-like PCB congeners were determined by gas chromatography coupled to high resolution mass spectrometry, with detection limits ranging between 0.01 and 0.13 pg/g. The dermal absorption to PCBs of children at different ages (6 months, 1 year and 3 years old) was estimated, and the non-cancer and cancer risks were evaluated. Total levels of PCBs ranged from 74.2 to 412 pg/g, with a mean TEQ concentration of 13.4 pg WHO-TEQ/kg. Bodysuits made of organic cotton presented a total mean PCB concentration substantially lower than clothes made of regular cotton (11.0 vs. 15.8 pg WHO-TEQ/kg). The dermal absorption to PCBs for infants was calculated in around 3·10⁻⁵ pg WHO-TEQ/kg·day, regardless the age. This value is > 10,000-fold lower than the dietary intake of PCBs, either through breastfeeding or food consumption. Furthermore, this exposure value would not pose any health risks for the infants wearing those bodysuits. Anyhow, as it is a very preliminary study, this should be confirmed by analyzing larger sets of textile samples. Further investigations should be also focused on the co-occurrence of PCBs and other toxic chemicals (i.e., formaldehyde, bisphenols and aromatic amines) in infant clothes.

Brominated flame retardants (BFRs) are chemicals employed to lower the flammability of several objects. These endocrine disruptor chemicals are lipophilic and persistent in the environment. Due to these characteristics some have been restricted or banned by the European Union, and replaced by several new chemicals, the novel BFRs (NBFRs). BFRs are widely detected in human samples, such as adipose tissue and some were linked with altered thyroid hormone levels, liver toxicity, diabetes and metabolic syndrome in humans. However, the disturbance in lipid metabolism caused by BFRs with emphases to NBFRs remains poorly understood. In this study, we used a pre-adipocyte (3T3-L1) cell line and a hepatocyte (HepG2) cell line to investigate the possible lipid metabolism disruption caused by four BFRs: hexabromobenzene (HBB), pentabromotoluene (PBT), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) and hexabromocyclododecane (HBCD). For that purpose, proliferation and Oil Red O assays, as well as, medium fatty acids profile evaluation using Gas chromatography and RNA extraction for quantitative RT-PCR assays were performed. We detected a significant reduction in the proliferation of preadipocytes and an increased lipid accumulation during differentiation caused by HBB. This BFR also lead to a significant increased expression of IL-1β and decreased expression of PGC-1α and adiponectin. Nevertheless, PBT, TBB and HBCD show to increase lipid accumulation in hepatocytes. PBT also display a significant increase of PPARγ gene expression. Lipid accumulation in the cells can occur by diverse mechanisms depending on the BFR. These results highlight the importance of endocrine disruptor compounds in obesity etiopathogeny.

To investigate tissue distribution, spatial difference, temperature variation, and potential health risks of PAEs in vegetables, celery was used as a model plant. Celery samples were collected from open fields and greenhouses from two provinces in China over four seasons. Celery tissues were analyzed for 16 PAE compounds by gas chromatography–tandem mass spectrometry. The total content of PAEs was 89.0–1130.3 μg kg⁻¹ dry weight (dw) in stems and 155.0–2730.8 μg kg⁻¹ dw in leaves. Concentrations of PAEs in celeries showed notable spatial differences (P < 0.05), and the levels in samples from open fields were lower than those in samples from plastic greenhouses. In celeries from greenhouses, higher PAE concentrations were observed for plants grown at high temperatures than in plants grown at low temperatures. Discrepancies in tissue distribution indicated different uptake pathways of PAE contaminants. Risk assessments to humans found that both carcinogenic risks and non-carcinogenic risks of PAEs via celery consumption were at an acceptable level. Further research should consider other exposure pathways of PAEs and pay special attention to reducing PAE contents in vegetables.

This is the first report about the presence of pesticide residues in water and sediments from Chacahua-Pastoria Lagoon System in the Oaxaca Coast, Mexico. Organochlorine and organophosphate pesticides were analyzed in water and sediment samples collected during rainy and dry seasons in 2018. The pesticides extraction was carried out by 525.2 EPA and QuEChERS methods for water and sediments samples, respectively. The quantification was done by gas chromatography coupled to electron microcapture (μECD) and flame photometric (FPD) detectors. Univariate and multivariate analysis were carried out to evaluate the distribution patterns, comparing between lagoons, seasons and matrices. The spatial distribution of malathion and organochlorines in water showed the highest values near to adjacent land with some patterns differences. DDT was the most frequent in water and sediments samples, showed the highest concentrations in the Pastoria Lagoon. These results indicate the need to establish a permanent monitoring programs to implement mitigation measures.