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Little information exists on the fate and impacts of boats constructed of fibreglass reinforced plastic (FRP) once they reach their end-of-life. In this study, the number of abandoned fishing boats constructed of FRP or constructed of plywood-wood and sheathed by FRP has been determined along the coast of Kerala, India, and chemical emissions have been estimated when boats are burned as a means of disposal. A total of 292 abandoned boats were observed across eight coastal transects constructed around selected landing centres, with abandonment ranging from 13 to 48 per km (average = 29 km-1). This results in the generation of 1420 kg of FRP debris (glass mat and epoxy resin) per km of coastline. A controlled combustion experiment, simulating open burning, revealed that 63% of original boat mass is emitted to the atmosphere, with the remainder forming a burnt residue. Total concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans emitted and remaining were found to be 2.6 ng Nm-3 and 249.6 µg kg-1, respectively, with respective calculated toxicity equivalence (TEQ) levels of 437.6 pg TEQ Nm-3 in air emissions and 26.6 µg TEQ kg-1 in the residue. These figures are equivalent to the total emission from FRP boat burning of about 17,000 µg TEQ t-1. Burning also generates significant quantities of potentially toxic metals, with resulting concentrations of Co, Cr and Cu close to or exceeding soil guideline values. The study calls for a greater awareness of the impacts arising from boat abandonment and burning amongst fishermen, and guidelines or regulatory protocols regarding safe and sustainable boat disposal or recycling.

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In the two rounds of the UNEP-coordinated 'Biennial interlaboratory assessments of POPs laboratories, which were implemented in 2016/2017 and 2018/2019, 56 and 46 laboratories submitted results for dioxin-like persistent organic pollutants (dl-POPs). Test matrices consisted of solutions of analytical standards and naturally contaminated sediment, air extract, fish and human milk. Performance assessment using z-scores so that satisfactory performance corresponded to 2 z = ±25%, which is recommended for laboratories submitting data to the global monitoring plan of the Stockholm Convention on POPs. Participation has shown that analytical capacity for analyzing dl-POPs exist in all UN regions; however, in Africa and Central and Eastern European countries capacities are (very) limited; in Latin America capacity is increasing. The presence of dioxin laboratories is not limited to industrialized or OECD countries but also present in developing countries such as China, Brazil, Egypt, Thailand, or Vietnam. Laboratories using established methods based on gas chromatographs coupled to high-resolution mass spectrometers (sector field instruments only) by far had the best results. Among the test samples, human milk and especially fish in the last round posed severe problems to all laboratories so that performance must improve, especially in foodstuffs at (very) low concentrations.

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In the past two decades, numerous studies on dioxin concentrations in breast milk have been conducted in China. However, information concerning dioxin concentrations in breast milk from women living in e-waste recycling sites remains limited. Thus, this study aimed to evaluate health risk owing dioxin intake in e-waste recycling areas in China. In 2015, 42 mothers were recruited from an e-waste recycling site, and the same number of mothers were recruited from a reference site. We collected 10-mL breast milk samples from each participant. Breast milk concentrations of polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs) were significantly higher in the exposed group than in the reference group. The total toxic equivalents (TEQ) of PCDDs/DFs were 9.68 pg/g lipid in the exposed group, a value two times higher than those in the reference group (4.18 pg/g lipid). The estimated daily intake (EDI) of PCDD/DFs was calculated to assess the risk of dioxins through breastfeeding. The infant EDI level was two times higher in the exposed group (54.21 pg TEQ/kg body wt/day) than in the reference group (23.41 pg TEQ/kg body wt/day). Our findings suggest that mothers and their breastfeeding infants living in an e-waste recycling site were exposed to higher dioxin concentrations than those living in a reference site.

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All the possible polychlorinated aromatic compounds in the classes of dibenzodioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) were studied by the quantum chemical methods of HF/6-311++G(d,p), B3LYP/6-311++G(d,p), and MP2/cc-pVTZ. The calculated stabilities and structures of these compounds were compared with the available data on their abundance and toxicity. Prediction models for trends in energy and planarity among these congeners were proposed. The results discussed here can help contribute to the understanding of the role of dioxin-like compounds (DLCs) in the environment.

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The lung has been reported to be one of the target organs of polychlorinated dibenzo-dioxins and polychlorinated dibenzo-furans (PCDD/Fs) in many toxicological studies. While the associations between PCDD/Fs exposure and lung function levels have not been investigated thoroughly. This study aimed to explore these associations and the potential mediating role of oxidative stress. In this study, 201 foundry workers and 222 non-exposed general residents were recruited from central China, and their lung function parameters were measured. Air and food samples were collected to determine the PCDD/Fs levels for individual PCDD/Fs exposure estimation. Serum PCDD/Fs levels were determined in a subgroup of individuals randomly selected from the study population to reflect the body burden. It was found that each 1-unit increase in ln-transformed concentration of PCDD/Fs exposure (fg TEQ/bw/day) was associated with a 0.47 L decrease in FVC and a 0.25 L decrease in FEV1. Each 1-unit increase in ln-transformed concentration of serum PCDD/Fs (fg TEQ/g lipid) was associated with a 0.36 L decrease in FVC and a 0.24 L decrease in FEV1. Urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG) was not only positively related to PCDD/Fs exposure, but also inversely associated with FVC and FEV1 are FVC (ß = -0.15, 95% CI: -0.22 to -0.08) and FEV1 (ß = -0.07, 95% CI: -0.13 to -0.02). Mediation analysis revealed that urinary 8-OHdG mediated 12.22% of the associations of external PCDD/Fs exposure with FVC levels, 28.61% and 27.87% of the associations of serum PCDD/Fs with FVC and FEV1 levels respectively. Our findings suggested that PCDD/Fs exposure was associated with decreased lung function levels by a mechanism partly involving oxidatively generated damage to DNA.

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BACKGROUND: Aryl hydrocarbon receptor (AhR), a ligand-activated transcription factor, is important for xenobiotic metabolism and binds to various endogenous and exogenous ligands in the skin. However, the functional role of AhR in patients with psoriasis (PS) and atopic dermatitis (AD) remains unclear. OBJECTIVE: We aimed to determine whether AhR-regulated factors (AhR, CYP1A1, interleukin [IL]-17, IL-22) were affected by AhR ligands (2,3,7,8-tetrachlorodibenzo-p-dioxin, TCDD) in chronic inflammatory skin diseases such as PS and AD. METHODS: The expression levels of AhR-related factors were determined by quantitative PCR, western blotting, and immunocytochemistry. Specific siRNA targeting AhR was used to inhibit gene expression in human peripheral blood mononuclear cells (PBMC). Cytokine assays were performed to determine the protein production of CD4+ T cells. RESULTS: In comparison with healthy controls, TCDD-treated PBMCs and CD4+ T cells from patients with PS and AD showed an increase in AhR gene levels as well as significantly increased expression of AhR-related factors (such as AhR, CYP1A1, IL-17, and IL-22). In contrast, 6-formyl indolo [3,2-b] carbazole (FICZ) inversely affected the differentiation of CD4+ T cells and their cytokine expression levels as compared with TCDD. CD4+ T cells from patients with AD and PS showed higher expression levels of AhR, CYP1A1, IL-17, and IL-22. CONCLUSION: Our results suggest that TCDD-induced AhR-related factor upregulation in AD and PS patients may increase the expression of AhR-regulatory genes, thereby contributing to the development of AD and PS.

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Polychlorinated dibenzo-dioxins and polychlorinated dibenzo-furans (PCDD/Fs) have been reported to induce reactive oxygen species and oxidative stress, but the dose-response relationships have not been explored in molecular epidemiological studies. In this study, a total of 602 participants were recruited, comprising of 215 foundry workers, 171 incineration workers and 216 residents living more than 5 km away from the plants as the reference group. Individual PCDD/Fs exposures were estimated according to PCDD/Fs levels of working and living ambient air and daily foods. Urinary 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) and 8-iso-prostaglandin-F2α (8-isoPGF2α) were determined to reflect oxidatively generated damage to DNA and lipid. Generalized linear models were used to access the associations between PCDD/Fs exposure and oxidative stress biomarkers. We found that PCDD/Fs exposure and urinary oxidative stress biomarkers of workers were all higher than those of the reference group. Significantly positive exposure-response relationships between individual PCDD/Fs exposures and urinary 8-oxodG and 8-iso-PGF2α were found. Each 1-unit increase in ln-transformed levels of PCDD/Fs exposure generated a 0.78 nmol/mmol creatinine increase in ln-transformed 8-oxodG and a 0.50 ng/mmol creatinine increase in ln-transformed 8-isoPGF2α in foundry workers, a 0.49 nmol/mmol creatinine increase in ln-transformed 8-oxodG and a 0.26 ng/mmol creatinine increase in ln-transformed 8-isoPGF2α in incineration workers, compared with the reference group. And such associations were not modified by tobacco use. Our findings could help to understand the dose-response relationships between PCDD/Fs and oxidatively generated damage to DNA and lipid, and provide an epidemiologic basis for conducting research on the carcinogenesis and other toxicity mechanisms of PCDD/Fs.

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Eggs from mature Chinook (Oncorhynchus tshawytscha) and Coho (Oncorhynchus kisutch) salmon were collected between 2004 and 2014 from the Salmon River fish hatchery in Altmar, New York. The egg samples were analyzed for seventeen polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), as well as four dioxin-like polychlorinated biphenyls (DL-PCBs) using USEPA methods 1613 and 1668. Salmonid eggs were chosen as a tissue of interest since salmon feed at all trophic levels of the food web as they grow, and spawn in a narrow range of ages providing consistent, representative, and temporal samples of contaminant exposure. First-order decay models indicate decreasing trends for all select contaminants in both species, expressed by a toxic equivalence (TEQ) half-life (t1/2) of 11 years in Chinook and Coho eggs. No significant statistical difference in contaminant elimination rates were noted between species. TEQ elimination rates for Coho and Chinook eggs were not significantly different (p > 0.05) when compared with published Lake Ontario whole-fish lake trout elimination rates. Our research demonstrates that salmonid eggs are an effective means to assess PCDD, PCDF, and DL-PCB exposures and long-term trends in the Great Lakes.

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The gold-standard matrix for measuring the internal levels of persistent organic pollutants (POPs) is the adipose tissue, however in epidemiological studies the use of serum is preferred due to the low cost and higher accessibility. The interpretation of serum biomarkers is tightly related to the understanding of the underlying causal structure relating the POPs, serum lipids and the disease. Considering the extended benefits of using serum biomarkers we aimed to further examine if through statistical modelling we would be able to improve the use and interpretation of serum biomarkers in the study of endometriosis. Hence, we have conducted a systematic comparison of statistical approaches commonly used to lipid-adjust the circulating biomarkers of POPs based on existing methods, using data from a pilot case-control study focused on severe deep infiltrating endometriosis. The odds ratios (ORs) obtained from unconditional regression for those models with serum biomarkers were further compared to those obtained from adipose tissue. The results of this exploratory study did not support the use of blood biomarkers as proxy estimates of POPs in adipose tissue to implement in risk models for endometriosis with the available statistical approaches to correct for lipids. The current statistical approaches commonly used to lipid-adjust circulating POPs, do not fully represent the underlying biological complexity between POPs, lipids and disease (especially those directly or indirectly affecting or affected by lipid metabolism). Hence, further investigations are warranted to improve the use and interpretation of blood biomarkers under complex scenarios of lipid dynamics.

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The association between genetic variations in the cytochrome P450 (CYP) family genes and pathological conditions related to long-term exposure to organochlorine compounds (OCs) deserves further elucidation. OCs are persistent organic pollutants with bioaccumulative and lipophilic characteristics. They can act as endocrine disruptors and perturb cellular mechanisms. Prolonged exposure to OCs has been associated with different pathological manifestations. CYP genes are responsible for transcribing enzymes essential in xenobiotic metabolism. Therefore, polymorphisms in these genetic sequences a. alter the metabolic pathways, b. induce false cellular responses, and c. may provoke pathological conditions. The main aim of this review is to define the interaction between parameters a, b and c at a mechanistic/molecular level, with references in clinical cases.

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Although Vietnam's massive herbicide exposure in 1960s and 1970s was clearly injurious to health, not all causal relationships have been clarified. We therefore explored associations among dioxins, steroid hormones, age and prostate cancer risk in men. We compared serum levels of dioxin, steroid hormones and prostate specific antigen (PSA) in men aged 56-81years from herbicide-exposed hotspots (n=50) with those from non-sprayed regions (n=48). Mean serum levels of dioxin congeners in the hotspot group were 1.5-11.3 times higher than the non-sprayed group depending on specific compound. Levels of testosterone, estradiol and 3ß-hydroxysteroid dehydrogenase (3ß-HSD) activity in the hotspot group were also significantly higher than in non-sprayed group. Estradiol levels were significantly related to levels of several specific dioxin derivatives in both group. Significant positive correlations were also found between DHT and 1234678-HpCDD or 1234678-HpCDF; and between 3ß-HSD activity and 123678-HxCDD, 123478-HxCDF, 123678-HxCDF, or HxCB#169. After adjusting for age, body mass index, and tobacco use, multiple linear regressions showed levels of dihydrotestosterone (DHT), estradiol, testosterone and 3ß-HSD activity were not associated with dioxins in the two groups; however, levels of DHT, testosterone and 3ß-HSD activity increased significantly with age in the hotspot group. The hotspot and non-sprayed groups did not significantly differ in PSA levels. But six of the hotspot subjects had PSA levels >3ng/mL, 3 of whom were suspected to have prostate cancer (PC) after digital rectal examination. Our findings suggest that dioxin exposure can lead to increased levels of several sex steroid hormones with age. The correlation of dioxin with steroid hormone levels and prostate cancer risk should be studied further.

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In this study, a fast and rugged method is presented for the analysis of PCBs, PAHs, PBDEs and PCDD/Fs in biological tissues using a simple Quick, Easy, Cheap, Efficient, Rugged and Safe (QuEChERS) extraction and a clean-up by Gel Permeation Chromatography (GPC) and silica Solid Phase Extraction (SPE). Development was performed on blue mussels (Mytilus edulis) and Atlantic salmon (Salmo salar) for evaluation of two ranges of lipid and water content of biological tissues. Statistical validation was performed with Atlantic salmon samples. Forty-five PAHs were analyzed including the priority list of the US EPA and the European Union with 41 PCBs, 24 PBDEs and 17 PCDD/Fs. Instrumental analyses were performed on Gas Chromatography - High Resolution Mass Spectrometry (GC-HRMS). Accuracy was evaluated for PCBs and PCDD/Fs with a certified reference material furnished by the National Research Council Canada (NRCC) and also compared with results obtained by the conventional Soxhlet extraction. Statistical validation showed recoveries for PCBs, PAHs, PBDEs and PCDD/Fs close to 100% with average Relative Standard Deviation (RSD) lower than 10% and internal standard recoveries in the range of 70% with average RSD ranging from 5-15%. Average calculated Method Detection Limits (MDLs) were lower than 0.05µg/Kg for PCBs, 0.2µg/Kg for PAHs and PBDEs and 1ng/Kg for PCDD/Fs. The method is a faster and cheaper alternative to the time-consuming conventional method that has been used in most environmental laboratories.

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In the present study, we report on the co-occurrence of persistent organic pollutants (POPs) adsorbed on nanoparticular titanium dioxide (TiO2). We report on the finding of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) on the surface of commercially available TiO2 nanoparticles, being formed during the fabrication process of the TiO2. Thereby, the samples comprise PCBs with higher congener numbers or, in the absence of PCBs, a high concentration of PCDDs and PCDFs. This new class of POPs on an active catalytic surface and the great range of applications of nanoparticular TiO2, such as in color pigments, cosmetics, and inks, give rise to great concern due to their potential toxicity.

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This study provides, for the first time, a baseline evaluation of dioxin-like biological activity in sediments and fish sampled in- and adjacent to anchorages along the Mediterranean and Red Sea coasts of Israel. It indicates the effect of past pollution, still present in the sediments of older Israeli harbors, with putative contribution of still existing sources of pollution. A commercial reporter gene bioassay was used to evaluate the biological activity of dioxin-like compounds extracted from the samples. HRGC/HRMS analysis of several samples contributed a profile of dioxin-like compounds in sediments and fish. The results point out 1,2,3,4,6,7,8-HeptaCDD, 2,3,4,6,7,8-HexaCDF, 1,2,3,4,6,7,8-HeptaCDF, РСВ-126 and РСВ-118 as major contributors to the dioxin-like activity in sediments. It indicates polychlorinated biphenyls non-selective absorption in fish livers, in contrary to a biased accumulation of poorly chlorinated and more potent dibenzodioxins and dibenzofurans.

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The possibility to monitor in real-time the emission of dioxins produced by incineration of waste or by industrial processes is nowadays a necessity considering the high toxicity of these compounds, their persistence in the environment and their ability to bio-accumulate in the food chain. Recently it has been demonstrated the potentiality of detecting dioxins in carbon tetrachloride via MIR Quantum Cascade Lasers. A fundamental step in real time monitoring of dioxins emission is the possibility to recognize the most toxic congeners within complex mixtures and at low concentrations. Taking into account the lack of spectroscopic data about these very toxic environmental pollutants and the necessity to monitor their emissions we have recorded infrared spectra of 13 of the 17 most toxic congeners of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) dissolved in carbon tetrachloride. In this way we have obtained a small database that we have used to test the ability of a linear regression algorithm to recognize each congener and its relative concentration in complex mixtures of these compounds.

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Biochar is discussed as an option for climate change mitigation via C sequestration and may promote sustainable resource efficiency. Large-scale field trials and commercial business with char materials have already started. Therefore char materials have to be assessed for toxic compounds. We tested genotoxic effects of different hydrochars and biochars with the Tradescantia micronucleus test. For this purpose chromosomal aberrations in pollen cells of Tradescantia in the form of micronuclei were evaluated microscopically after defined exposition to extracts from char materials. Hydrochars from hydrothermal carbonization mostly exhibited significantly negative results. Additional germination experiments with hydrochar showed total germination inhibition at additions above five percent v/v in comparison to biochar. However, biological post-treatment of previously toxic hydrochar was successful and toxic effects were eliminated completely. Some post-treated hydrochars even showed growth stimulating effects. Our results clearly demonstrate the necessity of risk assessment with bioindicators. The chosen tests procedures can contribute to biochar and hydrochar characterization for safe application.

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Risk assessment of soils is usually based on chemical measurements and assuming accidental soil ingestion and evaluating induced toxic and carcinogenic effects. Recently biological tools have been coupled to chemical-based risk assessment since they integrate the biological effects of all xenobiotics in soils. We employed integrated monitoring of soils based on chemical analyses, risk assessment and in vitro models in the highly urbanized semirural area of the Olona Valley in northern Italy. Chemical characterization of the soils indicated low levels of toxic and carcinogenic pollutants such as PAHs, PCDD/Fs, PCBs and HCB and human risk assessment did not give any significant alerts. HepG2 and BALB/c 3T3 cells were used as a model for the human liver and as a tool for the evaluation of carcinogenic potential. Cells were treated with soil extractable organic matters (EOMs) and the MTS assay, LDH release and morphological transformation were selected as endpoints for toxicity and carcinogenicity. Soil EOMs induced dose-dependent inhibition of cell growth at low doses and cytotoxicity after exposure to higher doses. This might be the result of block of cell cycle progression to repair DNA damage caused by oxidative stress; if this DNA damage cannot be repaired, cells die. No significant inductions of foci were recorded after exposure to EOMs. These results indicate that, although the extracts contain compounds with proven carcinogenic potential, the levels of these pollutants in the analyzed soils were too low to induce carcinogenesis in our experimental conditions. In this proposed case study, HepG2 cells were found an appropriate tool to assess the potential harm caused by the ingestion of contaminated soil as they were able to detect differences in the toxicity of soil EOMs. Moreover, the cell transformation assay strengthened the combined approach giving useful information on carcinogenic potential of mixtures.

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BACKGROUND: Although sources and routes of exposure to dioxins and polychlorinated biphenyls (PCBs) have been studied, information regarding exposure among children is limited. Breast-feeding and diet are two important contributors to early life exposure. To further understand other significant contributors to childhood exposure, we studied a cohort of children from a city with high environmental dioxin levels. OBJECTIVES: We investigated predictors of serum concentrations of polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs)/co-planar PCBs (C-PCBs), toxic equivalents (TEQs), and PCBs among 8- to 9-year-old boys in Chapaevsk, Russia. METHODS: We used general linear regression models to explore associations of log(10)-transformed serum concentrations of PCDDs/PCDFs/C-PCBs, TEQs, and PCBs at study entry with anthropometric, demographic, geographic, and dietary factors in 482 boys in Chapaevsk, Russia. RESULTS: The median (25th, 75th percentile) concentration for total 2005 TEQs was 21.1 pg/g lipid (14.4, 33.2). Boys who were older, consumed local foods, were breast-fed longer, and whose mothers were employed at the Khimprom chemical plant (where chlorinated chemicals were produced) or gardened locally had significantly higher serum dioxins and PCBs, whereas boys with higher body mass index or more educated parents had significantly lower serum dioxins and PCBs. Boys who lived < 2 km from Khimprom had higher total TEQs (picograms per gram lipid) [adjusted mean = 30.6; 95% confidence interval (CI), 26.8-35.0] than boys who lived > 5 km away (adjusted mean = 18.8; 95% CI, 17.2-20.6). CONCLUSIONS: Our findings suggest that there are specific local sources of dioxin and PCB exposure among children in Chapaevsk including maternal gardening, consumption of locally grown food, and residential proximity to the Khimprom plant.

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BACKGROUND: Polychlorinated biphenyls (PCBs), dibenzofurans (PCDFs), and dibenzodioxins (PCDDs) may affect the female reproductive system in animals and humans. In 1978-1979, a mass poisoning occurred in central Taiwan due to PCB/PCDF-contaminated cooking oil; this incident was called Yucheng ("oil disease" in Chinese). OBJECTIVE: The purpose of our study was to determine whether PCB/PCDF exposure affected fertility in exposed women. METHODS: After the event, we followed the exposed individuals and a reference group who were sex-, age-, and community-matched. In 2003, we obtained fertility histories from Yucheng and reference women by telephone interview. We used Kaplan-Meier survival curves and multivariable Cox regression to compare time to pregnancy (TTP) between Yucheng and reference women, and we performed multiple logistic regression to determine whether PCB/PCDF exposure caused infertility. RESULTS: In total, 412 women responded, with a median TTP of 4 months in Yucheng women and 3 months in reference women (p = 0.019). After adjusting for confounders by Cox regression, we found a fecundability ratio of 0.90 [95% confidence interval (CI), 0.80-1.00] for Yucheng women. Among the 408 women who had non-contraceptive sexual activity for > 12 months, 19.7% of Yucheng women and 9.7% of reference women did not become pregnant (i.e., they were infertile). After we adjusted for confounders by logistic regression, the infertility odds ratio was 2.34 (95% CI, 1.23-4.59) for Yucheng women compared with the reference group. CONCLUSIONS: We found prolonged TTP and reduced fertility among women previously exposed to PCBs/PCDFs. Because of the limited sample size and the relatively small decrease in the fertility rate, these effects require cautious interpretation and further investigation for confirmation.

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