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Polychlorinated naphthalenes (PCNs) are a new type of persistent organic pollutant (POP) characterized by persistence, bioaccumulation, dioxin-like toxicity, and long-range atmospheric transport. Focusing on one type of PCN, monochlorinated naphthalenes (CN-1, CN-2), this study aimed to examine their photodegradation in the environment. In this work, CN-1 and CN-2 were employed as the model pollutants to investigate their photodegradation process under UV-C irradiation. Factors like the pH, initial concentrations of CN-1, and inorganic anions were investigated. Next, the roles of hydroxyl radicals (•OH), superoxide anion radicals (O2•−), and singlet oxygen (1O2) in the photodegradation process were discussed and proposed via theory computation. The results show that the photodegradation of CN-1 and CN-2 follows pseudo-first-order kinetics. Acidic conditions promote the photodegradation of CN-1, while the effects of pH on the photodegradation of CN-2 are not remarkable. Cl−, NO3−, and SO32− accelerate the photodegradation of CN-1, whereas the effect of SO42− and CO32− is not significant. Additionally, the contributions of •OH and O2•− to the photodegradation of CN-1 are 20.47% and 38.80%, while, for CN-2, the contribution is 16.40% and 16.80%, respectively. Moreover, the contribution of 1O2 is 15.7%. Based on DFT calculations, C4 and C6 of the CN-1 benzene ring are prioritized attack sites for •OH, while C2 and C9 of CN-2 are prioritized attack sites. [ABSTRACT FROM AUTHOR]

Time trends and regional differences of polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), DDTs, polybrominated biphenyls (PBBs) and polybrominated diphenylethers (BDEs) were studied in unhatched osprey eggs collected by bird ringers in 1972–2017 from four areas in Finland. Two study areas were from Baltic Sea, Northern Quark and Finnish Archipelago Sea, while the two others were inland lake areas, eutrophicated Lake Vanajanselkä affected by industrial emissions, and Pristine SW Lake Area. The highest concentrations of most compound groups were in Lake Vanajanselkä consistent with high emissions, the predominance of bream as a prey, and higher concentrations in bream compared to other prey fish. Concentrations of all chlorinated compounds decreased significantly in all study areas. Average annual decreases were ∑PCDD/F 2.3–4.9%, ∑PCB 2.2–4.2%, ∑PCN 2.6–7.0% and ∑DDT 7.1–9.5%, primarily in line with decreased levels in prey fish. From 1972 PBBs and BDEs increased significantly until 1990s declining rapidly thereafter. PCDD/F congener profile was dominated by 2,3,4,7,8-PeCDF, except in Lake Vanajanselkä by 1,2,3,6,7,8-HxCDD. PCB congener profile was dominated by PCB 153 in all study areas, followed by PCB 180 and PCB 138. Among dioxin-like compounds PCBs contributed 82%, PCDDs 14% and PCDFs 4% to toxic equivalent quantity (∑TEQ). PCB 126 contributed most to ∑TEQ, followed by 1,2,3,7,8-PeCDD. BDE 47 being the dominant BDE congener, followed by BDE 100. ∑DDT concentrations were relatively similar across all study areas, with DDE contributing about 90%. Productivity of chicks per active nest was significantly decreased in Lake Vanajanselkä, and the likely explanation is embryotoxicity of dioxin-like compounds. It is plausible that dioxin-like compounds influenced embryonic survival among highly exposed ospreys prior to 2010, especially in Lake Vanajanselkä and Northern Quark. However, decreased survival due to DDE-induced eggshell thinning seems unlikely after 1985, and BDE levels were below those potentially causing adverse effects. [ABSTRACT FROM AUTHOR]

• Iron & steel industry contributed the most for unintentional PCNs emissions • Overall upward trend of unintentional PCNs emissions from 1960 to 2019 was revealed. • Per-capita emissions follows the typical inverted U-shaped environmental Kuznets curves. • Low-chlorinated PCNs dominate emissions by mass, while it's high-chlorinated PCNs by toxicity. Polychlorinated naphthalenes (PCNs) are detrimental to human health and the environment. With the commercial production of PCNs banned, unintentional releases have emerged as a significant environmental source. However, relevant information is still scarce. In this study, provincial emissions for eight PCNs homologues from 37 sources in the Chinese mainland during the period of 1960-2019 were estimated based on a source-specific and time-varying emission factor database. The results showed that the total PCNs emissions in 2019 reached 757.0 kg with Hebei ranked at the top among all the provinces and iron & steel industry as the biggest source. Low-chlorinated PCNs comprised 90% of emissions by mass, while highly chlorinated PCNs dominated in terms of toxicity, highlighting divergent priorities for mitigating emissions and safeguarding human health. The emissions showed an overall upward trend from 1960 to 2019 driven by emission increase from iron & steel industry in terms of source, and from North China and East China in terms of geographic area. Per-capita emissions followed an inverted U-shaped environmental Kuznets curve while emission intensities decreased with increasing per-capita Gross Domestic Product (GDP) following a nearly linear pattern when log-transformed. [Display omitted] [ABSTRACT FROM AUTHOR]

EFSA was asked for a scientific opinion on the risks for animal and human health related to the presence of polychlorinated naphthalenes (PCNs) in feed and food. The assessment focused on hexaCNs due to very limited data on other PCN congeners. For hexaCNs in feed, 217 analytical results were used to estimate dietary exposures for food‐producing and non‐food‐producing animals; however, a risk characterisation could not be performed because none of the toxicological studies allowed identification of reference points. The oral repeated dose toxicity studies performed in rats with a hexaCN mixture containing all 10 hexaCNs indicated that the critical target was the haematological system. A BMDL20 of 0.05 mg/kg body weight (bw) per day was identified for a considerable decrease in the platelet count. For hexaCNs in food, 2317 analytical results were used to estimate dietary exposures across dietary surveys and age groups. The highest exposure ranged from 0.91 to 29.8 pg/kg bw per day in general population and from 220 to 559 pg/kg bw per day for breast‐fed infants with the highest consumption of breast milk. Applying a margin of exposure (MOE) approach, the estimated MOEs for the high dietary exposures ranged from 1,700,000 to 55,000,000 for the general population and from 90,000 to 230,000 for breast‐fed infants with the highest consumption of breast milk. These MOEs are far above the minimum MOE of 2000 that does not raise a health concern. Taking account of the uncertainties affecting the assessment, the Panel concluded with at least 99% certainty that dietary exposure to hexaCNs does not raise a health concern for any of the population groups considered. Due to major limitations in the available data, no assessment was possible for genotoxic effects or for health risks of PCNs other than hexaCNs. [ABSTRACT FROM AUTHOR]

Abstract EFSA was asked for a scientific opinion on the risks for animal and human health related to the presence of polychlorinated naphthalenes (PCNs) in feed and food. The assessment focused on hexaCNs due to very limited data on other PCN congeners. For hexaCNs in feed, 217 analytical results were used to estimate dietary exposures for food‐producing and non‐food‐producing animals; however, a risk characterisation could not be performed because none of the toxicological studies allowed identification of reference points. The oral repeated dose toxicity studies performed in rats with a hexaCN mixture containing all 10 hexaCNs indicated that the critical target was the haematological system. A BMDL20 of 0.05 mg/kg body weight (bw) per day was identified for a considerable decrease in the platelet count. For hexaCNs in food, 2317 analytical results were used to estimate dietary exposures across dietary surveys and age groups. The highest exposure ranged from 0.91 to 29.8 pg/kg bw per day in general population and from 220 to 559 pg/kg bw per day for breast‐fed infants with the highest consumption of breast milk. Applying a margin of exposure (MOE) approach, the estimated MOEs for the high dietary exposures ranged from 1,700,000 to 55,000,000 for the general population and from 90,000 to 230,000 for breast‐fed infants with the highest consumption of breast milk. These MOEs are far above the minimum MOE of 2000 that does not raise a health concern. Taking account of the uncertainties affecting the assessment, the Panel concluded with at least 99% certainty that dietary exposure to hexaCNs does not raise a health concern for any of the population groups considered. Due to major limitations in the available data, no assessment was possible for genotoxic effects or for health risks of PCNs other than hexaCNs.

Flame retardants (FRs) are ubiquitous in environment and biota and may pose harm to human health. In recent years, concern regarding legacy and alternative FRs has been intensified due to their widespread production and increasing contamination in environmental and human matrices. In this study, we developed and validated a novel analytical method for simultaneous determination of legacy and alternative FRs, including polychlorinated naphthalenes (PCNs), short- and middle-chain chlorinated paraffins (SCCPs and MCCPs), novel brominated flame retardants (NBFRs), and organophosphate esters (OPEs) in human serum. Serum samples were prepared by liquid-liquid extraction using ethyl acetate, and purified with Oasis® HLB cartridge and Florisil–silica gel columns. Instrumental analyses were carried out using gas chromatography-triple quadrupole mass spectrometry, high-resolution gas chromatography coupled with high-resolution mass spectrometry, and gas chromatography coupled with quadrupole time-of-flight mass spectrometry, respectively. The proposed method was validated for linearity, sensitivity, precision, accuracy, and matrix effects. Method detection limits for NBFRs, OPEs, PCNs, SCCPs, and MCCPs were 4.6 × 10–4–8.6 × 10–2, 4.3 × 10–3–1.3, 1.1 × 10–5–1.0 × 10–4, 1.5, and 9.0 × 10–1 ng/mL, respectively. Matrix spike recoveries ranged from 73%–122%, 71%–124%, 75%–129%, 92%–126%, and 94%–126% for NBFRs, OPEs, PCNs, SCCPs, and MCCPs, respectively. The analytical method was applied for detection of real human serum. CPs were the dominant FRs in serum, indicating CPs were widely presented in human serum and should be pay more attention for their health risk. [Display omitted] [ABSTRACT FROM AUTHOR]

Few studies have been conducted on spatial and temporal trends in polychlorinated naphthalenes (PCNs) in coastal environments. Here, we describe 18 PCN congeners found in surface and dated sediment samples collected from highly industrialized bays of Korea. Measurable levels of PCN congeners were detected in all sediment samples, suggesting concurrent and historical contamination. The highest PCN concentrations were observed in sediment from rivers, streams, and the inner portions of the bays, which are surrounded by industrial complexes and commercial harbors. CNs 73, 66/67, and 52 were dominant in surface and dated sediment samples. Congener patterns and diagnostic ratios revealed that PCN contamination is originated from combustion processes and the use of polychlorinated biphenyl (PCB) technical mixtures. PCN concentrations in dated sediment increased from the 1980s to the mid-2000s and then decreased to 2015. Although the toxic equivalent (TEQ) levels of PCNs in our study did not exceed sediment quality guidelines proposed by international authorities, the cumulative risks from the TEQ concentrations of polychlorinated dibenzo-p-dioxins, furans, PCBs, and PCNs can be expected for benthic organisms. [ABSTRACT FROM AUTHOR]

This study focused on evaluation of the levels, seasonal variations and human health risks associated with polychlorinated naphthalenes (PCNs) in water and sediment samples of Markman Canal using solid phase and soxhlet extraction methods respectively, followed by clean-up and quantification with gas chromatograph coupled with microelectron capture detector. The sum of eight PCNs congener's (∑8PCNs) in water and sediments varied from 0.035 to 0.699 μg/L and 0.260 to 6744.16 μg/kg dw, respectively. Highest PCNs concentrations were recorded in water during winter, while sediment samples collected during spring contained maximum levels. The estimated toxic equivalency (TEQ) for water and sediments was 1.19 × 10–7–1.47 × 10–4 µg/L and 4.43 × 10−5–4.19 × 10−1 µg/kg consecutively. The PCN levels and TEQ values revealed that this waterbody is polluted but constitutes no excess health risk. Efforts should be made to control all the activities contributing to pollution of this canal. [ABSTRACT FROM AUTHOR]

This paper takes Poa annua L. as the research object and studies the law of physiological and ecological stress of 1-Chloronaphthalene (CN-1) and Octachloronaphthalene (CN-75) by using various physiological and biochemical indexes of Poa annua L. cultivated with soil under the stress of CN-1 and CN-75 of different concentrations. According to the research, the chlorophyll a and b first increase and then decrease with the increase of the concentration of CN-1, and continue to decrease with the increase of CN-75; Soluble sugar and soluble protein in plants decrease first and then increase with the increase of CN-1, and continue to decrease with the increase of CN-75; MDA in plants increases first and then decreases with the increase of the concentration of CN-1 and CN-75. The proline content in plants also increases first and then decreases with the increase of concentration of CN-1 and CN-75. Based on the research, it can be seen that the tolerance of the plant to CN-75 is not good as to CN-1. [ABSTRACT FROM AUTHOR]

Historical chlor-alkali production has led to substantial concentrations of persistent organic pollutant residues in the environment. This study systematically investigated the distribution of polycyclic aromatic hydrocarbons (PAHs), chlorinated/brominated-PAHs (Cl/Br-PAHs), polychlorinated naphthalenes (PCNs), and hexachlorobutadiene (HCBD) in sediment, lotus (Nelumbo nucifera), and fish samples from Ya-Er Lake, which is a site in China with historical chlor-alkali contamination. The average concentrations [(4.97–1.47) × 103 ng/g dry weight (dw)] of these pollutants in backfill sediments, which were dredged from the lake after chlor-alkali production stopped, were 2.68–70.87 times those in fresh lake sediments (0.622–218 ng/g dw) and reported concentrations in other areas. Correlation analyses indicated that Cl-PAHs, Br-PAHs, and PCNs likely originated from halogenation of parent PAHs in the study area, and the chlorination ratios were larger than those of bromination. The Cl (1/2/3) -PAHs/PAHs and Br (1) -PAHs/PAHs ratios were higher than those for PAHs with more halogen atoms. This contamination extended into the biota, with notable pollutant burdens found in lotus (Nelumbo nucifera , 0.305–77.3 ng/g dw) and even higher concentrations in fish (2.20–345 ng/g lipid weight). Estimated biological soil accumulation factors revealed significant enrichment in lotus organs (mean: 7.19) and fish muscle (mean: 10.65), especially the latter, which highlighted bioaccumulation and potential food chain transfer risks. The estimated daily intakes of PAHs, Cl/Br-PAHs, and HCBD through fish consumption currently pose negligible risks, while dietary intake of PCNs may present health concerns. Continuous monitoring and impact assessments are crucial for developing appropriate risk management strategies to safeguard public health. [Display omitted] • Historical chlor-alkali industry left a legacy of long-term aquatic contamination. • High levels of UPOPs contamination were found in sediments, lotus, and fish. • PAHs, Cl/Br-PAHs, PCNs, and HCBD bioaccumulated in lotus and fish muscle. • Exposure of locals to PCNs through fish consumption may pose a health hazard. [ABSTRACT FROM AUTHOR]

[Display omitted] • Data on food levels of polychlorinated naphthalenes (PCNs) have been reviewed. • Most studies has been conducted in China and Europe. • Most reported food levels of PCNs do not suggest potential risks for the consumers. • The available estimated daily intakes of PCNs seem not being of concern. In general, for most environmental persistent organic pollutants (POPs), dietary intake is the main way of exposure. Polychlorinated naphthalenes (PCNs) are a family of two-ringed aromatic compounds, which are ubiquitous environmental contaminants, being structurally similar to PCDD/Fs and PCBs. Although the production and use of PCNs were banned in the USA and Europe some decades ago, due to their persistent properties, PCNs remain still present in the environment, being able to enter the food chain. The present paper was aimed at reviewing the results of the studies focused on determining the levels of PCNs in foods. The human dietary intake of these compounds was also reviewed with the few available data. The information on the levels of PCNs in foodstuffs is currently more abundant than that found in a previous review (Domingo, 2004). Since then, China is the country that has contributed with the greatest number of studies. The results of most surveys seem to suggest that human health risks of PCNs due to dietary exposure should not be worrying. However, because of the important differences in the methodology of the published studies, the comparison of the results is not easy, although there seems to be a general trend towards a decrease in the levels of PCNs in foods. In the next few years, a continued reduction of the environmental levels of PCNs is still expected. Therefore, a direct repercussion of the concentrations of these pollutants in foodstuffs must be also noted. Consequently, a reduction of the dietary exposure to PCNs should be expected. Anyway, to establish the tolerable dietary intake of PCNs is a key issue for assessing human health risks of these pollutants. [ABSTRACT FROM AUTHOR]

Polychlorinated naphthalenes (PCNs) were included in the banned list of the Stockholm Convention due to their potential to provoke a wide range of adverse effects on living organisms and the environment. Many reviews have been written to clarify the state of knowledge and identify the research needs of this pollutant class. However, studies have yet to analyse the scientometric complexities of PCN literature. In this study, we used bibliometric R and vosviewer programs as a scientometric tool to fill this gap by focusing on articles indexed on Web of Science and Scopus databases and those published between 1973 and 2022. A total of 707 articles were published within this period with a publication/author, author/publication, and co-authors/publication ratios of 0.45, 2.19, and 4.86, respectively. Developed countries dominated most scientometric indices (number of publications, citations, and collaboration networks) in the survey period. Lotka's inverse square rule of author productivity showed that Lotka's laws do not fit PCN literature. An annual percentage growth rate of 7.46% and a Kolmogorov-Smirnoff goodness-of-fit of 0.88 suggests that more output on PCNs is likely in years to come. More research is needed from scholars from developing countries to measure the supremacy of the developed nations and to effectively comply with the Stockholm Convention agreement. [Display omitted] • We analyzed the knowledge structure and research trends of PCNs from 1973 to 2022. • Research on PCNs is likely to grow in future. • Developed countries dominated most of the scientometric indices. • More research on PCNs is needed especially in developing countries. [ABSTRACT FROM AUTHOR]

Concerns about dioxin-like compounds have increased; however, the monitoring of polychlorinated naphthalenes (PCNs) in food and the assessment of dietary intake remain limited. In this study, various foods were collected from Korean markets and analyzed for PCNs. Fishery products exhibited the highest mean concentration (48.0 pg/g ww) and toxic equivalent (TEQ) (0.0185 pg-TEQ/g ww). Agricultural products were the largest contributors (35.7%) to the total dietary intake of PCN TEQ , followed by livestock products (33.6%), fishery products (20.2%), and processed foods (10.5%). The mean intake of PCN TEQ for the Korean population was 0.901 pg-TEQ/day for males and 0.601 pg-TEQ/day for females. Generally, males and younger groups had higher daily intakes of PCN TEQ , but they did not exceed the tolerable weekly intakes. Nonetheless, it is important to manage potential health risks associated with PCNs and other dioxin-like compounds by identifying major food items contributing to PCN exposure and considering age and gender differences. [Display omitted] • The highest concentrations and TEQs of PCNs were found in fishery products. • Pork and rice are major contributors to PCN TEQ exposure in the Korean population. • Males were more exposed to PCN TEQ than females due to their dietary habits. • Children may be at a greater risk of PCN exposure per unit of body weight. • The intake of PCN TEQ was lower than TWIs, but continued monitoring is required. [ABSTRACT FROM AUTHOR]

Chlorophenols (CPs) and phenol are abundant in thermal and combustion procedures, such as stack gas production, industrial incinerators, metal reclamation, etc., which are key precursors for the formation of polychlorinated naphthalenes (PCNs). CPs and phenol can react with H or OH radicals to form chlorophenoxy radicals (CPRs) and phenoxy radical (PhR). The self-condensation of CPRs or cross-condensation of PhR with CPRs is the initial and most important step for PCN formation. In this work, detailed thermodynamic and kinetic calculations were carried out to investigate the PCN formation mechanisms from PhR with 2-CPR/3-CPR. Several energetically advantageous formation pathways were obtained. The rate constants of key elementary steps were calculated over 600~1200 K using the canonical variational transition-state theory (CVT) with the small curvature tunneling (SCT) contribution method. The mechanisms were compared with the experimental observations and our previous works on the PCN formation from the self-condensation of 2-CPRs/3-CPRs. This study shows that naphthalene and 1-monochlorinated naphthalene (1-MCN) are the main PCN products from the cross-condensation of PhR with 2-CPR, and naphthalene and 2-monochlorinated naphthalene (2-MCN) are the main PCN products from the cross-condensation of PhR with 3-CPR. Pathways terminated with Cl elimination are preferred over those terminated with H elimination. PCN formation from the cross-condensation of PhR with 3-CPR can occur much easier than that from the cross-condensation of PhR with 2-CPR. This study, along with the study of PCN formation from the self-condensation 2-CPRs/3-CPRs, can provide reasonable explanations for the experimental observations that the formation potential of naphthalene is larger than that of 1-MCN using 2-CP as a precursor, and an almost equal yield of 1-MCN and 2-MCN can be produced with 3-CP as a precursor. [ABSTRACT FROM AUTHOR]

Dried blood spots (DBSs) collected and archived in newborn screening programs (NSP) represent a potentially valuable resource for assessing exposure to a range of organic and inorganic chemicals in newborns. This study develops and optimizes a method to measure polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs) in DBS using the isotope dilution technique, ultrasonic-assisted liquid-liquid extraction, simple cleanup, triple quadrupole GC-MS/MS analysis, and background correction. We minimize the number of extraction repetitions and the volume of solvent, which helps increase throughput while minimizing the potential for contamination. We obtained high recovery and precision for most compounds, and method detection limits (MDLs) were sufficiently low to detect the more prevalent compounds based on representative sample of the US population. MDLs averaged 0.020 ng/mL (recovery: 107 %, precision: 4 %) for PCNs, 0.021 ng/mL (recovery: 97 %, precision: 4 %) for PCBs, 0.021 ng/mL (recovery: 117 %, precision: 2 %) for OCPs, and 0.021 ng/mL (recovery: 96 %, precision: 3 %) for PBDEs. To our knowledge, this is the first study presenting an analytical method and for PCNs in DBS, and one of the few studies providing an assessment of method performance for persistent organic pollutants in DBS. The optimized method can be applied to a wide range of applications, including exposure assessment, environmental epidemiology, forensics, environmental surveillance, and ecological monitoring. [Display omitted] • Dried blood spots are a valuable resource for assessing neonatal chemical exposure. • We developed and optimized a method to measure PCNs, PCBs, PBDEs and OCPs in DBS. • We used isotope dilution, liquid-liquid extraction, and triple quadrupole GC-MS/MS. • MDLs averaged 0.021 ng/mL (recovery: 104 %, precision: 3 %) for all POP compounds. • This is the first study presenting an analytical method for PCNs in DBS. [ABSTRACT FROM AUTHOR]

Both thermal and environmental processes are significant factors influencing the existing characteristics, e.g., congener distributions, and existing levels, of polychlorinated naphthalenes (PCNs) in the environment. Soil plays an important role in the life cycle of PCNs, but degradation of PCNs in soils has never been reported. In this study, we collected surface soil samples from 13 cities in the Yangtze River Delta, which is one of the most crowded areas of China and analyzed the samples for 75 PCNs. The long-range transportation from polluted areas was the major source for PCNs in remote areas, but the PCN profiles in remote areas reported in our previous studies were different from those in human settlement in this study, indicating there is a transformation of PCNs after emissions from anthropogenic activities. Two experiments were then designed to reveal the degradation mechanisms, including influencing factors, products, and pathways, of PCNs in surface soils. Based on the experiments, we found that the major factor driving the losses of PCNs in surface soils was volatilization, followed by photo irradiation and microbial metabolism. Under photo-irradiation, the PCN structures would be destroyed through a process of dechlorination followed by oxidation. In addition, the dechlorination pathways of PCNs have been established and found to be significantly influenced by the structure-related parameters. [Display omitted] • PCN characteristics in surface soil in Yangtze River Delta were reported. • Effect of three influence factors on PCN degradation in soil has been revealed. • The degradation of PCNs was verified to be dechlorination followed by oxidation. • Dechlorination pathways of PCNs were established. • Products for PCN degradation have been identified. [ABSTRACT FROM AUTHOR]

In this study, a novel three-dimensional hierarchical porous deep eutectic solvents-modified graphene aerogel (3D DES-GA) was synthesized for use as a solid-phase microextraction (SPME) fiber coating. The SPME fiber was characterized by its fluffy and hierarchical porous structure, uniform thickness, and rapid mass transfer capabilities. This fiber demonstrated a lifetime (≥160 uses) and excellent precision (with relative standard deviations of 2.4–6.6% for single fiber and 6.0–9.8% for fiber-to-fiber repeatability). The SPME fiber also exhibited remarkable extraction performance for polycyclic aromatic hydrocarbons and polychlorinated biphenyls, which are common persistent organic pollutants in environmental samples. When combined with gas chromatography-tandem mass spectrometry, the method allowed for high-efficiency extraction (enrichment factors ranging from 1225 to 4652 folds) and sensitive determination (limit of detection ranging from 0.010 to 0.056 pg g−1) of polychlorinated naphthalenes (PCNs) in complex samples. To validate this method, we applied it to the determination of four PCNs in five types of fish tissues. The results revealed the presence of 1-chloronaphthalene at concentrations of 7.0 ± 2.9–34.8 ± 2.1 pg g−1 and 1,4-dichloronaphthalene at concentrations of 6.0 ± 0.3–10.9 ± 1.4 pg g−1 in three fish species. Compared with reported sample pretreatment methods reported in the literature, this proposed headspace SPME method offers additional advantages, including simplicity of operation and reduced sample and organic solvent consumption. [Display omitted] • Hierarchical porous graphene aerogel was prepared by deep eutectic solvent modifying. • The functional graphene aerogel was synthesized for a new fiber coating of SPME. • The fiber coating exhibits fast mass transfer and high enrichment capacity. • As-prepared fiber coating exhibited excellent applicability for PCNs, PCBs and PAHs. • The proposed method was applied for sensitive detection of PCNs in complex samples. [ABSTRACT FROM AUTHOR]

The persistent organic pollutants (POPs) defined by the Stockholm Convention include polychlorinated naphthalenes (PCNs); of these, the most toxic, persistent, abundant, dioxin-like congeners found in human tissues are the hexachloronaphthalenes (HxCNs). Recent research also indicates that PCNs may disrupt hormonal homeostasis. The aim of this study was to evaluate the (anti)androgenic action of HxCN. Immature, castrated male Wistar rats were exposed per os to HxCN in corn oil at daily doses ranging from 0.3 to 3.0 mg kg−1 for 10 days. According to the OECD 441 protocol (Hershberger Bioassay), the anti-androgenic assay groups were co-exposed with testosterone propionate (TP), while the androgenic groups were not. TP was used as the reference androgen (subcutaneous daily doses of 0.4 mg kg−1), and flutamide (FLU) as the reference antiandrogen (per os daily doses of 3.0 mg kg−1). Five assessory sex tissues (ASTs) were weighed: ventral prostate, seminal vesicles, levator ani-bulbocavernosus muscle (LABC), Cowper's glands and glans penis. HxCN + TP significantly decreased the weight of the ventral prostate and seminal vesicle indicating an anti-androgenic action via 5α-reductase inhibition. These weight changes were also accompanied by abnormalities in cell morphology and hormonal disturbances: lowered levels of the testosterone and thyroid hormones thyroxine and triiodothyronine. Disturbances were also noted in the lipid profile, viz. total cholesterol, triglycerides and high-density lipoprotein and non-HDL fraction content. However, the direction of these changes differed depending on the size of the HxCN dose. No dose-effect relationship was noted for most of the obtained results; as such, exposure to even small HxCN doses run the risk of anti-androgenic effects in the general population, especially when encountered in combination with other POPs and endocrine-disrupting chemicals in the environment. [Display omitted] • HxCN demonstrated anti-androgenic activity in male rats. • HxCN exposure decreased ventral prostate and seminal vesicle weight. • Morphological changes were detected in the seminal vesicles and ventral prostate. • Exposure to HxCN decreased the level of thyroid hormones. • The antiandrogenic action of HxCN was connected with decreased testosterone levels. [ABSTRACT FROM AUTHOR]

Di-through octachlorinated naphthalenes (DiCNs, TrCNs, TeCNs, PeCNs, HxCNs, HpCNs and OcCN) in landfill leachates can be analyzed with the same cleanup procedure as dioxins. In this study, a modified method was developed by confirming the elution order of each isomer of polychlorinated naphthalenes (PCNs) in a chromatogram of a gas chromatograph/high resolution mass spectrometer (GC/HRMS) using an Rh-12 ms capillary column, which is mainly employed for the analysis of dioxins. Using this method, PCNs in landfill leachate samples and treated leachate samples from each corresponding wastewater treatment process were quantified. PCN concentrations in landfill leachates ranged from 8.0–12,000 pg/L, and DiCNs-PeCNs were detected in almost all samples. Removal of PCNs by flocculation and active carbon treatment was greater than that achieved by activated sludge treatment in wastewater treatment plants. Furthermore, by changing the temperature of the H2SO4 coated silica gel column in the modified method, it became possible to measure monochlorinated naphthalenes (MoCNs), which could not be measured previously. MoCN concentrations detected were much higher compared to concentrations of DiCNs-OcCN in most of landfill leachates. Unlike PCNs, MoCNs are not POPs, but they are nevertheless important for understanding the properties of landfill leachates.

Polychlorinated naphthalenes (PCNs) are organochlorine compounds comprising the naphthalene ring system, in which one to eight hydrogen atoms have been substituted with chlorine atoms, yielding 75 chlorinated congeners. They were considered as persistent organic pollutants in May 2015 at the Stockholm Convention owing to their toxicity, persistence, bioaccumulation and potential for long-range transport in the environment. PCNs were invented in the early 1900s to be applied as flame-retardants in consumer products. Flame-retardants are effective in minimizing fire-related problems. However, their negative environmental impacts have become of great concerns. Different analytical methods for the evaluation of PCNs in various environmental samples were reviewed in this article.. Their levels in human and some environmental samples across the globe are also mentioned. Reported data revealed that the highly toxic congeners (CNs 66, 67 and 73) are prevalent in most samples, there is need for their continuous monitoring in our environment.

The residues of polychlorinated naphthalenes (PCNs) produced in multiple industrial production and life processes are continuously entering environmental waters through atmospheric deposition and land drainage, and the water pollution caused by PCNs is continuing public concern due to their potential threat to aquatic ecosystems and public health. Herein, a new chlorine-functionalized covalent organic framework anchored graphene aerogel (COF-GA) was synthesized by covalent modification technology and used as fiber coating of solid-phase microextraction for synergically enhanced extraction of PCNs in environmental water. The extraction efficiency of COF-GA coated fiber was superior to commercial fiber due to the multiple interactions (π-π, hydrophobic interaction, and halogen bonding interaction). The COF-GA coated fiber has good stability, can avoid water vapor interference at 80 °C for a long time (30 −50 min) to maintain adsorption equilibrium, and can be reused at least 96 times. Combined with gas chromatography-tandem mass spectrometry, a sensitive method for the high-efficient enrichment (enrichment factors were 501 −7453 folds) and ultra-sensitive detection (LODs were 0.001 −0.428 pg/mL) of PCNs in environmental water was established. The enrichment factor for PCNs is significantly higher than in previous studies. This proposed method provides new technical support for the daily monitoring and risk assessment of trace PCNs in environmental water. [Display omitted] • A hydrophobic COF-GA was developed by covalent modification technology. • The developed COF-GA was used as a solid-phase microextraction fiber coating. • An ultra-sensitive detection method for PCNs in water was developed. • The proposed assay showed high enrichment, high sensitivity, and high precision. • Multiple interactions between COF-GA and PCNs were summarized. [ABSTRACT FROM AUTHOR]

Over the last two decades, Taiwan has effectively diminished atmospheric concentrations of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) through the adept utilization of advanced technologies and the implementation of air pollution control devices. Despite this success, there exists a dearth of data regarding the levels of other PM 2.5 -bound organic pollutants and their associated health risks. To address this gap, our study comprehensively investigates the spatial and seasonal variations, potential sources, and health risks of PCDD/Fs, Polychlorinated biphenyls (PCBs), and Polychlorinated naphthalene (PCNs) in Northern and Central Taiwan. Sampling collections were conducted at three specific locations, including six municipal waste incinerators in Northern Taiwan, as well as a traffic and an industrial site in Central Taiwan. As a result, the highest mean values of PM 2.5 (20.3–39.6 μg/m3) were observed at traffic sites, followed by industrial sites (14.4–39.3 μg/m3), and the vicinity of the municipal waste incinerator (12.4–29.4 μg/m3). Additionally, PCDD/Fs and PCBs exhibited discernible seasonal fluctuations, displaying higher concentrations in winter (7.53–11.9 and 0.09–0.12 fg I-TEQ WHO /m3) and spring (7.02–13.7 and 0.11-0.16 fg I-TEQ WHO /m3) compared to summer and autumn. Conversely, PCNs displayed no significant seasonal variations, with peak values observed in winter (0.05–0.10 fg I-TEQ WHO /m3) and spring (0.03–0.08 fg I-TEQ WHO /m3). Utilizing a Positive Matrix Factorization (PMF) model, sintering plants emerged as the predominant contributors to PCDD/Fs, constituting 77.9% of emissions. Woodchip boilers (68.3%) and municipal waste incinerators (21.0%) were identified as primary contributors to PCBs, while municipal waste incinerators (64.6%) along with a secondary copper and a copper sludge smelter (22.1%) were the principal sources of PCNs. Moreover, the study specified that individuals aged 19–70 in Northern Taiwan and those under the age of 12 years in Central Taiwan were found to have a significantly higher cancer risk, with values ranging from 9.26 x 10−9-1.12 x 10−7 and from 2.50 x 10−8-2.08 x 10−7respectively. [Display omitted] • In 20 years, ambient PCDD/Fs levels dropped from 63.8 to 6.99 fg I-TEQ/m3. • The traffic sites recorded the highest mean values of PM 2.5 (20.3–39.6 μg/m3). • No significant variations in PCN levels were found among different seasons. • PCDD/Fs (TEQ) were predominantly in the particle phase in winter than PCBs and PCNs. • PCDD/Fs account (>95%) of the overall risk via inhalation compared to PCBs and PCNs. [ABSTRACT FROM AUTHOR]

Polychlorinated naphthalenes (PCNs) are ubiquitous in the environment and have received extensive public concern due to their dioxin-like properties. 1,2,3,4,5,6,7-heptachloronaphthalene (1,2,3,4,5,6,7-HpCN) is one of the most toxic and detected PCNs. The chlorophenoxy radical (CPR) was demonstrated as a crucial intermediate specie for PCN formation in thermal and combustion conditions. In this study, the homogeneous gas-phase formations of PCNs from the self-condensation of 2,3,4,5-terachlorophenoxy radicals (2,3,4,5-TeCPRs) and the cross-condensation of pentachlorophenoxy radical (PCPR) with 2,3,4,5-TeCPR were researched by using the direct density functional theory (DFT) kinetic calculation. The possible formation mechanisms were investigated at the MPWB1K/6–311+G(3df,2p)//MPWB1K/6–31+G(d,p) level. The rate constants and their temperature dependence of key elementary reactions were deduced over the temperature range of 600–1200 K. This study reveals that pathways concluding with Cl elimination are energetically favored over those ending with H elimination. 1,2,3,4,5,6,7-HpCN is the main PCN product from the self-condensation of 2,3,4,5-TeCPRs, whereas 1,2,3,4,5,6,7-HpCN and 1,2,3,4,5,6,8-HpCN are the major PCN products from the cross-condensation of PCPR and 2,3,4,5-TeCPR. 1,2,3,4,5,6,7-HpCN is preferentially formed from self-condensation of 2,3,4,5-TeCPRs. Multi-chlorine substitutions suppress the PCN formations. The findings discussed in this paper aim to provide detailed insights into the formation mechanism of highly chlorinated PCNs from chlorophenol precursors under thermal and combustion conditions. [Display omitted] • The PCN formation mechanism from 2,3,4,5-TeCP and PCP as precursors. • The rate constants have been calculated for the key elementary reactions. • 1,2,3,4,5,6,7-HpCN is preferentially formed from dimerization of 2,3,4,5-TeCPRs. • Multichlorine substitutions suppress the PCN formations. [ABSTRACT FROM AUTHOR]

Per- and polyfluoroalkyl substances (PFASs) and polychlorinated naphthalenes (PCNs) are of growing concern due to their toxic effects on the environment and human health. There is an urgent need for strategies to monitor and analyze the coexistence of PFASs and PCNs, especially in food samples at trace levels, to ensure food safety. Herein, a novel β-cyclodextrin (β-CD) derived fluoro-functionalized covalent triazine-based frameworks named CD-F-CTF was firstly synthesized. This innovative framework effectively combines the porous nature of the covalent organic framework and the host-guest recognition property of β-CD enabling the simultaneous extraction of PFASs and PCNs. Under the optimal conditions, a simple and rapid method was developed to analyze PFASs and PCNs by solid-phase extraction (SPE) based simultaneous extraction and stepwise elution (SESE) strategy for the first time. When coupled with liquid chromatography−tandem mass spectrometry (HPLC−MS/MS) and gas chromatography−tandem mass spectrometry (GC−MS/MS), this method achieved impressive detection limits for PFASs (0.020 −0.023 ng/g) and PCNs (0.016 −0.075 ng/g). Furthermore, the excellent performance was validated in food samples with recoveries of 76.7–107 % (for PFASs) and 78.0–108 % (for PCNs). This work not only provides a simple and rapid technique for simultaneous monitoring of PFASs and PCNs in food and environmental samples, but also introduces a new idea for the designing novel adsorbents with multiple recognition sites. [Display omitted] • Novel bifunctional covalent triazine-based frameworks with host-guest recognition and fluorous affinity were prepared. • The material exhibited high selective adsorption for PFASs and PCNs. • A SESE-HPLC-MS/MS and SESE-GC-MS/MS method was developed. • The method was sensitive and practical for the determination of PFASs and PCNs in different types of foods. [ABSTRACT FROM AUTHOR]

Killer whales (Orcinus orca) historically restricted to certain Arctic regions due to extensive sea ice have recently been documented farther north and for longer durations in the Canadian Arctic. These apex predators accumulate high levels of persistent organic pollutants (POPs). The objective of this study was to evaluate the concentrations and profiles of POPs in killer whales of the Canadian Arctic, thus determining potential risks for Inuit communities if consumed. Biopsies were collected from 33 killer whales across areas of the Canadian Arctic between 2009 and 2021. Significant variability in POP concentrations was observed among whales. The cumulative POP concentrations ranged from 12 to >2270 mg/kg lw, representing ∼200-fold increase from the least to the most contaminated individual. The rank order of concentrations of the top five contaminant classes was ∑DDT, ∑PCB, ∑CHL, ∑Toxaphene, and Dieldrin. Several emerging Arctic contaminants were detected, including chlorpyrifos, endosulfan, pentachloroanisole, and polychlorinated naphthalenes, although at relatively lower concentrations than legacy POPs. Considering the elevated blubber POP levels in killer whales, recommended daily consumption thresholds, established based on human tolerable daily intake (TDI) values, were notably restricted for ∑PCB (<0.14 g), ∑DDT (<6.9 g), ∑CHL (<13 g), dieldrin (<8 g) and heptachlor epoxide (<5 g). Killer whales in the Canadian Arctic exhibited higher POP concentrations than other commonly hunted species such as polar bears, ringed seals, and Arctic char. We acknowledge that a more holistic risk assessment of diet is required to assess the cumulative impacts of contaminant mixtures as well as nutritional quality of tissues commonly consumed by northern communities. [Display omitted] • Climate change is increasing Inuit interactions with killer whales in the Canadian Arctic. • Some Nunavut communities within the Qikiqtaaluk region have expressed interest in hunting killer whales. • 200-fold difference in sum POPs from least to most contaminated killer whale blubber. • Killer whale contaminant levels far higher than traditional country foods. • Safe human consumption of killer whale blubber is limited to <0.1–10 g per day. [ABSTRACT FROM AUTHOR]

Polychlorinated dibenzo- p -dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) were assessed in coastal sediments from industrial bays in South Korea to evaluate the pollution levels and their environmental impact. The mean sediment concentrations of Σ 17 PCDD/Fs, Σ 18 PCBs, and Σ 15 PCNs were 198 ± 140, 3427 ± 7037, and 85 ± 336 pg/g dw, respectively. Generally, pollutant concentrations in the inner bay were higher than those in the outer bay, indicating the influence of industrial emissions and harbor activities. The primary sources were identified as steel manufacturing and wastewater treatment plants for PCDD/Fs, harbor and shipbuilding activities for PCBs, and combustion-related sources for PCNs. Notably, PCDD/F concentrations exceeded sediment guideline values. The combined effects of PCDD/Fs and PCBs demonstrated adverse impacts on aquatic organisms. Hence, the release of toxic pollutants into the marine environment could have potential biological effects due to the combined impact of these various compounds. [Display omitted] • Marine sediment samples were collected from major industrial bays in South Korea. • The spatial distributions and patterns of PCDD/Fs, PCBs, and PCNs were investigated. • Pollutant concentrations were higher in inner bays near industrial facilities. • Industrial emissions, shipbuilding, and combustion were major contributors. • Potential biological impacts from various chlorinated aromatics were imminent. [ABSTRACT FROM AUTHOR]

Air samples were collected around industrial parks in Jiangsu, China, to allow the concentrations, profiles, and risk assessment of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), polychlorinated naphthalenes (PCNs), and metals to be investigated. The concentrations of ΣPBDD/Fs and ΣPCNs were 1324.26–2080.98 fg/m3 (11.35–42.57 fg I-TEQ/m3) and 10,404.9–29,322.9 fg/m3 (1.32–7.19 fg I-TEQ/ m3), respectively. The highest concentration of ΣPBDD/Fs and ΣPCNs were observed at site C. PBDD/Fs were mainly dominated by PBDFs. The main contributor to the ΣPBDD/Fs in all samples was 1,2,3,4,6,7,8-HpBDF, which accounted for 25.75%–39.4%. For PCNs, the predominating homologues were tetra-, tri- and penta-CNs, which contributed 30.7%–43.3%, 24.7%–31.0%, and 10.6%–21.6%, respectively. As for metals, the pollution of As, Mn, Cr, and Ni in most samples exceeded National Ambient Air Quality Standards of China. Assessing the risk of inhalation exposure showed that there were potential carcinogenic risks to local residents. [ABSTRACT FROM AUTHOR]

Magnetic covalent organic frameworks (Fe3O4@TPPCl4) were synthesized via a one-pot process in which magnetic nanoparticles (Fe3O4@MNP) served as a magnetic core and 2,4,6-trihydroxy-1,3,5-benzenetricarbaldehyde (TP) and 2,2′,5,5′-tetrachlorobenzidine (PCl4) as two building blocks to form a shell. The as-prepared Fe3O4@TPPCl4 nanoparticles have superior features, including large surface area (186.5 m2 g−1), high porosity, strong magnetic responsiveness (42.6 emu g−1), high chlorine content, and outstanding thermal stability, which make them an ideal adsorbent for highly selective enrichment of polychlorinated naphthalenes (PCNs). Combining with atmospheric pressure gas chromatography tandem mass spectrometry (APGC-MS/MS), a simple analytical method of Fe3O4@TPPCl4-based magnetic solid-phase extraction (MSPE)-APGC-MS/MS was developed, which exhibited good linearity (r ≥ 0.9991) for eight PCNs in the concentration range 0.1–100 ng L−1. Moreover, low detection limits (0.005–0.325 ng L−1), high enrichment factors (46.62–81.97-fold), and good relative standard deviations (RSDs) of inter-day (n = 3, 1.64 to 7.44%) and day-to-day (n = 3, 2.62 to 8.23%) were achieved. This method was successfully applied to the selective enrichment of PCNs in fine particulate matter (PM)2.5 samples, and ultra-trace PCNs were found in the range 1.56–3.75 ng kg−1 with satisfactory recoveries (93.11–105.81%). The successful application demonstrated the great potential of Fe3O4@TPPCl4 nanoparticles as an adsorbent for enrichment of halogenated compounds. [ABSTRACT FROM AUTHOR]

Chlorophenols (CPs) and phenol are abundant in thermal and combustion procedures, such as stack gas production, industrial incinerators, metal reclamation, etc., which are key precursors for the formation of polychlorinated naphthalenes (PCNs). CPs and phenol can react with H or OH radicals to form chlorophenoxy radicals (CPRs) and phenoxy radical (PhR). The self-condensation of CPRs or cross-condensation of PhR with CPRs is the initial and most important step for PCN formation. In this work, detailed thermodynamic and kinetic calculations were carried out to investigate the PCN formation mechanisms from PhR with 2-CPR/3-CPR. Several energetically advantageous formation pathways were obtained. The rate constants of key elementary steps were calculated over 600~1200 K using the canonical variational transition-state theory (CVT) with the small curvature tunneling (SCT) contribution method. The mechanisms were compared with the experimental observations and our previous works on the PCN formation from the self-condensation of 2-CPRs/3-CPRs. This study shows that naphthalene and 1-monochlorinated naphthalene (1-MCN) are the main PCN products from the cross-condensation of PhR with 2-CPR, and naphthalene and 2-monochlorinated naphthalene (2-MCN) are the main PCN products from the cross-condensation of PhR with 3-CPR. Pathways terminated with Cl elimination are preferred over those terminated with H elimination. PCN formation from the cross-condensation of PhR with 3-CPR can occur much easier than that from the cross-condensation of PhR with 2-CPR. This study, along with the study of PCN formation from the self-condensation 2-CPRs/3-CPRs, can provide reasonable explanations for the experimental observations that the formation potential of naphthalene is larger than that of 1-MCN using 2-CP as a precursor, and an almost equal yield of 1-MCN and 2-MCN can be produced with 3-CP as a precursor.

In the past decades, the environmental presence and ecological risks of chlorinated paraffins (CPs), an emerging class of organic halogen compounds, have been receiving increasing attention worldwide. Short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) constitute the important CPs of considerable concern. In this review article, the state-of-the-art research status on the environmental transformation of CPs, including thermal decomposition, photolytic and photocatalytic degradation, biological metabolism, and atmospheric transformation, was summarized and integrated in detail. The degradation efficiency and transformation products of CPs in these environmental processes were evaluated, in which dechlorination was considered as the major reaction pathway. Notably, waste incineration of CPs has been demonstrated to generate a variety of persistent chlorinated aromatic hydrocarbons such as polychlorinated biphenyls and polychlorinated naphthalenes, which have more significant environmental impacts. Additionally, photodegradation and photocatalysis are suggested as the feasible techniques for efficient removal of SCCPs from water matrices. Overall, the current transformation studies of CPs could facilitate the comprehensive understanding of their environmental behaviors and fate as well as the development of promising remediation strategies for pollution control. [ABSTRACT FROM AUTHOR]

Urban green space is a special space for urban life and natural contact and has an important impact on human health. However, little information is available on dioxin-like persistent organic pollutants (POPs) in the soils from the specific areas. We measured the concentrations of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and polychlorinated biphenyls (PCBs) in the soils from urban green space in a metropolis, North China, and found total concentrations of PCDD/Fs, PCBs, and PCNs in the range of 11.5–91.4, 14.7–444, and 82.5–848 pg/g, respectively. It was worth to notice that the concentrations of PCDD/Fs in public park soil from urban center were significantly higher than those in the road greenbelts and resident lawns (Kruskal-Wallis test, p = 0.004). The source analysis indicated that sewage sludge from wastewater treatment plants were important sources of PCNs and PCDD/Fs in urban green land soils, and atmospheric deposition from municipal solid waste incinerator (MSWI) also play an important role in PCDD/F sources. The rough exposure risk evaluation showed that the residents were at a safe level with the daily doses being 0.172–3.144 fg/kg BW/day for children and 0.022–0.406 fg/kg BW/day for adult. Due to the complex and variable sources of PCDD/Fs in urban areas, dioxin-like POPs in urban green land should be given more attention to weaken human exposure. [ABSTRACT FROM AUTHOR]

Polychlorinated naphthalenes (PCNs) are organochlorine compounds comprising the naphthalene ring system, in which one to eight hydrogen atoms have been substituted with chlorine atoms, yielding 75 chlorinated congeners. They were considered as persistent organic pollutants in May 2015 at the Stockholm Convention owing to their toxicity, persistence, bioaccumulation and potential for long-range transport in the environment. PCNs were invented in the early 1900s to be applied as flame-retardants in consumer products. Flame-retardants are effective in minimizing fire-related problems. However, their negative environmental impacts have become of great concerns. Different analytical methods for the evaluation of PCNs in various environmental samples were reviewed in this article.. Their levels in human and some environmental samples across the globe are also mentioned. Reported data revealed that the highly toxic congeners (CNs 66, 67 and 73) are prevalent in most samples, there is need for their continuous monitoring in our environment. [ABSTRACT FROM AUTHOR]

Objectives Due to structural and toxicological similarities to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), polychlorinated naphthalenes (PCNs) were included in the Stockholm Convention on Persistent Organic Pollutants (POPs) in 2015. Hexachloronaphthalene (HxCN) is considered to be one of the most toxic congeners of PCNs. The objective of this study was to determine the maternal and fetal tissue concentrations of hexachloronaphthalene after a single administration. Material and Methods Pregnant female Outbred Wistar rats were used for the study. The [ 14 C]-HxCN was administered in a single oral dose of 0.3 mg/rat (150 kBq/rat) on gestational day 17 (GD17), GD18 or GD19. All dams were sacrificed on GD20. The blood and selected tissue samples taken from mothers and fetuses 24 h, 48 h or 72 h after exposure were evaluated for the distribution of HxCN. Results Maximum concentrations of HxCN in pregnant rats were found in the liver and adipose tissue. Relatively high levels of HxCN were also reported in the spleen, ovaries, adrenal glands and uterus, as well as in the sciatic nerve, brain and kidneys. Hexachloronaphthalene penetrates through the blood-brain barrier (BBB), as evidenced by twice the concentration in the brain compared to the blood concentration, and through the placental barrier, as indicated by the level of maternal-fetal compartment (placenta, amniotic fluid, litter). Among the examined fetal tissues, the highest levels of HxCN were found in the kidneys and in the brain. The concentrations in these organs were higher than that found in the maternal blood. Conclusions This paper is the first to detail the concentrations of HxCN in the maternal tissues and the transplacental transfer of the tested compound to the fetuses. The exposure of pregnant rats to HxCN results in its accumulation in the maternal liver, fat tissue, reproductive and nervous system, and particularly in the fetal brain. This demonstrates both the effective absorption and significant systemic accumulation which could lead to negative health implications. Int J Occup Med Environ Health 2018;31(5):685–695

Historical (or legacy) contaminants, such as metals and persistent organic pollutants (POPs; e.g., polychlorinated biphenyls) have been measured in circumpolar subpopulations of polar bears, especially from Hudson Bay, East Greenland, and Svalbard, but substantially less is currently known about new and/or emerging contaminants such as polychlorinated naphthalenes, current-use pesticides, organotins, and polycyclic aromatic compounds (PACs). The polar bear (Ursus maritimus) is an apex Arctic predator that accumulates high levels of bioaccumulative POPs and mercury (Hg), but there is currently no comprehensive profiling of the present knowledge on contaminants in tissue and body compartments in polar bears. Based on current literature reports and data, and including archived museum samples (as far back as the 1300s) and up to 2018, the aim of this review is to utilize available data to examine the comparative distribution and burden of mainly lipophilic contaminants in kidney, liver, fat, and other body compartments, such as milk, blood, and brain. Highlight outcomes from this review include the following: (1) the kidneys are one of the most important tissue depots of contaminants in polar bears; (2) there is a critical lack of data concerning the presence of metals of concern (other than Hg); and (3) there currently are no data available on the concentrations of many newer and emerging contaminants, such as PACs, which is especially relevant given the increasing oil and gas development in regions, such as the Beaufort Sea (Canada). Additionally, given the vulnerability of polar bear populations worldwide, there is a need to develop non-invasive approaches to monitor contaminant exposure in polar bears. [ABSTRACT FROM AUTHOR]

The pure rotational spectrum of the PCN radical (X3Σ-) has been measured for the first time using a combination of millimeter/submillimeter direct absorption and Fourier transform microwave (FTMW) spectroscopy. In the millimeter instrument, PCN was created by the reaction of phosphorus vapor and cyanogen in the presence of an ac discharge. A pulsed dc discharge of a dilute mixture of PCl3 vapor and cyanogen in argon was the synthetic method employed in the FTMW machine. Twenty-seven rotational transitions of PCN and six of P13CN in the ground vibrational state were recorded from 19 to 415 GHz, all which exhibited fine structure arising from the two unpaired electrons in this radical. Phosphorus and nitrogen hyperfine splittings were also resolved in the FTMW data. Rotational satellite lines from excited vibrational states with v2 = 1-3 and v1 = 1 were additionally measured in the submillimeter range. The data were analyzed with a Hund's case (b) effective Hamiltonian and rotational, fine structure, and hyperfine constants were determined. From the rotational parameters of both carbon isotopologues, the geometry of PCN was established to be linear, with a P-C single bond and a C-N triple bond, structurally comparable to other non-metal main group heteroatom cyanides. Analysis of the hyperfine constants suggests that the two unpaired electrons reside almost exclusively on the phosphorus atom in a π2 configuration, with little interaction with the nitrogen nucleus. The fine structure splittings in the vibrational satellite lines differ significantly from the pattern of the ground state, with the effect most noticeable with increasing v2 quantum number. These deviations likely result from spin-orbit vibronic perturbations from a nearby 1Σ+ state, suggested by the data to lie ∼12 000 cm-1 above the ground state. [ABSTRACT FROM AUTHOR]

Polychlorinated naphthalenes (PCNs) were characterized as persistent organic pollutants (POPs) that were widely distributed in the environment. Although the striking in vivo toxicity of these pollutants towards both animals and humans was well documented, their cytotoxicity and mechanism of action have not been extensively investigated. In this study, the in vitro antiproliferative activity of mono- and di-chloronaphthalenes as representative PCNs were evaluated and the results indicated strong growth inhibitory effects against mammalian cells, especially the human breast MCF-10A cell and human hepatic HL-7702 cells. 2-Chloronaphthalene with the most potent antiproliferative effects within the tested PCNs, which showed IC 50 values ranging from 0.3 mM to 1.5 mM against selected human cell lines, was investigated for its working mechanisms. It promoted cellular apoptosis of MCF-10A cells upon the concentration of 200 μM. It also induced the autophagy of MCF-10A cells in a dose-dependent manner, resulting in cell death via the interaction of autophagy and apoptosis. Thus, these findings supported the theoretical foundation for interventional treatment of PCNs toxicity and also provided implications for the use of chemopreventive agents against the toxic chlorinated naphthalenes in the environments. [Display omitted] • In vitro antiproliferative activity of mono-/di-chloronaphthalene as was evaluated. • Test PCNs inhibited the proliferation of mammalian cells, notably MCF-10A cells. • 2-Chloronaphthalene's IC50 value ranges from 0.3 to 1.5 mM in tested cell lines. • 2-Chloronaphthalene promotes autophagy and apoptosis of MCF-10A cells. [ABSTRACT FROM AUTHOR]

The knowledge of polychlorinated naphthalenes (PCNs) in the Antarctic atmosphere is quite limited compared to the Arctic. PCNs are a global concern because of their PBT characteristics (i.e., persistent, bioaccumulative, and toxic) and severe and often deadly biological effects on people and other animals. Therefore, the present study used a passive air sampling method to conduct long-term air monitoring of PCNs for almost a decade from 2013 to 2022, specifically on Fildes Peninsula, situated on King George Island, located in West Antarctica. The median sum of mono-CNs to octa-CN concentration (∑ 75 PCNs) in the Antarctic atmosphere was 12.4 pg/m3. In terms of homologues, mono-CNs to tri-CNs predominated. Among these, the prevalent congeners observed were PCN-1 and PCN-2, originating from mono-CNs, followed by PCN-5/7 from di-CNs, and PCN-24/14 from tri-CNs, respectively. Between 2013 and 2022, the total levels of PCNs were found to have decreased approximately fourfold. Ratio analyses and principal component analysis (PCA) showed that the long-range atmospheric transport and combustion-related sources as the potential PCN sources in the study area. This paper provides the most up-to-date temporal trend analysis of PCNs in the Antarctic continent and is the first to document all 75 congeners (mono-CNs to octa-CN homologue groups). [Display omitted] • This is the first study to report all 75 PCN congeners from the Antarctic continent. • A decreasing temporal trend was observed from 2013 to 2022. • The mono-CNs to tri-CNs consist of the dominating homologues group. • LRAT and combustion-related sources were the primary sources of the study area. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated naphthalenes (PCNs), and halogenated PAHs (XPAHs) are widespread organic pollutants found in the environment and food. Therefore, analytical methods have been developed to investigate the sources, occurrences, and transport of these compounds and assess the risk associated with them. This review summarizes the widely used methods for sampling, pretreatment, and instrumental analyses of these compounds in environmental (e.g., gas, particulate matter, water, snow, sediment, soil, and biota) and food samples. Additionally, the recently observed levels of these compounds in the environment and food have been summarized. Finally, the most effective gas chromatography column for future PAH analysis and the need of reference standards for XPAH analysis has been discussed. This review provides a comprehensive understanding of the recent analytical techniques used to analyze PAHs, PCNs, and XPAHs for the benefit of novice researchers and technicians. • A comprehensive understanding of analytical techniques for PAHs, PCNs, and XPAHs were provided. • Effective gas chromatography columns for future PAH analysis were discussed. • Concentrations of PAHs, PCNs, and XPAHs in various environmental samples were summarized. • Future prospects on the research for PAHs, PCNs, and XPAHs were provided. [ABSTRACT FROM AUTHOR]

Polychlorinated biphenyls (PCBs) are an important class of industrial pollutants that areubiquitous in the marine and freshwater environments (NAS, 1979). Although the “planar” or“non-ortho” PCB congeners are present in much lower concentrations than other PCBcongeners, they can be responsible for much of the dioxin-like (TCDD) toxicity in the marineecosystem. Further, their environmental fate may be different from other PCBs. Theirdetermination is, therefore, crucial for assessment of contaminant status of environmentalcompartments. Mono-ortho PCBs and polychlorinated naphthalenes (PCN) although less potent,also exhibit TCDD-like toxicity. Yet, only total PCBs are usually reported and the levels of non-and mono-ortho PCBs relative to total PCBs have rarely been studied and data on PCN areuncommon in oceanic samples (Jarnberg et al., 1993). Among the known sources, municipalwaste dischargers could be a significant contributor of these synthetic compounds to the ocean(i.e., Venkatesan, 1998; Zeng and Venkatesan, 1999).

Despite the growing interest in PCNs and the dioxin-like toxicity exhibited by a number of congeners, a comprehensive assessment of their contribution to the cocktail of dioxin-like contaminants is still lacking. To address such a shortcoming, this study investigated the PCN contamination in foodstuffs recently acquired in France, together with that of the regulatory polychlorinated dibenzodioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs). PCNs were ubiquitous at levels (∑70 PCNs = 2.5-150 pg g -1 wet weight) similar to those reported in other countries, with maximum concentrations observed in fish and fishery products from the North-East Atlantic Ocean. Their congener patterns further suggested unintentional releases of PCNs, while those of the other foodstuffs were correlated to the historical PCN profiles. Low risk from dietary exposure was estimated (∑70 PCNs-EDIs of 60-360 pg kg -1 bw d -1 , ∑24 PCNs-TEQ-EDIs of 8 × 10 -3 -2.2 × 10 -2 pg TEQ kg -1 bw d -1 ), with milk and dairy products being the highest contributors, followed by meat and meat products. Finally, the rather high contributions of PCNs to the total PCNs+PCDD/Fs+PCBs concentrations (0.9-50%, average of 9%) and the toxic equivalents (0.2-24%, average of 5%) show that these substances are not minor components of the PCNs+PCDD/Fs+PCBs cocktail.

Persistent organic pollutants (POPs) are highly toxic organic chemicals. Lakes are one of the main sinks of POPs. POPs can be accumulated in multiple matrices in lake ecosystems and biomagnified through the food web, and thus pose a potential threat not only to lake ecosystems, but also to human health. Given their potential persistent risks, they have received much attention over the past decades. This review comprehensively summarizes the data on the levels and distributions of POPs in selected typical lake ecosystems in China and worldwide, involving water, sediments, organisms, and surrounding soils and atmosphere. It was found that current publications on POPs in Chinese lakes are mainly related to lakes in the developed eastern plain area, with only a few studies concerning the less-developed Qinghai-Tibet Plateau area. Similarly, around the world, there are more research on POPs in developed countries and less in relatively less-developed areas. Moreover, there are significant differences in the levels of POPs in different matrices in different lake ecosystems. Legacy POPs, such as polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and polybrominated diphenyl ethers (PBDEs), were commonly detected and reported in different lakes, while emerging POPs like perfluorinated compounds (PFCs), polychlorinated naphthalenes (PCNs), Tetrabromobisphenol A (TBBPA), and hexabromocyclododecane (HCBD) were relatively less detected or reported. A comprehensive summarization on the levels and distributions of traditional and emerging POPs in lake ecosystems could be significant for further understanding the behaviors and risks of POPs in lake ecosystems. Image 1 • Levels of multiple POPs in typical lake ecosystems are comprehensively summarized. • POPs in different lake ecosystems displayed obviously different profiles. • Available data on POPs in lake ecosystems are mainly related to developed regions. • Further studies on emerging POPs in lake ecosystems are suggested. [ABSTRACT FROM AUTHOR]

A retrospective analysis of a number of historical medicinal grade cod liver oil samples produced in Northern Europe revealed relatively high contamination levels of PCNs, PCDD/Fs and PCBs. The total toxic equivalence (TEQ) associated with PCDD/Fs, dl-PCBs and PCNs was in the range 95–427 pg g-1 for Baltic cod liver oils and from 70 to 148 pg g-1 for oils sourced from the North Atlantic. The corresponding range for canned cod liver products (Baltic Sea) sampled in 2017 ranged from 52 to 104 pg g-1 fat (33–34 pg g-1 ww). The contribution from PCBs to the overall TEQ toxicity was around 3–6-fold higher than from PCDD/Fs and ranged from 24 to 318 pg TEQ g-1ww. The estimated summed TEQ intakes of PCDD/Fs, dl-PCBs and dl-PCNs resulting from the consumption of the daily recommended doses was highest for the Baltic cod liver oils ranging from 16 to 293 pg kg-1 body mass (bm) day-1 for an adult, 20–183 pg kg-1 bm day-1 for a teenager and 15–131 pg kg-1 bm day-1 for a child. The contribution to daily adult TEQ intake from PCNs alone, although relatively small is estimated to contribute up to 5-fold above the recent EFSA proposed TWI of 2 pg kg-1 bm. The results indicate that although currently produced fish oils may undergo rigorous purification procedures and show low contaminant levels, cod livers sourced from the Baltic and consumed locally, continue to contribute substantially to the dietary intake of these contaminants. • Historical medicinal grade cod-liver oils showed high TEQ levels with PCBs > PCDD/Fs > PCNs. • A cod liver oil from the Baltic Sea was most contaminated with a summed TEQ of 427 pg g-1. • Maximum estimated intake from recommended oil doses was 293 pg TEQ kg-1 bm day-1. [ABSTRACT FROM AUTHOR]

The three-dimensional quantitative structure-activity relationship (3D-QSAR) model is established for polychlorinated naphthalenes (PCNs) using the biological degradability (total score) results to modify CN-56 to design 37 new derivatives with higher degradability (increased by 14.55–38.79%). Furthermore, five new CN-56 derivatives are selected through evaluation of their persistent organic pollutant properties (toxicity, bioconcentration, long-range transport) and practicability (stability, insulativity, flame retardancy) using 3D-QSAR, density functional theory (DFT) and molecular docking methods. Environmental and health-based risk assessments are conducted using the multimedia fugacity model and fuzzy theory for complete screening of the new CN-56 derivatives. Whereas CN-56 is classed as high risk, three new derivatives can be classed as medium risk. The biodegradability mechanism analysis of the PCNs indicates that the electrostatic property is the main factor that affects the degradability, which provides a favorable theoretical reference to obtain environmentally friendly fire retardant and insulating materials. [ABSTRACT FROM AUTHOR]

In recent years, the Stockholm Convention has listed an additional set of persistent organic pollutants (POPs) for elimination or restricted use/release. Data on the occurrence of these contaminants in food is scarce. Validated analytical methodology was developed to investigate the occurrence of hexachlorobutadiene (HCBD), pentachlorobenzene (PCBz), hexachlorobenzene (HCB) pentachlorophenol (PCP) and polychlorinated naphthalenes (PCNs) in 120 retail foods and 19 total diet study samples. The foods covered the range of commonly consumed dietary items including dairy products, eggs (hen and other species), poultry, meat, fish, vegetables, etc. HCBD showed a low frequency of detection, whereas PCBz, HCB and PCNs occurred in most samples (ranges: <0.01 to 0.19 μg/kg; <0.01 to 3.16 μg/kg and 0.1 to 166 ng ΣPCNs/kg respectively). PCP (<0.01 to 1.9 μg/kg) was detected more frequently in meat products, offal and eggs. Fish, shellfish, eggs from all species, animal fats, meat, offal and meat products showed higher contamination levels, which is normal when investigating lipophilic POPs. These levels of occurrence are similar to more recently reported literature levels but perhaps lower, relative to historic data. This is not unexpected, given the restrictions/limitations on these chemicals within the UK and Western Europe. The estimated human exposure to population groups through dietary intake is correspondingly low and based on current toxicological knowledge, the levels in the examined samples do not suggest a cause for health concern. The data also provide a current baseline for HCBD, PCBz and PCP, and update existing data for PCN and HCB occurrence in foods. Unlabelled Image • First structured study investigating HCBD, PCBz, HCB, PCP and PCN collectively in food. • PCBz, HCB & PCNs occurred in most samples; HCBD & PCP occurred less frequently • Based on current toxicology, dietary intake from UK food unlikely to cause health concern [ABSTRACT FROM AUTHOR]

Abstract Polychlorinated naphthalenes (PCNs) in the environment in China have been studied extensively. However, there have been no reports on PCNs in human serum samples from China. In this context, we collected 480 serum samples from an industrial city in Eastern China. The concentration range for the sum of the mono-to octa-CNs was 14300–50700 pg/g lipid. The most predominant congener was CN-5/7, which accounted for 21.6%–51.1% of the total PCN concentration. Further analysis indicated that residues of PCN industrial technical products in the local environment appear to be the main source of CN-5/7 in the serum samples. On the other hand, the sum of the tetra-to octa-CNs concentration was obviously higher in males (1390 ± 929 pg/g lipid) than in females (267 ± 25 pg/g lipid). Moreover, the concentrations of combustion-related PCNs in the male 20–24, 25–29 and 30–34 years groups were obviously higher than those in the female samples. Therefore, industrial thermal processes are important sources of PCNs in male serum in addition to PCN products. The toxic equivalent (TEQ) concentrations of PCNs in the pooled serum samples ranged from 0.12 to 0.40 pg/g lipid. CN-10 and CN-66/67 were the dominant TEQ congeners in male serum, and CN-10, CN-1, and CN-2 were the main TEQ congeners in female serum. Graphical abstract Image 1 Highlights • Mono-to octa-CNs were determined in human serum. • CN-5/7 was the predominated congener. • PCN industrial technical product may be a source of CN-5/7 in serum. • Males are more affected by industrial thermal processes than females. [ABSTRACT FROM AUTHOR]

Metallurgical processes are currently the predominant anthropogenic sources of multiple unintentional persistent organic pollutants (POPs), including polycyclic aromatic hydrocarbons (PAHs), chlorinated and brominated PAHs (Cl-PAHs and Br-PAHs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), and polybrominated diphenyl ether (PBDEs). Understanding the formation of multiple POPs is important for source control. These POPs could be formed through fly ash-mediated heterogeneous reactions. In this study, we comprehensively investigated the thermochemical (150–450 °C) formation of these POPs on fly ash samples collected from a secondary aluminum smelter, secondary lead smelter, and iron ore sintering plant. The maximum concentrations of PCNs and PCBs were 154.5 and 181.3 times those in the original fly ash, respectively. Formation variations of PAHs, Cl-PAHs and Br-PAHs, and PBDEs were different from that of PCBs and PCNs. The PAHs concentration, which was the highest among the POPs in the original fly ash, decreased sharply by 95% at 150 °C. The ∑ 19 Cl-PAHs and ∑ 19 Br-PAHs increased marginally at 250 °C before decreasing slightly at 350 °C. The PBDE concentrations decreased under 250 °C and increased at 350 °C. PCNs, PCBs, and PCDD/Fs showed good correlations, all of which had a negative relationship with the PAHs. There were no significant correlations between PAHs and Cl/Br-PAHs. Low brominated congeners could be formed by destruction of higher brominated congeners because of thermal instability of the PBDEs. • Multiple POP formations on different metal smelting fly ash were compared. • The formation variations of PCNs, PCBs and PCDD/Fs were different from that of PAHs and Cl/Br-PAHs. • Positive correlations among PCDD/Fs, PCNs, PCBs formed on fly ash were observed. [ABSTRACT FROM AUTHOR]