Total Polychlorinated Naphthalenes Research Articles

Unintentional emissions of polychlorinated naphthalenes in China: Sources, composition, and historical trends

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.

Occurrence and Trophic Transfer of Polychlorinated Naphthalenes (PCNs) in the Arctic and Antarctic Benthic Marine Food Webs.

Information about the occurrence and trophic transfer of polychlorinated naphthalenes (PCNs) in polar ecosystems is vital but scarce. In this study, PCNs were analyzed in benthic marine sediment and several biological species, collected around the Chinese polar scientific research stations in Svalbard in the Arctic and South Shetland Island in Antarctica. Total PCNs in biota ranged from 28 to 249 pg/g of lipid weight (lw) and from 11 to 284 pg/g lw in the Arctic and Antarctic regions, respectively. The concentrations and toxic equivalent (TEQ) of PCNs in polar marine matrices remained relatively low, and the compositions were dominated by lower chlorinated homologues (mono- to trichlorinated naphthalenes). Trophic magnification factors (TMFs) were calculated for congeners, homologues, and total PCNs in the polar benthic marine food webs. Opposite PCN transfer patterns were observed in the Arctic and Antarctic regions, i.e., trophic dilution and trophic magnification, respectively. This is the first comprehensive study of PCN trophic transfer behaviors in remote Arctic and Antarctic marine regions, providing support for further investigations of the biological trophodynamics and ecological risks of PCNs.

Polychlorinated naphthalene concentrations and temporal trends in serum from the general Chinese adult population and effects of polychlorinated naphthalenes on thyroid function

Polychlorinated naphthalenes (PCNs) have stopped being produced and used but have been detected in human serum around the world. Investigating temporal trends in PCN concentrations in human serum will improve our understanding of human exposure to PCNs and the risks posed. We determined the PCN concentrations in serum collected from 32 adults in five consecutive years (2012–2016). The total PCN concentrations in the serum samples were 0.00–5443 pg/g lipid weight. We found no significant decreases in the total PCN concentrations in human serum and even found that the concentrations of some PCN congeners (e.g., CN20) increased over time. We found differences in the PCN concentrations in serum from males and females, the CN75 concentration being significantly higher in serum from females than males, meaning CN75 poses more serious risks to females than males. We found, using molecular docking techniques, that CN75 interferes with thyroid hormone transport in vivo and that CN20 affects thyroid hormone binding to receptors. These two effects are synergistic and can cause hypothyroidism-like symptoms.

Spatial and temporal trends of polychlorinated naphthalenes in the Arctic atmosphere at Ny-Ålesund and London Island, Svalbard

Polychlorinated naphthalenes (PCNs) are ubiquitous atmospheric pollutants that can even be found in the most remote region of the Arctic. However, temporal trend analysis and reports on mono- to octa-CN in the Arctic air are still scarce. In the present study, 8 years of atmospheric monitoring data of PCNs on Svalbard was investigated using XAD-2 resin passive air samplers (PASs) from 2011–2019. The concentrations of ∑75 PCNs in the Arctic air ranged from 4.56 to 85.2 pg/m3, with a mean of 23.5 pg/m3. The mono-CNs and di-CNs were the dominant homologue groups accounting for 80 % of the total concentrations. The most abundant congeners were PCN-1, PCN-2, PCN-24/14, PCN-5/7, and PCN-3, respectively. A declining time trend of PCN concentration was observed from 2013 to 2019. The reduction in PCN concentrations is likely due to declining global emissions and banned production. However, no significant spatial difference was observed among the sampling sites. The total PCN toxic equivalency (TEQ) concentrations in the Arctic atmosphere ranged from 0.043 to 1.93 fg TEQ/m3 (mean 0.41 fg TEQ/m3). The fraction of combustion-related congeners to ∑PCNs (tri- to octa-CN) analysis results indicated that the sources of PCNs in the Arctic air were contributed mainly from reemissions of historical Halowax mixtures and combustion-related sources. To the best of our knowledge, this is the first research to report all 75 PCN congeners and homologue groups in Arctic air. Therefore, this study provides data on recent temporal trend analysis as well as all the 75 PCN congeners in the Arctic atmosphere.

Polychlorinated naphthalenes (PCNs) in soils and plants from Svalbard, Arctic: Levels, distribution, and potential sources

As persistent organic pollutants (POPs) newly banned by the Stockholm Convention, polychlorinated naphthalenes (PCNs) have been widely detected in various environmental matrices. To date, however, the occurrence of PCNs in soils and plants in the Arctic environment has not been reported. In the current study, the concentrations and distribution of PCNs in Arctic soils and plants from Svalbard were analyzed. Total PCN concentrations ranged from 5.3 to 2550 pg/g dry weight (dw) in soils and 77 to 870 pg/g dw in plants. The higher levels of PCNs near the research stations and Longyearbyen town highlighted the significant influence of local anthropogenic emission sources. The composition of PCNs in Arctic soils and plants was dominated by lower chlorinated homologues, especially mono- to trichlorinated naphthalenes, which accounted for over 80 % of total PCNs in the soil and plant samples. The correlation analysis indicated the potential influences of total organic carbon (TOC) content on PCN concentrations in the soil, and octanol-air partition coefficients (KOA) or octanol-water partition coefficients (KOW) on PCN accumulation from soils to plants. To the best of our knowledge, this is the first study to report on the concentration and distribution of PCNs in Arctic soils and plants.

Contamination and sources of polychlorinated naphthalenes in the surface sediments of Chaobai River, China

In aquatic systems, sediment is both a sink for persistent organic pollutants (POPs) and a potential source of POPs release. Consequently, it is important to understand the pollution characteristics and sources of polychlorinated naphthalenes (PCNs) as POPs of Stockholm Convention in sediment for control of the ecological risk. Atmospheric deposition is a potential source of PCNs in sediment. However, there is no clear report on the contribution of atmospheric deposition to PCNs in sediments. In this study, the Chaobai River in China was selected because it is an important drinking water source that is not affected by wastewater discharge. Surface sediments from the river were analyzed for 75 PCN congeners by using high resolution gas chromatography combined with high resolution mass spectrometry. The total PCNs concentration ranged from 54 to 2266 (mean: 402) pg/g. The toxic equivalent quantity of 19 PCNs in surface sediments was 9.69 × 10−2, and CN73, CN66/CN67, and CN63 had the largest contributions to this value. Dichlorinated and trichlorinated naphthalenes were the dominant homologs. The PCN data from the sediment samples in this study were combined with data for PCNs in ambient air from a literature, which has a good match with this study in both temporal and spatial scales. The contribution of atmospheric deposition to PCNs in the surface sediment was evaluated by comparing congener characteristics and correlation analysis. Our study indicated atmospheric transportation and deposition are important pathways for transport of PCNs into surface sediments.

Polychlorinated naphthalenes in farmed Chinese mitten crabs in China: Concentration, distribution and source analysis

Polychlorinated naphthalenes (PCNs) are both highly toxic and bioaccumulative environmental contaminates. Dietary intake is the primary pathway for human exposure to PCNs, and PCN concentrations in aquatic foodstuffs are relatively high. Chinese mitten crab (Eriocheir sinensis) is one kind of popular aquatic foodstuffs in Asian countries. Farmed crabs could exposure to PCNs both through feed and environment. However, information on the occurrence of PCNs in farmed crabs is scarce. The present study investigated 75 PCN congeners in farmed Chinese mitten crabs, crab compound feed and sediments collected from Anhui Province and Shanghai in China. The total PCN concentrations in farmed Chinese mitten crabs from Anhui Province and Shanghai were 11.2–42.2 and 5.46–43.8 pg/g wet weight (ww), respectively. The PCN homologue profiles in crabs from both areas were similar, and both were dominated by di-CNs and penta-CNs. In contrast, lower chlorinated PCNs (di-CNs, tri-CNs and tetra-CNs) were the most common homologues in specimens of crab compound feed and sediment samples, indicating that selective bioaccumulation and metabolism of PCNs might occur in farmed crabs. No regional differences were found in the PCN congener profiles of farmed crabs, feed and sediment samples taken from Anhui Province and Shanghai. An assessment found no significant health risk associated with Chinese exposure to PCNs through farmed Chinese mitten crab consumption.

Partitioning and potential sources of polychlorinated naphthalenes in water-sediment system from the Yangtze River Delta, China

Spatial trends, partitioning behavior, and potential sources of polychlorinated naphthalenes (PCNs) in water-sediment system from the Yangtze River Delta (YRD) were investigated in this study. The total concentrations of 75 PCNs in water and sediment samples were 0.022–0.310 ng/L and 0.01–1.59 ng/g dry weight, respectively. The homolog patterns in the sediment and water samples were somewhat different. Di-to tetra-CNs made larger contributions in the sediment, while the mono-to tri-CNs were dominant homologs in the water. Overall, the low-chlorinated naphthalenes (mono-to tetra-CNs) were found to be the dominant homologs in the YRD water and sediment samples, and the homolog group contributions to the total PCNs concentrations decreased as the number of chlorine atoms increased. CN-5/7 and CN-24/14 were found at high concentrations in both the water and sediment. Partitioning and transfer of PCNs between water and sediment were assessed by calculating the partition coefficients and fugacity fractions. The partition coefficients showed that PCNs were not in equilibrium status in the water–sediment system, and hydrophobicity played an important role in PCNs partitioning. The fugacity fractions indicated that mono- to tri-CNs had stronger tendencies to escape from the sediment into the water, while the high-chlorinated naphthalenes close to equilibrium. Principal component analysis and correlation analysis indicated that industrial thermal processes and the use and disposal of products containing PCNs industrial products are sources of PCNs in the YRD water-sediment system.

Polychlorinated Naphthalenes across the Great Lakes: Lake Trout and Walleye Concentrations, Trends, and TEQ Assessment-2004-2018.

Polychlorinated naphthalenes (PCNs) were measured in lake trout and walleye over the period 2004-2018, utilizing isotope dilution techniques with high-resolution gas chromatography/high-resolution mass spectrometry to assess concentrations and toxic equivalence (TEQ). An age-trend model was applied to mitigate the effect of a changing lake trout age structure. Most Great Lakes Fish Monitoring and Surveillance Program sampling sites demonstrated significant half-life and percent decreases for lake trout total PCNs and total TEQ over the 2004-2018 period, the exceptions being Lake Erie lake trout and walleye which illustrated increasing concentrations. Great Lakes total PCN concentrations ranged between 5701 and 100 pg/g ww, whereas total PCN TEQ concentrations ranged between 8.89 and 0.13 pg-TEQ/g ww. Based on the average number of chlorines per naphthalene, we determined that the overall lake trout and walleye PCN congener distribution has significantly shifted to a lower-chlorinated composition in the Great Lakes (5.33 to 4.48 Cl/CN) and has resulted in a substantial 59.1% reduction of the overall total PCN TEQ burden. A prominent PCN concentration trend breakpoint was observed in Lake Ontario lake trout over the 2012-2016 period likely associated with hazardous waste cleanups, channel dredging, and spoils disposal in the Detroit River and western-basin of Lake Erie.

Polychlorinated naphthalenes (PCNs) in food products in Latvia: Congener-specific analysis, occurrence, and dietary exposure of the general population

A study was performed to evaluate the dietary exposure of the Latvian population to polychlorinated naphthalenes (PCNs). Based on the toxicological characteristics, provisional levels of occurrence, congener patterns, and the availability of analytical standards, twenty-six congeners were included in the analysis. Considering the planar structure of PCNs, an analytical protocol on the basis of destructive clean-up and isolation of analytes on carbon was applied, while GC-HRMS and isotope dilution were used for the detection and quantification of analytes. Commonly consumed foods were analyzed for the content of PCNs, followed by per capita intake calculations. By applying the available in vitro relative potency (REP) factors, putative toxic equivalents (TEQ) were determined, in order to assess the “dioxin-like” effect arising from the presence of PCNs in food. The daily intake (EDI) for total PCNs (∑PCN) and PCN-TEQ for the general population were calculated to be 116 pg kg−1 body weight (b.w.) and 0.036 pg TEQ kg−1 b.w., respectively. Fish and fish products were found to provide the main contribution to the dietary “dioxin-like” burden of PCNs, constituting ∼60% of the total PCN-TEQ intake. For some fish samples, PCN-TEQ could additionally contribute up to ∼3% to the regulated PCDD/F-PCB-TEQ, while for other matrices this contribution could be lower by an order of magnitude. The obtained data indicated that the estimated dietary exposure to PCNs is likely to be of low concern, although PCN-TEQ could be recognized as a contributor to the overall “dioxin-like” TEQ loading that results from the exposure to halogenated aromatics.

Atmospheric pressure ionization for gas chromatography-high resolution mass spectrometry determination of polychlorinated naphthalenes in marine sediments

In this work, the performance of the atmospheric pressure chemical ionization (APCI) and photoionization (APPI) was assessed to develop a new selective and sensitive gas chromatography-high resolution mass spectrometry (GC-HRMS) method for the determination of polychlorinated naphthalenes (PCNs) in sediment samples. The capability of both APCI and APPI sources for the ionization of PCNs was investigated, showing the formation of the molecular ion and the [M‒Cl+O]‒ ion in positive and negative ion modes, respectively. Positive ion APCI provided high responses using high corona ion current, while the use of high vapour pressure dopant-solvents, such as toluene in positive mode and diethyl ether in the negative mode, was required to achieve high ionization efficiencies in APPI. The performance of the two API sources in the PCN determination by GC-HRMS were compared and the best results were achieved using the GC-APPI(+)-HRMS (Orbitrap) system. The GC-APPI(+)-HRMS (Orbitrap) method was applied to the characterization of Halowax mixtures and the analysis of marine sediments collected near to the coastal area of Barcelona (NE, Spain), demonstrating a great detection capability with low method limits of detection (0.2–1.6 pg g−1 dry weight), good precision (RSD <15%) and trueness (relative error <13%). Total PCN concentrations ranged from 0.35 to 5.0 ng g−1 dry weight and the presence of related compounds, such as polychlorinated biphenyls (PCBs), was also detected by combining positive and negative ion modes, providing complementary information to better monitor of all PCN congener groups. The results presented here show the feasibility of the GC-APPI-HRMS method for the suitable determination of PCNs.

Concentrations, toxic equivalence, and age-corrected trends of legacy organic contaminants in Lake Champlain lake trout: 2012–2018

Our study is the first comprehensive, multi-year assessment of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), organochlorine pesticides (OCPs), polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDD/Fs) lake trout concentrations and trends in Lake Champlain (LC). Lake trout whole-fish, fillets, and eggs were collected over the 2012–2018 study period. Total PCB concentrations (395.7 ng/g wet weight (ww)) were the highest average concentration of any contaminant grouping reported in this study. Whole-fish lake trout modeling revealed highly significant (p < 0.05) log-linear correlations for all dioxin-like contaminants measured. Overall contaminant decreases for the 2012–2018 period ranged from 20.9% (total PCNs) to 39.3% (2378-TCDD). Contaminant decreases for total PCBs and total-5-PBDEs were 30.9% and 48.3%, respectively. Of particular significance were the measured total PBDE concentrations (74.3 ng/g ww) found in LC whole-fish lake trout. Log-linear forecasting indicates that whole-fish lake trout TEQs will be below the guidelines protective of wildlife thresholds during the periods 2035–2047 (TRGbird) and 2062–2088 (TRGmammal). Based on current USEPA guidelines, all lake trout fillets from Lake Champlain analyzed for this study exceed the human health cancer screening value of 0.15 pg-TEQ/g ww by a substantial margin (average = 8.61 pg-TEQ/g ww). Dioxin-like trend data collected for Lake Champlain indicates that the mechanisms of contaminant uptake, trends, and yearly percent decline reflect those found in the Great Lakes.

Polychlorinated naphthalenes, polychlorinated dibenzo-p-dioxins and dibenzofurans, and polychlorinated biphenyls in soils in an industrial park in Northwestern China: Levels, source apportionment, and potential human health risks

Seventeen soil samples collected in an industrial park located in Ningxia Province, Northwestern China were analyzed for polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and polychlorinated biphenyls (PCBs). The PCN, PCDD/F, and PCB concentration ranges were 183–3340, 7.00–215, and 45.1–355 pg/g, respectively. Positive matrix factorization showed that secondary ferrous metal smelters and cement kilns contributed more than 70% of the total PCN concentration. Historical use of Halowax 1051 also affected the PCN concentrations in soil. Principal component analysis indicated that the PCDD/F concentrations in soil in the study area were mainly affected by thermal processes in secondary ferrous metal smelters. CB-209 was an important contributor to total PCBs in the study area, and likely originated from the phthalocyanine-type pigments used in a local recycled paper mill. Samples S10, S1, S17, and S6 had high ∑TEQ (PCDD/Fs + PCNs + PCBs) concentrations, and the carcinogenic risks of PCDD/Fs, PCNs, and PCBs for workers from these samples were 0.487 × 10−6, 0.234 × 10−6, 0.230 × 10−6, and 0.210 × 10−6, respectively. According to our results, the health risks of PCDD/Fs, PCNs, and PCBs for workers in this area should be given more attention.

Temporal trends in polychlorinated naphthalene emissions from sintering plants in China between 2005 and 2015

The Chinese Government has established stringent policies since 2005 to control SO2, particulate matter, and NOx emissions from sintering plants with the aim of tackling severe air pollution in China. Notably, sintering is also important sources of polychlorinated naphthalenes (PCNs), but it is not clear whether the air pollution control policies have led to decreased PCN emissions. In this study, the PCN concentrations in 144 stack gas, 87 discarded fly ash, and 24 desulfurization by-product samples from 24 Chinese sintering plants were determined. This study revealed that desulfurization processes decreased PCN emissions by 47.2%–72.2%. However, these PCNs were not completely eliminated, and transformed to desulfurization by-product. PCN emission in such previously ignored solid residues, including of desulfurization by-product and fine particles, produced in the process of cutting down air pollutants emissions from Chinese sintering plants between 2005 and 2015 was found contained 324 kg, and these residues therefore need to be managed better than currently. Furthermore, PCN concentrations were higher from produced in old plants than produced in new plants, so it is necessary to increase the rate at which out-of-date sintering plants are eliminated. Phasing out old sintering processes decreased total PCN emissions in China by 1549 kg between 2005 and 2015.

Polychlorinated naphthalenes in human serum samples from an industrial city in Eastern China: Levels, sources, and sex differences

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.

The occurrence and distribution of polychlorinated naphthalenes (PCNs), focusing on tissue-specific bioaccumulation in crucian carp in South Korea

The occurrence and distribution of 41 congeners of polychlorinated naphthalenes (PCNs) were investigated in major tissues of crucian carp (muscle, gonad, liver, and blood) and in river sediment to assess the bioaccumulation potential of PCNs. The total PCN concentrations in sediment ranged from 4.37 to 19.5 pg/g dry weight (dw), mainly comprising CN-13, CN-33/34/37, and CN-38/40. Among fish tissues, higher PCN concentrations were observed in the gonads (29.6 ± 10.3 pg/g wet weight, ww) and liver (25.7 ± 4.35 pg/g ww) of crucian carp than in the muscle (2.17 ± 0.68 pg/g ww). CN-28/43, CN-33/34/37, CN-42, CN-52/60, CN-53/55, and CN-66/67 congeners were detected most frequently and had the highest concentration among all crucian carp tissues. We investigated the association between the PCN concentration in each tissue (muscle, liver, and gonad) and the size of the fish (total length and weight) and found positive correlations between the PCN concentration in the gonads and the total length and weight (p < 0.05, Spearman correlation).

Simultaneous Removal of Polychlorinated Dibenzo-p-dioxins/dibenzofurans, Polychlorinated Biphenyls, and Polychlorinated Naphthalenes From Flues Gases From Coke Gas Burning Using Selective Catalytic Reduction Equipment

The removal efficiencies of typical unintentionally produced persistent organic pollutants (UP-POPs) from flues gases from coke gas burning were obtained using selective catalytic reduction (SCR) equipment installed in a large coking plant. The total congeners of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) in the flue gases at the inlet and outlet of the SCR equipment and the dustfall were analyzed. The results show that the removal efficiency of the total PCDD/Fs was the highest (94.6%). The removal efficiencies of total PCBs and total PCNs were 74.7% and 78.4%, respectively. The homologue profile of UP-POPs in the flue gases at the inlet of the SCR equipment notably differed from that at the outlet. Highly chlorinated UP-POPs predominated over the homologue profile of UP-POPs in the inlet flue gas, while low-chlorinated UP-POPs were predominant in the outlet flue gas. The SCR equipment achieved a better removal efficiency with respect to highly chlorinated UP-POPs. Catalytic reduction and catalytic oxidation degradation are both important mechanisms for the removal of UP-POPs from flue gas using SCR equipment.

Concentrations and trophic magnification of polychlorinated naphthalenes (PCNs) in marine fish from the Bohai coastal area, China.

Polychlorinated naphthalenes (PCNs) have been found widely in the aquatic environment and can be transferred through food chains, which can magnify or dilute their toxic effects on humans. In this study, PCNs were analyzed in samples of 17 species of fish with different dietary habits collected in the Bohai coastal area in China. Dichloronaphthalenes, which have rarely been quantified in previous studies, were determined. The total PCN concentrations were from 7.3 to 214 pg/g wet weight, and the highest concentration was found in ditrema. The trichloronaphthalenes were the most abundant PCNs, followed by the dichloronaphthalenes and pentachloronaphthalenes. The relatively high contributions of the less-chlorinated homologs to the total PCN concentrations indicated that the main PCN sources around the Bohai were industrial thermal process emissions rather than technical PCN formulations. The trophic magnification factors of the PCN homologs were from 3.1 to 9.9, indicating that PCNs were biomagnified by fish. The trophic magnification factor of dichloronaphthalene and trichloronaphthalenes was 5.8 and 6.4, respectively, indicating for the first time that dichloronaphthalene and trichloronaphthalenes can undergo trophic magnification by fish. The two highest trophic magnification factors were for the pentachloronaphthalenes and hexachloronaphthalenes, probably because these PCNs having fewer vicinal carbon atoms without chlorine atoms attached are less easily biotransformed than the other homologs. The dioxin-like toxicities of the PCNs in the samples, expressed as potential toxic equivalences (TEQs), were assessed. The highest total TEQ was 0.0090 pg/g ww, in Pacific herring, and the hexachloronaphthalenes were the dominant contributors to the total TEQs in the fish samples. The PCN TEQs were much lower than the polychlorinated dibenzo-p-dioxin and dibenzofuran and dioxin-like polychlorinated biphenyl TEQs found in fish from the Bohai in previous studies, and made marginal contributions to overall human exposure to dioxin-like TEQs, suggesting that PCNs pose no toxicological concerns.

Polychlorinated naphthalenes (PCNs) in seafood: Estimation of dietary intake in Korean population

Polychlorinated naphthalenes (PCNs) were measured in 33 seafood species including fish, mollusks and crustaceans purchased from local markets in five Korean cities between 2012 and 2013. Five samples were collected from each species for the measurements. Thirty-seven PCN congeners from tetra-CN to octa-CN were measured. Octa-CN (octachloronaphthalene) was not detected in any of the samples. Tetra-CN and penta-CN were the predominant homologues of PCNs in seafood samples with PCN 51 and PCN 52/60 being the most abundant congeners in the samples. Total PCNs concentrations and their corresponding dioxin-like toxic equivalent (TEQ) values ranged from non-detection (ND) to 110pg/g on a wet weight (ww) basis and from ND to 0.14pg-TEQ/g ww, respectively. The estimated daily intake of total PCNs based on an absolute content and TEQ potency were estimated for the Koreans to be 570pg/day and 0.44pg-TEQ/day, respectively. However, the estimated TEQ value of PCNs intake from seafood, represented only a small fraction (3.0%) of the total TEQ intake from consumption of seafood in Korean population. This is the first report to exhibit the presence of PCNs in seafood samples collected from local markets in Korea and their intake by general population.

Congener specific determination of polychlorinated naphthalenes in sediment and biota by gas chromatography high resolution mass spectrometry

An isotope dilution congener-specific method for the determination of the most abundant and most toxic polychlorinated naphthalenes (PCNs) was developed using gas chromatography with high resolution mass spectrometry (GC-HRMS). The method was used to determine the concentration of 24 target congeners and total PCN concentrations in fish and sediment samples. Tissue samples were extracted using pressurized liquid extraction (PLE) and sediment samples were extracted using Soxhlet extraction. Sample extracts were cleaned up using either a manual two-stage open column procedure or an automated FMS Power Prep System with multi-analyte and multi-sample capability using a three-column cleanup procedure. Sediment extracts were cleaned up with a dual open column cleanup technique involving the use of both a multi-layered silica (silver nitrate/acid/base/neutral silica) column followed by column containing carbon-activated silica. Fish tissue extracts were cleaned up on the automated system involving the use of a high capacity ABN (acid/base/neutral column), carbon celite column, and a basic alumina column. The method is capable of producing instrument detection limits (IDLs) between 0.06 and 0.13pg for each PCN (on column), with method detection limits (MDLs) for the fish extracts ranging from 1.3 to 3.4pg/g (wet weight) and 0.46 to 1.2pg/g (dry weight) for sediments. The average accuracy of 34 spiked fish samples analysed over a period of several months was 100% with a precision (%RSD) of 12%. Similarly, the average accuracy for 28 spiked sediment samples was 104% with a precision (%RSD) of 12%. The application of the method to environmental samples was demonstrated through the analysis of sediment and fish samples obtained from Lake Ontario, Canada. The method is used both for the determination of 24 PCNs and to perform non-targeted screening for the remaining 51 PCN congeners, which are included in the total PCN quantification result. It is currently one of the most comprehensive and accurate congener-specific methods available and was developed from the existing techniques used for the determination of polychlorinated dioxins and furans to produce high quality data with only minor modifications in the clean-up procedure. It can therefore be readily adopted by other laboratories performing dioxin and POP analyses.