Polychlorinated naphthalenes in sediments from the Venice and Orbetello lagoons, Italy

The purpose of this study was to evaluate the contamination caused by polychlorinated naphthalenes in two polluted Mediterranean lagoons. Surface sediment samples from Venice and Orbetello lagoons were analysed using HRGC-HRMS. The levels of the sum of mono- to octa-CN ranged from 0.03 to 1.51 ng/g. Differences in PCN levels were observed as a function of the sampling site, with levels at the industrial sites exceeding those at the control sites. Although the PCN patterns and profiles resembled one another in different sediment samples, they differed considerably when compared with those in the technical PCN formulation Halowax 1014.     

Dioxin like compounds from municipal waste incinerator emissions: assessment of the presence of polychlorinated naphthalenes

Polychloronaphthalenes (PCN) were identified and quantified in emission samples collected from five different municipal waste incinerators (MWI). Polychlorodibenzo-p-dioxins (PCDD) and polychlorodibenzofurans (PCDF) were also determined to find a possible relationship between these classes of organochlorinated compounds. The analyses of PCDD/PCDF and PCN were carried out by high resolution gas chromatography coupled with high resolution mass spectrometry using a positive electron ionization source and operating in the selected ion monitoring analyzer mode (HRGC-HRMS/EI(+)-SIM). The total levels of PCN varied from 1.08 up to 21.36 ng/Nm3 (mono- to octachlorinated) and 0.33 to 5.72 ng/Nm3 (tetra- to octachlorinated), whereas the levels of PCDD/PCDF ranged between 1.14 and 276.26 ng/Nm3 (0.01 and 5 ng I-TEQ/Nm3), depending on the type of the MWI. These findings do not corroborate a PCN and PCDD/PCDF correlation.     

Assessment of the temporal and spatial distribution of atmospheric PCNs and their air–soil exchange using passive air samplers in Shanghai,East China

A total of 47 passive air samples and 25 soil samples were collected to study the temporal trend, distribution, and air–soil exchange of polychlorinated naphthalenes (PCNs) in Shanghai, China. Atmospheric PCNs ranged from 3.44 to 44.1 pg/m³ (average of 21.9 pg/m³) in summer and 13.6 to 153 pg/m³ (average of 40.0 pg/m³) in winter. In the soil samples, PCN concentrations were 54.7–1382 pg/g dry weight (average of 319 pg/g). Tri-CNs and tetra-CNs were two dominant homolog groups in air samples, while di-CNs were also found at comparable proportions to tri-CNs and tetra-CNs in soil samples. Most air and soil samples from the industrial and urban areas showed higher PCN concentrations than those from suburban areas. However, some soil samples in urban centers presented higher PCN concentrations than industrial areas. Analysis of PCN sources indicated that both industrial thermal process and historical usage of commercial PCN mixtures contributed to the PCN burden in most areas. The fugacity fraction results indicated a strong tendency of volatilization for lighter PCNs (tri- to hexa-CNs) in both seasons, and air–soil deposition for octa-CNs. Moreover, air–soil exchange fluxes indicate that soil was an important source of atmospheric PCNs in some areas. The results of this study provide information for use in the evaluation of the potential impact and human health risk of PCNs around the study areas.

     

Identification and characterization of the atmospheric emission of polychlorinated naphthalenes from electric arc furnaces

Electric arc furnaces (EAF) are well recognized as significant sources of dioxins. EAFs have also been speculated to be sources of polychlorinated naphthalenes (PCNs) due to the close correlation between dioxin and PCN formation. However, assessment on PCN emissions from EAFs has not been carried out. The primary aim of this preliminary study is to identify and characterize the atmospheric emission of PCNs from EAFs. In this preliminary study, stack gas samples from two typical EAFs with different scales (EAF-1, 160?t batch(-1); and EAF-2, 60?t batch(-1)) were collected by automatic isokinetic sampling technique, and PCN congeners in samples were analyzed by isotope dilution high-resolution gas chromatography combined with high-resolution mass spectrometry method. Emission concentrations of PCNs were 458 and 1,099?ng?m(-3) for EAF-1 and EAF-2, respectively. The emission factors of PCNs to air were 21.6 and 30.1?ng toxic equivalent t(-1) for EAF-1 and EAF-2, respectively, which suggested that EAF is an important source of PCN release. With regard to the characteristics of PCNs from EAFs, lower chlorinated homologues were dominant. The PCN congeners comprised of CN27/30, CN52/60, CN66/67, and CN73 were the most abundant congeners for tetra-, penta-, hexa-, and hepta-chlorinated homologues, respectively. EAFs were identified to be an important PCN source, and the obtained data are useful for developing a PCN inventory. The congener profiles of PCNs presented here might provide helpful information for identifying the specific sources of PCNs emitted from EAFs.     

Flux estimates and sedimentation of polychlorinated naphthalenes in the northern part of the Baltic Sea

The concentrations and fluxes of polychlorinated naphthalenes (PCNs) were measured in surface sediments, and settling particulate matter collected in sediment traps, at two coastal and two offshore sampling stations in the Gulf of Bothnia, northern Baltic Sea, Sweden. The PCN concentrations (of tetra- to hepta-chloro congeners) in the surface sediments ranged from 0.27 to 2.8 ng/g dry weight and were of the same order of magnitude as background concentrations reported previously in Europe. The PCN fluxes in the southern basin (0.93 and 0.86 microg/m2/year) of the Gulf of Bothnia were higher than those in the northern basin (0.58 and 0.49 microg/m2/year); they were also higher near the coast than in the open sea. These PCN fluxes are similar to the pre-industrial levels determined from lake sediments in northwest England. The PCN homologue distribution changed from a relatively even distribution in samples collected near the coast, to TeCNs dominating in the samples from the open sea. This indicates that higher chlorinated PCNs are deposited and retained in sediments to a higher degree near the coast. The total annual deposition of PCNs in sediments in the Gulf of Bothnia was estimated to be 91 kg/year.     

Correlation of polychlorinated naphthalenes with polychlorinated dibenzofurans formed from waste incineration

Isomer composition of polychlorinated naphthalenes (PCNs) was measured for municipal waste incinerator fly ash samples and for emission samples produced from soot and copper-deposit experiments conducted at the United States Environmental Protection Agency (US-EPA). Two types of PCN isomer patterns were identified. One pattern contained specific PCN isomers in which chlorine atoms are substituted as if the peri(alpha-) position were dechlorinated from the higher chlorinated PCNs one by one. In another pattern, the isomers had a tendency for the chlorine atoms to assume successive positions on the naphthalene ring, which may be caused by specifically oriented chlorination. Some of these isomers increased, together with several polychlorinated dibenzofuran (PCDF) and a few polychlorinated dibenzo-p-dioxin (PCDD) isomers. The ratios between some specific PCN, PCDF, and PCDD isomers measured for the fly ash samples agree with those obtained from the soot and copper-deposit experiments. The observations suggest that these isomers were formed possibly from de novo synthesis utilizing the carbon structure contained in soot under the catalytic effect of a copper compound. Typical isomers for PCNs and PCDFs produced from incineration emissions were identified.     

Formation and chlorination of polychlorinated naphthalenes (PCNs) in the post-combustion zone during MSW combustion

Non- to octa-chlorinated naphthalenes (PCNs) were analyzed in flue gas samples collected simultaneously at three different temperatures (450 degrees C, 300 degrees C and 200 degrees C, respectively) in the post-combustion zone during waste combustion experiments using a laboratory-scale fluidized-bed reactor. PCN homologue profiles in all samples were dominated by the lower chlorinated homologues (mono- to triCN), with successive reductions in abundance with each additional degree of chlorination. The isomer distribution patterns reflected ortho-directionality behavior of the first chlorine substituent, and the beta-positions, i.e. the 2,3,6,7-substitution sites, seemed to be favored for chlorination. Injection of naphthalene into the post-combustion zone resulted in increased PCN levels at 200 degrees C, demonstrating the occurrence of chlorination reactions in the post-combustion zone. However, the increases were restricted to the least-chlorinated homologue (monoCN), probably because there was insufficient residence time for further chlorination. In addition, an episode of poor combustion (manifested by high CO levels) was accompanied by extensive formation of 1,8-diCN, 1,2,3- and 1,2,8-triCN; congeners with substitution patterns that are not thermodynamically favorable. These are believed to be products of PAH breakdown reactions and/or chlorophenol condensation. Overall, PCN formation is likely to occur via more than one pathway, including chlorination of naphthalene that is already present, de novo synthesis from PAHs and, possibly, chlorophenol condensation.     

Analysis of some polyhalogenated organic pollutants in sediment and sewage sludge

A laminated sediment core collected in the southern part of the Baltic Proper was analysed for DDT compounds, polychlorinated biphenyls (PCB) including the coplanar congeners, polybrominated diphenyl ethers (PBDE) and polychlorinated naphthalenes (PCN). Two sewage sludge samples were also analysed for the same compounds.

The results of the sediment analyses indicate the presence of PCB, DDT and PBDE compounds in sediment layers dating from the 1950s and later. Neither coplanar PCB nor PCN were detected at any level of the sediment core. The PCB concentrations indicate a slight increase in levels during the last decades, while there were no changes in the levels of DDT compounds. In contrast, TeBDE levels increase 4- to 8-fold and one PeBDE congeners levels increase 10- to 20-fold. The results of sewage sludge analyses showed the concentration of the individual PBDE to be at about the same level as for the individual PCB congeners. The congener pattern in sludge samples indicates low-chlorinated products to be the main PCN source.     

Interlaboratory study for the polychlorinated naphthalenes (PCNs): phase 1 results

An interlaboratory study was initiated to investigate consistency in reported concentrations of polychlorinated naphthalenes (PCNs). Results are reported from the first phase of a study that examined the variability associated with different quantification methodologies, instrumentation and standards. Nine participating labs from seven countries quantified individual homolog groups, summation operator PCN (the sum of 2-8 chlorinated homologs), and selected congeners in two test solutions derived from Halowax 1014. The means of the reported summation operator PCN values were within less than 15% of the known concentrations of the two test solutions and the relative standard deviation among laboratories was 11%. However, the among laboratory variability was in the range 20-40% for individual PCN homologs and individual PCN congeners. These results suggest the need for additional interlaboratory studies and for the development of reference materials for PCN analysis. Future PCN interlaboratory comparison exercises are discussed that will utilize control materials and unknowns consisting of suitable environmental matrices.     

Occurrence,profile and possible sources of PCNs in Hong Kong soils,and a comparison with PCBs,PCDDs and PCDFs

Polychlorinated naphthalenes (PCNs) have been proposed for inclusion in the annexes of the Stockholm Convention by the European Union, signifying a probable increase in monitoring PCN levels at a global level. Investigations on PCN levels in the environment of Hong Kong have not been reported. In this preliminary investigation, PCN levels in surface soils samples were determined by isotope dilution HRGC/HRMS techniques, and compared with those of polychlorinated biphenyl (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The concentrations of PCNs in the soil samples were 35–883 pg g^?1 (average, 201; and median, 94 pg g^?1), which were lower than those of PCBs PCDDs and PCDFs. This comparison suggested that PCNs are currently not priority POPs compared with dioxins and PCBs in Hong Kong soils. PCDDs were the most important contributor to the sum of toxic equivalents of PCNs, PCBs, PCDDs and PCDFs. OCDD was the most dominant dioxin congener in Hong Kong surface soils. PCB-118 was the most abundant in 12 dl-PCB congeners. PCN congeners indicating thermal related sources (CN52/60, CN66/67 and CN73) were relatively abundant in their respective homologs, which suggested PCN contamination from thermal sources. The ratio of CN73 to CN74 in soil samples suggested the contribution of PCN contaminations in soils from both thermal-related sources and evaporative emissions of technical PCN mixtures.     

Human exposure to polychlorinated naphthalenes through the consumption of edible marine species

The concentrations of polychlorinated naphthalenes (PCNs) were determined in samples of 14 edible marine species (sardine, tuna, anchovy, mackerel, swordfish, salmon, hake, red mullet, sole, cuttlefish, squid, clam, mussel and shrimp), which are widely consumed by the population of Catalonia, Spain. The daily intake of PCNs associated with this consumption was also determined. A total of 42 composite samples were analyzed by HRGC/HRMS. The highest PCN levels (ng/kg of fresh weight) were found in salmon (227) followed by mackerel (95) and red mullet (68), while the lowest levels of total PCNs corresponded to shrimp (4.9) and cuttlefish (2.7). With the exception of cephalopods and shellfish species, in which tetra-CN was the predominant homologue, penta-CN (60%) was the predominant contributor to total PCNs. For a standard male adult, PCN intake through the consumption of edible marine species was 1.53 ng/day. The highest contributions to this intake (ng/day) corresponded to salmon (0.41), sole (0.28) and tuna (0.24). Concerning health risks, species-specific TEFs such as those reported by WHO and NATO for PCDD/Fs and dioxin-like PCBs are not currently available for PCN congeners. Although in general terms the results of the present study do not seem to suggest specific risks derived from exposure to PCNs through fish and seafood consumption, to establish the contribution of individual PCN congeners to total TEQ is clearly necessary for the assessment of human health risks.     

Polychlorinated naphthalenes (PCNs) in Irish foods: Occurrence and human dietary exposure

The concentrations of selected polychlorinated naphthalene (PCN) congeners (PCNs 52, 53, 66/67, 68, 69, 71/72, 73, 74 and 75) were determined in 100 commonly consumed foods, in the first study on occurrence of these contaminants in the Republic of Ireland. Congener selection was based on current knowledge on PCN occurrence and toxicology, and the availability of reliable reference standards. The determinations were carried out using validated analytical methodology based on 13C10 labelled internal standardisation and measurement by HRGC-HRMS. The results showed PCN occurrence in the majority of studied foods--milk, fish, dairy and meat products, eggs, animal fat, shellfish, offal, vegetables, cereal products, etc. ranging from 0.09 ng kg(-1) whole weight for milk to 59.3 ng kg(-1) whole weight for fish, for the sum of the measured PCNs. The most frequently detected congeners were PCNs 66/67, PCN 52, and PCN 73. The highest concentrations were observed in fish, which generally showed congener profiles that reflect some commercial mixtures. The data compares well with other recently reported data for Western Europe. The dioxin-like toxicity (PCN TEQ) associated with these concentrations is lower than that reported for chlorinated dioxins or PCBs in food from Ireland. The dietary exposure of the Irish adult population to PCNs was calculated following a probabilistic approach, using the full dataset of occurrence and current consumption data. The estimates of dietary intakes at approximately 0.14 pg TEQ kg bw(-1) month(-1) for adults on an average diet, reflects the relatively lower occurrence levels.     

Occurrence of polychlorinated naphthalenes, polychlorinated biphenyls and short-chain chlorinated paraffins in marine sediments from Barcelona (Spain)

Polychlorinated naphthalenes (PCNs), short-chain chlorinated paraffins (SCCPs) and polychlorinated biphenyls (PCBs) were analysed in marine sediment samples collected from the coastal area of Barcelona (Spain) and near of a submarine emissary coming from a waste water treatment plant located at the mouth of the Besòs River (Barcelona). An integrated sample treatment based on Soxhlet extraction followed by a simple clean-up with Florisil and graphitized carbon cartridge was employed. Gas chromatography coupled to ion-trap tandem mass spectrometry (GC-MS/MS) and gas chromatography-mass spectrometry in electron capture negative ionization mode, were used for PCN and SCCP determinations, respectively, while for PCB analysis gas chromatography with electron capture detection (GC-ECD) was used. The method developed provided low limits of detection (0.001-0.003 ng g(-1) dry weight (dw) for PCNs, 1.8 ng g(-1) for SCCPs and 0.006-0.014 ng g(-1)dw for PCBs) and good run-to-run precisions (lower than RSD 8%) for the analysis of sediment samples. Concentration levels ranging from 0.17 to 3.27 ng g(-1)dw for PCNs, between 0.21 and 1.17 microg g(-1)dw for SCCPs, and from 2.33 to 44.00 ng g(-1) (dw) for PCBs, were found in the coastal sediments, while for samples collected near to the submarine emissary higher levels (from 2.02 to 6.56 ng g(-1)dw for PCNs, between 1.25 and 2.09 microg g(-1)dw for SCCPs and from 22.34 to 37.74 ng g(-1)dw for PCBs) were obtained. The results obtained provide new data about the occurrence of PCN and SCCP in the coastal area of Barcelona.     

Polychlorinated naphthalenes in urban soils: analysis,concentrations, and relation to other persistent organic pollutants

We determined the concentrations of 35 PCNs, 12 PCBs, and 20 PAHs in 49 urban topsoils under different land use (house garden, roadside grassland, alluvial grassland, park areas, industrial sites, agricultural sites) and in nine rural topsoils. The sums of concentrations of 35 PCNs (sigma35 PCNs) were <0.1-15.4 microg kg(-1) in urban soils and <0.1 to 0.82 microg kg(-1) in rural soils. The PCN, PCB, and PAH concentrations were highest at industrial sites and in house gardens. While rural soils receive PCNs, PCBs, and PAHs by common atmospheric deposition, there are site-specific sources of PCNs, PCBs, and PAHs for urban soils such as deposition of contaminated technogenic materials. The PCN, PCB, and PAH concentrations decreased from the central urban to the rural area. In the same order the contribution of lower chlorinated PCNs and PCBs increased because they are more volatile and subject to increased atmospheric transport. The PCNs 52+60, and 73 were more abundant in soil samples than in Halowax mixtures, indicating that combustion contributed to the PCN contamination of the soils.     

Chlorinated naphthalene formation from the oxidation of dichlorophenols

Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at 600 degrees C were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same intermediate. Tautomerization of the intermediate and H2O elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.     

Occupational exposure

Concentrations of polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN), polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), hexachlorobenzene and methylsulphonyl metabolites of PCB were determined in blood plasma from potentially exposed workers and controls. Three of the potentially exposed subjects had worked with cable incineration and two were electricians. Extraction of the organochlorine compounds and lipids were performed using the lipophilic gel Lipidex. Different adsorbents and gel permeation chromatography were applied for further purification of the samples and separation of analytes. Determinations of the chlorinated compounds were made by using gas chromatography with electron-capture detection and gas chromatography-mass spectrometry. Only small differences in the concentrations of organochlorine compounds were found in the plasma from the three subject groups. Thus, specific exposure of the workers could not be confirmed.     

Occupational exposure

Concentrations of polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN), polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), hexachlorobenzene and methylsulphonyl metabolites of PCB were determined in blood plasma from potentially exposed workers and controls. Three of the potentially exposed subjects had worked with cable incineration and two were electricians. Extraction of the organochlorine compounds and lipids were performed using the lipophilic gel Lipidex. Different adsorbents and gel permeation chromatography were applied for further purification of the samples and separation of analytes. Determinations of the chlorinated compounds were made by using gas chromatography with electron-capture detection and gas chromatography-mass spectrometry. Only small differences in the concentrations of organochlorine compounds were found in the plasma from the three subject groups. Thus, specific exposure of the workers could not be confirmed.     

Characterization of polychlorinated naphthalenes in stack gas emissions from waste incinerators

Nine typical waste incinerating plants were investigated for polychlorinated naphthalene (PCN) contents in their stack gas. The incinerators investigated include those used to incinerate municipal solid, aviation, medical, and hazardous wastes including those encountered in cement kilns. PCNs were qualified and quantified by isotope dilution high resolution gas chromatography–high resolution mass spectrometry techniques. An unexpectedly high concentration of PCNs (13,000 ng?Nm^?3) was found in the stack gas emitted from one waste incinerator. The PCN concentrations ranged from 97.6 to 874 ng?Nm^?3 in the other waste incinerators. The PCN profiles were dominated by lower chlorinated homologues, with mono- to tetra-CNs being the main homologues present. Furthermore, the relationships between PCNs and other unintentional persistent organic pollutants involving polychlorinated dibenzo-p-dioxins and dibenzofurans, polychlorinated biphenyls, hexachlorobenzene, and pentachlorobenzene were examined to ascertain the closeness or otherwise of their formation mechanisms. A good correlation was observed between ΣPCN (tetra- to octa-CN) and ΣPCDF (tetra- to octa-CDF) concentrations suggesting that a close relationship may exist between their formation mechanisms. The results would provide an improved understanding of PCN emissions from waste incinerators.     

Air concentrations of PCDD/Fs, PCBs and PCNs using active and passive air samplers

The concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) were determined in air samples collected at four sampling sites located in two zones of Barcelona (Spain): near a municipal solid waste incinerator (MSWI) and a combined cycle power plant (3 sites), and at a background/control site. Samples were collected using high-volume active samplers. Moreover, 4 PUF passive samplers were deployed at the same sampling points during three months. For PCDD/Fs, total WHO-TEQ values were 27.3 and 10.9 fg WHO-TEQm(-3) at the urban/industrial and the background sites, respectively. The sum of 7 PCB congeners and the Sigma PCN levels were also higher at the industrial site than at the background site. In order to compare active and passive sampling, the accumulated amounts of PCDD/Fs, PCBs and PCNs in the four passive air samplers, as well as the total toxic equivalents in each sampling site were also determined. To assess the use of PUF passive samplers as a complementary tool for PCDD/F, PCB and PCN monitoring, sampling rates were calculated in accordance with the theory of passive air samplers. PUF disks allowed establishing differences among zones for the POP levels, showing that they can be a suitable method to determine POP concentrations in air in areas with various potential emission sources. Although both particle and gas phase were sorbed by the PUFs, data of gas phase congeners are more reproducible.     

Relative importance of polychlorinated naphthalenes compared to dioxins, and polychlorinated biphenyls in human serum from Korea: Contribution to TEQs and potential sources

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) in human have been studied extensively; however, polychlorinated naphthalenes (PCNs) have been studied less widely. The mean concentrations of PCNs, PCDDs, PCDFs, and PCBs in 61 healthy human volunteers were 2170 pg/g lipid, 452 pg/g lipid, 116 pg/g lipid, and 120 ng/g lipid respectively, and the mean toxic equivalents (TEQs) contributed by PCNs, PCDDs, PCDFs, and PCBs were 5.88, 5.22, 5.48, and 5.33 pg/g lipid, respectively. PCNs contributed to 26.8% of the total TEQs. 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF, PCB126, and hepta-CN-73 accounted for >62% of the total TEQs in the human serum samples. The overall serum PCN homologue profiles of all subjects were dominated by tetra- and penta-CN homologues, and the most predominant individual congener was hepta-CN-73, which contributed 17.5% of the total serum PCN concentration. Enrichment of hepta-CN-73 in the human serum samples might be due to contributors from combustion sources.