Congener Groups Research Articles

Polybrominated diphenyl ethers (PBDEs) in water, surface sediment, and suspended particulate matter from the Yellow River, China: Levels, spatial and seasonal distribution, and source contribution

Fourteen polybrominated diphenyl ether (PBDE) congeners were measured in water, suspended particulate matter (SPM), and sediment samples collected from the entire expanse of the Yellow River in dry and wet seasons. Higher concentrations of PBDEs were found in the middle and lower reaches of the river compared with those in the upper reaches, ascribed to the relatively developed and urbanized cities located in the areas near the middle and lower reaches. The PBDE concentrations in the samples collected during the dry season were lower than those in the samples collected during the wet season because of thaw and rainfall. The dominant congener, with a contribution of 44.6–90.3%, was BDE-209, which originated from the residual of commercial deca-BDE. Three groups of congeners in all the samples showed good correlations with the coefficient ranging from 0.662 to 0.999 (p < 0.01), indicating common sources and similar environmental behaviors. Regression analysis suggested that the local industrial product (IP) and population density (PD) were good indicators of PBDEs in the water and sediment of the Yellow River.

Distribution of polychlorinated naphthalenes (PCNs) in the whole blood of typical meat animals

The concentrations and distribution of polychlorinated naphthalenes (PCNs) in the whole blood of eight typical terrestrial meat animals (chicken, duck, rabbit, pig, cattle, sheep, horse and donkey) consumed daily in our life were investigated. The total concentrations (on a liquid volume basis) of PCNs were in a range from 305 to 987pg/L. Donkey blood contained the highest PCN concentrations. Mono-CNs were the dominant homolog group, accounting for 38%–71% PCNs. Apart from the mono-CNs and tri-CNs homolog groups, two hepta-CNs (mean: 9.5%) contributed most, followed by tetra-CNs (mean: 6.5%). The congeners CN1, 5/7, 24/14, 27/30, 52/60, 66/67, and 73 were the most abundant congeners or congener groups. The highest toxicity equivalencies (TEQs) were observed in cattle blood (117.4fg TEQ/L) then chicken blood (117.1fg TEQ/L). CN73 contributed 65% to total TEQs, followed by CN70 (20%) and CN66/67 (14%). The dietary intakes of PCNs were also estimated. Chicken meat, which forms the second largest component of meat product consumption in China, contributed most to the total TEQs (61%), followed by beef (27%) and pork (5.9%). The consumption of chicken might pose the highest risk from exposure to PCNs than other types of meat to populations who prefer to eat chicken meat.

Short-, Medium-, and Long-Chain Chlorinated Paraffins in Wildlife from Paddy Fields in the Yangtze River Delta.

Short-chain chlorinated paraffins (SCCPs) were added to Annex A of the Stockholm Convention on Persistent Organic Pollutants in April, 2017. As a consequence of this regulation, increasing production and usage of alternatives, such as medium- and long-chain chlorinated paraffins (MCCPs and LCCPs, respectively), is expected. Little is known about the environmental fate and behavior of MCCPs and LCCPs. In the present study, SCCPs, MCCPs, and LCCPs were analyzed in nine wildlife species from paddy fields in the Yangtze River Delta, China, using atmospheric pressure chemical ionization-quadrupole time-of-flight mass spectrometry. SCCPs, MCCPs, and LCCPs were detected in all samples at concentrations ranging from <91-43 000, 96-33 000, and 14-10 000 ng/g lipid, respectively. Most species contained primarily MCCPs (on average 44%), with the exception of collared scops owl and common cuckoo, in which SCCPs (43%) accumulated to a significantly (i.e., p < 0.05) greater extent than MCCPs (40%). Cl6 groups were dominant in most species except for yellow weasel and short-tailed mamushi, which contained primarily Cl7 groups. Principal components analysis, together with CP concentrations and carbon stable isotope analysis showed that habitat and feeding habits were key factors driving CP accumulation and congener group patterns in wildlife. This is the first report of LCCP exposure in wildlife and highlights the need for data on risks associated with CP usage.

Determination of short-chain chlorinated paraffins in multiple matrices of Arctic using gas chromatography-electron capture negative ion-low resolution mass spectrometry

Gas chromatography-electron capture negative ion-low resolution mass spectrometry (GC-ECNI-MS) was used for the quantification of short-chain chlorinated paraffins (SCCPs) in multiple matrices of Arctic. Samples were spiked with surrogate standards (13C10-trans-chlordane) and extracted with dichloromethane and hexane (1:1, v/v) using accelerated solvent extraction (ASE). The extract was cleaned using a multilayer Silica-Florisil column and e-HCH was added before instrument analysis. The SCCPs were analyzed using a gas chromatograph (GC) in electron capture negative ion (ECNI) mode coupled with a 7000B triple quadruple mass spectrometer (MS) in single quad mode. The calibration is performed using three commercial standards (chlorine contents of 51.5%, 55.5%, and 63.0%). A reasonable linear correlation for commercial standards was found between chlorine content and total response factor (R2?=?0.96). To ensure instrument sensitivity, the SCCP congeners were divided into four groups by the optimized combinations (C10, C11, C12 and C13) and subjected to analysis by four individual injections. This method is suited to analyse the total concentration of SCCPs and individual SCCP congener groups in the environmental analysis.• Accelerated solvent extraction offers a lower cost of time for per sample and reducing solvent consumption.• The presented quantification procedure makes the quantification of SCCPs independent from the chlorine content of the used standard mixtures.• The samples were subjected to analysis by four individual injections for the instrument sensitivity, and the total concentration of SCCPs and CP congener groups can be obtained at the same time.

Distribution and Pattern Profiles of Chlorinated Paraffins in Human Placenta of Henan Province, China

Due to the high production volume, wide industrial applications, and environmental persistence, chlorinated paraffins (CPs) have been observed in various environmental matrices. However, data are scarce regarding human exposure to CPs. In this study, 54 human placentas were collected and analyzed by gas chromatography quadrupole time-of-flight mass spectrometry (GC-QTOF-HRMS). Short-chain CPs (SCCPs) were detected in all samples, with the concentrations ranging from 98.5 to 3771 ng/g lw (lipid weight). Medium-chain CPs (MCCPs) were detected in 38 of the samples, with the concentrations being in the range from 80.8 to 954 ng/g lw. SCCPs with 6–7 chlorines were predominant in human placentas and were mostly within the 10–11 carbon chain groups. In most samples, C15H25Cl7 were found to be the most abundant MCCP congener groups. Pearson correlation analysis indicated that there was a significant positive correlation between the ΣSCCPs and ΣMCCPs concentrations in the placenta samples, whereas the concentratio...

Diversity and Abundance of High-Molecular-Weight Azaarenes in PAH-Contaminated Environmental Samples.

Azaarenes are N-heterocyclic polyaromatic pollutants that co-occur with polycyclic aromatic hydrocarbons (PAHs) in contaminated soils. Despite the known toxicity of some high-molecular-weight azaarenes, their diversity, abundance, and fate in contaminated soils remain to be elucidated. We applied high-resolution mass spectrometry and mass-defect filtering to four PAH-contaminated samples from geographically distant sites and detected 232 azaarene congeners distributed in eight homologous series, including alkylated derivatives and two hitherto unknown series. Four- and five-ring azaarenes were detected among these series, and the most abundant nonalkylated congeners groups (C13H9N, C15H9N, C17H11N, C19H11N, and C21H13N) were quantified. The profiles of congener groups varied among different sites. Three-ring azaarenes presented higher concentrations in unweathered sites, while four- and five-ring azaarenes predominated in weathered sites. Known toxic and carcinogenic azaarenes, such as benzo[c]acridine and dibenzo[a,h]acridine, were detected along with their multiple isomers. Our results highlight a previously unrecognized diversity and abundance of azaarenes in PAH-contaminated sites, with corresponding implications for environmental monitoring and risk assessment.

Short- and medium-chain chlorinated paraffins in aquatic foods from 18 Chinese provinces: Occurrence, spatial distributions, and risk assessment

Short-chain chlorinated paraffins (SCCPs) are classed as persistent organic pollutants and were included in the Stockholm Convention in May 2017. Large amounts of chlorinated paraffins (CPs) are produced in China than in any other countries. CPs can be released into the environment while being produced and used, and can bioaccumulate in aquatic biota and be ingested by humans. Dietary intake is the main route through which humans are exposed to CPs. It has previously been found that persistent organic pollutant concentrations are usually higher in aquatic foods than in other foods. The risk of human exposure to SCCPs in aquatic foods should therefore be of concerns. However, SCCP concentrations in aquatic foods have not been systematically studied. A total of 1620 aquatic food samples were collected, and 18 pooled samples were analyzed by two-dimensional gas chromatography coupled with electron-capture negative-ionization time-of-flight mass spectrometry. The mean SCCP and MCCP concentrations were 1472 and 80.5ng/gwet weight, respectively. The dominant SCCP and MCCP congener groups were C10Cl6–7 and C14Cl7–8, respectively. The concentrations were much higher than those have been found in aquatic foods in other countries. The CP concentrations in the samples consumed by local people from eastern and southern China were higher than the concentrations in samples from central and western China. Risk assessment results indicated that SCCPs and MCCPs in aquatic foods do not pose significant risks to residents of China.

Bioaccumulation and biomagnification of short and medium chain polychlorinated paraffins in different species of fish from Liaodong Bay, North China

Chlorinated paraffins (CPs) are highly complex technical mixtures, and the short chain chlorinated paraffins (SCCPs) are classed as persistent and have been included in the Stockholm Convention. However, there have been few studies of SCCPs and medium chain chlorinated paraffins (MCCPs) and their bioaccumulation and biomagnification in different species of fish. The present study investigated the levels, congener group profiles, bioaccumulation, and biomagnification of SCCPs and MCCPs in different species of fish from Liaodong Bay, North China. The ranges for the ΣSCCP and ΣMCCP concentrations were 376.3–8596 ng/g lipid weight (lw) and 22.37–5097 ng/g lw, respectively. The logarithms of bioaccumulation factors of ΣSCCPs ranged from 4.69 to 6.05, implying that SCCPs bioaccumulated in the fish. The trophic magnification factor of ΣSCCPs was 2.57, indicating that SCCPs could biomagnify in fish. Carbon chain length, the numbers of chlorine atoms, and octanol/water partition coefficients of the SCCPs and MCCPs might be important factors affecting the bioaccumulation of these chemicals in fish. The risk posed to human health by consumption of fish containing SCCPs was low. New SCCPs with nine carbons (C9) were detected in fish in this study.

Quantifying Short-Chain Chlorinated Paraffin Congener Groups.

Accurate quantification of short-chain chlorinated paraffins (SCCPs) poses an exceptional challenge to analytical chemists. SCCPs are complex mixtures of chlorinated alkanes with variable chain length and chlorination level; congeners with a fixed chain length (n) and number of chlorines (m) are referred to as a "congener group" CnClm. Recently, we resolved individual CnClm by mathematically deconvolving soft ionization high-resolution mass spectra of SCCP mixtures. Here we extend the method to quantifying CnClm by introducing CnClm specific response factors (RFs) that are calculated from 17 SCCP chain-length standards with a single carbon chain length and variable chlorination level. The signal pattern of each standard is measured on APCI-QTOF-MS. RFs of each CnClm are obtained by pairwise optimization of the normal distribution's fit to the signal patterns of the 17 chain-length standards. The method was verified by quantifying SCCP technical mixtures and spiked environmental samples with accuracies of 82-123% and 76-109%, respectively. The absolute differences between calculated and manufacturer-reported chlorination degrees were -0.9 to 1.0%Cl for SCCP mixtures of 49-71%Cl. The quantification method has been replicated with ECNI magnetic sector MS and ECNI-Q-Orbitrap-MS. CnClm concentrations determined with the three instruments were highly correlated (R2 > 0.90) with each other.

Concentrations and inhalation risk assessment of short-chain polychlorinated paraffins in the urban air of Dalian, China.

The concentrations of short-chain polychlorinated paraffins (SCCPs) in the urban air of Dalian, China, were monitored from March to October 2010 and from September to October 2016 with active high-volume sampler. The total concentration of SCCPs (particulate phase + gas phase) ranged from 15.12 to 66.44ngm-3, with an average of 30.26ngm-3 in 2010, and 65.30 to 91.00ngm-3, with an average of 78.15ngm-3 in 2016. Hexa-chlorinated dodecane and hexa-chlorinated undecane are the predominant components in the gas phase, while octa-chlorinated undecane and hepta-chlorinated tridecane are dominant in the particulate phase. In 2010, 82.57-97.16% of the total SCCPs were found in the gas phase, except that in winter, where 63.11% of the total SCCPs were in the particulate phase; the air concentrations of SCCPs in gas phase were summer > autumn > spring > winter, which was positively correlated with the change of the average ambient temperature, while it was the contrary in particulate phase. In autumn, the gas phase and the total air concentration of SCCPs in 2016 were 2.57 times more than that in 2010, while the congener group patterns of SCCPs were similar. Spearman's rank correlation analysis between the concentrations of SCCPs with meteorological parameters was conducted. The gas-particle distribution was examined through the relationship of the logarithm of the gas-particle partition coefficient with that of the subcooled vapor pressure and the octanol-air partitioning coefficient of SCCPs. Results indicated that the absorption mechanisms contributed more to the partitioning process. The exposure risk of SCCPs was evaluated, which illustrated that the estimated exposure of SCCPs via the outdoor environment in Dalian did not exceed the health concern threshold of the European risk assessment.

Temporal and spatial variation of polychlorinated biphenyls (PCBs) contamination in environmental compartments of highly polluted area in Central Russia

This study highlights the fact that serious contamination from polychlorinated biphenyls (PCBs) still exists in Serpukhov City (Russia). The research help to determine the temporal (16- and 24-year periods) and spatial PCBs distribution in the environmental compartments of the studied region. Samples of soil, sediments, water and plants were analysed in order to establish their contamination levels. The most recent data on the Serpukhov City's soil contamination showed that the PCBs concentrations varies from 0.0009 to 1169 mg/kg depending on the sampling point and the distance from the pollution source. The temporal trends of the contamination distribution with the soil depth showed contamination migration in the upper soil layers of the highly polluted site. The high level of water pollution (11.5 μg/L) in the proximity to the contamination source and the sediments contamination (0.098–119 mg/kg) were determined, as well as the water migration pathways of the PCBs that were prevalent in the studied region. The PCB congener group (by the level of chlorination) analysis showed that heptachlorinated biphenyls were only found in the soils in close proximity to the contamination place, while biphenyls with Cl ≤ 6 were found in the soil samples downstream of the condenser plant and with Cl ≤ 5 in the soil samples upstream of the plant. The plant uptake of PCBs, even on the extremely contaminated site, was shown. In turn, this research present new knowledge necessary for the development of a contaminated territory remediation strategy.

High-Throughput Determination and Characterization of Short-, Medium-, and Long-Chain Chlorinated Paraffins in Human Blood.

The industrial chlorinated paraffins (CPs) are comprised of short-chain (SCCPs), medium chain (MCCPs), and long chain (LCCPs) CPs. Although SCCPs and MCCPs are environmentally ubiquitous, little is known about CPs in humans. This study established a method for simultaneous determination of 261 SCCP, MCCP, and LCCP congener groups in one injection by reversed ultrahigh-pressure liquid chromatography coupled with chlorine-enhanced electron spray ionization-quadrupole time-of-flight mass spectrometry. The method yielded good peak shapes, high sensitivities, and low coeluted interferences for all examined CPs. LCCPs with carbon numbers of 21 to 27 were detected in their standard technical mixtures, and MCCPs and LCCPs impurities were detected in the LCCP and MCCP standard technical mixtures, respectively, causing quantification deviations when these mixtures were used for calibration. After considering these impurities' contribution to the total concentrations, the quantification accuracies for ∑SCCPs, ∑MCCPs, and ∑LCCPs ranged from 95.1 ± 8.4% to 105.6 ± 9.2% in the eight CP technical mixtures. The method was successfully applied to determine CPs in about 6 g human blood samples from a general population, and estimated ∑SCCP, ∑MCCP, and ∑LCCP concentrations to be 370-35 000, 130-3200, and 22-530 ng/g lipid weight (n = 50), respectively. A comparison of blood and soil/air CP profiles from the same areas suggested a relatively higher potential for the accumulation of SCCPs, compared with MCCPs, in humans.

Environmental behaviour of short-chain chlorinated paraffins in aquatic and terrestrial ecosystems of Ny-Ålesund and London Island, Svalbard, in the Arctic

The environmental behaviour of short-chain chlorinated paraffins (SCCPs) was investigated in both aquatic and terrestrial ecosystems in the Arctic. The mean concentrations of SCCPs in the aquatic and terrestrial samples were 178.9ng/g dry weight (dw) and 157.2ng/g dw, respectively. Short carbon chain (C10) and less-chlorinated (Cl6) congener groups were predominant in the Arctic samples, accounting for 48.6% and 34.8% of the total SCCPs, respectively. The enrichment of lighter SCCP congener groups (i.e., fewer chlorine atoms with shorter carbon chain lengths) indicated that the fractionation process occurred during long-range transport. The biomagnification factor (BMF) was 0.46 from gammarid to cod, which indicated that the SCCPs did not biomagnify between these two species. The soil–vegetation bioaccumulation factor (BAF) of SCCPs was 29.9, and C13 and Cl7, 8 congener groups tended to accumulate in the terrestrial vegetation. Regression analysis (BAFs=10.9×#C+5.6×#Cl−125.2, R=0.53, P<0.01) showed that the number of carbon and chlorine atoms influenced the bioaccumulative behaviour of SCCPs and suggested that the number of carbon atoms had a greater influence on the BAFs of SCCPs in the terrestrial ecosystem than did the number of chlorine atoms.

Temporal trends of polychlorinated biphenyls serum levels in subjects living in a highly polluted area from 2003 to 2015: a follow-up study.

A chemical factory located in Brescia, an industrialized town in North Italy, produced polychlorinated biphenyls (PCBs) since the 1930s to the 1980s, determining a relevant pollution of soil, food and people. Since 2001, following a survey carried out in the general population living in the town, the individuals with PCB serum levels higher than the reference entered a follow-up study. We performed a prospective cohort study including subjects with at least three PCB measures during the period 2003-2015. We evaluated the temporal trends of total PCB serum levels, the most common PCB congeners (PCB 138,153, 170, 180, 194 and 209), and toxic equivalency of dioxin-like PCBs using univariate and multivariate mixed models with and without a cubic-spline term for time. A total of 128 subjects were enrolled (46.1% males, mean age at enrolment 57.7 years). The geometric mean of PCBs decreased from 35.4ng/ml at 0-3 years to 29.3ng/ml at 4-8 years and to 23.0ng/ml at 9-12 years. A 3.8% reduction of total PCB serum levels per year was estimated using both univariate and multivariate mixed models adjusted for age; a similar reduction was found for the most common PCB congeners and for toxic equivalency. Total PCB serum levels decreased over time for each age group: -3.9%, -4.0% and -3.4% for subjects aged ≤55 years, 56-65 and ≥66 years, respectively. A significant decrease of serum concentrations of PCBs was observed in subjects with high serum levels of these chemicals at enrolment over a twelve year period. The decrease was evident for each PCB congener and age group.

Bioaccumulation of short chain chlorinated paraffins in a typical freshwater food web contaminated by e-waste in south china: Bioaccumulation factors, tissue distribution, and trophic transfer

Short chain chlorinated paraffins (SCCPs) are under review for inclusion into the Stockholm Convention on Persistent Organic Pollutants. However, limited information is available on their bioaccumulation and biomagnification in ecosystems, which is hindering evaluation of their ecological and health risks. In the present study, wild aquatic organisms (fish and invertebrates), water, and sediment collected from an enclosed freshwater pond contaminated by electronic waste (e-waste) were analyzed to investigate the bioaccumulation, distribution, and trophic transfer of SCCPs in the aquatic ecosystem. SCCPs were detected in all of the investigated aquatic species at concentrations of 1700–95,000 ng/g lipid weight. The calculated bioaccumulation factors (BAFs) varied from 2.46 to 3.49. The relationship between log BAF and the octanol/water partition coefficient (log KOW) for benthopelagic omnivorous fish species followed the empirical model of bioconcentration, indicating that bioconcentration plays an important role in accumulation of SCCPs. In contrast, the relationship for the benthic carnivorous fish and invertebrates was not consistent with the empirical model of bioconcentration, implying that the bioaccumulation of SCCPs in these species could be more influenced by other complex factors (e.g., habitat and feeding habit). Preferential distribution in the liver rather than in other tissues (e.g., muscle, gills, skin, and kidneys) was noted for the SCCP congeners with higher log KOW, and bioaccumulation pathway (i.e. water or sediment) can affect the tissue distribution of SCCP congeners. SCCPs underwent trophic dilution in the aquatic food web, and the trophic magnification factor (TMF) values of SCCP congener groups significantly correlated with their corresponding log KOW values (p < 0.0001). The present study results improved our understanding on the environmental behavior and fate of SCCPs in aquatic ecosystem.

Human Exposure to Short- and Medium-Chain Chlorinated Paraffins via Mothers' Milk in Chinese Urban Population.

Chlorinated paraffins (CPs) are high production volume synthetic chemicals, found ubiquitously in various environmental matrices. However, little information is available on CP contamination in mothers' milk. In this study, 1370 urban mothers' milk samples were collected from 12 Chinese provinces in 2007 and 16 provinces in 2011. CP geographical distribution and congener group profiles were studied to assess the CP levels and figure out the source of exposure in humans. Twenty-eight pooled samples were analyzed for 48 short-chain CP (SCCP) and medium-chain CP (MCCP) congener groups using the GC × GC-ECNI-HRTOFMS method. The median concentrations of SCCPs were 681 and 733 ng/g lipid in 2007 and 2011, respectively; median concentrations of MCCPs were 60.4 and 64.3 ng/g lipid in 2007 and 2011, respectively. Variations of more than 2 orders of magnitude in CP exposure levels were found between different provinces. The levels of CPs increased from 2007 to 2011, which indicates that CP production and use may be an important exposure source. This is the first global comprehensive and large-scale investigation of CPs in mothers' milk, and it lays foundations for improving our understanding of the metabolism of CPs in humans. The high CP concentrations found in Chinese mothers' milk should raise concern about potential toxic effects in both mothers and breastfeeding infants.

Association of breast adipose tissue levels of polychlorinated biphenyls and breast cancer development in women from Chaoshan, China.

Polychlorinated biphenyls (PCBs) are implied to be potential risk factors for breast cancer in wildlife and in in vivo and in vitro studies. Epidemiological studies revealed some individual or groups of PCB congeners associated with breast cancer risk, but consistent conclusions are scarce. This study aimed to explore the association between PCB exposure and breast cancer development. Breast adipose tissues were collected, and seven PCB congeners were analyzed by gas chromatography-mass spectrometry (GC-MS). Demographic characteristics, basic clinical data, and pathological diagnosis information were obtained from medical records. The differences in PCB exposure levels among different groups and indices were compared, and the correlation among PCB congeners was evaluated. The order of congener profile by molar concentration was PCB-153 > PCB-138 > PCB-180 > PCB-118 > PCB-101 > PCB-52 > PCB-28. ∑PCB level differed by occupation and residence and was significantly higher at 55-59-year-old group than at the other age groups. ∑PCB level was higher in postmenopausal than in premenopausal women. Decreasing ∑PCB levels were related with increasing parity among women with progesterone receptor (PR)-positive breast tumors. With increased clinical stage, the ∑PCB level increased significantly. ∑PCB level did not differ by tumor-node-metastasis classification and PR or human epidermal growth factor receptor 2 (HER2) expression but did differ by estrogen receptor (ER) expression (P=0.04) without a regularly increasing trend in breast adipose tissue. These results suggest a potential association between PCB exposure and breast cancer development. Further in vitro and in vivo studies are needed to confirm these findings and explain the underlying mechanisms. Graphical Abstract Total PCBs level among different clinical stages in breast cancer patients.

Dispersion of Short- and Medium-Chain Chlorinated Paraffins (CPs) from a CP Production Plant to the Surrounding Surface Soils and Coniferous Leaves.

Chlorinated paraffin (CP) production is one important emission source for short- and medium-chain CPs (SCCPs and MCCPs) in the environment. In this study, 48 CP congener groups were measured in the surface soils and coniferous leaves collected from the inner and surrounding environment of a CP production plant that has been in operation for more than 30 years to investigate the dispersion and deposition behavior of SCCPs and MCCPs. The average concentrations of the sum of SCCPs and MCCPs in the in-plant coniferous leaves and surface soils were 4548.7 ng g-1 dry weight (dw) and 3481.8 ng g-1 dw, which were 2-fold and 10-fold higher than those in the surrounding environment, respectively. The Gaussian air pollution model explained the spatial distribution of CPs in the coniferous leaves, whereas the dispersion of CPs to the surrounding surface soils fits the Boltzmann equation well. Significant fractionation effect was observed for the atmospheric dispersion of CPs from the production plant. CP congener groups with higher octanol-air partitioning coefficients (KOA) were more predominant in the in-plant environment, whereas the ones with lower KOA values had the elevated proportion in the surrounding environment. A radius of approximately 4 km from the CP production plant was influenced by the atmospheric dispersion and deposition of CPs.

Short- and medium-chain chlorinated paraffins in sediments from the middle reaches of the Yangtze River: Spatial distributions, source apportionment and risk assessment

Chlorinated paraffins (CPs) are easily adsorbed into sediments where they pose potential risks to the ecosystem and human health. Few studies have investigated short- and medium-chain CPs (SCCPs and MCCPs) in sediments. The aim of the present study was to comprehensively investigate contamination levels, spatial distributions, sources and risks posed by CPs in sediments from the middle reaches of the Yangtze River. The sediment samples were analyzed by two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC–TOFMS). The concentrations of SCCPs and MCCPs ranged from 4.19 to 41.6ng/g dry weight (dw) and not detected to 14.6ng/g dw, respectively. No significant correlation was found between the total organic carbon contents and CP concentrations (P>0.05). The spatial distributions showed that CP contamination levels in the sediments were related to local human activities. The dominant congener groups were C10-11Cl6–7 for SCCPs, and C14Cl7–8 for MCCPs. Correspondence analysis revealed that likely sources of SCCPs were the production and use of CP-42 and CP-52. Principal component analysis indicated that SCCPs and MCCPs in the sediments may come from different sources. Moreover, CPs with nine carbon atoms were quantitated for the first time in sediment samples, and the results indicated they should not be neglected in future analyses. Risk assessments indicated that CPs in the sediments did not pose a great ecological risk currently.

The rate-determining step in a low temperature PCDD/F formation from oxidative breakdown of native carbon in MSWI fly ash

We developed a phenomenological approach to explain the kinetic experimental data of PCDD/F formation/destruction based on a reaction mechanism model at the congener group level. In the present work, we investigated the formation and destruction of PCDD/F on fly ash as a function of time at 280 °C, chlorine mass balance, evolution of the total equivalent toxicity and kinetic modelling. We determined that the volatilization process is negligible and that the reactive processes at short reaction times only become important above 300 °C. The results provide a substantial improvement on existing studies. We experimentally demonstrated, for the first time, that there is a correlation between the oxidative breakdown of native carbon and PCDD/F de novo synthesis. Data processing by our kinetic model showed that the formation of oxygen complexes C(O) was the determining step for de novo synthesis of PCDD/F. Indeed, the calculated reaction time at which the PCDD/F concentration was at a maximum (850 min) was greater than that calculated for the oxygen complexes C(O) (435 min). Moreover, the experimental carbon conversion efficiency for PCDD/F production (0.0032% at 600 min maximum) was in a very good agreement with the theoretical conversion (0.0041%).