Dechlorane Plus Concentrations Research Articles

Assessment on the Occupational Exposure of Manufacturing Workers to Dechlorane Plus through Blood and Hair Analysis

Dechlorane Plus (DP), as a widely used flame retardant in different electrical and textile applications, has recently attracted great concern around the world. The present study investigated the DP levels and distribution in human samples from a DP manufacturing plant and a nearby area in east China. The DP concentrations ranged from 89.8 to 2958 ng/g lipid weight in whole blood and 4.08 to 2159 ng/g dry weight in hair. For the workers engaged in DP manufacturing process, their DP levels were significantly higher than those in most of the other two control groups from the nearby area. The values of anti-DP fractional abundance (fanti ratio) were commonly lower in the human samples from both the manufacturing plant and nearby area compared with those in the commercial products, and excretion as well as biotransformation are possible reasons for stereoselective accumulation of the syn-DP isomer in humans. Furthermore, a significantly positive relationship (p < 0.05) was obtained between (i) the concentrations (and fanti) in the paired blood and hair samples, indicating a similar distribution pattern of the two DP isomers in the paired samples; (ii) the DP levels in human body and the exposure time (p < 0.05), which suggests that further assessment could be needed to investigate potential long-term risks to the occupational population.

Levels and profiles of Dechlorane Plus in a major E-waste dismantling area in China

Dechlorane Plus (DP) is a high-production volume, chlorinated flame retardant comprising two major isomers, syn- and anti-DP. In this study, levels of DP were measured in soil and earthworm samples in farmland from a typical E-waste dismantling area in China. The concentrations of total DP ranged from 0.17 to 1,990ngg(-1)dw in soil samples and 3.43 to 89.2ngg(-1)lw in earthworm samples. Higher DP levels were found in some main E-waste dismantling sites than those in other sites. The ratios of anti-DP to total DP (f anti) ranged from 0.57 to 0.80 in soil samples and 0.47 to 0.81 in earthworm samples, respectively. The f anti in most samples in this study was in the range of the reported technical DP values. These results showed that improper E-waste dismantling activities could result in the emission of DP. Most earthworm samples showed very low BSAFs (biota-to-soil accumulation factors) for total DP. The values of BSAF were in the range of 0.0007-1.85, with an average value of 0.23. This study presents the first report of the DP in earthworms, which would be useful for ecological risk assessment of DP in terrestrial ecosystem.

Concentrations and trends of halogenated flame retardants in the pooled serum of residents of Laizhou Bay, China

The south coast of Laizhou Bay, in northeastern China, is a production area for halogenated flame retardants (HFR). In 2007, the authors measured serum concentrations of polybrominated diphenyl ethers (PBDEs) in Laizhou Bay residents. To assess the PBDE concentration trend, and determine the concentrations of the emerging flame retardants Dechlorane Plus (DP) and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH), the authors measured the concentrations of 8 PBDE congeners, 2 DP isomers, and TBPH in 10 composite samples, which were pooled from the serum collected from 305 Laizhou Bay residents in October 2011. The average concentration of the total PBDE (∑8 PBDE) concentration in all serum pools was 240 ng/g lipid weight, and the highest serum pool concentration (in the 30- to 39-yr-old male group) was 780 ng/g lipid weight. Brominated diphenyl ether-209 was the dominant congener, accounting for 87% of ∑8 PBDE. Compared with a previous study, ∑8 PBDE serum concentrations in the present study showed no change in order of magnitude, but the relative contribution of BDE-209 to ∑8 PBDE was higher. The average concentration of ∑DP in all serum pools was 3.6 ng/g lipid weight, ranging from 1.4 ng/g lipid weight (in the 50- to 59-yr-old male group) to 11 ng/g lipid weight (in the 20- to 29-yr-old male group). The concentration of DP was lower than in other reported studies. The study also detected TBPH in the 30- to 39-yr-old female group, suggesting that TBPH, as an emerging HFR, requires further monitoring.

Sex-dependent accumulation and maternal transfer of Dechlorane Plus flame retardant in fish from an electronic waste recycling site in South China

Knowledge is limited on sex-related accumulation and maternal transfer of Dechlorane Plus (DP) flame retardant in wildlife. In the present study, DP isomers were examined in liver and eggs of two fish species, northern snakehead and crucian carp, from an electronic waste recycling site in China. Hepatic ∑DP (sum of syn- and anti-DP) concentrations ranged 260–1920 ng/g lipid in northern snakehead and 340–1670 ng/g in crucian carp, with significantly higher levels in males relative to females. ∑DP concentrations ranged 4.6–310 ng/g lipid in the eggs, demonstrating their maternal transfer in the female fish. The mean eggs to liver concentration ratios (E/L ratios) were 0.03 and 0.03 in northern snakehead, and 0.26 and 0.25 in crucian carp, for syn- and anti-DP, respectively. A significantly negative correlation between the E/L ratios and the hepatic DP concentrations was observed, indicating a dose-dependent maternal transfer of DP isomers in the fish.

Dechlorane Plus flame retardant in terrestrial raptors from northern China

While a number of studies have addressed the environmental presence and behavior of the Dechlorane Plus (DP) flame retardant, there is still a dearth of information in terrestrial ecosystems. The present study revealed that median ∑DP (including anti- and syn-DP isomers) concentrations ranged from 10 to 810 ng/g lipid weight in muscle and liver tissues of six terrestrial raptor species collected in 2004–2006 from Beijing, China. Some concentrations rival the greatest DP burdens ever reported in global wildlife. Significant, positive correlations were observed between fanti (concentration ratio of anti-isomer to ∑DP) and ∑DP concentrations in the Eurasian sparrowhawk (Accipiter nisus) tissues. These results suggested that the DP burdens could be substantially driven by the accumulation of the anti-isomer in terrestrial birds. The tissue-specific accumulation of DP further suggested that factors (e.g., hepatic binding enzymes) other than lipid solubility could be important in determining tissue deposition of DP.

Dechlorane Plus flame retardant in kingfishers (Alcedo atthis) from an electronic waste recycling site and a reference site, South China: Influence of residue levels on the isomeric composition

Dechlorane Plus (DP) isomers were examined in common kingfishers (Alcedo atthis) and their prey fishes collected from an electronic waste (e-waste) recycling site and a reference site in South China, to investigate the possible influence of DP residue levels on the isomeric compositions. ∑DP (sum of syn-DP and anti-DP) concentrations in kingfishers from the e-waste recycling site ranged from 29 to 150 (median of 58) ng/g lipid weight (lw), which were one order of magnitude greater than those from the reference site (median = 3.9 ng/g lw). The isomer fractions of anti-DP (fanti) in kingfishers from the e-waste recycling site (mean of 0.65) were significantly smaller than those from the reference site (0.76). Additionally, the fanti values were negatively correlated to logarithm of ∑DP concentrations in the kingfishers (r2 = 0.41, p < 0.0001). These results suggested that DP residue levels could influence its isomeric composition in the piscivorous bird.

Brominated and Chlorinated Flame Retardants in Tree Bark from Around the Globe

Brominated and chlorinated flame retardants were measured in about 40 samples of tree bark from 12 locations around the globe. The analytes were polybrominated diphenyl ethers (PBDE), Dechlorane Plus (DP), decabromodiphenylethane (DBDPE), hexabromocyclododecane (HBCD), hexabromobenzene (HBB), pentabromoethylbenzene (PBEB), pentabromobenzene (PBBz), and tetrabromo-p-xylene (pTBX). The highest concentrations of these compounds were detected at an urban site in Downsview, Ontario, Canada. Total PBDE and DP concentrations ranged from 2.1 to 190 ng/g lipid weight and from 0.89 to 48 ng/g lipid weight, respectively. Relatively high levels of DP (46 ± 4 ng/g lipid weight) were found at a remote site at Bukit Kototabang in Indonesia. The concentrations of total PBDE, DP, PBEB, and HBCD in the tree bark samples were significantly associated with human population in the nearby areas (r(2) = 0.21-0.56; P < 0.05). In addition, the concentrations of total PBDE and DP were significantly associated (r(2) = 0.40-0.64; P < 0.05). with the corresponding atmospheric concentrations of these compounds over a concentration range of 2-3 orders of magnitude.

Levels and distribution of Dechlorane Plus and related compounds in surficial sediments of the Qiantang River in eastern China: The results of urbanization and tide

Dechloranes, including Mirex, Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), Dechlorane 604 (Dec 604) and Dechlorane Plus (DP), are a class of chlorinated flame retardants. To investigate the effect of urbanization and tide on the distribution of Dechloranes in sediment, we assayed surficial sediments collected from the Qiantang River in eastern China for the presence of these chemicals. The concentrations of Mirex, Dec 602, Dec 603, and DP ranged from below detection limit (BLD) to 0.68ng/g dry weight (dw), BLD–0.048ng/g dw, BLD–0.026ng/g dw, and BLD–1.1ng/g dw, respectively. Dechloranes 604 was not detected in any sediment samples. It was evident that local urban and industrial activities were the primary source of DP in surficial sediments in the Qiantang River, which was supported by the fact that the average DP concentration of sediment samples in urban sites was approximately three-fold higher than that in rural sites. An extremely high concentration of DP at a reservoir site in a rural area indicated that a dam can block the movement of DP in the Qiantang River by slowing down the river current and making the reservoir the primary sink of DP. Furthermore, the spatial distribution of Dechloranes suggested that concentrations of Dechloranes in sediment in the tide zone were much lower than those in the non-tidal zone, indicating that tide played an important role in transportation and re-distribution of Dechloranes in sediments of the Qiantang River.

Dechlorane Plus in serum from e-waste recycling workers: Influence of gender and potential isomer-specific metabolism

Dechlorane Plus (DP) and its dechlorinated product, anti-Cl11-DP, were measured in serum of 70 occupationally exposed workers in an e-waste recycling region and 13 residents of an urban area in South China. The DP levels were significantly higher in the workers (22–2200ng/g with median of 150ng/g lipid) than in the urban residents (2.7–91ng/g with median of 4.6ng/g lipid). The DP concentrations in females were found to be associated with their age but such relation was not found for males. Significant differences in DP levels and DP isomer composition were found between genders. The females had remarkably higher DP levels and fanti values (fraction of anti-DP to total DPs) in serum than the males. Anti-Cl11-DP was significantly correlated with anti-DP for both genders but with different slope of regression line. The ratios of anti-Cl11-DP to anti-DP (mean of 0.017) in males were significantly higher than those (mean of 0.010) in females. Combining with the lower fanti values in males, it is likely that males have higher metabolic potential for DPs than females which resulted in the lower DP loading in serum. However, the different patterns of selective uptake and/or excretion of different compounds between genders cannot be eliminated as a possible reason for the observed gender differences. This study is the first to report on the gender difference in DP accumulation in human, and its mechanism is worth further investigation.

Dechlorane Plus in eggs of two gull species (Larus michahellis and Larus audouinii) from the southwestern Mediterranean Sea

Dechlorane Plus (DP) and some of its possible degradation products were measured in eggs from the yellow-legged gull (Larus michahellis) and Audouin's gull (Larus audouinii) from a protected area in the southwestern Mediterranean Sea. Statistically significant differences were found between both gull species, with yellow-legged gull eggs showing the highest average total DP concentration (209 pg/g wet weight). According to stable nitrogen and carbon isotope values, variations in DP concentrations in the gull species studied are explained by foraging behavior and diet rather than by the trophic position. Both DP stereoisomers were quantified in all the samples studied, and a slight enrichment of the anti-DP could have occurred in both species. The quantification of anti-[DP-1Cl] only in ∼58 % of yellow-legged gulls support the hypothesis of a species-dependent factor influencing the bioaccumulation and/or biotransformation of Dechlorane-related compounds. This study reports on the first measurements of Dechlorane-related compounds in biota from the North African continent, contributing to the knowledge about DP environmental fate and distribution. In the light of our results, more research on differences in species-dependent bioaccumulation and biotransformation capabilities as well as ecological effects is encouraged in future Dechlorane-related compound studies.

Dechloranes in a river in northeastern China: Spatial trends in multi-matrices and bioaccumulation in fish (Enchelyopus elongatus)

Dechloranes (Decs), including Dechlorane Plus (DP) and Dechlorane (Dec) 602, 603, 604, are used as flame retardants. Fifty four samples were collected in a river in northeastern China and analyzed for Decs by gas chromatography/mass spectrometry. The average concentrations of total DP (syn- and anti-) in water, sediment, air, reed (Phragmites australis), and fish (E. elongatus) were 0.30±0.24 (mean±SD) ngL−1, 1.3±0.69ngg−1 dry weight (dw), 0.25±0.18ngm−3, 0.63±0.18ngg−1 wet weight (ww), and 29±20ngg−1 lipid weight (lw), respectively. While Dec 602 and Dec 603 were detected in most of sediment and fish samples, no Dec 604 was found in any of the investigated environmental matrices. The mean ratio of syn-DP to total DP (fsyn) in water, sediment, reed, and fish were 0.28, 0.25, 0.27 and 0.47, suggesting depletion in abiota and enrichment in biota for syn-DP. It was found that biota-sediment accumulation factor (BSAF) was 4.7 for Dec 602, 0.88 for syn-DP, and 0.33 for anti-DP.

Species- and tissue-specific accumulation of Dechlorane Plus in three terrestrial passerine bird species from the Pearl River Delta, South China

Little data is available on the bioaccumulation of Dechlorane Plus (DP) in terrestrial organisms. Three terrestrial passerine bird species, light-vented bulbul, long-tailed shrike, and oriental magpie-robin, were collected from rural and urban sites in the Pearl River Delta to analyze for the presence of DP and its dechlorinated products in muscle and liver tissues. The relationships between trophic level and concentration and isomeric composition of DP in birds were also investigated based on stable nitrogen isotope analysis. DP levels had a wide range from 3.9 to 930ngg−1lipid weight (lw) in muscle and from 7.0 to 1300ngg−1lw in liver. Anti-Cl11-DP and syn-Cl11-DP, two dechlorinated products of DP, were also detected in bird samples with concentrations ranged between not detected (nd)-41 and nd-7.6ngg−1lw, respectively. DP preferentially accumulated in liver rather than in muscle for all three bird species. Birds had significantly higher concentrations of DP in urban sites than in rural sites (mean, 300 vs 73ngg−1lw). The fractions of anti-DP (fanti) were higher in birds collected in rural sites than in urban sites. Significant positive correlation between DP levels and δ15N values but significant negative correlation between fanti and δ15N values were found for birds in both urban and rural sites, indicating that trophic level of birds play an important role in determining DP level and isomeric profile.

Detection of Dechlorane Plus and brominated flame retardants in marketed fish in Japan

Fish samples purchased from Japanese markets were analyzed for Dechlorane Plus (DP)(syn-, anti-), polybrominated diphenyl ether (PBDE), and hexabromocyclododecane (HBCD)(α, γ). Twenty fish were analyzed using gas chromatography–mass spectrometry for DP and PBDE, and using liquid chromatography–tandem mass spectrometry for HBCD. DP was detected in 18 samples and ∑DP concentrations were <0.2–14.2pgg−1wetwt. Among the DP isomers, anti-DP was the dominant residue observed in this study. PBDE was detected in all samples. Concentrations of ∑PBDE ranged from 2.2 to 878pgg−1 wet wt. HBCD was detected in 18 samples, and ∑HBCD concentrations were <0.02–21.9ngg−1wetwt. In fish landed near the East China Sea and the Sea of Japan, we detected relatively high concentrations of DP, PBDE, and HBCD. These results indicate that the seawaters around East Asia are contaminated with flame retardants. This study demonstrates the presence of DP in fish marketed in Japan for the first time.

Dechlorane Plus in the Atmosphere and Precipitation near the Great Lakes

Air (vapor and particle) and precipitation samples were collected at five sites (two urban, one rural, and two remote) on the shores of the Great Lakes from January 1, 2005 to December 31, 2009 as a part of the Integrated Atmospheric Deposition Network (IADN). The concentrations of the syn and anti isomers of Dechlorane Plus (DP), a highly chlorinated flame retardant, were measured in these samples. The highest concentrations of these compounds were generally observed at the rural site at Sturgeon Point, New York, which is located near DP's manufacturing facility in Niagara Falls, New York, and at the urban site at Cleveland, Ohio. A multiple linear regression model was applied to the concentrations of these compounds in the vapor phase, particle phase, precipitation, and for the three phases combined. This regression resulted in an overall (three phases combined) doubling time for the anti-DP isomer of 9.5 ± 3.6 years, but for the syn- and total DP (syn + anti) concentrations, the overall regression was not statistically significant. These results suggest that there has been no significant change in the atmospheric concentrations of these compounds over the 2005-2009 time period. The effect of distance from the source in Niagara Falls was highly significant; for example, doubling the distance from Niagara Falls decreased the DP concentrations by about 30%. The effect of the number of people living and working within a 25-km radius of the sampling site (population density) was also highly significant but small; for example if this population doubled or halved, then the atmospheric DP concentrations would increase or decrease by only a few percent.

Dechlorane plus and possible degradation products in white stork eggs from Spain

The occurrence of the emerging chlorinated flame retardant Dechlorane Plus (DP) and three of its possible degradation products was investigated in white stork eggs from two colonies in Spain. The average DP concentrations were 401 pg/g wet weight (w.w.) for the urban/industrial colony and 105 pg/g w.w. for the rural colony. One possible degradation product, anti-[DP-1Cl], was found in approximately 10% of the samples. No significant stereoisomer enrichments were detected in any colony based on the average anti-DP fractional abundances found which agrees with previous studies in herring gulls. The relationship between DP and PBDE contents in both colonies was explored leading to different scenarios, i.e. no correlation was found in the urban colony but they were statistically correlated in the rural colony. To the best of our knowledge, this is the first study to report DP in a species from a terrestrial food web, and also to report a DP degradation product in biota.

Levels and distribution of Dechlorane Plus in coastal sediments of the Yellow Sea, North China

Dechlorane Plus (DP) has been determined in surface sediments from three Chinese coastal bays, e.g. Jiaozhou, Sishili and Taozi Bay in North China. DP concentrations ranged from <1.2 to 187 pg g −1 dry weight (dw) (mean: 24.7 pg g −1 dw) in Jiaozhou Bay, <1.2 to 135 pg g −1 dw (mean 69.9 pg g −1 dw) in Sishili Bay and <1.2 to 66.7 pg g −1 dw (mean: 40.4 pg g −1 dw) in Taozi Bay, respectively. Additionally, two dechlorinated species were quantified, which accounted for 0.6–5.1% of the ∑DP concentration. The f syn values ( syn-isomer/( syn- + anti-isomer)) in sediments from Jiaozhou Bay (mean 0.29) were close to the technical DP mixture (0.2–0.4), probably indicating local inputs of DP. In contrast, sediments in Sishili and Taozi Bay showed much lower f syn values (mean 0.16). During transportation the DP isomers are subject to stereo selective degradation which partly resulted in the relative enrichment of anti-DP in coastal sediments.

Concentration and Bioaccumulation of Dechlorane Compounds in Coastal Environment of Northern China

Dechloranes, including Dechlorane Plus (DP), Mirex (Dechlorane), Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), and Dechlorane 604 (Dec 604), were determined using GC-MSD for water, sediment and oyster samples collected at 15 sampling sites near the Bohai and Huanghai Sea shore area of northern China in 2008. DP and Mirex were detected in most water, sediment, and oyster samples, which indicated widespread distribution of these two compounds. The mean concentrations in water, sediment and oyster samples, respectively, were 1.8 ng/L, 2.9 ng/g dry weight (dw) and 4.1 ng/g wet weight (ww) for total DP, and 0.29 ng/L, 0.90 ng/g dw, and 2.0 ng/g ww for Mirex. Dec 602 and Dec 603 were not detected in water but in small portions of the sediment and oyster samples, showing a low level of contamination by these two chemicals in the region. Strong and significant correlations were found between total DP and Mirex concentrations in water, sediment and oyster samples, probably suggesting similar local sources of these two chemicals. Dec 604 was not found in any samples. The biota-sediment accumulation factor (BSAF) of DP, Mirex, and Dec 602 declined along with the increase of their logarithm of octanol-water partition coefficients (log Kow), possibly indicating that compounds with lower log Kow (like Mirex and Dec 602) accumulated more readily in biota. The mean fractional abundance of syn-DP (fsyn) was 0.34 in water samples, a value lower than that in Chinese commercial mixture (0.41), while the mean fsyn for surface sediment (0.44) and oyster (0.45) samples were higher than technical values. Enrichment of syn-DP in oyster was in agreement with previously reported findings in Great Lakes fish. Enrichment of syn-DP in marine surface sediments, however, is contrary to data reported for fresh water sediments. To our knowledge this is the first report of Dec 602, Dec 603, and Dec 604 in a marine environment and also the first report of Dechloranes in marine biota.

Dechlorane Plus (DP) in air and plants at an electronic waste (e-waste) site in South China

Air and foliage samples ( Eucalyptus spp. and Pinus massoniana Lamb.) were collected from e-waste and reference sites in South China and analyzed for Dechlorane Plus (DP) and two dechlorinated DPs. DP concentrations in the air were 13.1–1794 pg/m 3 for the e-waste site and 0.47–35.7 pg/m 3 for the reference site, suggesting the recycling of e-waste is an important source of DP to the environment. Plant DP, with concentrations of 0.45–51.9 ng/g dry weight at the e-waste site and 0.09–2.46 ng/g at the reference site, exhibited temporal patterns similar to the air DP except for pine needle at the reference site. The air-plant exchange of DP could be described with the two-compartment model. Anti-Cl 11 DP was measured in most air and plant samples from the e-waste site. The ratios of anti-Cl 11 DP to anti-DP in the air and plants may indicate the preferential uptake of dechlorinated DP by plant compared with DP.

Quantification of Dechlorane Plus in Human Serum by Gas Chromatography Coupled with Negative Chemical Ionization Mass Spectrometry

Abstract A gas chromatography coupled with negative chemical ionization mass spectrometry (GC-NCI-MS) was developed for the determination of two dechlorane plus (DP) isomers in human serum sample. Target compound and serum lipid were extracted by liquid-liquid extraction. After the sulfuric acid treatment to remove extracted lipids from the samples, samples were further cleaned up with a silica/sulfuric acid column. Identification and quantification of DP were carried out by MS. The detection limit of instrument was 0.5–0.7 pg. The detection limit of the method was 15–20 pg per sample. Recoveries of DP spiked in human serum samples were in the range of 70.2%–85.7%. The developed method was further validated in human serum. DP concentrations were analyzed in 20 electronics dismantling workers and 20 reference humans; DP concentration in dismantling workers and reference humans were 7.8–465 ng g−1 lipid and 0.93–50.5 ng g−1 lipid, respectively.

Bioaccumulation of Several Brominated Flame Retardants and Dechlorane Plus in Waterbirds from an E-Waste Recycling Region in South China: Associated with Trophic Level and Diet Sources

The present study is primarily designed to examine the role played by dietary sources on polybrominated diphenyl ethers (PBDE) congener profiles in waterbirds collected in an e-waste recycling region in South China. Some emerging halogenated flame retardants (HFRs), such as dechlorane plus (DP), 2,3,4,5,6-pentabromoethyl benzene (PBEB), pentabromotoluene (PBT), and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), were also quantified. Stable isotopes (δ(15)N and δ(13)C) were analyzed to assess the trophic levels and dietary sources of the birds. PBDEs were found to be the predominant HFRs, followed by DP, PBT, PBEB, and BTBPE. The birds in which BDE209 was predominant have differential δ(13)C and δ(15)N signatures compared with other birds, suggesting that dietary source is one of the important factors in determining the PBDE congener profile in birds. The levels of ΣPBDEs, PBEB, and PBT were significantly correlated with the trophic level (δ(15)N) for avian species which are located in a food chain, indicating the biomagnification potential of these compounds. No correlation was found between DP concentrations and trophic level of the birds. There is a significantly negative correlation between the fraction of anti-DP and δ(15)N, suggesting that the metabolic capability of DP in birds increases with the trophic level of the birds.