Effect of sewage sludges contaminated with polybrominated diphenylethers on agricultural soils

The fate of polybrominated diphenyl ethers (PBDEs) in sewage sludge after agricultural application was analysed. This study was based on the analysis of sewage sludge and sludge amended soil samples collected during 2005. PBDE concentrations in sewage sludge ranged from 197 to 1185ng/g dry weight (dw), being deca-BDE-209 the predominant congener. PBDE levels in soils ranged between 21 and 690ng/g dw, being BDE-209 also the predominant congener in all soil samples. Sewage-sludge amendment at the research stations increased concentrations of all BDE congeners 1.2- to 45-fold, with the highest increases for BDE-209. Results obtained evidenced the cumulative effect of the sludge application rates. Moreover, high levels found at soils four years after the last sludge application indicate persistence of PBDEs in soils, including deca-BDE-209.     

Polybrominated diphenyl ethers in surface sediments of the Yangtze River Delta: Levels, distribution and potential hydrodynamic influence

A total of 32 surface sediments collected from the Yangtze River Estuary, Hangzhou Bay and the Qiantang River were analyzed for polybrominated diphenyl ethers (PBDEs). The concentrations of summation operatorPBDEs (sum of 12 PBDE congeners without BDE 209) and BDE 209 varied from n.d. to 0.55 and from 0.16 to 94.6 ng/g, respectively. The spatial variability of summation operatorPBDEs concentrations indicated that waste discharge from the urban areas might been the main source of PBDEs in the Yangtze River Delta. BDE 209 was the predominant congener (approximately 90-100%) detected among the 13 congeners, consistent with the fact that technical deca-BDE mixtures are presently the dominant technical PBDE mixtures used in China. Compared to published data acquired from other locales, PBDE congeners with less than four bromines were more abundant in the present study area. The hydrodynamic conditions may likely be a significant factor in dictating the observed levels and congener distribution patterns of PBDEs.     

Sodium borohydride reduction of individual polybrominated diphenyl ethers

Many chemicals in use today lack appropriate documentation on their environmental properties, fate, and effects. To counteract this lack of documentation it is vital to thoroughly investigate a compound’s fate in the environment before it comes into use. The present study is describing a novel method for assessing the reduction potential of polybrominated diphenyl ethers (PBDEs), as a part of a project aimed to create an experimental model for determination of chemical persistence. The reductive transformation of 15 PBDE congeners using sodium borohydride was determined. Pseudo-first-order reaction rate constants of the transformations were determined by monitoring the disappearance of the investigated congeners. The reductions lead primarily to formation of lower brominated PBDEs. Each PBDE congener was tested in a total of ten replicates which showed a relative standard deviation of 31% or less. The decaBDE, BDE-209 was approximately 3 times as prone to reductive transformation as BDE-207. The three nonaBDEs, BDE-206, BDE-207, and BDE-208, showed similar reductive potential. The reactivity of the tested octaBDEs was quite variable, from 5% to 24% of the reactivity of BDE-209 for BDE-196 and BDE-198, respectively. The heptaBDEs studied were in the range of the less reactive octaBDEs, except for BDE-181 which was as high as 13% of the reactivity of BDE-209. The results presented give a method for measuring the propensity of PBDEs, and possibly similar compounds, to undergo reductions. They indicate a potential route to a vital piece of information in the assessment of environmental persistence of chemicals.     

Bioaccumulation, maternal transfer and elimination of polybrominated diphenyl ethers in wild frogs

To investigate bioaccumulation, maternal transfer and elimination of polybrominated diphenyl ethers (PBDEs) in amphibians, we collected adult frogs (Rana limnocharis) from a rice field in an e-waste recycling site in China. We found that ∑PBDEs in the whole frogs and various tissues (brain, liver, testis and egg) ranged from 17.10 to 141.11 ng g⁻¹ wet weight. Various tissues exhibited a similar PBDE congener profile, which was characterized by intermediate brominated congeners (BDE-99 and BDE-153) as the largest contributors, with less lower brominated congeners (BDE-28 and BDE-47) and higher brominated congeners (BDE-209). The maternal transfer capacity of PBDEs declined with the increase in bromine numbers of PBDE congeners. We suggest that the bromine atom number (the molecular size, to some degree) might be a determining factor for the maternal transport of a PBDE congener rather than K_ow (Octanol-Water partition coefficient), which expresses a compound’s lipophilicity. ∑PBDEs concentrations in frogs decreased over time during a depuration period of 54 days when these wild frogs were brought to the lab from the e-waste recycling site. The half-life of ∑PBDEs was 35 days, with about 14 days for BDE-47, and 36 and 81 days for BDE-99 and BDE-153, respectively. The data shows that the elimination of PBDEs has no essential difference from aquatic and terrestrial species.     

Occurrence of polybrominated diphenyl ethers in soil from the central Loess Plateau, China: role of regional range atmospheric transport

Very few studies were conducted in highland and depositional areas in studying the transport and behavior of polybrominated diphenyl ethers (PBDEs). In this study, surface soils were collected from Huan County to investigate the level, profile, and potential influence of PBDEs via regional range atmospheric transport in the central part of the Loess Plateau (CLP) of China, one of the most extensive areas of loess deposition in the world. PBDEs were ubiquitous and log-normally distributed in soils from the CLP with mean concentrations of 0.91 and 0.54 ng g⁻¹ for ΣPBDEs (sum of PBDE congeners except for BDE-209) and BDE-209, respectively. BDE-209 was predominated congener (43.5%), followed by BDE-47 (15.7%), 99 (10.7%), and 153 (7.5%). Further principal component analysis on congener profiles showed that PBDEs in the CLP originated from similar source(s). Additionally, significant differences in the ratios of BDE-47 to 99 and BDE-153 to 154 were found between soil samples and commercial products, indicating that they have undergone fractionation during the process of regional range atmospheric transport. The deposition of PBDEs in the CLP could be influenced by the sources from surrounding regions. For example, Xi’an may have potential influence to the CLP based on geographical analysis and concentrations comparison of PBDEs in gaseous. Therefore, more studies are needed to clarify the atmospheric transport and fate of PBDEs in this region.     

Bioaccumulation kinetics of sediment-associated DE-83 in benthic invertebrates (Nereis succinea, polychaete)

Polychaetes (Nereis succinea) were exposed to DE-83 contaminated sediments to investigate the bioaccumulation and bioavailability of nona- and deca-BDEs in sediment. All the major congeners in DE-83 were bioavailable to the lugworms. The uptake coefficients (K_s) of nona- and deca-BDE congeners in lugworms were in the range of 0.18-0.65 (d⁻¹), with the values of BDE-207 and -208 slightly higher than those of BDE-206 and -209. Elimination of nona- and deca-BDE congeners from lugworms was very fast. The estimated half-lives of nona- and deca-BDE congeners in the lugworms were at 0.7 d. The bioavailability of nona- and deca-BDE congeners was very low, with BSAF of 0.017 for BDE-206 and -209 and 0.054 for BDE-207 and -208. These may be due to the large molecular size and high affinity of PBDEs to sediment particles. The contribution of BDE-206 in the profile of nona-BDEs in lugworm tissue decreased with exposure time while those of BDE-207 and -208 increased, which could be the result of the biotransformation of BDE-209 to BDE-207 and -208.     

Distribution of polybrominated diphenyl ethers in the surface sediments of the Taihu Lake, China

Twenty-eight sediment samples were collected from the Taihu Lake and analyzed to acquire information about the levels, distribution, possible sources, time trend and inventory of polybrominated diphenyl ethers (PBDEs) in the Taihu Lake. Our results showed that the most abundant BDE congeners in surface sediments were BDE-47, 99 and 209, with a median value of 0.124, 0.279, and 22.72 ng(gdw)(-1), respectively. The levels of BDE-209 in our samples were much higher relative to those of the other BDE congeners and made up more than 80% of the PBDEs levels in almost all samples. Disregarding BDE-209, among the seven PBDEs (BDE-28, 47, 99, 100, 153, 154, 183) more concerned, the most abundant ones were BDE-47 and 99, which contributed 44.65% (ranged from 29.02% to 73.11%), 24.24% (ranged from 2.27% to 39.66%) to ∑(7)PBDEs, respectively. The correlation between PBDE and TOC was poor, indicating that PBDEs concentrations in sediments of the Taihu Lake were controlled not only by TOC contents, but also by a combined effect of transport, mixing, depositional mechanisms associated with PBDEs, uncontaminated sediments, or fresh input of PBDEs. As expected, the time trend of PBDEs concentration in surface sediment from Taihu Lake were increasing, and the inventory of ∑(25)PBDEs and BDE-209 were estimated to be 3668 kg and 26296 kg.     

Molecular orbital studies on brominated diphenyl ethers. Part I--conformational properties

Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame retardants and quantities in the environment are on the rise. Because they are structurally related to polychlorinated biphenyls and also to thyroid hormones, there is serious concern that PBDEs may pose a danger to human health. Knowledge of their conformational properties is key to assessing their environmental fate and risk. The conformational properties of PBDEs were investigated by quantum chemical methods including semiempirical self-consistent field molecular orbital (SCF-MO), ab initio SCF-MO and density functional theory (DFT). Conformational analyses of model congeners 2,2',4,6'-tetrabromodiphenyl ether and 2,3,4,4',5,6-hexabromodiphenyl ether, based on energy maps calculated by semiempirical AM1 method, may indicate that all PBDE congeners except those with the tetra-ortho-bromination are conformationally flexible (or soft) due to low energy barriers for interconversion of stable conformers. The results of the conformational analyses are in conformity with recently published X-ray crystallographic data. For comparison with the results of the semiempirical method, higher level ab initio and DFT models were applied as well. The optimized geometries all lie well inside low energy regions on the maps and thus also ascertain the semiempirical calculations. According to computed geometric parameters and net atomic charges, the model B3LYP/3-21G* seemed to give better results than B3LYP/6-31G* and HF/6-31G*.     

Occurrence, compositional patterns, and possible sources of polybrominated diphenyl ethers in agricultural soil of Shanghai, China

The present study analyzed surface soil collected from agricultural region of Shanghai to determine the occurrence, compositional patterns and possible sources of polybrominated diphenyl ethers (PBDEs). The results showed that 32 PBDEs were detected among 44 target PBDEs. Total PBDE concentrations ranged from 129 to 1245 ng kg⁻¹ with a mean of 429 ng kg⁻¹. BDE209 was the predominant congener in a range of 33.2-796 ng kg⁻¹ with a mean of 254 ng kg⁻¹. Meanwhile, BDE47, BDE49, BDE153, BDE190, and BDE99 have the most abundant with high concentrations and detectable frequencies. PBDE congeners and homologues analysis and principal component analysis (PCA) also revealed that the major source of PBDE in the soil samples was associated with the prevalent use of technical decabromodiphenyl ether (Deca-BDE) and pentabromodiphenyl ether (Penta-BDE). The correlation analysis proved that there was a significant correlation between total organic carbon (TOC) and lower brominated PBDEs, indicating the significant diffuse nature of the sources of these congeners.     

Analysis of major congeners of polybromobiphenyls and polybromodiphenyl ethers in office dust using high resolution gas chromatography-mass spectrometry

The study focused on analysis of polybromobiphenyls (PBBs) and polybromodiphenyl ethers (PBDEs) congeners in office dust obtained in Pretoria, South Africa. Of the 32 congeners considered for identification, (BB-1, 2, 4, 10, 15, 26, 29, 30, 31, 38, 49, 80, 103, 153, 155, 209 and BDE-3, 15, 17, 28, 47, 66, 77, 85, 99, 100, 126, 138, 153, 154, 183, 209) only BB-2, 4, 30, 153, 209 and BDE-47, 66, 85, 99, 153 and 209 congeners were detected. The sum of PBBs concentration detected in office dust ranged from <dl − 196 ng g⁻¹ dry weight (dw) with a median and mean of 11.4 and 38.2 ng g⁻¹, respectively. On the other hand, the sum of PBDEs concentration detected ranged from 21.6 to 578.6 ng g⁻¹ dw with a median and mean of 162 and 169 ng g⁻¹ dw, respectively. A Spearman rank correlation between ∑₅PBBs and ∑₆PBDEs (r_s = 0.55, p = 0.003), indicated a statistical significant positive correlation for the similarity of pollution sources for both compound classes. However, no correlation was observed between the number of electronic materials and summation of concentrations of PBBs and PBDEs congeners detected. Concentrations of PBDEs detected in this study are substantially lower than reported in office dust in developed countries.     

Contamination and potential sources of polybrominated diphenyl ethers (PBDEs) in water and sediment from the artificial Lake Shihwa, Korea

Concentrations of polybrominated diphenyl ethers (PBDEs) were determined in water and sediment collected from the artificial Lake Shihwa and surrounding creeks. Total concentrations of 23 PBDE congeners in water and sediment ranged from 0.16 to 11.0 ng L⁻¹ and from 1.3 to 18 700 ng g⁻¹ dry weight, respectively. The concentrations of BDE 209 in water and sediment were 1-2 orders of magnitude higher than the total concentrations of other PBDE congeners. The concentrations of total PBDEs and BDE 209 in sediments were the highest compared to previously reported worldwide levels. The highest concentrations of PBDEs in water and sediments were found in creeks near industrial complexes. The PBDE concentrations gradually decreased with increasing distance from the creeks to the inshore and then offshore regions of the lake. BDE 209 was a major congener, accounting for 80% of the total PBDEs in water and sediment, consistent with a high consumption of deca-BDE for the brominated flame retardant market in Korea. Non-parametric multidimensional scaling ordination showed that surrounding creeks are major pathways of PBDE contamination associated with deca-BDE technical mixtures used in industrial complexes around Lake Shihwa. A significant correlation between total organic carbon and total PBDE concentration was found in sediments, and the correlation coefficients for individual PBDE congeners relatively increased from lower to higher brominated congeners.     

Predicting the bioavailability of sediment-associated polybrominated diphenyl ethers using a 45-d sequential Tenax extraction

A 45-d Tenax extraction was used to evaluate the bioavailability of polybrominated diphenyl ethers (PBDEs) in three spiked sediments. The effect of aging on desorption kinetics of PBDEs was investigated by incubating one of the sediments for 7, 14, 30 and 60 d at room temperature. Desorption kinetics were well described by a three-compartment model. The fraction of very slow desorption (Fvs) contributed the most of the desorbed PBDEs from sediments. The total desorption amount of PBDEs decreased with the increase of total organic carbon in the sediments, suggesting that organic matter is an important factor controlling the partition of PBDEs in sediments. The total desorption amount of PBDEs decreased while log [(Fslow+Fvs)/Frap] increased with logKow of PBDE congeners, indicating that the bioavailability of PBDEs in sediment decreases with logKow of the congeners. As the residential time of PBDEs in the sediment increased from 7 to 60 d, Frap of individual PBDE congeners decreased gradually with simultaneous increase of Fvs. There was a good positive correlation between Frap and F6/F24, indicating that either 6 h or 24 h Tenax extraction could be a proxy for Frap and bioavailability. In general, the results in present study suggest that the bioavailability of nona- and deca-BDEs in sediment is very low due to their strong hydrophobicity and large molecular size.