Hydroxypropyl-β-cyclodextrin extractability and bioavailability of phenanthrene in humin and humic acid fractions from different soils and sediments

Organic matter (OM) plays a vital role in controlling polycyclic aromatic hydrocarbon (PAH) bioavailability in soils and sediments. In this study, both a hydroxypropyl-β-cyclodextrin (HPCD) extraction test and a biodegradation test were performed to evaluate the bioavailability of phenanthrene in seven different bulk soil/sediment samples and two OM components (humin fractions and humic acid (HA) fractions) separated from these soils/sediments. Results showed that both the extent of HPCD-extractable phenanthrene and the extent of biodegradable phenanthrene in humin fraction were lower than those in the respective HA fraction and source soil/sediment, demonstrating the limited bioavailability of phenanthrene in the humin fraction. For the source soils/sediments and the humin fractions, significant inverse relationships were observed between the sorption capacities for phenanthrene and the amounts of HPCD-extractable or biodegradable phenanthrene (p?<?0.05), suggesting the importance of the sorption capacity in affecting desorption and biodegradation of phenanthrene. Strong linear relationships were observed between the amount of HPCD-extractable phenanthrene and the amount degraded in both the bulk soils/sediments and the humin fractions, with both slopes close to 1. On the other hand, in the case of phenanthrene contained in HA, a poor relationship was observed between the amount of phenanthrene extracted by HPCD and the amount degraded, with the former being much less than the latter. The results revealed the importance of humin fraction in affecting the bioavailability of phenanthrene in the bulk soils/sediments, which would deepen our understanding of the organic matter fractions in affecting desorption and biodegradation of organic pollutants and provide theoretical support for remediation and risk assessment of contaminated soils and sediments.     

Sorption-desorption behavior of polycyclic aromatic hydrocarbons in upstream and downstream river sediments

Sorption and desorption behaviors of phenanthrene and naphthalene were studied with the whole sediment, humic acid (HA) and humin samples from downstream and upstream sites along the Kishon River, Israel. The 13C nuclear magnetic resonance spectra and the sorption coefficients suggest that sorption occurs to both aromatic and aliphatic moieties of the sedimentary organic matter and that rigid paraffinic domains probably contribute to the sorption non-linearity. The carbon-normalized Freundlich affinity values for the two sorbates were significantly higher for the whole sediment and humin samples from the downstream region of the river than for the upstream sediment samples. On the basis of the measured affinity values, the sorbents can be arranged in the following order: humin>HA>whole sediment. Phenanthrene exhibited the lowest desorption from the whole sediment samples compared with the other sorbents. For naphthalene, the desorption hysteresis obtained with the whole sediment and humin samples were similar: both exhibited a decrease in desorption with decreasing solute concentration. The higher sorption affinities observed for all the organic fractions from the downstream sediment are suggested to be related to the low levels of polar domains and humin content. It is concluded that in bulk sediment samples, the overall contribution of the HA fraction to short-term sorption is of high importance, but the sorption non-linearity is controlled mainly by the humin complexes. The low desorption potential recorded for the whole sediment samples could affect the natural attenuation of the sorbed hydrophobic organic compounds.     

Long-term tillage effects on soil metolachlor sorption and desorption behavior

Sorption and desorption are two important processes that influence the amount of pesticides retained by soils. However, the detailed sorption mechanisms as influenced by soil tillage management are unclear. This study examined the sorption and desorption characteristics of metolachlor [2-chloro-N-(2-ethyl-6-methyphenyl)-N-(2-methoxy-1-methylethyl)-acetamide] using the soil samples collected from the long-term conservation tillage (CnT) and conventional tillage (CT) research plots established in 1979 in Darlinton, SC. Humic acid (HA) and humin were extracted from the soils and used in the sorption experiments along with the whole soil samples. The sorption experiments were conducted using a batch-equilibration method. Three sequential desorption rinses were carried out following the sorption experiments. By comparing metolachlor sorption and desorption results we observed hysteresis for all soil samples and their organic matter fractions. Sorption nonlinearity (N) and hysteresis were dependent on the structure and composition of soil organic matter (SOM), e.g., Freundlich isotherm exponents (N) of HA and humin from CnT were higher than those of CT treatment, which may be related to high aromaticity of SOM fractions in CT treatment. Sorption capacity (K'f) was positively correlated with soil organic carbon (SOC) content. These results show that long-term tillage management can greatly affect metolachlor sorption and desorption behavior probably by qualitative differences in the structural characteristics of the humic substances.     

The impact of vegetation on sedimentary organic matter composition and PAH desorption

Relationships between sedimentary organic matter (SOM) composition and PAH desorption behavior were determined for vegetated and non-vegetated refinery distillate waste sediments. Sediments were fractionated into size, density, and humin fractions and analyzed for their organic matter content. Bulk sediment and humin fractions differed more in organic matter composition than size/density fractions. Vegetated humin and bulk sediments contained more polar organic carbon, black carbon, and modern (plant) carbon than non-vegetated sediment fractions. Desorption kinetics of phenanthrene, pyrene, chrysene, and C₃-phenanthrene/anthracenes from humin and bulk sediments were investigated using Tenax^® beads and a two-compartment, first-order kinetic model. PAH desorption from distillate waste sediments appeared to be controlled by the slow desorbing fractions of sediment; rate constants were similar to literature values for k_slow and k_{very slow}. After several decades of plant colonization and growth (Phragmites australis), vegetated sediment fractions more extensively desorbed PAHs and had faster desorption kinetics than non-vegetated sediment fractions.     

Polybrominated diphenyl ethers in surface sediments from principal watersheds of Shanghai, China: levels, distribution, influencing factors, and risk assessment

Fourteen and 17 sediment samples were collected from three main rivers of Shanghai in July and November, respectively. Eight polybrominated diphenyl ether (PBDE) congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, and BDE-209) were detected in these samples to clarify the pollution status in the metropolis. Instrumental analyses showed that the concentrations of ∑₈PBDEs ranged from 10.97 to 64.05 ng/g dry weight (dw), with an average value of 29.71 ng/g dw. BDE-209 was the predominant congener accounting for more than 97 % of total PBDEs, followed by BDE-47 and BDE-99. Remarkable spatial and seasonal distributions of PBDE concentrations were observed, suggesting that local sources, seasonal climates, and hydrologic conditions might be the influencing factors. Moderate correlations (r ²?=?0.28–0.51, p?<?0.05) were found between total organic carbon and PBDEs, which indicated that organic carbon content influenced the distributions of PBDEs in sediment of Shanghai at some extent. Hazard quotients revealed PBDEs posed no potential risk to benthic organisms in the study area at present.     

A national survey of polybrominated diphenyl ethers (PBDEs) and indicator polychlorinated biphenyls (PCBs) in Chinese mothers' milk

Seven polybrominated diphenyl ethers (PBDEs) congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154 and BDE-183) and six indicator polychlorinated biphenyls (PCBs) congeners (CB-28, CB-52, CB-101, CB-138, CB-153 and CB-180) were measured in 24 pooled human milk samples comprised of 1237 individual samples from 12 provinces in China. The samples were taken to estimate the background body burden of general population and assess nursing infant exposure via human milk in China. The median concentrations of ∑₇PBDEs and ∑₆PCBs were 1.49 and 10.50 ng g⁻¹ lipid weight (lw), respectively. BDE-28, BDE-47 and BDE-153 were predominant PBDE congeners accounting for nearly 70% of ∑₇PBDEs. As for indicator PCBs, CB-153 was the most abundant congener, followed by CB-138. In our study, there was no significantly statistical relationship between concentrations of PBDEs in milk samples and maternal age as well as dietary habits. ∑₇PBDEs did not correlate to ∑₆PCBs in Chinese mothers’ milk. The human exposure to indicator PCBs in China was found to be significantly determined by maternal age, dietary habits and geographical factors. It is suggested that Chinese general population is probably exposed to PBDEs with multiple sources and pathways. The estimated daily intakes (EDI) of BDE-47, BDE-99 and BDE-153 for the Chinese nursing infant were much lower than corresponding threshold reference values suggested by USEPA.     

Method optimization to measure polybrominated diphenyl ether (PBDE) concentrations in soils of Bratislava, Slovakia

We modified an analytical method to determine polybrominated diphenyl ethers (PBDEs) in urban soils of Bratislava (Slovakia). Gel permeation chromatography (GPC) introduced as a clean-up step for soil extracts substantially reduced matrix enhancements when PBDEs were measured with gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS). The resulting method proved to be accurate, precise, and showed low detection limits. The sum of 15 PBDE concentrations in surface horizons of Bratislava soils ranged from 87 to 627 pg g⁻¹. PBDE concentrations were mostly higher in surface than deeper horizons probably because of atmospheric deposition and lack of substantial vertical transport. Lower brominated PBDEs undergo more soil-atmosphere exchanges or are more scavenged and transferred with litter fall to the soil organic matter than higher brominated ones as suggested by the correlation between lower brominated PBDEs and soil organic C (C_org) concentrations.     

Levels, compositions, and inventory of polybrominated diphenyl ethers in sewage sludge of Guangdong Province, South China

Polybrominated diphenyl ethers (PBDEs) were measured in sewage sludge samples collected from major wastewater treatment plants in Guangdong Province, South China. Concentrations of ∑₃₉PBDE (all 39 compounds including tri- to hepta- PBDE congeners except for BDE-209) ranged from 3.6 to 428 ng/g dw with a mean value of 67.4 ng/g dw and a median value of 25.9 ng/g dw, and those of BDE-209 ranged from 9.9 to 5,010 ng/g dw (mean 1,024 ng/g dw and median 824 ng/g dw). The PBDE mixtures detected were mainly comprised of penta-, octa-, and deca-BDEs, with deca-BDE as the dominant constituent. The most abundant congeners, excluding BDE-209, were BDE-47, BDE-99, and BDE-183. Good correlations were found among the concentrations of BDE-47, BDE-99, BDE-100, BDE-138, and BDE-154 (r?>?0.8). However, poor correlations were found between the concentrations of BDE-209 and all other congeners (r?<?0.3). This fact suggests that most tri- to hepta-BDEs detected did not originate from decomposition of deca-BDE. The estimated annual emission of ∑_allPBDEs, ∑₃₉PBDEs, penta-BDE, octa-BDE, and deca-BDE to the Pearl River Delta environment (PRD), based on the sludge samples analyzed, amounts to 232, 20.2, 5.5, 1.7, and 212 kg per year, implicating sewage sludge as a significant source of PBDEs to the PRD environment.     

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.     

Multi-year measurements of polybrominated diphenyl ethers (PBDEs) in the Arctic atmosphere

Weekly high-volume air samples have been collected in the Canadian High Arctic (Alert, Nunavut) since 1992. Fifteen polybrominated diphenyl ethers (PBDEs) are quantified in 104 samples over the time period of 2002–2004. To our knowledge, this study reports the first continuous multi-year measurements of PBDEs in Arctic air. Average air concentrations (in pg m⁻³) were 7.7 (0.40–47) and 1.6 (0.091–9.8) for 14 PBDEs (excluding BDE-209) and BDE-209, respectively, over the entire sampling period. BDE-28/33, 47, 99, 100, 153, 154, and 209 accounted for 90% (72–97%, n=104) of the 15 PBDEs. Occurrence of BDE-47, 99, and 209 suggests that PBDEs in Alert air were likely associated with the usage of “penta-BDE” and “deca-BDE” technical mixtures worldwide. Natural logarithm of concentrations for less brominated PBDEs correlated significantly with ambient temperatures in the summertime, suggesting importance of volatilization emissions in a local and/or regional scale. On the other hand, episodically elevated concentrations of the less brominated PBDEs in the wintertime and lack of seasonality for the non-volatile BDE-209 indicate potential inputs of particle-bound PBDEs through long-range transport (LRT), especially during the Arctic haze season. Inter-annual trend data further show that concentrations of the eight PBDEs increased inter-annually in 2002–2004 with doubling times of 2–6 years, which were similar to growth rates found in Arctic biotic samples. The results of this study and previous measurements suggest that potential sources of PBDEs in Arctic air include both volatilization emissions and LRT inputs.     

Sorption and desorption kinetics of diuron,fluometuron, prometryn and pyrithiobac sodium in soils

Abstract

The sorption and desorption characteristics of four herbicides (diuron, fluometuron, prometryn and pyrithiobac‐sodium) in three different cotton growing soils of Australia was investigated. Kinetics and equilibrium sorption and desorption isotherms were determined using the batch equilibrium technique. Sorption was rapid (> 80% in 2 h) and sorption equilibrium was achieved within a short period of time (ca 4 h) for all herbicides. Sorption isotherms of the four herbicides were described by Freundlich equation with an r² value > 0.98. The herbicide sorption as measured by the distribution coefficient (K_d) values ranged from 3.24 to 5.71 L/kg for diuron, 0.44 to 1.13 L/kg for fluometuron, 1.78 to 6.04 L/kg for prometryn and 0.22 to 0.59 L/kg for pyrithiobac‐sodium. Sorption of herbicides was higher in the Moree soil than in Narrabri and Wee Waa soils. When the K_d values were normalised to organic carbon content of the soils (K_oC), it suggested that the affinity of the herbicides to the organic carbon increased in the order: pyrithiobac‐sodium < fluometuron < prometryn < diuron. The desorption isotherms were also adequately described by the Freundlich equation. For desorption, all herbicides exhibited hysteresis and the hysteresis was stronger for highly sorbed herbicides (diuron and prometryn) than the weakly sorbed herbicides (fluometuron and pyrithiobac‐sodium). Hysteresis was also quantified as the percentage of sorbed herbicides which is not released during the desorption step ω = [n_ad / n_de ‐1] x 100). Soil type and initial concentration had significant effect on ω. The effect of sorption and desorption properties of these four herbicides on the off‐site transport to contaminate surface and groundwater are also discussed in this paper.     

Uptake, translocation and metabolism of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in maize (Zea mays L.)

A hydroponic experiment was conducted in the present study to investigate and compare plant uptake, translocation and metabolism of polybrominated diphenyl ethers (PBDEs) of BDE-15, BDE-28 and BDE-47 and polychlorinated biphenyls (PCBs) of PCB-15, PCB-28 and PCB-47 in maize. Root concentrations of BDE-15, BDE-28 and BDE-47 were consistently higher than PCB-15, PCB-28 and PCB-47, respectively. A significantly positive correlation was found between logRCF (root concentration factor) and logKow of these PBDEs and PCBs, suggesting a control role of their partitioning in plant uptake. The translocation factors (TFs, Cstem/Croot) of PBDEs were generally lower than those of PCBs of the same halogen-substitutions, demonstrating easier transport of PCBs than PBDEs. Metabolites mono-, di- and tri-BDEs and PCBs were detected, suggesting the existence of in vivo metabolism of PBDEs and PCBs in maize. Dehalogenation and rearrangement of halogen atoms were identified, and some similarities but also significant differences existed between the PBDEs and PCBs. PBDEs in maize were, in general, more susceptible to metabolism compared with PCBs of the same halogen-substitutions. This is the first comparative report on the uptake, translocation and metabolism of PBDEs and PCBs in plants.     

Carbonaceous matter and PBDEs on indoor/outdoor glass window surfaces in Guangzhou and Hong Kong,South China

Organic films, collected from indoor and outdoor window surfaces in Guangzhou and Hong Kong of South China, were analyzed to quantify their organic carbon (OC), elemental carbon (EC), and polybrominated diphenyl ethers (PBDEs) content. The highest concentrations of OC, EC, and BDE-209 were found in Guangzhou with values of 10 000 μg m^?2, 2200 μg m^?2, and 4000 ng m^?2, respectively, and the highest concentration of Σ₇PBDE (sum of BDE-28, -47, -99, -100, -153, -154 and -183) was found in Hong Kong with a value of 25 ng m^?2. In most cases, the concentrations of PBDEs were higher in the exterior films than those in the interior films with BDE-209 as the predominant congener in both cities, suggesting that PBDEs mainly come from ambient environment, and deca-BDE accounts for major PBDE consumption. The growth rates of organic film on window surfaces were fast at the beginning, and reached a consistent level afterwards. The evolution rates ranged from 2.6 to 11 nm day^?1 for “bulk film”, while from 0.06 to 0.92 nm day^?1 for “pure film”. The concentrations of PBDEs on the window surfaces did not increase with the growth time, suggesting that the window surface may provide a good place for photo-degradation of PBDEs.     

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.     

Effect of soil and sediment composition on acetochlor sorption and desorption

Background, aim, and scope  Herbicide fate and its transport in soils and sediments greatly depend upon sorption–desorption processes. Quantitative determination of herbicide sorption–desorption is therefore essential for both the understanding of transport and the sorption equilibrium in the soil/sediment–water system; and it is also an important parameter for predicting herbicide fate using mathematical simulation models. The total soil/sediment organic carbon content and its qualitative characteristics are the most important factors affecting sorption–desorption of herbicides in soil or sediment. Since the acetochlor is one of the most frequently used herbicides in Slovakia to control annual grasses and certain annual broad-leaved weeds in maize and potatoes, and posses various negative health effects on human beings, our aim in this study was to investigate acetochlor sorption and desorption in various soil/sediment samples from Slovakia. The main soil/sediment characteristics governing acetochlor sorption–desorption were also identified. Materials and methods  The sorption–desorption of acetochlor, using the batch equilibration method, was studied on eight surface soils, one subsurface soil and five sediments collected from the Laborec River and three water reservoirs. Soils and sediments were characterized by commonly used methods for their total organic carbon content, distribution of humus components, pH, grain-size distribution, and smectite content, and for calcium carbonate content. The effect of soil/sediment characteristics on acetochlor sorption–desorption was examined by simple correlation analysis. Results  Sorption of acetochlor was expressed as the distribution coefficient (K _d). K _d values slightly decreased as the initial acetochlor concentration increased. These values indicated that acetochlor was moderately sorbed by soils and sediments. Highly significant correlations between the K _d values and the organic carbon content were observed at both initial concentrations. However, sorption of acetochlor was most closely correlated to the humic acid carbon, and less to the fulvic acid carbon. The total organic carbon content was found to also significantly influence acetochlor desorption. Discussion  Since the strong linear relationship between the K _d values of acetochlor and the organic carbon content was already released, the corresponding K _oc values were calculated. Considerable variation in the K _oc values suggested that other soil/sediment parameters besides the total soil organic carbon content could be involved in acetochlor sorption. This was revealed by a significant correlation between the K _oc values and the ratio of humic acid carbon to fulvic acid carbon (C_HA/C_FA). Conclusions  When comparing acetochlor sorption in a range of soils and sediments, different K _d values which are strongly correlated to the total organic carbon content were found. Concerning the humus fractions, the humic acid carbon content was strongly correlated to the K _d values, and it is therefore a better predictor of the acetochlor sorption than the total organic carbon content. Variation in the K _oc values was attributed to the differences in distribution of humus components between soils and sediments. Desorption of acetochlor was significantly influenced by total organic carbon content, with a greater organic carbon content reducing desorption. Recommendations and perspectives  This study examined the sorption–desorption processes of acetochlor in soils and sediments. The obtained sorption data are important for qualitative assessment of acetochlor mobility in natural solids, but further studies must be carried out to understand its environmental fate and transport more thoroughly. Although, the total organic carbon content, the humus fractions of the organic matter and the C_HA/C_FA ratio were sufficient predictors of the acetochlor sorption–desorption. Further investigations of the structural and chemical characteristics of humic substances derived from different origins are necessary to more preciously explain differences in acetochlor sorption in the soils and sediments observed in this study.     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.     

Behavior of decabromodiphenyl ether (BDE-209) in soil: effects of rhizosphere and mycorrhizal colonization of ryegrass roots

A rhizobox experiment was conducted to investigate degradation of decabromodiphenyl ether (BDE-209) in the rhizosphere of ryegrass and the influence of root colonization with an arbuscular mycorrhizal (AM) fungus. BDE-209 dissipation in soil varied with its proximity to the roots and was enhanced by AM inoculation. A negative correlation (P < 0.001, R² = 0.66) was found between the residual BDE-209 concentration in soil and soil microbial biomass estimated as the total phospholipid fatty acids, suggesting a contribution of microbial degradation to BDE-209 dissipation. Twelve and twenty-four lower brominated PBDEs were detected in soil and plant samples, respectively, with a higher proportion of di- through hepta-BDE congeners in the plant tissues than in the soils, indicating the occurrence of BDE-209 debromination in the soil-plant system. AM inoculation increased the levels of lower brominated PBDEs in ryegrass. These results provide important information about the behavior of BDE-209 in the soil-plant system.     

Polybrominated diphenyl ethers (PBDEs) in soils along a rural-urban-rural transect: sources, concentration gradients, and profiles

This study reports concentrations of PBDEs in surface soil samples collected along a 140 km transect across Kuwait to assess the role of urban centers as sources of persistent organic pollutants to the surrounding environment. The ΣPBDE concentrations varied by a factor of ∼250 and ranged from 289 to 80,078 pg g⁻¹ d.w. The concentrations of PBDEs in Kuwait City were significantly higher (p < 0.01) than those collected from sites outside the city supporting the hypothesis that urban centers are sources of PBDEs. The congener profiles were dominated by BDE-209, accounting for 93% of the PBDEs in the soil samples. The concentrations of all congeners (except BDE-209) were highly correlated with percent organic carbon (%OC) (p > 0.05) when the data from Kuwait City was omitted from the analysis. These findings suggest that soil concentrations outside the urban centers were close to equilibrium with the atmosphere.     

Sorption–desorption of imidacloprid onto a lacustrine Egyptian soil and its clay and humic acid fractions

Sorption–desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption–desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kd_ads, varied according to its initial concentration and was ranged 40–84 for HA, 14–58 for clay and 1.85–4.15 for bulk soil. Freundlich sorption coefficient, Kf_ads, values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ～800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/n_ads values <1 for all sorbents. Values of the hysteresis index (H) were <1, indicating the irreversibility of imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.     

PBDEs in leachates from municipal solid waste dumping sites in tropical Asian countries: phase distribution and debromination

Polybrominated diphenyl ethers (PBDEs) are extensively used as flame retardants in many consumer products, and leachates from landfills have been identified as one of the possible sources of PBDEs in the environment. Meanwhile, the unprecedented economic and population growths of some Asian countries over the last decade have led to significant increases in the amount of waste containing PBDEs in that region. This study investigates the status of PBDEs in leachates from municipal solid waste dumping sites (MSWDS) in tropical Asian countries. A total of 46 PBDE congeners were measured, both in the adsorbed (n?=?24) and dissolved (n?=?16) phases, in leachate samples collected, from 2002 to 2010, from ten MSWDS distributed among the eight countries of Lao PDR, Cambodia, Vietnam, India, Indonesia, Thailand, the Philippines, and Malaysia. PBDEs were predominantly found in the adsorbed phase. Partitioning of PBDEs in the dissolved phase was associated with the presence of dissolved organic matter; the apparent organic carbon-normalized partition coefficients (K′_oc) of the BDE congeners were lower by two to four orders of magnitude than the K _oc predicted from the octanol–water partition coefficients (K _ow). The total PBDE concentrations from mono- to deca-BDEs ranged from 3.7 to 133,000 ng/L, and showed a trend toward higher concentrations in the more populous and industrialized Asian countries. The congener profiles in the leachates basically reflected the composition of PBDE technical mixtures. The occurrence of congeners not contained, or in trace concentrations, in technical products (e.g., BDEs 208, 207, 206, 202, 188, 179, 49, 17/25, 8, 1) was observed in most of the leachate samples, suggesting the debromination of technical mixtures, including BDE-209, in the MSWDS of tropical Asian countries. Moreover, the temporal trend indicated the reduction of BDE-209 over time, with a corresponding increase in and/or emergence of lower brominated PBDE congeners. The results indicated that MSWDS of tropical Asian countries are potential sources of environmental PBDEs, which may be transported to the aquatic environment via dissolution with dissolved organic matter. MSWDS could be amplifiers of PBDE toxicity in the environment, possibly through debromination.