Investigating a new approach for magnetic ionic liquids: Dispersive liquid-liquid microextraction coupled to pyrolysis gas-chromatography-mass spectrometry to determine flame retardants in sewage sludge samples.

This study addresses the analysis of emerging contaminants, often using chromatographic techniques coupled to mass spectrometry. However, sample preparation is often required prior to instrumental analysis, and dispersive liquid-liquid microextraction (DLLME) is a viable strategy in this context. DLLME stands out for its ability to reduce sample and solvent volumes. Notably, dispersive liquid-liquid microextraction using magnetic ionic liquids (MILs) has gained relevance due to the incorporation of paramagnetic components in the chemical structure, thereby eliminating the centrifugation step. A pyrolizer was selected in this work to introduce sample onto the GC column, since the MIL is extremely viscous and incompatible with direct introduction through an autosampler. This study is the first to report the use of a DLLME/MIL technique for sample introduction through a pyrolizer in gas chromatography coupled to mass spectrometry (GC-MS). This approach enables the MIL to be compatible with gas chromatography systems, resulting in optimized analytical and instrument performance. The analysis of polybrominated diphenyl ether flame retardants (PBDEs) was focused on the PBDE congeners 28, 47, 99, 100, and 153 in sewage sludge samples. The [P6,6,6,14+]2[MnCl42-] MIL was thoroughly characterized using UV-Vis, Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy, as well as thermal analysis. In the chromatographic method, a pyrolyzer was used in the sample introduction step (Py-GC-MS), and critical injection settings were optimized using multivariate approaches. Optimized conditions were achieved with a temperature of 220 °C, a pyrolysis time of 0.60 min, and an injection volume of 9.00 µL. DLLME optimization was performed through central compound planning (CCD), and optimized training conditions were achieved with 10.0 mg of MIL, 3.00 µL of acetonitrile (ACN) as dispersive solvent, extraction time of 60 s, and volume of a sample of 8.50 mL. Precision was observed to range from 0.11 % to 12.5 %, with limits of detection (LOD) of 44.4 µg L-1 for PBDE 28, 16.9 µg L-1 for PBDE 47 and PBDE 99, 33.0 µg L-1 for PBDE 100 and 375 µg L-1 for PBDE 153. PBDE 28 was identified and analyzed in the sludge sample at a concentration of 800 µg L-1. The use of MIL in dispersive liquid-liquid microextraction combined with pyrolysis gas chromatography-mass spectrometry enables identification and quantification of PBDEs in sewage sludge samples at concentrations down to the µg L-1 level.

Validation and Evaluation of Selected Organic Pollutants in Shrimp and Seawater Samples from the NW Portuguese Coast.

The development of coastal regions has contributed to the intensification of environmental contamination, which can accumulate in aquatic biota, such as shrimps. These crustaceans, besides being delicious and being a good source of nutrients, can also accumulate environmental pollutants. Amongst others, these include organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs), brominated flame retardants (BFRs), polychlorinated biphenyls (PCBs) and synthetic musks (SMs). These pollutants, classified as endocrine disruptors, are related to adverse effects in humans and since one of the major routes of exposition is ingestion, this is a cause for concern regarding their presence in food. The aim of the present study was to quantify the presence of environmental pollutants in shrimp samples and in the water from their habitat along the northwest Portuguese coast. In seawater samples, only two OCPs (lindane and DDD) and one BFR (BTBPE) were detected, and in shrimp samples, one OCP (DDD) and three SMs (HHCB, AHTN and ketone) were found. Bioaccumulation and the risk assessment of dietary exposure of SMs in shrimp samples were investigated. It was observed that all shrimp samples analyzed significantly presented bioaccumulation of the three SMs found. Concentrations of SMs detected in shrimp samples do not present a health risk for the adult Portuguese population.

NiFe2O4-based magnetic covalent organic framework nanocomposites for the efficient adsorption of brominated flame retardants from water.

A new kind of NiFe2O4-based magnetic covalent organic framework nanocomposites (NiFe2O4@COFs) was fabricated through facile synthesis approach under room temperature. The NiFe2O4@COFs exhibited higher adsorption capacity for brominated flame retardants than carbon nanotube material based on hydrophobic interactions, π-π stacking interaction, and van der Waals forces. In addition, the adsorption isotherm and the kinetic model were more suitable for Langmuir and pseudo-second-order model, respectively. NiFe2O4-based magnetic covalent organic framework nanocomposites combined with HPLC-UV (absorption wavelength: 214 nm) technology has excellent adsorption performance, which exhibited low detection limits (0.03-1.9 µg L-1), wide linear range (0.11-1000 µg L-1), good recoveries (91.5-102%) with a relative standard deviation of less than 2.9%. Finally, the prepared magnetic material was successfully used asadsorbents of magnetic solid-phase extraction and applied to the determination of five BFRs from the real water samples. The adsorption and removal of BFRs by NiFe2O4@COFs from water samples.

Polybrominated Diphenyl Ethers in Human Follicular Fluid Dysregulate Mural and Cumulus Granulosa Cell Gene Expression.

Polybrominated diphenyl ethers (PBDEs), a major class of flame retardants incorporated into numerous consumer products, leach out into dust resulting in widespread exposure. There is evidence from in vitro and in vivo animal studies that PBDEs affect ovarian granulosa cell function and follicular development, yet human studies of their association with female infertility are inconclusive. Here, we tested the hypothesis that exposure to the PBDEs in follicular fluid is associated with dysregulation of gene expression in the mural and cumulus granulosa cells collected from women undergoing in vitro fertilization by intracytoplasmic sperm injection. The median concentration of the ∑ 10PBDEs detected in the follicular fluid samples (n = 37) was 15.04 pg/g wet weight. RNA microarray analyses revealed that many genes were differentially expressed in mural and cumulus granulosa cells. Highest vs lowest quartile exposure to the Σ 10PBDEs or to 2 predominant PBDE congeners, BDE-47 or BDE-153, was associated with significant effects on gene expression in both cell types. Mural granulosa cells were generally more sensitive to PBDE exposure compared to cumulus cells. Overall, gene expression changes associated with BDE-47 exposure were similar to those for ∑ 10PBDEs but distinct from those associated with BDE-153 exposure. Interestingly, exposure to BDE-47 and ∑ 10PBDEs activated the expression of genes in pathways that are important in innate immunity and inflammation. To the best of our knowledge, this is the first demonstration that exposure to these environmental chemicals is associated with the dysregulation of pathways that play an essential role in ovulation.

Effective Biobased Phosphorus Flame Retardants from Starch-Derived bis-2,5-(Hydroxymethyl)Furan.

A series of biobased phosphorus flame retardants has been prepared by converting starch-derived bis-2,5-(hydroxymethyl)furan to the corresponding diacrylate followed by Michael addition of phosphite to generate derivatives with phosphorus moieties attached via P-C bonds. All compounds behave as effective flame retardants in DGEBA epoxy resin. The most effective is the DOPO derivative, 2,5-di[(3-dopyl-propanoyl)methyl]furan. When incorporated into a DGEBA blend at a level to provide 2% phosphorus, a material displaying a LOI of 30, an UL 94 rating of V0 and a 40% reduction in combustion peak heat release rate compared to that for resin containing no additive is obtained. The analogous compounds generated from bisphenol A and tetrabromobisphenol A exhibit similar flame-retarding properties.

Improved QuEChERS for Analysis of Polybrominated Diphenyl Ethers and Novel Brominated Flame Retardants in Capsicum Cultivars Using Gas Chromatography.

One of the main challenges for analytical laboratories and food safety authorities is the control of food contaminants hazardous to human health. For the first time, a simple, fast, and cost-effective sample preparation method is proposed as an extraction technique to determine 12 brominated flame retardants (BFRs) (seven polybrominated diphenyl ether (PBDE) congeners and five novel BFRs) in Capsicum cultivars. Different QuEChERS and dispersive solid-phase extract (d-SPE) sorbent compositions were evaluated in terms of recovery and matrix effects. The best results were obtained with citrate-buffered version QuEChERS and a cleanup step, with 150 mg of MgSO4, 50 mg of primary secondary amine (PSA), 50 mg of C18, and 5 mg of carbon. The limit of detection (LOD) was between 1.4 and 9.3 µg/kg and R2 > 0.99. Recoveries and matrix effects were between 66 and 104% and 0.58 and 2.18, respectively. The relative standard deviations from repeatability and reproducibility studies and estimation of measurement uncertainty were lower than 20%. Gas chromatography coupled with a mass spectrometer was used to confirm the presence of BFRs in the samples. Novel BFRs were detected lower than the LOD.

Solid-phase extraction of seventeen alternative flame retardants in water as determined by ultra-high-performance liquid chromatography-tandem mass spectrometry.

Flame retardants have evoked public concerns owing to their extensive usage in consumer products and potential adverse effects on human health. In this study, a rapid and sensitive solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry (SPE-UPLC-MS/MS) method was developed to determine hexabromocyclododecane (HBCD), tetrabromobisphenol-A (TBBPA), six bromophenols (BPs), and nine organophosphate flame retardants (OPFRs) in water. Because of the differences in elution conditions and ionization modes for group 1 (HBCD, TBBPA, and the BPs) and group 2 (OPFRs), we had to run them twice under the different conditions to analyse group 1 and group 2 using UPLC-MS/MS. The method detection limits were 0.1-2.5 ng/L, linearity range was 0.1-100.0 ng/L for group 1 (HBCD, TBBPA, and the BPs). The method detection limit was 0.10 ng/L, and the linearity range was 0.25-250 ng/L for the OPFRs. First, the pH values of the water samples were adjusted to the range of 2-3. Then, the acidified water samples were extracted by hydrophilic-lipophilic-balance solid phase extraction (HLB-SPE) cartridges, which were eluted with 12 mL of acetonitrile. Finally, the recoveries of HBCD, TBBPA, and the BPs were 76.2-98.1%, and the relative standard deviations (RSDs, n = 5) were 2.0-28.5%. Regarding the OPFRs, the recoveries were 72.4-110.3%, and the RSDs were 0.6-6.9%. The stability experiment showed that the concentration differences were less than 15%, meeting the requirement for quality control samples. This proposed method was successfully applied to surface water, ground water, raw water, finished water, tap water, and bottled water samples.

Iridium oxide (IV) nanoparticle-based electrocatalytic detection of PBDE.

Polybrominated diphenyl ethers (PBDEs) are a type of flame retardants which are currently banned in EU and USA due their hazardousness for humans and mammals. However, these compounds were highly used during more than 30 years and still persist in the environment since they are resistant to degradation. Herein we present a biosensor for the detection of PBDEs using screen printed carbon electrodes (SPCEs) based on the electrochemical monitoring of water oxidation reaction (WOR) catalyzed by iridium oxide (IV) nanoparticles (IrO2 NPs). Our assay shows a limit of detection of 21.5 ppb of PBDE in distilled water. We believe that such an IrO2 NPs-based electrocatalytic sensing system can lead to a rapid, sensitive, low cost and miniaturizable device for the detection of PBDEs.

Organophosphate flame retardants in leachates from six municipal landfills across China.

With the phasing out of brominated flame retardants, organophosphate flame retardants (OPFRs) have been widely used and further detected in multiple environmental media. However, municipal landfill leachates, an important source of contamination of OPFRs to aquatic environment, have not been fully understood, especially in a developing country like China. Thus, the occurrence, aqueous removal efficiency, environmental emission, and risk assessment of 10 OPFRs were investigated in leachates from six municipal landfills across China. The results indicated that except triethyl phosphate (TEP), the remaining 9 OPFRs were detected in both raw and final leachates with different frequencies higher than 33.3%. The range of total concentrations of OPFRs (ΣOPFRs) across China was 29.0-437 and 0.652-32.4 µg L-1 in raw and final leachates, respectively. Tris(2-chloroethyl) phosphate (TCEP) was the dominant species and accounted for 78.5% and 85.8% of average ΣOPFR concentration in raw and final leachates, respectively. This may be because TCEP is the most prevalently used OPFR in China. The overall aqueous removal efficiency of ΣOPFRs across China ranged from 57.7% to 99.8%. Tris(2-butoxyethyl) phosphate was the most removed species (98.8%), whereas TCEP was the least removed species (91.5%). The annual emissions of ΣOPFRs discharged into the aquatic environment from municipal landfills across China were estimated to be between 170 and 7094 g. Further risk assessment based on risk quotient values in the final leachates showed that most OPFRs posed negligible risk except TCEP (medium and high risk) and tributyl phosphate (medium risk).

Determination of polybrominated diphenyl ethers in human serum by gas chromatography - inductively coupled plasma mass spectrometry.

Polybrominated diphenyl ethers (PBDEs) are flame retardants that are added to a wide range of consumer products. Due to their extensive use in the past, their presence has been documented in multiple environmental compartments and living organisms, including humans. To assess the exposure of humans to PBDEs, a new simple, reliable, and sensitive method was developed for the determination of six PBDE congeners (BDE 28, BDE 47, BDE 99, BDE 100, BDE 153, BDE 154) in human serum by gas chromatography-inductively coupled plasma mass spectrometry (GC-ICP-MS). The PBDEs were extracted from 1 mL ofserum by 30 min of mechanical shaking with formic acid. Subsequently, 2 mL of iso-octane was added and 30 min of mechanical shaking was applied. For clean-up of the extract Florisil column was applied. The analytical method was validated by analysis of human serum standard reference materials SRM 1957 (Non-Fortified Human Serum) and SRM 1958 (Fortified Human Serum). Good agreement of the determined concentrations with those certified was found. The repeatability and reproducibility of the analytical method was within 5.9% and 6.1%, respectively, whereas the limits of detection (LODs) for the PBDEs analysed were between 0.0016 and 0.0039 ng mL-1 wet weight (ww). The feasibility of the method was tested by analysing human serum samples. In this study, the determined concentrations in sera were in a range similar to that of as those reported for certain other European countries.

Accelerated solvent extraction coupled to high-performance liquid chromatography-tandem mass spectrometry for simultaneous determination of 11 organophosphorus flame retardants in aquatic products.

BACKGROUND: A new method based on accelerated solvent extraction was developed for the extraction and determination of 11 organophosphorus flame retardants by using a high-performance liquid chromatography-tandem mass spectrometry technique. RESULTS: After optimization of the extraction temperature (80 °C), the extraction solvent (n-hexane), the flush volume (40%) and the static extraction time (4 min), all 11 organophosphorus flame retardants illustrated good linearities (R > 0.999). The limits of detection of the method ranged from 0.016 to 26.58 µg kg-1 in the different matrices. The recoveries were 90.4-111.2% with relative standard deviations 0.21-5.3% for the various aquatic products. CONCLUSION: The proposed method was applied successfully to detect 11 organophosphorus flame retardants in aquatic products, including grass carp, ribbon fish, mud fish, common eel, shrimp and frog. © 2018 Society of Chemical Industry.

Determination of organophosphate flame retardants in soil and fish using ultrasound-assisted extraction, solid-phase clean-up, and liquid chromatography with tandem mass spectrometry.

A solid-liquid extraction method in combination with high-performance liquid chromatography and tandem mass spectrometry was developed and optimized for extraction and analysis of organophosphorus flame retardants in soil and fish. Methanol was chosen as the optimum extraction solvent, not only in terms of extraction efficiency, but also for its broader analyte coverage. The subsequent clean-up by solid-phase extraction is required to eliminate matrix coextractives and reduce matrix effects. Recoveries of the optimized method were 50-121% for soil and 47-123% for biota, both with high precision (RSDs <12% in soil and <23% in biota). The method limits of detection ranged from 0.06 to 0.20 ng/g dry weight and between 0.02 and 0.30 ng/g wet weight for soil and biota samples, respectively. However, samples with a high lipid content produce several problems as solid-phase extraction cartridge clogging that increase variability and analysis time. The method was successfully applied for the determination of organophosphorus flame retardants in soil and fish from L'Albufera Natural Park (Valencia, Spain). Target compounds were detected in all soil and fish samples with values varying from 13.8 to 89.7 ng/g dry weight and from 3.3 to 53.0 ng/g wet weight, respectively.

Influence of natural organic matter on the extraction efficiency of flame retardants from surface waters.

The influence of natural organic matter (NOM) on the solid-phase extraction (SPE) efficiency was investigated for legacy and emerging flame retardants (FRs; n=26) in surface water. Three different groups of FRs were analyzed: polybrominated diphenyl ethers (PBDEs), halogenated flame retardants (HFRs), and organophosphorus flame retardants (OPFRs). In addition, five sorbents (Amberlite XAD-2, Amberlite IRA-743, Oasis HLB, Chromabond HR-P, and Chromabond HR-X) were evaluated for the extraction of FRs (n=33) in water, of which Oasis HLB eluted with dichloromethane and acetone:n-hexane (1:1, v/v) provided the highest overall recoveries. In subsequent NOM experiments, where FRs were extracted from water containing different NOM concentrations, both increased and decreased extraction efficiency with increasing NOM level were observed. Physicochemical and semi-empirical quantum chemistry properties were calculated for the FRs and used for analyzing relations between FRs. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) showed that the FRs separated into four different groups based on their properties. The FRs within each group responded similarly to increasing NOM, while differences in behavior were observed between the groups. This suggests that the structural properties of micropollutants highly influence NOM-FR interaction mechanisms. For instance, at high NOM levels, recoveries decreased substantially for FRs containing a moiety that can form strong hydrogen bonds (such as the double-bonded oxygen in e.g., OPFRs). Many of the compounds showed maximum extraction efficiency at higher levels of NOM. This suggests that binding of NOM to the sorbent and subsequent interaction between sorbent-bound NOM and FRs is an important mechanism for extraction of micropollutants from surface waters.

Simultaneous determination of the lipophilicity and dissociation constants of dialkyl phosphinic acids by negligible depletion hollow fiber membrane-protected liquid-phase microextraction.

Determination of the physicochemical properties, especially the lipophilicity (expressed as the logarithm of distribution coefficient, log D) and dissociation constant (pKa), is of great importance in the early stage of environmental risk assessment for an ionizable compound without these data. Currently, the log D and pKa values of dialkyl phosphinic acids (DPAs), the environmental hydrolysates of aluminum dialkyl phosphinates (ADPs) that is one class of emerging phosphorus-containing flame retardants, are not available. In this study, the log D and pKa values of three DPAs including methylethylphosphinic acid (MEPA), diethylphosphinic acid (DEPA) and methylcyclohexyl phosphinic acid (MHPA), were simultaneously determined by negligible depletion hollow fiber supported liquid phase microextraction (nd-HF-LPME) followed by ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). The pKa and log D of DPAs were determined by curve-fitting the experimental data with equations derived on the basis of the Henderson-Hasselbalch equation and compared with model calculated data. For MEPA, DEPA and MHPA, the pKa values were close and around 3, but the log Ds were strongly pH-dependent with values from -5.01 to 1.01. The log KOW of the neutral form (logKOW,HA) and ionic form (logKOW,A) were in the range of -0.67-1.02 and -3.86--1.33, respectively. The experimentally determined pKa values were highly in good agreement with ACD/pKa predicted values and the measured log KOW,HA values were closely related to KOWWIN calculated ones, suggesting ACD/pKa and KOWWIN are good alternative methods to estimate pKa and log KOW of DPAs, respectively. As far as we know, this is the first report on the pKa and log D data for DPAs, which are fundamental for the product design and evaluating the environmental behavior and effects of DPAs and ADPs.

[Remediation of Decabromodiphenyl Ether Contaminated Sediment Through Plant Roots Enhanced by Exogenous Microbes].

Decabromodiphenyl ether (BDE-209), a main ingredient of brominated flame retardants, has drawn more and more attention because of the pollution it caused in sediment. A pot experiment was conducted in a greenhouse to investigate the impact of Brevibacillus brevis and Enterococcus casselifavus on the enhancement of phytoremediation by Thalia dealbata, which is common in the river bank and was found to be an effective plant for BDE-209 removal. The concentration of organic acids, the amount of microorganisms and the ability of carbon utilization of soil microorganisms in different experimental groups were analyzed. The results showed that the removal rate of BDE-209 in the exogenous microbes containing groups were higher than that of the control. And B. brevis presented the highest enhancement of phytoremediation with the removal rate rising highest to 66% compared with the control (non-rhizosphere group 37.93% and no plant group 39.27%) after 60 days. The removal of BDE-209 in sediment, quantity of microorganism, concentration of organic acids and the ability of carbon utilization of soil microorganisms in rhizosphere sediment were higher than those in non-rhizosphere sediment.

Selective pressurized liquid extraction of replacement and legacy brominated flame retardants from soil.

Polybrominated diphenyl ethers (PBDEs) are a class of flame retardant registered as UN POPs due to their persistence in the environment, bioaccumulation potential and toxicity. Replacement novel brominated flame retardants (NBFRs) have exhibited similar health hazards and environmental distribution, becoming recognized as significant contaminants. This work describes the development and validation of a sensitive and reliable method for the simultaneous quantitation of PBDEs and NBFRs in environmental soil samples using selective pressurized liquid extraction (S-PLE) and gas chromatography coupled to triple quadrupole mass spectrometry (GC-(EI)-MS/MS). Under optimal conditions, extraction of eight PBDEs (-28, -47, -99, -100, -153, -154, -183 and -209) and five NBFRs; pentabromotoluene (PBT), pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) and bis(2,4,6-tribromophenoxy)ethane (BTBPE) was performed at 100°C and 1500psi using a 1:1 mixture of hexane and dichloromethane. The method utilized 33mL capacity PLE cells containing, from bottom to top, a single cellulose filter, 3g activated Florisil, 6g acid silica (10% w/w), 3g Na2SO4, another cellulose filter, 2g activated copper powder and 3g soil sample dispersed in 2g Na2SO4 and 1g of Hydromatrix. The method was evaluated by repeated extraction and analysis of all analytes from 3g soil at three spike concentrations. Good recoveries were observed for most analytes at each of the spiking levels with RSD values generally below 20%. MDLs ranged from 0.01 to 4.8ng/g dw for PBDEs and 0.01-0.55ng/g dw for NBFRs. The described one-step combined extraction and cleanup method reduces sample processing times compared with traditional procedures, while delivering comparable analytical performance. The method was successfully applied to environmental soil samples (n=5), detecting PBDEs in each sample and providing the first account of NBFR contamination in Australian soils.

Potential reference measurement procedures for PBDE in surface water at levels required by the EU Water Frame Directive.

Polybrominated diphenylethers (PBDE), used as flame retardants, are named as priority substances in the Directive 2000/60/EC of the European parliament and of the council establishing a framework for Community action in the field of water policy. An annual average environmental quality standard (EQS) for inland surface waters of 0.0005 µg/L (0.0002 µg/L for other surface waters) for PBDE congeners involved in the technical penta-PBDE mixtures containing PBDE with five bromine atoms has been established. The directives focus especially on the congeners PBDE 28, 47, 99, 100, 153 and 154 contained in the penta-PBDE mixture. Up to now, no reference measurement procedures have been established reaching the limits of quantification (LOQs) and the associated uncertainties as defined in the directives with results traceable to the SI. Within a recent European project on metrology, different approaches for the traceable quantification of PBDE, based on liquid/liquid or solid phase extraction followed by the detection with gas chromatography coupled to either inductively coupled plasma mass spectrometry or triple quadrupole mass spectrometry, were investigated and the related LOQs and expanded uncertainties of the results were compared. A complete uncertainty budget for each method was estimated according to the Guide to the Expression of Uncertainty in Measurement (GUM). All presented analytical procedures can serve as reference measurement procedures regarding the LOQs and their associated expanded uncertainties for monitoring the six priority PBDEs named above. LOQs as low as 0.026 ng/kg with an associated expanded uncertainty of 0.002 ng/kg could be achieved.

Microbial degradation of decabromodiphenyl ether (DBDE) in soil slurry microcosms.

Decabromodiphenyl ether (DBDE), which has been identified as an endocrine disrupting compound, is used as brominated flame retardant, and this can result in serious bioaccumulation within ecological systems. The objective of this study was to explore DBDE bioremediation (25 mg/kg) using laboratory scale soil slurry microcosms. It was found that effective biodegradation of DBDE occurred in all microcosms. Various biometabolites were identified, namely polybrominated diphenyl ethers congeners and hydroxylated brominated diphenyl ether. Reductive debrominated products such as tri-BDE to hepta-BDE congeners were also detected, and their total concentrations ranged from 77.83 to 91.07 ng/g. The mechanism of DBDE biodegradation in soil slurry microcosms is proposed to consist of a series of biological reactions involving hydroxylation and debromination. Catechol 2,3-oxygenase genes, which are able to bring about meta-cleavage at specific unbrominated locations in carbon backbones, were identified as present during the DBDE biodegradation. No obvious effect on the ecological functional potential based on community-level physiological profiling was observed during DBDE biodegradation, and one major facultative Pseudomonas sp. (99 % similarity) was identified in the various soil slurry microcosms. These findings provide an important basis that should help environmental engineers to design future DBDE bioremediation systems that use a practical microcosm system. A bacterial-mixed culture can be selected as part of the bioaugmentation process for in situ DBDE bioremediation. A soil/water microcosm system can be successfully applied to carry out ex situ DBDE bioremediation.

Size-exclusion simulated moving bed for separating organophosphorus flame retardants from a polymer.

Over 500,000t of flame retardants in electronic wastes are consigned to landfills each year. A room-temperature, size-exclusion simulated moving bed (SEC-SMB) was developed to recover high purity (>99%) flame retardants with high yield (>99%). The SSWD method for ternary mixtures was developed for SEC-SMB. Fourteen decision variables were optimized to obtain the lowest separation cost within 1min. The estimated cost is less than 10% of the purchase cost of the flame retardants. The estimated cost of the optimized SEC-SMB is less than 3% of that of a conventional batch SEC processes. Fast start-up methods were developed to reduce the SMB start-up time by more than 18-fold. SEC-SMB can be an economical method for separating small molecules from polymers.

Quantification of Hydroxylated Polybrominated Diphenyl Ethers (OH-BDEs), Triclosan, and Related Compounds in Freshwater and Coastal Systems.

Hydroxylated polybrominated diphenyl ethers (OH-BDEs) are a new class of contaminants of emerging concern, but the relative roles of natural and anthropogenic sources remain uncertain. Polybrominated diphenyl ethers (PBDEs) are used as brominated flame retardants, and they are a potential source of OH-BDEs via oxidative transformations. OH-BDEs are also natural products in marine systems. In this study, OH-BDEs were measured in water and sediment of freshwater and coastal systems along with the anthropogenic wastewater-marker compound triclosan and its photoproduct dioxin, 2,8-dichlorodibenzo-p-dioxin. The 6-OH-BDE 47 congener and its brominated dioxin (1,3,7-tribromodibenzo-p-dioxin) photoproduct were the only OH-BDE and brominated dioxin detected in surface sediments from San Francisco Bay, the anthropogenically impacted coastal site, where levels increased along a north-south gradient. Triclosan, 6-OH-BDE 47, 6-OH-BDE 90, 6-OH-BDE 99, and (only once) 6'-OH-BDE 100 were detected in two sediment cores from San Francisco Bay. The occurrence of 6-OH-BDE 47 and 1,3,7-tribromodibenzo-p-dioxin sediments in Point Reyes National Seashore, a marine system with limited anthropogenic impact, was generally lower than in San Francisco Bay surface sediments. OH-BDEs were not detected in freshwater lakes. The spatial and temporal trends of triclosan, 2,8-dichlorodibenzo-p-dioxin, OH-BDEs, and brominated dioxins observed in this study suggest that the dominant source of OH-BDEs in these systems is likely natural production, but their occurrence may be enhanced in San Francisco Bay by anthropogenic activities.