Subacute oral toxicity of BDE-15, CDE-15, and HODE-15 in ICR male mice: assessing effects on hepatic oxidative stress and metals status and ascertaining the protective role of vitamin E

The present study examined the effects of oral exposure of 4,4′-dibromodiphenyl ether (BDE-15), 4,4′-dichlorodiphenyl ether (CDE-15), and 4,4′-dihydroxydiphenyl ether (HODE-15) on hepatic oxidative stress (OS) and metal status in Institute of Cancer Research (ICR) male mice. Furthermore, the role of vitamin E in ameliorating potential OS caused by BDE-15, CDE-15, and HODE-15 was investigated. Three groups of mice were exposed to 1.20 mg/kg(body weight)/day of each of the three toxicants for 28 days. Results showed that none of the three toxicants altered growth rates of mice, but significantly increased (P?<?0.05) relative liver weights and decreased relative kidney weights. Pathological changes including cell swelling, inflammation and vacuolization, and hepatocellular hypertrophy in livers were observed. Significant decreases (P?<?0.05 and P?<?0.01) in superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx) activity, and glutathione (GSH) levels, together with increases in malondialdehyde (MDA) content were recorded in all toxicant-treated groups. Hepatic copper levels increased in all toxicant-treated groups. Hepatic zinc levels decreased in the liver of BDE-15-treated mice, whereas they increased in the livers of CDE-15-treated and HODE-15-treated mice. In conclusion, daily exposure to the three toxicants perturbed metal homeostasis and increased OS in mouse liver. Experimental data indicated the hepatic oxidative toxicity of the three toxicants followed the order BDE-15?<?HODE-15?<?CDE-15. Moreover, the study proved that daily supplementation of 50 mg/kg vitamin E is effective to ameliorate the hepatic OS status and metal disturbance in mice.     

Evaluation of HODE-15, FDE-15, CDE-15, and BDE-15 toxicity on adult and embryonic zebrafish (Danio rerio)

Diphenyl ether and its derivatives are widely used in the industry of spices, dyes, agrochemicals, and pharmaceuticals. Following the previous study, we selected 4,4′-dihydroxydiphenyl ether, 4,4′-difluorodiphenyl ether, 4,4′-dichlorodiphenyl ether, and 4,4′-dibromodiphenyl ether as research objects. The LC₅₀ (96 h) values for these compounds in adult zebrafish were determined with the acute test. Also, developmental toxicities of the four substances to zebrafish embryos were observed at 24, 48, 72, and 96 hpf. All the LC₅₀ (96 h) values of these compounds were between 1 and 10 mg/L, suggesting that they all had moderate toxicity to adult zebrafish. The embryonic test demonstrated that with increasing doses, 4,4′-dihydroxydiphenyl ether decreased the hatching rate, while 4,4′-difluorodiphenyl ether, 4,4′-dichlorodiphenyl ether, and 4,4′-dibromodiphenyl ether delayed the hatching time but had little effect on final hatchability at 96 hpf. All of these compounds inhibited larval growth, especially 4,4′-dihydroxydiphenyl ether. Exposure to these chemicals induced embryo yolk sac and pericardial edema. Spine deformation was visible in hatched larvae after 96 hpf 4,4′-dihydroxydiphenyl ether exposure, while tail curvature was observed for the halogenated compounds. The overall results indicated that 4,4′-dihydroxydiphenyl ether, 4,4′-difluorodiphenyl ether, 4,4′-dichlorodiphenyl ether, and 4,4′-dibromodiphenyl ether all had significant toxicity on adult and embryonic zebrafish.     

Physicochemical properties of selected polybrominated diphenyl ethers and extension of the UNIFAC model to brominated aromatic compounds

The aqueous solubilities (S(w)) at various temperatures from 283 K to 308 K and 1-octanol/water partition coefficients (K(ow)) for four polybrominated diphenyl ethers (PBDEs: 4,4'-dibromodiphenyl ether (BDE-15), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153)) were measured by the generator column method. The S(w) and K(ow) data revealed the effect of bromine substitution and basic structure on S(w) and K(ow). To estimate the infinite dilution activity coefficients (gamma(i)(w,infinity)) of the PBDEs in water from the S(w) data, enthalpies of fusion and melting points for those compounds were measured with a differential scanning calorimeter. Henry's Law constants (H(w)) of the PBDEs were derived from the determined gamma(i)(w,infinity) and literature vapor pressure data. Some physicochemical characteristics of PBDEs were also suggested by comparing the present property data with that of polychlorinated dibenzo-p-dioxins, brominated phenols and brominated benzenes in past studies. Furthermore, in order to represent different phase equilibria including solubility and partition equilibrium for other brominated aromatic compounds using the UNIFAC model, a pair of UNIFAC group interaction parameters between the bromine and water group were determined from the S(w) and K(ow) data of PBDEs and brominated benzenes. The ability of the determined parameters to represent both properties of brominated aromatics was evaluated.     

Identification of hydroxylated metabolites in 2,2',4,4'-tetrabromodiphenyl ether exposed rats

Faeces from day 1-5 of orally administered 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) in rat have been analysed for hydroxylated metabolites. Six hydroxylated tetrabrominated diphenyl ethers, as well as three hydroxylated tribrominated diphenyl ethers found, were structurally identified. They were 2'-hydroxy-2,4,4'-tribromodiphenyl ether, 3'-hydroxy-2,4,4'-tribromodiphenyl ether, 4'-hydroxy-2,2',4-tribromodiphenyl ether, 6-hydroxy-2,2',4,4'-tetrabromodiphenyl ether, 2'-hydroxy-2,3',4,4'-tetrabromodiphenyl ether, 3-hydroxy-2,2',4,4'-tetrabromodiphenyl ether, 5-hydroxy-2,2',4,4'-tetrabromodiphenyl ether, 4'-hydroxy-2,2',4,5'-tetrabromodiphenyl ether and 4-hydroxy-2,2',3,4'-tetrabromodiphenyl ether. The analysis was performed using gas chromatography-mass spectrometry (GC-MS). The identification of the hydroxylated polybrominated diphenyl ether (OH-PBDE) metabolites in the rat faeces was supported by similar relative retention times (RRTs) versus 2,2',3,4,4',5-hexabromodiphenyl ether (BDE-138) on two columns of different polarities compared to the authentic references. The identification of the OH-PBDE metabolites was also supported by full scan electron ionisation mass spectra. Two of the identified OH-PBDE metabolites have identical structures as natural products, which previously have been isolated from marine sponges and an ascidian.     

Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River,São Paulo,Brazil)

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO^●), singlet oxygen (¹O₂), and triplet excited states of chromophoric dissolved organic matter (³CDOM^*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23?±?0.07)?×?10^–2 and (7.99?±?1.61)?×?10^–3 mol Einstein^?1, respectively. In contrast, reactions with HO^● radicals and ³CDOM* dominate their degradation, with ¹O₂ exhibiting rates three to five orders of magnitude lower. The values of k_IMD,HO● and k_AMT,HO● were (3.51?±?0.06)?×?10⁹ and (4.97?±?0.37)?×?10⁹ L mol^?1 s^?1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with k_IMD,3AQ2S*?=?(1.02?±?0.08)?×?10⁹ L mol^?1 s^?1 and k_IMD,3CBBP*?=?(3.17?±?0.14)?×?10⁸ L mol^?1 s^?1; on the contrary, the values found for AMT are close, k_AMT,3AQ2S*?=?(8.13?±?0.35)?×?10⁸ L mol^?1 s^?1 and k_AMT,3CBBP*?=?(7.75?±?0.80)?×?10⁸ L mol^?1 s^?1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO₃^?, NO₂^?, CO₃^2?, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.

     

Effect of inorganic and organic solutes on zero-valent aluminum-activated hydrogen peroxide and persulfate oxidation of bisphenol A

The effect of varying inorganic (chloride, nitrate, sulfate, and phosphate) and organic (represented by humic acid) solutes on the removal of aqueous micropollutant bisphenol A (BPA; 8.8 μM; 2 mg/L) with the oxidizing agents hydrogen peroxide (HP; 0.25 mM) and persulfate (PS; 0.25 mM) activated using zero-valent aluminum (ZVA) nanoparticles (1 g/L) was investigated at a pH of 3. In the absence of the solutes, the PS/ZVA treatment system was superior to the HP/ZVA system in terms of BPA removal rates and kinetics. Further, the HP/ZVA process was not affected by nitrate (50 mg/L) addition, whereas chloride (250 mg/L) exhibited no effect on the PS/ZVA process. The negative effect of inorganic anions on BPA removal generally speaking increased with increasing charge in the following order: NO₃^? (no inhibition)?<?Cl^? (250 mg/L)?=?SO₄^2??<?PO₄^3? for HP/ZVA and Cl^? (250 mg/L; no inhibition)?<?NO₃^??<?SO₄^2??<?PO₄^3? for PS/ZVA. Upon addition of 20 mg/L humic acid representing natural organic matter, BPA removals decreased from 72 and 100% in the absence of solutes to 24 and 57% for HP/ZVA and PS/ZVA treatments, respectively. The solute mixture containing all inorganic and organic solutes together partly suppressed the inhibitory effects of phosphate and humic acid on BPA removals decreasing to 46 and 43% after HP/ZVA and PS/ZVA treatments, respectively. Dissolved organic carbon removals were obtained in the range of 30 and 47% (the HP/ZVA process), as well as 47 and 57% (the PS/ZVA process) for the experiments in the presence of 20 mg/L humic acid and solute mixture, respectively. The relative Vibrio fischeri photoluminescence inhibition decreased particularly for the PS/ZVA treatment system, which exhibited a higher treatment performance than the HP/ZVA treatment system.     

Brominated-chlorinated diphenyl ethers formed by thermolysis of polybrominated diphenyl ethers at low temperatures

Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardants (BFRs) used mainly as additives in different kinds of plastic material. Various PBDEs are found in all environmental compartments as well as in tissue and blood serum of animals and humans due to their persistence and tendency to bioaccumulate. Emission of PBDEs into the environment can occur during recycling of PBDE-containing plastic material or during their uncontrolled or insufficient combustion as e.g. in accidental fires or landfill fires. Under these circumstances, PBDEs can also function as precursor molecules for the formation of polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). In this study, we qualitatively investigated the reaction of two PBDE congeners, 2,2′,4,4′-tetrabromo diphenyl ether (BDE 47) and 2,2′,4,4′,5,5′-hexabromo diphenyl ether (BDE 153), as well as hexabromobenzene (HBB), a flame retardant used in the past, when exposed to temperatures between 250 °C and 500 °C. The formed reaction products were analysed by high resolution gas chromatography–low resolution mass spectrometry (HRGC-LRMS). Among others brominated–chlorinated diphenyl ethers were formed by chlorodebromination of the PBDEs. In addition, thermolysis of BDE 47 and BDE 153 in the presence of tetrachloromethane as model substance for an organic chlorine source was studied. Thermal treatment of HBB resulted in the formation of brominated–chlorinated benzenes.     

Formation of chlorinated phenols, dibenzo-p-dioxins, dibenzofurans, benzenes, benzoquinnones and perchloroethylenes from phenols in oxidative and copper (II) chloride-catalyzed thermal process

Formation of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and chlorinated phenols on CuCl(2) from unsubstituted phenol and three monochlorophenols was studied in a flow reactor over a temperature range of 100-425 degrees C. Heated nitrogen gas streams containing 8.0% oxygen were used as carrier gas. The 0.00024mol of unsubstituted phenol and 0.00039mol of each monochlorophenol were passed through a 1g and 1cm SiO(2) particle containing 0.5% (Cu by mass) CuCl(2). Chlorination preferentially occurred on ortho-(2, 6) and para-(4) positions. Chlorination increased up to 200 degrees C, and thereafter decreased as temperature increased. Chlorination of phenols plays an important role in the formation of the more chlorinated PCDD/Fs. Chlorinated benzenes are formed possibly from both chlorination of benzene and chlorodehydroxylation of phenols. Chlorinated phenols with ortho chlorine formed PCDD products, and major PCDD products were produced via loss of one chlorine. For PCDF formation, at least one unchlorinated ortho carbon was required.     

A novel BiVO4-GO-TiO2-PANI composite for upgraded photocatalytic performance under visible light and its non-toxicity

A novel non-toxic hybrid BiVO₄-GO-TiO₂-polyaniline (PANI) (BVGT-PANI) composite with superior photocatalysis was successfully prepared via a one-pot hydrothermal reaction. The structural and morphological characterizations of the synthesized compounds were analyzed by a series of techniques. We found excellent photocatalytic efficiencies for methylene blue (MB) and phenol degradation under visible light irradiation after adhering the PANI to the photocatalyst. The degradation rates of MB and phenol reach up to approximately 85% and 80%, respectively, after 3 h of irradiation. For photodegradation MB, BVGTA exhibit the highest k_app rate constant of about 1.06?×?10^?2 min^?1, which is about 1.63-fold faster than BVG and 2.94-fold faster than BVGT. For photodegradation of phenol, BVGTA exhibits the highest k_app rate constant, of about 8.86?×?10^?3min^?1, which is about 1.2-fold faster than BVG and 1.96-fold faster than BVGT. Furthermore, vitro toxicity test against Bacillus subtilis and Staphylococcus aureus demonstrated that the nanophotocatalyst is non-toxic.

     

Dechlorane Plus in surface soil of North China: levels,isomer profiles,and spatial distribution

Eighty-seven soil samples collected from North China were analyzed for Dechlorane Plus (DP). The concentrations of DP ranged from not detectable (ND) to 12.21 ng/g with a mean of 0.55 ng/g. The mean concentrations of total DP and syn-DP in four regions of North China were in the following order: Jingjin (Beijing and Tianjin)?>?Shandong?>?Shanxi?>?Hebei, while the mean concentrations of anti-DP in the four regions were in a different order: Shandong?>?Jingjin?>?Shanxi?>?Hebei. The mean f _syn values for Jingjin (0.27), Hebei (0.24), and Shanxi (0.24) were close to 0.25, while the mean f _syn value for Shandong (0.31) was closer to 0.35. In addition, the f _syn value for Shandong was significantly higher (P?<?0.01) than those of the other regions (Jingjin, Heibei, and Shanxi), indicating specific sources of DP. Syn-DP displayed a strong linear relationship with anti-DP (R ²?=?0.74), indicating that no obvious stereoselective process occurred in the soil of North China. Ordinary kriging was undertaken to map the spatial patterns of DP. High concentrations of DP in soils were present in south of Shanxi, central Hebei, south of Tianjin, and the south and northeast of Shandong, which were suggested to be connected with human activities such as e-waste dismantling.     

Experimental exposure of juvenile savannah monitors (Varanus exanthematicus) to an environmentally relevant mixture of three contaminants: effects and accumulation in tissues

Using varanids as indicators of pollution in African continental wetlands was previously proposed. The present study aimed at understanding experimentally how monitors absorb and accumulate pollutants and how they are affected. The relevance of non-destructive sampling was also evaluated. Savannah monitors (Varanus exanthematicus) were orally exposed during 6 months to a mixture of lead, 4,4′-dichlorodiphenyltrichloroethane (4,4′-DDT) and chlorpyrifos-ethyl (CPF) or to the vehicle only. Proportionally to their mass, exposed monitors received the same dose: 20 then 10 mg lead?kg^?1, 2 then 0.5 mg CPF?kg^?1 and 4 mg 4,4′-DDT?kg^?1. Individuals surviving contamination were euthanized after 4 or 6 months of experiment. Tissues were analysed for lead by atomic absorption spectrophotometry and for DDT and CPF by gas chromatography. Exposed monitors absorbed all three pollutants but only lead (essentially in bone, tail tips and phalanxes) and 4,4′-DDT plus its main metabolites (essentially in fat and liver) accumulated. CPF killed ten individuals. Clear correlations occurred between the total quantity of lead or 4,4′-DDT administered and concentrations in tissues. Tail tips and skin samples are recommended non-destructive indicators for lead and organochlorine pesticides contamination, respectively. This work confirms that monitors can be used as relevant indicators of environmental pollution by lead and organochlorine pesticides. Although varanids withstand heavy lead and DDT contamination, our results suggest that CPF can be lethal at very low doses to the herpetofauna and emphasize the importance of considering all taxa in impact assessment studies, including reptiles.     

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.     

Protease production by the keratinolytic Bacillus sp. CL18 through feather bioprocessing

Bacillus sp. CL18 was investigated to propose a bioprocess for protease production using feathers as organic substrate. In feather broth (FB), containing feathers as sole organic substrate (1–100 g l^?1), maximal protease production was observed at 30 g l^?1 (FB30) after 6 days of cultivation, whereas increased feather concentrations negatively affected protease production and feather degradation. Protease production peaks were always observed earlier during cultivations than maximal feather degradation. In FB30, 80% of initial feathers mass were degraded after 7 days. Addition of glucose, sucrose, starch, yeast extract (2 g l^?1), CaCl₂, or MgCl₂ (10 mmol l^?1) to FB30 decreased protease production and feather degradation. FB30 supplementation with NH₄Cl (1 g l^?1) resulted in less apparent negative effects on protease production, whereas peptone (2 g l^?1) increased protease yields earlier during cultivations (3 days). Through a central composite design employed to investigate the effects of peptone and NH₄Cl (0.5–4.5 g l^?1) on protease production and feather degradation, FB30 supplementation with peptone and NH₄Cl (0.5–1.1 g l^?1) increased protease production within a shorter cultivation time (5 days) and hastened complete feather degradation (6 days). Feather bioconversion concurs with sustainable production of value-added products.

     

Synthesis and tentative identification of novel polybrominated diphenyl ether metabolites in human blood

Hydroxylated polybrominated diphenyl ethers (OH-PDBEs) are exogenous, bioactive compounds that originate, to a large extent, from anthropogenic activities, although they are also naturally produced in the environment. In the present study nine new authentic OH-PBDE reference standards and their corresponding methyl ether derivatives (MeO-PBDEs) were synthesised and characterised by NMR spectroscopy and mass spectrometry. Seven of the authentic reference standards prepared were thereafter tentatively identified in a pooled human blood sample. The tentatively identified OH-PBDEs were 3-hydroxy-2,2',4,4',6-pentabromodiphenyl ether, 3'-hydroxy-2,2',4,4',6-pentabromodiphenyl ether, 3-hydroxy-2,2',4,4',5-pentabromodiphenyl ether, 3-hydroxy-2,2',4,4',5,6'-hexabromodiphenyl ether, 3'-hydroxy-2,2',4,4',5,6'-hexabromodiphenyl ether, 3-hydroxy-2,2',4,4',5,5'-hexabromodiphenyl ether and 4-hydroxy-2,2',3,4',5,5',6-heptabromodiphenyl ether. An additional seven OH-PBDEs were tentatively identified in the pooled human blood sample, of which one OH-PBDE, 4'-hydroxy-2,2',4,5,5'-pentabromodiphenyl ether, has not been identified in human blood before. The identification was performed using gas chromatography-mass spectrometry (GC-MS) recording the bromine ions m/z 79, 81. The tentative identification was supported by the peaks relative retention times (RRTs) compared to authentic references on two GC columns of different polarities for the hexa-, and heptabrominated OH-PBDEs, and three different GC columns for the pentabrominated OH-PBDEs. The OH-PBDE congeners most likely originate from human metabolism of a flame retardant, i.e. polybrominated diphenyl ethers (PBDEs), due to the relatively high concentrations of PBDEs in the same human blood sample and the fact that these PBDEs could form the tentatively identified OH-PBDEs via metabolic direct hydroxylation or via 1,2-shift.     

Distribution of polybrominated diphenyl ethers and dust particle size fractions adherent to skin in indoor dust,Pretoria, South Africa

In order to determine human exposure to the indoor toxicant, selection of dust fraction and understanding dust particle size distribution in settled indoor dust are very important. This study examined the influence of dust particle size on the concentration of polybrominated diphenyl ethers (PBDEs) congeners, assessed the distribution of dust particle size and characterized the main indoor emission sources of PBDEs. Accordingly, the concentrations of PBDE congeners determined in different indoor dust fractions were found to be relatively higher in the order of dust particle size: 45–106 μm?>?(<45 μm)?>?106–150 μm. The finding shows arbitrary selection of dust fractions for exposure determination may result in wrong conclusions. Statistically significant moderate correlation between the concentration of Σ₉PBDEs and organic matter content calculated with respect to the total dust mass was also observed (r?=?0.55, p?=?0.001). On average, of total dust particle size <250 μm, 93.4 % (m/m%) of dust fractions was associated with less than 150 μm. Furthermore, of skin adherent dust fractions considered (<150 μm), 86 % (v/v%) is in the range of particle size 9.25–104.7 μm. Electronic materials treated with PBDEs were found the main emission sources of PBDE congeners in indoor environment. Based on concentrations of PBDEs determined and mass of indoor dust observed, 150 μm metallic sieve is adequate for human exposure risk assessment. However, research in this area is very limited and more research is required to generalize the fact.     

Biosorption and degradation of decabromodiphenyl ether by <Emphasis Type="Italic">Brevibacillus brevis</Emphasis> and the influence of decabromodiphenyl ether on cellular metabolic responses

There is global concern about the effects of decabromodiphenyl ether (BDE209) on environmental and public health. The molecular properties, biosorption, degradation, accumulation, and cellular metabolic effects of BDE209 were investigated in this study to identify the mechanisms involved in the aerobic biodegradation of BDE209. BDE209 is initially absorbed by wall teichoic acid and N-acetylglucosamine side chains in peptidoglycan, and then, BDE209 is transported and debrominated through three pathways, giving tri-, hepta-, octa-, and nona-bromodiphenyl ethers. The C–C bond energies decrease as the number of bromine atoms on the diphenyl decreases. Polybrominated diphenyl ethers (PBDEs) inhibit protein expression or accelerate protein degradation and increase membrane permeability and the release of Cl^?, Na⁺, NH₄ ⁺, arabinose, proteins, acetic acid, and oxalic acid. However, PBDEs increase the amounts of K⁺, Mg²⁺, PO₄ ^3?, SO₄ ^2?, and NO₃ ^? assimilated. The biosorption, degradation, accumulation, and removal efficiencies when Brevibacillus brevis (1 g L^?1) was exposed to BDE209 (0.5 mg L^?1) for 7 days were 7.4, 69.5, 16.3, and 94.6 %, respectively.     

Non-target screening of extractable and non-extractable organic xenobiotics in riverine sediments of Ems and Mulde Rivers, Germany

Subaquatic sediment samples derived form Elbe and Mulde Rivers, Germany, were analyzed for extractable and non-extractable anthropogenic organic compounds by a non-target screening approach. Applied methodologies were gas chromatography-mass spectrometry, dispersion extraction and degradation procedures, particularly alkaline and acidic hydrolysis, boron tribromide treatment, ruthenium tetroxide oxidation as well as pyrolysis and TMAH (tetramethylammonium hydroxide)-thermochemolysis. Numerous compounds were identified, including halogenated benzenes, anisoles, styrenes, alkanes, diphenylmethane derivates, anilines, phenols and diphenyl ethers. The results were interpreted with respect to compound specific modes of incorporation as well as to potential sources (e.g. municipal, agricultural, industrial). Extractable and non-extractable fractions differed significantly with respect to their qualitative and quantitative composition. For example, quantities in the extractable and non-extractable fractions of chlorinated benzenes differed up to factor 50. Among other significant results, the investigation revealed hints for a dependence of the mode of incorporation of chlorinated benzenes on their substitution pattern.     

FTIR gas-phase kinetic study on the reactions of some acrylate esters with OH radicals and Cl atoms

Acrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon. These compounds are widely used in the production of plastics and resins. Atmospheric degradation processes of these compounds are currently not well understood. The kinetics of the gas phase reactions of OH radicals with methyl 3-methylacrylate and methyl 3,3-dimethylacrylate were determined using the relative rate technique in a 50 L Pyrex photoreactor using in situ FTIR spectroscopy at room temperature (298?±?2 K) and atmospheric pressure (708?±?8 Torr) with air as the bath gas. Rate coefficients obtained were (in units cm³ molecule^?1 s^?1): (3.27?±?0.33)?×?10^?11 and (4.43?±?0.42)?×?10^?11, for CH₃CH═CHC(O)OCH₃ and (CH₃)₂CH═CHC(O)OCH_3, respectively. The same technique was used to study the gas phase reactions of hexyl acrylate and ethyl hexyl acrylate with OH radicals and Cl atoms. In the experiments with Cl, N₂ and air were used as the bath gases. The following rate coefficients were obtained (in cm³ molecule^?1 s^?1): k₃ (CH₂═CHC(O)O(CH₂)₅CH₃?+?Cl)?=?(3.31?±?0.31)?×?10^?10, k₄(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?Cl)?=?(3.46?±?0.31)?×?10^?10, k₅(CH₂═CHC(O)O(CH₂)₅CH₃?+?OH)?=?(2.28?±?0.23)?×?10^?11, and k₆(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?OH)?=?(2.74?±?0.26)?×?10^?11. The reactivity increased with the number of methyl substituents on the double bond and with the chain length of the alkyl group in –C(O)OR. Estimations of the atmospheric lifetimes clearly indicate that the dominant atmospheric loss process for these compounds is their daytime reaction with the hydroxyl radical. In coastal areas and in some polluted environments, Cl atom-initiated degradation of these compounds can be significant, if not dominant. Maximum Incremental Reactivity (MIR) index and global warming potential (GWP) were also calculated, and it was concluded that these compounds have significant MIR values, but they do not influence global warming.     

Methods for synthesis of nonabromodiphenyl ethers and a chloro-nonabromodiphenyl ether

Polybrominated diphenyl ethers (PBDEs) have been used extensively as brominated flame retardants (BFRs) in textiles, upholstery and electronics. They are ubiquitous contaminants in wildlife and humans. A low concentration of nonabrominated diphenyl ethers (nonaBDEs) is present in commercial DecaBDE and they are also abiotic and biotic debromination products of decabromodiphenyl ether (BDE-209). The objective of the present work was to develop methods for synthesis of the three nonaBDEs, 2,2',3,3',4,4',5,5',6-nonabromodiphenyl ether (BDE-206), 2,2',3,3',4,4',5,6,6'-nonabromodiphenyl ether (BDE-207) and 2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (BDE-208), with the intention of making them available as authentic standards for analytical, toxicological and stability studies, as well as studies regarding physical-chemical properties. Two methods were developed, one based on perbromination of phenoxyanilines and the other via reductive debromination of BDE-209 by sodium borohydride followed by chromatographic separation of the three nonaBDE isomers formed. An additional nonabrominated compound, 4'-chloro-2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (Cl-BDE-208), was also synthesized in the present work. Cl-BDE-208, prepared by the perbromination of 4-chlorodiphenyl ether, may be used as an internal standard in analysis of highly brominated diphenyl ethers. BDE-206, BDE-207, BDE-208 and Cl-BDE-208 were characterized by 1H NMR, 13C NMR, electron ionization mass spectra and by their melting points. The structures of all three nonaBDEs have been characterized previously by X-ray crystallography.     

Organohalogen contaminants and metabolites in cerebrospinal fluid and cerebellum gray matter in short-beaked common dolphins and Atlantic white-sided dolphins from the western North Atlantic

Concentrations of several congeners and classes of organohalogen contaminants (OHCs) and/or their metabolites, namely organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), hydroxylated-PCBs (OH-PCBs), methylsulfonyl-PCBs (MeSO₂-PCBs), polybrominated diphenyl ether (PBDE) flame retardants, and OH-PBDEs, were measured in cerebrospinal fluid (CSF) of short-beaked common dolphins (n = 2), Atlantic white-sided dolphins (n = 8), and gray seal (n = 1) from the western North Atlantic. In three Atlantic white-sided dolphins, cerebellum gray matter (GM) was also analyzed. The levels of OCs, PCBs, MeSO₂-PCBs, PBDEs, and OH-PBDEs in cerebellum GM were higher than the concentrations in CSF. 4-OH-2,3,3′,4′,5-pentachlorobiphenyl (4-OH-CB107) was the only detectable OH-PCB congener present in CSF. The sum (Σ) OH-PCBs/Σ PCB concentration ratio in CSF was approximately two to three orders of magnitude greater than the ratio in cerebellum GM for dolphins.