benzofurans and octachlorodibenzofuran

Due to the promotion on Cl radical generation by enhanced oxidation, chlorination of hydrocarbon intermediates becomes a potential formation path for chloroaromatic precursors of PCDD/Fs (polychlorinated dibenzo-p-dioxins and dibenzofurans) in both MSW (municipal solid waste) incineration and gasification-combustion processes, in which intrinsic oxygen might have a significant effect on the competition between oxidation and chlorination. Thus, chlorination of benzene and phenol was experimentally studied on a homogeneous flow reaction system. Effects of temperature and ER (equivalence ratio) were assessed, and comparison was carried out to clarify the alteration in formation behaviors of chloroaromatics by extrinsic and intrinsic oxygen. At 600 °C, chlorobenzenes were already largely formed in benzene chlorination, and the addition of extrinsic oxygen barely affected it. On the contrary, with intrinsic oxygen, phenol tended to decompose to light compounds. With rising temperature, oxidation was promoted and extrinsic oxygen strongly inhibited the formation of chloroaromatics in benzene chlorination at 900 °C and higher temperature. For phenol chlorination, chlorobenzenes were still rarely generated. However, high proportions of octachloronaphthalene and octachlorodibenzofuran were observed, due to the enhancement in polymerization by high temperature. When increasing ER, oxidative decomposition was also promoted in both the chlorination of benzene and phenol. Extra extrinsic oxygen led to a further reduction of chloroaromatics during benzene chlorination, and till ER = 1.0 at 1000 °C, comparable performance to intrinsic oxygen could be achieved in the control of chloroaromatics. Based on these results, formation pathways of the major chloroaromatics from chlorination, oxidation and polymerization were summarized, and the roles of extrinsic and intrinsic oxygen in altering their formation behaviors were revealed.

Topics: Benzene; Benzofurans; Chlorobenzenes; Dibenzofurans, Polychlorinated; Halogenation; Hot Temperature; Incineration; Models, Chemical; Oxidation-Reduction; Oxygen; Phenols; Polychlorinated Dibenzodioxins; Solid Waste; Temperature

Winam Gulf of Lake Victoria is considered to be contaminated with toxic chemicals emanating from anthropogenic activities, especially near large industrial towns such as Kisumu. This has recently caused concerns about its water quality and impact on aquatic organisms and human beings. This study was justified by the need to generate baseline concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in surface sediment from selected sites in the lake and determine the influence of activities on their concentrations and potential risks to fish-eating birds living near the lake. Surface sediments (<30cm) from three different fish landing beaches, located 200m from the shore of Winam Gulf of Lake Victoria near Kisumu city, Homa Bay and Mbita (control) towns, were analysed. The total mean concentrations (in pgg(-1)drywt) were found to range from 17.4-812 (Σdl-PCBs), 36.6-813 (ΣPCDDs) and 1.45-46.4 (ΣPCDFs). The calculated Toxic Equivalents (TEQWHO(2005)) ranged from 0.001-0.43 (Σdl-PCBs) and 0.09-31 (ΣPCDD/Fs). The fish landing beaches at Kisumu city were found to be contaminated with respect to dl-PCBs and dioxins, followed by Homa Bay and Mbita. The relatively high levels of octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF) influenced the TEQ and the ΣPCDFs/ΣPCDDs ratios indicated chemical processes as partial sources of the dioxins. The levels of contaminants obtained in this study showed potential exposure to aquatic organisms and fish eating birds through food chain transfer.

Topics: Benzofurans; Dibenzofurans, Polychlorinated; Kenya; Lakes; Polychlorinated Biphenyls; Polychlorinated Dibenzodioxins; Water Pollutants, Chemical

Topics: Benzofurans; Environmental Pollutants; Halogenation; Photolysis; Polychlorinated Dibenzodioxins; Solvents

A deeper understanding of the microbial community structure is very important in bioremediation for polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs). However, this has been insufficiently addressed in previous studies. To obtain more information, we pyrosequenced the V4/V5 regions of the 16S rRNA genes of bacterial communities transited from polluted soil to batch microcosms that rapidly degraded high concentrations of octachlorodibenzofuran (OCDF). The analysis results contained an average of 11,842 reads per sample, providing the first detailed description of bacterial communities associated with PCDD/Fs. The community composition markedly changed to be concomitant with the degradation of OCDF, indicating that a distinctive population structure developed rapidly in the microcosm. Although oxygen gas was provided weekly to the microcosm, the growth of potential degraders, Sphingomonas, Pseudomonas, Rhodococcus, and Clostridium, was observed, but in consistently low quantities. While anaerobic Sedimentibacter initially emerged as an abundant pioneer, several aerobic participants, such as the genera Brevundimonas, Pseudoxanthomonas, and Lysobacter, exhibited a large increase in their 16S rRNA gene copies within the timeframe, which showed a temporal population dynamic, and indicated their collaborative contributions to the degradation of OCDF under hypoxic conditions. These results have provided a deeper insight into the microbial community structure and population dynamics of the OCDF-degrading microcosm.

Topics: Bacteria; Benzofurans; Biota; Biotransformation; DNA, Bacterial; DNA, Ribosomal; Molecular Sequence Data; Population Dynamics; RNA, Ribosomal, 16S; Sequence Analysis, DNA; Soil Microbiology; Soil Pollutants; Time Factors

Comprehensive congener fingerprints of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), including non-2,3,7,8-substituted congeners, in 142 surface sediment samples from the Baltic Sea were characterized by Principal Component Analysis (PCA). The pattern analysis revealed source specific indicators of chlorophenol use, high temperature processes, chlorine bleach/chloralkali production and a source signature suggested to originate from pulp/paper or related production. Congener patterns in sediments from offshore and pristine coastal areas showed strong resemblance to patterns of atmospheric deposition and flue gases, indicating that these sources have high impact in areas that are not affected by point sources. Prominent contributors to the patterns of hotspot areas along the Swedish coast included chlorophenol indicators and a source characterized by hexa-CDDs while the contribution of the traditional chlorine bleach pattern was weaker. This study demonstrates the importance of comprehensive PCDD/F congener analysis for identifying links to candidate sources.

Topics: Benzofurans; Dibenzofurans, Polychlorinated; Environmental Monitoring; Geography; Geologic Sediments; Oceans and Seas; Polychlorinated Dibenzodioxins; Principal Component Analysis; Seawater; Water Pollutants, Chemical

Polychlorodibenzothiophenes (PCDTs) are sulfur analogues of polychlorodibenzofurans (PCDFs) and have been detected in environmental samples. We used density functional theory calculations (Gaussian 98W) to predict the photodechlorination pathways of octachlorodibenzothiophene (OCDT) and octachlorodibenzofuran (OCDF) in hexane, and we compared the predicted pathways with those observed during UV irradiation experiments. OCDT and OCDF were observed to degrade through first-order dechlorination processes, and the rate constant for OCDT was less than one-third that for OCDF. The main experimental photodechlorination pathways of OCDT and OCDF led to hexachlorinated and tetrachlorinated congeners, respectively; that is, the photodechlorination pathway of OCDT differed from that of OCDF. On the assumption that the dechlorination mechanisms involved radical reactions, we used DFT calculations to estimate bond-dissociation energies and single-point energies of OCDT and OCDF and their dechlorinated congeners, and we used the resulting information, along with hypotheses regarding the rate-controlling step of the degradations, to predict theoretical degradation pathways. We propose that reaction of dechlorinated radicals with a hydrogen donor was the rate-controlling step for OCDT and that C-Cl bond dissociation by UV light was the rate-controlling step for OCDF.

Topics: Benzofurans; Models, Chemical; Models, Molecular; Molecular Structure; Photolysis; Thiophenes

Model dioxin compounds 4-chlorobiphenyl (4CB), octa-chlorodibenzo-p-dioxin (OCDD), and octachlorodibenzofuran (OCDF) were degraded by a mechanochemical (MC) process that involved milling with calcium oxide by use of a planetary ball mill. The degradation of 4CB produced mainly chloride ions and biphenyl, with the chlorine removal efficiency reaching about 100%. Biphenyl was transformed into terphenyls, quaterphenyls, cyclohexylbenzene, and bicyclohexyl through polymerization and hydrogenation reactions. Measurements of chloride ions after MC treatment of OCDD and OCDF showed about 100% dechlorination of both compounds; tetra- to heptachlorinated dibenzo-p-dioxins/furans (T4-H7CDD/Fs) were detected only at trace levels, and no other chlorinated organic compounds were observed. The residue after MC treatment was gray in color, indicating the possibility of carbonization, but the presence of amorphous graphite could not be confirmed.

Topics: Benzofurans; Biphenyl Compounds; Calcium Compounds; Chlorine; Environmental Pollutants; Gas Chromatography-Mass Spectrometry; Oxides; Polychlorinated Dibenzodioxins; Steel; Waste Management; X-Ray Diffraction

Previous studies with octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF) in juvenile or adult fish exposed via water revealed no toxicity, despite significant bioaccumulation. With 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), the fish early-life stage study has been shown to be the most sensitive test system. Therefore, the effects of OCDD and OCDF on the early-life stages of zebra fish (Brachydanio rerio) were determined during a flow-through test based on a column generator method. No statistically significant effect of OCDD and OCDF on the survival and hatching time of the eggs was found. Furthermore, no effects on survival, weight, general appearance or behaviour of the larvae were observed at the end of the exposure period of 32 days. GC-MS analysis of test solution samples revealed geometric mean measured concentrations of 32 (OCDD) and 34 ng/l (OCDF), respectively. Concentrations in surviving larvae at the end of the study were 61 (OCDD) and 94 (OCDF) micrograms/kg, respectively. These concentrations in zebra fish larvae were several orders of magnitude higher than concentrations in fish collected from the wild. In a review of the available laboratory fish experiments, we found a lack of biomagnification of OCDD and OCDF. We do not expect to find adverse effects of these compounds on the aquatic environment.

Topics: Animals; Benzofurans; Female; Growth; Male; No-Observed-Adverse-Effect Level; Polychlorinated Dibenzodioxins; Tissue Distribution; Zebrafish