Distribution and geochemical significance of dibenzofurans,phenyldibenzofurans and benzo[b]naphthofurans in source rock extracts from Niger Delta basin,Nigeria

The distribution and geochemical significance of dibenzofurans,phenyldibenzofurans and benzo[b]naptho-furans in source rocks from Niger Delta basin,Nigeria,were investigated by Rock-Eval pyrolysis and gas chro-matography--mass spectrometry(GC--MS).The data obtained from the source rocks evaluation showed that the rock samples contained type 1/III kerogen capable of generating oil and gas and were within immature to early mature stage.The relative abundance of the Cor,C1-and C2-dibenzofurans range from 1.75%to 29.82%,27.60%to 40.52%and 29.66%to 6889%,respectively.The diben-zofurans were dominated by C-dibenzofurans.Among the C1-dibenzofurans,2-+3-methyldibenzofuran was the most abundant in the rock samples while 1-methy ldibenzofuran appeared to be the least.The relative abundance of benzo[b]naphtho[1,2-d]furan(1,2]BNF),benzo[b]naph-tha[2,1-d]furan(2.1]BNF)and benzo[b]naphtha[2,3-d]fu-ran([2.3]BNF)in the rock extracts range from 12.01%to 52.58%,32.61%to 75.219%and 10.27%to 52.43%.The wide range of values recorded for the three isomers of benzo[b lnapthofurans in the samples suggest source rocks formed from mixed organic matter.Among the pheny ldibenzofuran isomers,4-pheny ldibenzofuran was the most abundant while 1-phenyldibenzofuran was the least.Phenyldibenzofuran ratio-1(PhFR-1)and pheny ldibenzofuran ratio-2(PhFR-2)values range from 0.13 to 1.20 and 0.11 to 2.11,respectively.The resuls showed that the relative abundance of PhFR-1 and PhFR-2 increase gradually with increasing burial depth and maturity(VRo≤0.77%,MPI-1≤0.62.Tmax s 443℃),and have a good correlations with calculated vitrinite reflectance.MPI-I and maximum Temperature(Tmax)-This range of values suggested immature to early mature source rocks.The source rocks were found to have shale and coul lithologics and deposited in a lacustrine/fuvial deltaic settings within immature to early mature stages based on the distribution of dibenzofurans,pheny ldiben-zofurans and benzo[b]naphthofurans in the source rocks.This study showed that dibenzof urans,phenyldibenzofu-rans and benzo[b]naphthofurans were ffcive in deter-mining the origin,depositional environment and thermal maturity of source rocks in Niger Delta basin,Nigeria.

Determination of the Most Toxic Polychlorodibenzofurans in Fresh Milk from Southwest Iran

Background: Today’s presence of polychlorinated dibenzofurans (PCDFs) in foodstuff, such as milk and milk products, is considered to be the major concern for human health. This study was aimed to determine the concentrations of the most toxic congeners of furans in pasteurized milk samples produced in southwest Iran. Material and method: 15 composite samples of pasteurized milk were collected from 3 major dairy factories in Khuzestan Province (southwest of Iran) in summer, autumn and winter from July 2011 to March 2012. After precipitation of the proteins, fat phase was reduced and extracted with hexane and ether. After dehydration, furans existed in fat percolated with hexane through a column chromatography that contained respectively silica gel/silver nitrate, silica gel, silica gel/sulphuric acid and with percolating output through another column that contained activated charcoal and silica gel and washed the lower column with a mixture of dichloromethane-hexane and toluene, concentrated and dissolved in mobile phase and analyzed using HPLC: 150 mm × 4.6 mm ID, 5 μm cosmosil 5 NPE column equipped with a UV detector at 254 and 235 nm, mobile phase: methanol/water (80:20, v/v) at flow rate of 1 ml/min. Results: All samples were found to be contaminated with furans. The average concentration of 2,3,7,8 TCDF and 2,3,4,7,8 PCDF were 1.91 pg/g and 1.77 pg/g in lipid content ranging from 2% to 3% respectively. The mean total content of furans in milk fat was 0.36 TEQ (Toxic Equivalency) pg/g which was below the recommended EU (European Union) threshold value 3 pg (WHO-PCDFs-TEQ/g fat). Also, result showed that there were statistically significant differences between each factory during 3 seasons.

Polychlorinated Dibenzofurans and Dibenzo-p-Dioxin in Tree Bark from an Industrialized Area: What the 2,3,7,8-Cl Substituted Congeners Tell Us, and What Is Missing

We analyzed polychlorinated dibenzofurans (PCDF) and dibenzo-p-dioxins (PCDD) in 27 tree bark samples from the industrialized area near Sauget, Illinois, USA. The trees were located within 4 km of the W. G. Krummrich (WGK) plant, the oldest and largest chemical plant in Sauget, with 24 of 27 samples collected from residential areas. The percent of total PCDF or PCDD profiles of ten 2,3,7,8- Cl substituted PCDF and seven PCDD congeners is homogeneous: 90% of the variance among the samples is explained by 3 eigenvalues in a principal components analysis. The homogeneity of the data suggests that samples were affected by similar types of sources which may have been influenced by electric power generation, chemical waste incineration, and large-scale thermal production of chlorinated chemicals. Quantitatively, the 2,3,7,8-Cl substituted congener analysis does not account for 90% of the concentration of tetra- and penta-Cl homologues and 80% of hexa-Cl and 50% of hepta-Cl homologues. The World Health Organization stated during establishment of toxic equivalence factors (TEF, 2005 version) that calculation of toxic equivalents (TEQs) is not suitable for abiotic matrices, such as tree bark, which are not involved in human exposures. Our results show that the non-2,3,7,8-Cl substituted congeners have high concentrations and should be included in analysis.

Two New Dibenzofurans from the Underground Parts of Ligularia intermedia

Two new dibenzofurans, 7,8-dimethoxy-4-methyldibenzofuran-1-carboxaldehyde, named ligumedial (1) and 7,8-dimethoxy-4-methyldibenzofuran-1-carboxylic acid, named ligumediaoic acid (2), have been isolated from the underground parts of Ligularia intermedia. Their structures were elucidated by spectroscopic methods.

Surface Electrostatic Potentials of Polychlorinated Dibenzofurans and Their Applications in Quantitative Structure-toxicity Relationships

Polychlorinated dibenzofurans (PCDFs) represent an important kind of serious pollutant. They are highly toxic and persistent in environment. In this paper, geometrical optimizations and subsequent calculations of electrostatic potentials (ESPs) on molecular surface have been performed for all 135 PCDF congeners at the HF/6-31G* level. The effects of substitution value and variation of substitution position upon the surface ESPs have been discussed. A series of statistic-based structural descriptors derived from the surface ESPs have been calculated. For some PCDF congeners, linear relationships between aryl hydrocarbon receptor (AhR) biding affinity and aryl hydrocarbon hydroxylase (AHH) induction potency as well as theoretical descriptors have been established by multiple linear regression method. It appears that the quantities derived from the surface ESPs, Vs,min, Vs , VS +, σ+ and Nvmin, 2 together with the molecular surface area and the energy gap between HOMO and LUMO can be well used to express the quantitative structure-toxicity relationships of PCDFs.

Study on the Intramolecular Hydrogen Bonds of Dibenzofurans, Xanthones and Anthraquinones with One or Two Positions Substituted by Hydroxyls

The thermodynamic properties of dibenzofurans （DFs）, xanthones （XTs） and an-thraquinones （AQs） with one and two positions substituted with hydroxyls in the ideal gas state at 298.15 K and 1.013×10^5 pa were calculated at the B3LYP/6-311G^＊ level using Gaussian 03 program. The isodesmic reactions were designed to calculate the standard free energy of formation （△fG^θ）. Three types of hydrogen bonds exist in the three kinds of chemicals and their bond energies were ascertained as 7-15, 15-23 and 49-58 kJ·mo1^-1 respectively by comparing the △fG^θ values. Electronic density topology analysis was applied to validate the strength of bond.

Polychlorinated dibenzo-p-dioxins and dibenzofurans in different tissues of the cormorants (Phalacrocorax carbo) from Dongting Lake,China

Tissue distribution provides important information regarding the pharmacokinetic behavior of pollutants and is invaluable when analyzing the risk posed to avian species by the exposure to such kind of pollutants. In this study, concentrations of polychlorinated dibenzo-p-dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） were determined in muscle, liver, spleen, kidney, stomach, gall bladder, skin, heart, pancreas, intestine and lung tissue extracts of cormorants collected from Dongting Lake, China. Tissue distribution results showed preferential accumulation of PCDD/Fs in both liver and skin. The total concentration of PCDD/Fs ranged from 421 to 5696 pg/g lipid weight. Octachlorinated dibenzo-p-dioxin （OCDD） was the predominant congener in all tissues and contributed between 31% and 82% to all 17 PCDD/Fs in different tissues. The liver/muscle ratios progressively increased with the degree of chlorination of PCDDs, except for OCDD. The relative toxic potential of PCDDs and PCDFs in tissues were calculated using the World Health Organization （WHO） Toxic Equivalency Factors （TEFs） for birds. The concentrations of WHO-toxic equivalent in different tissues ranged between 14.8 and 2021 pg/g lipid weight. These results indicated PCDD/Fs may have been bio-accumulated in cormorant via food-web. Furthermore, when compared with studies reported in the literatures, the PCDD/Fs levels in the cormorant collected from Dongting Lake were still relatively high.

Aspects of formation and degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans

The research progress on the mechanisms of formation and degradation of polychlorinated dibenzo-p-dioxins ( PCDDs ) and dibenzofurans ( PCDFs ) is reviewed. The primary sources of PCDD/Fs are chemical, thermal, photochemical and enzymatic reactions. Most of the thermal sources result in emissions into air. The studies on the photodegradation and biodegradation offer promise for destruction of PCDD/Fs in environment.

二噁英提取方法的比较

Labeled polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs)were extracted by three different methods,i.e.,soxhlet extraction,hot extraction and accelerated solvent extraction(ASE).The PCDD/Fs were detected by high resolution gas chromatography-high resolution mass spectrometry.Comparisons of the three methods were carried out by recovery of PCDD/Fs,solvent consumption and extraction time.The results showed that all of the method could extract labeled PCDD/Fs efficiently.ASE was a time saving procedure with lowest consumption of solvents compared with the other two methods.

土壤中二噁英的快速预处理及HRGC-HRMS分析

A rapid pretreatment method of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in soil and analysis by high resolution gas chromatograph-high resolution mass spectrometry was present.The extraction and alumina clean up of PCDD/Fs in soil was achieved by accelerated solvent extractor.Then the multi-layer silica-gel column was used for further clean up.The whole method has been evaluated on certified reference soil and farm soil.Accuracy and precision of this method was tested with satisfactory results.

Estimation of n-Octanol/water Partition Coeffi-cients(lgK_(ow)) and the Aqueous Solubility(-lg_(Sw)) of all PCDF Congeners by Density Functional Theory

Optimized calculation of dibenzofuran （DF） and 135 polychlorinated dibenzofurans （PCDFs） was carried out at the B3LYP/6-31G＊ level in GAUSSIAN 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained structural parameters were taken as theoretical descriptors to establish the novel quantitative structureproperty relationship （QSPR） model for predicting n-octanol/water partition coefficients （lgKow） of PCDFs. The new model of lgKow achieved in this work contains three variables： energy of the highest occupied molecular orbital （EHOMO）, the most negative atomic partial charge （q^-） and average molecular polarizability （a）, of which R^2= 0.9011 and SD = 0,17 with larger t values. In addition, the variation inflation factors （VIF） of variables in the present model are all less than 5.5, suggesting high accuracy of the lgKow model. And the results of cross-validation test （q^2 = 0.8688） and method validation also show this model exhibits optimum stability and better predictive power than semi-empirical method. At the same time, it is found that the aqueous solubility （-lgSw） has high relative correlation with constant volume molar heat capacity （Cv^0）, of which R^2 = 0.9777 and SD = 0.22. Moreover, lgKow and -lgSw values of all PCDF congeners were predicted respectively.

Chlorinated Dioxin and Furan Congener Profiles from Pentachlorophenol Sources

Pentachlorphenol (PCP) was widely used as a biocide and insecticide for wood preservation. Chlorinated dioxins and furans (2,3,7,8-substituted PCDD and PCDF congeners) were inadvertent byproducts of PCP production. As such, it is an important source of PCDD/F contamination in treated wood and in soil/ sediment near sites that produced or used PCP. It has been noted in the literature, that PCP congener profiles are similar to some combustion profiles, as well as sewage sludge and particulate deposition. In a very broad sense, this is true. OCDD and 1,2,3,4,6,7,8-HpCDD are typically the dominant constituents in these source categories. There is however, a distinct, consistent and repeatable feature in the lower chlorinated tetra, penta and hexa PCDD/F range of PCP related samples: an order of magnitude increase in concentration as a function of degree of chlorination. Because lower chlorinated furans concentrations make up less than 1% of the total PCDD/F in PCP, it is difficult to differentiate PCP from other OCDD dominated source profiles on bargraphs that use a linear-scale y axis. Using a log-scale y axis, however, PCP impacted profiles are obvious, and are not easily confused with congener profiles from other sources.

Pure Rotational Spectrum of Dibenzofuran in Range of 2-6 GHz

We report the observation and assignment of the rotational spectra of dibenzofuran measured in the range of 2-6 GHz with a newly constructed broadband chirped-pulse Fourier transform microwave(cp-FTMW)spectrometer.An analysis of the microwave spectra led to the assignment of 40 b-type transitions,resulting in the accurate determination of the rotational constants A=2278.19770(38)MHz,B=601.12248(10)MHz,and C=475.753120(98)MHz.

Enhancing mechanisms of N-doped biomass carbon on the vanadium-based catalyst for furan degradation at low temperature

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans(PCDD/Fs)have attracted widespread concern due to their high toxicity,and their difficult manipulation in laboratories has made the research process tough.Thus,in our work,furan is selected as the model compound owing to the same structure of a central oxygenate ring.Although catalytic oxidation is regarded as an effective and applicable method for the abatement of PCDD/Fs,the synthesis of low-temperature catalysts is still a challenging problem in practical applications.Considering this situation,we prepared a novel V_(2)O_(5)/TiO_(2)catalyst modified with N-doped hierarchical porous carbon(NHPC)via a wet impregnation method.The V/T-1%NHPC catalyst could achieve expectant low-temperature performances with 50%furan conversion at 150℃and a complete conversion at 200℃,which decreased 23℃and 40℃compared to the V/T catalyst respectively.Moreover,the addition of NHPC presented lifting chemical stability during long-time test.The addition of NHPC in V/T catalysts decreased the formation of crystalline V_(2)O_(5) and increased the percentages of V^(5+)and O_(lat),which improved the utilization of vanadium ions and the catalytic activity.Simultaneously,the higher binding energy shift of O_(lat) implied more reaction possibility with other oxidise reactants.Importantly,this work proved the lifting catalytic activity by the interaction between catalysts and NHPC,and proposed the promoting effects of the N element.The results showed that the content of the pyridinic N and graphitic N in NHPC changed after combining with V/T catalyst,which played crucial roles in the excellent catalytic performance.Overall,this work provides comprehensive research of the V/T-1%NHPC catalyst toward furan oxidation at low temperature and explain the effects of N-doped biomass carbon in catalytic activity clearly,which gave a new thought to design low-temperature catalysts in PCDD/Fs degradation.Besides,the internal functional mechanisms of N species are worth further exploration in future studies.

Effect of different operation conditions on PCDD/F inhibition by ammonium dihydrogen phosphate:concentrations,distributions and mechanisms

Phosphorus-containing compounds are considered as the potential alternatives of traditional inhibitors for suppressing the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs),but the suppression characteristics are scarcely studied.In this study,ammonium dihydrogen phosphate(ADP)was selected as the inhibitor to inhibit the PCDD/F formation via de novo synthesis at 350℃.The influence of oxygen content and addition method on PCDD/F inhibition was systematically investigated by means of statistical analysis and morphological characterization.The results showed that oxygen enhanced the formation of PCDD/Fs from 1470 ng g^(−1)(9.78 ng I-TEQ g^(−1))to 2110 ng g^(−1)(14.8 ng I-TEQ g^(−1)).ADP significantly inhibited the PCDD/F formation,with inhibition efficiencies ranging from 82.0%to 97.7%.Herein,a higher oxygen content and the premixed way intensified the suppression effect.Dibenzo-p-dioxin(DD)/dibenzofuran(DF)chlorination was proven to be effectively suppressed while chlorophenol(CP)route was not obviously influenced.With the addition of ADP,Cl source was significantly reduced and the formation of organic Cl was effectively inhibited.Also,it decreased the proportion of C–O/C=N and C=O,revealing the efficient inhibition of carbon oxidation.Meanwhile,the formation of copper phosphate and copper pyrophosphate was observed in XPS(X-ray photoelectron spectroscopy)spectra,indicating that the catalytic metal Cu was chelated and passivated by ADP.The premixed way had a better effect on reducing Cl resources,inhibiting oxidation and chelating metals,due to the direct contact with inhibitor.However,the separation method could only depend on the decomposed gases,resulting in a lower inhibition efficiency.

Detailed analysis of PCBs and PCDD/Fs impurities in a dielectric oil sample （ASKAREL Nr 1740） from an imported transformer in China

Homolog and congener profiles of polychlori- nated biphenyls （PCBs）, polychlorinated dibenzo-p- dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） in commercial PCBs formulations are useful information for the source appointment of PCBs contam- ination as well as the risk assessment caused by potential exposure. Dielectric oil （ASKAREL Nr 1740） in an imported transformer found in China was sampled and analyzed by isotope dilution technology using high resolution gas chromatography-high resolution mass spectrometry （HRGC/HRMS）. The detailed homolog and congener profiles of PCBs obtained were compared with those of known Aroclor formulations. High similarity in the homolog profile between the oil sample and Aroclor 1260was found, with the hexachlorinated and hepta- chlorinated biphenyls accounting for more than 80.2% of the total PCBs concentration. Severn indicator PCBs contribute about 30%, while 12 PCB congeners （i.e., # 153, #143, #168, #180, #149, #165, #138, #170, #190, #187, #174, #181） account for more than 50% of the total PCB concentrations. Total concentration ofPCDDs, PCDFs and dioxin-like PCBs （DL-PCBs） was found to be 740 ng TEQ/g, of which 620 ng TEQ/g came from DL-PCBs. The contribution of PCDDs to the total TEQ was neglectable. The concentration of PCDFs homologs follows the order of OCDF 〉 HxCDFs 〉 HpCDFs 〉 PeCDFs 〉 TeCDFs, which is in consistence with the previous study on Aroclor 1260. Three DL-PCBs congeners （i.e., #118, #156, #157） accounted for 77% of the total concentration of DL-PCBs, also they contribute 72% in the TEQ caused by DL-PCBs.

Brominated dioxins and furans in a cement kiln co-processing municipal solid waste

A field study and theoretical calculations were performed to clarify the levels, profiles, and distributions of polybrominated dibenzo-p-dioxins and dibenzofurans(PBDD/Fs) in a cement kiln co-processing solid waste, with a focus on the PBDF formation mechanism.The raw materials contributed greatly to input of PBDD/Fs into the cement kiln. The PBDD/F concentrations in the raw materials were much higher than those in particle samples from different process stages in the cement kiln. The PBDD/F concentrations in the clinkers were1.40% of the concentrations in the raw materials, which indicated that the high destruction efficiencies for PBDD/Fs by cement kiln. PBDD/F distribution patterns in particle samples collected from different process stages indicated the cement kiln backend was a major site for PBDD/F formation. PBDFs with high levels of halogenation, such as heptabrominated furans(Hp BDF), were the dominant contributors to the total PBDD/F concentrations and accounted for 42%–73% of the total PBDD/F concentrations in the particle samples. Our results showed that co-processing of municipal solid waste in a cement kiln may influence the congener profile of PBDD/Fs, especially for the higher halogenated PBDD fraction. In addition, there were significant correlations between the decabromodiphenyl ether and heptabrominated furan concentrations, which is an indicator of transformation from polybrominated diphenyl ethers to PBDD/Fs. Theoretical calculations were performed and demonstrated that elimination of HBr and Br_2 from polybrominated diphenyl ethers were the dominant formation pathways for PBDD/Fs. These pathways differed from that for polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs).

Supported Pt-Ni bimetallic nanoparticles catalyzed hydrodeoxygenation of dibenzofuran with high selectivity to bicyclohexane

Catalytic hydrodeoxygenation(HDO)is one of the most effective methods to upgrade the oxygen-containing compounds derived from coal tar to valuable hydrocarbons.Herein,an efficient bimetallic catalyst Pt_(1)Ni_(4)/MgO was prepared and applied in the HDO of dibenzofuran(DBF).High yield(95%)of the desired product bicyclohexane(BCH)was achieved at 240℃and 1.2 MPa of H_(2).Superior catalytic performance could be ascribed to the"relay catalysis"of Pt sites and Ni sites,and the reaction pathway is proposed as well.Scale-up experiment and recyclability test were also performed,which demonstrated the recyclability and promising potential application of Pt_(1)Ni_(4)/MgO.