某生活垃圾焚烧厂排放废气、飞灰、环境空气和土壤中各二噁英类单体分布特征

以某生活垃圾焚烧企业为研究对象,研究其烟道气废气、焚烧飞灰、企业周边环境空气和土壤中二噁英的水平和各二噁英类单体指纹分布特征,研究结果表明,废气中的二噁英呈现出冬季稍高于夏季的排放特征,呋喃对总∑TEQ的贡献率范围为72%-90%.飞灰作为垃圾焚烧中二噁英的主要捕集途径,TEQ浓度季度变化比废气更加明显,呋喃对总∑TEQ的贡献率范围为74%-81%.环境空气和土壤中二噁英的季度分布特征与废气、飞灰的分布特征一致,且主导风向土壤中二噁英的TEQ浓度明显高于次主导风向.环境空气单体指标中呋喃对总∑TEQ的贡献率与废气和飞灰规律一致,说明该区域环境空气中的二噁英与企业排放废气中的二噁英具有同源性.与废气、飞灰和环境空气相比,土壤中呋喃与二噁英的比值和呋喃对总∑TEQ的贡献率存在差异,说明土壤中的二噁英并非单一来源于企业排放废气.废气、飞灰、企业周边环境空气和土壤中的17种PCDD/Fs单体中含量最丰富的是O8CDD,PCDDs的浓度随着取代氯原子个数的增加而增大.17种PCDD/Fs单体中对毒性当量贡献最大的单体是2,3,4,7,8-P5CDF.2,3,7,8-T4CDD是引起废气中二噁英排放呈现出冬季稍高于夏季的特征污染因子,需要重点关注.

2-Nitrobenzofuran as Dienophile in Polar Diels-Alder Reaction： A Simple Dibenzofurans Synthesis

2-nitrobenzofuran is studied as dienophile in polar thermal Diels-Alder reactions with normal electron demand using several structurally different dienes. A very strong electron-acceptor group, such as nitro group, enhances the dienophilic character of these heterocyclic compounds and owing to the fact that this substituent is easily extruded under thermal conditions this reaction sequence becomes a simple method of organic compound＇s families with heteroatom rings preparation. Part of this work is specifically concerned with theoretical studies. The global and local electrophilicity and nucleophilicity indexes were calculated for the dienophile and dienes used in this work. A concise synthesis of dibenzofurans has been development via cycloaddition reactions.

金属载体强相互作用对二苯并呋喃加氢脱氧反应影响

煤焦油作为煤炭热解的主要产品之一,产量大、用途广,合理有效地利用中低温煤焦油可促进煤炭资源的清洁高效转化。通过催化加氢脱氧实现对中低温煤焦油中氧原子脱除,可提高油品的氢碳比和稳定性,获得高品质燃料。二苯并呋喃含量高,反应活性低,选择其作为模型化合物,用于加氢脱氧反应研究。金属载体强作用(SMSI)的调控被广泛用于多相催化领域,但其对加氢脱氧反应影响尚不清楚。为探究SMSI对加氢脱氧反应的作用机理,用镍钛锆水滑石作为催化剂前驱体,通过改变Zr的比例,制备不同金属载体强相互作用的Ni基催化剂(Ni/mZrO_(2)@TiO_(2-x),m=0~0.5),用于模型化合物二苯并呋喃的加氢脱氧反应。通过HRTEM、H_(2)-TPD和CO-pulse等表征发现催化剂在还原中部分载体被还原为TiO_(2-x)并在Ni颗粒表面形成包覆层,产生氧空位。随着Zr比例增大,SMSI强度降低,导致包覆层和氧空位含量减少。280℃、6 MPa下对不同SMSI强度的催化剂进行活性评价,发现随着SMSI强度降低(Zr比例增大),脱氧产物收率由60.7%增至94.8%后降至66.9%,在Ni/0.4ZrO_(2)@TiO_(2-x)催化剂上呈现最佳脱氧性能;且该催化剂经5次循环活性未出现明显下降,稳定性好。研究结果表明,催化剂加氢脱氧性能由SMSI产生的包覆层和氧空位共同决定,Ni的包覆程度与加氢性能呈负相关,而氧空位含量与脱氧性能呈正相关。

Polychlorinated dibenzo-p-dioxins and dibenzofurans in flue gas emissions from municipal solid waste incinerators in China

Polychlorinated dibenzo-p-dioxins and furans （PCDD/Fs） emissions in flue gas from two types of municipal solid waste incinerators （MSWIs） most commonly used in China were investigated in this study. The selected incinerators include two grate-type MSWIs： MSWI-A （350 t/d） and MSWI-B 050 t/d）, and two fluidized bed MSWIs： MSWI-C （400 t/d） and MSWI-D （400 t/d）, which are all equipped with semi-dry lime scrubber and bag filter except MSWI-D equipped with cyclone and wet scrubber （WS） as air pollutant control device （APCD）. Results indicated that the emission concentration and the international toxic equivalents （I-TEQs） of the PCDD/Fs from the stacks were in the range of 1.210-10.273 ng/Nm^3 and 0.019-0.201 ng I-TEQ/Nm^3, respectively. They were greatly lower than the emission regulation standard of PCDD/Fs in China （1.0 ng I-TEQ/Nm^3）. However, only the PCDD/Fs emission level from MSWI-C was below 0.1 ng I-TEQ/Nm^3. Although the homologue profiles were distinct, the contributions of the 2,3,7,8-subsituted congeners to the total I-TEQ were similar among all the investigated MSWIs. Two major 2,3,7,8-substituted congeners, 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDD, account for 47% and 9% （average values） of the total I-TEQ values, respectively. The correlation between PCDD/Fs levels and composition of flue gas was also discussed.

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in surface sediment and bivalve from the Changjiang Estuary, China

Surface sediments and bivalves were collected from the Changjiang Estuary in December 2003 and November 2004, respectively. Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in these samples were measured with high-resolution chromatography (HRGC)/High Resolution Mass Spectrometer (HRMS). The concentrations of total PCDD/Fs and toxic equivalent (TEQ) were 169.83±119.63 and 0.81±0.36 pg/g dry weight (dw) in sediments, and 580.33±240.17 and 7.24±3.65 pg/g dw in bivalves. The homolog compositions of PCDD/Fs were similar among samples, the most abundant congener was octa-chlorinated dibenzo-p-dioxin (OCDD) and then octa-chlorinated dibenzofuran (OCDF) and 1,2,3,4,6,7,8-hepta-chlorinated dibenzo-p-dioxin (HpCDD). The herbicide pentachlorophenol (PCP) and sodium pentachlorophenol (Na-PCP) were proved the main source of PCDD/Fs in this area.

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.

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.

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.

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.

EXAMINATION OF POLYCHLORINATED DIBENZO-P-DIOXINS AND POLYCHLORINATED DIBENZOFURANS INTO PROCESS WATER OF KRAFT PULP BLEACHING MILL FROM ASPECT OF ENVIRONMENTAL WATER QUALITY

Process water of a pulp mill with kraft cooking, oxygen delignification and chlorine bleaching or chlorine dioxide (ECF) bleaching was examined from an aspect of a new level for environmental water quality in Japan. According to the new level, a concentration of dioxins consisting of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (PCBs) in environmental water is restricted to less than 1 pg- TEQ/L. We clarified that the 2,3,7,8-tetrachlorodibenzofuran (TCDF) concentrations were 0.5 pg/L or less. In addition, a main source of 1,3,6,8- and 1,3,7,9-tetrachlorodibenzo-p-dioxins in the process water seemed to be an agrochemical in water supplied from a river.

准噶尔盆地玛湖凹陷西斜坡原油油源解析:基于单体烃碳同位素组成、分子比值与浓度定量分析

通过对玛湖凹陷中部(西斜坡)24个原油样品饱和烃组分、芳烃组分、二苯并噻吩(DBT)、甲基二苯并噻吩(MDBTs)、二苯并呋喃(DBF)和甲基二苯并呋喃(MDBFs)等化合物定量分析及正构烷烃单体C同位素组成分析,将油样分为Ⅰ、Ⅱ两类。与Ⅱ类原油相比,Ⅰ类原油具有:①相对较高的Pr/n-C17、Ph/n-C18值和较低的Pr/Ph值;②相对较高的伽马蜡烷/(C30藿烷+伽马蜡烷)值;③相对较高的C29甾烷异构化比值、三环萜烷/(三环萜烷+C30藿烷)值、三芳甾烷TA(Ⅰ)/(TA(Ⅰ)+TA(Ⅱ)值和甲基二苯并噻吩比值4-MDBT/1-MDBT;④相对较高的二苯并噻吩(DBT)和甲基二苯并噻吩(MDBTs)含量、较低的二苯并呋喃(DBF)和甲基二苯并呋喃(MDBFs)含量和较高的DBT/(DBT+DBF)和MDBTs/(MDBTs+MDBFs)值。其中,两类原油MDBFs含量和DBT/(DBT+DBF)、MDBTs/(MDBTs+MDBFs)值差异比较显著。此外,Ⅱ类原油正构烷烃单体C同位素分布型式具有一定程度的“倒转”,即随碳数增加δ^(13)C值先变轻,至n-C25达到最低值,之后变重,而Ⅰ类原油不具有“倒转”特征。Ⅰ类原油来源于下二叠统风城组烃源岩,Ⅱ类原油来源于中二叠统下乌尔禾组烃源岩与下二叠统风城组烃源岩的原油组分混合产物。Ⅰ类原油比Ⅱ类原油分布于相对较深的储层,两类原油具有不同的运聚通道和分布规律。

螺[7H-苯并[b]芴[3,4-d]呋喃-7,9′-[9H]芴]的合成与性能

氧杂螺环类化合物具有优良的空穴传输能力和荧光特性,其作为蓝光材料被广泛应用于有机发光半导体(OLED)器件。本文以二苯并呋喃和硼酸三异丙酯为起始原料,经硼酸化反应、Suzuki偶联以及Cadogan关环反应合成了目标产物螺[7H-苯并[b]芴[3,4-d]呋喃-7,9′-[9H]芴]。利用^(1)H NMR、^(13)C NMR、HR-MS(ESI)和IR表征了化合物结构,并通过TG-DSC和UV-vis对化合物的热稳定性能和光学性能进行了研究。结果显示:该化合物失重5%的温度为350.9℃,玻璃化温度(T)为241.8℃,吸收焓为71.1 J/g,表现出较好的热稳定性和较高的玻璃化温度。

生活垃圾焚烧厂周边住宅小区内二噁英类物质的暴露特征及健康风险评估

以长江中下游地区某生活垃圾焚烧处理厂为监测对象,研究其主导上、下风向住宅小区内的环境空气、土壤和室内积尘等各环境介质中二噁英的浓度水平和分布特征。研究结果表明,该生活垃圾焚烧厂排放废气中的二噁英毒性当量浓度为0.007~0.064 ng·m^(-3),满足《生活垃圾焚烧污染控制标准》(GB 18485—2014)中规定的二噁英毒性当量限值0.1 ng·m^(-3)。4个住宅小区内环境空气、土壤和室内积尘中二噁英毒性当量浓度分别是0.12~0.19 pg·m^(-3)、1.1~4.8 ng·kg^(-1)和1.1~5.3 ng·kg^(-1),均处于较低水平。住宅小区内环境空气中二噁英的浓度呈现出秋冬季稍高于春夏季的现象,与废气中二噁英排放特征一致,下风向小区C和小区D环境介质中二噁英的浓度明显高于其他点位,说明本研究区域内的二噁英主要来源于该生活垃圾焚烧厂,在秋冬季要加强焚烧企业的管控力度。通过比较同一住宅小区、同一监测时段室内积尘和土壤监测数据发现,室内积尘对人体的暴露风险要大于土壤暴露风险。通过人群健康风险评估发现,儿童的呼吸暴露量是成人的4倍,儿童经口摄入土壤或室内积尘的日均暴露量是成人的10倍,儿童的暴露应该得到更高的重视。

基于二苯并呋喃的D-A型分子设计合成及在OLED中的应用

本文设计并合成了一种基于二苯并呋喃、硫砜和咔唑结构的D-A型荧光材料分子,通过核磁共振1H-NMR、13C-NMR和质谱分析(ESI-MS)确定材料结构,通过热重分析(TGA)、循环伏安测试(CV)、紫外可见吸收检测(UV-Vis)及光致发光检测(PL)等测试对材料的热学和光谱学性质进行了研究,检测表征显示该材料适合用于OLED器件应用,最后将该材料作为双极型主体应用于绿色磷光器件中,获得较好的器件发光性能,1000 cd/m^(2)时的电流效率为29.5cd/A,外量子效率为13.9%。

Ni/Ce_(θ)M_(1-θ)O_(x)催化剂催化二苯并呋喃加氢脱氧性能研究

中低温煤焦油中杂原子氧的含量较高,会造成油品热值低和稳定性差的问题,而加氢脱氧是煤焦油加氢精制最有效的方法之一。采用水热法制备了掺杂金属离子的CeO_(2)的Ni/Ce_(θ)M_(1-θ)O_(x)催化剂(M=Fe,Ga,Zr),研究了催化剂表面氧空位相对含量对二苯并呋喃加氢脱氧反应的影响。采用透射电子显微镜(TEM)、X-射线衍射(XRD)对催化剂形貌和结构进行了分析,采用拉曼光谱和X射线光电子能谱(XPS)对催化剂表面氧空位进行了研究。利用高压反应釜对具有不同氧空位相对含量的Ni/Ce_(θ)M_(1-θ)O_(x)催化剂上二苯并呋喃的加氢脱氧活性进行了评价。结果表明,CeO_(2)掺杂Ga、Zr和Fe后,Ga、Zr和Fe进入CeO_(2)晶格形成了固溶体结构,导致CeO_(2)晶格畸变,促进了催化剂表面氧空位的产生。其中,Ni/CeθFe1-θOx催化剂的氧空位相对含量最高,具备最高的脱氧活性。反应180 min时,Ni/CeθFe1-θOx催化剂的含氧中间产物的选择性降低至40.03%,脱氧产物的选择性增加至59.81%,说明催化剂表面氧空位相对含量增多有利于提高其活性。

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.

凝析油藏充注方向示踪分子标志物:烷基二苯并呋喃

石油中的二苯并呋喃(DBF)及甲基二苯并呋喃(MDBF)具有和二苯并噻吩(DBT)和二苯并吡咯(咔唑)化合物类似的结构和性质,其异构体相对含量和总量既受热成熟作用的影响,又受运移分馏效应的控制。以氘代二苯并噻吩为标样,求得二苯并呋喃和烷基二苯并呋喃类化合物的绝对含量,其与咔唑类含氮化合物总量呈很好的正相关性。以北部湾盆地福山凹陷花场凝析油藏为实例的油藏充注方向示踪结果表明,二苯并呋喃类化合物总量可以作为良好的油藏充注示踪参数。对常规甾萜类生标物参数不准确甚至失效、含氮化合物总量误差较大的凝析油藏而言,烷基二苯并呋喃类含氧芳烃化合物不失为一类有效而又易得的替代示踪标志物。

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.