库车坳陷陆相烃源岩及原油中的氧芴系列化合物

分析了塔里木盆地库车坳陷三叠系、侏罗系7个湖相泥岩和3个煤岩以及5个陆相原油样品中的萘、联苯、氧芴、芴、二笨并噻吩、菲、蒽、惹烯、和苯并蒽系列10种重要芳烃化合物.研究发现,氧芴系列化合物在煤岩样品中丰度高,在湖相泥岩样品中丰度低.据岩、油芳烃总离子流图中氧芴系列化合物,特别是氧芴之相对丰度对比研究结果判识,沙3井白垩系原油、羊塔克5井下第三系和白垩系原油以及却勒1井下第三系原油可能为库车坳陷下侏罗统阳霞组或中侏罗统克孜勒努尔组的煤成油,英买7井奥陶系原油和牙哈1井下第三系原油可能为库车坳陷三叠系、侏罗系湖相泥岩成油.该研究结果对进一步开展库车坳陷油源对比研究和油气勘探具有一定的意义.     

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...     

Exposure and effects assessment of persistent organohalogen contaminants in arctic wildlife and fish

Persistent organic pollutants (POPs) encompass an array of anthropogenic organic and elemental substances and their degradation and metabolic byproducts that have been found in the tissues of exposed animals, especially POPs categorized as organohalogen contaminants (OHCs). OHCs have been of concern in the circumpolar arctic for decades. For example, as a consequence of bioaccumulation and in some cases biomagnification of legacy (e.g., chlorinated PCBs, DDTs and CHLs) and emerging (e.g., brominated flame retardants (BFRs) and in particular polybrominated diphenyl ethers (PBDEs) and perfluorinated compounds (PFCs) including perfluorooctane sulfonate (PFOS) and perfluorooctanic acid (PFOA) found in Arctic biota and humans. Of high concern are the potential biological effects of these contaminants in exposed Arctic wildlife and fish. As concluded in the last review in 2004 for the Arctic Monitoring and Assessment Program (AMAP) on the effects of POPs in Arctic wildlife, prior to 1997, biological effects data were minimal and insufficient at any level of biological organization. The present review summarizes recent studies on biological effects in relation to OHC exposure, and attempts to assess known tissue/body compartment concentration data in the context of possible threshold levels of effects to evaluate the risks. This review concentrates mainly on post-2002, new OHC effects data in Arctic wildlife and fish, and is largely based on recently available effects data for populations of several top trophic level species, including seabirds (e.g., glaucous gull (Larus hyperboreus)), polar bears (Ursus maritimus), polar (Arctic) fox (Vulpes lagopus), and Arctic charr (Salvelinus alpinus), as well as semi-captive studies on sled dogs (Canis familiaris). Regardless, there remains a dearth of data on true contaminant exposure, cause-effect relationships with respect to these contaminant exposures in Arctic wildlife and fish. Indications of exposure effects are largely based on correlations between biomarker endpoints (e.g., biochemical processes related to the immune and endocrine system, pathological changes in tissues and reproduction and development) and tissue residue levels of OHCs (e.g., PCBs, DDTs, CHLs, PBDEs and in a few cases perfluorinated carboxylic acids (PFCAs) and perfluorinated sulfonates (PFSAs)). Some exceptions include semi-field studies on comparative contaminant effects of control and exposed cohorts of captive Greenland sled dogs, and performance studies mimicking environmentally relevant PCB concentrations in Arctic charr. Recent tissue concentrations in several arctic marine mammal species and populations exceed a general threshold level of concern of 1 part-per-million (ppm), but a clear evidence of a POP/OHC-related stress in these populations remains to be confirmed. There remains minimal evidence that OHCs are having widespread effects on the health of Arctic organisms, with the possible exception of East Greenland and Svalbard polar bears and Svalbard glaucous gulls. However, the true (if any real) effects of POPs in Arctic wildlife have to be put into the context of other environmental, ecological and physiological stressors (both anthropogenic and natural) that render an overall complex picture. For instance, seasonal changes in food intake and corresponding cycles of fattening and emaciation seen in Arctic animals can modify contaminant tissue distribution and toxicokinetics (contaminant deposition, metabolism and depuration). Also, other factors, including impact of climate change (seasonal ice and temperature changes, and connection to food web changes, nutrition, etc. in exposed biota), disease, species invasion and the connection to disease resistance will impact toxicant exposure. Overall, further research and better understanding of POP/OHC impact on animal performance in Arctic biota are recommended. Regardless, it could be argued that Arctic wildlife and fish at the highest potential risk of POP/OHC exposure and mediated effects are East Greenland, Svalbard and (West and South) Hudson Bay polar bears, Alaskan and Northern Norway killer whales, several species of gulls and other seabirds from the Svalbard area, Northern Norway, East Greenland, the Kara Sea and/or the Canadian central high Arctic, East Greenland ringed seal and a few populations of Arctic charr and Greenland shark.     

程序升温脱附测定难挥发性有机物吸附相平衡

提出一种采用少量程序升温脱附实验就能计算挥发性有机物在不同温度下吸附等温线的方法.该方法以拟平衡吸附动力学为基础,建立难挥发性有机物从吸附剂表面程序升温脱附的模型,采用数值方法对该模型进行求解.采用该模型对程序升温脱附实验测定的图谱进行模拟,获得难挥发性有机物在吸附剂上的吸附相平衡参数,从而确定吸附等温线.运用所提出的...     

Presence and Biotransformation of three Heteroaromatic Compounds Compared to an Aromatic Hydrocarbon

The presence of nitrogen, oxygen and sulfur containing aromatic compounds, namely carbazole, dibenzofuran, dibenzothiophene and their alkylated derivatives was investigated in potential environmental sources of these compounds. The persistence vs biodegradation of the parental heteroaromatic compounds was determined using bacterial consortia collected from three marine beaches from coastal Newfoundland. Experiments were performed at 25 and 4°C and bacterial populations derive from differently contaminated environments. In separate studies, rainbow trout, Salmo gardneiri, were exposed to PACs through their diet and the bioelimination of glucuronide and sufate conjugates followed in the gall bladder bile after a single and during continuous exposure. Comparison was done between the presence and fate of the three heterocyclic PACs and that of fluorene. a PAH counterpart with similar structure and physical-chemical properties. The tissue distribution of the PACs (not presented) provides information on the potential narcotic and/or reproductive effect of the unreacted compounds and the metabolites on the potential toxicity of the oxidation products.     

载气流量及升温速率对污染土壤中多氯联苯热脱附的影响

利用小型管式炉进行了载气流量和升温速率对多氯联苯污染土壤的热脱附过程影响的实验研究。结果表明流量的增大对多氯联苯含量和毒性当量的去除效率影响不大,载气流量小于400 ml·min^-1时,气相中的脱附量明显增大,载气流量大于400 ml·min^-1则脱附量变化较小,而多氯联苯的毒性当量则随着载气流量增大呈线性增加趋势。实验结果还表明污染土壤中多氯联苯变化速率与升温速率呈明显的正线性相关,随着升温速率增加,污染土壤中多氯联苯去除效率总体呈上升趋势,毒性当量去除效率降低。总体结果分析可以看到升温速率越大,总体效果也越好。污染土壤经热脱附处理后气固相的二 英毒性当量则有不同程度提升,尤其气相内检测到了大量多氯二苯并呋喃生成。     

程序升温脱附活化能估算新模型

以吸附过程本征动力学模型为基础,提出了一种新的TPD非线性活化能估算模型.与经典TPD模型相比,这种新的TPD理论模型考虑了脱附过程中存在的吸附质分子再吸附现象的影响,更接近实际的脱附过程.采用TPD实验技术测定了二苯并呋喃在Norit RB1、Monolith和Chemviron 3种活性炭上、不同升温速率下的程序升温脱附图谱.以这些TPD图谱为基础,分别采用经典TPD模型和TPD非线性模型计算了二苯并呋喃在3种活性炭上的脱附活化能.结果表明,经典TPD模型所估算出来的二苯并呋喃的活化能要偏高TPD非线性模型估算结果约8％～12％,脱附过程中存在吸附质分子再吸附现象对脱附活化能有较大的影响.     

Mechanistic Studies on the Dibenzofuran Formation from Phenanthrene,Fluorene and 9–Fluorenone

We carried out molecular orbital theory calculations for the homogeneous gas‑phase formation of dibenzofuran from phenanthrene, fluorene, 9-methylfluorene and 9-fluorenone. Dibenzofuran will be formed if ∙OH adds to C_8a, and the order of reactivity follows as 9-fluorenone > 9-methylfluorene > fluorene > phenanthrene. The oxidations initiated by ClO∙ are more favorable processes, considering that the standard reaction Gibbs energies are at least 21.63 kcal/mol lower than those of the equivalent reactions initiated by ∙OH. The adding of ∙OH and then O₂ to phenanthrene is a more favorable route than adding ∙OH to C_8a of phenanthrene, when considering the greater reaction extent. The reaction channel from fluorene and O₂ to 9-fluorenone and H₂O seems very important, not only because it contains only three elementary reactions, but because the standard reaction Gibbs energies are lower than −80.07 kcal/mol.     

Carbazole–Dibenzofuran Dyads as Metal‐Free Single‐Component White‐Color Photoemitters

White‐color light emitters from single organic molecule without heavy metals are valuable for practical applications in organic light‐emitting devices. In this study, carbazole (Cz)–dibenzofuran (DBF) donor–acceptor dyads are designed for white‐color light emitters. Originally, these molecules show photoluminescence (PL) in near ultraviolet region. However, upon successive ultraviolet (UV) irradiation, white‐color PL appears, comprising dual‐color phosphorescence from the amorphous and crystalline state of the dyad. A continuous UV irradiation makes the twisting angle between the Cz and DBF planes flatten through the triplet‐excited state, which proceeds crystallization. Thermal annealing and UV irradiation can switch the blue‐ and white‐color phosphorescences from the dyad. Furthermore, charge injection generates white‐color electroluminescence. The materials with PL color modulation ability by UV‐light irradiation and heating can be applicable as light‐ and thermo‐sensors.