一氯苯在钒钛催化剂表面亲核取代反应的DFT计算

采用DFT计算方法对一氯苯在V2O5(001)和脱钛矿表面氧上的亲核取代反应的机理进行了分析。对不同DFT泛函在氯代芳香烃-过渡金属氧化物体系计算中的准确性进行了验证,发现采用B3LYP泛函得到的过渡态相对能量与标准值的偏差为9.63 kJ/mol,产物相对能量的偏差为8.79 kJ/mol,可以用于反应路径的推断。对亲核取代反应的机理进行了分析:首先苯环上与氯原子连接的碳原子受到表面氧的攻击,氯原子被驱离环平面;然后C—O健开始形成,同时C—Cl健断裂;最后苯酚盐结构形成,而驱离的氯原子与提供一个空轨道的过渡金属原子连接。与V2O5(001)表面及脱钛矿(100)和(101)表面相比,脱钛矿(001)表面的桥位氧是亲核取代最有可能发生的位置,吸附能为193.77 kJ/mol,吸附能垒为135.33 kJ/mol。     

Formation of polycyclic aromatic hydrocarbon via gas phase benzyne

Gas phase benzyne generated from the high temperature pyrolysis of phthalic anhydride is reduced to benzene. This newly formed benzene is then free to react further with more benzyne to yield more complex aromatic hydrocarbons.     

固定化醌耦合生物驱动的芬顿反应对芳香胺的降解

构建了蒽醌-2-磺酸改性聚氨酯泡沫(AQS-PUF)耦合生物驱动的芬顿反应过程,并研究了其对芳香胺的降解性能。结果表明:芬顿反应所需的H_2O_2来自于AQS-PUF厌氧生物还原-好氧自氧化循环过程,而Fe~(2+)来自于AQS-PUF介导的柠檬酸铁厌氧生物还原过程;芬顿反应的最适条件为0.20 mmol·L~(-1)固定化AQS,0.16 g·L~(-1)生物量,40 mmol·L~(-1)乳酸钠和4.5 mmol·L~(-1)柠檬酸铁;在最适条件下,通过厌氧-好氧(21 h/3 h)循环过程产生的H_2O_2最高可达42.9μmol·L~(-1),循环7次后,苯胺和2-氨基-8-N-(4, 6-二氯-1, 3, 5-三嗪-2-基)氨基-1-萘酚-3, 6-二磺酸钠的去除率分别为48.6%和43.3%。傅里叶红外光谱分析表明,反应过程中AQS-PUF的结构损伤程度很小,可重复使用。由此可见,AQS-PUF应用在生物驱动的芬顿反应中,不仅降低了对生物产H_2O_2能力的要求,而且加速了厌氧还原柠檬酸铁过程,从而使AQS-PUF耦合生物驱动的芬顿反应在处理芳香胺类污染物方面具有潜在的应用价值。     

The effect of EURO-0 vehicle substitution on polycyclic aromatic hydrocarbon and carbon monoxide concentrations in an urban area

From 1994 to 2003, daily air concentrations of particle-bound polycyclic aromatic hydrocarbons (PAHs) and carbon monoxide (CO) were regularly monitored at two traffic-oriented sampling sites (A and B) in urban Genoa, Italy. The data were used to estimate effects on air quality in real situations due to progressive substitution of EURO-0 vehicles, started in 1993, with less-polluting vehicles (EURO-1, EURO-2), mainly gasoline vehicles with a catalyst. PAH profile classification and diagnostic PAH ratios were used to identify 345 samples of predominantly traffic origin. At both sites, CO and PAH daily concentrations decreased exponentially with time and the apparent half-life values calculated were 6.3 and 5.5 for CO and 3.7 and 3.5 years for PAHs at sites A and B, respectively. At site A, monitored for traffic intensity, multiple regression analyses confirmed that daily PAH and CO concentrations were positively correlated with the number of non-catalytic vehicles estimated to cross this site during sampling and negatively correlated with seasonal variables (air temperature, ozone concentration, relative air humidity). The reduction in air pollution estimated for complete substitution of non-catalytic gasoline vehicles was 89% for BaP, 85% for total PAHs and 69% for CO.     

不同类型机动车尾气中芳香烃化合物含量分析

首次对北京市9种车辆、5种燃料在不同工况下排放芳香烃化合物的特征．进行了定量研究。结果表明,车型、燃料、净化器及工况等因素对排放量产生影响,电喷车比化油器车芳香烃化合物排放量低;汽油车排放量最高,柴油车其次,LPG及CNG车排放量最低;使用净化器可以降低芳香烃排放量;不同工况对排放量的影响随车型,燃料类型的不同而不同。     

Analyses of known and new types of polyhalogenated aromatic substances in oven ash from recycled aluminium production

Persistent aromatic bromine, chlorine and mixed chlorine-bromine compounds were analysed from recycled aluminium smelter (ALS) ashes to explore the impact of brominated flame retardants (BFR) on their formation. Polybrominated diphenyl ethers (PBDE) were the most abundant original BFRs found. Induction furnace ash contained tetra- to octa-BDEs about 2000ng g(-1) in similar congener ratios as the original scrap, but contents of nona- and deca-BDEs were only 25 and 5ng g(-1) indicating their significant degradation in ALS process. In the most non-polar fraction, PCB levels and profiles were similar as earlier ALS ash samples in 1990s. The highest PCB level measured was that of deca-CB (450ng g(-1)) in the induction furnace ash. In this fraction, bromo compounds were non-detectable (<5ng g(-1)). Fraction of the most polar compounds (from reversed toluene elution of carbon column ("dioxin fraction") contained PCDDs, PCDFs and polychlorinated dibenzothiophenes (PCDTs) in similar amounts and congener profiles as earlier investigated ALS ash samples. Bromine-containing dioxin and furan congeners were not detected. From individual PCDDs and PCDFs, octaCDF was the most abundant (205ng g(-1)) in induction furnace ash. In this fraction, the original BFR, tetrabromo-bisphenol-A, was identified. Its level in the induction furnace ash was approximated to be 388ng g(-1). In addition, 12 novel brominated and chlorinated compounds were found as abundant (8-441ng g(-1) in the induction furnace ash) contaminants from the fraction. Four of them were bisphenol derivatives, five biphenylols, then octachlorofluorenone (OCFL) and octachlorobiphenylene (OCBP). Their structures or structure types were deduced from total low-resolution EI mass spectra by theoretical isotope cluster simulation (ICLU) and through known fragmentation rules.     

Thermal desorption of polychlorobiphenyls from contaminated soils and their hydrodechlorination using Pd- and Rh-supported catalysts

This paper reports about a combined technology for soil remediation from PCBs using the thermal desorption technique coupled with the catalytic hydrogenation of recovered PCBs. The reactor is a bench scale rotating desorption furnace through which nitrogen is flushed and used as carrier gas of desorbed PCBs. The latter are condensed into an hexane or hexane-acetone (1:1 v/v) solution that is then hydrogenated using phosphate-supported Pd or Rh as catalyst. The analysis of the treated soil, under variable operative conditions (temperature and desorption time), shows that the total (99.8%) decontamination from PCBs occurs. The recovery yield of the desorbed PCBs is better than 75% and the subsequent hydrogenation reaches 63% of the collected PCBs in 5h or 100% in 12h.     

Assessment of polychlorobiphenyls in human/poultry fat and in hair/plumage from a contaminated area

HR gas chromatographic PCB patterns in human/poultry fat tissue and hair/plumage in samples from a polluted region of Bela Krajina /Slovenia/ were investigated. The concentration of PCBs in human adipose tissue was found to be 9.62 μg/g in comparison to 0.67 μg/g in the adipose tissue of the non-exposed population, and in poultry fat 12.80 μg/g on a fat basis. The corresponding values in human hair and poultry plumage were 0.90 μg/g and 0.20 μg/g of original weight. The difference in PCB patterns between fat and hair can be attributed to the different routes of contamination (ingestion, air transport), to the time of exposure and physicochemical properties (octanol- water partition coefficients, Henry's law constants and the metabolism) of some individual congeners. Hair could be used for the assessment of ingestion of contaminated food and of the PCB levels in the air. In fat tissue PCB congeners with higher metabolic stability are enriched, whereas in hair PCB congeners with higher concentrations in air and with high octanol- water partition coefficients predominate.     

Synthesis of polybrominated diphenyl ethers via symmetrical tetra- and hexabrominated diphenyliodonium salts

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants (BFRs) which have become widespread environmental pollutants due to their persistence and bioaccumulativeness. Pure authentic PBDE congeners are required for chemical analysis, assessments of their chemical/physical properties and toxicological studies. We here report an improved method for synthesis of authentic PBDE congeners applying bromophenols and symmetrical brominated diphenyliodonium salts as building blocks. Altogether, 13 PBDEs were synthesized of which seven are new. The improved coupling reaction between the bromophenol and the brominated diphenyliodonium salts resulted in enhanced yields for PBDEs substituted with more than six bromine atoms. Also, improvements in iodonium salt synthesis made it possible to synthesize symmetrical hexabromodiphenyliodonium salts for the first time, i.e. 2,2',3,3',4,4'-, 2,2',4,4',5,5'- and 2,2',4,4',6,6'-hexabromodiphenyliodonium salts and they made it possible to prepare octabrominated PBDEs via the actual coupling method. All synthesized compounds were characterized by (1)H NMR, (13)C NMR spectra and by their melting points. Also, all products except for the diphenyliodonium salts were characterized by mass spectra in electron ionization mode.     

Synthesis of zirconia-immobilized copper chelates for catalytic decomposition of hydrogen peroxide and the oxidation of polycyclic aromatic hydrocarbons

Chelating sorbents with diethylenetriaminepenta(methylene-phosphonic acid) (DTPMPA) and ethylenediaminetetraacetic acid ligands immobilized on zirconia matrix were prepared and subsequently saturated with Cu(II). All the Cu chelates catalyzed decomposition of H(2)O(2) yielding highly reactive hydroxyl radicals. All of them were also able to catalyze degradation of polycyclic aromatic hydrocarbons (anthracene, benzo[a]pyrene and benzo[b]fluoranthene). The most effective DTPMPA-based catalysts G-32 and G-35 (10 mg ml(-1) with 100 mmol H(2)O(2)) caused almost complete decomposition of 15 ppm anthracene and benzo[a]pyrene during a five day catalytic cycle at 30 degrees C. Anthracene-1,4-dione was the main product of anthracene oxidation by all catalysts. The catalysts were active in several cycles without regeneration.     

Dissipation of polycyclic aromatic hydrocarbons (PAHs) in the rhizosphere: Synthesis through meta-analysis

Polycyclic aromatic hydrocarbons (PAHs) are widespread and persistent organic pollutants with high carcinogenic effect and toxicity; their behavior and fate in the soil-plant system have been widely investigated. In the present paper, meta-analysis was used to explore the interaction between plant growth and dissipation of PAHs in soil based on the large body of published literature. Plants have a promoting effect on PAH dissipation in soils. There was no difference in PAH dissipation between soils contaminated with single and mixed PAHs. However, plants had a more obvious effect on PAH dissipation in freshly-spiked soils than in long-term field-polluted soils. Additionally, a positive effect of the number of microbial populations capable of degrading PAHs was observed in the rhizosphere compared with the bulk soil. Our meta-analysis established the importance of the rhizosphere effect on PAH dissipation in variety of the soil-plant systems.     

Variation in indoor levels of polycyclic aromatic hydrocarbons from burning various biomass types in the traditional grass-roofed households in Western Kenya

Biomass burning as fuel in the traditional grass-roofed rural households of Western Province of Kenya in open fire places, in poorly ventilated conditions, lead to accumulation of soot under the roofs. This study characterized and quantified the polycyclic aromatic hydrocarbons (PAHs) in accumulated soot in these households and determined the variation in PAHs concentrations with fuel biomass type. Soot samples collected from the households were extracted, cleaned and analysed by gas chromatography. The PAHs were identified using retention times, verified by gas chromatographic mass spectral analysis and quantified from peak area responses using the internal standard method. The PAHs levels significantly varied (P ≤ 0.05) with biomass type in the order: dung ≥ indigenous trees ≥ exotic trees ≥ shrubs and crop residues. Use of dung and wood from indigenous trees as fuel should be discouraged since they are higher emitters (P ≤ 0.05) of carcinogenic PAHs.     

The toxicity of tetrachlorobenzyltoluenes (Ugilec 141) and polychlorobiphenyls (Aroclor 1254 and PCB-77) compared in Ah-responsive and Ah-nonresponsive mice

The toxicity of the PCB substitute Ugilec 141, a mixture of tetrachlorobenzyltoluenes (TCBTs), is compared with the toxicity of a commercial mixture of polychlorobiphenyls (Aroclor 1254) and with the model toxic PCB-congener 3,3',4,4',-tetrachlorobiphenyl (PCB-77) as a positive control. Alterations in liver weight, hepatic cytochrome P450 content and EROD and PROD activity, plasma thyroxin and retinol level, hepatic retinoid level and liver and thyroid pathology, have been studied in Ah-responsive and Ah-nonresponsive mice. Ugilec 141 proved to induce similar toxicological changes, qualitatively and quantitatively, to Aroclor 1254. Therefore Ugilec may pose a similar environmental and health risk as PCBs. The criteria for acceptance of new substances, like Ugilec 141, on the European market are discussed.     

Synthesis of functionalized mesoporous material from rice husk ash and its application in the removal of the polycyclic aromatic hydrocarbons

Environmental Science and Pollution Research - The rice husk ash (RHA) was used as an alternative source of silica for the synthesis of the functionalized mesoporous material, which was used in the...     

Predicting the contents of BTEX and MTBE for the three types of tollbooth at a highway toll station via the direct and indirect approaches

This study was set out to assess the contents of five volatile organic compounds (VOCs), including BTEX (the acronym for benzene, toluene, ethylbenzene, and xylene) and methyl tertiary-butyl ether (MTBE), in three types of tollbooth (including the car lane/ticket-collecting, car lane/cash-collecting, and bus/truck lane tollbooths) at a highway toll station via the direct and indirect approaches. For the direct approach, VOC samples were collected from the breathing zone of booth attendants at all selected tollbooths during the three workshifts. For samples collected during the dayshift, we found VOC contents of BTEX and MTBE in both the car lane/ticket-collecting (=6.23, 21.93, 3.24, 8.56, and 5.63 ppb, respectively) and car lane/cash-collecting tollbooths (=5.98, 21.71, 3.25, 8.59, and 6.04 ppb, respectively) were quite comparable, but both were significantly higher than that in the bus/truck lane tollbooth (=3.13, 13.91, 2.05, 4.52, and 2.70 ppb, respectively). The same pattern can also be found for the other two workshifts. For the indirect approach, we conducted multivariate regression analyses to predict VOC contents for any given type of tollbooth by using the four independent variables of the vehicle flowrate, wind speed, relative humidity, and air temperature. We found that, except the vehicle flowrate, the other three factors did not have a significant effect on VOC contents in the three types of tollbooth. In addition, the magnitudes of the effect of the vehicle flowrate on VOC contents for the three types of tollbooth were: car lane/cash-collecting>bus/truck lane>car lane/ticket-collecting. All regression results yielded R²-values in the range of 0.41−0.74 indicating that the developed indirect approach was able to predict VOC contents for three types of tollbooth.     

Assessing contamination of smoked sprats (Sprattus sprattus) with polycyclic aromatic hydrocarbons (PAHs) and changes in its level during storage in various types of packaging

The analysis of material used in this study demonstrated that the amount of polycyclic aromatic hydrocarbons (PAHs) in smoked sprats varies from the level below the lowest detection limit in muscles up to 9.99 µg kg^?1 of benzo[a]pyrene (BaP) in fish skin. Such a high level of PAHs in skin was reported only in one of six batches of sprats, while mean BaP level was at 1.69 µg kg^?1. Regardless such a high BaP level in skin, its concentration in muscles did not exceed the maximum acceptable level. The study objective was to assess to what extent packaging materials adsorb PAH compounds from food. Changes in the PAH levels were monitored in fish during their storage in packages made of various materials. The storage time was from 0 to 168 hours. The obtained results varied considerably, therefore their scatter did not allow to confirm unequivocally the preliminary hypothesis about the reduction of PAHs due to their migration to packaging material. However, analysis of the packaging used in this study demonstrated a significant increase in the level of total 16 PAHs. When high-density polyethylene (HDPE) packaging was analysed, a six-fold increase in the total 16 PAHs was observed comparing to the blank sample.     

Comparison of polycyclic aromatic hydrocarbons and nitropolycyclic aromatic hydrocarbons in airborne particulates collected in downtown and suburban Kanazawa,Japan

In this study, airborne particulates were collected at three sites, two in a downtown area and the other in a suburban area of Kanazawa, Japan in each season for 7 years. Two polycyclic aromatic hydrocarbons (PAHs), pyrene (Py) and benzo[a]pyrene (BaP) and four nitropolycyclic aromatic hydrocarbons (NPAHs), 1-nitropyrene (NP) and 1,3-, 1,6-, and 1,8-dinitropyrenes (DNP) were determined by high-performance liquid chromatography with fluorescence and chemiluminescence detection. At the downtown sites, the mean concentration of each DNP was about two orders of magnitude lower than that of 1-NP and more than three orders of magnitude lower than those of Py and BaP. This tendency reflected the composition of PAHs and NPAHs in diesel-engine exhaust particulates. Concentrations of these PAHs and NPAHs were higher at the downtown sites than at the suburban site, suggesting the dilution of these compounds during the transportation from the downtown to the suburban area. The concentration ratios of NPAHs to PAHs were larger at the downtown sites than at the suburban site. Studies using UV light and sunlight showed that degradation of NPAHs was faster than that of PAHs. Thus, the lower concentrations of NPAHs in the suburban sites may be due to their being photodegraded faster than PAHs during the atmospheric transportation from the downtown area to the suburban area.