化学反应危害的识别及预防控制

1 问题的提出 化学反应过程常常由于一些非预期的因素,如进料错误、杂质、反应器过热、冷却系统故障、外部火灾和搅拌失效等,使反应偏离正常操作范围,造成异常放热.若此时无法将所产生的热量迅速移除,则可能导致加速反应,形成自加速放热现象.     

有机气溶胶组分对六氯苯光解的影响

以高压汞灯为光源,分别研究了六氯苯在正己烷和邻苯二甲酸二异辛酯(DIOP)为有机气溶胶表层模拟介质时的光解,发现六氯苯在正己烷和DIOP中的光解半衰期分别约为<5 min和5 h,相差70倍以上.研究发现蒽醌和甲氧酚类气溶胶组分对六氯苯的光解具有光敏化作用,其反应机制可能分别为能量转移和抽氢反应.六氯苯光解的主要产物是五氯酚.     

Study of metabolites from the degradation of polycyclic aromatic hydrocarbons (PAHs) by bacterial consortium enriched from mangrove sediments

The PAH metabolites produced during degradation of fluorene, phenanthrene and pyrene by a bacterial consortium enriched from mangrove sediments were analyzed using the on-fiber silylation solid-phase microextraction (SPME) combining with gas chromatography–mass spectrometry (GC–MS) method. Seventeen metabolites at trace levels were identified in different PAH degradation cultures based on the full scan mass spectra. In fluorene degradation cultures, 1-, 2-, 3- and 9-hydroxyfluorene, fluorenone, and phthalic acid were detected. In phenanthrene and pyrene degradation cultures, various common metabolites such as phenanthrene and pyrene dihydrodiols, mono-hydroxy phenanthrene, dihydroxy pyrene, lactone and 4-hydroxyphenanthrene, methyl ester, and phthalic acid were found. The detection of various common and novel metabolites demonstrates that SPME combining with GC–MS is a quick and convenient method for identification as well as monitoring the real time changes of metabolite concentrations throughout the degradation processes. The knowledge of PAH metabolic pathways and kinetics within indigenous bacterial consortium enriched from mangrove sediments contributes to enhance the bioremediation efficiency of PAH in real environment.     

Emission of PCDD/Fs and dioxin-like PCBs from metallurgy industries in S. Korea

The metallurgy industry and municipal waste incinerators are considered the main sources of polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs) in many countries. This study investigated the emission factors and total emissions of PCDD/Fs and dioxin-like polychlorinated biphenyls (PCBs) emitted from metallurgy industries (including ferrous and nonferrous foundries) in Korea. The toxic equivalency (TEQ) emission factor of PCDD/Fs was the highest for secondary copper production, at 24451 ng I-TEQ/ton. The total estimated emissions of PCDD/Fs from these sources were 35.259 g I-TEQ/yr, comprising 0.088 g I-TEQ/yr from ferrous foundries, 31.713 g I-TEQ/yr from copper production, 1.716 g I-TEQ/yr from lead production, 0.111 g I-TEQ/yr from zinc production, and 1.631 g I-TEQ/yr from aluminum production. The total estimated annual amounts of dioxin-like PCBs emitted from these sources were 13.260 g WHO-TEQ/yr, comprising 0.014 g WHO-TEQ/yr from ferrous foundries, 12.675 g WHO-TEQ/yr from copper production, 0.170 g WHO-TEQ/yr from lead production, 0.017 g WHO-TEQ/yr from zinc production, and 0.384 g WHO-TEQ/yr from aluminum production. The highest emission factor was found for secondary copper smelting, at 9770 ng WHO-TEQ/ton.     

The effects of elevated CO2 on clonal growth and nutrient content of submerge plant Vallisneria spinulosa

An approximately four months long glasshouse experiment was conducted to examine the effects of elevated carbon dioxide (CO(2)) concentration (1,000 +/- 50 micromol mol(-1)) in the atmosphere on biomass accumulation and allocation pattern, clonal growth and nitrogen (N), phosphorus (P) accumulation by the submerged plant Vallisneria spinulosa Yan. Elevated CO(2) significantly increased V. spinulosa total fresh biomass ( approximately 130%) after 120 days, due to more biomass accumulation in all morphological organs than in those at ambient CO(2) (390 +/- 20 micromol mol(-1)). About 75% of the additional total biomass at elevated CO(2) was accounted for by leaf and rhizome (above ground) biomass and only 25% of it belonged to root and turion (below ground). However, the turions biomass exhibited a greater increase rate than that of organ above ground, which caused reduction in the above/below ground biomass ratio. The clonal growth of V. spinulosa responded positively to elevated CO(2). The number of primary ramets increased up to 1.4-folds at elevated CO(2) and induced a dense growth pattern. For nutrients absorption, concentration of N in leaf and in turion was significantly (p 相似文献   

Chemical characterization of fine particles from on-road vehicles in the Wutong tunnel in Shenzhen, China

Vehicle populations in China have been increasing sharply since 1990s. Vehicle emissions including various gaseous pollutants and particulate matter cause deterioration of air quality. However, measurements of particulate mater from on-road vehicles in China are scarcely reported, and thus the chemical compositions of particles emitted from vehicles in China are unknown. In this research, tunnel experiments were performed to measure PM2.5 in the Wutong tunnel, Shenzhen, China. Detailed PM2.5 chemical compositions, with organic compounds determined by GC/MS, in the tunnel were presented. Elemental carbon and organic matter composed 63% and 34% of the total PM2.5 mass in the Wutong tunnel, respectively. Alkanes, PAHs, hopanes, fatty acids, and dicarboxylic acids were the major identified organic compounds, and their source profiles in the PM2.5 in the Wutong tunnel were characterized. The comparisons of our measurements with those in the literature were also made to demonstrate the characteristics of the vehicle source profiles in the Wutong tunnel. The experimental results in this paper can improve understanding of particulate matter emitted from vehicles in China.     

Formation and instability of aerobic granules under high organic loading conditions

The cultivation and instability of aerobic granular sludge in a sequencing batch reactor under high loading conditions were investigated. Compact bacteria-dominated aerobic granules with a mean diameter of 1 mm were formed at a chemical oxygen demand (COD) loading rate of 6.0 kg m(-3) d(-1) within 30 d. However, the compact bacteria-dominated aerobic granules were not stable and transited to large-sized filamentous ones gradually. With the formation of bacteria-dominated granules, the hydrophobicity and specific gravity of the sludge increased. When the granules were transited to filamentous ones, the hydrophobicity and specific gravity decreased. Both granules had a high COD removal efficiency, excellent settling ability and showed a clear, regular round-shaped outline. After the filamentous granules reached a diameter of 16 mm, due to the mass transfer limitation and the possible presence of anaerobes in the inner part of the granules, they began to disintegrate and be washed out of the reactor, follow by failure of the reactor.     

Polycyclic aromatic hydrocarbons (PAHs) in the aerosol in Beijing, China, measured by aminopropylsilane chemically-bonded stationary-phase column chromatography and HPLC/fluorescence detection

We developed a useful analytical method for the determination of polycyclic aromatic hydrocarbons (PAH) concentrations in the aerosol of China. We used an accelerated solvent extraction (ASE) method for the extraction of PAHs from the aerosol samples, in order to reduce the extraction time and the solvent volume used. The optimum purification method was developed, with aminopropylsilane chemically-bonded stationary-phase column chromatography, in order to remove many co-extractives which cannot be removed by conventional purification methods using silica-gel column chromatography. HPLC/fluorescence detection (FLD) was adopted as the analytical method, because it has very high sensitivity to PAH and it is easy to install, operate, and maintain as compared with GC/MS. With the analytical method developed in this study, the recovery and precision (RSD) for most of the PAHs ranged from 75% to 129% and from 2.8% to 22.7%, respectively. The concentrations of PAHs in the aerosol samples collected from October 2003 to April 2005 in Beijing, China were determined using the newly developed method. SigmaPAHs, which is the sum of the concentrations of all detected PAHs, was 177.8 +/- 239.9 ng m(-3) (n = 64). The SigmaPAHs concentration in the heating season (305.1 +/- 279.0 ng m(-3), n = 33) was 7.2 times higher than that in the non-heating season (42.3 +/- 32.0 ng m(-3), n = 31). These strong seasonal variations in atmospheric PAH concentration are possibly due to coal combustion for residential heating in winter.     

Photocatalytic oxidation of triclosan

In the spring of 2003, there was an outbreak of the severe respiratory syndrome (SARS) in Hong Kong. Health concerns have thus triggered an increased and predominant use of various types of household cleansing agents such as triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol). However, it has been reported recently that triclosan could be photochemically converted to toxic 2,8-dichlorodibenzo-p-dioxin (2,8-Cl(2)DD) in the environment. It is therefore necessary to develop environmentally friendly methods for the treatment of triclosan. To this end, photocatalytic degradation of triclosan in aqueous solution was conducted using TiO(2) (Degussa P25) under irradiation of UV light (lambda < 365 nm). It was found that triclosan could be degraded by this approach. Hydrogen peroxide was added to enhance the degradation process, and the optimal initial hydrogen peroxide concentration for triclosan degradation was 0.005% (w/v). Product identification indicated that triclosan oxidation occurred at its phenol moiety and yielded quinone and hydroquinone intermediates. The formation of a dichlorophenol intermediate in triclosan degradation suggested bond-breaking of the ether linkage occurred during the process. Moreover, no chlorinated dibenzo-p-dioxin congener was detected. These findings confirm that the photocatalytic degradation of triclosan is an environmentally friendly process.