负载型金属氧化物催化剂分解臭氧的研究

用浸渍法制备了活性炭、γ-氧化铝和分子筛负载的MnO2,CuO,Fe2O3催化剂,并考察了它们对臭氧分解的催化性能。结果表明,MnO2催化剂优于CuO,Fe2O3,催化剂,活性炭为载体的催化剂优于γ-氧化铝和分子筛为载体的催化剂。温度对臭氧催化分解影响很大,在90℃时,MnO2／AC催化剂对臭氧的去除率可达80％以上。当存在一定浓度的水蒸气时,湿度越大,催化性能越差。当臭氧初始质量浓度低于50mg／L时,随着臭氧初始浓度的增加,催化性能有一定的下降。     

上海市城郊臭氧浓度变化分析及模拟预报

利用上海市普陀、南汇、淀山湖3个臭氧观测站2005年的臭氧小时观测资料,首先对市区和郊区的大气臭氧浓度的污染特征和变化情况进行了分析,结果表明,上海市郊区的臭氧浓度和污染水平高于市区,且臭氧浓度日变化在市区呈现明显的双峰现象,而郊区则是单峰型变化规律。然后运用基于统计学理论的最小二乘支持向量机（LSSVM）方法对3个站的日（24h）平均和白日（12h）平均以及日最大值臭氧浓度进行预测,得到较好的预报效果。     

我国4种重要海水经济鱼类热忍受研究

为了探明我国重要海水经济鱼类的热忍受能力,分别采用急性升温和缓慢升温两种方法对大黄鱼Pseudosciaena crocea、鲈鱼Lateolabrax joponicus、真鲷Pagrosomus major、黑鲷Sparus macrocephalus进行了室内热效应模拟实验.研究结果表明:在夏季自然起始水温为28.5℃条件下,大黄鱼,鲈鱼和黑鲷的急性升温半致死温度(LT50)分别为34.2,33.9和36.4℃;大黄鱼,鲈鱼,真鲷和黑鲷的临界热最大值(critical thermal maxima,CTmax)分别为35.0,34.7,32.7和36.8℃.     

乐山市臭氧生成与前体物之间的关系及其敏感性和控制分析

为初步了解乐山市臭氧生成的主要特征和科学管控,采用Pearson相关性分析法分析一年来臭氧及其前体物之间的相关性,并采用OBM模式和VOCS/NOX比值法分别讨论臭氧生成的敏感性和控制性特征.结果 表明:乐山市氮氧化物与臭氧在夏秋两季呈现正相关,在春冬两季呈负相关;从臭氧的敏感性分析得出臭氧生成潜势PO3-NO:夏季＞...     

Ozone episodes during and after the 2018 Chinese National Day holidays in Guangzhou: Implications for the control of precursor VOCs

The impact of reducing industrial emissions of volatile organic compounds (VOCs) on ozone (O₃) pollution is of wide concern particularly in highly industrialized megacities. In this study, O₃, nitrogen oxides (NOx) and VOCs were measured at an urban site in the Pearl River Delta region during the 2018 Chinese National Day Holidays and two after-holiday periods (one with ozone pollution and another without). O₃ pollution occurred throughout the 7-day holidays even industrial emissions of VOCs were passively reduced due to temporary factory shutdowns, and the toluene to benzene ratios dropped from ∼10 during non-holidays to ∼5 during the holidays. Box model (AtChem2-MCM) simulations with the input of observation data revealed that O₃ formation was all VOC-limited, and alkenes had the highest relative incremental reactivity (RIR) during the holiday and non-holiday O₃ episodes while aromatics had the highest RIR during the non-pollution period. Box model also demonstrated that even aromatics decreased proportionally to levels with near-zero contributions of industrial aromatic solvents, O₃ concentrations would only decrease by less than 20% during the holiday and non-holiday O₃ episodes and ozone pollution in the periods could not be eliminated. The results imply that controlling emissions of industrial aromatic solvents might be not enough to eliminate O₃ pollution in the region, and more attention should be paid to anthropogenic reactive alkenes. Isoprene and formaldehyde were among the top 3 species by RIRs in all the three pollution and non-pollution periods, suggesting substantial contribution to O₃ formation from biogenic VOCs.     

Ambient volatile organic compounds at a receptor site in the Pearl River Delta region: Variations, source apportionment and effects on ozone formation

We present the continuously measurements of volatile organic compounds（VOCs） at a receptor site（Wan Qing Sha, WQS） in the Pearl River Delta（PRD） region from September to November of 2017. The average mixing ratios of total VOCs（TVOCs） was 36.3 ± 27.9 ppbv with the dominant contribution from alkanes（55.5%）, followed by aromatics（33.3%）. The diurnal variation of TVOCs showed a strong photochemical consumption during daytime,resulting in the formation of ozone（O₃）. Five VOC sources were ...     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

Inactivation of Ascaris eggs in soil by microwave treatment compared to UV and ozone treatment

This study reports on the effect of microwave radiation for inactivation of Ascaris lumbricoides eggs in 25 g of soil compared to ultraviolet irradiation and ozone expose. Microwave radiation at 700 W with 14% water content (w/w) achieved approximately 2.5 log inactivation of eggs in soil within 60 s. On the other hand, UV irradiation at 3 mW cm⁻² with and without shaking soil for 3600 s achieved approximately 0.32 and 0.01 log inactivation of eggs, respectively. In ozone treatment, 0.13 log inactivation of eggs was achieved with 5.8 ± 0.7 mg L⁻¹ of dissolved ozone dose for 30 min in a continuous diffusion reactor. In addition, the inactivation of eggs by three disinfection techniques was conducted in water in order to compare the inactivation efficiency of eggs in soil. The inactivation efficiency of microwave radiation was found to be no significant difference between in soil and water. However, the inactivation efficiency of UV irradiation was significantly increased in water while in ozone expose there was no significant difference between in soil and water. Microwave treatment thus proved to be the most efficient method in controlling A. lumbricoides eggs in soil.     

Integral assessment of estrogenic potentials in sediment-associated samples

Background, aim, and scope  The enzyme-linked receptor assay (ELRA) detects estrogenic and anti-estrogenic effects at the molecular level of receptor binding and is a useful tool for the integrative assessment of ecotoxicological potentials caused by hormonally active agents (HAA) and endocrine disrupting compounds (EDC). The main advantage of the ELRA is its high sample throughput and its robustness against cytotoxicity and microbial contamination. After a methodological adaptation to salinity of the ELRA, according to the first part of this study, which increased its salinity tolerance and sensitivity for 17-β-estradiol, the optimised ELRA was used to investigate 13 native sediments characterised by different levels of salinity and chemical contamination. The applicability of the ELRA for routine analysis in environmental assessment was evaluated. Salinity is often a critical factor for bioassays in ecotoxicological sediment assessment. Therefore, salinity of the samples was additionally adjusted to different levels to characterise its influence on elution and binding processes of receptor-binding substances. Materials and methods  The ELRA was carried out with the human estrogen receptor α (ER) in a 96-well microplate format using the experimental setup known from the competitive immunoassay based on ligand–protein interaction. It is an important improvement that a physiologically relevant receptor was used as a linking protein instead of an antibody. The microplates were coated with a 17-β-estradiol-BSA conjugate, and dilution series of estradiol and of native sediment samples were added and incubated with the ER. After a washing step, a biotinylated mouse anti-ER antibody was added to each well. Receptor binding to estradiol, agonistic and antagonistic receptor binding, were determined by a streptavidin-POD-biotin complex with subsequent measurement of the peroxidase activity at the wavelength of 450 nm using a commercial ELISA multiplate reader. The sediment elutriates and pore water samples of sediments were tested in a dilution series to evaluate at which dilution step the receptor-binding potential ends. In the elution process (see Section 2.1 to 2.2), a method was developed to adjust the salinity to the levels of the reference testings, which offers an appropriate option to adjust the salinity in both directions. Statistical evaluation was made with a combination of the Mann–Whitney U test and the pT-method. Results  This part of the study characterised the environmental factor ‘salinity’ for prospective applications of the ELRA. Using reference substances such as 17-β-estradiol, the ELRA showed sigmoid concentration-effect relations over a broad range from 0.05 μg/l to 100 μg/l under physiological conditions. After methodological optimisation, both sensitivity and tolerance of the assay against salinity could be significantly raised, and the ELRA became applicable under salinity conditions up to concentrations of 20.5‰. The mean relative inter-test error (n = 3) was around 11% with reference substances and below 5% for single sediments elutriates in three replicates each. For sediment testings, the pore water and different salinity-adjusted elutriates of 13 sediments were used. A clear differentiation of the receptor-binding potential could be reached by application of the pT-method. Thereby, pT-values from one to six could be assigned to the sediments, and the deviation caused by the different salinity conditions was one pT-value. The mean standard deviation in the salinity adaptation procedure of the elutriates was below 5%. Discussion  Although the ELRA has already been used for assessments of wastewater, sludge and soil, its applicability for samples to different salinity levels has not been investigated so far. Even if the ELRA is not as sensitive as the E-screen or the YES-assay, with regard to reference substances like 17-β-estradiol, it is a very useful tool for pre-screening, because it is able to integrate both estrogenic as well as anti-estrogenic receptor-binding effects. According to the results of sediment testing, and given the integrative power to detect different directions of effects, the ELRA shows sufficient sensitivity and salinity tolerance to discriminate receptor-binding potentials in environmental samples. Conclusions  The optimised ELRA assay is a fast, cost-effective, reliable and highly reproducible tool that can be used for high-throughput screening in a microplate format in detecting both estrogenic and anti-estrogenic effects. Additionally, the ELRA is robust against microbial contaminations, and is not susceptible towards cytotoxic interferences like the common cell-culture methods. The general applicability and sufficient sensitivity of the ELRA was shown in freshwater environments. Marine and brackish samples can be measured up to salinity levels of 20.5‰. Recommendations and perspectives  In view of the proven sensitivity, functionality and the fastness of the ELRA, it is recommendable to standardise the test method. At the moment, no adequate in vitro test procedure exists which is standardised to DIN or ISO levels. The E-screen and the yeast estrogen/androgen screens (YES/YAS) sometimes underlie strong cytotoxic effects, as reported in the first part of this study. Further development of an ELRA assay using human androgen receptors appears to be very promising to gain information about androgenic and anti-androgenic effects, too. This would offer a possibility to use the ELRA as a fast and reliable pre-screening tool for the detection of endocrine potentials, thus minimising time and cost-expensive animal experiments.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.