Kinetics of OH-initiated oxidation of oxygenated organic compounds in the aqueous phase: new rate constants, structure–activity relationships and atmospheric implications

The kinetics of OH oxidation of several organic compounds of atmospheric relevance were measured in the aqueous phase. Relative kinetics were performed using various organic references and OH sources. After validation of the protocol, temperature-dependent rate constants for the reactions of OH radical with ethyl ter-butyl ether (, E_a/R=580 (±560) K), n-butyl acetate ( (±0.4)×10⁹ M⁻¹ s⁻¹, E_a/R=1000 (±200) K), acetone ( (±0.05)×10⁹ M⁻¹ s⁻¹, E_a/R=1400 (±500) K), methyl ethyl ketone (, E_a/R=1200 (±200) K), methyl iso-butyl ketone (, E_a/R=1200 (±300) K) and methylglyoxal (, E_a/R=1100 (±300) K) were determined. A non-Arrhenius behavior was found for phenol, in good agreement with the contribution of an OH addition to the mechanism, which also includes H-abstraction by OH radicals. Global rate constants of acetaldehyde, propionaldehyde, butyraldehyde and valeraldehyde were studied at 298 K only, as these compounds partly hydrate in the aqueous phase. All the obtained data (except those of phenol) complemented by literature data were used to investigate three methods to estimate rate constants for H-abstraction reactions of OH radicals in aqueous solutions when measured data were not available: Evans-Polanyi-type correlations, comparisons with gas-phase data, structure activity relationships (SAR). The results show that the SAR method is promising; however, the data set is currently too small to extend this method to temperatures other than 298 K. The atmospheric impact of aqueous phase OH oxidation of water-soluble organic compounds is discussed with the determination of their global atmospheric lifetimes, taking into account both gas- and aqueous-phase reactivities. The results show that atmospheric droplets can act as powerful photoreactors to eliminate soluble organic compounds from the atmosphere.     

蚯蚓抗菌肽EABP-1的分离纯化及部分性质

经硫酸铵沉淀、超滤和阳离子交换分离 ,得到了一蚯蚓抗菌肽EABP 1,该肽的最大紫外吸收在 2 77.16nm ,SDS PAGE结果表明其Mr≈ 2 0× 10 3,精确的分子量没有确定 .最小抑菌浓度 (ρMIC)实验表明 ,EABP 1对鹑鸡肠球菌(Enterococcusgallinarum)、绿脓杆菌 (Pseudomonaspyocyanea)、鲍氏不动 (Acinetobacterbaumanii)、土生克雷伯 (Kleb siellaterrigena)的 ρMIC为 11.4μg/mL ,对粪肠球菌 (Enterococcusfaecalis)的 ρMIC为 2 2 .8μg/mL ,对真菌白色念株菌(Candidaalbicans)没有表现为完全的抑制作用 .图 1表 1参 10     

青岛市区土壤天然放射性核素的外照射水平估算研究

城市的辐射环境质量对于人居和发展规划有重要意义。利用伽玛能谱仪对青岛市区内的天然放射性核素进行了大规模高密度的现场测量,采用Beck公式计算了离地面1m高处的空气吸收剂量率,进而计算了外照射年有效剂量、外照射指数和等效镭浓度,对研究区的外照射水平进行了系统的评价。与和其他国家全国比较,虽然该区的空气吸收剂量率较高,但是其他衡量天然放射性核素外照射水平的指标均在容许范围之内。因此该区属于外照射水平的安全区域,人居环境不受影响。     

绿黄隆、甲黄隆在江苏省农区5种土壤中残留活性的研究

采用改进的玉米主根长土培生测法，研究绿黄隆、甲黄隆在江苏省典型农区土壤中残留活性。结果表明，两种除草剂在５种土壤中剂量与玉米主根长抑制率之间皆达极显著相关，土壤ｐＨ和有机质含量是主要影响因素，碱性轻质土壤中活性较高，酸性重质土壤中活性较低，活性大小顺序为：黄潮土＞高沙土＞砂姜黑土＞滨海盐土＞太湖水稻土。     

共生菌B1+B2聚乙烯醇降解酶活性优化研究

从PVA降解酶的角度对本实验室前期实验筛选到的共生菌B1 B2进行了研究.在考察共生菌的基本生长和酶活的关系以及PVA降解酶和氧化酶的关系后,研究了不同的营养条件对PVA降解酶活性的影响.通过对主要营养条件的单因素考察,设计正交实验,优化出影响PVA降解酶活性的最佳主要营养条件为酵母汁0.2gL-1、硝酸铵0.2gL-1、葡萄糖0.5gL-1.采用优化条件进行验证实验,PVA降解酶活性(1.61UmL-1)高于正交实验中的最高酶活(1.56UmL-1),研究结果对发酵生产PVA降解酶和提高该菌在PVA废水处理中的降解性能有一定的价值.图5表3参11     

岛屿生境下苦槠丛枝菌根(AM)与根际土壤磷酸酶活性的相关性研究

以浙江千岛湖典型生境片断化区域苦槠(Castanopsis sclerophylla)为材料,研究了水库形成后岛屿化导致的群落生境差异对苦槠AM侵染率的影响以及AM侵染率与根际土壤磷酸酶活性的相关性.结果表明,以生境面积为因子进行单因素方差分析,则不同岛屿生境对苦槠AM侵染率影响差异不显著;但以Pearson相关性分析,AM侵染率与岛屿面积之间呈显著负相关.苦槠根际土壤酸性磷酸酶活性在中岛、大岛与陆地间差异显著,但与AM侵染率之间无显著相关性.     

低温生物膜和活性污泥的生物活性比较

通过 (5± 1)℃下生物膜系统 (BF)和活性污泥系统 (AS)处理生活污水长达 8个多月的运行 ,对比研究了两系统的生物活性 .结果表明 ,活性污泥不仅生物活性较高 ,而且具有更有利的传质条件 .在水力停留时间HRT =8h的条件下 ,生物膜和活性污泥胞外分泌物中的还原糖含量分别为 1.75 %及 1.9% ,挥发性污泥组分 (VSS)中的ATP含量分别为 1.0 8mg/ g及 1.4 3mg/g ;电镜检测结果表明 ,生物膜结构致密 ,而活性污泥疏松多孔有利于物质传递 .图 5表 2参 14     

Effects of Cd2+ and Pb2+ on the substrate biofilms in the integrated vertical-flow constructed wetland

The effects of single Cd~(2+)and Pb~(2+),and combined Cd~(2+)and Pb~(2+)on dehydrogenase activity and polysaccharide content of the substrate biofilms in the integrated vertical-flow constructed wetland(IVCW)were studied.Dehydrogenase activities decreased linearly with the increasing concentrations of Cd~(2+)and Pb~(2+)at different times(6,24,72,and 120 h).The activities at both 6 and 24 h were significantly higher than that at 72 and 120 h in the case of single and combined treatments.The single Cd~(2+)...     

Relation of hepatic EROD activity and CYP1A level in Sebastiscus marmoratus exposed to benzo[a]pyrene

This study was designed to investigate the in vivo effects of benzo[a]pyrene (BaP) on hepatic ethoxyresorufin-O-deethylase (EROD) activity and its correlation with cytochrome P450 1A (CYP1A) protein levels in Sebastiscus marmoratus, which were exposed through a water column to BaP (10, 100, 1000 ng/L, respectively) or were treated with intraperitoneal injections of BaP (0.5, 1, 5, 10 mg/kg, respectively) every 7 d. The results showed that after 25 d of waterborne exposure to 1000 ng/L BaP, fish hepatic CYP1A levels and EROD activity were significantly induced. In contrast, EROD activity was not altered 7 d after second ip injections, whereas, CYP1A protein levels were increased. Dose-dependent increase of biliary BaP metabolites demonstrated that the catalytic activity of CYP1A was induced by treatment with BaP. The lowest observable effect concentration with regard to biliary BaP metabolites (100 ng/L) was much lower than that with reference to EROD activity (1000 ng/L). The results suggest that biliary polycyclic aromatic hydrocarbon (PAH) metabolites were shown to better reflect the contamination gradients of PAHs than EROD activity. It appeared to be necessary to measure CYP1A protein levels to complement the EROD activity in relevant toxicological assessments.     

Characteristics and ozone formation potential of volatile organic compounds in emissions from a typical Chinese coking plant

Coking industry is an important volatile organic compounds (VOCs) emission source in China, however, detailed information on VOCs emissions is lacking. Therefore, we selected a typical mechanized coking plant and collected air samples according to the Emission Standard of Pollutants for Coking Chemical Industry (GB16171-2012). Using gas chromatography-mass spectrometry method, we analyzed the VOCs in the air samples, and applied maximum increment reactivity (MIR) rule to estimate ozone formation potential (OFP) of the VOCs emitted from the coke production. More than 90 VOCs species were detected from the coking plant, including alkanes, alkenes, alkynes, aromatic hydrocarbons, halogenated hydrocarbons and oxygenated VOCs. The concentrations of VOCs (ρ(VOCs)) generated at different stages of the coking process are significantly different. ρ(VOCs) from coke oven chimney had the highest concentration (87.1 mg/m³), followed by coke pushing (4.0 mg/m³), coal charging (3.3 mg/m³) and coke oven tops (1.1 mg/m³). VOCs species emitted from the coke production processes were dominated by alkanes and alkenes, but the composition proportions were different at the different stages. Alkenes were the most abundant emission species in flue gases of the coke oven chimney accounting for up to 66% of the total VOCs, while the VOCs emissions from coke pushing and coal charging were dominated by alkanes (36% and 42%, respectively), and the alkanes and alkenes emitted from coke oven top were similar (31% and 29%, respectively). Based on above results, reduction of VOCs emissions from coke oven chimney flue gases is suggested to be an effective measure, especially for alkenes.