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.     

高氨氮对厌氧生物法处理城市垃圾渗沥液的影响

研究了高浓度氨氮对厌氧膜生物法处理城市垃圾渗沥液的影响。结果表明,COD去除率、沼气产量、沼气产率、辅酶F420和最大比产甲烷活性均随氨氮浓度的增加而减小;当氨氮浓度<3600mg/L时,不会对厌氧膜生物反应器的运行产生明显的影响;氨氮对厌氧污泥产甲烷活性的50%抑制浓度为4350mg/L;高浓度氨氮会造成系统VFA浓度增加;当氨氮浓度由4800mg/L降低到2000mg/L后,受重度抑制的厌氧微生物的活性可以在20d里恢复到未受抑制时的活性水平。     

不同挂膜方式对人工快渗系统处理性能的影响

针对人工快渗系统运行启动时间普遍较长的问题,研究了自然挂膜、活性污泥挂膜和优势菌挂膜3种方式对系统处理性能及微生物数量和酶活性的影响。结果表明,采用优势菌挂膜的启动时间比自然挂膜和活性污泥挂膜分别缩短了35 d、17 d,从第38天起,COD去除率稳定在90%以上,系统的抗水力负荷冲击能力也较强;TN去除率较自然挂膜和活性污泥挂膜分别提高了48.1%、37.9%,亚硝化菌和反硝化菌数量的增加为短程硝化反硝化脱氮提供了基础;细菌、真菌、放线菌的总量比自然挂膜和活性污泥挂膜分别高出1.66倍、1.02倍,纤维素酶、脲酶活性也相应提升,微生物的空间分布、酶的活性与各人工快渗系统对污染物的去除效果表现出一致性。     

Atrazine,chlorpyrifos, and iprodione effect on the biodiversity of bacteria,actinomycetes, and fungi in a pilot biopurification system with a green cover

The use of biopurification systems can mitigate the effects of pesticide contamination on farms. The primary aim of this study was to evaluate the effect of pesticide dissipation on microbial communities in a pilot biopurification system. The pesticide dissipation of atrazine, chlorpyrifos and iprodione (35 mg kg^?1 active ingredient [a.i.]) and biological activity were determined for 40 days. The microbial communities (bacteria, actinomycetes and fungi) were analyzed using denaturing gradient gel electrophoresis (DGGE). In general, pesticide dissipation was the highest by day 5 and reached 95%. The pesticides did not affect biological activity during the experiment. The structure of the actinomycete and bacterial communities in the rhizosphere was more stable during the evaluation than that in the communities in the control without pesticides. The rhizosphere fungal communities, detected using DGGE, showed small and transitory shifts with time. To conclude, rhizosphere microbial communities were not affected during pesticide dissipation in a pilot biopurification system.     

多环芳烃光解活性的量子化学研究

应用量子化学从头算HF／6-311 G(d)和B3LYP／6-311 G(d)方法计算了16种PAHs的多种量子化学参数,选取六种参数为分子结构的描述符,采用最小二乘法对16种PAHs的光解半衰期进行逐步多元线性回归分析,得到两个PAHs光解半衰期的QSAR模型,模型具有较高的相关系数,可有效地用于预测PAHs的光解半衰期,结果表明,HF方法所得模型优于B3LYP方法所得的模型,所得模型与基于半经验PM3算法的QSAR模型相比较,HF从头算方法所建立的QSAR模型比半经验PM3算法的结果要好,在所考查的诸多参数中,分子最高占有轨道特征值EHOMO对PAHs光解半衰期起着决定作用,最后,运用所得模型预测了3种PAHs的光解半衰期。     

汞和硒对剑尾鱼Na+/K+-ATPase活性的影响

应用浸浴法研究汞(Hg)对剑尾鱼(XiphophorushelleriHeckel)鳃和肝脏Na /K ATPase活性的影响以及硒(Se)对机体Na /K ATPase汞中毒的保护作用.结果表明,Hg和Se对剑尾鱼96hLC50分别为0.84mg/L和6.64mg/L.Hg对剑尾鱼鳃和肝脏Na /K ATPase活性的影响相似,与对照组相比,处理d1时低浓度Hg组鳃和肝脏ATPase活性没有明显变化(P>0.05),但高浓度Hg组ATPase活性变化显著(P<0.05),至d3和d5时,酶活性均极显著下降(P<0.01),鱼鳃和肝脏酶活性分别下降32%和60%,表明Hg处理对鳃和肝脏Na /K ATPase活性具有抑制作用.单独加Se组鱼鳃和肝脏Na /K ATPase活性在d3和d5显著提高(P<0.01).Hg Se组与Hg组相比,酶活性有明显差异(P<0.05或P<0.01),Se对剑尾鱼Hg中毒具有保护作用.剑尾鱼鳃和肝细胞Na /K ATPase活性可作为对水环境汞污染效应环境风险评价(ERA)的有效生物学标记.表2参16     

麻疯树核糖体失活蛋白(curcin)的化学修饰与其活性的关系

通过无细胞体系蛋白合成抑制活性的测定,结合荧光光谱和圆二色谱技术,对麻疯树核糖体失活蛋白(cur-c in)部分氨基酸残基进行特异性化学修饰,探讨维持curc in活性的必需氨基酸基团及修饰对curc in结构的影响.结果表明,组氨酸和半胱氨酸的修饰对活性没有影响.色氨酸和赖氨酸的修饰使curc in的活性分别下降了50%和100%,表明色氨酸和赖氨酸是维持curc in活性的重要残基.精氨酸修饰导致curc in的抑制活性完全丧失,内源荧光强度下降,最大发射波长发生红移,CD谱发生显著变化;表明精氨酸也是维持curc in活性的必需残基,并且对空间结构影响较大,推测对精氨酸的修饰破坏了精氨酸与其它基团的连接,导致curc in分子结构发生改变,失去和底物结合的能力,因而活性丧失.图3表1参34     

腐殖酸存在下镉和铅对土壤脱氢酶活性的影响

采用室内培养试验研究Cd和Pb污染红壤添加不同组分腐殖酸后,其脱氢酶活性的变化,结果表明,红壤遭受镉和铅污染后,脱氢酶活性显著降低,然而腐殖酸特别是胡敏酸的存在能够使脱氢酶活性得到显著回升,说明腐殖酸与重金属的相互作用对重金属污染土壤微生物活性的改善和修复功能,对土壤有一定的去污降毒作用.不同腐殖酸组分的效应大小为:灰色胡敏酸(GHA)>棕色胡敏酸(BHA)>富里酸(FA),表明分子量愈大、芳构化程度愈高的腐殖酸组分,其对重金属的钝化愈强,从而解除土壤重金属对生物毒害的能力愈强.     

Tactics, effectiveness and avoidance of mate guarding in the blue-footed booby (Sula nebouxii)

We examined the dynamics and avoidance of mate guarding, by males and females, in the blue-footed booby, in which the two social mates are usually simultaneously present on the territory but each of them is unmonitored by the other for one-quarter of its time. Both sexes were promiscuous and liable to switch mates. Cuckolded individuals did not increase their overall presence on the territory, but in response to the extra-pair (EP) courtships of their mates, both sexes doubled their rate of intra-pair (IP) courtship and sometimes showed aggression. The male or female's presence depressed the social mate's EP activity, but intra-pair courtship had no such effect, tending even to propitiate that EP activity. Similarly, when females responded to their social mates' EP courtship with approach or aggression, disruption of EP activity was short-lived. Promiscuous females modified their diurnal pattern of attendance, as if attempting to sidestep monitoring by their mates, but cuckolded males matched the modification. Both sexes tended to perform their EP activities at a distance when their mates were present, possibly to evade monitoring or disruption by their mates. Male and female boobies cannot monitor their mates continuously, they do little to facultatively adjust their presence on territory to the risk of infidelity, and their immediate responses to overt infidelity have only the briefest impact; but the information they acquire while monitoring their mates may be critical to constraining their mates' infidelity and also to calibrating their own reproductive investment.     

不同强度的声波对猕猴桃试管苗根系发育的影响

通过用不同强度的声波刺激中华猕猴桃(Actinidia chinensis)的组培试管苗，研究模拟声场的力学刺激对木本植物根系发育的生物学效应．结果表明：适度强度的声波刺激(100dB左右)可促进猕猴桃试管苗根系的生长发育，而根系质膜的通透性也相应降低以阻挡外界有害物质的侵入，使根系活力以及与之相关的根系总长、分根数等指标明显增强；但当声波强度超过一定范围后，对根系发育的促进效应就受到明显的抑制，当110dB时甚至开始抑制试管苗的根系发育．从细胞和分子生物学水平对环境应力影响根系发育的可能机理进行了讨论．图2表1参13