菲降解菌的降解特性及酶促反应动力学研究

通过对取自MBR膜生物反应器中的活性污泥加入菲进行富集培养、驯化,分离、纯化出一株能以菲为唯一碳源和能源的短杆状革兰氏阴性菌J-1,细菌长2～5μm,宽1～3μm;研究了初始底物浓度、温度、pH对菌株J-1降解菲的影响,探讨了菌株J-1胞内酶对菲降解的底物抑制动力学。试验表明:菌株J-1在48h内能将不同浓度菲的水溶液中的菲完全降解;菲浓度增加,达到完全降解的时间延长。温度对细菌的降解能力影响较大,菌株J-1对菲降解的最佳温度为28℃。1.15mg·L-1的菲,28℃时48h内能完全降解,而相同时间内10℃时的降解率仅为36.65%。菌株J-1对pH的波动具有一定的适应性,pH在一定范围内(6.0～8.4)变化对菲降解的影响不大,降解反应的最佳pH为7.2。菌株J-1对菲的降解符合一级动力学反应方程。较高的底物浓度对酶促降解反应具有抑制作用,酶促反应的最大速率常数vm=1.17mg·L-1·h-1,米氏常数Km=61.70mg·L-1;底物抑制常数kS=49.60mg·L-1;最佳底物浓度[S]opt=55.32mg·L-1。     

Carbonyl products of the gas phase reaction of ozone with 1,1-disubstituted alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃+R₁R₂C=CH₂ (HCHO+R₁R₂COO)+(1–)(R₁COR₂+H₂COO) where formaldehyde and the ketone R₁ COR₂ are the primary carbonyls and R₁R₂COO and H₂COO are the corresponding biradicals. Measured values of were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H₂COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R₁R₂COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.     

Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

热液成矿作用的地质地球化学动力学——以胶东牟平-乳山金矿带为例

通过对胶东牟平—乳山热液脉状金,铅锌矿床成矿动力学控制规律的研究,说明了建立热液成矿反应体系的方法,并得出以下认识:（1）区域断裂构造活动,通过影响成矿反应体系的热力学性质和条件,控制元素的富集和分散。（2）热液成矿过程中容矿断裂活动可划分为两种作用方式:脆性破裂和韧—脆性张开,构成热液成矿的两种构造动力学环境。（3）热液成矿反应体系是一种开放的动态的热力学体系。断裂的脆性破裂阶段,使体系处于强烈的过饱和状态,矿质在远离平衡状态下快速结晶,加剧物质分异;在脆—韧性张开阶段,矿质在接近平衡态体系中缓慢晶出。（4）热液演化晚期,金在残余溶液中富集;当断裂再次发生构造脉动震颤时,早期形成的块状黄铁矿矿石碎裂,富金溶液充填其中,形成含裂隙金和晶隙金的富矿石。成矿体系热力学演化与构造动力学条件有利的匹配控制着富矿石的形成。     

北大别饶拔寨石榴辉石岩P-T-t轨迹及其构造意义

P-T-t轨迹作为变质岩的重要研究方法之一，对揭示岩石的构造演化过程具有重要意义。北大别饶拔寨镁铁-超镁铁岩形成的构造环境和就位过程长期以来尚存争议。本文通过岩相学观察、矿物化学研究和温压计计算，揭示出饶拔寨石榴辉石岩经历了四个变质演化阶段：1）超高压变质阶段（M1）：主要根据石榴子石中金红石的出溶，单斜辉石中石英的出溶和磷灰石中不透明矿物的出溶，结合前人研究，认为饶拔寨石榴辉石岩经历过超高压变质阶段（≥2.5GPa）；2）高压麻粒岩相阶段（M2）：矿物组合为石榴子石（变斑晶）和单斜辉石（基质）+斜长石（基质），记录的温压条件为T=648~700℃，P=1.47~1.94GPa；3）中压麻粒岩相阶段（M3）：以石榴子石外围发育的主要由斜方辉石+斜长石组成的内圈"白眼圈"为特征，形成的温压条件为T=781~796℃，P=0.92~0.98GPa；4）角闪岩相阶段（M4）：以石榴子石变斑晶周围发育的外圈"白眼圈"为特征，其矿物组合为角闪石+斜长石的后成合晶，形成的温压条件为T=663~685℃，P=0.50~0.58GPa。石榴辉石岩的锆石SIMS U-Pb定年得到了3组不同的交点年龄，分别为208.1~202.1Ma、227.6Ma和817.7Ma。根据锆石包裹体中角闪石+斜长石的组合，推断208.1~202.1Ma代表了角闪岩相变质年龄的下限，227.6Ma则是高压麻粒岩相的下限年龄，而新元古代年龄（817.7Ma）与区域上的变质岩原岩年龄一致，可能代表了其原岩年龄。结合前人研究，饶拔寨石榴辉石岩记录了顺时针的P-T-t轨迹，揭示了板片俯冲（超高压变质）-碰撞-折返（降压升温过程，~227Ma）-抬升（降压降温过程，208~202Ma）的完整过程。     

Na depletion in modern adakites via melt / rock reaction within the sub-arc mantle

Interaction between slab-derived melt and mantle peridotite and the role of slab melt as a metasomatizing agent in the sub-arc mantle is being increasingly recognized. Adakite, the slab melt erupted on the surface, usually exhibits anomalously high MgO, CaO, Cr and Ni contents that indicate interaction with mantle peridotitite. Here we note that Cenozoic adakites have Na₂O contents below 5.8 wt.% with ∼95% samples lower than 5.0 wt.%, and are generally depleted in this component relative to experimental basalt partial melts (mostly beyond 5.0 wt.% and up to 9.0 wt.% Na₂O) produced under 1.5-3.0 GPa conditions that are most relevant to adakite production. We interpret the adakite Na depletion to be also a consequence of the melt / rock reaction that takes place within the hot mantle wedge. During ascent and reaction with mantle peridotite, primary adakite melts gain mantle components MgO, CaO, Cr and Ni but lose Na₂O, SiO₂ and perhaps K₂O to the mantle, leading to Na-rich mantle metasomatism. Selective assimilation of predominately mantle clinopyroxene, some spinel and minor olivine at high T/P has been considered to be an important process in producing high-Mg adakites from primary low-Mg slab melts [Killian, R., Stern, C. R., 2002. Constraints on the interaction between slab melts and the mantle wedge from adakitic glass in peridotite xenoliths. Eur. J. Mineral. 14, 25-36]. In such a process, Na depletion in the assimilated melt is the result of dilution due to the increase in melt mass. Phase relationships in the reaction system siliceous melt + peridotite and quantitative calculation suggest that assimilation of mantle clinopyroxene, olivine and spinel and fractional crystallization of sodic amphibole and orthopyroxene, under conditions of moderate T/P and increasing melt mass, is also an important process that modifies the composition of adakites and causes the Na depletion.     

Quartz deformation mechanisms during Barrovian metamorphism: Implications from crystallographic orientation of different generations of quartz in pelites

The behaviour of quartz during metamorphism is studied based on two case studies from the Barrovian terrains of Sulitjelma in arctic Scandinavia and Loch Tay in the Central Highlands Dalradian of Scotland. Both terrains preserve evidence for metamorphism in pelites involving nucleation and growth of garnet at different times in the deformation history. Data are presented on the size, shape and crystallographic orientation of quartz preserved as inclusions in garnet and as grains in the surrounding matrix. While quartz-grains remain small and dispersed between mica grains, deformation appears to be dominated by grain-boundary sliding accommodated by dissolution–precipitation. At amphibolite facies, textural coarsening occurs by dissolution of small quartz grains and growth of larger quartz grains, coupled with segregation of quartz from mica. As a result, quartz deforms by dislocation creep, developing crystallographic preferred orientations (CPO) consistent with both coaxial and non-coaxial strain. Quartz CPOs with <0001> axes lying parallel to foliation and stretching direction are commonly developed, and best explained by mechanical rotation of inequant (detrital?) quartz grains. There is no evidence for selective entrapment of quartz inclusions in garnet on the basis of quartz crystallographic orientation.     

Adsorption of Pentachlorophenol onto Oxide and Clay Minerals： Surface Reaction Model and Environmental Implications

The adsorption of pentachlorophenol （PCP） onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH = 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation, meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmnir equation with the correlation coefficient R〉0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order： hematite 〉 lepidocrocite 〉 goethite 〉 kaolinite 〉 quartz 〉 montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China.     

25～75℃酸性NaCl溶液中方铅矿的溶解动力学

在25～75℃、pH=0.43～2.45的1mol/LNaCl溶液中进行了方铅矿的溶解动力学实验。发现在远平衡条件下,方铅矿的溶解速率r与氢离子活度犤H+犦呈线性关系,溶解速率方程(速率定律)为:r=k犤H+犦,即对H+而言,溶解反应为一级。其中速率常数k为2.344×10-7mol/m2·s(25℃)、1.380×10-6mol/m2·s(50℃)、7.079×10-6mol/m2·s(75℃)。溶解反应的活化能为43.54kJ/mol,方铅矿的溶解机理为表面化学反应,速率决定步骤为表面配合物的离解。