Occurrence of Organic Matter in Calcimicrobialites across Permian-Triassic Boundary in Huayingshan Region, Sichuan, South China

Calcimicrobialites across the Permian-Triassic boundary in Huayingshan (华蓥山) region were investigated using the fluorescence microscopic measurements to understand the occurrence of organic matter. The microbialites are composed of micrite matrix and coarse spar cement. Abundant rhombic or magnetic needle-like carbonate minerals were observed adrift within the cement. The fluorescence microscopic measurement indicates the micrite matrix in microbialites shows the most abundant organic matter, with the rhombic or magnetic needle-like carbonate minerals and coarse spar cement coming to the 2nd and the 3rd, respectively. Organic matter is mainly preserved in the space between the grains of the micrite minerals but almost evenly distributed in the rhombic or magnetic needle-like carbonate minerals. As one of the common diagenesis types, dolomitization is observed to occur in the microbialites in Huayingshan. However, the carbonate cement in microbialites still has high content of element Sr as shown by the microprobe analysis, reflecting that the dolomitization might have happened in a restricted environment. Observation under the fluorescence microscope shows that dolomitization just led to the redistribution of organic matter in the grain space of dolomite minerals, inferring that the diagenesis has a slight effect on the preservation, and thus on the content of organic matter in the microbialites.     

Environmental Redox Changes of the Ancient Sea in the Yangtze Area during the Ordo-Silurian Transition

Extensive organic-matter （OM） rich facies （black shales） occur in the Ordo-Silurian boundary successions in the Yangtze area, South China. To investigate the redox changes of the Yangtze Sea during the Ordo-Silurian transition, two OM sections （Wangjiawan in Yichang, Hubei Province, and Sanjiaguan in Zhangjiajie, Hunan Province） straddling the Ordo-Silurian boundary are studied. The measurements finished in this study include contents of the total organic carbon （TOC）, pyrite sulphur, and different species of Fe, including dithionite-extractable Fe （FED）, pyrite Fe （FeP）, HCl-extractable Fe （FeH）, and total Fe （FeT）, in black shales, as well as other redox proxies, such as the SIC ratio, the ratio between highly reactive Fe （FeHR = FeD ＋ FeP） and FeT, and the FeP/（FeP ＋ FeH） ratio, known as the degree of pyritization （DOP）. In the Wangjiawan section, the Middle Ashgill sediments have high FeHR/FeT ratios （0.20-0.77; avg. 0.45）, high DOP values （0.21-0.72; avg. 0.54）, and a relatively constant sulfur content independent of the organic carbon content. By the contrast, the mid-early Hirnantian deposits generally have low FeHR/FeT ratios （0.10-0.35; avg. 0.21）, low DOP values （0.11- 0.40; avg. 0.28）, and SIC values are clustering on the normal marine value （SIC = 0.36）. The late Hirnantian and early Rhuddanian deposits, similar to those of the Middle Ashgill deposits, are characterized by high FeHR/FeT ratios （0.32-0.49; avg. 0.41）, high DOP values （0.46-0.68; avg. 0.53） and fairly constant sulfur contents. These data suggest the occurrences of marine anoxia on the Yangtze Sea shelf during intervals of the Mid Ashgill, Late Hirnantian and Early Rhuddanian, and ventilated and oxygenated marine conditions during the mid-early Hirnantian time. The mid-early Hirnantian ventilated event was concomitant with the global glacial period, likely resulted from the glacio-eustatic sea-level fall and subsequent circulation of cold, dense oxygenated waters     

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。     

A dynamic box model of bioactive elements in the southern Taiwan Strait

A dynamic box model was applied to study the characteristics of biogeochemical cycling of PO_4-P,NO_3-N,AOU,POC and PON in the southern Taiwan Strait region based on field data of the"Minnan Taiwan Bank Fishing Ground Upwelling Ecosystem Study" during the period of Dec.1987-Nov.1988.According to the unique hydrological and topographical features of the region,six boxesand three layers were considered in the model.The variation rates and fluxes of elements induced by hor-izontal current,upwelling,by diffusion,sinking of particles and biogeochemical processes were estimatedrespectively.Results further confirmed that upwellings had important effects in this region.Thenearshore upwelling areas had net input fluxes of nutrients brought by upwelling water,also had high de-pletion rates of nutrients and production rates of particulate organic matter and dissolved oxygen.Theabnormal net production of nutrients in the middle layer(10-30m) indicated the important role of bacte-ria in this high production region.Th     

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.     

The “Zero-order Model” revisited: Paul Schindler's influence on the development of trace metal scavenging models

In 1975 Paul Schindler produced the first oceanic trace metal scavenging model to explicitly include the role of surface chemistry as a control on trace metal water column residence times. The eighteen years that have elapsed since the publication of Schindler's seminal paper have seen the development of a variety of oceanic scavenging models; yet, the fundamental insight of his Zero-order Model remains the benchmark. This paper describes the role of Paul Schindler's work on surface chemistry in providing a framework for the current generation of trace element scavenging models.