藏南白垩系泥、页岩微量、稀土元素特征及氧化—还原环境分析

为了解藏南定日—岗巴盆地和江孜盆地白垩纪沉积时底层水体的氧化—还原环境,采用ICP-MS方法进行微量元素及稀土元素测试分析。结果表明:研究区微量元素在时空上均发生了变化,这与各元素对沉积水体的氧化—还原敏感程度有关。元素Al标准化后变化趋势也不尽相同,其垂向上的变化反映了沉积物底层水体氧化—还原状况、生物产率等沉积环境,与海平面升降、陆源碎屑输入、成岩作用再活化及沉积后氧化作用等多因素有关。V/(V+Ni)、U/Th、V/Cr、Ni/Co、Re/Mo、Uau及δU比值表明早白垩世及晚白垩世中、晚期藏南地区盆地内底层水体环境总体上为中等分层的含氧环境,但定日—岗巴盆地内晚白垩世早期Cenomanian-Turonian界线附近微量元素发生突变,显示为强烈的还原环境。稀土元素球粒陨石标准化后均表现为轻稀土富集的右倾型,LREE/HREE介于7.42～14.80之间,LaN/YbN变化范围为7.93～18.54,δEu负异常,δCe异常不明显,表明为含氧环境。因此微量、稀土元素微观分析与野外宏观露头观察相结合,不但可以作为地层划分对比的直接依据,且能更准确、有效地判断地层沉积时底层水体的环境状况。

沉积矿床中重要(变价)金属元素与古海洋环境关系综述--以新元古代-早古生代扬子板块周缘为例

对氧化—还原敏感元素和生命必需元素地球化学性质和相关沉积矿产形成机制及其时空分布特征的分析、总结和归纳,有助于对古海洋环境演化与相关沉积矿产形成关系的深入认识,这对沉积矿床学理论的发展具有重要意义。新元古代南华纪—早古生代早志留世,扬子板块周缘黑色岩系中依次沉积了举世瞩目的南华纪锰矿、震旦纪—早寒武世沉积磷块岩、早寒武世重晶石矿、镍—钼—钴多金属矿、钒矿和早志留世铀矿的完整沉积矿床系列,不同时代地层、同一时代不同沉积环境地层赋存不同类型的沉积矿产,有必要对其成矿机理进行系统研究、总结和归纳。笔者等在对氧化—还原敏感金属元素、生命必需元素和海底热液元素等元素地球化学性质综述的基础上,兼论了它们在结合黄铁矿矿物学对氧化—还原环境、生物生产力和盆地限制性分析方面具体作用;进一步结合新元古代—早古生代扬子板块古环境演化特征,对扬子板块周缘特定时代中特定沉积矿产的分布、成因机理进行分析、总结和归纳;最终得出扬子板块周缘相关沉积矿产,是在全球氧化事件、冰期—间冰期、Rodina大陆裂解大背景下,海洋中成矿金属元素得到长期积累,在特定时代区域性海水—海底热液—生物作用(根据不同矿种各有侧重)影响下,在相关重要元素地球化学性质的控制下、局部区域特殊氧化—还原环境的控制下形成的特定矿产的初步认识。最后,结合相关沉积矿床研究中存在的问题,提出下一步解决方案与展望。

Environmental Stresses and Redox Status of Ascorbate

To investigate the effects of environmental stresses on ascorbic acid content and its redox status, the effects of freezing and drought on ascorbate and dehydro-ascorbate content and activities of four enzymes involved in the ascorbate-glutathione cycle in some conifers were studied. The results showed that both freezing and drought induced the decrease in ascorbate content and the increase in dehydro-ascorbate content. The activities of ascorbate peroxidase (APX) and monodehydro-ascorbate reductase (MDAR) were decreased by freezing stress. At the beginning of exposure to air, water loss from detached needles induced the increase in the activities of APX and MDAR. Further water loss turned to decrease the APX and MDAR activities. The activities of dehydro-ascorbate reductase (DHAR) and glutathione reductase (GR) were not sensitive to changes in temperature and water content of the needles. It is concluded that moderate temperature or water stresses may induce the acclimation and increase in the ability of the H2O2 scavenging system, while strong stresses decrease the ability and induce injury of plant tissues. Correlation between ascorbate content and activities of related enzymes and cold tolerance of conifers were also reported.

Electrocatalytic H_(2)O_(2)generation for disinfection

Epidemics are threatening public health and social development.Emerging as a green disinfectant,H_(2)O_(2)can prevent the breakout of epidemics in migration.Electrochemical H_(2)O_(2)production powered by renewable electricity provides a clean and decentralized solution for on-site disinfection.This review firstly discussed the efficacy of H_(2)O_(2)in disinfection.Then necessary fundamental principles are summarized to gain insight into electrochemical H_(2)O_(2)production.The focus is on exploring pathways to realize a highly efficient H_(2)O_(2)production.Progress in advanced electrocatalysts,typically single-atom catalysts for the two-electron oxygen reduction reaction(2e−ORR),are highlighted to provide high H_(2)O_(2)selectivity design strategies.Finally,a rational design of electrode and electrolytic cells is outlined to realize the on-site disinfection.Overall,this critical review contributes to exploiting the potentials and constraints of electrochemical H_(2)O_(2)generation in disinfection and pinpoints future research directions required for implementation.

Study on oil–source correlation by analyzing organic geochemistry characteristics: a case study of the Upper Triassic Yanchang Formation in the south of Ordos Basin, China

In the south of the Ordos Basin, the oil source of the Upper Triassic Yanchang Formation is confused all the time, which affects further exploration. In this study, oil sources from the oil layers of Ch6, Ch8 and Ch9 are all analyzed and confirmed. Through their carbon isotope value and biomarkers, characteristics of crude oils from the Yanchang Formation are analyzed. Then, the oil–source relation is discussed, with the source rocks' features.Finally, the oil–source relation is calculated through cluster analysis. It is believed that the oils from the Yanchang Formation deposit in a similar redox environment, with weak oxidation–weak reduction, and have all entered maturity stage. Ch9 crude oil is more mature than crude oils from Ch6 and Ch8, and has more advanced plants and fewer algae. Gas chromatography(GC) and gas chromatography–mass spectrometry(GC–MS) analysis show that crude oils from Ch6 and Ch8 may come from Ch7, and Ch9 crude oil may not. Cluster analysis displays that crude oils from Ch6 and Ch8 have closer squared Euclidean distance with Ch7 source rocks than Ch9 crude oil does,indicating crude oils from Ch6 and Ch8 stem from Ch7 source rocks. And Ch9 crude oil has rather close squared Euclidean distance with Ch9 source rocks, illustrating Ch9 crude oil may be from Ch9 source rocks. This research may provide the theoretical basis for the next exploration deploy in the south of Ordos Basin.

四川盆地下寒武统筇竹寺组沉积地球化学特征与有机质富集机制

受构造—沉积分异影响,四川盆地不同地区下寒武统筇竹寺组沉积环境具有较大差异,前人针对不同区域筇竹寺组沉积地球化学特征差异性的系统性对比研究比较薄弱。通过收集整理前人公开发表的四川盆地筇竹寺组16口钻井、9条野外剖面地球化学数据,综合前人认识,针对四川盆地不同地区的筇竹寺组沉积地球化学特征进行对比分析,并探讨有机质富集机制,取得4点认识:①德阳—安岳裂陷槽北段较南段古水体环境更为还原,更有利于有机质的富集和优质烃源岩的形成与保存;②四川盆地北部由裂陷槽深水陆棚区到川东北浅水陆棚区,古沉积环境整体由缺氧向氧化过渡,而由川西南浅水陆棚到川中裂陷槽发育区、川西南浅水陆棚到川东南浅水陆棚,沉积水体则逐渐向更还原的环境过渡;③裂陷槽北段及中段整体反映出很高的古生产力水平,且四川盆地筇竹寺期广泛的热液影响背景为有机质富集提供了十分有利的条件;④裂陷槽北段及川西南浅水陆棚区筇竹寺组有机质丰度主要受古生产力强度影响,川东北和川东南浅水陆棚有机质丰度主要受控于古氧化还原环境,裂陷槽中段有机质丰度受古生产力和古氧化还原环境共同影响。研究成果对于深化四川盆地筇竹组沉积环境差异和烃源岩形成条件认识,支撑深层—超深层油气勘探具有重要的理论和实际意义。

Grey relational analysis on the relation between marine environmental factors and oxidation-reduction potential

The effects of marine environmental factors-temperature （T）, dissolved oxygen （DO）, salinity （S） and pH--on the oxidation-reduction potential （ORP） of natural seawater were studied in laboratory. The results show an indistinct relationship between these four factors and the ORE but they did impact the ORP. Common mathematical methods were not applicable for describing the relationship. Therefore, a grey relational analysis （GRA） method was developed. The degrees of correlation were calculated according to GILA and the values of T, pH, DO and S were 0.744, 0.710, 0.692 and 0.690, respectively. From these values, the relations of these factors to the ORP could be described and evaluated, and those of T and pH were relatively major. In general, ORP is influenced by the synergic effect of T, DO, pH and S, with no single factor having an outstanding role.

Redox physiology in animal function:The struggle of living in an oxidant environment

A strong focus of ecological research for several decades has been to understand the factors underlying the variation in animal life-histories. In recent times, ecological studies have begun to show that oxidative stress may represent another important modulator of competitive trade-offs among fitness traits or of positively integrated patterns of traits. Therefore, incorporating mechanisms underlying oxidative physiology into evolutionary ecology has the potential to help understand variation in life-history strategies. In this review, I provide a general overview of oxidative stress physiology, and subsequently focus on topics that have been neglected in previous ecological reviews on oxidative stress. Specifically, I introduce and discuss the adaptations that animals have evolved to cope with oxidative stress; the environmental stressors that can generate changes in oxidative balance; the role of reactive species in transduction of environmental stimuli and cell signaling; and the range of hormetic responses to oxidative stress [Current Zoology 56 （6）： 687-702, 2010].

Electrocatalytic water-splitting for the controllable and sustainable synthesis of deuterated chemicals

Tandem water electrolysis for the transformation of universal feedstock to value-added chemicals integrated with hydrogen generation and in situ utilization is a promising approach to address the economic challenges of electrochemical hydrogen evolution and storage.Herein,we present the controllable electrocatalytic deuteration of halides using inexpensive and reusable heavy water(D2 O)as a D-source for the preparation of valuable D-labelled chemicals and pharmaceuticals under mild conditions.This electrochemical deuteration method with high efficiency and selectivity furnishes a series of D-labelled chemicals and pharmaceuticals in high yields with excellent D-incorporation.The reaction efficiency and selectivity,that is,the precise substitution of deuterium atoms at different halogen positions,can be tuned by varying the applied voltages.The results show the great potential of green and economical electrocatalytic methods for producing value-added fine chemicals in addition to hydrogen evolution.

Molecular biomarker record of paleooceanographic environment in the East China Sea during the last 35000 years

By reference of the δ18O and δ13C isotopic compositions of G.sacculifer and accelerator mass spectrometry (AMS)14C dates, the U K 37 , ∑C – 21 /∑C +- 22 and Pr/Pn in core DGKS9603 have been used to characterize the changes of paleooceanographic environment occurring in the East China Sea (ECS) during the last 35000 years. The stratigraphic records of these proxies have shown that during the last 35 ka the Okinawa Trough has gone through 7 stronger cold-climate events (C1–C7) and 9 terrigenous matter-decreasing events (e2–e9), of which, the C1 corresponds to the cold episode occurring in the middle late Holocene, C2–C4 and C7 correspond to the H1–H4 events, respectively. e1 and e3–e8 correspond to the decrease of sea surface temperature (SST), respectively. The terrigenous inputs increased when Heinrich events occurred. Climate colding resulted in the decrease of terrigenous matter transported by rivers, and the increase of that transported by winter monsoon. Heinrich events are closely related to East Asia monsoon. During the Last Glacial Maximum (LGM, 15.5–25.8 Cal ka BP), reduction environment fluctuated strongly, bringing forth three stronger reduction events (R1–R3) and one weaker reduction event (O), of which, R1–R3 correspond to the decrease of SST and increase of terrigenous nutrient and O corresponds to the decrease of terrigenous nutrient. The fluctuation of reduction condition must be related to the change of sea surface productivity.

Carbon isotopes, sulfur isotopes, and trace elements of the dolomites from the Dengying Formation in Zhenba area, southern Shaanxi: Implications for shallow water redox conditions during the terminal Ediacaran

Carbon isotope, sulfur isotope, and trace element(including Rare Earth Elements, REE) analyses were conducted on the carbonates of the Dengying Formation at Lianghekou section in southern Shaanxi to reconstruct the terminal Ediacaran shallow-water environment on the northwestern margin of the Yangtze Platform. At Lianghekou section, samples in the middle 50-m of the Beiwan Member show characteristics of low ΣREE concentrations, no MREE-enriched REE distribution patterns, high Ce/Ce* values close to 1, and enriched redox-sensitive elements, whereas samples in the lower 30-m and upper 10-m show opposite characteristics of high ∑REE concentrations, MREE-enriched REE distribution patterns, low Ce/Ce* values around 0.6, and no redox-sensitive elements enriched, indicating that oxygenation did occur in the shallow water on the northwestern margin of the Yangtze Platform and redox conditions of the shallow water fluctuated from relatively oxygenated to anoxic and then back to oxygenated again. We propose that the anoxia appeared in middle of the Beiwan time may associate with the anoxic upwelled water. On one hand, abundant nutrients were brought in by this upwelling event, which stimulated the photosynthetic carbon fixation and increased the organic carbon burial under this anoxic condition, causing a peak of 3.6‰ in δ 13 C. On the other hand, because the anoxic upwelled water replaced the oxic shallow water, together with the increasing organic matter in the water column, bacterial sulfate reduction was enhanced and therefore quickly reduced the sulfate concentration, which eventually caused δ 34 S increasing to 50‰. However, as the upwelling gradually disappeared, δ 13 C and δ 34 SCAS values decreased as well in the late Beiwan time, indicating the shallow water went back to suboxic or oxic again.

Distribution, Morphology, and Chemical Composition of Fe-Mn Nodules in Albeluvisols of the Carpathian Foothills, Poland

Iron and manganese oxides are common components of soils. They frequently occur in nodules constituting important soil sorbents and play a crucial role in a number of chemical reactions in the soil environment. In addition, the oxides are very sensitive to environmental changes (moisture, pH, Eh) constituting important indicators of soil-forming processes and water movement in the landscape. The objectives of the study were: i) to examine the distribution and size of Fe-Mn nodules in Albeluvisols containing a fragipan horizon; ii) to determine the morphology and chemical composition of the nodules, and iii) to estimate the effect of the fragipan horizon on water movement within the soil profile. An investigation was carried out on five soil profiles containing a fragipan horizon and classified as Fragic Albeluvisols within the Carpathian Foothills in Poland. In the Albeluvisols studied, the maximum concentration of Fe-Mn nodules occurred in the horizon lying directly on the fragipan horizon. This suggests that the pan acts as a natural barrier restricting water infiltration and leads to the seasonal development of a perched water table promoting redox processes. The most common are coarse (1-0.5 mm) and medium (0.5-0.25 mm) irregular Fe-Mn nodules showing a gradual boundary and undifferentiated internal fabric. Eluvial horizons contained also larger amounts of round and dense nodules with a sharp boundary, suggesting frequent oxidation and reduction. The fragipan horizon contained mainly irregular and soft nodules, suggesting longer saturation with water during the year. Concentrations of trace elements (Cu, Zn) and P were higher within Fe-Mn nodules than in the surrounding soil materials, showing that iron and manganese oxides adsorbed and immobilised these elements.

Monodisperse Fe3O4 spheres: Large-scale controlled synthesis in the absence of surfactants and chemical kinetic process

Fe3 O4 has attracted tremendous interest in vast areas of biomedicine and catalysis as well as environment engineering.However,it is highly desired to fully understand the chemical kinetic process and propose a general,surfactantfree,large-scale synthesis approach for Fe3 O4 spheres.Herein,we developed a facile scalable solvothermal method in the absence of surfactants to produce Fe3 O4 spheres with the yield of 5.1 g,which present tunable sizes from 107 to 450 nm by modulated molar ratio of Fe3+/COO-in the solution.Particularly,it is observed that the reactants undergo a redox process,composed of a precipitation-dissolution equilibrium combined with a coordination reaction(termed as RPC),to the final product based on the LaMer model.It is worth noting that the generation of di-carboxyl group and its coordination with iron cations determine the formation of Fe3 O4 spheres.This work not only offers a strategy to precisely tailor the particle size in scalable synthesis process,but also gives the insight on the role of dihydric alcohol in the formation mechanism of Fe3 O4 spheres in the absence of surfactants.

Kinetics of FeSe_2 oxidation by ferric iron and its reactivity compared with FeS_2

The mobility and bioavailability of selenium is a major health and environmental issue and a main concern for geological disposal of high-level radioactive waste. Chemically and/or microbially mediated oxidation of insoluble Se-bearing particulate, such as iron selenides, to dissolved and mobile phases controls the transport and distribution of Se in the environment. The oxidation of ferroselite （FeSe2） by ferric iron was investigated in anoxic conditions. The redox reaction can be represented by： FeSe2 ＋ 2Fe3＋ = 2Se^0 ＋ 3Fe2＋. Kinetic studies indicated that the reaction can be described by second-order rate law, with rate constants of 0.49±0.01, 0.85±0.02, 1.84±0.04, and 3.29±0.13 L mol^-1 s^-1 at pH 1.62, 1.87, 2.23, and 2.49, respectively. The positive correlation between reaction rate and pH implies that diffusion of Fe3＋ oxidant to the mineral surface is the rate-determining step. The strong reactivity of FeSe2 towards Fe^3＋ suggests that ferric iron may play a significant role in FeSe2 oxidation process （e.g., by Se^4＋, 02, etc.） and Se^0 should be the first reaction product. Also, it was shown that the reduction rate of Fe^3＋ or Se^4＋ by pyrite （FeS2） can be significantly increased in the presence of FeSe2, suggesting a stronger reactivity of FeSe2 compared with pyrite. The results obtained extend our knowledge about the subtle interaction between Se, pyrite and iron selenides in the environment, and give insight into the transfer of selenium from iron selenides to bio-available selenium （i.e., selenite and selenate） in the Se-rich environment.