吉林南部辉南-靖宇地区岩石圈地幔氧化-还原状态及研究意义

吉林省南部辉南-靖宇地区第四纪碱性玄武岩中的地幔包体主要为尖晶石相二辉橄榄岩和方辉橄榄岩。二辉橄榄岩和方辉橄榄岩的平衡温度分别为770～1000℃和850～1025℃,对应的氧逸度(fO2)值分别为FMQ-0.70至+0.34(均值为FMQ-0.06)和FMQ-0.46至+0.05(均值为FMQ-0.15),它们与深海橄榄岩(abyssal peridotites)以及软流圈地幔的fO2相似。橄榄岩的fO2值,连同其全岩化学成分(如Mg#、Al2O3、CaO、Ni、Co和Cr)和矿物化学成分(如橄榄石的Fo、尖晶石的Cr#和Mg#,以及辉石的Mg#)特征,表明辉南-靖宇地区龙岗火山群下面的岩石圈地幔很可能是在晚中生代以来,伴随着华北克拉通和扬子板块的碰撞以及来自东侧太平洋板块和北侧蒙古-额霍次克(Mongolo-Okhotsk)板块分别向西和向南的俯冲叠加,原来的古老岩石圈失衡、塌陷(拆沉?),取而代之的深部软流圈底辟、上涌,又经历了低度部分熔融的产物。

N-乙酰半胱氨酸对博莱霉素大鼠肺脏氧化-还原状态的影响

目的 :探讨肺脏氧化 -还原状态与肺脏炎症、肺纤维化的关系及N 乙酰半胱氨酸对肺纤维化的影响。方法 :健康雌性Wistar大白鼠经支气管灌注博莱霉素 (BLM )造成肺间质纤维化。部分灌注BLM后每日腹腔注射N 乙酰半胱氨酸 (NAC) 4 0mg/kg。计数支气管肺泡灌洗液 (BALF)中细胞总分数 ,检测血清和BALF中谷胱甘肽(GSH)、丙二醛 (MDA)的含量。肺组织制成石蜡切片行HE染色进行病理和炎症积分分析。左肺匀浆后测羟脯氨酸 (HYP)含量。结果 :BLM组急性炎症期BALF细胞总数显著增高 ,中性粒细胞 (PMN)、淋巴细胞百分比显著增高 ,肺组织炎症积分增加 ,14d时HYP含量较对照组显著增加 (P <0 .0 5 ) ;NAC能够降低急性期BALF中细胞总数、PMN和淋巴细胞百分比 ,但在纤维化期细胞总数有所增加。NAC组肺组织炎症积分下降 ,但HYP含量较BLM组略增加 ;各组血清GSH和MDA水平无显著差异 ;BLM组BALFGSH水平第 17天显著降低 ,NAC能够显著提高BALFGSH水平。结论 :BALFGSH ,MDA水平较血清GSH ,MDA水平能更好的反映肺脏损伤情况和对治疗的反应 ;NAC(40mg/kg)能够减少肺组织炎症细胞的浸润和BALF中中性粒细胞百分比 ,表明小剂量NAC具有一定的抗炎作用 ,但其对肺纤维化大鼠胶原沉积无保护作用。

中国东部地幔氧化—还原状态的演化及其意义

利用二次尖晶石标样法(secondary spinel standard)精确测定了中国东部新生代玄武岩中地幔包体的尖晶石的Fe^(3+)/∑Fe,并采用橄榄石- 斜方辉石- 尖晶石氧逸度计估算了63个地幔包体记录的氧逸度。结果显示,中国东部岩石圈地幔氧化状态具有南高北低特点,其中,华北克位通岩石圈地幔的氧化状态最低,与大洋地幔氧化状态相近。

The in situ spectral methods for examining redox status of c-type cytochromes in metal-reducing/oxidizing bacteria

The membrane-associated c-type cytochromes(c-Cyts) have been well known as the key enzymes mediating extracellular electron transfer to terminal electron acceptors, resulting in biogeochemical elemental transformation, contaminant degradation, and nutrient cycling. Although c-Cyts-mediated metal reduction or oxidation have been mainly investigated with the purified proteins of metal reducing/oxidizing bacteria, the in vivo behavior of c-Cyts is still unclear, given the difficulty in measuring the proteins of intact cells. Fortunately, the in situ spectroscopy would be ideal for measuring the reaction kinetics of c-Cyts in intact cells under noninvasive physiological conditions. It can also help the establishment of kinetic/thermodynamic models of extracellular electron transfer processes, which are essential to understand the electron transfer mechanisms at the molecular scale. This review briefly summarizes the current advances in spectral methods for examining the c-Cyts in intact cells of dissimilatory metal reducing bacteria and Fe(Ⅱ)-oxidizing bacteria.

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.

海相沉积岩铁同位素体系及其古环境指示

铁(Fe)作为主要造岩元素及生命必需元素,广泛参与地球表层圈层所涉及的物理、化学和生物作用,在调节海洋初级生产力和驱动海洋生物地球化学循环过程扮演重要角色。Fe同位素作为较早开发的非传统稳定同位素体系,目前已成为示踪生物地球化学循环过程及古海洋环境演变的有效手段。本文在对全球海洋Fe循环和表生地质过程Fe同位素分馏机理进行系统总结的基础上,统计了地质历史时期不同类型海相沉积岩的Fe同位素组成,并通过实例探讨了海相沉积岩Fe同位素体系在研究重大地质事件环境演变的潜力,最后对海相沉积岩Fe同位素体系的未来发展方向进行了展望。

The complex role of physical exercise and reactive oxygen species on brain

Reactive oxygen species （ROS） are continuously generated during aerobic metabolism and at moderate level. They play a role in redox signaling, but in significant concentration they cause oxidative damage and neurodegeneration. Because of the enhanced sensitivity of brain to ROS, it is especially important to maintain the normal redox state in different types of neuron cells. In last decade it became clear that regular exercise beneficially affects brain function, and can play an important preventive and therapeutic role in stroke, Alzheimer, and Parkinson diseases. The effects of exercise appear to be very complex and could include neurogenesis via neurotrophic factors, increased capillariszation, decreased oxidative damage, and increased proteolyfic degradation by proteasome and neprilysin. Data from our and other laboratories indicate that exercise-induced modulation of ROS levels plays a role in the protein content and expression of brain-derived neurotrophic factor, tyrosinerelated kinase B （TrkB）, and cAMP response element binding protein, resulting in better function and increased neurogenesis. Therefore, it appears that exercise-induced modulation of the redox state is an important means, by which exercise benefits brain function, increases the resistance against oxidative stress, facilitates recovery from oxidative stress, and attenuates age-associated decline in cognition.

Effect of Potassium Nutrition of Different Varieties of Rice on the Redox Status in Microzone Rhizosphere Soils

Being divided into three groups-strong, moderate and weak-according to the different kinetic parameters (Fmax, km, Cmin) of potassium uptake by crops, 21 cultivars of rice have been studied to find out the relationships between their potassium nutrition and the oxidation-reduction status in the rhizosphere soils.Results show that, with no application of K fertilizer, there were higher contents of active reducing substances and ferrous iron in rhizosphere soils planted with cultivars, such as Zhongguo 91, week in absorbing potassium than in soils cropped with cultivars, Shanyou 64, stronger in absorbing potassium. As a result of K application, however, these toxic substances were decreased appreciably in the soil, particularly in the root zone where weakly K-absorbing cultivars were growing, and the parameter of soil redox (pH +pE) was increased, the most striking example of this being found in the rhizosphere soil where the more strongly K-absorbing cultivars were growing. On and close to the root surface in soils where rice plants were supplied with potassium fertilizer, rather more iron oxide had been accumulated compared with rice receiving no potash, and even greater amounts of red iron oxide precipitated on the rice root in neutral paddy soils. As shown by the concentration distribution of active reducing substances and ferrous iron in a microzone of the profile, the redox range of rice roots supplied with potassium may extend as far as several centimeters from the root surface. It can thus be seen that potassium nutrition exerts its effect first on the morphological properties of rice roots and their exudation of oxygen, then on the content of soluble oxygen and the count and species of oxygen-consuming microbes in the rhizosphere soil, and finally on the redox status of the soil.

The oceanic cycles of the transition metals and their isotopes

The stable isotope systems of the transition metals potentially provide constraints on the current and past operation of the biological pump,and on the state of ocean redox in Earth history.Here we focus on two exemplar metals,nickel(Ni)and zinc(Zn).The oceanic dissolved pool of both elements is isotopically heavier than the known inputs,implying an output with light isotope compositions.The modern oceanic cycle of both these elements is dominated by biological uptake into photosynthesised organic matter and output to sediment.It is increasingly clear,however,that such uptake is associated with only very minor isotope fractionation.We suggest that the isotopic balance is instead closed by the sequestration of light isotopes to sulphide in anoxic and organic-rich sediments,so that it is ocean chemistry that controls these isotope systems,and suggesting a different but equally interesting array of questions in Earth history that can be addressed with these systems.

Parameters Affecting the Color Mechanism of Manganese Containing Colored Glasses

Color is an important tool for glass industry to let the product gain additional aesthetic and functional properties forced by the market demands. In this context, it is necessary to understand the color forming mechanism better in order to get target color and improve the yield. A detailed experimental study to investigate the relationship between the manganese content on color formation and the redox condition was carried out. All experiments were carried out at different level of iron and manganese oxides. Color parameters （dominant wavelength, brightness （%）, purity （%） and L-a-b values） were examined for large interval of batch redoxes. In this paper, the results of above mentioned experimental studies were discussed together.

High-pressure experimental verification of rutile-ilmenite oxybarometer: Implications for the redox state of the subduction zone

The more oxidized mantle peridotites above subducting slabs than stable continental areas have been attributed to the infiltration of some oxidizing fluids released from the subducting slabs. However, knowledge for the redox states of the slabs itself is very limited. Until now, few oxybarometers can be directly used to constrain the redox states of the subducting slabs.The rutile-ilmenite oxybarometer was proposed and successfully applied to constrain the oxygen fugacity of mantle assemblages.However, its application to rocks equilibrated at crustal P-T conditions has been hampered by some uncertainties in an early solid solution model of ilmenite. With a newly-released solid solution model for the ilmenite, we have conducted high-P experiments(at 3 and 5 GPa, and 900–1300°C) to test the accuracy of this oxybarometer. The experiments were performed with their oxygen fugacities controlled by the CCO buffer(i.e., C+O_2=CO_2). We demonstrated that the oxygen fugacities calculated for our high-P experimental products by using the rutile-ilmenite oxybarometer were in excellent agreement with the fO_2 dictated by the CCO buffer, suggesting a wide applicability of this oxybarometer to crust rocks. As examples, the rutile-ilmenite oxybarometer has been used to constrain the oxygen fugacities of some metamorphic rocks such as eclogite, granulite and amphibolite usually observed from the subduction zones.

Influence of Soil Properties on Zinc Solubility Dynamics Under Different Redox Conditions in Non-Calcareous Soils

Zinc(Zn) deficiency in paddy soils is often a problem for rice production.Flooding can decrease metal availability in some noncalcareous soils through different mechanisms associated with soil redox status.Laboratory experiments were performed in order to better understand the processes that governed the dynamics of Zn in non-calcareous paddy soils at varying redox potentials(Eh).Airdried non-calcareous soil samples collected from four different paddy field sites in the Philippines were submerged and incubated in a reaction cell with continuous stirring and nitrogen purging for 4 weeks,and then purged with compressed air for another week to reoxidize the system.The Eh of the four soils started at 120 to 300 mV,decreased to —220 to —300 mV after 100 to 250 h of reduction,and was maintained at this low plateau for about 2 weeks before increasing again upon reoxidation.Zinc solubility showed contrasting patterns in the four soils,with two of the soils showing a decrease in soluble Zn as the Eh became low,probably due to zinc sulfide(ZnS) precipitation.In contrast,the other two soils showed that Zn solubility was maintained during the reduced phase which could be due to the competition with iron(Fe) for precipitation with sulfide.Differences in the relative amounts of S,Fe,and manganese(Mn) oxides in the four soils apparently influenced the pattern of Zn solubility after flooding.

Rare earth element and yttrium compositions of the Paleoproterozoic Yuanjiacun BIF in the Lüliang area and their implications for the Great Oxidation Event(GOE)

In China, most Precambrian banded iron formations （BIFs） are situated in the North China Craton. The Yuanjiacun iron depos- it, located in the Ltlliang area, is arguably the most representative Superior-type BIF. This iron deposit is coherent with the sedimentary rock succession of the Yuanjiacun Formation in the lower Lliliang Group, and was interpreted to be deposited at 2.3-2.1 Ga, based on ages of overlying and underlying volcanic strata. This age overlaps with the time range of the Great Oxidation Event （GOE, 2.4-2.2 Ga）. The Yuanjiacun BIF consists mainly of subhedral-xenomorphic magnetite and quartz and rarely other minerals with a lower degree of metamorphism, from greenschist to lower amphibolite facies. The geochemical characteristics of this BIF are similar to those of Superior-type BIFs. Prominent positive La, Y, and Eu anomalies normalized by the Post Archean Australian Shale （PAAS） indicate that the primary chemical precipitate is a result of solutions that repre- sent mixtures of seawater and high-T hydrothermal fluids. The contamination from crustal detritus found is negligible based on low abundances of Al2O3 and TiO2 （〈0.5%） and of trace elements such as Th, Hf, Zr, and Sc （〈1.5 ppm）, as well as the lack of co-variations between Al2O3 and TiO2. In particular, the Yuanjiacun BIF samples do not display significant negative Ce anom- alies like those of the Archean iron formations, but rather, the Yuanjiacun BIF samples exhibit prominent positive Ce anoma- lies, low Y/Ho ratios, and high light to heavy REE （（Pr/Yb）sN） ratios, which are essentially consistent with the late Paleoprote- rozoic （〈2.0 Ga） BIFs around the world. These characteristics of the Yuanjiacun BIF samples imply that the ancient ocean （2.3-2.1 Ga） was redox-stratified from oxic shallow water to deeper anoxic water. The specific redox conditions of the ancient ocean may be related to the GOE, which gave rise to the oxidation of Ce and Mn in the upper water, and to the presence of a Mn oxide shuttle in the ocean, resulting in varying REE patterns due to the precipitation and dissolution of this Mn oxide shut tle under different redox states. Therefore, the Yuanjiacun BIF appears to have formed near the redoxcline and lower-level reduced marine water.

Mo marine geochemistry and reconstruction of ancient ocean redox states

Molybdenum(Mo) proxies, including bulk concentration and isotopic composition, have been increasingly used to reconstruct ancient ocean redox states. This study systematically reviews Mo cycles and their accompanying isotopic fractionations in modern ocean as well as their application in paleo-ocean redox reconstruction. Our review indicates that Mo enrichment in sediments mainly records the adsorption of Fe-Mn oxides/hydroxides and chemical bonding of H2 S. Thus, Mo enrichment in anoxic sediments generally reflects the presence of H2 S in the water column or pore waters. In addition to the effect of euxinia, sedimentary Mo enrichment is related to the size of the oceanic Mo reservoir. Given these primary mechanisms for oceanic Mo cycling, Mo abundance data and Mo/TOC ratios acquired from euxinic sediments in geological times show that fluctuations of the oceanic Mo reservoir are well correlated with oxygenation of the atmosphere and oceans and suggest that oxygenation occurred in phases. Mo proxies suggest that Mo isotopes in strongly euxinic sediments reflect the contemporaneous Mo isotopic composition of seawater, but other processes such as iron-manganese(Fe-Mn) adsorption and weak euxinia can result in different fractionations. Diagenesis may complicate Mo enrichment and its isotopic fractionation in sediments. With appropriate constraints on the Mo isotopic composition of seawater and various outputs, a Mo isotope mass-balance model can quantitatively reconstruct global redox conditions over geological history. In summary, Mo proxies can be effectively used to reconstruct oceanic redox conditions on various timescales due to their sensitivity to both local and global marine redox conditions. However, given the complexity of geochemical processes, particularly the effects of diagenesis, further work is required to apply Mo proxies to ancient oceans.

Presentation matters： Identity of gold nanocluster capping agent governs intracellular uptake and cell metabolism

Au nanoclusters （AuNCs） hold tremendous potential to be employed in a wide variety of biological applications. Despite the rapid development in the field of NCs synthesis, a comprehensive understanding of how cells interact with this class of ultra-small nanoparticles （〈2 nm） having defined sizes and surface chemistry, remains poorly understood. In this study, we show that the choice of the surface ligand used to protect AuNCs can significantly perturb cellular uptake and intracellular redox signaling. A panel of monodisperse, atomically precise AuNCs with different core Au atom number （i.e., Auls, Au18 and Au25） protected with either mercaptopropionic acid （MPA） or glutathione （GSH） capping agent were synthesized and their effects on the generation of intracellular reactive oxygen species （ROS）, cytotoxicity and genotoxicity of the NCs were assessed. Both mitochondrial superoxide anion （O2^-） and cytoplasmic ROS were found to be higher in cells exposed to MPA but not GSH capped AuNCs. The unregulated state of intracellular ROS is correlated to the amount of internalized AuNCs. Interestingly, MPA-AuNCs induction of ROS level did not lead to any detrimental cellular effects such as cell death or DNA damage. Instead, it was observed that the increase in redox status corresponded to higher cellular metabolism and proliferative capacity. Our study illustrates that surface chemistry of AuNCs plays a pivotal role in affecting the biological outcomes and the new insights gained will be useful to form the basis of defining specific design rules to enable rational engineering of ultra-small complex nanostructures for biological applications.

Variation in Salt Tolerance of Wheat Cultivars:Role of Glycinebetaine and Ethylene

Four wheat （Triticum aestivum L.） cultivars 711, PBW343, 3765 and WH542 were screened for studying variations in glycinebetaine （GB） content and plant dry mass under 100 mmol L-1 NaCl stress. A tolerance index was calculated using plant dry mass data to select salt-tolerant and salt-sensitive types and find association between tolerance index and GB content. Tolerance index has been used as a good criterion to select the tolerant types under high salinity stress. Further, physiological differences in salt-tolerant cultivar 711 and salt-sensitive cultivar WH542 were examined. The salt-tolerant cultivar exhibited greater CB content, which was found correlative with ethylene. The cultivar also showed higher nitrogen （N） content and nitrate reductase activity, reduced glutathione and higher redox state resulting in maximal protection of plant dry mass than the salt-sensitive type. Thus, the content of CB may be considered as important physiological criteria for selecting salt-tolerant wheat types.

Immiscible metallic melts in the deep Earth: clues from moissanite(SiC)in volcanic rocks

The occurrence of moissanite(SiC), as xenocrysts in mantle-derived basaltic and kimberlitic rocks sheds light on the interplay between carbon, hydrogen and oxygen in the lithospheric and sublithospheric mantle. SiC is stable only at fO2< △IW-6, while the lithospheric mantle and related melts commonly are considered to be much more oxidized. SiC grains from both basaltic volcanoclastic rocks and kimberlites contain metallic inclusions whose shapes suggest they were entrapped as melts. The inclusions consist of Si^0+ Fe3Si7± FeSi2 Ti ± CaSi2Al2± FeSi2Al3± CaSi2, and some of the phases show euhedral shapes toward Si^0. Crystallographically-oriented cavities are common in SiC, suggesting the former presence of volatile phase(s), and the volatiles extracted from crushed SiC grains contain H2+ CH4± CO2± CO.Our observations suggest that SiC crystalized from metallic melts(Si-Fe-Ti-C ± Al ± Ca), with dissolved H2+ CH4± CO2± CO derived from the sublithospheric mantle and concentrated around interfaces such as the lithosphere-asthenosphere and crust-mantle boundaries. When mafic/ultramafic magmas are continuously fluxed with H2+ CH4 they can be progressively reduced, to a point where silicide melts become immiscible, and crystallize phases such as SiC. The occurrence of SiC in explosive volcanic rocks from different tectonic settings indicates that the delivery of H2+ CH4 from depth may commonly accompany explosive volcanism and modify the redox condition of some lithospheric mantle volumes. The heterogeneity of redox states further influences geochemical reactions such as melting and geophysical properties such as seismic velocity and the viscosity of mantle rocks.

Photophysical and photochemical processes of riboflavin (vitamin B_2) by means of the transient absorption spectra in aqueous solution

Using time-resolved techniques of 337 and 248 nm laser flash photolysis, the photo physical and photochemical processes of riboflavin (RF, vitamin B2) were studied in detail in aqueous solution. The excited triplet state of riboflavin (3RF*) was produced with 337 nm laser, while under 248 nm irradiation, both3RF* and hydrated electron (eaq) formed from photoionization could be detected. Photobiological implications have been inferred on the basis of reactivity of3RF* including energy transfer, electron transfer and hydrogen abstraction. The RF·+ was generated by oxidation of SO4 ·-radical with the aim of confirming the results of photolysis.