天然气水合物的上界面——硫酸盐还原-甲烷厌氧氧化界面

定义了海域天然气水合物成矿带的上界面。指出在地球深部存在最原始的、从根本上不依靠光合作用来生存的生命系统。根据对ODP岩心样品中微生物数量的统计,海底以下沉积层中的生物数量可能占据全球原核生物总量的70%,其生物总碳量和地球表面所有植物的碳总量相当。地球内部如此巨大的生物总量应该在地壳中的气体分布等方面起着重要作用。甲烷在地壳层中广泛存在,并主要是微生物成因的。微生物产甲烷的途径主要有两个,一是二氧化碳还原,另一个是醋酸盐发酵。相应地,参与产甲烷的微生物菌群主要是产甲烷菌和食醋酸菌。甲烷在沉积层中的厌氧氧化是一个不争的事实。该过程发生在海底以下一个非常局限的区带,称为硫酸盐还原-甲烷厌氧氧化区带。通常,这个区带很窄,仅为一个面,因此,硫酸盐还原-甲烷厌氧氧化区带又称硫酸盐还原-甲烷厌氧氧化界面。这是一个基本的生物地球化学界面,在功能上它起到屏蔽甲烷向海底和大气逸散的作用,是一个巨大的甲烷汇。甲烷的厌氧氧化同样是一个由微生物介导的过程,参与此过程的微生物主要是食甲烷古菌和硫酸盐还原菌。硫酸盐还原-甲烷厌氧氧化界面在海洋沉积层中一般深可达海底以下上百米,浅可至海底。此界面为天然气水合物的上界面,该界面以上没有甲烷...     

The importance of iron speciation (Fe+2/Fe+3) in determining mineral assemblages: an example from the high‐grade aluminous metapelites of southeastern Madagascar

Metapelitic granulites from the Anosyen domain of southeastern Madagascar are exposed in three intercalated formations: the Amparihy, Bakika and Ihosy formations. Although mineralogically distinct from each other, the rocks from these formations show very similar bulk‐rock compositions when measured on a Fe_T basis. The preserved mineral assemblages thus do not reflect differences in the ratios of the main rock‐forming oxides (i.e. Al₂O₃:Fe_T:MgO), but instead reflect variations in the pre‐metamorphic oxidation state of the protolith rocks. These differences in oxidation state are manifested via differences in iron speciation – either Fe⁺² or Fe⁺³. The relatively reduced rocks of the Amparihy Formation preserve the assemblage bi–sp–sill–g–cd, which contrasts markedly with the mostly garnet and spinel‐absent bi–cd–sill–mt assemblages preserved in the strongly oxidized rocks of the Ihosy Formation. Compositionally intermediate rocks of the Bakika Formation are garnet bearing, but sillimanite‐absent, and contain the assemblage sp–g–cd–mag. Modelling of these rocks in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O system suggests that they evolved along a heating and cooling P–T path with only limited decompression accompanying cooling on the retrograde path. Peak temperatures and pressures of ～880–920 °C and 6–6.5 kbar are inferred for the majority of the Anosyen domain, with slightly lower peak temperatures (～840 °C) estimated in the extreme northwest of the area. The high‐temperature and relatively low‐pressure nature of metamorphism suggests high geothermal gradients existed during orogenesis, which in southern Madagascar is related to the amalgamation of Gondwana (580–520 Ma). Although metamorphic temperatures may have been augmented via thermal advection from the emplacement of the syn‐ to post‐tectonic Ambalavao suite, the high geothermal gradients nevertheless suggest thin and consequently hot lithosphere existed prior to orogenesis.     

Dissolved oxygen variations in alpine glacial meltwaters

Recent models of chemical weathering in alpine glacial meltwaters suggest that sulphide oxidation is a major source of solute in the distributed component of the subglacial hydrological system. This reaction requires O₂, and may lower dissolved oxygen levels to below saturation with respect to the atmosphere. This should result in an inverse association between SO₇^2- and dissolved oxygen saturation. However, measurements of O₂ saturation in bulk meltwaters draining the Haut Glacier d'Arolla, Switzerland, show that there is a positive association between SO₄^2- and O₂ saturation. The O₂ content of glacial meltwaters depends on the initial content of snow and icemelt, which may be controlled by the rate of melting, and the kinetic balance between O₂ losses (e.g. sulphide oxidation, microbial respiration) and gains (e.g. diffusion of O₂ into solution).     

Valency Study of Vanadium in Stone Coal Ash of Jiangxi Province

Vanadium-bearing stone coal is a new vanadium resource;recovery ofV_2O_5 from the coal has been investigated.It has been found that a satisfactoryextraction of V_2O_5 depends on both the oxidation of V and its reaction with so-dium salt.V in the coal ash of Yushan mainly exists in two oxidation states:98％V(Ⅲ)and2％V(Ⅳ).The distribution of valency of V shows that organicmatter determines V valency at low temperatures,at about470℃,V(Ⅲ)iscompletely oxidized to V(Ⅳ);above500℃,the temperature is the most impor-tant factor for the oxidation of V .At higher temperatures no more V is oxidizedto V(Ⅴ);an equilibrium is established after92％of V is oxidized to V(Ⅴ).The roles of NaCl in the recovery of V_2O_5 from the coal ash were discussed.The best conditions for roasting are temperature750-800℃for1 h.underthe oxidation-chlorination atmosphere.When the ore:NaCl=100:10 by weight,η_roast reaches85.5％.According to the results,a flowsheet for V_2O_5 extrac-tion from coal ash has been proposed.     

绿砷钡铁石在广西的发现

本文研究了在广西德保铜锡矿床氧带化中发现的绿砷钡铁石,给出了它的物理性质、化学成分和晶胞参数等矿物学数据。     

Model studies of the impact of chemical inhomogeneity on SO2 oxidation in warm stratiform clouds

A one-dimensional, time-dependent model of the physics and chemistry of a warm stratiform cloud is used to study the possible impact of chemical inhomogeneity among cloud and raindrops on the oxidation of SO₂ in clouds. The effects of chemical inhomogeneity are examined using two contrasting models: In Model 1 a bulk-solution parameterization is adopted which effectively treats all cloud and raindrops as if they are chemically homogeneous; in Model 2 we allow the cloud and raindrops to have a dichotomous distribution. The dichotomous distribution in Model 2 is simulated by assuming that the two groups of cloud droplets nucleate from two chemically distinct populations of condensation nuclei; one being acidic and the other being alkaline. While the two models yield essentially identical results when the ambient levels of H₂O₂ are greater than the ambient levels of SO₂, the rate of conversion of SO₂ to sulfuric acid and the amount of sulfate removed in the precipitation can be significantly enhanced in Model 2 over that of Model 1 under conditions of oxidant limitation (i.e., H₂O₂ < SO₂). This enhancement is critically dependent upon the fraction of alkaline nuclei assumed to be present in Model 2 and arises from the rapid increase in the aqueous-phase reaction between O₃+S_IV at high pH. Our results suggest that cloud models which adopt a bulk-solution parameterization for cloud droplet chemistry, may underestimate the amount of in-cloud SO₂ oxidation under oxidant-limited conditions.     

Structural relationships between a brown coal and its kerogen and humic acid fractions

A South Australian Tertiary brown coal is fractionated into humic acid and kerogen fractions. These related samples are then subjected to a number of different analytical techniques including infrared and¹³C-Nuclear Magnetic Resonance spectroscopies and pertrifluoroacetic acid oxidation. Structural conclusions are drawn from an integrated consideration of the data. Brown coal aliphatic structure is concentrated in the kerogen and the solvent soluble polar acid fractions. The humic acids are the most aromatic and contain a high degree of hydrogen bonding. Only very minor amounts of long polymethylene chain structures are observed in the humic acids, in complete contrast to the kerogen fraction. Different organic detrital origins are proposed for the coal fractions.     

Importance of the oxidation/maturation pair in the evolution of humic coals

The natural thermal evolution of type III coals (Humic origin) is expressed during diagenesis by a loss of oxygen as CO₂ and H₂O. Other phenomena such as oxidation can cause extensive geochemical modifications and may complicate the effects of simple maturation.Humic coals from the Jurassic in southeastern Utah were studied by elemental analysis, Rock-Eval pyrolysis and infrared spectroscopy. In a van Krevelen diagram (atomic H/C vs atomic O/C), the samples fall within the envelope defined by 860 reference humic coals covering the entire range of diagenesis. Nevertheless, various criteria (geochemical, petrographic, geological and microscopic) cast doubt upon the interpretation that such a distribution of coal composition results from thermal maturation.The same criteria indicate the intervention of redox phenomena. Comparison of our results with those from artificial and natural oxidation shows that these coals were subjected to an oxidation process different from ordinary late alteration. This process was probably due to circulation of highly oxidizing saline water causing oxygen fixation and the transformation of carboxyls into carboxylate anions. The cations that were fixed are oxygenated and certainly contain calcium, but also uranium and perhaps several other cations (V, Mo, Fe...). Emphasis is placed on possible mechanisms that cause such phenomena.     

Methoxy formation in the reaction of CH3O2 radicals with NO

Formation of methoxy (CH₃O) radicals in the reaction (1) CH₃O₂+NOCH₃O+NO₂ at 298 K has been observed directly using time resolved LIF. The branching ratio % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdyMaae% 4qaiaabIeadaWgaaWcbaGaae4maaqabaGccaqGpbGaaeiiaiaabIca% ieqacaWF9aGaa8hiaiaa-nbicaWFGaGaeuiLdqKaai4waiaaboeaca% qGibWaaSbaaSqaaiaabodaaeqaaOGaae4taiaac2facaWFVaGaeuiL% dqKaai4waiaaboeacaqGibWaaSbaaSqaaiaabodaaeqaaOGaae4tam% aaBaaaleaacaqGYaaabeaakiaac2facaqGPaaaaa!4E31!\[\phi {\rm{CH}}_{\rm{3}} {\rm{O (}} = -- \Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}]/\Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}_{\rm{2}} ]{\rm{)}}\] has been determined by quantitative cw-UV-laser absorption at 257 nm of CH₃O₂ and CH₃ONO, the product of the consecutive methoxy trapping reaction (2) % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaae4qaiaabI% eadaWgaaWcbaGaae4maaqabaGccaqGpbacbeGaa83kaiaa-bcaieaa% caGFobGaa43taiaa+bcacaGFOaGaa83kaiaa+1eacaGFPaGaa4hiai% abgkziUkaabccacaqGdbGaaeisamaaBaaaleaacaqGZaaabeaakiaa% b+eacaqGGaGaaeOtaiaab+eacaqGGaGaa4hkaiaa-TcacaGFnbGaa4% xkaiaa+5cacaGFGaGaa4hiaiabeA8aMnaaBaaajqwaacqaaiaaboea% caqGibWaaSbaaKazcaiabaGaae4maaqabaqcKfaGaiaab+eaaSqaba% aaaa!55AC!\[{\rm{CH}}_{\rm{3}} {\rm{O}} + NO ( + M) \to {\rm{ CH}}_{\rm{3}} {\rm{O NO }}( + M). \phi _{{\rm{CH}}_{\rm{3}} {\rm{O}}} \] is found to be (1.0±0.2). The rate constant k ₁ is (7±2) 10^-12 cm³/molecule · s in good agreement with previous results.     

不同沉积环境成因煤显微组分的有机硫分布

运用扫描电镜能谱微区测试对不同沉积环境成因煤的有机显微组分进行有机硫含量的系统测定，结果表明在不同类型的煤中某一类显微组分的有机硫含量存在明显差异；同一煤中不同亚显微组分的有机硫含量也不同。综合分析发现煤显微组分有机硫含量主要受聚煤环境、组分凝胶化程度、氧化程度的影响，而聚煤环境为主导影响因素。