热液条件下CO2和H2反应产烃研究进展

热液条件下CO2和H2形成烷烃的反应,提供了自然条件下CO2转化为有机质的一条非生物途径。研究这一过程,对于油气费托非生物成因研究和海底热液生命起源的讨论具有重要意义。已有研究表明,热力学有利的温度、压强条件和合适的催化剂,是热液条件下CO2和H2发生反应形成烷烃的必需条件。在热力学有利的条件下,铬铁矿能够催化反应形成CH4、C2H6和C3H8,但还不清楚是否存在能够促使反应产生C4H10等长链烷烃的天然矿物催化剂。含一种或多种过渡金属元素的磁铁矿,可能是值得考察的对象。另外,研究热液条件下CO2和H2反应形成烷烃的过程和机理,建立反应所形成烷烃的C、H同位素综合判识指标,是今后值得探索的研究课题。     

热液条件下钙锰矿的合成及其影响因素

钙锰矿具有3× 3的大隧道构造, 广泛分布于大洋锰结壳和锰结核等环境中, 其性质和成因倍受关注.以改进方法制备的水钠锰矿(birnessite)为前驱物, Mg2+交换后得到Mg-水钠锰矿(或称布塞尔矿, buserite), 经热液处理合成了结晶度高的单相钙锰矿(todorokite), 采用X-射线衍射(XRD)、透射电镜(TEM)和选区电子衍射(SAED)等技术探讨了热液温度、体系压力和处理时间等因素对钙锰矿合成的影响.结果表明: 合成的钙锰矿与天然钙锰矿有相同的形貌和生长特征, 呈纤维状, 沿120°三连晶生长, 平均化学组成为Mg_0.16MnO_2.07 0.82H₂O.在实验条件下, 热液温度和处理时间是影响钙锰矿合成的主要因素; 而通过改变高压釜的填充度引起体系压力的变化对钙锰矿合成的影响较小, 体系压力并不是钙锰矿形成的主要影响因素.热液温度越高, Mg-水钠锰矿转化为钙锰矿的速率越快, 完全转化为钙锰矿所需的处理时间越短.热液温度分别为120℃、160℃和200℃时, Mg-水钠锰矿完全转化为钙锰矿所需的时间分别为6 h、4 h和2 h; 但热液温度高于160℃时, 易生成水锰矿杂质.延长处理时间与提高热液温度具有相似的影响规律.这进一步明确了钙锰矿的生成条件, 可为阐明钙锰矿的形成机制和促进其在材料科学中的应用提供理论依据.      

热液合成板状高结晶度三八面体蒙脱石

在热液条件下合成了板状的和高度结晶的三八面体蒙脱石。用淬冷玻璃与脱水的钠基蒙脱石分别在(a)500°C,100MPa下1天和11天;(b)300°C,100MPa下7天的条件下进行反应。产物的结晶度和颗粒大小取决于初始玻璃的化学组成,合成温度和热液改性的时间。XRD尖锐的峰和一定相对湿度下水合作用证明了产物结构的高度有序和大尺寸。透射电镜也被用来表征产物颗粒尺寸。通过改变初始材料的化学成分,产物的颗粒大小可以在10nm到几个微米之间变化。有序度最高和尺寸最大的产物是在500°C,100MPa的条件下用Na0.33(Mg1.83Al0.67)Si4O11成分的玻璃反应…     

热液条件下锐钛矿晶体生长的实验

为了解金属离子生长成为热液矿石矿物的过程和机理,使用氟钛酸钾稀溶液在100 MPa和200~400℃条件下开展了一系列等温不等时和等时变温实验.结果显示该热液条件下形成了不同形貌的锐钛矿.随着反应时间和温度的增加,锐钛矿由几十纳米生长至十几微米;10 h以内的晶体生长速度远高于10 h以后,相对高温下的晶体生长速度则高于低温,表明锐钛矿的热液生长与温度、过饱和程度密切相关.综合来看,粒子成核生长、定向附着和奥氏熟化先后控制了热液锐钛矿的生长,而金属在流体中的过饱和程度和溶解-沉淀过程则决定了其生长速度.因而锐钛矿的形态特征可用于指示其形成的温度、世代关系甚至含氟流体的演化历史.      

深海热液口化能合成共生作用的研究进展

海洋无脊椎动物和细菌间的化能合成共生作用的发现,改变了人们对深海热液口初级生产力主要来源的认知.近年的研究表明,营化能合成共生的动物隶属于纤毛门、软体动物门、环节动物门和节肢动物门;其中无脊椎动物作为宿主在与共生菌的长期共生过程中,伴随着部分器官和功能的退化或消失,逐渐形成和演化出了与此相适应的形态结构,并产生了一些特殊的行为;在深海热液口发现的所有化能合成共生菌都属于革兰氏阴性菌,它们的宿主大致可以分为2个群体;通过16 SrRNA基因编码分析,不同代谢类型的共生菌在系统发育中通常处于不同分支,形态也有所差异;共生菌独特的传播方式和进化模式也使其更加适应共生生活;由无脊椎动物和化能合成细菌构成的共生体系与环境相互作用,影响了深海热液口生态系统的演化.对共生菌蛋白质及代谢组学的研究,以及对宿主生理和代谢机制的研究将成为未来热液口化能合成共生作用研究的新热点.     

水热条件下费托型合成反应氢同位素分馏研究

费托型合成(F-TT)反应是地下烃类的三大成因之一,H同位素组成研究对其生烃过程和成因识别具有重要意义。本研究分别以无机CO和CO₂为碳源,水为氢源,研究在370℃和50 MPa的水热条件下, F-TT反应生烃过程中H同位素分馏情况。结果显示,不管是CO参与的经典F-T反应,还是CO₂参与的F-TT反应,烃类产物H同位素均呈正序分布(δD(C₁)<δD(C₂)<δD(C₃)<δD(C₄)<δD(C₅)<δD(C₆)),符合前人有关地下非生物成因烃的H同位素正序分布特征。本研究分别根据CO和CO₂为碳源的亚烷基机理和羰基插入机理,从反应原理、链增长机制和分馏过程,对2种生烃过程中的H同位素呈正序分布这一规律进行了详细机理阐述。由于热成因气H同位素也呈正序分布,所以烃类气体的H同位素分布特征不能够作为无机烃类来源的判识标志。但是,通过数据对比发现,按照甲烷的H同位素...     

费托合成:SiO2和Al2O3负载的Co2C催化剂的表征和评价

采用CO碳化SiO2和Al3O4负载的Co(NO3)2的方法制备了SiO2和Al3O4负载的Co2C催化剂,采用N2物理吸附、X射线衍射和H2-程序升温还原技术对催化剂进行了表征,并用于催化费托合成反应中.结果显示,需要较长碳化时间才可合成负载的Co2C催化剂;所制催化剂表现出CO加氢生成高碳醇的催化性能,其原因可能在于催化剂表面存在的金属Co物种使CO解离,表面Co物种有利于CO插入,从而导致醇的生成,但体相Co2C则不具有催化活性.     

含金黄铁矿的模拟合成实验及热液作用中金富集机制

热液矿床中金主要以包体金和裂隙金两种赋存状态产出,裂隙金构成富矿石。金的两种析出形式,分别为热液演化过程中金的两组成矿化学反应的结果。同时,金的活化和沉淀作用与热液流体中铁的活动有密切关系。为阐明热液富金矿石形成的机理,进行了含金黄铁矿的模拟合成实验。实验是在自紧式冷封高压釜（石英管衬套）中完成的。实验的物理化学条件模拟胶东玲珑等金矿的实测成矿参数ｔ＝４００～２００℃;ｐ＝５０～１０ＭＰａ;ｃ（ＮａＣｌ＋Ｎａ２Ｓ）＝０５～１ｍｏｌ／Ｌ;ｐＨ＝２～６５。装填物料为Ｆｅ２Ｏ３＋６Ｓ＋ＡｕＣｌ３·ＨＣｌ·４Ｈ２Ｏ或金粉。恒温时间为７～１２ｄ。合成黄铁矿具有完好的立方体或五角十二面体晶形。盐酸分步提取法实验证明,在黄铁矿晶体的核心部分含９０×１０－６～６０×１０－６的分散包体金,而黄铁矿边缘部分及以外的残余Ｆｅ２Ｏ３中仍含有大量的反应残余金粒。实验结果证明,在合成反应体系中只有少量的金与黄铁矿同时析出;而更多的金在残余溶液中富集,在自然热液成矿过程中这部分金可形成晚期裂隙金。实验结果与在胶东等地区热液金矿床观察到的事实吻合。     

水热条件对纤蛇纹石纳米管合成的影响研究

采用水热法在不同反应条件下合成了一系列纤蛇纹石纳米管.利用红外吸收光谱、扫描电镜和透射电镜系统地研究了水热反应中,反应温度、Si/Mg比、反应时间等不同反应参数对合成纤蛇纹石纳米管的晶体生长及其结构的影响.结果表明,温度的升高、Si/Mg比趋近0.68及反应时间的延长均有利于纤蛇纹石的生长,并获得最佳条件下合成的纤蛇纹石条件.     

Abiotic formation of hydrocarbons under hydrothermal conditions: Constraints from chemical and isotope data

To understand reaction pathways and isotope systematics during mineral-catalyzed abiotic synthesis of hydrocarbons under hydrothermal conditions, experiments involving magnetite and CO₂ and H₂-bearing aqueous fluids were conducted at 400 °C and 500 bars. A robust technique for sample storage and transfer from experimental apparatus to stable isotope mass spectrometer provides a methodology for integration of both carbon and hydrogen isotope characterization of reactants and products generated during abiogenic synthesis experiments. Experiments were performed with and without pretreatment of magnetite to remove background carbon associated with the mineral catalyst. Prior to experiments, the abundance and carbon isotope composition of all carbon-bearing components were determined. Time-series samples of the fluid from all experiments indicated significant concentrations of dissolved CO and C₁-C₃ hydrocarbons and relatively large changes in dissolved CO₂ and H₂ concentrations, consistent with formation of additional hydrocarbon components beyond C₃. The existence of relatively high dissolved alkanes in the experiment involving non-pretreated magnetite in particular, suggests a complex catalytic process, likely involving reinforcing effects of mineral-derived carbon with newly synthesized hydrocarbons at the magnetite surface. Similar reactions may be important mechanisms for carbon reduction in chemically complex natural hydrothermal systems. In spite of evidence supporting abiotic hydrocarbon formation in all experiments, an “isotopic reversal” trend was not observed for ¹³C values of dissolved alkanes with increasing carbon number. This may relate to the specific mechanism of carbon reduction and hydrocarbon chain growth under hydrothermal conditions at elevated temperatures and pressures. Over time, significant ¹³C depletion in CH₄ suggests either depolymerization reactions occurring in addition to synthesis, or reactions between the C₁-C₃ hydrocarbons and carbon species absorbed on mineral surfaces and in solution.     

The influence of carbon source on abiotic organic synthesis and carbon isotope fractionation under hydrothermal conditions

A series of laboratory experiments were performed to investigate the relative contributions of CO and other single-carbon compounds to abiotic synthesis of organic compounds in hydrothermal environments. Experiments were conducted by heating aqueous solutions of CO, CO₂, HCOOH, or CH₄ at 250 °C under reducing conditions, and observing production of CH₄ and other hydrocarbons. Native Fe was included in the experiments as a source of H₂ through reaction with water and as a potential catalyst. Experiments with CO or HCOOH as the carbon source resulted in rapid generation of CH₄ and other hydrocarbons that closely resembled typical products of Fischer-Tropsch organic synthesis. In contrast, experiments using CO₂ or CH₄ as the carbon source yielded no detectable hydrocarbon products. Carbon isotope measurements of reaction products from the CO experiments indicate that the CH₄ and other hydrocarbons were substantially depleted in ¹³C, with CH₄ δ¹³C values 30 to 34‰ lighter than the initial CO. Most of the fractionation apparently occurs during attachment of CO to the catalyst surface and subsequent reduction to surface-bound methylene. The initial step in polymerization of these methylene units to form hydrocarbons involves a small, positive fractionation, so that ethane and ethene are slightly enriched in ¹³C relative to CH₄. However, subsequent addition of carbon molecules to the growing hydrocarbon chain proceeds with no net observable fractionation, so that the isotopic compositions of the C₃₊ light hydrocarbons are controlled by isotopic mass balance. This result is consistent with a previously proposed model for carbon isotopic patterns of light hydrocarbons in natural samples. The abundance and isotopic composition of light hydrocarbons produced with HCOOH as the carbon source were similar to those generated with CO, but the isotopic compositions of non-volatile hydrocarbons diverged, suggesting that the higher hydrocarbons were formed by different mechanisms in the CO and HCOOH experiments. The experiments indicate that CO, and possibly HCOOH, may be critical intermediates in the abiotic formation of organic compounds in geologic environments, and suggest that the low levels of these compounds present in most hydrothermal systems could represent a bottleneck restricting the extent of abiotic organic synthesis in some circumstances.     

Geochemistry of high H2 and CH4 vent fluids issuing from ultramafic rocks at the Rainbow hydrothermal field (36°14′N, MAR)

The Flores diving cruise was part of the MAST III-AMORES (1995-1998) program funded by the European Union. One of the major achievements of the Flores cruise was the discovery of the Rainbow hydrothermal field hosted in ultramafic rocks south of the Amar segment on the Mid-Atlantic ridge (MAR). The Rainbow hydrothermal fluids exhibit temperatures of 365 °C, pH of 2.8, high chlorinity (750 mmol/kg), and low silica (6.9 mmol/kg). The uniformity in endmember major, minor, trace element concentrations and gas contents suggests that all Rainbow fluids originate from the same deep source. Although H₂S content is relatively low (1.20 mmol/kg), all vent fluids show extraordinary high H₂ (16 mmol/kg), CH₄ (2.5 mmol/kg) and CO (5 μmol/kg) endmember concentrations compared to fluids collected from other vent sites along the MAR. Hydrogen represents more than 40% of the total gas volume extracted from the fluids. At Rainbow, H₂ production is likely associated with alteration of olivine and orthopyroxene minerals during serpentinization. Given that exposures of ultramafic rock may be common, particularly along slow-spreading ridges, the production of H₂ may have important implications for microbial activity at and beneath the seafloor.     

Production of CO2 and H2 by Diking-Eruptive Events at Mid-Ocean Ridges: Implications for Abiotic Organic Synthesis and Global Geochemical Cycling

We have calculated the amounts of CO₂ and H₂ produced by complete degassing of mid-ocean ridge basalt (MORB) magma, and by degassing during transient diking-eruptive events. Our CO₂ calculations are based on a model estimate of an initial CO₂ content of 1800 ppm in MORB magma, which is equivalent to 2.2 × 10¹² mol CO₂ per year for magma production at worldwide ocean ridges. Observations indicate that many MORB magmas are emplaced in numerous small pulses of dikes and associated lava flows with very short emplacement times, which would result in release of relatively large amounts of CO₂ over short intervals. For example, a dike injected into the oceanic crust that extends from the top of its magma chamber at 2 km depth to the seafloor would degas 2.3 × 10⁴ mol CO₂ per m² surface area of dike, and produce another 4.0 × 10⁴ mol CO₂ per m² on complete crystallization.

Unlike CO₂, which is not strictly governed by crystallization-alteration processes, H₂ is produced from MORB by the reduction of H₂O by ferrous iron in the magma to form magnetite and H₂ as the magma cools and crystallizes. From published paired analyses of MORB glass and crystalline rock, we estimate that the amount of H₂ produced from one cubic meter of rock averages 301 mol. We suggest that the oxidizing agent is H₂O dissolved in the magma, which results in rapid generation of H₂. The amount of pre-alteration oxidation may be limited by the amount of H₂O dissolved in the magma; thus relatively water-rich magmas will undergo greater oxidation. For the case of the two-kilometer-high dike reaching the seafloor, the amount of H₂ released is 6.2 × 10⁵ moles H₂ per m² surface area of the dike. This is 10 times greater than the total CO₂ released by degassing and crystallization of the dike. Assuming that the H₂ generation rate for the entire basaltic layer of the oceanic crust is the same as for MORB lavas (312 mol/m³), then the annual global H₂ production rate is 6.3 × 10¹² mol H₂ per year. This amount is about three times greater than our calculated annual CO₂ production from MORBs. Given that the annual CO₂ production rate from MORBs over 3.3 Ga can account for all CO₂ found in the Earth's crust, hydrosphere, and atmosphere, it is likely that the H₂ produced at mid-ocean ridges plays a significant role as a reducing agent in the global redox state of the Earth's surface.

In contrast to time-averaged global production rates, the rapid release of CO₂ and H₂ in diking-eruptive events may locally result in formation of a separate gas phase containing H₂-CO₂-H₂O in that order of abundance. The amounts of CO₂ and H₂ produced could provide a significant energy source for autotrophic microorganisms. It has been demonstrated that such a CO₂-H₂-H₂O gas mixture yields methanol in magnetite-surface catalyzed reactions at seafloor hydrothermal conditions. Such abiotic synthesis reactions could have been important in early Earth processes.     

利用高铁钾长石粉合成13X沸石分子筛的实验研究

对江苏丰县的富钾页岩进行预处理，得到钾长石含量达76．4％的钾长石粉，其Fe2O3含量高达7．52％。以此钾长石粉为原料经过焙烧处理、水热合成实验，在铁含量较高情况下成功合成了13X沸石分子筛，并采用正交实验法确定了优化工艺参数。对实验产物的主要性能测试表明，合成的富铁沸石产品与13X沸石分子筛工业产品相似，吸附量达到国家化学工业产品标准，可用于对含重金属离子废水的吸附处理。     

The application of P–T–X(CO2) modelling in constraining metamorphism and hydrothermal alteration at the Damang gold deposit,Ghana

Orogenic gold mineralization at the Damang deposit, Ghana, is associated with hydrothermal alteration haloes around gold‐bearing quartz veins, produced by the infiltration of a H₂O–CO₂–K₂O–H₂S fluid following regional metamorphism. Alteration assemblages are controlled by the protoliths with sedimentary rocks developing a typical assemblage of muscovite, ankerite and pyrite, while intrusive dolerite bodies contain biotite, ankerite and pyrrhotite, accompanied by the destruction of hornblende. Mineral equilibria modelling was undertaken with the computer program thermocalc , in subsets of the model system MnO–Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–CO₂–H₂O–TiO₂–Fe₂O₃, to constrain conditions of regional metamorphism and the subsequent gold mineralization event. Metapelites with well‐developed amphibolite facies assemblages reliably constrain peak regional metamorphism at ~595 °C and 5.5 kbar. Observed hydrothermal alteration assemblages associated with gold mineralization in a wide compositional range of lithologies are typically calculated to be stable within P–T–X(CO₂) arrays that trend towards lower temperatures and pressures with increasing equilibrium fluid X(CO₂). These independent P–T–X(CO₂) arrays converge and the region of overlap at ~375–425 °C and 1–2 kbar is taken to represent the conditions of alteration approaching equilibrium with a common infiltrating fluid with an X(CO₂) of ~0.7. Fluid‐rock interaction calculations with M–X(CO₂) diagrams indicate that the observed alteration assemblages are consistent with the addition of a single fluid phase requiring minimum fluid/rock ratios on the order of 1.     

现代海底热液区重晶石的地球化学特征及其影响因素

重晶石是海底热液活动产物之一,其化学元素及Sr、S、O同位素组成可以有效地揭示热液流体的演化过程。本文通过分析研究全球23个热液区中重晶石的化学元素和Sr、S、O同位素组成,探讨了热液区重晶石的元素富集特征,以及沉积物、岩浆、微生物对重晶石的影响因素。结果表明：高温比低温使Sr更容易进入重晶石晶格,重晶石晶型和元素组成特征指示了不同的成矿条件;板状重晶石具有较高的SrO/BaO比值,反映了较高温的成矿条件;柱状重晶石具有较低的SrO/BaO比值,反映了较低温的成矿条件。研究推测Ca类质同象替代Ba的程度可能也受温度的影响。重晶石中的⁸⁷Sr/⁸⁶Sr、δ³⁴S、δ¹⁸O值变化范围较大,分别为0.703 73~0.717 49、3.7‰~36.1‰、3.3‰~18.8‰,表明不同热液区成矿流体受沉积物、岩浆作用、微生物作用等多种因素的影响。受沉积物来源影响的Sr、S使重晶石的⁸⁷Sr/⁸⁶Sr值及δ³⁴S值偏高,温度和热液—沉积物反应程度是主要控制因素;受岩浆来源的SO₂的歧化作用和后期H₂S的氧化作用影响重晶石的δ³⁴S值,扩张中心的演化程度是岩浆影响重晶石δ³⁴S值的主要控制因素;微生物还原作用伴随着S、O同位素分馏,直接影响重晶石的δ³⁴S和δ¹⁸O值,沉积环境条件和初级生产力是主要控制因素。