傅里叶变换拉曼探针测定九种气体的定量因子

采用傅里叶变换拉曼探针测定出９种与地球化学有关的气体拉曼定量因子;Ｈ２２．２５,ＳＯ２１．０６,ＣＯ２１．１３,Ｏ２０．９１,ＣＯ０．８７,Ｎ２１．００,Ｈ２Ｓ３．１１,ＣＨ４８．４２,Ｃ２Ｈ６３．３０。     

不同类型湿地CO2:CH4比例及其影响因素: 整合分析

湿地是温室气体二氧化碳(CO₂)和甲烷(CH₄)的主要来源之一,在全球碳循环中发挥着重要作用。由于CH₄在百年尺度上的全球增温潜势是CO₂的45倍,因此深入研究湿地CO₂:CH₄的排放比例及其影响因素对准确理解和预测湿地碳循环过程及其对未来全球变化的响应具有重要意义。本文采用文献整合分析方法,对比了不同类型湿地中CO₂:CH₄排放比例的特征及其影响因素。结果表明,藓类泥炭沼泽、滨海湿地和稻田中CO₂:CH₄排放比例显著高于草本沼泽、河流湿地和湖泊湿地等其他类型湿地;相关性分析研究发现,湿地CO₂:CH₄排放比例与pH和水位显著负相关,与盐度显著正相关。可见,藓类泥炭沼泽低水位和低pH抑制CH₄排放是导致其CO₂:CH₄排放比例较高的重要原因,而滨海湿地高盐分抑制CH₄排放是其CO₂:CH₄排放比例高的重要原因。与自然湿地相比,稻田CO₂:CH₄排放比例高与其人为施肥和稻草还田抑制CH₄排放有关。此外,大气温度、土壤温度、降水量、土壤含水率等因子也对湿地CO₂:CH₄排放比例具有重要影响,尽管它们之间的线性相关关系不显著。目前,湿地CO₂:CH₄排放比例和影响因素仍存在很大的不确定性,未来亟待加强不同类型湿地CO₂:CH₄排放比例及其关键影响因素研究。

     

考虑Klinkenberg因子状态的CO2-ECBM模拟研究

为了探究Klinkenberg效应及不同状态的Klinkenberg因子在注CO₂提高煤层气采收率(CO₂-Enhanced Coal Bed Methane,CO₂-ECBM)过程中的作用,借助COMSOL有限元软件模拟分析了Klinkenberg因子为0、固定Klinkenberg因子与动态Klinkenberg因子3种状态对CO₂-ECBM及有效渗透率的影响,以及CH4与CO₂压力随该因子的动态变化情况,并将CH4产气量与工程实际作了对比验证。结果表明,CH4与CO₂有效渗透率呈先缓慢增长再急速下降后逐渐趋于平缓的态势,相较于固定Klinkenberg因子或Klinkenberg因子为0,动态Klinkenberg因子影响下的CH4与CO₂有效渗透率更大,当Klinkenberg因子为动态变量时,受不同气体的摩尔质量与动力黏度影响,CO₂有效渗透率小于CH4有效渗透率。在动态Klinkenberg因子作用下...     

控制灌溉对稻田CH4和N2O综合排放及温室效应的影响

采用静态箱-气象色谱法对控制灌溉稻田CH₄和N₂O排放进行了观测,研究控制灌溉模式对稻田CH₄和N₂O排放的影响,并对其温室效应进行了评估。结果表明,控制灌溉稻田CH₄排放通量明显低于淹水灌溉稻田,且主要集中在分蘖前期和中期,全生育期CH₄排放量比淹水灌溉稻田减少73.2%～85.0%。控制灌溉稻田N₂O排放通量在水稻全生育期大部分时间都要大于淹水灌溉稻田,稻季N₂O排放量分别为106.65 mg/m2和96.40 mg/m2,控灌稻田较淹灌稻田增加了10.6%。控制灌溉稻田稻季排放CH₄和N₂O的全球增温潜势(GWPs)为726 kg/hm2,较淹水灌溉稻田减少了59.1%。控制灌溉模式能显著降低CH₄和N₂O综合排放的全球增温潜势。     

神农架大九湖泥炭湿地CH4通量特征及其影响因子

开展大九湖湿地生态系统CH₄通量研究,对深入了解碳循环机制、科学经营以及准确评估湿地生态系统碳收支等方面具有重要意义.以湖北省神农架林区大九湖亚高山泥炭湿地为研究区域,采用涡度相关法对CH₄通量进行原位连续观测,分析了泥炭湿地CH₄通量变化特征及其影响因素.结果表明,大九湖泥炭湿地在2015年8月至2016年5月期间表现为CH₄的源,日通量均值为15.57 nmol·m-2·s-1.CH₄通量具有“夜间极大值”(2:00或22:00) 和“三峰模式”(6:00、12:00和22:00) 两种昼夜变化规律;CH₄通量具有明显季节变化规律,8月释放最多(36.46 nmol·m-2·s-1),3月释放最少(3.92 nmol·m-2·s-1).相关性分析表明,大九湖泥炭湿地CH₄通量受空气温度(T_a)、土壤温度(T_s)、土壤含水量(SWC)和摩擦风速(U*)的共同影响;不同时间尺度上,各影响因子与CH₄通量的相关性有所差异.曲线拟合得出,CH₄通量与T_a和T_s呈指数增长趋势,与SWC呈二次曲线关系.      

腾冲火山区壳内岩浆囊现今温度:来自温泉逸出气体 CO2、CH4间碳同位素分馏的估计

温度是岩浆囊的重要物理参数,获取温度参数并监测其变化对更好地理解岩浆囊的物理化学性质和行为、评价火山的活动性和喷发危险性具有重要的理论和现实意义.本文通过对温泉逸出气体CO2和CH4碳同位素样品的采集、分析测试,利用Horita通过实验矫正的Richet的平衡分馏系数的理论计算数据,通过拟合得到的CO2-CH4碳同位素平衡分馏方程T(K)=3880.3(10001nα(CO2-CH4))-0.5984,计算了腾冲火山区现存3个岩浆囊的温度.结果表明:在整个腾冲火山区,由CO2和CH4的碳同位素分馏值计算的气体源区平衡温度最低397℃,最高1163℃,平均615℃.腾冲火山区的3个岩浆囊中,南部五合-龙江-浦川岩浆囊的现今温度在464～1163℃,平均773℃,温度最高;中部腾冲-和顺-热海岩浆囊的现今温度在438 ～773℃间,平均达566℃,温度次之;北部马站-曲石-永安岩浆囊的现今温度在397～651℃间,平均达524℃,温度最低.我们认为,腾冲火山区地下岩浆囊顶部气体富集区目前的温度变化范围为400～ 1200℃,岩浆囊的实际温度应高于平均值615℃.3个岩浆囊的边缘温度可能在400 ～600℃间,中心温度可能在700～1200℃间.3个岩浆囊中心的现今温度已达到流纹岩浆(600～900℃)、安山岩(800 ～ 1100℃)和玄武岩浆(1000～1250℃)的形成温度,进一步说明腾冲火山区目前3个岩浆囊是客观存在的.另外,我们发现在用δ-△图解法判断CO2-CH4间碳同位素分馏平衡的过程中,在保持2条拟合直线的斜率符号相反的条件下,无论如何剔除数据点,都不能使δ13CCO2-ΔCO2-CH4拟合直线的截距bCO2和δ13 CCH4-ΔCO2-CH14拟合直线的截距bCH4之差bΔ小于0.1245,说明2条拟合直线的交点不能落于δ轴上,而这一数值与Horita方程的常数项接近,这说明CO2-CH4间碳同位素分馏方程中确实存在常数项,CO2和CH4间在再高的温度下都存在碳同位素的分馏.δ-△图解法判断CO2-CH4间碳同位素分馏平衡准则应修正为:在保持2条拟合直线的斜率符号相反的条件下,δ13 CCO2-ΔCO2-CH4拟合直线和δ13CCH4-ΔCO2-CH4拟合直线应相交于δ轴附近截距差0.1245处.     

南海北部海区海底沉积物中孔隙水的Cl-和SO42-浓度异常特征及其对天然气水合物的指示意义

硫酸根含量是天然气水合物孔隙水中重要的参数之一,硫酸根与水合物的赋存关系已成为天然气水合物地球化学异常研究的重要组成部分。为了更深入地了解硫酸根浓度异常产生的原因和机制,建立一种实时、快速的测定方法就显得尤为重要。本文利用自行设计的天然气水合物反应装置,建立了海水中硫酸根在高压低温环境下的拉曼光谱定量测定方法。硫酸根的浓度（ρ）在2.0~70.0 g/L范围内,与其拉曼光谱参数（R）有良好的线性关系,线性回归方程为R=0.0013ρ-0.000066,相关系数r = 0.9998。方法检出限为0.2 g/L,精密度（RSD,n=12）为2.5%~3.4%,回收率为102.1%~123.8%。测试结果表明,采用拉曼光谱法可在线检测天然气水合物-水体系中硫酸根的浓度变化;相对于离子色谱法,具有不破坏原样品和方便快捷等优点。通过对硫酸根浓度变化的初步分析,发现其浓度呈阶梯状升高,认为天然气水合物的形成是一个气体溶解-成核-生长反复进行的过程,直至整个反应体系达到平衡。

     

纤钡锂石 BaMg2LiAl3[Si2O6]2（OH,F）8及其晶体结构

1974年在一水晶矿石英脉晶洞中,发现了一种含Ba、Li的硅酸盐新矿物--纤钡锂石。我们对纤钡锂石进行了光性研究、比重测定、差热及热失重分析、红外光谱分析、X射线单晶结构分析等工作,现分述如下。     

武汉市汤逊湖水-气界面CO2通量昼间变化观测及其影响因素分析

为探究亚洲最大城中湖武汉市汤逊湖水体溶存CO2浓度(pCO2)及水-气界面CO2通量(FCO2)日变化规律, 于冬季(1周)和夏季(3个昼间)对汤逊湖的两个样点(TXH1和TXH2)进行表层水样分析, 并用水质参数仪和风速仪现场测定环境气象因子(pH、DO、DO%、EC、水温、气温、风速), 在实验室测定碱度。用CO2SYS模型计算(水温、pH和碱度)水体pCO2, 薄边层模型计算湖泊水-气界面FCO2, 研究结果表明pCO2和FCO2在日尺度及季节尺度上有着显著性差异, 且两个取样点间有显著性差异。汤逊湖存在CO2"源/汇"功能转换, 整体上呈现"源"的特征。TXH1表层水pCO2均值为585.5±758.2 μatm, FCO2均值为3.52±20.58 mmol/(m2·d); TXH2表层水pCO2均值为799.3±579.4 μatm, FCO2均值为6.53±14.81 mmol/(m2·d)。冬季TXH2表层水pCO2均值(1032.1±183.5 μatm)高于TXH1(均值为348.2±119.8 μatm); 夏季TXH2表层水pCO2(均值为391.9±783.1 μatm)低于TXH1(均值为1000.7±1143.8 μatm); 冬季TXH2的FCO2平均值(13.94±3.91 mmol/(m2·d))高于TXH1的平均值(-1.36±2.80 mmol/(m2·d), 夏季TXH2的FCO2平均值(-6.43±17.77 mmol/(m2·d))低于TXH1的平均值(12.06±32.49 mmol/(m2·d))。pCO2和FCO2受环境因子EC、DO、水温、气温的影响, 并通过逐步回归分析得到DO和水温是影响FCO2的主要环境因子。通过pCO2和FCO2各时间点均值和总均值比较, 发现11:30~12:00时取样能较好地代表冬季8:00~15:30时之间的水-气界面碳释放, 8:00~9:00时取样能较好地代表夏季7:00~18:30时之间的水-气界面碳释放。     

莺歌海盆地LD10区高含CO2天然气充注期次精细厘定与成藏模式

莺歌海盆地LD10区中深层黄流组?梅山组重力流水道、海底扇储层已被证实具有重大的天然气资源潜力.但是前期测试结果显示气藏中混有高含量CO₂气体.因此,精细厘定天然气充注期次,明确CH₄、CO₂等时空分布规律对规避高CO₂风险至关重要.本研究在对不同产状流体包裹体岩相学特征精细观察的基础上,综合激光拉曼光谱分析和包裹体显微测温技术识别出3幕不同成分天然气充注,时间分别为:4.0~2.9 Ma、2.0~1.2 Ma和0.8~0.3 Ma.其中,第一幕充注以烃类气为主,伴有少量有机CO₂和N₂;第二幕和第三幕充注以大量无机CO₂、烃类气为主,伴有少量N₂.结合天然气及烃源岩地化特征、天然气组分分析及输导体系识别,总结了LD10区的成藏模式,以期为研究区下一步天然气勘探开发和规避高含量CO₂风险提供依据.      

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

汶川M_s 8.0地震破裂带CO_2、CH_4、Rn和Hg脱气强度

地震活动断裂带能够向大气释放大量的温室气体、放射性气体和有毒气体(CO_2、CH_4、Rn和Hg),并对大气环境的影响产生复杂的影响。利用静态暗箱法,对汶川M_s8.0地震破裂带CO_2、Rn和Hg脱气强度进行实地测量,并计算了CO_2和Hg脱气对大气的年贡献量。结果表明:(1)破裂带土壤气中CO_2、CH_4、Rn和Hg异常浓度最大值分别可以达到7.98%、2.38%、524.30k Bq/m~3和161.00ng/m~3;破裂带CO_2、Rn和Hg脱气平均通量是34.95g·m~(-2)d~(-1)、36.11m Bq·m~(-2)s~(-1)和26.56ng·m~(-2)h~(-1),最大值分别达到259.23g·m~(-2)d~(-1)、580.35m Bq·m~(-2)s~(-1)和387.67ng·m~(-2)h~(-1);(2)汶川Ms8.0地震破裂带向大气脱气的CO_2年贡献量是0.95Mt,Hg的年贡献量是15.94kg。汶川Ms8.0地震破裂带破裂CO_2、CH_4、Rn和Hg等的脱气强度,不仅与破裂带渗透率有关,还与断裂带浅部存在的气藏、煤层以及磷矿层等气体源有重要的联系。     

Gas seepage from Tokamachi mud volcanoes, onshore Niigata Basin (Japan): Origin, post-genetic alterations and CH4-CO2 fluxes

Methane and CO₂ emissions from the two most active mud volcanoes in central Japan, Murono and Kamou (Tokamachi City, Niigata Basin), were measured in from both craters or vents (macro-seepage) and invisible exhalation from the soil (mini- and microseepage). Molecular and isotopic compositions of the released gases were also determined. Gas is thermogenic (δ¹³C_CH4 from −32.9‰ to −36.2‰), likely associated with oil, and enrichments of ¹³C in CO₂ (δ¹³C_CO2 up to +28.3‰) and propane (δ¹³C_C3H8 up to −8.6‰) suggest subsurface petroleum biodegradation. Gas source and post-genetic alteration processes did not change from 2004 to 2010. Methane flux ranged within the orders of magnitude of 10¹-10⁴ g m⁻² d⁻¹ in macro-seeps, and up to 446 g m⁻² d⁻¹ from diffuse seepage. Positive CH₄ fluxes from dry soil were widespread throughout the investigated areas. Total CH₄ emission from Murono and Kamou were estimated to be at least 20 and 3.7 ton a⁻¹, respectively, of which more than half was from invisible seepage surrounding the mud volcano vents. At the macro-seeps, CO₂ fluxes were directly proportional to CH₄ fluxes, and the volumetric ratios between CH₄ flux and CO₂ flux were similar to the compositional CH₄/CO₂ volume ratio. Macro-seep flux data, in addition to those of other 13 mud volcanoes, supported the hypothesis that molecular fractionation (increase of the “Bernard ratio” C₁/(C₂ + C₃)) is inversely proportional to gas migration fluxes. The CH₄ “emission factor” (total measured output divided by investigated seepage area) was similar to that derived in other mud volcanoes of the same size and activity. The updated global “emission-factor” data-set, now including 27 mud volcanoes from different countries, suggests that previous estimates of global CH₄ emission from mud volcanoes may be significantly underestimated.     

N2CH4z.sbnd;CO2 fluids during formation of the Dôme de l'Agout,France

The Dôme de l'Agout consists of an ellipsoidal mass of gneisses and migmatites emerging from a large area of chlorite-sericite schists. Fluid inclusions in syn-metamorphic quartz segregations are typically one-phase at room temperature. Analyses by gas chromatography indicate that their main constituents are N₂, CH₄ and CO₂; such compositions are confirmed by freezing studies on individual inclusions. Nitrogen contents of the inclusions range from 2 to 72 mol% and tend to increase with increasing degree of metamorphism. CH₄ and CO₂ show an erratic distribution with the exception of the lowest grade samples, which invariably have very high CO₂ contents. The origin of the nitrogen remains unsolved; however, it seems likely that the nitrogen was not produced by mineral reactions in the presently exposed rocks but came from an external source and moved from the centre of the dome outwards.     

C02-CH4流体与金成矿作用：以阿尔泰山南缘和穆龙套金矿为例

造山型金矿的成矿作用与H20-CO2流体有着密切的联系。然而对阿尔泰山南缘和穆龙套金矿的流体包裹体研究表明，无水的CO2-CH4流体在中亚成矿域中一些金矿床中具有同样重要意义。阿尔泰山南缘萨热阔布金矿包裹体的Xch4达0.20～0.23，穆龙套金矿的XCH4为0.07～0.23。CH4扩大了流体不混溶的范围，有利于对Au的富集沉淀。CO2流体在Au成矿中的重要作用至少包括了三方面的意义，即：缓冲流体PH值范围、提高流体中的Au含量并使其维持与还原硫的络合作用进行迁移；扩大超临界流体的温度范围；增加流体不混溶的区域。CH4的加入扩大了流体不混溶的范围，有利于对Au的富集沉淀。     

Laboratory study of self-potential signals during releasing of CO2 and N2 plumes

Carbon Capture Sequestration (CCS) projects require, for safety reasons, monitoring programmes focused on surveying gas leakage on the surface. Generally, these programmes include detection of chemical tracers that, once on the surface, could be associated with CO₂ degassing. We take a different approach by analysing feasibility of applying electrical surface techniques, specifically Self-Potential. A laboratory-scale model, using water-sand, was built for simulating a leakage scenario being monitored with non-polarisable electrodes. Electrical potentials were measured before, during and after gas injection (CO₂ and N₂) to determine if gas leakage is detectable. Variations of settings were done for assessing how the electrical potentials changed according to size of electrodes, distance from electrodes to the gas source, and type of gas. Results indicated that a degassing event is indeed detectable on electrodes located above injection source. Although the amount of gas could not be quantified from signals, injection timespan and increasing of injection rate were identified. Even though conditions of experiments were highly controlled contrasting to those usually found at field scale, we project that Self-Potential is a promising tool for detecting CO₂ leakage if electrodes are properly placed.     

Prediction of CH4 and CO2 hydrate phase equilibrium and cage occupancy from ab initio intermolecular potentials

Presented is an improved model for the prediction of phase equilibria and cage occupancy of CH₄ and CO₂ hydrate in aqueous systems. Different from most hydrate models that employ Kihara potential or Lennard-Jones potential with parameters derived from experimental phase equilibrium data of hydrates, we use atomic site-site potentials to account for the angle-dependent molecular interactions with parameters directly from ab initio calculation results. Because of this treatment, our model can predict the phase equilibria of CH₄ hydrate and CO₂ hydrate in binary systems over a wide temperature-pressure range (from 243-318 K, and from 10-3000 bar for CH₄ hydrate; from 253-293 K, and from 5-2000 bar for CO₂ hydrate) with accuracy close to experiment. The average deviation of this model from experimental data is less than 3% in pressures for a given temperature. This accuracy is similar to previous models for pressures below 500 bar, but is more accurate than previous models at higher pressures. This model is also capable of predicting the cage occupancy and hydration number for CH₄ hydrate and CO₂ hydrate without fitting any experimental data. The success of this study validates the predictability of ab initio intermolecular potentials for thermodynamic properties.     

Characteristics of high heating rate biomass chars prepared under N2 and CO2 atmospheres

Partial substitution of coal by biomass in combustion systems in conjunction with advanced technologies for CO₂ capture and storage may result in a significant reduction of greenhouse gases emissions. This study investigates three biomass chars produced from rice husk, forest residuals and wood chips under N₂ and CO₂ atmospheres using a drop tube furnace (DTF) heated at 950 °C. The char constitutes an unburned residue which has been devolatilized under conditions resembling in thermal history those in full scale boilers. Higher weight losses were achieved under N₂ than under CO₂ for each type of biomass, and the highest weight loss was that of wood chips biomass, followed by forest residuals and then rice husk. The results indicate significant morphological differences between the biomass chars produced. The wood chips yielded thick-walled chars with a cenospheric shape very similar to those of low-rank vitrinite. The forest residual chars were angular in shape and often had a tenuinetwork structure, while the rice husk chars retained their vegetal structure. Overall, the studied biomass chars can be described as microporous solids. However, in the case of the rice husk, the silica associated to the char walls was essentially mesoporous, increasing the adsorption capacity of the rice husk chars. The atmosphere in the DTF affects the development of porosity in the chars. The pore volumes of the rice husk and forest residual chars prepared under a CO₂ atmosphere were higher than those of chars prepared under a N₂ atmosphere, whereas the opposite was the case with the wood chip chars. The chars that experienced the most drastic devolatilization were those with the lowest intrinsic reactivity. This indicates a more efficient reorganization of the chemical structure that reduces the number of active sites available for oxygen attack. Overall a similar morphology, optical texture, specific surface area and reactivity were found for the biomass chars generated under N₂ and CO₂, which is a similar result to that obtained for coal chars.     

Chemical and isotopic equilibrium between CO2 and CH4 in fumarolic gas discharges: Generation of CH4 in arc magmatic-hydrothermal systems

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH₄) within two subduction-related magmatic-hydrothermal environments.Apparent temperatures derived from carbon isotope partitioning between CH₄ and CO₂ of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H₂O-H₂-CO₂-CO-CH₄ geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH₄, CO₂ and H₂O implying that carbon isotope partitioning between CO₂ and CH₄ in both systems is controlled by aquifer temperature.N₂/³He and CH₄/³He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH₄ may have been primarily generated through the reduction of CO₂ by H₂ in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH₄ and subsequent re-equilibration with co-existing CO₂ cannot be ruled out entirely. CO₂/³He ratios and δ¹³C_CO2 values imply that the evolved CO₂ either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH₄ during thermometamorphism.