微生物碳酸酐酶对石灰岩的溶蚀驱动作用研究

来源于西南几个不同类型岩溶地区土壤样品分离出来的微生物菌株中,有很多能够产生分泌胞外碳酸酐酶.以一株编号为GLCa102的菌株为代表,模拟岩溶自然环境条件,研究其胞外碳酸酐酶对灰岩的溶蚀驱动作用.结果表明微生物碳酸酐酶能使灰岩溶出的导电离子总量和[Ca2+]提高40%以上,从而对灰岩有显著的酶促溶蚀驱动作用.本研究表明微生物碳酸酐酶在生物岩溶中有重要的作用和地位,同时为深入研究生物对石灰岩的溶蚀作用提供了一定的科学依据.     

碳酸酐酶对碳酸盐岩溶解的催化作用及其在大气CO2沉降中的意义

CO2向H+和HCO3-的转换是一相对慢速过程.因此,其动力学可能决定碳酸盐岩的溶解速率.在灰岩和白云岩的溶解实验中,使用了自然界普遍存在的碳酸酐酶(CA)来催化这一CO2转换反应,结果发现,对灰岩而言,加入CA后,其溶解速率在高CO2分压时可增加10倍,而对白云岩,其溶解速率增加主要在低CO2分压时,可达3倍左右.这一发现表明,化学风化(包括碳酸盐岩溶解和硅酸盐风化)作用在大气CO2沉降和全球碳循环里的所谓丢失的汇中的重要性需要重新评价.毫无疑问,已往的研究由于未认识到CA在风化中的催化作用,因此低估了风化作用的速率,同样也低估了风化作用对大气CO2沉降的贡献.另一方面,也表明了研究自然界不同水体中CA分布及其活度和CA在自然界风化作用中的作用的必要性.     

碳酸盐岩土壤CO2的动态特征及其对溶蚀作用的驱动

由于气候及人类活动等环境因素的影响，直接观测碳酸盐岩－大气系统中ＣＯ２剖面的动态及行为比较困难，作者以碳酸盐岩发育的土壤作为ＣＯ２产生，贮存，运移的介质，对土壤剖面中ＣＯ２的分布及动态特征，不同深度标准石灰岩溶蚀试片的溶蚀作用以及岩溶地下水的水化学参数进行了观测研究，并结合以往的研究资料，对岩溶作用的气体动力学机制进行了探讨，获得如下新认识，（１）土壤剖面ＣＯ２分布特征与气候密切相关，在旱季，土壤     

不同水流速度下温度对奥陶系碳酸盐岩溶蚀速度的影响

为了解不同水流速度下温度对碳酸盐岩溶蚀速度的影响,以自行设计、制造的能够模拟水流条件,并且可同时容纳24个样品的溶蚀试验装置为平台,以淮南张集矿、潞安漳村矿和兖州东滩矿奥陶系灰岩为代表性岩石试样,选取不同温度、水流速度及CO₂压力,进行了溶蚀试验。试验结果显示,在水流速度较低时(16.67 mL/min),环境温度的变化对溶蚀速度的影响比较微小(平均溶蚀变化量为0.000 6 g/cm²)。在水流速度较大时(60 mL/min),温度的改变对溶蚀速度影响较大(平均溶蚀变化量为0.0038 g/cm²)。也就是说在地下水的强径流带,温度对溶蚀速度的影响相对较大,溶蚀速度较快,所以岩溶较发育。     

不同温度条件下CO2水溶液对碳酸盐岩的溶蚀作用

普遍认为酸性流体的溶蚀作用是碳酸盐岩储层形成的重要制约因素。本文以一个全新的模拟实验方式对不同类型碳酸盐岩在CO2水溶液中的相对溶蚀能力进行了研究,结果发现随温度从常温至200℃,碳酸盐岩的溶蚀能力由弱变强再变弱,在60～90℃区间内溶蚀能力最强。白云岩不管在低温还在高温环境下,总比灰岩更难溶蚀,过渡类型的岩类介于二者之间,当温度大于150℃后,CO2对碳酸盐岩的溶蚀能力变得越来越弱。灰岩与白云岩的溶蚀差异也变得越来越小。这暗示碳酸盐岩在早成岩晚期—中成岩早期,CO2水溶液对灰岩的溶蚀作用有重要影响,而对白云岩的溶蚀作用影响较小,白云岩优质储层的形成可能与碳酸盐岩中钙质的流失或白云岩化作用有关。     

3种石生苔藓植物碳酸酐酶对石灰岩的溶蚀作用

以普定严重石漠化区域石生细叶小羽藓Haplocladium microphyllum Hedw.、银叶真藓Bryum argenteum Hedw. 和美灰藓Eurohypnum leptothollum(C. Muell. ) Ando.为研究材料,运用模拟土柱实验装置收集植物淋出液并测定其电导率、pH值、CA活性、钙镁元素含量并对石灰岩试片溶蚀进行估算。结果表明：岩溶生态系统中不同植物的碳酸酐酶活性差异较大,其中细叶小羽藓的溶蚀效果最为显著,产生的碳汇量最大;CA活性最高为美灰藓,为272.99 U·g-1·FW;最小的为细叶小羽藓的CA活性较低,为38.31 U·g-1·FW。淋出液均检测到CA的存在,银叶真藓淋溶6 d的CA活性最高,随着时间的推移,3种植物CA总体表现出先略降,然后升高,最后趋于平稳的趋势;pH值呈上升趋势;电导率呈下降趋势;淋出液中Ca2+和Mg2+浓度随淋溶时间的延长浓度逐渐降低,一定时间后趋于动态的平衡;说明石生植物对石灰岩有明显的酶促溶蚀驱动作用,且溶蚀率与CA活性成正相关。     

微藻及其碳酸酐酶对石灰岩土壤系统中钙元素迁移的驱动作用实验研究

本文以微藻(莱茵衣藻)为材料,通过室内模拟石灰岩土壤系统,对接种微藻的土柱进行不同淋滤条件的处理,系统监测了淋出液的电导率、Ca2+浓度和碳酸酐酶的活性。结果表明,以双蒸水进行淋滤的土柱,Ca2+总淋出量在24 d时仅为以微藻培养液进行淋滤土柱的11.9%,且淋出液碳酸酐酶的平均活性与Ca2+总淋出量间有较好的相关性,说明微藻及其碳酸酐酶对石灰岩土壤系统中的Ca元素迁移有较强的驱动作用。本文的研究结果为探讨藻类碳酸酐酶在岩溶发育中的作用提供了一定的科学依据,进一步深入研究将有助于弄清藻类及其碳酸酐酶对岩溶碳汇的作用。     

模拟污水对碳酸盐岩的溶蚀作用及其潜在的环境意义

碳酸盐岩是个巨大的碳源和钙源,在地球表面分布极广。随着近年来污水排放量的增加,对地表碳酸盐岩的溶蚀产生重大影响。为研究污水对碳酸盐岩的溶蚀作用及其环境效应,利用原子吸收分光光度计、pH计、酸滴定法、扫描电子显微镜-能量扩散X射线谱仪和X-射线粉晶衍射等,分别测定反应体系中的金属离子浓度、pH值、HCO3-浓度、碳酸盐岩被溶蚀前后表面形态和组分变化等指标。研究发现,模拟污水(含有几种重金属离子、H2PO4-、NH4+、脲和土壤微生物等)对碳酸盐岩的溶蚀结果有显著差异,如模拟污水对碳酸盐岩有强烈的溶蚀作用,使其释放更多的Ca和C;低浓度Pb(NO3)2溶液对碳酸盐岩溶蚀表现为吸收CO2;高浓度的Pb(NO3)2、CuCl2、CuSO4和土壤微生物扩增溶液对碳酸盐岩溶蚀表现为释放CO2;重金属盐溶液和复合污水对碳酸盐岩溶蚀后有次生矿物生成等。     

重庆中梁山碳酸盐岩溶蚀速率对季节的响应研究

在重庆市中梁山岩溶槽谷,选取林地、园地、耕地和菜地4种不同土地利用类型,通过野外下三叠统嘉陵江组白云质灰岩石试片的溶蚀试验分析不同土地利用方式下溶蚀速率对季节的响应关系。结果表明:不同土地利用方式将造成土壤性质发生不同的变化,进而对岩石的溶蚀速率产生明显的影响。但无论是从夏半年还是从全年来看,试片的溶蚀速率的大小变化均表现为:林地>菜地>耕地>园地。夏半年在全年的试片溶蚀作用过程中贡献较大,其绝对溶蚀量占全年比例都大于50%;除林地、菜地和园地土下50cm试片外,其余试片的夏半年溶蚀速率都大于全年溶蚀速率。究其原因,主要是由于夏半年气温高,降水量大,使土壤中CO2和水分等增加,从而有利于岩溶作用的进行      

Role of Carbonic Anhydrase as an Activator in Carbonate Rock Dissolution and Its Implication for Atmospheric CO_2 Sink

The conversion of CO2 into H+ and is a relatively slow reaction. Hence, its kinetics may be rate determiningin carbonate rock dissolution. Carbonic anhydrase (CA), which is widespread in nature, was used to catalyze the CO2 conversion process in dissolution experiments of limestone and dolomite. It was found that the rate of dissolution increases by a factor of about 10 after the addition of CA at a high CO2 partial pressure (Pco2) for limestone and about 3 at low Pcoj for dolomite. This shows that reappraisal is necessary for the importance of chemical weathering (including carbonate rock dissolution and silicate weathering) in the atmospheric CO2 sink and the mysterious missing sink in carbon cycling. It is doubtless that previous studies of weathering underestimated weathering rates due to the ignorance of CA as an activator in weathering, thus the contribution of weathering to the atmospheric CO2 sink is also underestimated. This finding also shows the need to examine the situ distribution and activ     

小秦岭地区花岗岩体中CO2—H2O包裹体的找矿意义

小秦岭地区与金矿成因有关的燕山期文峪花岗岩及其派生石英脉中发育了非常丰富的ＣＯ２－Ｈ２Ｏ包裹体,其流体为富含ＣＯ２的低盐度（＜１０％ＮａＣｌ）流体,这与含金石英脉内的包裹体类型及金矿成矿流体性质上十分相似。与金矿成因无关的华山岩体内包裹体类型则为水溶液包裹体,流体性质为贫ＣＯ２的低盐度流体。与金矿有关,但其周围矿化很差的娘娘山岩体内ＣＯ２－Ｈ２Ｏ包裹体数量很少。因此,ＣＯ２－Ｈ２Ｏ包裹体可以作为与金矿成因有关的花岗岩体关联程度的判别标志,而ＣＯ２－Ｈ２Ｏ包裹体的丰度可以作为金矿床品位和规模评价及成矿前景展望的依据     

Raman Micro-Spectroscopic Study of Sulfate Ion in the System Na2SO4 – H2O

This work aims to quantify sulfate ion concentrations in the system Na₂SO₄-H₂O using Raman micro-spectroscopy.Raman spectra of sodium sulfate solutions with known concentrations were collected at ambient temperature（293 K） and in the 500 cm^₁-4000 cm^-1 spectral region.The results indicate that the intensity of the SO₄^2- band increases with increasing concentrations of sulfate ion.A linear correlation was found between the concentration of SO₄^2-（c） and parameter I₁,which represents the ratio of the area of the SO₄^2- band to that of the O-H stretching band of water（A_s/A_w）:I₁=-0.00102+0.01538 c.Furthermore,we deconvoluted the O-H stretching band of water(2800 cm^-1-3800 cm^-1) at 3232 and 3430 cm^-1 into two sub-Gaussian bands,and then defined Raman intensity of the two sub-bands as A_Bi(3232 cm^-1) and A_B2(3430 cm^-1),defined the full width of half maximum（FWHM） of the two sub-bands as W_B1(3232 cm^-1) and W_B2(3430 cm^-1).A linear correlation between the concentration of SO₄^2-（c） and parameter I₂,which represents the ratio of Raman intensity of SO₄^2-（A_s）(in 981 cm^-1) to(A_B1+A_B2),was also established:I₂=-0.0111+0.3653 c.However,no correlations were found between concentration of SO₄^2-（c） and FWHM ratios,which includes the ratio of FWHM of SO₄^2-（W_s） to W_B1 W_B2 and W_B1+B2(the sum of W_B1 and W_B2),suggesting that FWHM is not suitable for quantitative studies of sulfate solutions with Raman spectroscopy.A comparison of Raman spectroscopic studies of mixed Na₂SO₄ and NaCI solutions with a constant SO₄^2- concentration and variable CI^- concentrations suggest that the I\ parameter is affected by CI^-,whereas the I₂ parameter was not.Therefore,even if the solution is not purely Na₂SO₄-H₂O,SO₄^2- concentrations can still be calculated from the Raman spectra if the H₂O band is deconvoluted into two sub-bands,making this method potentially applicable to analysis of natural fluid inclusions.     

Dissolution and Deformation Characteristics of Limestones Containing Different Calcite and Dolomite Content Induced by CO2-Water-Rock Interaction

To investigate the impacts of mineral composition on physical and mechanical properties of carbonate rocks, limestone specimens containing different contents in calcite and dolomite are selected to perform CO2-water-rock reaction experiments. The X-ray Diffraction (XRD) and Nuclear Magnetic Resonance (NMR) are carried out to examine the change characteristics of mineral dissolution and pore structure after reaction. The core flooding experiments with Fiber Bragg gratings are implemented to examine the stress sensitivity of carbonate rocks. The results show that the limestones containing pure calcite are more susceptible to acid dissolution compared to limestone containing impure dolomite. The calcite content in pure limestone decreases as the reaction undergoes. The dissolution of dolomite leads to the formation of calcite in impure limestone. Calcite dissolution leads to the formation of macropore and flow channels in pure limestone, while the effects of impure dolomite in impure limestone results in mesopore formation. When confining pressure is lower than 12 MPa, pure limestones demonstrate higher strain sensitivity coefficients compared to impure limestone containing dolomite after reaction. When confining pressure exceeds 12 MPa, the strain sensitivity coefficients of both pure and impure limestones become almost equal.     

CO2-H2O流体不混溶对Au溶解度的影响——以贵州省贞丰县水银洞金矿床为例

运用热力学原理和方法,研究了CO2-H2O流体不混溶作用对Au的溶解度的影响。结果表明,贵州水银洞金矿床的成矿流体是一种富含挥发分( fCO 2=70.79MPa)、酸性(pH=3.71)、还原性(fO 2=0.50×10-36MPa)、中温(267℃)、具有超压(180MPa)性质的含Au(a∑Au=3.744×10-8mol/L)流体。当超压流体的封闭层——炭质页岩因断裂作用而被破坏时,热液体系的压力发生骤降(28.50～35.30MPa),CO2-H2O流体发生不混溶作用,并有大量CO2溢出。CO2的流失可使成矿溶液的CO2逸度和O2逸度降低(fCO 2=0.80MPa、fO 2= 2.512×10-42MPa),酸碱度升高(pH=4.32),同时伴随温度的下降(224℃),成矿热液中Au溶解度的降低(a∑Au=3.790×10-9mol/L),从而快速沉淀下来成矿。     

Long‐Term Reaction Characteristics of CO2–Water–Rock Interaction: Insight into the Potential Groundwater Contamination Risk from Underground CO2 Storage

CO₂ sequestration into saline aquifers is considered to be one of the most promising options for reducing industrial CO₂ emissions to the atmosphere. However, there are still many uncertainties regarding the storage of CO₂ in the subsurface because of a lack of knowledge about CO₂–water–rock interaction within CO₂ reservoirs and the potential risk of CO₂ leakage. In this study, we construct a semi‐open type experimental system that can reproduce the interactions under conditions close to those of actual CO₂ reservoirs. Using the system, we conduct CO₂–water–rock interaction experiments for 8 months to monitor the long‐term reaction and the mobilization of harmful metal elements. Altered tuffaceous rock is used in the experiment because these tuffaceous rock formations (called “Green Tuff”) are a potential candidate for CO₂ storage in Japan. The results show that the major‐element water composition will converge to the point where host rock dissolution and secondary mineral precipitation are balanced; then, the interaction will proceed under a certain groundwater composition. In addition, we found that groundwater contamination by some metal elements (Ni, Ba, and Mn) may reach unsafe levels for drinking water as a result of CO₂‐water–rock interaction.