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1.
崔猛  符晓  郑俊杰  吕苏颖  熊辉辉  曾晨  韩尚宇 《岩土力学》2022,43(11):3027-3035
植物源脲酶诱导碳酸钙沉淀(enzyme induced carbonate precipitation,简称EICP)可以显著改善砂土的工程力学特性,但在具体操作时,参数取值无对应规范,固化效果有待提升。基于黄豆脲酶,研究了温度、脲酶浓度、尿素浓度、钙浓度、pH值、钙源种类等变量对脲酶活性与碳酸钙沉淀的影响,并进行了沉淀物(碳酸钙晶体)的扫描式电子显微镜(scanning electron microscope,简称SEM)与X射线衍射(X-ray diffraction,简称XRD)测试,在此基础上开展了黄豆脲酶固化砂的无侧限抗压强度与固化效果试验研究。结果表明:脲酶活性随脲酶浓度的增加而线性增长,但存在温度阈值,温度超过阈值后,脲酶将完全失活,且阈值随脲酶浓度的增大而降低;尿素浓度与pH值共同影响脲酶活性,二者存在一个最优组合,当尿素浓度在0.1~1.0 mol/L时最优pH值为7,当尿素浓度在1.0~1.5 mol/L时最优pH值为8。脲酶是沉淀反应的催化剂,脲酶浓度越高,反应越完全,碳酸钙沉淀率越高;尿素与钙溶液则主要通过掺入量影响碳酸钙沉淀量,掺量比例宜为1:1,且二者浓度与pH值可通过影响脲酶活性来影响碳酸钙的沉淀情况;不同钙源对碳酸钙沉淀量的影响幅度不大。不同钙源沉淀碳酸钙晶体的成分与密度基本相同,但晶体结构差异较大,氯化钙沉淀碳酸钙晶体以块状为主,表面分布球状、类球状晶体,胶结面大,可作为EICP技术中较为理想的钙源。基于黄豆脲酶和氯化钙钙源固化砂的无侧限抗压强度约为掺粉煤灰砂样的6倍,通过SEM图像可发现,沉淀碳酸钙晶体包裹并黏结砂粒成为整体,固化效果非常理想。  相似文献   

2.
微生物诱导碳酸钙沉淀(microbially induced calcium carbonate precipitation, MICP)是一种在自然界中广泛存在的生物矿化过程。由于MICP具有反应速度快、环境条件要求低、应用范围广、温室气体减排效应显著等特点,在地质、土木、水利、环境多个领域中广泛推广应用。文章在分析国内外相关研究成果的基础上,归纳整理出反硝化过程、硫酸盐还原作用、尿素分解作用等多种微生物诱导下碳酸钙矿化途径和作用机制。以尿素分解菌为代表,重点讨论微生物诱导碳酸盐沉淀过程中pH、温度、离子浓度等环境因素对生成矿物晶型晶貌等方面的影响,总结了MICP的环境应用机制,即环境中的重金属元素通过替换作用替换矿化矿物中的Ca2+或CO32?从而被固定。MICP作为一种简单高效的地质环境过程,在生态环境修复领域具有广阔的应用前景。   相似文献   

3.
The silicate and carbonate fraction of 98 non-metamorphic shale samples from the Australian platform and of different geological age were analysed for calcium, magnesium, ferrous iron and carbonate. Cainozoic and Mesozoic shales prove to be essentially calcitic, Cambrian and Proterozoic shales are essentially dolomitic and sideritic. A similar trend of high MgO values can be demonstrated for the silicate fraction of the old shales. Extensive literature study confirms these trends for shales and carbonate rocks from all over the world. Slates, hornfelses and schists are Mg rich and Ca poor, whether young or old.Ronov's model of the evolution of the earth's crust ocean and atmosphere, explaining these trends, is critically reviewed but rejected because of impossible storage problems of calcium in the Proterozoic. The increased magnesium content of the old sediments is explained by calcium carbonate sweating out of the sedimentary column, magnesium introduction from altering volcanic rocks within the sedimentary pile and magnesium introduction from connate brines in sandstones. The increasing calcium content of all kinds of sediments with decreasing age is claimed to be related to preferential weathering of extrusive volcanic rocks and sweating out of calcium carbonate from the sedimentary column.  相似文献   

4.
Cui  Ming-Juan  Lai  Han-Jiang  Hoang  Tung  Chu  Jian 《Acta Geotechnica》2021,16(2):481-489

Enzyme induced carbonate precipitation (EICP) is an emerging soil improvement method using free urease enzyme for urea hydrolysis. This method has advantages over the commonly used microbially induced carbonate precipitation (MICP) process as it does not involve issues related to bio-safety. However, in terms of efficiency of calcium carbonate production, EICP is considered lower than that of MICP. In this paper, a high efficiency EICP method is proposed. The key of this new method is to adopt a one-phase injection of low pH solution strategy. In this so-called one-phase-low-pH method, EICP solution consisting of a mixture of urease solution of pH?=?6.5, urea and calcium chloride is injected into soil. The test results have shown that the one-phase-low-pH method can improve significantly the calcium conversion efficiency and the uniformity of calcium carbonate distribution in the sand samples as compared with the conventional two-phase EICP method. Furthermore, the unconfined compressive strength of sand treated using the one-phase-low-pH method is much higher than that using the two-phase method and the one-phase-low-pH method is also simpler and more efficient as it involves less number of injections.

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5.
Fabrics of phosphatized calcium carbonate particles in various phosphorites have been studied using scanning electron microscopy coupled with X-ray dispersive microanalysis. Replacement of calcium carbonate by apatite has been observed in bivalve shell fragments and in foraminiferal tests; replacement proceeds at constant volume with excellent preservation of the original microtextures. In some deposits, replacement of carbonate by apatite is the main phosphogenic process. However, in general, the process seems to be far less important than might be believed purely on the basis of thin section observations. In many phosphorites, internal or external apatite moulds of bioclasts are common, including very small particles such as coccoliths in phosphatized chalks. Apatite precipitation was typically followed by carbonate dissolution. Later apatite precipitation within the dissolution voids may produce partial or total phosphate pseudomorphs of the original carbonate grain. In these examples direct replacement of carbonate by phosphate cannot be demonstrated.  相似文献   

6.
An experimental sedimentary system comprising a tank of 4 m3 capacity equipped for monitoring chemical, mineralogical, and biological changes has been used to investigate the mechanisms by which Pb and Zn may be removed from solution in sulphide-deficient brines and concentrated in sediments. In the experimental system, Pb and Zn together with ferric hydroxides (probably lepidocrosite), organic matter, and a variety of calcium and magnesium carbonate phases, were deposited from an aerobic, highly saline, Pb and Zn-rich brine supporting a vigorous growth of the green alga Chlorococcus sp. The resultant organic and Febearing carbonate sediments contained Pb up to 0.5% and Zn up to 1.0%. Overall concentration factors compared with the overlying brine were in the range 200 to 300. Pb was removed from solution mainly by coprecipitation with carbonate phases; the Pb content of the two major carbonate phases decreasing in the order aragonite to monohydrocalcite. Zn was deposited in association with the Fe-bearing minerals. Complexing of Pb and Zn by organic matter, and the direct precipitation of Pb and Zn carbonates and/or hydroxides made, at most, a secondary contribution to the overall concentration process.  相似文献   

7.
《Applied Geochemistry》1993,8(5):473-481
The Maqarin area, northern Jordan, hosts some unusual, hyperalkaline (pH= 12.5) groundwaters discharging from thermally metamorphosed bituminous marls which formed through spontaneous, in situ combustion of the bitumen. The groundwaters have evolved geochemically through hydration, recarbonation and sulphatization of high temperature minerals. Mineralogical relations of the carbonate phases were examined by XRD and cathodoluminescence in conjunction with a detailed investigation of stable isotope ratios by Nd-YAG laser microsampling. Carbon-13 contents trace the sequence of alteration reactions, involving high temperature decarbonation of host biomic marl, followed by in situ recarbonation of secondary calcium hydroxide and calcium-silicate-hydrates (CSH).Carbonation took place shortly after thermal metamorphism, when non-saturated conditions allowed an atmosphere rich in CO2 from adjacent combustion zones to access reaction sites. Low δ18OCaCO3 values suggest that the earliest phase of recarbonation took place by reaction with hydroxide at elevated temperatures while later phases formed at cooler temperatures. Variable14 activities show that soil CO2 was a component of the later recarbonating atmosphere. Once saturated conditions prevailed in the alteration zone, recarbonation ended and alteration evolved to hydroxide and sulphate dissolution reactions. The recarbonation reactions are a field-scale analogue of recarbonation and14C attenuation in cementitious barriers for radioactive waste repositories.  相似文献   

8.
Cui  Ming-Juan  Zheng  Jun-Jie  Chu  Jian  Wu  Chao-Chuan  Lai  Han-Jiang 《Acta Geotechnica》2021,16(5):1377-1389

Calcareous sands have abundant intraparticle pores and are prone to particle breakage. This often leads to poor engineering properties, which poses a challenge to coastal infrastructure construction. A study using bio-cementation to improve the engineering properties of calcareous sand is presented in this paper. The macro- and microscopic properties of bio-cemented calcareous sand were characterized by drained triaxial tests and scanning electron microscopy observations. Experimental results show that the precipitated calcium carbonate can effectively fill the intra- and interparticle pores and bond adjacent particles, thus enhancing the shear strength of calcareous sand. The special structures (e.g. abundant intraparticle pores and rough surface) and mineral components (i.e. calcium carbonate) of calcareous sand are beneficial for improving bacterial retention in soil, which leads to a relatively uniform and dense calcium carbonate distribution on the sand particle surface, exhibiting a layer-by-layer growth pattern. This growth pattern and the abundant interparticle pores would result in less effective calcium carbonate. The strength enhancement of bio-cemented calcareous sand is significantly lower than that of bio-cemented silica sand at the same calcium carbonate content, which may be caused by the differences in the following: (a) soil skeleton strength; (b) the amount of effective calcium carbonate; and (c) interparticle pore-filling of calcium carbonate.

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9.
为了研究碳酸盐岩储层原油裂解过程中硫、钙元素赋存状态的变化,采集塔河油田TK772井奥陶系鹰山组产层的原油,通过半开放实验体系"地层孔隙热压生排烃模拟仪"开展仿真地层条件的成气模拟实验,利用同步辐射X射线吸收近边结物(XANES)技术对固体产物中的硫、钙元素的化学赋存状态进行精确检测。结果表明,原油直接裂解(原油+灰岩实验(系列1))固体产物中含硫化合物以噻吩类和硫酸钙为主,是原油裂解过程中部分噻吩类物质被氧化的结果;含钙化合物以碳酸钙为主。有溶解硫酸盐存在的原油裂解(原油+灰岩+硫酸镁实验(系列2))固体产物中含硫化合物以硫酸钙为主,噻吩类为辅,可能是溶解硫酸盐(硫酸镁)的加入、硫酸盐热化学还原反应(TSR)和溶蚀-沉淀作用共同作用的结果。系列2中伴随着温压的升高,H2S的生成和硫酸钙相对百分含量增加,指示原油裂解过程中发生了硫酸盐热化学还原反应(TSR);硫酸钙的生成和富集表明,TSR过程产生的酸性流体可以对碳酸盐岩储层产生明显的溶蚀作用,同时可能会生成次生膏盐。  相似文献   

10.
非晶碳酸钙(amorphous calcium carbonate,ACC)是碳酸钙矿物体系中极不稳定的矿物相。但由海鞘类动物的研究表明,ACC可作为碳酸钙晶体矿物的前驱体在生物体内稳定存在,并且这些生物成因的ACC常常是由膜包裹着的。文中选用生物膜的主要成分卵磷脂(PC)为主要矿化调节剂,通过调控与碳酸钙矿化过程密切相关的无机离子Mg2+的浓度,模拟生物膜表面碳酸钙矿化作用过程。在空气/水界面处的膜脂调控下合成出可在溶液中稳定存在数天的非晶碳酸钙。该结果有力地证明了在生物矿化过程中,除了受生物体中可溶性有机大分子调控外,生物膜可能对ACC的形成和稳定也有显著的调控作用。  相似文献   

11.
Chalk deformation and large-scale migration of calcium carbonate   总被引:2,自引:0,他引:2  
Y. MIMRAN 《Sedimentology》1977,24(3):333-360
Sixty Upper Cretaceous chalk exposures were examined and sampled in Dorset, the Isle of Wight and Guildford, South England, in order to investigate the effects of tectonic deformation on the chalk fabric. Light and scanning-electron microscopes were used extensively, and chemical, mineralogical and isotopic analyses ware carried out. Two types of fabric modification were distinguished. The first type involves more than 90% volume loss by mechanical compaction at the early stages of deformation followed by dissolution and removal of calcium carbonate in the advanced stages of deformation. Chalks which have undergone this type of fabric modification are dense and consist of well rounded 0.5–3 μ calcite crystals with well developed pressure-solution contacts. These chalks contain a high proportion of calcispheres (many of which are plastically deformed) but very few well preserved planktonic foraminifera and coccoliths. They are relatively enriched in insoluble constituents and depleted in strontium. The second type of fabric modification involves introduction of calcium carbonate into the pore spaces. Chalks which have undergone this type of modification are dense and contain a high proportion of 3–5 μ polygonal interlocking calcite crystals. Fossils are virtually never deformed, and delicate foraminifera and coccoliths are well preserved. Insoluble constituents similar to those found in the unmodified chalks occur in low concentrations. Removal of calcium carbonate at crystal contacts has taken place in chalks which have been subjected to high effective tectonic stresses and at crystal peripheries in chalks which have been subjected to high pore fluid pressure. Dissolution at crystal peripheries is responsible for the extensive calcium carbonate losses, and it is termed herein ‘confining pressure solution’. Introduction of calcium carbonate occurs in rocks which were under low tectonic stresses. During deformation calcium carbonate migrates from chalks under high stresses towards those under tow stresses, while some goes into solution in sea water. Well developed joints and high pore fluid pressure might increase the rate of calcium carbonate removal by three orders of magnitude. Petrographic and isotopic data suggest-that all fabric modifications studied took place in meteoric water.  相似文献   

12.
菌剂添加对不同树种根际土壤微生物及碳酸钙溶蚀的影响   总被引:1,自引:0,他引:1  
本实验通过对云南省建水地区植被根际土壤中高产碳酸酐酶(CA)的微生物进行分离筛选和溶蚀效应的测定,将溶蚀效果较好的菌株制成菌悬液进行盆栽实验,探究该菌株对不同树种根际土壤微生物代谢活性和碳酸钙类岩石溶蚀效应的影响。结果表明:从根际土壤中筛选到一株能够高产CA,且具有较强溶蚀效果的沙雷氏菌,施加该菌剂的处理组显著增加了土壤微生物数量,提高微生物的代谢活性和多样性,并加速碳酸钙类岩石的溶蚀。本研究旨在为今后岩溶区生态恢复过程中植物树种的选择与微生物菌剂的联合应用提供一种技术手段,为岩溶地区生态系统的治理提供一定的理论支持。   相似文献   

13.
中国金属镁工业的环境效应与可持续发展   总被引:4,自引:1,他引:4  
中国的优质白云岩、菱镁矿资源丰富,为发展金属镁工业提供了良好条件。20世纪90年代末,以相对浪费能源、资源和牺牲区域环境质量为代价,依赖皮江法炼镁技术,中国发展成为世界上金属镁生产和出口的第一大国。现今中国社会和经济发展面临的能源、资源和环境挑战,决定了必须对皮江法炼镁技术进行变革,以实现金属镁工业的清洁生产和节约发展。以优质白云岩为原料,经煅烧和钙镁分离,生产轻质碳酸钙和氧化镁,进而采用碳热还原法提取金属镁的技术,较之传统的皮江法具有资源利用率高、节能高效、且可完全实现清洁生产等优势。这一创新技术体系,将在现今中国国情背景下,引导金属镁工业步入可持续发展之路,符合建立资源节约型、环境友好型国家的要求。  相似文献   

14.
To learn more about the kinetics and mechanisms of coarsening and melt inclusion formation, we investigated the effects of melt content, viscosity, and topology on the microstructural evolution of partially molten and melt-free calcite aggregates. Synthetic marbles with eutectic melts were produced by annealing mixtures of calcite and either calcium hydroxide or lithium carbonate for up to 80 h at a confining pressure of 300 MPa and temperatures of 973-1,023 K. The melts produced in the two systems are expected to differ significantly in viscosity. Generally, coarsening rates decrease with increasing melt fraction, probably because the diffusion length across melt pockets increases. Analysis of grain shapes in the samples with about 40% melt indicated that coarsening was accommodated by agglomeration in the samples of the calcium/lithium carbonate system. In the calcium carbonate/hydroxide system, classical Ostwald ripening occurred. For melt contents about 10% and below, melt-filled pores are either dropped from or dragged along with migrating grain boundaries, depending on the pore size and the grain boundary curvature. These data can be used to constrain the conditions where fluid or melt inclusions form under natural conditions. Combining our results and previous studies illustrates a systematic relation between the grain boundary mobility in calcite aggregates and the diffusion kinetics associated with second phases residing on the grain boundaries. In particular, boundaries with no porosity are most mobile, those boundaries dragging melt-filled pores are slower, those with gas-filled pores are slower yet, and those containing solid phases are slowest or may even be motionless.  相似文献   

15.
在利用气体扩散法制取碳酸钙的过程中,样品的叠加摆放会导致不同层位的沉淀过程不同步进而增大实验误差。文章研究了样品在干燥器中摆放高度对实验结果的影响,并改进了收集沉淀物的方法。结果显示,随着摆放高度的增加,溶液pH值、电导率和沉淀物重量均呈规律性下降。培养皿之间的相互遮挡也会在一定程度上影响碳酸钙的矿化进程。少量沉淀物残留于培养皿上和/或溶液中是造成沉淀物收集不完全(或重量数据不准确)的主要原因。文章的实验结果对于利用气体扩散法研究碳酸钙仿生合成具有一定的借鉴意义。   相似文献   

16.
Manganese carbonate can be converted to many kinds of manganese oxides when it is aerated in air and oxygen.Pure manganese carbonate can be changed into Mn3O4 and γ-MnOOH,and manganese carbonate ore can be converted to MnO2 under the air-aerating and oxygen-aerating circumstances.The oxidation process of manganese carbonate is a changing process of mineral association,and is also a converting process of valence of manganese itself.Not only equilibrium stat,but also nonequilibrium state are involved in this whole process,This process is an irreversible heterogeneous complex reaction,and oberys the nonequilibrium thermodynamic model,The oxidation rate of manganese cabonate is controlled by many factors,especially nonmanganese metallic ions which play an important role in the oxidation process of manganese carbonate.  相似文献   

17.
从南方湿热区自然环境中分离得到一株产脲酶矿化菌,并将其高产突变株应用到海砂室内MICP灌浆试验,结合扫描电子显微镜(SEM)、能谱仪(EDS)、拉曼(Raman)对固化后的产物进行细观形貌观测。通过分析碳酸钙的形貌、尺寸、空间分布、结晶状态等基本特征现象,初步探究南方湿热区产脲酶菌在碳酸钙结晶生长方面的调控作用及其固化土体的作用效果。结果表明:南方湿热区产脲酶菌固化土体具有可行性,但碳酸钙晶体形貌并不均一,晶体晶化过程、生物调控作用及土体结构均会对碳酸钙的生成情况造成影响;碳酸钙从无序到有序、分散到聚集、不稳定到稳定,最终生长聚集为完整的结构,在生长空间充足的环境下,碳酸钙更倾向于形成聚集体。研究结论可为进一步研究不同产脲酶菌诱导碳酸钙沉淀的作用过程与调控机制提供借鉴与参考。  相似文献   

18.
黄龙嗜冷细菌两种胞外单糖对碳酸钙矿化影响   总被引:2,自引:0,他引:2  
为了探究黄龙水体中嗜冷细菌的胞外代谢产物对钙华沉积速率及沉积产物的影响,本文从黄龙钙华水体中分离到优势土著嗜冷细菌,并以其标志性胞外代谢产物D-葡萄糖和D-核糖作为研究对象,研究了两种单糖组分在低温环境下对钙华沉积的影响,并通过X射线衍射(XRD)、扫描电子显微镜(SEM)、红外吸收光谱(FT-IR)等分析手段对碳酸钙晶型、形貌以及结构组成进行了表征。实验表明:D-葡萄糖在低温条件下能促进方解石型碳酸钙的沉积,并加快沉积速率。低浓度下(20 mg/L和40 mg/L)的沉积产物均为方解石型碳酸钙并对其形貌有一定的影响;高浓度下(80 mg/L和160 mg/L)能诱导少量的文石型碳酸钙的合成。D-核糖在低温条件下能促进碳酸钙的沉积,加快沉积速率。与D-葡萄糖不同,D-核糖仅能合成方解石型碳酸钙,但对方解石晶面的生长表现为抑制作用,且随浓度增大抑制作用益明显。此结果可为黄龙钙华生物成因的探究提供一定的理论研究基础。  相似文献   

19.
A laboratory study was conducted to evaluate the influence of hydration and recarbonation on the solidphase distribution of trace elements in retorted oil shale. The oil shale samples were retorted by the Paraho direct heating process and equilibrated with deionized—distilled water under controlled carbon dioxide conditions. A sequential extraction technique was then used to fractionate trace elements into soluble, KNO3-extractable (easily exchangeable), H2O-extractable (easily adsorbed), NaOh-extractable (organic), EDTA-extractable (carbonate), HNO3-extractable (sulfide), and residual (nonextractable silicate) phases. The chemical fractions present in retorted oil shale and hydrated and recarbonated retorted oil shale were compared to identify trace element mineralogical changes that may occur in retorted oil shale disposal environments.Trace elements examined in this study were found to reside predominantly in the HNO3-extractable and residual fractions. Hydration of retorted oil shale resulted in a shift in the majority of trace elements from residual to extractable forms. Cobalt, nickel, and zinc extractabilities were not significantly influenced by hydration, whereas antimony increased in the residual fraction. Subjecting retorted oil shale to atmospheric (0.033%) and 10% CO2(g) levels over a nine-month equilibration period resulted in partial and full recarbonation, respectively. As the influence of recarbonation increased, trace elements reverted to residual forms. Vanadium, choromium, copper, zinc, antimony, and molybdenum in the 10% CO2(g) recarbonated material were more resistant to sequential extraction than in retorted oil shale, whereas strontium, barium, and manganese were less resistant to sequential extraction. The extractabilities of cobalt, nickel, and lead were not affected by recarbonation. Recarbonation did not result in a predicted increase in EDTA-extractable trace elements. In general, the amounts of trace elements extracted by EDTA (and correlated to carbonate forms) were invariant with respect to equilibrium CO2(g) levels.A significant result of this study was that the mineralogical residencies of trace elements in retorted oil shale were altered in response to conditions that may be present in a disposal environment. Thus, the long-term release of trace elements in retorted oil shale disposal environments may not be adequately predicted by applying the toxicity characteristic leaching procedure (TCLP).  相似文献   

20.
Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH4+ production during urea hydrolysis were incorporated in the model and captured critical changes in the major metal species. The electrical phase increases were potentially due to ion exchange processes that modified charge structure at mineral/water interfaces. Our study revealed the potential of geophysical monitoring for geochemical changes during urea hydrolysis and the advantages of combining multiple approaches to understand complex biogeochemical processes in the subsurface.  相似文献   

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