Hydrothermal mixing,carbonate dissolution and sulfide precipitation in Mississippi Valley-type deposits

A large number of Mississippi Valley-Type (MVT) deposits are located within dissolution zones in carbonate host rocks. Some genetic models propose the existence of cavities generated by an earlier event such as a shallow karstification, that were subsequently filled with hydrothermal minerals. Alternative models propose carbonate dissolution caused by the simultaneous precipitation of sulfides. These models fail to explain either the deep geological setting of the cavities, or the observational features which suggest that the dissolution of carbonates and the precipitation of minerals filling the cavities are not strictly coeval. We present a genetic model inspired by the textural characteristics of MVT deposits that accounts for both the dissolution of carbonate and precipitation of sulfides and later carbonates in variable volumes. The model is based on the mixing of two hydrothermal fluids with a different chemistry. Depending on the proportion of the end members, the mixture dissolves and precipitates carbonates even though the two mixing solutions are both independently saturated in carbonates. We perform reactive transport simulations of mixing of a regional groundwater and brine ascending through a fracture, both saturated in calcite, but with different overall chemistries (Ca and carbonate concentrations, pH, etc). As a result of the intrinsic effects of chemical mixing, a carbonate dissolution zone, which is enhanced by acid brines, appears above the fracture, and another zone of calcite precipitation builds up between the cavity and the surrounding rock. Sulfide forms near the fracture and occupies a volume smaller than the cavity. A decline of the fluid flux in the fracture would cause the precipitation of calcite within the previously formed cavities. Therefore, dissolution of carbonate host rock, sulfide precipitation within the forming cavity, and later filling by carbonates may be part of the same overall process of mixing of fluids in the carbonate host rock.Editorial handling: C. Everett     

Timescales of interface-coupled dissolution-precipitation reactions on carbonates

In the Earth's upper crust, where aqueous fluids can circulate freely, most mineral transformations are controlled by the coupling between the dissolution of a mineral that releases chemical species into the fluid and precipitation of new minerals that contain some of the released species in their crystal structure, the coupled process being driven by a reduction of the total free-energy of the system. Such coupled dissolution-precipitation processes occur at the fluid-mineral interface where the chemical gradients are highest and heterogeneous nucleation can be promoted, therefore controlling the growth kinetics of the new minerals. Time-lapse nanoscale imaging using Atomic Force Microscopy (AFM) can monitor the whole coupled process under in situ conditions and allow identifying the time scales involved and the controlling parameters. We have performed a series of experiments on carbonate minerals (calcite, siderite, dolomite and magnesite) where dissolution of the carbonate and precipitation of a new mineral was imaged and followed through time. In the presence of various species in the reacting fluid (e. g. antimony, selenium, arsenic, phosphate), the calcium released during calcite dissolution binds with these species to form new minerals that sequester these hazardous species in the form of a stable solid phase. For siderite, the coupling involves the release of Fe²⁺ ions that subsequently become oxidized and then precipitate in the form of Fe^III oxyhydroxides. For dolomite and magnesite, dissolution in the presence of pure water (undersaturated with any possible phase) results in the immediate precipitation of hydrated Mg-carbonate phases. In all these systems, dissolution and precipitation are coupled and occur directly in a boundary layer at the carbonate surface. Scaling arguments demonstrate that the thickness of this boundary layer is controlled by the rate of carbonate dissolution, the equilibrium concentration of the precipitates and the kinetics of diffusion of species in a boundary layer. From these parameters a characteristic time scale and a characteristic length scale of the boundary layer can be derived. This boundary layer grows with time and never reaches a steady state thickness as long as dissolution of the carbonate is faster than precipitation of the new mineral. At ambient temperature, the surface reactions of these dissolving carbonates occur on time-scales of the order of seconds to minutes, indicating the rapid surface rearrangement of carbonates in the presence of aqueous fluids. As a consequence, many carbonate-fluid reactions in low temperature environments are controlled by local thermodynamic equilibria rather than by the global equilibrium in the whole system.     

The Effect of the CO32- to Ca2+ Ion activity ratio on calcite precipitation kinetics and Sr2+ partitioning

Background  

A proposed strategy for immobilizing trace metals in the subsurface is to stimulate calcium carbonate precipitation and incorporate contaminants by co-precipitation. Such an approach will require injecting chemical amendments into the subsurface to generate supersaturated conditions that promote mineral precipitation. However, the formation of reactant mixing zones will create gradients in both the saturation state and ion activity ratios (i.e., ). To better understand the effect of ion activity ratios on CaCO₃ precipitation kinetics and Sr²⁺ co-precipitation, experiments were conducted under constant composition conditions where the supersaturation state (Ω) for calcite was held constant at 9.4, but the ion activity ratio was varied between 0.0032 and 4.15.     

Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

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.     

Kinetic biomineralization through microfluidic chip tests

A homogeneous microfluidic chip was used to investigate the pore-scale characteristics during the process of microbially induced calcium carbonate precipitation (MICP). An image-processing scheme was developed to measure the projecting areas of the precipitated calcium carbonate. Calcium carbonate first precipitated on the bacterium side before spreading to the rest of the chip. The distribution of calcium carbonate was more uniform along the length of the microchip than along the width. Raman back-scattering spectroscopy was used to examine the chemical composition of the precipitate, identifying calcite and vaterite as the main mineral phases. Bacterium traces were noted on crystal surfaces in SEM images, suggesting a higher adsorptive capacity for irregular precipitates than well-shaped crystals.

     

运用STOMP数值模拟器进行多空介质中尿素水解以及方解石沉淀数值模拟

遍布于美国能源部所辖野外场地的地下放射性核素和痕量金属污染对美国能源部的长期监管职能提出了最严峻的挑战。目前较有前景的一个原地固化污染物方法是利用尿素酶催化尿素水解,进而推动方解石沉淀及与之共同沉淀。运用STOMP数值模拟器实施一系列反应性溶质数值模拟来研究系统中水流、运移、反应与反应导致的介质性质变化之间的紧密的非线性耦合,并在研究中系统性增加反应系统的复杂度和物理-化学的非均质性以考察模拟效果。通过调整反应速率表达式中尿素酶浓度和沉淀反应常数,对尿素水解和方解石沉淀速率进行了敏感度分析。结果显示:尿素水解速率是矿物沉淀总量的决定性因素,沉淀物的空间分布既取决于水解速率也取决于沉淀速率;在一维水流柱6个空隙体积的时间段模拟中,观察到了5%的最大空隙度减少;当二维模拟中考虑一个低渗透性包裹体时,被改变的流场重新对生成的沉淀组成物进行了分布,形成了扭曲的反应锋面。模拟结果也显示沉淀在低渗透性区域边界上形成,这说明位于这个区域里面的污染物可能被囊裹而从流线中被隔离起来。     

Effect of the addition of granitic powder to an acidic soil from Galicia (NW Spain) in comparison with lime

The impact of diffuse pollution, agricultural land use and climate change on the long-term response of subsurface–surface water quality is not well understood, but is a prerequisite for evaluation of water management options. The goal of this study is to model geochemical evolution of water chemistry from the infiltration through soil into the unsaturated zone, transport through bedrocks and granular aquifers to a river in order to identify zones of steep concentration gradients and high dynamics under transient flow conditions. A numerical model was constructed comprising a 2-D 1,500 m × 150 m vertical cross-section of typical sedimentary rock formations, a glacio-fluvial quaternary gravel aquifer in the valley and soil layers. The model coupled saturated/un-saturated flow and reactive transport under steady state and transient conditions. Geochemical interactions, include intra-aqueous kinetic reactions of oxygen with dissolved organic matter, as well as kinetics of carbonate dissolution/precipitation. This model section was chosen to provide insight in to the principal processes and time scales affecting water chemistry along different flow paths. The numerical simulator MIN3P was used, a finite volume program for variably saturated subsurface flow and multi-component reactive transport. The results show that subsurface water residence times range from approximately 2 to 2,000 years. Different zones are to be expected with respect to the development of mineral equilibria; namely, purely atmospherically influenced, as well as open and closed system carbonate dissolution. Short-term responses to daily averaged changes in precipitation, however, are only visible to some extent in the shallower and near-river parts of flow system and solute loads. This can most likely be explained by directional changes in flow paths, indicating that equilibrium geochemical condition predominate at the hillslope scale, i.e. water quality depends on transport pathways rather than on kinetic effects. The extent of reducing conditions is controlled by the presence of organic-rich layers (i.e. peat deposits), the dissolution kinetics of aquifer organic matter and the subsequent mixing with oxygenated water by hydrodynamic dispersion.     

Precipitation of calcium carbonate from hydrated lime of variable reactivity, granulation and optical properties

Different sources of lime for the production of precipitated calcium carbonate were studied. The reactivity of lime, its optical properties and those of the final products are reported and discussed, and a comparison made between lime from different sources. The influence of the temperature of hydration water on the optical properties and particle sizes after hydration and precipitation was also studied. It was found that coarser granulations of lime have better optical properties than finer granulations. The hydration temperature does not have an appreciable impact on the optical properties, but influences the intermediate, i.e. the calcium hydroxide particle sizes and subsequently the particle sizes of the precipitated calcium carbonate. Furthermore, the maximum temperatures of lime hydration from different European sources do not vary significantly, but they differ in the kinetics of the hydration process.     

Phosphatization of calcium carbonate in phosphorites: microstructure and importance

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.     

The impact of hydrological changes on travertine deposits related to thermal springs in the Pamukkale area (SW Turkey)

Pamukkale thermal waters (35 °C), exhibiting calcium-bicarbonate-sulfate composition and high carbon dioxide concentration, are of a predominantly meteoric origin. The meteoric fluid, circulating through faults and fractures, is heated by magmatic intrusions at great depth, and ascends from deep reservoirs to the surface. Mixing with relatively cold groundwater in the near surface zone promotes different saturation conditions with respect to calcium carbonate that later precipitates at depth and/or the surface. Dissolution-deposition processes of calcium carbonate both at surface and depth environments may help to reconstruct past climate direction in the field. During wet climate conditions a high-rate of calcium carbonate accumulation would be expected to occur at the surface because thermal fluid would be under-saturated with respect to calcium carbonate at depth because of a relatively higher mixing ratio with cold groundwater. During dry climate conditions the thermal fluid would be super-saturated at depth because of the highly acidic environment. Hydrometeorological studies reveal that the annual precipitation at the Pamukkale hydrothermal field tends to decrease with time. This climatic change in the area was also detected from geological records. While humid climate conditions prevailed during the late Quaternary, the area has recently been affected by arid/semi-arid climate conditions, followed by some episodic transitions. This study has shown how the system has possibly reacted to different climate conditions since antiquity.     

碳酸钙矿物表面润湿性的控制机理

系统论述了碳酸钙矿物浮选中常用的捕收剂和抑制剂及其相关作用机理。这些药剂通过包括静电作用、氢键、半胶束吸附和化学吸附等多种机理,吸附在碳酸钙矿物表面,从而控制矿物表面的润湿性。捕收剂的功能在于增强矿物表面的疏水性,抑制剂的功能在于增强矿物表面的亲水性。选择合适的捕收剂和抑制剂复配方案对高效浮选分离至关重要。     

黄豆脲酶诱导碳酸钙沉淀多变量试验研究

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。     

Impact of chemical clogging on de-watering well productivity: numerical assessment

Among the processes leading to a decrease in productivity, chemical clogging is often mentioned as one of the major features. De-watering of a confined aquifer caused by an unsuitable pumping scheme produces a phenomenon involving the diffusion of oxygen in the aquifer which disturbs the geochemical conditions in the initial system. Coupled chemical and transport processes are proposed in an assessment of the impact of de-watering on the precipitation of carbonate and iron oxide. The reactions are studied for waters showing low dissolved iron concentrations such as commonly observed in drinking water supplies. The quantity and distribution of precipitated iron oxide and calcium carbonate are used in a permeability model to calculate the productivity loss. For the conditions used in the simulations, the carbonate precipitate can be neglected compared to iron deposits which remain weak. The spatial distribution is heterogeneous and quite similar to the patterns observed in the field. This shape is mainly caused by a competition between the diffusion of oxygen due to the de-watering process and the rate of precipitation of iron oxide. However, the loss of well productivity remains moderate. It is clearly shown that de-watering of the well and the associated chemical incrustations that this induces cannot alone explain field data. More complex processes involving biological clogging and accurate hydrodynamic behaviour in the closest part of the well remain to be included in the modelling approach in order to provide valuable insights into the problem of well ageing.     

微生物沉积碳酸钙固化珊瑚砂的试验研究

向珊瑚砂中注入巴斯德芽孢杆菌菌液、氯化钙和尿素的混合液,利用微生物沉积碳酸钙固化珊瑚砂;并对珊瑚砂固化体进行了渗透、强度及微观结构等试验。试验结果表明,巴斯德芽孢杆菌的活性随时间呈衰减趋势,但衰减速度缓慢,能较好地满足珊瑚砂固化的需要。随着菌液、氯化钙和尿素的混合液注入次数的增加,珊瑚砂柱渗透性逐步降低,最终渗透性降低了1～2个数量级。微生物固化后的珊瑚砂柱应力-应变曲线大致可分为3段,即应力随应变缓慢增加段、快速增加段以及突降段。试样发生压裂脆性破坏,无侧限抗压强度最高达到14 MPa左右。抗压强度随干密度增加而增大,随渗透性降低而增大。微生物固化后珊瑚砂颗粒被生成的碳酸钙完整的包裹,孔隙间极少见生成的碳酸钙,与普通硅砂微生物固化后的微观结构不同,较好地解释了渗透性降低不多的原因。     

Impact of Carbonate Precipitation on Riverine Inorganic Carbon Mass Transport from a Mid-continent, Forested Watershed

Physiochemical controls on the carbonate geochemistry of large river systems are important regulators of carbon exchange between terrestrial and marine reservoirs on human time scales. Although many studies have focused on large-scale river carbon fluxes, there are few investigations of mechanistic aspects of carbonate mass balance and transport at the catchment scale. We determined elemental and carbonate geochemistry and mass balances for net carbonate dissolution fluxes from the forested, mid-latitude Huron River watershed, established on carbonate-rich unconfined glacial drift aquifers. Shallow groundwaters are near equilibrium with respect to calcite at pCO₂ values up to 25 times atmospheric values. Surface waters are largely groundwater fed and exhibit chemical evolution due to CO₂ degassing, carbonate precipitation in lakes and wetlands, and anthropogenic introduction of road salts (NaCl and CaCl₂). Because the source groundwater Mg²⁺/HCO₃ ^? ratio is fairly constant, this parameter permits mass balances to be made between carbonate dissolution and back precipitation after groundwater discharge. Typically, precipitation does not occur until IAP/K calcite values exceed 10 times supersaturation. Stream chemistry changes little thereafter even though streams remain highly supersaturated for calcite. Our data taken together with historical United States Geological Survey (USGS) data show that alkalinity losses to carbonate precipitation are most significant during periods of lowest discharge. Thus, on an annual basis, the large carbon flux from carbonate dissolution in soil zones is only decreased by a relatively small amount by the back precipitation of calcium carbonate.     

基于石灰石粉钙源的微生物固化砂土试验研究

微生物诱导碳酸钙沉积（MICP）作用是一种新型的土体改良技术。钙源作为MICP反应中重要的反应物,对微生物诱导碳酸钙沉积的效果有重要的影响。目前应用最广泛的钙源——氯化钙（CaCl2）,具有成本高,环境污染性大的缺点。为此,文章提出利用石灰石粉提取钙源,通过在石灰石粉中加入乙酸溶液,释放钙离子用于微生物固化土体。通过开展无侧限抗压强度试验以及微观结构的扫描电镜观测、碳酸钙含量测定等分析,验证利用石灰石粉提取的钙源用于微生物诱导碳酸钙沉积作用固化土体的可行性,同时与醋酸钙和氯化钙固化砂柱进行了对比分析。研究结果表明：（1）石灰石粉用于微生物固化土体具有可行性,固化后砂柱的强度和碳酸钙含量较高,结构完整性高;（2）不同钙源固化砂柱的力学特性不同但均呈典型的脆性破坏模式,其中醋酸钙固化砂柱的无侧限抗压强度略高于石灰石钙源固化砂柱,氯化钙固化砂柱的无侧限抗压强度则远低于前两者且表面更加粗糙,孔隙更多,破坏后的完整性更低;（3）不同钙源固化砂柱的碳酸钙含量不同。醋酸钙和石灰石钙源固化砂柱的碳酸钙含量相近,而氯化钙固化砂柱中碳酸钙含量较低。不同钙源固化砂柱的碳酸钙含量和无侧限抗压强度基本呈正相关关系;（4）醋酸钙和石灰石钙源固化砂柱中砂土颗粒的表面和接触点间均沉积大量碳酸钙,碳酸钙晶体主要为薄片状堆叠的方解石。氯化钙固化砂柱中碳酸钙沉积量低于前两者,碳酸钙晶体主要为六面体状的方解石;（5）不同钙源主要通过影响微生物成矿过程的晶型、晶貌、晶体含量、晶体分布及胶结特征来改变固化效果。     

Calcite and barite precipitation in CaCO<Subscript>3</Subscript>-BaSO<Subscript>4</Subscript>-NaCl and BaSO<Subscript>4</Subscript>-NaCl-CaCl<Subscript>2</Subscript> aqueous systems: kinetic and microstructural study

During the production of hydrocarbons from subterranean reservoirs, scaling with calcium carbonate and barium sulfate causes flux decline and dangerous problems in production facilities. This work is intended to study the effect of calcium ions on the precipitation of barium sulfate (barite); then, the effect of the formed barite on calcium carbonate crystallization. The conductometric and pH methods were used to follow the progress of the precipitation reaction in aqueous medium. The obtained precipitates were characterized by FTIR, RAMAN, SEM, and XRD. It was shown that Ca²⁺ in the reaction media does not affect the microstructure of barite even for higher calcium–barium molar ratio. It influences the precipitation kinetics and the solubility of barite by the formation of CaSO₄° ion pairing as a predominant role of complex formation (CaSO4) and the increase of the ionic strength. In Ca(HCO₃)₂-BaSO₄-NaCl aqueous system, experiments have showed that added or formed barite in the reaction media accelerates calcite precipitation. No effect on the microstructure of heterogeneous formed calcite which remain calcite shape. However the presence of carbonate ions affects slightly the microstructure of barite.     

营养盐浓度对胶结砂试样物理力学特性试验研究

采用2次注入菌液方式,制备不同浓度营养盐处理的微生物诱导碳酸钙沉淀（MICP）胶结砂样。通过固结排水三轴试验和碳酸钙定量化学试验测定试样强度参数及碳酸钙（CaCO3）含量,分析了营养盐浓度对胶结砂物理力学特性的影响及碳酸钙沉淀量试样强度指标间的关系。结果表明,同等反应时间、同等体积营养盐溶液条件下,随着营养盐浓度的提高试样强度逐渐升高,且达到一定峰值后再下降;碳酸钙晶体分布形态较好条件下,变形模量随着试样干密度的增加而增加;碳酸钙晶体分布形态和沉淀含量共同影响MICP试样强度的提高,试验中0.5 M试样强度提高效果最好,碳酸钙含量、黏聚力、内摩擦角分别为6.03%、46.9 kPa和41.31°。     

Speleothems in gypsum caves and their paleoclimatological significance

This article highlights the relationship between speleothems growing inside gypsum caves and the particular climate that existed during their development. Speleothems in gypsum caves normally consist of calcium carbonate (calcite) or calcium sulphate (gypsum) and the abundance of such deposits greatly differs from zone to zone. Observations carried out over the last 20 years in gypsum caves subjected to very different climates (Italy, Spain, New Mexico, northern Russia, Cuba, Argentina) highlight wide variation in their cave deposits. In arid or semi-arid climates, the speleothems are mainly composed of gypsum, whilst in temperate, humid or tropical regions, carbonate formations are largely predominant. In polar zones no speleothems develop. These mineralogical details could be useful paleoclimatic indicators of climate change. The interpretation proposed is based on the fact that in gypsum karst the kind of speleothems deposited is determined by competition between the two principal mechanisms that cause precipitation of calcite and gypsum. These mechanisms are completely different: calcite speleothem evolution is mainly controlled by CO₂ diffusion, while gypsum deposits develop mostly due to evaporation. Therefore, the prevalence of one kind of speleothem over the other, and the relationship between the solution–precipitation processes of calcite and gypsum, may provide evidence of a specific paleoclimate. Additionally, other non-common deposits in gypsum caves like moonmilk, cave rafts and dolomite speleothems can be used as markers for the prevalence of long, dry periods in humid areas, seasonal changes in climate, or rainfall trends in some gypsum areas. Moreover, the dating of gypsum speleothems could contribute paleoclimatic data relating to dry periods when calcite speleothems are not deposited. In contrast, the dating of calcite speleothems in gypsum caves could identify former wet periods in arid zones.