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1.
Tufa sediments are freshwater carbonates that precipitate in karst regions after degassing of carbon dioxide from groundwater in contact with the atmosphere. When laminated, these carbonates can provide high‐resolution records for the study of climate, hydrological and environmental conditions at the time of their precipitation. The formation of these carbonates directly depends on the hydrological regime, and in karst regions discontinuous discharges are often recorded. This study investigates the record of recent laminated tufa sediments precipitated downstream overflow springs in Trabaque Canyon (central Spain). The hydrological dynamics of the karst system were monitored for over three years and a stable isotope record was obtained from laminated tufa carbonates precipitated from an overflow spring. Additionally, a hydrological model of overflow springs was generated and a tufa δ18O record under constrained parameters was simulated. Temperature is the dominant control of the variation in tufa δ13C and δ18O values within each lamina, although when comparing different laminae, δ13CDIC and δ18O of river water are also major controls. The positive correlation between tufa δ13C values and water temperature is caused by the fractionation occurred by carbon dioxide degassing due to the thermal dependence of carbon dioxide solubility. Additionally, the system recorded a temperature‐independent degassing process caused by the large gradient between groundwater and atmospheric carbon dioxide that is limited to the proximity of the spring. This study cautions on the risk of assuming continuous deposition when studying laminated tufa sediments and highlights the potential of their stable isotope records to provide hydrological information of their aquifers during the past.  相似文献   

2.
Freshwater carbonates (tufas) develop today from the Arctic to the tropics, many being localized about springs and upper water courses. Some Quaternary tufas, especially in the Mediterranean region, extend over tens of square kilometres and exceed 30 m in thickness. Radiometric dating of Holocene deposits shows that many have accumulated at an average rate of 1 mm year?1. However, local precipitation may be much faster and some Holocene deposits may even have outpaced their tropical marine carbonate counterparts. Recently, the study of active sites has attempted to quantify the precipitation mechanisms which lead to tufa deposition. However, field observation and sampling procedures suffer from the inherent disadvantages of uncontrolled fluctuations in environmental conditions during the study programme. These disadvantages compromise any interpretations, particularly where controls on spar versus micrite precipitation are concerned. Many of these problems have been overcome in the current study by the construction and operation of laboratory mesocosm flumes which simulate the natural conditions (e.g. pH, flow rate, ambient temperature and daylight) in which freshwater carbonate (tufa) is deposited. Three mesocosms were supplied with natural river water from tufa precipitating streams and two mesocosms were supplied with UV‐treated (sterile) river water from the same source. One of the untreated flume mesocosms was linked with a calcium reactor, which replaced calcium ions removed during the precipitation process in order to maintain tufa growth over extended experimental runs. Low‐magnesium calcite precipitates (both rhombic sparite grown from long‐crystallite dendrites and short‐crystallite dendrite triad precursors) and micrite peloids (grown from spherulitic precursors) were precipitated in intimate association with biofilm (extracellular polymeric substances) within the four mesocosms supplied with natural river water. Virtually, no tufa‐like precipitate was obtained from the flumes supplied with UV‐treated river water. A second extended run flume experiment was also carried out for comparison purposes using a calcium hydroxide solution in deionized water. Collectively, these experiments provide convincing evidence confirming that the presence of a microbial biofilm strongly influences the precipitation of carbonates in riverine freshwater settings. In particular, experimental results show that micro‐peloidal micrite and short‐crystallite calcite dendrites are only produced in the presence of microbial extracellular polymeric substances.  相似文献   

3.
Many Recent and fossil freshwater tufa stromatolites contain millimetre‐scale, alternating laminae of dense micrite and more porous or sparry crystalline calcites. These alternating laminae have been interpreted to represent seasonally controlled differences in the biotic activity of microbes, and/or seasonally controlled changes in the rate of calcification. Either way, couplets of these microbially mediated alternating calcified laminae are generally agreed to represent annual seasonality. Combined stable isotope (δ18O and δ13C) and trace element (Mg, Sr, Ba) geochemistry from Recent tufa stromatolites show that seasonal climatic information is available from these calcites. Variability in δ18O (and in one case Mg concentration) has been shown to be controlled primarily by stream temperature change, usually driven by solar insolation. In arid climates, seasonal evaporation can also cause δ18O enrichment by at least 1‰. Variability in δ13C results potentially from: (1) seasonal change in plant uptake of 12C‐enriched CO2; (2) seasonal change in degassing of 12C‐enriched CO2 in the aquifer system; and (3) precipitation of calcite along the aquifer or river flow path, a process that increases δ13C of dissolved inorganic carbon (DIC) in the remaining water. Mechanisms 2 and 3 are linked because calcite precipitates in aquifers where degassing occurs, e.g. air pockets. The latter mechanism for δ13C enrichment has also been shown to cause sympathetic variation between trace element/Ca ratios and δ13C because trace elements with partition coefficients much greater than 1 (e.g. Sr, Ba) remain preferentially in solution. Since degassing in air pockets will be enhanced during decreased recharge when water saturation of the aquifer is lowest, sympathetic variation in trace element/Ca ratios and δ13C is a possible index of recharge and therefore precipitation intensity. High‐resolution geochemical data from well‐dated tufa stromatolites have great potential for Quaternary palaeoclimate reconstructions, possibly allowing recovery of annual seasonal climatic information including water temperature variation and change in rainfall intensity. However, careful consideration of diagenetic effects, particularly aggrading neomorphism, needs to be the next step. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

4.
Spring‐fed rivers of the Barkly karst in tropical northern Australia form an array of tufa and related freshwater carbonate deposits. One of these deposits, calcite rafts, is precipitated at the water–air interface principally as a consequence of CO2 degassing and evaporation. Calcite rafts have been reported in cave environments but have not been described in detail from fluvial systems. Observations using scanning electron microscopy coupled with water chemistry data reveal that they form by a combination of physical, chemical and biological processes. They grow downwards into the water column and form a dentate lower surface, while a flat upper surface occurs at the water–air interface. The rafts are readily inhabited by microorganisms, particularly diatoms, which frequently become entombed by calcite as the rafts develop. The decay of the biological material leaves voids, creating a pock‐marked texture. The rafts are subject to secondary calcite growth along the crystal edges. Once they become submerged in the water column after disturbance of the water surface, they may become completely covered by this overgrowth, creating a homogeneous veneer. The rafts form in quiescent settings, principally behind tufa dams in large, lake‐like water bodies along each river. Therefore, they can be used in conjunction with adjacent exposures of other tufa facies to decipher palaeohydrological conditions. Although the rafts are extremely thin and fragile, they are readily preserved within fossil waterhole facies, and their occurrence has been identified in rocks from the Quaternary to the Tertiary.  相似文献   

5.
The oxygen and carbon isotopic composition of surficial carbonates is a key technique for reconstructing past environments and climates. The understanding of modern isotopic systems is, however, a vital first step before applying these techniques to fossil examples. In this study the δ18O of aragonite shells from three different freshwater mollusc species and the δ18O of tufa stromatalites are analysed and compared to the modern temperature and isotopic regime of the river system in which they form (the river Gipping, Sproughton, southeast England). In all cases this range of carbonates appear to form in isotopic equilibrium with the δ18O of modern waters at water temperatures experienced during the summer months. It is, therefore, likely that in Quaternary interglacial deposits of the UK and western Europe the δ18O of fossil freshwater molluscs and tufa stromatolite carbonates will provide an indication of past summer temperature regimes and not mean annual temperatures, as has been previously suggested. The paper concludes by discussing the implications of this study for the isotopic analysis of interglacial deposits in Britain and western Europe.  相似文献   

6.
桂林漓江水体溶解无机碳迁移与水生光合碳固定研究   总被引：1，自引：0，他引：1  
章程  肖琼 《中国岩溶》2021,40(4):555-564
河流溶解无机碳含量昼夜变化主要受碳酸盐反向沉积、水生光合利用和脱气作用控制,被水生光合利用的溶解无机碳是岩溶碳汇的组成部分,脱气作用比例的大小是影响碳汇稳定性的决定因素。本文以漓江中游省里—冠岩之间15 km长河段为研究对象,开展昼夜高分辨率水化学自动化监测与高频取样,分析水生植物光合作用利用HCO3-1及相关钙沉降过程。结果表明,监测河段水生光合利用的无机碳转化通量为859 kgC?d-1,单位流程光合作用溶解无机碳转化量和钙沉降量分别为2.06 t?（d?km）-1和0.78 t?（d?km）-1。光合作用与钙沉降消耗DIC约占总转化量的70 %,以光合有机碳和CaCO3形式储存于河床,成为岩溶碳汇组成部分。无机碳转化量约占输入DIC总量的6.0 %（其中1.7%以CO2形式返回大气）,说明夏季低水位期间强烈的水生植物光合利用溶解无机碳,可有效遏制白天水气界面CO2脱气过程发生,低脱气比例证实漓江水体的溶解无机碳还是比较稳定的。   相似文献   

7.
Continental carbonates of Quaternary age in southern Italy commonly exhibit the facies of calcareous tufa, often reported as related to shallow aquifers fed by meteoric waters and to organic processes. A close spatial relationship exists between the mappable tufa deposits and major Quaternary extensional faults. With respect to the Ca‐Mg‐HCO3 composition of limestone aquifers’ springs, tufa‐depositing springs exhibit higher salinity and alkalinity, are slightly warmer, have lower pH and are enriched in SO4 and CO2. Their δ13C values are systematically positive and compatible with a deep‐seated carbon source. A clear input of soil‐derived organic carbon is indicated only for small, non‐mappable tufas deposited by perched springs. The dataset indicates that the large tufa deposits owe their origin to a supplementary source of CO2 advected by degassing through active faults, as a necessary prerequisite for inducing a rise of total dissolved salts and alkalinity. Meteoric waters that have come from a shallow aquifer are able to precipitate only limited amount of carbonates.  相似文献   

8.
层状钙华及其地球化学指标的古气候/环境意义   总被引：8，自引：0，他引：8       下载免费PDF全文
层状钙华作为高分辨率古气候环境重建记录已被国内外许多学者所关注.钙华的微层厚度、氧碳同位素组成和微量元素的含量都呈现出随季节变化的周期性特点.钙华年层的形成与方解石沉积速率或者微生物生长活性的季节变化有关;氧同位素组成的变化主要受温度和沉积水体的δ18O控制,但蒸发作用(尤其是在干旱区)也有重要影响;钙华的稳定碳同位素...  相似文献   

9.
We present a continuous ∼14-yr-long (1985 to 1999) high-resolution record of trace element (Mg, Sr, Ba, U) and stable isotope (δ13C, δ18O) variations in a modern freshwater tufa from northwestern Queensland, Australia. By utilizing the temperature dependence of the δ18O signal, an accurate chronology was developed for the sampled profile, which allowed a comparison of the chemical records with hydrological and meteorological observations. As a consequence, it was possible to constrain the relevant geochemical processes relating climate variables, such as temperature and precipitation, to their chemical proxies in the tufa record. Temperatures calculated from the Mg concentrations of the tufa samples provide close approximations of average annual water temperature variations. Furthermore, we demonstrate that temporal changes in (Mg/Ca)water can be estimated using an empirically derived equation relating (Mg/Ca)water to the (Sr/Ba) ratio measured in the tufa samples. By means of this relationship, it is theoretically possible to determine the (Mg/Ca) ratio of paleowaters, and hence to derive reliable estimates of former water temperatures from the Mg concentrations of fossil tufas from the study area. Sympathetic variations in Sr, Ba, and δ13C along the sampled profile record changes in water chemistry, which are most probably caused by variable amounts of calcite precipitation within the vadose zone of the karst aquifer. This process is thought to be markedly subdued whenever the amount of wet-season precipitation exceeds a given threshold. Accordingly, distinct minima in Sr, Ba, and δ13C are interpreted to reflect years with above-average rainfall. The pronounced seasonal and annual variability of the U concentration along the profile is thought to primarily record changes in the U flux from the soil to the water table. We suggest that during intensive rain events U is transported to the phreatic zone by complexing organic colloids, giving rise to conspicuous U maxima in the tufa after above-average wet seasons. This study demonstrates the potential of freshwater tufas to provide valuable information on seasonal temperature and rainfall variations. If tufa deposits turn out to be reasonably resistant to secondary processes, combined investigation of speleothems and tufas from the same area could become a promising approach in future research. While speleothems offer continuous records of long-term paleoenvironmental changes, tufas could provide high-resolution time windows into selected periods of the past.  相似文献   

10.
Carbonate concretions, lenses and bands in the Pleistocene, Palaeogene and Upper Triassic coalfields of Japan consist of various carbonate minerals with varied chemical compositions. Authigenic carbonates in freshwater sediments are siderite > calcite > ankerite > dolomite >> ferroan magnesite; in brackish water to marine sediments in the coal measures, calcite > dolomite > ankerite > siderite >> ferroan magnesite; and in the overlying marine deposits, calcite > dolomite >> siderite. Most carbonates were formed progressively during burial within a range of depths between the sediment-water interface and approximately 3 km. The mineral species and the chemical composition of the carbonates are controlled primarily by the initial sedimentary facies of the host sediments and secondarily by the diagenetic evolution of pore water during burial. Based on the regular sequence and burial depth of precipitation of authigenic carbonates in a specific sedimentary facies, three diagenetic stages of carbonates are proposed. Carbonates formed during Stage I (< 500 m) strongly reflect the initial sedimentary facies, e.g. low Ca-Mg siderite in freshwater sediments which are initially rich in iron derived from lateritic soil on the nearby landmass, and Mg calcite and dolomite in brackish-marine sediments whose pore waters abound in Ca2+ and Mg2+ originating in seawater and calcareous shells. Carbonates formed during Stage II (500–2000 m) include high Ca-Mg siderite, ankerite, Fe dolomite and Fe–Mg calcite in freshwater sediments. The assemblage of Stage II carbonates in brackish-marine sediments in the coal measures is similar to that in freshwater sediments. This suggests similar diagenetic environments owing to an effective migration and mixing of pore water due to the compaction of host sediments. Carbonates formed during Stage III (> 2000 m) are Fe calcite and extremely high Ca-Mg siderite; the latter is exclusively in marine mudstones. The supply of Ca is partly from the alteration of silicates in the sediments at elevated burial temperatures. After uplift, calcite with low Mg content precipitates from percolating groundwater and fills extensional cracks.  相似文献   

11.
Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ13C) and oxygen (δ18O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO2 degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ13C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO2 degassing and tufa precipitation rate downstream. The Δ13C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous 12CO2 degassing downstream leaving the carbon pool enriched in 13C. In the case of oxygen, the isotope fractionation (Δ18O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ18O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ18O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.  相似文献   

12.
The Denizli Basin is a fault‐bounded Neogene–Quaternary depression located in the Western Anatolian Extensional Province, Western Turkey. The basin is a unique geological site with abundant active and fossil (Quaternary) travertine and tufa deposits. Fluid inclusion microthermometry and isotopic analysis were applied to study the genesis of the Ball?k fossil travertine deposits, located in the south‐eastern part of the basin. Microthermometry on fluid inclusions indicates that the main travertine precipitating and cementing fluids are characterized by low salinity (<0·7 wt% NaCl equivalent) and variable temperatures that cluster at <50°C and ca 100°C. Fluids of meteoric origin have been heated by migration to the deeper subsurface, possibly in a local high geothermal gradient setting. A later uncommon cementation phase is related to a fluid with a significantly higher salinity (25·5 to 26·0 wt% bulk). The fluid obtained its salinity by interaction with Late Triassic evaporite layers. Strontium isotopes indicate that the parent carbonate source rock of the different travertine precipitates is very likely to be the Triassic limestone of the Lycian Nappes. Carbon isotopes suggest that the parent CO2 gas originated from thermal decarbonation of the Lycian limestones with minor contributions of magmatic degassing and organic soil CO2. Oxygen isotopes confirm the meteoric origin of the fluids and indicate disequilibrium precipitation because of evaporation and degassing. Results were integrated within the available geological data of the Denizli Basin in a generalized travertine precipitation model, which enhanced the understanding of fossil travertine systems. The study highlights the novel application of fluid inclusion research in unravelling the genesis of continental carbonates and provides several recommendations for hydrocarbon exploration in travertine‐bearing sedimentary basins. The findings suggest that travertine bodies and their parent carbonate source rocks have the potential to constitute interesting subsurface hydrocarbon reservoirs.  相似文献   

13.
海相碳酸盐的沉淀方式被认为与水体氧化还原条件密切相关,即太古宙至古元古代缺氧的铁化海水中碳酸盐沉淀抑制剂Fe2+和Mn2+强力抑制灰泥在水柱中成核,但允许文石直接在海底生长,从而导致大量文石以海底沉淀方式产出,而新元古代适度的氧化海水则有利于灰泥以水柱沉淀方式形成。然而,碳酸盐沉淀方式的长期变化还可能受控于其他因素,其与海水氧化还原条件之间的关系还需要通过大量具体实例来验证。针对上述科学问题,笔者选择碳酸盐沉淀方式尚处于过渡时期的华北中元古界碳酸盐岩为研究对象,开展碳酸盐沉淀方式及与之对应的氧化还原条件研究。结果表明,华北高于庄组三段(约1.56 Ga)、雾迷山组四段下部(约1.48 Ga)和铁岭组二段(约1.44 Ga)发育大量灰泥水柱沉淀,其Ⅰ/(Ca+Mg)值较高(普遍大于0.5 μmol/mol)、Ce负异常(低至0.8),指示适度氧化的条件;而高于庄组四段下部(约1.55 Ga)和雾迷山组二段中部(约1.50 Ga)则发育大量纤维状文石海底沉淀,其Ⅰ/(Ca+Mg)值约为0,指示次氧化至缺氧的环境。因此,本研究首次用大量实例证实了前寒武纪海水氧化还原条件对碳酸盐沉淀方式的重要调控作用,并且后者可作为海水氧化还原条件分析的重要指标,适用于高效开展长序列、多剖面的低氧背景下前寒武纪碳酸盐岩地层的氧化还原条件分析。  相似文献   

14.
Francolite (carbonate-fluor-apatite) is known to form in sediments where intense organic-matter decay occurs, but under oxic-to-suboxic conditions, because the alkalinity rise accompanying bacterial sulfate reduction (anoxic conditions) increases francolite solubility, hence preventing its supersaturation and precipitation. However, lagoonal, organic matter-rich, cryptalgal carbonates of Jurassic age located in the French Jura Mountains contain francolite that formed during early diagenesis, under anoxic-sulfidic and highly alkaline conditions. To explain this paradoxical situation, we propose the following “chain of reactions”: the presence of abundant biomass in the sediment would supply the “raw material” to the reactional system, i.e., the initial P budget, released through organic decay. The development of cryptalgal, bacterial mats at the sediment–water interface would have limited exchanges between the water column and the pore space, hampering pore water renewal and favoring the early onset of sulfate-reducing reactions. The onset of sulfate reduction would increase pore water alkalinity, potentially preventing francolite precipitation. In addition, the presence of sulfide ions would induce organic matter sulfurization, resulting in a relative pH rise. Alkalinity and pH rises would trigger the development of conditions leading to carbonate supersaturation, inducing bacterial-structure calcification. The sudden fall in alkalinity induced by early calcification would allow francolite precipitation, despite sulfidic conditions.  相似文献   

15.
天津蓟县中元古界雾迷山组是一套厚度超过3 000 m的叠层石碳酸盐岩沉积序列,在该序列中潮下相叠层石生物层、凝块石生物丘与潮坪相泥晶白云岩、泻湖相白云质泥页岩一起构成若干个环潮坪型米级旋回--“雾迷山旋回层”。在雾迷山组下部发育微指状叠层石,并被古生物学家定义为“Pseudogymnosolen mopanyuensis-Scuphus-Yangzhuang columnaris”组合,即假裸枝叠层石科叠层石,沉积学家将其解释为元古代文石（灰华）海底沉淀物所构成的叠层石,代表从太古代海底结壳状文石沉淀物叠层石到新元古代碎屑结构相、富泥碳酸盐叠层石过渡时期的特殊产物。因此,雾迷山组巨厚的叠层石碳酸盐岩沉积序列,记录了元古代文石灰华海底沉淀物所构成的特殊的叠层石大规模消亡的层位,为研究前寒武纪以叠层石为代表的微生物碳酸盐岩所经历的漫长而复杂的地质历史演变提供了宝贵的材料。  相似文献   

16.
The recent discoveries of deeply buried Cretaceous reservoir bodies in the Atlantic Ocean revealed that relationships between the distribution of spring carbonate deposits and faults are poorly understood. The well‐exposed Quaternary deposits at Obruktepe (Denizli Basin, Turkey) provide an opportunity to reconstruct the three‐dimensional sedimentary architecture of such a system. Integration of sedimentological, lithofacies and geochemical analyses reveals complexity in the lateral relationships between sedimentary environments, faults and geothermal spring carbonates. Five environmental systems are distinguished based on the lithofacies analysis: (i) vent; (ii) smooth slope; (iii) travertine‐terrace; (iv) tufa‐barrage; and (v) flood systems. Encrusting, baffling and settling sedimentary processes are reflected in data acquired at several scales, from lithofacies observations to the morphology and arrangement of geobodies, together with microfabrics and stable carbon and oxygen isotope data. Mean values of +4·9‰ δ13C and −8·74‰ δ18O Vienna PeeDee Belemnite reflect geothermal circulation of springwaters. The environmental distribution and lithofacies indicate a lateral continuum between travertine and tufa deposits within this hot spring system. This finding supports two depositional models in which water flow variation is the main control on both CaCO3 precipitation and the resulting formation of travertine and tufa. The proposed models address the factors responsible for the development of these complex mound‐shaped carbonate spring deposits, and how they are related to fluid circulation at depth and in association with faults.  相似文献   

17.
Microbial carbonate mud in the modern (<4 kyr) palustrine environment of the Florida Everglades is surprisingly susceptible to early diagenetic alteration. The low‐Mg calcite crystals show an open, trellis‐like crystal structure that yields a high surface area to volume ratio. This textural complexity, likely to be a result of organic influence, leads to abundant reaction sites vulnerable to both dissolution and subsequent precipitation. Rapid degradation of organics is attributed to both aerobic and anaerobic metabolisms. Geochemical signatures suggest increased denitrification within the freshwater environment and increased sulphate reduction at the (slightly) brackish mangrove transition zone. A transition from a freshwater to brackish depositional environment is likely to follow the Holocene sea‐level transgression. The textural complexity in these microbial carbonates causes an unexpectedly low preservation potential of original textural and geochemical signatures, even in low‐Mg calcite. Given the potential for early diagenesis of palustrine and perhaps other microbial carbonates, they should be used cautiously as archives for palaeoenvironmental proxies.  相似文献   

18.
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.  相似文献   

19.
Tufas, which are freshwater carbonates, are potential archives of terrestrial paleoclimate. Time series of stable isotopic compositions commonly show regular seasonal patterns controlled by temperature-dependent processes, and some perturbation intrinsic to the locality. We examined three tufa-depositing sites in southwestern Japan with similar temperate climates, to understand the origin of local characteristics in the isotopic records. Seasonal change in the oxygen isotope is principally reflected by temperature-dependent fractionation between water and calcite but was perturbed after heavy rainfalls overwhelming the stability of the δ18O value of the groundwater at one site. Isotopic mass balance indicates an undersaturated and relatively small aquifer at this locality. Water δ18O values at the other two sites were stable, reflecting a regular seasonal change in the δ18O value of tufa. Perturbation of the δ13C values in tufa is largely due to CO2 degassing from the stream, which significantly increases the δ13C values of dissolved inorganic carbon (DIC). At a site with remarkably high pCO2 in springwater and a sensitive response of flow rate to rainfall, the amount of CO2 degassing changed distinctly with flow rate. In contrast, the other two sites having low pCO2 springwater reflect a regular seasonal pattern of δ13C in DIC and tufa specimens.  相似文献   

20.
A continuous 60-year record (1938–1998) of stable isotope compositions of carbon and oxygen, as well as trace metal (Mg, Sr, Ba) concentrations in a laminated calcite crust precipitated in a short artificial tunnel on a non-equilibrium groundwater-fed karstic river is presented. Chemical and isotopic records have been compared to hydrometeorological data, available for the last 48 years. An attempt is made to relate isotopic and geochemical variations in the crust to environmental parameters, such as temperature, precipitation and changes in vegetation cover, as well as to postdepositional recrystallisation of the older crust material. Isotopic composition of the crust is largely influenced by non-equilibrium precipitation, which favours the incorporation of isotopically depleted C and O into the carbonate. Furthermore, because of the complicated hydrological situation, there is no observable correlation between the stable oxygen isotope composition of water and temperature. The result is that the 18O isotopic thermometers overestimate the measured precipitation temperatures. Temperatures calculated from Mg/Ca ratios of water and the carbonate match the δ18O palaeotemperatures within ± 2.4 °C in the older part of the crust, precipitated before the onset of industrial pollution of the river. It was demonstrated that the application of Mg palaeothermometry in natural systems, where the Mg/Ca ratio of water is influenced not only by temperature, but also by other environmental parameters such as precipitation, surface runoff, groundwater retention time and anthropogenic influences, is subject to a large uncertainty, up to 10 °C.  相似文献   

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