Vadose CO2 gas drives dissolution at water tables in eogenetic karst aquifers more than mixing dissolution

Most models of cave formation in limestone that remains near its depositional environment and has not been deeply buried (i.e. eogenetic limestone) invoke dissolution from mixing of waters that have different ionic strengths or have equilibrated with calcite at different _pCO₂ values. In eogenetic karst aquifers lacking saline water, mixing of vadose and phreatic waters is thought to form caves. We show here calcite dissolution in a cave in eogenetic limestone occurred due to increases in vadose CO₂ gas concentrations and subsequent dissolution of CO₂ into groundwater, not by mixing dissolution. We collected high‐resolution time series measurements (1 year) of specific conductivity (SpC), temperature, meteorological data, and synoptic water chemical composition from a water table cave in central Florida (Briar Cave). We found SpC, _pCO₂ and calcite undersaturation increased through late summer, when Briar Cave experienced little ventilation by outside air, and decreased through winter, when increased ventilation lowered cave CO_2(g) concentrations. We hypothesize dissolution occurred when water flowed from aquifer regions with low _pCO₂ into the cave, which had elevated _pCO₂. Elevated _pCO₂ would be promoted by fractures connecting the soil to the water table. Simple geochemical models demonstrate that changes in _pCO₂ of less than 1% along flow paths are an order of magnitude more efficient at dissolving limestone than mixing of vadose and phreatic water. We conclude that spatially or temporally variable vadose CO_2(g) concentrations are responsible for cave formation because mixing is too slow to generate observed cave sizes in the time available for formation. While this study emphasized dissolution, gas exchange between the atmosphere and karst aquifer vadose zones that is facilitated by conduits likely exerts important controls on other geochemical processes in limestone critical zones by transporting oxygen deep into vadose zones, creating redox boundaries that would not exist in the absence of caves. Copyright © 2014 John Wiley & Sons, Ltd.     

Heterogeneous distributions of CO2 may be more important for dissolution and karstification in coastal eogenetic limestone than mixing dissolution

Mixing dissolution, a process whereby mixtures of two waters with different chemical compositions drive undersaturation with respect to carbonate minerals, is commonly considered to form cavernous macroporosity (e.g. flank margin caves and banana holes) in eogenetic karst aquifers. On small islands, macroporosity commonly originates when focused dissolution forms globular chambers lacking entrances to the surface, suggesting that dissolution processes are decoupled from surface hydrology. Mixing dissolution has been thought to be the primary dissolution process because meteoric water would equilibrate rapidly with calcium carbonate as it infiltrates through matrix porosity and because pCO₂ was assumed to be homogeneously distributed within the phreatic zone. Here, we report data from two abandoned well fields in an eogenetic karst aquifer on San Salvador Island, Bahamas, that demonstrate pCO₂ in the phreatic zone is distributed heterogeneously. The pCO₂ varied from less than log ?2.0 to more than log ?1.0 atm over distances of less than 30 m, generating dissolution in the subsurface where water flows from regions of low to high pCO₂ and cementation where water flows from regions of high to low pCO_2. Using simple geochemical models, we show dissolution caused by heterogeneously distributed pCO₂ can dissolve 2.5 to 10 times more calcite than the maximum amount possible by mixing of freshwater and seawater. Dissolution resulting from spatial variability in pCO₂ forms isolated, globular chambers lacking initial entrances to the surface, a morphology that is characteristic of flank margin caves and banana holes, both of which have entrances that form by erosion or collapse after cave formation. Our results indicate that heterogeneous pCO₂, rather than mixing dissolution, may be the dominant mechanism for observed spatial distribution of dissolution, cementation and macroporosity generation in eogenetic karst aquifers and for landscape development in these settings. Copyright © 2015 John Wiley & Sons, Ltd.     

Dissolution in a variably confined carbonate platform: effects of allogenic runoff,hydraulic damming of groundwater inputs,and surface–groundwater exchange at the basin scale

In variably confined carbonate platforms, impermeable confining units collect rainfall over large areas and deliver runoff to rivers or conduits in unconfined portions of platforms. Runoff can increase river stage or conduit heads in unconfined portions of platforms faster than local infiltration of rainfall can increase groundwater heads, causing hydraulic gradients between rivers, conduits and the aquifer to reverse. Gradient reversals cause flood waters to flow from rivers and conduits into the aquifer where they can dissolve limestone. Previous work on impacts of gradient reversals on dissolution has primarily emphasized individual caves and little research has been conducted at basin scales. To address this gap in knowledge, we used legacy data to assess how a gradient of aquifer confinement across the Suwannee River Basin, north‐central Florida affected locations, magnitudes and processes of dissolution during 2005–2007, a period with extreme ranges of discharge. During intense rain events, runoff from the confining unit increased river stage above groundwater heads in unconfined portions of the platform, hydraulically damming inputs of groundwater along a 200 km reach of river. Hydraulic damming allowed allogenic runoff with SI_CAL < ?4 to fill the entire river channel and flow into the aquifer via reversing springs. Storage of runoff in the aquifer decreased peak river discharges downstream and contributed to dissolution within the aquifer. Temporary storage of allogenic runoff in karst aquifers represents hyporheic exchange at a scale that is larger than found in streams flowing over non‐karst aquifers because conduits in karst aquifers extend the area available for exchange beyond river beds deep into aquifers. Post‐depositional porosity in variably confined carbonate platforms should thus be enhanced along rivers that originate on confining units. This distribution should be considered in models of porosity distribution used to manage water and hydrocarbon resources in carbonate rocks. Copyright © 2013 John Wiley & Sons, Ltd.     

Geochemistry of meteoric diagenesis in carbonate islands of the northern Bahamas: 2. Geochemical modelling and budgeting of diagenesis

Geochemical characterization and numerical modelling of surface water and ground water, combined with hydrological observations, provide quantitative estimates of meteoric diagenesis in Pleistocene carbonates of the northern Bahamas. Meteoric waters equilibrate with aragonite, but water‐ rather than mineral‐controlled reactions dominate. Dissolutional lowering of the undifferentiated bedrock surface is an order of magnitude slower than that within soil‐filled topographic hollows, generating small‐scale relief at a rate of 65–140 mm ka^?1 and a distinctive pocketed topography. Oxidation of organic matter within the subsoil and vadose zones generates an average P of 4·0 × 10^?3 atm, which drives dissolution during vadose percolation and/or at the water table. However, these dissolution processes together account for <60% of the average rock‐derived calcium in groundwaters pumped from the freshwater lens. The additional calcium may derive from oxidation of organic carbon within the lens, accounting for the high P of the lens waters. Mixing between meteoric waters of differing chemistry is diagenetically insignificant, but evapotranspiration from the shallow water table is an important drive for subsurface cementation. Porosity generation in the shallow vadose zone averages 1·6–3·2% ka^?1. Phreatic meteoric diagenesis is focused near the water table, where dissolution generates porosity at 1·4–2·8% ka^?1. Maximum dissolution rates, however, are similar to those of evaporation‐driven precipitation, which occludes porosity of 4·0 ± 0·6% ka^?1. This drives porosity inversion, from primary interparticle to secondary mouldic, vug and channel porosity. In the deeper freshwater lens, oxidation of residual organic carbon and reoxidation of reduced sulphur species from deeper anaerobic oxidation of organic carbon may generate porosity up to 0·06% ka^?1. Meteoric diagenesis relies critically on hydrological routing and vadose thickness (controlled by sea level), as well as the geochemical processes active. A thin vadose zone permits direct evaporation from the water table and drives precipitation of meteoric phreatic cements even where mineral stabilization is complete. Copyright © 2007 John Wiley & Sons, Ltd.     

Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2 concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2 ]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.     

Organic and inorganic matter in Louisiana coastal waters: Vermilion, Atchafalaya, Terrebonne, Barataria, and Mississippi regions

Chromophoric dissolved organic matter (CDOM) spectral absorption, dissolved organic carbon (DOC) concentration, and the particulate fraction of inorganic (PIM) and organic matter (POM) were measured in Louisiana coastal waters at Vermilion, Atchafalaya, Terrebonne, Barataria, and Mississippi River locations, in 2007-2008. The range of CDOM was 0.092 m⁻¹ at Barataria in June 2008 to 11.225 m⁻¹ at Mississippi in February 2008. An indicator of organic matter quality was predicted by the spectral slope of absorption coefficients from 350 to 412 nm which was between 0.0087 m⁻¹ at Mississippi in May 2008 and 0.0261 m⁻¹ at Barataria in June 2008. CDOM was the dominant component of light attenuation at Terrebonne and Barataria. Detritus and CDOM were the primary components of light attenuation at Vermilion, Atchafalaya, and Mississippi. DOC ranged between 65 and 1235 μM. PIM ranged between 1.1 and 426.3 mg L⁻¹ and POM was between 0.3 and 49.6 mg L⁻¹.     

Multiple injected and natural conservative tracers quantify mixing in a stream confluence affected by acid mine drainage near Silverton,Colorado

The acidic discharge from Cement Creek, containing elevated concentrations of dissolved metals and sulphate, mixed with the circumneutral‐pH Animas River over a several hundred metre reach (mixing zone) near Silverton, CO, during this study. Differences in concentrations of Ca, Mg, Si, Sr, and SO₄^2? between the creek and the river were sufficiently large for these analytes to be used as natural tracers in the mixing zone. In addition, a sodium chloride (NaCl) tracer was injected into Cement Creek, which provided a Cl^? ‘reference’ tracer in the mixing zone. Conservative transport of the dissolved metals and sulphate through the mixing zone was verified by mass balances and by linear mixing plots relative to the injected reference tracer. At each of seven sites in the mixing zone, five samples were collected at evenly spaced increments of the observed across‐channel gradients, as determined by specific conductance. This created sets of samples that adequately covered the ranges of mixtures (mixing ratios, in terms of the fraction of Animas River water, %AR). Concentratis measured in each mixing zone sample and in the upstream Animas River and Cement Creek were used to compute %AR for the reference and natural tracers. Values of %AR from natural tracers generally showed good agreement with values from the reference tracer, but variability in discharge and end‐member concentrations and analytical errors contributed to unexpected outlier values for both injected and natural tracers. The median value (MV) %AR (calculated from all of the tracers) reduced scatter in the mixing plots for the dissolved metals, indicating that the MV estimate reduced the effects of various potential errors that could affect any tracer. Copyright © 2006 John Wiley & Sons, Ltd.     

Inverse modeling for seawater intrusion in coastal aquifers: Insights about parameter sensitivities,variances, correlations and estimation procedures derived from the Henry problem

Inverse modeling studies employing data collected from the classic Henry seawater intrusion problem give insight into several important aspects of inverse modeling of seawater intrusion problems and effective measurement strategies for estimation of parameters for seawater intrusion. Despite the simplicity of the Henry problem, it embodies the behavior of a typical seawater intrusion situation in a single aquifer. Data collected from the numerical problem solution are employed without added noise in order to focus on the aspects of inverse modeling strategies dictated by the physics of variable-density flow and solute transport during seawater intrusion. Covariances of model parameters that can be estimated are strongly dependent on the physics. The insights gained from this type of analysis may be directly applied to field problems in the presence of data errors, using standard inverse modeling approaches to deal with uncertainty in data.     

Bed sediment sources and mixing in the glacierized upper Fraser River watershed,east‐central British Columbia

The geochemical, mineralogical and lithological composition of modern stream bed material is examined in order to characterize sources and evaluate downstream mixing of sediments in the upper Fraser River drainage basin, British Columbia. The <63 µm fraction is emphasized for its relative mobility and ease of analysis using instrumental neutron activation. Overall, the composition of the stream sediments closely re?ects bedrock distribution. Samples dominated by limestone and dolostone, calcite and dolomite, and related elements (Ca, Mg, Sr etc.) correspond to Lower and Middle Cambrian carbonate bedrock largely con?ned to the Moose River sub‐basin. Clastic and non‐quartzite metamorphic lithologies, primary and secondary aluminosilicate minerals and related elements (Al, Cs, Rb etc.) are largely derived from Miette Group bedrock and associated with the uppermost Fraser River sub‐basin. Except in the case of the Moose River/Fraser River junction, the determination of proportional tributary contributions is complicated by variable or delayed mixing, localized ?oodplain or valley side sources, and limited contrast between source areas. At present the Moose River sub‐basin contributes a greater proportion of the total and ?ne‐grained sediment loads of the combined Fraser River than would be expected from drainage basin area alone. The imbalance is related to greater relief, precipitation and runoff in the Moose River sub‐basin; however, the spatial association of carbonate‐rich stream sediments, ice cover and carbonate bedrock exposure indicates that glaciers play a particularly important roll in generating ?ne‐grained ?uvial sediment. Since differences in glacier cover and glacier potential in the two major sub‐basins are likely to be persistent, and since relative sediment yields from the sub‐basins can be determined from sediment composition, a potential indicator of glacier variation and climate change during the Holocene is therein available. Copyright © 2004 John Wiley & Sons, Ltd.     

The role of gypsum and/or dolomite dissolution in tufa precipitation: lessons from the hydrochemistry of a carbonate–sulphate karst system

The precipitation of freshwater carbonates (tufa) along karstic rivers is enhanced by degassing of carbon dioxide (CO₂) downstream of karstic springs. However, in most karstic springs CO₂ degassing is not enough to force the precipitation of tufa sediments. Little is known about the role of dissolution of gypsum or dolomite in the hydrochemistry of these systems and how this affects the formation of tufa deposits. Here we present a monitoring study conducted over a year in Trabaque River (Spain). The river has typical karst hydrological dynamics with water sinking upstream and re‐emerging downstream of the canyon. Mixing of calcium–magnesium bicarbonate and calcium sulphate waters downstream of the sink enhances the dissolution of carbonates and potentially plays a positive role in the formation of tufa sediments. However, due to the common‐ion effect, dissolution of dolomite and/or gypsum causes precipitation of underground calcite cements as part of the incongruent dissolution of dolomite/dedolomitization process, which limits the precipitation of tufa sediments. Current precipitation of tufa is scant compared to previous Holocene tufa deposits, which likely precipitated from solutions with higher saturation indexes of calcite (SIcc values) than nowadays. Limited incongruent dissolution of dolomite/dedolomitization favours higher SIcc values. This circumstance occurs when waters with relatively high supersaturation of dolomite and low SO₄^2? composition sink in the upper sector of the canyon. In such a scenario, the process of mixing waters enhances the exclusive dissolution of limestones, preventing the precipitation of calcite within the aquifer and favouring the increase of SIcc values downstream of the springs. Such conditions were recorded during periods of high water level of the aquifers and during floods. This research shows that the common‐ion effect caused by the dissolution of gypsum and/or dolomite rocks can limit [or favour] the precipitation of tufa sediments depending on the occurrence [or not] of incongruent dissolution of dolomite/dedolomitization. Copyright © 2016 John Wiley & Sons, Ltd.     

塔里木盆地顺北超深层碳酸盐岩输导体系三维地震属性多尺度表征及连通性分析

塔里木盆地顺北地区7000 m超深层广泛发育碳酸盐岩断控岩溶储层,其复杂的溶洞-裂缝系统为油气提供了良好的运移通道和储集空间.本文分尺度精细刻画断控岩溶输导体系三维内部结构.首先采用断裂增强滤波技术,提高超深层地震数据信噪比.其次,根据断控岩溶输导结构的地震反射特征,将其划分为大、中、小三种不同尺度结构模式.大尺度结构包括大型走滑断裂、溶洞及伴随的岩溶塌陷,具有规则的断裂强反射和“串珠状”反射的震相特征;中尺度结构主要为走滑断裂附近横向发育的次生断层及伴随的岩溶局部塌陷,具有杂乱强反射震相特征;小尺度结构为弥漫整个输导介质的背景裂缝,具有杂乱弱反射震相特征.单一的地震属性很难全面地描述断控岩溶输导介质,通过属性分析,明确了三类结构模式的敏感地震属性群,利用贝叶斯聚类融合技术,分别对三类结构模式的敏感地震属性群进行融合.最后,将三类结构模式的融合地震属性分别采样到三维输导介质网格中进行量化分析,最终建立缝洞连通体结构模型,为后续的岩性物性预测和流体识别提供三维输导体系连通体模型.

     

A high‐altitude temporary spring in a compartmentalized carbonate aquifer: the role of low‐permeability faults and karst conduits

The aim of this research was to refine the actual conceptual model related to the activation of high‐altitude temporary springs within the carbonate Apennines in southern Italy. The research was carried out through geophysical, hydrogeological, hydrochemical and isotopic investigations at the Acqua dei Faggi experimental site during five hydrologic years. The research demonstrated that, in carbonate aquifers where low‐permeability faults cause the aquifer system to be compartmentalized, high‐altitude temporary springs may be recharged by groundwater. In such settings, neither surface water infiltration in karst systems nor perched temporary aquifers play a role of utmost importance. The rare (once or a few time a year) activation of such springs is due to the fact that groundwater unusually reach the threshold head that allows the spring to flow. The activation of the studied high‐altitude temporary spring also depended on relationships between a low‐permeability fault core and a karst system that locally interrupts the low‐permeability barrier. In fact, when the hydraulic head did not reach the karst system, the concentrated head loss within the fault core did not allow the spring to flow, because the groundwater entirely flowed through the fault towards the downgradient compartment. Copyright © 2009 John Wiley & Sons, Ltd.     

Organic carbon transport in the Songhua River,NE China: Influence of land use

Carbon transported by rivers is an important component of the global carbon cycle. Here, we report on organic carbon transport along the third largest river in China, the Songhua River, and its major tributaries. Water samples were collected seasonally or more frequently to determine dissolved organic carbon (DOC) and particulate organic carbon (POC) concentrations and C/N and stable carbon isotopic ratios. Principal component analysis and multiple regression analysis of these data, in combination with hydrological records for the past 50 years, were used to determine the major factors influencing the riverine carbon fluxes. Results indicate that the organic carbon in the Songhua River basin is derived mainly from terrestrial sources. In the 2008–2009 hydrological year, the mean concentrations of DOC and POC were 5.87 and 2.36 mg/L, and the estimated fluxes of the DOC and POC were 0.30 and 0.14 t·km^?2·year^?1, respectively. The riverine POC and DOC concentrations were higher in subcatchments with more cropland, but the area‐specific fluxes were lower, owing to decreased discharge. We found that hydrological characteristics and land‐use type (whether forest or cropland) were the most important factors influencing carbon transport in this system. Agricultural activity, particularly irrigation, is the principal cause of changes in water discharge and carbon export. Over the last 50 years, the conversion of forest to cropland has reduced riverine carbon exports mainly through an associated decrease in discharge following increased extraction of water for irrigation.     

Strontium isotope identification of water mixing and recharge sources in a river system (Oder River,central Europe): A quantitative approach

This study uses Sr isotope composition (⁸⁷Sr/⁸⁶Sr) and Sr content of waters of the Oder, one of the largest rivers in central Europe, to fingerprint natural and anthropogenic contributions to its Sr budget and to evaluate water mixing processes in its hydrological system. It also demonstrates a simple method of quantifying natural and anthropogenic Sr inputs in the watershed. The method has potential for environmental and archaeological research because past Sr geochemistry of river water can easily be reconstructed. For the first time, a catchment‐scale impact of anthropogenic sources on the Sr budget of a middle‐size river is shown in a quantitative way. The water of the Oder is characterized by a relatively uniform Sr isotope composition, from 0.7100 to 0.7108, contrasting with strong variations in Sr concentration, from 0.25 to 1.27 mg/L. There is a general seasonal trend in variability, with waters becoming more radiogenic and dilute with respect to the Sr in the spring time. This Sr systematics differs significantly from the Sr budgets of the majority of the Oder tributaries that exhibit more radiogenic composition and systematically lower Sr concentrations. A mixing scenario in the Oder involves Sr contribution from four principal water sources: (a) shallow ground waters with Sr derived from near‐surface weathering of silicates, (b) moderately radiogenic mine waters from the Upper Silesian Coal Basin, (c) unradiogenic mine waters from the Permian sequence of the copper district, and (d) unradiogenic ground waters from shallow‐seated Palaeogene, Neogene, and Mesozoic aquifers. The Sr budget of the Oder is primarily controlled by inputs of dissolved Sr from anthropogenic sources, which overprint the natural background, controlled by geology. Thus, about 47.5% of Sr originates from agriculture, industrial, and municipal additions, 31.5% from mine water inputs, and only 21% from natural sources, that is, rock weathering and atmospheric precipitation. Reconstruction of the past Sr chemistry of the Oder reveals that its present‐day Sr isotope composition is temporary and significantly different from that of the preindustrial times.     

Detecting the flow relationships between deep and shallow aquifers in an exploited groundwater system,using long‐term monitoring data and quantitative hydrogeology: the Acque Albule basin case (Rome,Italy)

Five years of hydrogeological monitoring and field activities performed in the complex hydrogeological system of the Acque Albule basin (AAB) were conducted to define the hydrogeological setting, the relationship between deep and shallow aquifers and a conceptual groundwater flow model of this exploited area using conventional quantitative techniques. The basin, which is located close to Rome (Italy) on the west side of the Apennine chain and just north of the Colli Albani volcano, subsided after development of a north–south fault system (about 115 000 y bp). The AAB experiences intense hydrothermal activity, which has produced a large travertine deposit (80‐m thick). The travertine deposit constitutes a fractured aquifer that is the final destination of more than 5 m³ s^‐1 of water and is strongly dewatered by quarry activities. The complex hydrogeology of this basin was investigated, revealing two main hydraulically connected aquifers, one thermalised and partly confined into the limestone bedrock and one unconfined in the travertine. The two aquifers are separated by a non‐continuous clayey aquiclude. The hydrogeological survey and geological characterisation contributed to the development of the groundwater flow conceptual model. Analysis and comparison of the monitored levels highlighted the pattern of flow between the deep and shallow parts of the flow system. Copyright © 2012 John Wiley & Sons, Ltd.     

Upwelling and surface cold patches in the Yellow Sea in summer: Effects of tidal mixing on the vertical circulation

A three-dimensional, prognostic, wave–tide–circulation coupled numerical model is developed to study the effects of tidal mixing on the summertime vertical circulation in the Yellow Sea (YS). The distribution and mechanisms of upwelling are investigated by numerical means. Validated by historical tide gauge data, satellite sea surface temperature (SST) data, and cruise observation data, the model shows satisfactory performances in reproducing the dominant tidal system and three-dimensional sea temperature structure. Model results suggest that strong tidal mixing plays an important role in the formation of the vertical circulation in the YS. The Yellow Sea Cold Water Mass (YSCWM) is fringed by typical tidal mixing fronts (TMFs), which separate the cold, stratified water at the offshore side from the warm, well-mixed, shallow water at the other side. Considerable baroclinic gradient across the TMF makes the frontal zone the spot where the most active vertical circulation occurs; a secondary circulation is triggered with a distinct upwelling branch occurring mainly on the mixed side of the front. The numerical model produces systematic upwelling belts surrounding the YSCWM, and the upwelling is essentially induced by the TMF over sloping topography. The relative importance of tidal mixing and wind forcing for upwelling is further examined in numerical experiments. The southerly wind enhances the upwelling off the western coasts, but its overall influences in the whole YS are less important than tidal mixing. As shown by both satellite data and numerical modeling, the summertime SST field in the YS is featured by the stable existence of several site-selective surface cold patches (SCPs), most of which scatter in the waters off convex coastlines. One of the SCPs is found off Subei Bank, and the others are located off the eastern tip of Shandong Peninsula and off the three tips of Korean Peninsula. Two processes give rise to the SCP: on the one hand, TMF-induced upwelling supplies cold water from the deep layer; on the other hand, tidal mixing itself can stir the bottom water upward and homogenize the water column vertically. In the waters around the tips of peninsula in the YS, the tidal currents are extraordinarily strong, which provides a possible explanation for the site-selectivity of the SCPs.     

Dissolved major ions,Sr and 87Sr/86Sr of coastal lakes from Larsemann hills,East Antarctica: Solute sources and chemical weathering in a polar environment

Dissolved major ions, Sr concentrations and ⁸⁷Sr/⁸⁶Sr ratios of 10 coastal lakes from the Larsemann Hills, East Antarctica have been studied to constrain their solute sources, transport and glacial weathering patterns in their catchments. In absence of perennial river/streams, lakes serve as only reliable archive to study land surface processes in these low-temperature regions. The lake water chemistry is mostly Na-Cl type and it does not show any significant depth variations. Sr isotope compositions of these lakes vary from 0.7110 to 0.7211 with an average value of 0.7145, which is higher than modern seawater value. In addition to oceanic sources, major ions and Sr isotopic data show appreciable amount of solute supply from chemical weathering of silicate rocks in lake catchments and dissolution of Ca-Mg rich salts produced during the freezing of seawaters. The role of sulphide oxidation and carbonate weathering are found to be minimal on lake hydro-chemistry in this part of Antarctica. Inverse model calculations using this chemical dataset provide first-order estimates of dissolved cations and Sr; they are mostly derived from oceanic (seawater + snow) sources (cations approximately 76%) and (Sr approximately 92%) with minimal supplies from weathering of silicates (cations approximately 15%); (Sr approximately 2%) and Ca-rich minerals (cations approximately 9%); (Sr approximately 7%). The silicate weathering rate and its corresponding atmospheric CO₂ consumption rate estimates for Scandrett lake catchment (3.6 ± 0.3 tons/km²/year and 0.5 × 10⁵ moles/km²/year), are lower than that of reported values for the average global river basins (5.4 tons/km²/year and 0.9 × 10⁵ tons/km²/year) respectively. The present study provides a comprehensive report of chemical weathering intensity and its role in atmospheric CO₂ consumption in low-temperature pristine environment of Antarctica. These estimates underscore the importance of Antarctica weathering on atmospheric CO₂ budget, particularly during the past warmer periods when the large area was exposed and available for intense chemical weathering.