A geochemical traverse across the Eastern Carpathians (Romania): constraints on the origin and evolution of the mineral water and gas discharges

The inner sector of the Eastern Carpathians displays a large number of Na–HCO₃, CO₂-rich, meteoric-originated cold springs (soda springs) and bore wells, as well as dry mofettes. They border the southern part of the Pliocene–Quaternary Calimani–Gurghiu–Harghita (CGH) calc-alkaline volcanic chain. Both volcanic rocks and CO₂-rich emissions are situated between the eastern part of the Transylvanian Basin and the main east Carpathian Range, where active compression tectonics caused diapiric intrusions of Miocene halite deposits and associated saline, CO₂-rich waters along active faults. The regional patterns of the distribution of CO₂ in spring waters (as calculated pCO₂) and the distribution pattern of the ³He/⁴He ratio in the free gas phases (up to 4.5 R_m/R_a) show their maximum values in coincidence with both the maximum heat-flow measurements and the more recent volcanic edifices. Moving towards the eastern external foredeep areas, where oil fields and associated brines are present, natural gas emissions become CH₄-dominated. Such a change in the composition of gas emissions at surface is also recorded by the ³He/⁴He ratios that, in this area, assume ‘typical’ crustal values (R_m/R_a=0.02).In spite of the fact that thermal springs are rare in the Harghita volcanic area and that equilibrium temperature estimates based on geothermometric techniques on gas and liquid phases at surface do not suggest the presence of shallow active hydrothermal systems, a large circulation of fluids (gases) is likely triggered by the presence of mantle magmas stored inside the crust. If total ³He comes from the mantle or from the degassing of magmas stored in the crust, CO₂ might be associated to both volcanic degassing and thermometamorphism of recently subducted limestones.     

The mineral springs of the Scrajo spa (Sorrento peninsula,Italy): a case of “natural” seawater intrusion

This paper deals with the mineral springs feeding the Scrajo spa in the Sorrento peninsula southeast of Naples, approximately 6 km from Castellammare di Stabia, another spa location. The Scrajo mineral water is sulphureous, salt-bromine-iodic and CO₂-rich. The two hydromineral areas fall within the groundwater basin of Mt. Faito formed chiefly by limestones. Due to the high permeability of the limestones, there is considerable rainwater infiltration which recharges a basal fresh groundwater resting on denser seawater. This groundwater body feeds the mineral springs of the Scrajo spa, the springs of Castellammare di Stabia and some submarine springs. All the data gathered for the Scrajo springs led to propose the following mineralisation scheme: (1) The basal fresh groundwater of Mt. Faito (on underlying seawater) receives endogenous contributions of CO₂ and H₂S which cause a “natural” seawater intrusion within the fresh groundwater; (2) The upwelling of gases would appear to occur via the major faults which bound Sorrento peninsula to the NW; (3) During the year, the chemistry of the springs changes according to different degrees of seawater intrusion: the minimum occurs in June and the maximum in November. The close interaction between the sea and the Scrajo’s mineral waters (but also those of Castellammare di Stabia) highlights their particular vulnerability not only to over-extraction of groundwater but also to climate change. Finally, a hypothesis is presented to explain the connection between the mineral waters rich in CO₂ and H₂S and the concentration of karst phenomena observed in the Scrajo area.     

腾冲新生代火山区温泉CO2气体排放通量研究

近期研究表明,不仅火山喷发期会向当时的大气圈输送大量的温室气体,火山间歇期同样会释放大量的温室气体。在火山活动间歇期,火山区主要以喷气孔、温(热)泉以及土壤微渗漏等形式向大气圈释放温室气体。腾冲是我国重要的新生代火山区,同时也是重要的水热活动区,那里出露大量的温泉,然而目前未见腾冲火山区温泉气体排放通量的研究报道。本文利用数字皂膜通量仪测量了腾冲新生代火山区温泉中CO₂的排放通量。研究结果表明,腾冲新生代火山区温泉向当今大气圈输送的CO₂通量达3.58×10³ t·a^-1,相当于意大利锡耶纳Bassoleto地热区温泉中CO₂的排放规模。腾冲火山区温泉的CO₂释放通量主要受深部岩浆囊、断裂分布、地下水循环、围岩成分等多方面因素的影响。本文根据温泉中CO₂的排放特征,将腾冲温泉分为南北两区,南区温泉CO₂通量远高于北区的温泉,热海地热区的通量为腾冲CO₂通量的最大值。在北温泉区,CO₂通量主要受控于断裂的分布;而在南温泉区,除受到断裂控制外,热海地热区底部的岩浆囊及其与围岩的相互作用成为CO₂气体的重要物质来源,同时高温的岩浆囊为温泉及CO₂的形成提供了重要热源。     

Seasonal variation in nature and chemical compositions of spring water in Cuihua Mountain,Shaanxi Province,central China

Two springs (Cuihua Spring, Shuiqiuchi Spring) in Cuihua Mountain of the Qinling Mountains were observed and sampled monthly during 2004 and 2005 to trace their physical properties and chemical compositions with seasons. Although both pH values and cation (Ca²⁺, Mg²⁺, K⁺, and Na⁺) contents of Cuihua Spring are higher than those of Shuiqiuchi Spring, seasonal variations in both springs are obvious. The pH values of both spring waters are between 5.69 and 6.98, lower than that of rainwater during summer and autumn. From January to November, the pH values of both springs similarly vary from high to low and then to high again. Variations in electric conductivities of two spring waters are contrary, although their electric conductivities are positively correlative with the cation content respectively. This can be attributed to different water sources of the two springs or different acidic rocks they passed. The contents of HCO₃ ⁻, Ca²⁺, Mg²⁺, K⁺, and Na⁺ are low, indicating a low silicate weathering that the strata in this district are mainly composed of granite and schist of quartz and mica. Differing from change in spring water in karst regions of South China where abundant precipitation and dilution of rainwater cause low pH and electric conductivity in summer and autumn, the seasonal variations in the pH values and the electric conductivities of two springs in Qinling Mountains are attributed to seasonal changes in CO₂ produced by microorganisms’ activity in soil within respective year, rather than rainfall. The microorganisms’ activity in soil produces more CO₂ during summer and autumn. Therefore, the water nature of springs in silicate regions chiefly reflects the seasonal changes of CO₂ produced by the microorganisms in soil.     

Controls on chemistry during fracture-hosted flow of cold CO2-bearing mineral waters,Daylesford, Victoria,Australia: Implications for resource protection

Mineral springs from Daylesford, Australia discharge at ambient temperatures, have high CO₂ contents, and effervesce naturally. Mineral waters have high HCO₃ and Na concentrations (up to 4110 and 750 mg/L, respectively) and CO₂ concentrations of 620–2520 mg/L. Calcium and Mg concentrations are 61–250 and 44–215 mg/L, respectively, and Si, Sr, Ba, and Li are the most abundant minor and trace elements. The high P_CO2 of these waters promotes mineral dissolution, while maintaining low pH values, and geochemical modelling indicates that the CO₂-rich mineral water must have interacted with both sediments and basalts. Amorphous silica concentrations and silica geothermometry indicate that these waters are unlikely to have been heated above ambient temperatures and therefore reflect shallow circulation on the order of several hundreds of metres. Variations in minor and trace element composition from closely adjacent spring discharges indicate that groundwater flows within relatively isolated fracture networks. The chemical consistency of individual spring discharges over at least 20 a indicates that flow within these fracture networks has remained isolated over long periods. The mineral water resource is at risk from mixing with potentially contaminated surface water and shallow groundwater in the discharge areas. Increased δ²H values and Cl concentrations, and lower Na concentrations indicate those springs that are most at risk from surface contamination and overpumping. Elevated NO₃ concentrations in a few springs indicate that these springs have already been contaminated during discharge.     

The origin of mineral waters in Kiseljak near Sarajevo,Bosnia and Herzegovina

The mineral water deposits in Kiseljak are located in the central Dinarids, Bosnia and Herzegovina, in the southwestern edge of Sarajevo–Zenica basin that was formed in the zone of Busova?a fault. Busova?a fault reaches deep into the Earth’s crust and is characterised by the presence of mineral and thermomineral water enriched with CO₂ and CO₂ springs (mofetes) in the direction of Ilid?a–Kiseljak–Busova?a. Deposits are constructed of layers of Palaeozoic to Cretaceous age. Primary aquifer of mineral waters is Permian clastites and evaporites and secondary Anisian carbonates. Mineral water and CO₂ are of different origin. The water is of atmospheric origin. Due to slow circulation, water descends in the primary aquifer where it becomes enriched with CO₂ and minerals. Due to high pressure in the primary aquifer mineral water ascends along Busova?a fault, mounts into the secondary aquifer and rises at spring sources. Water is a mixture of two or more waters of different mineralization. Mixing of water occurs in the zone of secondary aquifer even at greater depths without the influence of contemporary climatic factors. Intensive water mixing is indicated by the high ratio of Ca/Sr, Na/Cl and Ca/SO₄ and the mixing diagram. CO₂ is thermometamorphic, arising from the catalytic activity of SiO₂ on carbonates in the deeper layers of the Earth’s crust, where quartz porphyry broke through Palaeozoic formations.     

Flue gas and pure CO2 sorption properties of coal: A comparative study

Presently many research projects focus on the reduction of anthropogenic CO₂ emissions. It is intended to apply underground storage techniques such as flue gas injection in unminable coal seams. In this context, an experimental study has been performed on the adsorption of pure CO₂ and preferential sorption behavior of flue gas. A coal sample from the Silesian Basin in Poland (0.68% V Rr), measured in the dry and wet state at 353 K has been chosen for this approach. The flue gas used was a custom class industrial flue gas with 10.9% of CO₂, 0.01% of CO, 9% of H₂, 3.01% of CH₄, 3.0% of O₂, 0.106% of SO₂ and nitrogen as balance.Adsorption isotherms of CO₂ and flue gas were measured upto a maximum of 11 MPa using a volumetric method. Total excess sorption capacities for CO₂ on dry and wet Silesia coal ranged between 1.9 and 1.3 mmol/g, respectively. Flue gas sorption capacities on dry and wet Silesia coal were much lower and ranged between 0.45 and 0.2 mmol/g, respectively, at pressures of 8 MPa. The low sorption capacity of wet coal has resulted from water occupying some of the more active adsorption sites and hence reducing the heterogeneity of adsorption sites relative to that of dry coal. Desorption tests with flue gas were conducted to study the degree of preferential sorption of the individual components. These experiments indicate that CO₂ is by far the prefered sorbing component under both wet and dry conditions. This is followed by CH₄. N₂ adsorbs very little on the coal in the presence of CO₂ and CH₄. It is also observed that the adsorption of CO₂ onto coal is not significantly hindered by the addition of other gases, other than dilution effect of the pressure.In addition to the sorption experiments, the density of the flue gas mixture has been determined up to 18 MPa at 318 K. A very good precision of these measurements were documented by volumetric methods.     

The Starzach site in Southern Germany: a site with naturally occurring CO<Subscript>2</Subscript> emissions recovering from century-long gas mining as a natural analog for a leaking CCS reservoir

In this paper, we present the Starzach site, a region featuring numerous natural CO₂ emission spots, such as mofettes, that reappeared after a longer period of extensive industrial CO₂ mining. We discuss the results of a detailed literature study on the geological setting and the activities related to the gas mining in combination with own measurements to introduce the site as an example on how gas leakage from an insecure CCS reservoir could manifest at the surface. The site is in particular interesting for such investigations as the CO₂ emissions started to replenish after the end of the CO₂ mining and offers the unique possibility to investigate an increase in degassing activity as it might be expected for an active CCS site where leakage is suspected. Based on the geological setting and soil, gas emission, and isotope investigations, we further discuss the source of the CO₂ emission and the gas ascent to the ground surface via deep-reaching faults, latter being so far excluded by previous work. The combination of our extensive literature review and recent field investigations allowed us to draw new geological conclusions for the site that were under discussion for a long time and to give insight into the site’s potential for CCS-related analog studies in the future.     

Coal seam gas distribution and hydrodynamics of the Sydney Basin,NSW, Australia

This paper reviews various coal seam gas (CSG) models that have been developed for the Sydney Basin, and provides an alternative interpretation for gas composition layering and deep-seated CO₂ origins. Open file CSG wells, supplemented by mine-scale information, were used to examine trends in gas content and composition at locations from the margin to the centre of the basin. Regionally available hydrochemistry data and interpretations of hydrodynamics were incorporated with conventional petroleum well data on porosity and permeability. The synthesised gas and groundwater model presented in this paper suggests that meteoric water flow under hydrostatic pressure transports methanogenic consortia into the subsurface and that water chemistry evolves during migration from calcium-rich freshwaters in inland recharge areas towards sodium-rich brackish water down-gradient and with depth. Groundwater chemistry changes result in the dissolution and precipitation of minerals as well as affecting the behaviour of dissolved gases such as CO₂. Mixing of carbonate-rich waters with waters of significantly different chemistries at depth causes the liberation of CO₂ gas from the solution that is adsorbed into the coal matrix in hydrodynamically closed terrains. In more open systems, excess CO₂ in the groundwater (carried as bicarbonate) may lead to precipitation of calcite in the host strata. As a result, areas in the central and eastern parts of the basin do not host spatially extensive CO₂ gas accumulations but experience more widespread calcite mineralisation, with gas compositions dominated by hydrocarbons, including wet gases. Basin boundary areas (commonly topographic and/or structural highs) in the northern, western and southern parts of the basin commonly contain CO₂-rich gases at depth. This deep-seated CO₂-rich gas is generally thought to derive from local to continental scale magmatic intrusions, but could also be the product of carbonate dissolution or acetate fermentation.     

Rare earth elements,neodymium and strontium isotopic systematics in mineral waters: evidence from the Massif Central,France

Rare Earth Elements (REEs), and Sr and Nd isotope distributions, have been studied in mineralized waters from the Massif Central (France). The CO₂-rich springs are characterized by a neutral pH (6–7) associated with total dissolved solids (TDS) from 1 to 7 g l⁻¹. The waters result from the mixing of very mineralized water pools, thought to have equilibrated at a temperature of around 200°C with superficial waters. These two mineral water pools evidenced by Sr isotopes and dissolved REEs could reflect 2 different stages of water–rock interaction and an equilibrium with different mineral assemblages.The concentrations of individual dissolved REEs and total dissolved REEs (ΣREE), in the mineral waters examined, vary over several orders of magnitude but are not dependent on the main parameters of the waters (TDS, T°C, pH, Total Organic C). The dissolved REE concentrations presented as upper continental crust normalized patterns show HREE enrichment in most of the samples. The time evolution of REE patterns does not show significant fluctuations except in 1 borehole, located in the Limagne d’Allier area, which was sampled on 16 occasions over an 18 month period. Ten samples are HREE-enriched, whereas 6 samples show flat patterns.The aqueous speciation of REEs shows that CO²⁻₃ complexes dominate (>80%) over the free metal, F⁻, SO²⁻₄ and HCO⁻₃ complexes. The detailed speciation demonstrates that the fractionation of REEs (i.e. the HREE enrichment) in CO₂-rich and pH neutral fluids is due essentially to the predominance of the CO²⁻₃ complexes.The Sr isotopic composition of the mineral waters in the Massif Central shows different mixing processes; in the Cézallier area at least 3 end-member water types exist. The most dilute end-member is likely to originate as poorly mineralized waters with minimal groundwater circulation. Two other mineralized end-members are identified, although the link between the geographical location of spring outflow and the mixing proportion between the 2 end-members is not systematic. The range in ϵ_Nd(0) for mineralized waters in the Massif Central correlates well with that of the known parent rocks except for 4 springs. One way to explain the ϵ_Nd(0) in these instances is a contribution from drainage of volcanic rocks. The isotopic systematics help to constrain the hydrogeological models for this area.     

Stable carbon isotope ratios and the existence of a gas phase in the evolution of carbonate ground waters

The chemical and stable isotope compositions of unpolluted ground waters in carbonate terranes are a function of the pH, , ¹³C content of the ground water recharge, the ¹³C content of the carbonate rock, and the manner in which the rock is dissolved or precipitated. Physico-chemical models show that significantly different relationships exist between Ca²⁺ plus Mg²⁺, HCO₃^?, pH and ¹³C content of unpolluted ground waters when carbonate solution occurs in the presence or absence of a gas phase. A study was made of these relationships in waters from 21 springs and 13 wells in Nittany Valley, Pennsylvania. Assuming that CO₂ in the recharge zone has a ¹³C contents below ?21%. vs PDB, the data indicate that ground water flow to wells and springs, and carbonate rock solution probably occurs chiefly in the absence of a gas phase. This is in spite of the fact that most of such flow is under water table conditions. ¹³C contents averaged ?12·3%. for the spring waters and ?13·3%. for the well waters. Five well waters polluted by septic tank or sewage effluents had carbon isotopic compositions from ?13·5 to ?16·4%.,vs ?11·3 to?12·7 %. for the eight well waters relatively free of organic wastes.     

Mantle-derived CO_2 in Hot Springs of the Rehai Geothermal Field,Tengchong,China

Gas concentrations and isotopic compositions of He and CO2 were determined on free gas samples from ten hot springs of the Rehai geothermal field, Tengchong, China. The results showed that hot-spring CO2 gas, together with He,was derived mainly from the mantle, indicating the accumulation of mantle-derived volatiles beneath the survey area. The δ^13C values of CO2, higher than those of the typical mantle-derived carbon and the isotopic composition of hot-spring-free CO2 in unequilibrium with dissolved CO2, are recognized only in the Rehai geothermal field, suggesting that there seems to be a still-degassing magmatic intrusion at depths, which provides mantle-derived volatiles to the hydrothermal system above. The accumulation of those volatiles has probably played an important role in triggering earthquakes in this region.In addition, the isotopic characteristics of He and C also indicate that the magmatic intrusion seems to have been derived from the MORB source, and could be contaminated by crustal materials during its upwelling through the continental crust.     

Fluorapatite and fluorite solubility controls on geothermal waters in Yellowstone National Park

Potential solubility controls on phosphorus in Yellowstone National Park geothermal waters were investigated using the analytical phosphate estimates of Stauffer and Thompson (1978), the computer program, WATEQF, and adopting the equilibrium constant: $\text{log}\text{K}{}_{\mathrm{25°}}\text{= ?61.4}$ for fluorapatite (FAP = Ca₅(PO₄)₃F) dissolution. The near-boiling high-Cl geyser and spring effluents are at or near saturation with respect to (with) FAP. The sixteen representative springs in this category had FAP saturation indices ($\text{S.I. =}\text{log}\text{IAP/K}{}_{\mathrm{r}}$) ranging from ? 3.2 to +4.9 and averaging +0.9. The strongly positive indices were all associated with the highly alkaline conditions resulting from adiabatic cooling in the near surface environment. Hot spring waters indicating extensive dilution (reduced Cl) by meteoric water have lower pH's, and despite PO₄ and Ca concentrations an order of magnitude higher than the geysers, are still frequently undersaturated with FAP. The travertine-depositing “Mixed-water” springs are invariably supersaturated with FAP at ground surface and at or near saturation with hydroxylapatite. Supersaturation may result from kinetic inhibition of apatite crystallization by the elevated Mg²⁺, HCO₃^?, and lower temperatures in these springs. The phosphates may be residuals of the meteoric dilution water.Separately, if Strübel's temperature-dependent estimates of fluorite (CaF₂) solubility are adopted, the high-Cl geysers and springs on “Geyser Hill” and at Norris are consistently undersaturated with CaF₂ at the 90–100° orifice temperatures. The apparent disequilibrium may reflect fluorite equilibration at the much higher temperatures (> 200°C) in the deeper enthalpy reservoirs.     

Chemistry of fluids from a natural analogue for a geological CO2 storage site (Montmiral, France): Lessons for CO2–water–rock interaction assessment and monitoring

Chemical and isotope studies of natural CO₂ accumulations aid in assessing the chemical effects of CO₂ on rock and thus provide a potential for understanding the long-term geochemical processes involved in CO₂ geological storage. Several natural CO₂ accumulations were discovered during gas and oil exploration in France’s carbogaseous peri-Alpine province (south-eastern France) in the 1960s. One of these, the Montmiral accumulation at a depth of more than 2400 m, is currently being exploited. The chemical composition of the water collected at the wellhead has changed in time and the final salinity exceeds 75 g/L. These changes in time can be explained by assuming that the fraction of the reservoir brine in the recovered brine–CO₂–H₂O mixture varies, resulting in variable proportions of H₂O and brine in the sampled water. The proportions can be estimated in selected samples due to the availability of gas and water flowrate data. These data enabled the reconstruction of the chemical and isotope composition of the brine. The proportions of H₂O and brine can also be estimated from isotope (δ²H, δ¹⁸O) composition of collected water and δ¹⁸O of the sulfates or CO₂. The reconstituted brine has a salinity of more than 85 g/L and, according to its Br⁻ content and isotope (δ²H, δ¹⁸O, δ³⁴S) composition, originates from an evaporated Triassic seawater that underwent dilution by meteoric water. The reconstitution of the brine’s chemical composition enabled an evaluation of the CO₂–water–rock interactions based on: (1) mineral saturation indices; and (2) comparison with initial evaporated Triassic seawater. Dissolution of K- and SO₄-containing minerals such as K-feldspar and anhydrite, and precipitation of Ca and Mg containing minerals that are able to trap CO₂ (carbonates) are highlighted. The changes in concentration of these elements in the brine, which are attributed to CO₂ interactions, illustrate the relevance of monitoring the water quality at future industrial CO₂ storage sites.     

天然气水合物成因探讨

天然气水合物是未来的能源资源。其分布于极地地区、深海地区及深水湖泊中。在海洋里,天然气水合物主要分布于外大陆边缘和洋岛的周围,其分布与近代火山的分布范围具有一致性。同位素组成表明天然气水合物甲烷主要是由自养产甲烷菌还原CO₂形成的。典型的大陆边缘沉积物有机碳含量低（＜0．5％～1．0％）,不足以产生天然气水合物带高含量的甲烷。赋存天然气水合物的沉积物时代主要为晚中新世-晚上新世,具有一定的时限性,并且天然气水合物与火山灰或火山砂共存,表明其形成与火山-热液体系有一定联系。火山与天然气水合物空间上的一致性表明,天然气水合物甲烷的底物可能主要是由洋底火山喷发带来的CO2。由前人研究结果推断 HCO^－₃在脱去两个O原子的同时,可能发生了亲核重排,羟基 H原子迁移到 C原子上,形成了甲酰基（HCO^－）,使甲烷的第一个 H原子来源于水。探讨了甲烷及其水合物的形成机制,提出了天然气水合物成因模型。     

Mopping up leaking carbon: A natural analog at Wadi Namaleh,Jordan

Carbon capture and sequestration (CCS) is one of the important options available for partially stemming greenhouse gas emissions from large point sources. The possibility of leaking from deep storage needs to be addressed. The Wadi Namaleh area in southern Jordan provides an interesting case study of how excess CO₂ can be trapped in the form of carbonates in the near surface, even when the local geology is not obviously conducive for such a process.Carbonate veins are formed in surface alteration zones of rhyolite host rock in this arid region. The alteration zones are limited to areas where surface soil or colluvium are present. Oxygen, deuterium and carbon isotopes of the carbonates and near-surface ground water in the area suggest that the source of carbon is deep seated CO₂, and that the carbonate precipitated in local meteoric water under ambient temperature conditions. Analysis of strontium in the carbonate, fresh rhyolite and altered host shows that the source for calcium is aeolian. Trace elements show that metal and REE mobility are constrained to the alteration zone.Thus, interaction of H₂O, CO₂ and atmospheric wet and dry deposition lead to the formation of the clayey (montmorillonite) alteration zone. This zone acts to trap seeping CO₂ and water, and thus produces conditions of progressively more efficient trapping of carbon dioxide by means of a positive feedback mechanism. Replication of these conditions in other areas will minimize CO₂ leakage from man-made CCS sites.     

Seasonality of bedrock weathering chemistry and CO2 consumption in a small watershed, the White River, Vermont

The draw down of CO₂ from the atmosphere during mineral weathering plays a major role in the global budget of this greenhouse gas. Silicate minerals remove twice the CO₂ of carbonate minerals per mole of calcium in runoff during weathering. Bedrock weathering chemistry was investigated in the White River watershed of northeastern USA to investigate whether there are seasonal differences in carbonate and silicate weathering chemistry. Geographic Information Systems analyses of bedrock geology were combined with major element concentrations in river waters to gain an understanding of the consistency of mineral weathering during three seasons. The percent of carbonate mineralogy comprising the bedrock in tributaries of the White River varied from less than 5% to 45% by area. A mass balance calculation using major element concentrations in waters was applied to estimate the seasonal relationships between bedrock geology and bicarbonate flux. In all tributaries and the main stem of the White River the highest calculated percent of bicarbonate from carbonate mineral weathering was measured in the late fall. The results suggest that carbonate and silicate bedrock weathering processes are seasonally controlled. Thus single season sampling could not accurately represent an entire year's geochemical budget. In the White River, water samples obtained solely during the summer would consistently underestimate the total yearly source of bicarbonate from carbonate bedrock weathering. The same sample set would also provide data that would lead to an underestimation of the yearly atmospheric CO₂ draw down by bedrock weathering in the watershed. For example at four of the seven locations studied there was an almost two-fold difference between summer and spring calculated atmospheric CO₂ consumption rates.     

The shallow ground water chemistry of arsenic,fluorine, and major elements: Eastern Owens Lake,California

Owens Lake in SE California became essentially dry by the 1920s after the Los Angeles Aqueduct was constructed and diversion of water from the Owens River began. Frequent dust storms at Owens Lake produce clouds of efflorescent salts which present human health hazards as a result of their small particle size and elevated concentrations of As and SO₄. This study was conducted to characterize the evolution of major elements in ground water in eastern Owens Lake and to examine the factors controlling the concentrations of dissolved As and F. Evapoconcentration of shallow ground waters at the lakebed surface produces high pH, high alkalinity brines with major ion compositions that are consistent with those predicted by the Hardie–Eugster Model. Evaporite minerals identified in the surface salts using XRD were halite (NaCl), thenardite (Na₂SO₄), trona (Na₃H(CO₃)₂·2H₂O), pirssonite (Na₂Ca(CO₃)₂·2H₂O), and nesquehonite (MgCO₃·3H₂O). Significant correlations between both As and F with Li in shallow ground waters indicate that As and F are not partitioned into surface salts until very high salinities are reached (>9.0 m). Leaching experiments show that As and F can be readily released from lakebed salts when exposed to natural precipitation. Conservative behavior of As and F results from the high pH values and low Ca activities of shallow ground waters that contribute to: (1) redox stability of As(V) even at moderately reducing conditions, (2) a decrease in the adsorption affinities of As and F to mineral surfaces, (3) undersaturation with respect to fluorite (CaF₂(s)).     

Transport of perfluorocarbon tracers and carbon dioxide in sediment columns – Evaluating the application of PFC tracers for CO2 leakage detection

Perfluorocarbon compounds (PFCs) have high chemical and thermal stability, low background levels in natural systems, and easy detectability. They are proposed as tracers for monitoring potential CO₂ leakage associated with geological carbon sequestration (GCS). The fate of the PFCs in porous media, and in particular, the transport of these compounds relative to CO₂ gas in geological formations, has not been thoroughly studied. We conducted column tests to study the transport of perfluoro-methylcyclo-pentane (PMCP), perfluoro-methylcyclo-hexane (PMCH), ortho-perfluoro-dimethylcyclo-hexane (ortho-PDCH), and perfluoro-trimethylcyclo-hexane (PTCH) gas tracers in a variety of porous media. The influence of water content and sediment minerals on the retardation of the tracers was tested. The transport of PFC tracers relative to ¹³CO₂ and the conservative tracer sulfur hexafluoride (SF₆) was also investigated. Results show that at high water content, the PFCs and SF₆ transported together. In dry and low-water-content sediments, however, the PFCs were retarded relative to SF₆ with the degree of retardation increasing with the molecular weight of the PFC. When water was present in the medium, the transport of CO₂ was greatly retarded compared to SF₆ and the PFC tracers. However, in dry laboratory sediments, the migration of CO₂ was slightly faster than all the tracers. The type of minerals in the sediments also had a significant impact on the fate of the tracers. In order to use the PFC tracer data obtained from the ground surface or shallow subsurface in a GCS site to precisely interpret the extent and magnitude of CO₂ leakage, the retardation of the tracers and the interaction of CO₂ with the reservoir overlying formation water should be carefully quantified.     

Hydrochemical and isotope characteristics of spring water and travertine in the Baishuitai area (SW China) and their meaning for paleoenvironmental reconstruction

A method of combining hydrochemical data logging and in situ titrating with measurement of stable carbon and oxygen isotopes was used to reveal the hydrochemical and isotopic characteristics in the Baishuitai travertine scenic area of SW China. It was found that the travertine-forming springs have a very high concentration of calcium and bicarbonate, and accordingly very high CO₂ partial pressures, which are not likely to be produced by biological activity in soil alone. Further analysis of the stable carbon isotopes of the springs shows that the high pressure of CO₂ is mainly related to an endogenic CO₂ source. That means the Baishuitai travertine is endogenic in origin. This is contrast to the commonly accepted saying that the travertine deposition in this study simply is a product of warm and humid conditions in a karst ecological environment. Rapid CO₂ degassing from the water is triggered by the much higher partial pressures in water than that of the surrounding air. Consequently, as the waters flow downstream of the spring the pH increases, the waters become supersaturated with respect to calcite, and travertine is deposited. The preferential release of ¹²CO₂ to the atmosphere results in a progressive increase of travertine ¹³C downstream. This is concluded with a preliminary discussion of variation in travertine-forming water temperatures, according to differences in stable oxygen isotopic compositions of the travertine formed in different epochs at Baishuitai. It was found that the change in water temperature is as high as 13 °C, i.e., from 23 °C at about 2500 years b.p., to 10 °C at present. This may mainly reflect that the effect of geothermal source on water temperature is decreasing. The problems involved in paleoenvironmental reconstruction with endogene travertine are also discussed. They are the impacts of "dead carbon" in radiocarbon dating and the enrichment in ¹³C of travertine by endogenic CO₂ and degassing of CO₂ from water, which has to be considered in paleovegetation reconstruction when using ¹³C data of the endogene carbonate deposits.