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.     

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.     

Formation of phreatic caves in an eogenetic karst aquifer by CO2 enrichment at lower water tables and subsequent flooding by sea level rise

Formation of extensive phreatic caves in eogenetic karst aquifers is widely believed to require mixing of fresh and saltwater. Extensive phreatic caves also occur, however, in eogenetic karst aquifers where fresh and saltwater do not mix, for example in the upper Floridan aquifer. These caves are thought to have formed in their modern settings by dissolution from sinking streams or by convergence of groundwater flow paths on springs. Alternatively, these caves have been hypothesized to have formed at lower water tables during sea level low‐stands. These hypotheses have not previously been tested against one another. Analyzing morphological data and water chemistry from caves in the Suwannee River Basin in north‐central Florida and water chemistry from wells in the central Florida carbonate platform indicates that phreatic caves within the Suwannee River Basin most likely formed at lower water tables during lower sea levels. Consideration of the hydrological and geochemical constraints posed by the upper Floridan aquifer leads to the conclusion that cave formation was most likely driven by dissolution of vadose CO₂ gas into the groundwater. Sea level rise and a wetter climate during the mid‐Holocene lifted the water table above the elevation of the caves and placed the caves tens of meters below the modern water table. When rising water tables reached the land surface, surface streams formed. Incision of surface streams breached the pre‐existing caves to form modern springs, which provide access to the phreatic caves. Phreatic caves in the Suwannee River Basin are thus relict and have no causal relationship with modern surficial drainage systems. Neither mixing dissolution nor sinking streams are necessary to form laterally extensive phreatic caves in eogenetic karst aquifers. Dissolution at water tables, potentially driven by vadose CO₂ gas, offers an underappreciated mechanism to form cavernous porosity in eogenetic carbonate rocks. Copyright © 2012 John Wiley & Sons, Ltd.     

Tidal pumping and biogeochemical processes: Dissolution within the tidal capillary fringe of eogenetic coastal carbonates

Growing evidence suggests microbial respiration of dissolved organic carbon (DOC) may be a principal driver of subsurface dissolution and cave formation in eogenetic carbonate rock. Analyses of samples of vadose zone gasses, and geochemical and hydrological data collected from shallow, uncased wells on San Salvador Island, Bahamas, suggest tidally varying water tables may help fuel microbial respiration and dissolution through oxygenation. Respiration of soil organic carbon transported to water tables generates dysaerobic to anaerobic groundwater, limiting aerobic microbial processes. Positive correlations of carbon dioxide (CO₂), radon-222 (²²²Rn) and water table elevation indicate, however, that tidal pumping of water tables pulls atmospheric air that is rich in oxygen, and low in CO₂ and ²²²Rn, into contact with the tidal capillary fringe during falling tides. Ratios of CO₂ and O₂ in vadose gas relative to the atmosphere indicate this atmospheric oxygen fuels respiration within newly-exposed, wetted bedrock. Deficits of expected CO₂ relative to O₂ concentrations indicate some respired CO₂ is likely removed by carbonate mineral dissolution. Tidal pumping also appears capable of transferring oxygen to the freshwater lens, where it could also contribute to respiration and dissolution; dissolved oxygen concentrations at the water table are at least 5% saturated and decline to anaerobic conditions 1–2 m below. Our results demonstrate how tidal pumping of air to vadose zones can drive mineral dissolution reactions that are focused near water tables and may contribute to the formation of laterally continuous vuggy horizons and potentially caves. © 2020 John Wiley & Sons, Ltd.     

Seasonal δ13CDIC sourcing and geochemical flux in telogenetic epikarst of south-central Kentucky

Telogenetic epikarst carbon sourcing and transport processes and their associated hydrogeochemical responses are complex and dynamic. Carbon dioxide (CO₂) transport rates in the epikarst zone are often driven by hydrogeochemical responses, which influence carbonate dissolution and conduit formation. This study examines the influence of land use on carbon sourcing and carbonate dissolution kinetics through a comparative analysis of separate, but similar, epikarst systems in south-central Kentucky. The use of high-resolution hydrogeochemical data from multiple data loggers and isotope analysis from collected water samples reflects the processes within these epikarst aquifers, which are estimated to contribute significantly to bedrock dissolution. Results indicate that, in an agricultural setting, long-term variability and dissolution is governed by seasonal production of CO₂ . In a more urbanized, shallower epikarst system, land cover may affect CO₂ transport between the soil and underlying bedrock. This concentration of CO₂ potentially contributes to ongoing dissolution and conduit development, irrespective of seasonality. The observed responses in telogenetic epikarst systems seem to be more similar to eogenetic settings, which is suggested to be driven by CO₂ transport occurring independent of high matrix porosity. The results of this study indicate site-specific responses with respect to both geochemical and δ¹³C_DIC changes on a seasonal scale, despite regional geologic similarities. The results indicate that further comparative analyses between rural and urban landscapes in other karst settings is needed to delineate the impact of land use and seasonality on dissolution and carbon sourcing during karst formation processes. © 2019 John Wiley & Sons, Ltd.     

Carbon dioxide concentration in temperate climate caves and parent soils over an altitudinal gradient and its influence on speleothem growth and fabrics

Carbon dioxide (CO₂) concentrations in caves and parent soils in the Italian Alps have been studied along a 2100 m altitudinal range – corresponding to a mean annual temperature (MAT) range of 12°C – in order to investigate the relationship between MAT, soil pCO₂ and cave air pCO₂, and to test the influence of soil pCO₂ on speleothem growth and fabric to ultimately gain insight into their palaeoclimatic significance in temperate climate settings. Our findings indicate that soil CO₂ is linearly correlated to MAT and its mean annual concentration is described by the equation: soil CO₂ (ppmv) = 1112 + 460 MAT. Soil pCO₂ can also be exponentially correlated to actual evapotranspiration. The pCO₂ in the aquifer is linearly correlated to MAT at the infiltration site and is more influenced by summer soil pCO₂. Cave air CO₂ in the innermost part of the caves exhibits a similar seasonal pattern, and commonly reaches concentrations of about 15% to 35%, with respect to the corresponding soil values, and is exponentially correlated to the MAT at the infiltration site. The combination of these parameters (soil pCO₂, dripwater pCO₂ and cave air pCO₂) results in speleothem growth and controls their fabrics which are typical of four MAT/elevation belts broadly corresponding to the present‐day vegetation zones. In the lower montane zone [100–800 m above sea level (a.s.l.)] speleothems mostly consist of columnar fabric, in the upper montane zone (800–1600 m a.s.l.) both columnar and dendritic fabrics are common, the Subalpine zone (1600–2200 m a.s.l.) is characterized mostly by moonmilk deposits, whereas in the Alpine zone (above 2200 m a.s.l.) no speleothems are forming today. Therefore, fabric changes in fossil speleothem can potentially be used to reconstruct MAT changes in temperate climate karst areas. Copyright © 2015 John Wiley & Sons, Ltd.     

Hydrogeochemical characteristics of surface water and groundwater in the karst basin,southwest China

Groundwater is a very significant water source used for irrigation and drinking purposes in the karst region, and therefore understanding the hydrogeochemistry of karst water is extremely important. Surface water and groundwater were collected, and major chemical compositions and environmental isotopes in the water were measured in order to reveal the geochemical processes affecting water quality in the Gaoping karst basin, southwest China. Dominated by Ca²⁺, Mg²⁺, HCO₃^? and SO₄^2?, the groundwater is typically characterized by Ca? Mg? HCO₃ type in a shallow aquifer, and Ca? Mg? SO₄ type in a deeper aquifer. Dissolution of dolomite aquifer with gypsiferous rocks and dedolomitization in karst aquifers are important processes for chemical compositions of water in the study basin, and produce water with increased Mg²⁺, Ca²⁺ and SO₄^2? concentrations, and also increased TDS in surface water and groundwater. Mg²⁺/Ca²⁺ molar ratios in groundwater decrease slightly due to dedolomitization, while the mixing of discharge of groundwater with high Mg²⁺/Ca²⁺ ratios may be responsible for Mg²⁺/Ca²⁺ ratios obviously increasing in surface water, and Mg²⁺/Ca²⁺ ratios in both surface water and groundwater finally tending to a constant. In combination with environmental isotopic analyses, the major mechanism responsible for the water chemistry and its geochemical evolution in the study basin can be revealed as being mainly from the water–rock interaction in karst aquifers, the agricultural irrigation and its infiltration, the mixing of surface water and groundwater and the water movement along faults and joints in the karst basin. Copyright © 2009 John Wiley & Sons, Ltd.     

Carbon flux and landscape evolution in epigenic karst aquifers modeled from geochemical mass balance

This paper considers the contributions of epigenic karst processes as a major element of the carbon cycle and a significant agent of landscape evolution. Geochemical models developed from monitoring data and water samples are used to estimate the variation and magnitude of dissolved inorganic carbon (DIC) flux in karst landscapes at several scales, from local to global. At the local scale, the Cumberland River watershed of southeast Kentucky, these geochemical models are also used to evaluate the potential role of sulfur in the production of DIC and to compute an estimated rate of landscape erosion. Geochemical modeling using ionic species and modeled discharge reveal a variable rate of DIC flux driven by large fluctuations in calcite saturation and discharge. Ratios of reaction products and principal component analyses (PCA) suggest that some bedrock dissolution may be driven by the oxidation of reduced sulfur derived from brines entrained into the karst aquifers. Over the 3730 km² of carbonate exposure in the Cumberland River, 25.8–62.4 Gg/yr of carbon dioxide (CO₂) is conveyed from the atmosphere through the dissolution of carbonate. At the global scale, this translates to 123–296 Tg/yr of CO₂ delivered by karst processes into the aqueous system. The bedrock portion of DIC equates to a flux of 32.6 ± 2.6 m³ – 35.2 ± 2.8 m³ of bedrock during the period of study of which 29% was dolomite. This translates to a landscape erosion rate of 13.1–17.9 mm/ka in the 3.45–4.32 km² of carbonate exposure in the studied watershed. Based upon 16+ km of cave survey data spanning a vertical range of 72 to 75 m above base level, this suggests that cave development in the watershed spans the Plio‐Pleistocene. Using the modeled erosion rates, the ages of cave levels, 4.03–5.71, 3.08–4.56, 1.57–2.43, 1.01–1.67, 0.45–0.91, and < 0.45 Ma, are in good agreement with regional studies of Plio‐Pleistocene landscape evolution in the Appalachian Lowland Plateaus. Copyright © 2015 John Wiley & Sons, Ltd.     

Spatial and temporal variations of pCO2, dissolved inorganic carbon and stable isotopes along a temperate karstic watercourse

This study investigated CO₂ degassing and related carbon isotope fractionation effects in the Wiesent River that drains a catchment in the karst terrain of the Franconian Alb, Southern Germany. The river was investigated by physico‐chemical and stable isotope analyses of water and dissolved inorganic carbon during all seasons along 65‐km long downstream transects between source and mouth. Calculated pCO₂ values at the source were 21 400 ± 2400 µatm. The pCO₂ rapidly decreased in the river water and dropped to an average of 1240 ± 330 µatm near the mouth. About 90% of this decrease occurred within the first 6 km of the river. The river was supersaturated with respect to CO₂ over its entire course and must have acted as a continuous year‐round CO₂ source to the atmosphere. The average CO₂ flux from the karst river was estimated with 450 mmol m^?2 day^?1 with higher fluxes up to 5680 mmol m^?2 day^?1 at the source. At the source, δ¹³C_DIC values showed no seasonal variations with an average of ?14.2 ± 0.2‰. This indicated that groundwater retained high pCO₂ mainly from soil CO₂. The contribution of soil CO₂ to dissolved inorganic carbon was estimated at 65% to 72%. The downstream CO₂ loss caused a positive shift in δ¹³C_DIC values of 2‰ between source and mouth because of the preferential loss of the ¹²C isotope during degassing. Considering the findings of this study and the fact that carbonate lithology covers a significant part of the earth's surface, CO₂ evasion from karst regions might contribute notably to the annual carbon dioxide release from global freshwater systems. Copyright © 2015 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.     

Dissolution-filling mechanism of atmospheric precipitation controlled by both thermodynamics and kinetics

Affected by structural uplift,the Ordovician carbonate rockbed in the Tarim Basin,China,was exposed to dissolution and reformation of atmospheric precipitation many times,and formed a large quantity of karst caves serving as hydrocarbon reservoir.However,drilling in Tahe area showed that many large karst caves,small pores and fractures are filled by calcite,resulting in decrease in their reservoir ability.Calcite filled in the karst caves has very light oxygen isotopic composition and87Sr/86Sr ratio.Its 18OPDB ranges from 21.2‰to 13.3‰with the average of 16.3‰and its87Sr/86Sr ratio ranges from0.709561 to 0.710070 with the average of 0.709843.The isotope composition showed that calcite is related to atmospheric precipitation.Theoretic analyses indicated that the dissolving and filling actions of the precipitation on carbonate rocks are controlled by both thermodynamic and kinetic mechanisms.Among them,the thermodynamic factor determines that the precipitation during its flow from the earth surface downward plays important roles on carbonate rocks from dissolution to saturation,further sedimentation,and finally filling.In other words,the depth of the karstification development is not unrestricted,but limited by the precipitation beneath the earth surface.On the other hand,the kinetic factor controls the intensity,depth,and breadth of the karstification development,that is,the karstification is also affected by topographic,geomorphologic,climatic factors,the degree of fracture or fault,etc.Therefore,subject to their joint effects,the karstification of the precipitation on the Ordovician carbonate rocks occurs only within a certain depth(most about 200 m)under the unconformity surface,deeper than which carbonate minerals begin to sedimentate and fill the karst caves that were formed previously.     

Limestone Dissolution Processes in Beke Doline Aggtelek National Park,Hungary

Aggtelek National Park, Hungary, is a limestone karst upland characterized by karren, dolines and river caves. For a period of two years, climatic and carbonate dissolution variables were monitored at four depths in a 7·5 m shaft through the soil fill in the floor of a typical large (150 m diameter) doline. Results are compared to other monitoring stations in the shallow soils on side slopes. Runoff and groundwater flow are focused into the base of the doline soil fill, where moisture is maintained at 70–90 per cent field capacity and temperatures permit year-round production of soil CO₂. The capacity to dissolve calcite (limestone) ranges from c. 3 g m⁻² per year beneath thin soils on the driest slopes to 17–30 g m⁻² per year in the top 1–2 m of doline fill and at its base 5–7 m below. © 1997 John Wiley & Sons, Ltd.     

Seawater–freshwater mixing and resulting calcite dissolution: an example from a coastal alluvial aquifer in eastern South Korea

Abstract

In order to evaluate groundwater quality and geochemical reactions arising from mixing between seawater and dilute groundwater, we performed a hydrochemical investigation of alluvial groundwater in a limestone-rich coastal area of eastern South Korea. Two sites were chosen for comparison: an upstream site and a downstream site. Data of major ion chemistry and ratios of oxygen–hydrogen isotopes (δ¹⁸O, δD) revealed different major sources of groundwater salinity: recharge by sea-spray-affected precipitation in the upstream site, and seawater intrusion and diffusion zone fluctuation in the downstream site. The results of geochemical modelling showed that Ca²⁺ enrichment in the downstream area is caused by calcite dissolution enhanced by the ionic strength increase, as a result of seawater–groundwater mixing under open system conditions with a constant P_CO2 value (about 10^?1.5 atm). The results show that, for coastal alluvial groundwater residing on limestone, significant hydrochemical change (especially increased hardness) due to calcite dissolution enhanced by seawater mixing should be taken into account for better groundwater management. This process can be effectively evaluated using geochemical modelling.

Editor D. Koutsoyiannis; Associate editor Y. Guttman

Citation Chae, G.-T., Yun, S.-T., Yun, S.-M., Kim, K.-H., and So, C.-S., 2012. Seawater–freshwater mixing and resulting calcite dissolution: an example from a coastal alluvial aquifer in eastern South Korea. Hydrological Sciences Journal, 57 (8),1–12.     

Temporal cycles of karst denudation in northwest Georgia,U.S.A.

Time patterns of karst denudation in northwest Georgia (U.S.A.) were investigated at three spring sites for 12 months and at five stream sites for 10 years. Rainfall was evenly distributed and showed no significant seasonality. At the springs, as well as the streams, water hardness was largely controlled by discharge. At the springs, soil pCO₂ and water pH were strongly correlated (r + -0·69 to -0·83). Solute transport in spring waters was highly seasonal, with two conduit flow springs removing more limestone in the winter, and the diffuse flow spring removing more during the growing season. At the stream sites, most denudation occurred during the winter and spring seasons, and least during the summer. Fourier analysis showed that variations in denudation occur on deterministic (long-wave) as well as stochastic (shortwave) time scales. As contributing variables, discharge varied in short-wave and long-wave cycles, whereas soil pCO₂ showed only a long-wave cycle. The 12 month deterministic cycles were the most important, with changes in discharge taking precedence over soil pCO₂. Time series regression explains up to 69 per cent of changes in denudation through rain and soil pCO₂. Time cycles in available water are the key controlling factor of denudation, and amounts of available soil CO₂ may not be as important in the temporal patterns of karst downwearing as has been believed previously.     

Rates of dissolution of aluminosilicates in seawater

Dissolution of eight clay minerals, four zeolites, and quartz in seawater has been monitored for81/2 years. For most of the minerals, dissolution can be described as a first-order reaction in which dissolved silica approaches from undersaturation steady concentration values with time. Characteristic reaction rate constants (k₁) are of the order of 10^?7 sec^?1. One of the zeolites, clinoptilolite, shows a different dissolution behavior: SiO₂ concentration in solution reaches a high value within one year, followed by a decline to a lower value, suggestive of precipitation of another silicate phase (possibly sepiolite).A mathematical solution is given for a kinetic equation combining the parabolic-rate and first-order rate processes. It is shown that in a wide range of silicate dissolution reactions taking place over long periods of time, the presence of the parabolic-rate dissolution processes cannot be detected, thereby making its inclusion in the kinetic equations unnecessary. The experimental rates of dissolution are comparable to the SiO₂^? dissolution rates in oceanic sediments near the sediment/water interface. But deeper in the sediment, the calculated dissolution rates are significantly lower than the near-interface and experimental values.     

Air-sea CO2 exchange of beach and near-coastal waters of the Chukchi Sea near Barrow, Alaska

Partial pressure of CO₂ in equilibrium with sample water (pCO₂) for the coastal water in the Chukchi Sea was continuously observed in summer, 2008. Average daily CO₂ flux calculated from the pCO₂ and gas transfer coefficients ranged from −0.144 to −0.0701 g C m⁻² day⁻¹ depending on which gas transfer coefficient was used. The pCO₂ before the landfast ice sheets melted appeared to be highly biologically controlled based on the following information: (1) the diurnal pattern of pCO₂ was strongly correlated with Photosynthetic Photon Flux Density (PPFD); (2) high chlorophyll density was observed during periods of peak uptake; and (3) the day-to-day variation in the pCO₂ strongly correlated with the presence or absence of near-shore ice sheets. The lowest pCO₂ of 35 ppm together with the highest PPFD of 1362 μmol E m⁻² s⁻¹ were observed in the afternoon on June 28 in the presence of sea ice. The very low pCO₂ observed in late June was likely caused by high photosynthetic rates related to high phytoplankton densities typically observed from spring to early summer near the ice edge, and by water low in salinity and CO₂ released by melting sea ice early in the season.     

Low carbon dioxide partial pressure in a productive subtropical lake

The purposes of this study were to assess if Lake Apopka (FL, USA) was autotrophic or heterotrophic based on the partial pressure of dissolved carbon dioxide (pCO₂) in the surface water and to evaluate factors that influence the long-term changes in pCO₂. Monthly average pH, alkalinity and other limnological variables collected between 1987 and 2006 were used to estimate dissolved inorganic carbon (DIC), pCO₂ and CO₂ flux between surface water and atmosphere. Results indicated that average pCO₂ in the surface water was 196 μatm, well below the atmospheric pCO₂. Direct measurements of DIC concentration on three sampling dates in 2009 also supported pCO₂ undersaturation in Lake Apopka. Supersaturation in CO₂ occurred in this lake in only 13% of the samples from the 20-year record. The surface-water pCO₂ was inversely related to Chl a concentrations. Average annual CO₂ flux was 28.2 g C m⁻² year⁻¹ from the atmosphere to the lake water and correlated significantly with Chl a concentration, indicating that biological carbon sequestration led to the low dissolved CO₂ concentration. Low pCO₂ and high invasion rates of atmospheric CO₂ in Lake Apopka indicated persistent autotrophy. High rates of nutrient loading and primary production, a high buffering capacity, a lack of allochthonous loading of organic matter, and the dominance of a planktivorous–benthivorous fish food web have supported long-term net autotrophy in this shallow subtropical eutrophic lake. Our results also showed that lake restoration by the means of nutrient reduction resulted in significantly lower total phosphorus (TP) and Chl a concentrations, and higher pCO₂.     

Motile phytoplankton species such as Gonyostomum semen can significantly reduce CO2 emissions from boreal lakes

Boreal lakes typically have high levels of allochthonous dissolved organic matter (DOM), causing light limitation of photosynthetic CO₂ consumption while stimulating CO₂ production. They are therefore considered as important sources of atmospheric CO₂. However, boreal lakes are also experiencing a marked expansion of bloom-forming motile phytoplankton organisms that can circumvent the shading effect of DOM by performing phototaxis and that thus might have an impact on the lakes’ CO₂ balance. We tested this idea in a DOM-rich lake using the widespread raphidophyte flagellate Gonyostomum semen as model organism. Employing continuous field measurements, we found that G. semen can reduce the partial pressure of CO₂ even at low algal densities. Periods with high algal densities were associated with CO₂ undersaturation and invasion of atmospheric CO₂. The mean daily net losses of CO₂ to the atmosphere during and after a G. semen bloom were estimated at 12.9 and 70.4 mmol C m^–2 day^–1, respectively. G. semen caused steep pCO₂ gradients in space and time, which make it difficult to unveil the species’ impact without employing continuous pCO₂ vertical profiling. This suggests that the effect of G. semen on the CO₂ balance of boreal lakes might have been overlooked in the past. Taken together, our data suggest that G. semen can significantly reduce the CO₂ emissions from boreal lakes despite high concentrations of allochthonous DOM. G. semen and other motile phytoplankton species should therefore be considered when estimating CO₂ emissions from boreal lakes, especially if these organisms continue their expansion.     

Convective stability analysis of the long-term storage of carbon dioxide in deep saline aquifers

Deep saline aquifers are one of the most suitable geologic formations for carbon sequestration. The linear and global stability analysis of the time-dependent density-driven convection in deep saline aquifers is presented for long-term storage of carbon dioxide (CO₂). The convective mixing that can greatly accelerate the CO₂ dissolution into saline aquifers arises because the density of brine increases upon the dissolution of CO₂ and such a density difference may induce instability. The effects of anisotropic permeability on the stability criteria, such as the critical time for the appearance of convective phenomena and the critical wavelength of the most unstable perturbation, are investigated with linear and global stability analysis. The linear stability analysis provides a sufficient condition for instability while the global stability analysis yields a sufficient condition for stability. The results obtained from these two approaches are not exactly the same but show a consistent trend, both indicating that the anisotropic system becomes more unstable when either the vertical or horizontal permeability increases.