云南白水台钙华水池中水化学日变化及其生物控制的发现

为弄清云南白水台泉及其下游钙华水池中水化学的日变化,选取1号泉及其流经的两个钙华水池(6号和10号)作为研究对象并对其水温、pH值和电导率进行了自动监测。根据Ca2 、HCO3-与电导率存在的线性关系,用WATSPAC软件计算了水中方解石的饱和指数和PCO2。监测发现:泉水不存在显著的水化学日动态变化,而两个钙华水池表现出显著的日动态变化。其中10号钙华水池在白天温度较高时水中的CO2大量逸出并通过水下水生植物的光合作用加速了水中碳酸钙的沉积。6号钙华水池水生植物生长茂盛,其叶片和部分枝干露出水面,因而光合作用主要发生在空中,所以此处水化学表现为白天pH值降低和电导率升高的反常现象,即由温度主导的根呼吸作用,在白天释放更多的CO2进入水体而使沉积下来的碳酸钙重新溶解。     

水生植物对岩溶水化学日变化的影响——以桂林岩溶水文地质试验场为例

以桂林岩溶水文地质试验场为研究点,以研究水生植物对岩溶水化学日变化的影响为目的,着重研究水葫芦和水藻对岩溶水的pH、电导率、溶解氧含量、方解石饱和指数以及CO2 分压日变化的影响。试验结果表明: 在不同水生植物生长的岩溶水中,水化学的日动态变化规律是不同的。在水藻生长的水池出水口处,水的pH、电导、溶解氧含量、饱和指数以及CO2 分压所受的影响主要以水生植物的光合作用为主;而在有水葫芦生长的岩溶水中,水生植物的光合作用影响降低,而温度和根呼吸作用的影响增强。在以桂林岩溶水文地质试验场S31号泉水池出水口堰板处和堰板下游约3m 处为监测点试验时,试验结果表明其水生植物的影响占70%以上,强于温度作用的影响。      

Influences of air CO<Subscript>2</Subscript> on hydrochemistry of drip water and implications for paleoclimate study in a stream-developed cave,SW China

Cave air CO₂ is a vital part of the cave environment. Most studies about cave air CO₂ variations are performed in caves with no streams; there are few studies to date regarding the relationship of cave air CO₂ variations and drip water hydrochemistry in underground stream–developed caves. To study the relationship of underground stream, drip water, and cave air CO₂, monthly and daily monitoring of air CO₂ and of underground stream and drip water was performed in Xueyu Cave from 2012 to 2013. The results revealed that there was marked seasonal variation of air CO₂ and stream hydrochemistry in the cave. Daily variations of cave air CO₂, and of stream and drip water hydrochemistry, were notable during continuous monitoring. A dilution effect was observed by analyzing hydrochemical variations in underground stream and drip water after rainfall. High cave air CO₂ along with low pH and low δ¹³C_DIC in stream and drip water indicated that air CO₂ was one of the dominant factors controlling stream and drip water hydrochemistry on a daily scale. On a seasonal scale, stream flows may promote increased cave air CO₂ in summer; in turn, the higher cave air CO₂ could inhibit degassing of drip water and make calcite δ¹³C more negative. Variation of calcite δ¹³C (precipitated from drip water) was in reverse of monthly temperature, soil CO₂, and cave air CO₂. Therefore, calcite δ¹³C in Xueyu Cave could be used to determine monthly changes outside the cave. However, considering the different precipitation rate of sediment in different seasons, it was difficult to use stalagmites to reconstruct environmental change on a seasonal scale.     

Geochemical controls on a calcite precipitating spring

A small spring fed stream was found to precipitate calcite by mainly inorganic processes and in a nonuniform manner. The spring water originated by rainwater falling in a 0.8 km² basin, infiltrating, and dissolving calcite and dolomite followed by dissolution of gypsum or anhydrite. The Ca²⁺/Mg²⁺ indicates that calcite is probably precipitated in the subsurface from a supersaturated solution. This water emerges from the spring still about 5 times supersaturated with respect to calcite and continues calcite precipitation. When 10 times supersaturation is reached, due to CO₂ degassing the precipitation is more rapid. The calcite accumulation from the stream with a flow of 5 l/s is calculated to be 12600 kg/yr with the highest rates in areas where CO₂ degassing is the greatest. The non-equilibrium, as shown by the high calcite supersaturation, is also reflected in a variable partitioning pattern for Sr²⁺ between the water and calcite.     

Cave air control on dripwater geochemistry, Obir Caves (Austria): Implications for speleothem deposition in dynamically ventilated caves

There are very few process studies that demonstrate the annual variation in cave environments depositing speleothems. Accordingly, we initiated a monitoring program at the Obir Caves, an Austrian dripstone cave system characterized by a seasonally changing air flow that results in a predictable pattern of high pCO₂ during summer and low pCO₂ in winter. Although similar seasonal changes in soil pCO₂ occur, they are not directly connected with the changes in the subsurface since the dripwaters are fed from a well-mixed source showing little seasonal variation. Cold season flushing by relatively CO₂-poor air enhances degassing of CO₂ in the cave and leads to a high degree of supersaturation of dripwater with regard to calcite. Forced calcite deposition during the cold season also gives rise to a pronounced pattern of synchronous seasonal variations in electrical conductivity, alkalinity, pH, Ca and δ¹³C_DIC which parallel variations recorded in δ¹³C_{cave air}. Chemical components unaffected by calcite precipitation (e.g., δD, δ¹⁸O, SiO₂, SO₄) lack a seasonal signal attesting to a long residence in the karst aquifer. Modeling shows that degassing of CO₂ from seepage waters results in kinetically-enhanced C isotopic fractionation, which contrasts with the equilibrium degassing shown from the Soreq cave in Israel. The Obir Caves may serve as a case example of a dripstone cave whose seepage waters (and speleothems) show intra-annual geochemical variability that is primarily due to chemical modification of the groundwater by a dynamic, bidirectional subsurface air circulation.     

CO2 gas pools in Jiyang sag,China

The CO₂ gas pools of Jiyang sag are located along the Gaoqing–Pingnan fault within a region of alkaline basalts. The concentration of CO₂ in the gas pools is in the range of 68.85–96.99%. All of the geochemical tracers for the CO₂ gas pools support the suggestion that CO₂ was mainly derived from mantle degassing. The δ¹³C values of CO₂ in the gas pools are in the range of −5.67–−3.41‰, which are higher than those of organogenic CO₂, and near to those of abiogenic CO₂. Their ³He/⁴He ratios are 2.80–4.47×10⁶, i.e. the R/Ra ratios are 2.00–3.19, showing that the Jiyang sag had undergone strong mantle degassing. CO₂/³He ratios are 0.59–0.89×10⁹, which are identical to those for N-MORB, indicating that CO₂ in these CO₂ gas pools was mainly derived from the mantle. Accompanying the intrusion of mantle-derived magma, the mantle-derived CO₂ migrated upwards along deep faults and was trapped in advantageous structures forming gas pools.     

Diurnal Variations of Carbon Dioxide, Methane, and Nitrous Oxide Vertical Fluxes in a Subtropical Estuarine Marsh on Neap and Spring Tide Days

Measuring fluxes of greenhouse gases (GHGs) is fundamental to estimating their impact on global warming. We examined diurnal variations of carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) vertical fluxes in a tidal marsh ecosystem. Measurements were recorded on neap and spring tide days in April and September 2010 in the Shanyutan wetland of the Min River estuary, southeast China. Here, we define a positive flux as directing into the atmosphere. CH₄ fluxes on the diurnal scale were positive throughout, and CH₄ emissions into the atmosphere on neap tide days were higher than on spring tide days. CH₄ releases from the marsh ecosystem on neap tide days were higher in the daytime; however, on spring tide days, daily variations of CH₄ emissions were more complex. The marsh ecosystem plays a twofold role in both releasing and assimilating CO₂ and N₂O gases on the diurnal scale. Average CO₂ fluxes were positive on the daily scale both on neap and spring days and were greater on the neap tide days than on spring tide days. Diurnal variations of N₂O fluxes fluctuated more. Over the diurnal period, soil temperature markedly controlled variations of CH₄ emissions compared to other soil factors, such as salinity and redox potential. Tidal water height was a key factor influencing GHGs fluxes at the water–air interface. Compared with N₂O, the diurnal course of CO₂ and CH₄ fluxes in the marsh ecosystem appeared to be directly controlled by marsh plants. These results have implications for sampling and scaling strategies for estimating GHGs fluxes in tidal marsh ecosystems.     

Stable isotopic and elemental characteristics of recent tufa from a karstic Krka River (south‐east Slovenia): useful environmental proxies?

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

Seasonal and diurnal variations of COO in air: Initial observations from Pasadena, CA

The budget of atmospheric CO₂ is widely studied using records of temporal and spatial variations of concentrations, δ¹³C and δ¹⁸O values. However, the number and diversity of sources and sinks prevents these alone from fully constraining the budget. Molecules containing two rare isotopes can serve as additional tracers and potentially provide additional, independent, constraints. We present data documenting seasonal and diurnal variations of CO₂ having a mass of 47 u (mostly ¹³C¹⁸O¹⁶O) in air from Pasadena, CA. We report these data using the ‘mass 47 anomaly’ (Δ₄₇), which is defined as the deviation of R⁴⁷(=[47]/[44]) from that expected for a random distribution of isotopologues. Between February 2004 and December 2005, Δ₄₇ showed a seasonal pattern that differed significantly from that expected based on thermodynamic equilibrium. During the year 2004 Δ₄₇ was 0.76‰ in winter, increased to 0.87‰ in summer and gradually decreased through the autumn to 0.81‰ at the end of the year. Δ₄₇ then increased again through the winter and spring of 2005 to 0.97‰ in summer followed by a decrease to 0.88‰ at the end of 2005. The seasonal variations cannot be accounted for by variations in the relative contribution of local fossil fuel sources. Diurnal variations were the combined effect of both fuel combustion and respiration having Δ₄₇ values of 0.41‰ and ca. 0.77‰, respectively. The seasonal cycle may be interpreted as a competition between low Δ₄₇ values in respiration and higher Δ₄₇ values resulting from CO₂-water exchange in photosynthesis.     

A geochemical evaluation of perennial spring activity and associated mineral precipitates at Expedition Fjord,Axel Heiberg Island,Canadian High Arctic

Two groups of perennial springs are observed in the Canadian High Arctic at Expedition Fjord on Axel Heiberg Island at Colour Peak and Gypsum Hill. Saline discharge (∼1.3–2.5 molal NaCl) produces a variety of calcite (travertine) and gypsum-rich precipitates. Saturation index calculations of the spring waters at Colour Peak suggest CO₂ degassing from the waters causes calcite precipitation. Gypsum precipitation dominates at Gypsum Hill, where spring waters have lower alkalinity and higher SO₄ concentrations. Mineral accumulations form both channel and rimstone pool morphologies as a result of varying slope conditions. At Colour Peak, confined flow in steep slope areas develop massive structures in contrast to more friable, porous accumulations in areas where waters fan out on shallower slopes; these morphological variations lead to corresponding varying apparent rates of mineral precipitation. Mineral precipitation at Gypsum Hill is far less notable as a result of lower discharge rates and annual degradation by icing formation. Microscopic observations and geochemical analyses of the channel precipitates at Colour Peak reveal alternating light (calcite spar) and dark (anhedral microcrystalline calcite combined with organic matter and non-carbonate minerals) laminae. Rimstone pools forming in lower sections of spring discharge are composed of accumulations of large euhedral calcite crystals interbedded with allochthonous inputs. High concentration of dissolved solids is responsible for slow travertine precipitation rates, which occurs during winter. This precipitation is further retarded during summer months by the introduction of crystal growth inhibitors such as Fe³⁺ and deposition of organic matter and soil sediments.     

Carbon-oxygen isotopic covariation in hydrothermal calcite during degassing of CO2

The effect of the outgassing of CO₂ from a hydrothermal fluid on the C- and O-isotopic compositions of calcite, which is precipitated from this fluid, is quantitatively modelled in terms of batch and Rayleigh distillation equations. Both CO₂ degassing and calcite precipitation are considered to be the removal mechanisms for dissolved carbon species from the fluid. Combined degassing-precipitation models are then developed by taking H₂CO₃ and HCO ₃ ^– , respectively, as the dominant dissolved carbon species. A positive correlation array between ¹³C and ¹³O values of calcite can be yielded by the precipitation of calcite from a H₂CO ₃ ^– -dominant fluid, accompanied by a progressive decrease in temperature during CO₂ degassing, whereas calcite precipitated from a HCO ₃ ^– -dominant fluid under the same conditions tends to display much smaller variation in ¹³C values than in ¹⁸O values. The combined processes of CO₂ degassing and calcite precipitation result in lowering the ¹³C value of calcites with respect to those precipitated in a closed system simply due to temperature effect. Carbon and oxygen isotopic data for calcite from the Kushikino gold-mining area in Japan illustrate the application of quantitative modelling, and degassing of CO₂ is suggested as a more likely cause for the precipitation of the calcite and quartz in this mining area.     

Modeling speleothem δC variability in a central Sierra Nevada cave using C and Sr/Sr

Carbon isotopes in speleothems can vary in response to a number of complex processes active in cave systems that are both directly and indirectly related to climate. Progressing downward from the soil zone overlying the cave, these processes include soil respiration, fluid-rock interaction in the host limestone, degassing of CO₂ and precipitation of calcite upflow from the speleothem drip site, and calcite precipitation at the drip site. Here we develop a new approach to independently constrain the roles of water-rock interaction and soil processes in controlling stalagmite δ¹³C. This approach uses the dead carbon proportion (dcp) estimated from coupled ¹⁴C and ²³⁰Th/U measurements, in conjunction with Sr isotope analyses on stalagmite calcite from a central Sierra Nevada foothills cave in California, a region characterized by a highly seasonal Mediterranean-type climate, to determine the roles of water-rock interaction and soil processes in determining stalagmite δ¹³C. Increases in stalagmite dcp between 16.5 and 8.8 ka are coincident with decreased δ¹³C, indicating a varying yet substantial contribution from the soil organic matter (SOM) reservoir, likely due to significantly increased average age of SOM in the soil veneer above the cave during wet climatic intervals.We use geochemical and isotope mixing models to estimate the host-carbonate contribution throughout the δ¹³C time series and determine the degree of degassing and calcite precipitation that occurred prior to precipitation of stalagmite calcite. The degree of degassing and prior calcite precipitation we calculate varies systematically with other climate indicators, with less degassing and prior calcite precipitation occurring during wetter climatic intervals and more during drier intervals. Modeled δ¹³C values and degassing calculations suggest that some degree of prior calcite precipitation is necessary at all time intervals to explain measured stalagmite δ¹³C values, even during relatively wet intervals. These results illustrate the importance of constraining degassing and prior calcite precipitation in the interpretation of speleothem δ¹³C records, particularly those from caves that formed in seasonal semi-arid to arid environments.     

Growth patterns and implications of complex dendrites in calcite travertines from Lýsuhóll, Snæfellsnes, Iceland

Calcite dendrite crystals are important but poorly understood components of calcite travertine that forms around many hot springs. The Lýsuhóll hot-spring deposits, located in western Iceland, are formed primarily of siliceous sinters that were precipitated around numerous springs that are now inactive. Calcite travertine formed around the vent and on the discharge apron of one of the springs at the northern edge of the area. The travertine is formed largely of two types (I and II) of complex calcite dendrite crystals, up to 1 cm high, that grew through the gradual addition of trilete sub-crystals. The morphology of the dendrite crystals was controlled by flow direction and the competition for growth space with neighbouring crystals. Densely crowded dendrites with limited branching characterize the rimstone dams whereas widely spaced dendrites with open branching are found in the pools. Many dendrite bushes in the pools nucleated around plant stems. Growth of the dendrite crystals was seasonal and incremental. Calcite precipitation was driven by rapid CO₂ degassing of CO₂-rich spring waters during the spring and summer. During winter, when snow covered the ground and temperatures were low, opal-A precipitated on the exposed surfaces of the dendrites. Segmentation of dendrite branches by discontinuities coated with opal-A and overgrowth development around sub-crystals resulted from this seasonal growth cycle. The calcite dendrite crystals in the Lýsuhóll travertine differ in morphology from those at other hot springs, such as those at Lake Bogoria, Kenya, and Waikite in New Zealand. Comparison with the calcite dendrite crystals found at those sites shows that dendrite morphology is site-specific and probably controlled by carbonate saturation levels that, in turn, are controlled by the rate of CO₂ degassing and location in the spring outflow system.     

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.     

Pleistocene speleothems of Mallorca: implications for palaeoclimate and carbonate diagenesis in mixing zones

The Pleistocene speleothems of Sa Bassa Blanca cave, Mallorca, are excellent indicators of palaeoclimate variations, and are samples that allow evaluation of the products and processes of mixing‐zone diagenesis in an open‐water cave system. Integrated stratigraphic, petrographic and geochemical data from a horizontal core of speleothem identified two main origins for speleothem precipitates: meteoric‐marine mixing zone and meteoric‐vadose zone. Mixing‐zone precipitates formed at and just below the water–air interface of cave pools during interglacial times, when the cave was flooded as a result of highstand sea‐level. Mixing‐zone precipitates include bladed and dendritic high‐Mg calcite, microporous‐bladed calcite with variable Mg content, and acicular aragonite; their presence suggests that calcium‐carbonate cementation is significant in the studied mixing‐zone system. Fluid inclusion salinities, δ¹³C and δ¹⁸O compositions of the mixing‐zone precipitates suggest that mixing ratio was not the primary control on whether precipitation or dissolution occurred, rather, the proximity to the water table and degassing of CO₂ at the interface, were the major controls on precipitation. Thus, simple two‐end‐member mixing models may apply only in mixing zones well below the water table. Meteoric‐vadose speleothems include calcite and high‐Mg calcite with columnar and bladed morphologies. Vadose speleothems precipitated during glacial stages when sea level was lower than present. Progressive increase in δ¹³C and δ¹⁸O of the vadose speleothems resulted from cooling temperatures and more positive seawater δ¹⁸O associated with glacial buildup. Such covariation could be considered as a valid alternative to models predicting invariant δ¹⁸O and highly variable δ¹³C in meteoric calcite. Glacio‐eustatic oscillations of sea‐level are recorded as alternating vadose and mixing‐zone speleothems. Short‐term climatic variations are recorded as alternating aragonite and calcite speleothems precipitated in the mixing zone. Fluid‐inclusion and stable‐isotope data suggest that aragonite, as opposed to calcite, precipitated during times of reduced meteoric recharge.     

Temperature-driven meltwater production and hydrochemical variations at a glaciated alpine karst aquifer: implication for the atmospheric CO<Subscript>2</Subscript> sink under global warming

About two hydrological years of continuous data of discharge, temperature, electrical conductivity and pH have been recorded at the Glarey spring in the Tsanfleuron glaciated karst area in the Swiss Alps, to understand how glaciated karst aquifer systems respond hydrochemically to diurnal and seasonal recharge variations, and how calcite dissolution by glacial meltwater contributes to the atmospheric CO₂ sink. A thermodynamic model was used to link the continuous data to monthly water quality data allowing the calculation of CO₂ partial pressures and calcite saturation indexes. The results show diurnal and seasonal hydrochemical variations controlled chiefly by air temperature, the latter influencing karst aquifer recharge by ice and snowmelt. Karst process-related atmospheric CO₂ sinks were more than four times higher in the melting season than those in the freezing season. This finding has implication for understanding the atmospheric CO₂ sink in glaciated carbonate rock terrains: the carbon sink will increase with increasing runoff caused by global warming, i.e., carbonate weathering provides a negative feedback for anthropogenic CO₂ release. However, this is a transient regulation effect that is most efficient when glacial meltwater production is highest, which in turn depends on the future climatic evolution.     

Carbon sequestration and decreased CO2 emission caused by terrestrial aquatic photosynthesis: Insights from diel hydrochemical variations in an epikarst spring and two spring-fed ponds in different seasons

Whether carbonate weathering could produce a stable carbon sink depends primarily on the utilization of dissolved inorganic carbon (DIC) by aquatic phototrophs (the so-called Biological Carbon Pump-BCP effect). On this basis, water temperature (T), pH, electrical conductivity (EC) and dissolved oxygen (DO) were synchronously monitored at 15-min resolution for one and two days respectively in January and October 2013 in Maolan Spring and the spring-fed midstream and downstream ponds in Maolan Nature Reserve, China. A thermodynamic model was used to link the continuous data to allow calculation of CO₂ partial pressures (pCO₂) and calcite saturation indexes (SI_C). A floating static chamber was placed on the water surface successively at all sites to quantify CO₂ exchange flux between atmosphere and water so as to evaluate the BCP effect. Results show that, in both winter and autumn, remarkable diel variations of hydrochemical parameters were present in the midstream pond where DO, pH, and SI_C increased in the day and decreased during the night while EC, $\left[{{\text{HCO}}_3}^{-}\right]$, [Ca²⁺] and pCO₂ showed inverse changes mainly due to the metabolic processes of the flourishing submerged plants, with photosynthesis dominating in the day and respiration dominating at night. However, hydrochemical parameters in the spring and downstream pond show less change since few submerged plants developed there. It was determined that the BCP effect in the midstream pond was 285 ± 193 t C km⁻² a⁻¹ in winter and 892 ± 300 t C km⁻² a⁻¹ in autumn, indicating a potential significant role of terrestrial aquatic photosynthesis in stabilizing the carbonate weathering-related carbon sink.     

Preliminary estimate of CO2 output from Pantelleria Island volcano (Sicily,Italy): evidence of active mantle degassing

Total CO₂ output from fumaroles, bubbling and water dissolved gases and soil gases was investigated at Pantelleria Island volcano, Italy. The preliminary results indicate an overall output of 0.39 Mt a⁻¹ of CO₂ from the island. The main contribution to the total output was from diffuse soil degassing (about 0.32 Mt a⁻¹), followed by dissolved CO₂ (0.034 Mt a⁻¹), focussed soil degassing (0.028 Mt a⁻¹) and bubbling CO₂ (0.013 Mt a⁻¹). The contribution of CO₂ from fumarole gases was found to be negligible (1.4×10⁻⁶ Mt a⁻¹). Carbon-13 values for CO₂ coupled with those for associated He in gases from fumaroles and sites of focussed soil degassing clearly rule out any significant organic CO₂ component and suggest a common mantle origin for these gas species. The inferred mantle source beneath Pantelleria would seem to have peculiar geochemical characteristics, quite distinct from those of mantle producing MORB but compatible with those of magmatic sources of central Mediterranean and central European volcanoes. These findings indicate that the Pantelleria volcanic complex is a site of active mantle degassing that is worthy of attention for future geochemical surveillance of the island.     

Origin and palaeoenvironmental significance of lamination in stalagmites from Katerloch Cave,Austria

The origin and environmental dependencies of lamination in stalagmites from Katerloch, common in speleothems from other cave sites, are examined in detail. Petrographic observations and chemical analyses (including isotopes) of stalagmites and modern calcite were combined with multi‐annual cave monitoring. All investigated stalagmites are composed of low‐Mg calcite and show white, porous laminae and typically thinner, translucent dense laminae. The binary lamination pattern results from changes in the calcite fabric: white, porous laminae are characterized by a high porosity and abundant fluid inclusions and also by enhanced vertical growth and thinning towards the flanks. Translucent, dense laminae exhibit a compact fabric and constant thickness of individual growth layers. U‐Th dating supports an annual origin of the lamination and the seasonally changing intensity of cave ventilation provides a robust explanation for the observed relationships between lamination, stable C isotopic compositions and trace elements (Mg, Sr and Ba). The seasonally variable air exchange, driven by temperature contrasts between the cave interior and outside atmosphere, modulates the rate and amount of CO₂ degassing from the drip water and affects the hydrochemistry and consequently the fabric of the precipitating calcite. Although cave air composition and drip rate are both major variables in controlling CO₂ degassing from the drip water, the seasonally changing ventilation in Katerloch exerts the primary control and the results suggest a secondary (amplifying/attenuating) influence of the drip rate. Drip rate, however, might be the controlling parameter for lamina development at cave sites experiencing only small seasonal cave air exchange. Importantly, the seasonally variable composition of drip water does not reflect the seasonal cycle of processes in the soil zone, but results from exchange with the cave atmosphere. The alternating porous and dense calcite fabric is the expression of a variable degree of lateral coalescence of smaller crystallites forming large columnar crystals. The white, porous laminae represent partial coalescence and form during the warm season: low calcite δ¹³C values are linked to low δ¹³C values of cave air and drip water during that time. This observation corresponds to times of reduced cave ventilation, high pCO₂ of cave air, low drip water pH, lower calcite supersaturation and typically high drip rates. In contrast, the translucent, dense laminae represent more or less complete lateral coalescence (inclusion‐free) during the cold season (high calcite, drip water and cave air δ¹³C values), i.e. times of enhanced cave ventilation, low cave air pCO₂, increased drip water pH, relatively high calcite supersaturation and typically low drip rates. In essence, the relative development of the two lamina types reflects changes in the seasonality of external air temperature and precipitation, with a strong control of the winter air temperature on the intensity of cave‐air exchange. Thick translucent, dense laminae are favoured by long, cold and wet winters and such conditions may be related closely to the North Atlantic Oscillation mode (weak westerlies) and enhanced Mediterranean cyclone activity during the cold season. Studies of speleothem lamination can thus help to better understand (and quantify) the role of seasonality changes, for example, during rapid climate events.