Hydrogeochemistry and environmental impact of geothermal waters from Yangyi of Tibet,China

The Yangyi geothermal field, located 72 km northwest to Lhasa City, capital of Tibet, has a high reservoir temperature up to at least 207.2 °C. The geothermal waters from both geothermal wells and hot springs belong to the HCO₃ (+CO₃)–Na type. Factor analysis of all the chemical constituents shows that they can be divided into two factors: F₁ factor receives the contributions of SO₄²⁻, Cl⁻, SiO₂, As, B, Na⁺, K⁺, and Li⁺; whereas F₂ factor is explained by HCO₃⁻, F⁻, CO₃²⁻, Ca²⁺, and Sr²⁺. The F₁ factor can be regarded as an indicator of the reservoir temperature distribution at Yangyi, but its variable correlation with the results of different geothermometers (Na–K, quartz and K–Mg) does not allow one to draw further inferences. Different from F₁, the F₂ factor is an indicator of a group of hydrogeochemical processes resulting from the CO₂ pressure decrease in geothermal water during its ascent from the deep underground, including transformation of HCO₃⁻ to CO₃²⁻, precipitation of Ca²⁺ and Sr²⁺, and release of F⁻ from some fluoride-bearing minerals of reservoir rocks. The plot of enthalpy vs. chloride, prepared on the basis of Na–K equilibrium temperatures, suggests that a parent geothermal liquid (PGL) with Cl⁻ concentration of 185 mg/L (that of sample YYT-8) and enthalpy of 1020 J/g (corresponding to a temperature of 236–237 °C, i.e., somewhat higher than that of sample YYT-6) is present in the geothermal reservoir of the Yangyi area, below both the Qialagai valley and the Bujiemu valley, although the samples less affected by mixing and cooling (YYT-6 and YYT-7) come from the second site. The discharge of geothermal waters with high contents of toxic elements such as B, As and F into the Luolang River, the only drinking water source for local residents, has caused slight pollution of the river water. Great care should therefore be taken in the geothermal water resource management at Yangyi.     

Oxygen diffusion rates in quartz exchanged with CO2

Oxygen self diffusion rates were determined in quartz samples exchanged with¹⁸O-enriched CO₂ between 745 and 900°C and various pressures, and the diffusion profiles were measured using an ion microprobe. The activation energy (Q) and preexponential factor (D₀) at P(CO₂) = P(tot) = 100 bar, for diffusion parallel to the c-axis are 159 ( ± 13) kJ/g atom and 2.10 (+0.75/ −0.55) × 10⁻⁸ cm²/s. This rate is approximately 100 times slower than that obtained from hydrothermal experiments and 100 times faster than a previous 1-bar quartz-O₂ exchange experiment. The oxygen diffusion rate measured at 0.6 bar, 888°C, and at 900°C in vacuum is in agreement with the previous 1-bar exchange experiments with¹⁸O₂. The effect of higher CO₂ pressures is small. At 900°C, the diffusion rate exchanged with CO₂ is = 2.35 × 10⁻¹⁵ cm²/s at 100 bar, 2.24 × 10⁻¹⁵ cm²/s at 3.45 kbar and 8.13 × 10⁻¹⁵ cm²/s at 7.2 kbar.There is probably a diffusing species, other than oxygen, that enhances the oxygen diffusion rate in these quartz-CO₂ systems, relative to that occurring at very low pressures or in a vacuum. The effect of this diffusing species, however, is not as strong as that associated with H₂O. Preserved oxygen isotope fractionations between coexisting minerals in a slowly cooled, high-grade metamorphic terrane will vary depending upon whether a water-rich phase was present or not. Closure temperatures will be approximately 100°C higher in rocks where no water-rich phase was present during cooling. The measured fractionations between coexisting minerals in metamorphic rocks may potentially be used as a sensor of water presence during retrogression.     

Dynamics and design of systems for geological storage of dissolved CO2

The standard approach for geologic storage of CO₂ consists of injecting it as a supercritical CO₂ phase. This approach places stringent requirements on the caprock, which must display: (1) high entry pressure to prevent the buoyancy driven upwards escape of CO₂; (2) low permeability to minimize the upwards flux of brine displaced by the CO₂; and (3) high strength to ensure that pressure build up does not cause caprock failure. We propose an alternative approach for cases when the above requirements are not met. The approach consists of extracting brine from the storage formation and then re-injecting it so that it mixes with CO₂ at depth in the injection well. Mixing at depth reduces the pressure required for brine and CO₂ at the surface. This CO₂-saturated brine will sink to the aquifer bottom because it is denser than resident brine, which eliminates the risk of buoyant escape of CO₂. The method is particularly favorable when the aquifer dips, because CO₂-saturated brine will tend to flow downslope. We perform two- and three-dimensional numerical simulations to study how far upslope the extraction well needs to be located to ensure a very long operation without CO₂ ever breaking through. Several sets of simulations were carried out to evaluate the effect of slope, temperature, pressure and CO₂ concentration, which is significantly reduced if flue gas (i.e., without capture) is mixed with the brine. We analyze energy requirements to find that the system requires high permeability to be viable, but its performance is improved by taking advantage of the thermal energy of the extracted brine.     

Gas exchange between Baikal and the atmosphere during under-ice period

In the under-ice period, gas exchange between Baikal and the atmosphere is taking place through a system of coastal and perennial fractures and airholes in the ice, as well as through the surface of the ice-free part of the lake at the Angara source [24]. The total area of the open water never exceeds 0.03% of lake water area. The emission of CO₂ in the course of ice sublimation over the entire period is ≤0.02 g CO₂ from 1 m². The transport of dissolved gases from under-ice water into the atmosphere is limited by molecular diffusion in microfractions of ice cover. The narrow daily variations of CO₂ in the air in lake coastal zone is due to the effect of populated localities on its coast and large coniferous forests, which serve as diffuse sources of CO₂, as well as diurnal variations of the direction and velocity of air mass transport by local winds.     

Bolide impacts, acid rain, and biospheric traumas at the Cretaceous-Tertiary boundary

Large projectiles impacting the Earth will cause severe shock heating and chemical reprocessing of the Earth's atmosphere. This occurs during atmospheric entry and, more importantly, as a result of the supersonic plume ejected on impact. In particular, very large amounts of nitric oxide would result from the impact of the putative Cretaceous-Tertiary bolide(s). We present models of the shock chemistry, the conversion of NO to NO₂ and thence to nitrous and nitric acids, and the global dispersion of the NO₂ and acids. Two plausible projectiles are considered: an ice-rich long-period comet and a much smaller rock-metal asteroid. The comet produces semi-global atmospheric NO₂ mixing ratios of 0.1% while the asteroid produces these high mixing ratios only in the immediate region of the impact. The comet produces concentrated nitrous and nitric acid rain with apH ≈ 0–1.5 globally. The asteroid produces rain with apH ≈ 0–1 near the impact and≈ 4–5 globally. Immediate environmental effects of these nitrogen species include inhibition of photosynthesis due to extinction of solar radiation by NO₂, foliage damage due to exposure to NO₂ and HNO₃, toxicosis resulting from massive mobilization of soil trace metals, and respiratory damage due to exposure to NO₂. The acid rain decreases the pH of the oceanic mixed layer affecting the stability of calcite with important implications for the survival of calcareous-shelled organisms and for exhalation of CO₂ from the mixed layer to the atmosphere. Longer-term environmental effects perhaps≈ 1000years in duration include a global warming due to the sudden CO₂ injection and the simultaneous extinction of the ocean micro-organisms which normally help remove CO₂ from the atmosphere-mixed layer system. Havens for survival include carbonate-buffered lakes and burrows. This acid rain theory therefore serves to explain the peculiar selectivity of the extinctions seen at the Cretaceous-Tertiary boundary. The first few years of acid rain will lead to massive weathering rates of continental soils characterized by large ratios of the relatively insoluble metals (e.g. Be²⁺, Al³⁺, Hg²⁺, Cu⁺, Fe²⁺, Fe³⁺, Tl³⁺, Pb²⁺, Cd²⁺, Mn²⁺, Sr²⁺) to the more soluble metals (Ca²⁺, Mg²⁺) which should have left a clear signal in the fossils of neritic organisms and in unperturbed neritic sediments near river deltas if such sediments still exist for the Cretaceous-Tertiary time frame.     

Cooling of the mesosphere and lower thermosphere due to doubling of CO2

A new parameterization of infrared radiative transfer in the 15-m CO₂ band has been incorporated into the Spectral mesosphere/lower thermosphere model (SMLTM). The parameterization is applicable to calculations of heating rates above approximately 15 km for arbitrary vertical profiles of the CO₂ concentration corresponding to the surface mixing ratio in the range 150–720 ppm. The sensitivity of the mesosphere and lower thermosphere (MLT) to doubling of CO₂ has been studied. The thermal response in the MLT is mostly negative (cooling) and much stronger than in the lower atmosphere. An average cooling at the stratopause is about 14 K. It gradually decreases to approximately 8 K in the upper mesosphere and again increases to about 40–50 K in the thermosphere. The cooling and associated thermal shrinking result in a substantial density reduction in the MLT that reaches 40–45% in the thermosphere. Various radiative, chemical, and dynamical feedbacks potentially important for the thermal response in the MLT are discussed. It is noted that the results of simulations are strikingly similar to observations of long-term trends in the MLT. This suggests that during the last 3–4 decades the thermal structure in the real upper atmosphere has undergone substantial changes driven by forcing comparable with that due to doubling of CO₂.     

CO2 absorption of sandy soil induced by rainfall pulses in a desert ecosystem

Soil CO₂ flux is strongly influenced by precipitation in many ecosystem types, yet knowledge of the effects of precipitation on soil CO₂ flux in semi‐arid desert ecosystems remains insufficient, particularly for sandy soils. To address this, we investigated the response of sandy soil CO₂ flux to rainfall pulses in a desert ecosystem in northern China during August–September 2011. Significant changes (P < 0.05) were found in diel patterns of soil CO₂ flux induced by small (2.1 mm), moderate (12.4 mm) and large (19.7 mm) precipitation events. Further analysis indicated that rainfall pulses modified the response of soil CO₂ flux to soil temperature, including hysteresis between soil CO₂ flux and soil temperature, with F_s higher when T_s was increasing than when T_s was decreasing, and the linear relationship between them. Moreover, our results showed that rainfall could result in absorption of atmospheric CO₂ by soil, possibly owing to mass flow of CO₂ induced by a gradient of gas pressure between atmosphere and soil. After each precipitation event, soil CO₂ flux recovered exponentially to pre‐rainfall levels with time, with the recovery times exhibiting a positive correlation with precipitation amount. On the basis of the amounts of precipitation that occurred at our site during the measurement period (August–September), the accumulated rain‐induced carbon absorption evaluated for rainy days was 1.068 g C m^?2; this corresponds approximately to 0.5–2.1% of the net primary production of a typical desert ecosystem. Thus, our results suggest that rainfall pulses can strongly influence carbon fluxes in desert ecosystems. Copyright © 2014 John Wiley & Sons, Ltd.     

The importance of ocean temperature to global biogeochemistry

Variations in the mean temperature of the ocean, on time scales from millennial to millions of years, in the past and projected for the future, are large enough to impact the geochemistry of the carbon, oxygen, and methane geochemical systems. In each system, the time scale of the temperature perturbation is key. On time frames of 1-100 ky, atmospheric CO₂ is controlled by the ocean. CO₂ temperature-dependent solubility and greenhouse forcing combine to create an amplifying feedback with ocean temperature; the CaCO₃ cycle increases this effect somewhat on time scales longer than ∼5-10 ky. The CO₂/T feedback can be seen in the climate record from Vostok, and a model including the temperature feedback predicts that 10% of the fossil fuel CO₂ will reside in the atmosphere for longer than 100 ky. Timing is important for oxygen, as well; the atmosphere controls the ocean on short time scales, but ocean anoxia controls atmospheric pO₂ on million-year time scales and longer. Warming the ocean to Cretaceous temperatures might eventually increase pO₂ by approximately 25%, in the absence of other perturbations. The response of methane clathrate to climate change in the coming century will probably be small, but on longer time scales of 1-10 ky, there may be a positive feedback with ocean temperature, amplifying the long-term climate impact of anthropogenic CO₂ release.     

Thermal diffusivity of lunar rocks under atmospheric and vacuum conditions

Thermal diffusivity, k, of three lunar rocks (10049 and 10069; Type A, Apollo 11 and 14311; Apollo 14) and a terrestrial basalt (alkaline olivine basalt, Oki-do?go, Japan) was measured under one atmosphere and in vacuum conditions (10^?3 ～ 10^?5 mmHg) in the temperature range from 85 to 850°K. The semi-empirical curve of k =A + B/T +CT³ is fitted to the data in each condition. The porosity of rocks strongly affects the thermal diffusivity at low temperature ( T ? 500°K) in vacuum condition. At 150°K, thermal diffusivity of lunar rocks with porosity of 5.5% (10049) and 11% (10069) at one atmosphere is about 1.7 and 3.2 times of that in vacuum, respectively. The difference between the values at one atmosphere and those in vacuum decreases as the temperature increases. Measurements of k should be made at gas pressures at least lower than 10^?3 mmHg to estimate the value under lunar surface conditions.     

Magmatic gas scrubbing: implications for volcano monitoring

Despite the abundance of SO_2(g) in magmatic gases, precursory increases in magmatic SO_2(g) are not always observed prior to volcanic eruption, probably because many terrestrial volcanoes contain abundant groundwater or surface water that scrubs magmatic gases until a dry pathway to the atmosphere is established. To better understand scrubbing and its implications for volcano monitoring, we model thermochemically the reaction of magmatic gases with water. First, we inject a 915°C magmatic gas from Merapi volcano into 25°C air-saturated water (ASW) over a wide range of gas/water mass ratios from 0.0002 to 100 and at a total pressure of 0.1 MPa. Then we model closed-system cooling of the magmatic gas, magmatic gas-ASW mixing at 5.0 MPa, runs with varied temperature and composition of the ASW, a case with a wide range of magmatic–gas compositions, and a reaction of a magmatic gas–ASW mixture with rock. The modeling predicts gas and water compositions, and, in one case, alteration assemblages for a wide range of scrubbing conditions; these results can be compared directly with samples from degassing volcanoes. The modeling suggests that CO_2(g) is the main species to monitor when scrubbing exists; another candidate is H₂S_(g), but it can be affected by reactions with aqueous ferrous iron. In contrast, scrubbing by water will prevent significant SO_2(g) and most HCl_(g) emissions until dry pathways are established, except for moderate HCl_(g) degassing from pH<0.5 hydrothermal waters. Furthermore, it appears that scrubbing will prevent much, if any, SO_2(g) degassing from long-resident boiling hydrothermal systems. Several processes can also decrease or increase H_2(g) emissions during scrubbing making H_2(g) a poor choice to detect changes in magma degassing.We applied the model results to interpret field observations and emission rate data from four eruptions: (1) Crater Peak on Mount Spurr (1992) where, except for a short post-eruptive period, scrubbing appears to have drastically diminished pre-, inter-, and post-eruptive SO_2(g) emissions, but had much less impact on CO_2(g) emissions. (2) Mount St. Helens where scrubbing of SO_2(g) was important prior to and three weeks after the 18 May 1980 eruption. Scrubbing was also active during a period of unrest in the summer of 1998. (3) Mount Pinatubo where early drying out prevented SO_2(g) scrubbing before the climactic 15 June 1991 eruption. (4) The ongoing eruption at Popocatépetl in an arid region of Mexico where there is little evidence of scrubbing.In most eruptive cycles, the impact of scrubbing will be greater during pre- and post-eruptive periods than during the main eruptive and intense passive degassing stages. Therefore, we recommend monitoring the following gases: CO_2(g) and H₂S_(g) in precursory stages; CO_2(g), H₂S_(g), SO_2(g), HCl_(g), and HF_(g) in eruptive and intense passive degassing stages; and CO_2(g) and H₂S_(g) again in the declining stages. CO_2(g) is clearly the main candidate for early emission rate monitoring, although significant early increases in the intensity and geographic distribution of H₂S_(g) emissions should be taken as an important sign of volcanic unrest and a potential precursor. Owing to the difficulty of extracting SO_2(g) from hydrothermal waters, the emergence of >100 t/d (tons per day) of SO_2(g) in addition to CO_2(g) and H₂S_(g) should be taken as a criterion of magma intrusion. Finally, the modeling suggests that the interpretation of gas-ratio data requires a case-by-case evaluation since ratio changes can often be produced by several mechanisms; nevertheless, several gas ratios may provide useful indices for monitoring the drying out of gas pathways.     

BIFoR FACE: Water–soil–vegetation–atmosphere data from a temperate deciduous forest catchment,including under elevated CO2

The ecosystem services provided by forests modulate runoff generation processes, nutrient cycling and water and energy exchange between soils, vegetation and atmosphere. Increasing atmospheric CO₂ affects many linked aspects of forest and catchment function in ways we do not adequately understand. Global levels of atmospheric CO₂ will be around 40% higher in 2050 than current levels, yet estimates of how water and solute fluxes in forested catchments will respond to increased CO₂ are highly uncertain. The Free Air CO₂ Enrichment (FACE) facility of the University of Birmingham's Institute of Forest Research (BIFoR) is the only FACE in mature deciduous forest. The site specializes in fundamental studies of the response of whole ecosystem patches of mature, deciduous, temperate woodland to elevated CO₂ (eCO₂). Here, we describe a dataset of hydrological parameters – seven weather parameters at each of three heights and four locations, shallow soil moisture and temperature, stream hydrology and CO₂ enrichment – retrieved at high frequency from the BIFoR FACE catchment.     

The influence of plants on atmospheric carbon monoxide and dinitrogen oxide

It is shown by laboratory experiments and extensivein-situ measurements that higher plants (Vicia faba, Platanus acerifolia, Fagus silvatica, andPinus silvestris) produce carbon monoxide. The measurements were carried out under natural conditions with respect to the concentrations of O₂ and H₂O, and temperature. The CO₂- and CO-mixing ratios were varied in the ranges 350 to 530 ppm and 3–270 ppb, respectively. The CO-production rates were found to be light dependent with an average value per cm² of leaf area of 3×10^–13 g/sec for a radiation intensity of 5×10⁴ erg/cm² sec. The production rates are independent of the CO₂- and CO-mixing ratios employed in the test atmosphere. Considering the production rate of 3×10^–13 g/cm² sec to be representative for global conditions the total CO-production by plants is estimated to be 0.5–1.0×10¹⁴ g/year. In contrast to carbon monoxide atmospheric dinitrogen oxide is not influenced by plants in the same manner.     

Major ion chemistry of two cratonic rivers in the tropics: Weathering rates and their controlling factors

Continental weathering plays a dominant role in regulating the global carbon cycle, soil chemistry and nutrient supply to oceans. The CO₂-mediated silicate weathering acts as a major CO₂ sink, whereas sulphuric acid-mediated carbonate dissolution releases CO₂ to the atmosphere–ocean system. In this study, dissolved major ions and silica concentrations of two tropical (Damodar and Subarnarekha) river systems from India have been measured to constrain the type and rate of chemical weathering for these basins. The total dissolved solids (TDS) of these rivers, a measure of total solute supply from all possible sources, are about 2–3 times higher than that of the global average for rivers. Mass balance calculations involving inverse modelling estimate that 63 ± 11% of total cations are derived from rock weathering, of which 27 ± 7% of cations are supplied through silicate weathering. The sulphide-S concentrations are estimated by comparing the water chemistry of these two rivers with that of a nearby river (Brahmani) with similar lithology but no signatures of sulphide oxidation. The outflows of Damodar and Subarnarekha rivers receive 17% and 55% of SO₄ through sulphide oxidation, respectively. The sulphide oxidation fluxes from the ore mining areas, such as upper Damodar (0.52 × 10⁹ mol/yr) and lower Subarnarekha (0.66 × 10⁹ mol/yr) basins, are disproportionally (~9 times) higher compared to their fractional areal coverage to the global drainage area. The corresponding CO₂ release rate (2.84 × 10⁴ mol/km²/yr) for the Damodar basin is lower by five times than its CO₂ uptake rate (1.38 × 10⁵ mol/km²/yr). The outcomes of this study underscore the dominance of sulphide oxidation in controlling the dissolved chemical (cationic and sulphur) fluxes.     

Supersaturation and evasion of CO2 and CH4 in surface waters at Mer Bleue peatland,Canada

Carbon dioxide (CO₂) and methane (CH₄) concentrations and evasion rates were measured in surface waters draining Mer Bleue peatland (Ontario, Canada) between spring and autumn 2005. All sites exhibit a consistent pattern of supersaturation throughout the year, which is broadly related to hydrological and temperature changes between spring snowmelt and autumn freezing. Both measurements and estimates of CO₂ and CH₄ evasion from open water to the atmosphere suggest that parts of the catchment (including beaver dams) are significant degassing hot spots. We present data showing how vertical gaseous carbon fluxes compare with lateral carbon fluxes and make an initial estimate of the importance to the overall carbon budget of CO₂ and CH₄ evasion to the atmosphere from water surfaces at Mer Bleue. Copyright © 2007 John Wiley & Sons, Ltd.     

Carbon sinks/sources in the Yellow and East China Seas—Air-sea interface exchange,dissolution in seawater,and burial in sediments

The sinks/sources of carbon in the Yellow Sea(YS) and East China Sea(ECS), which are important continental shelf seas in China, could exert a great influence on coastal ecosystem dynamics and the regional climate change process. The CO_2 exchange process across the seawater-air interface, dissolved and particulate carbon in seawater, and carbon burial in sediments were studied to understand the sinks/sources of carbon in the continental shelf seas of China. The YS and the ECS generally have different patterns of seasonal air-sea CO_2 exchange. In the YS, regions west of 124°E can absorb CO_2 from the atmosphere during spring and winter, and release CO_2 to the atmosphere during summer and autumn. The entire YS is considered as a CO_2 source throughout the year with respect to the atmosphere, but there are still uncertainties regarding the exact air-sea CO_2 exchange flux. Surface temperature and phytoplankton production were the key controlling factors of the air-sea CO_2 exchange flux in the offshore region and nearshore region of the YS, respectively. The ECS can absorb CO_2 during spring, summer, and winter and release CO_2 to the atmosphere during autumn. The annual average exchange rate in the ECS was-4.2±3.2 mmol m~(-2) d~(-1) and it served as an obvious sink for atmospheric CO_2 with an air-sea exchange flux of 13.7×10~6 t. The controlling factors of the air-sea CO_2 exchange in the ECS varied significantly seasonally. Storage of dissolved inorganic carbon(DIC) and dissolved organic carbon(DOC) in the YS and the ECS were 425×10~6 t and 1364×10~6 t, and 28.2×10~6 t and 54.1×10~6 t,respectively. Long-term observation showed that the DOC content in the YS had a decreasing trend, indicating that the "practical carbon sink" in the YS was decreasing. The total amount of particulate organic carbon(POC) stored in the YS and ECS was10.6×10~6 t, which was comparable to the air-sea CO_2 flux in these two continental shelf seas. The amounts of carbon sequestered by phytoplankton in the YS and the ECS were 60.42×10~6 t and 153.41×10~6 t, respectively. Artificial breeding of macroalgae could effectively enhance blue carbon sequestration, which could fix 0.36×10~6–0.45×10~6 t of carbon annually. Organic carbon(OC) buried in the sediments of the YS was estimated to be 4.75×10~6 t, and OC of marine origin was 3.03×10~6 t, accounting for5.0% of the TOC fixed by phytoplankton primary production. In the ECS, the corresponding depositional flux of OC in the sediment was estimated to be 7.4×10~6 t yr~(-1), and the marine-origin OC was 5.5×10~6 t, accounting for 5.4% of the phytoplankton primary production. Due to the relatively high average depositional flux of OC in the sediment, the YS and ECS have considerable potential to store a vast amount of "blue carbon."     

Effects of soil compaction,rain exposure and their interaction on soil carbon dioxide emission

Soils release more carbon, primarily as carbon dioxide (CO₂), per annum than current global anthropogenic emissions. Soils emit CO₂ through mineralization and decomposition of organic matter and respiration of roots and soil organisms. Given this, the evaluation of the effects of abiotic factors on microbial activity is of major importance when considering the mitigation of greenhouse gases emissions. Previous studies demonstrate that soil CO₂ emission is significantly affected by temperature and soil water content. A limited number of studies have illustrated the importance of bulk density and soil surface characteristics as a result of exposure to rain on CO₂ emission, however, none examine their relative importance. Therefore, this study investigated the effects of soil compaction and exposure of the soil surface to rainfall and their interaction on CO₂ release. We conducted a factorial laboratory experiment with three soil types after sieving (clay, silt and sand soil), three different bulk densities (1·1 g cm^–3, 1·3 g cm^–3, 1·5 g cm^–3) and three different exposures to rainfall (no rain, 30 minutes and 90 minutes of rainfall). The results demonstrated CO₂ release varied significantly with bulk density, exposure to rain and time. The relationship between rain exposure and CO₂ is positive: CO₂ emission was 53% and 42% greater for the 90 minutes and 30 minutes rainfall exposure, respectively, compared to those not exposed to rain. Bulk density exhibited a negative relationship with CO₂ emission: soil compacted to a bulk density of 1·1 g cm^–3 emitted 32% more CO₂ than soil compacted to 1·5 g cm^–3. Furthermore we found that the magnitude of CO₂ effluxes depended on the interaction of these two abiotic factors. Given these results, understanding the influence of soil compaction and raindrop impact on CO₂ emission could lead to modified soil management practices which promote carbon sequestration. Copyright © 2012 John Wiley & Sons, Ltd.     

Transfer of carbon dioxide and methane through the soil‐water‐atmosphere system at Mer Bleue peatland,Canada

Surface waters associated with peatlands, supersaturated with CO₂ and CH₄ with respect to the atmosphere, act as important pathways linking a large and potentially unstable global repository of C to the atmosphere. Understanding the drivers and mechanisms which control C release from peatland systems to the atmosphere will contribute to better management and modelling of terrestrial C pools. We used non‐dispersive infra‐red (NDIR) CO₂ sensors to continuously measure gas concentrations in a beaver pond at Mer Bleue peatland (Canada); measurements were made between July and August 2007. Concentrations of CO₂ in the surface water (10 cm) reached 13 mg C l^?1 (epCO₂ 72), and 26 mg C l^?1 (epCO₂ 133) at depth (60 cm). The study also showed large diurnal fluctuations in dissolved CO₂ which ranged in amplitude from ～1·6 mg C l^?1 at 10 cm to ～0·2 mg C l^?1 at 60 cm depth. CH₄ concentration and supersaturation (epCH₄) measured using headspace analysis averaged 1·47 mg C l^?1 and 3252, respectively; diurnal cycling was also evident in CH₄ concentrations. Mean estimated evasion rates of CO₂ and CH₄ over the summer period were 44·92 ± 7·86 and 0·44 ± 0·25 µg C m^?2s^?1, respectively. Open water at Mer Bleue is a significant summer hotspot for greenhouse gas emissions within the catchment. Our results suggest that CO₂ concentrations during the summer in beaver ponds at Mer Bleue are strongly influenced by biological processes within the water column involving aquatic plants and algae (in situ photosynthesis and respiration). In terms of carbon cycling, soil‐stream connectivity at this time of year is therefore relatively weak. Copyright © 2008 John Wiley & Sons, Ltd.     

Carbon monoxide on the primitive earth

The reaction of CO + OH^? in aqueous solution to give formate was studied as a carbon monoxide sink on the primitive earth and in the present ocean. The reaction is first order in OH^? and first order in the molar CO concentration. The second order rate constant is given by log k(M^?1hr^?1) = 15.83?4886/T between 25°C and 60°C. Using the solubility of CO in sea water, and assuming a pH of 8 for a primitive ocean of the present size, the halflife of CO in the atmosphere is calculated to be 12 × 10⁶ yr at 0°C and 5.5 × 10⁴ yr at 25°C.Three other CO sinks would have been important in the primitive atmosphere: CO + H₂ → H₂CO driven by various energy sources, CO + OH → CO₂ + H, and the Fischer-Tropsch reaction of CO + H₂ → hydrocarbons, etc. It is concluded that the lifetime of a CO atmosphere would have been very short on the geological time scale although the relative importance of these four CO sinks is difficult to estimate.The CO + OH^? reaction to give formate is a very minor CO sink on the earth at the present time.     

Modification of “Pressed” Atmospheres in Active Regions of Ultracool Stars

Ultracool stars usually have active regions, which is confirmed by their high-power radiofrequency emission modulated by the star axial rotation. The interpretation of this emission is commonly based on the electron cyclotron maser mechanism realized in the active regions. A plasma mechanism of radiofrequency emission is not considered, because ultracool star atmospheres are tightly “pressed” against the star surface, and the plasma frequency is much lower than the electron gyrofrequency (f_L ? f_B) at the coronal levels. This paper explores active regions of ultracool stars for the possible existence of a system of coronal magnetic loops carrying electric current generated by photospheric convection. It is shown that current dissipation induces a temperature increase inside the loops to about 10⁷ K, which causes an increase in the scale of height of the inhomogeneous atmosphere and, at the coronal levels, effectuates condition f_L ? f_B, at which the plasma mechanism of radiofrequency emission prevails over the electron cyclotron maser mechanism. The magnetic loop parameters, intensity of electric currents generated by the photospheric convection, and efficiency of plasma heating inside the magnetic loops are evaluated on the example of the brown dwarf TVLM513-46546. The scale of the height of the modified atmosphere, which appears to be comparable to the star radius, is calculated; it is shown that the soft X-ray flow created by the hot modified atmosphere inside a coronal magnetic loop is about equal to that observed for brown dwarf TVLM513-46546.     

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.