Fluxes of high- versus low-temperature water-rock interactions in aerial volcanic areas: Example from the Kamchatka Peninsula, Russia

Volcanic areas play a key role in the input of elements into the ocean and in the regulation of the geological carbon cycle. The aim of this study is to investigate the budget of silicate weathering in an active volcanic area. We compared the fluxes of the two major weathering regimes occurring at low temperature in soils and at high temperature in the active volcanic arc of Kamchatka, respectively. The volcanic activity, by inducing geothermal circulation and releasing gases to the surface, produces extreme conditions in which intense water-rock interactions occur and may have a strong impact on the weathering budgets. Our results show that the chemical composition of the Kamchatka river water is controlled by surface low-temperature weathering, atmospheric input and, in some limited cases, strongly imprinted by high-temperature water-rock reactions. We have determined the contribution of each source and calculated the rates of CO₂ consumption and chemical weathering resulting from low and high-temperature water/rock interactions. The weathering rates (between 7 and 13.7 t/km²/yr for cations only) and atmospheric CO₂ consumption rates (∼0.33-0.46 × 10⁶ mol/km²/yr for Kamchatka River) due to rock weathering in soils (low-temperature) are entirely consistent with the previously published global weathering laws relating weathering rates of basalts with runoff and temperature. In the Kamchatka River, CO₂ consumption derived from hydrothermal activity represents about 11% of the total HCO₃ flux exported by the river. The high-temperature weathering process explains 25% of the total cationic weathering rate in the Kamchatka River. Although in the rivers non-affected by hydrothermal activity, the main weathering agent is carbonic acid (reflected in the abundance of in rivers), in the region most impacted by hydrothermalism, the protons responsible for minerals dissolution are provided not only by carbonic acid, but also by sulphuric and hydrochloric acid. A clear increase of weathering rates in rivers impacted by sulphuric acid can be observed. In the Kamchatka River, 19% of cations are released by hydrothermal acids or the oxidative weathering of sulphur minerals.Our results emphasise the important impact of both low and high-temperature weathering of volcanic rocks on global weathering fluxes to the ocean. Our results also show that besides carbonic acid derived from atmospheric CO₂, hydrochloric acid and especially sulphuric acid are important weathering agents. Clearly, sulphuric acid, with hydrothermal activity, are key parameters that cause first-order increases of the chemical weathering rates in volcanic areas. In these areas, accurate determination of weathering budgets in volcanic area will require to better quantify sulphuric acid impact.     

Atmospheric CO2 consumption by chemical weathering in North America

CO₂ consumption by chemical weathering is an integral part of the boundless carbon cycle, whose spatial patterns and controlling factors on continental scale are still not fully understood. A dataset of 338 river catchments throughout North America was used to empirically identify predictors of bicarbonate fluxes by chemical weathering and interpret the underlying controlling factors. Detailed analysis of major ion ratios enables distinction of the contributions of silicate and carbonate weathering and thus quantifying CO₂ consumption. Extrapolation of the identified empirical model equations to North America allows the analysis of the spatial patterns of the CO₂ consumption by chemical weathering.Runoff, lithology and land cover were identified as the major predictors of the riverine bicarbonate fluxes and the associated CO₂ consumption. Other influence factors, e.g. temperature, could not be established in the models. Of the distinguished land cover classes, artificial surfaces, dominated by urban areas, increase bicarbonate fluxes most, followed by shrubs, grasslands, managed lands, and forests. The extrapolation results in an average specific bicarbonate flux of 0.3 Mmol km⁻² a⁻¹ by chemical weathering in North America, of which 64% originates from atmospheric CO₂, and 36% from carbonate mineral dissolution. Chemical weathering in North America thus consumes 50 Mt atmospheric CO₂-C per year. About half of that originates from 10% of the area of North America.The estimated strength of individual predictors differs from previous studies. This highlights the need for a globally representative set of regionally calibrated models of CO₂ consumption by chemical weathering, which apply very detailed spatial data to resolve the heterogeneity of earth surface processes.     

CO<Subscript>2</Subscript> Air–Sea Exchange due to Calcium Carbonate and Organic Matter Storage,and its Implications for the Global Carbon Cycle

Release of CO₂ from surface ocean water owing to precipitation of CaCO₃ and the imbalance between biological production of organic matter and its respiration, and their net removal from surface water to sedimentary storage was studied by means of a quotient θ = (CO₂ flux to the atmosphere)/(CaCO₃ precipitated). θ depends not only on water temperature and atmospheric CO₂ concentration but also on the CaCO₃ and organic carbon masses formed. In CO₂ generation by CaCO₃ precipitation, θ varies from a fraction of 0.44 to 0.79, increasing with decreasing temperature (25 to 5°C), increasing atmospheric CO₂ concentration (195–375 ppmv), and increasing CaCO₃ precipitated mass (up to 45% of the initial DIC concentration in surface water). Primary production and net storage of organic carbon counteracts the CO₂ production by carbonate precipitation and it results in lower CO₂ emissions from the surface layer. When atmospheric CO₂ increases due to the ocean-to-atmosphere flux rather than remaining constant, the amount of CO₂ transferred is a non-linear function of the surface layer thickness because of the back-pressure of the rising atmospheric CO₂. For a surface ocean layer approximated by a 50-m-thick euphotic zone that receives input of inorganic and organic carbon from land, the calculated CO₂ flux to the atmosphere is a function of the CaCO₃ and C_org net storage rates. In general, the carbonate storage rate has been greater than that of organic carbon. The CO₂ flux near the Last Glacial Maximum is 17 to 7×10¹² mol/yr (0.2–0.08 Gt C/yr), reflecting the range of organic carbon storage rates in sediments, and for pre-industrial time it is 38–42×10¹² mol/yr (0.46–0.50 Gt C/yr). Within the imbalanced global carbon cycle, our estimates indicate that prior to anthropogenic emissions of CO₂ to the atmosphere the land organic reservoir was gaining carbon and the surface ocean was losing carbon, calcium, and total alkalinity owing to the CaCO₃ storage and consequent emission of CO₂. These results are in agreement with the conclusions of a number of other investigators. As the CO₂ uptake in mineral weathering is a major flux in the global carbon cycle, the CO₂ weathering pathway that originates in the CO₂ produced by remineralization of soil humus rather than by direct uptake from the atmosphere may reduce the relatively large imbalances of the atmosphere and land organic reservoir at 10²–10⁴-year time scales.     

Chemical weathering, river geochemistry and atmospheric carbon fluxes from volcanic and ultramafic regions on Luzon Island, the Philippines

We investigated rates of chemical weathering of volcanic and ophiolitic rocks on Luzon Island, the Philippines. Luzon has a tropical climate and is volcanically and tectonically very active, all factors that should enhance chemical weathering. Seventy-five rivers and streams (10 draining ophiolites, 65 draining volcanic bedrock) and two volcanic hot springs were sampled and analyzed for major elements, alkalinity and ⁸⁷Sr/⁸⁶Sr. Cationic fluxes from the volcanic basins are dominated by Ca²⁺ and Mg²⁺ and dissolved silica concentrations are high (500-1900 μM). Silica concentrations in streams draining ophiolites are lower (400-900 μM), and the cationic charge is mostly Mg²⁺. The areally weighted average CO₂ export flux from our study area is 3.89 ± 0.21 × 10⁶ mol/km²/yr, or 5.99 ± 0.64 × 10⁶ mol/km²/yr from ophiolites and 3.58 ± 0.23 × 10⁶ mol/km²/yr from volcanic areas (uncertainty given as ±1 standard error, s.e.). This is ∼6-10 times higher than the current best estimate of areally averaged global CO₂ export by basalt chemical weathering and ∼2-3 times higher than the current best estimate of CO₂ export by basalt chemical weathering in the tropics. Extrapolating our findings to all tropical arcs, we estimate that around one tenth of all atmospheric carbon exported via silicate weathering to the oceans annually is processed in these environments, which amount to ∼1% of the global exorheic drainage area. Chemical weathering of volcanic terranes in the tropics appears to make a disproportionately large impact on the long-term carbon cycle.     

Carbon river fluxes and weathering CO2 consumption in the Congo and Amazon river basins

Data on carbon river fluxes recently obtained by the authors for the Congo basin within the framework of the PIRAT Program (INSU-CNRS/ORSTOM) are compared with results previously obtained for the Amazon basin. A special interest is devoted to the bicarbonate river fluxes and to their relationships with river discharges. The flux of atmospheric and soil CO₂ consumed by rock weathering is estimated to be 3.1 × 10⁵ and 0.5 × 10⁵ moles/a/km² respectively for the Amazon and the Congo basin. These CO₂ fluxes represent, respectively, 67.4% and 74.7% of the total bicarbonate river fluxes. A comparison to other large river basins shows that this contribution is directly related to the proportion of carbonate rock areas. A transfer function between the weathering CO₂ flux and the river discharge is calculated for each basin and allows the reconstitution of the variations of this flux using the river discharge fluctuations during the last century. These interannual CO₂ fluctuations present average increasing trends of 10% for Amazon basin and only 0.7% for the Congo basin during the last century.     

中国大陆新生代典型火山区温室气体释放的规模及其成因

火山活动能够将地球深部的碳输送到大气圈,是地质碳排放和深部碳循环的重要形式.火山作用不仅在喷发期能够释放大量温室气体,而且在休眠期也能释放巨量的温室气体.在全球变暖的背景下,定量化地研究火山活动对大气圈温室气体含量增加的贡献具有至关重要的意义.本文利用密闭气室法等该领域国际先进的测试技术,测量并计算了长白山、腾冲、五大连池及青藏高原南部的羊八井等典型火山区的温室气体释放规模.结果显示,我国大陆新生代典型火山区向大气圈输送的温室气体总通量约为8.13×10⁶t·a^-1,接近10⁷t·a^-1级别,相当于全球火山活动导致的温室气体(主要为CO₂)释放总量的6%左右.太平洋构造域火山区的温室气体在释放通量与总量方面均低于特提斯构造域,并且太平洋构造域火山气体的地壳混染程度较低,显示出大洋俯冲带与大陆俯冲带火山区温室气体释放的成因差异.     

Modern carbon burial in Lake Qinghai,China

The quantification of carbon burial in lake sediments, and carbon fluxes derived from different origins are crucial to understand modern lacustrine carbon budgets, and to assess the role of lakes in the global carbon cycle. In this study, we estimated carbon burial in the sediment of Lake Qinghai, the largest inland lake in China, and the carbon fluxes derived from different origins. We find that: (1) The organic carbon burial rate in lake sediment is approximately 7.23 g m⁻² a⁻¹, which is comparable to rates documented in many large lakes worldwide. We determined that the flux of riverine particulate organic carbon (POC) is approximately 10 times higher than that of dissolved organic carbon (DOC). Organic matter in lake sediments is primarily derived from POC in lake water, of which approximately 80% is of terrestrial origin. (2) The inorganic carbon burial rate in lake sediment is slightly higher than that of organic carbon. The flux of riverine dissolved inorganic carbon (DIC) is approximately 20 times that of DOC, and more than 70% of the riverine DIC is drawn directly and/or indirectly from atmospheric CO₂. (3) Both DIC and DOC are concentrated in lake water, suggesting that the lake serves as a sink for both organic and inorganic carbon over long term timescales. (4) Our analysis suggests that the carbon burial rates in Lake Qinghai would be much higher in warmer climatic periods than in cold ones, implying a growing role in the global carbon cycle under a continued global warming scenario.     

Impact of nitrogenous fertilizers on carbonate dissolution in small agricultural catchments: Implications for weathering CO2 uptake at regional and global scales

The goal of this study was to highlight the occurrence of an additional proton-promoted weathering pathway of carbonate rocks in agricultural areas where N-fertilizers are extensively spread, and to estimate its consequences on riverine alkalinity and uptake of CO₂ by weathering. We surveyed 25 small streams in the calcareous molassic Gascogne area located in the Garonne river basin (south-western France) that drain cultivated or forested catchments for their major element compositions during different hydrologic periods. Among these catchments, the Hay and the Montoussé, two experimental catchments, were monitored on a weekly basis. Studies in the literature from other small carbonate catchments in Europe were dissected in the same way. In areas of intensive agriculture, the molar ratio (Ca + Mg)/HCO₃ in surface waters is significantly higher (0.7 on average) than in areas of low anthropogenic pressure (0.5). This corresponds to a decrease in riverine alkalinity, which can reach 80% during storm events. This relative loss of alkalinity correlates well with the content in surface waters. In cultivated areas, the contribution of atmospheric/soil CO₂ to the total riverine alkalinity (CO_{2 ATM-SOIL}/HCO₃) is less than 50% (expected value for carbonate basins), and it decreases when the nitrate concentration increases. This loss of alkalinity can be attributed to the substitution of carbonic acid (natural weathering pathway) by protons produced by nitrification of N-fertilizers (anthropogenic weathering pathway) occurring in soils during carbonate dissolution. As a consequence of these processes, the alkalinity over the last 30 years shows a decreasing trend in the Save river (one of the main Garonne river tributaries, draining an agricultural catchment), while the nitrate and calcium plus magnesium contents are increasing.We estimated that the contribution of atmospheric/soil CO₂ to riverine alkalinity decreased by about 7-17% on average for all the studied catchments. Using these values, the deficit of CO₂ uptake can be estimated as up to 0.22-0.53 and 12-29 Tg¹ yr⁻¹ CO₂ on a country scale (France) and a global scale, respectively. These losses represent up to 5.7-13.4% and only 1.6-3.8% of the total CO₂ flux naturally consumed by carbonate dissolution, for France and on a global scale, respectively. Nevertheless, this loss of alkalinity relative to the Ca + Mg content relates to carbonate weathering by protons from N-fertilizers nitrification, which is a net source of CO₂ for the atmosphere. This anthropogenic CO₂ source is not negligible since it could reach 6-15% of CO₂ uptake by natural silicate weathering and could consequently partly counterbalance this natural CO₂ sink.     

Land–sea carbon and nutrient fluxes and coastal ocean CO2 exchange and acidification: Past,present, and future

Epochs of changing atmospheric CO₂ and seawater CO₂–carbonic acid system chemistry and acidification have occurred during the Phanerozoic at various time scales. On the longer geologic time scale, as sea level rose and fell and continental free board decreased and increased, respectively, the riverine fluxes of Ca, Mg, DIC, and total alkalinity to the coastal ocean varied and helped regulate the C chemistry of seawater, but nevertheless there were major epochs of ocean acidification (OA). On the shorter glacial–interglacial time scale from the Last Glacial Maximum (LGM) to late preindustrial time, riverine fluxes of DIC, total alkalinity, and N and P nutrients increased and along with rising sea level, atmospheric PCO₂ and temperature led, among other changes, to a slightly deceasing pH of coastal and open ocean waters, and to increasing net ecosystem calcification and decreasing net heterotrophy in coastal ocean waters. From late preindustrial time to the present and projected into the 21st century, human activities, such as fossil fuel and land-use emissions of CO₂ to the atmosphere, increasing application of N and P nutrient subsidies and combustion N to the landscape, and sewage discharges of C, N, P have led, and will continue to lead, to significant modifications of coastal ocean waters. The changes include a rapid decline in pH and carbonate saturation state (modern problem of ocean acidification), a shift toward dissolution of carbonate substrates exceeding production, potentially leading to the “demise” of the coral reefs, reversal of the direction of the sea-to-air flux of CO₂ and enhanced biological production and burial of organic C, a small sink of anthropogenic CO₂, accompanied by a continuous trend toward increasing autotrophy in coastal waters.     

CO<Subscript>2</Subscript> flux variation and its contribution area in the debris-covered area of Koxkar Glacier,Mt. Tianshan in China

During the formation and development of glacial meltwater runoff, hydrochemical erosion is abundant, especially the hydrolysis of K/Na feldspar and carbonates, which can consume H⁺ in the water, promote the formation of bicarbonate by dissolving atmospheric CO₂, and affect the regional carbon cycle. From July 21, 2015, to July 18, 2017, the CO₂ concentration and flux were observed by the eddy covariance (EC) method in the relatively flat and open moraine cover area of Koxkar Glacier in western Mt. Tianshan, China. We found that: (1) atmospheric CO₂ fluxes ranged from ??408.95 to 81.58 mmol m^?2 day^?1 (average ? 58.68 mmol m^?2 day^?1), suggesting that the study area is a significant carbon sink, (2) the CO₂ flux footprint contribution areas were primarily within 150 m of the EC station, averaging total contribution rates of 93.30%, 91.39%, and 90.17% of the CO₂ flux in the snow accumulation, snow melting, and glacial melting periods, respectively. Therefore, the contribution areas with significant influences on CO₂ flux observed at EC stations were concentrated, demonstrating that grassland CO₂ flux around the glaciers had little effect at the EC stations, (3) in the predominant wind direction, under stable daytime atmospheric stratification, the measurement of CO₂ flux, as interpreted by the Agroscope Reckenholz Tanikon footprint tool, was 79.09% ± 1.84% in the contribution area. This was slightly more than seen at night, but significantly lower than the average under unstable atmospheric stratification across the three periods of interest (89%). The average distance of the farthest point of the flux footprint under steady state atmospheric conditions was 202.61?±?69.33 m, markedly greater than that under non-steady state conditions (68.55?±?10.34 m). This also indicates that the CO₂ flux observed using EC was affected primarily by hydrochemical erosion reactions in the glacier area, (4) a good negative correlation was found between net glacier exchange (NGE) of CO₂ and air temperature on precipitation-free days. Strong ice and snow ablation could promote hydrochemical reactions of soluble substances in the debris area and accelerated sinking of atmospheric CO₂. Precipitation events might reduce snow and ice melting, driven by reduced regional temperatures. However, a connection between NGE and precipitation, when less than 8.8 mm per day, was not obvious. When precipitation was greater than 8.8 mm per day, NGE decreased with increasing precipitation, (5) graphically, the slope of NGE, related to daily runoff, followed a trend: snow melting period?>?snow accumulation period?>?early glacial ablation period?>?late glacier ablation period?>?dramatic glacier ablation period. The slope was relatively large during snow melting, likely because of CO₂ sinking caused by water–rock interactions. The chemical reaction during elution in the snow layer might also promote atmospheric CO₂ drawdown. At the same time, the damping effect of snow cover and the almost-closed glacier hydrographic channel inhibited the formation of regional runoff, possibly providing sufficient time for the chemical reaction, thus promoting further CO₂ drawdown.     

The control of Phanerozoic atmosphere and seawater composition by basalt–seawater exchange reactions

We present results from a long term geochemical cycling model, with a focus on the sensitivity of atmospheric carbon dioxide, oxygen, and the major element composition of seawater to seafloor spreading rates. This model incorporates rock weathering, basalt–seawater exchange reactions, and the formation and destruction of chemical sediments and organic matter. Hydrothermal reactions between seafloor and seawater involving calcium, magnesium, sodium, potassium, sulfate and carbon are the high temperature counterparts to low temperature redox, weathering, precipitation and diagenetic reactions. A major source of uncertainty is the extent to which these exchange fluxes are controlled by seafloor spreading rate. In addition, the return fluxes of these components to the atmospheric and primary silicate reservoirs reflect not only the overall rates of subduction and metamorphism, but the distribution of the overlying sedimentary burden and authigenic minerals formed during basalt alteration as well. In particular, we show how the stoichiometry of exchange fluxes (Mg/Ca and SO₄/Ca) may buffer atmospheric CO₂ and O₂ concentrations.     

Climatic and lithologic controls on the temporal and spatial variability of CO2 consumption via chemical weathering: An example from the Australian Victorian Alps

A detailed geochemical study on river waters of the Australian Victorian Alps was carried out to determine: (i) the relative significance of silicate, carbonate, evaporite and sulfide weathering in controlling the major ion composition and; (ii) the factors regulating seasonal and spatial variations of CO₂ consumption via silicate weathering in the catchments. Major ion chemistry implies that solutes are largely derived from evaporation of precipitation and chemical weathering of carbonate and silicate lithologies. The input of solutes from rock weathering was determined by calculating the contribution of halite dissolution and atmospheric inputs using local rain and snow samples. Despite the lack of carbonate outcrops in the study area and waters being undersaturated with respect to calcite, the dissolution of vein calcite accounts for up to 67% of the total dissolved cations, generating up to 90% of dissolved Ca and 97% of Mg. Dissolved sulfate has δ³⁴S values of 16 to 20‰_CDT, indicating that it is derived predominantly from atmospheric deposition and minor gypsum weathering and not from bacterial reduction of FeS₂. This militates against sulphuric acid weathering in Victorian rivers. Ratios of Si vs. the atmospheric corrected Na and K concentrations range from ~ 1.1 to ~ 4.3, suggesting incongruent weathering from plagioclase to smectite, kaolinite and gibbsite.Estimated long-term average CO₂ fluxes from silicate weathering range from ~ 0.012 × 10⁶ to 0.039 × 10⁶ mol/km²/yr with the highest values in rivers draining the basement outcrops rather than sedimentary rocks. This is about one order of magnitude below the global average which is due to low relief, and the arid climate in that region. Time series measurements show that exposure to lithology, high physical erosion and long water–rock contact times dominate CO₂ consumption fluxes via silicate weathering, while variations in water temperature are not overriding parameters controlling chemical weathering. Because the atmospheric corrected concentrations of Na, K and Mg act non-conservative in Victorian rivers the parameterizations of weathering processes, and net CO₂ consumption rates in particular, based on major ion abundances, should be treated with skepticism.     

Chemistry of the heavily urbanized Bagmati River system in Kathmandu Valley, Nepal: export of organic matter, nutrients, major ions, silica, and metals

Water quality in less-developed countries is often subject to substantial degradation, but is rarely studied in a systematic way. The concentration and flux of major ions, carbon, nitrogen, silicon, and trace metals in the heavily urbanized Bagmati River within Kathmandu Valley, Nepal, are reported. The concentrations of all chemical species increased with distance downstream with the exceptions of protons and nitrate, and showed strong relationships with population density adjacent to the river. Total dissolved nitrogen (TDN), dominated by NH₄, was found in high concentrations along the Bagmati drainage system. The export of dissolved organic carbon (DOC) and TDN were 23 and 33 tons km^?2 year^?1, respectively, at the outlet point of the Kathmandu Valley, much higher than in relatively undeveloped watersheds. The cationic and silica fluxes were 106 and 18 tons km^?2 year^?1 at the outlet of the Bagmati within Kathmandu Valley, and 36 and 32 tons km^?2 year^?1 from the relatively pristine headwater area. The difference between headwaters and the urban site suggests that the apparent weathering flux is three times higher than the actual weathering rate in the heavily urbanized Bagmati basin. Fluxes of cations and silica are above the world average, as well as fluxes from densely populated North American and European watersheds. End-member composition of anthropogenic sources like sewage or agricultural runoff is needed to understand the drivers of this high rate of apparent weathering.     

Impact of Carbonate Precipitation on Riverine Inorganic Carbon Mass Transport from a Mid-continent, Forested Watershed

Physiochemical controls on the carbonate geochemistry of large river systems are important regulators of carbon exchange between terrestrial and marine reservoirs on human time scales. Although many studies have focused on large-scale river carbon fluxes, there are few investigations of mechanistic aspects of carbonate mass balance and transport at the catchment scale. We determined elemental and carbonate geochemistry and mass balances for net carbonate dissolution fluxes from the forested, mid-latitude Huron River watershed, established on carbonate-rich unconfined glacial drift aquifers. Shallow groundwaters are near equilibrium with respect to calcite at pCO₂ values up to 25 times atmospheric values. Surface waters are largely groundwater fed and exhibit chemical evolution due to CO₂ degassing, carbonate precipitation in lakes and wetlands, and anthropogenic introduction of road salts (NaCl and CaCl₂). Because the source groundwater Mg²⁺/HCO₃ ^? ratio is fairly constant, this parameter permits mass balances to be made between carbonate dissolution and back precipitation after groundwater discharge. Typically, precipitation does not occur until IAP/K calcite values exceed 10 times supersaturation. Stream chemistry changes little thereafter even though streams remain highly supersaturated for calcite. Our data taken together with historical United States Geological Survey (USGS) data show that alkalinity losses to carbonate precipitation are most significant during periods of lowest discharge. Thus, on an annual basis, the large carbon flux from carbonate dissolution in soil zones is only decreased by a relatively small amount by the back precipitation of calcium carbonate.     

Direct effect of ice sheets on terrestrial bicarbonate, sulphate and base cation fluxes during the last glacial cycle: minimal impact on atmospheric CO2 concentrations

Chemical erosion in glacial environments is normally a consequence of chemical weathering reactions dominated by sulphide oxidation linked to carbonate dissolution and the carbonation of carbonates and silicates. Solute fluxes from small valley glaciers are usually a linear function of discharge. Representative glacial solute concentrations can be derived from the linear association of solute flux with discharge. These representative glacial concentrations of the major ions are 25% of those in global river water. A 3-D thermomechanically coupled model of the growth and decay of the Northern Hemisphere ice sheets was used to simulate glacial runoff at 100-year time steps during the last glacial cycle (130 ka to the present). The glacially derived fluxes of major cations, anions and Si over the glaciation were estimated from the product of the glacial runoff and the representative glacial concentration. A second estimate was obtained from the product of the glacial runoff and a realistic upper limit for glacial solute concentrations derived from theoretical considerations. The fluxes over the last glacial cycle are usually less than a few percent of current riverine solute fluxes to the oceans. The glacial fluxes were used to provide input to an oceanic carbon cycling model that also calculates changes in atmospheric CO₂. The potential change in atmospheric CO₂ concentrations over the last glacial cycle that arise from perturbations in glacial solute fluxes are insignificant, being <1 ppm.     

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.     

Human perturbations on the global biogeochemical cycles of coupled Si–C and responses of terrestrial processes and the coastal ocean

We present a model of the global biogeochemical cycle of silicon (Si) that emphasizes its linkages to the carbon cycle and temperature. The Si cycle is a crucial part of global nutrient biogeochemistry regulating long-term atmospheric CO₂ concentrations due to silicate mineral weathering reactions involving the uptake of atmospheric CO₂ and production of riverine dissolved silica, cations and bicarbonate. In addition and importantly, the Si cycle is strongly coupled to the other nutrient cycles of N, P, and Fe; hence siliceous organisms represent a significant fraction of global primary productivity and biomass. Human perturbations involving land-use changes, burning of fossil fuel, and inorganic N and P fertilization have greatly altered the terrestrial Si cycle, changing the river discharge of Si and consequently impacting marine primary productivity primarily in coastal ocean waters.     

腾冲新生代火山区温泉CO2气体排放通量研究

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

Accumulation of mantle gases in a permanently stratified volcanic lake (Lac Pavin,France)

Lac Pavin is a volcanic crater lake in the Massif Central (France), characterized by a permanent vertical density stratification resulting from a strong and persistent chemocline between about 60 and 70 m depth. The deep water below the chemocline forms the monimolimnion, in which most dissolved ions as well as helium, carbon dioxide, and methane are strongly enriched. The ³He/⁴He isotope ratio of the excess helium is (9.09 ± 0.01) · 10⁻⁶, or (6.57 ± 0.01) R_a. These findings clearly indicate a flux of mantle-derived magmatic gases into the monimolimnion.In order to derive the fluxes of magmatic volatiles into Lac Pavin, it is essential to understand the hydrologic characteristics of the lake. Previously published two-box models have assumed groundwater input at the lake bottom, a short residence time in the monimolimnion, and biogenic origin of the CO₂. We propose an alternative model with a flux of magmatic gases, but not of water, into the monimolimnion, and a weak diffusive coupling between the monimolimnion and the overlying mixolimnion which leads to a long deep-water residence time (≈ 70 yr). We reassess the carbon budget of the lake and conclude that the major part of the accumulated CO₂ in the monimolimnion is of magmatic origin. From the model-derived water exchange rates, we calculated a mantle ⁴He flux of (6 ± 2) · 10¹¹ atoms m⁻² s⁻¹. This value lies near the lower end of the range found in comparable volcanic lakes. The flux of magmatic CO₂ is estimated as (1.2 ± 0.4) · 10⁻⁷ mol m⁻² s⁻¹, which is also comparatively low. The monimolimnion appears to be in steady state with respect to these fluxes, therefore no further, potentially hazardous, accumulation of CO₂ takes place.     

Coastal Ocean Last Glacial Maximum to 2100 CO2-Carbonic Acid-Carbonate System: A Modeling Approach

Using coupled terrestrial and coastal zone models, we investigated the impacts of deglaciation and anthropogenic inputs on the CO₂–H₂O–CaCO₃ system in global coastal ocean waters from the Last Glacial Maximum (LGM: 18,000 year BP) to the year 2100. With rising sea level and atmospheric CO₂, the carbonate system of coastal ocean water changed significantly. We find that 6 × 10¹² metric tons of carbon were emitted from the coastal ocean, growing due to the sea level rise, from the LGM to late preindustrial time (1700 AD) because of net heterotrophy and calcification processes. This carbon came to reside in the atmosphere and in the growing vegetation on land and in uptake of atmospheric CO₂ through the weathering of rocks on land. It appears that carbonate accumulation, mainly, but not exclusively, in coral reefs from the LGM to late preindustrial time could account for about 24 ppmv of the 100 ppmv rise in atmospheric CO₂, lending some support to the “coral reef hypothesis”. In addition, the global coastal ocean is now, or soon will be, a sink of atmospheric CO₂. The temperature rise of 4–5°C since the LGM led to increased weathering rates of inorganic and organic materials on land and enhanced riverine fluxes of total C, N, and P to the coastal ocean of 68%, 108%, and 97%, respectively, from the LGM to late preindustrial time. During the Anthropocene, these trends have been exacerbated owing to rising atmospheric CO₂, due to fossil fuel combustion and land-use practices, other human activities, and rising global temperatures. River fluxes of total reactive C, N, and P are projected to increase from late preindustrial time to the year 2100 by 150%, 380%, and 257%, respectively, modifying significantly the behavior of these element cycles in the coastal ocean, particularly in proximal environments. Despite the fact that the global shoal water carbonate mass has grown extensively since the LGM, the pH_T (pH values on the total proton scale) of global coastal waters has decreased from ~8.35 to ~8.18 and the carbonate ion concentration declined by ~19% from the LGM to late preindustrial time. The latter represents a rate of decline of about 0.028 μmol CO₃ ^2? per decade. In comparison, the decrease in coastal water pH_T from the year 1900 to 2000 was about 8.18–8.08 and is projected to decrease further from about 8.08 to 7.85 between 2000 and 2100, according to the IS92a business-as-usual scenario of CO₂ emissions. Over these 200 years, the carbonate ion concentration will fall by ~120 μmol kg^?1 or 6 μmol kg^?1 per decade. This decadal rate of decline of the carbonate ion concentration in the Anthropocene is 214 times the average rate of decline for the entire Holocene. Hence, when viewed against the millennial to several millennial timescale of geologic change in the coastal ocean marine carbon system, one can easily appreciate why ocean acidification is the “other CO₂ problem”.