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1.
This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg–1 pH of 7.6 and p(CO2) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg–1, pH of 7.70 and p(CO2) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO2) up to 5.6 times the atmospheric P(CO2). 相似文献
2.
This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg?1 pH of 7.6 and p(CO2) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg?1, pH of 7.70 and p(CO2) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO2) up to 5.6 times the atmospheric P(CO2). 相似文献
3.
It is recognized that karst processes are actively involved in the current global carbon cycle based on twenty years research, and the carbon sink occurred in karst processes is possibly an important part of “missing sink” in global carbon cycle. In this paper, an overview is given on karst carbon cycle research, and influence factors, formed carbon pools (background carbon sink) and sink increase potentials of current karst carbon cycle are analyzed. Carbonate weathering could contribute to the imbalance item (BIM) and land use change item (ELUC) in the global carbon cycle model, owing to its uptake of both atmospheric CO2 (carbon sink effect) and CO2 produced by soil respiration (carbon source reduction effect). Karst carbon sink includes inorganic carbon sink resulted from hydrogeochemical process and organic carbon sink generated by aquatic photosynthetic DIC conversion, forming relatively stable river (reservoir) water body or sediment carbon sink. The sizes of both sinks are controlled by terrestrial ecosystems and aquatic ecosystems, respectively. Desertification rehabilitation and carbon sequestration by aquatic plants are two effective ways to increase the carbon sink in karst area. It is estimated that the rate of carbon sink is at least 381 000 t CO2/a with vegetation restoration and afforestation in southwest China karst area, while the annual organic carbon sink generated by aquatic photosynthesis is about 84 200 t C in the Pearl River Basin. The development of a soil CO2 based model for assessment of regional dissolution intensity will help to improve the estimation accuracy of carbon sink increase and potential, thus provide a more clear and efficient karst sink increase scheme and pathway to achieve the goals of “double carbon”. With the deep investigation on karst carbon cycle, mechanism and carbon sink effect, and the improvement of watershed carbon sink measurement methods and regional sink increase evaluation approaches. Karst carbon sink is expected to be included in the list of atmospheric CO2 sources/sinks of the global carbon budget in the near future. 相似文献
4.
It is widely accepted that chemical weathering of Ca–silicate rocks could potentially control long-term climate change by providing feedback interaction with atmospheric CO2 drawdown by means of precipitation of carbonate, and that in contrast weathering of carbonate rocks has not an equivalent impact because all of the CO2 consumed in the weathering process is returned to the atmosphere by the comparatively rapid precipitation of carbonates in the oceans. Here, it is shown that the rapid kinetics of carbonate dissolution and the importance of small amounts of carbonate minerals in controlling the dissolved inorganic C (DIC) of silicate watersheds, coupled with aquatic photosynthetic uptake of the weathering-related DIC and burial of some of the resulting organic C, suggest that the atmospheric CO2 sink from carbonate weathering may previously have been underestimated by a factor of about 3, amounting to 0.477 Pg C/a. This indicates that the contribution of silicate weathering to the atmospheric CO2 sink may be only 6%, while the other 94% is by carbonate weathering. Therefore, the atmospheric CO2 sink by carbonate weathering might be significant in controlling both the short-term and long-term climate changes. This questions the traditional point of view that only chemical weathering of Ca–silicate rocks potentially controls long-term climate change. 相似文献
5.
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. 相似文献
6.
《China Geology》2018,1(1):17-27
On the basis of proposing the existence of a karst carbon cycle and carbon sink at a watershed scale, this paper provides four pieces of evidence for the integration of geology and ecology during the carbon cycle processes in the karst dynamic system, and estimated the karst carbon sink effect using the methods of comparative monitoring of paired watersheds and the carbon stable isotope tracer technique. The results of the soil carbon cycle in Maocun, Guilin, showed that the soil carbon cycle in the karst area, the weathering and dissolution of carbonate rocks under the soil, resulted in a lower soil respiration of 25% in the karst area than in a non-karst area (sandstone and shale), and the carbon isotope results indicated that 13.46% of the heavy carbon of the limestone is involved in the soil carbon cycle. The comparative monitoring results in paired watersheds, suggesting that the HCO3- concentration in a karst spring is 10 times that of a rivulet in a non-karst area, while the concentration of inorganic carbon flux is 23.8 times. With both chemical stoichiometry and carbon stable isotopes, the proportion of carbon in karst springs derived from carbonate rocks was found to be 58.52% and 37.65% respectively. The comparison on carbon exchange and isotopes at the water-gas interface between the granite and carbonate rock basins in the Li River showed that the CO2 emission of the karst water is 10.92 times that of the allogenic water from the non-karst area, while the carbon isotope of HCO3- in karst water is lighter by 8.62‰. However, this does not mean that the karst water body has a larger carbon source effect. On the contrary, it means the karst water body has a greater karst carbon sink effect. When the karst subterranean stream in Zhaidi, Guilin, is exposed at the surface, carbon-rich karst water stimulated the growth of aquatic plants. The values of carbon stable isotopes in the same species of submerged plants gradually becomes heavier and heavier, and the 512 m flow process has a maximum range of 15.46‰. The calculation results showed that 12.52% of inorganic carbon is converted into organic carbon. According to the data that has been published, the global karst carbon sink flux was estimated to be 0.53-0.58 PgC/a, equivalent to 31.18%-34.41% of the global forest carbon sink flux. In the meanwhile, the karst carbon sink flux in China was calculated to be 0.051 PgC/a, accounting for 68% of its forest carbon sink flux. 相似文献
7.
我国南方岩溶区与北方黄土区都是巨大的碳库。碳酸盐的溶蚀及再结晶是两个碳库与大气ＣＯ２交换的重要过程。碳的区域平衡是评价化学风化消耗或逸散ＣＯ２的基础。岩溶区与黄土区在地球化学风化的环境背景、溶蚀过程、产物运移和归宿等差异很大。黄土区化学风化消耗大气ＣＯ２通量较岩溶区小。目前评价两类地区土壤与大气ＣＯ２的源汇关系尚不成熟,需要定量认识土壤ＣＯ２与下伏碳酸盐岩溶蚀或与下伏黄土次生碳酸盐化作用。岩溶区湖泊沉积物中有机质分解产生的ＨＣＯ３－制约外源及内生碳酸盐溶解和自生碳酸盐形成。 相似文献
8.
Cheng Zeng Vivian Gremaud Haitao Zeng Zaihua Liu Nico Goldscheider 《Environmental Earth Sciences》2012,65(8):2285-2297
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. 相似文献
9.
The hydrogeochemical and carbon isotope characteristics of the Krka River, Slovenia, were investigated to estimate the carbon transfer from the land ecosystem in the watershed. During the 3-year sampling period (2008–2010), temperature, pH, electrical conductivity, major ion content, dissolved inorganic carbon (DIC) and dissolved organic carbon content, and the isotopic composition of DIC (δ13CDIC) were monitored in the main stream of the Krka River and its tributaries. The major solute composition of analysed waters is dominated by an input of HCO3 ?, Ca2+ and Mg2+ originating from carbonate dissolution. The Mg2+/Ca2+ and Mg2+/HCO3 ? molar ratio values ranging from 0.24 to 0.71 and 0.05 to 0.30, respectively, indicate a high degree of dolomite dissolution relative to calcite. Dissolved CO2 concentrations in the river were up to tenfold supersaturated relative to the atmosphere, resulting in supersaturation with respect to calcite and degassing of CO2 downstream. The δ13C values in river water range from ?15.6 to ?9.4 ‰ and are controlled by the input of tributaries, exchange with atmospheric CO2, degradation of organic matter, and dissolution of carbonates. The mass balance calculations for riverine DIC suggest that the contribution from carbonate dissolution and degradation of organic matter have major influence, whereas the exchange with atmospheric CO2 has minor influence on the inorganic carbon pool in the Krka River. 相似文献
10.
《Chemie der Erde / Geochemistry》2017,77(2):267-279
Carbon capture and sequestration (CCS) is one of the important options available for partially stemming greenhouse gas emissions from large point sources. The possibility of leaking from deep storage needs to be addressed. The Wadi Namaleh area in southern Jordan provides an interesting case study of how excess CO2 can be trapped in the form of carbonates in the near surface, even when the local geology is not obviously conducive for such a process.Carbonate veins are formed in surface alteration zones of rhyolite host rock in this arid region. The alteration zones are limited to areas where surface soil or colluvium are present. Oxygen, deuterium and carbon isotopes of the carbonates and near-surface ground water in the area suggest that the source of carbon is deep seated CO2, and that the carbonate precipitated in local meteoric water under ambient temperature conditions. Analysis of strontium in the carbonate, fresh rhyolite and altered host shows that the source for calcium is aeolian. Trace elements show that metal and REE mobility are constrained to the alteration zone.Thus, interaction of H2O, CO2 and atmospheric wet and dry deposition lead to the formation of the clayey (montmorillonite) alteration zone. This zone acts to trap seeping CO2 and water, and thus produces conditions of progressively more efficient trapping of carbon dioxide by means of a positive feedback mechanism. Replication of these conditions in other areas will minimize CO2 leakage from man-made CCS sites. 相似文献
11.
To accurately predict future CO2 levels in the atmosphere, which is crucial in predicting global climate change, the sources and sinks of the atmospheric
CO2 and their change over time must be determined. In this paper, some typical cases are examined using published and unpublished
data. Firstly, the sensitivity of carbonate rock weathering (including the effects by both dissolution and reprecipitation
of carbonate) to the change of soil CO2 and runoff will be discussed, and then the net amount of CO2 removed from the atmosphere in the carbonate rock areas of mainland China and the world will be determined by the hydrochem-discharge
and carbonate-rock-tablet methods, to obtain an estimate of the contribution of carbonate rock weathering to the atmospheric
CO2 sink. These contributions are about 0.018 billion metric tons of carbon/a and 0.11 billion metric tons of carbon/a for China
and the world, respectively. Further, by the DBL (Diffusion Boundary Layer)-model calculation, the potential CO2 sink by carbonate rock dissolution is estimated to be 0.41 billion metric tons of carbon/a for the world. Therefore, the
potential CO2 source by carbonate reprecipitation is 0.3 billion metric tons of carbon/a.
Received: 12 May 1999 · Accepted: 16 August 1999 相似文献
12.
Carbon Fluxes and Sinks: the Consumption of Atmospheric and Soil CO2 by Carbonate Rock Dissolution 总被引：2，自引：0，他引：2
Carbonate rock outcrops cover 9%–16% of the continental area and are the principal source of the dissolved inorganic carbon (DIC) transferred by rivers to the oceans, a consequence their dissolution. Current estimations suggest that the flux falls between 0.1–0.6 PgC/a. Taking the intermediate value (0.3 PgC/a), it is equal to 18% of current estimates of the terrestrial vegetation net carbon sink and 38% of the soil carbon sink. In China, the carbon flux from carbonate rock dissolution is estimated to be 0.016 PgC/a, which accounts for 21%, 87.5%–150% and 2.3 times of the forest, shrub and grassland net carbon sinks respectively, as well as 23%–40% of the soil carbon sink flux. Carbonate dissolution is sensitive to environmental and climatic changes, the rate being closely correlated with precipitation, temperature, also with soil and vegetation cover. HCO3- in the water is affected by hydrophyte photosynthesis, resulting in part of the HCO3? being converted into DOC and POC, which may enhance the potential of carbon sequestration by carbonate rock dissolution. The possible turnover time of this carbon is roughly equal to that of the sea water cycle (2000a). The uptake of atmospheric/soil CO2 by carbonate rock dissolution thus plays an important role in the global carbon cycle, being one of the most important sinks. A major research need is to better evaluate the net effect of this sink in comparison to an oceanic source from carbonate mineral precipitation. 相似文献
13.
表层岩溶系统因碳酸盐岩－水－CO2(气)三相的化学动态不平衡过程而产生特殊的碳循环环节,参加循环的碳包括碳酸盐岩中的碳、大气和土壤空气CO2部分。中国南方表层岩溶系统的碳循环非常活跃,并敏感地响应岩溶动力因素的变化,从而促进了地球化学过程和生物化学过程的结合,成为大气CO2汇的重要项。中国南方表层岩溶系统的碳循环通过驱动环境的元素迁移,促进土壤有机质的积累,并影响植物所需要的矿物质营养元素的全量和有效态,进而影响岩溶区的植物物种、特有性和作物的发育。 相似文献
14.
Pedogenic goethites in each of two Early Permian paleosols appear to record mixing of two isotopically distinct CO2 components—atmospheric CO2 and CO2 from in situ oxidation of organic matter. The δ13C values measured for the Fe(CO3)OH component in solid solution in these Permian goethites are −13.5‰ for the Lower Leonardian (∼283 Ma BP) paleosol (MCGoeth) and −13.9‰ for the Upper Leonardian (∼270 Ma BP) paleosol (SAP). These goethites contain the most 13C-rich Fe(CO3)OH measured to date for pedogenic goethites crystallized in soils exhibiting mixing of the two aforementioned CO2 components. δ13C measured for 43 organic matter samples in the Lower Leonardian (Waggoner Ranch Fm.) has an average value of −20.3 ± 1.1‰ (1s). The average value yields a calculated Early Permian atmospheric Pco2 value of about 1 × PAL, but the scatter in the measured δ13C values of organic matter permits a calculated maximum Pco2 of 11 × PAL (PAL = present atmospheric level). Measured values of the mole fraction of Fe(CO3)OH in MCGoeth and SAP correspond to soil CO2 concentrations in the Early Permian paleosol profiles of 54,000 and 50,000 ppmV, respectively. Such high soil CO2 concentrations are similar to modern soils in warm, wet environments.The average δ13C values of pedogenic calcite from 9 paleosol profiles stratigraphically associated with MCGoeth (Waggoner Ranch Fm.) range from −6.5‰ to −4.4‰, with a mean δ13C value for all profiles of −5.4‰. Thus, the value of Δ13C between the pedogenic calcite data set and MCGoeth is 8.1 (±0.9)‰, which is in reasonable accord with the value of 7.7‰ expected if atmospheric Pco2 and organic matter δ13C values were the same for both paleosol types. Furthermore, the atmospheric Pco2 calculated for the Early Permian from the average measured carbon isotopic compositions of the paleosol calcite and organic matter is also analytically indistinguishable from 1 × PAL, with a maximum calculated atmospheric Pco2 (permitted by one standard deviation of the organic matter δ13C value) of ∼5 × PAL.If, however, measured average δ13C values of the plant organic matter are more positive than the original soil organic matter as a result of diagenetic loss of 13C-depleted, labile organic compounds, calculated Permian atmospheric Pco2 using these 13C-enriched organic values would underestimate the actual atmospheric Pco2 using either goethite or calcite. This is the first stratigraphically constrained, intrabasinal study to compare ancient atmospheric CO2 concentrations calculated from pedogenic goethite and calcite. These results demonstrate that the two different proxies record the same information about atmospheric CO2.The Fe(CO3)OH component in pedogenic goethite from a Triassic paleosol in Utah is significantly enriched in 13C relative to Fe(CO3)OH in goethites from soils in which there are mixtures of two isotopic CO2 components. Field-relationships and the δ13C value (−1.9‰) of the Triassic goethite indicate that this ancient paleosol profile experienced mixing of three isotopically distinct CO2 components at the time of goethite crystallization. The three components were probably atmospheric CO2, CO2 from in situ oxidation of organic matter and CO2 from in situ dissolution of preexisting calcite. Although mixing of three isotopically distinct CO2 components, as recorded by Fe(CO3)OH in goethite, has been described in modern soil, this is the first example from a documented paleosol. Its preservation affirms the need for careful, case-by-case assessment of ancient paleosols to establish that goethite in any particular soil is likely to be a valid proxy of atmospheric Pco2. 相似文献
15.
Charles N. Alpers David L. Dettman Kyger C. Lohmann Dragan Brabec 《Journal of Geochemical Exploration》1990,38(1-2)
Stable isotope ratios of oxygen and carbon were determined for CO2 in soil gas in the vicinity of the massive sulfide deposit at Crandon, Wisconsin with the objective of determining the source of anomalously high CO2 concentrations detected previously by McCarthy et al. (1986). Values of δ13C in soil gas CO2 from depths between 0.5 and 1.0 m were found to range from −12.68‰ to −20.03‰ (PDB). Organic carbon from the uppermost meter of soil has δ13C between −24.1 and −25.8‰ (PDB), indicating derivation from plant species with the C3 (Calvin) type of photosynthetic pathway. Microbial decomposition of the organic carbon and root respiration from C3 and C4 (Hatch-Slack) plants, together with atmospheric CO2 are the likely sources of carbon in soil gas CO2. Values of δ18O in soil-gas CO2 range from 32 to 38‰ (SMOW). These δ18O values are intermediate between that calculated for CO2 gas in isotopic equilibrium with local groundwaters and that for atmospheric CO2. The δ18O data indicate that atmospheric CO2 has been incorporated by mixing or diffusion. Any CO2 generated by microbial oxidation of organic matter has equilibrated its oxygen isotopes with the local groundwaters.The isotopic composition of soil-gas CO2 taken from directly above the massive sulfide deposit was not distinguishable from that of background samples taken 1 to 2 km away. No enrichment of the δ13C value of soil-gas CO2 was observed, contrary to what would be expected if the anomalous CO2 were derived from the dissolution of Proterozoic marine limestone country rock or of Paleozoic limestone clasts in glacial till. Therefore, it is inferred that root respiration and decay of C3 plant material were responsible for most CO2 generation both in the vicinity of the massive sulfide and in the “background” area, on the occasion of our sampling. Interpretation of our data is complicated by the effects of rainfall, which significantly reduced the magnitude of the CO2 anomaly. Therefore, we cannot rule out the possible mechanism of carbonate dissolution driven by pyrite oxidation, as proposed by Lovell et al. (1983) and McCarthy et al. (1986). Further work is needed on seasonal and daily variations of CO2 concentrations and stable isotope ratios in various hydrogeologic and ecologic settings so that more effective sampling strategies can be developed for mineral exploration using soil gases. 相似文献
16.
Physico-chemical environment of pedogenic carbonate formation in Devonian vertic palaeosols, central Appalachians, USA 总被引：1，自引：0，他引：1
The morphology and geochemistry of pedogenic carbonate found in vertic claystone palaeosols in the Devonian Catskill Formation in central Pennsylvania preserve a record of the physical and chemical environment of carbonate precipitation. The carbonate is characterized by three distinct petrographic generations. Pedogenic rhizoliths and nodules are the earliest precipitated generation, and typically consist of dull red-brown luminescent micrite. Clear, equant calcite spar cement fills voids in the centres of rhizoliths, as well as circumgranular cracks and septarian voids in nodules. Early spar cements are non-luminescent to dull luminescent, whereas later spar cements exhibit bright yellow-orange luminescence. Late stage pedogenic fractures are always occluded with very bright yellow-orange luminescent spar cements. The incorporation of progressively higher concentrations of Mn (up to 34000 ppm) into successively younger calcite spar cements, without concomitant increases in Fe, suggests carbonate precipitation from an evolving meteoric water in which Mn2+ became increasingly mobile over time. The increased mobility is possibly due to decreasing Eh, resulting from oxidation of organic matter after rapid soil burial on the floodplain. The amount of Fe2+ available for incorporation into calcite was limited because most iron was immobile, having been earlier oxidized and bound to the palaeosol clay matrix as a poorly crystallized ferric oxide or oxyhydroxide mineral. Carbon isotope compositions of pedogenic carbonate correlate with the inferred depth of carbonate precipitation. Rhizoliths preserved below the lowest stratigraphic occurrences of pedogenic slickensides are consistently depleted in 13C relative to nodules, which formed stratigraphically higher, within the zone of active soil shrink and swell processes. Nodular carbonate, precipitated in proximity to deep cracks in the soil, is enriched due to increased gas exchange with isotopically heavy atmospheric CO2. Accordingly, rhizolith compositions will most accurately estimate palaeoatmospheric levels of CO2; the use of nodule compositions may result in overestimation of PCO2 by as much as 30%. 相似文献
17.
The onset of pelagic sedimentation attending the radiation of pelagic calcifiers during the Mesozoic was an important divide in Earth history, shifting the locus of significant carbonate sedimentation from the shallow shelf environments of the Paleozoic to the deep sea. This shift would have impacted the CO2 cycle, given that decarbonation of subducted pelagic carbonate is an important return flux of CO2 to the atmosphere. Coupled with the fact that the mean residence time of continental platform and basin sedimentary carbonate exceeds that of the oceanic crust, it thus becomes unclear whether carbon cycling would have operated on a substantially different footing prior to the pelagic transition. Here, we examine this uncertainty with sensitivity analyses of the timing of this transition using a coupled model of the Phanerozoic atmosphere, ocean, and shallow lithosphere. For purposes of comparison, we establish an age of 250 Ma (i.e., after the Permo-Triassic extinctions) as the earliest opportunity for deposition of extensive biogenic pelagic carbonate on the deep seafloor, an age that predates known occurrences of pelagic calcifiers (and intact seafloor). Although an approximate boundary, we do show that attempts to shift this datum either significantly earlier or later in time produce model results that are inconsistent with observed trends in the mass–age distribution of the rock record and with accepted trends in seawater composition as constrained by proxy data. Significantly, we also conclude that regardless of the timing of the onset of biogenic pelagic carbonate sedimentation, a carbon sink involving seawater-derived dissolved inorganic carbon played a critical role in carbon cycling, particularly in the Paleozoic. This CaCO3 sink may have been wholly abiogenic, involving calcium derived either directly from seawater (thus manifest as a direct seafloor deposit), or alternatively from basalt–seawater reactions (represented by precipitation of CaCO3 in veins and fissures within the basalt). Despite the uncertainty in the source and magnitude of this abiogenic CaCO3 flux, it is likely a basic and permanent feature of global carbon cycling. Subduction of this CaCO3 would have acted as a basic return circuit for atmospheric CO2 even in the absence of biogenically derived pelagic carbonate sedimentation. Lastly, model calculations of the ratio of dissolved calcium to carbonate ion (Ca2+/CO3 2?) show this quantity underwent significant secular evolution over the Phanerozoic. As there is increasing recognition of this ratio’s role in CaCO3 growth and dissolution reactions, this evolution, together with progressive increases in nutrient availability and saturation state, may have created a tipping point ultimately conducive to the appearance of pelagic calcifiers in the Mesozoic. 相似文献
18.
Climatic dependence of stable carbon and oxygen isotope signals recorded in speleothems: From soil water to speleothem calcite 总被引：3，自引：0，他引：3
Understanding the relationship between stable isotope signals recorded in speleothems (δ13C and δ18O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO2.The water entering the cave flows as a thin film towards the drip site. CO2 degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scale of several 10-100 s. The δ13C value of the drip water is mainly determined by the isotopic composition of soil CO2. The evolution of the δ18O value of the carbonate species is determined by the long exchange time Tex, between oxygen in carbonate and water of several 10,000 s. Even if the oxygen of the CO2 in soil water is in isotopic equilibrium with that of the water, dissolution of limestone delivers oxygen with a different isotopic composition changing the δ18O value of the carbonate species. Consequently, the δ18O value of the rainwater will only be reflected in the drip water if it has stayed in the rock for a sufficiently long time.After the water has entered the cave, the carbon and oxygen isotope composition of the drip water may be altered by CO2-exchange with the cave air. Exchange times, , of about 3000 s are derived. Thus, only drip water, which drips in less than 3000 s onto the stalagmite surface, is suitable to imprint climatic signals into speleothem calcite deposited from it.Precipitation of calcite proceeds with time constants, τp, of several 100 s. Different rate constants and equilibrium concentrations for the heavy and light isotopes, respectively, result in isotope fractionation during calcite precipitation. Since Tex ? τp, exchange with the oxygen in the water can be neglected, and the isotopic evolution of carbon and oxygen proceed analogously. For drip intervals Td < 0.1τp the isotopic compositions of both carbon and oxygen in the solution evolve linearly in time. The calcite precipitated at the apex of the stalagmite reflects the isotopic signal of the drip water.For long drip intervals, when calcite is deposited from a stagnant water film, long drip intervals may have a significant effect on the isotopic composition of the DIC. In this case, the isotopic composition of the calcite deposited at the apex must be determined by averaging over the drip interval. Such processes must be considered when speleothems are used as proxies of past climate variability. 相似文献
19.
Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition.Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO2. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg2+/Ca2+ ratio of 0.4.Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca2+ and Mg2+ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg2+ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry. 相似文献
20.
Modelling carbon isotopes of carbonates in cave drip water 总被引：2，自引：0，他引：2
C isotopes in cave drip water are affected by both the C isotope composition of soil air and host rock carbonate. Furthermore, the C isotope composition of cave drip water strongly depends on the calcite dissolution system, i.e., open, closed and intermediate conditions. Here, we present a calcite dissolution model, which calculates the 14C activity and δ13C value of the dissolved inorganic carbon of the drip water. The model is based on the chemical equations describing calcite dissolution (). The most important improvement, relative to previous models, is the combination of the open and closed system conditions in order to simulate the C isotope composition during intermediate states of calcite dissolution and the application to carbon isotope measurements on cave drip waters from Grotta di Ernesto, Italy. The major changes in the C isotope composition of the drip water occur in response to variations in the open-closed system ratio. Additionally, the 14C activity and the δ13C value of the drip water depend on changes in the partial pressure of soil CO2. Radiocarbon and δ13C values of the Grotta di Ernesto drip water are well reproduced by the model. 相似文献