Fe(CO₃)OH in goethite from a mid-latitude North American Oxisol: estimate of atmospheric CO₂ concentration in the Early Eocene “climatic optimum”     

Crayton J. Yapp 《Geochimica et cosmochimica acta》2004,68(5):935-947

Measured mole fractions (X) and δ¹³C values of the Fe(CO₃)OH component in pedogenic goethite from a mid-latitude Oxisol of Early Eocene age (≈52 Ma B.P.) range from 0.0014 to 0.0064 and −20.1 to −15.4‰, respectively. These values of X imply that concentrations of CO₂ gas in the paleosol were ≈7400 to ≈34,000 ppm. δ¹³C and 1/X are correlated and define a linear, soil-CO₂ diffusive mixing line with a positive slope. Such positive slopes are characteristic of mixing of two isotopically distinct CO₂ endmembers (atmospheric CO₂ and CO₂ from oxidation of soil organic matter). From the intercept of the mixing line, it is calculated that the δ ¹³C value of organic matter in the ancient soil was ≈−28.0‰. The magnitude of the slope implies an Early Eocene atmospheric CO₂ concentration of ≈2700 ppm.A simple model for forest soils suggests that a “canopy effect” may cause atmospheric CO₂ concentrations deduced from pedogenic minerals to underestimate the actual concentrations of atmospheric CO₂. If a significant forest canopy were present at the time of formation of pedogenic goethite in the Ione Fm, the concentration of 2700 ppm calculated for atmospheric CO₂ could be slightly low, but the underestimate is expected to be < ≈300 ppm (i.e., less than the analytical uncertainty). The relatively high concentration of 2700 ppm inferred for atmospheric CO₂ at ≈52 Ma B.P. would have been coincident with the Early Eocene climatic optimum. This result seems to support the case for an important role for variations of atmospheric CO₂ in the modification of global paleoclimate.  相似文献   

Goethite, calcite, and organic matter from Permian and Triassic soils: carbon isotopes and CO₂ concentrations     

Neil J. Tabor  Crayton J. Yapp 《Geochimica et cosmochimica acta》2004,68(7):1503-1517

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   

Quantifying the carbon source of pedogenic calcite veins in weathered limestone: implications for the terrestrial carbon cycle     

Zou  Lin  Dong  Lin  Ning  Meng  Huang  Kangjun  Peng  Yongbo  Qin  Shujian  Yuan  Honglin  Shen  Bing 《中国地球化学学报》2019,38(4):481-496

The continent is the second largest carbon sink on Earth’s surface. With the diversification of vascular land plants in the late Paleozoic, terrestrial organic carbon burial is represented by massive coal formation, while the development of soil profiles would account for both organic and inorganic carbon burial. As compared with soil organic carbon, inorganic carbon burial, collectively known as the soil carbonate, would have a greater impact on the long-term carbon cycle. Soil carbonate would have multiple carbon sources, including dissolution of host calcareous rocks, dissolved inorganic carbon from freshwater, and oxidation of organic matter, but the host calcareous rock dissolution would not cause atmospheric CO₂ drawdown. Thus, to evaluate the potential effect of soil carbonate formation on the atmospheric pCO₂ level, different carbon sources of soil carbonate should be quantitatively differentiated. In this study, we analyzed the carbon and magnesium isotopes of pedogenic calcite veins developed in a heavily weathered outcrop, consisting of limestone of the early Paleogene Guanzhuang Group in North China. Based on the C and Mg isotope data, we developed a numerical model to quantify the carbon source of calcite veins. The modeling results indicate that 4–37 wt% of carbon in these calcite veins was derived from atmospheric CO₂. The low contribution from atmospheric CO₂ might be attributed to the host limestone that might have diluted the atmospheric CO₂ sink. Nevertheless, taking this value into consideration, it is estimated that soil carbonate formation would lower 1 ppm atmospheric CO₂ within 2000 years, i.e., soil carbonate alone would sequester all atmospheric CO₂ within 1 million years. Finally, our study suggests the C–Mg isotope system might be a better tool in quantifying the carbon source of soil carbonate.

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BRYOCARB: A process-based model of thallose liverwort carbon isotope fractionation in response to CO₂, O₂, light and temperature     

Benjamin J. Fletcher 《Geochimica et cosmochimica acta》2006,70(23):5676-5691

Evidence from laboratory experiments indicates that fractionation against the heavy stable isotope of carbon (Δ¹³C) by bryophytes (liverworts and mosses) is strongly dependent on atmospheric CO₂. This physiological response may therefore provide the basis for developing a new terrestrial CO₂ proxy [Fletcher, B.J., Beerling, D.J., Brentnall, S.J., Royer, D.L., 2005. Fossil bryophytes as recorders of ancient CO₂ levels: experimental evidence and a Cretaceous case study. Global Biogeochem. Cycles19, GB3012]. Here, we establish a theoretical basis for the proxy by developing an extended model of bryophyte carbon isotope fractionation (BRYOCARB) that integrates the biochemical theory of photosynthetic CO₂ assimilation with controls on CO₂ supply by diffusion from the atmosphere. The BRYOCARB model is evaluated against measurements of the response of liverwort photosynthesis and Δ¹³C to variations in atmospheric O₂, temperature and irradiance at different CO₂ concentrations. We show that the bryophyte proxy is at least as sensitive to variations in atmosphere CO₂ as the two other leading carbon isotope-based approaches to estimating palaeo-CO₂ levels (δ¹³C of phytoplankton and of paleosols). Mathematical inversion of BRYOCARB provides a mechanistic means of estimating atmospheric CO₂ levels from fossil bryophyte carbon that can explicitly account for the effects of past differences in O₂ and climate.  相似文献   

Characterization of soil organic carbon in drained thaw-lake basins of Arctic Alaska using NMR and FTIR photoacoustic spectroscopy   总被引：2，自引：0，他引：2  

Joel A. Pedersen  Myrna A. SimpsonJames G. Bockheim  Kartik Kumar 《Organic Geochemistry》2011,42(8):947-954

Arctic soils contain a large fraction of Earth’s stored carbon. Temperature increases in the Arctic may enhance decomposition of this stored carbon, shifting the role of Arctic soils from a net sink to a new source of atmospheric CO₂. Predicting the impact of Arctic warming on soil carbon reserves requires knowledge of the composition of the stored organic matter. Here, we employ solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared-photoacoustic spectroscopy (FTIR-PAS) to investigate the chemical composition of soil organic matter collected from drained thaw-lake basins ranging in age from 0 to 5500 years before present (y BP). The ¹³C NMR and FTIR-PAS data were largely congruent. Surface horizons contain relatively large amounts of O-alkyl carbon, suggesting that the soil organic matter is rich in labile constituents. Soil organic matter decreases with depth with the relative amounts of O-alkyl carbon decreasing and aromatic carbon increasing. These data indicate that lower horizons are in a more advanced stage of decomposition than upper horizons. Nonetheless, a substantial fraction of carbon in lower horizons, even for ancient thaw-lake basins (2000-5500 y BP), is present as O-alkyl carbon reflecting the preservation of intrinsically labile organic matter constituents. Climate change-induced increases in the depth of the soil active layer are expected to accelerate the depletion of this carbon.  相似文献   

Paleoenvironmental implications of concentration and C/C ratios of Fe(CO₃)OH in goethite from a mid-latitude Cenomanian laterite in southwestern Minnesota     

Weimin Feng  Crayton J. Yapp 《Geochimica et cosmochimica acta》2009,73(9):2559-7116

A mid-Cretaceous (∼95 Ma) laterite in southwestern Minnesota contains pisolites that consist primarily of gibbsite, quartz, and kaolinite with smaller amounts of goethite (α-FeOOH) and hematite. The presence of minor berthierine (an Fe(II) sheet silicate) suggests that this Cenomanian laterite experienced some degree of low temperature reductive diagenesis during its burial history. The prospects for extracting useful paleoenvironmental information from the pisolitic goethite were explored by studying measured mole fraction (X_m) and δ¹³C_m values of the Fe(CO₃)OH component in solid solution in the goethite using the method of incremental vacuum dehydration-decarbonation.Data arrays that occupy distinctly different domains in plots of δ¹³C_m vs. 1/X_m suggest the existence of two generations of goethite in the pisolites. The apparently younger generation of goethite (“generation 2”) evolves CO₂ at 170 °C, while the older generation (“generation 1”) evolves CO₂ at 220 °C. The distribution of the data suggests that generation 2 goethite is a proxy for mixing of CO₂ from three distinct CO₂ sources in an oxidative environment which post-dated the reductive diagenesis. The small amount of generation 1 goethite seems to have persisted through the reductive diagenesis, and nine of the generation 1 goethite data appear to define a proxy, two-endmember, soil CO₂ mixing line. Such two-component mixing is consistent with expectations for a highly evolved, carbonate-free laterite (i.e., the pre-diagenetic Cenomanian weathering system). The δ¹³C_m values of these nine data points range from −23.1‰ to −13.7‰, whereas X_m values range from 0.0007 to 0.0222. Linear regression of these nine data yields a slope of 0.0064, which corresponds to an ancient tropospheric CO₂ concentration of about 1900 ppmV.Isotopic data from pisolitic kaolinite indicate a paleotemperature of about 24 °C at a paleolatitude of ∼40°N. This is substantially warmer than modern continental temperatures at such latitudes and is consistent with published indications of a generally warmer mid-Cretaceous climate. Moreover, the correspondence of a warmer mid-Cretaceous climate with the inferred, relatively high concentration of Cenomanian tropospheric CO₂ (∼1900 ppmV) is consistent with the idea that variations of atmospheric CO₂ have a relation to climate change. The results of this study emphasize the importance of careful evaluation of incremental dehydration-decarbonation data from natural goethites to assess the possibility that more than one generation of goethite is present in a sample. However, the results also indicate that the carbon isotope information recorded in admixed goethite generations may be sorted out and used in paleoenvironmental interpretations.  相似文献   

Contribution des écosystèmes continentaux à la séquestration du carbone     

《Comptes Rendus Geoscience》2003,335(6-7):577-595

This article focuses on the contribution of natural ecosystems (forests, grasslands) and agrosystems to carbon sequestration either in biomass or in soil. Carbon stocks are important (650 Gt in biomass, 1500 to 2000 Gt in soils as compared with 750 for atmospheric CO₂), and also fluxes that led to CO₂ emissions in the past (due to deforestation or cultivation) and which now turn to carbon sequestration (2 Gt_C/year). This article shows great spatial variations in stocks and fluxes and great measurement difficulties, especially for stock variations. Anthropic actions such as reforestation (mainly in the North), changes in land use or in crop management, can increase carbon sequestration in biomass or soil, with a residence time of several decades, which is not insignificant with respect to the Kyoto protocol and which also has other environmental benefits. To cite this article: M. Robert, B. Saugier, C. R. Geoscience 335 (2003).  相似文献   

Hydrochemical and PCO2 variations of a cave stream in a subtropical karst area,Chongqing, SW China: piston effects,dilution effects,soil CO2 and buffer effects     

Junbing Pu  Daoxian Yuan  Heping Zhao  Licheng Shen 《Environmental Earth Sciences》2014,71(9):4039-4049

The role of CO₂ in karst has been of interest for decades, and emphasized by IGCP 379, International Geoscience Programme, UNESCO started in 1995. There are still open questions about the dynamics of carbon in karst systems, particularly the flux of carbon between the surface and subsurface and between different components in the karst subsurface. This research report focuses on the variations of hydrochemistry and PCO₂ (partial pressures of carbon dioxide) in subtropical karst groundwater, using high-resolution auto-monitoring hydrochemical data (15-min intervals). The aim of this study was to understand how hydrochemistry and PCO₂ in karst systems respond to recharge over different time scales and what the controlling factors are. An auto-monitoring hydrochemistry station was installed about 300 m upstream from the exit in the active stream channel of Xueyu Cave, a typical subtropical karst cave. Four years of high-resolution continuous pH, specific conductivity (Spc), temperature and water-level data were collected. 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 (SIc) levels on a continuous basis. Seasonal, diurnal and storm-scale variations were captured in the hydrochemistry and calculated PCO₂ records, indicating that the cave stream is a dynamic and variable system. Seasonal features (higher specific conductivity and lower pH in summer; lower specific conductivity and higher pH in winter) tend to covary with temperature which influences the production of CO₂ in soils, thus being the driving force for the variations (the soil CO₂ effect). Due to the buffer effect of a thick vadose zone and large void cave space, diurnal variations are not obvious compared with epikarst springs in SW China. Storm-scale fluctuations due to storm events occur during the summer rainy season. Piston flow effects, dilution and soil CO₂ effects determine the variations in different storm events. At the beginning of the rains, the piston effect drives the variations, characterized by increase in Spc, SIc and pH in the cave stream and decrease in PCO₂. With heavy rainfall, decrease in Spc shows control by the dilution effect, while decrease in SIc and pH and increase in PCO₂ indicates the greater influence of soil CO₂. These results imply that the soil and cave voids are important factors influencing the hydrochemical evolution of karst groundwater. Future works need to use such high-resolution technology widely for tracing the PCO₂ and hydrochemical variations in different karst aquifers.  相似文献   

The oxygen geochemical cycle: dynamics and stability     

Antonio C. LasagaHiroshi Ohmoto 《Geochimica et cosmochimica acta》2002,66(3):361-381

The first and possibly only major rise of atmospheric oxygen, from p_O2 ≤ 0.1% PAL (the present atmospheric level) to p_O2 ≥ 10% PAL, appears to have occurred sometime before 2 Ga ago, although the exact time of and the cause(s) for the rise have been hotly debated. Equally important questions on the atmospheric oxygen concern its stability, especially the mechanisms regulating the atmospheric p_O2 level and the causes and magnitude of p_O2 variations since the first major rise of atmospheric oxygen. Previous efforts to model the p_O2 variation during the Phanerozoic time have typically relied on secondary information, such as the carbon and sulfur isotopic records of sedimentary rocks, and on simple dynamics of the geochemical cycles of O, C, S, and P based on box-type models. As a result, many kinetic questions about the variation and stability of atmospheric oxygen could not have been answered. Here we quantitatively evaluate the dynamics and stability of atmospheric O₂ and CO₂, using recent experimental data, field observations, and a new model for the C-O coupled geochemical cycles. We examine the change with time in the fluxes of various compounds (O₂, CO₂, phosphate, organic C, carbonate C, C-bearing reduced volcanic gases, and C-free reduced volcanic gases) among the various reservoirs (atmosphere, soil, surface ocean, deep ocean, the lower crust and mantle, and upper crust) under a variety of scenarios. Our model does not assume steady-state fluxes for any of the reservoirs. Rather, the model incorporates the kinetic experimental data on oxidation of coal, a proxy for kerogen, the dynamics of soil formation and erosion, the kinetics of decomposition of organic matter in the Oceans by aerobic and anaerobic bacteria, the equilibrium ocean-atmosphere carbonate model, the observed relationships among the organic burial flux, dissolved O₂ content of deep ocean, and sedimentation rates, and the three-box model ocean. The important parameters that strongly influence the dynamics of atmospheric O₂, are found to be (a) the total area of soil formation on Earth; (b) the average soil depth; (c) the average rate of physical erosion of soils, which is linked to the average rate of accumulation of clastic sediments in the oceans; (d) the composition and flux of volcanic gas; and (e) the level of atmospheric CO₂. We develop kinetic equations linking these parameters to the production and consumption fluxes of atmospheric oxygen and also to stable p_O2 values. Considering the likely ranges of variations in these parameters in geologic history, we suggest that the atmospheric p_O2 level is likely to have stayed within a very narrow range of 0.6-2 PAL and that the entire ocean, except for local euxinic basins, is likely to have been basically oxygenated since the first major rise of atmospheric oxygen more than 2 Ga ago.  相似文献   

Variation characteristics of CO₂ in a newly-excavated soil profile,Chinese Loess Plateau: Excavation-induced ancient soil organic carbon decomposition          下载免费PDF全文

Chao Song  Man Liu  Qiu-yao Dong  Lin Zhang  Pan Wang  Hong-yun Chen  Rong Ma 《地下水科学与工程》2022,10(1):19-32

Soils of the Chinese Loess Plateau(CLP)contain substantial amounts of soil inorganic carbon(SIC),as well as recent and ancient soil organic carbon(SOC).With the advent of the Anthropocene,human perturbation,including excavation,has increased soil CO₂ emission from the huge loess carbon pool.This study aims to determine the potential of loess CO₂ emission induced by excavation.Soil CO₂ were continuously monitored for seven years on a newly-excavated profile in the central CLP and the stable C isotope compositions of soil CO₂ and SOC were used to identify their sources.The results showed that the soil CO₂ concentrations ranged from 830μL·L^-1 to 11190μL·L^-1 with an annually reducing trend after excavation,indicating that the human excavation can induce CO₂ production in loess profile.Theδ¹³ C of CO₂ ranged from–21.27‰to–19.22‰(mean:–20.11‰),with positive deviation from top to bottom.The range of δ¹³CSOC was–24.0‰to–21.1‰with an average of–23.1‰.Theδ¹³ C-CO₂ in this study has a positive relationship with the reversed CO₂ concentration,and it is calculated that 80.22%of the soil CO₂ in this profile is from the microbial decomposition of SOC and 19.78%from the degasification during carbonate precipitation.We conclude that the human excavation can significantly enhance the decomposition of the ancient OC in loess during the first two years after perturbation,producing and releasing soil CO₂ to atmosphere.  相似文献   

Isotope geochemistry of caliche developed on basalt   总被引：1，自引：0，他引：1  

L.Paul Knauth  Mauro Brilli 《Geochimica et cosmochimica acta》2003,67(2):185-195

Enormous variations in oxygen and carbon isotopes occur in caliche developed on < 3 Ma basalts in 3 volcanic fields in Arizona, significantly extending the range of δ¹⁸O and δ¹³C observed in terrestrial caliche. Within each volcanic field, δ¹⁸O is broadly co-variant with δ¹³C and increases as δ¹³C increases. The most ¹⁸O and ¹³C enriched samples are for subaerial calcite developed on pinnacles, knobs, and flow lobes that protrude above tephra and soil. The most ¹⁸O and ¹³C depleted samples are for pedogenic carbonate developed in soil atmospheres. The pedogenic caliche has δ¹⁸O fixed by normal precipitation in local meteoric waters at ambient temperatures and has low δ¹³C characteristic of microbial soil CO₂. Subaerial caliche has formed from ¹⁸O-rich evapoconcentrated meteoric waters that dried out on surfaces after local rains. The associated ¹³C enrichment is due either to removal of ¹²C by photosynthesizers in the evaporating drops or to kinetic isotope effects associated with evaporation. Caliche on basalt lava flows thus initially forms with the isotopic signature of evaporation and is subsequently over-layered during burial by calcite carrying the isotopic signature of the soil environment. The large change in carbon isotope composition in subsequent soil calcite defines an isotopic biosignature that should have developed in martian examples if Mars had a “warm, wet” early period and photosynthesizing microbes were present in the early soils. The approach can be similarly applied to terrestrial Precambrian paleocaliche in the search for the earliest record of life on land. Large variations reported for δ¹⁸O of carbonate in Martian meteorite ALH84001 do not necessarily require high temperatures, playa lakes, or flood runoff if the carbonate is an example of altered martian caliche.  相似文献   

Seasonal patterns of carbon chemistry and isotopes in tufa depositing groundwaters of southwestern Japan     

M. Hori  K. Hoshino  A. Kano 《Geochimica et cosmochimica acta》2008,72(2):480-492

Annually laminated carbonates, known as tufas, commonly develop in limestone areas and typically record seasonal patterns of oxygen- and carbon-isotope compositions. δ¹⁸O values are principally controlled by seasonal changes of water temperature, whereas δ¹³C values are the result of complex reactions among the gaseous, liquid, and solid sources of carbon in the system. We examined the processes that cause the seasonal patterns of δ¹³C in groundwater systems at three tufa-depositing sites in southwestern Japan by applying model calculations to geochemical data. Underground inorganic carbon species are exchanged with gaseous CO₂, which is mainly introduced to the underground hydrological system by natural atmospheric ventilation and by diffusion of soil air. These processes control the seasonal pattern of δ¹³C, which is low in summer and high in winter. Among the three sites we investigated, we identified two extreme cases of the degree of carbon exchange between liquid and gaseous phases. For the case with high radiocarbon composition (Δ¹⁴C) and low pCO₂, there was substantial carbon exchange because of a large contribution of atmospheric CO₂ and a small water mass. For the other extreme case, which was characterized by low Δ¹⁴C and high pCO₂, the contribution of atmospheric CO₂ was small and the water mass was relatively large. Our results suggest that at two of the three sites water residence time within the soil profile was longer than 1 year. Our results also suggested a short residence time (less than 1 year) of water in the soil profile at the site with the smallest water mass, which is consistent with large seasonal amplitude of the springwater temperature variations. The Δ¹⁴C value of tufas is closely related to the hydrological conditions in which they are deposited. If the initial Δ¹⁴C value of a tufa-depositing system is stable, ¹⁴C-chronology can be used to date paleo-tufas.  相似文献   

Seasonal dynamics of CO2 profiles across a soil chronosequence,Santa Cruz,California     

Marjorie Schulz  David Stonestrom  Guntram Von Kiparski  Corey Lawrence  Carrie Masiello  Art White  John Fitzpatrick 《Applied Geochemistry》2011

Concentrations of CO₂ in soil atmosphere and CO₂ efflux were measured across a marine terrace soil chronosequence near Santa Cruz, California. Soil development, specifically the formation of an argillic horizon, has created a two-tier soil gas profile in the older terrace soils. The soil above the argillic horizon has seasonal variations in soil CO₂ associated with plant respiration. The older soils with dense argillic horizons maintain a year round ～1%CO₂ below the argillic horizon. The CO₂efflux during the growing season is higher on the older terraces.  相似文献   

Stable isotopic composition of soil calcite (O,C) and gypsum (S) overlying Cu deposits in the Atacama Desert,Chile: Implications for mineral exploration,salt sources,and paleoenvironmental reconstruction     

《Applied Geochemistry》2013

Soils overlying two porphyry Cu deposits (Spence, Gaby Sur) and the Pampa del Tamarugal, Atacama Desert, Northern Chile were collected in order to investigate the extent to which saline groundwaters influence “soil” chemistry in regions with thick Miocene and younger sediment cover. Soil carbonate (calcite) was analyzed for C and O isotopes and pedogenic gypsum for S isotopes. Soil calcite is present in all soils at the Spence deposit, but increases volumetrically above two fracture zones that cut the Miocene gravels, including gravels that overlie the deposit. The C isotope composition of carbonate from the soils overlying fracture zones is indistinguishable from pedogenic carbonate elsewhere at the Spence deposit; all δ¹³C_VPDB values fall within a narrow range (1.40–4.23‰), consistent with the carbonate having formed in equilibrium with atmospheric CO₂. However, δ¹⁸O_VPDB for carbonate over both fracture zones is statistically different from carbonate elsewhere (average δ¹⁸O_VPDB = 0.82‰ vs. −2.23‰, respectively), suggesting involvement of groundwater in their formation. The composition of soils at the Tamarugal anomaly has been most strongly affected by earthquake-related surface flooding and evaporation of groundwater; δ¹³C_VPDB values (−4.28‰ to −2.04‰) are interpreted to be a mixture of dissolved inorganic C (DIC) from groundwater and atmospheric CO₂. At the Spence deposit, soils only rarely contain sufficient SO₄ for S isotope analysis; the SO₄-bearing soils occur only above the fracture zones in the gravel. Results are uniform (3.7–4.9‰ δ³⁴S_CDT), which is near the middle of the range for SO₄ in groundwater (0.9–7.3‰). Sulfur in soils at the Gaby Sur deposit (3.8–6.1‰ δ³⁴S_CDT) is dominated by gypsum, which primarily occurs on the flanks and tops of hills, suggesting deposition from SO₄-rich fogs. Sulfate in Gaby Sur deposit gypsum is possibly derived by condensation of airborne SO₄ from volcanic SO₂ from the nearby Andes. At the Gaby Sur deposit and Tamarugal anomaly, pedogenic stable isotopes cannot distinguish between S from porphyry or redeposited SO₄ from interior salars.The three sites studied have had different histories of salt accumulation and display variable influence of groundwater, which is interpreted to have been forced to the surface during earthquakes. The clear accumulation of salts associated with fractures at the Spence deposit, and shifts in the isotopic composition of carbonate and sulfate in the fractures despite clear evidence of relatively recent removal of salts indicates that transfer from groundwater is an ongoing process. The interpretation that groundwaters can influence the isotopic composition of pedogenic calcrete and gypsum has important implications for previous studies that have not considered this mechanism.  相似文献   

Coexisting goethite and gibbsite from a high-paleolatitude (55°N) Late Paleocene laterite: Concentration and C/C ratios of occluded CO₂ and associated organic matter     

Neil J. Tabor  Crayton J. Yapp 《Geochimica et cosmochimica acta》2005,69(23):5495-5510

A Late Paleocene (∼60 Ma BP) lateritic soil from Northern Ireland (the Antrim paleosol, herein referred to as Nire) contains coexisting goethite, gibbsite, phyllosilicate, and hematite. The Fe(III) oxides exhibit pisolitic and Liesegang-type morphologies that are mutually exclusive in hand specimens. X-ray diffraction (XRD) measurements of Al substituted for Fe in goethite indicate two populations: (1) low-Al, Liesegang-type goethites (∼0 mol% Al) and (2) high-Al, pisolitic goethites (∼9 to ∼24 mol% Al). Selective dissolution and incremental vacuum dehydration-decarbonation were used to determine the concentration and δ¹³C values of CO₂ occluded in the respective structures of the goethites and gibbsites in this complex mixture of Nire lateritic minerals. The Fe(CO₃)OH component in the high-Al goethites appears to retain a proxy carbon isotopic record of vadose zone CO₂ in the ancient soil. The δ¹³C values of CO₂ occluded in coexisting goethites and gibbsites indicate that these minerals did not form in equilibrium with the same environmental CO₂.The measured mole fractions (X) of Fe(CO₃)OH in the high-Al goethites range from 0.0059 (±0.0005) to 0.0077 (±0.0006) and correspond to soil CO₂ concentrations of ∼28,000 to ∼37,000 ppmV. The average values of X and δ¹³C for the four high-Al goethites are 0.0067 ± 0.0007 and −20.1 ± 0.5‰, respectively. The δ¹³C value of the organic matter undergoing oxidation in this midlatitude (∼55°N) Late Paleocene soil appears to have been ∼ −28.2‰. Taken together, these data indicate an atmospheric CO₂ concentration of ∼2400 ppmV (± ∼1200 ppmV) at ∼60 Ma BP. The inferred high concentration of atmospheric CO₂ would have been coincident with the warm global climate of the Late Paleocene and is consistent with the idea that CO₂ plays an important role in climate variation.  相似文献   

Topographic controls on the depth distribution of soil CO2 in a small temperate watershed     

《Applied Geochemistry》2015

Accurate measurements of soil CO₂ concentrations (pCO₂) are important for understanding carbonic acid reaction pathways for continental weathering and the global carbon (C) cycle. While there have been many studies of soil pCO₂, most sample or model only one, or at most a few, landscape positions and therefore do not account for complex topography. Here, we test the hypothesis that soil pCO₂ distribution can predictably vary with topographic position. We measured soil pCO₂ at the Susquehanna Shale Hills Critical Zone Observatory (SSHCZO), Pennsylvania, where controls on soil pCO₂ (e.g., depth, texture, porosity, and moisture) vary from ridge tops down to the valley floor, between planar slopes and slopes with convergent flow (i.e., swales), and between north and south-facing aspects. We quantified pCO₂ generally at 0.1–0.2 m depth intervals down to bedrock from 2008 to 2010 and in 2013. Of the variables tested, topographic position along catenas was the best predictor of soil pCO₂ because it controls soil depth, texture, porosity, and moisture, which govern soil CO₂ diffusive fluxes. The highest pCO₂ values were observed in the valley floor and swales where soils are deep (≥0.7 m) and wet, resulting in low CO₂ diffusion through soil profiles. In contrast, the ridge top and planar slope soils have lower pCO₂ because they are shallower (≤0.6 m) and drier, resulting in high CO₂ diffusion through soil profiles. Aspect was a minor predictor of soil pCO₂: the north (i.e., south-facing) swale generally had lower soil moisture content and pCO₂ than its south (i.e., north-facing) counterpart. Seasonally, we observed that while the timing of peak soil pCO₂ was similar across the watershed, the amplitude of the pCO₂ peak was higher in the deep soils due to more variable moisture content. The high pCO₂ observed in the deeper, wetter topographic positions could lower soil porewater pH by up to 1 pH unit compared to porewaters equilibrated with atmospheric CO₂ alone. CO₂ is generally the dominant acid driving weathering in soils: based on our observations, models of chemical weathering and CO₂ dynamics would be improved by including landscape controls on soil pCO₂.  相似文献   

Stable isotopes of carbon dioxide in soil gas over massive sulfide mineralization at Crandon, Wisconsin     

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   

Stable isotopes of pedogenic carbonates from the Somma–Vesuvius area,southern Italy,over the past 18 kyr: palaeoclimatic implications     

G. Zanchetta  M. Di Vito  A. E. Fallick  R. Sulpizio 《第四纪科学杂志》2000,15(8):813-824

Stable isotopes were measured in the carbonate and organic matter of palaeosols in the Somma–Vesuvius area, southern Italy in order to test whether they are suitable proxy records for climatic and ecological changes in this area during the past 18000 yr. The ages of the soils span from ca. 18 to ca. 3 kyr BP. Surprisingly, the Last Glacial to Holocene climate transition was not accompanied by significant change in δ¹⁸O of pedogenic carbonate. This could be explained by changes in evaporation rate and in isotope fractionation between water and precipitated carbonate with temperature, which counterbalanced the expected change in isotope composition of meteoric water. Because of the rise in temperature and humidity and the progressive increase in tree cover during the Holocene, the Holocene soil carbonates closely reflect the isotopic composition of meteoric water. A cooling of about 2°C after the Avellino eruption (3.8 ka) accounts for a sudden decrease of about 1‰ in δ¹⁸O of pedogenic carbonate recorded after this eruption. The δ¹³C values of organic matter and pedogenic carbonate covary, indicating an effective isotope equilibrium between the organic matter, as the source of CO₂, and the pedogenic carbonate. Carbon isotopes suggest prevailing C₃ vegetation and negligible mixing with volcanogenic or atmospheric CO₂. Copyright © 2000 John Wiley & Sons, Ltd.  相似文献   

Effects of soil organic matter composition on unfrozen water content and heterotrophic CO₂ production of frozen soils     

Stina Harrysson Drotz  Tobias Sparrman  Mats Nilsson 《Geochimica et cosmochimica acta》2010,74(8):2281-2290

Several recent studies have highlighted the importance of soil organic matter (SOM) mineralization at high latitudes during winter for ecosystem carbon (C) balances, and the ability of the soil to retain unfrozen water at sub-zero temperatures has been shown to be a major determinant of C mineralization rates. Further, SOM is believed to strongly influence the liquid water contents in frozen surface layers of boreal forest soils and tundra, but the mechanisms and specific factors involved are currently unknown. Here we evaluate the effects of the chemical composition of SOM on the amount of unfrozen water, the pore size equivalents in which unfrozen water can exist, and the microbial heterotrophic activity at sub-zero temperatures in boreal forest soils. To do this, we have characterized the chemical composition of SOM in forest soil samples (surface O-horizons) using solid state CP-MAS (cross polarization magic angle spinning) NMR spectroscopy. The acquired information was then used to elucidate the extent to which different fractions of SOM can explain the observed variations in unfrozen water content, pore size equivalents, and biogenic CO₂ production rates in the examined soil samples under frozen conditions (−4 °C). The data evaluation was done by the use of principal component analysis (PCA) and projections to latent structures by means of partial least square (PLS). We conclude that aromatic, O-aromatic, methoxy/N-alkyl and alkyl C are the major SOM components affecting frozen boreal forest soil’s ability to retain unfrozen water and sustain heterotrophic activity (95% confidence level). Our results reveal that solid carbohydrates have a significant negative impact (95% confidence level) on CO₂ production in frozen boreal spruce forest soils, in contrast to the positive effects of carbohydrate polymers during unfrozen conditions. We conclude that the hierarchy of environmental factors controlling SOM mineralization changes as soils freeze. The effect of SOM composition on pore size distribution and unfrozen water content has a superior influence on SOM mineralization and hence on heterotrophic CO₂ production of frozen soils.  相似文献   

全球变化条件下的土壤呼吸效应   总被引：52，自引：7，他引：52  

彭少麟  李跃林  任海  赵平 《地球科学进展》2002,17(5):705-713

土壤呼吸是陆地植物固定CO₂尔后又释放CO₂返回大气的主要途径，是与全球变化有关的一个重要过程。综述了全球变化下CO₂浓度上升、全球增温、耕作方式的改变及氮沉降增加的土壤呼吸效应。大气CO₂浓度的上升将增加土壤中CO₂的释放通量，同时将促进土壤的碳吸存；在全球增温的情形下，土壤可能向大气中释放更多的CO₂，传统的土地利用方式可能是引发温室气体CO₂产生的重要原因，所有这些全球变化对土壤呼吸的作用具有不确定性。认为土壤碳库的碳储量增加并不能减缓21世纪大气CO₂浓度的上升。据此讨论了该问题的对策并提出了今后土壤呼吸的一些研究方向。其中强调，尽管森林土壤碳固定能力有限，但植树造林、森林保护是一项缓解大气CO₂上升的可行性对策；基于现有田间尺度CO₂通量测定在不确定性方面的进展，今后应继续朝大尺度田间和模拟程序方面努力；着重回答全球变化条件下的土壤呼吸过程机理；区分土壤呼吸的不同来源以及弄清土壤呼吸黑箱系统中土壤微生物及土壤动物的功能。当然，土壤呼吸的测定方法尚有待改善。  相似文献