Initial responses of carbonate-rich shelf sediments to rising atmospheric pCO2 and “ocean acidification”: Role of high Mg-calcites

Carbonate-rich sediments at shoal to shelf depths (<200 m) represent a major CaCO₃ reservoir that can rapidly react to the decreasing saturation state of seawater with respect to carbonate minerals, produced by the increasing partial pressure of atmospheric carbon dioxide (pCO₂) and “acidification” of ocean waters. Aragonite is usually the most abundant carbonate mineral in these sediments. However, the second most abundant (typically ∼24 wt%) carbonate mineral is high Mg-calcite (Mg-calcite) whose solubility can exceed that of aragonite making it the “first responder” to the decreasing saturation state of seawater. For the naturally occurring biogenic Mg-calcites, dissolution experiments have been used to predict their “stoichiometric solubilities” as a function of mol% MgCO₃. The only valid relationship that one can provisionally use for the metastable stabilities for Mg-calcite based on composition is that for the synthetically produced phases where metastable equilibrium has been achieved from both under- and over-saturation. Biogenic Mg-calcites exhibit a large offset in solubility from that of abiotic Mg-calcite and can also exhibit a wide range of solubilities for biogenic Mg-calcites of similar Mg content. This indicates that factors other than the Mg content can influence the solubility of these mineral phases. Thus, it is necessary to turn to observations of natural sediments where changes in the saturation state of surrounding waters occur in order to determine their likely responses to the changing saturation state in upper oceanic waters brought on by increasing pCO₂. In the present study, we investigate the responses of Mg-calcites to rising pCO₂ and “ocean acidification” by means of a simple numerical model based on the experimental range of biogenic Mg-calcite solubilities as a function of Mg content in order to bracket the behavior of the most abundant Mg-calcite phases in the natural environment. In addition, observational data from Bermuda and the Great Bahama Bank are also presented in order to project future responses of these minerals. The numerical simulations suggest that Mg-calcite minerals will respond to rising pCO₂ by sequential dissolution according to mineral stability, progressively leading to removal of the more soluble phases until the least soluble phases remain. These results are confirmed by laboratory experiments and observations from Bermuda. As a consequence of continuous increases in atmospheric CO₂ from burning of fossil fuels, the average composition of contemporary carbonate sediments could change, i.e., the average Mg content in the sediments may slowly decrease. Furthermore, evidence from the Great Bahama Bank indicates that the amount of abiotic carbonate production is likely to decline as pCO₂ continues to rise.     

Microbial dissolution of calcite at T = 28 °C and ambient pCO2

This study used batch reactors to quantify the mechanisms and rates of calcite dissolution in the presence and absence of a single heterotrophic bacterial species (Burkholderia fungorum). Experiments were conducted at T = 28°C and ambient pCO₂ over time periods spanning either 21 or 35 days. Bacteria were supplied with minimal growth media containing either glucose or lactate as a C source, NH₄⁺ as an N source, and H₂PO₄⁻ as a P source. Combining stoichiometric equations for microbial growth with an equilibrium mass-balance model of the H₂O-CO₂-CaCO₃ system demonstrates that B. fungorum affected calcite dissolution by modifying pH and alkalinity during utilization of ionic N and C species. Uptake of NH₄⁺ decreased pH and alkalinity, whereas utilization of lactate, a negatively charged organic anion, increased pH and alkalinity. Calcite in biotic glucose-bearing reactors dissolved by simultaneous reaction with H₂CO₃ generated by dissolution of atmospheric CO₂ (H₂CO₃ + CaCO₃ → Ca²⁺ + 2HCO₃⁻) and H⁺ released during NH₄⁺ uptake (H⁺ + CaCO₃ → Ca²⁺ + HCO₃⁻). Reaction with H₂CO₃ and H⁺ supplied ∼45% and 55% of the total Ca²⁺ and ∼60% and 40% of the total HCO₃⁻, respectively. The net rate of microbial calcite dissolution in the presence of glucose and NH₄⁺ was ∼2-fold higher than that observed for abiotic control experiments where calcite dissolved only by reaction with H₂CO₃. In lactate bearing reactors, most H⁺ generated by NH₄⁺ uptake reacted with HCO₃⁻ produced by lactate oxidation to yield CO₂ and H₂O. Hence, calcite in biotic lactate-bearing reactors dissolved by reaction with H₂CO₃ at a net rate equivalent to that calculated for abiotic control experiments. This study suggests that conventional carbonate equilibria models can satisfactorily predict the bulk fluid chemistry resulting from microbe-calcite interactions, provided that the ionic forms and extent of utilization of N and C sources can be constrained. Because the solubility and dissolution rate of calcite inversely correlate with pH, heterotrophic microbial growth in the presence of nonionic organic matter and NH₄⁺ appears to have the greatest potential for enhancing calcite weathering relative to abiotic conditions.     

不同类型湿地CO2:CH4比例及其影响因素: 整合分析

湿地是温室气体二氧化碳(CO₂)和甲烷(CH₄)的主要来源之一,在全球碳循环中发挥着重要作用。由于CH₄在百年尺度上的全球增温潜势是CO₂的45倍,因此深入研究湿地CO₂:CH₄的排放比例及其影响因素对准确理解和预测湿地碳循环过程及其对未来全球变化的响应具有重要意义。本文采用文献整合分析方法,对比了不同类型湿地中CO₂:CH₄排放比例的特征及其影响因素。结果表明,藓类泥炭沼泽、滨海湿地和稻田中CO₂:CH₄排放比例显著高于草本沼泽、河流湿地和湖泊湿地等其他类型湿地;相关性分析研究发现,湿地CO₂:CH₄排放比例与pH和水位显著负相关,与盐度显著正相关。可见,藓类泥炭沼泽低水位和低pH抑制CH₄排放是导致其CO₂:CH₄排放比例较高的重要原因,而滨海湿地高盐分抑制CH₄排放是其CO₂:CH₄排放比例高的重要原因。与自然湿地相比,稻田CO₂:CH₄排放比例高与其人为施肥和稻草还田抑制CH₄排放有关。此外,大气温度、土壤温度、降水量、土壤含水率等因子也对湿地CO₂:CH₄排放比例具有重要影响,尽管它们之间的线性相关关系不显著。目前,湿地CO₂:CH₄排放比例和影响因素仍存在很大的不确定性,未来亟待加强不同类型湿地CO₂:CH₄排放比例及其关键影响因素研究。

     

Carbon isotope evidence implying high O2/CO2 ratios in the Permo-Carboniferous atmosphere

Theoretical models predict a marked increase in atmospheric O₂ to ∼35% during the Permo-Carboniferous (∼300 Ma) occurring against a low (∼0.03%) CO₂ level. An upper O₂ value of 35%, however, remains disputed because ignition data indicate that excessive global forest fires would have ensued. This uncertainty limits interpretation of the role played by atmospheric oxygen in Late Paleozoic biotic evolution. Here, we describe new results from laboratory experiments with vascular land plants that establish that a rise in O₂ to 35% increases isotopic fractionation (Δ¹³C) during growth relative to control plants grown at 21% O₂. Despite some effect of the background atmospheric CO₂ level on the magnitude of the increase, we hypothesize that a substantial Permo-Carboniferous rise in O₂ could have imprinted a detectable geochemical signature in the plant fossil record. Over 50 carbon isotope measurements on intact carbon from four fossil plant clades with differing physiological ecologies and ranging in age from Devonian to Cretaceous reveal a substantial Δ¹³C anomaly (5‰) occurring between 300 and 250 Ma. The timing and direction of the Δ¹³C excursion is consistent with the effects of a high O₂ atmosphere on plants, as predicted from photosynthetic theory and observed in our experiments. Preliminary calibration of the fossil Δ¹³C record against experimental data yields a predicted O₂/CO₂ mixing ratio of the ancient atmosphere consistent with that calculated from long-term models of the global carbon and oxygen cycles. We conclude that further work on the effects of O₂ in the combustion of plant materials and the spread of wildfire is necessary before existing data can be used to reliably set the upper limit for paleo-O₂ levels.     

D/H ratios of atmospheric H2 in urban air: results using new methods for analysis of nano-molar H2 samples

We present the results of a study of the concentration and D/H ratio of molecular hydrogen from air in the Los Angeles Basin and adjacent San Gabriel Mountains. These data define a mixing relationship in dimensions of D/H ratio vs. 1/(H₂) which constrains the δD_VSMOW of unpolluted winter air in this region to be ca. +100 to +125 ‰ and that of urban H₂ sources to be ca. −270 ‰. This study makes use of a new method for measuring the deuterium content of molecular hydrogen in small samples (∼100 to 500 cc) of air, which we describe in detail. The method consists of an off-line separation of H₂ followed by introduction to the mass spectrometer in a continuous flow of He. Off-line, all components of an atmospheric gas sample, with the exception of He, H₂, and Ne are condensed by exposure to a cold-trap held at 30 Kelvin. This separation is followed by cryo-transfer of non-condensable gases to a small volume molecular sieve finger, with assist from a mercury piston pump. At the mass spectrometer, the sample is put in line with a continuous flow of He where it is focused on to an additional column of molecular sieve before subsequent introduction into the ion source. Analyses of DH/H₂ ratio have accuracy and precision of ±4 to 7 per mil. Comparison of sample peak area to peak areas of standards of known size allows for determination of H₂ concentration with accuracy and precision of ∼±5%, relative. The method reduces sample size and processing time by several orders of magnitude compared to previous methods, allowing for sampling at proportionately higher spatial and temporal resolution.     

GEOCARBSULF: A combined model for Phanerozoic atmospheric O2 and CO2

A model for the combined long-term cycles of carbon and sulfur has been constructed which combines all the factors modifying weathering and degassing of the GEOCARB III model [Berner R.A., Kothavala Z., 2001. GEOCARB III: a revised model of atmospheric CO₂ over Phanerozoic time. Am. J. Sci. 301, 182-204] for CO₂ with rapid recycling and oxygen dependent carbon and sulfur isotope fractionation of an isotope mass balance model for O₂ [Berner R.A., 2001. Modeling atmospheric O₂ over Phanerozoic time. Geochim. Cosmochim. Acta65, 685-694]. New isotopic data for both carbon and sulfur are used and new feedbacks are created by combining the models. Sensitivity analysis is done by determining (1) the effect on weathering rates of using rapid recycling (rapid recycling treats carbon and sulfur weathering in terms of young rapidly weathering rocks and older more slowly weathering rocks); (2) the effect on O₂ of using different initial starting conditions; (3) the effect on O₂ of using different data for carbon isotope fractionation during photosynthesis and alternative values of oceanic δ¹³C for the past 200 million years; (4) the effect on sulfur isotope fractionation and on O₂ of varying the size of O₂ feedback during sedimentary pyrite formation; (5) the effect on O₂ of varying the dependence of organic matter and pyrite weathering on tectonic uplift plus erosion, and the degree of exposure of coastal lands by sea level change; (6) the effect on CO₂ of adding the variability of volcanic rock weathering over time [Berner, R.A., 2006. Inclusion of the weathering of volcanic rocks in the GEOCARBSULF model. Am. J. Sci.306 (in press)]. Results show a similar trend of atmospheric CO₂ over the Phanerozoic to the results of GEOCARB III, but with some differences during the early Paleozoic and, for variable volcanic rock weathering, lower CO₂ values during the Mesozoic. Atmospheric oxygen shows a major broad late Paleozoic peak with a maximum value of about 30% O₂ in the Permian, a secondary less-broad peak centered near the Silurian/Devonian boundary, variation between 15% and 20% O₂ during the Cambrian and Ordovician, a very sharp drop from 30% to 15% O₂ at the Permo-Triassic boundary, and a more-or less continuous rise in O₂ from the late Triassic to the present.     

低硅埃达克岩和高硅埃达克岩问题

低硅埃达克岩(low-SiO2adakites,LSA,SiO2<60%)和高硅埃达克岩(high-SiO2adakites,HSA,SiO2>60%)的术语是Martin等(2005)提出来的。本文不赞同上述分类,因为,他们的低硅埃达克岩是赞岐岩而不是埃达克岩。赞岐岩是幔源的,埃达克岩是壳源的,虽然埃达克岩可以与地幔混合形成高镁的埃达克岩,但仍然是壳源的。不应当把壳源的岩浆和幔源的岩浆混淆起来。     

A high temperature equation of state for the H2O-CaCl2 and H2O-MgCl2 systems

An equation of state (EOS) is developed for salt-water systems in the high temperature range. As an example of the applications, this EOS is parameterized for the calculation of density, immiscibility, and the compositions of coexisting phases in the CaCl₂-H₂O and MgCl₂-H₂O systems from 523 to 973 K and from saturation pressure to 1500 bar. All available volumetric and phase equilibrium measurements of these binaries are well represented by this equation. This EOS is based on a Helmholtz free energy representation constructed from a reference system containing hard-sphere and polar contributions plus an empirical correction. For the temperature and pressure range in this study, the electrolyte solutes are assumed to be associated. The water molecules are modeled as hard spheres with point dipoles and the solute molecules, MgCl₂ and CaCl₂, as hard spheres with point quadrupoles. The free energy of the reference system is calculated from an analytical representation of the Helmholtz free energy of the hard-sphere contributions and perturbative estimates of the electrostatic contributions. The empirical correction used to account for deviations of the reference system predictions from measured data is based on a virial expansion. The formalism allows generalization to aqueous systems containing insoluble gases (CO₂, CH₄), alkali chlorides (NaCl, KCl), and alkaline earth chlorides (CaCl₂, MgCl₂). The program of this model is available as an electronic annex (see EA1 and EA2) and can also be downloaded at: http://www.geochem-model.org/programs.htm.     

A 1000-year record of Mg/Li and Li/Ca ratios of ostracod shells in Lake Qinghai,NE Tibetan Plateau

正1 Introduction Lake Qinghai,famous as the largest inland saline lake in China,located on the high-altitude northeastern Tibetan Plateau,and four junctional zones of the East Asian summer monsoon(EASM),Indian summer monsoon(ISM),East Asian winter monsoon and the westerly jet stream prevail,making it sensitive to global climate change     

Impact of climate and CO2 on a millennium-long tree-ring carbon isotope record

We present one millennium-long (1171-year), and three 100 year long annually resolved δ¹³C tree-ring chronologies from ecologically varying Juniperus stands in the Karakorum Mountains (northern Pakistan), and evaluate their response to climatic and atmospheric CO₂ changes. All δ¹³C records show a gradual decrease since the beginning of the 19th century, which is commonly associated with a depletion of atmospheric δ¹³C due to fossil fuel burning. Climate calibration of high-frequency δ¹³C variations indicates a pronounced summer temperature signal for all sites. The low-frequency component of the same records, however, deviates from long-term temperature trends, even after correction for changes in anthropogenic CO₂. We hypothesize that these high-elevation trees show a response to both climate and elevated atmospheric CO₂ concentration and the latter might explain the offset with target temperature data. We applied several corrections to tree-ring δ¹³C records, considering a range of potential CO₂ discrimination changes over the past 150 years and calculated the goodness of fit with the target via calibration/verification tests (R², residual trend, and Durbin-Watson statistics). These tests revealed that at our sites, carbon isotope fixation on longer timescales is affected by increasing atmospheric CO₂ concentrations at a discrimination rate of about 0.012‰/ppmv. Although this statistically derived value may be site related, our findings have implications for the interpretation of any long-term trends in climate reconstructions using tree-ring δ¹³C, as we demonstrate with our millennium-long δ¹³C Karakorum record. While we find indications for warmth during the Medieval Warm Period (higher than today’s mean summer temperature), we also show that the low-frequency temperature pattern critically depends on the correction applied. Patterns of long-term climate variation, including the Medieval Warm Period, the Little Ice Age, and 20th century warmth are most similar to existing evidence when a strong influence of increased atmospheric CO₂ on plant physiology is assumed.     

A hydrothermal investigation of the system FeOFe2O3TiO2: A discussion with new data

New experimental data on the system FeOFe₂O₂TiO₂ using a new oxygen buffer are presented. It is found that there is a narrow range of oxygen fugacity above 550°C within which hematite and ilmenite coexist stably.     

CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids: Implications for modeling the solubility of CO2 in silicic melts

The solubility of CO₂ in dacitic melts equilibrated with H₂O-CO₂ fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO₂ is dissolved in dacitic glasses as molecular CO₂ and carbonate. The quantification of total CO₂ in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm⁻¹ can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO_2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO₂ species concentrations from the MIR spectra we have measured total CO₂ contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO₂ solubility in dacitic melts on x^fluid_CO2,total shows a strong positive deviation from linearity with almost constant CO₂ solubility at x_CO2fluid > 0.8 (maximum CO₂ solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO₂. A similar nonlinear variation of CO₂ solubility with x_CO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO₂ (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO₂ molecules.A thermodynamic model describing the dependence of the CO₂ solubility in hydrous rhyolitic and dacitic melts on T, P, f_CO2 and the mol fraction of water in the melt (x_water) has been developed. An exponential variation of the equilibrium constant K₁ with x_water is proposed to account for the nonlinear dependence of x_CO2,totalmelt on x_CO2fluid. The model reproduces the CO₂ solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low x_CO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO₂ at low pressures (a Henrian behavior of the CO₂ solubility is observed at low pressure and low H₂O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the x_CO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO₂ is much lower in rhyolitic melts (31.7 cm³/mol) than in dacitic melts (46.6 cm³/mol). The dissolution enthalpy for CO₂ in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO₂ solubility in silicic melts.     

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

A hydrothermal investigation of the system FeO, Fe2O3, TiO2

Phase relations in the system FeO---Fe₂O₃---TiO₂, at temperatures ranging between 300°C and 700°C, have been investigated experimentally with special refference to the reaction Fe₃O₄ + TiO₂ = Fe₂O₃ + FeTiO₃. Pressure was varied between 500 and 2000 bars but its effect was negligible. Magnetite and rutile are the stable assemblage at temperatures above 550 dgC, and hematite and ilmenite are stable for lower temperatures. The equilibrium oxygen fugacity is estimated to be 10^−17.5 bars at equilibrium temperature. It is suggested that intermediate hematite-ilmenite solid solutions are inhomogeneous, consisting of ‘domains’ of hematite and ilmenite. The ‘domains’ are too small to be resolved by X-ray diffraction techniques. The top of the solvus curve in the hematite-ilmenite solution corresponds to a temperature of 660°C. Regular solution theory is not applicable to the solid solution.     

N2-CH4（CO2）混合气体在线标样制备及其拉曼定量因子测定

利用混合气体的标准样品对激光拉曼探针进行标定,可以快速准确地对包裹体中的无机及有机气相组分进行定量分析。而常用的商用钢瓶装混合气体标样,存在费用高、气体组成单一固定等缺点。本文设计了一套在线标样制备装置,提出一种在线配置不同浓度和压力条件下混合气体标样的方法。利用高纯度(纯度99.999%)的N2、CH4以及CO2钢瓶气,经过在线混合增压,在5 MPa和10 MPa条件下制备了N2摩尔分数为30%、50%和70%的N2-CH4以及N2-CO2混合气体在线标样。该方法制备的标样与70%N2+30%CO2的商用钢瓶气标样对比表明,CO2与N2的拉曼相对峰高以及相对峰面积值的误差在4%以内,具有较高的准确度和重现性。通过不同压力和浓度条件下CH4以及CO2的拉曼相对定量因子测定表明,气体的相对定量因子在5~10 MPa压力条件下与压力及组成无关。地质样品应用结果表明,本方法可以方便、灵活、准确地按任意比例将两瓶及两瓶以上纯气体钢瓶样品进行混合及增压,为激光拉曼标定、气体组成原位测量等提供了一种新的技术思路。     

A pedogenic goethite record of soil CO2 variations as a response to soil moisture content

The terrestrial carbon cycle and the role of atmospheric CO₂ concentrations in controlling global temperatures can be inferred from the study of ancient soils (paleosols). Soil-formed goethite and calcite have been the primary minerals used as a geochemical proxy for reconstructing atmospheric pCO₂ from ancient terrestrial records. In the case of goethite, optimum sampling strategies for reconstructing pCO₂ focus on the portion of the soil profile that displays steep gradients in both soil CO₂ concentration and δ¹³C values of soil CO₂ such that a keeling plot can be developed for a given soil and atmospheric pCO₂ can be calculated from it. We report data from a Carboniferous paleosol that depart from the expected linear trends. The results indicate that pedogenic goethite is sensitive to variations in the isotopic composition of soil CO₂, over a range of timescales, and can record these variations in the carbon isotope composition and mole fraction of Fe(CO₃)OH in solid solution with goethite. We explore possible environmental conditions that can drive these changes as a function of either moisture controlled variations in soil respired CO₂ or in the residence time of carbon in soils. The implications of this result are overestimation of paleoatmospheric pCO₂ from pedogenic goethite.