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1.
In this work 3-[2-(2-aminoethylamino)ethylamino]propyl trimethoxysilane (TRI) was employed to functionalize MWCNT containing hydroxyl groups (OH-MWCNT), and the XRD, FTIR, TGA and CHNS elemental analysis techniques were used to characterize the resulted adsorbents. The characterization results for amine-MWCNT showed amine groups effectively attached to the surface of the MWCNT. The equilibrium adsorption capacity of pure CO2 and CH4 and their binary mixture on the pristine MWCNT, OH-MWCNT and amine-MWCNT was measured through a set of equilibrium adsorption experiments at 303.2 and 318.2 K. Capacities of all three types of adsorbents for CO2 adsorption were higher than those for methane adsorption. Also, amine-MWCNT demonstrated better performance on CO2 adsorption than the other two adsorbents, especially at low partial pressures. The capacity of amine-MWCNT for pure CO2 adsorption was 2.5 and 4 times as much as those for pristine MWCNT and OH-MWCNT, respectively, at the temperature of 303.2 K and the pressure of 0.2 bar. The binary adsorption experiment revealed that CO2/CH4 selectivity for pristine MWCNT and amine-MWCNT in all molar fractions of CO2 is about 1.77 and 7, respectively.  相似文献   

2.
In this work, permeation of mixed gases H2S/CH4 through commercial polyphenylene oxide (PPO) hollow fiber and poly (ester urethane) urea (PEUU) flat membranes was studied at pressures of 345–689 kPa, at ambient temperature and at 313.15 K. Various H2S concentrations of about 100–5000 ppm in CH4 binary synthetic gas mixtures as well as a real natural gas sample obtained from a gas refinery containing 0.3360 mol.% H2S (equivalent to 3360 ppm) were tested. It was observed that the permeance of components was affected by the balance between competitive sorption and plasticization effects. Separation factors of H2S/CH4 were in the range of 1.3–2.9, 1.8–3.1 and 2.2–4.3 at pressures of 345, 517 and 689 kPa, respectively. In the range of 101–5008 ppm of H2S in CH4, the effect of temperature on the separation factor was nearly negligible; however, permeances of both components of the mixtures increased with temperature. Additionally, the results obtained by PEUU membrane indicated that it was a better choice for hydrogen sulfide separation from H2S/CH4 mixtures than PPO. For PPO membrane, removal of hydrogen sulfide from high-concentration (up to 5008 ppm) binary mixtures of H2S/CH4 was compared with that of low concentration (as low as 101 ppm) through PPO. At concentrations of 101–968 ppm, plasticization was dominant compared with the competitive sorption, while for the H2S feed concentrations of 3048 ppm, the competitive sorption effect was dominant. For H2S concentration of 5008 ppm, the balance between these two effects played an important role for explanation of its trend.  相似文献   

3.
This study assesses the ability of two low-cost adsorbents made from waste of Rapanea ferruginea treated with ethanol (WRf) and its H2SO4-treated analog (WRf/H2SO4) for the removal of two cationic dyes methylene blue (MB) and crystal violet (CV) from aqueous solutions. The adsorbent was characterized by scanning electron microscopy, Fourier transform infrared spectrometry, thermogravimetric analysis, point of zero charge (pHpzc), specific surface, and functional groups. The adsorption of dye onto the adsorbents was studied as a function of pH solution (2–12), contact time (up to 120 min) and initial concentration (20–120 mg/L), and temperature (25, 35, and 55 °C). The influence of these parameters on adsorption capacity was studied using the batch process. The response surface methodology (RSM) was used in the experimental design, modeling of the process, and optimizing of the variables and was optimized by the response involving Box–Behnken factorial design (15 runs). The results show that the data correlated well with the Sips isotherm. The maximum adsorption capacities of MB and CV onto WRf were found to be 69 and 106 mg/g, and onto WRf/H2SO4, the adsorption capacities were 33 and 125 mg/g, respectively. The kinetic data revealed that adsorption of cationic dyes onto the adsorbents closely follows the pseudo-second-order kinetic model. Regression analysis showed good fit of the experimental data to the second-order polynomial model, with coefficient of determination (R2) values for MB (R2?=?0.9685) and MB (R2?=?0.9832) for WRf and CV (R2?=?0.9685) and CV (R2?=?0.9832) for WRf/H2SO4 indicated that regression analysis is able to give a good prediction of response for the adsorption process in the range studied. The results revealed that waste from R. ferruginea is potentially an efficient and low-cost adsorbent for adsorption of MB and CV.  相似文献   

4.
Stability and phase relations of coexisting enstatite and H2 fluid were investigated in the pressure and temperature regions of 3.1–13.9 GPa and 1500–2000 K using laser-heated diamond-anvil cells. XRD measurements showed decomposition of enstatite upon heating to form forsterite, periclase, and coesite/stishovite. In the recovered samples, SiO2 grains were found at the margin of the heating hot spot, suggesting that the SiO2 component dissolved in the H2 fluid during heating, then precipitated when its solubility decreased with decreasing temperature. Raman and infrared spectra of the coexisting fluid phase revealed that SiH4 and H2O molecules formed through the reaction between dissolved SiO2 and H2. In contrast, forsterite and periclase crystals were found within the hot spot, which were assumed to have replaced the initial orthoenstatite crystals without dissolution. Preferential dissolution of SiO2 components of enstatite in H2 fluid, as well as that observed in the forsterite H2 system and the quartz H2 system, implies that H2-rich fluid enhances Mg/Si fractionation between the fluid and solid phases of mantle minerals.  相似文献   

5.
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6.
Rapid increases in the amounts of fullerene C60 nanoparticles (nC60) being produced and used will inevitably lead to increases in the amounts released into the aquatic environment. This will have implications for human and ecosystem health. Wastewater treatment plants are key barriers to nC60 being released into aquatic systems, but little information is available on how adsorption processes in wastewater treatment plants affect the fates of nC60. We investigated the effects of the surface properties of activated sludge on the adsorption of nC60 and related mechanisms by modeling the adsorption kinetics and equilibrium process and performing correlation analyses. The adsorption of nC60 closely followed the pseudo-second-order kinetic model (R > 0.983), the Freundlich isotherm model (R > 0.990), and the linear partitioning isotherm model (R > 0.966). Different adsorption coefficients, 1.070–4.623 for the Freundlich partitioning model and 1.788–6.148 for the linear partitioning model, were found for different types of activated sludge. The adsorption coefficients significantly positively correlated with the zeta (ζ) potential (R = 0.877) and hydrophobicity (R = 0.661) and negatively correlated with particle size (R = ?0.750). The results show that nC60 adsorption is strongly affected by the surface properties of activated sludge because changes in surface properties cause changes in the electrostatic and hydrophobic interactions that occur.  相似文献   

7.
CO2 is a greenhouse gas, whose emissions threaten the existence of human beings. Its inherently safe sequestration can be performed via CO2 mineralization, which is relatively slow under natural conditions. In this work, an energy-saving membrane electrolysis technique was proposed for accelerating the CO2 mineralization of wollastonite into SiO2 and CaCO3 products. The electrolysis process involved splitting NH4Cl into HCl and NH3·H2O via hydrogen oxidation and water reduction at the anode and cathode of the electrolytic system, respectively. In contrast to the chlor-alkali electrolysis, this method did not involve Cl? oxidation and the standard potential of the anode was reduced. Additionally, NH4Cl was used as the electrolyte instead of NaCl; as a result, the generation of NH3·H2O instead of NaOH occurred in the catholyte and the cathodic pH dramatically decreased, thus reducing the cathodic potential for hydrogen evolution. The observed changes led to a 73.5% decrease in the energy consumption. Moreover, after the process of CO2 mineralization was optimized, SiO2 with a specific surface area of 221.8 m2 g?1 and CaCO3 with a purity of 99.9% were obtained.  相似文献   

8.
It is demonstrated that single titanium dioxide (TiO2) has high potential for photodegradation of pollutants. However, it is still far from becoming an effective photocatalyst system, due to issues of adsorption process, separation, as well as dissolution. Therefore, this study highlights the high adsorption capacity, simplified separation, and the promising stability of TiO2(SY) (synthesized via sol–gel method) photocatalyst, fabricated using chitosan–TiO2(SY) and supported by glass substrate (Cs–TiO2(SY)/glass substrate) photocatalysts. Chitosan (Cs), with abundant –R–NH and NH2 groups, promotes the adsorption sites of methyl orange (MO) and OH groups for major attachment to TiO2(SY). Meanwhile, the glass substrate increases stability and assists separation of the photocatalysts. Initially, nano-TiO2(SY) has been characterized using high-resolution transmission electron microscope. Cs–TiO2(SY)/glass substrate was fabricated via dip-coating. The distribution and interface between the photocatalytic components were characterized by Fourier transform infrared absorption spectroscopy, UV–Vis diffuse reflectance spectroscopy, field emission scanning electron microscopy, and energy-dispersive spectrometer. UV–Vis analysis of the multilayer photocatalyst (2, 4, 6, and 8 layers) was further carried out by the adsorption–photodegradation, with MO as model of pollutant. Seventy percent of the total removal of MO via optimized eight layers of photocatalyst was achieved within 1 h of UV irradiation. The adsorption photocatalyst achieved 50 % with no exposure to UV light for 15 min of irradiation. It is concluded that suitable photocatalytic conditions and sample parameters possessing the multilayer photocatalyst of Cs–TiO2(SY) are beneficial toward the adsorption–photodegradation process in wastewater treatment.  相似文献   

9.
The carbon molecular sieves (CMSs) prepared by carbonaceous materials as precursors are effective in CO2/N2 separation. However, selectivity of these materials is too low, since hydrocarbon cracking for developing the desired microporosity in carbonaceous materials has not been done effectively. Hence, in this study, cobalt and nickel impregnation on the precursor was conducted to introduce catalysts for hydrocarbon cracking. Cobalt and nickel impregnation, carbonization under N2 atmosphere, and chemical vapor deposition (CVD) by benzene were conducted on the extruded mixtures of activated carbon and coal tar pitch under different conditions to prepare CMSs. The best CMS prepared by carbon deposition on the cobalt-impregnated samples exhibited CO2 adsorption capacity of 54.79 mg/g and uptake ratio of 28.9 at 0 °C and 1 bar. In terms of CO2 adsorption capacity and uptake ratio, CMSs prepared by carbon deposition on non-impregnated and cobalt-impregnated samples presented the best results, respectively. As benzene concentration and CVD time increased, equilibrium adsorption capacity of CO2 decreased, and uptake ratio increased. Cobalt was found to be the best catalyst for benzene cracking in the CVD process.  相似文献   

10.
Using a diamond-anvil cell and synchrotron X-ray diffraction, the compressional behavior of a synthetic qandilite Mg2.00(1)Ti1.00(1)O4 has been investigated up to about 14.9 GPa at 300 K. The pressure–volume data fitted to the third-order Birch–Murnaghan equation of state yield an isothermal bulk modulus (K T0) of 175(5) GPa, with its first derivative \(K_{T0}^{{\prime }}\) attaining 3.5(7). If \(K_{T0}^{{\prime }}\) is fixed as 4, the K T0 value is 172(1) GPa. This value is substantially larger than the value of the adiabatic bulk modulus (K S0) previously determined by an ultrasonic pulse echo method (152(7) GPa; Liebermann et al. in Geophys J Int 50:553–586, 1977), but in general agreement with the K T0 empirically estimated on the basis of crystal chemical systematics (169 GPa; Hazen and Yang in Am Miner 84:1956–1960, 1999). Compared to the K T0 values of the ulvöspinel (Fe2TiO4; ~148(4) GPa with \(K_{T0}^{{\prime }} = 4\)) and the ringwoodite solid solutions along the Mg2SiO4–Fe2SiO4 join, our finding suggests that the substitution of Mg2+ for Fe2+ on the T sites of the 4–2 spinels can have more significant effect on the K T0 than that on the M sites.  相似文献   

11.
Three isotypic crystals, SiO2 (α-cristobalite), ε-Zn(OH)2 (wülfingite), and Be(OH)2 (β-behoite), with topologically identical frameworks of corner-connected tetrahedra, undergo displacive compression-driven phase transitions at similar pressures (1.5–2.0 GPa), but each transition is characterized by a different mechanism resulting in different structural modifications. In this study, we report the crystal structure of the high-pressure γ-phase of beryllium hydroxide and compare it with the high-pressure structures of the other two minerals. In Be(OH)2, the transition from the ambient β-behoite phase with the orthorhombic space group P212121 and ambient unit cell parameters a = 4.5403(4) Å, b = 4.6253(5) Å, c = 7.0599(7) Å, to the high-pressure orthorhombic γ-polymorph with space group Fdd2 and unit cell parameters (at 5.3(1) GPa) a = 5.738(2) Å, b = 6.260(3) Å, c = 7.200(4) Å takes place between 1.7 and 3.6 GPa. This transition is essentially second order, is accompanied by a negligible volume discontinuity, and exhibits both displacive and reversible character. The mechanism of the phase transition results in a change to the hydrogen bond connectivities and rotation of the BeO4 tetrahedra.  相似文献   

12.
The crystal structure of Pb6Bi2S9 is investigated at pressures between 0 and 5.6 GPa with X-ray diffraction on single-crystals. The pressure is applied using diamond anvil cells. Heyrovskyite (Bbmm, a = 13.719(4) Å, b = 31.393(9) Å, c = 4.1319(10) Å, Z = 4) is the stable phase of Pb6Bi2S9 at ambient conditions and is built from distorted moduli of PbS-archetype structure with a low stereochemical activity of the Pb2+ and Bi3+ lone electron pairs. Heyrovskyite is stable until at least 3.9 GPa and a first-order phase transition occurs between 3.9 and 4.8 GPa. A single-crystal is retained after the reversible phase transition despite an anisotropic contraction of the unit cell and a volume decrease of 4.2%. The crystal structure of the high pressure phase, β-Pb6Bi2S9, is solved in Pna2 1 (a = 25.302(7) Å, b = 30.819(9) Å, c = 4.0640(13) Å, Z = 8) from synchrotron data at 5.06 GPa. This structure consists of two types of moduli with SnS/TlI-archetype structure in which the Pb and Bi lone pairs are strongly expressed. The mechanism of the phase transition is described in detail and the results are compared to the closely related phase transition in Pb3Bi2S6 (lillianite).  相似文献   

13.
The high-pressure behavior of a vanadinite (Pb10(VO4)6Cl2, a = b = 10.3254(5), c = 7.3450(4) Å, space group P63/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V 0 = 681(1) Å3, K 0 = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a 0 = 10.3302(2) Å, K 0(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c 0 = 7.3520(3) Å, K 0(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K 0(a):K 0(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe a (0) = 35(2) GPa for the a-axis, Fe c (0) = 98(4) GPa for the c-axis and Fe V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed.  相似文献   

14.
The water-saturated phase relations have been determined for a primitive magnesian andesite (57 wt% SiO2, 9 wt% MgO) from the Mt. Shasta, CA region over the pressure range 200–800 MPa, temperature range of 915–1,070 °C, and oxygen fugacities varying from the nickel–nickel oxide (NNO) buffer to three log units above NNO (NNO+3). The phase diagram of a primitive basaltic andesite (52 wt% SiO2, 10.5 wt% MgO) also from the Mt. Shasta region (Grove et al. in Contrib Miner Petrol 145:515–533; 2003) has been supplemented with additional experimental data at 500 MPa. Hydrous phase relations for these compositions allow a comparison of the dramatic effects of dissolved H2O on the crystallization sequence. Liquidus mineral phase stability and appearance temperatures vary sensitively in response to variation in pressure and H2O content, and this information is used to calibrate magmatic barometers-hygrometers for primitive arc magmas. H2O-saturated experiments on both compositions reveal the strong dependence of amphibole stability on the partial pressure of H2O. A narrow stability field is identified where olivine and amphibole are coexisting phases in the primitive andesite composition above 500 MPa and at least until 800 MPa, between 975–1,025 °C. With increasing H2O pressure (\({P}_{\text {H}_2{\rm O}}\)), the temperature difference between the liquidus and amphibole appearance decreases, causing a change in chemical composition of the first amphibole to crystallize. An empirical calibration is proposed for an amphibole first appearance barometer-hygrometer that uses Mg# of the amphibole and \(f_{\text {O}_2}\):
$$ P_{\text{H}_{2}{\rm O}}({\rm MPa})=\left[{\frac{{\rm Mg\#}}{52.7}}-0.014 * \Updelta {\rm NNO}\right]^{15.12} $$
This barometer gives a minimum \({P}_{\text{H}_{2}{\rm O}}\) recorded by the first appearance of amphibole in primitive arc basaltic andesite and andesite. We apply this barometer to amphibole antecrysts erupted in mixed andesite and dacite lavas from the Mt. Shasta, CA stratocone. Both high H2O pressures (500–900 MPa) and high pre-eruptive magmatic H2O contents (10–14 wt% H2O) are indicated for the primitive end members of magma mixing that are preserved in the Shasta lavas. We also use these new experimental data to explore and evaluate the empirical hornblende barometer of Larocque and Canil (2010).
  相似文献   

15.
Dried, mature leaves of Aegle Marmelos tree were converted to a powder, which was used as a biosorbent for dyes in water with methylene blue as a case study. The biosorbent had a surface area of 52.63 mg/g, and FTIR spectra showed the presence of –COOH, –NH2, –R–SC=O (thioester) and R1–S(=O, =O)-N(–R2, –R3) groups on the surface. The particles were found to be porous in nature from scanning electron micrographs, and EDX measurements showed the elements C, O, Na, Mg, K, Ca and Fe on the surface. Batch adsorption experiments showed that the adsorption of the dye was preferred at near-neutral conditions. Adsorption equilibrium was achieved in ~120 min with maximum dye uptake of 19.9 mg/g. Investigation into the kinetics of adsorption indicated that second-order kinetics gave the best fit to the experimental data, and a rate coefficient of 8.0 × 10?2 to 32.3 × 10?2 g mg?1 min?1 was obtained.  相似文献   

16.
The transition between rutile and α-PbO2 structured TiO2 (TiO2II) has been investigated at 700–1,200 °C and 4.2–9.6 GPa. Hydrothermal phase equilibrium experiments were performed in the multi-anvil apparatus to bracket the phase boundary at 700, 1,000, and 1,200 °C. The equilibrium phase boundary is described by the equation: P (GPa)=1.29+0.0065 T ( °C). In addition, growth of TiO2II was observed in experiments at 500 and 600 °C, although growth of rutile was too slow to bracket unambiguously the equilibrium boundary at these temperatures. Water was not detected in either rutile or TiO2II, and dry synthesis experiments at 1,200 °C were consistent with the phase boundary determined in the fluid-bearing experiments, suggesting that the equilibrium is unaffected by the presence of water. Our bracket of the phase boundary at 700 °C is consistent with the reversed, dry experiments of Akaogi et al. (1992) and the reversals of Olsen et al. (1999). The new data suggest that the phase boundary is linear, in agreement with Akaogi et al. (1992), but in striking contrast to the phase diagram inferred by Olsen et al. (1999). The natural occurrence of TiO2II requires formation pressures considerably higher than the graphite–diamond phase boundary.  相似文献   

17.
The pressure–volume–temperature (P–V–T) relation of CaIrO3 post-perovskite (ppv) was measured at pressures and temperatures up to 8.6 GPa and 1,273 K, respectively, with energy-dispersive synchrotron X-ray diffraction using a DIA-type, cubic-anvil apparatus (SAM85). Unit-cell dimensions were derived from the Le Bail full profile refinement technique, and the results were fitted using the third-order Birth-Murnaghan equation of state. The derived bulk modulus \( K_{T0} \) at ambient pressure and temperature is 168.3 ± 7.1 GPa with a pressure derivative \( K_{T0}^{\prime } \) = 5.4 ± 0.7. All of the high temperature data, combined with previous experimental data, are fitted using the high-temperature Birch-Murnaghan equation of state, the thermal pressure approach, and the Mie-Grüneisen-Debye formalism. The refined thermoelastic parameters for CaIrO3 ppv are: temperature derivative of bulk modulus \( (\partial K_{T} /\partial T)_{P} \) = ?0.038 ± 0.011 GPa K?1, \( \alpha K_{T} \) = 0.0039 ± 0.0001 GPa K?1, \( \left( {\partial K_{T} /\partial T} \right)_{V} \) = ?0.012 ± 0.002 GPa K?1, and \( \left( {\partial^{2} P/\partial T^{2} } \right)_{V} \) = 1.9 ± 0.3 × 10?6 GPa2 K?2. Using the Mie-Grüneisen-Debye formalism, we obtain Grüneisen parameter \( \gamma_{0} \) = 0.92 ± 0.01 and its volume dependence q = 3.4 ± 0.6. The systematic variation of bulk moduli for several oxide post-perovskites can be described approximately by the relationship K T0  = 5406.0/V(molar) + 5.9 GPa.  相似文献   

18.
High pressure in situ synchrotron X-ray diffraction experiment of strontium orthophosphate Sr3(PO4)2 has been carried out to 20.0 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a volume of V 0 = 498.0 ± 0.1 Å3, an isothermal bulk modulus of K T  = 89.5 ± 1.7 GPa, and first pressure derivative of K T ′ = 6.57 ± 0.34. If K T ′ is fixed at 4, K T is obtained as 104.4 ± 1.2 GPa. Analysis of axial compressible modulus shows that the a-axis (K a  = 79.6 ± 3.2 GPa) is more compressible than the c-axis (K c  = 116.4 ± 4.3 GPa). Based on the high pressure Raman spectroscopic results, the mode Grüneisen parameters are determined and the average mode Grüneisen parameter of PO4 vibrations of Sr3(PO4)2 is calculated to be 0.30(2).  相似文献   

19.
The effect of alkalis on the solubility of H2O and CO2 in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H2O/(H2O + CO2) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H2O solubility (melt equilibrated with pure H2O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO2 content in melts equilibrated with CO2-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO2 contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO2 solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO2 solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO2 solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.  相似文献   

20.
The present analysis adjusts previous estimates of global ocean CaCO3 production rates substantially upward, to 133 × 1012 mol yr?1 plankton production and 42 × 1012 mol yr?1 shelf benthos production. The plankton adjustment is consistent with recent satellite-based estimates; the benthos adjustment includes primarily an upward adjustment of CaCO3 production on so-called carbonate-poor sedimentary shelves and secondarily pays greater attention to high CaCO3 mass (calcimass) and turnover of shelf communities on temperate and polar shelves. Estimated CaCO3 sediment accumulation rates remain about the same as they have been for some years: ~20 × 1012 mol yr?1 on shelves and 11 × 1012 mol yr?1 in the deep ocean. The differences between production and accumulation of calcareous materials call for dissolution of ~22 × 1012 mol yr?1 (~50 %) of shelf benthonic carbonate production and 122 × 1012 mol yr?1 (>90 %) of planktonic production. Most CaCO3 production, whether planktonic or benthonic, is assumed to take place in water depths of <100 m, while most dissolution is assumed to occur below this depth. The molar ratio of CO2 release to CaCO3 precipitation (CO2↑/CaCO3↓) is <1.0 and varies with depth. This ratio, Ψ, is presently about 0.66 in surface seawater and 0.85 in ocean waters deeper than about 1000 m. The net flux of CO2 associated with CaCO3 reactions in the global ocean in late preindustrial time is estimated to be an apparent influx from the atmosphere to the ocean, of +7 × 1012 mol C yr?1, at a time scale of 102–103 years. The CaCO3-mediated influx of CO2 is approximately offset by CO2 release from organic C oxidation in the water column. Continuing ocean acidification will have effects on CaCO3 and organic C metabolic responses to the oceanic inorganic C cycle, although those responses remain poorly quantified.  相似文献   

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