Controlling factors of the δ 11B-pH proxy and its research direction     

J. Xiao  Z. D. Jin  Y. K. Xiao  M. Y. He 《Environmental Earth Sciences》2014,71(4):1641-1650

Significant boron isotope fractionation occurs in nature (?70 ‰ to +75 ‰) due to the high geochemical reactivity of boron and the large relative mass difference between ¹⁰B and ¹¹B. Since the 1990s, reconstruction of ancient seawater pH using the isotopic composition of boron in bio-carbonates (δ ¹¹B_carb), and then calculation of the past pCO₂ have become important issues for the international isotope geochemistry community, and are called the δ ¹¹B-pH proxy. Although many achievements have been made by this proxy, various aspects of boron systematics require rigorous evaluation. Based on the previous researches, mechanism of boron isotope fractionation, variation of boron isotope (δ ¹¹B) in nature (especially in bio-carbonates) and controlling factors of the δ ¹¹B-pH proxy, such as the dissociation constant of B(OH)₃ in seawater (pK_a), the δ ¹¹B of seawater (δ ¹¹B_SW), the boron isotopic fractionation factor between B(OH) ₄ ^? and B(OH)₃ (α _4–3), and the incorporated species of boron into bio-carbonates, are reviewed in detail and the research directions of this proxy are proposed. Generally, the controversy about pK_a, δ ¹¹B_sw, and α _4–3 is relatively less, but whether boron incorporated into bio-carbonates only in the form of B(OH) ₄ ^? remains doubtful. In the future, it is required that the physicochemical processes that control boron incorporation into carbonates be rigorously characterized and that the related chemical and isotopic fractionation be quantified. It is also necessary and important to establish a “best-fit empirically equation” between δ ¹¹B_carb and pH of seawater based on the precipitation experiments of inorganic or culture experiments of corals or foraminifera. In addition, extended application of the δ ¹¹B-pH proxy to the earlier part of the Phanerozoic relying on the Brachiopods is worthy of studying. Like other geochemical indicators, there are limiting factors of δ ¹¹B; however, it remains a very powerful tool in the reconstruction of past seawater pH at present.  相似文献   

Evidence for ocean acidification in the Great Barrier Reef of Australia   总被引：1，自引：0，他引：1  

Gangjian Wei  Malcolm T. McCulloch  Graham Mortimer  Luhua Xie 《Geochimica et cosmochimica acta》2009,73(8):2332-2346

Geochemical records preserved in the long-lived carbonate skeleton of corals provide one of the few means to reconstruct changes in seawater pH since the commencement of the industrial era. This information is important in not only determining the response of the surface oceans to ocean acidification from enhanced uptake of CO₂, but also to better understand the effects of ocean acidification on carbonate secreting organisms such as corals, whose ability to calcify is highly pH dependent. Here we report an ∼200 year δ¹¹B isotopic record, extracted from a long-lived Porites coral from the central Great Barrier Reef of Australia. This record covering the period from 1800 to 2004 was sampled at yearly increments from 1940 to the present and 5-year increments prior to 1940. The δ¹¹B isotopic compositions reflect variations in seawater pH, and the δ¹³C changes in the carbon composition of surface water due to fossil fuel burning over this period. In addition complementary Ba/Ca, δ¹⁸O and Mg/Ca data was obtained providing proxies for terrestrial runoff, salinity and temperature changes over the past 200 years in this region. Positive thermal ionization mass spectrometry (PTIMS) method was utilized in order to enable the highest precision and most accurate measurements of δ¹¹B values. The internal precision and reproducibility for δ¹¹B of our measurements are better than ±0.2‰ (2σ), which translates to a precision of better than ±0.02 pH units. Our results indicate that the long-term pre-industrial variation of seawater pH in this region is partially related to the decadal-interdecadal variability of atmospheric and oceanic anomalies in the Pacific. In the periods around 1940 and 1998 there are also rapid oscillations in δ¹¹B compositions equivalent changes in pH of almost 0.5 U. The 1998 oscillation is co-incident with a major coral bleaching event indicating the sensitivity of skeletal δ¹¹B compositions to loss of zooxanthellate symbionts. Importantly, from the 1940s to the present-day, there is a general overall trend of ocean acidification with pH decreasing by about 0.2-0.3 U, the range being dependent on the value assumed for the fractionation factor α_(B3-B4) of the boric acid and borate species in seawater. Correlations of δ¹¹B with δ¹³C during this interval indicate that the increasing trend towards ocean acidification over the past 60 years in this region is the result of enhanced dissolution of CO₂ in surface waters from the rapidly increasing levels of atmospheric CO₂, mainly from fossil fuel burning. This suggests that the increased levels of anthropogenic CO₂ in atmosphere has already caused a significant trend towards acidification in the oceans during the past decades. Observations of surprisingly large decreases in pH across important carbonate producing regions, such as the Great Barrier Reef of Australia, raise serious concerns about the impact of Greenhouse gas emissions on coral calcification.  相似文献   

Coupled phase and aqueous species equilibrium of the H₂O-CO₂-NaCl-CaCO₃ system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite     

Zhenhao Duan  Dedong Li 《Geochimica et cosmochimica acta》2008,72(20):5128-5145

A model is developed for the calculation of coupled phase and aqueous species equilibrium in the H₂O-CO₂-NaCl-CaCO₃ system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite. The vapor-liquid-solid (calcite, halite) equilibrium together with the chemical equilibrium of H⁺, Na⁺, Ca²⁺, , Ca(OH)⁺, OH⁻, Cl⁻, , , CO_2(aq) and CaCO_3(aq) in the aqueous liquid phase as a function of temperature, pressure, NaCl concentrations, CO_2(aq) concentrations can be calculated, with accuracy close to those of experiments in the stated T-P-m range, hence calcite solubility, CO₂ gas solubility, alkalinity and pH values can be accurately calculated. The merit and advantage of this model is its predictability, the model was generally not constructed by fitting experimental data.One of the focuses of this study is to predict calcite solubility, with accuracy consistent with the works in previous experimental studies. The resulted model reproduces the following: (1) as temperature increases, the calcite solubility decreases. For example, when temperature increases from 273 to 373 K, calcite solubility decreases by about 50%; (2) with the increase of pressure, calcite solubility increases. For example, at 373 K changing pressure from 10 to 500 bar may increase calcite solubility by as much as 30%; (3) dissolved CO₂ can increase calcite solubility substantially; (4) increasing concentration of NaCl up to 2 m will increase calcite solubility, but further increasing NaCl solubility beyond 2 m will decrease its solubility.The functionality of pH value, alkalinity, CO₂ gas solubility, and the concentrations of many aqueous species with temperature, pressure and NaCl_(aq) concentrations can be found from the application of this model. Online calculation is made available on www.geochem-model.org/models/h2o_co2_nacl_caco3/calc.php.  相似文献   

Modelling the geochemical cycle of boron: Implications for the long-term δ11B evolution of seawater and oceanic crust     

《Chemical Geology》2006,225(1-2):61-76

The boron geochemical cycle has been simulated using a time-dependent geochemical box model that was coupled to a one-dimension model of seawater–oceanic crust interactions. Boron elemental and isotopic compositions of oceanic rocks as a function of depth were calculated by mass balance, using the temperature and porosity profiles of the crust as well as the available experimental and empirical distribution coefficients and fractionation factors between mineral and water. Ranges of boron elemental and isotopic variations of seawater were calculated for crust–seawater interactions that take place from the ridge-axis to the off-axis closure of the hydrothermal system. The present-day δ¹¹B of seawater (40‰) could represent a steady-state value. However, depending on crustal permeability, lifetime of water–rock interactions, and expansion rate of the oceanic ridge, the δ¹¹B of seawater may vary from 30‰ to 50‰ at the 10 million year scale.Some boron isotope compositions of Cretaceous biogenic carbonates and ophiolitic serpentinites from Oman are comparable to modern rock samples, suggesting that the δ¹¹B of Cretaceous seawater was close to the present-day value. Low δ¹¹B values of some biogenic carbonates cannot be attributed to low pH values of past seawater, but more probably to δ¹¹B variations of seawater or diagenetic alteration by crustal aqueous fluids. Boron isotope composition of hydrothermally altered serpentines could be considered as a promising proxy of the seawater composition.  相似文献   

Temperature independent thermal expansivities of calcium aluminosilicate melts between 1150 and 1973 K in the system anorthite-wollastonite-gehlenite (An-Wo-Geh): A density model     

Marcel Potuzak  Mette Solvang 《Geochimica et cosmochimica acta》2006,70(12):3059-3074

The thermal expansivities of 10 compositions from within the anorthite-wollastonite-gehlenite (An-Wo-Geh) compatibility triangle have been investigated using a combination of calorimetry and dilatometry on the glassy and liquid samples. The volumes at room temperature were derived from densities measured using the Archimedean buoyancy method. For each sample, density was measured at 298 K using glass that had a cooling-heating history of 10-10 K min⁻¹. The thermal expansion coefficient of the glass from 298 K to the glass transition interval was measured by a dilatometer and the heat capacity was measured using a differential scanning calorimeter from 298 to 1135 K. The thermal expansion coefficient and the heat flow were determined at a heating rate of 10 K min⁻¹ on glasses which were previously cooled at 10 K min⁻¹. Supercooled liquid density, molar volume and molar thermal expansivities were indirectly determined by combining differential scanning calorimetric and dilatometric measurements assuming that the kinetics of enthalpy and shear relaxation are equivalent. The data obtained on supercooled liquids were compared to high-temperature predictions from the models of (Lange, R.A., Carmichael, I.S.E., 1987. Densities of Na₂O-K₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-TiO₂-SiO₂ liquids: New measurements and derived partial molar properties. Geochim. Cosmochim. Acta51, 2931-2946; Courtial, P., Dingwell, D.B., 1995. Nonlinear composition dependence of molar volume of melts in the CaO-Al₂O₃-SiO₂ system. Geochim. Cosmochim. Acta59 (18), 3685-3695; Lange, R.A., 1997. A revised model for the density and thermal expansivity of K₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂ liquids from 700 to 1900 K: extension to crustal magmatic temperatures. Contrib. Mineral. Petrol.130, 1-11). The best linear fit combines the supercooled liquid data presented in this study and the high temperature data calculated using the Courtial and Dingwell (1995) model. This dilatometric/calorimetric method of determining supercooled liquid molar thermal expansivity greatly increases the temperature range accessible for thermal expansion. It represents a substantial increase in precision and understanding of the thermodynamics of calcium aluminosilicate melts. This enhanced precision demonstrates clearly the temperature independence of the melt expansions in the An-Wo-Geh system. This contrasts strongly with observations for neighboring system such as anorthite-diopside and raises the question of the compositional/structural origins of temperature dependence of thermal expansivity in multicomponent silicate melts.  相似文献   

Adsorption of methylene blue and crystal violet on low-cost adsorbent: waste fruits of <Emphasis Type="Italic">Rapanea ferruginea</Emphasis> (ethanol-treated and H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-treated)     

Tamiris Chahm  Bruna Aparecida Martins  Clovis Antonio Rodrigues 《Environmental Earth Sciences》2018,77(13):508

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 (pH_pzc), 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