The Role of CaCO<Subscript>3</Subscript> Reactions in the Contemporary Oceanic CO<Subscript>2</Subscript> Cycle

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.     

Understanding the Cyclicity of Chemical Weathering and Associated CO<Subscript>2</Subscript> Consumption in the Brahmaputra River Basin (India): The Role of Major Rivers in Climate Change Mitigation Perspective

Weathering of rocks that regulate the water chemistry of the river has been used to evaluate the CO₂ consumption rate which exerts a strong influence on the global climate. The foremost objective of the present research is to estimate the chemical weathering rate (CWR) of the continental water in the entire stretch of Brahmaputra River from upstream to downstream and their associated CO₂ consumption rate. To establish the link between the rapid chemical weathering and thereby enhance CO₂ drawdown from the atmosphere, the major ion composition of the Brahmaputra River that drains the Himalaya has been obtained. Major ion chemistry of the Brahmaputra River was resolved on samples collected from nine locations in pre-monsoon, monsoon and post-monsoon seasons for two cycles: cycle I (2011–2012) and cycle II (2013–2014). The physico-chemical parameters of water samples were analysed by employing standard methods. The Brahmaputra River was characterized by alkalinity, high concentration of Ca²⁺ and HCO₃ ^? along with significant temporal variation in major ion composition. In general, it was found that water chemistry of the river was mainly controlled by rock weathering with minor contributions from atmospheric and anthropogenic sources. The effective CO₂ pressure (log\({{\text{P}}_{{\text{C}}{{\text{O}}_{\text{2}}}}}\)) for pre-monsoon, monsoon and post-monsoon has been estimated. The question of rates of chemical weathering (carbonate and silicate) was addressed by using TDS and run-off (mm year^?1). It has been found that the extent of CWR is directly dependent on the CO₂ consumption rate which may be further evaluated from the perspective of climate change mitigation The average annual CO₂ consumption rate of the Brahmaputra River due to silicate and carbonate weathering was found to be 0.52 (×10⁶ mol Km^?2 year^?1) and 0.55 (×10⁶ mol Km^?2 year^?1) for cycle I and 0.49 (×10⁶ mol Km^?2 year^?1) and 0.52 (×10⁶ mol Km^?2 year^?1) for cycle II, respectively, which were significantly higher than that of other Himalayan rivers. Estimation of CWR of the Brahmaputra River indicates that carbonate weathering largely dominates the water chemistry of the Brahmaputra River.     

Spatial Distribution of Nitrous Oxide (N<Subscript>2</Subscript>O) in the Reloncaví Estuary–Sound and Adjacent Sea (41°–43° S), Chilean Patagonia

Fjords and estuaries exchange large amounts of solutes, gases, and particulates between fluvial and marine systems. These exchanges and their relative distributions of compounds/particles are partially controlled by stratification and water circulation. The spatial and vertical distributions of N₂O, an important greenhouse gas, along with other oceanographic variables, are analyzed from the Reloncaví estuary (RE) (~41° 30′ S) to the gulf of Corcovado in the interior sea of Chiloé (43° 45′ S) during the austral winter. Freshwater runoff into the estuary regulated salinity and stratification of the water column, clearly demarking the surface (<5 m depth) and subsurface layer (>5 m depth) and also separating estuarine and marine influenced areas. N₂O levels varied between 8.3 and 21 nM (corresponding to 80 and 170 % saturation, respectively), being significantly lower (11.8 ± 1.70) at the surface than in subsurface waters in the Reloncaví estuary (14.5 ± 1.73). Low salinity and NO₃ ^?, NO₂ ^?, and PO₄ ^3? levels, as well as high Si(OH)₄ values were associated with low surface N₂O levels. Remarkably, an accumulation of N₂O was observed in the subsurface waters of the Reloncaví sound, associated with a relatively high consumption of O₂. The sound is exposed to increasing anthropogenic impacts from aquaculture and urban discharge, occurring simultaneously with an internal recirculation, which leads to potential signals of early eutrophication. In contrast, within the interior sea of Chiloé (ISC), most of water column was quasi homohaline and occupied by modified subantarctic water (MSAAW), which was relatively rich in N₂O (12.6 ± 2.36 nM) and NO₃ ^? (18.3 ± 1.63 μM). The relationship between salinity, nutrients, and N₂O revealed that water from the open ocean, entering into ISC (the Gulf of Corcovado) through the Guafo mouth, was the main source of N₂O (up to 21 nM), as it gradually mixed with estuarine water. In addition, significant relationships between N₂O excess vs. AOU and N₂O excess vs. NO₃ ^? suggest that part of N₂O is also produced by nitrification. Our results show that the estuarine and marine waters can act as light source or sink of N₂O to the atmosphere (air–sea N₂O fluxes ranged from ?1.57 to 5.75 μmol m^?2 day^?1), respectively; influxes seem to be associated to brackish water depleted in N₂O that also caused a strong stratification, creating a barrier to gas exchange.     

Sediment Denitrification in Two Contrasting Tropical Shallow Lagoons

Sediment denitrification was monthly evaluated in two tropical coastal lagoons with different trophic states using the ¹⁵N isotope pairing technique. Denitrification rates were very low in both environments, always <5.0 μmol N₂ m^?2 h^?1 and were not significantly different between them. Oxygen consumption varied from 426 to 4248 μmol O₂ m^?2 h^?1 and was generally three times higher in the meso-eutrophic than the oligotrophic lagoon. The low denitrification activity was ascribed to both low water NO₃ ^? concentrations (<2.0 μM) and little nitrate supply from nitrification. There was no correlation of denitrification with nitrate or ammonium fluxes. Sediments in temperate environments with similar oxygen consumption rates usually presented a higher proportion of nitrification–denitrification rates. Sediment oxygen consumption was a good predictor of sediment denitrification in both studied lagoons.     

Silica gel/gold nanoparticles/(NS)<Subscript>2</Subscript> ligand nanoporous platform-modified ionic liquid carbon paste electrode for potentiometric ultratrace assessment of Ag(I)

A novel ionic liquid carbon paste electrode has been developed using sol–gel/Au nanoparticle (SGAN) involving (NS)₂ compound of N,N′-di-(cyclopentadienecarbaldehyde)-1, 2-di (o-aminophenylthio) ethane (CCAE) as an appropriate neutral ion-carrier for ultrahigh-sensitive potentiometric determination of Ag(I). Colloidal gold nanoparticles (AuNPs) also well dispersed self-assembly into the 3-(mercaptopropyl)-trimethoxysilane (MPTS)-derived sol–gel network through Au–S covalent bond engendering continuous and super-conductive nanoporous three-dimensional array. The room-temperature ionic liquid, 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIM.PF₆), was applied as a super-conductive pasting agent (binder). The SGAN/CCAE/IL-CPE exhibited a significantly enhanced sensitivity and preferential selectivity toward Ag(I) over a wide concentration range of 2.4 × 10^?9 to 2.2 × 10^?2 mol L^?1 (R ² = 0.9996) with a lower limit of detection of 7.9 × 10^?10 M and a Nernstian slope of 58.5 (±0.3) mV decade^?1. The electrode has a short response time of ～5 s and long-time durability of about 2 months without any considerable divergence in potentials. Moreover, the potentiometric examinations could be carried out within the wide pH range of 3.5–9.5. Eventually, the practical utility of the proposed Ag(I)-sensor was evaluated by volumetric titration of AgNO₃ solution by sodium chloride and recovery of silver content in some real samples using flame atomic absorption spectroscopy as a confident reference.     

Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.     

Nitrous Oxide Emissions from Intertidal Zone of the Yellow River Estuary in Autumn and Winter During 2011–2012

Much uncertainty exists in spatial and temporal variations of nitrous oxide (N₂O) emissions from coastal marshes in temperate regions. To investigate the spatial and temporal variations of N₂O fluxes and determine the environmental factors influencing N₂O fluxes across the coastal marsh dominated by Suaeda salsa in the Yellow River estuary, China, in situ measurements were conducted in high marsh (HM), middle marsh (MM), low marsh (LM), and mudflat (MF) in autumn and winter during 2011–2012. Results showed that mean N₂O fluxes and cumulative N₂O emission indicated intertidal zone of the examined marshes as N₂O sources over all sampling seasons with range of 0.0051 to 0.0152 mg N₂O m^?2 h^?1 and 7.58 to 22.02 mg N₂O m^?2, respectively. During all times of day and the seasons measured, N₂O fluxes from the intertidal zone ranged from ?0.0004 to 0.0644 mg N₂O m^?2 h^?1. The freeze/thaw cycles in sediments during early winter (frequent short-term cycle) and midwinter (long-term cycle) were one of main factors affecting the temporal variations of N₂O emission. The spatial variations of N₂O fluxes in autumn were mainly dependent on tidal fluctuation and plant composition. The ammonia-nitrogen (NH₄ ⁺–N) in sediments of MF significantly affected N₂O emissions (p < 0.05), and the high concentrations of Fe in sediments might affect the spatial variation of N₂O fluxes. This study highlighted the large spatial variation of N₂O fluxes across the coastal marsh (coefficient of variation (CV) = 127.86 %) and the temporal variation of N₂O fluxes during 2011–2012 (CV = 137.29 %). Presently, the exogenous C and N loadings of the Yellow River estuary are increasing due to human activities; thus, the potential effects of exogenous C and N loadings on N₂O emissions during early winter should be paid more attention as the N₂O inventory is assessed precisely.     

Freshwater-Saltwater Mixing Effects on Dissolved Carbon and CO<Subscript>2</Subscript> Outgassing of a Coastal River Entering the Northern Gulf of Mexico

The delivery of dissolved carbon from rivers to coastal oceans is an important component of the global carbon budget. From November 2013 to December 2014, we investigated freshwater-saltwater mixing effects on dissolved carbon concentrations and CO₂ outgassing at six locations along an 88-km-long estuarine river entering the Northern Gulf of Mexico with salinity increasing from 0.02 at site 1 to 29.50 at site 6 near the river’s mouth. We found that throughout the sampling period, all six sites exhibited CO₂ supersaturation with respect to the atmospheric CO₂ pressure during most of the sampling trips. The average CO₂ outgassing fluxes at site 1 through site 6 were 162, 177, 165, 218, 126, and 15 mol m^?2 year^?1, respectively, with a mean of 140 mol m^?2 year^?1 for the entire river reach. In the short freshwater river reach before a saltwater barrier, 0.079 × 10⁸ kg carbon was emitted to the atmosphere during the study year. In the freshwater-saltwater mixing zone with wide channels and river lakes, however, a much larger amount of carbon (3.04 × 10⁸ kg) was emitted to the atmosphere during the same period. For the entire study period, the river’s freshwater discharged 0.25 × 10⁹ mol dissolved inorganic carbon (DIC) and 1.77 × 10⁹ mol dissolved organic carbon (DOC) into the mixing zone. DIC concentration increased six times from freshwater (0.24 mM) to saltwater (1.64 mM), while DOC showed an opposing trend, but to a lesser degree (from 1.13 to 0.56 mM). These findings suggest strong effects of freshwater-saltwater mixing on dissolved carbon dynamics, which should be taken into account in carbon processing and budgeting in the world’s estuarine systems.     

CO<Subscript>2</Subscript> mineralization of natural wollastonite into porous silica and CaCO<Subscript>3</Subscript> powders promoted via membrane electrolysis

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.     

Depth of volcanic basalt degassing forecasted from CO2 fluid inclusions

Fluid inclusions have recorded the history of degassing in basalt. Some fluid inclusions in olivine and pyroxene phenocrysts of basalt were analyzed by micro-thermometry and Raman spectroscopy in this paper. The experimental results showed that many inclusions are present almost in a pure CO2 system. The densities of some CO2 inclusions were computed in terms of Raman spectroscopic characteristics of CO2 Fermi resonance at room temperature. Their densities change over a wide range, but mainly between 0.044 g/cm3 and 0.289 g/cm3. Their micro-thermometric measurements showed that the CO2 inclusions examined reached homogenization between 1145.5℃ and 1265℃ . The mean value of homogenization temperatures of CO2 inclusions in basalts is near 1210℃. The trap pressures (depths) of inclusions were computed with the equation of state and computer program. Distribution of the trap depths makes it know that the degassing of magma can happen over a wide pressure (depth) range, but mainly at the depth of 0.48 km to 3.85 km. This implicates that basalt magma experienced intensive degassing and the CO2 gas reservoir from the basalt magma also may be formed in this range of depths. The results of this study showed that the depth of basalt magma degassing can be forecasted from CO2 fluid inclusions, and it is meaningful for understanding the process of magma degassing and constraining the inorganogenic CO2 gas reservoir.     

CO<Subscript>2</Subscript> content of andesitic melts at graphite-saturated upper mantle conditions with implications for redox state of oceanic basalt source regions and remobilization of reduced carbon from subducted eclogite

We have performed experiments to determine the effects of pressure, temperature and oxygen fugacity on the CO₂ contents in nominally anhydrous andesitic melts at graphite saturation. The andesite composition was specifically chosen to match a low-degree partial melt composition that is generated from MORB-like eclogite in the convective, oceanic upper mantle. Experiments were performed at 1–3 GPa, 1375–1550?°C, and fO₂ of FMQ ?3.2 to FMQ ?2.3 and the resulting experimental glasses were analyzed for CO₂ and H₂O contents using FTIR and SIMS. Experimental results were used to develop a thermodynamic model to predict CO₂ content of nominally anhydrous andesitic melts at graphite saturation. Fitting of experimental data returned thermodynamic parameters for dissolution of CO₂ as molecular CO₂: ln(K ⁰) = ?21.79?±?0.04, ΔV ⁰?=?32.91?±?0.65 cm³mol^?1, ΔH ⁰?=?107?±?21 kJ mol^?1, and dissolution of CO₂ as CO₃ ^2?: ln(K ⁰ ) = ?21.38?±?0.08, ΔV ⁰?=?30.66?±?1.33 cm³ mol^?1, ΔH ⁰?=?42?±?37 kJ mol^?1, where K ⁰ is the equilibrium constant at some reference pressure and temperature, ΔV ⁰ is the volume change of reaction, and ΔH ⁰ is the enthalpy change of reaction. The thermodynamic model was used along with trace element partition coefficients to calculate the CO₂ contents and CO₂/Nb ratios resulting from the mixing of a depleted MORB and the partial melt of a graphite-saturated eclogite. Comparison with natural MORB and OIB data suggests that the CO₂ contents and CO₂/Nb ratios of CO₂-enriched oceanic basalts cannot be produced by mixing with partial melts of graphite-saturated eclogite. Instead, they must be produced by melting of a source containing carbonate. This result places a lower bound on the oxygen fugacity for the source region of these CO₂-enriched basalts, and suggests that fO₂ measurements made on cratonic xenoliths may not be applicable to the convecting upper mantle. CO₂-depleted basalts, on the other hand, are consistent with mixing between depleted MORB and partial melts of a graphite-saturated eclogite. Furthermore, calculations suggest that eclogite can remain saturated in graphite in the convecting upper mantle, acting as a reservoir for C.     

Thermoelastic properties of chromium oxide Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> (eskolaite) at high pressures and temperatures

A new synchrotron X-ray diffraction study of chromium oxide Cr₂O₃ (eskolaite) with the corundum-type structure has been carried out in a Kawai-type multi-anvil apparatus to pressure of 15 GPa and temperatures of 1873 K. Fitting the Birch–Murnaghan equation of state (EoS) with the present data up to 15 GPa yielded: bulk modulus (K _0,T0), 206 ± 4 GPa; its pressure derivative K′_0,T , 4.4 ± 0.8; (?K _0,T /?T) = ?0.037 ± 0.006 GPa K^?1; a = 2.98 ± 0.14 × 10^?5 K^?1 and b = 0.47 ± 0.28 × 10^?8 K^?2, where α _0,T  = a + bT is the volumetric thermal expansion coefficient. The thermal expansion of Cr₂O₃ was additionally measured at the high-temperature powder diffraction experiment at ambient pressure and α _0,T0 was determined to be 2.95 × 10^?5 K^?1. The results indicate that coefficient of the thermal expansion calculated from the EoS appeared to be high-precision because it is consistent with the data obtained at 1 atm. However, our results contradict α ₀ value suggested by Rigby et al. (Brit Ceram Trans J 45:137–148, 1946) widely used in many physical and geological databases. Fitting the Mie–Grüneisen–Debye EoS with the present ambient and high-pressure data yielded the following parameters: K _0,T0 = 205 ± 3 GPa, K′_0,T  = 4.0, Grüneisen parameter (γ ₀) = 1.42 ± 0.80, q = 1.82 ± 0.56. The thermoelastic parameters indicate that Cr₂O₃ undergoes near isotropic compression at room and high temperatures up to 15 GPa. Cr₂O₃ is shown to be stable in this pressure range and adopts the corundum-type structure. Using obtained thermoelastic parameters, we calculated the reaction boundary of knorringite formation from enstatite and eskolaite. The Clapeyron slope (with \({\text{d}}P/{\text{d}}T = - 0.014\) GPa/K) was found to be consistent with experimental data.     

Dynamics of greenhouse gases in the river–groundwater interface in a gaining river stretch (Triffoy catchment,Belgium)

This study investigates the occurrence of greenhouse gases (GHGs) and the role of groundwater as an indirect pathway of GHG emissions into surface waters in a gaining stretch of the Triffoy River agricultural catchment (Belgium). To this end, nitrous oxide (N₂O), methane (CH₄) and carbon dioxide (CO₂) concentrations, the stable isotopes of nitrate, and major ions were monitored in river and groundwater over 8 months. Results indicated that groundwater was strongly oversaturated in N₂O and CO₂ with respect to atmospheric equilibrium (50.1 vs. 0.55 μg L^?1 for N₂O and 14,569 vs. 400 ppm for CO₂), but only marginally for CH₄ (0.45 vs. 0.056 μg L^?1), suggesting that groundwater can be a source of these GHGs to the atmosphere. Nitrification seemed to be the main process for the accumulation of N₂O in groundwater. Oxic conditions prevailing in the aquifer were not prone for the accumulation of CH₄. In fact, the emissions of CH₄ from the river were one to two orders of magnitude higher than the inputs from groundwater, meaning that CH₄ emissions from the river were due to CH₄ in-situ production in riverbed or riparian zone sediments. For CO₂ and N₂O, average emissions from groundwater were 1.5?×?10⁵ kg CO₂ ha^?1 year^?1 and 207 kg N₂O ha^?1 year^?1, respectively. Groundwater is probably an important source of N₂O and CO₂ in gaining streams but when the measures are scaled at catchment scale, these fluxes are probably relatively modest. Nevertheless, their quantification would better constrain nitrogen and carbon budgets in natural systems.     

Dissolution sequestration mechanism of CO<Subscript>2</Subscript> at the Shiqianfeng saline aquifer in the Ordos Basin,northwestern China

This study focused on the target injection layers of deep saline aquifers in the Shiqianfeng Fm. in the Carbon Capture and Sequestration (CCS) Demonstration Projects in the Ordos Basin, northwestern China. The study employed a combination method of experiments and numerical simulation to investigate the dissolution mechanism and impact factors of CO₂ in these saline aquifers. The results showed (1) CO₂ solubility in different types of water chemistry were shown in ascending order: MgCl₂-type water < CaCl₂-type water < Na₂SO₄-type water < NaCl-type water < Na₂CO₃-type water < distilled water. These results were consistent with the calculated results undertaken by TOUGHREACT with about 5% margin of error. CO₂ solubility of Shiqianfeng Fm. saline was 1.05 mol/L; (2) compared with distilled water, the more complex the water’s chemical composition, the greater the increase in HCO₃ ^?concentration. While the water’s composition was relatively simple, the tested water’s HCO₃ ^?concentrations were in close accord with the calculated value undertaken by the TOUGHREACT code, and the more complex the water’s composition, the poorer the agreement was, probably due to the complex and unstable HCO₃ ^? complicating matters when in an aqueous solution system including both tested HCO₃ ^?concentration and calculated HCO₃ ^?concentration; (3) the CO₂ solubility in the saline at the temperature conditions of 55 °C and 70 °C were 1.17 and 1.02 mol/L. When compared with the calculated value of 1.20 and 1.05 mol/L, they were almost the same with only 1 and 3% margin of error; concentrations of HCO₃ ^? were 402.73 mg/L (0.007 mol/L) and 385.65 mg/L (0.006 mol/L), while the simulation results were 132.16 mg/L (0.002 mol/L) and 128.52 mg/L (0.002 mol/L). From the contrast between the tested data and the calculated data undertaken by the TOUGHREACT code, it was shown that TOUGHRACT code could better simulate the interaction between saline and CO₂ in the dissolution sequestration capacity. Therefore, TOUGHREACT code could be used for the inter-process prediction of CO₂ long-term geological storage of CO₂; (4) The Ca²⁺ concentration and SO₄ ^2?concentration in saline water had less effect on the solubility of CO₂ and HCO₃ ^?concentration. In addition, TDS and pH values of saline affected not only the solubility of CO₂, but also the conversion of CO₂ to HCO₃ ^? due to that they can affect the activity and acid-base balance. So in fact, we just need to consider that the TDS and pH values are main impact factors in the dissolution sequestration capacity of CO₂ geological sequestration in deep saline aquifers.     

A review on the mechanism and affecting factors of nitrous oxide emission in constructed wetlands

Constructed wetlands (CWs) are considered important sources of nitrous oxide (N₂O). Various reports in the literature indicate that CWs have high N₂O emission rates. The release of N₂O from CWs treating wastewater emissions range from ?16.7 to 188 mg N₂O m^?2day^?1. N₂O in CWs is produced mainly by nitrification, denitrification, nitrifier denitrification, and nitrate-ammonification. Denitrification is considered the major source of N₂O under most conditions. In recent years, two main methods of sampling N₂O gas in CWs have been employed, including the headspace equilibration technique and the closed static chambers technique. N₂O emission may be affected by various operating parameters and environmental conditions. One of the main environmental factors affecting the removal of nitrogen in CWs is dissolved oxygen, which affects nitrification and denitrification processes, thus greatly influencing N₂O emission. CW gas dynamics is affected mainly by season and weather conditions, especially temperature and moisture. Aquatic plants, flow regime, oxidation–reduction potential, nitrate concentration, C/N ratio and other factors can affect N₂O emission in CWs.     

Volatile (H<Subscript>2</Subscript>O,CO<Subscript>2</Subscript>, Cl,S) budget of the Central American subduction zone

After more than a decade of multidisciplinary studies of the Central American subduction zone mainly in the framework of two large research programmes, the US MARGINS program and the German Collaborative Research Center SFB 574, we here review and interpret the data pertinent to quantify the cycling of mineral-bound volatiles (H₂O, CO₂, Cl, S) through this subduction system. For input-flux calculations, we divide the Middle America Trench into four segments differing in convergence rate and slab lithological profiles, use the latest evidence for mantle serpentinization of the Cocos slab approaching the trench, and for the first time explicitly include subduction erosion of forearc basement. Resulting input fluxes are 40–62 (53) Tg/Ma/m H₂O, 7.8–11.4 (9.3) Tg/Ma/m CO₂, 1.3–1.9 (1.6) Tg/Ma/m Cl, and 1.3–2.1 (1.6) Tg/Ma/m S (bracketed are mean values for entire trench length). Output by cold seeps on the forearc amounts to 0.625–1.25 Tg/Ma/m H₂O partly derived from the slab sediments as determined by geochemical analyses of fluids and carbonates. The major volatile output occurs at the Central American volcanic arc that is divided into ten arc segments by dextral strike-slip tectonics. Based on volcanic edifice and widespread tephra volumes as well as calculated parental magma masses needed to form observed evolved compositions, we determine long-term (10⁵ years) average magma and K₂O fluxes for each of the ten segments as 32–242 (106) Tg/Ma/m magma and 0.28–2.91 (1.38) Tg/Ma/m K₂O (bracketed are mean values for entire Central American volcanic arc length). Volatile/K₂O concentration ratios derived from melt inclusion analyses and petrologic modelling then allow to calculate volatile fluxes as 1.02–14.3 (6.2) Tg/Ma/m H₂O, 0.02–0.45 (0.17) Tg/Ma/m CO₂, and 0.07–0.34 (0.22) Tg/Ma/m Cl. The same approach yields long-term sulfur fluxes of 0.12–1.08 (0.54) Tg/Ma/m while present-day open-vent SO₂-flux monitoring yields 0.06–2.37 (0.83) Tg/Ma/m S. Input–output comparisons show that the arc water fluxes only account for up to 40 % of the input even if we include an “invisible” plutonic component constrained by crustal growth. With 20–30 % of the H₂O input transferred into the deeper mantle as suggested by petrologic modeling, there remains a deficiency of, say, 30–40 % in the water budget. At least some of this water is transferred into two upper-plate regions of low seismic velocity and electrical resistivity whose sizes vary along arc: one region widely envelopes the melt ascent paths from slab top to arc and the other extends obliquely from the slab below the forearc to below the arc. Whether these reservoirs are transient or steady remains unknown.     

Thermal equation of state of CaIrO<Subscript>3</Subscript> post-perovskite

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.     

Generation of CO2-rich melts during basalt magma ascent and degassing

To test mechanisms of basaltic magma degassing, continuous decompressions of volatile-bearing (2.7–3.8 wt% H₂O, 600–1,300 ppm CO₂) Stromboli melts were performed from 250–200 to 50–25 MPa at 1,180–1,140 °C. Ascent rates were varied from 0.25 to ~1.5 m/s. Glasses after decompression show a wide range of textures, from totally bubble-free to bubble-rich, the latter with bubble number densities from 10⁴ to 10⁶ cm^?3, similar to Stromboli pumices. Vesicularities range from 0 to ~20 vol%. Final melt H₂O concentrations are homogeneous and always close to solubilities. In contrast, the rate of vesiculation controls the final melt CO₂ concentration. High vesicularity charges have glass CO₂ concentrations that follow theoretical equilibrium degassing paths, whereas glasses from low vesicularity charges show marked deviations from equilibrium, with CO₂ concentrations up to one order of magnitude higher than solubilities. FTIR profiles and maps reveal glass CO₂ concentration gradients near the gas–melt interface. Our results stress the importance of bubble nucleation and growth, and of volatile diffusivities, for basaltic melt degassing. Two characteristic distances, the gas interface distance (distance either between bubbles or to gas–melt interfaces) and the volatile diffusion distance, control the degassing process. Melts containing numerous and large bubbles have gas interface distances shorter than volatile diffusion distances, and degassing proceeds by equilibrium partitioning of CO₂ and H₂O between melt and gas bubbles. For melts where either bubble nucleation is inhibited or bubble growth is limited, gas interface distances are longer than volatile diffusion distances. Degassing proceeds by diffusive volatile transfer at the gas–melt interface and is kinetically limited by the diffusivities of volatiles in the melt. Our experiments show that CO₂-oversaturated melts can be generated as a result of magma decompression. They provide a new explanation for the occurrence of CO₂-rich natural basaltic glasses and open new perspectives for understanding explosive basaltic volcanism.     

Nutrient dynamics in pore water of tidal marshes near the Yangtze Estuary and Hangzhou Bay, China

Tidal marshes act as a buffer system for nutrients in the pore water and play important roles in controlling the budget of nutrients and pollutants that reach the sea. Spatial and seasonal dynamics of pore water nutrients were surveyed in three tidal marshes (Chongming Island, Hengsha Island, and Fengxian tidal flat) near the Yangtze Estuary and Hangzhou Bay from August 2007 to May 2008. Nutrient variations in pore water closely followed seawater quality in the estuaries, while the average concentration of NH₄ ⁺–N, the main form of inorganic nitrogen in pore water, was over two orders of magnitude higher than that in seawater which was dominated by nitrate. NH₄ ⁺–N export (13.81 μmol m^?2 h^?1) was lower than the import of (NO₃ ^?+NO₂ ^?)–N (?24.17 μmol m^?2 h^?1) into sediment over the 1-year period, hence reducing N-eutrophication in coastal waters. The export of SiO₃ ^2?–Si and PO₄ ^3?–P from tidal marshes regulated nutrient level and composition and lifted the ratio beyond potentidal element limitation in the coastal system. Moreover, macrophyte plants (Spartina alterniflora and Phragmites australis) played significant roles in controlling nutrient concentration in pore water and its exchange between marshes and estuaries. Fengxian marsh was characterized by higher nutrient concentrations and fluxes than other marshes in response to the more serious eutrophication in Hangzhou Bay than in the Yangtze Estuary.     

Oyster (<Emphasis Type="Italic">Crassostrea virginica</Emphasis>) Aquaculture Shifts Sediment Nitrogen Processes toward Mineralization over Denitrification

Filter-feeding bivalves, like oysters, couple pelagic primary production with benthic microbial processes by consuming plankton from the water column and depositing unassimilated material on sediment. Conceptual models suggest that at low to moderate oyster densities, this deposition can stimulate benthic denitrification by providing denitrifying bacteria with organic carbon and nitrogen (N). While enhanced denitrification has been found at oyster reefs, data from oyster aquaculture are limited and equivocal. This study measured seasonal rates of denitrification, as well as dissimilatory nitrate reduction to ammonium (DNRA), and dissolved inorganic N fluxes at a rack and bag eastern oyster (Crassostrea virginica) aquaculture farm. Consistent with models, denitrification was enhanced within the farm, with an average annual increase of 350% compared to a reference site. However, absolute denitrification rates were low relative to other coastal systems, reaching a maximum of 19.2 μmol m^?2 h^?1. Denitrification appeared to be nitrate (NO₃ ^?) limited, likely due to inhibited nitrification caused by sediment anoxia. Denitrification may also have been limited by competition for NO₃ ^? with DNRA, which accounted for an average of 76% of NO₃ ^? reduction. Consequently, direct release of ammonium (NH₄ ⁺) from mineralization to the water column was the most significant benthic N pathway, with seasonal rates exceeding 900 μmol m^?2 h^?1 within the farm. The enhanced N processes were spatially limited however, with significantly higher rates directly under oysters, compared to in between oyster racks. For commercial aquaculture farms like this, with moderate oyster densities (100–200 oysters m^?2), denitrification may be enhanced, but nonetheless limited by biodeposition-induced sediment anoxia. The resulting shift in the sediment N balance toward processes that regenerate reactive N to the water column rather than remove N is an important consideration for water quality.