Balancing the Oceanic Calcium Carbonate Cycle: Consequences of Variable Water Column ��

The paired chemical reactions, Ca²⁺ + 2HCO₃ ^? ? CaCO₃ + CO₂ + H₂O, overestimate the ratio of CO₂ flux to CaCO₃ flux during the precipitation or dissolution of CaCO₃ in seawater. This ratio, which has been termed ??, is about 0.6 in surface seawater at 25°C and at equilibrium with contemporary atmospheric CO₂ and increases towards 1.0 as seawater cools and pCO₂ increases. These conclusions are based on field observations, laboratory experiments, and equilibrium calculations for the seawater carbonate system. Yet global geochemical modeling indicates that small departures of ?? from 1.0 would cause dramatic, rapid, and unrealistic change in atmospheric CO₂. ?? can be meaningfully calculated for a water sample whether or not it is in equilibrium with the atmosphere. The analysis presented here demonstrates that the atmospheric CO₂ balance can be maintained constant with respect to seawater CaCO₃ reactions if one considers the difference between CaCO₃ precipitation and burial and differing values for ?? (both <1.0) in regions of precipitation and dissolution within the ocean.     

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.     

Air–water CO<Subscript>2</Subscript> flux in an algae bloom year for Lake Hongfeng,Southwest China: implications for the carbon cycle of global inland waters

The carbon cycle of global inland waters is quantitatively comparable to other components in the global carbon budget. Among inland waters, a significant part is man-made lakes formed by damming rivers. Man-made lakes are undergoing a rapid increase in number and size. Human impacts and frequent algae blooms lead to it necessary to make a better constraint on their carbon cycles. Here, we make a primary estimation on the air–water CO₂ transfer flux through an algae bloom year for a subtropical man-made lake—Hongfeng Lake, Southwest China. To do this a new type of glass bottles was designed for content and isotopic analysis of DIC and other environmental parameters. At the early stage of algae bloom, CO₂ was transferred from the atmosphere to the lake with a net flux of 1.770 g·C·m^?2. Later, the partial pressure (pCO₂) of the aqueous CO₂ increased rapidly and the lake outgassed to the atmosphere with a net flux of 95.727 g·C·m^?2. In the remaining days, the lake again took up CO₂ from the atmosphere with a net flux of 14.804 g·C·m^?2. As a whole, Lake Hongfeng released 4527 t C to the atmosphere, accounting for one-third of the atmosphere/soil CO₂ sequestered by chemical weathering in the whole drainage. With an empirical mode decomposition method, we found air temperature plays a major role in controlling water temperature, aqueous pCO₂ and hence CO₂ flux. This work indicates a necessity to make detailed and comprehensive carbon budgets in man-made lakes.     

http://dx.doi.org/10.1016/j.gsf.2016.07.005

The Hadean history of Earth is shrouded in mystery and it is considered that the planet was born dry with no water or atmosphere. The Earth-Moon system had many features in common during the birth stage. Solidification of the dry magma ocean at 4.53 Ga generated primordial continents with komatiite. We speculate that the upper crust was composed of fractionated gabbros and the middle felsic crust by anorthosite at ca. 21 km depth boundary, underlain by meta-anorthosite (grossular + kyanite + quartz) down to 50–60 km in depth. The thickness of the mafic KREEP basalt in the lower crust, separating it from the underlying upper mantle is not well-constrained and might have been up to ca. 100–200 km depending on the degree of fractionation and gravitational stability versus surrounding mantle density. The primordial continents must have been composed of the final residue of dry magma ocean and enriched in several critical elements including Ca, Mg, Fe, Mn, P, K, and Cl which were exposed on the surface of the dry Earth. Around 190 million years after the solidification of the magma ocean, “ABEL bombardment” delivered volatiles including H₂O, CO₂, N₂ as well as silicate components through the addition of icy asteroids. This event continued for 200 Myr with subordinate bombardments until 3.9 Ga, preparing the Earth for the prebiotic chemical evolution and as the cradle of first life. Due to vigorous convection arising from high mantle potential temperatures, the primordial continents disintegrated and were dragged down to the deep mantle, marking the onset of Hadean plate tectonics.     

Fluid inclusion and H–O–C isotope geochemistry of the Yaochong porphyry Mo deposit in Dabie Shan,China: a case study of porphyry systems in continental collision orogens

The Yaochong porphyry Mo deposit in Xinxian County, Henan Province, China, is located in the Hong’an terrane, that is, the western part of the Dabie orogen. The Dabie orogen is part of a >1,500 km long, Triassic continental collision belt between the North China Block and the South China Block. Four types of vein are present. Paragenetically, from early to late, they are as follows: stage 1 quartz + K-feldspar ± pyrite ± magnetite vein; stage 2 quartz + K-feldspar + molybdenite ± pyrite vein; stage 3 quartz + polymetallic sulfides ± K-feldspar vein; and stage 4 quartz ± carbonate ± fluorite vein. Four compositional types of fluid inclusion, pure CO₂, CO₂ bearing, aqueous, and solid bearing, are present in quartz from the first three stages; only low-salinity aqueous fluid inclusions occur in quartz from the last stage. All the estimated salinities are ≤13.1 wt% NaCl eq., and no halite crystals were identified. Homogenization temperatures for the fluid inclusions from stages 1 to 4 are in the ranges of 262–501, 202–380, 168–345, and 128–286 °C, respectively, and estimated depths decrease from 6.9 to 8.9 km, through 6.2–7.2, to ~4.7 km. Quartz separates from the veins yielded a δ¹⁸O value of 7.7–11.2 ‰, corresponding to δ¹⁸O_H2O values of ?1.3 to 6.9 ‰ using temperature estimates from fluid inclusion data; δD_H2O values of fluid inclusion vary from ?80 to ?55 ‰, and δ¹³C_CO2 from ?2.3 to 2.7 ‰, suggesting that the ore-fluids evolved from magmatic to meteoric sources. We conclude that the ore-forming fluid system at Yaochong was initially high temperature, high salinity, and CO₂-rich and then progressively evolved to CO₂-poor, lower salinity, and lower temperature, by mixing with meteoric water, which results in ore precipitation.     

Greenhouse gases abatement by catalytic dry reforming of methane to syngas over samarium oxide-supported cobalt catalyst

Anthropogenic activities often result in the emissions of methane (CH₄) and carbon dioxide (CO₂) which are the principal components of greenhouse gases. The mitigation of these gases to avert further occurrence of global warming has attracted a lot of research interest. In this study, the potential of greenhouse gases abatement via catalytic CO₂ (dry) reforming of methane to syngas over samarium oxide-supported cobalt (20 wt% Co/80 wt% Sm₂O₃) catalyst was investigated. The 20 wt% Co/80 wt% Sm₂O₃ material was synthesized via wet impregnation method and characterized using different instrument techniques. The methane dry reforming reaction, as well as its kinetics over the catalyst, was studied in a stainless steel fixed-bed continuous flow reactor at feed (CH₄:CO₂) ratios range of 0.1–1.0, temperature range of 923–1023 K and gas hourly space velocity (GHSV) of 30,000 h^?1. The 20 wt% Co/80 wt% Sm₂O₃ catalyst showed promising catalytic activity evident from the highest CH₄ and CO₂ conversion of ~71 and ~74% as well as the highest hydrogen (H₂) and carbon monoxide (CO) yield of ~62 and ~73%, respectively. Moreover, the methane dry reforming over the 20 wt% Co/80 wt% Sm₂O₃ catalyst produces H₂/CO ratio close to unity hence suitable for use as a chemical intermediate for synthesis of oxygenated fuels. The kinetic data obtained from the methane dry reforming were fitted to power law model. Apparent activation energies of 88.62, 80.12, 108.12 and 100.91 kJ mol^?1 were obtained for CH₄, CO₂, H₂ and CO, respectively. The characterization of the spent 20 wt% Co/80 wt% Sm₂O₃ catalyst after 4 h of time-on-stream has confirmed the presence of amorphous carbon which can easily be gasified.     

Comparison of CO2 Dynamics and Air–Sea Gas Exchange in Differing Tropical Reef Environments

An array of MAPCO₂ buoys, CRIMP-2, Ala Wai, and Kilo Nalu, deployed in the coastal waters of Hawaii, have produced multi-year high temporal resolution CO₂ records in three different coral reef environments off the island of Oahu, Hawaii. This study, which includes data from June 2008 to December 2011, is part of an integrated effort to understand the factors that influence the dynamics of CO₂–carbonic acid system parameters in waters surrounding Pacific high-island coral reef ecosystems and subject to differing natural and anthropogenic stresses. The MAPCO₂ buoys are located on the Kaneohe Bay backreef, and fringing reef sites on the south shore of Oahu, Hawaii. The buoys measure CO₂ and O₂ in seawater and in the atmosphere at 3-h intervals, as well as other physical and biogeochemical parameters (conductivity, temperature, depth, chlorophyll-a, and turbidity). The buoy records, combined with data from synoptic spatial sampling, have allowed us to examine the interplay between biological cycles of productivity/respiration and calcification/dissolution and biogeochemical and physical forcings on hourly to inter-annual time scales. Air–sea CO₂ gas exchange was also calculated to determine whether the locations were sources or sinks of CO₂ over seasonal, annual, and interannual time periods. Net annualized fluxes for CRIMP-2, Ala Wai, and Kilo Nalu over the entire study period were 1.15, 0.045, and ?0.0056 mol C m^?2 year^?1, respectively, where positive values indicate a source or a CO₂ flux from the water to the atmosphere, and negative values indicate a sink or flux of CO₂ from the atmosphere into the water. These values are of similar magnitude to previous estimates in Kaneohe Bay as well as those reported from other tropical reef environments. Total alkalinity (A_T) was measured in conjunction with pCO₂, and the carbonic acid system was calculated to compare with other reef systems and open ocean values around Hawaii. These findings emphasize the need for high-resolution data of multiple parameters when attempting to characterize the carbonic acid system in locations of highly variable physical, chemical, and biological parameters (e.g., coastal systems and reefs).     

Air–Water CO<Subscript>2</Subscript> Fluxes and Net Ecosystem Production Changes in a Baja California Coastal Lagoon During the Anomalous North Pacific Warm Condition

The present study examines the temporal variability of air–water CO₂ fluxes (FCO₂) and seawater carbonate chemistry in a Baja California coastal lagoon during an exceptionally warm anomaly that was developed in Northeast Pacific coasts during 2014. This oceanographic condition led to a summer-like season (weak upwelling condition) during the study period, which reached a maximum surface temperature anomaly of 2 °C in September 2014. San Quintín Bay acts as a source of CO₂ to the atmosphere in 2014 (3.3 ± 4.8 mmol C m^?2 day^?1) with the higher positive fluxes mainly observed in summer months (9.0 ± 5.3 mmol C m^?2 day^?1). Net ecosystem production (NEP) switched seasonally between net heterotrophy and net autotrophy during the study period, with an annual average of 2.2 ± 7.1 mmol C m^?2 day^?1, which indicates that San Quintín Bay was a net autotrophic system during the atypical warm oceanographic condition in 2014. This pattern of seasonal variations in the carbon balance at San Quintín Bay appears to be linked to the life cycle of benthic communities, which play an important role in the whole-ecosystem metabolism. Under the limited input from external sources coupled with an increase in seawater temperatures, the recycled benthic carbon and nutrient fluxes play a major role to sustain water-column processes within the bay. Since the upwelling condition may influence the magnitude of the air–water CO₂ fluxes, our results clearly indicated that San Quintín Bay is a net source of carbon to the atmosphere regardless of the adjacent oceanic conditions. Our study sheds light on the carbon dynamics and its metabolic implications in a shallow coastal ecosystem under a regional warm anomaly and contributes potentially relevant information in view of the likely future scenario of global climate change.     

Geochemical alterations in surface waters of Govind Ballabh Pant Sagar,Northern Coalfield,India

Major ions showed high concentrations, ionic strength and chemical activity in the surface waters of Govind Ballabh Pant Sagar reservoir. Various geochemical ratios showed the dominance of silicate over carbonate weathering and major ions such as Na⁺ + K⁺ account for about 52 % of the cation budget. The high Na⁺ and K⁺ showed sedimentation of rock/coal particles consisting of highly weathered silicate minerals contributed by the discharge of mine water, fly ash mixing during transportation, etc. Further, Ca²⁺ + Mg²⁺/Na⁺ + K⁺ ratio was <1 (0.92) indicating the occurrence of silicate weathering in the reservoir catchment. The comparative assessment showed that the proportion of Ca²⁺ + Mg²⁺/Na⁺ + K⁺ tends to be lower along the coal mining belts compared to non-coal mining regions in the world. The Ca²⁺/SO₄ ^2? ratio <1 revealed not only H₂CO₃ but H₂SO₄ also acting as a source of protons for rock weathering. The cause underlying these differences can be related directly to geological substrate and anthropogenic activities.     

In situ observation of crystal growth in a basalt melt and the development of crystal size distribution in igneous rocks

The speciation of CO₂ in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO₂ into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO₂ re-appeared. Infrared extinction coefficients of both carbonate and molecular CO₂ decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/t = 0.98) and basaltic andesite (NBO/t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/t = 0.09) and phonolite melts (NBO/t = 0.14), the equilibrium CO₂ + O^2? = CO₃ ^2? in the melt shifts toward CO₂ with increasing temperature, with ln K = ?4.57 (±1.68) + 5.05 (±1.44) 10³ T ^?1 for dacite melt (ΔH = ?42 kJ mol^?1) and ln K = ?6.13 (±2.41) + 7.82 (±2.41) 10³ T ^?1 for phonolite melt (ΔH = ?65 kJ mol^?1), where K is the molar ratio of carbonate over molecular CO₂ and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that ΔS and ΔH are linear functions of NBO/t. Based on this relationship, a general model for CO₂ speciation in silicate melts is developed, with ln K = a + b/T, where T is temperature in Kelvin and a = ?2.69 ? 21.38 (NBO/t), b = 1,480 + 38,810 (NBO/t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO₂, and therefore, the diffusion coefficient of CO₂ is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO₂ solubility and speciation on melt composition, in accordance with available solubility data.     

Melting of clinopyroxene + magnesite in iron-bearing planetary mantles and implications for the Earth and Mars

The assemblage clinopyroxene + magnesite was observed in Earth’s high-pressure metamorphic samples, and its stability in subducting slabs was confirmed by experiments. Recent studies also suggested that the fO₂ variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO₂ equilibria in the Martian mantle. Although there is no direct evidence for the stability of the cpx + mc assemblage in Mars mantle, its high-pressure–high-temperature decomposition to cpx + fo + CO₂ makes it a good analogue for the source of carbon metasomatism, in particular, to study nakhlites formation. Iron, which is present in the Earth’s and Martian mantles, may, however, influence the speciation of carbon. We performed experiments on a clinopyroxene + magnesite assemblage at 1.8 and 3.0 GPa and temperatures corresponding to the Earth’s and Martian mantles. The role of iron and of fO₂ was investigated by (1) replacing all or part of the magnesite by siderite FeCO₃, (2) adding Fe⁰ and (3) using graphite C capsules. A carbonate-silicate melt forms at both Earth and Mars conditions. Clinopyroxene and olivine are the main solid phases in the iron-free experiments. Fe²⁺ and Fe⁰ decrease their melting temperatures and increase the silicate fraction in the melt. The produced carbonate-silicate melts may be involved in the formation of some carbon-rich lavas on Earth (e.g., carbonatites, ultramafic lamprophyres, or kamafugites). Our results may also be used to interpret ophiolite samples or inclusions. In particular, we show that wüstite may form in equilibrium with carbonate-silicate melt in opx-(and silica-) poor regions of the mantle below 3 GPa. Our results also confirm the hypothesis of carbon metasomatism in the Martian nakhlites source. Immiscibility or reduction could explain the absence or rarity of C in Martian lavas.     

CO2 Input Dynamics and Air–Sea Exchange in a Large New England Estuary

Repeated surveys of the Kennebec estuary, a macrotidal river estuary in Maine, USA, between 2004 and 2008 found spatial and temporal variability both in sources of carbon dioxide (CO₂) to the estuary and the air–sea flux of estuary CO₂. On an annual basis, the surveyed area of the Kennebec estuary had an area-weighted average partial pressure of CO₂ (pCO₂) of 559 μatm. The area-weighted average CO₂ flux to the atmosphere was 3.54 mol C m^?2 year^?1. Overall, the Kennebec estuary was an annual source of 7.2?×?10⁷ mol CO₂ to the atmosphere. Distinct seasonality in estuarine pCO₂ was observed, with shifts in the seasonal pattern evident between lower and higher salinities. Fluxes of CO₂ from the estuary were elevated following two summertime storms, and inputs of riverine CO₂ outweighed internal estuarine CO₂ inputs in nearly all months. River and estuarine inputs of CO₂ represented 68 and 32 % of the total CO₂ contributions to the estuary, respectively. This study examines the variability of CO₂ in a large New England estuary, and highlights the comparatively high contribution of CO₂ from riverine sources.     

Geochemistry and quality of groundwater of Gummanampadu sub-basin, Guntur District, Andhra Pradesh, India

Groundwater survey has been carried out in the area of Gummanampadu sub-basin located in Guntur District, Andhra Pradesh, India for assessing the factors that are responsible for changing of groundwater chemistry and consequent deterioration of groundwater quality, where the groundwater is a prime source for drinking and irrigation due to non-availability of surface water in time. The area is underlain by the Archaean Gneissic Complex, over which the Proterozoic Cumbhum rocks occur. The results of the plotting of Ca²⁺ + Mg²⁺ versus HCO₃ ^? + CO₃ ^2?, Ca²⁺ + Mg²⁺ versus total cations, Na⁺ + K⁺ versus total cations, Cl^? + SO₄ ^2? versus Na⁺ + K⁺, Na⁺ versus Cl^?, Na⁺ versus HCO₃ ^? + CO₃ ^2?, Na⁺ versus Ca²⁺ and Na⁺: Cl^? versus EC indicate that the rock–water interaction under alkaline condition is the main mechanism in activating mineral dissociation and dissolution, causing the release of Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, CO₃ ^2?, SO₄ ^2? and F^? ions into the groundwater. The ionic relations also suggest that the higher concentrations of Na⁺ and Cl^? ions are the results of ion exchange and evaporation. The influences of anthropogenic sources are the other cause for increasing of Mg²⁺, Na⁺, Cl^?, SO₄ ^2? and NO₃ ^? ions. Further, the excess alkaline condition in water accelerates more effective dissolution of F^?-bearing minerals. Moreover, the chemical data plotted in the Piper’s, Gibbs’s and Langelier–Ludwig’s diagrams, computed for the chloro-alkaline and saturation indices, and analyzed in the principal component analysis, support the above hypothesis. The groundwater quality is, thus, characterized by Na⁺ > Ca²⁺ > Mg²⁺ > K⁺: HCO₃ ^? + CO₃ ^2? > Cl^? > SO₄ ^2? > NO₃ ^? > F^? facies. On the other hand, majority of groundwater samples are not suitable for drinking with reference to the concentrations of TDS, TH, Mg²⁺ and F^?, while those are not good for irrigation with respect to USSL’s and Wilcox’s diagrams, residual sodium carbonate, and magnesium hazard, but they are safe for irrigation with respect to permeability index. Thus, the study recommends suitable management measures to improve health conditions as well as to increase agricultural output.     

Carbon Dioxide Fluxes and Their Environmental Control in a Reclaimed Coastal Wetland in the Yangtze Estuary

Large areas of natural coastal wetlands have suffered severely from human-driven damages or conversions (e.g., land reclamations), but coastal carbon flux responses in reclaimed wetlands are largely unknown. The lack of knowledge of the environmental control mechanisms of carbon fluxes also limits the carbon budget management of reclaimed wetlands. The net ecosystem exchange (NEE) in a coastal wetland at Dongtan of Chongming Island in the Yangtze estuary was monitored throughout 2012 using the eddy covariance technique more than 14 years after this wetland was reclaimed using dykes to stop tidal flooding. The driving biophysical variables of NEE were also examined. The results showed that NEE displayed marked diurnal and seasonal variations. The monthly mean NEE showed that this ecosystem functioned as a CO₂ sink during 9 months of the year, with a maximum value in September (?101.2 g C m^?2) and a minimum value in November (?8.2 g C m^?2). The annual CO₂ balance of the reclaimed coastal wetland was ?558.4 g C m^?2 year^?1. The ratio of ecosystem respiration (ER) to gross primary production (GPP) was 0.57, which suggests that 57 % of the organic carbon assimilated by wetland plants was consumed by plant respiration and soil heterotrophic respiration. Stepwise multiple linear regressions suggested that temperature and photosynthetically active radiation (PAR) were the two dominant micrometeorological variables driving seasonal variations in NEE, while soil moisture (M _s) and soil salinity (PS_s) played minor roles. For the entire year, PAR and daytime NEE were significantly correlated, as well as temperature and nighttime NEE. These nonlinear relationships varied seasonally: the maximum ecosystem photosynthetic rate (A _max), apparent quantum yield (?), and Q ₁₀ reached their peak values during summer (17.09 μmol CO₂?m^?2 s^?1), autumn (0.13 μmol CO₂?μmol^?1 photon), and spring (2.16), respectively. Exceptionally high M _s or PS_s values indirectly restricted ecosystem CO₂ fixation capacity by reducing the PAR sensitivity of the NEE. The leaf area index (LAI) and live aboveground biomass (AGB_L) were significantly correlated with NEE during the growing season. Although the annual net CO₂ fixation rate of the coastal reclaimed wetland was distinctly lower than the unreclaimed coastal wetland in the same region, it was quite high relative to many inland freshwater wetlands and estuarine/coastal wetlands located at latitudes higher than this site. Thus, it is concluded that although the net CO₂ fixation capacity of the coastal wetland was reduced by land reclamation, it can still perform as an important CO₂ sink.     

Isotope Constraints on the Aquatic Carbon Budget: Langat Watershed,Malaysia

Langat River drains a tropical watershed in the southwest of the Malaysian Peninsula. The watershed is heavily urbanized in its downstream portion. Water samples were collected from May 2010 to December 2011, at three localities along the main stem river, 1 location at its Semenyih tributary and from an upstream groundwater source. Concentration and δ¹³C data of riverine DIC and DOC indicate the dominance of C3 plant-derived material as the primary source of carbon, with δ¹³C_DIC values enriched in ¹³C relative to that of the C3 source. This enrichment is likely due to CO₂ outgassing, as calculated concentrations of riverine CO₂ are significantly higher than ambient atmospheric values, with methanogenic activity a theoretically possible contributing factor, particularly at the upstream location. The Langat River therefore acts as a net source of CO₂, with a total sub-basin flux of 19.7 × 10³ t C year^?1. This is comparable to the sum of riverine DOC, DIC and POC loss rates from the sub-basin, calculated as 24.5 × 10³ t C year^?1, and highlights the significance of CO₂ evasion from water bodies to the atmosphere for balancing the budget of the terrestrial carbon cycle. The DIC and DOC concentration and δ¹³C data also suggests that in the more urbanized downriver areas, much of the organic carbon input may be anthropogenicaly derived due to ubiquity of sewage treatment plants and landfill sites. Such human-induced perturbations to riverine carbon cycling should be taken into account in future studies of urbanized watersheds.     

Sabatier-based CO2-methanation by catalytic conversion

The catalytic conversion of CO₂ is an important component for the reintegration of secondary products like CO₂ or H₂ into the energy supply. An example is the “power to gas” concept with a conversion of CO₂ into CH₄. The CO₂ is transferred into a carrier of chemical energy, with the possibility to feed the produced CH₄ into the existing network of natural gas. At temperatures of around 350 °C, hydrogenation of CO₂ to CH₄ is possible by the Sabatier reaction CO₂ + 4H₂ → CH₄ + 2H₂O. One prerequisite for efficient kinetics of the Sabatier reaction is the application and optimization of catalysts. The focus of catalyst development is given to their performance under the conditions to be expected in the special application. As a part of the project Geoenergy-Research (GeoEn), we address questions related to the catalytic utilization of CO₂ produced in the course of the oxyfuel combustion of lignite. In this contribution, we report on the experimental setup in laboratory scale, which enables an advanced characterization of the catalytic performance, including thermodesorption measurements at atmospheric pressure in order to determine the amount of adsorbed CO₂ under real conditions. We also show data for activation energies, the catalytic performance as function of temperature and the long time stability of a commercial Ru-based catalyst.     

Coastal Ocean Last Glacial Maximum to 2100 CO2-Carbonic Acid-Carbonate System: A Modeling Approach

Using coupled terrestrial and coastal zone models, we investigated the impacts of deglaciation and anthropogenic inputs on the CO₂–H₂O–CaCO₃ system in global coastal ocean waters from the Last Glacial Maximum (LGM: 18,000 year BP) to the year 2100. With rising sea level and atmospheric CO₂, the carbonate system of coastal ocean water changed significantly. We find that 6 × 10¹² metric tons of carbon were emitted from the coastal ocean, growing due to the sea level rise, from the LGM to late preindustrial time (1700 AD) because of net heterotrophy and calcification processes. This carbon came to reside in the atmosphere and in the growing vegetation on land and in uptake of atmospheric CO₂ through the weathering of rocks on land. It appears that carbonate accumulation, mainly, but not exclusively, in coral reefs from the LGM to late preindustrial time could account for about 24 ppmv of the 100 ppmv rise in atmospheric CO₂, lending some support to the “coral reef hypothesis”. In addition, the global coastal ocean is now, or soon will be, a sink of atmospheric CO₂. The temperature rise of 4–5°C since the LGM led to increased weathering rates of inorganic and organic materials on land and enhanced riverine fluxes of total C, N, and P to the coastal ocean of 68%, 108%, and 97%, respectively, from the LGM to late preindustrial time. During the Anthropocene, these trends have been exacerbated owing to rising atmospheric CO₂, due to fossil fuel combustion and land-use practices, other human activities, and rising global temperatures. River fluxes of total reactive C, N, and P are projected to increase from late preindustrial time to the year 2100 by 150%, 380%, and 257%, respectively, modifying significantly the behavior of these element cycles in the coastal ocean, particularly in proximal environments. Despite the fact that the global shoal water carbonate mass has grown extensively since the LGM, the pH_T (pH values on the total proton scale) of global coastal waters has decreased from ~8.35 to ~8.18 and the carbonate ion concentration declined by ~19% from the LGM to late preindustrial time. The latter represents a rate of decline of about 0.028 μmol CO₃ ^2? per decade. In comparison, the decrease in coastal water pH_T from the year 1900 to 2000 was about 8.18–8.08 and is projected to decrease further from about 8.08 to 7.85 between 2000 and 2100, according to the IS92a business-as-usual scenario of CO₂ emissions. Over these 200 years, the carbonate ion concentration will fall by ~120 μmol kg^?1 or 6 μmol kg^?1 per decade. This decadal rate of decline of the carbonate ion concentration in the Anthropocene is 214 times the average rate of decline for the entire Holocene. Hence, when viewed against the millennial to several millennial timescale of geologic change in the coastal ocean marine carbon system, one can easily appreciate why ocean acidification is the “other CO₂ problem”.     

Iron weathering products in a CO2 + (H2O or H2O2) atmosphere: Implications for weathering processes on the surface of Mars

Various iron-bearing primary phases and rocks have been weathered experimentally to simulate possible present and past weathering processes occurring on Mars. We used magnetite, monoclinic and hexagonal pyrrhotites, and metallic iron as it is suggested that meteoritic input to the martian surface may account for an important source of reduced iron. The phases were weathered in two different atmospheres: one composed of CO₂ + H₂O, to model the present and primary martian atmosphere, and a CO₂ + H₂O + H₂O₂ atmosphere to simulate the effect of strong oxidizing agents. Experiments were conducted at room temperature and a pressure of 0.75 atm. Magnetite is the only stable phase in the experiments and is thus likely to be released on the surface of Mars from primary rocks during weathering processes. Siderite, elemental sulfur, ferrous sulfates and ferric (oxy)hydroxides (goethite and lepidocrocite) are the main products in a water-bearing atmosphere, depending on the substrate. In the peroxide atmosphere, weathering products are dominated by ferric sulfates and goethite. A kinetic model was then developed for iron weathering in a water atmosphere, using the shrinking core model (SCM). This model includes competition between chemical reaction and diffusion of reactants through porous layers of secondary products. The results indicate that for short time scales, the mechanism is dominated by a chemical reaction with second order kinetics (k = 7.75 × 10⁻⁵ g⁻¹/h), whereas for longer time scales, the mechanism is diffusion-controlled (De_A = 2.71 × 10⁻¹⁰ m²/h). The results indicate that a primary CO₂- and H₂O-rich atmosphere should favour sulfur, ferrous phases such as siderite or Fe²⁺-sulfates, associated with ferric (oxy)hydroxides (goethite and lepidocrocite). Further evolution to more oxidizing conditions may have forced these precursors to evolve into ferric sulfates and goethite/hematite.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

The hydrogeochemistry and isotope geochemistry of groundwater from 85 wells in fractured dolomite aquifers of Central Slovenia were investigated. This groundwater represents waters strongly influenced by chemical weathering of dolomite with an average of δ¹³C_CARB value of +2.2 ‰. The major groundwater geochemical composition is HCO₃ ^? > Ca²⁺ > Mg²⁺. Several differences in hydrogeochemical properties among the classes of dolomites were observed when they were divided based on their age and sedimentological properties, with a clear distinction of pure dolomites exhibiting high Mg²⁺/Ca²⁺ ratios and low Na⁺, K⁺ and Si values. Trace element and nutrient concentrations (SO₄ ^2?, NO₃ ^?) were low, implying that karstic and fractured dolomite aquifers are of good quality to be used as tap water. Groundwater was generally slightly oversaturated with respect to calcite and dolomite, and dissolved CO₂ was up to 46 times supersaturated relative to the atmosphere. The isotopic composition of oxygen (δ¹⁸O_H2O), hydrogen (δD_H2O) and tritium ranged from ?10.3 to ?8.4 ‰, from ?68.5 to ?52.7 ‰ and from 3.5 TU to 10.5 TU, respectively. δ¹⁸O and δD values fell between the GMWL (Global Meteoric Water Line) and the MMWL (Mediterranean Meteoric Water Line) and indicate recharge from precipitation with little evaporation. The tritium activity in groundwater suggests that groundwater is generally younger than 50 years. δ¹³C_DIC values ranged from ?14.6 to ?9.3 ‰ and indicated groundwater with a contribution of degraded organic matter/dissolved inorganic carbon in the aquifer. The mass balances for groundwater interacting with carbonate rocks suggested that carbonate dissolution contributes from 43.7 to 65.4 % and degradation of organic matter from 34.6 to 56.3 %.     

CO<Subscript>2</Subscript> flux variation and its contribution area in the debris-covered area of Koxkar Glacier,Mt. Tianshan in China

During the formation and development of glacial meltwater runoff, hydrochemical erosion is abundant, especially the hydrolysis of K/Na feldspar and carbonates, which can consume H⁺ in the water, promote the formation of bicarbonate by dissolving atmospheric CO₂, and affect the regional carbon cycle. From July 21, 2015, to July 18, 2017, the CO₂ concentration and flux were observed by the eddy covariance (EC) method in the relatively flat and open moraine cover area of Koxkar Glacier in western Mt. Tianshan, China. We found that: (1) atmospheric CO₂ fluxes ranged from ??408.95 to 81.58 mmol m^?2 day^?1 (average ? 58.68 mmol m^?2 day^?1), suggesting that the study area is a significant carbon sink, (2) the CO₂ flux footprint contribution areas were primarily within 150 m of the EC station, averaging total contribution rates of 93.30%, 91.39%, and 90.17% of the CO₂ flux in the snow accumulation, snow melting, and glacial melting periods, respectively. Therefore, the contribution areas with significant influences on CO₂ flux observed at EC stations were concentrated, demonstrating that grassland CO₂ flux around the glaciers had little effect at the EC stations, (3) in the predominant wind direction, under stable daytime atmospheric stratification, the measurement of CO₂ flux, as interpreted by the Agroscope Reckenholz Tanikon footprint tool, was 79.09% ± 1.84% in the contribution area. This was slightly more than seen at night, but significantly lower than the average under unstable atmospheric stratification across the three periods of interest (89%). The average distance of the farthest point of the flux footprint under steady state atmospheric conditions was 202.61?±?69.33 m, markedly greater than that under non-steady state conditions (68.55?±?10.34 m). This also indicates that the CO₂ flux observed using EC was affected primarily by hydrochemical erosion reactions in the glacier area, (4) a good negative correlation was found between net glacier exchange (NGE) of CO₂ and air temperature on precipitation-free days. Strong ice and snow ablation could promote hydrochemical reactions of soluble substances in the debris area and accelerated sinking of atmospheric CO₂. Precipitation events might reduce snow and ice melting, driven by reduced regional temperatures. However, a connection between NGE and precipitation, when less than 8.8 mm per day, was not obvious. When precipitation was greater than 8.8 mm per day, NGE decreased with increasing precipitation, (5) graphically, the slope of NGE, related to daily runoff, followed a trend: snow melting period?>?snow accumulation period?>?early glacial ablation period?>?late glacier ablation period?>?dramatic glacier ablation period. The slope was relatively large during snow melting, likely because of CO₂ sinking caused by water–rock interactions. The chemical reaction during elution in the snow layer might also promote atmospheric CO₂ drawdown. At the same time, the damping effect of snow cover and the almost-closed glacier hydrographic channel inhibited the formation of regional runoff, possibly providing sufficient time for the chemical reaction, thus promoting further CO₂ drawdown.