Dissolved Carbon System Research Articles

Henry Elderfield. 25 April 1943—19 April 2016

Henry (always known as Harry) Elderfield was a marine geochemist whose pioneering measurements of strontium and its isotopes, rare earth elements and manganese in seawater and sediment pore waters gave him insights into the circulation of fluids into, through and out of the oceanic crust and marine sediments and their control of the chemical composition of the oceans. He provided the basis for proxies of past ocean temperatures, pH and water mass distributions. These he used to reveal changes in global temperature and sea-levels on timescales spanning the last 50 million years (Myr) with emphasis on the last 1 Myr of glacial/interglacial history. His work on a proxy for pH, coupled with understanding of the dissolved carbon system in seawater, allowed examination of problems of ocean acidification caused by past changes of atmospheric CO 2 . His manner of gentle persuasion underpinned by rigorous chemistry was passed on to more than 40 research students, and his proxy methods are in daily use by hundreds worldwide.

Trajectory and timescale of oxygen and clumped isotope equilibration in the dissolved carbonate system under normal and enzymatically-catalyzed conditions at 25 °C

The abundance of 18O isotopes and 13C-18O isotopic “clumps” (measured as δ18O and Δ47, respectively) in carbonate minerals have been used to infer mineral formation temperatures. An inherent requirement or assumption for these paleothermometers is mineral formation in isotopic equilibrium. Yet, apparent disequilibrium is not uncommon in biogenic and abiogenic carbonates formed in nature and in synthetic carbonates prepared under laboratory settings, as the dissolved carbonate pool (DCP) from which minerals precipitate is often out of δ18O and Δ47 equilibrium. For this, a complete understanding of both equilibrium and kinetics of isotopic partitioning and 13C-18O clumping in DCP is crucial. To this end, we analyzed Δ47 of inorganic BaCO3 samples from Uchikawa and Zeebe (2012) (denoted as UZ12), which were quantitatively precipitated from NaHCO3 solutions at various times over the course of isotopic equilibration at 25 °C and pHNBS of 8.9. Our data show that, although the timescales for δ18O and Δ47 equilibrium in DCP are relatively similar, their equilibration trajectories are markedly different. As opposed to a simple unidirectional and asymptotic approach toward δ18O equilibrium (first-order kinetics), Δ47 equilibration initially moves away from equilibrium and then changes its course towards equilibrium. This excess Δ47 disequilibrium is manifested as a characteristic “dip” in the Δ47 equilibration trajectory, a feature consistent with an earlier study by Staudigel and Swart (2018) (denoted as SS18). From the numerical model of SS18, the non-first-order kinetics for Δ47 equilibration can be understood as a result of the difference in the exchange rate for oxygen isotopes bound to 12C versus 13C, or an isotope effect of ~25‰. We also developed an independent model for the Exchange and Clumping of 13C and 18O in DCP (ExClump38 model) to trace the evolution of singly- and doubly-substituted isotopic species (i.e., δ13C, δ18O and Δ47). The model suggests that the dip in the Δ47 equilibration trajectory is due largely to kinetic carbon isotope fractionation for hydration and hydroxylation of CO2. We additionally examined the BaCO3 samples prepared from NaHCO3 solutions supplemented with carbonic anhydrase (CA), an enzyme known to facilitate δ18O equilibration in DCP by catalyzing CO2 hydration (UZ12). These samples revealed that, while CA effectively shortens the time required for Δ47 equilibrium in DCP, the overall pattern and magnitude of the dip in the Δ47 equilibration trajectory remain unchanged. This suggests no additional isotope effects due to the CA enzyme within the tested CA concentrations. With the ExClump38 model, we test various physicochemical scenarios for the timescales and trajectories of isotopic equilibration in DCP and discuss their implications for the Δ47 paleothermometry.

Gas hydrate dissociation prolongs acidification of the Anthropocene oceans

AbstractAnthropogenic warming of the oceans can release methane (CH4) currently stored in sediments as gas hydrates. This CH4 will be oxidized to CO2, thus increasing the acidification of the oceans. We employ a biogeochemical model of the multimillennial carbon cycle to determine the evolution of the oceanic dissolved carbonate system over the next 13 kyr in response to CO2 from gas hydrates, combined with a reasonable scenario for long‐term anthropogenic CO2 emissions. Hydrate‐derived CO2 will appreciably delay the neutralization of ocean acidity and the return to preindustrial‐like conditions. This finding is the same with CH4 release and oxidation in either the deep ocean or the atmosphere. A change in CaCO3 export, coupled to CH4 release, would intensify the transient rise of the carbonate compensation depth, without producing any changes to the long‐term evolution of the carbonate system. Overall, gas hydrate destabilization implies a moderate additional perturbation to the carbonate system of the Anthropocene oceans.

The major ion, 87Sr/86Sr, and δ11B geochemistry of groundwater in the Wyodak-Anderson coal bed aquifer (Powder River Basin, Wyoming, USA)

We developed a multicomponent, 1D advective transport model that describes the downgradient evolution of solute concentrations, 87Sr/86Sr ratios, and δ11B values in the Wyodak-Anderson Coal Bed (WACB) aquifer located in the Powder River Basin, Wyoming, USA. The purpose of the study was to evaluate the chemical vulnerability of groundwater to potential environmental change stemming from the extraction of coal bed methane and shale gas. Model calculations demonstrate that coupling between microbial activity and the dissolved carbonate system controls major ion transport in the WACB aquifer. The analysis of 87Sr/86Sr ratios further reveals the importance of ion-exchange reactions. Similarly, δ11B data emphasize the significance of pH-dependent surface reactions and demonstrate the vulnerability of the aquifer to the long-term acidification of recharge water.

Determination of in situ dissolved inorganic carbon concentration and alkalinity for marine sedimentary porewater

Dissolved inorganic carbon (DIC) concentration and total alkalinity in marine sediment vary with biological activity, mineral diagenesis and past bottom ocean water composition. Reliable interpretation of this data is often compromised due to precipitation of calcium carbonate (CaCO3) during sediment recovery, processing and sample storage.Here we present and test a method that corrects for this precipitation and consequently allows quantification of in situ carbonate system chemistry. Our method relies on the over-determination of the dissolved carbonate system by (i) measuring DIC, alkalinity and calcium, and (ii) explicitly assuming CaCO3 saturation in the sediment. We experimentally tested this method using data from Integrated Ocean Drilling Program (IODP) Site U1368 in the South Pacific Gyre. Our results show that we can accurately reproduce in situ aqueous carbonate system chemistry if DIC, alkalinity and calcium concentration are measured simultaneously. At Site U1368, the correction for sampling associated precipitation is equivalent to 4.5 and 8.9% of the measured DIC and alkalinity, respectively. The method is well suited for any sediment porewater that is saturated with respect to calcium carbonate; consequently, it is applicable for approximately 50% of the global oceanic seafloor.

Carbonate chemistry and projected future changes in pH and CaCO 3 saturation state of the South China Sea

To study the dissolved carbonate system in the South China Sea (SCS) and to understand the water mass exchange between the SCS and the West Philippine Sea (WPS), pH, total alkalinity and total CO 2 were measured aboard the R/V Ocean Researcher 1. Because of the sill that separates these two seas in the Luzon Strait with a maximum depth of 2200 m, the SCS Deep Water has characteristics similar to those of water at about 2200 m in the WPS. The minimum pH and the maxima of normalized alkalinity and total CO 2 commonly found in the open oceans at mid-depth also prevail in the WPS but are, however, very weak in the SCS. Rivers and inflows from Kuroshio Surface and Deep Waters through the Luzon Strait as well as those through the Mindoro Strait transport carbon to the SCS year-round. Meanwhile, the outflowing Taiwan Strait water as well as the SCS Surface and Intermediate Waters of the Luzon Strait transports carbon out of the SCS year-round. The Sunda Shelf is also a channel for carbon transport into the SCS in the wet season and out of the SCS in the dry season. fCO 2 data and mass balance calculations indicate that the SCS is a weak CO 2 source in the wet season but an even weaker CO 2 sink in the dry season. With these facts taken together, the SCS is likely a very weak CO 2 source. Anthropogenic CO 2 penetrates to about 1500 m in depth in the SCS, and the entire SCS contains 0.60 ± 0.15 × 10 15 g of excess carbon. Typical profiles of pH as well as the degree of saturation of each of calcite and aragonite in 1850 and 1997 are presented, and those for 2050 AD are projected. The maximum decrease in pH is estimated to be 0.16 pH units in the surface layer when the amount of CO 2 is doubled. It is anticipated that aragonite in the upper continental slope will likely start to dissolve, thereby neutralizing excess CO 2 by around 2050 AD. This paper is unique in that it presents the results of the first attempt ever to estimate the past, present and future physico-chemical properties of the world's largest marginal sea.

A mid-depth front separating the South China Sea water and the Philippine sea water

In order to understand the influence of the South China Sea (SCS) water on the Kuroshio, and to study the dissolved carbonate system, we participated in six WOCE cruises aboard R/V Ocean Researcher 1. The areas studied were the northeast South China Sea and the West Philippine Sea near the Luzon Strait. Temperature, salinity, pH, alkalinity and total CO2 were measured. Our data indicate that, although the Kuroshio and the SCS waters flow in and out of the Luzon Strait near surface, the SCS water seems mainly to flow out of the SCS at mid-depth. There exists a “mid-depth front” near 122°E between 350 and 1350 m in all seasons and years that we studied. The water mass between 350 and 1350 m east of the front belongs to the West Philippine Sea proper water, while on the west is the mixed water of the South China Sea and the West Philippine Sea.

Carbon isotope fractionation by marine phytoplankton in culture: The effects of CO2 concentration, pH, temperature, and species

Closed cultures of marine phytoplankton were established under variable conditions of CO2 concentration, temperature, growth rate (by light limitation), and pH (but with nearly identical [CO2aq]) in order to assess the relative influence of these variables on the extent of carbon isotope fractionation relative to dissolved inorganic carbon sources. Culture biomass was not allowed to increase beyond levels that would significantly affect the dissolved carbon system in the closed cultures. In experiments with Skeletonema costatum and Emiliania huxleyi, increasing CO2 concentrations led to increased carbon isotope discrimination (resulting in organic matter progressively depleted in δ13C, i.e., a greater, more negative ϵp). ϵp values for E. huxleyi were 8–10‰ less than for S. costatum under identical conditions. For the S. costatum cultures, there was nearly a 20 ‰ range in [CO2aq]‐dependent ϵp. The effect was nonlinear with a leveling off at high [CO2aq]. Over a pH range of 7.5–8.3 but at a constant [CO2aq] there was a variation in carbon isotope fractionation by S. costatum of about 9 ‰ with a minimum at pH 7.8–7.9. There was a temperature effect of ∼8‰ on fractionation even after equilibrium temperature dependency of δ13C of CO2aq was taken into account. No growth rate effect was found for S. costatum over a modest range of growth rates. Culture experiments used to determine the carbon isotope fractionation by phytoplankton species must be conducted under well‐defined conditions of temperature, pH, and CO2 concentrations. Hindcasts of ancient atmospheric pCO2 from measurements of δ13C of organic carbon in marine sediments will require careful calibration because of the variety of possible factors that influence δ13Corg.