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 Sensitivity of the Phanerozoic Inorganic Carbon System to the Onset of Pelagic Sedimentation

The onset of pelagic sedimentation attending the radiation of pelagic calcifiers during the Mesozoic was an important divide in Earth history, shifting the locus of significant carbonate sedimentation from the shallow shelf environments of the Paleozoic to the deep sea. This shift would have impacted the CO₂ cycle, given that decarbonation of subducted pelagic carbonate is an important return flux of CO₂ to the atmosphere. Coupled with the fact that the mean residence time of continental platform and basin sedimentary carbonate exceeds that of the oceanic crust, it thus becomes unclear whether carbon cycling would have operated on a substantially different footing prior to the pelagic transition. Here, we examine this uncertainty with sensitivity analyses of the timing of this transition using a coupled model of the Phanerozoic atmosphere, ocean, and shallow lithosphere. For purposes of comparison, we establish an age of 250 Ma (i.e., after the Permo-Triassic extinctions) as the earliest opportunity for deposition of extensive biogenic pelagic carbonate on the deep seafloor, an age that predates known occurrences of pelagic calcifiers (and intact seafloor). Although an approximate boundary, we do show that attempts to shift this datum either significantly earlier or later in time produce model results that are inconsistent with observed trends in the mass–age distribution of the rock record and with accepted trends in seawater composition as constrained by proxy data. Significantly, we also conclude that regardless of the timing of the onset of biogenic pelagic carbonate sedimentation, a carbon sink involving seawater-derived dissolved inorganic carbon played a critical role in carbon cycling, particularly in the Paleozoic. This CaCO₃ sink may have been wholly abiogenic, involving calcium derived either directly from seawater (thus manifest as a direct seafloor deposit), or alternatively from basalt–seawater reactions (represented by precipitation of CaCO₃ in veins and fissures within the basalt). Despite the uncertainty in the source and magnitude of this abiogenic CaCO₃ flux, it is likely a basic and permanent feature of global carbon cycling. Subduction of this CaCO₃ would have acted as a basic return circuit for atmospheric CO₂ even in the absence of biogenically derived pelagic carbonate sedimentation. Lastly, model calculations of the ratio of dissolved calcium to carbonate ion (Ca²⁺/CO₃ ^2?) show this quantity underwent significant secular evolution over the Phanerozoic. As there is increasing recognition of this ratio’s role in CaCO₃ growth and dissolution reactions, this evolution, together with progressive increases in nutrient availability and saturation state, may have created a tipping point ultimately conducive to the appearance of pelagic calcifiers in the Mesozoic.     

Dissolution of Carbonate Sediments Under Rising <Emphasis Type="Italic">p</Emphasis>CO<Subscript>2</Subscript> and Ocean Acidification: Observations from Devil’s Hole,Bermuda

Rising atmospheric pCO₂ and ocean acidification originating from human activities could result in increased dissolution of metastable carbonate minerals in shallow-water marine sediments. In the present study, in situ dissolution of carbonate sedimentary particles in Devil’s Hole, Bermuda, was observed during summer when thermally driven density stratification restricted mixing between the bottom water and the surface mixed layer and microbial decomposition of organic matter in the subthermocline layer produced pCO₂ levels similar to or higher than those levels anticipated by the end of the 21st century. Trends in both seawater chemistry and the composition of sediments in Devil’s Hole indicate that Mg-calcite minerals are subject to selective dissolution under conditions of elevated pCO₂. The derived rates of dissolution based on observed changes in excess alkalinity and estimates of vertical eddy diffusion ranged from 0.2 mmol to 0.8 mmol CaCO₃ m⁻² h⁻¹. On a yearly basis, this range corresponds to 175–701 g CaCO₃ m⁻² year⁻¹; the latter rate is close to 50% of the estimate of the current average global coral reef calcification rate of about 1,500 g CaCO₃ m⁻² year⁻¹. Considering a reduction in marine calcification of 40% by the year 2100, or 90% by 2300, as a result of surface ocean acidification, the combination of high rates of carbonate dissolution and reduced rates of calcification implies that coral reefs and other carbonate sediment environments within the 21st and following centuries could be subject to a net loss in carbonate material as a result of increasing pCO₂ arising from burning of fossil fuels.     

Diel Aquatic CO<Subscript>2</Subscript> System Dynamics of a Bermudian Mangrove Environment

Mangrove ecosystems play an important, but understudied, role in the cycling of carbon in tropical and subtropical coastal ocean environments. In the present study, we examined the diel dynamics of seawater carbon dioxide (CO₂) and dissolved oxygen (DO) for a mangrove-dominated marine ecosystem (Mangrove Bay) and an adjacent intracoastal waterway (Ferry Reach) on the island of Bermuda. Spatial and temporal trends in seawater carbonate chemistry and associated variables were assessed from direct measurements of dissolved inorganic carbon, total alkalinity, dissolved oxygen (DO), temperature, and salinity. Diel pCO₂ variability was interpolated across hourly wind speed measurements to determine variability in daily CO₂ fluxes for the month of October 2007 in Bermuda. From these observations, we estimated rates of net sea to air CO₂ exchange for these two coastal ecosystems at 59.8 ± 17.3 in Mangrove Bay and 5.5 ± 1.3 mmol m⁻² d⁻¹ in Ferry Reach. These results highlight the potential for large differences in carbonate system functioning and sea-air CO₂ flux in adjacent coastal environments. In addition, observation of large diel variability in CO₂ system parameters (e.g., mean pCO₂: 390–2,841 μatm; mean pH_T: 8.05–7.34) underscores the need for careful consideration of diel cycles in long-term sampling regimes and flux estimates.     

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).     

A physicochemical framework for interpreting the biological calcification response to CO2-induced ocean acidification

A generalized physicochemical model of the response of marine organisms’ calcifying fluids to CO₂-induced ocean acidification is proposed. The model is based upon the hypothesis that some marine calcifiers induce calcification by elevating pH, and thus Ω_A, of their calcifying fluid by removing protons (H⁺). The model is explored through two end-member scenarios: one in which a fixed number of H⁺ is removed from the calcifying fluid, regardless of atmospheric pCO₂, and another in which a fixed external-internal H⁺ ratio ([H⁺]_E/[H⁺]_I) is maintained. The model is able to generate the full range of calcification response patterns observed in prior ocean acidification experiments and is consistent with the assertion that organisms’ calcification response to ocean acidification is more negative for marine calcifiers that exert weaker control over their calcifying fluid pH. The model is empirically evaluated for the temperate scleractinian coral Astrangia poculata with in situ pH microelectrode measurements of the coral’s calcifying fluid under control and acidified conditions. These measurements reveal that (1) the pH of the coral’s calcifying fluid is substantially elevated relative to its external seawater under both control and acidified conditions, (2) the coral’s [H⁺]_E/[H⁺]_I is approximately the same under control and acidified conditions, and (3) the coral removes fewer H⁺ from its calcifying fluid under acidified conditions than under control conditions. Thus, the carbonate system dynamics of A. poculata’s calcifying fluid appear to be most consistent with the fixed [H⁺]_E/[H⁺]_I end-member scenario. Similar microelectrode experiments performed on additional taxa are required to assess the model’s general applicability.     

Carbonate Chemistry and Air–Sea CO2 Flux in a NW Mediterranean Bay Over a Four-Year Period: 2007–2011

The Service d’Observation de la Rade de Villefranche-sur-Mer is designed to study the temporal variability of hydrological conditions as well as the abundance and composition of holo- and meroplankton at a fixed station in this bay of the northwest Mediterranean. The weekly data collected at this site, designated as “Point B” since 1957, represent a long-term time series of hydrological conditions in a coastal environment. Since 2007, the historical measurements of hydrological and biological conditions have been complemented by measurements of the CO₂–carbonic acid system parameters. In this contribution, CO₂–carbonic acid system parameters and ancillary data are presented for the period 2007–2011. The data are evaluated in the context of the physical and biogeochemical processes that contribute to variations in CO₂ in the water column and exchange of this gas between the ocean and atmosphere. Seasonal cycles of the partial pressure of CO₂ in seawater (pCO₂) are controlled principally by variations in temperature, showing maxima in the summer and minima during the winter. Normalization of pCO₂ to the mean seawater temperature (18.5 °C), however, reveals an apparent reversal of the seasonal cycle with maxima observed in the winter and minima in the summer, consistent with a biogeochemical control of pCO₂ by primary production. Calculations of fluxes of CO₂ show this area to be a weak source of CO₂ to the atmosphere during the summer and a weak sink during the winter but near neutral overall (range ?0.3 to +0.3 mmol CO₂ m^?2 h^?1, average 0.02 mmol CO₂ m^?2 h^?1). We also provide an assessment of errors incurred from the estimation of annual fluxes of CO₂ as a function of sampling frequency (3-hourly, daily, weekly), using data obtained at the Hawaii Kilo Nalu coastal time-series station, which shows similar behavior to the Point B location despite significant differences in climate and hydrological conditions and the proximity of a coral reef ecosystem.     

Nutrient Inputs, Phytoplankton Response, and CO2 Variations in a Semi-Enclosed Subtropical Embayment, Kaneohe Bay, Hawaii

The marine shelf areas in subtropical and tropical regions represent only 35% of the total shelf areas globally, but receive a disproportionately large amount of water (65%) and sediment (58%) discharges that enter such environments. Small rivers and/or streams that drain the mountainous areas in these climatic zones deliver the majority of the sediment and nutrient inputs to these narrow shelf environments; such inputs often occur as discrete, episodic introductions associated with storm events. To gain insight into the linked biogeochemical behavior of subtropical/tropical mountainous watershed-coastal ocean ecosystems, this work describes the use of a buoy system to monitor autonomously water quality responses to land-derived nutrient inputs and physical forcing associated with local storm events in the coastal ocean of southern Kaneohe Bay, Oahu, Hawaii, USA. The data represent 2.5 years of near-real time observations at a fixed station, collected concurrently with spatially distributed synoptic sampling over larger sections of Kaneohe Bay. Storm events cause most of the fluvial nutrient, particulate, and dissolved organic carbon inputs to Kaneohe Bay. Nutrient loadings from direct rainfall and/or terrestrial runoff produce an immediate increase in the N:P ratio of bay waters up to values of 48 and drive phytoplankton biomass growth. Rapid uptake of such nutrient subsidies by phytoplankton causes rapid declines of N levels, return to N-limited conditions, and subsequent decline of phytoplankton biomass over timescales ranging from a few days to several weeks, depending on conditions and proximity to the sources of runoff. The enhanced productivity may promote the drawing down of pCO₂ and lowering of surface water column carbonate saturation states, and in some events, a temporary shift from N to P limitation. The productivity-driven CO₂ drawdown may temporarily lead to air-to-sea transfer of atmospheric CO₂ in a system that is on an annual basis a source of CO₂ to the atmosphere due to calcification and perhaps heterotrophy. Storms may also strongly affect proximal coastal zone pCO₂ and hence carbonate saturation state due to river runoff flushing out high pCO₂ soil and ground waters. Mixing of the CO₂-charged water with seawater causes a salting out effect that releases CO₂ to the atmosphere. Many subtropical and tropical systems throughout the Pacific region are similar to Kaneohe Bay, and our work provides an important indication of the variability and range of CO₂ dynamics that are likely to exist elsewhere. Such variability must be taken into account in any analysis of the direction and magnitude of the air?Csea CO₂ exchange for the integrated coastal ocean, proximal and distal. It cannot be overemphasized that this research illustrates several examples of how high frequency sampling by a moored autonomous system can provide details about ecosystem responses to stochastic atmospheric forcing that are commonly missed by traditional synoptic observational approaches. Finally, the work exemplifies the utility of combining synoptic sampling and real-time autonomous observations to elucidate the biogeochemical and physical responses of coastal subtropical/tropical coral reef ecosystems to climatic perturbations.     

Is Ocean Acidification an Open-Ocean Syndrome? Understanding Anthropogenic Impacts on Seawater pH

Ocean acidification due to anthropogenic CO₂ emissions is a dominant driver of long-term changes in pH in the open ocean, raising concern for the future of calcifying organisms, many of which are present in coastal habitats. However, changes in pH in coastal ecosystems result from a multitude of drivers, including impacts from watershed processes, nutrient inputs, and changes in ecosystem structure and metabolism. Interaction between ocean acidification due to anthropogenic CO₂ emissions and the dynamic regional to local drivers of coastal ecosystems have resulted in complex regulation of pH in coastal waters. Changes in the watershed can, for example, lead to changes in alkalinity and CO₂ fluxes that, together with metabolic processes and oceanic dynamics, yield high-magnitude decadal changes of up to 0.5 units in coastal pH. Metabolism results in strong diel to seasonal fluctuations in pH, with characteristic ranges of 0.3 pH units, with metabolically intense habitats exceeding this range on a daily basis. The intense variability and multiple, complex controls on pH implies that the concept of ocean acidification due to anthropogenic CO₂ emissions cannot be transposed to coastal ecosystems directly. Furthermore, in coastal ecosystems, the detection of trends towards acidification is not trivial and the attribution of these changes to anthropogenic CO₂ emissions is even more problematic. Coastal ecosystems may show acidification or basification, depending on the balance between the invasion of coastal waters by anthropogenic CO₂, watershed export of alkalinity, organic matter and CO₂, and changes in the balance between primary production, respiration and calcification rates in response to changes in nutrient inputs and losses of ecosystem components. Hence, we contend that ocean acidification from anthropogenic CO₂ is largely an open-ocean syndrome and that a concept of anthropogenic impacts on marine pH, which is applicable across the entire ocean, from coastal to open-ocean environments, provides a superior framework to consider the multiple components of the anthropogenic perturbation of marine pH trajectories. The concept of anthropogenic impacts on seawater pH acknowledges that a regional focus is necessary to predict future trajectories in the pH of coastal waters and points at opportunities to manage these trajectories locally to conserve coastal organisms vulnerable to ocean acidification.     

Biocalcification in the Eastern Oyster (<Emphasis Type="Italic">Crassostrea virginica)</Emphasis> in Relation to Long-term Trends in Chesapeake Bay pH

Anthropogenic carbon dioxide (CO₂) emissions reduce pH of marine waters due to the absorption of atmospheric CO₂ and formation of carbonic acid. Estuarine waters are more susceptible to acidification because they are subject to multiple acid sources and are less buffered than marine waters. Consequently, estuarine shell forming species may experience acidification sooner than marine species although the tolerance of estuarine calcifiers to pH changes is poorly understood. We analyzed 23 years of Chesapeake Bay water quality monitoring data and found that daytime average pH significantly decreased across polyhaline waters although pH has not significantly changed across mesohaline waters. In some tributaries that once supported large oyster populations, pH is increasing. Current average conditions within some tributaries however correspond to values that we found in laboratory studies to reduce oyster biocalcification rates or resulted in net shell dissolution. Calcification rates of juvenile eastern oysters, Crassostrea virginica, were measured in laboratory studies in a three-way factorial design with 3 pH levels, two salinities, and two temperatures. Biocalcification declined significantly with a reduction of ∼0.5 pH units and higher temperature and salinity mitigated the decrease in biocalcification.     

Land–sea carbon and nutrient fluxes and coastal ocean CO2 exchange and acidification: Past,present, and future

Epochs of changing atmospheric CO₂ and seawater CO₂–carbonic acid system chemistry and acidification have occurred during the Phanerozoic at various time scales. On the longer geologic time scale, as sea level rose and fell and continental free board decreased and increased, respectively, the riverine fluxes of Ca, Mg, DIC, and total alkalinity to the coastal ocean varied and helped regulate the C chemistry of seawater, but nevertheless there were major epochs of ocean acidification (OA). On the shorter glacial–interglacial time scale from the Last Glacial Maximum (LGM) to late preindustrial time, riverine fluxes of DIC, total alkalinity, and N and P nutrients increased and along with rising sea level, atmospheric PCO₂ and temperature led, among other changes, to a slightly deceasing pH of coastal and open ocean waters, and to increasing net ecosystem calcification and decreasing net heterotrophy in coastal ocean waters. From late preindustrial time to the present and projected into the 21st century, human activities, such as fossil fuel and land-use emissions of CO₂ to the atmosphere, increasing application of N and P nutrient subsidies and combustion N to the landscape, and sewage discharges of C, N, P have led, and will continue to lead, to significant modifications of coastal ocean waters. The changes include a rapid decline in pH and carbonate saturation state (modern problem of ocean acidification), a shift toward dissolution of carbonate substrates exceeding production, potentially leading to the “demise” of the coral reefs, reversal of the direction of the sea-to-air flux of CO₂ and enhanced biological production and burial of organic C, a small sink of anthropogenic CO₂, accompanied by a continuous trend toward increasing autotrophy in coastal waters.     

Topographic controls on the depth distribution of soil CO2 in a small temperate watershed

Accurate measurements of soil CO₂ concentrations (pCO₂) are important for understanding carbonic acid reaction pathways for continental weathering and the global carbon (C) cycle. While there have been many studies of soil pCO₂, most sample or model only one, or at most a few, landscape positions and therefore do not account for complex topography. Here, we test the hypothesis that soil pCO₂ distribution can predictably vary with topographic position. We measured soil pCO₂ at the Susquehanna Shale Hills Critical Zone Observatory (SSHCZO), Pennsylvania, where controls on soil pCO₂ (e.g., depth, texture, porosity, and moisture) vary from ridge tops down to the valley floor, between planar slopes and slopes with convergent flow (i.e., swales), and between north and south-facing aspects. We quantified pCO₂ generally at 0.1–0.2 m depth intervals down to bedrock from 2008 to 2010 and in 2013. Of the variables tested, topographic position along catenas was the best predictor of soil pCO₂ because it controls soil depth, texture, porosity, and moisture, which govern soil CO₂ diffusive fluxes. The highest pCO₂ values were observed in the valley floor and swales where soils are deep (≥0.7 m) and wet, resulting in low CO₂ diffusion through soil profiles. In contrast, the ridge top and planar slope soils have lower pCO₂ because they are shallower (≤0.6 m) and drier, resulting in high CO₂ diffusion through soil profiles. Aspect was a minor predictor of soil pCO₂: the north (i.e., south-facing) swale generally had lower soil moisture content and pCO₂ than its south (i.e., north-facing) counterpart. Seasonally, we observed that while the timing of peak soil pCO₂ was similar across the watershed, the amplitude of the pCO₂ peak was higher in the deep soils due to more variable moisture content. The high pCO₂ observed in the deeper, wetter topographic positions could lower soil porewater pH by up to 1 pH unit compared to porewaters equilibrated with atmospheric CO₂ alone. CO₂ is generally the dominant acid driving weathering in soils: based on our observations, models of chemical weathering and CO₂ dynamics would be improved by including landscape controls on soil pCO₂.     

Development of detection and monitoring techniques of CO2 leakage from seafloor in sub-seabed CO2 storage

Carbon dioxide capture and storage (CCS) in sub-seabed geological formations is currently being studied as a potential option to mitigate the accumulation of anthropogenic CO₂ in the atmosphere. To investigate the validity of CO₂ storage in the sub-seafloor, development of techniques to detect and monitor CO₂ leaked from the seafloor is vital. Seafloor-based acoustic tomography is a technique that can be used to observe emissions of liquid CO₂ or CO₂ gas bubbles from the seafloor. By deploying a number of acoustic tomography units in a seabed area used for CCS, CO₂ leakage from the seafloor can be monitored. In addition, an in situ pH/pCO₂ sensor can take rapid and high-precision measurements in seawater, and is, therefore, able to detect pH and pCO₂ changes due to the leaked CO₂. The pH sensor uses a solid-state pH electrode and reference electrode instead of a glass electrode, and is sealed within a gas permeable membrane filled with an inner solution. Thus, by installing a pH/pCO₂ sensor onto an autonomous underwater vehicle (AUV), an automated observation technology is realized that can detect and monitor CO₂ leakage from the seafloor. Furthermore, by towing a multi-layer monitoring system (a number of pH/pCO₂ sensors and transponders) behind the AUV, the dispersion of leaked CO₂ in a CCS area can also be observed. Finally, an automatic elevator can observe the time-series dispersion of leaked CO₂. The seafloor-mounted automatic elevator consists of a buoy equipped with pH/pCO₂ and depth sensors, and uses an Eulerian method to collect spatially continuous data as it ascends and descends.Hence, CO₂ leakage from the seafloor is detected and monitored as follows. Step 1: monitor CO₂ leakage by seafloor-based acoustic tomography. Step 2: conduct mapping survey of the leakage point by using the pH/pCO₂ sensor installed in the AUV. Step 3: observe the impacted area by using a remotely operated underwater vehicle or the automatic elevator, or by towing the multi-layer monitoring system.     

Sm-Nd in marine carbonates and phosphates: Implications for Nd isotopes in seawater and crustal ages

This study explores the possibility of establishing Nd isotopic variations in seawater over geologic time. Calcite, aragonite and apatite are examined as possible phases recording seawater values of ?_Nd. Modern, biogenic and inorganically precipitated calcite and aragonite from marine environments were found to have Nd concentrations of from 0.2 to 70 ppb, showing that primary marine CaCO₃ contains little REE and that Nd/Ca is not greatly enhanced relative to seawater during carbonate precipitation. Very young marine limestone and dolomite containing no continental detritus have ~200 ppb Nd. All the carbonates are LREE enriched ($\text{?0.16 ≤f}{}^{\mathrm{<mtext>Sm</mtext><mtext>Nd</mtext>}}\text{≤?0.45}$). Modern and very young Atlantic and Pacific carbonates have ?_Nd in the range of shallow Atlantic and Pacific seawater respectively, implying that they derive their REE from local seawater. The Nd in well preserved carbonate fossils is ≤4 × 10⁴ ppb, much greater than in their modern counterparts but like the high values found for carbonates in other studies. We believe the high REE contents (at the 500 ppb level) in some detritusfree carbonates are due to REE-rich Fe-hydroxide in/on the carbonate. In favorable cases, such material may record seawater ?_Nd values, however introduction of extraneous REE may obscure the original isotopic composition of pure CaCO₃ because of its very low intrinsic primary REE abundance.Modern biogenic apatite is also shown to have very low REE content (<150 ppb Nd) but appears to quickly scavenge REE from seawater. Inorganically precipitated apatite from phosphorites has high concentrations of seawater-derived REE. Young phosphorite apatite from the Atlantic and Pacific oceans has ?_Nd in the range of the seawater from these oceans. Older apatite samples of similar age from different localities bordering common oceans record similar values of ?_Nd(T). Sedimentary apatite has ?_Sr(T) values in good agreement with the curves for ${}^{87}\text{Sr}{}^{86}\text{Sr}$ of seawater as a function of time. Individual conodonts from a single formation yield the same ?_Sr(T) and ?_Nd(T). Other workers have shown that sedimentary apatite preserves seawater REE patterns. These characteristics suggest that sedimentary apatite can be used to determine ?_Nd(T) in ancient seawater. The seawater values so inferred range between ?1.7 and ?8.9 over the last 700 my and lie in the range of modern seawater, showing no evidence for drastic changes. High values of seawater ?_Nd(T) in the Triassic and latest Precambrian may correlate with the breakup of large continental landmasses. The initial ?_Nd(T) =?15.0 of a 2 AE old phosphorite implies the presence of ~ 1.5 AE old continental crust at 2 AE ago. The approach outlined here can be used to constrain the age of the exposed crust as a function of time.     

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.     

Deccan traps mantle degassing in the terminal Cretaceous marine extinctions

Mantle degassing continually releases gases onto the earth's surface. Over geologically long time intervals, a general equilibrium probably exists between mantle CO₂ release and uptake by surficial sinks. However, during periods of rapid plate movement, or continental flood basalt volcanism, the increased rate of mantle CO₂ release may exceed that of uptake, leading to CO₂ accumulation in the atmosphere and the marine mixed layer (top 50–100 m). This in turn triggers chemical changes in the mixed layer, climatic warming, and bioevolutionary turnover. The Cretaceous/Tertiary ($\text{K}\text{T}$) transition at 65 Ma seems to have been a time of major mantle degassing which induced a perturbation of the carbon cycle. During the $\text{K}\text{T}$ transition, Deccan Traps volcanism, perhaps the greatest episode of continental flood basalt volcanism in the Phanerozoic, flooded an estimated 2.6 × 10⁶ km² of India with basaltic lavas, releasing 5 × 10¹⁷ moles of CO₂ into the earth's atmosphere over a duration 0.53–1.36 Ma at the rate of 3.9 × 10¹¹ to 9.6 × 10¹¹ moles CO₂ per year. The modern mean annual rate of mantle CO₂ release from all sources is 4.1 × 10¹² moles CO₂ per year; assuming a comparable rate of release prior to the Deccan Traps volcanism, the Deccan Traps addition would have elevated the rate of mantle CO₂ release by 10–25%. Sluggish marine circulation and warm, deep, oceans (14–15°C) would have exacerbated CO₂ buildup in the atmosphere, accounting for the Cretaceous to Tertiary drop in oxygen-18 via climatic warming, and, in the marine mixed layer (top 50–100 m), explaining the selective nature of the terminal Cretaceous marine extinctions via a pH change. The extinctions were most severe amongst the calcareous microplankton of the mixed layer; calcareous microplankton (planktonic foraminifera and coccolithophorids) begin to have pH problems at 7.8 and 7.5, respectively. Failure of the coccolithophorids would have disrupted the Williams-Riley pump (algal productivity-gravity pump of CO₂ from the atmosphere and mixed layer into the deep oceans) producing dead ocean conditions (severely reduced photosynthesis and CaCO₃ production). Failure of the Williams-Riley pump is reflected in the extinctions themselves, and in the loss of biogenic CaCO₃ to the sea floor, causing the $\text{K}\text{T}$ boundary hiatus and (or) the $\text{K}\text{T}$ boundary clay. Failure of the pump today would elevate atmospheric pCO₂ severalfold; the $\text{K}\text{T}$ failure would have responded comparably. Dead ocean conditions would, in themselves, have produced a major CO₂ buildup. Early Tertiary “Strangelove” conditions in the mixed layer, characterized by a dominance of the thoracosphaerids, braarudosphaerids and small planktonic foraminifera, were coeval with the main pulse of Deccan Traps volcanism. Overall, the record is one of gradual $\text{K}\text{T}$ bioevolutionary turnover during a period of disequilibrium between the rate of mantle CO₂ degassing and uptake by sinks. Mantle degassing during the Deccan Traps volcanism unifies the $\text{K}\text{T}$ biological and physicochemical records.     

南海全新世大暖期海表水的高酸性证据

利用正热电离质谱高精度测定了南海化石珊瑚样品的δ¹¹B 比值,定量地重建了中晚全新世以来南海海表水的pH值。结果显示南海海表水pH值并不像预先设想的那样稳定。其中古海水pH值最低为6100aB.P.前的7.91;   最高为4300aB.P.前和1200aB.P.前的8.29。南海海表水pH值从全新世大暖期开始,整体上呈缓慢增加趋势,而到现代以后明显下降。珊瑚δ¹¹B记录表明南海海表水在中晚全新世有两个高酸性的时期,一个发生在全新世大暖期,一个为现代。全新世大暖期时南海出现的高海平面、偏强的东亚夏季风和偏弱的冬季风可能是导致其海表水出现高酸性的原因。现代南海海表水pH值显著偏低,背离了中晚全新世以来南海海表水pH值逐渐增加的趋势,这很可能说明人类大量排放的CO₂确实改变了南海海表水自然变化的规律,南海在变酸。     

Neoproterozoic cap carbonates: a critical appraisal of existing models and the plumeworld hypothesis

Evidence for glaciation during the mid-late Neoproterozoic is widespread on Earth, reflecting three or more ice ages between 730 Ma and 580 Ma. Of these, the late Neoproterozoic Marinoan glaciation of approximately 635 Ma stands out because of its ubiquitous association with a characteristic, microcrystalline cap dolostone that drapes glacially influenced rock units worldwide. The Marinoan glaciation is also peculiar in that evidence for low altitude glaciation at equatorial latitudes is compelling. Three models have been proposed linking abrupt deglaciation with this global carbonate precipitation event: (i) overturn of an anoxic deep ocean; (ii) catastrophically accelerated rates of chemical weathering because of supergreenhouse conditions following global glaciation (Snowball Earth Hypothesis); and (iii) massive release of carbonate alkalinity from destabilized methane clathrates. All three models invoke extreme alkalinity fluxes into seawater during deglaciation but none explains how such alkalinity excess from point sources could be distributed homogeneously around the globe. In addition, none explains the consistent sequence of precipitation events observed within cap carbonate successions, specifically: (i) the global blanketing of carbonate powder in shallow marine environments during deglaciation; (ii) widespread and disruptive precipitation of dolomite cement; followed by (iii) localized barite precipitation and seafloor cementation by aragonite. The conceptual model presented here proposes that low latitude deglaciation was so massive and abrupt that the resultant meltwater plume could extend worldwide, physically separating the surface and deep ocean reservoirs for ≥10³ years. It is proposed that cap dolostones formed primarily by microbially mediated precipitation of carbonate whitings during algal blooms within this low salinity plumeworld rather than by abiotic precipitation from normal salinity seawater. Many of the disruption features that are characteristic of cap dolostones can be explained by microbially mediated, early diagenetic dolomitization and cementation. The re-initiation of whole ocean circulation degassed CO₂ into the atmosphere in areas of upwelling, triggering localized, abiotic CaCO₃ precipitation in the form of aragonite fans that overlie cap dolostones in NW Canada and Namibia. The highly oxygenated shallow marine environments of the glacial and post-glacial Neoproterozoic world provided consistently favourable conditions for the evolutionary development of animals and other oxygenophiles.     

Initial responses of carbonate-rich shelf sediments to rising atmospheric pCO2 and “ocean acidification”: Role of high Mg-calcites

Carbonate-rich sediments at shoal to shelf depths (<200 m) represent a major CaCO₃ reservoir that can rapidly react to the decreasing saturation state of seawater with respect to carbonate minerals, produced by the increasing partial pressure of atmospheric carbon dioxide (pCO₂) and “acidification” of ocean waters. Aragonite is usually the most abundant carbonate mineral in these sediments. However, the second most abundant (typically ∼24 wt%) carbonate mineral is high Mg-calcite (Mg-calcite) whose solubility can exceed that of aragonite making it the “first responder” to the decreasing saturation state of seawater. For the naturally occurring biogenic Mg-calcites, dissolution experiments have been used to predict their “stoichiometric solubilities” as a function of mol% MgCO₃. The only valid relationship that one can provisionally use for the metastable stabilities for Mg-calcite based on composition is that for the synthetically produced phases where metastable equilibrium has been achieved from both under- and over-saturation. Biogenic Mg-calcites exhibit a large offset in solubility from that of abiotic Mg-calcite and can also exhibit a wide range of solubilities for biogenic Mg-calcites of similar Mg content. This indicates that factors other than the Mg content can influence the solubility of these mineral phases. Thus, it is necessary to turn to observations of natural sediments where changes in the saturation state of surrounding waters occur in order to determine their likely responses to the changing saturation state in upper oceanic waters brought on by increasing pCO₂. In the present study, we investigate the responses of Mg-calcites to rising pCO₂ and “ocean acidification” by means of a simple numerical model based on the experimental range of biogenic Mg-calcite solubilities as a function of Mg content in order to bracket the behavior of the most abundant Mg-calcite phases in the natural environment. In addition, observational data from Bermuda and the Great Bahama Bank are also presented in order to project future responses of these minerals. The numerical simulations suggest that Mg-calcite minerals will respond to rising pCO₂ by sequential dissolution according to mineral stability, progressively leading to removal of the more soluble phases until the least soluble phases remain. These results are confirmed by laboratory experiments and observations from Bermuda. As a consequence of continuous increases in atmospheric CO₂ from burning of fossil fuels, the average composition of contemporary carbonate sediments could change, i.e., the average Mg content in the sediments may slowly decrease. Furthermore, evidence from the Great Bahama Bank indicates that the amount of abiotic carbonate production is likely to decline as pCO₂ continues to rise.     

Experimental evidence for carbonate precipitation and CO2 degassing during sea ice formation

Chemical and stable carbon isotopic modifications during the freezing of artificial seawater were measured in four 4 m³ tank incubations. Three of the four incubations were inoculated with a nonaxenic Antarctic diatom culture. The 18 days of freezing resulted in 25 to 27 cm thick ice sheets overlying the residual seawater. The ice phase was characterized by a decrease in temperature from −1.9 to −2.2°C in the under-ice seawater down to −6.7°C in the upper 4 cm of the ice sheet, with a concurrent increase in the salinity of the under-ice seawater and brine inclusions of the ice sheet as a result of physical concentration of major dissolved salts by expulsion from the solid ice matrix. Measurements of pH, total dissolved inorganic carbon (C_T) and its stable isotopic composition (δ¹³C_T) all exhibited changes, which suggest minimal effect by biological activity during the experiment. A systematic drop in pH and salinity-normalized C_T by up to 0.37 pH_SWS units and 376 μmol C kg⁻¹ respectively at the lowest temperature and highest salinity part of the ice sheet were coupled with an equally systematic ¹³C enrichment of the C_T. Calculations based on the direct pH and C_T measurements indicated a steady increase in the in situ concentration of dissolved carbon dioxide (CO₂(aq)) with time and increasing salinity within the ice sheet, partly due to changes in the dissociation constants of carbonic acid in the low temperature-high salinity range within sea ice. The combined effects of temperature and salinity on the solubility of CO₂ over the range of conditions encountered during this study was a slight net decrease in the equilibrium CO₂(aq) concentration as a result of the salting-out overriding the increase in solubility with decreasing temperature. Hence, the increase in the in situ CO₂(aq) concentration lead to saturation or supersaturation of the brine inclusions in the ice sheet with respect to atmospheric pCO₂ (≈3.5 × 10⁻⁴ atm). When all physico-chemical processes are considered, we expect CO₂ degassing and carbonate mineral precipitation from the brine inclusions of the ice sheet, which were saturated or highly supersaturated with respect to both the anhydrous (calcite, aragonite, vaterite) and hydrated (ikaite) carbonate minerals.