Distribution of carbonate in surface sediments of the Pacific Ocean

The distribution of carbonate on the floor of the Pacific has been remapped on the basis of 1313 points from 80 references stored in the World Ocean Sediment Data Bank of Scripps Institution of Oceanography. Percent distribution maps and carbonate versus depth diagrams generally agree with previously published information and reflect the major controlling factors of carbonate sedimentation (depth, hydrography, fertility, and sedimentary processes). While carbonate distributions are of limited use in attempting to construct dissolution profiles, major trends are identifiable. In particular, the degree of lowering of the equatorial calcite compensation depth (CCD) together with an estimate of the differences in supply rates between the equator and the subtropical gyre can be used to estimate dissolution rate increase below the lysocline. There is considerable variation in the sharpness of the ‘CCD transition’ a concept defined here. This variation is thought to reflect both geographic differences in dissolution rate gradients and redeposition processes (carbonate, deep-sea sediments, calcite, and compensation depth)

Ongoing transients in carbonate compensation

Uptake of anthropogenic CO2 is acidifying the oceans. Over the next 2000 years, this will modify the dissolution and preservation of sedimentary carbonate. By coupling new formulas for the positions of the calcite saturation horizon, zsat, the compensation depth, zcc, and the snowline, zsnow, to a biogeochemical model of the oceanic carbonate system, we evaluate how these horizons will change with ongoing ocean acidification. Our model is an extended Havardton-Bear-type box model, which includes novel kinetic descriptions for carbonate dissolution above, between, and below these critical depths. In the preindustrial ocean, zsat and zcc are at 3939 and 4750 m, respectively. When forced with the IS92a CO2 emission scenario, the model forecasts (1) that zsat will rise rapidly (“runaway” conditions) so that all deep water becomes undersaturated, (2) that zcc will also rise and over 1000 years will pass before it will be stabilized by the dissolution of previously deposited CaCO3, and (3) that zsnow will respond slowly to acidification, rising by ∼1150 m during a 2000 year timeframe. A further simplified model that equates the compensation and saturation depths produces quantitatively different results. Finally, additional feedbacks due to acidification on calcification and increased atmospheric CO2 on organic matter productivity strongly affect the positions of the compensation horizons and their dynamics.

Extensive dissolution of live pteropods in the Southern Ocean

The carbonate chemistry of the surface ocean is rapidly changing with ocean acidification, a result of human activities. In the upper layers of the Southern Ocean, aragonite—a metastable form of calcium carbonate with rapid dissolution kinetics—may become undersaturated by 2050 (ref. 2). Aragonite undersaturation is likely to affect aragonite-shelled organisms, which can dominate surface water communities in polar regions. Here we present analyses of specimens of the pteropod Limacina helicina antarctica that were extracted live from the Southern Ocean early in 2008. We sampled from the top 200m of the water column, where aragonite saturation levels were around 1, as upwelled deep water is mixed with surface water containing anthropogenic CO2. Comparing the shell structure with samples from aragonite-supersaturated regions elsewhere under a scanning electron microscope, we found severe levels of shell dissolution in the undersaturated region alone. According to laboratory incubations of intact samples with a range of aragonite saturation levels, eight days of incubation in aragonite saturation levels of 0.94– 1.12 produces equivalent levels of dissolution. As deep-water upwelling and CO2 absorption by surface waters is likely to increase as a result of human activities2,4, we conclude that upper ocean regions where aragonite-shelled organisms are affected by dissolution are likely to expand

Stable oxygen and carbon isotope compositional fields for skeletal and diagenetic components in New Zealand Cenozoic nontropical carbonate sediments and limestones: a synthesis and review

The stable oxygen isotope composition (d¹⁸O) of a precipitated carbonate depends mainly on the isotope composition, salinity, and temperature of the host fluid, whereas the stable carbon isotope composition (d¹³C) reflects the source of CO2 for precipitation, such as meteoric or sea water, shell dissolution, or various biochemical origins, including microbial oxidation of organic matter and methane. Despite the potentially complex array of controls, natural waters tend to show a characteristic range of isotope values which in turn are mimicked or tracked by the carbonate minerals precipitated from them. Consequently, plots of d¹⁸O versus d¹³C for carbonate materials can help identify their depositional and/or diagenetic environment(s)

Kinetic model of carbonate dissolution in Martian meteorite ALH84001

The magnetites and sulfides located in the rims of carbonate globules in the Martian meteorite ALH84001 have been claimed as evidence of past life on Mars. Here, we consider the possibility that the rims were formed by dissolution and reprecipitation of the primary carbonate by the action of water. To estimate the rate of these solution-precipitation reactions, a kinetic model of magnesite-siderite carbonate dissolution was applied and used to examine the physicochemical conditions under which these rims might have formed. The results indicate that the formation of the rims could have taken place in < 50 yr of exposure to small amounts of aqueous fluids at ambient temperatures. Plausible conditions pertaining to reactions under a hypothetical ancient Martian atmosphere (1 bar CO2), the modern Martian atmosphere (8 mbar CO2), and the present terrestrial atmosphere (0.35 mbar CO2) were explored to constrain the site of the process. The results indicated that such reactions likely occurred under the latter two conditions. The possibility of Antarctic weathering must be entertained, which, if correct, would imply that the plausibly biogenic minerals (single-domain magnetite of characteristic morphology and sulfide) reported from the rims may be the products of terrestrial microbial activity. This model is discussed in terms of the available isotope data and found to be compatible with the formation of ALH84001 rims. Particularly, anticorrelated variations of radiocarbon with δ13C indicate that carbonate in ALH84001 was affected by solution-precipitation reactions immediately after its initial fall (ca. 13,000 yr ago) and then again during its recent exposure prior to collection

Impact of nitrogen fertilizers on the natural weathering-erosion processes and fluvial transport in the Garonne basin

Knowledge of the impact of N-fertilizers on the weathering-erosion processes of soils in intensively cultivated regions is of prime importance. Nitrification of NH4− fertilizers produces HNO3 in the basin of the Garonne river, enhancing soil degradation. Their influence on the weathering rates was determined by calculating the consumption rate of atmospheric/soil CO2 by soil weathering and erosion, and its contribution to the total dissolved riverine HCO3−. This contribution was found to be less than 50% which corresponds normally to a complete carbonate dissolution by carbonic acid, suggesting that part of the alkalinity in the river waters is due to carbonate dissolution by an acid other than carbonic acid, probably HNO3

Orbital frequencies in the carbonate sedimentary record: distorted by diagenesis?

The most important archive of Earth’s climate change through geologic history is the sedimentary rock record. Rhythmic sedimentary alternations are usually interpreted as a consequence of periodic variations in the orbital parameters of the Earth. This interpretation enables the application of cyclostratigraphy as a very precise chronometer, when based on the assumption that orbital frequencies are faithfully recorded in the sedimentary archive. However, there are numerous uncertainties with the application of this concept. Particularly in carbonates, sediment properties such as mineralogical composition and fossil associations are severely altered during post-depositional alteration (diagenesis). We here point out that the assumption of a 1:1 recording of orbital signals in many cases is questionable for carbonate rhythmites. We use computer simulations to show the effect of diagenetic overprint on records of orbital signals in the carbonate record. Such orbital signals may be distorted in terms of frequency, amplitude, and phase by diagenetic processes, and cycles not present in the insolation record may emerge. This questions the routine use of carbonate rhythmites for chronostratigraphic datin

In-situ cosmogenic ³⁶Cl denudation rates of carbonates in Guizhou karst area

This study quantifies surface denudation of carbonate rocks by the first application of in-situ cosmogenic &lt;sup&gt;36&lt;/sup&gt;Cl in China. Concentrations of natural Cl and in-situ cosmogenic &lt;sup&gt;36&lt;/sup&gt;Cl in bare carbonates from Guizhou karst areas were measured with isotope dilution by accelerator mass spectrometer. The Cl concentration varied from 16 to 206 ppm. The &lt;sup&gt;36&lt;/sup&gt;Cl concentrations were in range of (0.8–2.4)×106 atom g−1, resulting in total denudation rates of 20–50 mm ka−1 that averaged over a 104–105 a timescale. The &lt;sup&gt;36&lt;/sup&gt;Cl-denudation rates showed roughly a negative correlation with the local mean temperature. This preliminary observation may suggest the variations of proportions of chemical weathering and physical erosion in denudation process, depending upon local climatic conditions

Long-time evolution of sequestered CO2_2 in porous media

CO$_2$ sequestration in subsurface reservoirs is important for limiting atmospheric CO$_2$ concentrations. However, a complete physical picture able to predict the structure developing within the porous medium is lacking. We investigate theoretically reactive transport in the long-time evolution of carbon in the brine-rock environment. As CO$_2$ is injected into a brine-rock environment, a carbonate-rich region is created amid brine. Within the carbonate-rich region minerals dissolve and migrate from regions of high concentration to low concentration, along with other dissolved carbonate species. This causes mineral precipitation at the interface between the two regions. We argue that precipitation in a small layer reduces diffusivity, and eventually causes mechanical trapping of the CO$_2$. Consequently, only a small fraction of the CO$_2$ is converted to solid mineral; the remainder either dissolves in water or is trapped in its original form. We also study the case of a pure CO$_2$ bubble surrounded by brine and suggest a mechanism that may lead to a carbonate-encrusted bubble due to structural diffusion

Dissolution dominating calcification process in polar pteropods close to the point of aragonite undersaturation

Thecosome pteropods are abundant upper-ocean zooplankton that build aragonite shells. Ocean acidification results in the lowering of aragonite saturation levels in the surface layers, and several incubation studies have shown that rates of calcification in these organisms decrease as a result. This study provides a weight-specific net calcification rate function for thecosome pteropods that includes both rates of dissolution and calcification over a range of plausible future aragonite saturation states (Omega_Ar). We measured gross dissolution in the pteropod Limacina helicina antarctica in the Scotia Sea (Southern Ocean) by incubating living specimens across a range of aragonite saturation states for a maximum of 14 days. Specimens started dissolving almost immediately upon exposure to undersaturated conditions (Omega_Ar,0.8), losing 1.4% of shell mass per day. The observed rate of gross dissolution was different from that predicted by rate law kinetics of aragonite dissolution, in being higher at Var levels slightly above 1 and lower at Omega_Ar levels of between 1 and 0.8. This indicates that shell mass is affected by even transitional levels of saturation, but there is, nevertheless, some partial means of protection for shells when in undersaturated conditions. A function for gross dissolution against Var derived from the present observations was compared to a function for gross calcification derived by a different study, and showed that dissolution became the dominating process even at Omega_Ar levels close to 1, with net shell growth ceasing at an Omega_Ar of 1.03. Gross dissolution increasingly dominated net change in shell mass as saturation levels decreased below 1. As well as influencing their viability, such dissolution of pteropod shells in the surface layers will result in slower sinking velocities and decreased carbon and carbonate fluxes to the deep ocean