Description: Surface area measurements as well as organic carbon, nitrogen and phosphorus analyses on various grain size fractions of carbonate mud samples confirm that in natural environments of carbonate deposition, surface sorption processes take place which are similar to those described earlier for dissolved organics and artificially suspended calcite particles in both seawater and synthetic solutions. The specific surface area of the sediment increases from 1.8m2/g for the coarse-grained fraction to 12.5 m2/g for the fine material; likewise organic carbon, nitrogen and phosphorus increase with increasing surface area so that there are 1.20 mg C, 0.175 mg N and 0.06–0.20 mg P associated with every square meter of carbonate surface irrespective of the mineralogy of the sediment particles. It appears that the organic matter in these sediments is similar in composition, structure and quantity to the organic layers produced in sorption experiments. With their apparently defined structure and ubiquitous nature, these layers could determine the mineralogy and orientation of submarine carbonate cement or could even be a prerequisite to calcification in general.

Description: Humic acid dissolved in artificial seawater influenced the morphology, internal structure, and composition of aragonite when precipitation was induced with dilute Na2CO3 solution. At sodium humate concentrations of around 20 mg/1, numerous brownish spherical aragonite bodies developed within one day at 25 °C. The spheres ranged in size from 10–100 microns and resembled natural marine ooids. They formed with gentle agitation of the solution as well as with no water movement at all. The typical structure of natural ooids consisting of concentric alternating aragonite and organic laminae was experimentally duplicated as layers of aragonite crystals alternating with humate membranes; however, in contrast to natural ooids, the individual aragonite crystals here were oriented radially with their c-axes. The aragonite of the spheres contained about 20 wt. % more strontium than the aragonite precipitated experimentally without the addition of sodium humate, and organic carbon content of the spherical aragonite was about 7% by weight.

Description: Pristinely preserved mineral pseudomorphs called glendonites, up to 1.6 m long, from the Palaeogene strata of Denmark allow detailed crystallographic characterisation and add to the understanding of the transformation of the precursor mineral, ikaite (CaCO3 center dot 6H(2)O), to calcite, which constitutes the glendonite. We describe Danish pseudomorphs after ikaite from two localities and formations: the Early Eocene Fur Formation and the Late Oligocene Brejning Formation. This detailed study highlights that key aspects such as morphology and mode of occurrence of these ancient glendonites are identical to those of their parent mineral ikaite, when it grows in marine sediments. Systematic distortion of the angles in glendonite and marine sedimentary ikaite relative to the ideal ikaite symmetry may arise due to the incorporation of organic matter into the crystal structure, and we demonstrate the similarity between modern and ancient ikaite formation zones in the marine sedimentary realm with respect to organic matter.

Description: Highlights • Glendonites are widely distributed in Ediacaran Doushantuo Formation of South China. • Host strata are characterized by positive δ13C and record excursion EP1. • Calcitic glendonites are characterized by variable and extremely negative δ13C. • Doushantuo glendonites represent a cooling event prior to EN3 or Shuram excursion. • Low T°C, phosphate, and anoxic conditions facilitated glendonite/ikaite formation. Abstract: Glendonites are pseudomorphs of syndepositional or early authigenic ikaite (CaCO3·6H2O) that often forms at near-freezing temperatures. Silicified glendonite has been reported from inner-shelf deposits of the lower Ediacaran Doushantuo Formation at a single stratigraphic section in South China, where they are stratigraphically associated with the positive δ13C excursion EP1 but predate the negative δ13C excursion EN3 (=Shuram excursion), indicating a period of cool climate somewhere between ~609 Ma and ~551 Ma. This interpretation predicts a wider geographic distribution of Ediacaran glendonites in equivalent strata in the Yangtze Block of South China. To test this prediction, we conducted a regional survey of Doushantuo Formation and found that, although glendonites are not universally present, they occur in expected stratigraphic intervals and in association with EP1 at two new sections representing inner-shelf and intrashelf basin facies. The wide but not ubiquitous distribution of Doushantuo glendonites indicates that ikaite precipitation and glendonite formation was controlled by both regional climatic and local geochemical factors. Glendonites at the new localities are stellate clusters pseudomorphed by calcite spar and sometimes are rimmed with silica. The calcite spar is characterized by highly variable and mostly negative δ13C values as low as −37‰, indicating that diagenetic transformation of precursor ikaite to calcitic glendonite may be related to anaerobic oxidation of organic matter or methane in sediment. The new data suggest an early Ediacaran cold period prior to EN3 or the Shuram excursion and facilitation of glendonite/ikaite formation by both climatic and local geochemical conditions such as redox conditions and phosphate concentrations.

Description: High alkalinity values observed in coastal seas promote the uptake of CO2 from the atmosphere. However, the alkalinity budget of coastal areas and marginal seas is poorly understood, even though some of the recently observed alkalinity enhancement can be ascribed to riverine fluxes and anaerobic processes in shelf sediments. Here, we investigate the alkalinity budget of the Baltic Sea to identify previously unrecognized alkalinity sources. We quantify the generation of alkalinity and dissolved calcium (Ca) in this marginal sea applying simple mass balance calculations. Using this approach, we identify alkalinity and Ca sources of approximately 324 Gmol yr-1 and 122 Gmol yr-1, respectively, that cannot be ascribed to the riverine input. The magnitude of the Ca source suggests that a major fraction of the excess alkalinity (244 Gmol yr-1) is induced by the dissolution of calcium carbonate (CaCO3). A review of available field data shows that carbonate-bearing rocks at the coast and the seabed of the Baltic Sea are rapidly eroded and may provide sufficient CaCO3 to close the Ca budget. Hence, dissolution of eroded CaCO3 is the most likely source for the Ca enrichment observed in Baltic Sea water. This hypothesis is supported by mass accumulation rates of sediments derived from radioisotope data that are evaluated to derive a basin-wide rate of mud to muddy sand accumulation at the bottom of the Baltic Sea. The resulting value (139 Tg yr-1) exceeds current estimates of riverine particle fluxes into the Baltic Sea by more than one order of magnitude and confirms that rates of till erosion are sufficiently high to account for the Ca and most of the alkalinity excess in Baltic Sea water. Finally, we show that deliberate addition of CaCO3 to sediments deposited in the Baltic Sea could neutralize significant amounts of CO2 and help to achieve net-zero greenhouse gas emissions in the Baltic region.

Description: Calcium carbonate hexahydrate (ikaite) is a rare mineral that forms as metastable species in the organic-carbon-rich sediments of the King George Basin, Bransfield Strait, Antarctica, as a consequence of early diagenetic decomposition of organic matter under cold water (−1.4 °C) and high pressure (200 bar) conditions. Large crystals grow in the sediment immediately below the diagenetic transition between microbial sulfate reduction and methanogenesis at ~320 cm below sea floor (bsf). This process is reflected in the dissolved sulfate, total carbon dioxide, and methane concentrations, as well as in the carbon, hydrogen, and oxygen isotope chemistries of the interstitial fluids and dissolved gases of the host sediment. The ikaite crystal faithfully records in its zonal structure the changing carbon isotope ratio of the total dissolved carbon dioxide pool as it gradually diminishes during methanogenesis (δ13Cikaite = −17.5 to −21.4‰). These changes in the crystal’s host environment follow general Rayleigh carbon isotope fractionation. The oxygen isotopes of the ikaite carbonate (δ18Oikaite = 1.46 to 4.45‰) also show a strong zonal distribution, unrelated to temperature of formation, but perhaps controlled by the degree of recrystallization of ikaite to calcite. The crystal water of the ikaite is depleted 11‰ in 2H/1H (VSMOW) relative to the coexisting interstitial water, which is in excellent agreement with the isotope fractionation of other hydrated minerals. In addition to the in situ temperature and pressure, nucleation of the ikaite crystals in the Bransfield Basin sediments may be induced by the high alkalinity, high phosphate concentrations, and dissolved organic compounds. Intense microbial metabolism generates such compounds; of these, aspartic acid and glutamic acid may play an important role, as they do in biological and extracellular carbonate mineral precipitation. All indications are that low temperatures (such as of polar environments), high calcium carbonate supersaturation caused by interstitial methanogenesis, and a sufficiently large supply of dissolved phosphate and amino acids favor metastable ikaite formation. These conditions, modified by recrystallization, may be preserved in calcite glendonites, thinolites, and other calcitic pseudomorphs derived from ikaite and found throughout the ancient sedimentary record.

Description: Carbon dioxide, ammonia, and reactive phosphate in the interstitial water of three sediment cores of the West African continental margin result from oxidation of sedimentary organic matter by bacterial sulfate reduction. The proposed model is a modification of one initially suggested by Richards (1965) for processes in anoxic waters: (CH2O)106 (NH3)8 (H3PO4) (0.7-0.2) + 53 SO4**2- =106 CO2 + 106 H20 + 8 NH3 + (0.7 - 0.2) H3PO4 + 53 S**2- The amount of reduced interstitial sulfate, the carbon-to-nitrogen-to-phosphorus atomic ratio of the sedimentary organic matter, as well as small amounts of carbon dioxide, which precipitated as interstitial calcium carbonate, are included in the general oxidation-reduction reaction. Preferential loss of nitrogen and phosphorus from organic matter close to the surface was recorded in both the interstitial water and sediment composition. It appeared that in deeper sections of the core organic carbon compounds were oxidized which were probably in an even lower oxidation state than that indicated by the proposed model. An estimated 2 % of the amount of organic matter still present was oxidized after it became incorporated into the sediment; whereas sulfide sulfur contents indicate that a much larger percentage (15-20%) seemed to have been subject to bacterial oxidation during the Pleistocene period, when a very thin oxidizing layer on the sediment allowed the above decomposition process to start relatively early favoured by almost fresh organic matter, and by almost unrestricted exchange of sulfate with the overlying water.