Calcium carbonate, near sediment-water interface

Numerous models have been proposed for the processes occurring near the sediment-water interface in deep sea sediments that lead to a balance between dissolution and retention of calcium carbonate in these sediments. Investigation of these processes is currently one of the most active areas of research in the study of calcium carbonate behavior in the oceans. A major difficulty in studying and modeling these processes is that many of the most important changes take place over distances of only a few millimeters in a highly dynamic environment. 

Thus, the fossil fuel "neutralizing capacity of seawater is largely dependent on the carbonate ion concentration and that of marine sediments depends on the calcium carbonate which is near enough to the sediment-water interface to react with the overlying water. 

Other reactions of probable less importance than those above leading to undersaturated conditions with respect to calcium carbonate near the sediment-water interface include nitrate reduction and fermentation (e.g., Aller, 1980). Such reactions may also be important near the sediment-water interface of continental shelf and slope sediments, where bioturbation and bioirrigation can result in enhanced transport of reactants. Generally, as water depth increases over continental slope sediments, the depth within the sediment at which significant sulfate reduction commences also increases. It is probable that the influence of reactions other than sulfate reduction on carbonate chemistry may increase with increasing water depth. 

One major paper attacking the problem of the relationship between the preservation of calcium carbonate in shallow anoxic marine sediments and their chemistry was by Aller (1982). The study was conducted at sites in Long Island Sound. The calcium carbonate content of the sediments decreased with increasing water depth. At the shallow FOAM (Friends of Anaerobic Muds) site shell layers associated with storms resulted in irregular variations in the carbonate content of the sediment. Ca2+ loss from the pore waters, indicative of calcium carbonate precipitation, was found only at the FOAM site below -20 cm depth. During the winter, elevated Ca2+ to CL ratios were observed near the sediment-water interface... 

The process of removal of calcium by marine organisms in the water column is well known. Production of calcium carbonate by water column biological processes may be estimated from primary productivity and from the mean chemical composition of plankton. After death of the organisms and removal of the organic protective layer, the skeletons may undergo dissolution if they encounter water undersaturated with respect to their mineral composition. Active dissolution of calcium carbonate occurs mainly near the sediment-water interface in deep waters that are undersaturated with respect to both calcite and aragonite (see Chapter 4). Thus, calcium is regenerated from calcareous skeletons and, finally, only a small fraction of the initial production of these materials accumulates in sediments. An... 

In sUiciclastic sediments, the major source of carbonates is also primarily derived from benthic organisms. These include bivalves, other mollusks, sea urchins, and foraminifera. In these sediments there is often a zone of considerable under saturation produced near the sediment-water interface, where the oxidation of organic matter and bacterially produced sulfides can result in almost complete dissolution of sediment carbonate. Carbonates from organisms that burrow beneath this zone of intense diagenetic activity are often well preserved. In organic-rich siliciclastic sediments sulfate reduction may be very extensive, with the increase in alkalinity outweighing the decrease in pH, resulting in the precipitation of calcium carbonate. 

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