The subterranean estuary: a reaction zone of ground water and sea water

Subsidence of the Atlantic-type continental margin off New York

The exchange of groundwater between land and sea is a major component of the hydrological cycle. This exchange, called submarine groundwater discharge (SGD), is comprised of terrestrial water mixed with sea water that has infiltrated coastal aquifers. The composition of SGD differs from that predicted by simple mixing because biogeochemical reactions in the aquifer modify its chemistry. To emphasize the importance of mixing and chemical reaction, these coastal aquifers are called subterranean estuaries. Geologists recognize this mixing zone as a site of carbonate diagenesis and dolomite formation. Biologists have recognized that terrestrial inputs of nutrients to the coastal ocean may occur through subterranean processes. Further evidence of SGD comes from the distribution of chemical tracers in the coastal ocean. These tracers originate within coastal aquifers and reach the ocean through SGD. Tracer studies reveal that SGD provides globally important fluxes of nutrients, carbon, and metals to coastal waters.

https://moritz.botany.ut.ee/~olli/eutrsem/Moore_2010.pdf

The Effect of Submarine Groundwater Discharge on the Ocean

Present-day production of CaCO3 in tne world ocean is calculated to be about 5 billion tons (bt) per year, of which about 3 bt accumulate in sediments; the other 40% is dissolved. Nearly half of the carbonate sediment accumulates on reefs, banks, and tropical shelves, and consists largely of metastable aragonite and magnesian calcite. Deep-sea carbonates, predominantly calcitic coccoliths and planktonic foraminifera, have orders of magnitude lower productivity and accumulation rates than shallow-water carbonates, but they cover orders of magnitude larger basin area. Twice as much calcium is removed from the oceans by present-day carbonate accumulation as is estimated to be brought in by rivers and hydrothermal activity (1.6 bt), suggesting that outputs have been overestimated or inputs underestimated, that one or more other inputs have not been identified, and/or that the oceans are not presently in steady state. One “missing” calcium source might be groundwater, although its present-day input is probably much smaller than that of rivers. If, as seems likely, CaCO3 accumulation presently exceeds terrestial and hydrothermal input, this imbalance presumably is offset by decreased accumulation and increased input during lowered sea level: shallow-water accumulation decreases by an order of magnitude with a 100 m drop in sea level, while groundwater influx increases because of heightened piezometric head and the diagenesis of metastable aragonite and magnesian calcite from subaerially exposed shallow-water carbonates.

Production and accumulation of calcium carbonate in the ocean: Budget of a nonsteady state

Dozens of studies in the past decade have reported carbon isotope variations in Neoproterozoic carbonate rocks and linked them to perturbations of the global carbon cycle. Paul Knauth and Martin Kennedy have taken a sideways look at the data by concentrating on the oxygen isotope measurements (for over 20,000 samples) that are necessarily obtained as part of the carbon isotope analysis but are often overlooked. They arrive at the striking conclusion that the combined oxygen and carbon isotope systematics are identical to those of well-understood Phanerozoic examples that lithified in coastal pore fluids receiving a groundwater influx of photosynthetic carbon from terrestrial phytomass. Rather than being perturbations to the carbon cycle, widely reported decreases in 13C/12C in Neoproterozoic carbonates are more easily interpreted by analogy to the Phanerozoic examples. And that could suggest a 'greening' of the Earth under a ground-hugging mat of photosynthetic algae, mosses and fungi in the late Precambrian. Such an event, producing oxygen and phytomass, could even be indirectly responsible for the critical transition from the essentially microbial world of the Precambrian to the metazoan world of the Cambrian. The low 13C/12C ratio in some Neoproterozoic carbonates is considered to be evidence of carbon cycle perturbations unique to the Precambrian. Here, all published oxygen and carbon isotope data for Neoproterozoic marine carbonates are compiled. The combined isotope systematics are found to be identical to those of well-understood Phanerozoic examples, suggesting an influx of photosynthetic carbon rather than perturbations to the carbon cycle — and implying an explosion of photosynthesizing communities on late Precambrian land surfaces. Many aspects of the carbon cycle can be assessed from temporal changes in the 13C/12C ratio of oceanic bicarbonate. 13C/12C can temporarily rise when large amounts of 13C-depleted photosynthetic organic matter are buried at enhanced rates1, and can decrease if phytomass is rapidly oxidized2 or if low 13C is rapidly released from methane clathrates3. Assuming that variations of the marine 13C/12C ratio are directly recorded in carbonate rocks, thousands of carbon isotope analyses of late Precambrian examples have been published to correlate these otherwise undatable strata and to document perturbations to the carbon cycle just before the great expansion of metazoan life. Low 13C/12C in some Neoproterozoic carbonates is considered evidence of carbon cycle perturbations unique to the Precambrian. These include complete oxidation of all organic matter in the ocean2 and complete productivity collapse such that low-13C/12C hydrothermal CO2 becomes the main input of carbon4. Here we compile all published oxygen and carbon isotope data for Neoproterozoic marine carbonates, and consider them in terms of processes known to alter the isotopic composition during transformation of the initial precipitate into limestone/dolostone. We show that the combined oxygen and carbon isotope systematics are identical to those of well-understood Phanerozoic examples that lithified in coastal pore fluids, receiving a large groundwater influx of photosynthetic carbon from terrestrial phytomass. Rather than being perturbations to the carbon cycle, widely reported decreases in 13C/12C in Neoproterozoic carbonates are more easily interpreted in the same way as is done for Phanerozoic examples. This influx of terrestrial carbon is not apparent in carbonates older than ∼850 Myr, so we infer an explosion of photosynthesizing communities on late Precambrian land surfaces. As a result, biotically enhanced weathering generated carbon-bearing soils on a large scale and their detrital sedimentation sequestered carbon5. This facilitated a rise in O2 necessary for the expansion of multicellular life.

The late Precambrian greening of the Earth

The first broad program of scientific shallow drilling on the U.S. Atlantic continental shelf has delineated rocks of Pleistocene to Late Cretaceous age, including phosphoritic Miocene strata, widespread Eocene carbonate deposits that serve as reflective seismic markers, and several regional unconformities. Two sites, off Maryland and New Jersey, showed light hydrocarbon gases having affinity to mature petroleum. Pore fluid studies showed that relatively fresh to brackish water occurs beneath much of the Atlantic continental shelf, whereas increases in salinity off Georgla and beneath the Florida-Hatteras slope suggest buried evaporitic strata. The sediment cores showed engineering properties that range from good foundation strength to a potential for severe loss of strength through interaction between sediments and man-made structures.

U.s. Geological survey core drilling on the atlantic shelf.

/pdf/preliminary-summary-of-the-1976-atlantic-margin-coring-322cpl9dzu.pdf

Preliminary summary of the 1976 Atlantic Margin Coring Project of the U.S. Geological Survey

The organic geochemistry of black sedimentary barite: significance and implications of trapped fatty acids

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U.s. Geological survey core drilling on the atlantic shelf.

Preliminary summary of the 1976 Atlantic Margin Coring Project of the U.S. Geological Survey

The organic geochemistry of black sedimentary barite: significance and implications of trapped fatty acids