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Cyronak, T, Andersson AJ, D'Angelo S, Bresnahan P, Davidson C, Griffin A, Kindeberg T, Pennise J, Takeshita Y, White M.  2018.  Short-term spatial and temporal carbonate chemistry variability in two contrasting seagrass meadows: Implications for pH buffering capacities. Estuaries and Coasts. 41:1282-1296.   10.1007/s12237-017-0356-5   AbstractWebsite

It has been hypothesized that highly productive coastal ecosystems, such as seagrass meadows, could lead to the establishment of ocean acidification (OA) refugia, or areas of elevated pH and aragonite saturation state (Omega(a)) compared to source seawater. However, seagrass ecosystems experience extreme variability in carbonate chemistry across short temporal and small spatial scales, which could impact the pH buffering capacity of these potential refugia. Herein, short-term (hourly to diel) and small-scale (across 0.01-0.14 km(2)) spatiotemporal carbonate chemistry variability was assessed within two seagrass meadows in order to determine their short-term potential to elevate seawater pH relative to source seawater. Two locations at similar latitudes were chosen in order to compare systems dominated by coarse calcium carbonate (Bailey's Bay, Bermuda) and muddy silicate (Mission Bay, CA, USA) sediments. In both systems, spatial variability of pH across the seagrass meadow at any given time was often greater than diel variability (e.g., the average range over 24 h) at any one site, with greater spatial variability occurring at low tide in Mission Bay. Mission Bay (spatial Delta pH = 0.08 +/- 0.08; diel Delta pH = 0.12 +/- 0.01; mean +/- SD) had a greater average range in both temporal and spatial seawater chemistry than Bailey's Bay (spatial Delta pH = 0.02 +/- 0.01; diel Delta pH = 0.03 +/- 0.00; mean +/- SD). These differences were most likely due to a combination of slower currents, a larger tidal range, and more favorable weather conditions for photosynthesis (e.g., sunny with no rain) in Mission Bay. In both systems, there was a substantial amount of time (usually at night) when seawater pH within the seagrass beds was lower relative to the source seawater. Future studies aimed at assessing the potential of seagrass ecosystems to act as OA refugia for marine organisms need to account for the small-scale, high-frequency carbonate chemistry variability in both space and time, as this variability will impact where and when OA will be buffered or intensified.

Mackenzie, FT, Andersson AJ.  2013.  The marine carbon system and ocean acidification during Phanerozoic time. Geochemical Perspectives. 2:1-227.   10.7185/geochempersp.2.1   AbstractWebsite

The global CO2-carbonic acid-carbonate system of seawater, although certainly a well-researched topic of interest in the past, has risen to the fore in recent years because of the environmental issue of ocean acidification (often simply termed OA). Despite much previous research, there remain pressing questions about how this most important chemical system of seawater operated at the various time scales of the deep time of the Phanerozoic Eon (the past 545 Ma of Earth's history), interglacial-glacial time, and the Anthropocene (the time of strong human influence on the behaviour of the system) into the future of the planet. One difficulty in any analysis is that the behaviour of the marine carbon system is not only controlled by internal processes in the ocean, but it is intimately linked to the domains of the atmosphere, continental landscape, and marine carbonate sediments.

Andersson, AJ, Bates NR, Mackenzie FT.  2007.  Dissolution of carbonate sediments under rising pCO(2) and ocean acidification: Observations from Devil's Hole, Bermuda. Aquatic Geochemistry. 13:237-264.   10.1007/s10498-007-9018-8   AbstractWebsite

Rising atmospheric pCO(2) 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 pCO(2) 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 pCO(2). 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 pCO(2) arising from burning of fossil fuels.

Andersson, AJ, Mackenzie FT, Lerman A.  2006.  Coastal ocean CO(2)-carbonic acid-carbonate sediment system of the Anthropocene. Global Biogeochemical Cycles. 20   10.1029/2005gb002506   AbstractWebsite

[1] There is little doubt that human activities such as burning of fossil fuels and land use practices have changed and will continue to change the cycling of carbon in the global coastal ocean. In the present study, two biogeochemical box models were used to investigate the consequences of increasing atmospheric CO(2) and subsequent ocean acidification and increasing riverine transport of organic matter and nutrients arising from human activities on land on the global coastal ocean between the years 1700 and 2300. Numerical simulations show that the net flux of CO(2) between coastal ocean surface water and the atmosphere is likely to change during this time from net evasion to net invasion owing to increasing atmospheric CO(2), increasing net ecosystem production arising from increasing nutrient loading to this region, and decreasing net ecosystem calcification due to lower carbonate ion concentration and subsequent lower surface water saturation state with respect to carbonate minerals. Model calculations show that surface water saturation state with respect to calcite will decrease 73% by the year 2300 under a business-as-usual scenario, which in concert with increasing temperature will cause overall biogenic calcification rate to decrease by 90%. Dissolution of carbonate minerals increased by 267% throughout the model simulation. This increase was in part due to increased invasion of atmospheric CO(2), but mainly due to greater deposition and remineralization of land-derived and in situ produced organic matter in the sediments, producing CO(2) that caused pore water pH and carbonate saturation state to decrease. This decrease, in turn, drove selective dissolution of metastable carbonate minerals. As a consequence, the relative carbonate composition of the sediments changed in favor of carbonate phases with lower solubility than that of an average 15 mol% magnesian calcite phase. Model projected changes in surface water carbonate saturation state agree well with observations from the Hawaiian Ocean Time series and the calculated air-sea CO(2) exchanged agrees well with a recent independent estimate of this flux derived from measurements from diverse coastal ecosystems scaled up to the global coastal ocean area.