Posts Tagged 'dissolution'

Evidence for shelf acidification during the onset of the Paleocene‐Eocene Thermal Maximum

A transect of paleoshelf cores from Maryland and New Jersey contains an ~0.19 m to 1.61 m thick interval with reduced percentages of carbonate during the onset of the Paleocene‐Eocene Thermal Maximum (PETM). Outer paleoshelf cores are barren of nannofossils and correspond to two minor disconformities. Middle paleoshelf cores contain a mixture of samples devoid of nannofossils and those with rare specimens characterized by significant dissolution (i.e., etching). The magnitude of the decrease in carbonate cannot be explained by dilution by clastic material or dissolution resulting from the oxidation of organic matter during early diagenesis. The observed preservation pattern implies a shoaling of the calcite compensation depth (CCD) and lysocline to the middle shelf. This reduced carbonate interval is observed during the onset of the PETM on other continental margins raising the possibility that extreme shoaling of the CCD and lysocline was a global signal, which is more significant than in previous estimates for the PETM. An alternative scenario is that shoaling was restricted to the northwest Atlantic, enhanced by regional and local factors (eutrophication from rivers, microbial activity associated with warming) that exacerbated the impact of acidification on the shelf.
Continue reading ‘Evidence for shelf acidification during the onset of the Paleocene‐Eocene Thermal Maximum’

Seasonal net ecosystem metabolism of the near-shore reef system in La Parguera, Puerto Rico

Changes in ocean chemistry as a direct response to rising atmospheric carbon dioxide (CO2) concentrations is causing a reduction of pH in the surface ocean. While the dynamics and trends in carbonate chemistry are reasonably constrained for open ocean waters, the ways in which ocean acidification (OA) manifests within the shallow near-shore waters, where coral reefs reside, is less understood. Constraining near-reef variability in carbonate chemistry and net ecosystem metabolic processes across diel, seasonal, and annual scales is important in evaluating potential biogeochemical thresholds of OA that could result in ecological community changes. The OA Test-Bed at La Parguera Marine Reserve in Puerto Rico provides long-term carbonate chemistry observations at high-temporal resolution within a Caribbean near-shore coral reef ecosystem. A 1-D model was developed using the carbon mass balance approach to yield information about net ecosystem production and calcification processes occurring in the water column adjacent to the reef. We present results of nine years of sustained monitoring at the Enrique mid-shelf forereef, which provides for the characterization of temporal dynamics in carbonate chemistry and net ecosystem metabolic processes encompassing near-shore and upstream locations. Results indicate that net heterotrophy and net dissolution dominate over most of the year, while net autotrophic conditions coupled with calcification dominated from only January to mid-April. The average carbonate dissolution rate observed during summer is estimated at −2.19g CaCO3m−2 day−1 and net community dissolution persists 76% of the seasonal year despite the water column remaining super-saturated with respect to aragonite. This corresponds to −0.62 kg CaCO3m−2 year−1, classifying the Enrique fore-reef and off-reef areas in a net dissolutional state. The combination of thermodynamically-driven depressed aragonite saturation state and high rates of respiration during the summer cause conditions that jeopardize the most soluble carbonate minerals and the free energy in the system for calcification. These data suggest that the reef area and associated ecosystems upstream of the sampling location are experiencing a net loss of CaCO3, possibly compromising coral ecosystem health and reef accretion processes necessary for maintenance as sea level increases. Resiliency from other climate-scale stressors including rising sea surface temperatures and coral bleaching is likely to be compromised in a system exhibiting net carbonate loss.

Continue reading ‘Seasonal net ecosystem metabolism of the near-shore reef system in La Parguera, Puerto Rico’

The dissolution behavior of biogenic calcites in seawater and a possible role for magnesium and organic carbon

We present the dissolution kinetics of mixed planktic foraminifera, the benthic foraminifera Amphistegina, the coccolithophore Emiliania huxleyi, and the soft coral Rhythismia fulvum in seawater. Dissolution rates were measured across a large range of saturation states (Ω = 0.99–0.2) by dissolving 13C-labeled calcites in natural seawater undersaturated with respect to calcite. 13C-label was incorporated into biogenic calcite by culturing marine calcifiers in 13C-labeled natural seawater. Net dissolution rates were calculated as the slope of seawater δ13C versus time in a closed seawater-calcite system. All calcites show distinct, nonlinear, dependencies on seawater saturation state when normalized by mass or by specific surface area. For example, coccolith calcite dissolves at a similar rate to inorganic calcite near equilibrium when normalized by surface area, but dissolves much more slowly far from equilibrium. Mass loss from foraminiferal tests is correlated with a decrease in Mg/Ca of the solid, indicating that Mg-rich phases are preferentially leached out at even mild undersaturations. Dissolution also appears to strongly affect test B/Ca. Finally, we provide an interpretation of surface area-normalized biogenic calcite dissolution rates as a function of their Mg and organic carbon content. Near-equilibrium dissolution rates of all calcites measured here show a strong, nonlinear dependence on Mg content. Far-from-equilibrium dissolution rates decrease strongly as a function of organic carbon content. These results help to build a framework for understanding the underlying mechanisms of rate differences between biogenic calcites, and bear important implications for the dissolution of high-Mg calcites in view of ocean acidification.

Continue reading ‘The dissolution behavior of biogenic calcites in seawater and a possible role for magnesium and organic carbon’

A kinetic pressure effect on calcite dissolution in seawater

This study provides laboratory data of calcite dissolution rate as a function of seawater undersaturation state (1 − Ω ) under variable pressure. 13C-labeled calcite was dissolved in unlabeled seawater and the evolving δ13C composition of the fluid was monitored over time to evaluate the dissolution rate. Results show that dissolution rates are enhanced by a factor of 2–4 at 700 dbar compared to dissolution at the same Ω under ambient pressure (10 dbar). This dissolution rate enhancement under pressure applies over an Ω range of 0.65–1 between 10 dbar and 700 dbar. Above 700 dbar (up to 2500 dbar), dissolution rates become independent of pressure. The observed enhancement is well beyond the uncertainty associated with the thermodynamic properties of calcite under pressure (partial molar volume ΔV), and thus should be interpreted as a kinetic pressure effect on calcite dissolution. Dissolution at ambient pressure and higher pressures yield non-linear dissolution kinetics, the pressure effect does not significantly change the reaction order n in Rate = k(1 −Ω )n, which is shown to vary from 3.1 ± 0.3 to 3.8 ± 0.5 from 10 dbar to 700 dbar over Ω  = 0.65–0.9. Furthermore, two different dissolution mechanisms are indicated by a discontinuity in the rate-undersaturation relationship, and seen at both ambient and higher pressures. The discontinuity, Ωcritical = 0.87 ± 0.05 and 0.90 ± 0.03 at 10 dbar and 1050 dbar respectively, are similar within error. The reaction order, n, at Ω  > 0.9 is 0.47 ± 0.27 and 0.46 ± 0.15 at 10 dbar and 700 dbar respectively. This Ωcritical is considered to be the threshold between step retreat dissolution and defect-assisted dissolution. The kinetic enhancement of dissolution rates at higher pressures is related to a decrease in the interfacial energy barrier at dissolution sites. The impact of pressure on the calcite dissolution kinetics implies that sinking particles would dissolve at shallower depths than previously thought.

Continue reading ‘A kinetic pressure effect on calcite dissolution in seawater’

Coralline algal skeletal mineralogy affects grazer impacts

In macroalgal‐dominated systems, herbivory is a major driver in controlling ecosystem structure. However, the role of altered plant–herbivore interactions and effects of changes to trophic control under global change are poorly understood. This is because both macroalgae and grazers themselves may be affected by global change, making changes in plant–herbivore interactions hard to predict. Coralline algae lay down a calcium carbonate skeleton, which serves as protection from grazing and is preserved in archival samples. Here, we compare grazing damage and intensity to coralline algae in situ over 4 decades characterized by changing seawater acidity. While grazing intensity, herbivore abundance and identity remained constant over time, grazing wound width increased together with Mg content of the skeleton and variability in its mineral organization. In one species, decreases in skeletal organization were found concurrent with deeper skeletal damage by grazers over time since the 1980s. Thus, in a future characterized by acidification, we suggest coralline algae may be more prone to grazing damage, mediated by effects of variability between individuals and species.

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Ocean acidification and molluscan shell taphonomy: can elevated seawater pCO2 influence taphonomy in a naticid predator–prey system?


• Tested for taphonomic effects of elevated pCO2 in a naticid predator-prey system
• High pCO2 induced greater shell dissolution rates, which differed across species
• Breakage force differed across species and drill hole category
• No pCO2 effect on shell breakage force
• Limited species-specific drill hole diameter increase under high pCO2


The size and frequency of gastropod drill holes in shells of their prey are common indicators of predator-prey ecology in the fossil record. Taphonomic processes occurring after predation, however, can influence the preservation of shells in a given fossil assemblage and can thus influence ecological inferences based on preserved shells. To determine if ocean acidification (OA) has the capacity to influence prey shell taphonomy in a gastropod drilling predation system, we tested for effects of elevated pCO2 on dissolution rates, breakage force, and drill hole diameters in non-fragmented shells of two prey species of the cannibalistic naticid gastropod, Euspira heros. Drilled and non-drilled shells of Littorina littorea and E. heros were exposed to control (~300 μatm) and elevated (~800 and 4000 μatm) pCO2 treatments for five weeks. Dry shell weight and drill hole diameter (outer and inner) were recorded for individual shells before and after exposure; the force required for shell breakage was recorded at the end of the exposure period. Shell mass loss in 800 and 4000 μatm, respectively, were ~1 and 7% for E. heros, and ~0 and 4% for L. littorea, compared to ~0% in the control for both species. Shell breakage force was unaffected by elevated pCO2, but was affected by species and drill hole presence, with E. heros shells requiring a force of ~220 and 269 Newtons in drilled and non-drilled shells, respectively, compared to ~294 and 415 Newtons in L. littorea. At 4000 μatm, outer drill hole diameter significantly increased by ~12% for E. heros, while inner drill hole diameter significantly increased by ~13% in E. heros and ~10% in L. littorea. Ultimately, this study provides the first documentation of molluscan shell taphonomy in the context of OA for a gastropod drilling predation system and sets the stage for future research.


Continue reading ‘Ocean acidification and molluscan shell taphonomy: can elevated seawater pCO2 influence taphonomy in a naticid predator–prey system?’

Impact of ocean acidification and warming on the diversity and the functioning of macroalgal communities (full thesis in French)

Predicted ocean acidification and warming for the end of the century may have drastic consequences on the structure and functioning of marine ecosystems. However, a lack of knowledge persists on the impact of future changes on the response of marine communities. This thesis aims to provide new understanding of the impact of ocean acidification and warming at the community level. For this, two ecosystems have been considered: rockpools, characterized by high physico-chemical variations, and maerl beds, with smaller variations. In the laboratory, artificial assemblages were created from the main calcareous and fleshy macroalgal and grazer species present in these two ecosystems. Created assemblages have been subjected to ambient and future temperature and pCO2 conditions. Ocean acidification and warming altered the structure and functioning of maerl bed assemblages, through an increase in the productivity of non-calcareous macroalgae and a decline in maërl calcification rates. The physiology of grazers is negatively impacted by future changes, which altered assemblages’ trophic structure. On the other hand, ocean acidification and warming had no effect on the productivity of rockpool assemblages. The highly variable environment may thus increase the resistance of rockpool communities to future changes, compared to communities from more stable environments, such as maerl beds.

Continue reading ‘Impact of ocean acidification and warming on the diversity and the functioning of macroalgal communities (full thesis in French)’

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Ocean acidification in the IPCC AR5 WG II

OUP book