Posts Tagged 'chemistry'

Calcite dissolution kinetics at the sediment-water interface in natural seawater

The absorption, or uptake, of anthropogenic CO2 by the oceans results in a decrease in pH and carbonate ion concentration, [CO32 −]; as a consequence, the saturation state of seawater with respect to CaCO3 minerals (calcite, aragonite) falls, leading to a shallowing of their saturation depths and triggering an increase in their dissolution at the seafloor. Nearly one-third of the seabed is composed of CaCO3-rich sediments, and their dissolution is the ultimate marine sink of anthropogenic CO2. Despite numerous past studies, much confusion and uncertainty still surround our understanding of the rates and kinetics of CaCO3 dissolution at the deep seafloor. Results from in situ studies disagree with laboratory studies, most of which have been carried out under conditions, e.g., mineral suspensions, that are not representative of processes at the seafloor. Herein, we report measurements of the dissolution rate of calcite, formed into synthetic sediment disks by mixing various amounts of this mineral with montmorillonite. These disks were placed in a stirred-flow reactor and exposed to a range of saturation states and shear stress conditions to simulate conditions at the sediment-water interface. The dissolution rates, normalized to the interfacial area of the sediment disks, were linearly dependent on the undersaturation state of the experimental seawater solution and displayed a square-root dependence on the calcite content, under both quiescent and stirred conditions. The rate of release of reaction products from the sediment increased with stirring rate, i.e., shear stress, until it became invariant at higher stirring rates. This latter result argues that calcite dissolution is transport (water-side) controlled for shear stress levels known to exist at the seafloor, which advises a simpler kinetic description of benthic calcite dissolution.

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An evaluation of potentiometric pH sensors in coastal monitoring applications

A wealth of historical coastal water pH data has been collected using potentiometric glass electrodes, but the accuracy and stability of these sensors is poorly understood. Here we compared pH measurements from five potentiometric sensors incorporated into profiling Sea-Bird instrument packages and compared them to spectrophotometric measurements on discrete bottle samples collected at two to three depths associated with each cast. Differences ranged from −0.509 to +0.479 with a mean difference of −0.055 pH units. Ninety-two percent of the measurements were within ± 0.2 pH units, but 1% of the measurements had differences greater than 0.322. Sensor performance was affected by depth, but most of the difference was associated with calibration shortcomings. Sensor drift within a day was negligible; moreover, differences between bottle samples and electrode measurements within a sampling day were smaller than differences across days. Bootstrap analysis indicated that conducting a daily in situ calibration would reduce the mean difference to 0.002 pH units and increase the number of samples within a 0.2 pH unit error to 98%.

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Scales and drivers of seasonal pCO2 dynamics and net ecosystem exchange along the coastal waters of southeastern Arabian Sea

The impact of seasonal coastal upwelling on the dynamics of dissolved inorganic carbon (DIC) and sea-air fluxes of CO2 along the coastal waters of Kochi was investigated during 2015, as a part of Ecosystem Modelling Project. The surface water pCO2 varied from 396 to 630 μatm during the study period. Significant inter-seasonal variations were found in the distribution of physico-chemical variables and surface pCO2. An increase of 102.1 μatm of pCO2 was noticed over a two-decade period with a rate of 5.3 μatm y− 1. There was an agreement between the fluxes of CO2 and net ecosystem production (NEP) with respect to the trophic status while NEP was higher than CO2 fluxes by a factor of 3.9. The annual net ecosystem exchange (NEE) was estimated to be 15.02 mmol C m− 2 d− 1 indicating that the coastal waters of Kochi are highly heterotrophic in nature.

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Autonomous observing platform CO2 data shed new light on the Southern Ocean carbon cycle.

While the number of surface ocean CO2 partial pressure (pCO2) measurements has soared the recent decades, the Southern Ocean remains undersampled. Williams et al. [2017] now present pCO2 estimates based on data from pH-sensor equipped Bio-Argo floats, which have been measuring in the Southern Ocean since 2014. The authors demonstrate the utility of these data for understanding the carbon cycle in this region, which has a large influence on the distribution of CO2 between the ocean and atmosphere. Biogeochemical sensors deployed on autonomous platforms hold the potential to shape our view of the ocean carbon cycle in the coming decades.

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Sensitivity of future ocean acidification to carbon climate feedbacks

Carbon-climate feedbacks have the potential to significantly impact the future climate by altering atmospheric CO2 concentrations (Zaehle et al., 2010). By modifying the future atmospheric CO2 concentrations, the carbon-climate feedbacks will also influence the future trajectory for ocean acidification. Here, we use the CO2 emissions scenarios from 4 Representative Concentration Pathways (RCPs) with an Earth System Model to project the future trajectories of ocean acidification with the inclusion of carbon-climate feedbacks. We show that simulated carbon-climate feedbacks can significantly impact the onset of under-saturated aragonite conditions in the Southern and Arctic Oceans, the suitable habitat for tropical coral and the deepwater saturation states. Under higher emission scenarios (RCP8.5 and RCP6.0), the carbon-climate feedbacks advance the onset of under-saturation conditions and the reduction in suitable coral reef habitat by a decade or more. The impact of the carbon-climate feedback is most significant for the medium (RCP4.5) and low emission (RCP2.6) scenarios. For RCP4.5 scenario by 2100, the carbon-climate feedbacks nearly double the area of surface water under-saturated respect to aragonite and reduce by 50 % the surface water suitable for coral reefs. For RCP2.6 scenario by 2100, the carbon-climate feedbacks reduce the area suitable for coral reefs by 40 % and increase the area of under-saturated surface water by 20 %. The high sensitivity of the impact of ocean acidification to the carbon-climate feedbacks in the low to medium emissions scenarios is important because our recent commitments to reduce CO2 emissions are trying to move us on to such an emissions scenario. The study highlights the need to better characterise the carbon-climate feedbacks to ensure we do not excessively stress the oceans by under-estimating the future impact of ocean acidification.

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Design and fabrication of a ratiometric planar optode for simultaneous imaging of pH and oxygen

This paper presents a simple, high resolution imaging approach utilizing ratiometric planar optode for simultaneous measurement of dissolved oxygen (DO) and pH. The planar optode comprises a plastic optical film coated with oxygen indicator Platinum(II) octaethylporphyrin (PtOEP) and reference quantum dots (QDs) embedded in polystyrene (PS), pH indicator 5-Hexadecanoylamino-fluorescein (5-Fluorescein) embedded in Hydromed D4 matrix. The indicator and reference dyes are excited by utilizing an LED (Light Emitting Diode) source with a central wavelength of 405 nm, the emission respectively matches the different channels (red, green, and blue) of a 3CCD camera after eliminating the excitation source by utilizing the color filter. The result shows that there is low cross-sensitivity between the two analytes dissolved oxygen and pH, and it shows good performance in the dynamic response ranges of 0–12 mg/L and a dynamic range of pH 6−8. The optode has been tested with regard to the response times, accuracy, photostability and stability. The applied experiment for detecting pH/Oxygen of sea-water under the influence of the rain drops is demonstrated. It is shown that the planar optode measuring system provides a simple method with low cross-talk for pH/Oxygen imaging in aqueous applications.

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Marine paleoclimatic proxies: A shift from qualitative to quantitative estimation of seawater parameters

Understanding past climate during contrasting boundary conditions can help in assessing imminent climate changes. Marine sediments offer a vast archive of past climate. Various indirect methods called proxies are used to infer principal climate parameters like temperature, salinity, productivity, monsoon intensity, ocean circulation, seawater pH, and others, from the marine sediments. The relationship between a climate parameter and marine paleoclimate proxy may vary from region to region. Additionally, the marine proxies are often affected by more than one climate parameter, thus making it difficult to assess the change in any particular parameter from a single proxy. Diagenetic alteration can also significantly affect the parameter-proxy relationship. A growing emphasis now is on quantifying changes in key climatic parameters in the past. Proxies for quantitative estimation of seawater temperature, runoff, sea-level and pH are now fairly well established. Similar robust quantitative proxies for dissolved oxygen concentration and productivity are, however, still being developed. Additionally, the uncertainty associated with quantitative estimation of past climate has to be reduced. Therefore, continuous efforts are being made to develop novel paleoclimate proxies and to evaluate existing proxies in different regions of the world oceans.

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Ocean acidification in the IPCC AR5 WG II

OUP book