Posts Tagged 'chemistry'

Solid state sensor for simultaneous measurement of total alkalinity and pH of seawater

A novel design is demonstrated for a solid state, reagent-less sensor capable of rapid and simultaneous measurement of pH and Total Alkalinity (AT) using ion sensitive field effect transistor (ISFET) technology to provide a simplified means of characterization of the aqueous carbon dioxide system through measurement of two “master variables”: pH and AT. ISFET-based pH sensors that achieve 0.001 precision are widely used in various oceanographic applications. A modified ISFET is demonstrated to perform a nL-scale acid-base titration of AT in under 40 s. This method of measuring AT, a Coulometric Diffusion Titration, involves electrolytic generation of titrant, H+, through the electrolysis of water on the surface of the chip via a microfabricated electrode eliminating the requirement of external reagents. Characterization has been performed in seawater as well as titrating individual components (i.e. OH, HCO3, CO32-, B(OH)4, PO43-) of seawater AT. The seawater measurements are consistent with the design in reaching the benchmark goal of 0.5% precision in AT over the range of seawater AT of ~2200-2500 μmol kg-1 which demonstrates great potential for autonomous sensing.

Continue reading ‘Solid state sensor for simultaneous measurement of total alkalinity and pH of seawater’

The potential of 230Th for detection of ocean acidification impacts on pelagic carbonate production

Concentrations of dissolved 230Th in the ocean water column increase with depth due to scavenging and downward particle flux. Due to the 230Th scavenging process, any change in the calcium carbonate (CaCO3) fraction of the marine particle flux due to changes in biological CaCO3 hard shell production as a consequence of progressing ocean acidification would be reflected in the dissolved 230Th activity. Our prognostic simulations with a biogeochemical ocean general circulation model using different scenarios for the reduction of CaCO3production under ocean acidification and different greenhouse gas emission scenarios (RCPs 8.5 to 2.6) reveal the potential for deep 230Th measurements to detect reduced CaCO3 production at the sea surface. The time of emergence of an acidification induced signal on dissolved 230Th is of the same order of magnitude as for alkalinity measurements. Yet, deep ocean 230Th concentrations are less affected by seasonal and multiyear variability than surface alkalinity. Thus, deep ocean 230Th observations could be advantageous to guide monitoring and detection campaigns. Furthermore, given that the precision of 230Th measurements may potentially improve in the near future, earlier detection of ocean acidification impact signals would be possible. Our results indicate that the deep Pacific Ocean and the deep Southern Ocean are the most suitable regions for selected regular reoccupations of deep reaching 230Th stations.

Continue reading ‘The potential of 230Th for detection of ocean acidification impacts on pelagic carbonate production’

Phytoplankton community responses to iron and CO2 enrichment in different biogeochemical regions of the Southern Ocean

The ongoing rise in atmospheric CO2 concentration is causing rapid increases in seawater pCO2levels. However, little is known about the potential impacts of elevated CO2 availability on the phytoplankton assemblages in the Southern Ocean’s oceanic regions. Therefore, we conducted four incubation experiments using surface seawater collected from the subantarctic zone (SAZ) and the subpolar zone (SPZ) in the Australian sector of the Southern Ocean during the austral summer of 2011–2012. For incubations, FeCl3 solutions were added to reduce iron (Fe) limitation for phytoplankton growth. Ambient and high (~750 µatm) CO2 treatments were then prepared with and without addition of CO2-saturated seawater, respectively. Non-Fe-added (control) treatments were also prepared to assess the effects of Fe enrichment (overall, control, Fe-added, and Fe-and-CO2-added treatments). In the initial samples, the dominant phytoplankton taxa shifted with latitude from haptophytes to diatoms, likely reflecting silicate availability in the water. Under Fe-enriched conditions, increased CO2 level significantly reduced the accumulation of biomarker pigments in haptophytes in the SAZ and AZ, whereas a significant decrease in diatom markers was only detected in the SAZ. The CO2-related changes in phytoplankton community composition were greater in the SAZ, most likely due to the decrease in coccolithophore biomass. Our results suggest that an increase in CO2, if it coincides with Fe enrichment, could differentially affect the phytoplankton community composition in different geographical regions of the Southern Ocean, depending on the locally dominant taxa and environmental conditions.

Continue reading ‘Phytoplankton community responses to iron and CO2 enrichment in different biogeochemical regions of the Southern Ocean’

Rapid decline in pH of coral calcification fluid due to incorporation of anthropogenic CO2

Marine calcifying organisms, such as stony corals, are under threat by rapid ocean acidification (OA) arising from the oceanic uptake of anthropogenic CO2. To better understand how organisms and ecosystems will adapt to or be damaged by the resulting environmental changes, field observations are crucial. Here, we show clear evidence, based on boron isotopic ratio (δ11B) measurements, that OA is affecting the pH of the calcification fluid (pHCF) in Porites corals within the western North Pacific Subtropical Gyre at two separate locations, Chichijima Island (Ogasawara Archipelago) and Kikaijima Island. Corals from each location have displayed a rapid decline in δ11B since 1960. A comparison with the pH of the ambient seawater (pHSW) near these islands, estimated from a large number of shipboard measurements of seawater CO2 chemistry and atmospheric CO2, indicates that pHCF is sensitive to changes in pHSW. This suggests that the calcification fluid of corals will become less supersaturated with respect to aragonite by the middle of this century (pHCF = ~8.3 when pHSW = ~8.0 in 2050), earlier than previously expected, despite the pHCF-upregulating mechanism of corals.

Continue reading ‘Rapid decline in pH of coral calcification fluid due to incorporation of anthropogenic CO2’

Retrodiction of secular variations in deep-sea CaCO3 burial during the Cenozoic

Deep-sea sediments record changes in oceanic carbonate chemistry and CaCO3sedimentation rate through temporal variations in the total burial of CaCO3 and the position of the carbonate snowline, i.e., the ocean depth at which CaCO3-free sediments are first recorded. This paper links mathematically secular changes in snowline to those in the burial rate through a set of relatively simple equations. When the available Cenozoic deep-sea burial records are employed to predict secular variations in snowline, the process fails at some time in the past, indicating that these records are not consistent with each other. The burial records are more likely the source of this problem, as they involve far more uncertainties than the snowline records. As a consequence, we introduce a method for estimating carbonate burial through the use of a canonical CaCO3-depth profile, which can respond dynamically to secular changes in carbonate sedimentation and the positions of both the snowline and the carbonate saturation horizon. The resulting synthetic CaCO3burial record is consistent with snowline records and indicates that the burial rates offered by Davies and Worsley (1981) are generally too high, with highly questionable maxima at 25 and 47 Ma BP. Our estimates of burial are more consistent with the range advanced by Mackenzie and Morse (1992); nevertheless, our results differ from the latter with respect to timing and magnitude of the variations. Our approach allows simultaneous calculation of the mean carbonate ion concentration of the deep sea. We find that carbonate-ion levels fell through the Cenozoic and are similar to those calculated by Tyrrell and Zeebe (2004), using a different model. Secular variations in CaCO3 burial are found to be primarily driven by changes in the Ca2+–CO32 ion product within the bottom-waters, with an increase in the sedimentation rate of CaCO3 of secondary importance over the Cenozoic.

Continue reading ‘Retrodiction of secular variations in deep-sea CaCO3 burial during the Cenozoic’

Assessment of the environmental impacts of ocean acidification (OA) and carbon capture and storage (CCS) leaks using the amphipod Hyale youngi

This study aims to ascertain the effects of CO2 induced water acidification and leaks from Carbon Capture and Storage activities on the South American amphipod Hyale youngi. A 10-day acute toxicity test was performed using sediments from two sites located inside the Santos Estuarine System. They were subjected to five pH treatments (8.1, 7.6, 7.0, 6.5, and 6.0). Metals (Cd, Cu, Cr, Pb, Ni and Zn) and the metalloid As were analyzed to determine the influence of their acidification-related mobility on the amphipods mortality. The results showed that mortality becomes significant when compared to control in pH 6.5 in the Canal de Piaçaguerasediment (contaminated) and at pH 6.0 in Ilha das Palmas sediment (reference).

Continue reading ‘Assessment of the environmental impacts of ocean acidification (OA) and carbon capture and storage (CCS) leaks using the amphipod Hyale youngi’

Seasonal variations of Fucus vesiculosus fertility under ocean acidification and warming in the western Baltic Sea

Ocean warming and acidification may substantially affect the reproduction of keystone species such as Fucus vesiculosus (Phaeophyceae). In four consecutive benthic mesocosm experiments, we compared the reproductive biology and quantified the temporal development of Baltic Sea Fucus fertility under the single and combined impact of elevated seawater temperature and pCO2 (1100 ppm). In an additional experiment, we investigated the impact of temperature (0–25°C) on the maturation of North Sea F. vesiculosus receptacles. A marked seasonal reproductive cycle of F. vesiculosus became apparent in the course of 1 year. The first appearance of receptacles on vegetative apices and the further development of immature receptacles of F. vesiculosus in autumn were unaffected by warming or elevated pCO2. During winter, elevated pCO2 in both ambient and warmed temperatures increased the proportion of mature receptacles significantly. In spring, warming and, to a lesser extent, elevated pCO2 accelerated the maturation of receptacles and advanced the release of gametes by up to 2 weeks. Likewise, in the laboratory, maturation and gamete release were accelerated at 15–25°C relative to colder temperatures. In summary, elevated pCO2 and/or warming do not influence receptacle appearance in autumn, but do accelerate the maturation process during spring, resulting in earlier gamete release. Temperature and, to a much lesser extent, pCO2 affect the temporal development of Fucus fertility. Thus, rising temperatures will mainly shift or disturb the phenology of F. vesiculosus in spring and summer, which may alter and/or hamper its ecological functions in shallow coastal ecosystems of the Baltic Sea.

Continue reading ‘Seasonal variations of Fucus vesiculosus fertility under ocean acidification and warming in the western Baltic Sea’


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