The chemical confinement of a pH sensitive fluorophore to a thin-reaction layer adjacent to an electrode surface is explored as a potentially innovative route to improving the spatial resolution of fluorescence electrochemical microscopy. A thin layer opto-electrochemical cell is designed, facilitating the visualization of a carbon fiber (diameter 7.0 μm) electrochemical interface. Proton consumption is driven at the interface by the reduction of benzoquinone to hydroquinone and the resulting interfacial pH change is revealed using the fluorophore 8-hydoxypyrene-1,3,6-trisulfonic acid. It is demonstrated that the proton depletion zone may be constrained and controlled by the addition of a finite acid concentration to the system. Simulation of the resulting fluorescence intensity profiles is achieved on the basis of a finite difference model, with excellent agreement between the theoretical and experimental results.

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We report single-entity measurements of the degree of calcification of individual phytoplankton cells. Electrogenerated acid is used to dissolve the calcium carbonate (CaCO3) shell (coccosphere) of individual coccolithophores and the...

Coccoliths are plates of biogenic calcium carbonate secreted by calcifying marine phytoplankton; annually these phytoplankton are responsible for exporting >1 billion tonnes (1015 g) of calcite to the deep ocean. Rapid and reliable methods for assessing the degree of calcification are technically challenging because the coccoliths are micron sized and contain picograms (pg) of calcite. Here we pioneer an opto‐eletrochemical acid titration of individual coccoliths which allows 3D reconstruction of each individual coccolith via in situ optical imaging enabling direct inference of the coccolith mass. Coccolith mass ranging from 2 to 400 pg are reported herein, evidencing both inter‐ and intra‐species variation over four different species. We foresee this scientific breakthrough, which is independent of knowledge regarding the species and calibration‐free, will allow continuous monitoring and reporting of the degree of coccolith calcification in the changing marine environment.

Calcite dissolution kinetics at the single particle scale are determined. It is demonstrated that at high undersaturation and in the absence of inhibitors the particulate mineral dissolution rate is controlled by a saturated calcite surface in local equilibrium with dissolved Ca2+ and CO3 2– coupled with rate determining diffusive transport of the ions away from the surface. Previous work is revisited and inconsistencies arising from the assumption of a surface-controlled reaction are highlighted. The data have implications for ocean modeling of climate change.

In the vicinity of an electrode creating a highly oxidising environment the fluorescence – arising from the presence of chlorophyll-a – of single cellular phytoplankton becomes inhibited.

Superoxide produced at silver electrode in seawater.

By varying the total and the relative concentrations of a strong acid (HClO) and a pH-sensitive fluorescent dye (8-hydroxypyrene-1,3,6-trisulfonate), this work demonstrates that both the hydrogen evolution reaction or the oxygen reduction reaction can be selectively and optically studied at an electrochemical interface. The local pH shift driven by the redox reaction can be visualized through fluorescence imaging of the interface. The use of finite strong acid concentrations further serves to constrain the pH change to a thin layer adjacent to the surface. This chemical confinement of the fluorophore improves the system's resolution and enables micrometer scale heterogeneity on the electrode surface to be readily visualized.