Simple and clear evidence for positive feedback limitation by bipolar behavior during scanning electrochemical microscopy of unbiased conductors

On the basis of an experimentally validated simple theoretical model, it is demonstrated unambiguously that when an unbiased conductor is probed by a scanning electrochemical tip (scanning electrochemical microscopy, SECM), it performs as a bipolar electrode. Though already envisioned in most recent SECM theories, this phenomenon is generally overlooked in SECM experimental investigations. However, as is shown here, this may alter significantly positive feedback measurements when the probed conductor is not much larger than the ti

An isotopic (Δ¹⁴C, δ¹³C, and δ¹⁵N) investigation of the composition of particulate organic matter and zooplankton food sources in Lake Superior and across a size-gradient of aquatic systems

Food webs in aquatic systems can be supported both by carbon from recent local primary productivity and by carbon subsidies, such as material from terrestrial ecosystems, or past in situ primary productivity. The importance of these subsidies to respiration and biomass production remains a topic of debate. While some studies have reported that terrigenous organic carbon supports disproportionately high zooplankton production, others have suggested that phytoplankton preferentially support zooplankton production in aquatic ecosystems. Here we apply natural abundance radiocarbon (Δ14C) and stable isotope (δ13C, δ15N) analyses to show that zooplankton in Lake Superior selectively incorporate recently fixed, locally produced (autochthonous) organic carbon even though other carbon sources are readily available. Estimates from Bayesian isotopic modeling based on Δ14C and δ13C values show that the average lake-wide median contributions of recent in-lake primary production and terrestrial, sedimentary, and bacterial organic carbon to the bulk POM in Lake Superior were 58%, 5%, 33%, and 3%, respectively. However, isotopic modeling estimates also show that recent in situ production contributed a disproportionately large amount (median, 91%) of the carbon in mesozooplankton biomass in Lake Superior. Although terrigenous organic carbon and old organic carbon from resuspended sediments were significant portions (median, 38%) of the available basal food resources, these contributed only a small amount to mesozooplankton biomass. Comparison of zooplankton food sources based on their radiocarbon composition showed that terrigenous organic carbon was relatively more important in rivers and small lakes, and the proportion of terrestrially derived material used by zooplankton correlated with the hydrologic residence time and the ratio of basin area to water surface area

Investigating the Mechanism and Electrode Kinetics of the Oxygen vertical bar Superoxide (O-2 vertical bar O-2(center dot-)) Couple in Various Room-Temperature Ionic Liquids at Gold and Platinum Electrodes in the Temperature Range 298-318 K

The reduction of oxygen was studied over a range of temperatures (298-318 K) in n -hexyltrietliylammonium bis(trifluorometlianesulfonyl)imide, [N 6,2,2,2] [NTf2], and 1-butyl-2,3-methylimidazorium bis(trifluoromethanesulfonyl)imide, [Qdmim] [NTf2] on both gold and platinum microdisk electrodes, and the mechanism and electrode kinetics of the reaction investigated. Three different models were used to simulate the CVs, based on a simple electron transfer ('E'), an electron transfer coupled with a reversible homogeneous chemical, step ('ECrev') and an electron transfer followed by adsorption of the reduction product ('EC(ads)'), and where appropriate, best fit parameters deduced, including the heterogeneous rate constant, formal electrode potential., transfer coefficient, and homogeneous rate constants for the ECrev mechanism, and adsorption/desorption rate constants for the EC(ads) mechanism. It was concluded from the good simulation fits on gold that a simple E process operates for the reduction of oxygen in [N6,2,2,2][NTf2], and an ECrev process for [Qdmim J[NTf2], with the chemical, step involving the reversible formation of the O2-⋯ [C4dmim] - ion-pair. The E mechanism was found to loosely describe the reduction of oxygen in [N6,2,2,2] [NTf2] on platinum as the simulation fits were reasonable although not perfect, especially for the reverse wave. The electrochemical kinetics are slower on Pt, and observed broadening of the oxidation peak is likely due to the adsorption of superoxide on the electrode surface in a process more complex than simple Langmuirian. In [C 4dmim] [NTf2] the O2- ⋯ predominantly ion-pairs with the solvent rather than adsorbs on the surface, and an EC16V quantitatively describes the reduction of oxygen on Pt also. © 2009 American Chemical Society

Intermittent contact-scanning electrochemical microscopy (IC-SECM): a new approach for tip positioning and simultaneous imaging of interfacial topography and activity

A new scanning electrochemical microscopy (SECM) tip positioning method that allows surface topography and activity to be resolved simultaneously and independently is presented. The tip, controlled by a piezoelectric positioner operated in closed loop, is oscillated normal to the substrate surface. Changes in the oscillation amplitude, caused by the intermittent contact (IC) of the tip with the substrate surface, are used as a feedback signal to control the tip height. The method is illustrated with amperometric feedback approach curve measurements to inert (insulating) and active (conducting) substrates using 12.5 and 1 mu m radii Pt disk electrodes. Imaging of gold bands on a glass substrate demonstrates the capabilities for simultaneous topography and activity mapping. The prospect for using IC methodology more widely with other types of tips is highlighted briefly