Local etching of copper films by the Scanning Electrochemical Microscope in the feedback mode: A theoretical and experimental investigation

International audienceA model of the Scanning Electrochemical Microscope (SECM) as a lithographic tool is presented and used to get quantitative kinetic information from lithographic experiments. It is illustrated in the specific case of the local etching by anodic dissolution of a copper substrate by the SECM in the feedback mode. A theoretical model presents the expected profile of the etched hole in the simple case of the positive feedback behaviour. A steady-state behaviour is expected for the dimensionless shape of the hole, which depends only on the tip-substrate separation distance. The hole depth is then expected to linearly depend on the etching time. The model is then confronted to different experimental conditions where a Cu substrate is locally oxidized by a tip-electrogenerated Fe(bpy)(3)(3+) oxidant. The experiments agree with the theoretical predictions (steady-state dimensionless profile and linear evolution of the depth with time). Even though the system behaves under positive feedback, the kinetics of the etching process can readily be extracted from the hole characterization and its conversion into Faradaic yield. (C) 2011 Elsevier Ltd. All rights reserved

Surface Reactivity from Electrochemical Lithography: Illustration in the Steady-State Reductive Etching of Perfluorinated Surfaces

The scanning electrochemical microscope (SECM) in the lithographic mode is used to assess quantitatively, from both theoretical and experimental points of view, the kinetics of irreversible transformation of electroactive molecular moieties immobilized on a surface as self-assembled monolayers (SAMs). The SECM tip allows the generation of an etchant that transforms the surface locally and irreversibly. The resulting surface patterning is detectable by different surface analyses. The quantification of the surface transformation kinetics is deduced from the evolution of the pattern dimen sions with the etching time. The special case of slow etching kinetics is presented; it is predicted that the pattern evolution follows the expansion of the etchant at the substrate surface. The case of a chemically unstable etchant is considered. The model is then tested by inspecting the slow reductive patterning of a perfluorinated SAM. Good agreement is found with different independent SECM interrogation modes, depending on the insulating or conducting nature of the covered substrate. The surface transformation measurements are also compared to the reduction of solutions of perfluoroalkanes. The three-orders-of-magnitude-slower electron transfer observed at the immobilized molecules likely describes the large reorganization associated with the generation of a perfluoroalkyl-centered radical anion

Excess nitrogen as a marker of intense dinitrogen fixation in the Western Tropical South Pacific Ocean: impact on the thermocline waters of the South Pacific

As part of the Oligotrophy to UlTra-oligotrophy PACific Experiment cruise, which took place in the Western Tropical South Pacific during the austral summer (March–April 2015), we present data on nitrate, phosphate and on particulate and dissolved organic matter. The stoichiometric nitrogen-to-phosphorus ratios of the inorganic and organic material and the tracer N* are described. N* allows to trace changes in the proportion of fixed nitrogen due to diazotrophy and/or denitrification. Our results showed that the Melanesian archipelago waters between 160° E and 170° W are characterized by a deficit of nitrate and phosphate in the productive layer, significant dinitrogen fixation rates and an excess of particulate organic nitrogen compared to the canonical ratio of Redfield. A positive N* anomaly was observed in the productive layer reflecting the combined effect of phosphate uptake by diazotrophic organisms and remineralization of excess particulate organic nitrogen. The South Pacific Gyre waters between 170° W and 160° W were depleted in nitrate but rich in phosphate. Surface waters exhibited very low dinitrogen fixation rates, an absence of excess particulate organic nitrogen and a N* signal close to zero. The higher iron availability coupled with an absence of nitrate in the suface water of the Melanesian archipelago could stimulate the diazotrophic activity, which in turn will introduce excess nitrogen, deplete the surface waters in phosphate and be the explanation for the positive N* anomaly in the Melanesian archipelago waters. In the thermocline waters, the N* tracer revealed its full complexity, with notably the cumulative effect of the remineralization of particulate organic nitrogen and the effects of the mixing of water masses. At the global ocean scale, calculation of N* signal from the new Global Ocean Data Analysis Project version 2 database showed a strong spatial decoupling between the thermocline waters of the Eastern Tropical South Pacific and those of the Western Tropical South Pacific. A strongly positive N* anomaly was observed in the thermocline waters of the Western Tropical South Pacific in the Coral/Tasman Seas and in the southern part of the subtropical gyre between latitude 23° S and 32° S. A strong negative N* signal was observed in the waters of the Eestern Tropical South Pacific between latitude 5° S and 20° S–23° S. We hypothesise that the nitrogen excess observed in the thermocline waters of the Western Tropical South Pacific is transported eastward and then northward by the circulation of the South Pacific subtropical gyre and could influence positively the thermocline waters of the South Pacific being thus at the origin of the westward increase of the strongly negative N* signal transported by the South Equatorial Current

In-depth characterization of diazotroph activity across the western tropical South Pacific hotspot of N2 fixation (OUTPACE cruise)

Here we report N2 fixation rates from a  ∼ 4000km transect in the western and central tropical South Pacific, a particularly undersampled region in the world ocean. Water samples were collected in the euphotic layer along a west to east transect from 160°E to 160°W that covered contrasting trophic regimes, from oligotrophy in the Melanesian archipelago (MA) waters to ultra-oligotrophy in the South Pacific Gyre (GY) waters. N2 fixation was detected at all 17 sampled stations with an average depth-integrated rate of 631±286µmol N m−2 d−1 (range 196–1153µmol N m−2 d−1) in MA waters and of 85±79µmol N m−2 d−1 (range 18–172µmol N m−2 d−1) in GY waters. Two cyanobacteria, the larger colonial filamentous Trichodesmium and the smaller UCYN-B, dominated the enumerated diazotroph community ( > 80%) and gene expression of the nifH gene (cDNA > 105 nifH copies L−1) in MA waters. Single-cell isotopic analyses performed by nanoscale secondary ion mass spectrometry (nanoSIMS) at selected stations revealed that Trichodesmium was always the major contributor to N2 fixation in MA waters, accounting for 47.1–83.8% of bulk N2 fixation. The most plausible environmental factors explaining such exceptionally high rates of N2 fixation in MA waters are discussed in detail, emphasizing the role of macro- and micro-nutrient (e.g., iron) availability, seawater temperature and currents

Carbonate system distribution, anthropogenic carbon andacidification in the Western Tropical South Pacific (OUTPACE 2015transect)

The western tropical South Pacific was sampled along a longitudinal 4000 km transect (OUTPACE cruise, 18 Feb., 3 Apr. 2015) for measurement of carbonates parameters (total alkalinity and total inorganic carbon) between the Melanesian Archipelago (MA) and the western part of the South Pacific gyre (WGY). This manuscript reports this new dataset and derived properties: pH on the total scale (pHT) and the CaCO3 saturation state with respect to calcite (Ωcal) and aragonite (Ωara). We also estimate anthropogenic carbon (CANT) distribution in the water column using the TrOCA method (Tracer combining Oxygen, inorganic Carbon and total Alkalinity). Along the OUTPACE transect, CANT inventories of 37–43 mol m−2 were estimated with higher CANT inventories in MA waters (due to a deeper penetration of CANT in the intermediate waters) than in the WGY waters although highest CANT concentrations were detected in the sub-surface waters of WGY. By combining our OUTPACE dataset with data available in GLODAPv2 (1974–2009), temporal changes in oceanic inorganic carbon were evaluated. An increase of 1.3 to 1.6 µmol kg−1 a−1 for total inorganic carbon in the upper thermocline waters is estimated whereas CANT increases of 1.1 to 1.2 µmol kg−1 a−1. In the MA intermediate waters (27 kg m−3 < σθ < 27.2 kg m−3) an increase of 0.4 µmol kg−1 a−1 of CANT is detected. Our results suggest a clear progression of ocean acidification in the western tropical South Pacific with a decrease of the oceanic pH of up to −0.0027 a−1 and a shoaling of the saturation depth for aragonite of up to 200 m since the pre-industrial period

Sensitive Determination of the Dissolved Phosphate Pool for an Improved Resolution of Its Vertical Variability in the Surface Layer: New Views in the P-Depleted Mediterranean Sea

An accurate understanding of the biogeochemistry of dissolved phosphate pool in the upper waters of P-depleted oceanic regions is constrained by the low sensitivity of routine phosphate measurements. In this study, by using the sensitive Liquid Waveguide Capillary Cell method, we report the first extensive cross-basin survey of nanomolar dissolved inorganic phosphate (DIP) and dissolved organic phosphate (DOP) concentration in P-depleted surface waters of the Mediterranean Sea during the stratification period. In the north western Mediterranean Sea (NWMS), DIP above the mixed layer depth (MLD) ranged between 4.9 and 26.5 nM. Along an E-W transect crossing Ionian and Tyrrhenian Seas (E-W transect), DIP above the MLD was lower, ranging between 0.9 and 11.4 nM. Contrarily to the traditional view of a depleted and invariant surface dissolved phosphate pool, a significant vertical variability of DIP and DOP was revealed in upper waters. A positive gradient of DIP was observed above the phosphacline, between the MLD and the deep chlorophyll maximum (DCM) depth, suggesting a potential diffusion of new phosphate to near-surface waters, even under stratified conditions. Interestingly, despite this apparent DIP availability, a significant negative gradient of DOP concentration was observed in the same layer. Finally, the positive gradient in DIP coincided with a significant increase in N:P ratio, suggesting a higher rate of increase of N than of P. The results obtained in this study indicate that acquiring nanomolar DIP data is a sine qua non condition for the comprehension and prediction of the biogeochemical functioning of P-depleted oceanic regions, such as the Mediterranean Sea

Phosphorus cycling in the upper waters of the Mediterranean Sea (PEACETIME cruise): relative contribution of external and internal sources

International audienceAbstract. The study of phosphorus cycling in phosphate-depleted oceanic regions, such as the Mediterranean Sea, has long suffered from methodological limitations, leading to a simplistic view of a homogeneous surface phosphate pool with concentrations below the detection limit of measurement above the phosphacline. During the PEACETIME (Process studies at the air-sea interface after dust deposition in the Mediterranean Sea) cruise, carried out from 10 May to 11 June 2017, we conducted co-located measurements of phosphate pools at the nanomolar level, alkaline phosphatase activities and atmospheric deposition of phosphorus, across a longitudinal gradient from the west to the central Mediterranean Sea. In the phosphate-depleted layer (PDL), between the surface and the phosphacline, nanomolar phosphate was low and showed little variability across the transect spanning from 6 ± 1 nmol L−1 in the Ionian basin to 15 ± 4 nmol L−1 in the westernmost station. The low variability in phosphate concentration contrasted with that of alkaline phosphatase activity, which varied over 1 order of magnitude across the transect. Nanomolar phosphate data revealed gradients of phosphate concentration over density inside the PDL ranging between 10.6 ± 2.2 µmol kg−1 in the westernmost station to values close to zero towards the east. Using the density gradients, we estimated diapycnal fluxes of phosphate to the PDL and compared them to atmospheric deposition, another external source of phosphate to the PDL. Phosphate supply to the PDL from dry deposition and diapycnal fluxes was comparable in the western part of the transect. This result contrasts with the longtime idea that, under stratification conditions, the upper waters of the Mediterranean Sea receive new P almost exclusively from the atmosphere. The contribution of atmospheric deposition to external P supply increased under the occurrence of rain and Saharan dust. Although this finding must be taken cautiously given the uncertainties in the estimation of diapycnal fluxes, it opens exciting questions on the biogeochemical response of the Mediterranean Sea, and more generally of marine oligotrophic regions, to expected changes in atmospheric inputs and stratification regimes. Taken together, external sources of phosphate to the PDL contributed little to total phosphate requirements which were mainly sustained by in situ hydrolysis of dissolved organic phosphorus. The results obtained in this study show a highly dynamic phosphorus pool in the upper layer of the euphotic zone, above the phosphacline, and highlight the convenience of combining highly sensitive measurements and high-resolution sampling to precisely depict the shape of phosphate profiles in the euphotic zone with still unexplored consequences on P fluxes supplying this crucial layer for biogeochemical cycles