27 research outputs found
Estimates of new and total productivity in central Long Island Sound from in situ measurements of nitrate and dissolved oxygen
Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Estuaries and Coasts 36 (2013): 74-97, doi:10.1007/s12237-012-9560-5.Biogeochemical cycles in estuaries are regulated by a diverse set of physical and
biological variables that operate over a variety of time scales. Using in situ optical sensors, we
conducted a high-frequency time-series study of several biogeochemical parameters at a mooring
in central Long Island Sound from May to August 2010. During this period, we documented
well-defined diel cycles in nitrate concentration that were correlated to dissolved oxygen, wind
stress, tidal mixing, and irradiance. By filtering the data to separate the nitrate time series into
various signal components, we estimated the amount of variation that could be ascribed to each
process. Primary production and surface wind stress explained 59% and 19%, respectively, of the
variation in nitrate concentrations. Less frequent physical forcings, including large-magnitude wind events and spring tides, served to decouple the relationship between oxygen, nitrate, and
sunlight on about one-quarter of study days. Daytime nitrate minima and dissolved oxygen
maxima occurred nearly simultaneously on the majority (> 80%) of days during the study period;
both were strongly correlated with the daily peak in irradiance. Nighttime nitrate maxima
reflected a pattern in which surface-layer stocks were depleted each afternoon and recharged the
following night. Changes in nitrate concentrations were used to generate daily estimates of new
primary production (182 ± 37 mg C m-2 d-1) and the f-ratio (0.25), i.e., the ratio of production
based on nitrate to total production. These estimates, the first of their kind in Long Island Sound,
were compared to values of community respiration, primary productivity, and net ecosystem
metabolism, which were derived from in situ measurements of oxygen concentration. Daily
averages of the three metabolic parameters were 1660 ± 431, 2080 ± 419, and 429 ± 203 mg C
m-2 d-1, respectively. While the system remained weakly autotrophic over the duration of the
study period, we observed very large day-to-day differences in the f-ratio and in the various
metabolic parameters.This work was supported by the Yale
Institute for Biospheric Studies, the Sounds Conservancy of the Quebec-Labrador Foundation,
and the Yale School of Forestry and Environmental Studies Carpenter-Sperry Fund.2014-01-0
Physicochemical Characterization of Passive Films and Corrosion Layers by Differential Admittance and Photocurrent Spectroscopy
Two different electrochemical techniques, differential admittance and photocurrent spectroscopy, for the characterization of electronic and solid state properties of passive films and corrosion layers are described and critically evaluated. In order to get information on the electronic properties of passive film and corrosion layers as well as the necessary information to locate the characteristic energy levels of the passive film/electrolyte junction like: flat band potential (Ufb), conduction band edge (EC) or valence band edge (EV), a wide use of Mott-Schottky plots is usually reported in corrosion science and passivity studies. It has been shown, in several papers, that the use of simple M-S theory to get information on the electronic properties and energy levels location at the film/electrolyte interface can be seriously misleading and/or conflicting with the physical basis underlying the M-S theory. A critical appraisal of this approach to the study of very thin and thick anodic passive film grown on base-metals (Cr, Ni, Fe, SS etc..) or on valve metals (Ta, Nb, W etc..) is reported in this work, together with possible alternative approach to overcome some of the mentioned inconsistencies. At this aim the theory of amorphous semiconductor Schottky barrier, introduced several years ago in the study of passive film/electrolyte junction, is reviewed by taking into account some of the more recent results obtained by the present authors. Future developments of the theory appears necessary to get more exact quantitative information on the electronic properties of passive films, specially in the case of very thin film like those formed on base metals and their alloys.
The second technique described in this chapter, devoted to the physico-chemical characterization of passive film and corrosion layers, is a more recent technique based on the analysis of the photo-electrochemical answer of passive film/electrolyte junction under illumination with photons having suitable energy. Such a technique usually referred to as Photocurrent Spectroscopy (PCS) has been developed on the basis of the large research effort carried out by several groups in the 1970âs and aimed to investigate the possible conversion of solar energy by means of electrochemical cells. In this work the fundamentals of semiconductor/electrolyte junctions under illumination will be highlighted both for crystalline and amorphous materials. The role of amorphous nature and film thickness on the photo-electrochemical answer of passive film/solution interface is reviewed as well the use of PCS for quantitative analysis of the film composition based on a semi-empirical correlation between optical band gap and difference of electronegativity of film constituents previously suggested by the present authors. In this frame the results of PCS studies on valve metal oxides and valve metal mixed oxides will be discussed in order to show the validity of the proposed method. The results of PCS studies aimed to get information on passive film composition and carried out by different authors on base metals (Fe, Cr, Ni) and their alloys, including stainless steel, will be also compared with compositional analysis carried out by well-established surface analysis techniques