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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Analytical chemistry 49 (1977), S. 2149-2154 
    ISSN: 1520-6882
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 5 (1976), S. 154-168 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The bremsstrahlung spectrum from a thick specimen bombarded with 20 ke V electrons is studied with emphasis on the shape rather than the absolute intensity in the energy range 1-10 keV. Monte Carlo calculations are described in detail and used to compare the absorption corrections for characteristic and continuous (bremsstrahlung) radiation from a thick specimen and to determine the extent to which anisotropy modifies the intensity distribution of the continuum. The absorption corrections are found to differ by roughly 5% for f(χ) = 0.5 and 10% for f(χ) = 0.2, but it is shown that the ratio of the corrections can be predicted by using the ratio of two Philibert-type formulae. Anisotropy has little influence on the absorption correction but changes in atomic number or geometry may result in the intensity distribution being altered by typically 5-10% across the energy range 1-10keV. Numerical integration gives values for the generated brems-strahlung intensity which are used in constructing an expression to represent the functional form of the background. Although experimental spectra confirm this to be superior to the combination of Kramers' law and a characteristic absorption expression, several sources of error at low energies, including bremsstrahlung from the Be window, are pointed out and improvements suggested. In order to eliminate the principal uncertainty, that of the overall efficiency curve for a Si(Li) detector and pulse-processor, it is recommended that a stored spectrum be used as a ‘background standard’ for explicit background corrections. Errors are then reduced to the 0.1% absolute concentration level, which is suitable for quantitative analysis.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 6 (1977), S. 94-103 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Pile-up rejection is commonly achieved through use of an auxiliary inspection channel with short time constants but low energy events can be missed because of electronic noise. A formula is derived to predict the detection efficiency of such a channel and the effect of adjusting the discriminator threshold or changing the time constants is demonstrated. When pulses are missed, spectrum distortion and counting losses are greater than would be predicted from the specified pulse pair resolution time so it is important to optimize the inspector adjustment. A mathematical analysis leads to formulae which can be used to correct for residual counting losses and sum peaks, and the relationship between empirical parameters obtained for these formulae and time constants in the electronics is demonstrated. The present state of the art in noise performance dictates that 1 μs is about the best resolution time that can be achieved for 1 ke V pulses. For further improvements, a fast beam switching technique could be used which would improve pulse pair resolution by a factor of three or more and thus afford adequate protection for the very low energy pulses that would be encountered with thin-window or windowless solid-state detectors.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 7 (1978), S. 132-137 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Linear and non-linear least-squares profile-fitting procedures are compared in their ability to resolve severely overlapping peaks in X-ray spectra. With linear methods, errors due to inaccuracies in peak position and width are likely to be greater than statistical errors for a spectrom with 500 K counts unless the spectrometer can maintain a temporal and count are stability of 1 eV or better. While non-linear, iterative, procedures can accomodate changes in position and width of peaks, they are difficult to analyse therotically so simulations have been designed to examine performance. Examples are given where, despite exact knowledge of peak width and separation, the best fit in the ‘chi-square’ sense corresponds to peak heights which are totally incorrect. Estimates of statistical error are virtually meaningless when convergence occurs to such inapprooriate minima but rather precise starting values for the unknown parameters are required to ensure convergence to a relistic solution. In view of these potential difficulties and the lack of any theoritical analysis of the instabilties introduced by statistical noise, errors in background subtraction or unsuitable parameterization of peak models, it is felt that linear method are preferable. Thus, high spectrometer stability still seems to be unavoidable if one is to exploit the availabler statistical accuracy in an X-ray spectrum.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Publication Date: 2022-05-25
    Description: Author Posting. © Elsevier B.V., 2007. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Deep Sea Research Part II: Topical Studies in Oceanography 54 (2007): 1999-2019, doi:10.1016/j.dsr2.2007.06.019.
    Description: The annual phytoplankton bloom occurring north of the Crozet Plateau provides a rare opportunity to examine the hypothesis that natural iron fertilisation can alleviate HNLC conditions normally associated with the Southern Ocean. Therefore, during CROZEX, a large multidisciplinary study performed between November 2004 and January 2005, measurements of total dissolved iron (DFe, ≤ 0.2 μm) were made on seawater from around the islands and atmospheric iron deposition estimated from rain and aerosol samples. DFe concentrations were determined by flow injection analysis with N,N-dimethyl- pphenylenediamine dihydrochloride (DPD) catalytic spectrophotometric detection. DFe concentrations varied between 0.086 nM and 2.48 nM, with low values in surface waters. Enrichment of dissolved iron (〉1 nM) at close proximity to the islands suggests that the plateau and the associated sediments are a source of iron. Waters further north also appear to be affected by this input of coastal and shelf origin, although dissolved iron concentrations decrease as a function of distance to the north of the plateau with a gradient of ~0.07 nM.km-1 at the time of sampling. Using lateral and vertical diffusion coefficients derived from Ra isotope profiles and also estimates of atmospheric inputs, it was then possible to estimate a DFe concentration of ~0.55 nM to the north of the islands prior to the bloom event, which is sufficient to initiate the bloom, the lateral island source being the largest component. A similar situation is observed for other Sub-Antarctic Islands such as Kerguelen, South Georgia, that supply dissolved iron to their surrounding waters, thus, enhancing chlorophyll concentrations.
    Description: These cruises were the two first of the Crozex project, which was a contribution to a British BICEP (Biophysical Interactions and Control of Export Production)-NERC program. This work was also supported by NERC Grant NE/B502844/1 and a NERC PhD studentship for M.F.
    Keywords: Dissolved iron ; Crozet Islands ; Crozet Islands ; HNLC
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
    Format: application/pdf
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  • 6
    Publication Date: 2022-05-26
    Description: Author Posting. © Elsevier B.V., 2007. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Deep Sea Research Part II: Topical Studies in Oceanography 54 (2007): 1989-1998, doi:10.1016/j.dsr2.2007.06.003.
    Description: Elevated levels of productivity in the wake of Southern Ocean island systems are common despite the fact that they are encircled by high nutrient low chlorophyll (HNLC) waters. In the Crozet Plateau region, it has been hypothesized that iron from island runoff or sediments of the plateau could be fueling the austral summer phytoplankton bloom. Here, we use radium isotopes to quantify the rates of surface ocean iron supply fueling the bloom in the Crozet Plateau region. A 1-D eddy-diffusion-mixing model applied to a 228Ra profile (t1/2 = 5.75 yr) at a station north of the islands suggested fast vertical mixing in the upper 300 m (Kz = 11-100 cm2 s- 1) with slower mixing between 300 and 1000 m (Kz = 1.5 cm2 s-1). This estimate is discussed in the context of Kz derived from the CTD/LADCP data. In combination with the dissolved Fe profile at this location, we estimated a vertical flux of between 5.6 and 31 nmol Fe m-2 d-1. The cross-plateau gradients in the short-lived radium isotopes, 224Ra (t1/2 = 3.66 d) and 223Ra (t1/2 = 11.4 d), yielded horizontal eddy diffusivities (Kh) of 39 m2 s-1 and 6.6 m2 s-1, respectively. If we assume that the islands (surface runoff) alone were supplying dissolved Fe to the bloom region, then the flux estimates range from 2.3 to 14 nmol Fe m-2 d-1. If the plateau sediments are considered a source of Fe, and conveyed to the bloom region through deep winter mixing combined with horizontal transport, then this flux may be as high as 64 to 390 nmol Fe m-2 d-1. Combined, these Fe sources are sufficient to initiate and maintain the annual phytoplankton bloom.
    Description: This work was funded by grants from the Natural Environment Research Council [NE/B502844/1] and the National Science Foundation (ANT-0443869 to M.A.C).
    Keywords: Radium isotopes ; Iron ; Productivity ; Ocean mixing ; Southern Ocean
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
    Format: application/pdf
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