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Aquatic Geochemistry (v.9, #1)
Analysis of the Major Fe Bearing Mineral Phases in Recent Lake Sediments by EXAFS Spectroscopy by Lorenzo Spadini; Markus Bott; Bernhard Wehrli; Alain Manceau (pp. 1-17).
Extended X-ray absorption fine structure (EXAFS) spectroscopy and chemical analyses were combined to determine the Fe bearing minerals in recent lake sediments from Baldeggersee (Switzerland). The upper section of a laminated sediment core, deposited under eutrophic conditions, was compared to the lower part from an oligotrophic period. Qualitative analysis of FeK EXAFS agreed well with chemical data: In the oligotrophic section Fe(II)–O and Fe(III)–O specieswere present, whereas a significant fraction of Fe(II)–S sulfides was strongly indicated in the eutrophic part. A statistical analysis was performed by least square fitting of normalized reference spectra. The set of reference minerals included Fe(III) oxides and Fe(II) sulfides, carbonates and phosphates. In the oligotrophic regime no satisfying fit was obtained using the set of reference spectra, indicating that siderite (FeCO3) was not present in a significant amount in these carbonate-rich sediments. Simulated EXAFS spectra for a(Cax, Fe1-x)CO3solid solution allowed reconstructing the specificfeatures of the experimental spectra, suggesting that this phase was the dominant Fe carrier in the oligotrophic section of the core. In the eutrophic part, mackinawite was positively identified and represented the dominant Fe(II) sulfide phase. This finding agreed with chemical extraction, which indicated that18–40 mol% of Fe was contained in the acid volatile iron sulfide fraction. EXAFS spectra of the eutrophic section were best fitted by considering the admixture of mackinawite and the Fe–Ca carbonate phase inferred to be predominant in the oligotrophic regime.
Keywords: acid volatile sulfides; EXAFS; iron carbonates; lake sediments; lake sediments; mackinawite; selective extraction; solid solution; speciation
Sediment Phosphorus Chemistry and Microbial Biomass along a Lowland New Zealand Stream by R. W. McDowell (pp. 19-40).
An evaluation of the distribution of P concentrations in streamflow, P fractions andthe microbial biomass P pool was made of bed and bank sediments along a lowlandstream in New Zealand. Agricultural intensification increased downstream. However,most P fractions decreased downstream (total P decreased from c. 400 to 250 mg kg-1) in bed sediments, while P in streamflow remained relatively constant (generally < 0.005 mg l-1) and sediment microbial P increased from 2 to 8 mg kg-1. An investigation of P release from dried and rewetted sediments showed that solution P (CaCl2-P) increased, on average > 300%, and proportional to the size of the microbial biomass P pool before drying, except in sediments with much organic carbon (OC). When supplied with a P source (1 mg l-1) and then simultaneously with a C source (glucose, 100 mg l-1), all sediment behaved similarly and biotic sorption accounted for, on average, 27 and 34% of the total sediment uptake, respectively (maximum of 58%). The quantity of P taken up was related to the initial size of the microbial biomass P pool, and the availability of P as influenced by organic P complexes and OC. The sediment microbial biomass represents a transient, but small store of P could be useful to indicate bioavailable P inputs.
Keywords: Stream; fluvial; sediment; phosphorus; microbial biomass P
Determination of the Optimum Sampling Intervals in Sediment Pore Waters Using the Autocovariance Function by John W. Morse; Steven F. Dimarco; Karen S. Sell; Andrew B. Hebert (pp. 41-57).
An approach to scaling that has found considerable utility inthe field of physical oceanography is based on theauto-covariance function (ACF). It is demonstrated to alsobe useful in determining the characteristic length scale of thedominant variance of dissolved sulfide and ferrous iron inanoxic pore waters. The method begins with the analysisof a data series in which the measurement sampling intervalis smaller than the expected length scales. A least squarespolynomial fit to the data representing a background field isthen removed from the data series making possible the analysisof the variability superimposed on the background field. Thecharacteristic length scale is then defined as the distancein which the measurements become uncorrelated. This usuallyoccurs at a significance-level or zero-crossing of the ACF.Characteristic lengths obtained for sediments from a varietyof coastal environments are not distinguishable betweensecond and third order polynomial fits with average valuesand standard deviations of, respectively, 7.0 ± 2.7 mm and6.1 ± 2.3 mm. These values are close to the typical burrowdiameter of 7.5 mm used by Aller (1978) in his bioirrigationmodel for sediment diagenesis. These results indicate thatmacrofauna dwelling in the sediment are probably responsiblefor the variability, although in the seagrass meadow rhizomesmay also play a role.
Keywords: scaling; sediment biogeochemistry; diagenesis; pore water; iron; hydrogen sulfide