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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Biogeochemistry 29 (1995), S. 159-181 
    ISSN: 1573-515X
    Keywords: iron ; microbial mat ; porewater ; pyrite ; sedimentary geochemistry ; Spartina alterniflora ; sulfur
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract This study combines an analysis of porewater chemistry with new, solid phase wet chemical extractions to examine the seasonal cycling of Fe in vegetated and unvegetated (cyanobacterial mat) saltmarsh sediments. Saltmarsh sediments are shown to contain more solid phase reactive Fe than other marine sediments studied so far. From the partitioning and speciation of solid Fe, and solid/soluble reduced S analysis in 10 sediment cores, we have observed that a majority of solid Fe in these sediments is cycled rapidly and completely between oxidized reactive Fe and reduced Fe as pyrite. Vegetated porewaters showed a lower pH and much higher Fe(II) concentrations on average than unvegetated porewaters in the top 10 cm, whereas sulfate, alkalinity, and sulfide concentrations were similar in the two environments. The amorphous Fe(III) oxide fraction showed a high negative correlation to solid and soluble reduced S (r 2 = −0.86 and −0.71, respectively) in surface vegetated sediments whereas the crystalline Fe(III) oxide fraction showed a high negative correlation (r 2 = −0.96) to sulfide only at depth. Though reactive Fe was observed in unvegetated sediments, no seasonal trend was apparent and the speciation of solid Fe revealed that most of it was reduced. Solid phase and porewater chemistry support the dominant role of the biota (Spartina alterniflora and bacteria) in controlling the reactivity of Fe and suggest that the current definition of solid phase, reactive Fe should be expanded to include crystalline Fe(III) minerals which are available for pyrite formation in saltmarsh sediments. In support of previous saltmarsh studies, we present evidence that the redox cycle of solid Fe is controlled by sulfate reduction and sediment oxidation which respond to both annual cycles (light, temperature) and to short-term, episodic effects such as weather and tides.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1573-515X
    Keywords: Dissolved sulfur species ; inorganic solid sulfur ; pyrite ; salt marshes ; soluble iron ; short term changes ; 210Pb ; 137Cs ; 7Be
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Porewater species and solid inorganic sulfur speciation were measured before and after the spring tide (which occurs over a 6–7 day period) during a portion of the summer seasons of 1987, 1988 and 1989 in Great Marsh, Delaware. Samples were taken from two locations in the marsh (near creek and mid-marsh) inhabited by the short form of Spartina alterniflora. In 1987, pyrite and thiosulfate decreased over the spring tide. Other porewater species also underwent large changes in concentration — in some cases order of magnitude. However, in 1988 and 1989, there was no evidence for short term changes of pyrite. In 1988, drought conditions were prevalent throughout the sampling whereas in 1989 wet conditions were prevalent. Porewater parameters demonstrated that oxidation was extensive during the sampling period in 1988 and related to dessication. Both climatic and spring tidal flooding conditions have a pronounced affect on the chemistry of the system. Data from atmospherically derived radionuclides (210Pb,137Cs,7Be) indicate that bioturbation is not as important at the mid-marsh site as at the near creek site. Porewater chloride and7Be data support infiltration of overlying waters at both sites. The decrease in pyrite over the spring tide in the 1987 samples is related to oxidation. The possible oxidants are discussed and Fe(III) is the favored direct oxidant based upon a review of field and laboratory data. Iron(III) was measured in several filtered porewater samples. However, we cannot indicate with certainty that the Fe(III) is always soluble. The Fe(III) measured may be colloidal or complexed. Pyrite oxidation is noted when the Fe(III) to Fe(II) ratio, pH and alkalinity are all low.
    Type of Medium: Electronic Resource
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