Secondary mineralization pathways induced by dissimilatory iron reduction of ferrihydrite under advective flow   总被引：6，自引：0，他引：6  

Colleen M Hansel  Shawn G Benner  Jim Neiss  Ravi K Kukkadapu 《Geochimica et cosmochimica acta》2003,67(16):2977-2992

Iron (hydr)oxides not only serve as potent sorbents and repositories for nutrients and contaminants but also provide a terminal electron acceptor for microbial respiration. The microbial reduction of Fe (hydr)oxides and the subsequent secondary solid-phase transformations will, therefore, have a profound influence on the biogeochemical cycling of Fe as well as associated metals. Here we elucidate the pathways and mechanisms of secondary mineralization during dissimilatory iron reduction by a common iron-reducing bacterium, Shewanella putrefaciens (strain CN32), of 2-line ferrihydrite under advective flow conditions. Secondary mineralization of ferrihydrite occurs via a coupled, biotic-abiotic pathway primarily resulting in the production of magnetite and goethite with minor amounts of green rust. Operating mineralization pathways are driven by competing abiotic reactions of bacterially generated ferrous iron with the ferrihydrite surface. Subsequent to the initial sorption of ferrous iron on ferrihydrite, goethite (via dissolution/reprecipitation) and/or magnetite (via solid-state conversion) precipitation ensues resulting in the spatial coupling of both goethite and magnetite with the ferrihydrite surface. The distribution of goethite and magnetite within the column is dictated, in large part, by flow-induced ferrous Fe profiles. While goethite precipitation occurs over a large Fe(II) concentration range, magnetite accumulation is only observed at concentrations exceeding 0.3 mmol/L (equivalent to 0.5 mmol Fe[II]/g ferrihydrite) following 16 d of reaction. Consequently, transport-regulated ferrous Fe profiles result in a progression of magnetite levels downgradient within the column. Declining microbial reduction over time results in lower Fe(II) concentrations and a subsequent shift in magnetite precipitation mechanisms from nucleation to crystal growth. While the initial precipitation rate of goethite exceeds that of magnetite, continued growth is inhibited by magnetite formation, potentially a result of lower Fe(III) activity. Conversely, the presence of lower initial Fe(II) concentrations followed by higher concentrations promotes goethite accumulation and inhibits magnetite precipitation even when Fe(II) concentrations later increase, thus revealing the importance of both the rate of Fe(II) generation and flow-induced Fe(II) profiles. As such, the operating secondary mineralization pathways following reductive dissolution of ferrihydrite at a given pH are governed principally by flow-regulated Fe(II) concentration, which drives mineral precipitation kinetics and selection of competing mineral pathways.  相似文献   

A millennial-scale record of Holocene tsunamis on the Kronotskiy Bay coast, Kamchatka, Russia     

Tatiana K PineginaJoanne Bourgeois  Lilia I BazanovaIvan V Melekestsev  Olga A Braitseva 《Quaternary Research》2003,59(1):36-47

Deposits from as many as 50 large tsunamis during the last 7000 years are preserved on the Pacific coast of the Kamchatka Peninsula near the mouth of the Zhupanova River, southern Kronotskiy Bay. These deposits are dated and correlated using Holocene marker tephra layers. The combined, preserved record of tsunami deposits and of numerous marker tephras on Kamchatka offers an unprecedented opportunity to study tsunami frequency. For example, from the stratigraphy along southern Kronotskiy Bay, we estimate frequency of large tsunamis (>5 m runup). In the last 3000 years, the minimum frequency is about one large tsunami per 100 years, and the maximum about one large tsunami per 30 years; the latter frequency occurred from about 0 to 1000 A.D. This time interval corresponds to a period of increased seismicity and volcanic activity that appears to be recorded in many places on the Kamchatka Peninsula.  相似文献   

Determination of food web support and trophic position of the mummichog,Fundulus heteroclitus, in New Jersey smooth cordgrass (Spartina alterniflora), common reed (Phragmites australis), and restored salt marshes     

C. A. Currin  S. C. Wainright  K. W. Able  M. P. Weinstein  C. M. Fuller 《Estuaries and Coasts》2003,26(2):495-510

The invasion ofPhragmites australis into tidal marshes formerly dominated bySpartina alterniflora has resulted in considerable interest in the consequences of this invasion for the ecological functions of marsh habitat. We examined the provision of trophic support for a resident marsh fish,Fundulus heteroclitus, in marshes dominated byP. australis, byS. alterniflora, and in restored marshes, using multiple stable isotope analysis. We first evaluated our ability to distinguish among potential primary producers using the multiple stable isotope approach. Within a tidal creek system we found significant marsh and elevation effects on microalgal isotope values, and sufficient variability and overlap in primary producer isotope values to create some difficulty in identifying unique end members. The food webs supportingF. heteroclitus production were examined using dual isotope plots. At both sites, the δ¹³C values ofF. heteroclitus were clustered over values for benthic microalgae (BMI) and approximately midway between δ¹³C values ofSpartina andPhragmites. Based on comparisons of fish and primary producer δ¹³C, δ¹⁵N, and δ³⁴S values, and consideration ofF. heteroclitus feeding habits, we conclude that BMI were a significant component of the food web supportingF. heteroclitus in these brackish marshes, especially recently-hatched fish occupying pools on the marsh surface. A 2‰ difference in δ¹³C betweenFundulus occupying nearly adjacentSpartina andPhragmites marshes may be indicative of relatively less reliance on BMI and greater reliance onPhragmites production inPhragmites-dominated marshes, a conclusion consistent with the reduced BMI biomass found inPhragmites marshes. The mean δ¹³C value ofF. heteroclitus from restored marshes was intermediate between values of fish from naturally occurringSpartina marshes and areas invaded byPhragmites. We also examined the isotopic evidence for ontogenetic changes in the trophic position of larval and juvenileF. heteroclitus. We found significant positive relationships betweenF. heteroclitus δ¹⁵N values and total length, reflective of an increase in trophic position as fish grow.F. heteroclitus δ¹⁵N values indicate that these fish are feeding approximately two trophic levels above primary producers.  相似文献   

Deconvolving the δO seawater component from subseasonal coral δO and Sr/Ca at Rarotonga in the southwestern subtropical Pacific for the period 1726 to 1997     

Lei Ren  Braddock K. Linsley  Daniel P. Schrag 《Geochimica et cosmochimica acta》2003,67(9):1609-1621

To reconstruct oceanographic variations in the subtropical South Pacific, 271-year long subseasonal time series of Sr/Ca and δ¹⁸O were generated from a coral growing at Rarotonga (21.5°S, 159.5°W). In this case, coral Sr/Ca appears to be an excellent proxy for sea surface temperature (SST) and coral δ¹⁸O is a function of both SST and seawater δ¹⁸O composition (δ¹⁸O_sw). Here, we focus on extracting the δ¹⁸O_sw signal from these proxy records. A method is presented assuming that coral Sr/Ca is solely a function of SST and that coral δ¹⁸O is a function of both SST and δ¹⁸O_sw. This method separates the effects of δ¹⁸O_sw from SST by breaking the instantaneous changes of coral δ¹⁸O into separate contributions by instantaneous SST and δ¹⁸O_sw changes, respectively. The results show that on average δ¹⁸O_sw at Rarotonga explains ∼39% of the variance in δ¹⁸O and that variations in SST explains the remaining ∼61% of δ¹⁸O variance. Reconstructed δ¹⁸O_sw shows systematic increases in summer months (December-February) consistent with the regional pattern of variations in precipitation and evaporation. The δ¹⁸O_sw also shows a positive linear correlation with satellite-derived estimated salinity for the period 1980 to 1997 (r = 0.72). This linear correlation between reconstructed δ¹⁸O_sw and salinity makes it possible to use the reconstructed δ¹⁸O_sw to estimate the past interannual and decadal salinity changes in this region. Comparisons of coral δ¹⁸O and δ¹⁸O_sw at Rarotonga with the Pacific decadal oscillation index suggest that the decadal and interdecadal salinity and SST variability at Rarotonga appears to be related to basin-scale decadal variability in the Pacific.  相似文献   

Submarine hydrothermal mineralization in the Okinawa Trough, SW of Japan: an overview   总被引：3，自引：0，他引：3  

G. P. Glasby  K. Notsu   《Ore Geology Reviews》2003,23(3-4):299-339

The Okinawa Trough is a heavily sedimented, rifted back-arc basin formed in an intracontinental rift zone. Submarine hydrothermal activity is located within the six back-arc rifts located in the middle and southern Okinawa Trough and its distribution is controlled principally by tectonic factors. Subduction of the Daito and Gagua Ridges beneath the Ryukyu Arc has resulted in fracturing of the brittle lithosphere beneath the Okinawa Trough. Hydrothermal activity is strongest in the volcanic arc-rift migration phenomenon (VAMP) area plus the JADE site and Southernmost Part of the Okinawa Trough (SPOT) area which form the prolongation of these two ridges. These areas are characterized by extremely high heat flow locally. Submarine hydrothermal fluids from the Okinawa Trough tend to be strongly influenced by interaction of the hydrothermal fluids with organic matter in the sediment resulting in high alkalinity and NH₄⁺ concentrations of the fluids. The fluids also contain high concentrations of CO₂ of magmatic origin. Submarine hydrothermal mineralization in the trough is diverse. The CLAM site consists principally of carbonate chimneys. Interaction of the hydrothermal fluid with organic matter in the sediment is particularly strong at this site. This is most probably a sediment-hosted deposit in which sulphide minerals have deposited within the sediment column leaving ‘spent ore-fluids’ to emerge at the seafloor. The JADE site consists of active and inactive sulphide–sulphate chimneys and mounds. The Zn–Pb-rich sulphides at this site contain the highest concentrations of Pb, Ag and Au so far recorded in submarine hydrothermal sulphide deposits. At Minami-Ensei Knoll and Hatoma Knoll, active and inactive chimneys consist principally of anhydrite and barite as a result of phase separation of the hydrothermal fluids beneath the seafloor. An intense black smoker has recently been discovered at Yonaguni Knoll in the SPOT area. If it is confirmed that sulphide mineralization is dominant at this site, this could be a highly prospective area. The most prospective areas for economic-grade minerals in the Okinawa Trough appear to be the JADE site and the SPOT area.  相似文献   

Metamorphic and deformational imprint of Cambrian–Lower Ordovician rifting in the Ossa-Morena Zone (Iberian Massif, Spain)     

I. Expsito  J. F. Simancas  F. Gonzlez Lodeiro  F. Bea  P. Montero  K. Salman 《Journal of Structural Geology》2003,25(12):2077-2087

The high-temperature metamorphism recorded in the Valuengo and Monesterio areas constitutes a rare occurrence in the Ossa-Morena Zone of Southwest Iberia, where low-grade metamorphism dominates. The metamorphism of the Valuengo area has been previously considered either Cadomian or Variscan in age, whereas that of Monesterio has been interpreted as a Cadomian imprint. However, these areas share important metamorphic and structural features that point towards a common tectonometamorphic evolution. The metamorphism of the Valuengo and Monesterio areas affects Late Proterozoic and Early Cambrian rocks, and is syn-kinematic with a top-to-the-north mylonitic foliation, which was subsequently deformed by early Variscan folds and thrusts. The U–Pb zircon age (480±7 Ma) we have obtained for an undeformed granite of the Valuengo area is consistent with our geological observations constraining the age of the metamorphism. We propose that this high-temperature metamorphic imprint along a NW–SE ductile extensional shear zone is related to the crustal extension that occurred in the Ossa-Morena Zone during the Cambro-Ordovician rifting. In the same way, the tectonothermal effect of the preorogenic rifting stage may have been wrongly attributed to orogenic processes in other regions as well as in this one.  相似文献   

Raman scattering and X-ray diffraction study of the thermal decomposition of an ettringite-group crystal     

S. K. Deb  M. H. Manghnani  K. Ross  R. A. Livingston  P. J. M. Monteiro 《Physics and Chemistry of Minerals》2003,30(1):31-38

 A Raman scattering and X-ray diffraction study of the thermal decomposition of a naturally occurring, ettringite-group crystal is presented. Raman spectra, recorded with increasing temperature, indicate that the thermal decomposition begins at ≈55 °C, accompanied by dehydration of water molecules from the mineral. This is in contrast to previous studies that reported higher temperature breakdown of ettringite. The dehydration is completed by 175 °C and this results in total collapse of the crystalline structure and the material becomes amorphous. The Raman scattering results are supported by X-ray diffraction results obtained at increasing temperatures. Received: 9 July 2001 / Accepted: 14 August 2002  相似文献   

Kinetics and Mechanism of Trithionate and Tetrathionate Oxidation at Low pH by Hydroxyl Radicals     

Gregory K. Druschel  Robert J. Hamers  George W. Luther III  Jillian F. Banfield 《Aquatic Geochemistry》2003,9(2):145-164

The oxidation kinetics of trithionate (S₃O₆^2- ) and tetrathionate (S₄O ₆ ^2- ) with hydroxyl radicals (OH^*) have been investigated in systems analogous to acid mine drainage (AMD) environments. The discovery of hydroxyl radical (OH^*) formation on pyrite surfaces (Borda et al., 2003) suggests hydroxyl radicals may affect the oxidation kinetics of intermediate sulfur species such as tetrathionate. Cyclic voltammetry experiments in acidic solutions indicate that the reaction of S₄O ₆ ^2- with OH^* goes through an unknown intermediate, tentatively assigned as S₃O ₄ ^n- . An outer-sphere electron transfer mechanism for the reaction of S₄O ₆ ^2- with OH^* to form S₃O ₄ ^n- is proposed based on experimental results. Oxidation rates for trithionate and tetrathionate in the presence of Fenton's reagent (which forms hydroxyl radicals) are too fast to be directly measured using UV-Vis spectrophotometry, electrochemical, or stop-flow spectrophotometry methods. Competitive reaction kinetics within the context of the Haber—Weiss mechanism suggests that the rate constant for the oxidation of trithionate and tetrathionate with OH^* is in excess of 10⁸ M^-1 sec^-1.  相似文献   

Oxygen isotope systematics in Diploastrea heliopora: new coral archive of tropical paleoclimate     

Tsuyoshi Watanabe  Michael K. Gagan  Heather Scott-Gagan  Wahyoe S. Hantoro 《Geochimica et cosmochimica acta》2003,67(7):1349-1358

Diploastrea heliopora forms dense, robust, dome-shaped coral colonies throughout the reef ecosystems of the tropical Pacific and Indian Oceans. This slow-growing (2 to 6 mm/yr) coral has the potential to yield continuous paleoclimate records spanning up to 1000 yr for the warmest waters on Earth, the Indo-Pacific Warm Pool, and has a long fossil history as a single recognizable species. Despite the potential of Diploastrea to be an important new paleoclimate archive, little is known about the systematics of geochemical tracers incorporated into its skeleton. To fill this knowledge gap, we compared skeletal δ¹⁸O signatures in live Diploastrea and Porites colonies from Southwest Lagoon, near Amédée Lighthouse, New Caledonia (at the southern latitudinal limit for Diploastrea) and Alor, Indonesia (in the core area of the Indo-Pacific Warm Pool). We designed a new microsampling technique to minimize smoothing and distortion of the isotopic records due to the complex calyx architecture and slow growth of Diploastrea. High-resolution isotope profiles from the septal portion of the Diploastrea corallite are attenuated, whereas those restricted to the central columella are similar in quality to those extracted from the well-established Porites coral archive. The δ¹⁸O-temperature relationship for the columellar portion of Diploastrea (−0.18‰/°C) is in good agreement with that derived for a nearby Porites (−0.19‰/°C; Quinn et al., 1996), on the basis of comparison with an in situ sea surface temperature record from Amédée Lighthouse. There is a measurable difference of 0.3 ± 0.1‰ between the kinetic/biological disequilibrium offsets from seawater δ¹⁸O composition for Diploastrea and Porites. Despite this offset in mean δ¹⁸O, Diploastrea accurately records the regional differences in mean temperature and salinity between New Caledonia and the Indo-Pacific Warm Pool. Additional tests show that Diploastrea records El Niño-Southern Oscillation (ENSO) interannual variability in sea surface temperature and salinity across the southwestern Pacific, indicating that it should yield dependable paleo-ENSO records. Based on these results, we propose that D. heliopora has the potential to provide an important new coral archive of tropical paleoclimate.  相似文献   

Quantitative charge state analysis of manganese biominerals in aqueous suspension using scanning transmission X-ray microscopy (STXM)     

K. Pecher  D. McCubbery  E. Kneedler  J. Bargar  L. Cox  B. Tonner 《Geochimica et cosmochimica acta》2003,67(6):1089-1098

We have applied Scanning Transmission Soft X-ray Microscopy (STXM) to investigate the charge state distribution of Mn in two kinds of Mn-biominerals, Mn nodules collected from Lake Michigan sediments and Mn precipitates formed by spores of a marine bacillus SG-1 under transport limited reaction conditions. A data analysis technique was developed, which allows for extraction of spatially resolved 2-d charge state maps of manganese on a submicron level. We find that the charge state of Mn dominates the spectral shape of L-edge spectra of environmentally important single oxidation state Mn minerals and that spectra of mixed oxidation state oxides can be modelled by a combination of appropriate single oxidation state reference spectra. Two-dimensional maps of charge state distributions clearly reveal domains of different oxidation states within single particles of Mn-micronodules. Spots of preferred accumulation of Mn(II) were found, which indicates biogenic precipitation of Mn(II)-species as a first step of nodule formation. The presence of Mn(III) in the studied sediment samples suggests the involvement of one-electron oxidation processes and reaction conditions which inhibit or slow down the disproportionation of Mn(III)-products. Under transport limited conditions, Mn oxidation products formed by spores of the marine bacillus SG-1 can vary from cell to cell. The presence of significant amounts of Mn(III) containing species points to the involvement of one-electron oxidation reactions as in the case of the micro-nodules. Our technique and the results obtained form a new basis for the mechanistic understanding of the formation of Mn biominerals in the environment.  相似文献