Density functional theory predictions of equilibrium isotope fractionation of iron due to redox changes and organic complexation     

Shawn D. Domagal-Goldman  James D. Kubicki 《Geochimica et cosmochimica acta》2008,72(21):5201-5216

We present molecular orbital/density functional theory (MO/DFT) calculations that predict a greater isotopic fractionation in redox reactions than in reactions involving ligand exchange. The predicted fractionation factors, reported as 1000·ln(^56-54α), associated with equilibrium between Fe-organic and Fe-H₂O species were <1.6‰ in vacuo and <1.2‰ in solution when the oxidation state of the system was held constant. These fractionation factors were significantly smaller than those predicted for equilibrium between different oxidation states of Fe, for which 1000·ln(^56-54α) was >2.7‰ in vacuo and >2.2‰ in solution when the bound ligands were unchanged. The predicted ⁵⁶Fe/⁵⁴Fe ratio was greater in complexes containing Fe³⁺ and in complexes with shorter Fe-O bond lengths; both of these trends follow previous theoretical results. Our predictions also agree with previous experimental measurements that suggest that the largest biological fractionations will be associated with processes that change the oxidation state of Fe, and that identification of biologically controlled Fe isotope fractionation may be difficult when abiotic redox fractionations are present in the system. The models studied here also have important implications for future theoretical isotope calculations, because we have discovered the necessity of using vibrational frequencies instead of reduced masses when predicting reduced partition functions in aqueous-phase species.  相似文献   

Physiological and behavioral responses of Bathynerita naticoidea (Gastropoda: Neritidae) and Methanoaricia dendrobranchiata (Polychaeta: Orbiniidae) to hypersaline conditions at a brine pool cold seep     

Ahna L. Van Gaest  Craig M. Young  John J. Young  Alicia R. Helms  & Shawn M. Arellano 《Marine Ecology》2007,28(1):199-207

Bathynerita naticoidea (Gastropoda: Neritidae) and Methanoaricia dendrobranchiata (Polychaeta: Orbiniidae) are two of the most abundant invertebrates associated with cold‐seep mussel beds in the Gulf of Mexico. At the methane seep known as Brine Pool NR‐1 (27 °43.415 N, 91 °16.756 W; 650 m depth), which is surrounded by a broad band of mussels (Bathymodiolus childressi), these species have distinctly different patterns of abundance, with the gastropod being found mostly at the outer edge of the mussel bed (average density in November 2003: 817 individuals·m⁻² in outer zone, 20·m⁻² in inner zone) and the polychaete being found almost exclusively near the inner edge (average density in November 2003: 3155 individuals·m⁻² in inner zone, 0·m⁻² in outer zone), adjacent to the brine pool itself. The salinity of the brine pool exceeds 120, so we hypothesized that M. dendrobranchiata should be more tolerant of high salinities than B. naticoidea. The opposite proved to be true. The gastropods were capable of withstanding salinities at least as high as 85, whereas the polychaetes died at salinities higher than 75. Both species were osmoconformers over the range of salinities (35–75) tested. Behavioral responses of B. naticoidea to salinities of 50, 60, and 70 were investigated in inverted vertical haloclines. Gastropods generally did not enter water of salinity greater than 60, but tolerated short periods at 60. Behavioral avoidance of brine should limit the vertical distribution of B. naticoidea in the inner zone to the top 2.5–5 cm of the mussel bed. Behavior is also a likely (though unproven) mechanism for controlling horizontal distribution of this species across the mussel bed. Methanoaricia dendrobranchiata can tolerate short excursions into the brine, but probably avoids hypersaline conditions by aggregating on the tops of the mussels.  相似文献   

A chronological assessment of Lake Okeechobee (Florida) sediments using multiple dating markers     

Shawn P. Schottler  Daniel R. Engstrom 《Journal of Paleolimnology》2006,36(1):19-36

Reconstructing recent limnological history often relies on lead-210 dating to accurately ascribe a chronology to a sediment profile. In Lake Okeechobee, Florida, a large, shallow subtropical lake that may experience severe mixing, multiple dating methods are required to confirm that conformable sedimentation has been preserved and that the assumptions of the ²¹⁰Pb method are satisfied. This study uses stratigraphic profiles of heavy metals, ¹³⁷Cs, PCBs and pollen as independent dating markers to validate the sediment chronology as determined by ²¹⁰Pb for three cores from the central mud zone of the lake. Unsupported ²¹⁰Pb and most dating markers show distinct concentration/depth profiles, suggesting that the sediments have not been severely mixed for at least the last 75 years. Onset and maximum activity of the radioisotope ¹³⁷Cs in the cores coincides with the ²¹⁰Pb-dated interval of 1945–1970. This agrees well with the known timing of atmospheric deposition of ¹³⁷Cs that resulted from above-ground nuclear testing during late 1940s until 1963. Sediment core profiles of atmospherically deposited metals such as Zn and Pb, which reflect regional increases during industrialization and decreases after regulation in the 1970s, exhibit expected concentration increases and peaks coinciding within 5–15 years of the predicted ²¹⁰Pb dates. Uranium, a contaminant in some phosphate fertilizers, shows large concentration increases at core depths dated to be about 1950 by ²¹⁰Pb, matching the intensification of agriculture after WWII. PCBs, which are expected to peak in the early 1970s, were measured in one core, and the observed peak corresponds to a ²¹⁰Pb date of about 1960. Pollen makers were unable to verify specific events, but increases in disturbance taxa and declines in native types correspond generally with the expected dates assigned by ²¹⁰Pb dating. Conformity between the ²¹⁰Pb defined dates and independent markers of < ±15 years confirm that Lake Okeechobee sediments do preserve a sequential and reliable stratigraphic history of the lake, useful for reconstructing past limnological conditions.  相似文献   

A Permeable Reactive Barrier for Treatment of Heavy Metals   总被引：8，自引：0，他引：8  

Ralph D. Ludwig  Rick G. McGregor  David W. Blowes  Shawn G. Benner  Keith Mountjoy 《Ground water》2002,40(1):59-66

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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   

Steady, annual, and monthly recharge implied by deep unconfined aquifer flow     

David W. Ostendorf  Paula L. S. Rees  Shawn P. Kelley  Alan J. Lutenegger 《Journal of Hydrology》2004,290(3-4):259-274

We consider the response of a deep unconfined horizontal aquifer to steady, annual, and monthly recharge. A groundwater divide and a zero head reservoir constrain the aquifer, so that sinusoidal monthly and aperiodic annual recharge fluctuations create transient specific discharge near the reservoir and an unsteady water table elevation inland. One existing and two new long-term data sets from the Plymouth-Carver Aquifer in southeastern Massachusetts calibrate and confirm hydraulic properties in a set of analytical models. [Geohydrology and simulated groundwater flow, 1992] data and a new power law for tritiugenic helium to tritium ratios calibrate the steady recharge that drives the classical parabolic model of steady hydraulics [Applied Hydrogeology, 2001]. Observed water table and gradient fluctuations calibrate the transient recharge models. In the latter regard, monitoring wells within 1 km of Buttermilk Bay exhibit appreciable specific discharge and reduced water table fluctuations. We apply [Trans Am Geophys Union 32(1951)238] periodic model to the monthly hydraulics and a recharge convolution integral [J Hydrol 126(1991)315] to annual flow. An infiltration fraction of 0.79 and a consumptive use coefficient of 1.08×10⁻⁸ m/s °C relate recharge to precipitation and daylight weighted temperature across all three time scales. Errors associated with this recharge relation decrease with increasing time scale.  相似文献   

Assessing vulnerability: an integrated approach for mapping adaptive capacity,sensitivity, and exposure     

Shawn W. Margles Weis  Vera N. Agostini  Lynnette M. Roth  Ben Gilmer  Steven R. Schill  John English Knowles  Ruth Blyther 《Climatic change》2016,136(3-4):615-629

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Site Response in Las Vegas Valley, Nevada from NTS Explosions and Earthquake Data     

Arthur Rodgers  Hrvoje Tkalcic  David McCallen  Shawn Larsen  Catherine Snelson 《Pure and Applied Geophysics》2006,163(1):55-80

We report site response in Las Vegas Valley (LVV) from historical recordings of Nevada Test Site (NTS) nuclear explosions and earthquake recordings from permanent and temporary seismic stations. Our data set significantly improves the spatial coverage of LVV over previous studies, especially in the northern, deeper parts of the basin. Site response at stations in LVV was measured for frequencies in the range 0.2–5.0 Hz using Standard Spectral Ratios (SSR) and Horizontal-Vertical Spectral Ratios (HVR). For the SSR measurements we used a reference site (approximately NEHRP B ``rock' classification) located on Frenchman Mountain outside the basin. Site response at sedimentary sites is variable in LVV with average amplifications approaching a factor of 10 at some frequencies. We observed peaks in the site response curves at frequencies clustered near 0.6, 1.2 and 2.0 Hz, with some sites showing additional lower amplitude peaks at higher frequencies. The spatial pattern of site response is strongly correlated with the reported depth to basement for frequencies between 0.2 and 3.0 Hz, although the frequency of peak amplification does not show a similar correlation. For a few sites where we have geotechnical shear velocities, the amplification shows a correlation with the average upper 30-meter shear velocities, V₃₀. We performed two-dimensional finite difference simulations and reproduced the observed peak site amplifications at 0.6 and 1.2 Hz with a low velocity near-surface layer with shear velocities 600–750 m/s and a thickness of 100–200 m. These modeling results indicate that the amplitude and frequencies of site response peaks in LVV are strongly controlled by shallow velocity structure.  相似文献   

Topographically moderated soil water seasons impact vegetation dynamics in semiarid mountain catchments: Illustrations from the Dry Creek Experimental Watershed,Idaho, USA     

Michael J. Poulos  Toni J. Smith  Shawn G. Benner  Jennifer L. Pierce  Alejandro N. Flores  Mark S. Seyfried  James P. McNamara 《水文研究》2021,35(12):e14421

Water stored in soils, in part, controls vegetation productivity and the duration of growing seasons in wildland ecosystems. Soil water is the dynamic product of precipitation, evapotranspiration and soil properties, all of which vary across complex terrain making it challenging to decipher the specific controls that soil water has on growing season dynamics. We assess how soil water use by plants varies across elevations and aspects in the Dry Creek Experimental Watershed in southwest Idaho, USA, a mountainous, semiarid catchment that spans low elevation rain to high elevation snow regimes. We compare trends in soil water and soil temperature with corresponding trends in insolation, precipitation and vegetation productivity, and we observe trends in the timing, rate and duration of soil water extraction by plants across ranges in elevation and aspect. The initiation of growth-supporting conditions, indicated by soil warming, occurs 58 days earlier at lower, compared with higher, elevations. However, growth-supporting conditions also end earlier at lower elevations due to the onset of soil water depletion 29 days earlier than at higher elevations. A corresponding shift in peak NDVI timing occurs 61 days earlier at lower elevations. Differences in timing also occur with aspect, with most threshold timings varying by 14–30 days for paired north- and south-facing sites at similar elevations. While net primary productivity nearly doubles at higher elevations, the duration of the warm-wet period of active water use does not vary systematically with elevation. Instead, the greater ecosystem productivity is related to increased soil water storage capacity, which supports faster soil water use and growth rates near the summer solstice and peak insolation. Larger soil water storage does not appear to extend the duration of the growing season, but rather supports higher growing season intensity when wet-warm soil conditions align with high insolation. These observations highlight the influence of soil water storage capacity in dictating ecological function in these semiarid steppe climatic regimes.  相似文献   

Bounce Rock—A shergottite‐like basalt encountered at Meridiani Planum,Mars     

Jutta ZIPFEL  Bradley L. JOLLIFF  Ralf GELLERT  Kenneth E. HERKENHOFF  Rudolf RIEDER  Robert ANDERSON  James F. BELL III  Johannes BRÜCKNER  Joy A. CRISP  Philip R. CHRISTENSEN  Benton C. CLARK  Paulo A. De SOUZA Jr.  Gerlind DREIBUS  Claude D’USTON  Thanasis ECONOMOU  Steven P. GOREVAN  Brian C. HAHN  Göstar KLINGELHÖFER  Timothy J. McCOY  Harry Y. McSWEEN Jr.  Douglas W. MING  Richard V. MORRIS  Daniel S. RODIONOV  Steven W. SQUYRES  Heinrich WÄNKE  Shawn P. WRIGHT  Michael B. WYATT  Albert S. YEN 《Meteoritics & planetary science》2011,46(1):1-20

Abstract– The Opportunity rover of the Mars Exploration Rover mission encountered an isolated rock fragment with textural, mineralogical, and chemical properties similar to basaltic shergottites. This finding was confirmed by all rover instruments, and a comprehensive study of these results is reported here. Spectra from the miniature thermal emission spectrometer and the Panoramic Camera reveal a pyroxene‐rich mineralogy, which is also evident in Mössbauer spectra and in normative mineralogy derived from bulk chemistry measured by the alpha particle X‐ray spectrometer. The correspondence of Bounce Rock’s chemical composition with the composition of certain basaltic shergottites, especially Elephant Moraine (EET) 79001 lithology B and Queen Alexandra Range (QUE) 94201, is very close, with only Cl, Fe, and Ti exhibiting deviations. Chemical analyses further demonstrate characteristics typical of Mars such as the Fe/Mn ratio and P concentrations. Possible shock features support the idea that Bounce Rock was ejected from an impact crater, most likely in the Meridiani Planum region. Bopolu crater, 19.3 km in diameter, located 75 km to the southwest could be the source crater. To date, no other rocks of this composition have been encountered by any of the rovers on Mars. The finding of Bounce Rock by the Opportunity rover provides further direct evidence for an origin of basaltic shergottite meteorites from Mars.  相似文献