Molecular modeling of Al and benzene interactions with Suwannee fulvic acid     

Chad C. Trout 《Geochimica et cosmochimica acta》2007,71(15):3859-3871

The effects that Al³⁺ and benzene interactions exhibit on a model fulvic acid were investigated. Energy minimizations of the structures mimicking the interactions of Al³⁺-Suwannee fulvic acid (SFA), benzene-SFA and Al³⁺-benzene-SFA were run with a solvation sphere of 60 H₂O molecules with the semi-empirical methods PM3 and PM5. The semi-empirical method PM3 was run with Gaussian 98 and CAChe Workstation Pro 6.1.1 to compare the results of the energy minimization algorithms in the two programs. PM5 calculations were run with CAChe Workstation Pro 6.1.1. Molecular dynamics (MD) simulations were run in Cerius² (Accelrys Inc., San Diego, CA) using the Universal Force Field (UFF) 1.02 [Rappé A. K., Casewit C., Colwell K., Goddard W., and Skiff W. (1992) UFF, a full periodic-table force-field for molecular mechanics and molecular dynamics simulations. J. Am. Chem. Soc.114(25), 10024-10035] and COMPASS force field [Sun H. (1998) COMPASS: an ab initio force-field optimized for condensed-phase applications—overview with details on alkane and benzene compounds. J. Phys. Chem. B102, 7338-7364]. Single point calculations were run on the minimized structures at the B3LYP/6-31G(d) level to obtain more accurate estimates of the energy on the minimized structures derived from the PM3, PM5, and UFF methods and to normalize energies to the same reference state. This methodology was used as the standard of comparison for all the models to assess whether or not a given configuration was reasonably stable.The PM3/G03 energy minimizations predicted the lowest B3LYP/6-31G(d) potential energies of the methodologies examined in this study. Thus, this method is considered the most reliable of those tested. The PM3/G03 method predicted that there would be aromatic-aromatic interactions between benzene and SFA. The presence of Al³⁺ was predicted not to interfere with aromatic-aromatic interactions between benzene and SFA, but benzene may influence the location of metal complexation to SFA.  相似文献   

Forgotten coast,forgotten people: sustainable development and disproportionate impacts from Hurricane Michael in Gulf County,Florida     

Boda  Chad S.  Scown  Murray W.  Faran  Turaj 《Natural Hazards》2022,111(1):877-899

Natural Hazards - A central challenge for sustainable development is how societies are to avoid, minimize or address impacts from anthropogenic climate change. However, competing perspectives on...  相似文献   

Similarity Scaling Over a Steep Alpine Slope   总被引：5，自引：5，他引：0  

Daniel F. Nadeau  Eric R. Pardyjak  Chad W. Higgins  Marc B. Parlange 《Boundary-Layer Meteorology》2013,147(3):401-419

In this study, we investigate the validity of similarity scaling over a steep mountain slope (30–41 $^\circ $ ). The results are based on eddy-covariance data collected during the Slope Experiment near La Fouly (SELF-2010); a field campaign conducted in a narrow valley of the Swiss Alps during summer 2010. The turbulent fluxes of heat and momentum are found to vary significantly with height in the first few metres above the inclined surface. These variations exceed by an order of magnitude the well-accepted maximum 10 % required for the applicability of Monin–Obukhov similarity theory in the surface layer. This could be due to a surface layer that is too thin to be detected or to the presence of advective fluxes. It is shown that local scaling can be a useful tool in these cases when surface-layer theory breaks down. Under convective conditions and after removing the effects of self-correlation, the normalized standard deviations of slope-normal wind velocity, temperature and humidity scale relatively well with $z/\varLambda $ , where $z$ is the measurement height and $\varLambda (z)$ the local Obukhov length. However, the horizontal velocity fluctuations are not correlated with $z/\varLambda $ under all stability regimes. The non-dimensional gradients of wind velocity and temperature are also investigated. For those, the local scaling appears inappropriate, particularly at night when shallow drainage flows prevail and lead to negative wind-speed gradients close to the surface.  相似文献   

Stable carbon isotope ratios in lake and swamp sediments as a proxy for prehistoric forest clearance and crop cultivation in the Neotropics   总被引：2，自引：0，他引：2  

Chad S. Lane  Sally P. Horn  Claudia I. Mora 《Journal of Paleolimnology》2004,32(4):375-381

Close correspondence between stable carbon isotope ratios ( ¹³ C), pollen, and charcoal profiles in sediment cores from Laguna Zoncho and Machita swamp, Costa Rica, shows that prehistoric forest clearance and crop cultivation can be detected in the stable carbon isotope ratios of total organic carbon ( ¹3C _TOC ). Analyses of δ 13C _TOC complement evidence from pollen, charcoal, and phytoliths and provide a proxy that is sensitive to the intensity and/or proximity to core sites of prehistoric forest clearance and agriculture in watersheds. Stable carbon isotope analyses are particularly useful in situations in which other evidence of forest clearance and agriculture is limited.  相似文献   

Noble gas composition of the solar wind as collected by the Genesis mission     

Veronika S. Heber  Rainer Wieler  Chad Olinger  Donald S. Burnett 《Geochimica et cosmochimica acta》2009,73(24):7414-7432

We present the elemental and isotopic composition of noble gases in the bulk solar wind collected by the NASA Genesis sample return mission. He, Ne, and Ar were analyzed in diamond-like carbon on a silicon substrate (DOS) and ^84,86Kr and ^129,132Xe in silicon targets by UV laser ablation noble gas mass spectrometry. Solar wind noble gases are quantitatively retained in DOS and with exception of He also in Si as shown by a stepwise heating experiment on a flown DOS target and analyses on other bulk solar wind collector materials. Solar wind data presented here are absolutely calibrated and the error of the standard gas composition is included in stated uncertainties. The isotopic composition of the light noble gases in the bulk solar wind is as follows: ³He/⁴He: (4.64 ± 0.09) × 10⁻⁴, ²⁰Ne/²²Ne: 13.78 ± 0.03, ²¹Ne/²²Ne: 0.0329 ± 0.0001, ³⁶Ar/³⁸Ar 5.47 ± 0.01. The elemental composition is: ⁴He/²⁰Ne: 656 ± 5, and ²⁰Ne/³⁶Ar 42.1 ± 0.3. Genesis provided the first Kr and Xe data on the contemporary bulk solar wind. The preliminary isotope and elemental composition is: ⁸⁶Kr/⁸⁴Kr: 0.302 ± 0.003, ¹²⁹Xe/¹³²Xe: 1.05 ± 0.02, ³⁶Ar/⁸⁴Kr 2390 ± 150, and ⁸⁴Kr/¹³²Xe 9.5 ± 1.0. The ³He/⁴He and the ⁴He/²⁰Ne ratios in the Genesis DOS target are the highest solar wind values measured in exposed natural and artificial targets. The isotopic composition of the other noble gases and the Kr/Xe ratio obtained in this work agree with data from lunar samples containing “young” (∼100 Ma) solar wind, indicating that solar wind composition has not changed within at least the last 100 Ma. Genesis could provide in many cases more precise data on solar wind composition than any previous experiment. Because of the controlled exposure conditions, Genesis data are also less prone to unrecognized systematic errors than, e.g., lunar sample analyses. The solar wind is the most authentic sample of the solar composition of noble gases, however, the derivation of solar noble gas abundances and isotopic composition using solar wind data requires a better understanding of fractionation processes acting upon solar wind formation.  相似文献   

The variation and controls of mean transit times in Australian headwater catchments     

Ian Cartwright  Uwe Morgenstern  William Howcroft  Harald Hofmann  Robin Armit  Michael Stewart  Chad Burton  Dylan Irvine 《水文研究》2020,34(21):4034-4048

Determining mean transit times in headwater catchments is critical for understanding catchment functioning and understanding their responses to changes in landuse or climate. Determining whether mean transit times (MTTs) correlate with drainage density, slope angle, area, or land cover permits a better understanding of the controls on water flow through catchments and allows first-order predictions of MTTs in other catchments to be made. This study assesses whether there are identifiable controls on MTTs determined using ³H in headwater catchments of southeast Australia. Despite MTTs at baseflow varying from a few years to >100 years, it was difficult to predict MTTs using single or groups of readily-measured catchment attributes. The lack of readily-identifiable correlations hampers the prediction of MTTs in adjacent catchments even where these have similar geology, land use, and topography. The long MTTs of the Australian headwater catchments are probably in part due to the catchments having high storage volumes in deeply-weathered regolith, combined with low recharge rates due to high evapotranspiration. However, the difficulty in estimating storage volumes at the catchment scale hampers the use of this parameter to estimate MTTs. The runoff coefficient (the fraction of rainfall exported via the stream) is probably also controlled by evapotranspiration and recharge rates. Correlations between the runoff coefficient and MTTs in individual catchments allow predictions of MTTs in nearby catchments to be made. MTTs are shorter in high rainfall periods as the catchments wet up and shallow water stores are mobilized. Despite the contribution of younger water, the major ion geochemistry in individual catchments commonly does not correlate with MTTs, probably reflecting heterogeneous reactions and varying degrees of evapotranspiration. Documenting MTTs in catchments with high storage volumes and/or low recharge rates elsewhere is important for understanding MTTs in diverse environments.  相似文献   

Verification of tropical cyclone deposits with oxygen isotope analyses of coeval ostracod valves     

Chad S. Lane  Brooklyn Hildebrandt  Lisa M. Kennedy  Allison LeBlanc  Kam-Biu Liu  Amy J. Wagner  Andrea D. Hawkes 《Journal of Paleolimnology》2017,57(3):245-255

Reconstruction of prehistoric tropical cyclone (TC) activity often relies on the identification of distinctive overwash deposits (tempestites) in coastal lagoon sediments. Similar sediment deposits, however, can result from high-energy events other than TCs. In this study we assessed the utility of using the geochemistry of ostracod valves, specifically their stable oxygen isotope composition (δ¹⁸O), as a potential validation variable that could reduce the chances of misidentifying an overwash deposit as having been generated by a TC, when in fact it formed from another high-energy depositional process (type 1 error). We applied this technique to a sediment core recovered from Laguna Alejandro, Dominican Republic, which had already been analyzed for other sedimentary TC proxies. Negative δ¹⁸O anomalies identified in the ostracod valve stable isotope record are associated with TC deposits and are most easily explained by large influxes of ¹⁸O-depleted meteoric waters typical of intense tropical storms. There is potential for this technique to be used to identify TC landfalls that are not represented by overwash deposits. We, however, propose a more conservative approach and suggest this technique be used to validate the origin of a storm deposit and reduce the odds of a type 1 error.  相似文献   

Analytical and Numerical Modeling of Solute Intrusion,Recovery, and Rebound in Fractured Bedrock     

Ranjeet M. Nagare  Young-Jin Park  Trevor Butterfield  Chad Belenky  Sheldon Scyrup 《Ground water》2020,58(1):56-69

Contaminated groundwater in fractured bedrock can expose ecosystems to undesired levels of risk for extended periods due to prolonged back-diffusion from rock matrix to permeable fractures. Therefore, it is key to characterize the diffusive mass loading (intrusion) of contaminants into the rock matrix for successful management of contaminated bedrock sites. Even the most detailed site characterization techniques often fail to delineate contamination in rock matrix. This study presents a set of analytical solutions to estimate diffusive mass intrusion into matrix blocks, it is recovered by pumping and concentration rebound when pumping ceases. The analytical models were validated by comparing the results with (1) numerical model results using the same model parameters and (2) observed chloride mass recovery, rebound concentration, and concentration in pumped groundwater at a highly fractured bedrock site in Alberta, Canada. It is also demonstrated that the analytical solutions can be used to estimate the total mass stored in the fractured bedrock prior to any remediation thereby providing insights into site contamination history. The predictive results of the analytical models clearly show that successful remediation by pumping depends largely on diffusive intrusion period. The results of initial mass from the analytical model was used to successfully calibrate a three-dimensional discrete fracture network numerical model further highlighting the utility of the simple analytical solutions in supplementing the more detailed site numerical modeling. Overall, the study shows the utility of simple analytical methods to support long-term management of a contaminated fractured bedrock site including site investigations and complex numerical modeling.  相似文献   

Observations of Thin Layers in Coastal Hawaiian Waters     

Margaret A. McManus  Jeff C. Sevadjian  Kelly J. Benoit-Bird  Olivia M. Cheriton  Amanda H. V. Timmerman  Chad M. Waluk 《Estuaries and Coasts》2012,35(4):1119-1127

Thin layers of plankton have been documented in a wide variety of environments. The growing body of observations indicates that these features are a critical component of marine ecosystem dynamics and functioning. In the past two decades, much of the research on thin layers was undertaken in temperate coastal waters. Here, we report the first known observations of thin layers of phytoplankton in tropical Hawaiian waters. We conducted an overnight shipboard study during which time we made high-resolution observations of physical and optical structure in the water column. During the overnight cruise, we observed the greatest number of thin layers in the early evening hours when thermal stratification was strongest and most persistent due to a combination of warm air and surface water, as well as light winds. A comparison of these observations with those from temperate regions leads us to hypothesize that the nature and persistence of the physical structure is very important in determining the persistence of thin layered structures. Because plankton biomass is generally lower in tropical regions, the heterogeneous aggregation of food in thin subsurface layers may be more critical to the marine ecosystem than it is in temperate regions where plankton are generally more abundant.  相似文献   

Evolution of the Taupo Volcanic Center, New Zealand: petrological and thermal constraints from the Omega dacite     

Sarah E. Gelman  Chad D. Deering  Francisco J. Gutierrez  Olivier Bachmann 《Contributions to Mineralogy and Petrology》2013,166(5):1355-1374

The 20 ka ~0.1 km³ Omega dacite, which erupted shortly after the 26.5 ka Oruanui super-eruption, compositionally stands out among Taupo Volcanic Zone (TVZ) magmas, which are overwhelmingly characterized by rhyolites (>90 % by volume). The previously reported presence of inherited zircons in this zircon-undersaturated magma has provided unequivocal evidence for the involvement of upper-crustal material in a 1–10 year timescale prior to the Omega eruption. However, whether this crustal involvement is characterized by wholesale, melting of preexisting crust or subordinate bulk assimilation into an already differentiated magma body remains unclear. To disentangle these processes, we describe the mineral chemistry of the major phases present in the Omega dacite and determine intensive parameters describing magma chamber conditions. Dominantly unimodal populations of plagioclase (An_50–60), orthopyroxene (Mg# from 58 to 68), and clinopyroxene (Mg# from 65 to 73), along with coexisting equilibrium pairs of Fe–Ti oxides, constrain pre-eruptive temperatures to 850–950 °C, a pressure between ~3 and 7 kbars, and an oxygen fugacity of ~NNO. MELTS thermodynamic modeling suggests that this phase assemblage is in equilibrium with the bulk rock and glass compositions of the Omega dacite at these estimated P–T–fO₂ pre-eruptive conditions. Combining these petrological observations with insights into conductive thermal models of magma–crust interactions, we argue that the Omega dacite more likely formed in the mid-to-lower crust via protracted processing through fractional crystallization coupled with some assimilation (AFC). Incorporation of crustal material is likely to have occurred at various stages, with the inherited zircons (and potentially parts of glomerocrysts) representing late and subordinate upper-crustal assimilants. This petrogenetic model is consistent with the presence of a differentiating crustal column, consisting of a polybaric fractional crystallization and assimilation history. On the basis of petrological, thermal, and geophysical considerations, upper-crustal reservoirs, which feed large-scale rhyolitic volcanism in the TVZ, most likely take the form of large, long-lived crystal mush zones. Following large eruptions, such as the Oruanui event, this mush is expected to crystallize significantly (up to 70–80 vol% crystals) due to syn-eruptive decompression. Hence, the Omega dacite, immediately post-dating the Oruanui event, potentially represents incoming deeper recharge of less-evolved magma that was able to penetrate the nearly solidified upper-crustal mush. Over the past 20,000 years, similar intermediate recharge magmas have incrementally reheated, reconstructed, and reactivated the upper-crustal mush zone, allowing a gradual return to rhyolitic volcanism at the Taupo Volcanic Center.  相似文献