排序方式： 共有9条查询结果，搜索用时 31 毫秒
1
1.
Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from −0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ56Fe values (relative to IRMM-14) ranging from −0.18(±0.02) to −2.290(±0.006) ‰, and corresponding δ57Fe values of −0.247(±0.014) and −3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus’s theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry. 相似文献
2.
Roy T. Churchwell Steve Kendall Stephen C. Brown Arny L. Blanchard Tuula E. Hollmen Abby N. Powell 《Estuaries and Coasts》2018,41(1):280-292
River deltas along Alaska’s Beaufort Sea coast are used by hatch-year semipalmated sandpipers (Calidris pusilla) after leaving their terrestrial natal sites, but the drivers of their use of these stopover sites on the first “hop” of fall migration are unknown. We quantified sandpiper temporal distribution and abundance as related to food resources at three river deltas during the beginning of their fall migration (post-breeding period) to compare the habitat quality among these deltas. We conducted population counts, sampled invertebrates, and captured birds to collect blood samples from individuals for triglyceride and stable isotope analyses to determine fattening rates and diet. Patterns of sandpiper and invertebrate abundance were complex and varied among deltas and within seasons. River deltas were used by sandpipers from late July to late August, and peak sandpiper counts ranged from 1000 to 4000 individuals, of which 98% were hatch-year semipalmated sandpipers. Isotopic signatures from blood plasma samples indicated that birds switched from a diet of upland tundra to delta invertebrate taxa as the migration season progressed, suggesting a dependence on delta invertebrates. Despite differences in diet among deltas, we found no differences in fattening rates of juvenile sandpipers as indicated by triglyceride levels. The number of sandpipers was positively associated with abundance of Amphipoda and Oligochaeta at the Jago and Okpilak-Hulahula deltas; an isotopic mixing model indicated that sandpipers consumed Amphipoda and Oligochaeta at Jago, mostly Chironomidae at Okpilak-Hulahula and Spionidae at Canning. Regardless of the difference in sandpiper diets at the Beaufort Sea deltas, their similar fattening rates throughout the season indicate that all of these stopover sites provide a critical food resource for hatch-year sandpipers beginning their first migration. 相似文献
3.
Transition metal stable isotope signatures can be useful for tracing both natural and anthropogenic signals in the environment, but only if the mechanisms responsible for fractionation are understood. To investigate isotope fractionations due to electrochemistry (or redox processes), we examine the stable isotope behavior of iron and zinc during the reduction reaction + 2e− = Mmetal as a function of electrochemical driving force, temperature, and time. In all cases light isotopes are preferentially electroplated, following a mass-dependent law. Generally, the extent of fractionation is larger for higher temperatures and lower driving forces, and is roughly insensitive to amount of charge delivered. The maximum fractionations are δ56/54Fe = −4.0‰ and δ66/64Zn = −5.5‰, larger than observed fractionations in the natural environment and larger than those predicted due to changes in speciation. All the observed fractionation trends are interpreted in terms of three distinct processes that occur during an electrochemical reaction: mass transport to the electrode, chemical speciation changes adjacent to the electrode, and electron transfer at the electrode. We show that a large isotope effect adjacent the electrode surface arises from the charge-transfer kinetics, but this effect is attenuated in cases where diffusion of ions to the electrode surface becomes the rate-limiting step. Thus while a general increase in fractionation is observed with increasing temperature, this appears to be a result of thermally enhanced mass transport to the reacting interface rather than an isotope effect associated with the charge-transfer kinetics. This study demonstrates that laboratory experiments can successfully distinguish isotopic signatures arising from mass transport, chemical speciation, and electron transfer. Understanding how these processes fractionate metal isotopes under laboratory conditions is the first step towards discovering what role these processes play in fractionating metal isotopes in natural systems. 相似文献
4.
Filter-feeding bivalves, like oysters, couple pelagic primary production with benthic microbial processes by consuming plankton from the water column and depositing unassimilated material on sediment. Conceptual models suggest that at low to moderate oyster densities, this deposition can stimulate benthic denitrification by providing denitrifying bacteria with organic carbon and nitrogen (N). While enhanced denitrification has been found at oyster reefs, data from oyster aquaculture are limited and equivocal. This study measured seasonal rates of denitrification, as well as dissimilatory nitrate reduction to ammonium (DNRA), and dissolved inorganic N fluxes at a rack and bag eastern oyster (Crassostrea virginica) aquaculture farm. Consistent with models, denitrification was enhanced within the farm, with an average annual increase of 350% compared to a reference site. However, absolute denitrification rates were low relative to other coastal systems, reaching a maximum of 19.2 μmol m?2 h?1. Denitrification appeared to be nitrate (NO3 ?) limited, likely due to inhibited nitrification caused by sediment anoxia. Denitrification may also have been limited by competition for NO3 ? with DNRA, which accounted for an average of 76% of NO3 ? reduction. Consequently, direct release of ammonium (NH4 +) from mineralization to the water column was the most significant benthic N pathway, with seasonal rates exceeding 900 μmol m?2 h?1 within the farm. The enhanced N processes were spatially limited however, with significantly higher rates directly under oysters, compared to in between oyster racks. For commercial aquaculture farms like this, with moderate oyster densities (100–200 oysters m?2), denitrification may be enhanced, but nonetheless limited by biodeposition-induced sediment anoxia. The resulting shift in the sediment N balance toward processes that regenerate reactive N to the water column rather than remove N is an important consideration for water quality. 相似文献
5.
6.
Roy T. Churchwell Steve J. Kendall Arny L. Blanchard Kenneth H. Dunton Abby N. Powell 《Estuaries and Coasts》2016,39(3):798-814
Unlike lower latitude coastlines, the estuarine nearshore zones of the Alaskan Beaufort Sea are icebound and frozen up to 9 months annually. This annual freezing event represents a dramatic physical disturbance to fauna living within intertidal sediments. The main objectives of this study were to describe the benthic communities of Beaufort Sea deltas, including temporal changes and trophic structure. Understanding benthic invertebrate communities provided a baseline for concurrent research on shorebird foraging ecology at these sites. We found that despite continuous year-to-year episodes of annual freezing, these estuarine deltas are populated by a range of invertebrates that represent both marine and freshwater assemblages. Freshwater organisms like Diptera and Oligochaeta not only survive this extreme event, but a marine invasion of infaunal organisms such as Amphipoda and Polychaeta rapidly recolonizes the delta mudflats following ice ablation. These delta sediments of sand, silt, and clay are fine in structure compared to sediments of other Beaufort Sea coastal intertidal habitats. The relatively depauperate invertebrate community that ultimately develops is composed of marine and freshwater benthic invertebrates. The composition of the infauna also reflects two strategies that make life on Beaufort Sea deltas possible: a migration of marine organisms from deeper lagoons to the intertidal and freshwater biota that survive the 9-month ice-covered period in frozen sediments. Stable isotopic analyses reveal that both infaunal assemblages assimilate marine and terrestrial sources of organic carbon. These results provide some of the first quantitative information on the infaunal food resources of shallow arctic estuarine systems and the long-term persistence of these invertebrate assemblages. Our data help explain the presence of large numbers of shorebirds in these habitats during the brief summer open-water period and their trophic importance to migrating waterfowl and nearshore populations of estuarine fishes that are the basis of subsistence lifestyles by native inhabitants of the Beaufort Sea coast. 相似文献
7.
The goal of this study is to determine reduced partition function ratios for a variety of species of zinc, both as a metal and in aqueous solutions in order to calculate equilibrium stable isotope partitioning. We present calculations of the magnitude of Zn stable-isotope fractionation (66,67,68Zn/64Zn) between aqueous species and metallic zinc using measured vibrational spectra (fit from neutron scattering studies of metallic zinc) and a variety of electronic structure models. The results show that the reduced metal, Zn(0), will be light in equilibrium with oxidized Zn(II) aqueous species, with the best estimates for the Zn(II)-Zn(0) fractionation between hexaquo species and metallic zinc being Δ66/64Znaq-metal ∼ 1.6‰ at 25 °C, and Δ66/64Znaq-metal ∼ 0.8‰ between the tetrachloro zinc complex and metallic zinc at 25 °C using B3LYP/aug-cc-pVDZ level of theory and basis set. To examine the behavior of zinc in various aqueous solution chemistries, models for Zn(II) complex speciation were used to determine which species are thermodynamically favorable and abundant under a variety of different conditions relevant to natural waters, experimental and industrial solutions. The optimal molecular geometries for [Zn(H2O)6]2+, [Zn(H2O)6]·SO4, [ZnCl4]2− and [Zn(H2O)3(C3H5O(COO)3)]− complexes in various states of solvation, protonation and coordination were calculated at various levels of electronic structure theory and basis set size. Isotopic reduced partition function ratios were calculated from frequency analyses of these optimized structures. Increasing the basis set size typically led to a decrease in the calculated reduced partition function ratios of ∼0.5‰ with values approaching a plateau using the aug-cc-pVDZ basis set or larger. The widest range of species were studied at the B3LYP/LAN2DZ/6-31G∗ level of theory and basis-set size for comparison. Aqueous zinc complexes where oxygen is bound to the metal center tended to have the largest reduced partition function ratios, with estimated fractionations ranging from 2.2 to 2.9‰ (66Zn/64Zn) at 25 °C relative to metallic zinc. The tetrahedrally coordinated tetrachloro zinc complex, where zinc is bound exclusively to chloride, had the lowest reduced partition function ratio for a Zn(II) species (Δ66/64Znaq-metal ∼ 1-1.3‰ at 25 °C). Increasing the number of waters in the second shell of solvation of the above complexes led to variable results, most commonly leading to a decrease of ∼0.2 to 0.3‰ in calculated Δ66/64Znaq-metal at 25 °C.These estimates are useful in the interpretation of observed fractionations during the electrochemical deposition of zinc, where aqueous-metal fractionations of up to 5.5‰ are observed. The models show these are not caused by an equilibrium fractionation process. These results suggest that the redox cycle of zinc during industrial processing may be responsible for isotopically distinct reservoirs of zinc observed in polluted environments. The leaching of metallic zinc or zinc tailings from industrial sites could lead to the observed heavy signature in river systems, the magnitude of which will be reliant on the source material and the aqueous species that form. 相似文献
8.
Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples. 相似文献
9.
Redox processes are ubiquitous in Earth science and are often associated with large isotope fractionations. In a previous study, voltage-dependent amplification of stable isotope fractionation was observed for an Fe reduction process. Here, we describe experiments showing a similar effect for a second transition metal, zinc. After electrochemical reduction, the composition of plated Zn metal is enriched in the light isotope (64Zn) with respect to the Zn2+ leftover in solution, with a voltage-dependent fractionation factor. Results from voltage-dependent electroplating experiments are in good agreement with a second data set following equilibrium fractional isotope evolution of Zn isotopes during an electroplating process which stepwise removes most of the Zn from the aqueous reservoir. Taken together, the results indicate a voltage-dependent isotope fractionation (in permil) of 66Zn with respect to 64Zn to be equal to −3.45 to 1.71 V. The negative slope trend is in contrast with previously published results on iron isotope fractionation during electroplating which shows a positive slope. These results are interpreted using an extension of Marcus theory, which predicts isotope fractionations as a function of driving force in an electrochemical system. Taken together with observations of natural fractionation of redox-sensitive and non redox-active elements, our modified Marcus theory provides a framework for quantitatively predicting transition metal isotope geochemical signatures during environmentally relevant redox processes in terms of simple energetic parameters. 相似文献
1