On the role of Mn(IV) vacancies in the photoreductive dissolution of hexagonal birnessite   总被引：4，自引：0，他引：4  

Kideok D. Kwon  Keith Refson 《Geochimica et cosmochimica acta》2009,73(14):4142-1527

Photoreductive dissolution of layer type Mn(IV) oxides (birnessite) under sunlight illumination to form soluble Mn(II) has been observed in both field and laboratory settings, leading to a consensus that this process is a key driver of the biogeochemical cycling of Mn in the euphotic zones of marine and freshwater ecosystems. However, the underlying mechanisms for the process remain unknown, although they have been linked to the semiconducting characteristics of hexagonal birnessite, the ubiquitous Mn(IV) oxide produced mainly by bacterial oxidation of soluble Mn(II). One of the universal properties of this biogenic mineral is the presence of Mn(IV) vacancies, long-identified as strong adsorption sites for metal cations. In this paper, the possible role of Mn vacancies in photoreductive dissolution is investigated theoretically using quantum mechanical calculations based on spin-polarized density functional theory (DFT). Our DFT study demonstrates unequivocally that Mn vacancies significantly reduce the band-gap energy for hexagonal birnessite relative to a hypothetical vacancy-free MnO₂ and thus would increase the concentration of photo-induced electrons available for Mn(IV) reduction upon illumination of the mineral by sunlight. Calculations of the charge distribution in the presence of vacancies, although not fully conclusive, show a clear separation of photo-induced electrons and holes, implying a slow recombination of these charge-carriers that facilitates the two-electron reduction of Mn(IV) to Mn(II).  相似文献   

Arsenic contamination of lake sediments in Florida: evidence of herbicide mobility from watershed soils   总被引：1，自引：0，他引：1  

Thomas J. Whitmore  Melanie A. Riedinger-Whitmore  Joseph M. Smoak  Keith V. Kolasa  Ethan A. Goddard  Richard Bindler 《Journal of Paleolimnology》2008,40(3):869-884

Organic arsenical herbicides, which include monosodium methylarsonate (MSMA), have been applied to golf courses and lawns throughout Florida, USA, since the 1950s. These products convert rapidly to inorganic forms of arsenic (As) in soils and are mobilized readily. Leachates have been known to contaminate groundwater and surface waters, although past studies have not examined whether use of these products has led to significant As accumulation in lake sediments. We used paleolimnological methods to document the depositional history and inventories of total As in sediments and porewaters of Little Lake Jackson in Florida, which is adjacent to three golf courses. Six sediment cores, four of which were ²¹⁰Pb dated, showed porewater total As concentrations as high as 435 μg l⁻¹, and dry-sediment total As concentrations as high as 148 mg kg⁻¹. Approximately 537 kg of total As is present in >19,000 metric tons of sediment (dry mass), and an additional 18 kg of As is dissolved in 10.8 × 10⁴ m³ of porewaters. Total As content in surface sediments (mean = 47.3 mg kg⁻¹) exceeds the consensus-based sedimentary concentration for probable toxicity effects in freshwater benthic fauna. Surface and subsurface waters flow to the lake from topographically higher areas to the west, where golf courses and residential areas are located. Total As concentrations were elevated highly in monitoring wells and in a stream that flows between the golf courses and lake, but As was below detection limits in wells that were located at the distal perimeter of the golf courses. Subsurface and surface waters exit the lake towards topographically lower areas to the east. Nearly all As in sediments remains bound in the solid phase, indicating that As sedimentary profiles largely reflect depositional history. Sedimentary As concentrations are correlated strongly with aluminum and iron, which suggests that As was scavenged from lake waters during the past. Sedimentary As concentrations increased until the 1980s, then declined somewhat to the present time. Dissolved As was scavenged efficiently from the water column when hypolimnetic waters were oxygenated persistently, but after eutrophication led to a seasonally anoxic hypolimnion in the 1980s, apparently less As was co-precipitated, and more was lost to hydrological outflow. Arsenic accumulation in sediments might be common in areas where As derived from organic arsenical herbicide applications is directed by shallow water tables towards adjacent lakes.  相似文献   

Multi-method global sensitivity analysis of flood inundation models   总被引：1，自引：0，他引：1  

Florian Pappenberger  Keith J. Beven  Marco Ratto  Patrick Matgen 《Advances in water resources》2008

Global sensitivity analysis is a valuable tool in understanding flood inundation models and deriving decisions on strategies to reduce model uncertainty. In this paper, a sensitivity analysis of a one-dimensional flood inundation model (HEC-RAS) on the River Alzette, Luxembourg, is presented. It is impossible to define sensitivity in a unique way and different methods can lead to a difference in ranking of importance of model factors. In this paper five different methods (Sobol, Kullback–Leibler entropy, Morris, regionalised sensitivity analysis and regression) are applied and the outcomes on selected examples compared. It is demonstrated that the different methods lead to completely different ranking of importance of the parameter factors and that it is impossible to draw firm conclusions about the relative sensitivity of different factors. Moreover, the uncertainty inherent in the sensitivity methods is highlighted.  相似文献   

Identification of Burrowing Shrimp Food Sources Along an Estuarine Gradient Using Fatty Acid Analysis and Stable Isotope Ratios     

Katelyn M. Bosley  Louise A. Copeman  Brett R. Dumbauld  Keith L. Bosley 《Estuaries and Coasts》2017,40(4):1113-1130

Two species of burrowing shrimp occur in high densities in US West Coast estuaries, the ghost shrimp, Neotrypaea californiensis, and the blue mud shrimp, Upogebia pugettensis. Both species of shrimp are considered ecosystem engineers as they bioturbate and irrigate extensive galleries within the sediment. While their burrows comprise a dominant habitat type in west coast estuaries, little is known about these shrimps’ diet and their role in estuarine food webs. The primary goals of this study were to identify major components of burrowing shrimp diets and detect variation in these diets along an estuarine gradient using combined fatty acid (FA) and stable isotope (SI) analyses. Shrimp and potential food sources including eelgrass blades, epiphytes, Ulva, sedimentary particulate organic matter (SPOM), burrow walls, and particulate organic material (POM) were sampled at different locations within Yaquina Bay, Oregon in August 2012. Both SI and FA analyses indicated differences in food resources assimilated by shrimp along the estuarine gradient. SI values showed that diets for U. pugettensis consisted of carbon sources derived primarily from POM and SPOM, while POM and epiphytes were primary carbon sources for N. californiensis. Shrimp from lower estuarine sites had high levels of 16:1ω7 and 20:5ω3 FAs suggesting their diet is enriched with marine diatoms. Shrimp from upriver showed greater proportion of FA associated with dinoflagellates and terrestrial sources as indicated by a high percentage of C₁₈ polyunsaturated FAs (PUFAs). This is the first study to evaluate diets of these two shrimp species using complimentary FA and SI approaches.  相似文献   

Source Wavelet Phase Extraction     

Diako Hariri Naghadeh  Christopher Keith Morley 《Pure and Applied Geophysics》2016,173(6):2011-2032

  相似文献   

Setting limits for acceptable change in sediment particle size composition following marine aggregate dredging     

Cooper KM 《Marine pollution bulletin》2012,64(8):1667-1677

In the UK, Government policy requires marine aggregate extraction companies to leave the seabed in a similar physical condition after the cessation of dredging. This measure is intended to promote recovery, and the return of a similar faunal community to that which existed before dredging. Whilst the policy is sensible, and in line with the principles of sustainable development, the use of the word 'similar' is open to interpretation. There is, therefore, a need to set quantifiable limits for acceptable change in sediment composition. Using a case study site, it is shown how such limits could be defined by the range of sediment particle size composition naturally found in association with the faunal assemblages in the wider region. Whilst the approach offers a number of advantages over the present system, further testing would be required before it could be recommended for use in the regulatory context.  相似文献   

Numerical study of three-dimensional shelf circulation on the Scotian Shelf using a shelf circulation model     

Kyoko Ohashi  Jinyu Sheng  Keith R. Thompson  Charles G. Hannah  Harold Ritchie 《Continental Shelf Research》2009

A numerical shelf circulation model was developed for the Scotian Shelf, using a nested-grid setup consisting of a three-dimensional baroclinic inner model embedded inside a two-dimensional barotropic outer model. The shelf circulation model is based on the Princeton Ocean Model and driven by three-hourly atmospheric forcing provided by a numerical weather forecast model and by tidal forcing specified at the inner model's open boundaries based on pre-calculated tidal harmonic constants. The outer model simulates the depth-mean circulation forced by wind and atmospheric pressure fields over the northwest Atlantic Ocean with a horizontal resolution of 1/12°. The inner model simulates the three-dimensional circulation over the Gulf of St. Lawrence, the Scotian Shelf, and the adjacent slope with a horizontal resolution of 1/16°. The performance of the shelf circulation model is assessed by comparing model results with oceanographic observations made along the Atlantic coast of Nova Scotia and in the vicinity of Sable Island (on the Scotian Shelf) during two periods: October 2000–March 2001 and April–June 2002. Analysis of model results on Sable Island Bank indicates that tidal currents account for as much as ∼80% of the total variance of near-bottom currents, and currents driven by local winds account for ∼30% of the variance of the non-tidal near-bottom currents. Shelf waves generated remotely by winds and propagating into the region also play an important role in the near-bottom circulation on the bank.  相似文献   

Perceptual models of uncertainty for socio-hydrological systems: a flood risk change example   总被引：2，自引：2，他引：0  

Ida K. Westerberg  Keith J. Beven  Gemma Coxon  Tobias Krueger 《水文科学杂志》2017,62(11):1705-1713

Characterizing, understanding and better estimating uncertainties are key concerns for drawing robust conclusions when analyzing changing socio-hydrological systems. Here we suggest developing a perceptual model of uncertainty that is complementary to the perceptual model of the socio-hydrological system and we provide an example application to flood risk change analysis. Such a perceptual model aims to make all relevant uncertainty sources – and different perceptions thereof – explicit in a structured way. It is a first step to assessing uncertainty in system outcomes that can help to prioritize research efforts and to structure dialogue and communication about uncertainty in interdisciplinary work.  相似文献   

Deep learning,hydrological processes and the uniqueness of place     

Keith Beven 《水文研究》2020,34(16):3608-3613

  相似文献   

Thermal Monitoring of Natural Source Zone Depletion          下载免费PDF全文

Kayvan Karimi Askarani  Emily B. Stockwell  Keith R. Piontek  Tom C. Sale 《Ground Water Monitoring & Remediation》2018,38(3):43-52

Natural depletion of subsurface petroleum liquids releases energy in the form of heat. The rate of natural source zone depletion (NSZD) can be derived from subsurface temperature data. An energy balance is performed to resolve NSZD‐generated energy in terms of W/m². Biodegradation rates are resolved by dividing the NSZD energy by the heat of reaction in joules/mol. Required temperature data are collected using data loggers, wireless connections, and automated data storage and analysis. Continuous thermal resolution of monthly NSZD rates at a field site indicates that apparent monthly NSZD rates vary through time, ranging from 10,000 to 77,000 L/ha/year. Temporal variations in observed apparent NSZD rates are attributed to processes governing the conversion of CH₄ to CO₂, as opposed to the actual rates of NSZD. Given a year or more of continuous NSZD rate data, it is anticipated that positive and negative biases in apparent NSZD rates will average out, and averaged apparent NSZD rates will converge to true NSZD rates. An 8.4% difference between average apparent NSZD rates over a 31‐month period using the thermal monitoring method and seven rounds of CO₂ efflux measurements using CO₂ traps supports the validity of both CO₂ trap and thermal monitoring methods. A promising aspect of thermal monitoring methods is that continuous data provide a rigorous approach to resolving the true mean NSZD rates as compared to temporally sparse CO₂ trap NSZD rate measurements. Overall, a vision is advanced of real‐time sensor‐based groundwater monitoring that can provide better data at lower costs and with greater safety, security, and sustainability.  相似文献