Theoretical considerations of electrochemical phase formation for an ideal Frank-van der Merwe system - Ag on Au(111) and Au(100)

: Static calculation and preliminary kinetic Monte Carlo simulation studies are undertaken for the nucleation and growth on a model system which follows a Frank-van der Merwe mechanism. In the present case, we consider the deposition of Ag on Au(100) and Au(111) surfaces. The interactions were calculated using the embedded atom model. The kinetics of formation and growth of 2D Ag structures on Au(100) and Au(111) is investigated and the influence of surface steps on this phenomenon is studied. Very different time scales are predicted for Ag diffusion on Au(100) and Au(111), thus rendering very different regimes for the nucleation and growth of the related 2D phases. These observations are drawn from the application of a model free of any adjustable parameter.

Isotopic composition of tropospheric and soil N2O from successive depths of agricultural plots with contrasting crops and nitrogen amendments

Agricultural soils are the dominant contributor to increases in atmospheric nitrous oxide (N2O). Few studies have investigated the natural N and O isotopic composition of soil N2O. We collected soil gas samples using horizontal sampling tubes installed at successive depths under five contrasting agricultural crops (e.g., unamended alfalfa, fertilized cereal), and tropospheric air samples. Mean d 15N and d 18O values of soil N2O ranged from -28.0 to +8.9‰, and from +29.0 to +53.6‰. The mean d 15N and d 18O values of tropospheric N2O were +4.6 ± 0.7‰ and +48.3 ± 0.2‰, respectively. In general, d values were lowest at depth, they were negatively correlated to soil [N2O], and d 15N was positively correlated to d 18O for every treatment on all sampling dates. N2O from the different agricultural treatments had distinct d 15N and d 18O values that varied among sampling dates. Fertilized treatments had soil N2O with low d values, but the unamended alfalfa yielded N2O with the lowest d values. Diffusion was not the predominant process controlling N2O concentration profiles. Based on isotopic and concentration data, it appears that soil N2O was consumed, as it moved from deeper to shallower soil layers. To better assess the main process(es) controlling N2O within a soil profile, we propose a conceptual model that integrates data on net N2O production or consumption and isotopic data. The direct local impact of agricultural N2O on the isotopic composition of tropospheric N2O was recorded by a shift toward lower d values of locally measured tropospheric N2O on a day with very high soil N2O emissions.

Isotope Hydrology of the Oldman River basin, southern Alberta, Canada

The partially semi-arid Oldman River basin (OMRB), located in southern Alberta (Canada), has an area of 28 200 km2, is forested in its western headwater part, and is used for agriculture in its eastern part. Hydrometric measurements indicate that flow in the Oldman River has decreased by ~34% between 1913 and 2003, and it is predicted that water withdrawals will increase in the next 20 years. The objective of this study was to determine whether isotope ratio measurements can provide further insight into the water dynamics of the Oldman River and its tributaries. Surface water samples were collected monthly between December 2000 and March 2003. Groundwater samples were taken from 58 wells during one-time sampling trips. Runoff within the OMRB is currently about 70 mm year-1, with a corresponding runoff ratio of 0Ð18. Seasonal flow characteristics are markedly different upstream and downstream of the Oldman River reservoir. Upstream, sharp increases in flow in late spring and early summer are followed by a rapid decrease to base flow levels. Downstream, a prolonged high flow peak is observed due to the storage effect of the Oldman River reservoir. The seasonal variation in the isotopic composition of surface water from upstream sites is small. This suggests that peak runoff is not predominantly generated by melting snow accumulated during the preceding winter, but mainly by relatively well-mixed young groundwater. A significant increase in the d18O and d2H values in the downstream part of the basin was observed. The increase in the isotopic values is partly due to surface water and groundwater influx with progressively higher d18O and d2H values in the eastern part, and partly due to evaporation. Hence, the combination of hydrometric data with isotope measurements yields valuable insights into the water dynamics in the OMRB that may be further refined with more intensive measurement programmes in the future.

Tracing nitrate and sulfate in river basins using isotope techniques

The objective of this paper is to outline how stable isotope techniques can contribute to the elucidation of the sources and the fate of riverine nitrate and sulphate in watershed studies. The example used is the Oldman River Basin (OMRB), located in southern Alberta (Canada). Increasing sulphate concentrations and decreasing d34S values along the flowpath of the Oldman River indicate that oxidation of pyrite in tills is a major source of riverine sulphate in the agriculturally used portion of the OMRB. Chemical and isotopic data showed that manure-derived nitrogen contributes significantly to the increase in nitrate concentrations in the Oldman River and its tributaries draining agricultural land. It is suggested that hydrological conditions control agricultural return flows to the surface water bodies in southern Alberta and impart significant seasonal variations on concentrations and isotopic compositions of riverine nitrate. Combining isotopic, chemical, and hydrometric data permitted us to estimate the relative contribution of major sources to the total solute fluxes. Hence, we submit that isotopic measurements can make an important contribution to the identification of nutrient and pollutant sources and to river basin management.

Nitrogen budget for the Oldman River Basin, southern Alberta, Canada

The Oldman River Basin (OMRB), located in southern Alberta (Canada), with an area of 28,200 km2, is mainly forested in its western part and is used for intensive agriculture in its eastern part. The objective of this paper is to estimate the nitrogen (N) budget for the Oldman River Basin as a whole and its sub-basins, and to discuss differences in the N budget between various sub-basins. Better knowledge of the N budget in this watershed may be also utilized for understanding N dynamics in similar watersheds within semi-arid climatic regions. The model used is a mass balance spreadsheet model that takes into account N inputs and N export through surface water. During the last 120 years, anthropogenic N inputs to the OMRB have increased circa 40 fold. By the end of the 20th century, the OMRB received an annualN input of about 5174 kg N km-2 yr-1, whereas only about 25 kg N km-2 yr-1 were exported via riverine flow. For the sub-basins, annual N inputs ranged from 2516 to 19011 kg N km-2 yr-1, and annual N export via riverine flows varied between 6 and 277 kg N km-2 yr-1. Over 85% of total N inputs to the OMRB are due to anthropogenic activities, including manure (55%), synthetic fertilizer (27%), and N fixation on agricultural lands (4%). Sewage accounted for less than 1%, and N inputs from atmospheric deposition and fixation in forests represented 6 and 8% respectively. Despite increasing anthropogenic N inputs, N export with riverine flow currently accounts for only 1% of the inputs, indicating thatmost of theNinputs are currently retained in the OMRB or are re-emitted into the atmosphere.

Isotopic Assessment of Sources of Surface Water Nitrate within the Oldman River Basin, Southern Alberta, Canada

Concentrations and isotopic compositions of NO-3 from the Oldman River (OMR) and some of its tributaries (Alberta, Canada) have been determined on a monthly basis since December 2000 to assess temporal and spatial variations of riverine NO-3 sources within the OMR basin. For the OMR sites, NO-3 -N concentrations reached up to 0.34 mg L-1, d15N-NO-3 values varied between –0.3 and +13.8‰, and d18O-NO-3 values ranged from –10.0 to +5.7‰. For the tributary sites, NO-3 -N concentrations were as high as 8.81 mg L-1, d15N-NO-3 values varied between –2.5 and +23.4‰, and d18O-NO-3 values ranged from –15.2 to +3.4‰. Tributaries in the western, relatively pristine forested part of the watershed add predominantly NO-3 to the OMR with d15N-NO-3 indicative of soil nitrification. In contrast, tributaries in the eastern agriculturally-urban-industrially-used part of the basin contribute NO-3 with d15N-NO-3 values of about +16‰ indicative of manure and/or sewage derived NO-3. This difference in d15N-NO-3 values of tributaries was found to be independent of the season, but rather indicates a spatial change in the NO-3 source, which correlates with land use changes within the OMR basin. As a consequence of tributary influx, d15N-NO-3 values in the Oldman River increased from +6‰ in the downstream direction (W to E), although [NO-3 -N] increased only moderately (generally

Isotopic assessment of sources and processes affecting sulfate and nitrate in surface water and groundwater of Luxembourg

Surface water and deep and shallow groundwater samples were taken from selected parts of the Grand-Duchy of Luxembourg to determine the isotopic composition of nitrate and sulfate, in order to identify sources and/or processes affecting these solutes. Deep groundwater had sulfate concentrations between 20 and 40 mg/L, d34Ssulfate values between -3.0 and -20.0‰, and d18Osulfate values between +1.5 and +5.0‰; nitrate was characterized by concentrations varying between

Analyticity of smooth eigenfunctions and spectral analysis of the Gauss map

We provide a sufficient condition of analyticity of infinitely differentiable eigenfunctions of operators of the form Uf(x) = integral a(x, y) f(b( x, y)) mu(dy) acting on functions f: [u, v] --> C ( evolution operators of one-dimensional dynamical systems and Markov processes have this form). We estimate from below the region of analyticity of the eigenfunctions and apply these results for studying the spectral properties of the Frobenius-Perron operator of the continuous fraction Gauss map. We prove that any infinitely differentiable eigenfunction f of this Frobenius-Perron operator, corresponding to a non-zero eigenvalue admits a (unique) analytic extension to the set C\(-infinity, 1]. Analyzing the spectrum of the Frobenius Perron operator in spaces of smooth functions, we extend significantly the domain of validity of the Mayer and Ropstorff asymptotic formula for the decay of correlations of the Gauss map.

Identifying the influence of geology, land use, and anthropogenic activities on riverine sulfate on a watershed scale by combining hydrometric, chemical and isotopic approaches

Throughout the last few decades, sulfate concentrations in streamwater have received considerable attention due to their dominant role in anthropogenic acidification of surface waters. The objectives of this study conducted in the Oldman River Basin in Alberta (Canada) were to determine the influence of geology, land use and anthropogenic activities on sources, concentrations and fluxes of riverine sulfate on a watershed scale. This was achieved by combining hydrological, chemical and isotopic techniques. Surface water samples were collected from the main stem and tributaries of the Oldman River on a monthly basis between December 2000 and March 2003 and analyzed for chemical and isotopic compositions. At a given sampling site, sulfate sources were primarily dependent on geology and did not vary with time or flow condition. With increasing flow distance a gradual shift from ?34S values > 10 ‰ and ?18O values > 0 ‰ of riverine sulfate indicating evaporite dissolution and soil-derived sulfate in the predominantly forested headwaters, to negative ?34S and ?18O values suggested that sulfide oxidation was the predominant sulfate source in the agriculturally used downstream part of the watershed. Significant increases in sulfate concentrations and fluxes with downstream distance were observed, and were attributed to anthropogenically enhanced sulfide oxidation due to the presence of an extensive irrigation drainage network with seasonally varying water levels. Sulfate-S exports in an artificially drained subbasin (64 kg S/ha/yr) were found to exceed those in a naturally drained subbasin (4 kg S/ha/yr) by an order of magnitude. Our dataset suggests that the naturally occurring process of sulfide oxidation has been enhanced in the Oldman River Basin by the presence of an extensive network of drainage and irrigation canals.