MODELING THE IMPACT OF MULTICOMPONENT VOCs ON GROUND WATER USING THE STEFAN‐MAXWELL EQUATION1

ABSTRACT: Computer programs that model the fate and transport of organic contaminants through porous media typically use Fick's first law to calculate vapor phase diffusion. Fick's first law, however, is limited to the case of a single, dilute species diffusing into a stagnant, high concentration, bulk vapor phase. When dealing with more than one diffusing species and at higher concentrations, the multicomponent coupling effects on vapor phase diffusion and advection of the various constituents become significant. VLEACH, a one‐dimensional finite difference model developed for the U.S. Environmental Protection Agency (USEPA), is typical of the models using Fick's first law to model vapor‐phase diffusion. The VLEACH model was modified to accommodate up to 10 components and to calculate the binary diffusion coefficients for each of the components based on molecular weight, molecular volume, temperature and pressure, and to address the coupling effects on multiple component vapor phase diffusion and its impact on ground water. The resulting model was renamed MC‐CHEMSOIL. At low vapor phase concentrations, MC‐CHEMSOIL predicts identical ground water impacts (dissolved phase loading) to those from VLEACH 2.2a. At higher vapor phase concentrations, however, the relative difference between the models exceeded 20 percent.     

MODELING SEDIMENT AND PHOSPHORUS LOSSES IN AN AGRICULTURAL WATERSHED TO MEET TMDLs1

ABSTRACT: This paper studies the effectiveness of alternative farm management strategies at improving water quality to meet Total Maximum Daily Loads (TMDLs) in agricultural watersheds. A spatial process model was calibrated using monthly flow, sediment, and phosphorus (P) losses (1994 to 1996) from Sand Creek watershed in south‐central Minnesota. Statistical evaluation of predicted and observed data gave r² coefficients of 0.75, 0.69, and 0.49 for flow (average 4.1 m³/s), sediment load (average 0.44 ton/ha), and phosphorus load (average 0.97 kg/ha), respectively. The calibrated model was used to evaluate the effects of conservation tillage, conversion of crop land to pasture, and changes in phosphorus fertilizer application rate on pollutant loads. TMDLs were developed for sediment and P losses based on existing water quality standards and guidelines. Observed annual sediment and P losses exceeded these TMDLs by 59 percent and 83 percent, respectively. A combination of increased conservation tillage, reduced application rates of phosphorus fertilizer, and conversion of crop land to pasture could reduce sediment and phosphorus loads by 23 percent and 20 percent of existing loads, respectively. These reductions are much less than needed to meet TMDLs, suggesting that control of sediment using buffer strips and control of point sources of phosphorus are needed for the remaining reductions.     

CHEMISTRY OF COALBED METHANE DISCHARGE WATER INTERACTING WITH SEMI‐ARID EPHEMERAL STREAM CHANNELS1

ABSTRACT: The objective of this study was to examine the chemistry of Coalbed Methane (CBM) discharge water reacting with semi‐arid ephemeral stream channels in the Powder River Basin, Wyoming. The study area consisted of two ephemeral streams: Burger Draw and Sue Draw. These streams are tributaries to the perennial Powder River. Samples were collected bimonthly from three CBM discharge points and seven channel locations in Burger Draw and Sue Draw. Samples were also collected bimonthly from the Powder River above and below the confluence of Burger Draw. Before sample collection, the pH and electrical conductivity (EC) were measured in the field. Samples were transported to the laboratory and analyzed for alkalinity, major cations, and anions. From the measurement of sodium (Na), calcium (Ca), and magnesium (Mg), practical sodium adsorption ratio (SARp) and true sodium adsorption ratio (SARt) were calculated. Results suggest pH and EC of CBM discharge water was 7.1 and 4.3 dS/m, respectively. The CBM discharge water consisted of higher concentrations of sodium and alkalinity compared to other components. The pH of CBM discharge water increased significantly (p = 0.000) in the downstream channel of Burger Draw from 7.1 to 8.84 before it joined with the Powder River. Dissolved calcium concentration of CBM discharge water decreased significantly (p = 0.000) in the downstream channel water. Subsequently, SARp increased approximately from 24 to 29. The SARt also increased significantly (p = 0.001) in the downstream channel water. For instance, SARt of CBM discharge water increased from 32.93 to 45.5 downstream channels after the confluence of Sue Draw with the Burger Draw. The only significant difference in water chemistry above and below the confluence of Burger Draw with the Powder River was pH, which increased from 8.36 to 8.52. The significant increase in SAR values of CBM discharge water in Burger Draw and Sue Draw tributaries suggest a careful monitoring of salinity and sodicity is needed if CBM discharge water is used for irrigation in semi‐arid environments. Results discussed in this study will be useful to downstream water users who depend on water for irrigation.     

MODELING THE IMPACTS OF WATER LEVEL CHANGES ON A GREAT LAKES COMMUNITY1

ABSTRACT: Recent research that couples climate change scenarios based on general circulation models (GCM) with Great Lakes hydrologic models has indicated that average water levels are projected to decline in the future. This paper outlines a methodology to assess the potential impact of declining water levels on Great Lakes waterfront communities, using the Lake Huron shoreline at Goderich, Ontario, as an example. The methodology utilizes a geographic information system (GIS) to combine topographic and bathymetric datasets. A digital elevation surface is used to model projected shoreline change for 2050 using water level scenarios. An arbitrary scenario, based on a 1 m decline from February 2001 lake levels, is also modeled. By creating a series of shoreline scenarios, a range of impact and cost scenarios are generated for the Goderich Harbor and adjacent marinas. Additional harbor and marina dredging could cost as much as CDN $7.6 million. Lake freighters may experience a 30 percent loss in vessel capacity. The methodology is used to provide initial estimates of the potential impacts of climate change that can be readily updated as more robust climate change scenarios become available and is adaptable for use in other Great Lakes coastal communities.     

Political will,political skill,and political behavior

The current study used Mintzberg's (1983) conceptualization of political will and political skill to evaluate the predictors and consequences of political behavior at work. As elements of political will, we hypothesized that need for achievement and intrinsic motivation would predict the use of political behavior at work. Furthermore, we argued that political skill would moderate the relationship between political behavior and emotional labor. Data gathered from employees (N = 193) representing a wide array of organizations substantiated the proposed relationships. Specifically, need for achievement and intrinsic motivation were positively associated with political behavior. In turn, those opting to employ political behavior at work experienced a higher degree of emotional labor, but this relationship was found to operate differently at low and high levels of political skill. Specifically, emotional labor was a consequence of political behavior for those low in political skill, but emotional labor reactions from political behavior were neutralized for individuals high in political skill. Implications of these results, strengths and limitations, and directions for future research are discussed. Copyright © 2005 John Wiley & Sons, Ltd.     

Carbon sequestration: Do N inputs and elevated atmospheric CO2 alter soil solution chemistry and respiratory C losses?

Soil respiration is a large C flux which is of primary importance in determining C sequestration. Here we ask how it is altered by atmospheric CO₂ concentration and N additions. Swards of Lolium perenne L. were grown in a Eutric cambisol under controlled conditions with and without the addition of 200 kg NO^? ₃ ?N ha^?1, at either 350 ppm or 700 ppm CO₂, for 3 months. Soil respiration and net canopy photosynthesis were both increased by added N and elevated CO₂, but soil respiration increased proportionately less than fixation by photosynthesis. Thus, both elevated CO₂ and N appeared to increase potential C sequestration, although adding N at elevated CO₂ reduced the C sequestered as a proportion of that fixed relative to elevated CO₂ alone. Across all treatments below-ground respiratory C losses were predicted by root biomass, but not by soil solution C and N concentrations. Specific root-dependent respiration was increased by elevated CO₂, such that below-ground respiration per unit biomass and per unit plant N was increased.     

An automated wet deposition system to compare the effects of reduced and oxidised N on ombrotrophic bog species: Practical considerations

Critical N loads for ombrotrophic bogs, which often contain rare and N-sensitive plants (especially those in lower plant groups: lichens, mosses and liverworts), are based on very few experimental data from measured, low background N deposition areas. Additionally the relative effects of reduced versus oxidised N are largely unknown. This paper describes an automated field exposure system (30 km S. of Edinburgh, Scotland) for treating ombrotrophic bog vegetation with fine droplets of oxidised N (NaNO₃) and reduced N (NH₄Cl). Whim Moss exists in an area of low ambient N deposition (ca. 8 kg N ha^?1 y^?1), the sources and quantification of which are described. The wet N treatment system is run continuously, and is controlled/activated by wind speed and rainfall to provide a unique simulation of “real worl” treatment patterns (no rain=no treatment). Simulated precipitation is supplied at ionic concentrations below 4 mM in rainwater collected on site. Treatments provide a replicated dose response to 16, 32 and 64 kg N ha^?1 y^?1 adjusted for ambient deposition (8 kg N ha^?1 y^?1). The 16 and 64 kg N ha^?1 y^?1 are duplicated with a P+K supplement. Baseline soil chemistry and foliar nutrient status was established for all 44 plots for Calluna vulgaris, Sphagnum capillifolium, Hypnum jutlandicum and Cladonia portentosa.     

Quantifying dry NH3 deposition to an ombrotrophic bog from an automated NH3 field release system

Providing an accurate estimate of the dry component of N deposition to low N background, semi-natural habitats, such as bogs and upland moors dominated by Calluna vulgaris is difficult, but essential to relate nitrogen deposition to effects in these communities. To quantify the effects of NH₃ inputs to moorland vegetation growing on a bog at a field scale, a field release NH₃ fumigation system was established at Whim Moss (Scottish Borders) in 2002. Gaseous NH₃ from a line source was released along of a 60 m transect, when meteorological conditions (wind speed >2.5 m s^?1 and wind direction in the sector 180–215°) were met, thereby providing a profile of decreasing NH₃ concentration with distance from the source. In a complementary study, using a NH₃ flux chamber system, the relationships between NH₃ concentrations and cuticular resistances were quantified for a range of NH₃ concentrations and micrometeorological conditions for moorland vegetation. Cuticular resistances increased with NH₃ concentration from 11 s m^?1 at 3.0 μg m^?3 to 30 s m^?1 at 30 μg m^?3. The NH₃ concentration data and the concentration-dependent canopy resistance are used to calculate NH₃ deposition taking into account leaf surface wetness. The implications of using an NH₃ concentration-dependent cuticular resistance and the importance for refining critical loads are discussed.     

Correlating the spatial distribution of atmospheric ammonia with δ15n values at an ammonia release site

A field ammonia (NH₃) release experiment and open top chambers containing moorland monoliths continuously fumigated with NH₃ or sprayed with NH₄Cl were used to assess the potential for using δ¹⁵N values in determining the area of influence around a point NH₃ emission source. δ¹⁵N values are being increasingly used as environmental tracers and we tested the hypothesis that the δ¹⁵N signal from an NH₃ emission source is observable in nearby vegetation. Using modified monitoring devices, atmospheric NH₃ concentrations were found to decrease with distance from source, with δ¹⁵N values also reflecting this trend, producing a signal shift with changing concentration. Open top chamber studies of δ¹⁵N values of Calluna vulgaris (L.) Hull indicated a correlation with deposition treatments in current year shoots. Analysis of Calluna shoots from the NH₃ release showed a similar trend of δ¹⁵N enrichment. Significant linear correlations between δ¹⁵N and percent N in plant material were found, both in the controlled conditions of the open top chambers and at the NH₃ release site, illustrating the possible use of this technique in N deposition biomonitoring.     

Linking field experiments to long-term simulation of impacts of nitrogen deposition on heathlands and moorlands

The results from three long-term field manipulation studies of the impacts of increased nitrogen deposition (0–120 kg N ha^?1 yr^?1) on lowland and upland heathlands in the UK were compared, to test if common responses are observed. Consistent increases in Calluna foliar N content and decreases in litter C:N ratios were found across all sites, while increases in N leaching were not observed at any site over the range 0–80 kg ha^?1 yr^?1. However, the response of Calluna biomass did vary between sites, possibly reflecting site differences in nutrient status and management histories. Five versions of a simulation model of heathland responses to N were developed, each reflecting different assumptions about the fate and turnover of soil N. Model outputs supported the deduction from mass balance calculations at two of the field sites that N additions have resulted in an increase in immobilisation; the latter was needed to prevent the model overestimating measured N leaching. However, this version of the model significantly underestimated Calluna biomass. Model versions, which included uptake of organic N by Callunaand re-mobilisation of N from the soil organic store provided some improvement in the fit between modelled and field biomass data, but re-mobilisation also led to an overestimation of N leaching. Quantification of these processes and their response to increased N deposition are therefore critical to interpreting experimental data and predicting the long-term impacts of atmospheric deposition on heathlands and moorlands.