Comparison of Model Chemistry and Density Functional Theory Thermochemical Predictions with Experiment for Formation of Ionic Clusters of the Ammonium Cation Complexed with Water and Ammonia; Atmospheric Implications

The G2, G3, CBS-QB3, and CBS-APNO model chemistry methods and the B3LYP, B3P86, mPW1PW, and PBE1PBE density functional theory (DFT) methods have been used to calculate ΔH° and ΔG° values for ionic clusters of the ammonium ion complexed with water and ammonia. Results for the clusters NH4+(NH3)n and NH4+(H2O)n, where n = 1−4, are reported in this paper and compared against experimental values. Agreement with the experimental values for ΔH° and ΔG° for formation of NH4+(NH3)n clusters is excellent. Comparison between experiment and theory for formation of the NH4+(H2O)n clusters is quite good considering the uncertainty in the experimental values. The four DFT methods yield excellent agreement with experiment and the model chemistry methods when the aug-cc-pVTZ basis set is used for energetic calculations and the 6-31G* basis set is used for geometries and frequencies. On the basis of these results, we predict that all ions in the lower troposphere will be saturated with at least one complete first hydration shell of water molecules.

Atmospheric Implications for Formation of Clusters of Ammonium and 1−10 Water Molecules

A mixed molecular dynamics/quantum mechanics model has been applied to the ammonium/water clustering system. The use of the high level MP2 calculation method and correlated basis sets, such as aug-cc-pVDZ and aug-cc-pVTZ, lends confidence in the accuracy of the extrapolated energies. These calculations provide electronic and free energies for the formation of clusters of ammonium and 1−10 water molecules at two different temperatures. Structures and thermodynamic values are in good agreement with previous experimental and theoretical results. The estimated concentration of these clusters in the troposphere was calculated using atmospheric amounts of ammonium and water. Results show the favorability of forming these clusters and implications for ion-induced nucleation in the atmosphere.

Abandoned Coal Mine Drainage and Its Remediation: Impacts on Stream Ecosystem Structure and Function

The effects of abandoned mine drainage (AMD) on streams and responses to remediation efforts were studied using three streams (AMD-impacted, remediated, reference) in both the anthracite and the bituminous coal mining regions of Pennsylvania (USA). Response variables included ecosystem function as well as water chemistry and macroinvertebrate community composition. The bituminous AMD stream was extremely acidic with high dissolved metals concentrations, a prolific mid-summer growth of the filamentous alga, Mougeotia, and .10-fold more chlorophyll than the reference stream. The anthracite AMD stream had a higher pH, substrata coated with iron hydroxide(s), and negligible chlorophyll. Macroinvertebrate communities in the AMD streams were different from the reference streams, the remediated streams, and each other. Relative to the reference stream, the AMD stream(s) had (1) greater gross primary productivity (GPP) in the bituminous region and undetectable GPP in the anthracite region, (2) greater ecosystem respiration in both regions, (3) greatly reduced ammonium uptake and nitrification in both regions, (4) lower nitrate uptake in the bituminous (but not the anthracite) region, (5) more rapid phosphorus removal from the water column in both regions, (6) activities of phosphorus-acquiring, nitrogenacquiring, and hydrolytic-carbon-acquiring enzymes that indicated extreme phosphorus limitation in both regions, and (7) slower oak and maple leaf decomposition in the bituminous region and slower oak decomposition in the anthracite region. Remediation brought chlorophyll concentrations and GPP nearer to values for respective reference streams, depressed ecosystem respiration, restored ammonium uptake, and partially restored nitrification in the bituminous (but not the anthracite) region, reduced nitrate uptake to an undetectable level, restored phosphorus uptake to near normal rates, and brought enzyme activities more in line with the reference stream in the bituminous (but not the anthracite) region. Denitrification was not detected in any stream. Water chemistry and macroinvertebrate community structure analyses capture the impact of AMD at the local reach scale, but functional measures revealed that AMD has ramifications that can cascade to downstream reaches and perhaps to receiving estuaries.

Collision-Induced Dissociation Of Dipeptides In Negative Ion Electrospray Ionization Tandem Mass Spectrometry

This purpose of this project was to investigate the collision-induced dissociation of dipeptides in negative ion electrospray ionization tandem mass spectrometry, with a focus on the mechanism of the production of imidazole-type fragments not previously reported from the fragmentation of the dipeptides being studied. The majority of the dipeptides studied were alanine N-terminal or serine C-terminal dipeptides. All dipeptides were dissolved in 50:50 methanol:water, 3 mM ammonium formate. Collision-induced dissociation in the collision cell of a triple quadrupole mass spectrometer was used to fragment [M-H]- precursor ions. Accurate mass measurements confirmed the molecular formula of the imidazole-type fragments. Further MS/MS studies were performed to provide information about the fragmentation mechanism for the formation of the imidazole-type fragments. The m/z values of intermediate ions in the formation of the imidazole-type fragments were confirmed through second-generation product ion scans and precursor ion scans. More sophisticated instrumentation will be required to further probe the structure of the intermediate ions.

Hydrologic and Water Quality Assessment of Miller Run: A Study of Bucknell University’s Impact

Human development causes degradation of stream ecosystems due to impacts on channel morphology, hydrology, and water quality. Urbanization, the second leading cause of stream impairment, increases the amount of impervious surface cover, thus reducing infiltration and increasing surface runoff of precipitation, which ultimately affects stream hydrologic process and aquatic biodiversity. The main objective of this study was to assess the overall health of Miller Run, a small tributary of the Bull Run and Susquehanna River watersheds, through an integrative hydrologic and water quality approach in order to determine the degree of Bucknell University’s impact on the stream. Hydrologic conditions, including stage and discharge, and water quality conditions, including total suspended solids, ion, nutrient, and dissolved metal concentrations, specific conductivity, pH, and temperature, were measured and evaluated at two sampling sites (upstream and downstream of Bucknell’s main campus) during various rain events from September 2007 to March 2008. The primary focus of the stream analysis was based on one main rain event on 26 February 2008. The results provided evidence that Miller Run is impacted by Bucknell’s campus. From a hydrologic perspective, the stream’s hydrograph showed the exact opposite pattern of what would be expected from a ‘normal’ stream. Miller run had a flashier downstream hydrograph and a broader upstream hydrograph, which was more than likely due to the increased amount of impervious surface cover throughout the downstream half of the watershed. From a water quality perspective, sediment loads increased at a faster rate and were significantly higher downstream compared to upstream. These elevated sediment concentrations were probably the combined result of sediment runoff from upstream and downstream construction sites that were being developed over the course of the study. Sodium, chloride, and potassium concentrations, in addition to specific conductivity, also significantly increased downstream of Bucknell’s campus due to the runoff of road salts. Calcium and magnesium concentrations did not appear to be impacted by urbanization, although they did demonstrate a significant dilution effect downstream. The downstream site was not directly affected by elevated nitrate concentrations; however, soluble reactive phosphorus concentrations tended to increase downstream and ammonium concentrations significantly peaked partway through the rain event downstream. These patterns suggest that Miller Run may be impacted by nutrient runoff from the golf course, athletic fields, and/or fertilizers applications on the main campus. Dissolved manganese and iron concentrations also appeared to slightly increase downstream, demonstrating the affect of urban runoff from roads and parking lots. pH and temperature both decreased farther downstream, but neither showed a significant impact of urbanization. More studies are necessary to determine how Miller Run responds to changes in season, climate, precipitation intensity, and land-use. This study represents the base-line analysis of Miller Run’s current hydrologic and water quality conditions; based on these initial findings, Bucknell should strongly consider modifications to improve storm water management practices and to reduce the campus’s overall impact on the stream in order to enhance and preserve the integrity of its natural water resources.