Physical Sciences and Mathematics Commons^™

Molecular Characteristics Of The Water Soluable Organic Matter In Size Resolved Aerosols Collected Over The North Atlantic Ocean, Sarah Catherine Gurganus

Chemistry & Biochemistry Theses & Dissertations

Aerosol particulate matter is acknowledged to have effects on health and the environment and further investigation into the molecular characteristics of aerosols is necessary in order to fully understand the potential links between the molecular characteristics and the impacts that these particles have on health and the environment. Aerosols are often discussed with reference to their size because particles of different sizes can often be associated with different primary sources. This study presents a molecular-level chemical characterization of the water soluble organic matter fraction of 17 aerosol impactor samples representing 3 air mass influences (North American, North African, and marine) …

Production Mechanisms, Number Concentration, Size Distribution, Chemical Composition, And Optical Properties Of Sea Spray Aerosols, Nicholas Meskhidze, Markus D. Petters, Kostas Tsigaridis, Tim Bates, Colin O'Dowd, Jeff Reid, Ernie R. Lewis, Brett Gantt, Magdalena D. Anguelova, Prakash V. Bhave, Andrew Wozniak

Chemistry & Biochemistry Faculty Publications

(First paragraph)

The impact of sea spray aerosols on global climate remains one of the most uncertain components of the aerosol–radiation–climate problem, but has received less attention than the impacts of terrestrial and anthropogenic aerosols. The last decade has produced a large body of information regarding the sources and composition of marine aerosols, resulting in a reassessment of the complex role that sea spray particles play in climate and various geophysical phenomena. As sea spray aerosol contributes substantially to the preindustrial, natural background which provides the baseline on top of which anthropogenic forcing should be quantified, and because the ocean …

Quantifying The Impact Of Boreal Forest Fires On Tropospheric Oxidants Over The Atlantic Using Aircraft And Satellites (Bortas) Experiment: Design, Execution And Science Overview, P. I. Palmer, M. Parrington, J. D. Lee, A, C. Lewis, A. R. Rickard, P. F. Bernath, T. J. Duck, D. L. Waugh, D. W. Tarasick, S. Andrews

Chemistry & Biochemistry Faculty Publications

We describe the design and execution of the BORTAS (Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) experiment, which has the overarching objective of understanding the chemical aging of air masses that contain the emission products from seasonal boreal wildfires and how these air masses subsequently impact downwind atmospheric composition. The central focus of the experiment was a two-week deployment of the UK BAe-146-301 Atmospheric Research Aircraft (ARA) over eastern Canada, based out of Halifax, Nova Scotia. Atmospheric ground-based and sonde measurements over Canada and the Azores associated with the planned …

Improved Method For Quantifying The Air-Sea Flux Of Volatile And Semi-Volatile Organic Carbon, Emily Hauser, Rebecca M. Dickhut, Renee Falconer, Andrew S. Wozniak

Chemistry & Biochemistry Faculty Publications

A method for quantifying the diffusive air-sea exchange of gaseous organic carbon (OC) was developed. OC compounds were separated into two operational pools-those that were kinetically air limited in diffusion across the air-sea interface and those that were water limited-during simultaneous air/water sampling. The method separates OC compounds into low Henry's law constant (low-H) semivolatile OC (SOC) and high Henry's law constant (high-H) volatile OC (VOC) pools that can be categorized by relating diffusion kinetic parameters to Henry's Law constant. Air limited (low-H; H << similar to 0.1 L atm mol(^-1)) compounds were collected in pure water traps and were quantified as dissolved OC, whereas …

Global And Long-Term Comparison Of Sciamachy Limb Ozone Profiles With Correlative Satellite Data (2002-2008), S. Mieruch, M. Weber, C. Von Savigny, A. Rozanov, H. Bovensmann, J. P. Burrows, P. F. Bernath, C. D. Boone, L. Froidevaux, L. L. Gordley, M. G. Mlynczak, J. M. Russell Iii, L. W. Thomason, K. A. Walker, J. M. Zawodny

Chemistry & Biochemistry Faculty Publications

SCIAMACHY limb scatter ozone profiles from 2002 to 2008 have been compared with MLS (2005–2008), SABER (2002–2008), SAGE II (2002–2005), HALOE (2002–2005) and ACE-FTS (2004–2008) measurements. The comparison is performed for global zonal averages and heights from 10 to 50 km in one km steps. The validation was performed by comparing monthly mean zonal means and by comparing averages over collocated profiles within a zonal band and month. Both approaches yield similar results. For most of the stratosphere SCIAMACHY agrees to within 10% or better with other correlative data. A systematic bias of SCIAMACHY ozone of up to 100% between …

Analysis Of Iasi Tropospheric O₃ Data Over The Arctic During Polarcat Campaigns In 2008, M. Pommier, C. Clerbaux, K. S. Law, G. Ancellet, P. Bernath, P.-F. Coheur, J. Hadji-Lazaro, D. Hurtmans, P. Nédélec, J.-D. Paris, F. Ravetta, T. B. Ryerson, H. Schlager, A. J. Weinheimer

Chemistry & Biochemistry Faculty Publications

Ozone data retrieved in the Arctic region from infrared radiance spectra recorded by the Infrared Atmospheric Sounding Interferometer (IASI) on board the MetOp-A European satellite are presented. They are compared with in situ and lidar observations obtained during a series of aircraft measurement campaigns as part of the International Polar Year POLARCAT activities in spring and summer 2008. Different air masses were sampled during the campaigns including clean air, polluted plumes originating from anthropogenic sources, forest fire plumes from the three northern continents, and stratospheric-influenced air masses. The comparison between IASI O₃ [0–8 km], [0–12 km] partial columns and …

Process-Evaluation Of Tropospheric Humidity Simulated By General Circulation Models Using Water Vapor Isotopologues: 1. Comparison Between Models And Observations, Camille Risi, David Noone, John Worden, Christian Frankenberg, Gabriele Stiller, Michael Kiefer, Bernd Funke, Kaley Walker, Peter Bernath, Matthias Schneider, Debra Wunch, Vanessa Sherlock, Nicholas Deutscher, David Griffith, Paul O. Wennberg, Kimberly Strong, Dan Smale, Emmanuel Mahieu, Sabine Barthlott, Frank Hase, Omaira García, Justus Notholt, Thorsten Warneke, Geoffrey Toon, David Sayres, Sandrine Bony, Jeonghoon Lee, Derek Brown, Ryu Uemura, Christophe Sturm

Chemistry & Biochemistry Faculty Publications

The goal of this study is to determine how H₂O and HDO measurements in water vapor can be used to detect and diagnose biases in the representation of processes controlling tropospheric humidity in atmospheric general circulation models (GCMs). We analyze a large number of isotopic data sets (four satellite, sixteen ground-based remote-sensing, five surface in situ and three aircraft data sets) that are sensitive to different altitudes throughout the free troposphere. Despite significant differences between data sets, we identify some observed HDO/H₂O characteristics that are robust across data sets and that can be used to evaluate …

Process-Evaluation Of Tropospheric Humidity Simulated By General Circulation Models Using Water Vapor Isotopic Observations: 2. Using Isotopic Diagnostics To Understand The Mid And Upper Tropospheric Moist Bias In The Tropics And Subtropics, Camille Risi, David Noone, John Worden, Christian Frankenberg, Gabriele Stiller, Michael Kiefer, Bernd Funke, Kaley Walker, Peter Bernath, Matthias Schneider, Sandrine Bony, Jeonghoon Lee, Derek Brown, Christophe Sturm

Chemistry & Biochemistry Faculty Publications

Evaluating the representation of processes controlling tropical and subtropical tropospheric relative humidity (RH) in atmospheric general circulation models (GCMs) is crucial to assess the credibility of predicted climate changes. GCMs have long exhibited a moist bias in the tropical and subtropical mid and upper troposphere, which could be due to the mis-representation of cloud processes or of the large-scale circulation, or to excessive diffusion during water vapor transport. The goal of this study is to use observations of the water vapor isotopic ratio to understand the cause of this bias. We compare the three-dimensional distribution of the water vapor isotopic …

Observation Of Sulfate Aerosols And So₂ From The Sarychev Volcanic Eruption Using Data From The Atmospheric Chemistry Experiment (Ace), D. Doeringer, A. Eldering, C. D. Boone, G. González Abad, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

[1] Infrared spectra measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on the SCISAT satellite were used to analyze the Sarychev volcanic aerosol after the eruption in June 2009. Evidence of the Sarychev eruptions was first detected in July 2009 from enhanced SO₂ concentrations and atmospheric extinction. By February 2010, the atmosphere had returned to pre-Sarychev conditions. In July 2009, the volcanic plume was found between 8.5 km and 17.5 km in altitude at mid- and high latitudes (55°N–70°N). The first SO₂ and sulfate aerosol retrievals carried out using the infrared solar occultation spectra recorded with …

Fourier Transform Mass Spectrometry For The Molecular Level Characterization Of Natural Organic Matter: Instrument Capabilities, Applications, And Limitations, Rachel L. Sleighter, Patrick G. Hatcher, Goran Nikolić (Ed.)

Chemistry & Biochemistry Faculty Publications

No abstract provided.

Fossil And Contemporary Aerosol Particulate Organic Carbon In The Eastern United States: Implications For Deposition And Inputs To Watersheds, Andrew S. Wozniak, James E. Bauer, Rebecca M. Dickhut

Chemistry & Biochemistry Faculty Publications

Atmospheric particulate matter samples were collected from mid-Atlantic and northeastern U. S. (Virginia and New York, respectively) sites to assess the fossil versus contemporary sources contributing to aerosol organic carbon (OC) and the implications for its deposition to watersheds. Mean particulate matter total OC (TOC) deposition rates (wet + dry deposition) were calculated to be 1.6 and 2.4 mg C m^-2 d^-1 for the Virginia and New York sites, respectively. Wet deposition of particulate TOC was determined to be the dominant depositional mode, accounting for >65% (Virginia) and >80% (New York) of total aerosol TOC deposition. Isotopic mass …

Anthropogenic Osmium In Rain And Snow Reveals Global-Scale Atmospheric Contamination, Cynthia Chen, Peter N. Sedwick, Mukul Sharma

OES Faculty Publications

Osmium is one of the rarer elements in seawater, with typical concentration of ≈10 x 10^-15 g g^-1 ( 5.3 x 10^-14 mol kg^-1. The osmium isotope composition (¹⁸⁷Os/¹⁸⁸Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (≈ 1.3) and mantle/cosmic dust (≈ 0.13). Here, we show that the ¹⁸⁷Os/¹⁸⁸Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (approximate to 0.2) …

Open-Ocean Carbon Monoxide Photoproduction, Aron Stubbins, Günther Uher, Cliff S. Law, Kenneth Mopper, Carol Robinson, Robert C. Upstill-Goddard

Chemistry & Biochemistry Faculty Publications

Sunlight-initiated photolysis of chromophoric dissolved organic matter (CDOM) is the dominant source of carbon monoxide (CO) in the open-ocean. A modelling study was conducted to constrain this source. Spectral solar irradiance was obtained from two models (GCSOLAR and SMARTS2). Water-column CDOM and total light absorption were modelled using spectra collected along a Meridional transect of the Atlantic ocean using a 200-cm pathlength liquid waveguide UV-visible spectrophotometer. Apparent quantum yields for the production of CO (AQY_CO) from CDOM were obtained from a parameterisation describing the relationship between CDOM light absorption coefficient and AQY_CO and the CDOM spectra collected. …

Effect Of Humic Substance Photodegradation On Bacterial Growth And Respiration In Lake Water, Alexandre M. Anesio, William Granéli, George R. Aiken, David J. Kieber, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

This study addresses how humic substance (HS) chemical composition and photoreactivity affect bacterial growth, respiration, and growth efficiency (BGE) in lake water. Aqueous solutions of HSs from diverse aquatic environments representing different dissolved organic matter sources (autochthonous and allochthonous) were exposed to artificial solar UV radiation. These solutions were added to lake water passed through a 0.7-μm pore-size filter (containing grazer-free lake bacteria) followed by dark incubation for 5, 43, and 65 h. For the 5-h incubation, several irradiated HSs inhibited bacterial carbon production (BCP) and this inhibition was highly correlated with H₂O₂ photoproduction. The H_{2 …}

Styrene Monomer Solubility In Artificial And Natural Seawaters Of The Lower Chesapeake Bay, Eric Joseph Miller

Chemistry & Biochemistry Theses & Dissertations

Used for making a variety of plastic products, styrene monomer is an aromatic hydrocarbon frequently shipped in bulk quantities through the Port of Hampton Roads, Virginia. Despite its common use around the world and its high aquatic toxicity, little research has been conducted on the chemical's aqueous solubility and reactions during a major spill. In this study, the solubility of styrene monomer was measured in artificial seawater and natural waters collected from four sites on the lower Chesapeake Bay and Elizabeth River. The samples represented a range of different water chemistries in terms of salinity (13.8 — 29.0%) and the …

Binding Of Pb And Zn To Aluminium Oxide And Proton Stoichiometry, Wing H. Leung, A. Kimaro

Virginia Journal of Science

The interaction of Pb and Zn with Al₂O₃ in aqueous solution was studied as a function of pH and metal ion concentration. Results indicated the complexation of metal ions by oxide surfaces is strongly pH dependent; the extent of adsorption is a function of pH with an abrupt change within approximately 2 pH units. The adsorption of Pb and Zn on aluminium oxide can be interpreted in terms of a surface complexation formed by association with one surface AlOH group, thus releasing one bound hydrogen ion. -AlOH + M²⁺ = -AlOM⁺ + H⁺ . …

Humic Substances As Interferences In The Analysis Of Nitrite In Water, Stephanie Ann Tebault

Chemistry & Biochemistry Theses & Dissertations

Humic substances are of current interest because of their roles in environmental processes involving pollutants. It is also becoming recognized that humic substances may interfere in analysis of environmental samples though the possible adverse effects do not appear to be fully appreciated. The present effort focuses on determining whether humic materials interfere in the analysis of nitrite in water using the Griess reaction. This is a well-known reaction using nitrosation to gjve a diazonium salt followed by coupling with an appropriate reagent to form a dye. This colorimetric method continues to be applied in the laboratory and the field for …

Zinc Speculation And Ligand Fluxes In Chesapeake Bay And Elizabeth River Pore Waters, Duncan Glover Byers

Chemistry & Biochemistry Theses & Dissertations

Presented here are the first data on the vertical concentrations, complexation, speciation, and fluxes of total dissolved zinc and zinc complexing ligands, and zinc speciation in sediment pore waters in the Chesapeake Bay and Elizabeth River, Virginia.

Sediment pore waters were collected in mid and southern Chesapeake Bay in November 1997 and in the Elizabeth River (Pinner's Point) in March, April, and July 1998. Flux experiments were conducted in Elizabeth River sediment cores in April and July 1998. [TDZn] and zinc complexation were determined using differential pulse anodic stripping voltammetry at a hanging mercury drop electrode (DPASV-HMDE).

[TDZn] in the …

Concentrations, Complexation And Speciation Of Total Dissolved Zinc In The Chesapeake Bay, Charles William Henry Iii

Chemistry & Biochemistry Theses & Dissertations

This is the first research to examine the horizontal, vertical, and temporal variability of total dissolved zinc, organic complexation of zinc, and zinc speciation in the Chesapeake Bay. Filtered (0.45μm) surface and bottom water samples were taken along the salinity gradient of the Chesapeake Bay in October 1993, March 1995, July 1995, and October 1995. Analysis by Differential Pulse Anodic Stripping Voltammetry (DP ASV) indicated that total dissolved zinc concentrations in the Bay ranged from 2.9 ± 0.7nM to 38.8 ± 2nM. Total zinc was highest at the northern end of the Bay (low salinity), approximately 10 times lower at …

Surface Flow Structure Of The Gulf Stream From Composite Imagery And Satellite-Tracked Drifters, C. P. Mullen, A. D. Kirwan Jr.

CCPO Publications

A unique set of coutemporaneous satellite-tracked drifters and five-day composite Advanced Very High Resolution Radionmeter (AVHRR) satellite imagery of the North Atlantic has been analyzed to examine the surface flow structure of the Gulf Stream. The study region was divided into two sections, greater than 37 degrees N and less than 37 degrees N, in order to answer the question of geographic variability. Fractal and spectral analyses methods were applied to the data. Fractal analysis of the Lagrangian trajectories showed a fractal dimension of 1.21 +/- 0.02 with a scaling range of 83 - 343 km. The fractal dimension of …

Reactions Of Aqueous Chlorine With Valine In Model Solutions And In Wastewater, Erika Forrer Mccormick

Chemistry & Biochemistry Theses & Dissertations

Solutions of the amino acid valine were chlorinated to seven chlorine-to-nitrogen mole (Cl/N) ratios and analyzed by high performance liquid chromatography, gas chromatography/mass spectroscopy, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. The chlorination products found were N-chlorovaline, isobutyraldehyde, isobutyronitrile, and N-chloroisobutyraldimine. Their product distribution depends on the level of chlorination and pH. The main products identified at the lower CI/N mole ratios were N-chlorovaline and isobutyraldehyde, whereas at the higher CI/N mole ratios isobutyronitrile and N-chloroisobutyraldimine were identified as the main products. The concentration and the chlorination products of valine in municipal wastewater were also determined. The chlorination products of …

Permanganate Colorimetric Rapid Method For Chemical Oxygen Demand In Seawater, Myung Zoon Czae, Taekee Hong, Myung Hoon Kim

Chemistry & Biochemistry Faculty Publications

No abstract provided.