Chemistry Commons^™

A Chemical Ionization Mass Spectrometer For Continuous Underway Shipboard Analysis Of Dimethylsulfide In Near-Surface Seawater, Eric S. Saltzman, Warren J. De Bruyn, M. J. Lawler, Christa Marandino, C. A. Mccormick

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

A compact, low-cost atmospheric pressure, chemical ionization mass spectrometer ('mini-CIMS') has been developed for continuous underway shipboard measurements of dimethylsulfide (DMS) in seawater. The instrument was used to analyze DMS in air equilibrated with flowing seawater across a porous Teflon membrane equilibrator. The equilibrated gas stream was diluted with air containing an isotopically-labeled internal standard. DMS is ionized at atmospheric pressure via proton transfer from water vapor, then declustered, mass filtered via quadrupole mass spectrometry, and detected with an electron multiplier. The instrument described here is based on a low-cost residual gas analyzer (Stanford Research Systems), which has been modified …

Open Ocean Dms Air/Sea Fluxes Over The Eastern South Pacific Ocean, C. A. Marandino, Warren J. De Bruyn, S. D. Miller, E. S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Air/sea fluxes of dimethylsulfide (DMS) were measured by eddy correlation over the Eastern South Pacific Ocean during January 2006. The cruise track extended from Manzanillo, Mexico, along 110 degrees W, to Punta Arenas, Chile. Bulk air and surface ocean DMS levels were also measured and gas transfer coefficients (k(DMS)) were computed. Air and seawater DMS measurements were made using chemical ionization mass spectrometry (API-CIMS) and a gas/liquid membrane equilibrator. Mean surface seawater DMS concentrations were 3.8 +/- 2.2 nM and atmospheric mixing ratios were 340 +/- 370 ppt. The air/sea flux of DMS was uniformly out of the ocean, with …

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) …

Sustainability: Energy & Global Chemistry, Kurt W. Kolasinski

Chemistry Faculty Publications

No abstract provided.

Preparation And Characterization Of Some Substituted Benzyl N-Nitrosocarbamates Containing An N-2-(Methylthio)Ethyl Or A Bis(2-Aminoethyl)Sulfide Functionality, Satya Venkata, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

The synthesis and characterization of some substituted benzyl N-nitrosocarbamates with an N-2-(methylthio)ethyl or a bis(2-aminoethyl)sulfide functionality is reported, as a part of a long-term goal to design and prepare novel photolabile structures that could be used as substances for controlled release of alkylating and/or crosslinking agents. The synthesis was accomplished by reaction of benzyl chloroformates with the corresponding amines, resulting in the preparation of carbamates. The latter were subsequently nitrosated, utilizing two different N-nitrosation methods, to yield the target structures.

Remote Measurements Of On-Road Emissions From Heavy-Duty Diesel Vehicles In California; Year 1, 2008, Gary A. Bishop, Nicolas E. Holubowitch, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

Portable Emission Measurements Of Yellowstone Park Snowcoaches And Snowmobiles, Gary A. Bishop, Ryan Stadtmuller, Donald H. Stedman, John D. Ray

Fuel Efficiency Automobile Test Publications

As part of the National Park Service’s Temporary Winter Use Plans Environmental Assessment, the University of Denver has been collecting in-use tailpipe emissions data from snowcoaches and snowmobiles in Yellowstone National Park. During the winter of 2006, using a portable emissions monitoring system, tailpipe data were collected from 10 snowcoaches and 2 four-stroke snowmobiles. These vehicles were operated over a standard route within the park, and the snowcoaches all carried identical passenger loads. These snowcoaches were newer in age with more advanced fuel management technology than those studied earlier, and average emissions were lower as a result (120, 1.7, and …

On-Road Motor Vehicle Emissions Including Nh3, So2 And No2, Donald H. Stedman, Gary A. Bishop, Allison Peddle

Fuel Efficiency Automobile Test Publications

No abstract provided.

On-Road Motor Vehicle Emissions Including Ammonia, Sulfur Dioxide And Nitrogen Dioxide (Presentation), Donald H. Stedman, Gary A. Bishop, Allison Peddle

Fuel Efficiency Automobile Test Publications

No abstract provided.

Organic Chemostratigraphic Markers Characteristic Of The (Informally Designated) Anthropocene Epoch, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Recognizing the tremendous collective impact of humans on the environment in the industrial age, the proposed designation of the current time period as the Anthropocene Epoch has considerable merit. One of the signature activities during this time continues to be the intensive extraction, processing, and combustion of fossil fuels. While fossil fuels themselves are naturally-occurring, they are most often millions of years old and associated with deeply buried strata. They may be found at the surface, for example, as natural oil seeps or coal seam outcrops, but these are relatively rare occurrences. Fossil fuels and their myriad by-products become the …

Determining Chemical Signatures Of Geologic Materials For Establishing Provenience Of Anasazi Red And Gray Wares Using Esem-Eds And Icp-Ms, Champagne Springs Ruins, Co, Steven Mathew Di Naso

All-Inclusive List of Electronic Theses and Dissertations

Compositional analyses of prehistoric ceramics and geological materials allow archaeologists to establish provenience of artifacts through comparative analysis of the materials used in prehistoric ceramic production. Where pottery clay pastes and tempering constituents originate from locally or regionally available geological materials, identifying their chemical composition and their geographic location and distribution facilitates a better understanding of the inter and intra socio-spatial and socioeconomic patterns among neighboring communities. The Champagne Springs Ruins were occupied during the late Pueblo I (A.D. 700 -A.D. 900) to early Pueblo II (A.D. 900 TO A.D. 1100) periods. The traditional view of local ceramic production from …

Environmental Effects On Corrosion Properties Of Alloy 22, Mano Misra

Publications (YM)

This document presents detailed technical report for four Subtasks that were conducted independently. All four Subtasks investigated environmental effects on corrosion properties of Alloy 22. The four Subtasks that were investigated are as follows: Subtask 1: Experimental Determination of Parameters for the General Corrosion Model. Subtask 2: Corrosion under Dust Deposits Containing Hygroscopic Salts. Subtask 3: Heated Electrode Approach for the Study of Corrosion Under Aggressive Conditions. Subtask 4: Effect of Hydrogen Permeation on the Stability of the Passive Film of Alloy 22.

Monitoring Metal Containing Particulates Distribution On A College Campus Using Dandelion (Taraxacum Officinale) Leaves As Receptors., Suresh Chandra Regmi

Electronic Theses and Dissertations

This study aims to determine the distribution of particulates carrying heavy metals at selected sites on a college campus using dandelion leaves as collectors. As a comparison, sites far away from the campus surrounding Bristol Motor Speedway Car Racing Stadium were also monitored. To reduce the probability of memory effects from the long-term atmospheric deposition or absorption of metals from soil a seasonal plant, dandelion, was used to monitor the metal contents. The metals monitored are cadmium, calcium, copper, chromium, iron, lead, and zinc. Fourteen sites were monitored and samples were collected once a week initially (growing time of the …

Preparation Of Halogenated Derivatives Of Thiazolo[5,4-D]Thiazole Via Direct Electrophilic Aromatic Substitution, Vladimir Benin, Alan T. Yeates, Douglas Dudis

Chemistry Faculty Publications

Chlorination and bromination reactions of thiazolo[5,4-d]thiazole led to the generation of its mono- and dihalogenated derivatives. These are the first instances of successful direct electrophilic aromatic substitution in the thiazolo[5,4-d]thiazole ring system. X-ray analysis demonstrates that both 2-bromothiazolo[5,4-d]-thiazole and 2,5-dibromothiazolo[5,4-d]thiazole are planar structures, with strongly manifested π-stacking in the solid state. Theoretical analysis of the pyridine-catalyzed halogenation (MP2/6-31+G(d) and B3LYP/6-31+G(d)calculations) reveals that introduction of one halogen actually leads to a slightly enhanced reactivity towards further halogenation. Several halogenation mechanisms have been investigated: 1) The direct C-halogenation with N-halopyridine as electrophile; …

Comparative Kinetics And Distribution To Target Tissues Of Organophosphates Using Physiologically-Based Pharmacokinetic Modeling, Rick E. Vermillion

Theses and Dissertations

A physiologically-based pharmacokinetic model has been developed to examine the effects of organophosphates on the levels of acetylcholine in different tissues throughout the mammalian body. Many organophosphate-like chemical and kinetic characteristics are tested without reference to a specific chemical. Characteristics include partition coefficients, metabolic constants, the inhibition coefficient, the aging rate, and the regeneration rate. Two separate exposure scenarios are tested and compared against a baseline. The baseline consists of a direct inhalation exposure. The first exposure scenario examines the effects of bronchial scrubbing (via inhalation) and the second scenario is a study of dermal exposures and compares the levels …

Oxygenation Of The Root Zone And Tce Remediation: A Plant Model Of Rhizosphere Dynamics, Ian F. Thompson

Theses and Dissertations

This study analyzes rhizosphere conditions that enhance the effective aerobic degradation of TCE in wetland bioremediation systems. A plant model was built using Stella 9.0 modeling software and uses numerical integration evaluation; it addresses movement of oxygen through plant vascular and aerenchymal systems, and into the rhizosphere where oxygen and other substrates influence bacteria. Methanotrophs and heterotrophs are assumed to be influential bacteria groups. Variations of humidity-induced-convection, methane, soil carbon, and copper concentrations are evaluated. Varying concentrations and hydraulic loadings of TCE are assessed with respect to TCE consumption rate and TCE treatment efficiency. Soil conditions most directly affected TCE …

C–N Bond Rotation And E–Z Isomerism In Some N-Benzyl-N-Methylcarbamoyl Chlorides: A Dft Study, Michael Horwath, Vladimir Benin

Chemistry Faculty Publications

The current report presents the first theoretical study of the restricted CN bond rotation in carbamoyl chlorides. Several N-benzyl-N-methylcarbamoyl chlorides were investigated, with varying pattern of substitution in the aromatic ring. Optimizations and frequency calculations were conducted employing DFT at the B3LYP/6-31+G(d) level of theory. Each of the studied structures exhibits a pair of rotamers (s-Z and s-E), generated upon rotation around the C(O)N bond. The s-E isomer is the global minimum in every case, but the preference for it is usually less than 1 kcal/mol. Two possible transition state structures were identified …

Dms Air/Sea Flux And Gas Transfer Coefficients From The North Atlantic Summertime Coccolithophore Bloom, Christa Marandino, Warren J. De Bruyn, Scott Miller, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Dimethylsulfide (DMS) atmospheric and oceanic concentrations and eddy covariance air/sea fluxes were measured over the N. Atlantic Ocean during July 2007 from Iceland to Woods Hole, MA, USA. Seawater DMS levels north of 55 degrees N ranged from 3 to 17 nM, with variability related to the satellite-derived distributions of coccoliths and to a lesser extent, chlorophyll. For the most intense bloom region southwest of Iceland, DMS air/sea fluxes were as high as 300 mu mol m(-2) d(-1), larger than current model estimates. The observations imply that gas exchange coefficients in this region are significantly greater than those estimated using …

Salt Marshes As A Source Of Chromophoric Dissolved Organic Matter (Cdom) To Southern California Coastal Waters, Catherine D. Clark, Liannea P. Litz, Stanley B. Grant

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

To determine chromophoric dissolved organic matter (CDOM) sources in Southern California coastal waters, optical properties of a river outlet and adjacent tidally flushed salt marshes were monitored (dry season; June July 2001). Average absorption coefficients doubled at ebb vs. flood tides (4.8 +/- 1.5 vs. 2.1 +/- 0.9 m(-1); 300 nm), suggesting significant salt marsh CDOM inputs into coastal waters. Average spectral slopes were not statistically different for any sites or tides (0.010 +/- 0.002 nm(-1)), consistent with salt marsh CDOM dominating coastal waters. Three-dimensional fluorescence excitation-emission matrices (EEMs) at ebb tide showed contributions from terrestrial, protein, and marine humic-like …

Simulation Of Arsenic Partitioning In Tributaries To Drinking Water Reservoirs, Eid A. Alkhatib

Chemistry & Physics Faculty Publications

Arsenic released by bottom sediments was determined by experiments in which the sediments were artificially re-suspended using a particle entrapment simulator (PES) to simulate river conditions. Sediment cores were collected from various tributaries to drinking water reservoirs in Connecticut spiked with arsenic, and run in the PES at simulated bed-flow shear stresses from 0.0 to 0.6 N/m2. Under equilibrium conditions, the dissolved fraction of arsenic was found to range from 8.3 to 22.1 ug/1, which in most cases exceeded EPA Maximum Contaminant Level (MCL) of 10 ug/1. Experimental results from these simulations have shown that bed-flow shear stress causes an …

Soil Chemistry Northwest New Mexico, Larry V. Benson

United States Geological Survey: Datasets

These data result from soil chemistry samples extracted from several regions in northwest New Mexico and were used in the following publications:

Larry V. Benson, J. Stein, H. Taylor, R. Friedman, and T. C. Windes. 2006. The agricultural productivity of Chaco Canyon and the source(s) of pre-Hispanic maize found in the Pueblo Bonito Great House. In: J. E. Staller, R. H. Tykot, and B. F. Benz, eds. Histories of Maize: Multidisciplinary Approaches to the Prehistory, Linguistics, Biogeography, Domestication, and Evolution of Maize, 289–314. Elsevier/Academic Press.

Larry V. Benson. 2017. The Chuska Slope as an agricultural alternative to Chaco …

Wet Weather Impact On Trihalomethane Formation Potential In Tributaries To Drinking Water Reservoirs, Eid A. Alkhatib, R. Peters

Chemistry & Physics Faculty Publications

During rain storm events, land surface runoff and resuspension of bottom sediments cause an increase in Trihalomethane (THM) precursors in rivers. These precursors, when chlorinated at water treatment facilities will lead to the formation of THMs and hence impact drinking water resources. In order to evaluate the wet weather impact on the potential formation of THMs, river samples were collected before, during and after three rain storms ranging from 15.2 to 24.9 mm precipitation. The samples were tested for THM formation potential and other indicators including UV254 absorbance, turbidity and volatile suspended solid (VSS). Average levels of THMs increased from …

The Application Of Lc-Ms Technologies For The Detection Of Triazine Herbicides In Water, Michael Cahill

Theses

The triazine herbicides, including, simazine (6-chloro-N,N’-diethyl-1,3,5-triazine-2,4- diamine), atrazine (2-chloro-4-ethylamino-6-isopropylamino-l,3,5-triazine) and cyanazine were developed as selective weed killers. Their design function is to disrupt the photosynthesis of broad-leafed plants. In the intensive production of grasses (e.g. wheat, cereals, etc.) broad-leafed plants growing in the grass production area are economically costly, competitors with the grasses for nutrients; their removal is facilitated by triazines herbicides and simazine and atrazine are the predominant compounds used. Significant amounts of triazine herbicides are consumed by the agricultural industry each year. However, due to the indiscriminate use of pesticides/herbicides, traces of herbicides have been found in run-off …

Origin And Paleoclimatic Significance Of Late Quaternary Loess In Nebraska: Evidence From Stratigraphy, Chronology, Sedimentology, And Geochemistry, Daniel R. Muhs, E. Arthur Bettis Iii, John N. Aleinikoff, John P. Mcgeehin, Jossh Beann, Gary Skipp, Brian D. Marshall, Helen M. Roberts, William C. Johnson, Rachel Benton

United States Geological Survey: Staff Publications

Loess is one of the most extensive surficial geologic deposits in mid-continental North America, particularly in the central Great Plains region of Nebraska. Last-glacial-age loess (Peoria Loess) reaches its greatest known thickness in the world in this area. New stratigraphic, geochronologic, mineralogic, and geochemical data yield information about the age and provenance of Peoria Loess, as well as evaluation of recent climate models.

Calibrating Feat Instruments Without Gas Cylinders, Allison Peddle, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

Signal To Noise Improvements In On-Road No, So2, And Nh3 Measurements Using A Multi-Component Classical Least Squares Fitting Approach (Presentation), Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

A Decade Of On-Road Emissions Measurements, Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

A multi-year, on-road emission measurement program carried out in the cities of Chicago, IL, Denver, CO, Los Angeles, CA and Phoenix, AZ shows large, fuel specific tailpipe emissions reductions at all of the sites for carbon monoxide (CO), hydrocarbons (HC) and nitric oxide (NO). CO emissions decrease between 56% (Denver) and 71% (Chicago), HC emissions decrease between 27% (Phoenix) and 63% (Denver) and NO emissions have dropped between 48% (West LA) and 68% (Chicago). Three observed factors common to all of the sites are that the emission reductions are occurring in vehicles of all ages, that the influence of engine …

Organic Geochemical Investigation Of A Highly Contaminated Urban Waterway: The Gowanus Canal, Brooklyn, New York, Usa, Michael A. Kruge, Kevin K. Olsen, Eric A. Stern

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The Gowanus Canal is an industrial waterway constructed in the mid-19^th century by widening and deepening a natural tidal channel. It is ca. 3 km in length and empties into Gowanus Bay, an arm of New York Harbor. Its banks, reinforced by bulkheads and piers, became the site of intensive industrial activity, including oil refining, coal gasification, soap making and tanning. Even though much of the industrial activity along the canal has ceased, its sediments remain highly enriched in organic and inorganic contaminants, with combined sewer outfalls continuing to transport pollutants into the canal. The canal area remains densely …

Groundwater Characterization At Yucca Mountain Task 2: Surface Complexation And Solid Phase Sorption, Kenneth Czerwinski, Anthony Hechanova, Amy J. Smiecinski

Publications (YM)

The purpose and scope of this report is to present an overview of the experiments, methods, results, and conclusions from research performed for the project “Groundwater Characterization at Yucca Mountain Task 2: Surface Complexation and Solid Phase Dissolution”. The impact of surface complexation, alteration phase formation, and solution competition with metal ions on the solubility and speciation of actinide elements (U, Pu, Np) will be examined. In particular the role of iron (as Fe2+ and Fe3+) and silicate (as SO3 2-) concentrations on speciation, solubility, sorption, and secondary phase formation of actinides will be investigated. While a large body of …

Basic Research Needs For Geosciences: Facilitating 21st Century Energy Systems, U.S. Department Of Energy, Office Of Basic Energy Sciences, Donald J. Depaolo, Franklin M. Orr Jr.

Publications (YM)

Executive Summary

Serious challenges must be faced in this century as the world seeks to meet global energy needs and at the same time reduce emissions of greenhouse gases to the atmosphere. Even with a growing energy supply from alternative sources, fossil carbon resources will remain in heavy use and will generate large volumes of carbon dioxide (CO₂). To reduce the atmospheric impact of this fossil energy use, it is necessary to capture and sequester a substantial fraction of the produced CO₂. Subsurface geologic formations offer a potential location for long-term storage of the requisite large …