Determination of the source and fate of natural (higher plant lipids, marine
lipids, etc.) and anthropogenically (e.g., petroleum, coal emissions) derived
hydrocarbons and oxygenated compounds in the environment was accomplished
using gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS)
to characterize or identify molecular biomarkers to be utilized as tracers....
SOCs volatility and persistence properties cause many SOCs to become ubiquitous in the environment as well as accumulate in areas with lower temperatures such as polar or orographic regions. Many anthropogenic SOCs pose a serious risk to human and ecosystem health because of their persistent, bioaccumulative, and toxic properties in...
More than 65,000 organic chemicals are currently in commercial production with
approximately 1000 added each year. Many chemicals are released into the environment as organic mixtures derived from complex hazardous or solid wastes. Of these, more than 1000 chemicals are of environmental concern because of their production quantities, toxicity, persistence,...
The atmospheric transport of anthropogenic semivolatile organic compounds (SOCs) from Asian sources to the Western U.S. was investigated. In addition, the SOC extraction method was optimized. Hansen solubility parameter plots were used to aid in the pressurized liquid extraction (PLE) solvent selection of air sampling media in order to minimize...
Sources of polar/water-soluble organic compounds conjunctly with apolar biomarkers were characterized in natural organic matter. This multi-biomarker approach was accomplished by a simple analytical method consisting of extraction with dichloromethane:methanol (2:1, v/v), silylation and analysis by gaschromatography- mass spectrometry (GC-MS). Polar and apolar biomarkers, derived mainly from higher plants and...
The transport and deposition of airborne contaminants, including semivolatile
organic compounds (SOCs), to high elevation ecosystems is
recognized as a potential threat to these ecosystems. The objectives of
this research were to develop an analytical method to measure a wide
range of SOCs in high elevation lake sediment and to...
............................................................................ 1
1.1 Semi-volatile organiccompound deposition to high elevation
ecosystem
A facile route to bicyclo(2.1.1)hexanes was developed involving
the intramolecular photocyclization of 1, 5-hexadien-3-one to
bicyclo(2.1.1)hexan-2-one. A study of the chemistry of bicyclo-(2.1.1)hexan-2-one was undertaken. Deuterium exchange and borohydride
reduction demonstrated the strain present in the ketone.
Further evidence was obtained from the failure to introduce substituents
alpha to the...
Part 1
The pyrolysis of cis-1-trimethylsiloxy-1-cyclopr opyl-3-cyclononene in the temperature range 285-350° is described. Instead
of siloxy-Cope rearrangement, undesired desiloxylation took place.
Part 2
Gas-phase pyrolytic rearrangement of 2-phenyl-1-trimethylsiloxy-1-vinylcyclononane was investigated in a static system
in the temperature range 213-330°. It was discovered that
three major products resulted: cis- and...
Alkylation of propylene oxide with 2-lithiofuran gave alcohol I,
which was smoothly converted to acetylfuran II. hydrogenation of II
over rhodium on charcoal followed by Jones' oxidation afforded ketone
III. Further transformation into IV was accomplished via a Wittig
reaction followed by saponification with methanolic sodium hydroxide.
Hydroboration of the...
Intramolecular cyclization of organometallic compounds represents
a promising tool for synthesis. The reaction involves exothermic
consumption of intramolecular double bonds via insertion
into a carbon metal sigma bond. This represents an intramolecular
example of the reaction type responsible for metal catalyzed polymerization
of olefins.
Organolithium reagents were found to cyclize...
The electronegativities of -SF₅, -CF₃SO₂, and -SO₂F have been measured with gas phase X-ray photoelectron spectroscopy. Of these three groups previously measured values were found only for -SF₅. The electronegativities of -Cl, -Br, -CF₃, and -CF₃, were concurrently measured to determine how the findings of this research compare with other...
In this thesis steady-state (i.e. steady-state with respect to the applied voltage waveform) transient current-transient voltage [i(t)-v(t)], transient brightness-transient current [b(t)-i(t)], transient brightness-transient voltage [b(t)-v(t)], transient current [i(t)], transient brightness [b(t)], and detrapped charge analysis are introduced as novel organic light emitting device (OLED) characterization methods. These analysis methods involve...
Sensory properties of four important volatile sulfur compounds, dimethyl disulfide (DMDS), diethyl disulfide (DEDS), methanethiol (MeSH) and ethanethiol (EtSH), were determined in base Oregon Pinot noir wine in order to understand their impacts on wine aroma. Detection thresholds of these four compounds in base wine were determined first. All four...
Twelve N, N'-bis(hydroxy- and methoxybenzoyl)ethylenedi-amines and piperazines have been prepared, tested for antifungal
activity, and screened for gross pharmacological activity in mice.
All twelve compounds showed some activity against Candida albicans,
Trichophyton mentagrophytes and Microsporum gypseum but in every
case the activity was less than that of salicylanilide used as...
The two naturally occurring cyclopropene fatty acids, sterculic
and malvalic, have been synthesized. The cyclopropene ring was
made by inserting a methylene unit into an acetylenic linkage.
The synthesis of methyl sterculate was repeated using diethyl
aluminum chloride, diazomethane, and methyl stearolate.
Methyl malvalate was totally synthesized. Diethyl malonate
was...
It is often perceived that late maturity of grape gives a more complex aroma
profile to Pinot noir wine, however, there is little understanding of the basic flavor
chemistry of grape maturity on wine aroma. The aroma contributing compounds in
Pinot noir were first identified by aroma extract dilution analysis...
Experiments were designed to answer key questions about diatom-derived organic matter cycling (i.e., production and degradation) in coastal systems. Dissolved organic matter (DOM) production was examined in axenic batch cultures of five diatom species. Dissolved organic carbon (DOC) release rates varied between species, but were significantly higher for all species...
Quaternary Ammonium Compounds, Qams, are an important class of
chemicals which present interesting challenges to analysts. This thesis
reports results of investigations on uses of ion-pairing techniques for
separations and detection of Qams. Special apparatus for post-column
solvent extraction of liquid chromatographic eluates was developed as
part of this work....
The effect of the conjugation with cyclopropyl rings
on the activation parameters for the formation of
carbenes from the corresponding diazo compounds was
investigated using diisopropylcarbene (46), cyclopropyl-isopropylcarbene
(47), and dicyclopropylcarbene (48).
Each of these three carbenes was generated by the
thermolysis of the parent benzenesulfonylhydrazone
potassium salts using DMSO...
The aroma of Tuber gibbosum, a native Oregon truffle, was
characterized using two distinct techniques. Volatile aroma
constituents were identified by chemical analysis, and sensory
characteristics were determined by examining response of the
general populace to the truffle aroma.
Truffle samples from four maturity ranges, as determined
by microscopic examination...
Resonance Electron Capture Mass Spectrometry (REC-MS) is a sensitive
experimental technique for the study of gas-phase compounds with positive electron
affinity. This technique was used to study a class of compounds known as
baloetbylenes containing chlorine and bromine substitutions. Haloetbylenes are an
important class of compounds because ethylene is the...
An improved procedure for the preparation of β-(3-cyclohexenyl) propionic acid from 4-vinylcyclohexene was developed. The
Friedel-Crafts cyclization of β-(3-(3-cyclohexenyl) propionyl chloride
with aluminum chloride was shown to give one bicyclic chlorine
containing ketone in 41% yield. This ketone was identified by a combination of spectral and chemical methods as a...
The photodebromination of selected bromoarenes has been studied at 300 nm
to determine the the possible mechanistic pathways leading to product.
Irradiation of 4-bromobiphenyl (BpBr) at this wavelength leads to the product
biphenyl. The quantum yield of intersystem crossing (0.98) and quenching
studies with cis-1 ,3-pentadiene suggest that the reaction...
An oscillating plasma glow discharge detector for gas
chromatography is used to obtain fingerprint information
about an analyte by combining both the average cell
current and oscillation frequency signals. Five homologs
each of the n-alkanes, 1-alkenes, 1-alkynes, 2-ketones and
aldehydes are studied. Although triplicate determinations
had some scatter due to...
This dissertation is separated into two parts according to the two major distinct research projects. In Part I, the full account of synthetic studies toward C10-functionalized lycopodium alkaloids is described. In Part II, the detailed discussion on the exploration of the Pummerer cyclization methodology and its application to the total...
Aromatic Nitro Compounds. The n-values for the reduction of
the isomers of nitrophenol and nitrobenzoic acid and for several
other nitro compounds are determined in dimethylsulfoxide by controlled
potential coulometry. A procedure is given in which one
mole of nitro compound may be determined with errors of less than
one...
Acids contribute important flavor characteristics to
many foods and beverages. They occur naturally in these
products, arise from fermentation processes, or can be
added. Most acids taste sour. However, little is known
about their time-intensity characteristics of sourness.
This project was set forth to see if selected acids could be...
A method was developed to quantify organochlorine pesticides in whale scat. This method would ideally replace analysis of pesticides in blood and tissue samples, which are difficult to acquire. Scat samples were collected from one stranded gray whale and three live whales. The samples were extracted with pressurized liquid extraction,...
The object of this study is the synthesis of trans-cyclopentane-1, 2-dicarboxylic acid. Five procedures designed for the synthesis of
this trans diacid are described in the literature. The procedure
devised by Perkin in 1887, Fuson and Cole in 1938, and by Brenner
in 1961 were investigated to determine which of...
This study focuses on one widespread characteristic of poor soil quality: hydrophobic soil. Previous research has produced conclusive evidence to show that soil hydrophobicity is affected by soil organic matter (SOM) and soil water content (WC). Hydrophobicity that responds to changes in WC is a unique form of surface hydrophobicity...
Volatile hydrophobic compounds (HOCs) brought into soil and sediment
systems represent a serious threat to the environment. Dissolved
organic carbon (DOC) may exert an important influence over the total
aqueous solubility and mobility of organic pollutants through their
incorporation into micelles or the formation of soluble complexes.
To date, however,...
Volatile organic emissions (VOCs) from the kiln drying
of lumber are of concern to government, research agencies,
and the forest products industry. In the Pacific
Northwest, neither the quantity of VOC emissions from kilns
drying Douglas-fir is available, nor the effects of drying
schedule and lumber-related characteristics on the
emissions....
Three approaches toward the core of halichlorine and pinnaic acid are described. The first approach entails a racemic transannular nitrone-olefin [3+2] cycloaddition from nitrone 238. Construction of the nitrone 238 began with aldehyde 241. Another key feature in this route involved a ring-closing metathesis for the formation of a 14-membered...
The data set presented here includes the discrete depth profile data and time series data
from the vertical profiling cruises carried out as a portion of the “Coastal Ocean Advances in Shelf Transport” (COAST) project. The primary purpose for collection of this data set was to calibrate the optical parameters...
Irradiation of a tryptamine linked through its side-chain nitrogen to an alkylidene malonate residue results in an intramolecular [2 + 2] cycloaddition to the indole 2,3-double bond. The resultant cyclobutane undergoes spontaneous retro-Mannich fission to produce a spiro[indoline-3,3-pyrrolenine] with relative configuration defined by the orientation of substituents in the transient...
Hop derived bitter compounds, including alpha-acids, reduced and non-reduced iso-alpha-acids, were evaluated for their contribution to peak bitter intensity in lager beer. Alpha-acids are the precursors to the major bittering components in beer (iso-alpha-acids). Typically, alpha-acids do not survive the brewing process, but if a product is dry-hopped, they may...
Brown marmorated stink bug (BMSB), (Halyomorpha halys, Hemiptera: Pentatomidae) is an invasive species that damages numerous agricultural crops including grapes. Related damage include lower berry weight with increased exposure and cracked berries as a result of BMSB feeding activity. The insect is currently detected in 43 US states including Oregon,...
This study investigated the effect of plant surface
area (plant density) on the efficiency of organic carbon
removal in a bench-scale constructed wetland.
Constructed wetlands are commonly assumed to be biofilm
reactors in which organic carbon removal occurs primarily
through sedimentation and aerobic degradation by attached
microbial biofilms. In conventional...
Ambient high-volume (hi-vol) air samples were collected between March 15th and May 30th 2002, at Cheeka Peak Observatory (CPO), located on the tip of the Olympic Peninsula, Washington State. This sampling campaign was in conjunction with the 2002 Inter-Continental Transport and Chemical Transformation (ITCT 2K2) Campaign and the Photochemical Ozone...
The emission of organic compounds from wood manufacturing
facilities is an important regulatory concern due to their effects on ambient
air quality. Control technologies, such as oxidizers and biofiltration, are
used to remove organics from air streams; however, most removal
technologies have high costs or cause additional negative environmental
impact....
Alpha acids are found in the lupulin glands of hops cones. These acids have no bitterness of their own, but can be isomerized and subsequently hydrogenated to form bitter iso-α-acids and tetrahydroiso-α-acids respectively. Current literature values for the detection thresholds of iso-α-acid and tetrahydroiso-α-acid in lager beer have been reported...
Dissolved organic matter (DOM) is a critical component of the carbon cycle linking terrestrial and aquatic ecosystems. Although many factors influence DOM fluxes and quality in rivers, controls on DOM compositions in catchments of the western U.S. are poorly understood. UV and fluorescent spectroscopy is a simpler, faster, and less...
Intimate associations with reactive metal species permanently protect soil organic matter (SOM) from microbial access and oxidation, contributing to the build-up of organic carbon (C) stocks in soils. It is increasingly recognized, however, that such associations can be reversible and that reactive metal species might even facilitate the oxidation of...
Globally, the forestry sector is the second largest contributor of greenhouse gases, and sustainable forest management is a major target of international environmental policy. However, there is the assumption underlying many policy recommendations that an increase in above-ground carbon stocks correspond to long term increases in ecosystem carbon stocks, the...
Constituents of the wine matrix, including ethanol, affect adsorption of sulfur volatiles on solid-phase microextraction (SPME) fibers, which can impact sensitivity and accuracy of volatile sulfur analysis in wine. Several common wine sulfur volatiles, including hydrogen sulfide (H2S), methanethiol (MeSH), dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS), diethyl...
The objectives of this study are to 1) qualitatively and quantitatively measure the odor-active compounds in ‘Marion’ blackberry; 2) compare the aroma profiles of advanced selections and new cultivars of thornless blackberry cultivars with ‘Marion’; 3) study the development of furaneol in ‘Marion’ during ripening and; 4) investigate the distribution...
This study investigates the relationship between total and ionic copper in samples taken from the Tualatin River and wastewater treatment facilities (WWTFs) that discharge into the Tualatin River. Copper speciation was analyzed by determining conditional stability constants and densities of copper binding ligands on the dissolved organic matter (DOM) in...
Marine microorganisms play a significant role in the cycling of nutrients in the open ocean through production, consumption, and degradation of organic matter (OM). Carbon (C), nitrogen (N), and phosphorus (P) are essential ingredients in every known recipe for life. However, the cycling of each of these elements proceeds at...
The Arctic has long been considered to be a pristine environment, far
from population centers and pollution sources. The detection of synthetic
organochlorine compounds in various elements of the Arctic food web has confirmed
the global dispersion of pollutants, particularly of persistent compounds such as
organochlorines and heavy metals. Levels...
The mechanisms governing short- and long-term belowground carbon dynamics need to be understood. As part of a larger project developed to assess the effect of quantity and quality of litter inputs on the rate of soil organic matter (SOM) formation, I examined SOM in the H. J. Andrews Detritus Input...
The seasonal distribution of bioavailable organochiorine contaminants in surface
water and the potential environmental factors influencing their bioavailability were
evaluated. The study was carried at the lower Willamette River at Portland Harbor, Oregon
where surface water runoff varied according to season. Bioavailable water concentrations of
DDTs and PCBs were determined...
Summertime, wind-driven upwelling off the Oregon coast delivers nutrient rich water to the surface that fuels the autotrophic production of particulate organic carbon (POC). This POC can be transported horizontally by fluid motions and vertically by sinking to the bottom where it can be entrained in the benthic boundary layer...
The use of semi-volatile organic compounds (SOCs) as molecular markers to identify the contributions of regional and long-range atmospheric transport, as well as current and historic sources, and contaminant deposition in remote ecosystems of the Western U.S. was investigated. Trans-Pacific air masses influenced by Siberian biomass burning events had elevated...
The specific objectives of this dissertation are to determine subsurface flow
behaviors across different antecedent wetness conditions from a top-down perspective
and to mechanistically assess the hydrological controls on DOC and N transport at the
hillslope and catchment scale. The study area is a small catchment where hillslopes
issue directly...
Arctic soils are warming, making vast stores of organic carbon available for conversion to CO₂. This could create a positive feedback loop and accelerate global warming, but the processes that convert this carbon into CO₂ are not well understood. We investigated how the combined activities of sunlight and microbes degrade...
High vegetative growth of Pinot Noir vine is a common problem in most vineyards of Oregon's Willamette Valley, where sunlight exposure and heat accumulation are limited. Consequently, growers in this region commonly use vineyard management strategies to regulate vine vigor and improve grape and wine quality. Wine quality is greatly...
This report presents results of an investigation of water and streambed-sediment quality in selected tributaries of the South Umpqua River. Concentrations of inorganic constituents in water (major and minor ions, nutrients, and trace elements) and streambed sediment (primarily trace elements), along with standard field parameters, are tabulated for samples collected...
Forest soils contain a substantial portion of global terrestrial carbon stores. Forest management can influence the soil carbon pool and how soil organic matter functions. The long-term productivity of forests is an ongoing goal where land managers utilize biomass and timber. A site-specific understanding of intensively managed forests can ensure...