Adverse effects associated with overdose of NSAIDs are rarely reported in cattle, and the risk level is unknown. If high doses of NSAIDs can be safely administered to cattle, this may provide a longer duration of analgesia than using current doses where repeated administration is not practical. Meloxicam was administered to 5 mid-lactation Holstein dairy cows orally at 30 mg/kg, which is 30 times higher than the recommended 1 mg/kg oral dose. Plasma and milk meloxicam concentrations were determined using high-pressure liquid chromatography with mass spectroscopy (HPLC-MS). Pharmacokinetic analysis was performed by using noncompartmental analysis. The geometric mean maximum plasma concentration (Cmax) was 91.06 µg/mL at 19.71 h (Tmax), and the terminal elimination half-life (T1/2) was 13.79 h. The geometric mean maximum milk concentration was 33.43 µg/mL at 23.74 h, with a terminal elimination half-life of 12.23 h. A thorough investigation into the potential adverse effects of a meloxicam overdose was performed, with no significant abnormalities reported. The cows were humanely euthanized at 10 d after the treatment, and no gross or histologic lesions were identified. As expected, significantly higher plasma and milk concentrations were attained after the administration of 30 mg/kg meloxicam with similar half-lives to previously published reports. However, no identifiable adverse effects were observed with a drug dose 30 times greater than the industry uses within 10 days of treatment. More research is needed to determine the tissue withdrawal period, safety, and efficacy of meloxicam after a dose of this magnitude in dairy cattle.

The Midwest wine industry has shown a marked increase in growers, hectares planted, wineries, and wine production. This growth coincides with the release of cold-hardy cultivars such as Brianna and Frontenac gris, in 2001 and 2003, respectively. These white grape varieties account for one-third of the total area grown in the state of Iowa. It is generally accepted that the wine aroma profile plays a crucial role in developing a local, sustainable brand. However, the identity of Brianna/Frontenac Gris-based wine aromas and their link to the grape berry chemistry at harvest is unknown. This study aims to preliminarily characterize key odor-active compounds that can influence the aroma profile in wines made from Brianna and Frontenac gris grapes harvested at different stages of ripening. Brianna and Frontenac gris grapes were harvested approximately 7 days apart, starting at 15.4 °Brix (3.09 pH) and 19.5 °Brix (3.00 pH), respectively. Small batch fermentations were made for each time point with all juices adjusted to the same °Brix prior to fermentation. Odor-active compounds were extracted from wine headspace using solid-phase microextraction (SPME) and analyzed by gas chromatography-mass spectrometry (GC-MS) and simultaneous olfactometry (O). Over 30 odor-active compounds were detected. Aromas in Brianna wines developed from "cotton candy" and "floral", to "banana" and "butterscotch", then finally to "honey", "caramel" and an unknown neutral aroma. Frontenac gris wines changed from an unknown neutral aroma to "fruity" and "rose". Results from the lay audiences' flavor and aroma descriptors also indicate a shift with harvest date and associated °Brix. To date, this is the first report of wine aromas from Brianna and Frontenac gris by GC-MS-O. Findings from this research support the hypothesis that aroma profiles of Brianna and Frontenac gris wines can be influenced by harvesting the grapes at different stages of ripening.

The primary hurdle for diagnosis of some diseases is the long incubation required to culture and confirm the presence of bacteria. The concept of using microbial VOCs as "signature markers" could provide a faster and noninvasive diagnosis. Finding biomarkers is challenging due to the specificity required in complex matrices. The objectives of this study were to (1) build/test a lab-scale platform for screening of microbial VOCs and (2) apply it to Mycobacterium avium paratuberculosis; the vaccine strain of M. bovis Bacillus Calmette-Guérin; and M. kansasii to demonstrate detection times greater those typically required for culture. SPME-GC-MS was used for sampling, sample preparation, and analyses. For objective (1), a testing platform was built for headspace sampling of bacterial cultures grown in standard culture flasks via a biosecure closed-loop circulating airflow system. For (2), results show that the suites of VOCs produced by Mycobacteria ssp. change over time and that individual strains produce different VOCs. The developed method was successful in discriminating between strains using a pooled multi-group analysis, and in timepoint-specific multi- and pair-wise comparisons. The developed testing platform can be useful for minimally invasive and biosecure collection of biomarkers associated with human, wildlife and livestock diseases for development of diagnostic point-of-care and field surveillance.

In this research dataset, we summarize for the first time volatile organic compounds (VOCs) emitted in vivo from ripening wine grapes. We studied four cold-hardy cultivars grown in the Midwestern U.S.: St. Croix, Frontenac, Marquette, and La Crescent. These cultivars have gained popularity among local growers and winemakers, but still very little is known about their performance compared with long-established V. vinifera grapes. Volatiles were collected using two novel approaches: biogenic emissions from grape clusters on a vine and single grape berries. A third approach was headspace collection of volatiles from crushed grapes. Solid-phase microextraction (SPME) was used to collect volatiles. Vacuum-assisted SPME was used in the case of single grape berry. Collected VOCs were analyzed using separation and identification on a gas chromatograph mass spectrometer (GC-MS). More than 120 VOCs were identified using mass spectral libraries. The dataset provides evidence that detecting biogenic emissions from growing grapes is feasible. The dataset provides a record of temporal and spatial variability of VOCs, many of which could potentially impart aroma and flavor in the wine. The number of VOCs detected followed the order from single berry (the least) to crushed berry (the most). Thus, more information for potential use in harvesting in order to obtain the desired flavor is found in data from crushed grapes.

In this research, we propose a novel concept for a non-destructive evaluation of volatiles emitted from ripening grapes using solid-phase microextraction (SPME). This concept is novel to both the traditional vinifera grapes and the cold-hardy cultivars. Our sample models are cold-hardy varieties in the upper Midwest for which many of the basic multiyear grape flavor and wine style data is needed. Non-destructive sampling included a use of polyvinyl fluoride (PVF) chambers temporarily enclosing and concentrating volatiles emitted by a whole cluster of grapes on a vine and a modified 2 mL glass vial for a vacuum-assisted sampling of volatiles from a single grape berry. We used SPME for either sampling in the field or headspace of crushed grapes in the lab and followed with analyses on gas chromatography-mass spectrometry (GC-MS). We have shown that it is feasible to detect volatile organic compounds (VOCs) emitted in-vivo from single grape berries (39 compounds) and whole clusters (44 compounds). Over 110 VOCs were released to headspace from crushed berries. Spatial (vineyard location) and temporal variations in VOC profiles were observed for all four cultivars. However, these changes were not consistent by growing season, by location, within cultivars, or by ripening stage when analyzed by multivariate analyses such as principal component analysis (PCA) and hierarchical cluster analyses (HCA). Research into aroma compounds present in cold-hardy cultivars is essential to the continued growth of the wine industry in cold climates and diversification of agriculture in the upper Midwestern area of the U.S.

Finding farm-proven, robust sampling technologies for measurement of odorous volatile organic compounds (VOCs) and evaluating the mitigation of nuisance emissions continues to be a challenge. The objective of this research was to develop a new method for quantification of odorous VOCs in air using time-weighted average (TWA) sampling. The main goal was to transform a fragile lab-based technology (i.e., solid-phase microextraction, SPME) into a rugged sampler that can be deployed for longer periods in remote locations. The developed method addresses the need to improve conventional TWA SPME that suffers from the influence of the metallic SPME needle on the sampling process. We eliminated exposure to metallic parts and replaced them with a glass tube to facilitate diffusion from odorous air onto an exposed SPME fiber. A standard gas chromatography (GC) liner recommended for SPME injections was adopted for this purpose. Acetic acid, a common odorous VOC, was selected as a model compound to prove the concept. GC with mass spectrometry (GC⁻MS) was used for air analysis. An SPME fiber exposed inside a glass liner followed the Fick's law of diffusion model. There was a linear relationship between extraction time and mass extracted up to 12 h (R² > 0.99) and the inverse of retraction depth (1/Z) (R² > 0.99). The amount of VOC adsorbed via the TWA SPME using a GC glass liner to protect the SPME was reproducible. The limit of detection (LOD, signal-to-noise ratio (S/N) = 3) and limit of quantification (LOQ, S/N = 5) were 10 and 18 µg·m-3 (4.3 and 7.2 ppbV), respectively. There was no apparent difference relative to glass liner conditioning, offering a practical simplification for use in the field. The new method related well to field conditions when comparing it to the conventional method based on sorbent tubes. This research shows that an SPME fiber exposed inside a glass liner can be a promising, practical, simple approach for field applications to quantify odorous VOCs.

Understanding the aroma profile of wines made from cold climate grapes is needed to help winemakers produce quality aromatic wines. The current study aimed to add to the very limited knowledge of aroma-imparting compounds in wines made from the lesser-known Frontenac and Marquette cultivars. Headspace solid-phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS) with simultaneous olfactometry was used to identify and quantify selected, aroma-imparting volatile organic compounds (VOC) in wines made from grapes harvested at two sugar levels (22° Brix and 24° Brix). Aroma-imparting compounds were determined by aroma dilution analysis (ADA). Odor activity values (OAV) were also used to aid the selection of aroma-imparting compounds. Principal component analysis and hierarchical clustering analysis indicated that VOCs in wines produced from both sugar levels of Marquette grapes are similar to each other, and more similar to wines produced from Frontenac grapes harvested at 24° Brix. Selected key aroma compounds in Frontenac and Marquette wines were ethyl hexanoate, ethyl isobutyrate, ethyl octanoate, and ethyl butyrate. OAVs >1000 were reported for three aroma compounds that impart fruity aromas to the wines. This study provides evidence that aroma profiles in Frontenac wines can be influenced by timing of harvesting the berries at different Brix. Future research should focus on whether this is because of berry development or accumulation of aroma precursors and sugar due to late summer dehydration. Simultaneous chemical and sensory analyses can be useful for the understanding development of aroma profile perceptions for wines produced from cold-climate grapes.

Poultry production systems are associated with emissions of odorous volatile organic compounds (VOCs), ammonia (NH 3 ), hydrogen sulfide (H 2 S), greenhouse gases, and particulate matter. Development of mitigation technologies for these emissions is important. Previous laboratory-scale research on microbial-mineral treatment has shown to be effective for mitigation of NH 3 , H 2 S and amines emissions from poultry manure. The aim of this research was to assess the effectiveness of surface application of a microbial-mineral treatment for other important odorants, i.e., phenolics and sulfur-containing VOCs. Microbial-mineral litter additive consisting of 20% (w/w) of bacteria powder (six strains of heterotrophic bacteria) and 80% of mineral carrier (perlite-bentonite) was used at a dose of 500 g∙m -2 (per ~31 kg of manure). Samples of air were collected in two series, 4 and 7 days after application of additives. An odor profile of the poultry manure was determined using simultaneous chemical and sensory analysis. Reduction levels of VOCs determined on Day 4 was between 31% and 83% for mineral adsorbent treatment and in the range of 9% and 96% for microbial-mineral additive, depending on the analyzed compound. Reduction levels on Day 7 were considerably lower than on Day 4, suggesting that the odorous VOCs treatment efficacy is relatively short. There was no significant difference between treatments consisting of microbial-mineral additive and mineral carrier alone.

The aroma profile of red wine is complex and research focusing on aroma compounds and their links to viticultural and enological practices is needed. Current research is limited to wines made from cold-hardy cultivars (interspecific hybrids of vinifera and native N. American grapes). The objective of this research was to develop a fully automated solid phase microextraction (SPME) method, using tandem gas chromatography-mass spectrometry (GC-MS)-olfactometry for the simultaneous chemical and sensory analysis of volatile/semi-volatile compounds and aroma in cold-hardy red wines. Specifically, the effects of SPME coating selection, extraction time, extraction temperature, incubation time, sample volume, desorption time, and salt addition were studied. The developed method was used to determine the aroma profiles of seven selected red wines originating from four different cold-hardy grape cultivars. Thirty-six aroma compounds were identified from Maréchal Foch, St. Croix, Frontenac, Vincent, and a Maréchal Foch/Frontenac blend. Among these 36 aroma compounds, isoamyl alcohol, ethyl caproate, benzeneethanol, ethyl decanoate, and ethyl caproate are the top five most abundant aroma compounds. Olfactometry helps to identify compounds not identified by MS. The presented method can be useful for grape growers and wine makers for the screening of aroma compounds in a wide variety of wines and can be used to balance desired wine aroma characteristics.

Cold-hardy grape cultivars have become popular in northern regions. Wines from these cultivars are low in tannins and lighter in color compared to Vitis vinifera. The northern regions are striving to enhance desired ″full body″ and red color qualities in the wine produced from cold-hardy grapes. The objective of this study was to compare tannin and pigment content in skins and seeds of three cold-hardy red grape cultivars, at two time points, from two locations, using the Adams-Harbertson (A-H) assay. The A-H assay is based on protein precipitation and spectrophotometry. Total tannin concentrations detected in Frontenac, Marquette, and St. Croix berries, ranged from 0.29 to 0.66 mg/berry catechin equivalents (CE). Bitter seed tannins were most abundant in Marquette berries (0.54 ± 0.66 mg/berry CE). Softer skin tannins were most abundant in St. Croix berries (0.24 ± 0.19 mg/berry CE). Monomeric anthocyanins contributed to over 60% of the total color at pH 4.9 and were highest in St. Croix skins (74.21% of the total color at pH 4.9). Varying amounts of short polymeric pigments and long polymeric pigments were present in grape skins, indicating that pigmented tannins had already formed by harvest. This is the first evaluation of tannins and pigments in Frontenac, Marquette, and St. Croix berries.

Bovine tuberculosis is a zoonotic disease of global public health concern. Development of diagnostic tools to improve test accuracy and efficiency in domestic livestock and enable surveillance of wildlife reservoirs would improve disease management and eradication efforts. Use of volatile organic compound analysis in breath and fecal samples is being developed and optimized as a means to detect disease in humans and animals. In this study we demonstrate that VOCs present in fecal samples can be used to discriminate between non-vaccinated and BCG-vaccinated cattle prior to and after Mycobacterium bovis challenge.

The rapid growth of the biofuels industry resulted in new research needs in chemical analysis. Methods for screening and quantification of impurities resulting from changes in feedstock, process and purification are needed. Direct sample injection methods are often not sensitive for lower concentrations. This research, developed an analytical method to simultaneously quantify fermentation volatile by-products in industrial corn-based ethanol. These include acetaldehyde, ethyl vinyl ether, 1,1-diethoxyethane, isoamyl alcohol, isoamyl acetate, styrene, 2-pentylfuran, ethyl hexanoate, ethyl octanoate, and ethyl decanoate. Headspace solid-phase microextraction (SPME) coupled with gas chromatography–mass spectrometry (GC–MS) and GC-FID were used. The effects of SPME coating, concentration, time, and salting out were tested. The optimized method used Carboxen/PDMS 85 µm coating with 10% (v/v) ethanol, 20 s headspace extraction, and no salt addition. The method had values of R2 between 0.93 and >0.99 and relative standard deviations between 0.10 and 11.96%. The method detection limits were between 9.5 × 10−4 to 9.7 × 10−8 mol/L.This is one of the most comprehensive quantification methods for volatile impurities in raw ethanol to date. This new method was used to quantify 10 prevalent impurities in corn-based industrial ethanol. Copyright © 2015 The Institute of Brewing & Distilling

Most alcoholic beverages contain small amounts of chemicals other than ethanol, the congeners. These are byproducts of the fermentation process of the substrate. Congeners are implicated in contributing to hangover (veisalgia) symptoms and it is therefore considered expedient to remove these substances. This research compared 12 established vodka brands with a new product by GC-MS-olfactometry. A new vodka produced in Iowa from corn was found to be the purest while another corn-based vodka and a potato-based vodka contained eight and 12 impurities each. Eight other commercially available vodkas contained 15-19 impurities and three vodkas showed more than 30 impurities. Neither the raw material nor the country of origin made a difference to the level of the impurities. However, the treatment process was of great importance in terms of reaching lower impurity levels. Multiple distillations and filtration did not seem to benefit the quality, nor did charcoal and activated carbon alone. However, one vodka based on a multiple distilled neutral grain spirit process from corn contained zero measurable volatile impurities. The particular treatment process involved ozonation, followed by granular activated carbon and a nano-noble-metal catalysis and adsorption. Copyright (C) 2015 The Institute of Brewing & Distilling

Volatile compounds emitted into headspace from illicit street drugs have been identified, but until now odor impact of these compounds have not been reported. Data in support of identification of these compounds and their odor impact to human nose are presented. In addition, data is reported on odor detection thresholds for canines highlighting differences with human ODTs and needs to address gaps in knowledge. New data presented here include: (1) compound identification, (2) gas chromatography (GC) column retention times, (3) mass spectral data, (4) odor descriptors from 2 databases, (5) human odor detection thresholds from 2 databases, (6) calculated odor activity values, and (7) subsequent ranking of compounds by concentration and ranking of compounds by odor impact (reported as calculated odor activity values). For further interpretation and discussion, see Rice and Koziel [1] and Rice [2].

Fermentation of sugar to produce ethanol also produces volatile byproducts. This study was aimed at purifying corn-based ethanol for industrial and pharmaceutical use. The research was on treatment for 10 impurities removal after distillation. The ethanol headspace was sampled with solid-phase microextraction and analyzed with gas chromatography mass spectrometry. A 40 mg/L ozone treatment resulted in >56% and >36% removal of styrene and 2-pentylfuran, respectively, without significant generation of byproducts. A 60 g/L activated carbon (AC) treatment with 270 min adsorption time resulted in 84%, >72%, and >78% removal of ethyl hexanoate, ethyl octanoate, and ethyl decanoate respectively. CO2-based stripping, at 675 L-Stripping gas/L-Sample, removed 65%, >82%, and >83% acetaldehyde, ethyl vinyl ether, and 1,1-diethoxyethane respectively. A combination of three approaches effectively removes these 8 impurities. (C) 2015 Elsevier B.V. All rights reserved.

Recent US legislation permitting recreational use of marijuana in certain states brings the use of marijuana odor as probable cause for search and seizure to the forefront of forensic science, once again. This study showed the use of solid-phase microextraction with multi-dimensional gas chromatography-mass spectrometry and simultaneous human olfaction to characterize the total aroma of marijuana. The application of odor activity analysis offers an explanation as to why high volatile chemical concentration does not equate to most potent odor impact of a certain compound. This suggests that more attention should be focused on highly odorous compounds typically present in low concentrations, such as nonanal, decanol, o-cymene, benzaldehyde, which have more potent odor impact than previously reported marijuana headspace volatiles.

This report highlights the importance of an individual chemical's odor impact in the olfactory identification of marijuana, cocaine, and heroin. There are small amounts of highly odorous compounds present in headspace of these drugs, with very low odor detection thresholds, that are more likely responsible for contributing to the overall odor of these drugs. Previous reports of the most abundant compounds in headspace can mislead researchers when dealing with whole odor of these drugs. Surrogate scent formulations, therefore, must match the odor impact of key compounds and not just the chemical abundance of compounds. The objective of this study was to compare odorous volatile organic compounds (VOCs) emitted from illicit drug samples of marijuana, cocaine, and heroin to surrogate smell formulations using simultaneous sensory (via human olfaction) and chemical analyses. Use of solid phase microextraction (SPME) allowed VOCs in drug headspace to be extracted and pre-concentrated on site, and analyzed by multidimensional gas chromatography-mass spectrometry-olfactometry (MDGC-MS-O). Use of MDGC-MS-O allowed for further separation of odorous compounds and simultaneous detection by the human nose of the separate odor parts that make up the total aroma of these drugs. The compounds most abundant in headspace were not the most odor impactful when ranked by odor activity values (OAVs) (defined as ratio of concentration to odor detection threshold, ODT). There were no apparent correlations between concentrations and OAVs. A 1g marijuana surrogate lacked in odor active acids, aldehydes, ethers, hydrocarbons, N-containing, and S-containing VOCs and was overabundant in odor active alcohols and aromatics compared with real marijuana. A 1g cocaine surrogate was overabundant in odor active alcohols, aldehydes, aromatics, esters, ethers, halogenates, hydrocarbons, ketones and N-containing compounds compared with real. A 1g heroin surrogate should contain less odor active acids, alcohols, aromatics, esters, ketones, and N-containing compounds. Drug quantity, age and adulterants can affect VOC emissions and their odor impact. The concept of odor activity value, then, is useful to researchers without access to more sophisticated instrumentation. Odor activity values can be calculated from published odor detection thresholds. More research is warranted to expand the database, and determine odor detection thresholds for compounds of interest. Additional information could be obtained from establishing ODTs of key odorants for canines.

Deep digital septic conditions represent some of the most refractory causes of severe lameness in cattle. The objective of this study was to determine the distribution of tulathromycin, gamithromycin and florfenicol into the synovial fluid of the metatarsophalangeal (MTP) joint of cattle after single subcutaneous administration of drug to evaluate the potential usefulness of these single-dose, long-acting antimicrobials for treating bacterial infections of the joints in cattle.

.................................................................................................................. vi CHAPTER 1. GENERAL INTRODUCTION .................................................................... 1 SPME ......................................................................................................................................................... 1 Multidimensional gas chromatography – mass spectrometry – olfactometry (MDGC-MS-O) ................ 2 Volatile organic compounds emitted from illegal drugs ........................................................................... 2 Research Motivation ................................................................................................................................. 3 Thesis Organization ................................................................................................................................... 3 References ................................................................................................................................................ 4 CHAPTER 2. CHARACTERIZING THE SMELL OF MARIJUANA BY ODOR IMPACT OF VOLATLE COMPOUNDS. AN APPLICATION OF SIMULTANEOUS CHEMICAL AND SENSORY ANALYSIS. ........................................ 5 Abstract ..................................................................................................................................................... 5 Introduction .............................................................................................................................................. 5 1. Odor activity value ........................................................................................................................ 7 Materials and Methods ............................................................................................................................. 8 Results and discussion ............................................................................................................................ 11 1. Permeation of marijuana volatiles through packaging ............................................................... 11 2. Application of OAV to marijuana volatiles .................................................................................. 16 3. Simultaneous chemical and sensory analysis of fresh marijuana ............................................... 18 4. Odor impact based on OAV ........................................................................................................ 25 Conclusions ............................................................................................................................................. 25 References .............................................................................................................................................. 27 CHAPTER 3. CHARACTERIZING THE SMELL OF MARIJUANA BY ODOR IMPACT OF VOLATLE COMPOUNDS. AN APPLICATION OF SIMULTANEOUS CHEMICAL AND SENSORY ANALYSIS (Supporting Information) ............................................................................................ 30 SI Table 1. Legal cases based on probable cause for search and seizure. .............................................. 30 Review of research using SPME for forensic applications ...................................................................... 31