Chemical fingerprints encode mother-offspring similarity, colony membership, relatedness and genetic quality in fur seals

Chemical communication underpins virtually all aspects of vertebrate social life, yet remains poorly understood because of its highly complex mechanistic basis. We therefore used chemical fingerprinting of skin swabs and genetic analysis to explore the chemical cues that may underlie mother–offspring recognition in colonially breeding Antarctic fur seals. By sampling mother–offspring pairs from two different colonies, using a variety of statistical approaches and genotyping a large panel of microsatellite loci, we show that colony membership, mother–offspring similarity, heterozygosity, and genetic relatedness are all chemically encoded. Moreover, chemical similarity between mothers and offspring reflects a combination of genetic and environmental influences, the former partly encoded by substances resembling known pheromones. Our findings reveal the diversity of information contained within chemical fingerprints and have implications for understanding mother–offspring communication, kin recognition, and mate choice

TERPENE AND TERPENOID EMISSIONS AND SECONDARY ORGANIC AEROSOL PRODUCTION

Approximately 90% of fine aerosol in the Midwestern United States has a regional component with a sizable fraction attributed to secondary production of organic aerosol (SOA). The Ozark Forest is an important source of biogenic SOA precursors like isoprene (\u3e 150 mg m-2 d-1), monoterpenes (10-40 mg m-2 d-1), and sesquiterpenes (10-40 mg m-2d-1). Anthropogenic sources include secondary sulfate and nitrate and biomass burning (51-60%), vehicle emissions (17-26%), and industrial emissions (16-18%). Vehicle emissions are an important source of volatile and vapor-phase, semivolatile aliphatic and aromatic hydrocarbons that are important anthropogenic sources of SOA precursors. The short lifetime of SOA precursors and the complex mixture of functionalized oxidation products make rapid sampling, quantitative processing methods, and comprehensive organic molecular analysis essential elements of a comprehensive strategy to advance understanding of SOA formation pathways. Uncertainties in forecasting SOA production on regional scales are large and related to uncertainties in biogenic emission inventories and measurement of SOA yields under ambient conditions. This work presents a bottom-up approach to develop a conifer emission inventory based on foliar and cortical oleoresin composition, development of a model to estimate terpene and terpenoid signatures of foliar and bole emissions from conifers, development of processing and analytic techniques for comprehensive organic molecular characterization of SOA precursors and oxidation products, implementation of the high-volume sampling technique to measure OA and vapor-phase organic matter, and results from a 5 day field experiment conducted to evaluate temporal and diurnal trends in SOA precursors and oxidation products. A total of 98, 115, and 87 terpene and terpenoid species were identified and quantified in commercially available essential oils of Pinus sylvestris, Picea mariana, and Thuja occidentalis, respectively, by comprehensive, two-dimensional gas chromatography with time-of-flight mass spectrometric detection (GC × GC-ToF-MS). Analysis of the literature showed that cortical oleoresin composition was similar to foliar composition of the oldest branches. Our proposed conceptual model for estimation of signatures of terpene and terpenoid emissions from foliar and cortical oleoresin showed that emission potentials of the foliar and bole release pathways are dissimilar and should be considered for conifer species that develop resin blisters or are infested with herbivores or pathogens. Average derivatization efficiencies for Methods 1 and 2 were 87.9 and 114%, respectively. Despite the lower average derivatization efficiency of Method 1, distinct advantages included a greater certainty of derivatization yield for the entire suite of multi- and poly-functional species and fewer processing steps for sequential derivatization. Detection limits for Method 1 using GC × GC- ToF-MS were 0.09-1.89 ng μL-1. A theoretical retention index diagram was developed for a hypothetical GC × 2GC analysis of the complex mixture of SOA precursors and derivatized oxidation products. In general, species eluted (relative to the alkyl diester reference compounds) from the primary column (DB-210) in bands according to n and from the secondary columns (BPX90, SolGel-WAX) according to functionality, essentially making the GC × 2GC retention diagram a Carbon number-functionality grid. The species clustered into 35 groups by functionality and species within each group exhibited good separation by n. Average recoveries of n-alkanes and polyaromatic hydrocarbons (PAHs) by Soxhlet extraction of XAD-2 resin with dichloromethane were 80.1 ± 16.1 and 76.1 ± 17.5%, respectively. Vehicle emissions were the common source for HSVOCs [i.e., resolved alkanes, the unresolved complex mixture (UCM), alkylbenzenes, and 2- and 3-ring PAHs]. An absence of monoterpenes at 0600-1000 and high concentrations of monoterpenoids during the same period was indicative of substantial losses of monoterpenes overnight and the early morning hours. Post-collection, comprehensive organic molecular characterization of SOA precursors and products by GC × GC-ToFMS in ambient air collected with ~2 hr resolution is a promising method for determining biogenic and anthropogenic SOA yields that can be used to evaluate SOA formation models

Data processing for Life Sciences measurements with hyphenated Gas Chromatography-Ion Mobility Spectrometry

[eng] Recent progress in analytical chemistry instrumentation has increased the amount of data available for analysis. This progress has been encompassed by computational improvements, that have enabled new possibilities to analyze larger amounts of data. These two factors have allowed to analyze more complex samples in multiple life science fields, such as biology, medicine, pharmacology, or food science. One of the techniques that has benefited from these improvements is Gas Chromatography - Ion Mobility Spectrometry (GC-IMS). This technique is useful for the detection of Volatile Organic Compounds (VOCs) in complex samples. Ion Mobility Spectrometry is an analytical technique for characterizing chemical substances based on the velocity of gas-phase ions in an electric field. It is able to detect trace levels of volatile chemicals reaching for some analytes ppb concentrations. While the instrument has moderate selectivity it is very fast in the analysis, as an ion mobility spectrum can be acquired in tenths of milliseconds. As it operates at ambient pressure, it is found not only as laboratory instrumentation but also in-site, to perform screening applications. For instance it is often used in airports for the detection of drugs and explosives. To enhance the selectivity of the IMS, especially for the analysis of complex samples, a gas chromatograph can be used for sample pre-separation at the expense of the length of the analysis. While there is better instrumentation and more computational power, better algorithms are still needed to exploit and extract all the information present in the samples. In particular, GC-IMS has not received much attention compared to other analytical techniques. In this work we address some of the data analysis issues for GC-IMS: With respect to the pre-processing, we explore several baseline estimation methods and we suggest a variation of Asymmetric Least Squares, a popular baseline estimation technique, that is able to cope with signals that present large peaks or large dynamic range. This baseline estimation method is used in Gas Chromatography - Mass Spectrometry signals as well, as it suits both techniques. Furthermore, we also characterize spectral misalignments in a several months long study, and propose an alignment method based on monotonic cubic splines for its correction. Based on the misalignment characterization we propose an optimal time span between consecutive calibrant samples. We the explore the usage of Multivariate Curve Resolution methods for the deconvolution of overlapped peaks and their extraction into pure components. We propose the use of a sliding window in the retention time axis to extract the pure components from smaller windows. The pure components are tracked through the windows. This approach is able to extract analytes with lower response with respect to MCR, compounds that have a low variance in the overall matrix Finally we apply some of these developments to real world applications, on a dataset for the prevention of fraud and quality control in the classification of olive oils, measured with GC-IMS, and on data for biomarker discovery of prostate cancer by analyzing the headspace of urine samples with a GC-MS instrument[cat] Els avenços recents en instrumentació química i el progrés en les capacitats computacionals obren noves possibilitats per l’anàlisi de dades provinents de diversos camps en l’àmbit de les ciències de la vida, com la biologia, la medicina o la ciència de l’alimentació. Una de les tècniques que s’ha beneficiat d’aquests avenços és la cromatografia de gasos – espectrometria de mobilitat d’ions (GC-IMS). Aquesta tècnica és útil per detectar compostos orgànics volàtils en mostres complexes. L’IMS és una tècnica analítica per caracteritzar substàncies químiques basada en la velocitat d’ions en fase gasosa en un camp elèctric, capaç de detectar traces d’alguns volàtils en concentracions de ppb ràpidament. Per augmentar-ne la selectivitat, un cromatògraf de gasos pot emprar-se per pre-separar la mostra, a expenses de la durada de l’anàlisi. Tot i disposar de millores en la instrumentació i més poder computacional, calen millors algoritmes per extreure tota la informació de les mostres. En particular, GC-IMS no ha rebut molta atenció en comparació amb altres tècniques analítiques. En aquest treball, tractem alguns problemes de l’anàlisi de dades de GC-IMS: Pel que fa al pre-processat, explorem algoritmes d’estimació de la línia de base i en proposem una millora, adaptada a les necessitats de l’instrument. Aquest algoritme també s’utilitza en mostres de cromatografia de gasos espectrometria de masses (GC-MS), en tant que s’adapta correctament a ambdues tècniques. Caracteritzem els desalineaments espectrals que es produeixen en un estudi de diversos mesos de durada, i proposem un mètode d’alineat basat en splines cúbics monotònics per a la seva correcció i un interval de temps òptim entre dues mostres calibrants. Explorem l’ús de mètodes de resolució multivariant de corbes (MCR) per a la deconvolució de pics solapats i la seva extracció en components purs. Proposem l’ús d’una finestra mòbil en el temps de retenció. Aquesta millora permet extreure més informació d’analits. Finalment utilitzem alguns d’aquests desenvolupaments a dues aplicacions: la prevenció de frau en la classificació d’olis d’oliva, mesurada amb GC-IMS i la cerca de biomarcadors de càncer de pròstata en volàtils de la orina, feta amb GC-MS

Analysis and Treatment of Emerging Polar Contaminants

Two major classes of polar compounds have recently become a major focus as sources of contamination of water systems. Pharmaceuticals and personal care products (PPCPs) enter water through wastewater streams, and many of these compounds survive current wastewater treatment processes. High production volume chemicals (HPVCs), defined as chemicals produced in excess of one million pounds per year have numerous entries into surface and drinking waters due to their ubiquity. The commonality between many of these compounds is their polarity, which makes them water-soluble. While both PPCPs and HPVCs have been entering into the environment for decades, advances in analyte detection have increased the ability of scientists to identify these compounds in surface, waste and drinking waters. Methods for polar compound suites have been developed using a number of technologies, however these processes are often time consuming and require specialized instrumentation. In this study, a fast, robust method for the detection and treatment of emerging polar contaminants was developed with accompanying instrumentation. A liquid chromatography system, hyphenated to a universal gas phase detector, flame ionization detector (FID), was designed. By using pure subcritical water as a mobile phase, temperature was used to control chromatographic retention. This instrument may be used for rapid screening of environmental samples with minimal preparation. Using subcritical water chromatography allowed for testing of mass transfer between subcritical water and organic phases, which provides data on the transport of polar contaminants between solvent phases. A second component of the work in this dissertation was to test a treatment protocol for waste streams, which demonstrated the reduction of selected analytes within the PPCP and HPVC classes. Subcritical water wet oxidation allowed for the breakdown of all polar organic molecules dissolved in a water sample. As a thermochemical process, the oxidation reaction further reduced select compounds that remain after current biological waste removal processes, and provided a value-added process to current wastewater treatment, in which a needed process, disinfection, can be coupled to additional contaminant removal

Características químicas e toxicológicas de partículas de queima doméstica de biomassa

Biomass combustion for residential heating is recognised as an important source of particulate matter, not only in the ambient air, but also inside the dwellings. Exposure to biomass burning particles has been linked to a vast array of adverse health effects. The physical and chemical properties of inhaled particles are thought to greatly affect the biological responses. Over the years, many studies have focused on emission source profiles of residential biomass combustion. However, with the advent and growing market share of new small-scale appliances automatically fed with compressed biofuels, research efforts need to be devoted to the characterisation of emissions from these appliances either from new commercially available pellets or from pellets made from potentially relevant raw materials. Despite the wealth of publications on emissions and composition of particles from residential biomass combustion, the impact of this source on the indoor air quality has been scarcely studied, especially with regard to the chemical and toxicological characteristics of the particles. The two main objectives of this thesis were: i) to obtain chemical and toxicological profiles for pellet-fuelled heating systems, and ii) to evaluate the impact of traditional appliances on indoor air quality, properties of particulate matter, deposited dose in the respiratory tract and biological responses. For the fulfilment of the first objective, four types of pellets were selected (two brands of ENplus A1 certified pellets, one brand of non-certified pellets, and laboratory-produced acacia pellets) to carry out experiments in a laboratory combustion facility to determine emission factors of gaseous compounds and particulate matter (PM10). To achieve the second objective, particulate samples were collected in two households equipped with distinct combustion appliances (open fireplace and woodstove) in the absence of other indoor sources. The dose of inhaled indoor particles deposited in the human respiratory tract was estimated using an exposure dose model (ExDoM2). The chemical composition of PM10 from both laboratory experiments and residential microenvironments was analysed for water soluble inorganic ions, organic and elemental carbon and detailed organic speciation. Additionally, in samples collected indoors, major and trace elements were also determined. A battery of in vitro assays was used to assess the ecotoxicity, cytotoxicity and mutagenicity of the PM10 samples. The results obtained from the laboratory measurements indicated that the alternative woody raw material selected for pelletising contributed to a dramatic increase in particulate emissions, with distinctive chemical properties and increased toxicological potential. It was observed that even certified material does not always meet emission requirements set by the Ecodesign directive. Particles from pellet combustion were mainly composed of water soluble inorganic constituents. The carbonaceous fraction of particulate samples from commercial pellets was dominated by elemental carbon, while organic carbon was the most abundant constituent in samples from the combustion of acacia pellets. The results showed that particles from acacia pellets were the most ecotoxic and cytotoxic, while mutagenicity was not detected for any biofuel. In the sampling campaign carried out in residential microenvironments while using different combustion devices, higher exposures, higher doses in the human respiratory tract and higher toxicity of the particles collected during the operation of the open fireplace were observed, as a result of the lower combustion efficiency. When using this combustion equipment, a higher increase in particulate matter levels (over 12 times compared to background concentrations) was registered compared to that measured with the woodstove (2-fold increase). The carbonaceous material accounted for a PM10 mass fraction of about 44% in samples from the room equipped with fireplace, while the woodstove operation almost halved the total particulate carbon content. Water soluble ions and trace elements showed variable contributions to the mass of the indoor particles and were generally higher during the operation of the woodstove. Several chemical markers of biomass combustion were detected in both residential microenvironments, highlighting the input of this source to indoor particles. The bioreactivity assessment showed that particles emitted by the fireplace were the most ecotoxic and cytotoxic, while mutagenicity was not detected in any of the tested samples. Combustion-related organic compounds in indoor particles, such as polycyclic aromatic hydrocarbons, displayed significant correlations with the increase in toxicity. In view of the results obtained, homeowners should be encouraged to upgrade the wood burning technology in order to reduce the products of incomplete combustion inside their dwellings.A combustão de biomassa para aquecimento residencial é reconhecida como uma fonte importante de material particulado não apenas no ar ambiente, mas também no interior das habitações. A exposição a partículas resultantes da queima de biomassa tem sido associada a um vasto leque de efeitos adversos na saúde. Sabe-se que as propriedades físicas e químicas das partículas inaladas afetam acentuadamente as respostas biológicas. Ao longo dos anos, muitos estudos tiveram como foco os perfis de emissão da combustão residencial de biomassa. No entanto, com o aparecimento e a crescente quota de mercado de novos equipamentos de pequena escala alimentados automaticamente com biocombustíveis prensados, a investigação deve ser direcionada para a caracterização das emissões desses sistemas de combustão alimentados quer com novos pellets disponíveis no mercado, quer com pellets produzidos a partir de novas matérias primas potencialmente relevantes. Apesar da abundância de publicações dedicadas às emissões e composição das partículas da queima residencial de biomassa, o impacto desta fonte na qualidade do ar interior tem sido pouco estudado, sobretudo no que diz respeito às características químicas e toxicológicas do material particulado. Os dois objetivos principais desta tese foram: i) obter os perfis químicos e toxicológicos para sistemas alimentados a pellets, e ii) avaliar o impacto de equipamentos tradicionais na qualidade do ar interior, propriedades do material particulado, dose depositada no trato respiratório e respostas biológicas. Para atingir o primeiro objetivo, foram selecionados quatro tipos de pellets (duas marcas de pellets com certificação ENplus A1, uma marca de pellets sem certificação e pellets de acácia produzidos em laboratório) para realizar experiências numa instalação laboratorial de combustão e determinar fatores de emissão de gases e material particulado (PM10). Para atingir o segundo objetivo, realizaram-se amostragens de partículas em duas habitações com equipamentos de combustão distintos (lareira aberta e recuperador de calor), na ausência de outras fontes interiores. A dose de partículas inaladas no interior das habitações e depositadas no trato respiratório humano foi estimada utilizando um modelo de exposição/dose (ExDoM2). A composição química das PM10 resultantes quer dos ensaios laboratoriais, quer dos microambientes residenciais, foi analisada em termos de iões inorgânicos solúveis em água, carbono orgânico e elementar e especiação orgânica detalhada. Adicionalmente, nas amostras de partículas colhidas no interior das habitações, foram também determinados elementos maioritários e traço. Foi utilizada uma bateria de ensaios in vitro para avaliar a ecotoxicidade, citotoxicidade e mutagenicidade das amostras de PM10. Os resultados obtidos nos ensaios laboratoriais indicaram que o material lenhoso alternativo selecionado para a peletização contribuiu para um aumento dramático das emissões de partículas, as quais apresentaram propriedades químicas distintas e um potencial toxicológico elevado. Observou-se que mesmo o material certificado nem sempre cumpre os requisitos de emissão estabelecidos pela diretiva Ecodesign. As partículas emitidas pela combustão de pellets apresentaram na sua composição maioritariamente iões inorgânicos solúveis em água. O carbono elementar dominou a fração de material carbonáceo nas partículas dos pellets comerciais, ao passo que o carbono orgânico constitui a componente mais abundante nas amostras resultantes da queima de pellets de acácia. Os resultados mostraram que as partículas dos pellets de acácia foram as mais ecotóxicas e citotóxicas, enquanto não foi detetada mutagenicidade para nenhum biocombustível. Na campanha de amostragem realizada em microambientes residenciais durante a utilização de diferentes equipamentos de combustão, observou-se uma exposição mais elevada, dose depositada no trato respiratório humano mais alta e uma toxidade superior para as partículas colhidas durante a operação da lareira aberta, refletindo a menor eficiência de combustão deste equipamento. Durante a sua utilização, foi registado um aumento superior nos níveis de material particulado (mais de 12 vezes relativamente às concentrações de fundo) em comparação com o observado para o recuperador de calor (aumento de 2 vezes). O material carbonáceo representou cerca de 44% da massa de PM10 nas amostras colhidas durante a operação da lareira, enquanto a operação do recuperador de calor reduziu quase pela metade o conteúdo total de carbono nas partículas. Os iões solúveis em água e os elementos apresentaram contribuições variáveis para a massa das partículas no interior das habitações, sendo geralmente superiores durante a operação do recuperador de calor. Em ambos os microambientes residenciais foram detetados vários traçadores químicos de combustão de biomassa, assinalando a contribuição desta fonte para as partículas interiores. A avaliação da biorreatividade revelou que as partículas emitidas pela lareira foram as mais ecotóxicas e citotóxicas, enquanto que não foi detetada mutagenicidade em quaisquer das amostras testadas. Vários constituintes detetados nas partículas internas, como os hidrocarbonetos aromáticos policíclicos, apresentaram correlações significativas com o aumento da toxicidade. Considerando os resultados obtidos, os proprietários devem ser encorajados a atualizar a tecnologia de combustão, a fim de reduzir os produtos de combustão incompleta dentro das suas habitações.Programa Doutoral em Ciências e Engenharia do Ambient

Techniques to Enhance the Attributes of Wines Produced from Grapes Grown in Arkansas

Grapevines (Vitis spp.) are one of the most widely-planted horticultural crops, and the United States plays a major role in grape and wine production. Arkansas has a long history of grape and wine production with grapes grown in Arkansas including mostly native species, such as muscadines, and hybrids (crosses of Vitis spp.), such as Chambourcin. In addition, the University of Arkansas System Division of Agriculture (UA System) grape breeding program has cultivars and selections that have shown potential for wine production. The objectives of this research were to: evaluate effects of specific inactivated yeast application to Chambourcin grapevines on attributes of grapes and wine; determine impacts of winemaking methods on Noble muscadine wine attributes; evaluate impacts of winemaking methods on Enchantment wine attributes; and explore attributes of wines from UA System white wine genotypes (Opportunity, A-2359, and A-2574). In 2018 and 2019 at a commercial Arkansas vineyard, four rows of Chambourcin grapevines were sprayed with inactivated yeast (spray treatment) and four rows were unsprayed (control treatment). Berries were sampled from each treatment during ripening and at harvest and wines were produced from each treatment. Sprayed Chambourcin berries had higher skin elasticity, lower pH, and higher anthocyanins than control berries. Wines from sprayed grapevines had higher red color than control wines over 12-months storage, higher concentrations of fruity ester aroma compounds in analytical studies, and higher red color and better mouthfeel in sensory studies. This is the first data on inactivated yeast application to Chambourcin, but it shows potential for grapes with better winemaking attributes and wines with deeper red colors and improved sensory attributes. In 2018, Noble muscadine grapes were used to produce wines with different skin contact times and with and without the addition of a glycosidic enzyme. Noble wines with increased skin contact had higher anthocyanins and red color and spicy, dark-fruit aromas. Wines with 0-days skin contact had strawberry and candy aromas characteristic of muscadine juice. Noble wines without glycosidic enzyme had fruitier, more pleasant aromas. Therefore, skin contact time and glycosidic enzyme addition impacted the color and sensory attributes of Noble muscadine wine. Wines were produced from Enchantment grapes in 2017 and 2018 with and without the addition of tannin and oak. Enchantment wines had V. vinifera-like anthocyanins and deep red color. Enchantment wines with oak were associated with oaky, roasted, and caramelized aromas, and wines with tannin had lower overall aromas. These results suggested the potential of Enchantment grapes for producing high-quality, deeply red-colored wines with aging potential. Wines were produced from Opportunity, A-2359, and A-2574 in 2015, 2017, and 2018. The aroma/flavor of Opportunity wines was described as spicy, green apple, and peach, A-2359 wine was described as floral, grapefruit, and Muscat, and A-2574 wine was described as spicy, rose, and peach. This demonstrated that UA System white wine grapes produced wines with unique/pleasant sensory characteristics and could provide new opportunities for the Arkansas grape and wine industry. Therefore, viticultural and enological techniques enhanced the attributes of wines produced from grapes grown in Arkansas

Recent Advances in Gas Chromatography

Gas chromatography is one of the most used analytical techniques in the industry. It is a powerful tool with a wide range of applications. This book presents recent advances in gas chromatography, multidimensional gas chromatography, and gas chromatography mass spectrometry. It also discusses inverse gas chromatography. The main focus is the use of gas chromatography techniques to analyze petroleum fluids, biomass, and ionic liquids in medical and petrochemical industries