Flüchtige organische Verbindungen (Volatile organic compounds (VOC)) sind ubiquitär vorkommende kohlenstoffhaltige Substanzen. Untersuchungen haben relevante VOC-Konzentrationen im Inneren von Gebäuden nachgewiesen. Da der Innenraum zum typischen Aufenthaltsort des modernen Menschen geworden ist, sind diese Schadstoffe in das Interesse der Forschung gerückt. Kinder reagieren unter Schadstoffexposition besonders sensibel, denn viele wichtige Organsysteme befinden sich noch in ihrer Entwicklung. In der vorliegenden Arbeit wurden Leipziger Daten der LISA-Studie („Einfluss von Lebensbedingungen und Verhaltensweisen auf die Entwicklung von Immunsystem und Allergien im Ost-West-Vergleich“) hinsichtlich möglicher Effekte einer VOC-Exposition auf Erkrankungen der Kinder im 4. Lebensjahr analysiert. Bei der LISA-Studie handelt es sich um eine multizentrische prospektive Geburts-Kohortenstudie, in die von November 1997 bis Januar 1999 insgesamt 3097 gesunde und reife Neugeborene deutscher Herkunft mit einem Geburtsgewicht > 2500 g rekrutiert wurden. Die Berechnungen der vorliegenden Arbeit erfolgten mit VOC-Messwerten um den 3. Geburtstag der Kinder. Die jeweiligen logistischen Regressionsmodelle wurden auf das Geschlecht, die atopische Familienanamnese, eine passive Tabakrauchexposition, das Aufstellen neuer Möbel im Kinderzimmer, Renovierungen und die Erneuerung des Fußbodenbelags in der Wohnung adjustiert. Es ließen sich VOC bestimmen, die bei Konzentrationserhöhungen eine erhöhte Chance für eine akute Bronchitis zur Folge hatten. Als Risikofaktor einer akuten Bronchitis ließ sich außerdem die Erneuerung des Fußbodenbelags in der Wohnung ermitteln. Während sich für eine akute Bronchitis in Abhängigkeit der VOC-Konzentration erstmals eine Dosis-Wirkungs-Kurve ableiten ließ, war dies für allergische Erkrankungen nicht möglich. Weitere Untersuchungen sind notwendig um Pathomechanismen der VOC-Einwirkungen auf den kindlichen Organismus aufzuklären.

The oxidation of volatile organic compounds (VOCs) plays a role in both regional and global air quality through the formation of secondary organic aerosols (SOA). More than 1000TgC/yr of non-methane VOCs are emitted from biogenic sources (significantly greater than from anthropogenic sources). Despite this magnitude and potential importance for air quality, the body of knowledge around the identities, quantities and oxidation processes of these compounds is still incomplete (e.g., Goldstein & Galbally, 2007; Robinson et al., 2009). Two-dimensional gas chromatography paired with time-of-flight mass spectrometry (GC×GC/TOFMS) is a powerful analytical technique which is explored here for its role in better characterizing biogenic VOCs (BVOCs) and thus SOA precursors. This work presents measurements of BVOCs collected during two field campaigns and analyzed using GC×GC/TOFMS. The first campaign, the Bio-hydro-atmosphere Interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS), took place in a Ponderosa pine forest in Colorado. The second campaign, Particle Investigations at a Northern Ozarks Tower: NOx, Oxidant, Isoprene Research (PINOT NOIR) Study, was conducted in the Ozark region of Missouri. Tens to hundreds of BVOCs were quantified in each set of samples, including primary emissions, atmospheric oxidation products, stress indicators and semi-volatile leaf surface compounds. These findings highlight that there is a largely uncharacterized diversity of BVOCs in ambient samples. Our findings demonstrate that GC×GC can distinguish between compounds with the same molecular weight and similar structures, which have highly variable potentials for production of SOA (Lee et al., 2006). This work represents some of the first analysis of ambient BVOCs with this technology, which is anticipated to contribute greatly to characterization of atmospheric SOA precursors and ultimately, regional and global modeling of SOA and fine particulate matter.

Atmospheric particulate matter is known to have significant effects on human health, visibility, and global climate. The magnitudes of these effects, however, depend in complex ways on chemical composition, relative humidity, temperature, phase state, and other parameters. Current regional air quality models such as CMAQ (Community Multiscale Air Quality model) ignore many of these considerations, and consider that the formation of secondary organic aerosol (SOA) can be calculated by assuming thermodynamic ideality in the organic particulate matter (OPM) phase as well as negligible uptake of water into the OPM phase. Theoretical predictions and model simulations considering non-ideality and water uptake show that the standard model assumptions can lead to large errors in predicted SOA mass, and that the magnitude of these errors is sensitive to the composition of the OPM phase. The SOA module in CMAQ v4.7.1 has been revised in this work to allow consideration of the effects of both non-ideality and water uptake. First, a reasonable specific surrogate structure was assigned to each of the lumped products assumed to be produced by reaction of the different precursor hydrocarbons considered in CMAQ (e.g., isoprene, benzene, and toluene). Second, the CMAQ code was modified to allow iterative calculation (at each point in space and time) of the gas/particle partitioning coefficient for each of the SOA-forming products and for water. Third, model simulations were performed for the Eastern US at a resolution of 36-km x 36-km for late summer 2006, under a range of relative humidity conditions. When compared with an appropriate base case, the modified code produced increases in SOA ranging from 0.17 to 0.51 micrograms per cubic meter. The average change was 0.30 micrograms per cubic meter, corresponding to a 37% increase in SOA formation. Incorporation of phase separation effects would likely lead to further increases in predicted SOA levels.

Surface-modification of phthalocyanine-based two-dimensional conjugated metal-organic framework (2D c-MOF) films by grafting aliphatic alkyl chains is developed for achieving high-performance polarity-selective chemiresistive sensing toward humidity and polar alcohols. 2D conjugated metal–organic frameworks (2D c-MOFs) are emerging as electroactive materials for chemiresistive sensors, but selective sensing with fast response/recovery is a challenge. Phthalocyanine-based Ni2[MPc(NH)8] 2D c-MOF films are presented as active layers for polarity-selective chemiresisitors toward water and volatile organic compounds (VOCs). Surface-hydrophobic modification by grafting aliphatic alkyl chains on 2D c-MOF films decreases diffused analytes into the MOF backbone, resulting in a considerably accelerated recovery progress (from ca. 50 to ca. 10 s) during humidity sensing. Toward VOCs, the sensors deliver a polarity-selective response among alcohols but no signal for low-polarity aprotic hydrocarbons. The octadecyltrimethoxysilane-modified Ni2[MPc(NH)8] based sensor displays high-performance methanol sensing with fast response (36 s)/recovery (13 s) and a detection limit as low as 10 ppm, surpassing reported room-temperature chemiresistors.

This corrigendum corrects an omission from the Acknowledgement section. The research leading to the results published in this manuscript was also supported by the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020.

Forest canopies are complex and highly diverse environments. Their diversity is affected by pronounced gradients in abiotic and biotic conditions, including variation in leaf chemistry. We hypothesised that branch-localised defence induction and vertical stratification in mature oaks constitute sources of chemical variation that extend across trophic levels. To test this, we combined manipulation of plant defences, predation monitoring, food-choice trials with herbivores and sampling of herbivore assemblages. Both induction and vertical stratification affected branch chemistry, but the effect of induction was stronger. Induction increased predation in the canopy and reduced herbivory in bioassays. The effects of increased predation affected herbivore assemblages by decreasing their abundance, and indirectly, their richness. In turn, we show that there are multiple factors contributing to variation across canopies. Branch-localised induction, variation between tree individuals and predation may be the ones with particularly strong effects on diverse assemblages of insects in temperate forests.

Modern indoor environments contain a vast array of contaminating sources. Emissions from these sources produce contaminant concentrations that are substantially higher indoors than outside. Because we spend most of our time indoors, exposure to indoor pollutants may be orders-of-magnitude greater than that experienced outdoors. Phthalate esters have been recognized as major indoor pollutants. They are mainly used as plasticizers to enhance the flexibility of polyvinylchloride (PVC) products, as well as in humectants, emollients, and antifoaming agents. Phthalates are found in a wide range of consumer products including floor and wall coverings, car interior trim, floor tiles, gloves, footwear, insulation on wiring, and artificial leather. Because these phthalate additives are not chemically bound to the polymer matrix, slow emission from the products to the surrounding air or other media usually occurs. Biomonitoring data suggest that over 75% of the U.S. population is exposed to phthalates. The ubiquitous exposure to phthalates is of concern because toxicological investigations have demonstrated considerable adverse health effects of phthalates and their metabolites. Studies have shown that exposure to phthalates results in profound and irreversible changes in the development of the reproductive tract, especially in males, raising the possibility that phthalate exposures could be the leading cause of reproductive disorders in humans. In addition, effects such as increases in prenatal mortality, reduced growth and birth weight, skeletal, visceral, and external malformations are possibly associated with phthalate exposure. Epidemiologic studies in children also show associations between phthalate exposure in the home and the risk of asthma and allergies. Given the ubiquitous nature of phthalates in the environment and the potential for adverse human health impacts, there is a critical need to understand indoor emissions of phthalates and to identify the most important sources and pathways of exposure. In this study, a model that integrates the fundamental mechanisms governing emissions of semi-volatile organic compounds (SVOCs) from polymeric materials and their subsequent interaction with indoor surfaces and airborne particles was developed. The emissions model is consistent with analogous mechanistic models that predict emission of volatile organic compounds (VOCs) from building materials. Reasonable agreement between model predictions and gas-phase di-2-ethylhexyl phthalate (DEHP) concentrations was achieved for data collected in a previously published experimental study that measured emissions of DEHP from vinyl flooring in two very different chambers. The analysis showed that while emissions of highly volatile VOCs are subject to “internal“ control (through the material-phase diffusion coefficient), emissions of the very low volatility SVOCs are subject to “external“– control (through partitioning into the gas phase, the convective mass transfer coefficient, and adsorption onto interior surfaces). Because of the difficulties associated with sampling and analysis of SVOCs, only a few chamber studies quantifying their emissions from building materials and consumer products are available. To more rigorously validate the SVOCs emission model and more completely understand the mechanisms governing the release of phthalate from polymeric building materials, the emission of DEHP from vinyl flooring was studied for up to 140 days in a specially-designed stainless steel chamber. In the duplicate chamber study, the gas-phase concentration in the chamber increased slowly and reached a steady state level of 0.9 µg/m3 after 30 days. By increasing the area of vinyl flooring and decreasing that of the stainless steel surface in the chamber, the time to reach steady state was significantly reduced, compared to the previous study (1 month vs. 5 months). The adsorption isotherm of DEHP on the interior stainless steel chamber surface was explicitly measured using two different methods (solvent extraction and thermal desorption). Strong adsorption of DEHP onto the stainless steel surface was observed and found to follow a simple linear relationship. In addition, parameters measured in the experiments were then applied in the fundamental SVOCs emission model. Good agreement was obtained between the predictions of the model and the gas-phase DEHP chamber concentrations, without resorting to fitting of model parameters. These chamber studies have shown that the tendency of SVOCs to adsorb strongly to interior surfaces has a very strong influence on the emission rate. Compared to the experimental chamber systems, however, the real indoor environment has many other types of surface that will adsorb phthalates to different extents. The emission rate measured in a test chamber may therefore be quite different to the emission rate from the same material in the indoor environment. For this reason, both a two-room model and a more representative three-compartment model were developed successively to estimate the emission rate of DEHP from vinyl flooring, the evolving gas-phase and adsorbed surface concentrations, and human exposures (via inhalation, dermal absorption and oral ingestion of dust) in a realistic indoor environment. Adsorption isotherms for phthalates and plasticizers on interior surfaces, such as carpet, wood, dust and human skin, were derived from previous field and laboratory studies. A subsequent sensitivity analysis revealed that the vinyl flooring source characteristics, as well as mass-transfer coefficients and ventilation rates, are important variables influencing the steady-state DEHP concentration and resulting exposures. A simple uncertainty analysis suggested that residential exposure to DEHP originating from vinyl flooring may fall somewhere between about 5 µg/kg/d and 180 µg/kg/d. The roughly 40-fold range in exposure reveals the inherent difficulty in using biomonitoring results to identify specific sources of exposure in the general population. This research represents the first attempt to explicitly elucidate the fundamental mechanisms governing the release of phthalates from polymeric building materials as well as their subsequent interaction with interior surfaces. The mechanistic models developed can most likely be extended to predict concentration and exposure arising from other sources of phthalates, other sources of other semi-volatile organic compounds (such as biocides and flame retardants), as well as emissions into other environmental media (food, water, saliva, and even blood). The results will be of value to architects, governments, manufacturers, and engineers who wish to specify low-emitting green materials for healthy buildings. It will permit health professionals to identify and control health risks associated with many of the SVOCs used in indoor materials and consumer products in a relatively inexpensive way. / Ph. D.

Depuis quatre décennies, la prévalence des affections respiratoires chroniques de l'enfant a considérablement augmenté dans les pays développés. Les conditions de survenue de ces affections sont complexes, mais de nombreux travaux suggèrent la contribution importante de l'exposition par inhalation aux polluants de l'air intérieur. Dans ce contexte, cette thèse vise à évaluer l’exposition cumulée à une gamme de polluants chimiques et biologiques de l’air intérieur dans un échantillon donné de logements. Il a également pour objectif de créer une typologie des logements en fonction de leur multi-contamination, et vise à construire des modèles explicatifs des concentrations des polluants en fonction des caractéristiques de l’habitat et des habitudes de vie des occupants.Une enquête environnementale a été menée dans 150 logements issus de la cohorte Pélagie, suivie en Bretagne depuis 2002. Des prélèvements ont permis de mesurer la concentration de 8 aldéhydes, 4 THM, 22 autres COV, 9 COSV et 4 genres de moisissures dans l’air de ces logements. Celles-ci, ainsi que 4 allergènes ont également été dosés dans des échantillons de poussières. Les paramètres d’ambiance (température, humidité relative et dioxyde de carbone) ont été mesurés. Un questionnaire renseigné par les familles a permis de collecter des informations sur les logements et leurs occupants : structure et historique du bâtiment, revêtements, ménage, chauffage, aération, utilisation de certains produits ou réalisation d’activités particulières. Ces données ont été analysées par des approches statistiques multivariées, et des modèles de régression linéaire et logistique ont été mis en oeuvre pour relier les concentrations des contaminants aux caractéristiques des logements. Ces mesures ont mis en évidence une contamination importante et systématique des logements par une grande part des contaminants chimiques et biologiques, à des niveaux parfois élevés au regard d’études comparables et des valeurs guides lorsqu’elles existent. Des analyses en composantes principales ont permis de mettre en évidence des sous-groupes de composés qui ont pu être interprétés en termes de sources, et de sélectionner un certain nombre de composés traceurs représentatifs de chaque sous-groupe. Une analyse factorielle multiple a permis de répartir les logements en 7 classes, chacune présentant un profil de multi-contamination particulier. Enfin, les modèles de régression linéaire et logistique construits pour les composés traceurs permettent d’expliquer entre 5 et 60% de la variabilité des concentrations, et mettent en évidence la multiplicité des sources, l’importance de la description précise des environnements intérieurs, et l’impact des paramètres d’ambiance sur ces concentrations. Ce travail décrit donc une contribution importante à l’évaluation des expositions aux contaminants de l’air intérieur et fournit un certain nombre d’éléments quant à la prédiction des expositions dans les environnements intérieurs. / For the last four decades, the prevalence of chronic respiratory affections in children has increased dramatically in developed countries. Occurring conditions of these affections are complex, but many studies suggest the important contribution of inhalation exposure to indoor air pollutants. In this context, this thesis aims to assess the cumulative exposure to a range of chemical and biological pollutants in indoor air in a given sample of dwellings. It also aims to create a typology of these dwellings based on their multi-contamination, and to build explanatory models for concentrations of pollutants based on characteristics of the dwellings and lifestyle of the occupants. An environmental survey was conducted in 150 dwellings from the Pelagie cohort, followed in Brittany since 2002. We measured the concentration of 8 aldehydes, 4 THMs, 22 other VOCs, 9 SVOCs and 4 mold genera in the air of these dwellings. Molds as well as four allergens were also measured in dust samples. Ambient parameters (temperature, relative humidity and carbon dioxide) were also measured. A questionnaire completed by families allowed collecting information on dwellings and their occupants: structure and history of the building, wall and floor coatings, cleaning, heating and ventilation habits, use of certain products or performing specific activities. These data were analyzed by multivariate statistical approaches, and linear and logistic regression models were used to link the concentrations of the contaminants with the housing characteristics. These measures showed an important and systematic contamination of the dwellings by a large amount of both chemical and biological contaminants, sometimes at relatively high levels regarding comparable studies and guideline values when they exist. Principal components analysis allowed to identify subgroups of compounds that could be interpreted in terms of sources, and to select representative compounds of each subgroup. A multiple factor analysis was used to classify the dwellings into 7 categories, each with a special multi-contamination profile. Finally, linear and logistic regression models built for the representative compounds explained between 5 and 60% of the variability of the concentrations, and highlighted the multiplicity of sources, the importance of a precise description of indoor environments, and the impact of the ambient parameters on these concentrations. This work thus describes an important contribution to the exposure assessment to indoor air contaminants and provides elements for prediction of exposures in indoor environments.

Along with industrial and economic growth there is a persistent risk of permanently increasing air pollution. Air pollution has especially grown in the second half of the 20th century due to intense development of energy, industry and transport sectors. These pollution sources still remain the largest air polluters. Solvents, paints, glues, ink and other substances, emitting volatile organic compounds to air are used in such industries like reel, metal and wood coating, covering with glue sticks, footwear production, production of pharmaceutical products, printing, dry (chemical) surface cleaning etc. Emissions of volatile organic compounds make harm both to people and environment as well as damage the ozone layer. Volatile organic compounds also affect smog formation and green house effect. In the paper it is hypothesised that after implementation of EU legislation, observing the given emission limit values, improving technologies and implementing new treatment technologies, applying the measures to reduce pollution with volatile organic compounds and replacing the materials, emitting volatile organic compounds, with less polluting ones or those without pollution, air emission of volatile organic compounds will reduce dramatically. This master’s paper reviews the measures and ways to manage pollution with volatile organic compounds (VOC): directives and their requirements, transferred to the national laws of the member states, addressed to solve the VOC pollution problem... [to full text]

Conventional sources of emissions have been a prime target for policymakers in designing pollution control strategies. However, the evolution of shale gas activities is a growing concern over the impact of unconventional sources on urban and regional air quality. Owing to the development of Barnett Shale production, the fast-growing Dallas-Fort Worth (DFW) metroplex has encountered both types of these emissions. Oil and gas activities result in emissions of ozone precursors, notably volatile organic compounds (VOC). The major objective of this study was to evaluate the spatio-temporal distribution of VOC in order to highlight the influence of unconventional emissions. The study utilized measurements from automated gas chromatography (AutoGC) monitors to analyze the patterns of the total non-methane organic compounds (TNMOC) and relative contributions from marker species of traffic versus oil and gas activities. In this study, data from 2001-2014 was obtained from the Texas Commission on Environmental Quality (TCEQ) for fifteen monitoring sites within the North Texas region. With over a thousand wells in a 10 mile radius, two of the rural sites measured twice as much TNMOC as compared to the urban site in Dallas. Source apportionment analysis was conducted using Positive Matrix Factorization (PMF) technique. The target site located in the urban zone resolved an eight factor model. Natural gas signature was the dominant source of emission with a 52% contribution followed by 31% from two separate traffic-related sources. Considering ethane to be the dominant species in oil and gas emissions, it was observed that the rising ethane/NOx ratio correlated with increasing annual average ozone post-2007. In this period, higher concentration of ozone was found to be associated with stronger winds from the Barnett Shale area – a region that did not seem to contribute to high ozone during 2001-2007. With traffic emissions having flattened over the years, the recent increase in oil- and gas-related emissions has a negative impact on the air quality in this area. Results indicate that the area has failed to observe a declining trend in ozone despite effective reductions in NOx and traffic-related VOC emissions. The findings of the study would be helpful in proper evaluation of the ozone-forming potential of unconventional VOC emissions. Although these emissions may not be strong enough to cause harm through direct exposure, underestimating their potential towards ozone formation could hinder the progress in ozone attainment in growing urban areas. After all, a major portion of the study area continues to be in nonattainment of the EPA designated ozone standards. The study therefore draws the attention of policymakers towards the new influx of emissions that have emerged as a powerful source within the DFW metropolitan area.