Development of a dynamic headspace concentration technique for the non-contact sampling of human odor samples and the creation of canine training aids

Human scent and human remains detection canines are used to locate living or deceased humans under many circumstances. Human scent canines locate individual humans on the basis of their unique scent profile, while human remains detection canines locate the general scent of decomposing human remains. Scent evidence is often collected by law enforcement agencies using a Scent Transfer Unit, a dynamic headspace concentration device. The goals of this research were to evaluate the STU-100 for the collection of human scent samples, and to apply this method to the collection of living and deceased human samples, and to the creation of canine training aids. The airflow rate and collection material used with the STU-100 were evaluated using a novel scent delivery method. Controlled Odor Mimic Permeation Systems were created containing representative standard compounds delivered at known rates, improving the reproducibility of optimization experiments. Flow rates and collection materials were compared. Higher air flow rates usually yielded significantly less total volatile compounds due to compound breakthrough through the collection material. Collection from polymer and cellulose-based materials demonstrated that the molecular backbone of the material is a factor in the trapping and releasing of compounds. The weave of the material also affects compound collection, as those materials with a tighter weave demonstrated enhanced collection efficiencies. Using the optimized method, volatiles were efficiently collected from living and deceased humans. Replicates of the living human samples showed good reproducibility; however, the odor profiles from individuals were not always distinguishable from one another. Analysis of the human remains samples revealed similarity in the type and ratio of compounds. Two types of prototype training aids were developed utilizing combinations of pure compounds as well as volatiles from actual human samples concentrated onto sorbents, which were subsequently used in field tests. The pseudo scent aids had moderate success in field tests, and the Odor pad aids had significant success. This research demonstrates that the STU-100 is a valuable tool for dog handlers and as a field instrument; however, modifications are warranted in order to improve its performance as a method for instrumental detection.

Ketones in hydrothermal petroleums and sediments from Guaymas Basin

The polar compound (NSO) fractions of seabed petroleums and sediment extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry. The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolysates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore samples are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds correlated with samples exhibiting a high degree of thermal maturity. Several homologous series of related ketone isomers are enriched in the interiors of the hydrothermal vent samples or in hydrothermally-altered sequences of the downcore sediments (DSDP Holes 477 and 481A). The n-alkanones range in carbon number from C11 to C33 with a Cmax from 14 to 23, distributions that are similar to those of the n-alkanes. The alkan-2-ones are usually in highest concentrations, with lower amounts of 3-, 4-, 5-, 6-, 7- (and higher) alkanones, and they exhibit no carbon number preference (there is an odd carbon number preference of alkanones observed for downcore samples). The alkanones are enriched in the interiors of the hydrothermal vent spires or in downcore hydrothermally-altered sediments, indicating an origin at depth or in the hydrothermal fluids and not from an external biogenic deposition. Minor amounts of C13 and C18 isoprenoid ketones are also present. Simulation of the natural hydrothermal alternation process by laboratory hydrous pyrolysis techniques provided information regarding the mode of alkanone formation. Hydrous pyrolysis of n-C32H66 at 350°C for 72 h with water only or water with inorganic additives has been studied using a stainless steel reaction vessel. In each experiment oxygenated hydrocarbons, including alkanones, were formed from the n-alkane. The product distributions indicate a reaction pathway consisting of n-alkanes and a-olefins as primary cracking products with internal olefins and alkanones as secondary reaction products. Hydrous pyrolyses of Messel shale spiked with molecular probes have been performed under similar time and temperature constraints to produce alkanone distributions like those found in the hydrothermal vent petroleums.

Potencial antioxidante de extratos hidroalcoólicos de mirtilo, polpa de açaí e goji berry: efeito na estabilidade oxidativa e sensorial em queijo petit suisse

The consumer interest in healthy foods with high amounts of antioxidants is one of the important factors for reducing the risk of disease and it has encouraged researchers and industry to develop innovative and functional products and ingredients. To that end, the objective of this research was to study the bioactive compounds present in the acai pulp, blueberry and goji berry samples, as well as the phenolic compounds form of extraction using the response surface methodology (RSM), antioxidant and antimicrobial activity of it, identification and quantification of compounds by high-performance liquid chromatography (HPLC) and, at the end, the development of petit suisse cheeses added with freeze-dried extracts of the samples. A 2³ factorial design was used to analyze the solvent effect (ethanol and water), time (30 and 60 min) and temperature (30 °C and 60 °C) on the extraction and determination of total phenolic compounds (TPC) and antioxidant activity (AA). The variables time and temperature had a positive effect on the antioxidant activity (AA) in their highest levels with 60 min and 60 °C respectively. The ethanol solvent 80 % is more efficient in TPC extraction with AA in all arrays. The identification of phenolic compounds performed by HPLC revealed the presence of catechin, epicatechin, rutin, myricetin, chlorogenic acid, coumaric acid and ferulic acid. Regarding the AA the acai pulp showed higher activity in vitro when extracted by 60 °C for 60 min, but none of the three extracts analyzed under these conditions showed antibacterial activity against Staphylococcus aureus and Salmonella bongori in the concentrations tested (95.00 to 2.34 mg/mL. For petit suisse cheeses added with phenolic extract of the samples, the sample containing goji berry achieved greater sensory acceptance among judges (75.67%), second only to the commercial sample used for comparison with 91.56 % of acceptance. In relation to the storage time, the oxidation was evaluated by the level of thiobarbituric acid reactive substances and color analysis. Both analysis were satisfactory, making the extracts addition an alternative to preserve the product properties and give it a high content of bioactive and nutritive compounds.

Estudo das propriedades físico-químicas e avaliação de compostos bioativos em camarinhas ('Corema album' L.D. Don)

As camarinhas ('Corema album' L. D. Don) são pequenos frutos selvagens que se desenvolvem em arbustos dunares ao longo das costas da Península Ibérica. Apesar de serem ainda pouco conhecidas, as camarinhas são pequenos frutos que podem pertencer ao vasto grupo dos frutos vermelhos, vulgarmente conhecidos pelos seus efeitos benéficos na saúde. Desta forma, neste estudo foram realizadas várias análises às camarinhas no que respeita a propriedades de natureza física e química e em particular a alguns compostos com efeitos bioativos. Com a realização deste trabalho pretendeu-se avaliar as propriedades físico-químicas das camarinhas, bem como dos compostos bioativos com potenciais benefícios para a saúde. Nesse sentido, as bagas de camarinha foram avaliadas quanto às suas propriedades físicas (dimensões, peso, cor e textura), propriedades químicas (humidade, acidez, ºBrix, fibra, açúcares totais, açúcares redutores e vitamina C) e propriedades fenólicas (compostos fenólicos totais, orto-difenóis, flavonóides, taninos e atividade antioxidante, por DPPH e ABTS), em diferentes extratos de amostras de polpas e de grainhas liofilizadas. Os primeiros extratos ainda foram submetidos a uma simulações das condições do trato digestivo, para avaliar a bioacessibilidade dos compostos fenólicos e da atividade antioxidante. Este trabalho teve ainda como objetivo conhecer a bioacessibilidade dos compostos fenólicos totais e da sua atividade antioxidante, através do método da simulação “in vitro” das diferentes etapas do trato gastrointestinal. No que diz respeito às propriedades físicas analisadas, as camarinhas frescas demonstraram uma altura média de 8,6 mm, um diâmetro médio de 9,4 mm e uma massa média de 0,7 g. Relativamente à caraterização da cor, estas apresentavam uma cor clara (L*=79,8). Quanto à textura apresentaram alguma elasticidade média (2,9 mm) e uma baixa dureza (1,9 N). Nas análises químicas as camarinhas revelaram ser compostas, maioritariamente, por água (87,9%), por açúcares totais e fibras. Para além disso, apresentavam um teor em sólidos solúveis totais de 6,3 ºBrix, uma acidez de 1,4 g ácido tartárico/100 g e um teor de vitamina C de 2,8 mg de ácido ascórbico/100 g.Na quantificação dos compostos fenólicos totais e flavonóides, os extratos de acetona:água das amostras de polpas de camarinha branca apresentaram os valores mais elevados, 1614,1 mg EAG/100 g e 143,7 mg EQ/100 g, respetivamente. Relativamente à quantificação dos orto-difenóis e dos taninos os extratos de metanol e de acetona:água das amostras de grainhas de camarinha branca registaram os valores de 23,4 mg EAG/100 g e 915,7 mg/100 g, respetivamente. Na atividade antioxidante por DPPH e ABTS os extratos de acetona:água das amostras de polpas de camarinha branca apresentaram, respetivamente, os valores de 40,1 µmol ET/g e de 79,6 µmol ET/g. Na avaliação da bioacessibilidade verificou-se que ocorreu uma maior percentagem de compostos fenólicos disponíveis para absorção e uma maior preservação da sua atividade antioxidante nos extratos das grainhas, comparativamente aos extratos das polpas. Com este estudo concluiu-se que as camarinhas são pequenos frutos portadores de um grande potencial em diversos compostos bioativos benéficos para a saúde dos consumidores.

Utilização de bagaço de maçã como ingrediente alimentar em iogurte com potencial efeito benéfico para a saúde

O desenvolvimento de alimentos funcionais evoluiu consideravelmente ao longo dos anos e a capacidade tecnológica para produzir um alimento com compostos fisiologicamente ativos tem crescido significativamente. O presente trabalho teve como objetivo criar um novo alimento, utilizando um subproduto proveniente da indústria agroalimentar. O alimento seleccionado foi o iogurte natural, o qual foi enriquecido com um extrato de bagaço de maçã. O bagaço de maçã contém compostos fenólicos e fibra, mostrando atividade antioxidante significativa e por conseguinte apresenta um potencial efeito positivo na saúde. Avaliaram-se características químicas do bagaço de maçã e das farinhas obtidas a partir deste subproduto, designadamente: acidez, teor em açúcares totais e redutores, cinza, matéria gorda, humidade, proteína bruta, fibra dietética insolúvel e solúvel. O extrato aquoso obtido a partir do subproduto foi também caracterizado quanto ao seu conteúdo fenólico e atividade antioxidante. O iogurte produzido com incorporação do extrato de bagaço de maçã foi estudado do ponto de vista de parâmetros químicos tais como acidez, açúcares totais, cinza, humidade, proteína bruta, pH e fibra bruta, conteúdo em fenólicos totais e atividade antioxidante. O subproduto, os extratos e o iogurte foram também avaliados quanto à sua carga microbiológica. Na caracterização química do bagaço foram obtidos os seguintes valores, expressos em base seca: 2,0±0,01% de acidez (expressa em equivalentes de ácido málico); 15,96±1,53% de açúcares totais; 13,35±1,91% de açúcares redutores; 1,88±0,07% de cinza, 2,49±0,5% de matéria gorda, 81,17±1,98% de humidade e 5,01±0,01% de proteína bruta. Quanto ao seu conteúdo em fibra dietética, o bagaço contém na sua composição 65,80% de fibra dietética insolúvel e 4,90% de fibra dietética solúvel. A farinha obtida após secagem a 60 °C do bagaço de maçã apresentou, na base seca, 1,9±0,04% de acidez, 10,57±1,31% de açúcares totais; 8,50±1,00% de açúcares redutores; 2,22±0,04%de cinza, 4,73±0,11% de matéria gorda, 6,34±0,62% de humidade e 5,40±0,26% de proteína. A atividade antioxidante do extrato aquoso, (AQ_6X10) obtido do bagaço de maçã, utilizado para incorporação no iogurte, determinada através do método ABTS foi de 5,00±1,28µmol TE/g amostra e apresentou um teor em compostos fenólicos de 221,42±0,734 mg EAG/ 100g de extrato, na base seca. Ao nível microbiológico o extrato revelou parâmetros aceitáveis, de acordo com a tabela 13 (anexos 3), para utilização como ingrediente alimentar. Os iogurtes produzidos foram analisados quimicamente. O iogurte, com extrato aquoso de bagaço de maçã incorporado, apresentou 89,64±0,00% de humidade, 0,93±0,00% de acidez (expressa em equivalentes de ácido láctico); 6,42±0,26% de açúcares totais; 0,74%±0,00% de cinza, 3,83±0,00% de proteína bruta e 0,2±0,00% de fibra bruta. O seu conteúdo em compostos fenólicos foi de 12,41±1,69mg EAG/ 100g de iogurte, e a sua atividade antioxidante foi 54,84±4,40 µmol TE/g iogurte. Avaliou-se ainda o iogurte no que diz respeito ao crescimento de bactérias lácticas e constatou-se, por comparação com o iogurte de controlo, que estas se desenvolveram normalmente ao longo do processo de fabrico. A análise microbiológica revelou ainda que o iogurte é seguro do ponto de vista alimentar de acordo com a Tabela 15 (anexos 3). A análise sensorial realizada aos iogurtes demonstrou que o iogurte fortificado apresentou uma aceitação muito boa pelo painel de provadores. O presente estudo demonstrou que o bagaço de maçã, um subproduto das indústrias agroalimentares, é seguro do ponto de vista microbiológico, podendo ser utilizado na preparação de ingredientes alimentares para serem incorporados, por exemplo em iogurte, conferindo-lhe características que se destacam pelo maior teor em fibra e atividade antioxidante em relação ao iogurte não enriquecido, e atributos sensoriais apelativos em termos de textura e sabor.

Valorização integrada de resíduos e subprodutos da extração do azeite: extração e caraterização de compostos bioativos do bagaço de azeitona

Dissertação de Mestrado, Tecnologia de Alimentos, Instituto Superior de Engenharia, Universidade do Algarve, 2016

Estudo de composto com propriedades funcionais em flor de cardo submetida a diferentes tratamentos de secagem

O cardo é uma planta que encontra-se associada ao fabrico de queijo, pois é responsável pelo fenómeno da coagulação do leite. No entanto, têm aumentado o número de estudos realizados nesta planta, relacionados com a composição química, de forma a perceber os benefícios para a saúde. O objetivo desta dissertação foi caracterizar a flor de cardo relativamente à sua atividade antioxidante, composição em compostos fenólicos e avaliar a sua estabilidade ao longo do trato digestivo. Para tal, foram estudas amostras de flor de cardo da espécie C. cardunculus spp flavescens, após liofilização e secagem em estufa com convecção forçada a diferentes temperaturas (40ºC, 50ºC e 60ºC). Após cada tratamento, efetuaram-se duas extrações sucessivas com soluções de metanol (98% v/v) e de acetona (60% v/v). Os extratos obtidos foram depois utilizados para quantificar os teores em compostos fenólicos totais, em orto-difenois e em flavonóides. A atividade antioxidante foi determinada utilizando os métodos DPPH e ABTS. Por fim, procedeu-se à avaliação da bioacessibilidade dos compostos presentes submetendo os vários extratos a condições simulantes do trato digestivo. Pela análise dos resultados obtidos foi possível constatar que a quantidade de compostos fenólicos e atividade antioxidante na flor de cardo varia consoante a temperatura de secagem, ocorrendo a diminuição à medida que se aumenta a temperatura. Os resultados obtidos para a bioacessibilidade mostraram um comportamento distinto dos extratos de metanol e de acetona. No entanto, em ambos os casos ocorreu uma diminuição na quantidade de compostos disponíveis para absorção intestinal.

Messa a punto delle condizioni ottime di infusione di foglie di Ilex guayusa mediante disegno sperimentale Box-Behnken

Ilex guayusa, a tree native from the Amazon Rainforest, represents an important part of the culinary traditions and folk medicine of the indigenous tribes. In fact, infusions of different parts of the tree have been used as natural remedies. Particularly, the infusion obtained by the dry leaves of guayusa is a source of phenolic compounds, which are considered as antioxidant substances and have been associated with numerous benefits for human health. Currently, the growing interest of consumers towards healthy food and drinks has led to the rapid spread of this drink. However, the scientific literature about the content of polar compounds in infusion of guayusa leaves is scarce. Therefore, the aims of the present work were to enhance the extraction conditions of phenolic compounds from guayusa leaves by infusion and to characterize them via HPLC-ESI-TOF-MS. To reach these objectives, a Box-Behnken design (BBD) was applied to test the effect of different extraction conditions (time 2, 8 and 14 min), temperature (25, 62.5 and 100 °C) and solid ratio (0.25, 0.375 and 0.50 g) on the sum of phenolic content. On the one hand, the optimal conditions were 1 min infusion, 100 °C and 0.370 g of dry leaves. On the other hand, the 99% of the nine phenolic compounds identified were phenolic acids derivatives from hydroxycinnamic acid and the 1% belonged to the flavonoid family. The major compound was dicaffeoylquinic acid (68%). The difference between the results obtained and those of other researches is probably due to the stochastic nature of the vegetable matrix samples, since their chemical composition is susceptible to multiple factors. To sum up, the use of experimental design provided greater quantity of phenolic compounds than other extraction techniques such as blanching, or only to the oxidation process. Besides, the high resolution of the TOF spectrometer allowed the characterization of new isomers of the compounds previously described.

(Table 1) Concentration of organohalogenated compounds in clean and contaminated hair of polar bears (Ursus maritimus) from East Greenland

In this pilot study, we report on levels of persistent organohalogenated contaminants (OHCs) in hair of polar bears (Ursus maritimus) from East Greenland sampled between 1999 and 2001. To our knowledge, this is the first study on the validation of polar bear hair as a non-invasive matrix representative of concentrations and profiles in internal organs and blood plasma. Because of low sample weights (13-140 mg), only major bioaccumulative OHCs were detected above the limit of quantification: five polychlorinated biphenyl (PCB) congeners (CB 99, 138, 153, 170 and 180), one polybrominated diphenyl ether (PBDE) congener (BDE 47), oxychlordane, trans-nonachlor and ß-hexachlorocyclohexane. The PCB profile in hair was similar to that of internal tissues (i.e. adipose, liver, brain and blood), with CB 153 and 180 as the major congeners in all matrices. A gender difference was found for concentrations in hair relative to concentrations in internal tissues. Females (n = 6) were found to display negative correlations, while males (n = 5) showed positive correlations, although p-values were not found significant. These negative correlations in females may reflect seasonal OHC mobilisation from periphery adipose tissue due to, for example, lactation and fasting. The lack of significance in most correlations may be due to small sample sizes and seasonal variability of concentrations in soft tissues. Further research with larger sample weights and sizes is therefore necessary to draw more definitive conclusions on the usefulness of hair for biomonitoring OHCs in polar bears and other fur mammals.

(Table 1) Concentrations of neutral and phenolic organohalogen compounds in adipose tissue, blood, brain and liver of polar bears (Ursus maritimus) from East Greenland

The tissue-specific composition of sum classes of brominated and chlorinated contaminants and metabolic/degradation byproducts was determined in adult male and female polar bears from East Greenland. Significantly (p < 0.05) higher concentrations of SUM-PCBs, various other organochlorines such as SUM-CHL, p,p'-DDE, SUM-CBz, SUM-HCHs, octachlorostyrene (OCS),SUM-mirex, dieldrin, the flame retardants SUM-PBDEs, and total-(R)-hexabromocyclododecane (HBCD), SUM-methylsulfonyl (MeSO2)-PCBs and 3-MeSO2-p,p'-DDE, were found in the adipose and liver tissues relative to whole blood and brain. In contrast, SUM-hydroxyl (OH)-PCB, 4-OH-heptachlorostyrene and SUM-OH-PBDE concentrations were significantly highest (p < 0.05) in whole blood, whereas the highest concentrations of SUM-OH-PBBs were found in the adipose tissue. Based on the total concentrations of all organohalogens in all three tissues and blood, the combined body burden was estimated to be 1.34 ± 0.12 g, where >91% of this amount was accounted for by the adipose tissue alone, followed by the liver, whole blood, and brain. These results show that factors such as protein association and lipid solubility appear to be differentially influencing the toxicokinetics, in terms of tissue composition/localization and burden, of organohalogen classes with respect to chemical structure and properties such as the type of halogenation (e.g., chlorination or bromination), and the presence or absence of additional phenyl group substituents (e.g., MeO and OH groups). The tissue- and blood-specific accumulation (or retention) among organohalogen classes indicates that exposure and any potential contaminant-mediated effects in these polar bears are likely tissue or blood specific.

Polar organic marker compounds in atmospheric aerosols during the LBA-SMOCC 2002 biomass burning experiment in Rondonia, Brazil: sources and source processes, time series, diel variations and size distributions

Measurements of polar organic marker compounds were performed on aerosols that were collected at a pasture site in the Amazon basin (Rondonia, Brazil) using a high-volume dichotomous sampler (HVDS) and a Micro-Orifice Uniform Deposit Impactor (MOUDI) within the framework of the 2002 LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazonia - Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate) campaign. The campaign spanned the late dry season (biomass burning), a transition period, and the onset of the wet season (clean conditions). In the present study a more detailed discussion is presented compared to previous reports on the behavior of selected polar marker compounds, including levoglucosan, malic acid, isoprene secondary organic aerosol (SOA) tracers and tracers for fungal spores. The tracer data are discussed taking into account new insights that recently became available into their stability and/or aerosol formation processes. During all three periods, levoglucosan was the most dominant identified organic species in the PM(2.5) size fraction of the HVDS samples. In the dry period levoglucosan reached concentrations of up to 7.5 mu g m(-3) and exhibited diel variations with a nighttime prevalence. It was closely associated with the PM mass in the size-segregated samples and was mainly present in the fine mode, except during the wet period where it peaked in the coarse mode. Isoprene SOA tracers showed an average concentration of 250 ng m(-3) during the dry period versus 157 ng m(-3) during the transition period and 52 ng m(-3) during the wet period. Malic acid and the 2-methyltetrols exhibited a different size distribution pattern, which is consistent with different aerosol formation processes (i.e., gas-to-particle partitioning in the case of malic acid and heterogeneous formation from gas-phase precursors in the case of the 2-methyltetrols). The 2-methyltetrols were mainly associated with the fine mode during all periods, while malic acid was prevalent in the fine mode only during the dry and transition periods, and dominant in the coarse mode during the wet period. The sum of the fungal spore tracers arabitol, mannitol, and erythritol in the PM(2.5) fraction of the HVDS samples during the dry, transition, and wet periods was, on average, 54 ng m(-3), 34 ng m(-3), and 27 ng m(-3), respectively, and revealed minor day/night variation. The mass size distributions of arabitol and mannitol during all periods showed similar patterns and an association with the coarse mode, consistent with their primary origin. The results show that even under the heavy smoke conditions of the dry period a natural background with contributions from bioaerosols and isoprene SOA can be revealed. The enhancement in isoprene SOA in the dry season is mainly attributed to an increased acidity of the aerosols, increased NO(x) concentrations and a decreased wet deposition.

Bioactive compounds and quantification of total ellagic acid in strawberries (Fragaria x ananassa Duch.)

Strawberries are one of the most popular edible fruits in Brazil and their consumption has increased with the development of new varieties available at almost all seasons. Fruit of seven full-ripened strawberry cultivars (Dover, Camp Dover, Camarosa, Sweet Charlie, Toyonoka, Oso Grande and Piedade) were characterized in relation to the total phenolics, vitamin C, flavonoids, free and total ellagic acid contents and antioxidant capacity. Camp Dover had the lowest values for anthocyanins and total phenolics but the highest total flavonoid content. Dover presented the highest anthocyanin, total phenolics and ellagic acid contents and also elevated antioxidant capacity. The best conditions for the determination of the total ellagic acid content in strawberries were also optimized and the results showed that the extraction with 80% acetone, and hydrolysis using 2 N TFA at 120 degrees C for 60 min allowed a 99% recovery. (C) 2007 Elsevier Ltd. All rights reserved.

Summertime total ozone variations over middle and polar latitudes

The statistical relationship between springtime and summertime ozone over middle and polar latitudes is analyzed using zonally averaged total ozone data. Shortterm variations in springtime midlatitude ozone demonstrate only a modest correlation with springtime polar ozone variations. However by early summer, ozone variations throughout the extratropics are highly correlated. Analysis of correlation functions indicates that springtime midlatitude ozone, not polar ozone, is the best predictor for summertime polar ozone. Long-term total ozone trends at middle and high latitudes are also different for spring and nearly identical for summer. About 39% of the observed southern midlatitude ozone decline in December can be attributed to the polar ozone depletion up to November. In the Northern Hemisphere, the corresponding contribution is about 15%, but the error bars are too large to make an accurate estimate.

Measurement of volatile organic compounds and total OH reactivity in the atmosphere

Volatile organic compounds play a critical role in ozone formation and drive the chemistry of the atmosphere, together with OH radicals. The simplest volatile organic compound methane is a climatologically important greenhouse gas, and plays a key role in regulating water vapour in the stratosphere and hydroxyl radicals in the troposphere. The OH radical is the most important atmospheric oxidant and knowledge of the atmospheric OH sink, together with the OH source and ambient OH concentrations is essential for understanding the oxidative capacity of the atmosphere. Oceanic emission and / or uptake of methanol, acetone, acetaldehyde, isoprene and dimethyl sulphide (DMS) was characterized as a function of photosynthetically active radiation (PAR) and a suite of biological parameters, in a mesocosm experiment conducted in the Norwegian fjord. High frequency (ca. 1 minute-1) methane measurements were performed using a gas chromatograph - flame ionization detector (GC-FID) in the boreal forests of Finland and the tropical forests of Suriname. A new on-line method (Comparative Reactivity Method - CRM) was developed to directly measure the total OH reactivity (sink) of ambient air. It was observed that under conditions of high biological activity and a PAR of ~ 450 μmol photons m-2 s-1, the ocean acted as a net source of acetone. However, if either of these criteria was not fulfilled then the ocean acted as a net sink of acetone. This new insight into the biogeochemical cycling of acetone at the ocean-air interface has helped to resolve discrepancies from earlier works such as Jacob et al. (2002) who reported the ocean to be a net acetone source (27 Tg yr-1) and Marandino et al. (2005) who reported the ocean to be a net sink of acetone (- 48 Tg yr-1). The ocean acted as net source of isoprene, DMS and acetaldehyde but net sink of methanol. Based on these findings, it is recommended that compound specific PAR and biological dependency be used for estimating the influence of the global ocean on atmospheric VOC budgets. Methane was observed to accumulate within the nocturnal boundary layer, clearly indicating emissions from the forest ecosystems. There was a remarkable similarity in the time series of the boreal and tropical forest ecosystem. The average of the median mixing ratios during a typical diel cycle were 1.83 μmol mol-1 and 1.74 μmol mol-1 for the boreal forest ecosystem and tropical forest ecosystem respectively. A flux value of (3.62 ± 0.87) x 1011 molecules cm-2 s-1 (or 45.5 ± 11 Tg CH4 yr-1 for global boreal forest area) was derived, which highlights the importance of the boreal forest ecosystem for the global budget of methane (~ 600 Tg yr-1). The newly developed CRM technique has a dynamic range of ~ 4 s-1 to 300 s-1 and accuracy of ± 25 %. The system has been tested and calibrated with several single and mixed hydrocarbon standards showing excellent linearity and accountability with the reactivity of the standards. Field tests at an urban and forest site illustrate the promise of the new method. The results from this study have improved current understanding about VOC emissions and uptake from ocean and forest ecosystems. Moreover, a new technique for directly measuring the total OH reactivity of ambient air has been developed and validated, which will be a valuable addition to the existing suite of atmospheric measurement techniques.