Methylsiloxanes from Vehicle Emissions Detected in Aerosol Particles.

Methylsiloxanes have gained growing attention as emerging pollutants due to their toxicity to organisms. As man-made chemicals with no natural source, most research to date has focused on volatile methylsiloxanes from personal care or household products and industrial processes. Here, we show that methylsiloxanes can be found in primary aerosol particles emitted by vehicles based on aerosol samples collected in two tunnels in São Paulo, Brazil. The aerosol samples were analyzed with thermal desorption-proton transfer reaction-mass spectrometry (TD-PTR-MS), and methylsiloxanes were identified and quantified in the mass spectra based on the natural abundance of silicon isotopes. Various methylsiloxanes and derivatives were found in aerosol particles from both tunnels. The concentrations of methylsiloxanes and derivatives ranged 37.7-377 ng m-3, and the relative fractions in organic aerosols were 0.78-1.9%. The concentrations of methylsiloxanes exhibited a significant correlation with both unburned lubricating oils and organic aerosol mass. The emission factors of methylsiloxanes averaged 1.16 ± 0.59 mg kg-1 of burned fuel for light-duty vehicles and 1.53 ± 0.37 mg kg-1 for heavy-duty vehicles. Global annual emissions of methylsiloxanes in vehicle-emitted aerosols were estimated to range from 0.0035 to 0.0060 Tg, underscoring the significant yet largely unknown potential for health and climate impacts.

Nanoplastics measurements in Northern and Southern polar ice.

It has been established that various anthropogenic contaminants have already reached all the world's pristine locations, including the polar regions. While some of those contaminants, such as lead and soot, are decreasing in the environment, thanks to international regulations, other novel contaminants emerge. Plastic pollution has been shown as a durable novel pollutant, and, since recently, smaller and smaller plastics particles have been identified in various environments (air, water and soil). Considerable research already exists measuring the plastics in the 5 mm to micrometre size range (microplastics). However, far less is known about the plastics debris that fragmented to the sub-micrometre size (nanoplastics). As these small particles are light, it is expected that they have already reached the most remote places on Earth, e.g. transported across the globe by air movement. In this work, we used a novel method based on Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry (TD-PTR-MS) to detect and measure nanoplastics of different types in the water sampled from a Greenland firn core (T2015-A5) and a sea ice core from Antarctica. We identify polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS), polyvinyl chloride (PVC), and Tire wear nanoparticles in the 14 m deep Greenland firn core and PE, PP and PET in sea ice from Antarctica. Nanoplastics mass concentrations were on average 13.2 ng/mL for Greenland firn samples and 52.3 ng/mL for Antarctic sea ice. We further discuss the possible sources of nanoplastics that we found at these remote locations, which likely involve complex processes of plastic circulation (emission from both land and sea surface, atmospheric and marine circulation).

Micro- and Nanoplastics in Alpine Snow: A New Method for Chemical Identification and (Semi)Quantification in the Nanogram Range.

We present a new method for chemical characterization of micro- and nanoplastics based on thermal desorption-proton transfer reaction-mass spectrometry. The detection limit for polystyrene (PS) obtained is <1 ng of the compound present in a sample, which results in 100 times better sensitivity than those of previously reported by other methods. This allows us to use small volumes of samples (1 mL) and to carry out experiments without a preconcentration step. Unique features in the high-resolution mass spectrum of different plastic polymers make this approach suitable for fingerprinting, even when the samples contain mixtures of other organic compounds. Accordingly, we got a positive fingerprint of PS when just 10 ng of the polymer was present within the dissolved organic matter of snow. Multiple types of microplastics (polyethylene terephthalate (PET), polyvinyl chloride, and polypropylene carbonate), were identified in a snowpit from the Austrian Alps; however, only PET was detected in the nanometer range for both snowpit and surface snow samples. This is in accordance with other publications showing that the dominant form of airborne microplastics is PET fibers. The presence of nanoplastics in high-altitude snow indicates airborne transport of plastic pollution with environmental and health consequences yet to be understood.

Evaluation of a New Reagent-Ion Source and Focusing Ion-Molecule Reactor for Use in Proton-Transfer-Reaction Mass Spectrometry.

We evaluate the performance of a new chemical ionization source called Vocus, consisting of a discharge reagent-ion source and focusing ion-molecule reactor (FIMR) for use in proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOF) measurements of volatile organic compounds (VOCs) in air. The reagent ion source uses a low-pressure discharge. The FIMR consists of a glass tube with a resistive coating, mounted inside a radio frequency (RF) quadrupole. The axial electric field is used to enhance ion collision energies and limit cluster ion formation. The RF field focuses ions to the central axis of the reactor and improves the detection efficiency of product ions. Ion trajectory calculations demonstrate the mass-dependent focusing of ions and enhancement of the ion collision energy by the RF field, in particular for the lighter ions. Product ion signals are increased by a factor of 10 when the RF field is applied (5000-18 000 cps ppbv-1), improving measurement precision and detection limits while operating at very similar reaction conditions as traditional PTR instruments. Because of the high water mixing ratio in the FIMR, we observe no dependence of the sensitivity on ambient sample humidity. In this work, the Vocus is interfaced to a TOF mass analyzer with a mass resolving power up to 12 000, which allows clear separation of isobaric ions, observed at nearly every nominal mass when measuring ambient air. Measurement response times are determined for a range of ketones with saturation vapor concentrations down to 5 × 104 µg m-3 and compare favorably with previously published results for a PTR-MS instrument.

Fine micro- and nanoplastics concentrations in particulate matter samples from the high alpine site Sonnblick, Austria.

We report atmospheric fine micro- and nanoplastics concentrations from particulate matter (PM) samples of two size fractions (PM10, fine micro- and nanoplastics, and PM1, nanoplastics), which were collected at the remote high alpine station Sonnblick Observatory, Austria. Active sampling was performed from June 2021 until April 2022. Analysis was done using TD-PTR-MS to detect 6 different plastic types. Polyethylene terephthalate (PET), polyethylene (PE) and polypropylene/polypropylene carbonate (PP/PPC) were found to be the dominating species. PET was detected in almost all samples, while the other plastic types occurred more episodically. Furthermore, polyvinyl chloride (PVC), polystyrene (PS) and tire wear particles were detected in single samples. Considering the three main plastic types, average plastics concentrations were 35 and 21 ng m-³ with maximum concentrations of 165 and 113 ng m-³ for PM10 and PM1, respectively. Average polymer concentrations were higher in the summer/fall period than in winter/spring. In summer/fall, PM10 plastics concentrations were higher by a factor of 2 compared to PM1, while concentrations of both size classes were comparable in the winter/spring period. This suggests that in the colder season plastic particles arriving at the Eastern Alpine crests are mainly present as nanoplastics. The contribution of micro- and nanoplastics to organic matter at the remote site was found to be comparable to data determined at an urban site. We found significant correlations between the PET concentration and tracers originating from anthropogenic activities such as elemental carbon, nitrate, ammonium, and sulphate as well as organic carbon and arabitol.

An upgraded CFA - FLC - MS/MS system for the semi-continuous detection of levoglucosan in ice cores.

A new Continuous Flow Analysis (CFA) system coupled with Fast Liquid Chromatography - tandem Mass Spectrometry (FLC-MS/MS) has been recently developed for determining organic markers in ice cores. In this work we present an upgrade of this innovative technique, optimized for the detection of levoglucosan in ice cores, a crucial tracer for reconstructing past fires. The upgrade involved a specific optimization of the chromatographic and mass spectrometric parameters, allowing for a higher sampling resolution (down to 1 cm) and the simultaneous collection of discrete samples, for off-line analysis of water stable isotopes and additional chemical markers. The robustness and repeatability of the method has been tested by the analysis of multiple sticks of ice cut from the same shallow alpine ice core, and running the system for several hours on different days. The results show similar and comparable trends between the ice sticks. With this upgraded system, a higher sensitivity and a lower limit of detection (LOD) was achieved compared to discrete analysis of alpine samples for levoglucosan measurements. The new LOD was as low as 66 ng L-1, a net improvement over the previous LOD of 600 ng L-1.

Nanoplastics and ultrafine microplastic in the Dutch Wadden Sea - The hidden plastics debris?

Plastic pollution in the marine environment has been identified as a global problem; different polymer types and fragment sizes have been detected across all marine regions, from sea ice to the equator and the surface to the deep sea. However, quantification of marine plastics debris in the size range of nanoplastics (<1 µm) and ultrafine microplastics (<10 µm) is not constrained, because such minuscule particles are challenging to measure. In this work, we applied a novel analytical assay using Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry (TD-PTR-MS), which is suitable to detect and identify plastics in the nanogram range. From two stations in the Wadden Sea (the Netherlands), we measured nanoplastics directly from seawater aliquots, and from filters with different mesh sizes. Our results show the presence of Polystyrene (PS) and Polyethylene terephthalate (PET) nanopalstics as well as ultrafine microplastics in the Wadden Sea water column. The mass concentration of PS nanoplastics was 4.2 µg/L on average, indicating a substantial contribution of nanoplastics to the Wadden Sea's total plastic budget.

A large contribution of methylsiloxanes to particulate matter from ship emissions.

The chemical and stable carbon isotopic composition of the organic aerosol particles (OA) emitted by a shuttle passenger ship between mainland Naples and island Capri in Italy were investigated. Various methylsiloxanes and derivatives were found in particulate ship emissions for the first time, as identified in the mass spectra of a thermal desorption - proton transfer reaction - mass spectrometer (TD-PTR-MS) based on the natural abundance of silicon isotopes. Large contributions of methylsiloxanes to OA (up to 59.3%) were found under inefficient combustion conditions, and considerably lower methylsiloxane emissions were observed under cruise conditions (1.2% of OA). Furthermore, the stable carbon isotopic composition can provide a fingerprint for methylsiloxanes, as they have low δ13C values in the range of -44.91‰ ± 4.29‰. The occurrence of methylsiloxanes was therefore further supported by low δ13C values of particulate organic carbon (OC), ranging from -34.7‰ to -39.4‰, when carbon fractions of methylsiloxanes in OC were high. The δ13C values of OC increased up to around -26.7‰ under cruise conditions, when carbon fractions of methylsiloxanes in OC were low. Overall, the δ13C value of OC decreased linearly with increasing carbon fraction of methylsiloxanes in OC, and the slope is consistent with a mixture of methylsiloxanes and fuel combustion products. The methylsiloxanes in ship emissions may come from engine lubricants.

Non-Invasive Monitoring of Inflammation in Inflammatory Bowel Disease Patients during Prolonged Exercise via Exhaled Breath Volatile Organic Compounds.

The aim of this study was to investigate volatile organic compounds (VOCs) in exhaled breath as possible non-invasive markers to monitor the inflammatory response in inflammatory bowel disease (IBD) patients as a result of repeated and prolonged moderate-intensity exercise. We included 18 IBD patients and 19 non-IBD individuals who each completed a 30, 40, or 50 km walking exercise over three consecutive days. Breath and blood samples were taken before the start of the exercise event and every day post-exercise to assess changes in the VOC profiles and cytokine concentrations. Proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) was used to measure exhaled breath VOCs. Multivariate analysis, particularly ANOVA-simultaneous component analysis (ASCA), was employed to extract relevant ions related to exercise and IBD. Prolonged exercise induces a similar response in breath butanoic acid and plasma cytokines for participants with or without IBD. Butanoic acid showed a significant correlation with the cytokine IL-6, indicating that butanoic acid could be a potential non-invasive marker for exercise-induced inflammation. The findings are relevant in monitoring personalized IBD management.

Nanoplastics transport to the remote, high-altitude Alps.

Plastic materials are increasingly produced worldwide with a total estimated production of >8300 million tonnes to date, of which 60% was discarded. In the environment, plastics fragment into smaller particles, e.g. microplastics (size < 5 mm), and further weathering leads to the formation of functionally different contaminants - nanoplastics (size <1 µm). Nanoplastics are believed to have entirely different physical (e.g. transport), chemical (e.g. functional groups at the surface) and biological (passing the cell membrane, toxicity) properties compared to the micro- and macroplastics, yet, their measurement in the environmental samples is seldom available. Here, we present measurements of nanoplastics mass concentration and calculated the deposition at the pristine high-altitude Alpine Sonnblick observatory (3106 MASL), during the 1.5 month campaigh in late winter 2017. The average nanoplastics concentration was 46.5 ng/mL of melted surface snow. The main polymer types of nanoplastics observed for this site were polypropylene (PP) and polyethylene terephthalate (PET). We measured significantly higher concentrations in the dry sampling periods for PET (p < 0.002) but not for PP, which indicates that dry deposition may be the preferential pathway for PET leading to a gradual accumulation on the snow surfaces during dry periods. Air transport modelling indicates regional and long-range transport of nanoplastics, originating preferentially from European urban areas. The mean deposition rate was 42 (+32/-25) kg km-2 year-1. Thus more than 2 × 1011 nanoplastics particles are deposited per square meter of surface snow each week of the observed period, even at this remote location, which raises significant toxicological concerns.

Exhaled Breath Reflects Prolonged Exercise and Statin Use during a Field Campaign.

Volatile organic compounds (VOCs) in exhaled breath provide insights into various metabolic processes and can be used to monitor physiological response to exercise and medication. We integrated and validated in situ a sampling and analysis protocol using proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) for exhaled breath research. The approach was demonstrated on a participant cohort comprising users of the cholesterol-lowering drug statins and non-statin users during a field campaign of three days of prolonged and repeated exercise, with no restrictions on food or drink consumption. The effect of prolonged exercise was reflected in the exhaled breath of participants, and relevant VOCs were identified. Most of the VOCs, such as acetone, showed an increase in concentration after the first day of walking and subsequent decrease towards baseline levels prior to walking on the second day. A cluster of short-chain fatty acids including acetic acid, butanoic acid, and propionic acid were identified in exhaled breath as potential indicators of gut microbiota activity relating to exercise and drug use. We have provided novel information regarding the use of breathomics for non-invasive monitoring of changes in human metabolism and especially for the gut microbiome activity in relation to exercise and the use of medication, such as statins.

Biogenic volatile release from permafrost thaw is determined by the soil microbial sink.

Warming in the Arctic accelerates thawing of permafrost-affected soils, which leads to a release of greenhouse gases to the atmosphere. We do not know whether permafrost thaw also releases non-methane volatile organic compounds that can contribute to both negative and positive radiative forcing on climate. Here we show using proton transfer reaction-time of flight-mass spectrometry that substantial amounts of ethanol and methanol and in total 316 organic ions were released from Greenlandic permafrost soils upon thaw in laboratory incubations. We demonstrate that the majority of this release is taken up in the active layer above. In an experiment using 14C-labeled ethanol and methanol, we demonstrate that these compounds are consumed by microorganisms. Our findings highlight that the thawing permafrost soils are not only a considerable source of volatile organic compounds but also that the active layer regulates their release into the atmosphere.

Bidirectional Ecosystem-Atmosphere Fluxes of Volatile Organic Compounds Across the Mass Spectrum: How Many Matter?

Terrestrial ecosystems are simultaneously the largest source and a major sink of volatile organic compounds (VOCs) to the global atmosphere, and these two-way fluxes are an important source of uncertainty in current models. Here, we apply high-resolution mass spectrometry (proton transfer reaction-quadrupole interface time-of-flight; PTR-QiTOF) to measure ecosystem-atmosphere VOC fluxes across the entire detected mass range (m/z 0-335) over a mixed temperate forest and use the results to test how well a state-of-science chemical transport model (GEOS-Chem CTM) is able to represent the observed reactive carbon exchange. We show that ambient humidity fluctuations can give rise to spurious VOC fluxes with PTR-based techniques and present a method to screen for such effects. After doing so, 377 of the 636 detected ions exhibited detectable gross fluxes during the study, implying a large number of species with active ecosystem-atmosphere exchange. We introduce the reactivity flux as a measure of how Earth-atmosphere fluxes influence ambient OH reactivity and show that the upward total VOC (∑VOC) carbon and reactivity fluxes are carried by a far smaller number of species than the downward fluxes. The model underpredicts the ∑VOC carbon and reactivity fluxes by 40-60% on average. However, the observed net fluxes are dominated (90% on a carbon basis, 95% on a reactivity basis) by known VOCs explicitly included in the CTM. As a result, the largest CTM uncertainties in simulating VOC carbon and reactivity exchange for this environment are associated with known rather than unrepresented species. This conclusion pertains to the set of species detectable by PTR-TOF techniques, which likely represents the majority in terms of carbon mass and OH reactivity, but not necessarily in terms of aerosol formation potential. In the case of oxygenated VOCs, the model severely underpredicts the gross fluxes and the net exchange. Here, unrepresented VOCs play a larger role, accounting for ~30% of the carbon flux and ~50% of the reactivity flux. The resulting CTM biases, however, are still smaller than those that arise from uncertainties for known and represented compounds.

Corrigendum: Collocated observations of cloud condensation nuclei, particle size distributions, and chemical composition.

This corrects the article DOI: 10.1038/sdata.2017.3.

Quantifying sesquiterpene and oxygenated terpene emissions from live vegetation using solid-phase microextraction fibers.

Biogenic terpenes play important roles in ecosystem functioning and atmospheric chemistry. Some of these compounds are semi-volatile and highly reactive, such as sesquiterpenes and oxygenated terpenes, and are thus difficult to quantify using traditional air sampling and analysis methods. We developed an alternative approach to quantify emissions from live branches using a flow through enclosure and sample collection on solid-phase microextraction (SPME) fibers. This method allows for collection and analysis of analytes with minimal sample transfer through tubing to reduce the potential for losses. We characterized performance characteristics for 65 microm polydimethylsiloxane-divinylbenzene (PDMS/DVB) fibers using gas chromatography followed by mass spectrometry and optimized experimental conditions and procedures for field collections followed by laboratory analysis. Using 10-45 min sampling times and linear calibration curves created from mixtures of terpenes, emissions of methyl chavicol, an oxygenated terpene, and an array of sesquiterpenes were quantified from a Ponderosa pine branch. The detection limit was 4.36 pmol/mol (ppt) for methyl chavicol and 16.6 ppt for beta-caryophyllene. Concentrations determined with SPME fibers agreed with measurements made using proton transfer reaction mass spectrometry (PTR-MS) within the estimated error of the method for well calibrated compounds. This technique can be applied for quantification of biogenic oxygenated terpene and sesquiterpene emissions from live branches in the field.

Characterisation of the semi-volatile component of Dissolved Organic Matter by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry.

Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. PTR-MS is used for various environmental applications including monitoring of volatile organic compounds (VOCs) emitted from natural and anthropogenic sources, chemical composition measurements of aerosols, etc. Here we apply thermal desorption PTR-MS for the first time to characterise the chemical composition of dissolved organic matter (DOM). We developed a clean, low-pressure evaporation/sublimation system to remove water from samples and coupled it to a custom-made thermal desorption unit to introduce the samples to the PTR-MS. Using this system, we analysed waters from intact and degraded peat swamp forest of Kalimantan, Indonesian Borneo, and an oil palm plantation and natural forest in Sarawak, Malaysian Borneo. We detected more than 200 organic ions from these samples and principal component analysis allowed clear separation of the different sample origins based on the composition of organic compounds. The method is sensitive, reproducible, and provides a new and comparatively cheap tool for a rapid characterisation of water and soil DOM.

Collocated observations of cloud condensation nuclei, particle size distributions, and chemical composition.

Cloud condensation nuclei (CCN) number concentrations alongside with submicrometer particle number size distributions and particle chemical composition have been measured at atmospheric observatories of the Aerosols, Clouds, and Trace gases Research InfraStructure (ACTRIS) as well as other international sites over multiple years. Here, harmonized data records from 11 observatories are summarized, spanning 98,677 instrument hours for CCN data, 157,880 for particle number size distributions, and 70,817 for chemical composition data. The observatories represent nine different environments, e.g., Arctic, Atlantic, Pacific and Mediterranean maritime, boreal forest, or high alpine atmospheric conditions. This is a unique collection of aerosol particle properties most relevant for studying aerosol-cloud interactions which constitute the largest uncertainty in anthropogenic radiative forcing of the climate. The dataset is appropriate for comprehensive aerosol characterization (e.g., closure studies of CCN), model-measurement intercomparison and satellite retrieval method evaluation, among others. Data have been acquired and processed following international recommendations for quality assurance and have undergone multiple stages of quality assessment.

Methyl chloride emissions from halophyte leaf litter: dependence on temperature and chloride content.

Methyl chloride (CH(3)Cl) is the most abundant natural chlorine containing compound in the atmosphere, and responsible for a significant fraction of stratospheric ozone destruction. Understanding the global CH(3)Cl budget is therefore of great importance. However, the strength of the individual sources and sinks is still uncertain. Leaf litter is a potentially important source of methyl chloride, but factors controlling the emissions are unclear. This study investigated CH(3)Cl emissions from leaf litter of twelve halophyte species. The emissions were not due to biological activity, and emission rates varied between halophyte species up to two orders of magnitude. For all species, the CH(3)Cl emission rates increased with temperature following the Arrhenius relation. Activation energies were similar for all investigated plant species, indicating that even though emissions vary largely between plant species, their response to changing temperatures is similar. The chloride and methoxyl group contents of the leaf litter samples were determined, but those parameters were not significantly correlated to the CH(3)Cl emission rate.

Volatile organic compound emissions from dairy cows and their waste as measured by proton-transfer-reaction mass spectrometry.

California dairies house approximately 1.8 million lactating and 1.5 million dry cows and heifers. State air regulatory agencies view these dairies as a major air pollutant source, but emissions data are sparse, particularly for volatile organic compounds (VOCs). The objective of this work was to determine VOC emissions from lactating and dry dairy cows and their waste using an environmental chamber. Carbon dioxide and methane were measured to provide context for the VOCs. VOCs were measured by proton-transfer-reaction mass spectrometry (PTR-MS). The compounds with highest fluxes when cows plus waste were present were methanol, acetone + propanal, dimethylsulfide, and m/z 109 (likely 4-methyl-phenol). The compounds with highest fluxes from fresh waste (urine and feces) were methanol, m/z 109, and m/z 60 (likely trimethylamine). Ethanol fluxes are reported qualitatively, and several VOCs that were likely emitted (formaldehyde, methylamine, dimethylamine) were not detectable by PTR-MS. The sum of reactive VOC fluxes measured when cows were present was a factor of 6-10 less than estimates historically used for regulatory purposes. In addition, ozone formation potentials of the dominant VOCs were -10% those of typical combustion or biogenic VOCs. Thus dairy cattle have a comparatively small impact on ozone formation per VOC mass emitted.

Compuestos orgánicos volántiles en la atmósfera de la Gran Sabana I: concentraciones y química atmosférica / Volatile organic compounds in the atmosphere of La Gran Sabana I: concentrations and atmospheric chemistry

Los compuestos orgánicos volátiles (COV) fueron analizados utilizando espectrometría de masa con transferencia de protones (PTR-MS). Las mediciones se realizaron básicamente en la Estación Científica de Parupa entre el 17 de enero y el 6 de febrero 2000. Mediante la recolección de aire en "canisters" se hicieron algunas transeptas: Kavanayén-Parupa-Luepa-Kamá-Yuruani-Jaspe-Kukenán. También se midieron el CO y parámetros meteorológicos. Las variaciones de las concentraciones de CH3CN y CO indican que, con la excepción de un día, las mediciones prácticamente no estuvieron afectadas por quema de vegetación y los niveles medidos corresponderían al "background" regional (CH3CN 0,15 ppbv; CO 50 ppbv). Los hidrocarburos aromáticos muestran concentraciones extremadamente bajas (e,g., benceno 0,038 ppbv, tolueno 0,018 ppbv), mostrando claramente las características prístinas de la región. En el caso del isopreno, a lo largo del día se observa un aumento de la concentración a partir de niveles muy bajos en la madrugada, con valores de 0,49 ppbv a medio día y 0,8 ppbv a 19:00. Esto se explica en función de las emisiones locales y del transporte desde los bosques ubicados vientos arriba de Parupa. Los productos de oxidación del isopreno (e.g., MVK + MACR) presentan un ciclo diurno similar, La presencia de cantidades significativas de hidroperóxidos de isopreno (0,08 ppbv), indica que la oxidación del isopreno se produce en presencia de niveles muy bajos de NO. Se registraron niveles relativamente altos de metanol (1,54 ppbv), acetona (1,49 ppbv), acetaldehído (0,85 ppbv), ácido fórmico (2 ppbv) y ácido acético (1 ppbv), explicables en función de una significativa producción natural y de sus respectivos tiempos de vida atmosféricos. Se concluye i)Las variaciones observadas de las concentraciones de los COV se deben fundamentalmente a las interacciones entre la biofera y la atmósfera. ii)Existe un transporte significativo de varios COV (e.g., isopreno, metanol), desde los bosques de la Guayana Esequiba, iii)Los ácidos fórmico y acético deben jugar un importante papel en el equilibrio ácido-base de los ecosistemas de la Gran Sabana. iv)Las pequeñas quemas dispersas que ocurrieron en La Gran Sabana, durante el periódo del estudio, no produjeron un efecto significativo sobre la atmósfera regional