Measurements and modelling of airflows in houses using passive sampling and HAM software

Passive samplers have been predominantly used to monitor environmental conditions in single volumes. However, measurements using a calibrated passive sampler- Solid Phase Microextraction (SPME) fibre, in three houses with cold pitched roof, successfully demonstrated the potential of the SPME fibre as a device for monitoring air movement in two volumes. The roofs monitored were pitched at 15° - 30° with insulation thickness varying between 200-300 mm on the ceiling. For effective analysis, two constant sources of volatile organic compounds were diffused steadily in the house. Emission rates and air movement from the house to the roof was predicted using developed algorithms. The airflow rates which were calibrated against conventional tracer gas techniques were introduced into a HAM software package to predict the effects of air movement on other varying parameters. On average it was shown from the in situ measurements that about 20-30% of air entering the three houses left through gaps and cracks in the ceiling into the roof. Although these field measurements focus on the airflows, it is associated with energy benefits such that; if these flows are reduced then significantly energy losses would also be reduced (as modelled) consequently improving the energy efficiency of the house. Other results illustrated that condensation formation risks were dependent on the airtightness of the building envelopes including configurations of their roof constructions.

Global and regional temperature-change potentials for near-term climate forcers

We examine the climate effects of the emissions of near-term climate forcers (NTCFs) from 4 continental regions (East Asia, Europe, North America and South Asia) using radiative forcing from the task force on hemispheric transport of air pollution source-receptor global chemical transport model simulations. These simulations model the transport of 3 aerosol species (sulphate, particulate organic matter and black carbon) and 4 ozone precursors (methane, nitric oxides (NOx), volatile organic compounds and carbon monoxide). From the equilibrium radiative forcing results we calculate global climate metrics, global warming potentials (GWPs) and global temperature change potentials (GTPs) and show how these depend on emission region, and can vary as functions of time. For the aerosol species, the GWP(100) values are −37±12, −46±20, and 350±200 for SO2, POM and BC respectively for the direct effects only. The corresponding GTP(100) values are −5.2±2.4, −6.5±3.5, and 50±33. This analysis is further extended by examining the temperature-change impacts in 4 latitude bands. This shows that the latitudinal pattern of the temperature response to emissions of the NTCFs does not directly follow the pattern of the diagnosed radiative forcing. For instance temperatures in the Arctic latitudes are particularly sensitive to NTCF emissions in the northern mid-latitudes. At the 100-yr time horizon the ARTPs show NOx emissions can have a warming effect in the northern mid and high latitudes, but cooling in the tropics and Southern Hemisphere. The northern mid-latitude temperature response to northern mid-latitude emissions of most NTCFs is approximately twice as large as would be implied by the global average.

A Lagrangian model of air-mass photochemistry and mixing using a trajectory ensemble: the Cambridge Tropospheric Trajectory model of Chemistry And Transport (CiTTyCAT) version 4.2

A Lagrangian model of photochemistry and mixing is described (CiTTyCAT, stemming from the Cambridge Tropospheric Trajectory model of Chemistry And Transport), which is suitable for transport and chemistry studies throughout the troposphere. Over the last five years, the model has been developed in parallel at several different institutions and here those developments have been incorporated into one "community" model and documented for the first time. The key photochemical developments include a new scheme for biogenic volatile organic compounds and updated emissions schemes. The key physical development is to evolve composition following an ensemble of trajectories within neighbouring air-masses, including a simple scheme for mixing between them via an evolving "background profile", both within the boundary layer and free troposphere. The model runs along trajectories pre-calculated using winds and temperature from meteorological analyses. In addition, boundary layer height and precipitation rates, output from the analysis model, are interpolated to trajectory points and used as inputs to the mixing and wet deposition schemes. The model is most suitable in regimes when the effects of small-scale turbulent mixing are slow relative to advection by the resolved winds so that coherent air-masses form with distinct composition and strong gradients between them. Such air-masses can persist for many days while stretching, folding and thinning. Lagrangian models offer a useful framework for picking apart the processes of air-mass evolution over inter-continental distances, without being hindered by the numerical diffusion inherent to global Eulerian models. The model, including different box and trajectory modes, is described and some output for each of the modes is presented for evaluation. The model is available for download from a Subversion-controlled repository by contacting the corresponding authors.

Isoprene emissions and climate

Biogenic volatile organic compounds (BVOCs) play an important role in atmospheric chemistry and the carbon cycle. Isoprene is quantitatively the most important of the non-methane BVOCs (NMBVOCs), with an annual emission of about 400–600 TgC; about 90% of this is emitted by terrestrial plants. Incorporating a mechanistic treatment of isoprene emissions within land-surface schemes has recently become a focus for the modelling community, the aim being to quantify the potential magnitude of associated climate feedbacks. However, these efforts are hampered by major uncertainties about why plants emit isoprene and the relative importance of different environmental controls on isoprene emission. The availability and reliability of observations of isoprene fluxes from different types of vegetation is limited, and this also imposes constraints on model development. Nevertheless, progress is being made towards the development of mechanistic models of isoprene emission which, in conjunction with atmospheric chemistry models, will ultimately allow improved quantification of the feedbacks between the terrestrial biosphere and climate under past and future climate states.

Meteorology, air quality, and health in London: the ClearfLo project

The ClearfLo project provides integrated measurements of the meteorology, composition and particulate loading of London's urban atmosphere to improve predictive capability for air quality. Air quality and heat are strong health drivers and their accurate assessment and forecast are important in densely populated urban areas. However, the sources and processes leading to high concentrations of main pollutants such as ozone, nitrogen dioxide, and fine and coarse particulate matter in complex urban areas are not fully understood, limiting our ability to forecast air quality accurately. This paper introduces the ClearfLo project's interdisciplinary approach to investigate the processes leading to poor air quality and elevated temperatures. Within ClearfLo (www.clearflo.ac.uk), a large multi-institutional project funded by the UK Natural Environment Research Council (NERC), integrated measurements of meteorology, gaseous and particulate composition/loading within London's atmosphere were undertaken to understand the processes underlying poor air quality. Long-term measurement infrastructure installed at multiple levels (street and elevated), and at urban background, kerbside and rural locations were complemented with high-resolution numerical atmospheric simulations . Combining these (measurement/modeling) enhances understanding of seasonal variations in meteorology and composition together with the controlling processes. Two intensive observation periods (winter 2012 and summer Olympics 2012) focus upon the vertical structure and evolution of the urban boundary layer, chemical controls on nitrogen dioxide and ozone production, in particular the role of volatile organic compounds, and processes controlling the evolution, size, distribution and composition of particulate matter. The paper shows that mixing heights are deeper over London than in the rural surroundings and the seasonality of the urban boundary layer evolution controls when concentrations peak. The composition also reflects the seasonality of sources such as domestic burning and biogenic emissions.

Parasitoids select plants more heavily infested with their caterpillar hosts: a new approach to aid interpretation of plant headspace volatiles

Plants produce volatile organic compounds (VOCs) in response to herbivore attack, and these VOCs can be used by parasitoids of the herbivore as host location cues. We investigated the behavioural responses of the parasitoid Cotesia vestalis to VOCs from a plant–herbivore complex consisting of cabbage plants (Brassica oleracea) and the parasitoids host caterpillar, Plutella xylostella. A Y-tube olfactometer was used to compare the parasitoids' responses to VOCs produced as a result of different levels of attack by the caterpillar and equivalent levels of mechanical damage. Headspace VOC production by these plant treatments was examined using gas chromatography–mass spectrometry. Cotesia vestalis were able to exploit quantitative and qualitative differences in volatile emissions, from the plant–herbivore complex, produced as a result of different numbers of herbivores feeding. Cotesia vestalis showed a preference for plants with more herbivores and herbivore damage, but did not distinguish between different levels of mechanical damage. Volatile profiles of plants with different levels of herbivores/herbivore damage could also be separated by canonical discriminant analyses. Analyses revealed a number of compounds whose emission increased significantly with herbivore load, and these VOCs may be particularly good indicators of herbivore number, as the parasitoid processes cues from its external environment

Radiative forcing and climate metrics for ozone precursor emissions: the impact of multi-model averaging

Multi-model ensembles are frequently used to assess understanding of the response of ozone and methane lifetime to changes in emissions of ozone precursors such as NOx, VOCs (volatile organic compounds) and CO. When these ozone changes are used to calculate radiative forcing (RF) (and climate metrics such as the global warming potential (GWP) and global temperature-change potential (GTP)) there is a methodological choice, determined partly by the available computing resources, as to whether the mean ozone (and methane) concentration changes are input to the radiation code, or whether each model's ozone and methane changes are used as input, with the average RF computed from the individual model RFs. We use data from the Task Force on Hemispheric Transport of Air Pollution source–receptor global chemical transport model ensemble to assess the impact of this choice for emission changes in four regions (East Asia, Europe, North America and South Asia). We conclude that using the multi-model mean ozone and methane responses is accurate for calculating the mean RF, with differences up to 0.6% for CO, 0.7% for VOCs and 2% for NOx. Differences of up to 60% for NOx 7% for VOCs and 3% for CO are introduced into the 20 year GWP. The differences for the 20 year GTP are smaller than for the GWP for NOx, and similar for the other species. However, estimates of the standard deviation calculated from the ensemble-mean input fields (where the standard deviation at each point on the model grid is added to or subtracted from the mean field) are almost always substantially larger in RF, GWP and GTP metrics than the true standard deviation, and can be larger than the model range for short-lived ozone RF, and for the 20 and 100 year GWP and 100 year GTP. The order of averaging has most impact on the metrics for NOx, as the net values for these quantities is the residual of the sum of terms of opposing signs. For example, the standard deviation for the 20 year GWP is 2–3 times larger using the ensemble-mean fields than using the individual models to calculate the RF. The source of this effect is largely due to the construction of the input ozone fields, which overestimate the true ensemble spread. Hence, while the average of multi-model fields are normally appropriate for calculating mean RF, GWP and GTP, they are not a reliable method for calculating the uncertainty in these fields, and in general overestimate the uncertainty.

Airborne measurements of trace gases and aerosols over the London metropolitan region

The Emissions around the M25 motorway (EM25) campaign took place over the megacity of London in the United Kingdom in June 2009 with the aim of characterising trace gas and aerosol composition and properties entering and emitted from the urban region. It featured two mobile platforms, the UK BAe-146 Facility for Airborne Atmospheric Measurements (FAAM) research aircraft and a ground-based mobile lidar van, both travelling in circuits around London, roughly following the path of the M25 motorway circling the city. We present an overview of findings from the project, which took place during typical UK summertime pollution conditions. Emission ratios of volatile organic compounds (VOCs) to acetylene and carbon monoxide emitted from the London region were consistent with measurements in and downwind of other large urban areas and indicated traffic and associated fuel evaporation were major sources. Sub-micron aerosol composition was dominated by secondary species including sulphate (24% of sub-micron mass in the London plume and 29% in the non-plume regional aerosol), nitrate (24% plume; 20% regional) and organic aerosol (29% plume; 31% regional). The primary sub-micron aerosol emissions from London were minor compared to the larger regional background, with only limited increases in aerosol mass in the urban plume compared to the background (~12% mass increase on average). Black carbon mass was the major exception and more than doubled in the urban plume, leading to a decrease in the single scattering albedo from 0.91 in the regional aerosol to 0.86 in the London plume, on average. Our observations indicated that regional aerosol plays a major role on aerosol concentrations around London, at least during typical summertime conditions, meaning future efforts to reduce PM levels in London must account for regional as well as local aerosol sources.

Vehicular particulate matter emissions in road tunnels in Sao Paulo, Brazil

In the metropolitan area of Sao Paulo, Brazil, ozone and particulate matter ( PM) are the air pollutants that pose the greatest threat to air quality, since the PM and the ozone precursors ( nitrogen oxides and volatile organic compounds) are the main source of air pollution from vehicular emissions. Vehicular emissions can be measured inside road tunnels, and those measurements can provide information about emission factors of in-use vehicles. Emission factors are used to estimate vehicular emissions and are described as the amount of species emitted per vehicle distance driven or per volume of fuel consumed. This study presents emission factor data for fine particles, coarse particles, inhalable particulate matter and black carbon, as well as size distribution data for inhalable particulate matter, as measured in March and May of 2004, respectively, in the Janio Quadros and Maria Maluf road tunnels, both located in Sao Paulo. The Janio Quadros tunnel carries mainly light-duty vehicles, whereas the Maria Maluf tunnel carries light-duty and heavy-duty vehicles. In the Janio Quadros tunnel, the estimated light-duty vehicle emission factors for the trace elements copper and bromine were 261 and 220 mu g km(-1), respectively, and 16, 197, 127 and 92 mg km(-1), respectively, for black carbon, inhalable particulate matter, coarse particles and fine particles. The mean contribution of heavy-duty vehicles to the emissions of black carbon, inhalable particulate matter, coarse particles and fine particles was, respectively 29, 4, 6 and 6 times higher than that of light-duty vehicles. The inhalable particulate matter emission factor for heavy-duty vehicles was 1.2 times higher than that found during dynamometer testing. In general, the particle emissions in Sao Paulo tunnels are higher than those found in other cities of the world.

Within-canopy sesquiterpene ozonolysis in Amazonia

Through rapid reactions with ozone, which can initiate the formation of secondary organic aerosols, the emission of sesquiterpenes from vegetation in Amazonia may have significant impacts on tropospheric chemistry and climate. Little is known, however, about sesquiterpene emissions, transport, and chemistry within plant canopies owing to analytical difficulties stemming from very low ambient concentrations, high reactivities, and sampling losses. Here, we present ambient sesquiterpene concentration measurements obtained during the 2010 dry season within and above a primary tropical forest canopy in Amazonia. We show that by peaking at night instead of during the day, and near the ground instead of within the canopy, sesquiterpene concentrations followed a pattern different from that of monoterpenes, suggesting that unlike monoterpene emissions, which are mainly light dependent, sesquiterpene emissions are mainly temperature dependent. In addition, we observed that sesquiterpene concentrations were inversely related with ozone (with respect to time of day and vertical concentration), suggesting that ambient concentrations are highly sensitive to ozone. These conclusions are supported by experiments in a tropical rain forest mesocosm, where little atmospheric oxidation occurs and sesquiterpene and monoterpene concentrations followed similar diurnal patterns. We estimate that the daytime dry season ozone flux of -0.6 to -1.5 nmol m(-2) s(-1) due to in-canopy sesquiterpene reactivity could account for 7%-28% of the net ozone flux. Our study provides experimental evidence that a large fraction of total plant sesquiterpene emissions (46%-61% by mass) undergo within-canopy ozonolysis, which may benefit plants by reducing ozone uptake and its associated oxidative damage.

Aerosol properties, in-canopy gradients, turbulent fluxes and VOC concentrations at a pristine forest site in Amazonia

Aerosol physical and chemical properties were measured in a forest site in central Amazonia (Cuieiras reservation, 2.61S; 60.21W) during the dry season of 2004 (Aug-Oct). Aerosol light scattering and absorption, mass concentration, elemental composition and size distributions were measured at three tower levels (Ground: 2 m; Canopy: 28 m, and Top: 40 m). For the first time, simultaneous eddy covariance fluxes of fine mode particles and volatile organic compounds (VOC) were measured above the Amazonian forest canopy. Aerosol fluxes were measured by eddy covariance using a Condensation Particle Counter (CPC) and a sonic anemometer. VOC fluxes were measured by disjunct eddy covariance using a Proton Transfer Reaction Mass Spectrometer (PTR-MS). At nighttime, a strong vertical gradient of phosphorus and potassium in the aerosol coarse mode was observed, with higher concentrations at Ground level. This suggests a source of primary biogenic particles below the canopy. Equivalent black carbon measurements indicate the presence of light-absorbing aerosols from biogenic origin. Aerosol number size distributions typically consisted of superimposed Aitken (76 nm) and accumulation modes (144 nm), without clear events of new particle formation. Isoprene and monoterpene fluxes reached respectively 7.4 and 0.82 mg m(-2) s(-1) around noon. An average fine particle flux of 0.05 +/- 0.10 10(6) m(-2) s(-1) was calculated, denoting an equilibrium between emission and deposition fluxes of fine mode particles at daytime. No significant correlations were found between VOC and fine mode aerosol concentrations or fluxes. (C) 2009 Elsevier Ltd. All rights reserved.

Nanostructured copper thin film used for catalysis

Catalytic properties of copper thin films deposited in small channels and cavities were tested using Raman microscopy and mass spectroscopy (MS) techniques, mainly. The catalytic surface conditions were addressed visually and chemically by optical microscopy and X-ray photoelectron spectroscopy (XPS), respectively. The experimental conditions of present work induced copper oxidation; eventually a number of carbon species and graphite remained on the catalytic surface. Quartz crystal microbalance and mass spectroscopy data support both adsorption and catalysis phenomena. MS showed CO2 formation during n-hexane heating process but not to 2-propanol, probably due to redox reactions. XPS of copper surface present in the cavity after catalysis tests detected Cu2O and a range of possible carbon species. The adsorption and catalytic performance of copper films deposited in cavities and microchannels were quite similar. A simple miniaturized device for microanalysis was proposed. (C) 2007 Elsevier B.V. All rights reserved.

Optical VOCs detection using poly(3-alkylthiophenes) with different side-chain lengths

The use of conjugated polymers in the gas and volatile organic compounds (VOCs) detections represents an advance in the development of the electronic noses. Polythiophenes show good thermal and environmental stability, are easily synthesized and they have been studied as gas and VOCs sensors using different principles or transduction techniques. Among these techniques, optical sensing has been attracted attention, mainly due to its versatility. However, conjugated polymer-based optical sensors are still less studied. This paper describes the use of two poly(3-alkylthiophenes) for VOCs optical detection. The sensing measurements were carried out using visible spectroscopy. Both polymers showed good sensitivity to the VOCs, showing fast and reversible responses with some hysteresis, and were unable to detect hydroxylated samples. Furthermore, it was demonstrated that the thickness of polymer films influences the intensity of the optical response. Although there is similarity in the superficial composition of the polymers films, demonstrated by their surface energies, they showed significant differences in their optical properties upon exposure to the VOCs. (c) 2009 Elsevier B.V. All rights reserved.

Development of a dynamic headspace solid-phase microextraction procedure coupled to GC–qMSD for evaluation the chemical profile in alcoholic beverages

In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC–qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as the type of fibre coating, extraction time and temperature, sample stirring and ionic strength, were optimized. The performance of five commercially available SPME fibres was evaluated and compared, namely polydimethylsiloxane (PDMS, 100 μm); polyacrylate (PA, 85 μm); polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 μm); carboxen™/polydimethylsiloxane (CAR/PDMS, 75 μm) and the divinylbenzene/carboxen on polydimethylsiloxane (DVB/CAR/PDMS, 50/30 μm) (StableFlex). An objective comparison among different alcoholic beverages has been established in terms of qualitative and semi-quantitative differences on volatile and semi-volatile compounds. These compounds belong to several chemical families, including higher alcohols, ethyl esters, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, furanic compounds, terpenoids, C13-norisoprenoids and volatile phenols. The optimized extraction conditions and GC–qMSD, lead to the successful identification of 44 compounds in white wines, 64 in beers and 104 in whiskys. Some of these compounds were found in all of the examined beverage samples. The main components of the HS-SPME found in white wines were ethyl octanoate (46.9%), ethyl decanoate (30.3%), ethyl 9-decenoate (10.7%), ethyl hexanoate (3.1%), and isoamyl octanoate (2.7%). As for beers, the major compounds were isoamyl alcohol (11.5%), ethyl octanoate (9.1%), isoamyl acetate (8.2%), 2-ethyl-1-hexanol (5.9%), and octanoic acid (5.5%). Ethyl decanoate (58.0%), ethyl octanoate (15.1%), ethyl dodecanoate (13.9%) followed by 3-methyl-1-butanol (1.8%) and isoamyl acetate (1.4%) were found to be the major VOCs in whisky samples.

Design gráfico da pluma de contaminação por compostos orgânicos voláteiss utilizando software CAD na investigação de passivo ambiental em um posto revendedor de combustíveis em Natal/RN

Among the potentially polluting economic activities that compromise the quality of groundwater are the gas stations. The city of Natal has about 120 gas stations, of which only has an environmental license for operation. Discontinuities in the offices were notified by the Public Ministry of Rio Grande do Norte to carry out the environmental adaptations, among which is the investigation of environmental liabilities. The preliminary and confirmatory stages of this investigation consisted in the evaluation of soil gas surveys with two confirmatory chemical analysis of BTEX, PAH and TPH. To get a good evaluation and interpretation of results obtained in the field, it became necessary three-dimensional representation of them. We used a CAD software to graph the equipment installed in a retail service station fuel in Natal, as well as the plumes of contamination by volatile organic compounds. The tool was concluded that contamination is not located in the current system of underground storage of fuel development, but reflects the historical past in which tanks were removed not tight gasoline and diesel