Reference values for structure emissions measured on site in new residential buildings in Finland

A 3-year research project was established in 1999 to create numerical reference data for material emissions during the time of construction and during the first year. Seven buildings, representing the present construction practice in Finland, were investigated. Material emissions were measured by using the field and laboratory cell (FLEC) during the time of construction, in the newly finished, and in the 6- and 12-month-old buildings. The emission rates for volatile organic compounds (VOCs), formaldehyde, and ammonia were determined.The highest total VOCs (TVOC) emissions were measured in the newly finished buildings from the ceiling structure and from some of the PVC floor coverings. These emissions were up to 1300–2000 μg m⁻² h⁻¹. Individual VOCs with emission rates above 50 μg m⁻² h⁻¹ included 2-(2-butoxyethoxy) ethanol and its acetate, C4–C16-substituted alkylbenzenes, and xylenes. The mean TVOC emission decreased at least to the Finnish M1-class level (200 μg m⁻² h⁻¹) from all surfaces and in all the buildings in 6–12 months. The ammonia and formaldehyde emissions from the ceiling structure were 20–60 μg m⁻² h⁻¹ in the newly finished buildings and the M1-levels (30/50 μg m⁻² h⁻¹) were exceeded in some cases. These emissions even increased in some buildings during the follow-up period indicating the difference between emissions measured in the laboratory and on site from real structures. Reference values based on the means and 95th percentile are presented to be utilised in both quality control and while investigating indoor air quality problems which are suspected to be caused by a defect structure.     

Composition and emissions of VOCs in main- and side-stream smoke of research cigarettes

It is well known that mainstream (MS) and sidestream (SS) cigarette smoke contains a vast number of chemical substances. Previous studies have emphasized SS smoke rather than MS smoke to which smokers are exposed, and most have used chamber tests that have several disadvantages such as wall losses. Emissions from standard research cigarettes have been measured, but relatively few constituents have been reported, and only the 1R4F (low nicotine) cigarette type has been tested. This study provides a comprehensive characterization of total, MS and SS smoke emissions for the 1R5F (ultra low nicotine), 2R4F (low nicotine), and 1R3F (standard nicotine) research cigarettes research cigarettes, including emission factors for a number of toxic compounds (e.g., benzene) and tobacco smoke tracers (e.g., 2,5-dimethyl furan). Emissions of volatile organic compounds (VOCs) and particulate matter (PM) are quantified using a dynamic dilution emission measurement system that is shown to produce accurate, rapid and reproducible results for over 30 VOCs and PM. SS and MS emissions were accurately apportioned based on a mass balance of total emissions. As expected, SS emissions greatly exceeded MS emissions. The ultra low nicotine cigarette had lower emissions of most VOCs compared to low and standard nicotine cigarettes, which had similar emissions. Across the three types of cigarettes, emissions of benzene (296–535 μg cig⁻¹), toluene (541–1003 μg cig⁻¹), styrene (90–162 μg cig⁻¹), 2-dimethyl furan (71–244 μg cig⁻¹), naphthalene (15–18 μg cig⁻¹) and other VOCs were generally comparable to or somewhat higher than literature estimates using chamber tests.     

Sensitivity of ozone concentrations to diurnal variations of surface emissions in Mexico City: A WRF/Chem modeling study

Sensitivity of ozone (O₃) concentrations in the Mexico City area to diurnal variations of surface air pollutant emissions is investigated using the WRF/Chem model. Our analysis shows that diurnal variations of nitrogen oxides (NO_x = NO + NO₂) and volatile organic compound (VOC) emissions play an important role in controlling the O₃ concentrations in the Mexico City area. The contributions of NO_x and VOC emissions to daytime O₃ concentrations are very sensitive to the morning emissions of NO_x and VOCs. Increase in morning NO_x emissions leads to decrease in daytime O₃ concentrations as well as the afternoon O₃ maximum, while increase in morning VOC emissions tends to increase in O₃ concentrations in late morning and early afternoon, indicating that O₃ production in Mexico City is under VOC-limited regime. It is also found that the nighttime O₃ is independent of VOCs, but is sensitive to NO_x. The emissions of VOCs during other periods (early morning, evening, and night) have only small impacts on O₃ concentrations, while the emissions of NO_x have important impacts on O₃ concentrations in the evening and the early morning.This study suggests that shifting emission pattern, while keeping the total emissions unchanged, has important impacts on air quality. For example, delaying the morning emission peak from 8 am to 10 am significantly reduced the morning peaks of NO_x and VOCs, as well as the afternoon O₃ maxima. It suggests that without reduction of total emission, the daytime O₃ concentrations can be significantly reduced by changing the diurnal variations of the emissions of O₃ precursors.     

Ethanol emission from loose corn silage and exposed silage particles

Silage on dairy farms has been identified as a major source of volatile organic compound (VOC) emissions. However, rates of VOC emission from silage are not accurately known. In this work, we measured ethanol (a dominant silage VOC) emission from loose corn silage and exposed corn silage particles using wind tunnel systems. Flux of ethanol was highest immediately after exposing loose silage samples to moving air (as high as 220 g m^?2 h^?1) and declined by as much as 76-fold over 12 h as ethanol was depleted from samples. Emission rate and cumulative 12 h emission increased with temperature, silage permeability, exposed surface area, and air velocity over silage samples. These responses suggest that VOC emission from silage on farms is sensitive to climate and management practices. Ethanol emission rates from loose silage were generally higher than previous estimates of total VOC emission rates from silage and mixed feed. For 15 cm deep loose samples, mean cumulative emission was as high as 170 g m^?2 (80% of initial ethanol mass) after 12 h of exposure to an air velocity of 5 m s^?1. Emission rates measured with an emission isolation flux chamber were lower than rates measured in a wind tunnel and in an open setting. Results show that the US EPA emission isolation flux chamber method is not appropriate for estimating VOC emission rates from silage in the field.     

Intra- and inter-annual variability of VOC emissions from natural and semi-natural vegetation in Europe and neighbouring countries

Biogenic VOC emission estimates from the earth's surface are crucial input parameters in air quality models. Knowledge accumulated in the last years about BVOC source distributions and chemical compound species emission profiles in Europe as well as the demand of air quality modellers for a finer resolution in space and time of BVOC estimates have led to the set-up of new emission modelling systems. An updated fast BVOC emission modelling platform explicitly considering the seasonality of emission potentials and leaf temperature gradients in forest canopies by the semi-empirical emission module (seBVOC) will be proposed and used for estimating hourly values of chemical compound-specific emissions in Europe (33–68° north; 10° west to 40° east) in the years 1997, 2000, 2001, and 2003. Spatial resolution will be 10 km by 10 km. The database used contains latest land and forest distributions, updated foliar biomass densities, leaf area indices (LAI), and plant as well as chemical compound-specific emission potentials, if available. Meteorological input parameters for the respective years will be generated using the non-hydrostatic meteorological model MM5. Highest BVOC emissions occur in daytime hours around noon from the end of May to mid-August in the Mediterranean area and from the mid of June to the end of July in the boreal forests. Comparison of 3 BVOC model approaches will reveal that for July 2003, the European isoprene and monoterpene totals range from 1124 Gg to 1446 Gg and from 338 Gg to 1112 Gg, respectively. Small-scale deviations may be as high as ±0.6 Mg km^?2 for July 2003, reflecting the current uncertainty range for BVOC estimates. Key sources of errors in inventories are still insufficiently detailed land use data for some areas and lacking chemically speciated plant-specific emission potentials in particular in boreal, south-eastern, and northern African landscapes. The hourly emissions of isoprene, speciated terpenes, and oxyVOC have been made available by the NatAir database.     

Biogenic VOC emissions from fresh leaf mulch and wood chips of Grevillea robusta (Australian Silky Oak)

The emissions of VOC from freshly cut and shredded Grevillea robusta (Australian Silky Oak) leaves and wood have been measured. The VOC emissions from fresh leaf mulch and wood chips lasted typically for 30 and 20 h respectively, and consisted primarily of ethanol, (E)-2-hexenal, (Z)-3-hexen-1-ol and acetaldehyde. The integrated emissions of the VOCs were 0.38±0.04 g kg⁻¹ from leaf mulch, and 0.022±0.003 g kg⁻¹ from wood chips. These emissions represent a source of VOCs in urban and rural air that has previously been unquantified and is currently unaccounted for. These VOCs from leaf mulch and wood chips will contribute to both urban photochemistry and secondary organic aerosol formation. Any CH₄ emissions from leaf mulch and wood chips were <1×10⁻¹¹ g g dry mass⁻¹ s⁻¹.     

Reactions between ozone and building products: Impact on primary and secondary emissions

Reactions of ozone on common building products were studied in a dedicated emission test chamber system. Fourteen new and unused products were exposed to 100–160 ppb of ozone at 23 °C and 50% RH during 48 h experiments. Ozone deposition velocities calculated at steady state were between 0.003 cm s⁻¹ (alkyd paint on polyester film) and 0.108 cm s⁻¹ (pine wood board). All tested product showed modified emissions when exposed to ozone and secondary emissions of several aldehydes were identified. Carpets and wall coverings emitted mainly C₅–C₁₀ n-aldehydes, typical by-products of surface reactions. Linoleum, polystyrene tiles and pine wood boards also showed increased emissions of formaldehyde, benzaldehyde and hexanal associated with reduced emissions of unsaturated compounds suggesting the occurrence of gas-phase reactions. The ozone removal on the different tested products was primarily associated with surface reactions. The relative contribution of gas-phase reactions to the total ozone removal was estimated to be between 5% and 30% for pine wood boards depending on relative humidity (RH) and on the incoming ozone concentration and 2% for polystyrene tiles. On pine wood board, decreasing ozone deposition velocities were measured with increasing ozone concentrations and with RH increasing in the range 30–50%.     

Speciation of volatile organic compounds from poultry production

Volatile organic compounds (VOCs) emitted from poultry production are leading source of air quality problems. However, little is known about the speciation and levels of VOCs from poultry production. The objective of this study was the speciation of VOCs from a poultry facility using evacuated canisters and sorbent tubes. Samples were taken during active poultry production cycle and between production cycles. Levels of VOCs were highest in areas with birds and the compounds in those areas had a higher percentage of polar compounds (89%) compared to aliphatic hydrocarbons (2.2%). In areas without birds, levels of VOCs were 1/3 those with birds present and compounds had a higher total percentage of aliphatic hydrocarbons (25%). Of the VOCs quantified in this study, no single sampling method was capable of quantifying more than 55% of compounds and in several sections of the building each sampling method quantified less than 50% of the quantifiable VOCs. Key classes of chemicals quantified using evacuated canisters included both alcohols and ketones, while sorbent tube samples included volatile fatty acids and ketones. The top five compounds made up close to 70% of VOCs and included: 1) acetic acid (830.1 μg m^?3); 2) 2,3-butanedione (680.6 μg m^?3); 3) methanol (195.8 μg m^?3); 4) acetone (104.6 μg m^?3); and 5) ethanol (101.9 μg m^?3). Location variations for top five compounds averaged 49.5% in each section of the building and averaged 87% for the entire building.     

Confronting environmental pressure,environmental quality and human health impact indicators of priority air emissions

This paper evaluates the ranking of 21 priority air pollutants with three indicator schemes: environmental pressure indicator (EPI), environmental quality indicator (EQI), and human health effect indicator (HEI). The EPI and EQI compare the emissions and concentrations with the target emissions and target concentrations, respectively. The HEI comprehends the steps from cause (i.e. national emissions) to effect (i.e. human health effects), and is the total human health burden, expressed in Disability Adjusted Life Years per year of exposure (DALYs year^?1). We estimated a health burden in the Netherlands of 41 × 10³ DALYs year^?1 caused by Dutch air emissions of PM10 and its precursors in the year 2003. The burden due to 17 carcinogenic substances emitted to air, was much lower (140 DALYs year^?1). In contrast, when the same substances were evaluated regarding environmental pressure and environmental quality, carbon tetrachloride (pressure) and benzo[a]pyrene (quality) were of highest importance, whereas the importance of PM10 was substantially lower. This result is remarkable, because for the majority of substances evaluated, the target concentrations and target emissions are based on preventing human health damage. The differences in relevance are explained by the different weighting of interests in the indicators. The HEI is based on concentration–response relations, whereas the EPI and EQI also depend on other, policy-based, principles and on technical feasibility. Therefore, to effectively prioritize emission reduction measures in policy-making, substances should not only be evaluated as to whether emission targets and environmental quality targets are reached, but they should be evaluated regarding their human health impact as well. In this context, the HEI is a suitable indicator to evaluate the human health impact.     

VOC concentration profiles in an ozone non-attainment area: A case study in an urban and industrial complex metroplex in southern Taiwan

VOCs are important precursors of the atmospheric ozone formation species. This study investigated the airborne concentrations of 52 VOCs at two air quality monitoring stations, Daliao and Tzouying, during wintertime in southern Taiwan. Airborne VOCs samples were taken in stainless steel canisters four times per day and analyzed via gas chromatography/mass spectrometry. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential in this ozone non-attainment region. Toluene, propane, isopentane, propene, n-butane, n-pentane and isoprene contributed 78–79% of the 52 VOCs in Daliao. Toluene, 1-butene, isopentane, propene, propane, n-undecane, and n-butane contributed 71–77% of the 52 VOCs in Tzouying. The VOCs concentrations were higher in Daliao due to the high toluene emissions from a paint plant and a solvent plant in the nearby industrial district. The 24-h VOC concentrations averaged 25 ppb higher in Tzouying than in Daliao. The ozone formation potential of airborne VOCs was 1687–2730 and 1717–2261 μg-O₃/g-VOCs in Daliao and Tzouying, respectively. Ozone concentrations in Tzouying were 44 ppb higher than in Daliao during the 1200–1600 sampling period.     

Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes

This study presents carbon (δ¹³C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption–gas chromatography–isotope ratio mass spectrometry (TD–GC–irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ¹³C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ¹³C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.     

Natural VOC emissions from forests in Poland

On the basis of the last inventory of forests and climatic conditions in Poland, a national evaluation of the emissions of reactive volatile organic compounds (VOCs) was carried out. Calculations took into account the composition and age structure of forests as well as the temperature dependencies of VOC emission rate for the main European forest-forming tree species. In the case of isoprene, the dependence on illumination level and day length was also taken into account. Estimations were made for all 49 administrative regions of Poland. Depending on weather conditions in different years, the total VOC emission of Polish forests can be in the range 186–763 kt yr⁻¹. For instance, for a moderately warm year, 1992, it was estimated at 440.6 kt, which represents 25% of the total VOC emissions in Poland.     

Volatile organic compound emissions from Siberian larch

We determined hourly emissions of isoprene, monoterpenes and sesquiterpenes from Siberian larch, one of the major tree species in Siberian forests. Summer volatile organic compounds (VOCs) emission from Siberian larch consisted mainly of monoterpenes (about 90%). The monoterpene emission spectrum remained constant during the measurement period, almost half was sabinene and other major monoterpenes were Δ³-carene, β- and α-pinene. During spring and summer, about 10% of the VOCs were sesquiterpenes, mainly α-farnesene. The sesquiterpene emissions declined to 3% in the fall. Isoprene, 2-methyl-3-buten-2-ol (MBO) and 1,8-cineole contributed to less than 3% of the VOC emission during the whole period. The diurnal variation of the emissions could be explained using a temperature-dependent parameterization. Emission potentials normalized to 30 °C were 5.2–21 μg g_dw⁻¹ h⁻¹ (using β-value of 0.09 °C⁻¹) for monoterpenes and 0.4–1.8 μg g_dw⁻¹ h⁻¹ (using β-value of 0.143 °C⁻¹, mean of determined values) for sesquiterpenes. Normalized monoterpene emission potentials were highest in late summer and elevated again in late fall. Sesquiterpene emission potentials were also highest in late summer, but decreased towards fall.     

Global atmospheric emission inventory of polycyclic aromatic hydrocarbons (PAHs) for 2004

The global atmospheric emissions of the 16 polycyclic aromatic hydrocarbons (PAHs) listed as the US EPA priority pollutants were estimated using reported emission activity and emission factor data for the reference year 2004. A database for emission factors was compiled, and their geometric means and frequency distributions applied for emission calculation and uncertainty analysis, respectively. The results for 37 countries were compared with other PAH emission inventories. It was estimated that the total global atmospheric emission of these 16 PAHs in 2004 was 520 giga grams per year (Gg y^?1) with biofuel (56.7%), wildfire (17.0%) and consumer product usage (6.9%) as the major sources, and China (114 Gg y^?1), India (90 Gg y^?1) and United States (32 Gg y^?1) were the top three countries with the highest PAH emissions. The PAH sources in the individual countries varied remarkably. For example, biofuel burning was the dominant PAH source in India, wildfire emissions were the dominant PAH source in Brazil, while consumer products were the major PAH emission source in the United States. In China, in addition to biomass combustion, coke ovens were a significant source of PAHs. Globally, benzo(a)pyrene accounted for 0.05% to 2.08% of the total PAH emission, with developing countries accounting for the higher percentages. The PAH emission density varied dramatically from 0.0013 kg km^?2 y in the Falkland Islands to 360 kg km^?2 y in Singapore with a global mean value of 3.98 kg km^?2 y. The atmospheric emission of PAHs was positively correlated to the country's gross domestic product and negatively correlated with average income. Finally, a linear bivariate regression model was developed to explain the global PAH emission data.     

A revised estimate of copper emissions from road transport in UNECE-Europe and its impact on predicted copper concentrations

Comparisons of measured and model-predicted atmospheric copper concentrations show a severe underestimation of the observed concentrations by the models. This underestimation may be (partly) due to underestimated emissions of copper to air. Since the phase out of asbestos brake lining material, the composition of brake lining material has changed and may contain up to ∼15% copper. This makes brake wear from vehicles potentially an important source of atmospheric (particulate) copper concentrations. In this paper, we reassess the copper emissions due to exhaust emissions and brake wear from road transport. Overall, our reassessments result in an estimate of total copper emission to air in UNECE-Europe of 4.0–5.5 ktonnes yr⁻¹, which is substantially higher than the previous estimate of 2.8 ktonnes yr⁻¹. Copper concentrations over Europe are calculated with the LOTOS-EUROS model using the revised emission data as model input. The results show that the revised emission estimates are a major step towards gap closure of predicted versus observed copper concentrations in ambient air. Brake wear emissions may be responsible for 50–75% of the total copper emissions to air for most of Western Europe. The hypothesis that road transport is an important source of copper emissions is tested and confirmed by (1) reviewing available literature data of chemically speciated PM data from road tunnel studies and (2) the gradient observed in copper concentrations from ambient PM monitoring going from rural sites to street stations. The literature review and observational data suggest that the majority of the emitted PM10 brake wear particles is in the PM2.5–10 size range. The results of this study indicate that modification of brake lining composition is an important mitigation option to reduce copper exposure of the population in Western Europe.     

The effect of the increase in urban temperature on the concentration of photochemical oxidants

An atmospheric dispersion model, where the inputs of meteorological field were calculated using a meteorological model, was used to reproduce the observed air pollution conditions for the typical fine day in summer period, especially the concentration of the photochemical oxidants. As well, the effects of an increase in the urban temperature and VOC emissions on the concentration of photochemical oxidants were also considered. The following conclusions were drawn.The observed air pollution levels were well modeled by the atmospheric dispersion model using in this study, although modeled NO levels were slightly lower than the observed levels. An analysis of the temperature data showed that a 1 °C increase in temperature leads to a maximal photochemical oxidant concentration of 5.3 ppb, which is an increase of 11%. Additionally, the effect on the photochemical oxidant concentration due to an increase in the vegetation-derived VOCs was more than double the effect due to an increase in the photochemical reactions. It was found that the temperature and photochemical oxidant concentration were linearly related up to a temperature increase of 3 °C. When the temperature increases up to 3 °C, the concentration of photochemical oxidants increases by 19 ppb. An analysis of the effect of vegetation-derived VOCs on photochemical oxidant concentrations showed that, the concentration of photochemical oxidants was 30 ppb higher in the afternoon by the effect of vegetation-derived VOCs, so even in metropolitan areas with relatively little vegetation, vegetation-derived VOCs have a strong impact on photochemical oxidant concentrations.     

A biogenic volatile organic compound emission inventory for Hong Kong

Biogenic volatile organic compounds (BVOCs) in the atmosphere react to form ozone and secondary organic aerosols, which deteriorate air quality, affect human health, and indirectly influence global climate changes. The present study aims to provide a preliminary assessment of BVOC emissions in Hong Kong (HKSAR). Thriteen local tree species were measured for their isoprene emission potential. Tree distribution was estimated for country park areas based on field survey data. Plant emission data obtained from measurements and the literature, tree distribution estimation data, land use information, and meteorological data were combined to estimate annual BVOC emissions of 8.6×10⁹ g C for Hong Kong. Isoprene, monoterpenes, and other VOCs contributed about 30%, 40%, and 30% of the estimated total annual emissions, respectively. Although hundreds of plant species are found in Hong Kong country parks, the model results indicate that only 10 tree species contribute about 76% of total annual VOC emissions. Prominent seasonal and diurnal variations in emissions were also predicted by the model. The present study lays a solid foundation for future local research, and results can be applied for studying BVOC emissions in nearby southern China and Asian regions that share similar climate and plant distributions.     

The flux of isoprene from a willow coppice plantation and the effect on local air quality

Isoprene fluxes from a Salix viminalis (willow) plantation in western Sweden were measured using the relaxed eddy accumulation (REA) technique. Fluxes of up to 0.23 μg m⁻² s⁻¹ could be observed. A standard emission factor at 303 K and a PAR flux of 1000 μ mol m⁻² s⁻¹ was estimated to 0.98 μg m⁻² s⁻¹ by using the G93 algorithm. The chemistry of an air parcel passing over a willow coppice plantation was investigated utilising a Lagrangian box model in which the measured isoprene fluxes were used as input data. Dispersion after the field was accounted for by a procedure based on the Gaussian plume model. The calculations indicate that, in most cases, the isoprene emissions have a small effect on the local air quality.     

An industrial emissions inventory of calcium for Europe

The base cations calcium, magnesium and potassium, have been observed to be declining in air and precipitation in both Europe and North America. There is good evidence that this is the result of declining emissions of fly ash from industrial plant, as a result of increased abatement and industrial decline. This may have the effect of offsetting the effects of declines in acidic emissions, in terms of net deposited acidity. In order to reconcile source strengths of base cations, an industrial emissions inventory of calcium, the dominant base cation in air and precipitation, has been compiled. The main sources identified were: cement plants; iron and steel plants; and coal combustion from both large and small boilers. The overall emission was calculated to be between approximately 750 and 800 ktonnes Ca yr^-1. The dominant source was coal combustion from domestic and small boilers. Of the point sources, cement production dominated over coal combustion, and iron and steel plant. The emission factors used are very uncertain, which gives the inventory a large uncertainty. Furthermore, the emissions are compiled on a base year of 1990, and large changes have taken place in the industrial structuring of the largest contributing countries. Despite the uncertainties, the compilation of the inventory represents a vital first step in understanding the sources of deposited calcium and its effect on net deposited acidity.