Compilation of a database on the composition of anthropogenic VOC emissions for atmospheric modeling in Europe

To analyse and generate air pollution control strategies and policies, e.g. efficient abatement strategies or action plans that lead to a fulfilment of air quality aims, atmospheric dispersion models (CTMs) have to be used. These models include a chemical model, where the numerous volatile organic compounds (VOCs) species are lumped together in classes. On the other hand, emission inventories usually report only total non-methane VOC (NMVOC), but not a subdivision into these classes. Thus, VOC species profiles are needed that resolve total NMVOC emission data. The objective of this publication is to present the results of a compilation of VOC species profiles that dissolve total VOC into single-species profiles for all relevant anthropogenic emission source categories and the European situation. As in atmospheric dispersion models usually modules for generating biogenic emissions are directly included, only anthropogenic emissions are addressed. VOC species profiles for 87 emission source categories have been developed. The underlying data base can be used to generate the data for all chemical mechanisms. The species profiles have been generated using recent measurements and studies on VOC species resolution and thus represent the current state of knowledge in this area. The results can be used to create input data for atmospheric dispersion models in Europe.The profiles, especially those for solvent use, still show large uncertainties. There is still an enormous need for further measurements to achieve an improved species resolution. In addition, the solvent use directive and the DECOPAINT directive of the European Commission will result in a change of the composition of paints; more water-based and high-solid paints will be used; thus the species resolution will change drastically in the next years. Of course, the species resolution for combustion and production processes also requires further improvement.     

Managing ammonia emissions from livestock production in Europe

Around 75% of European ammonia (NH(3)) emissions come from livestock production. Emissions occur at all stages of manure management: from buildings housing livestock; during manure storage; following manure application to land; and from urine deposited by livestock on pastures during grazing. Ammoniacal nitrogen (total ammoniacal-nitrogen, TAN) in livestock excreta is the main source of NH(3). At each stage of manure management TAN may be lost, mainly as NH(3), and the remainder passed to the next stage. Hence, measures to reduce NH(3) emissions at the various stages of manure management are interdependent, and the accumulative reduction achieved by combinations of measures is not simply additive. This TAN-flow concept enables rapid and easy estimation of the consequences of NH(3) abatement at one stage of manure management (upstream) on NH(3) emissions at later stages (downstream), and gives unbiased assessment of the most cost-effective measures. We conclude that rapid incorporation of manures into arable land is one of the most cost-effective measures to reduce NH(3) emissions, while covering manure stores and applying slurry by band spreader or injection are more cost-effective than measures to reduce emissions from buildings. These measures are likely to rank highly in most European countries.     

Natural emissions of methane from geological seepage in Europe

Recent studies have shown that geological emissions of methane are an important greenhouse-gas source. Remarkable amounts of methane, estimated in the order of 40–60 Tg yr^?1, are naturally released into the atmosphere from the Earth's crust through faults and fractured rocks. The main source is natural gas, both microbial and thermogenic, produced in hydrocarbon-prone sedimentary basins and injected into the atmosphere through macro-seeps (onshore and offshore mud volcanoes and other seeps) and microseepage, an invisible but pervasive flux from the soil. This source is now evaluated for Europe on the basis of a literature survey, new field measurements and derived emission factors. The up-scaling criteria recommended by the EMEP/CORINAIR guidelines are applied to the local point and area source data.In Europe, 25 countries host oil and/or natural gas reservoirs and potentially, or actually, emit geological methane. Flux data, however, are available only from 10 countries: the onshore or offshore petroliferous sectors of Denmark, Italy, Greece, Romania, Spain, Switzerland, United Kingdom and Black Sea countries (Bulgaria, Ukraine, Georgia). Azerbaijan, whose emissions due to mud volcanism are known to be relevant, is included in the estimate.The sum of emissions, regional estimates and local measurements, related to macro-seeps leads to a conservative total value of about 2.2 Tg yr^?1. Together with the potential microseepage fluxes from the petroliferous basins, estimated on the basis of the Total Petroleum System concept (around 0.8 Tg yr^?1), the total European seepage is projected to 3 Tg yr^?1. This preliminary figure would represent, in terms of magnitude, the second natural methane source for Europe after wetlands. The estimate will have to be refined by increasing the number of seepage measurements both on lands, where there is high potential for microseepage (e.g., Germany, Hungary, Romania, Ukraine, Belarus, Russia, Georgia) and in coastal marine areas (the North Sea, the Black Sea, offshore Greece and Italy) where emission factors and the extent of the underwater seeping area are not completely known.     

(M)VOC and composting facilities. Part 1: (M)VOC emissions from municipal biowaste and plant refuse

GOAL, SCOPE AND BACKGROUND: Malodorous volatiles derived from the decomposition of biowaste within the process of composting might pose a risk to human health. Different techniques of process engineering have been developed to minimise the burden of malodorous compounds in air possibly affecting compost workers and residents in the vicinity. METHODS: In the present study, three different composting facilities were examined for the emission of volatiles to estimate the impact of process engineering on the dispersal of odorous compounds and to discuss its relevance for human health. RESULTS AND DISCUSSION: Concentrations of single compounds belonging to alcohols, ketones, furanes, sulfur-containing compounds and especially terpenes ranged from 10(2) up to nearly 10(6) ng/m3 depending on the sampling sites and the process engineering. The ratio of MVOC and total VOC measured changed throughout the process of biodegradation. A certain combination of volatile compounds coincided with the occurrence of typical compost odour. CONCLUSION: The type of process engineering seemed to have a major impact on the emission of volatiles, as amounts of (microbial) volatiles emitted were characteristic for the different techniques used. Thus, the MVOC emission basically depends on the degree of biodegradation. It is likely that the concentrations workers are exposed to can have an impact on human health. RECOMMENDATIONS AND OUTLOOK: It is obvious that less sophisticated types of process engineering give rise to greater amounts of bioaerosols and volatiles and, therefore, technical devices have to be improved and controlled regularly to minimise adverse health effects on workers.     

The contribution from shipping emissions to air quality and acid deposition in Europe

A global three-dimensional Lagrangian chemistry-transport model STOCHEM is used to describe the European regional acid deposition and ozone air quality impacts along the Atlantic Ocean seaboard of Europe, from the SO2, NOx, VOCs and CO emissions from international shipping under conditions appropriate to the year 2000. Model-derived total sulfur deposition from international shipping reaches over 200 mg S m(-2) yr(-1) over the southwestern approaches to the British Isles and Brittany. The contribution from international shipping to surface ozone concentrations during the summertime, peaks at about 6 ppb over Ireland, Brittany and Portugal. Shipping emissions act as an external influence on acid deposition and ozone air quality within Europe and may require control actions in the future if strict deposition and air quality targets are to be met.     

Emissions of biogenic VOC from forest ecosystems in central Europe: Estimation and comparison with anthropogenic emission inventory

This paper describes a method of estimating emission fluxes of biogenic volatile organic compounds (BVOCs) based on the approach proposed by Guenther et al. (1995) and the high-resolution Corine land-cover 2000 database (1 × 1 km resolution). The computed emission fluxes for the Czech Republic (selected for analysis as being representative of a heavily cultivated, central European country) are compared with anthropogenic emissions, both for the entire country and for individual administrative regions. In some regions, BVOC emissions are as high as anthropogenic emissions; however, in most regions the BVOC emissions are approximately 50% of the anthropogenic emissions. The yearly course of BVOC emissions (represented by monoterpenes and isoprene) is presented, along with the spatial distribution of annual mean values. Differences in emission distributions during winter (January) and summer (June) are also considered.     

Primary emissions of fine carbonaceous particles in Europe

The European emissions of BC and OC in fine particles are calculated for the years 1990, 1995 and 2000 applying the RAINS model that, beyond fuel-sector distinction, explicitly includes various combustion technologies and the penetration of abatement options. The emission factors used are developed considering specific European conditions. The main sources of carbonaceous aerosols in Europe are emissions from traffic and residential combustion of solid fuels. Between 1990 and 2000, the BC and OC emissions are estimated to decline from 0.89 to 0.68 Tg and from 1.4 to 1.0 Tg, respectively. Most of the reduction occurred in the early 1990s in Eastern Europe owing to structural changes that resulted in energy efficiency improvements in industry and lower consumption of solid fuels in residential–commercial sector; the latter having strong impact on BC and OC emissions. Furthermore, the growth in transport volumes, and expected increase in emissions, was offset by introduction of stricter legislation for road transport from 1995. Focusing on the most important sectors, transport and residential combustion, the variation in measured carbonaceous emission shares and its impact on total emissions was evaluated. This analysis indicates a range of about −25% to +20% for BC and −7% and +15% for OC, compared to the central case.     

Intra- and inter- laboratory variability in paper industry PCDD/PCDF analysis

Studies were conducted to quantify variability for pulp industry wastewater effluent, pulp and sludge analyses. Intralaboratory variability studies indicated that there is a potential for greater between batch variability in results than for within a batch. Intralaboratory relative standard deviations for replicate analyses ranged from 6% to 60%. Interlaboratory studies, using standard reference materials showed relative standard deviations from 4% to 135%. There appeared to be little dependance of variability on concentration, suggesting matrix effects were very important. In general, effluent variability was greater than observed for pulps or sludges. Analysis of reference standards indicated that 13% to 17% variability can be attributed to differences in calibration standards. A limited study of full congener PCDD/PCDF analysis variability showed it to be greater than observed for TCDD/TCDF.     

Comparison of models for describing measured VOC emissions from wood-based panels under dynamic chamber test condition

Measured emission factors are the experimental data used to represent emission characteristics of volatile organic compounds (VOCs) from testing materials under dynamic chamber test conditions. A simple empirical model that describes the measured emission factors will be very useful for practical purposes. In this study, a power law model was compared with a widely used first-order exponential decay model in their ability to describe measured emission factors of wood-based panel materials. It was demonstrated that the power law model is a better choice than the first-order model for describing emission characteristics for short-term (less than 100 h) experimental data. The power law model was also more superior in predicting long-term (up to 900 h) emission factors.     

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.     

Idle emissions from heavy-duty diesel and natural gas vehicles at high altitude

Idle emissions of total hydrocarbon (THC), CO, NOx, and particulate matter (PM) were measured from 24 heavy-duty diesel-fueled (12 trucks and 12 buses) and 4 heavy-duty compressed natural gas (CNG)-fueled vehicles. The volatile organic fraction (VOF) of PM and aldehyde emissions were also measured for many of the diesel vehicles. Experiments were conducted at 1609 m above sea level using a full exhaust flow dilution tunnel method identical to that used for heavy-duty engine Federal Test Procedure (FTP) testing. Diesel trucks averaged 0.170 g/min THC, 1.183 g/min CO, 1.416 g/min NOx, and 0.030 g/min PM. Diesel buses averaged 0.137 g/min THC, 1.326 g/min CO, 2.015 g/min NOx, and 0.048 g/min PM. Results are compared to idle emission factors from the MOBILE5 and PART5 inventory models. The models significantly (45-75%) overestimate emissions of THC and CO in comparison with results measured from the fleet of vehicles examined in this study. Measured NOx emissions were significantly higher (30-100%) than model predictions. For the pre-1999 (pre-consent decree) truck engines examined in this study, idle NOx emissions increased with model year with a linear fit (r2 = 0.6). PART5 nationwide fleet average emissions are within 1 order of magnitude of emissions for the group of vehicles tested in this study. Aldehyde emissions for bus idling averaged 6 mg/min. The VOF averaged 19% of total PM for buses and 49% for trucks. CNG vehicle idle emissions averaged 1.435 g/min for THC, 1.119 g/min for CO, 0.267 g/min for NOx, and 0.003 g/min for PM. The g/min PM emissions are only a small fraction of g/min PM emissions during vehicle driving. However, idle emissions of NOx, CO, and THC are significant in comparison with driving emissions.     

Estimation of wind blown dust emissions in Europe and its vicinity

The assessment of the wind blown dust emission for Europe and selected regions of North Africa and Southwest Asia was carried out using a mesoscale model. The mesoscale model was parameterized based on the current literature review. The model provides data on PM₁₀ emission from several dust reservoirs (anthropogenic, agriculture, semi- and natural) with spatial resolution of 10 × 10 km and temporal resolution of 1 h. The spatial variability of PM₁₀ emission depends on soil texture, land cover/land use as well as meteorological conditions. Lands covered with water or permanently wet were excluded from the model. The land covered with vegetation is treated as dust reservoir whose dust emission capacity depends on the type of vegetation and cover. The dust reservoirs are divided into reservoirs with stable and unstable surface. The changes of emission in time depend on meteorological parameters.The wind blown dust emission should be treated as a non-continuous spatio-temporal process. The emissions are estimated with high uncertainty. The estimated PM₁₀ yearly total load emitted by wind from the European territory is highly differentiated in space and time and is equal to 0.74 Tg. The total load of PM₁₀ emitted by wind from North African and Southwest Asian land surface located in the vicinity of European boundaries is assessed as nearly 50% (0.43 Tg) of the total load estimated for the whole Europe.The average yearly PM₁₀ emission factor for Europe was estimated at 0.139 Mg km^?2.The PM₁₀ emission from agricultural areas is estimated at 52% of the total wind blown emission from the domain of the European Union project “Improving and applying methods for the calculation of natural and biogenic emissions and assessment of impacts to the air quality” - NatAir.PM₁₀ emission factor for natural areas of Europe is estimated at 0.021 Mg km^?2. Appropriate factors for agricultural areas and anthropogenic areas are 0.157 Mg km^?2 and 0.118 Mg km^?2, respectively. The latter two factors are probably underestimated due to omitting in the model of other dust emission mechanisms than aeolian erosion.     

Current and future emissions of selected heavy metals to the atmosphere from anthropogenic sources in Europe

Current atmospheric emissions of As, Cd, Cr, Ni, and Pb (reference year 2000) from major anthropogenic sources in Europe are presented in this paper. Combustion of fuels in stationary sources was the main emission source for As, Cd, Cr, and Ni (more than a half of the total anthropogenic emissions), while combustion of gasoline was the main source of for lead. There is a continuous reduction of heavy metal emissions in Europe during the last 40 years. Better knowledge of heavy metal sources, emissions, pathways, and fate in the environment, and progress in developing efficient emission control equipment has resulted in more efficient regulatory efforts to curb heavy metal emissions from anthropogenic sources very substantially. There is a potential for further reduction of these emissions until the year 2010 up to about 40% for As, Cd, Cr, and Ni and about 57% for Pb, as estimated within various emission scenarios presented in the paper.     

Recent trends and projections of primary NO2 emissions in Europe

An assessment of recent trends in primary NO₂ emissions has been carried out for ten case study locations across the European Union. Estimates of the percentage of NO_x from road traffic emitted as primary NO₂ (f-NO₂) have been derived for 1995, 2000 and 2005 by combining the results of a literature survey of primary NO₂ emission factors for different vehicle types and technologies with an emission inventory. Estimates of f-NO₂ have also been derived from ambient monitoring data at roadside sites in each case study location using a model.The results of the analysis of trends show that f-NO₂ has increased in recent years and that the rate of increase has been greatest since 2000. f-NO₂ has increased from 8.6% in 2000 to 12.4% in 2004 as an average across the monitoring sites and from an average of 6.3% in 2000 to 10.6% in 2005 as an average of the emission inventory based calculations for the case study countries. f-NO₂ is predicted to increase further to an average of 19.6% in 2010 and 32.0% in 2020 as a result of the further penetration of exhaust after treatment technologies for diesel vehicles in the fleets. This increase is expected to be offset by the large reduction in NO_x emissions over this period, resulting in an increase in NO₂ emissions from road traffic to 2015, followed by a decline to close to 2004 levels by 2020. Estimates of future ambient NO₂ concentrations have also been calculated for the roadside monitoring sites included in the study. At 29 out of 45 of these sites the annual mean NO₂ limit value is predicted to be exceeded in 2010. At 22 of these sites, the annual mean concentration is expected to remain above the limit value until 2020 and beyond.     

The contribution of reactive carbon emissions from vegetation to the carbon balance of terrestrial ecosystems

From November 1998 to October 2000, measurements of soil respiration were performed on the Spanish plateau for two patches of non-irrigated barley, one managed with conventional tillage (CT) and the other with reduced tillage (RT). Soil CO2 flux showed seasonal variation on both patches, with an increase from March to October, peaking in May, and a decrease during the winter period by a factor of around 2. The mean value for both combined years was 2.03 and 1.70 micromol m(-2) S(-1), in the CT and RT patches, respectively. In order to analyse the influence of RT on soil CO2 flux, two tests were performed. The first one was the Kruskal-Wallis test to compare whether the differences between the medians in both patches were statistically significant. The results obtained revealed statistically significant differences during the second year, at a 85% and 95% significance level, use being made of annual data and that recorded during the period of maximum interest, March-October, respectively. The decrease in soil respiration in the RT patch was around 24%. The second test was aimed at describing and comparing the influence of soil temperature on soil CO2 flux. By using the data of both patches recorded during the first year, an empirical equation on 10-cm soil temperature was fitted and tested on the data corresponding to the second year in each of the patches. Then, a comparison between the medians of the differences between the estimated and observed values was again performed by means of the Kruskal-Wallis test. The over-prediction of the model in the RT patch, statistically significant at a 90% significance level, was roughly 23%, confirming again the decrease in soil respiration one year after this agricultural management practice had been implemented.     

Quantifying emissions of primary biological aerosol particle mass in Europe

Atmospheric concentration measurements of tracers for primary biological aerosol particles (PBAPs) have been used to obtain estimates of their release into the atmosphere. Emission flux data of surrogate compounds, for which concurrent concentration measurements were available, were used to quantify the release of PBAPs as PM₁₀ mass. Results indicate fungal spores to be the most important contributors. One other main source is plant debris. Area-based emission rates of 24 kg km^?2 and year (range 6–90) have been assessed. Results scaled for Europe indicate a contribution of PBAPs to PM₁₀ concentrations in the low percentage range, with a maximum in summer when concentration levels are small. This is consistent with the range of measurements. Despite of the large uncertainties, results contribute to clarify the potential contribution of biological particles to global load of particle mass.     

Seasonal variability in CH4 emissions from a landfill in a cool, semiarid climate

Methane exchange with the atmosphere was measured during three seasons at the Rooney Road landfill in Jefferson County, CO. Substantial spatial and temporal variability in exchange rates were observed. Mean fluxes to the atmosphere were 534, 1290, and 538 mg CH4/m2/day, respectively, in the fall of 1994, winter of 1994-1995, and summer of 1995. Median fluxes were 12.42, 8.62, and 5.65 mg CH4/m2/day, respectively, during those seasons. Forty-three of 177 measurements had small negative fluxes, suggesting methanotrophic activity in the landfill cover soils. Despite probable methanotrophic activity in cover soils, landfills without gas collection systems may emit substantial CH4 to the atmosphere, with large spatial and seasonal variability.     

The impact of NOx,CO and VOC emissions on the air quality of Zurich airport

To study the impact of emissions at an airport on local air quality, a measurement campaign at the Zurich airport was performed from 30 June 2004 to 15 July 2004. Measurements of NO, NO₂, CO and CO₂ were conducted with open path devices to determine real in-use emission indices of aircraft during idling. Additionally, air samples were taken to analyse the mixing ratios of volatile organic compounds (VOC). Temporal variations of VOC mixing ratios on the airport were investigated, while other air samples were taken in the plume of an aircraft during engine ignition. CO concentrations in the vicinity of the terminals were found to be highly dependent on aircraft movement, whereas NO concentrations were dominated by emissions from ground support vehicles. The measured emission indices for aircraft showed a strong dependence upon engine type. Our work also revealed differences from emission indices published in the emission data base of the International Civil Aviation Organisation. Among the VOC, reactive C₂–C₃ alkenes were found in significant amounts in the exhaust of an engine compared to ambient levels. Also, isoprene, a VOC commonly associated with biogenic emissions, was found in the exhaust, however it was not detected in refuelling emissions. The benzene to toluene ratio was used to discriminate exhaust from refuelling emission. In refuelling emissions, a ratio well below 1 was found, while for exhaust this ratio was usually about 1.7.     

Regime-dependent effect of tourism on carbon emissions in the Mediterranean countries

Environmental Science and Pollution Research - This study aims to test the effects of the number of tourist arrivals and tourism receipts on carbon emissions for the Mediterranean countries. The...