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

ARTICLE IN PRESS

Atmospheric Environment 41 (2007) 4148–4160 www.elsevier.com/locate/atmosenv

Compilation of a database on the composition of anthropogenic VOC emissions for atmospheric modeling in Europe J. Theloke, R. Friedrich Institute of Energy Economics and the Rational Use of Energy (IER), Universita¨t Stuttgart, Hessbruehlstr. 49a, D-70565 Stuttgart, Germany Received 2 June 2006; received in revised form 20 November 2006; accepted 8 December 2006

Abstract 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 highsolid 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. r 2007 Elsevier Ltd. All rights reserved. Keywords: VOC species profiles; Atmospheric modeling; CTM; Anthropogenic emissions; Traffic; Solvent use; Combustion processes; Production processes

1. Introduction

Corresponding author. Tel.: +49 711 685 878 56;

fax: +49 711 685 878 73. E-mail address: [email protected] (J. Theloke). 1352-2310/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.atmosenv.2006.12.026

Volatile organic compounds (VOCs) represent an inhomogeneous substance category; its numerous substances cause various impacts. They are responsible for the increase in ground-level ozone concentrations during sunny summer periods and also for the formation of secondary organic aerosols

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(Finlayson-Pitts and Pitts, 1999). Furthermore, they contribute to the depletion of stratospheric ozone and to the enforcement of the greenhouse effect. Some components have a carcinogenic, teratogenic or mutagenic character (Wickert et al., 2000). A number of regulations, e.g. various directives of the European Commission, are in force or currently prepared to limit as well the emissions of VOCs as the concentration of secondary pollutants, for example ozone. Especially owing to the highly non-linear relationship between emissions of VOCs and concentrations of secondary pollutants in the atmosphere, the use of atmospheric dispersion models (CTMs) is necessary for identifying air pollution control strategies and policies, e.g. efficient abatement strategies or action plans, that lead to a fulfilment of thresholds. These models include a chemical model, which simulates the chemical transformation of the different VOC species. Owing to limited computer calculation capacity the transformation of the hundreds of different species is not treated separately in the chemistry models; instead individual VOC species are aggregated to groups, their reactivity being a main parameter for the allocation of the single species to these groups. Especially Stockwell et al. (1997) developed a species aggregation method for the regional atmospheric chemistry model (RACM). Other quite often used chemical mechanisms are CBMIV (Gery and Whitten, 1989), Euro-RADM (Stockwell and Kley, 1994), RADM II (Stockwell et al., 1990), EMEP (Simpson, 1992), SAPRC (Carter, 1990, 2000), MELCHIOR (Lattuati, 1997) and the master chemical mechanism (MCM) (Saunders et al., 2003; Jenkin et al., 2003; Pilling et al., 2002). It is clear that for operating an atmospheric dispersion model, VOC emissions species resolution into classes according to its chemical mechanism are needed. Generally, these data are provided by taking total VOC emissions for the different emission source categories from existing emission inventories and then applying VOC species profiles that express the share, which the different VOC classes have on total VOC. These VOC species profiles are more or less characteristic for the different source categories. Of course, as atmospheric dispersion models are in use, such profiles exist and are applied. However, the profiles used are commonly not published at all or are published only in internal reports; the origin of the data especially is not documented. Thus, there is a need for documented VOC species profiles and it is the objective of this study to provide these.

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Previous publications of VOC species profiles include works of Stockwell et al. (1990) and Middleton et al. (1990) for the United States and Orthofer et al. (1991) for Austria. Derwent et al. (1996) published an entire VOC species resolution for the UK. However, the breakdown for emission sources is missing; thus, it cannot be used for scenario calculations with varying shares of different source categories and fewer substances (about 100) were considered than in the present publication. Orthofer et al. (1991) published a VOC species resolution for Austria aggregated to eight reactivity categories, which, however, does not contain some newer results. The same applies for Stockwell et al. (1990) and Middleton et al. (1990). Here, the species resolution refers to the USA. McInnes (1996) does not consider all emission source groups and the species resolution is not very detailed for many emission source groups. Passant (2002) has compiled a very detailed single-species resolution for many source groups for UK. The objective of this publication is to present the results of a compilation of VOC 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. 2. Approach/method In the following, species profiles for 87 emission source categories are presented. These emission sources cover all relevant anthropogenic sources of non-methane volatile organic compounds (NMVOC). To generate these data, information about results of measurements of VOC species were systematically collected and analysed, so that the presented species profiles represent the current state of knowledge. As far as possible, the VOC profiles that have been generated resolved into 306 single species or species classes. As available results of VOC species resolution measurements are very limited, in many cases information was available only from one country, e.g. Germany, Austria (Orthofer et al., 1991) or the UK (Passant, 2002). Given the common market within the EU, we nevertheless assume that the species resolution presented here can be applied for all EU member countries. The origin of the data that have been used to prepare the VOC species profiles is described for the

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different source categories in the following paragraphs. The different emission sources can be distinguished into four main categories:

   

Transport Solvent use Production and storage processes Combustion processes.

These main categories are further subdivided to 87 subcategories, which can be assigned to specific new format for reporting (NFR) codes (defined by convention on long-range transboundary air pollution (CLRTAP) (TFEIP, 2002) and to SNAP97 codes defined by (CORINAIR, 1998) (Table 1). 2.1. Transport The species resolution of VOCs for road transport substantially relies on measurements conducted by Schmitz et al. (2000) and Hassel et al. (2000). The composition of VOC emissions of common road vehicles with different engines has been measured, including diesel engines and gasoline engines with and without three-way catalytic converter. Five identical vehicles were measured on a chassis

dynamometer under conditions according to USTEST 75 and a highway test developed by the TU¨V Rheinland (Schmitz et al., 2000; Hassel et al., 1999). The species composition of the emissions alters towards reactive individual substances with increasing speed. Schmitz et al. (2000) and Hassel et al. (1999) have measured hydrocarbons and oxygen containing VOCs with different methods. The species composition of the emissions from vehicles with unregulated catalytic converter is based on Patyk and Ho¨pfner (1995). Data on the species resolution of VOC emissions from two-stroke and LPG engines originate from Veldt (1992). For air transport, the species resolution of the emissions from the LTO cycles was extracted from McInnes (1996), while data on gasoline evaporation was taken from Obermeier (1995). 2.2. Solvent use In comparison to older studies the species resolution of emissions from solvent use was significantly improved; the procedure and assumptions are described in detail in Theloke et al. (2000). Mainly information from literature, industrial associations and expert knowledge was used,

Table 1 Assignment of source groups numbered in this publication to SNAP97 and NFR codes Number

Source group

SNAP

NFR codes

1

Vehicles gasoline without catalyst, highway

1A 3 b

2

Vehicles gasoline without catalyst, rural

3

Vehicles gasoline without catalyst, urban, warm phase

4

Vehicles gasoline without catalyst, urban, cold start phase

5

Vehicles gasoline with three way catalyst, highway

6

Vehicles gasoline, with three way catalyst, rural

7

Vehicles gasoline with three way catalyst, urban, warm phase

8

Vehicles gasoline with three way catalyst, urban, cold start phase

070101 070201 070301 070102 070202 070302 070103 070203 070303 070103 070203 070303 070101 070201 070301 070102 070202 070302 070103 070203 070303 070103 070203 070303

1A 3 b

1A 3 b

1A 3 b

1A 3 b

1A 3 b

1A 3 b

1A 3 b

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Table 1 (continued ) Number

Source group

SNAP

NFR codes

9 10

Vehicles gasoline with catalyst Vehicles diesel, highway

1A 3 b 1A 3 b

11

Vehicles diesel, rural

12

Vehicles diesel, urban, warm phase

13

Vehicles diesel, urban, cold start phase

14 15 16 17 18 19 20

Vehicles two stroke, highway Vehicles two stroke, rural mode Vehicles two stroke urban mode, warm phase Vehicles two stroke urban mode, cold start phase Vehicles liquified petrol gas (LPG) Aircraft commercial and public Paint application

21

Paint application for constructions and buildings and domestic use

22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50

Metal degreasing Dry cleaning Electronic component manufacturing Other industrial cleaning Polyester processing Polyvinychloride processing Polyurethane processing Polystyrene foam processing Rubber processing Pharmaceutical products manufacturing Paints and inks manufacturing Glues manufacturing Asphalt blowing Adhesives manufacturing Magnetic tapes manufacturing Photographs manufacturing Textile finishing and leather tanning Other chemical manufacturing Printing industry Domestic solvent use Application of glues and adhesives Preservation of wood Underseal treatment and conservation of vehicles Vehicles dewaxing Plant protectives—solvent use Cooling lubricants and other lubricants Concrete additives Other propellants Glas and mineral wool enduction

51

Fat, edible and non edible oil extraction

0701 070101 070201 070301 070102 070202 070302 070103 070203 070303 070103 070203 070303 0704, 0705 0704, 0705 0704, 0705 0704, 0705 0704, 0705 0805 060101, 060102, 060105, 060106, 060107, 060108 and 060109 060103, 060104 060201 060202 060203 060204 060301 060302 060303 060304 060305 060306 060307 060309 060310 60311a 60311b 60311c 060312 060314 060403 060408 060405 060406 060407 060409 060412 060412 060412 060412 060401 060402 060404

1A 3 b

1A 3 b

1A 3 b

1A 1A 1A 1A 1A 1A 3A

3A 3B 3B 3B 3B 3C 3C 3C 3C 3C 3C 3C 3C 3C 3C 3C 3C 3C 3C 3D 3D 3D 3D 3D 3D 3D 3D 3D 3D 3D 3D

3 3 3 3 3 3

b b b b b a ii

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Source group

SNAP

NFR codes

52 53 54 55 56 57 58 59

Domestic use of pharmaceutical products Paint remover De-icing and tobacco production Universities and scientific laboratories Gasoline evaporation Refinery processing Gas distribution Coal combustion

060411 060412 060412 060412 0706 040104 0506 01;02;03

60 61 62 63 64

Wood combustion Oil combustion Gas combustion Coking plant Bread manufacturing, beer brewery, wine manufacturing, Fermentation of bread

65 66 67

Sugar manufacturing Chemical production Ethene and propene production

68 69

Chlorethane and -ethene Polyethylene production

70 71 72 73 74 75 76 77 78 79

Polyvinylchloride production Polypropylene production Styrene production Polystyrene production Styrene/butadiene production ABS production Ethylbenzene production Acrylnitril production Wood pressboard Paper manufacturing

80 81

Metal foundry Road asphalt Batch mix/hot mix Gas-fired

82

Road asphalt batch mix/hot mix oil fired

83

Road asphalt drum hot mix gas-fired

84

Road asphalt drum hot mix oil-fired

85 86 87

Asphalt blowing Methane sources Methanol store

01;02;03 01;02;03 01;02;03 0104 040605 040606 040407 040608 040625 0405 040501 040502 040505 040506 040507 040508 040509 040510 040511 040512 040515 040518 040520 040601 040602 040604 0402 040610 040611 040610 040611 040610 040611 040610 040611 060310 0503 040522

3D 3D 3D 3D 1A 3 b 1B 2 a 1B 2 b 1A 1, 1A 1A 4, 1A 1A 1, 1A 1A 4, 1A 1A 1, 1A 1A 1c 2D 2

especially Bra¨utigam and Kruse (1992) (paint application and manufacture of paints, underseal treatment and conservation of vehicles, domestic solvent use), Theloke et al. (2000) (antifreeze agents), Theloke (2005) (preservation of wood, concrete additives, glass and mineral wool enduction, vehicles dewaxing, polyester processing, poly-

2 5 2 5 2

2D 2B 5 2B 5 2B 5 2B 5 2B 5 2B 5 2B 5 2B 5 2B 5 2B 5 2B 5 2B 5 2D 1 2D 1 2C 2A 5 2A 5 2A 5 2A 5 3C 1B 2b 2B 5

vinylchloride processing, pharmaceutical products manufacturing, plant protective application, antifreeze agents, domestic solvent use, magnetic tapes manufacturing, films and photographs manufacturing, degreasing, application and manufacturing of glues and adhesives), Berner et al. (1996) (degreasing), BUWAL (1995), Hohenstein et al. (1996) (dry

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cleaning), Jepsen et al. (1999) (printing applications, inks manufacturing), Jepsen et al. (2004) (inks manufacturing), VCI (1997) (inks manufacturing), Baumann and Rothardt (1999) (inks manufacturing), EEA (1996) (fat, edible and non edible oil extraction), LBA (1993) (universities and scientific research facilities), Marti (1999) (polystyrol processing), DECHEMA (1997) (degreasing), Obermeier (1995) (domestic solvent use, antifreeze agents) and O¨ko et al. (1999) (degreasing, paint removing). Based on the study of Rudd and Marlowe (1998), the substantial resolution of the substance categories ‘white Spirit’ and ‘solvent naphtha’ (light and heavy) was significantly improved. A comparison of the domestic solvent consumption aggregated to chemical substance categories with data from the solvent industry showed consistency (Theloke et al., 2001). Despite these improvements, the individual species resolution of solvent emissions remains subject to large uncertainties, since it is difficult to get satisfying data from industry due to confidentiality reasons. As a consequence, for some categories rather old VOC species resolution have been updated by using expert estimations on recent trends (such as from aromatic solvent paints systems to aromatic-free solvent paint systems). 2.3. Production and storage processes Different publications were used for the species resolution of VOC emitted from the following production processes. The species resolution of VOC emissions from chemical production, ethylbenzene production, acrylnitrile production, paper manufacturing, ethene and propene production, chlorethane and ethane production, polyethylene production, polyvinylchloride production, polypropylene production, styrene production, polystyrene production, styrene/butadiene production, ABS production, road asphalt batch mix/hot mix gasfired, road asphalt batch mix/hot mix oil fired, road asphalt drum hot mix gas-fired, road asphalt drum hot mix oil-fired and asphalt blowing, were extracted from McInnes (1996). The species resolution of VOC emissions from metal foundries bears on Obermeier (1995). The species resolution of emissions from bread manufacturing, beer brewery, wine manufacturing, fermentation of bread, sugar manufacturing, wood pressboard manufacturing, methane sources, and methanol store bases on Obermeier (1995).

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2.4. Combustion processes For the species resolution of combustion processes a distinction between the different fuel types coal, wood, oil and gas combustion are provided. The species resolution of coal, oil and gas combustion processes is based on Derwent (2001), for wood combustion processes it is based on Fritsche et al. (1992). Species resolution of emissions from gas distribution was based on Obermeier (1995). 3. Results The resulting VOC species profiles for 87 different emission sources are available as an electronic supplementary table to this article. The figures in the table represent the share of the total VOC emissions of each category in %, which consists of the respective species. 3.1. Speciation of emissions on the example of Germany If the profiles contained in the electronic supplemented table are applied, e.g. for Germany, a distribution into species classes results as shown in Fig. 1. About half of the VOC emissions in Germany 1998 were aliphatic and aromatic hydrocarbons. For oxygen-containing VOCs alcohols, especially isopropanol, is the main fraction. The rest consists of alkenes, esters, glycol derivates, aldehydes and ketones, to a smaller part also alkynes and halogenated hydrocarbons. About 3% of the emissions could not be allocated. The emissions amounted to 1,761,700 t a 1 in total in 1998 in Germany (UBA, 2000). Different emission sources have quite different species profiles. To illustrate this, the following figures show the species profiles for the most important source categories, namely solvent use (55% of total emissions), transport (37%), stationary combustion (4%) and production processes (4%). Fig. 2 shows the share of the VOC classes on the VOC emissions from the sector solvent use in 1998. Twenty eight percent of the emissions are alkanes, 24% alcohols and 22% aromatics. Furthermore, esters (9%), glycol derivates (7%), ketones (6%), halogenated hydrocarbons (1%), ethers (1%), terpenes (1%), as well as small amounts of organic acids, aldehydes, amines and amides, are contained. The VOC emissions from transport (mainly road transport) in Germany consisted in 1998

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ketones 3%

not allocated 3%

alkynes 1%

Halogenated hydrocarbons Carbonic acids 1% 0.04%

aldehydes 4% alkanes 33%

glycol derivates 4% esters 5%

alkenes 8%

aromatics 23%

alcohols 14%

Fig. 1. Speciation of the anthropogenic VOC emissions from all sectors into substance classes for Germany 1998 (total 1,761,700 t a 1).

ethers 1.3 %

halogenated hydrocarbons 1.3%

not allocated 2.2 %

alkenes Carbonic acids 0.1 % 1.1 % alkynes 0.02% aldehydes 0.02%

ketones 6% glycol derivates 7%

alkanes 28 %

esters 9%

aromatics 22 %

alcohols 24 %

Fig. 2. Speciation of the VOC emissions from solvent use into substance classes in Germany 1998 (Theloke et al., 2001) (total: 973,578 t a 1).

mainly of alkanes (41%), aromatics (27%) and alkenes (16%) (Fig. 3). Stationary combustion processes in Germany 1998 lead to the emission of 37% aromatics, 29% alkanes, 19% alkenes and 8% aldehydes (Fig. 4).

Fig. 5 shows the VOC emissions from production processes, which turns out to be a very heterogeneous source group compared with the other source categories. Important production processes are, for instance, bread manufacturing,

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not allocated 3%

alkynes 3%

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ketones 1%

aldehydes 9% alkanes 41% alkenes 16%

aromatics 27%

Fig. 3. Speciation of the VOC emissions from transport in Germany 1998 (UBA, 2000) (total: 650,566 t a 1).

alkynes 4%

ketones 2%

not allocated 1%

aldehydes 8% aromatics 37%

alkenes 19%

alkanes 29%

Fig. 4. Speciation of the VOC emissions from stationary combustion in Germany 1998 (UBA, 2000) (total: 70,879 t a 1).

ethylene production and synthetics production. About 31% consists of alkanes, 29% of alcohols and 15% of alkenes. Furthermore, aromatics (5%), aldehydes (4%) halogenated hydrocarbons

(3%), ethers (2%), ketones (0.2%) and small amounts of alkynes have been emitted; 11% of the emissions from production processes could not be attributed.

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aldehydes 4%

halogenated ethers ketones alkynes 0.2% hydrocarbons 2.4% 0.03% 2.7%

aromatics 5%

alkanes 31%

not allocated 11%

alkenes 15%

alcohols 29%

Fig. 5. Speciation of the VOC emissions from production processes to substance classes in Germany 1998 (UBA, 2000) (total: 66,677 t a 1).

Obviously, the different source groups possess quite different species profiles or ‘finger prints’. Combustion processes typically emit pure hydrocarbons and in addition oxygen containing compounds, e.g. aldehydes. Solvents consist of other oxygen containing VOC groups like alcohols, esters, glycol derivates and ketones. In addition, the pure hydrocarbons in solvents are different from those in exhaust or flue gases, as they, on the average, usually possess more carbon atoms. Production processes are a very inhomogeneous group of processes with many different VOC species profiles. 4. Uncertainties The uncertainty of the reported species profiles data is quite large. For transport emission sources, the VOC species resolution rely on measurements; however, the number of measured vehicles are very few. For combustion-, process- and productionrelated emission sources, the uncertainties are caused owing to the relative small number of available measurement data compared with the large number of individual emission sources. The species resolution of VOC emissions emitted in vaporisation processes and from solvent use is usually based on the knowledge of the composition

of the used solvents. It has to be taken into account that there is a variety of different VOC compositions in the different available solvent containing goods, depending on the application. To a certain part, the composition of organic solvents depends on seasonal differences. Fortunately, the very large uncertainty of the share of single species is reduced when species are aggregated to classes. To assess the uncertainties, ideally a statistical analysis should be carried out. However, the number of measurements is generally too small for this. Thus, uncertainty estimations have to be based on expert knowledge. Such expert estimates reveal that the uncertainty of the species profiles have a similar order of magnitude than other sources of uncertainties in CTM models (e.g. meteorology, transport parameter, boundary layer conditions, chemical mechanisms, deposition, etc.). What can be done in addition is to compare generated emission data with measured ambient concentrations. However, such results would contain several reasons for uncertainties apart from those of the VOC species resolution. They are as follows:



Uncertainty of the emission estimate for total VOC.

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Uncertainties of the modelling of transport and chemical transformation from emission to measurement site. Measurement uncertainties. Uncertainty for a species resolution into single species and not species classes as selected single species are measured.

Nevertheless, in the following we show two results of such comparisons, as these give an impression of the overall uncertainty for modelling VOC species concentrations and thus a sort of upper limit for the uncertainties of the VOC species profiles. Results from two evaluation experiments in Augsburg (EVA: Evaluierungsexperiment Augsburg) Ku¨hlwein et al. (2002), Mannschreck (2000), Friedrich and Reis (2004) and Paris (ESQUIF: Etude et Simulation de la QUalitE` de l’air en Ile de France) (Vautard et al., 2003) are shown. The EVA experiment was carried out in March and October 1998, ESQUIF in summer 1999. In both studies, the VOC species profiles published in this article have been used. The results of these evaluation experiments are shown in Figs. 6 and 7. In both figures the ratios of modelled to measured ambient concentrations of various species are shown. Fig. 6 shows species, where lower discrepancies between measured and modelled concentration of up to a factor of 2 occur. Only for propane the ESQUIF-experiment revealed a larger difference (factor 3). One reason for that could be the

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underestimation of the emissions from liquid petrol gas heating activities. Fig. 7 shows species, where in the EVA experiments higher discrepancies occured; however, in the ESQUIF experiment the considered VOC species are in same magnitude as in Fig. 6 (up to a factor of 2). Larger ratios between modelled and measured ambient air concentrations have been found in the EVA experiment, especially for the components ndecane and n-nonane caused mainly by the use of white spirits as solvents. The components propylbenzene and 1,3,5-trimethylbenzene originate partly from white spirits, and also from traffic activities. The reasons for this considerable discrepancies could not be explained until now. The differences above are caused as well from the estimation of the total NMVOC emissions as from the species resolution; thus, the uncertainties of the species resolution are lower. Furthermore, the species resolution for combustion seems to be less uncertain than the species resolution for solvent use.

5. Conclusions and outlook VOC species profiles for 87 emission source categories have been compiled for use in atmospheric dispersion models. These species profiles distribute total VOC emissions of anthropogenic VOC sources. The underlying data base can be used for all chemical mechanisms as well. The profiles have been generated using recent measurements and

i-Pentane n-Octane Ethylbenzene Propene Propane 2-Methylpentane Benzene 3-Methylpentane Ethene 2-Methylhexane 3-Methylhexane n-Heptane Ethine Ethane 2.3-Dimethylpentane

ESQUIF EVA

0.1

0.5

1

2

10

(HCi/CO)modelled / (HCi/CO)measured Fig. 6. Results of the city experiments in Augsburg, Germany (EVA), Ku¨hlwein et al. (2002) and Paris, France (ESQUIF), Vautard et al. (2003).

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n-Decane ESQUIF

n-Nonane

EVA

Propylbenzene 1,3,5-TMB n-Hexane n-Butane o-Xylene 1,2,4-TMB Toluene n-Pentane i-Butane m/p-Xylene 0.1

0.5

1 2 10 (HCi/CO)modelled / (HCi/CO)measured

100

Fig. 7. Results of the city experiments in Augsburg, Germany (EVA), Ku¨hlwein et al. (2002) and Paris, France (ESQUIF), Vautard et al. (2003).

studies on VOC species. The results can be used to create input data for atmospheric dispersion models in Europe. In fact, the species profiles have already been used for a large number of model applications and other purposes, e.g. in the city experiment in Augsburg, Germany (EVA), Ku¨hlwein et al. (2002) and Paris, France (ESQUIF), Vautard et al. (2003), in Pregger et al. (2000, 2001, 2004), and last but not least in a bibliographic study concerning the speciation of VOC within the project INTERREG III for the Rhine valley, Sambat et al. (2005). In addition, the species resolution has been provided for the CTM’s CHIMERE, EURAD, and EMEP. The emission source profiles, especially those for solvent use, still show large uncertainties. There is a need for further measurements to achieve an improved species resolution. In addition, the solvent use directive (VOC Directive, 1999) and the DECOPAINT directive (DECOPAINT, 2004) 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 for solvents use will change drastically in the next years. Appendix A. Supplementary Materials Supplementary data associated with this article can be found in the online version at doi:10.1016/ j.atmosenv.2006.12.026.

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