Environ. Sci. Technol. 2001, 35, 1982-1988
Design of an Inventory System for the Volatile Organic Compounds Emitted by Various Activities ARGYRO LAGOUDI, EURIPIDES LOIS,* KOSTAS FRAGIOUDAKIS, ALEXANDROS KARAVANAS, AND MARIA LOIZIDOU Chemical Engineering Department, National Technical University of Athens, 9 Heroon Polytechniou, 15773, Athens, Greece
In this study an inventory system was designed which fulfills the reporting requirements of the current European Union legislation for air emissions. Given the reporting requirements deriving from the EU Directives, International Conventions, and Inventory Methodologies developed at the EU level, there are significant differences in the required data in terms of industrial categories, definitions of point and area sources, whether TVOC or individual species must be determined, and expression of VOCs emissions. On the basis of this concept, an inventory system was structured that aims to comply with the framework set by the European Union for the evaluation of VOCs emissions from industrial activities and other facilities in Greece. This inventory can be very helpful to all the EU members states, as well as the Eastern European countries that are in pre-accesion phase, who must implement the European legislation concerning VOCs emissions.
Introduction The investigation of volatile organic compounds (VOCs) emissions in the atmosphere is of great interest. This interest is because of the great variety of VOCs existing in the atmosphere in high concentrations (1, 2) which can cause serious impacts on the environment and public health. These compounds play an important role in many environmental problems including depletion of the stratospheric ozone, formation of ground-level photochemical ozone, and enhancement of the global greenhouse effect. Also, they can cause serious health effects by presenting toxic, carcinogenic, mutagenic, or neurotoxic actions, which vary depending on the individual organic compounds (3, 4, 5). The significant problems induced by VOCs emissions led the European Union (EU) to take action against the release of VOCs in the atmosphere. Within this context, one of the priorities at the EU level, as well as worldwide, is the evaluation, prevention, and control of VOCs emissions from certain activities. The European Commission has issued Directive 94/63/EC “for the control of volatile organic compounds emitted from storage and transfer of gasoline in oil terminals and oil service stations”, which aims at 80% reduction of emissions from oil terminals within the next seven years. Also, the EU has issued Directive 99/13/EC on “the limitation of emissions of volatile organic compounds due to the use of organic solvents in certain activities and * Corresponding author phone: + (30 1) 7723 190; fax: +(30 1) 6197 750; e-mail:
[email protected]. 1982
9
ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 35, NO. 10, 2001
installations”, which deals with the control of volatile organic compounds emitted from industries that use solvents. The aim of this directive is to prevent or minimize the direct and indirect effects of the emissions of volatile organic compounds to the environment, and the potential risks to public health. According to this directive, member states are obliged to determine VOCs emissions from certain industrial activities and ensure that the operators of the industrial activities comply with the emission limits set in this directive. Moreover, Directive 96/61 “concerning integrated pollution prevention and control (IPPC)” provides the implementation of an inventory concerning VOCs emissions for the activities included in the provisions of this directive with high VOCs emissions. The European Commission has issued Decision 2000/479/EC on the implementation of a European Pollutant Emission Register (EPER) according to Article 15 of Council Directive 96/61/EC concerning integrated pollution prevention and control, and issued a related Guidance Document including implementation guidelines to the member states (6). The “Protocol to the 1979 Convention on long-range transboundary air pollution concerning the control of emissions of volatile organic compounds or their transboundary fluxes” (Geneva Protocol 1991), which was developed under the UN/ECE Long-Range Transboundary Air Pollution Convention, aims at the control and reduction of national VOCs emissions in order to reduce their transboundary fluxes and the fluxes of the resulting secondary photochemical oxidant products so as to protect human health and the environment from adverse effects (7). Also, the Protocol to Abate Acidification, Eutrophication, and Ground Level Ozone developed at Gothenburg (Sweden) in 1999, provides for the reduction of VOCs emissions from the industrial activities using solvents. The provisions of this Convention are similar to those of Directive 99/13/EC. Therefore, Greece (as well as all the other European member states and the European countries that are in preaccession phase) is obliged to implement an inventory concerning VOCs emissions from the industrial activities included in the IPPC Directive that emit VOCs, the activities using solvents, and the activities dealing with the transport and storage of gasoline, and to develop a national strategic plan aimed at reducing VOCs emissions based on the provisions of the Directives 96/61/EC, 99/13/EC, and 94/63/EC. The lack of reliable data in Greece concerning VOCs emissions (as well as the necessity for the design of an integrated inventory system that will combine the inventory needs concerning VOCs required by the European legislation and International Conventions) led the Hellenic Ministry for the Environment, Physical Planning and Public Works, to set up a project to design an integrated VOCs emissions inventory, and also to provide instructions for the implementation of the inventory. The design of the inventory is presented in this paper. Design of an inventory system requires analysis of the current inventory methodologies used, taking into account that the data extracted from a national inventory system can be used to report to international and European statistical services and agencies, if they are compatible with the reporting requirements of these agencies. Several European and international organizations have structured inventory programs, providing methodologies for the determination of VOCs emissions at a national level. The major activities that have been organized for the collection of air emissions data (including VOCs emissions) are UNECE - EMEP (United 10.1021/es000051w CCC: $20.00
2001 American Chemical Society Published on Web 04/17/2001
Nations Economic Commission for Europe - Cooperative Program for Monitoring and Evaluation of the Long Range Transmission of Air Pollutants in Europe) and CORINAIR developed by the European Environmental Agency (EEA) (in particular, the European Topic Centre on Air Emissions) which aim to cover the needs for reporting on the state of the environment in Europe, and to provide information for the Long-Range Transboundary Air Pollution Convention (LRTAP) and the Framework Climate Change Convention (IPCC) (8-13). Under the cooperation of the two major inventory programs, CORINAIR and EMEP, the Atmospheric Emission Inventory Guidebook (14) was produced to provide information for reporting on the LRTAP Convention, EMEP, and CORINAIR (EEA). The nomenclature used by this guidebook is also compatible with that of the IPCC Program. Finally, U. S. EPA has developed a methodology for the inventory of VOCs emissions, although it must be mentioned that the U. S. legislation differs significantly from the EU legislation, and therefore the requirements given by EPA do not apply in European countries (15). The main problem of these inventories was the lack of compatibility in the reporting data collected, as there were significant differences in terms of substances, source sectors, geographical coverage, and resolution. In this study, an inventory system was designed to take into account all the reporting requirements of the European Union legislation, as well as the inventory methodologies used for the evaluation of the state of the environment in Europe. This inventory system will be very helpful to all the EU members states, and the Eastern European countries in pre-accession phase that must implement the European legislation concerning VOCs emissions. Also, the inventory system will be of importance to environmental researchers because it will point out the information required for regulatory purposes and provide the best form of that information.
Design of the Inventory System The design of the inventory system was based on a suitable combination of the reporting requirements deriving from the European Union Legislation concerning industrial VOCs emissions (94/63/EC, 99/13/EC, 96/61/EC), taking into account the inventory methodologies that have been developed by European and International Organizations. Toward this direction, the formulation of an inventory system that will be accurate, applicable on a large-scale, dynamic, cost-effective, able to collect up-to-date data, and compatible with the requirements of the EU legislation was attempted. This system includes (1) determination of the point and area sources that must be inventoried; (2) collection of detailed information from the industrial units concerned, based on a combination of actions; (3) performance of measurements of VOCs emissions in a representative number of industries; (4) estimation of VOCs emissions using emission factors, mass balances, and process simulation software; (5) data handling; and (6) data input in a suitable database and geographic information system (GIS). To ensure the completeness and transparency of the inventory system, as well as its compatibility with other inventories, the main elements that must be designed and determined include the selection of the sources and VOCs that will be investigated, and the development of questionnaires, sampling and measurement methodology, calculation techniques, and a database system. Definition of Area and Point Sources. To define the area and point sources, the main parameters that must be taken into account are the desired accuracy of the VOC emissions estimations (according to the regulatory requirements), the importance of each source category according to the expected magnitude of emissions, and the available budget.
TABLE 1. Solvent Consumption Thresholds for Each Industrial Category Included in Directive 99/13/EC activity heatset web offset printing publication rotogravure other rotogravure, flexography, rotary screen printing, laminating/varnishing units rotary screen printing on textile/cardboard surface cleaning vehicle coating and refinishing coil coating other coating, including metal, plastic, textile, fabric, film and paper coating winding wire coating coating of wooden surfaces dry cleaning wood impregnation coating of leather footwear manufacture wood and plastic lamination, adhesive coating manufacture of coating preparations, varnishes, inks and adhesives rubber conversion vegetable oil and animal fat extraction and vegetable oil refining activities manufacturing of pharmaceutical products
amount (t/yr) >15 > 25 > 15 > 30 >1 > 0.5 > 25 >5 >5 > 15 _ > 25 > 10 >5 >5 > 100 > 15 > 10 > 50
An analysis of the objectives derived from the legislation requirements and inventory guidelines is given below. (1) The quantitative objectives of Directive 99/13/EC refer to individual activities using organic solvents. Therefore, to implement the provisions of this directive, it is important to collect data concerning the capacity of the individual activities and the VOCs emissions related to them. This directive applies to industrial activities that exceed an annual solvent consumption threshold, which is different for each individual industrial category. The industrial categories covered by this directive and their respective solvent consumption thresholds are presented in Table 1. (2) The quantitative objectives of the Directive 94/63/EC refer to the total annual loss of gasoline from individual terminals and service stations. Therefore, the collection of data concerning terminals and service stations must be performed on an individual basis. This directive applies to all new terminals and the existing terminals with a throughput exceeding 10,000 t/year, and service stations with a throughput exceeding 100 m3/year. (3) Directive 96/61/EC defines that all the activities that emit more than 100 t/year NMVOC must be inventoried individually, as well as all the activities that emit specific compounds. Table 2 presents the categories included in this directive that emit NMVOC based on the Guidance document for EPER (6) that are not included in the previous directives (99/13/EC and 94/63/EC). (4) According to the Atmospheric Inventory Guidebook and CORINAIR, point sources are considered those emitting more than 1000 t/year of TVOC. It is estimated that, on the basis of this definition, the number of industrial activities that can be considered as point sources will be very small for each country, if there are any, because the inventory threshold is significantly high. (5) The Geneva protocol 1991 refers to national emissions and therefore all sources are considered as area sources. (6) The Guidelines given by U.S. EPA for VOCs inventories propose to assume an industrial category as an area source and to use emission factors for the estimation of the VOCs emissions, when the emissions from this category are lower than 5% of the total VOCs emissions. VOL. 35, NO. 10, 2001 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
9
1983
TABLE 2. Activities Included in IPPC Directive (96/61/EC) Emitting NMVOC (the production capacity cutoff is given in parentheses) that Are Not Included in the Directive 99/13/EC Activities included in IPPC Directive emitting NMVOC not included in Directive 99/13/EC 1.2. Mineral oil and gas refineries 1.3. Coke ovens 2.1./2.2/2.4 Metal ore roasting or sintering installations, installations for the production of pig iron or steel including continuous casting (> 2.5 t/h) and ferrous metal foundries (> 20 t/ day) 2.5. Installations for the production of nonferrous metals and for the smelting of these metals (> 4 t/ day for lead and cadmium or > 20 t/day for all other metals) 3.1/3.3/3.4 Installations for the production of cement clinker (>500 t/day) or lime (>50 t/day) in rotary kilns or in other furnaces (>50 t/day), glass (20 t/day), mineral substances (> 20 t/ day) 4.1 Chemical installations for the production of basic organic chemicals 4.2. Chemical installations for the production of basic inorganic chemicals 4.6. Chemical installations for the production of explosives 5.2. Installations for the incineration of municipal waste (>3 tonnes/hour) 6.1. Industrial plants for the production of: (a) pulp from timber or other fibrous materials (b) paper and board (>20 t/day) 6.2. Plants for the pretreatment or dyeing of fibers or textiles (>10 t/day) 6.8. Installations for the production of carbon or electrographite
TABLE 3. Selected Industrial Categories code no.a
industrial category as classified by NSSG
154 171 173 183 191 201 202
manufacture of vegetable and animal oils and fats preparation and spinning of textile fibers finishing of textiles dressing and dyeing of fur/manufacture of articles of fur tanning and dressing of leather saw milling and planing of wood, impregnation of wood manufacture of veneer sheets/manufacture of plywood, lining-board, particle board, fiber board and other panels and boards manufacture of pulp, paper and paperboard manufacture of articles of paper and paperboard printing and service activities related to printing manufacture of refined petroleum products manufacture of basic chemicals manufacture of paints, varnishes and similar coatings, printing ink and mastics manufacture of pharmaceuticals, medical chemicals and botanical products manufacture of soap and detergents, cleaning and polishing preparations, perfumes and toilet preparations manufacture of other chemical products-photographic material manufacture of rubber products treatment and coating of metals; general mechanical engineering manufacture of machinery for the production and use of mechanical power, except aircraft, vehicle and cycle engines manufacture of television and radio transmitters and apparatus for line telephony and line telegraphy building and repairing of ships and boats manufacture of furniture
211 212 222 232 241 243 244 245 246 251 285 291 322 351 361 a
number of units 65 82 67 40 24 36 23 28 108 126 18 66 44 96 76 26 25 33 51 6 92 274
Code no. according to Industrial Classification of the National Statistical Service of Greece.
On the basis of the above-mentioned information, the activities that must be inventoried as point sources will be different for each sector. In particular the activities that must be considered as point sources are (1) all the industrial activities using solvents included in the categories given in Directive 99/13/EC and exceeding the solvent consumption thresholds given in this directive; (2) all the new terminals and the existing terminals with a throughput exceeding 10,000 t/year and service stations with a throughput exceeding 100 m3/year (Directive 94/63/EC); (3) all the activities covered by the Directive 96/61/EC, which are not included in the previous two directives and which emit more that 100 t/year NMVOC. The number of activities covered by this condition is expected to be small because the industrial activities included in this category are not the main VOC sources. Selection and Classification of the Sources that Must be Investigated. The main activities that contribute to the increase of VOCs concentrations in the atmosphere are the 1984
9
ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 35, NO. 10, 2001
industrial processes using solvents, as well as the storage and transfer of oil products. However, there are several other activities emitting VOCs that represent a small part of the total VOCs emissions. Taking into account that only the EU Directives provide an obligation for reporting data for each individual activity, the selection of the industrial categories to be surveyed was based on the activities defined in the Directives 99/13/EC, 94/63/EC, and 96/61/EC, and therefore the activities investigated were those presented in Tables 1 and 2 and gasoline terminals. In particular for Greece, the most important industrial sectors were classified on the basis of statistical data concerning the installations and activities operating in Greece. Table 3 presents the most important activities emitting VOCs emissions and the number of these units, taking into account mainly Directives 99/13/EC and 94/63/ EC, as well as the most important activities included in 96/ 61/EC that emit VOCs and that are found in Greece. Table
TABLE 4. Number of Small Scale Facilities in Each Area Source area source
gasoline stations
dry cleaning stores
Athens Piraeus Thessaloniki West Attiki East Attiki Patra Volos Larisa Heracleo Chania Kalamata Kavala Eleusina Ptolemaeda
332 380 299 279 355 78 51 88 60 47 33 25 43 21
923 511 399 361 269 81 59 53 51 34 31 24 24 13
4 presents the number of gasoline stations and dry cleaning stores in 14 selected areas of Greece. Determination of VOCs that Must be Evaluated. The number of VOCs that are emitted in the atmosphere has been found to be higher than 300, including aliphatic compounds, aromatics, aldehydes, ketones, esters, etc. Because of the fact that there are so many VOCs, the registration of all the VOCs emitted in the atmosphere is not economically and technically feasible (16-21). The most crucial problems induced by the emissions of VOCs are the creation of photochemical ozone and the cause of health effects. The VOCs that contribute to the creation of photochemical ozone have a significant indirect impact on human health. This is due to the fact that the individual VOCs, according to their photochemical ozone creation potential (POCP), participate in photochemical oxidation reactions with nitrogen dioxide in the atmosphere. These reactions result in the ozone formation, a pollutant with serious impact on human health, animals, and plants (22-24). On the other hand, several compounds cause significant health effects, although the impact of the majority of them is not yet defined. Specifically, a number of VOCs have been characterized as carcinogenic or mutagenic, including benzene and polycyclic aromatic hydrocarbons. Also, human exposure to several aromatic, aliphatic, and halogenated compounds, and aldehydes has been found to cause nasal and ocular irritations, effects on the central nervous system, allergic reactions of blood, and inspiration difficulties (25-28). It must be mentioned that there is a significant difficulty in the selection of the most important VOCs on the basis of their contribution to environmental problems, because the compounds that are of interest because of their toxic, carcinogenic, or mutagenic action are different from the compounds with high photochemical ozone creation potential. The investigation of VOCs emissions was based on the obligations imposed by the EU Directives for VOCs: (1) The reporting requirements of Directive 99/13/EC refer to the total mass of VOCs (TVOCs), whereas the individual organic compounds that must be evaluated are the compounds that are classified as carcinogenic, mutagenic, toxic (classified as R45, R46, R49, R60, or R61 according to Directive 67/548/EEC), and halogenated. (2) Directive 94/63/EC refers to the evaluation of the percentage of fugitive emissions of the total amount of stored or transferred product, and particularly to the determination of any gaseous compound which evaporates from gasoline. (3) In the Geneva Protocol, reporting requirements refer to TVOCs. However, according to the provisions of Article 2, highest priority must be given to the reduction and control
of emissions of substances with the greatest photochemical ozone creation potential (POCP). (4) According to Directive 96/61/EC, all the sources emitting NMVOC with a total mass of volatile organic compounds exceeding 100 t/year must be inventoried. Also, in cases where some specific organic compounds are emitted, an inventory must be performed for these specific compounds. On the basis of Commission Decision 2000/479/EC these compounds include 1,2-dichloroethane, dichloromethane, hexachlorobenzene, hexachlorocyclohexane, pentachlorophenol, tetrachloroethylene, tetrachloromethane, trichlorobenzenes, 1,1,1- trichloroethane, trichloroethylene, trichloromethane, and benzene. The concentration of VOCs can be calculated individually for each one of these compounds or as a total carbon. On the basis of a combination of the above-mentioned requirements, the inventory must include the following (1) Concerning terminals, determination of TVOC emissions expressed as fugitive emissions as a percentage of the total amount of stored or transferred product (2) Concerning industrial activities, determination of the total volatile organic emissions per point source which covers any organic compound having, at 293.15 K, a vapor pressure of 0.01 kPa or more, or having a corresponding volatility under the particular conditions of use (based on the definition given in Directive 99/13/EC). (3) Also, identification and determination of the most important compounds emitted from each activity in terms of their carcinogenic, mutagenic, toxic (R45, R46, R49, R60, R61), and halogenated character. Also, compounds presenting high photochemical ozone creation potential are of great interest. The individual compounds that must be examined are different for each industrial category, based on the compounds emitted by each activity. The most important VOCs emitted by each industrial category are presented in Table 5, classified according to their ozone formation and toxicity potential. The ozone formation priority of each compound is defined according to the classification of the Geneva Protocol (7), and the toxicity is classified according to the notifications of the European Union. Determination Methods. Following are the main classes for the determination of emissions that are used, based on the Guidance Document to EPER implementation (6). Class M: emission data that are based on measurements using standardized or accepted methods; often additional calculations are needed to convert the results of measurements into annual emission data. Class C: emission data that are based on calculations using nationally or internationally accepted estimation methods and emission factors, which are representative for the industrial sectors. Class E: emission data that are based on non-standardized estimations derived from best assumptions or expert guesses. The use of the first class (M) results in the most accurate method for the evaluation of VOCs emissions. However, in many cases there are no measuring data and therefore calculations must be used for the estimation of VOCs emissions. The use of estimations is acceptable for meeting the European Union obligations, assuming that these estimations are as accurate as possible. The most accurate calculation method for the determination of VOCs emissions from solvents used by industrial activities is the use of mass balances. Sampling and Measurements. Existing measuring data can be obtained for the industrial activities, and their accuracy can be validated by examining the measuring method used. Also, a representative number of industries will be investigated by performing measurements of VOCs emissions in order to use these data for the determination of VOCs VOL. 35, NO. 10, 2001 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
9
1985
TABLE 5. VOC Emissions Per Classified Industrial Category According to Photochemical Ozone Creation Potential and Toxicity cat.
ozone formation compounds
ozone formation priority
154
aromatic aliphatic
high medium
171
aromatic aliphatic ketones aromatic aliphatic aromatic aliphatic aromatic
high medium low high medium high medium high
aromatic aliphatic aromatic aliphatic aromatic aliphatic aromatic, olefins aliphatic alcohols aromatic, olefins aldehydes aliphatic aromatic aliphatic, alcohols ketones, ethers aliphatic, alcohols aromatic aliphatic aromatic aliphatic aromatic aliphatic ketones
high medium high medium high medium high medium medium high high medium high medium low medium high medium high medium high medium low
321
aromatic aliphatic
high medium
322
aromatic aliphatic
high medium
361
aromatic aliphatic
high medium
505/515
aromatic, olefins aliphatic aliphatic
high medium medium
183 191 201 202 211 212 222 232 243 245 251 291 285
930
emissions for the particular industrial unit, creating a reference for each category, and comparing these data with the data calculated by using other methods. Therefore, the number of industries where measurements will be performed must be at least 20% of the total number, and these industries should be representative of the relative industrial categories. Measurements will be performed for total volatile organic compounds, and also for a number of selected individual VOCs for each source as they are classified in Table 3. Portable instruments will be used, located in at least three positions around the source and in the source. The equipment will include a portable gas chromatograph and autosampler with the ability to measure samples from Tedlar or Teflon bags, equipped with a PID/FID detector for the measurement of TVOC, BTX, and halogenated VOC. Also, equipment for the measurement of meteorological parameters (wind direction and velocity, and temperature) must be used. Use of Calculation Techniques. The VOCs emissions from the industrial activities where measurements will not be performed will be determined by calculation techniques. A 1986
9
ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 35, NO. 10, 2001
toxic compounds
toxicity priority
dichloroethane dichloromethane toluene aromatic aliphatic ketones
high medium low
formaldehyde naphthalene, toluene benzene chloroform, formaldehyde, trichloroethylene formaldehyde cresols formaldehyde, acetaldehyde chloroform, trichloroethylene, dichloromethane chloroform, trichloroethylene toluene benzene trichloroethylene, dichloroethane perchloroethylene, formaldehyde benzene formaldehyde, acetaldehyde, toluene xylene, ethyl benzene benzene formaldehyde, perchloroethylene dichloromethane, trichloroethylene perchloroethylene 1,3-butadiene, benzene
medium low high medium medium low medium medium medium low high medium medium high medium low high medium medium medium high
benzene, carbon tetrachloride perchloroethylene, formaldehyde carbon tetrachloride chloroform, dichloromethane trichloroethylene, trichloroethane, toluene, ethylbenzene, xylenes benzene, dichloroethylene chloroform, dichloromethane, perchloroethylene, trichloroethylene benzene dichloromethane, perchloroethylene, trichloroethylene, formaldehyde benzene formaldehyde, dichloromethane perchloroethylene, trichloroethylene benzene toluene, xylene, ethylbenzene perchloroethylene, trichloroethylene trichloroethane, toluene
high medium high medium low high medium high medium high medium medium high low medium low
combination of the following methods will be used according to the applicability of each method in the examined case: (1) calculation of mass balances based on the estimation of the percentages of evaporation and recovery of the organic solvent and the pollution reduction equipment, (2) evaluation of VOCs emitted from a certain manufacturing process using process simulation software, (3) calculation of the specific emission factors based on information for each industry concerning the emissions of solvents and the pollution reduction equipment used, (4) calculation of total hydrocarbon losses in the case of storage of petroleum products, by using suitable software, e.g. TANKS (29), and (5) calculation of general emission factors which are applicable for the calculation of emissions from area sources. The calculations will be made on the data collected by mailed questionnaires, during on-site visits, or by collection of information from various unions, organizations, or national sources.
Particularly for Greece, the collection of data will include collection of general information concerning the activities and the emission loads of the industrial categories from the National Statistical Service of Greece, the Ministry for the Environment, Planning, and Public Works (MEPPW), the Union of Greek Industries, and other bodies. Also, the collection of detailed information for each point source is achieved using the relevant permit applications, sending specific questionnaires, and performing on-site visits. Provisions of the directives specify that operators of point sources are obligated to report data using a special questionnaire that will be sent by the Ministry of Environment. The questionnaire will also be available at the Internet site of the Ministry. The return of this questionnaire will be performed by e-mail or regular mail. The facilities that are not determined as point sources will be inventoried as area sources based on existing statistical data of the statistical agency. Development of Questionnaires. Two questionnaires were developed that could be used for the collection of essential information during on-site visits or by mailing them to the units. The first questionnaire is addressed to industrial facilities that formulate, use, or release organic solvents, and the second questionnaire is addressed to facilities that produce, transport, or sell petroleum products. The development of the questionnaires was based on the necessary information for the calculation of VOCs emissions using mass balances or emission factors and the examination of compliance with the relative directives. Topics covered by the first questionnaire include company identity and general data, operating procedure data (quantity of products and raw materials), description of the production operations and processes, solvents consumption during the operating procedure (percentage and nature of organic solvent, solvent consumption during operating procedure, nominal capability of solvents consumption, solvents consumption per produced product), VOCs emissions based on measurement or calculations performed by the industrial activity, and information on the techniques used for the reduction of VOCs emissions during the process and at the end of the process. The topics covered by the second questionnaire include company identity and general data, meteorological data of the area of concern (yearly average temperature, wind velocity, and sun radiation), characteristics of the storage tanks used (tank height, diameter, active volume, fillings/ year, color, condition, presence of heating shell and ventilation system, type of the tank’s roof, and nature of tank’s rings), physical and chemical data for the stored products (molecular weight, density, and vapor pressure of product, Reid vapor pressure), and losses of the stored products. Quality Assurance - Quality Control Scheme. The collection of reliable results during the inventory project can be assured by using an integrated Quality Assurance - Quality Control Scheme (QA/QC). A protocol must be developed that will describe in detail all the control procedures performed during the inventory. This protocol is essential in order to validate the inventory results and evaluate the performance of the inventory system. The QA/QC scheme will be based on the use of audit and control processes for all the procedures that will be performed during the inventory. Specifically, this scheme will examine the fulfillment of the following requirements: (1) representative classification of the industrial units and other activities; (2) development of a complete list of the emission sources concerned; (3) collection of a significant statistical sample of questionnaires; (4) validation of the reliability and accuracy of the collected information; (5) use of standard sampling and analysis methods; (6) collection of a sufficient number of samples in order to perform statistical analysis; (7) estimation of the
degree of uncertainty of the determined emissions; (8) validation of the final results; and (9) detailed registration of all the steps performed during the inventory procedure. Construction of a Database System. A comprehensive database system should be designed to register all the information concerning VOCs emission point sources. This database will be developed in order to include all the information collected by the questionnaires and all the data extracted by the performance of measurements and the use of calculation techniques. The database will be supported by a GIS application. The GIS will interact with the database providing a full-system optical image capability. Both the database and the GIS system will be designed to be fully compatible with the EIONET (European Information and Observation Network) and the National Environmental Updating and Monitoring System.
Discussion Taking into account the reporting requirements deriving from the EU Directives, International Conventions, and Inventory Methodologies developed at the EU level, it can be concluded that there are significant differences in the required data in terms of industrial categories, definitions of point and area sources, definitions of VOCs and individual VOCs that must be determined, and expression of VOCs emissions. Therefore, it is extremely difficult to design a general inventory system that will cover all the reporting needs concerning VOCs emissions. Also, it can be concluded that the EU Directives provide the need for reporting data on an individual source basis, in comparison with the International Conventions and EU Inventory Methodologies where data on a national or sectoral scale are needed (CORINAIR, Atmospheric Emission Inventory Guidebook, etc.). Therefore, an inventory system must be mainly based on the requirements of the EU Directives, and cover also the main needs of the European and International Organizations (EEA, OECD, etc.). On the basis of this concept, an inventory system was structured that aims to evaluate VOCs emissions from industrial activities and other facilities in Greece. In particular, the criteria given in Directives 99/13/EC, 94/63/EC, and 96/ 61/EC were combined to create a system compatible with all the EU requirements concerning VOCs emissions and able to provide accurate and representative data to the European databases. This inventory can be very helpful to all the EU members states, as well as the Eastern European countries that are in pre-accesion phase who must implement the European legislation concerning VOCs emissions.
Literature Cited (1) Shah, J. J.; Singh, H. B. Environ. Sci. Technol. 1988, 22, 13811388. (2) Singh, H.; Salas, L.; Smith, A. J.; Shigeishi, H. Atmos. Environ. 1981, 15, 601-612. (3) Air Quality Guidelines for Europe, Word Health Organization (WHO) Regional Publications, European Series No. 23; WHO: Copenhagen, Denmark, 1987. (4) Indoor Air Quality: Organic pollutants, Word Health Organization (WHO) Regional Office for Europe, European Reports and Studies 111; WHO: Copenhagen, Denmark, 1989. (5) Chemicals, Industrial Processes and Industries Associated with Cancer in Humans. IARC Monographs, Vol. 1 to 29. International Agency for Research on Cancer: Lyon, France, 1982. (6) Guidance Document for EPER Implementation. European Commission, Directorate General for Environment; European Commission: Brussels, Belgium, November 2000. (7) Protocol to the 1979 Convention on long-range transboundary air pollution concerning the control of emissions of Volatile Organic Compounds or their transboundary fluxes. United Nations, UN-ECE, ECE/EB. AIR/30, 1991. (8) CORINAIR 90: Summary Report nr. 2. Final Draft Report to the European Environment Agency from the European Toxic Centre on Air Emissions, January 1996. VOL. 35, NO. 10, 2001 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
9
1987
(9) Review of CORINAIR 90 - Proposals for air emissions 94. European Environment Agency from the European Topic Centre on Air Emissions, report 1995. (10) Recommendations for revised data system for air emission inventories. European Environment Agency, European Toxic Centre on Air Emissions, final report 1995/2. 1995. (11) Stanners, D.; Bourdau P. The Dobris Assessement, EUROPE’S ENVIRONMENT. European Environment Agency: Copenhagen, Denmark, 1995. (12) Environment in the European Union at the turn of the century, Environmental Assessment Report No. 2. European Environmental Agency: Copenhagen, Denmark, 1999. (13) Draft Guidelines for National Greenhouse Gas Inventories: Reference Manual, IPCC, Vol 3; 1994. (14) Atmospheric Emission Inventory Guidebook, EMEP Task Force on Emission Inventories, EEA: Copenhagen, Denmark, September 1999. (15) U.S. EPA. Volume II: Point Sources, Chapter 1: Introduction to Stationary Point Source Emission Inventory Development; EIIP Document Series Volumes I - X, EPA-454/R-97-004; U.S. Environmental Protection Agency, U.S. Government Printing Office: Washington, DC, August 1996. (16) Derwent, R. G. Hydrocarbons in the atmosphere: their sources, distributions and fates. In Proceedings of the International Conference on Volatile Organic Compounds in the Environment, London, 1993. (17) Murlis, J. Volatile Organic Compounds: UK policy. In Proceedings of the International Conference on Volatile Organic Compounds in the Environment, London, 1993. (18) Gillham, C. A.; Leech, P. K.; Eggleston, H. S. UK emissions of air pollutants 1970-1990. Warren Spring Laboratory Report LR 887 (AR); Stevenage, UK, 1992. (19) Report on VOCs from Solvent Usage Operations; ENV/AIR/87.4. Organization for Economic Cooperation and Development, Environment Directorate: Paris, 1987.
1988
9
ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 35, NO. 10, 2001
(20) Sema Metra Conseil, La situation d’elimination des solvants uses dans les pyas de la CEE: Diagnostic de Besoin d’ action communautaire. Paris, October 1986. (21) Fisk, D. J. Volatile Organic Compounds, A European overview. In Proceedings of the International Conference on Volatile Organic Compounds in the Environment, London, 1995. (22) Atkinson, R. Atmos. Environ. 1990, 24A, 1-41. (23) Carter, W. P. L. Development of ozone reactivity scales for volatile organic compounds. Final report to U.S. Environmental Protection Agency. SAPRAC, University of California at Riverside: Riverside, CA, 1990. (24) Anderson-Skold, Y.; Calendar, K.; and Grenfelt, P. Photochemical ozone creation potentials - a study of different concepts. Swedish Environmental Research Institute: Gothenburg, Sweden, 1991. (25) An Introduction for Health Professionals, report number 523217/81322. American Lung Association, American Medical Association, U.S. Consumer Product Safety Commission, U.S. Environmental Protection Agency, Indoor Air Pollution. U.S. Government Printing Office: Washington, DC, 1994. (26) Nielsen, G. D.; Vinggaard, A. M. Pharmacol. Toxicol. 1988, 63, 293-304. (27) Molhave, L.; Jenser, J. G.; Larsen, S. Atmos. Environ. 1991, 25A (7), 1283-1293. (28) Cometto Muniz, J. E.; Cain, W. S. Nasal irritation and odor from homologous series of chemicals. In Proceedings of the 6th International Conference on Indoor Air Quality and Climate; Jaakkola, J. K., Ilmarinen R., Seppanen, O., Eds.; Helsinki. 1993; Vol. 1, pp 561-567. (29) Tanks (computer software package), Version 4, U.S. Environmental Protection Agency; U.S. Government Printing Office: Washington, DC, 2000.
Received for review March 13, 2000. Revised manuscript received February 12, 2001. Accepted February 15, 2001. ES000051W
