Volatile Organic Compounds, 1991 in United States

Volatile Organic Compounds, 1991

PROTOCOL TO THE 1979
CONVENTION ON LONG-RANGE TRANSBOUNDARY AIR POLLUTION
CONCERNING THE CONTROL OF EMISSIONS OF VOLATILE ORGANIC COMPOUNDS
OR THEIR TRANSBOUNDARY FLUXES (1991)

The Parties,

Determined to implement the Convention on Long-range Transboundary Air
Pollution,

Concerned that present emissions of volatile organic compounds (VOCs) and
the resulting secondary photochemical oxidant products are causing
damage, in exposed parts of Europe and North America, to natural
resources of vital environmental and economic importance and, under
certain exposure conditions, have harmful effects on human health,

Noting that under the Protocol concerning the Control of Emissions of
Nitrogen Oxides or their Transboundary Fluxes, adopted in Sofia on 31
October 1988, there is already agreement to reduce emissions of oxides of
nitrogen,

Recognizing the contribution of VOCs and nitrogen oxides to the formation
of tropospheric ozone,

Recognizing also that VOCs, nitrogen oxides and resulting ozone are
transported across international boundaries, affecting air quality in
neighbouring States,

Aware that the mechanism of photochemical oxidant creation is such that
the reduction of emissions of VOCs is necessary in order to reduce the
incidence of photochemical oxidants,

Further aware that methane and carbon monoxide emitted by human
activities are present at background levels in the air over the ECE
region and contribute to the formation of episodic peak ozone levels;
that, in addition, their global-scale oxidation in the presence of
nitrogen oxides contributes to the formation of the background levels of
tropospheric ozone upon which photochemical episodes are superimposed;
and that methane is expected to become the subject of control actions in
other forums,

Recalling that the Executive Body for the Convention identified at its
sixth session the need to control emissions of VOCs or their
transboundary fluxes, as well as to control the incidence of
photochemical oxidants, and the need for Parties that had already reduced
these emissions to maintain and review their emission standards for VOCs,

Acknowledging the measures already taken by some Parties which have had
the effect of reducing their national annual emissions of nitrogen oxides
and VOCs,

Noting that some Parties have set air quality standards and/or objectives
for tropospheric ozone and that standards for tropospheric ozone
concentrations have been set by the World Health Organization and other
competent bodies,

Determined to take effective action to control and reduce national annual
emissions of VOCs or the transboundary fluxes of VOCs and the resulting
secondary photochemical oxidant products, in particular by applying
appropriate national or international emission standards to new mobile
and new stationary sources and retrofitting existing major stationary
sources, and also by limiting the content of components in products for
industrial and domestic use that have the potential to emit VOCs,

Conscious that volatile organic compounds differ greatly from each other
in their reactivity and in their potential to create tropospheric ozone
and other photochemical oxidants and that, for any individual compounds,
potential may vary from time to time and from place to place depending on
meteorological and other factors,

Recognizing that such differences and variations should be taken into
consideration if action to control and reduce emissions and transboundary
fluxes of VOCs is to be as effective as possible in minimizing the
formation of tropospheric ozone and other photochemical oxidants,

Taking into consideration existing scientific and technical data on
emissions, atmospheric movements and effects on the environment of VOCs
and photochemical oxidants, as well as on control technologies,

Recognizing that scientific and technical knowledge of these matters is
developing and that it will be necessary to take such developments into
account when reviewing the operation of the present Protocol and deciding
on further action,

Noting that the elaboration of an approach based on critical levels is
aimed at the establishment of an effect-oriented scientific basis to be
taken into account when reviewing the operation of the present
Protocol, and at deciding on further internationally agreed measures to
limit and reduce emissions of VOCs or the transboundary fluxes of VOCs
and photochemical oxidants,

Have agreed as follows:

Article 1

DEFINITIONS

For the purposes of the present Protocol,

1.”Convention” means the Convention on Long-range Transboundary Air
Pollution, adopted in Geneva on 13 November 1979;

2.”EMEP” means the Cooperative Programme for Monitoring and Evaluation of
the Long-range Transmission of Air Pollutants in Europe;

3.”Executive Body” means the Executive Body for the Convention
constituted under article 10, paragraph 1, of the Convention;

4.”Geographical scope of EMEP” means the area defined in article 1,
paragraph 4, of the Protocol to the 1979 Convention on Long-range
Transboundary Air Pollution on Long-term Financing of the Cooperative
Programme for Monitoring and Evaluation of the Long-range Transmission of
Air Pollutants in Europe (EMEP), adopted in Geneva on 28 September 1984;

5.”Tropospheric ozone management area” (TOMA) means an area specified in
annex I under conditions laid down in article 2, paragraph 2 (b);

6.”Parties” means, unless the context otherwise requires, the Parties to
the present Protocol;

7.”Commission” means the United Nations Economic Commission for Europe;

8.”Critical levels” means concentrations of pollutants in the atmosphere
for a specified exposure time below which direct adverse effects on
receptors, such as human beings, plants, ecosystems or materials do not
occur according to present knowledge;

9.”Volatile organic compounds”, or “VOCs”, means, unless otherwise
specified, all organic compounds of anthropogenic nature, other than
methane, that are capable of producing photochemical oxidants by
reactions with nitrogen oxides in the presence of sunlight;

10.”Major source category” means any category of sources which emit air
pollutants in the form of VOCs, including the categories described in
annexes II and III, and which contribute at least 1% of the total
national emissions of VOCs on an annual basis, as measured or calculated
in the first calendar year after the date of entry into force of the
present Protocol, and every fourth year thereafter;

11.”New stationary source” means any stationary source of which the
construction or substantial modification is commenced after the expiry of
two years from the date of entry into force of the present Protocol;

12.”New mobile source” means any on-road motor vehicle which is
manufactured after the expiry of two years from the date of entry into
force of the present Protocol;

13.”Photochemical ozone creation potential” (POCP) means the potential of
an individual VOC, relative to that of other VOCs, to form ozone by
reaction with oxides of nitrogen in the presence of sunlight, as
described in annex IV.

Article 2

BASIC OBLIGATIONS

1. The Parties shall control and reduce their emissions of VOCs 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.

2. Each Party shall, in order to meet the requirements of paragraph 1
above, control and reduce its national annual emissions of VOCs or their
transboundary fluxes in any one of the following ways to be specified
upon signature:

(a) It shall, as soon as possible and as a first step, take effective
measures to reduce its national annual emissions of VOCs by at least 30%
by the year 1999, using 1988 levels as a basis or any other annual level
during the period 1984 to 1990, which it may specify upon signature of or
accession to the present Protocol; or

(b) Where its annual emissions contribute to tropospheric ozone
concentrations in areas under the jurisdiction of one or more other
Parties, and such emissions originate only from areas under its
jurisdiction that are specified as TOMAs in annex I, it shall, as soon as
possible and as a first step, take effective measures to:

(i) Reduce its annual emissions of VOCs from the areas so
specified by at least 30% by the year 1999, using 1988 levels
as a basis or any other annual level during the period
1984-1990, which it may specify upon signature of or
accession to the present Protocol; and

(ii) Ensure that its total national annual emissions of VOCs by
the year 1999 do not exceed the 1988 levels; or

(c) Where its national annual emissions of VOCs were in 1988 lower
than 500,000 tonnes and 20 kg/inhabitant and 5 tonnes/km2, it shall, as
soon as possible and as a first step, take effective measures to ensure
at least that at the latest by the year 1999 its national annual
emissions of VOCs do not exceed the 1988 levels.

3. (a) Furthermore, no later than two years after the date of entry into
force of the present Protocol, each Party shall:

(i) Apply appropriate national or international emission
standards to new stationary sources based on the best
available technologies which are economically feasible,
taking into consideration annex II;

(ii) Apply national or international measures to products that
contain solvents and promote the use of products that are low
in or do not contain VOCs, taking into consideration annex
II, including the labeling of products specifying their VOC
content;

(iii) Apply appropriate national or international emission
standards to new mobile sources based on the best available
technologies which are economically feasible, taking into
consideration annex III; and

(iv) Foster public participation in emission control programmes
through public announcements, encouraging the best use of all
modes of transportation and promoting traffic management
schemes.

(b) Furthermore, no later than five years after the date of entry into
force of the present Protocol, in those areas in which national or
international tropospheric ozone standards are exceeded or where
transboundary fluxes originate or are expected to originate, each Party
shall:

(i) Apply the best available technologies that are economically
feasible to existing stationary sources in major source
categories, taking into consideration annex II;

(ii) Apply techniques to reduce VOC emissions from petrol
distribution and motor vehicle refueling operations, and to
reduce volatility of petrol, taking into consideration
annexes II and III.

4. In carrying out their obligations under this article, Parties are
invited to give highest priority to reduction and control of emissions of
substances with the greatest POCP, taking into consideration the
information contained in annex IV.

5. In implementing the present Protocol, and in particular any product
substitution measures, Parties shall take appropriate steps to ensure
that toxic and carcinogenic VOCs, and those that harm the stratospheric
ozone layer, are not substituted for other VOCs.

6. The Parties shall, as a second step, commence negotiations, no later
than six months after the date of entry into force of the present
Protocol, on further steps to reduce national annual emissions of
volatile organic compounds or transboundary fluxes of such emissions and
their resulting secondary photochemical oxidant products, taking into
account the best available scientific and technological developments,
scientifically determined critical levels and internationally accepted
target levels, the role of nitrogen oxides in the formation of
photochemical oxidants and other elements resulting from the work
programme undertaken under article 5.

7. To this end, the Parties shall cooperate in order to establish:

(a) More detailed information on the individual VOCs and their POCP
values;

(b) Critical levels for photochemical oxidants;

(c) Reductions in national annual emissions or transboundary fluxes of
VOCs and their resulting secondary photochemical oxidant products,
especially as required to achieve agreed objectives based on critical
levels;

(d) Control strategies, such as economic instruments, to obtain
overall cost-effectiveness to achieve agreed objectives;

(e) Measures and a timetable commencing no later than 1 January 2000
for achieving such reductions.

8. In the course of these negotiations, the Parties shall consider
whether it would be appropriate for the purposes specified in paragraph 1
to supplement such further steps with measures to reduce methane.

Article 3

FURTHER MEASURES

1. Measures required by the present Protocol shall not relieve Parties
from their other obligations to take measures to reduce total gaseous
emissions that may contribute significantly to climate change, to the
formation of tropospheric background ozone or to the depletion of
stratospheric ozone, or that are toxic or carcinogenic.

2. Parties may take more stringent measures than those required by the
present Protocol.

3. The Parties shall establish a mechanism for monitoring compliance with
the present Protocol. As a first step based on information provided
pursuant to article 8 or other information, any Party which has reason to
believe that another Party is acting or has acted in a manner
inconsistent with its obligations under this Protocol may inform the
Executive Body to that effect and, simultaneously, the Parties concerned.
At the request of any Party, the matter may be taken up at the next
meeting of the Executive Body.

Article 4

EXCHANGE OF TECHNOLOGY

1. The Parties shall, consistent with their national laws, regulations
and practices, facilitate the exchange of technology to reduce emissions
of VOCs, particularly through the promotion of:

(a) The commercial exchange of available technology;

(b) Direct industrial contacts and cooperation, including joint
ventures;

(d) The provision of technical assistance.

2. In promoting the activities specified in paragraph 1 of this article,
the Parties shall create favourable conditions by facilitating contacts
and cooperation among appropriate organizations and individuals in the
private and public sectors that are capable of providing technology,
design and engineering services, equipment or finance.

3. The Parties shall, no later than six months after the date of entry
into force of the present Protocol, commence consideration of procedures
to create more favourable conditions for the exchange of technology to
reduce emissions of VOCs.

Article 5

RESEARCH AND MONITORING TO BE UNDERTAKEN

The Parties shall give high priority to research and monitoring related
to the development and application of methods to achieve national or
international tropospheric ozone standards and other goals to protect
human health and the environment. The Parties shall, in particular,
through national or international research programmes, in the work-plan
of the Executive Body and through other cooperative programmes within the
framework of the Convention, seek to:

(a) Identify and quantify effects of emissions of VOCs, both
anthropogenic and biogenic, and photochemical oxidants on human health,
the environment and materials;

(b) Determine the geographical distribution of sensitive areas;

(c) Develop emission and air quality monitoring and model calculations
including methodologies for the calculation of emissions, taking into
account, as far as possible, the different VOC species, both
anthropogenic and biogenic, and their reactivity, to quantify the
long-range transport of VOCs, both anthropogenic and biogenic, and
related pollutants involved in the formation of photochemical oxidants;

(d) Improve estimates of the performance and costs of technologies for
control of emissions of VOCs and record the development of improved and
new technologies;

(e) Develop, within the context of the approach based on critical
levels, methods to integrate scientific, technical and economic data in
order to determine appropriate rational strategies for limiting VOC
emissions and obtain overall cost-effectiveness to achieve agreed
objectives;

(f) Improve the accuracy of inventories of emissions of VOCs, both
anthropogenic and biogenic, and harmonize the methods of their
calculation or estimation;

(g) Improve their understanding of the chemical processes involved in
the creation of photochemical oxidants;

(h) Identify possible measures to reduce emissions of methane.

Article 6

REVIEW PROCESS

1. The Parties shall regularly review the present Protocol, taking into
account the best available scientific substantiation and technological
development.

2. The first review shall take place no later than one year after the
date of entry into force of the present Protocol.

Article 7

NATIONAL PROGRAMMES, POLICIES AND STRATEGIES

The Parties shall develop without undue delay national programmes,
policies and strategies to implement the obligations under the present
Protocol that shall serve as a means of controlling and reducing
emissions of VOCs or their transboundary fluxes.

Article 8

INFORMATION EXCHANGE AND ANNUAL REPORTING

1. The Parties shall exchange information by notifying the Executive Body
of the national programmes, policies and strategies that they develop in
accordance with article 7, and by reporting to it progress achieved
under, and any changes to, those programmes, policies and strategies. In
the first year after entry into force of this Protocol, each Party shall
report on the level of emissions of VOCs in its territory and any TOMA in
its territory, by total and, to the extent feasible, by sector of origin
and by individual VOC, according to guidelines to be specified by the
Executive Body for 1988 or any other year taken as the base year for
article 2.2 and on the basis upon which these levels have been
calculated.

2. Furthermore each Party shall report annually:

(a) On the matters specified in paragraph 1 for the previous calendar
year, and on any revision which may be necessary to the reports already
made for earlier years;

(b) On progress in applying national or international emission
standards and the control techniques required under article 2, paragraph
3;

3. In addition, Parties within the geographical scope of EMEP shall
report, at intervals to be specified by the Executive Body, information
on VOC emissions by sector of origin, with a spatial resolution, to be
specified by the Executive Body, appropriate for purposes of modeling the
formation and transport of secondary photochemical oxidant products.

4. Such information shall, as far as possible, be submitted in accordance
with a uniform reporting framework.

Article 9

CALCULATIONS

EMEP shall, utilizing appropriate models and measurements, provide to the
annual meetings of the Executive Body relevant information on the
long-range transport of ozone in Europe. In areas outside the
geographical scope of EMEP, models appropriate to the particular
circumstances of Parties to the Convention therein shall be used.

Article 10

ANNEXES

The annexes to the present Protocol shall form an integral part of the
Protocol. Annex I is mandatory while annexes II, III and IV are
recommendatory.

Article 11

AMENDMENTS TO THE PROTOCOL

1. Any Party may propose amendments to the present Protocol.

2. Proposed amendments shall be submitted in writing to the Executive
Secretary of the Commission, who shall communicate them to all Parties.
The Executive Body shall discuss the proposed amendments at its next
annual meeting, provided that those proposals have been circulated by the
Executive Secretary to the Parties at least 90 days in advance.

3. Amendments to the Protocol, other than amendments to its annexes,
shall be adopted by consensus of the Parties present at a meeting of the
Executive Body, and shall enter into force for the Parties which have
accepted them on the ninetieth day after the date on which two thirds of
the Parties have deposited their instruments of acceptance thereof.
Amendments shall enter into force for any Party which has accepted them
after two thirds of the Parties have deposited their instruments of
acceptance of the amendment, on the ninetieth day after the date on which
that Party deposited its instrument of acceptance of the amendments.

4. Amendments to the annexes shall be adopted by consensus of the Parties
present at a meeting of the Executive Body and shall become effective 30
days after the date on which they have been communicated, in accordance
with paragraph 5 of this article.

5. Amendments under paragraphs 3 and 4 of this article shall, as soon as
possible after their adoption, be communicated by the Executive Secretary
to all Parties.

Article 12

SETTLEMENT OF DISPUTES

If a dispute arises between two or more Parties as to the interpretation
or application of the present Protocol, they shall seek a solution by
negotiation or by any other method of dispute settlement acceptable to
the parties to the dispute.

Article 13

SIGNATURE

1. The present Protocol shall be open for signature at Geneva from 18
November 1991 until 22 November 1991 inclusive, then at the United
Nations Headquarters in New York until 22 May 1992, by the States members
of the Commission as well as States having consultative status with the
Commission, pursuant to paragraph 8 of Economic and Social Council
resolution 36 (IV) of 28 March 1947, and by regional economic integration
organizations, constituted by sovereign States members of the Commission,
which have competence in respect of the negotiation, conclusion and
application of international agreements in matters covered by the
Protocol, provided that the States and organizations concerned are
Parties to the Convention.

2. In matters within their competence, such regional economic integration
organizations shall, on their own behalf, exercise the rights and fulfill
the responsibilities which the present Protocol attributes to their
member States. In such cases, the member States of these organizations
shall not be entitled to exercise such rights individually.

Article 14

RATIFICATION, ACCEPTANCE, APPROVAL AND ACCESSION

1. The present Protocol shall be subject to ratification, acceptance or
approval by Signatories.

2. The present Protocol shall be open for accession as from 22 May 1992
by the States and organizations referred to in article 13, paragraph 1.

Article 15

DEPOSITARY

The instruments of ratification, acceptance, approval or accession shall
be deposited with the Secretary-General of the United Nations, who will
perform the functions of Depositary.

Article 16

ENTRY INTO FORCE

1. The present Protocol shall enter into force on the ninetieth day
following the date on which the sixteenth instrument of ratification,
acceptance, approval or accession has been deposited.

2. For each State and organization referred to in article 13, paragraph
1, which ratifies, accepts or approves the present Protocol or accedes
thereto after the deposit of the sixteenth instrument of ratification,
acceptance, approval or accession, the Protocol shall enter into force on
the ninetieth day following the date of deposit by such Party of its
instrument of ratification, acceptance, approval or accession.

Article 17

WITHDRAWAL

At any time after five years from the date on which the present Protocol
has come into force with respect to a Party, that Party may withdraw from
it by giving written notification to the Depositary. Any such withdrawal
shall take effect on the ninetieth day following the date of its receipt
by the Depositary, or on such later date as may be specified in the
notification of the withdrawal.

Article 18

AUTHENTIC TEXTS

The original of the present Protocol, of which the English, French and
Russian texts are equally authentic, shall be deposited with the
Secretary-General of the United Nations.

In witness whereof the undersigned, being duly authorized thereto, have
signed the present Protocol.

Done at Geneva this eighteenth day of November one thousand nine hundred
and ninety-one.

ANNEX I

DESIGNATED TROPOSPHERIC OZONE MANAGEMENT AREAS (TOMAs)

The following TOMAs are specified for the purposes of this Protocol:

Canada

TOMA No. 1: The Lower Fraser Valley in the Province of British Columbia.

This is a 16,800-km2 area in the southwestern corner of the Province of
British Columbia averaging 80 km in width and extending 200 km up the Fraser
River Valley from the mouth of the river in the Strait of Georgia to
Boothroyd, British Columbia. Its southern boundary is the Canada/ United
States international boundary and it includes the Greater Vancouver Regional
District.

TOMA No. 2: The Windsor-Quebec Corridor in the Provinces of Ontario and
Quebec.

This is a 157,000-km2 area consisting of a strip of land 1,100 km long and
averaging 140 km in width stretching from the City of Windsor (adjacent to
Detroit in the United States) in the Province of Ontario to Quebec City in the
Province of Quebec. The Windsor-Quebec Corridor TOMA is located along the
north shore of the Great Lakes and the St. Lawrence River in Ontario and
straddles the St. Lawrence River from the Ontario-Quebec border to Quebec City
in Quebec. It includes the urban centres of Windsor, London, Hamilton,
Toronto, Ottawa, Montreal, Trois-Rivieres and Quebec City.

Norway

The total Norwegian mainland as well as the exclusive economic zone south of
62 degrees N latitude in the region of the Economic Commission for Europe
(ECE), covering an area of 466,000 km2.

ANNEX II

CONTROL MEASURES FOR EMISSIONS OF VOLATILE ORGANIC COMPOUNDS (VOCs)
FROM STATIONARY SOURCES

INTRODUCTION

1. The aim of this annex is to provide the Parties to the Convention with
guidance in identifying best available technologies to enable them to meet the
obligations of the Protocol.

2. Information regarding emission performance and costs is based on official
documentation of the Executive Body and its subsidiary bodies, in particular
documents received and reviewed by the Task Force on Emissions of VOCs from
Stationary Sources. Unless otherwise indicated, the techniques listed are
considered to be well established on the basis of operational experience.

3. Experience with new products and new plants incorporating low-emission
techniques, as well as with the retrofitting of existing plants, is
continuously growing; the regular elaboration and amendment of the annex will
therefore be necessary. Best available technologies identified for new plants
can be applied to existing plants after an adequate transition period.

4. The annex lists a number of measures spanning a range of costs and
efficiencies. The choice of measures for any particular case will depend on a
number of factors, including economic circumstances, technological
infrastructure and any existing VOC control implemented.

5. This annex does not, in general, take into account the specific species of
VOC emitted by the different sources, but deals with best available
technologies for VOC reduction. When measures are planned for some sources, it
is worthwhile to consider giving priority to those activities which emit
reactive rather than non-reactive VOCs (e.g. in the solvent-using sector).
However, when such compound-specific measures are designed, other effects on
the environment (e.g. global climate change) and on human health should also
be taken into account.

I. MAJOR SOURCES OF VOC EMISSIONS FROM STATIONARY SOURCES

6. The major sources of anthropogenic non-methane VOC emissions from
stationary sources are the following:

(a) Use of solvents;

(b) Petroleum industry including petroleum-product handling;

(d) Small-scale combustion sources (e.g. domestic heating and small
industrial boilers);

(e) Food industry;

(f) Iron and steel industry;

(g) Handling and treatment of wastes;

(h) Agriculture.

7. The order of the list reflects the general importance of the sources
subject to the uncertainties of emission inventories. The distribution of VOC
emissions according to different sources depends greatly on the fields of
activity within the territory of any particular Party.

II. GENERAL OPTIONS FOR VOC-EMISSION REDUCTION

8. There are several possibilities for the control or prevention of VOC
emissions. Measures for the reduction of VOC emissions focus on products
and/or process modifications (including maintenance and operational control)
and on the retrofitting of existing plants. The following list gives a
general outline of measures available, which may be implemented either singly
or in combination:

(a) Substitution of VOCs, e.g. the use of water-based degreasing baths,
and paints, inks, glues or adhesives which are low in or do not contain VOCs;

(b) Reduction by best management practices such as good housekeeping,
preventive maintenance programmes, or by changes in processes such as closed
systems during utilization, storage and distribution of low-boiling organic
liquids;

(c) Recycling and/or recovery of efficiently collected VOCs by control
techniques such as adsorption, absorption, condensation and membrane
processes; ideally, organic compounds can be reused on-site;

(d) Destruction of efficiently collected VOCs by control techniques such
as thermal or catalytic incineration or biological treatment.

9. The monitoring of abatement procedures is necessary to ensure that
appropriate control measures and practices are properly implemented for an
effective reduction of VOC emissions. Monitoring of abatement procedures will
include:

(a) The development of an inventory of those VOC-emission reduction
measures, identified above, that have already been implemented;

(b) The characterization and quantification of VOC emissions from
relevant sources by instrumental or other techniques;

(d) Regularly scheduled reporting on (a), (b) and (c), using harmonized
procedures, to regulatory authorities;

(e) Comparison, with the objectives of the Protocol, of VOC-emission
reductions achieved in practice.

10. The investment/cost figures have been collected from various sources. On
account of the many influencing factors, investment/cost figures are highly
case-specific. If the unit “cost per tonne of VOC abated” is used for
cost-efficient strategy considerations, it must be borne in mind that such
specific figures are highly dependent on factors such as plant capacity,
removal efficiency and raw gas VOC concentration, type of technology, and the
choice of new installations as opposed to retrofitting. Illustrative cost
figures should also be based on process-specific parameters, e.g. mg/m2
treated (paints), kg/m3 product or kg/unit.

11. Cost-efficient strategy considerations should be based on total costs per
year (including capital and operational costs). VOC-emission reduction costs
should also be considered within the framework of the overall process
economics,e.g. the impact of control measures and costs on the costs of
production.

TABLE 1. A SUMMARY OF AVAILABLE VOC CONTROL TECHNIQUES,
THEIR EFFICIENCIES AND COSTS

———————————————————>
Technique Lower concentration
in air flow
——————————>
Efficiency Cost
———————————————————>
Thermal incineration ** High High

Catalytic incineration ** High Medium

Adsorption * High High
(activated carbon filters)

Absorption — —

(Waste gas washing)

Condensation * — —

Biofiltration Medium to Low
high
———————————————————>

[TABLE 1, cont.]

<————————————————————————
Technique Higher concentration Application
in air flow
——————–
Efficiency Cost
<————————————————————————
Thermal incineration ** High Medium Wide for high concentration
flows

Catalytic incineration ** Medium Medium More specialized for lower
concentration flows

Adsorption * Medium Medium Wide for low concentration
(activated carbon filters) flows

Absorption High Medium Wide for high concentration
(Waste gas washing) flows

Condensation * Medium Low Special cases of high
concentration flows only

Biofiltration Low *** Low Mainly in low concentration
flows, including odour
control
<————————————————————————–

Concentration: Lower < 3 g/m3 (in many cases 5g/m3

Efficiency: High >95%
Medium 80-95%
Low 500 ECU/t VOC abated
Medium 150-500 ECU/t VOC abated
Low 95%, II = 80-95%, III =
Source of emission Emission control measures Reduction
efficiency
—————————————————————————–>
Industrial surface Conversion to:
coating – powder paints I
– low in/not containing VOCs I – III
– high solids I – III
Incineration: – thermal I – II
– catalytic I – II
Activated carbon adsorption I – II

Paper surface Incinerator I – II
coating Radiation cure/waterborne inks I – III

Car manufacturing Conversion to:
– powder paints I
– water-based systems I – II
– high solid coating II
Activated carbon adsorption I – II
Incineration with heat recovery
– thermal I – II
– catalytic I – II
Commercial painting Low in/not containing VOCs I – II
Low in/not containing VOCs II – III

Printing Low-solvent/water-based inks II – III
Letterpress: radiation cure I
Activated carbon adsorption I – II
Absorption
Incineration I – II
– thermal
– catalytic
Biofiltration including buffer I
filter

Metal degreasing Change-over to systems low I
in/not containing VOCs
Closed machines
Activated carbon adsorption II
Cover, chilled freeboards III

Dry-cleaning Recovery dryers and good house- II – III
keeping (closed cycles)
Condensation II
Activated carbon adsorption II

Flat wood panelling Coatings low in/not
containing VOCs I

[TABLE 2 cont.]
<———————————————–
Source of emission Abatement costs
and savings

Petroleum refineries

– Fugitive emissions Regular inspection and III
maintenance

– Process-unit Flares/process furnace I
turnarounds vapour recovery

– Waste-water separator Floating cover II

– Vacuum process system Surface contact condensors I
Non-condensable VOCs piped
to heaters or furnaces

– Incineration of sludge Thermal incineration I

Storage of crude oil
and products

– Petrol Internal floating roofs I – II
with secondary seals
Floating roof tanks with II
secondary seals

– Crude oil Floating roof tanks with II
secondary seals

– Petrol marketing Vapour recovery unit I – II
terminals (loading and
unloading of trucks,
barges and trains)

– Petrol service stations Vapour balance on tank trucks I – II
(Stage I)
Vapour balance during refuelling I (- II **)
(refuelling nozzles) (Stage II)

[TABLE 3 cont.]
<———————————————–
Source of emission Abatement costs
and savings

Fugitive emissions Leak detection and repair
programme
– regular inspection III

Storage and handling – See table 3 –

General measures:
Process emissions – carbon adsorption I – II
– incineration: – thermal I – II
– catalytic I – II
– absorption
– biofiltration n.a.
– flaring
– Formaldehyde production – incineration: – thermal I
– catalytic I
– Polyethylene production – flaring I
– catalytic incineration I – II
– Polystyrene production – thermal incineration I
– flaring

Process modifications (examples):
– Vinyl chloride production – substitution of air by oxygen II
in the oxychlorination step
– flaring I
– Polyvinylchloride production – slurry stripping of monomer II

– Nitro-2-methyl-1-propanol-1
absorption I
– Polypropylene production – high yield catalyst I
– Ethylene oxide production – substitution of air by oxygen I
————————————————————————–>

[TABLE 4 cont.]
<———————————————–
Source of emission Abatement costs
and savings
<———————————————–
Fugitive emissions

Low costs
Storage and handling

Process emissions n.a.
Medium to high
costs
n.a.
n.a.
n.a.

– Formaldehyde production High costs
– Polyethylene production Medium costs
– Polystyrene production Medium costs

– Vinyl chloride production n.a.
Medium costs
– Polyvinylchloride production n.a.

Savings

– Polypropylene production n.a.
– Ethylene oxide production n.a.
<————————————————-

n.a. Not available

D. Stationary combustion

47. Optimal VOC-emission reduction from stationary combustion depends on the
efficient use of fuel at the national level (table 5). It is also important
to ensure the effective combustion of fuel by the use of good operational
procedures, efficient combustion appliances and advanced combustion-management
systems.

48. For small systems in particular, there is still a considerable reduction
potential, especially in the burning of solid fuels. VOC reduction in general
is achievable by the replacement of old stoves/boilers and/or fuel-switching
to gas. The replacement of single room stoves by central heating systems
and/or the replacement of individual heating systems in general reduces
pollution; however, overall energy efficiency has to be taken into account.
Fuel-switching to gas is a very effective control measure, provided the
distribution system is leakproof.

49. For most countries, the VOC-reduction potential for power plants is
negligible. On account of the uncertain replacement/fuel-switch involved, no
figures can be given regarding the overall reduction potential and the related
costs.

TABLE 5. VOC-EMISSION CONTROL MEASURES FOR STATIONARY COMBUSTION SOURCES

————————————————————-
Source of emission Emission control measures

————————————————————-
Small-scale combustion Energy savings, e.g. insulation
sources Regular inspection
Replacement of old furnaces
Natural gas and fuel oil
instead of solid fuels
Central heating system
District heating system

Industrial and Energy savings
commercial Better maintenance
sources Fuel-type modification
Change of furnace and load
Change of burning conditions

Stationary internal Catalytic converters
combustion sources Thermal reactors
—————————————————————

E. Food industry

50. The food industry sector covers a wide range of VOC-emitting processes
from large and small plants (table 6). The major sources of VOC emissions
are:

(a) Production of alcoholic beverages;

(b) Baking;

(d) Animal rendering.

Alcohol is the principal VOC from (a) and (b). Aliphatic hydrocarbons are the
principal VOC from (c).

51. Other potential sources include:

(a) Sugar industry and sugar use;

(b) Coffee and nut roasting;

(d) Fish meal processing;

(e) Preparation of cooked meats, etc.

52. VOC emissions are typically odorous, of low concentration with high
volume flow and water content. For this reason, the use of biofilters has
been used as an abatement technique. Conventional techniques such as
absorption, adsorption,thermal and catalytic incineration have also been used.
The principal advantage of biofilters is their low operational cost compared
with other techniques. Nevertheless, periodic maintenance is required.

53. It may be feasible for larger fermentation plants and bakeries to recover
alcohol by condensation.

54. Aliphatic hydrocarbon emissions from oil extraction are minimized by
using closed cycles and good housekeeping to prevent losses from valves and
seals, etc. Different oil seeds require different volumes of mineral oil for
extraction. Olive oil can be extracted mechanically, in which case no mineral
oil is necessary.

55. The technologically feasible overall reduction potential in the food
industry is estimated to be up to 35%.

TABLE 6. VOC-EMISSION CONTROL MEASURES, REDUCTION EFFICIENCY AND
COSTS FOR THE FOOD INDUSTRY

—————————————————————————-
Source of emission Emission control measures Reduction Abatement
efficiency costs
—————————————————————————-
In general Closed cycles
Bio-oxidation II Low *
Condensation and treatment I High
Adsorption/absorption
Thermal/catalytic incineration

Vegetable-oil Process-integrated measures III Low
processing Adsorption
Membrane technique
Incineration in process furnace

Animal rendering Biofiltration II Low *
—————————————————————————–

* Owing to the fact that these processes are usually applied to gases with
low VOC concentrations, the costs per cubic metre of gas are low,
although VOC abatement per tonne is high.

F. Iron and steel industry (including ferro-alloys, casting etc.)

56. In the iron and steel industry, VOC emissions may be from a variety of
sources:

(a) Processing of input materials (cokeries, agglomeration plants:
sintering, pelletizing, briquetting; scrap-handling);

(b) Metallurgical reactors (submerged arc furnaces; electric arc
furnaces; converters, especially if using scrap, (open) cupolas; blast
furnaces);

57. Reducing the carbon carrier in raw materials (e.g. on sintering belts)
reduces the potential of VOC emissions.

58. In the case of open metallurgical reactors, VOC emissions may occur
especially from contaminated scrap and under pyrolytic conditions. Special
attention has to be paid to the collection of gases from charging and tapping
operations, in order to minimize fugitive VOC emissions.

59. Special attention has to be paid to scrap which is contaminated by oil,
grease, paint, etc., and to the separation of fluff (non-metallic parts) from
metallic scrap.

60. The processing of products usually entails fugitive emissions. In the
case of casting, emissions of pyrolysis gases occur, chiefly from organically
bonded sands. These emissions can be reduced by choosing low-emission bonding
resins and/or minimizing the quantity of binders. Biofilters have been tested
on such flue gases. Oil mist in the air from rolling mills can be reduced to
low levels by filtration.

61. Coking plants are an important VOC emission source. Emissions arise
from: coke oven gas leakage, the loss of VOCs normally diverted to an
associated distillation plant, and from the combustion of coke oven gas and
other fuel. VOC emissions are reduced mainly by the following measures:
improved sealing between oven doors and frames and between charging holes and
covers; maintaining suction from ovens even during charging; dry quenching
either by direct cooling with inert gases or by indirect cooling with water;
pushing directly into the dry quenching unit; and efficient hooding during
pushing operations.

G. Handling and treatment of waste

62. Concerning municipal solid waste control, the primary objectives are to
reduce the amount of waste produced and to reduce the amount to be treated.
In addition, the waste treatment should be optimized from an environmental
point of view.

63. If landfill processes are used, VOC-emission control measures for the
treatment of municipal waste should be linked to an efficient collection of
the gases (mostly methane).

64. These emissions can be destroyed (incineration). Another option is the
purification of the gas (bio-oxidation, absorption, activated carbon,
adsorption) leading to use of the gas for energy production.

65. The landfill of industrial waste containing VOCs leads to VOC emissions.
This point has to be taken into account in the definition of waste-management
policies.

66. The overall reduction potential is estimated to be 30%, though this
figure includes methane.

H. Agriculture

67. The principal sources of VOC emissions from agriculture are:

(a) Burning of agricultural waste, particularly straw and stubble;

(b) Use of organic solvents in pesticide formulations;

68. VOC emissions are reduced by:

(a) Controlled disposal of straw as opposed to the common practice of
open-field burning;

(b) Minimal use of pesticides with high organic solvent contents, and/or
the use of emulsions and water-based formulations;

(d) Abatement of exhaust gases from animal houses, manure drying plant,
etc., by use of biofilters, adsorption, etc.

69. In addition, alterations of feed reduce emissions of gas from animals,
and the recovery of gases for use as fuel is a possibility.

70. It is not currently possible to estimate the reduction potential of VOC
emissions from agriculture.

V. PRODUCTS

71. In circumstances in which abatement by control techniques is not
appropriate, the sole means of reducing VOC emissions is by altering the
composition of products used. The main sectors and products concerned are:
adhesives used in households, light industry, shops and offices; paints for
use in households; household cleaning and personal care products; office
products such as correcting fluids and car maintenance products. In any other
situation in which products like those mentioned above are used (e.g.
painting, light industry), alterations in product composition are highly
preferable.

72. Measures aimed at reducing VOC emissions from such products are:

(a) Product substitution;

(b) Product reformulation;

73. Instruments designed to influence market choice include:

(a) Labelling to ensure that consumers are well informed of the VOC
content;

(b) Active encouragement of low-VOC-content products (e.g. the "Blue
Angel" scheme);

74. The efficiency of these measures depends on the VOC content of the
products involved and the availability and acceptability of alternatives.
Reformulation should be checked to ensure that products do not create problems
elsewhere (e.g.increased emissions of chlorofluorocarbons (CFCs).

75. VOC-containing products are used for industrial as well as domestic
purposes. In either case the use of low-solvent alternatives may entail
changes in application equipment and in work practices.

76. Paints commonly used for industrial and domestic purposes have an average
solvent content of about 25 to 60%. For most applications, low-solvent or
solvent-free alternatives are available or under development:

(a) Paint for use in the light industry:

Powder paint = 0% VOC content in product

Waterborne paint = 10% VOC content in product

Low-solvent paint = 15% VOC content in product

(b) Paint for domestic use:

Waterborne paint = 10% VOC content in product

Low-solvent paint = 15% VOC content in product

Switching over to alternative paints is expected to result in an overall
VOC-emission reduction of about 45 to 60%.

77. Most adhesive products are used in industry, while domestic uses account
for less than 10%. About 25% of the adhesives in use contain VOC solvents.
For these adhesives, the solvent content varies widely and may constitute half
the weight of the product. For several application areas, low-solvent/
solvent-free alternatives are available. This source category therefore
offers a high reduction potential.

78. Ink is mainly used for industrial printing processes, with solvent
contents differing widely, up to 95%. For most printing processes,
low-solvent inks are available or under development in particular for printing
on paper (see para. 28).

79. About 40 to 60% of VOC emissions from consumer products (including office
products and those used in car maintenance) are from aerosols. There are
three basic ways of reducing VOC emissions from consumer products:

(a) Substitution of propellants and the use of mechanical pumps;

(b) Reformulation;

80. The potential reduction of VOC emissions from consumer products is
estimated to be 50%.

ANNEX III

CONTROL MEASURES FOR EMISSIONS OF VOLATILE ORGANIC COMPOUNDS (VOCs)
FROM ON-ROAD MOTOR VEHICLES

INTRODUCTION

1. This annex is based on information on emission control performance and
costs contained in official documentation of the Executive Body and its
subsidiary bodies; in the report on Volatile Organic Compounds from On-road
Vehicles: Sources and Control Options, prepared for the Working Group on
Volatile Organic Compounds; in documentation of the Inland Transport Committee
of the Economic Commission for Europe (ECE) and its subsidiary bodies (in
particular, documents TRANS/SC1/WP.29/R.242, 486 and 506); and on
supplementary information provided by governmentally designated experts.

2. The regular elaboration and amendment of this annex will be necessary in
the light of continuously expanding experience with new vehicles incorporating
low-emission technology and the development of alternative fuels, as well as
with retrofitting and other strategies for existing vehicles. The annex
cannot be an exhaustive statement of technical options; its aim is to provide
guidance to Parties in identifying economically feasible technologies for
fulfilling their obligations under the Protocol. Until other data become
available, this annex concentrates on on-road vehicles only.

I. MAJOR SOURCES OF VOC EMISSIONS FROM MOTOR VEHICLES

3. Sources of VOC emissions from motor vehicles have been divided into: (a)
tailpipe emissions; (b) evaporative and refuelling emissions; and (c)
crankcase emissions.

4. Road transport (excluding petrol distribution) is a major source of
anthropogenic VOC emissions in most ECE countries and contributes between 30
and 45% of total man-made VOC emissions in the ECE region as a whole. By far
the largest source of road transport VOC emissions is the petrol-fuelled
vehicle which accounts for 90% of total traffic emissions of VOCs (of which 30
to 50% are evaporative emissions). Evaporative and refuelling emissions
result primarily from petrol use, and are considered very low in the case of
diesel fuels.

II. GENERAL ASPECTS OF CONTROL TECHNOLOGIES FOR
VOC EMISSIONS FROM ON-ROAD MOTOR VEHICLES

5. The motor vehicles considered in this annex are passenger cars, light-duty
trucks, on-road heavy-duty vehicles, motor cycles and mopeds.

6. While this annex deals with both new and in-use vehicles, it is primarily
focused on VOC-emission control for new vehicle types.

7. This annex also provides guidance on the influence of changes in petrol
properties on evaporative VOC emissions. Fuel substitution (e.g. natural gas,
liquefied petroleum gas (LPG), methanol) can also provide VOC-emission
reductions but this is not considered in this annex.

8. Cost figures for the various technologies given are manufacturing cost
estimates rather than retail prices.

9. It is important to ensure that vehicle designs are capable of meeting
emission standards in service. This can be done through ensuring conformity
of production, full useful-life durability, warranty of emission-control
components, and recall of defective vehicles. For in-use vehicles, continued
emission-control performance can also be ensured by an effective inspection
and maintenance programme, and measures against tampering and misfuelling.

10. Emissions from in-use vehicles can be reduced through programmes such as
fuel volatility controls, economic incentives to encourage the accelerated
introduction of desirable technology, low-level oxygenated fuel blends, and
retrofitting. Fuel volatility control is the single most effective measure
that can be taken to reduce VOC emissions from in-use motor vehicles.

11. Technologies that incorporate catalytic converters require the use of
unleaded fuel. Unleaded petrol should therefore be generally available.

12. Measures to reduce VOC and other emissions by the management of urban and
long-distance traffic, though not elaborated in this annex, are important as
an efficient additional approach to reducing VOC emissions. Key measures for
traffic management aim at improving the modal split through tactical,
structural, financial and restrictive elements.

13. VOC emissions from uncontrolled motor vehicles contain significant levels
of toxic compounds, some of which are known carcinogens. The application of
VOC reduction technologies (tailpipe, evaporative, refuelling and crankcase)
reduces these toxic emissions in generally the same proportion as the VOC
reductions achieved. The level of toxic emissions can also be reduced by
modifying certain fuel parameters (e.g., reducing benzene levels in petrol).

III. CONTROL TECHNOLOGIES FOR TAILPIPE EMISSIONS

(a) Petrol-fuelled passenger cars and light-duty trucks

14. The main technologies for controlling VOC emissions are listed in table
1.

15. The basis for comparison in table 1 is technology option B, representing
non-catalytic technology designed in response to the requirements of the
United States for 1973/1974 or of ECE regulation 15-04 pursuant to the 1958
Agreement concerning the Adoption of Uniform Conditions of Approval and
Reciprocal Recognition of Approval for Motor Vehicles Equipment and Parts.
The table also presents achievable emission levels for open- and closed-loop
catalytic control as well as their cost implications.

16. The "uncontrolled" level (A) in table 1 refers to the 1970 situation in
the ECE region, but may still prevail in certain areas.

17. The emission level in table 1 reflects emissions measured using standard
test procedures. Emissions from vehicles on the road may differ significantly
because of the effect, inter alia, of ambient temperature, operating
conditions, fuel properties, and maintenance. However, the reduction
potential indicated in table 1 is considered representative of reductions
achievable in use.

18. The best currently available technology is option D. This technology
achieves large reductions of VOC, CO and NOx emissions.

19. In response to regulatory programmes for further VOC emission reductions
(e.g. in Canada and the United States), advanced closed-loop three-way
catalytic converters are being developed (option E). These improvements will
focus on more powerful engine-management controls, improved catalysts,
on-board diagnostic systems (OBD) and other advances. These systems will
become best available technology by the mid-1990s.

20. A special category are two-stroke engine cars which are used in parts of
Europe; these cars currently have very high VOC emissions. Hydrocarbon
emissions from two-stroke engines are typically between 45.0 and 75.0 grams
per test, according to the European driving cycle. Attempts are under way to
apply engine modifications and catalytic after-treatment to this type of
engine. Data are needed on the reduction potentials and durability of these
solutions. Furthermore, different two-stroke engine designs are currently
being developed that have the potential for lower emissions.

TABLE 1. TAILPIPE EMISSION CONTROL TECHNOLOGIES FOR PETROL-FUELLED
PASSENGER CARS AND LIGHT-DUTY TRUCKS

—————————————————————————–
Technology option Emission level (%) Cost *
——————–
4-stroke 2-stroke ($ US)
—————————————————————————–
A. Uncontrolled situation 400 900 —

B. Engine modifications 100 — **
(engine design, carburetion and (1.8 g/km)
ignition systems, air injection)

C. Open-loop catalyst 50 — 150-200

D. Closed-loop three-way catalyst 10-30 — 250-450***

E. Advanced closed-loop three-way 6 — 350-600***
catalyst
——————————————————————————

* Additional production-cost estimates per vehicle, relative to technology
option B.

** Costs for engine modifications from options A to B are estimated at $ US
40-100.

*** Under technology options D and E, CO and NOx emissions are also
substantially reduced, in addition to VOC reductions. Technology
options B and C can also result in some CO and/or NOx control.

(b) Diesel-fuelled passenger cars and trucks

21. Diesel-fuelled passenger cars and light-duty trucks have very low VOC
emissions, generally lower than those resulting from closed-loop catalytic
control on petrol-fuelled cars. However, their emissions of particulates and
NOx are higher.

22. No ECE country currently has rigorous tailpipe VOC control programmes for
heavy-duty diesel-fuelled vehicles, because of their generally low VOC
emission rates. However, many countries have diesel particulate control
programmes, and the technology that is employed to control particulates (e.g.,
combustion chamber and injection system improvements) has the net end result
of lowering VOC emissions as well.

23. Tailpipe VOC emission rates from heavy-duty diesel-fuelled vehicles are
expected to be reduced by two thirds as the result of a vigorous particulate
control programme.

24. VOC species emitted from diesel-fuelled engines are different from those
emitted by petrol-fuelled engines.

25. VOC emission control technologies for motor cycles are summarized in
table 2. Current ECE regulations (R.40) can normally be met without requiring
reduction technologies. The future standards of Austria and Switzerland may
require oxidizing catalytic converters for two-stroke engines in particular.

26. For two-stroke mopeds with small oxidizing catalytic converters, a
VOC-emission reduction of 90% is achievable, at additional production costs of
$US 30-50. In Austria and Switzerland, standards requiring this technology
are already in force.

TABLE 2. TAILPIPE EMISSION CONTROL TECHNOLOGIES
AND PERFORMANCE FOR MOTOR CYCLES

—————————————————————————–
Technology option Emission level (%) Cost ($US)*
——————–
2-stroke 4-stroke
—————————————————————————–
A. Uncontrolled 400 100 —
(9.6 g/km) (2 g/km)

B. Best non-catalyst 200 60 —

C. Oxidizing catalytic
converter,
secondary air 30-50 20 50

D. Closed-loop three-way not
catalytic converter applicable 10 ** 350
—————————————————————————–
* Additional production-cost estimates per vehicle.

** Expected to be available by 1991 for a few specific motor cycle types
(prototypes already constructed and tested).

IV. CONTROL TECHNOLOGIES FOR EVAPORATIVE AND REFUELLING EMISSIONS

27. Evaporative emissions consist of fuel vapour emitted from the engine and
fuel system. They are divided into: (a) diurnal emissions, which result from
the "breathing" of the fuel tank as it is heated and cooled over the course of
a day; (b) hot-soak emissions produced by the heat from the engine after it is
shut down; (c) running losses from the fuel system while the vehicle is in
operation; and (d) resting losses such as from open-bottom canisters (where
used) and from some plastic fuel-system materials which are reportedly subject
to permeation losses, in which petrol slowly diffuses through the material.

28. The control technology typically used for evaporative emissions from
petrol-fuelled vehicles includes a charcoal canister (and associated plumbing)
and a purge system to burn the VOCs in a controlled manner in the engine.

29. Experience with existing evaporative-emission control programmes in the
United States indicates that evaporative-emission control systems have not
provided the degree of control desired, especially during severe ozone-prone
days. This is partly because the volatility of in-use petrol is much higher
than that of certification-test petrol. It is also due to an inadequate test
procedure that resulted in inadequate control technology. The United States
evaporative-emission control programme in the 1990s will emphasize
reduced-volatility fuels for use in summer and an improved test procedure to
encourage advanced evaporative control systems that will result in the in-use
control of the four emission sources mentioned in paragraph 27 above. For
countries with high volatility petrol, the single most cost-effective measure
to reduce VOC emissions is to reduce volatility of in-use petrol.

30. In general, effective evaporative-emission control requires the
consideration of: (a) control of petrol volatility, adjusted to climatic
conditions; and (b) an appropriate test procedure.

31. A list of control options, reduction potentials and cost estimates is
given in table 3, with option B as the best available control technology at
present. Option C will soon become best available technology and will
represent a significant improvement over option B.

32. The fuel economy benefits associated with evaporative-emission controls
are estimated at less than 2%. The benefits are due to the higher energy
density, and low Reid-vapour-pressure (RVP) of fuel, and to the combustion
rather than venting of captured vapours.

33. In principle, emissions that are released during refuelling of vehicles
can be recovered by systems installed at petrol stations (Stage II) or by
systems on board of vehicles. Controls at petrol stations are a
well-established technology, while on-board systems have been demonstrated
using several prototypes. The question of in-use safety of on-board vapour
recovery systems is presently under study. It may be appropriate to develop
safety performance standards in conjunction with on-board vapour recovery
systems to assure their safe design. Stage II controls can be implemented
more quickly since service stations in a given area can be fitted with these
controls. Stage II controls benefit all petrol-fuelled vehicles while
on-board systems only benefit new vehicles.

34. While evaporative emissions from motor cycles and mopeds are at present
uncontrolled in the ECE region, the same general control technologies as for
petrol-fuelled cars can be applied.

TABLE 3. EVAPORATIVE-EMISSION CONTROL MEASURES AND REDUCTION
POTENTIALS FOR PETROL-FUELLED PASSENGER CARS AND
LIGHT-DUTY TRUCKS

—————————————————————————–
Technology option VOC reduction Cost ($ US) 2/
potential (%) 1/
—————————————————————————–
A. Small canister, lenient RVP 3/ 95 33
stringent RVP limits, 4/
1990s US Test Procedure 5/
—————————————————————————–

1/ Relative to uncontrolled situation.

2/ Additional production-cost estimates per vehicle.

3/ Reid vapour pressure.

4/ Based on United States data, assuming an RVP limit of 62 kPa during
warm season at a cost of $ US 0.0038 per litre. Taking account of the fuel
economy benefit associated with low RVP petrol, the adjusted cost estimate is
$ US 0.0012 per litre.

5/ United States Test Procedure in the 1990s will be designed for the
more effective control of multiple diurnal emissions, running losses,
operation under high ambient temperature, hot-soak conditions following
extended operation, and resting losses.

ANNEX IV

CLASSIFICATION OF VOLATILE ORGANIC COMPOUNDS (VOCs) BASED ON
THEIR PHOTOCHEMICAL OZONE CREATION POTENTIAL (POCP)

1. This annex summarizes the information available and identifies the still
existing elements to develop in order to guide the work to be carried out. It
is based on information regarding hydrocarbons and ozone formation contained
in two notes prepared for the Working Group on Volatile Organic Compounds
(EB.AIR/WG.4/R.11 and R.13/Rev.1); on the results of further research carried
out, in particular in Austria, Canada, Germany, Netherlands, Sweden, the
United Kingdom, the United States of America and the EMEP Meteorological
Synthesizing Centre-West (MSC-W); and on supplementary information provided by
governmentally designated experts.

2. The final aim of the POCP approach is to provide guidance on regional and
national control policies for volatile organic compounds (VOCs), taking into
account the impact of each VOC species as well as sectoral VOC emissions in
episodic ozone formation expressed in terms of the photochemical ozone
creation potential (POCP), which is defined as the change in photochemical
ozone production due to a change in emission of that particular VOC. POCP may
be determined by photochemical model calculations or by laboratory
experiments. It serves to illustrate different aspects of episodic oxidant
formation; e.g. peak ozone or accumulated ozone production during an episode.

3. The POCP concept is being introduced because there is a large variation
between the importance of particular VOCs in the production of ozone during
episodes. A fundamental feature of the concept is that, in the presence of
sunlight and NOx, each VOC produces ozone in a similar way despite large
variations in the circumstances under which ozone is produced.

4. Different photochemical model calculations indicate that substantial
reduction of VOCs and NOx emissions are necessary (order of magnitude above
50% in order to achieve significant ozone reduction). Moreover the maximum
concentrations of ozone near the ground are reduced in a less than
proportional way when VOC emissions are reduced. This effect is shown in
principle by theoretical scenario calculation. When all species are reduced
by the same proportion, maximum ozone values (above 75 ppb hourly average) in
Europe are reduced depending on the existing ozone level by only 10-15% if the
mass of non-methane man-made VOC emissions is reduced by 50%. By contrast, if
emissions of the most important (in terms of POCP and mass values or
reactivity) non-methane man-made VOC species were reduced by 50% (by mass),
the calculated result is a 20-30% reduction of peak episodic ozone
concentration. This confirms the merits of a POCP approach to determine
priorities for VOC emission control and clearly shows that VOCs may at least
be divided into large categories, according to their importance in episodic
ozone formation.

5. POCP values and reactivity scales have been calculated as estimates, each
based on a particular scenario (e.g. emission increases and decreases, air
mass trajectories) and targeted towards a particular objective (e.g. peak
ozone concentration, integrated ozone, average ozone). POCP values and
reactivity scales are dependent on chemical mechanisms. Clearly there are
differences between the different estimates of POCPs, which in some cases can
span more thana factor of four. The POCP numbers are not constant but vary in
space and time.To give an example: the calculated POCP of ortho-xylene in the
so-called “France-Sweden” trajectory has a value of 41 on the first day and of
97 on the fifth day of the travelling time. According to calculations of the
Meteorological Synthesizing Centre-West (MSC-W) of EMEP, the POCP of
ortho-xylene for O3 over 60 ppb, varies between 54 and 112 (5 to 95
percentiles) for the grids of the EMEP area. The variation of the POCP in
time and space is not only caused by the VOC composition of the air parcel due
to man-made emissions but is also a result of meteorological variations. The
fact is that any reactive VOC can contribute to the episodical formation of
photochemical oxidants to a higher or lower extent, depending on the
concentrations of NOx and VOC and meteorological parameters. Hydrocarbons
with very low reactivity, like methane, methanol, ethane and some chlorinated
hydrocarbons contribute in a negligible manner to this process. There are
also differences as a result of meteorological variations between particular
days and over Europe as a whole. POCP values are implicitly dependent on how
emission inventories are calculated. Currently there is no consistent method
or information available across Europe. Clearly, further work has to be done
on the POCP approach.

6. Natural isoprene emissions from deciduous trees, together with nitrogen
oxides (NOx) mainly from man-made sources, can make a significant contribution
to ozone formation in warm summer weather in areas with a large coverage of
deciduous trees.

7. In table 1, VOC species are grouped according to their importance in the
production of episodic peak ozone concentrations. Three groups have been
selected. Importance in table 1 is expressed on the basis of VOC emission per
unit mass. Some hydrocarbons, such as n-butane, become important because of
their mass emission although they may not appear so according to their OH
reactivity.

8. Tables 2 and 3 show the impacts of individual VOCs expressed as indices
relative to the impact of a single species (ethylene) which is given an index
of 100. They indicate how such indices, i.e. POCPs, may give guidance for
assessing the impact of different VOC emission reductions.

9. Table 2 shows averaged POCPs for each major source category based on a
central POCP estimate for each VOC species in each source category. Emission
inventories independently determined in the United Kingdom and Canada have
been used in this compilation and presentation. For many sources, e.g. motor
vehicles, combustion installations, and many industrial processes, mixtures of
hydrocarbons are emitted. Measures to reduce specifically the VOC compounds
identified in the POCP approach as very reactive are in most cases
unavailable. In practice, most of the possible reduction measures will reduce
emissions by mass irrespective of their POCPs.

10. Table 3 compares a number of different weighting schemes for a selected
range of VOC species. In assigning priorities within a national VOC control
programme, a number of indices may be used to focus on particular VOCs. The
simplest but least effective approach is to focus on the relative mass
emission,or relative ambient concentration.

TABLE 1. CLASSIFICATION OF VOCs INTO THREE GROUPS ACCORDING
TO THEIR IMPORTANCE IN EPISODIC OZONE FORMATION

—————————————————————————-
More important

Alkenes
Aromatics
Alkanes > C6 alkanes except 2,3 dimethylpentane
Aldehydes All aldehydes except benzaldehyde
Biogenics Isoprene

Less important

Alkanes C3 – C5 alkanes and 2,3 dimethylpentane
Ketones Methyl ethyl ketone and methyl t-butyl ketone
Alcohols Ethanol
Esters All esters except methyl acetate

Least important
Alkanes Methane and ethane
Alkynes Acetylene
Aromatics Benzene
Aldehydes Benzaldehyde
Ketones Acetone
Alcohols Methanol
Esters Methyl acetate
Chlorinated hydrocarbons Methyl chloroform,
Methylene chloride,
Trichloroethylene and tetrachloroethylene
—————————————————————————–

11. Relative weighting based on OH reactivity addresses some but by no means
all of the important aspects of the atmospheric reactions which generate ozone
in the presence of NOx and sunlight. The SAPRC (Statewide Air Pollution
Research Centre) weightings address the situation in California. Because of
differences in the model conditions appropriate to the Los Angeles basin and
Europe, major differences in the fates of photochemical, labile species, such
asaldehyde, result. POCPs calculated with photochemical models in the
Netherlands, United States of America, United Kingdom, Sweden and by EMEP
(MSC-W) address different aspects of the ozone problem in Europe.

12. Some of the less-reactive solvents cause other problems, e.g. they are
extremely harmful to human health, difficult to handle, persistent, can cause
negative environmental effects at other levels (e.g. in the free troposphere
or the stratosphere). In many cases the best available technology for
reducing solvent emission is the application of non-solvent using systems.

13. Reliable VOC emission inventories are essential to the formulation of any
cost-effective VOC control policies and in particular those based on the POCP
approach. National VOC emissions should therefore be specified according to
sectors, at least following guidelines specified by the Executive Body, and
should as far as possible be complemented by data on species and time
variations of emissions.

TABLE 2. SECTORAL POCPs OF THE VARIOUS EMISSION SECTORS AND THE
PERCENTAGE BY MASS OF VOCs IN EACH OZONE CREATION CLASS

—————————————————————————–
Sector Sectoral POCP | Percentage mass in each
| ozone creation class
——————————————-
Canada | United | More Less Least | Unknown
| Kingdom | Important |
—————————————————————————–
Petrol-engined vehicle exhaust 63 61 76 16 7 1
Diesel vehicle exhaust 60 59 38 19 3 39
Petrol-engined vehicle evaporation — 51 57 29 2 12
Other transport 63 — — — — —
Stationary combustion — 54 34 24 24 18
Solvent usage 42 40 49 26 21 3
Surface coating 48 51 — — — —
Industrial process emissions 45 32 4 41 0 55
Industrial chemicals 70 63 — — — —
Petroleum refining and distribution 54 45 55 42 1 2
Natural gas leakage — 19 24 8 66 2
Agriculture — 40 — — 100 —
Coal mining — 0 — — 100 —
Domestic waste landfill — 0 — — 100 —
Dry cleaning 29 — — — — —
Wood combustion 55 — — — — —
Slash burn 58 — — — — —
Food industry — 37 — — — —
——————————————————————————

TABLE 3. COMPARISON BETWEEN WEIGHTING SCHEMES
(EXPRESSED RELATIVE TO ETHYLENE = 100) FOR 85 VOC SPECIES

—————————————————————————->
OH Canada SAPRC UK UK
VOC Scale by mass MIR POCP range
[a] [b] [c] [d] [e]
—————————————————————————->
Methane 0.1 — 0 0.7 0-3
Ethane 3.2 91.2 2.7 8.2 2-30
Propane 9.3 100 6.2 42.1 16-124
n-Butane 15.3 212 11.7 41.4 15-115
i-Butane 14.2 103 15.7 31.5 19-59
n-Pentane 19.4 109 12.1 40.8 9-105
i-Pentane 18.8 210 16.2 29.6 12-68
n-Hexane 22.5 71 11.5 42.1 10-151
2-Methylpentane 22.2 100 17.0 52.4 19-140
3-Methylpentane 22.6 47 17.7 43.1 11-125
2,2-Dimethylbutane 10.5 — 7.5 25.1 12-49
2,3-Dimethylbutane 25.0 — 13.8 38.4 25-65
n-Heptane 25.3 41 9.4 52.9 13-165
2-Methylhexane 18.4 21 17.0 49.2 11-159
3-Methylhexane 18.4 24 16.0 49.2 11-157
n-Octane 26.6 — 7.4 49.3 12-151
2-Methylheptane 26.6 — 16.0 46.9 12-146
n-Nonane 27.4 — 6.2 46.9 10-148
2-Methyloctane 27.3 — 13.2 50.5 12-147
n-Decane 27.6 — 5.3 46.4 8-156
2-Methylnonane 27.9 — 11.7 44.8 8-153
n-Undecane 29.6 21 4.7 43.6 8-144
n-Duodecane 28.4 — 4.3 41.2 7-138
Methylcyclohexane 35.7 18 22.3 — —
Methylene chloride — — – 1 0-3
Chloroform — — — — —
Methyl chloroform — — — 0.1 0-1
Trichloroethylene — — — 6.6 1-13
Tetrachloroethylene — — — 0.5 0-2
Allyl chloride — — — — —
Methanol 10.9 — 7 12.3 9-21
Ethanol 25.5 — 15 26.8 4-89
i-Propanol 30.6 — 7 — —
Butanol 38.9 — 30 — –
i-Butanol 45.4 — 14 — —
Ethylene glycol 41.4 — 21 — —
Propylene glycol 55.2 — 18 — —
But-2-diol — — — — —
Dimethyl ether 22.3 — 11 — —
Methyl-t-butyl ether 11.1 — 8 — —
Ethyl-t-butyl ether 25.2 — 26 — —

Acetone 1.4 — 7 17.8 10-27
Methyl ethyl ketone 5.5 — 14 47.3 17-80
Methyl-i-butyl ketone — — — — —

Methyl acetate — — — 2.5 0-7
Ethyl acetate — — — 21.8 11-56
i-Propyl acetate — — — 21.5 14-36
n-Butyl acetate — — — 32.3 14-91
i-Butyl acetate — — — 33.2 21-59

Propylene glycol methyl
Ether — — — — —
Propylene glycol methyl
Ether acetate — — — — —

Ethylene 100 100 100 100 100
Propylene 217 44 125 103 75-163
1-Butene 194 32 115 95.9 57-185
2-Butene 371 — 136 99.2 82-157
1-Pentene 148 — 79 105.9 40-288
2-Pentene 327 — 79 93.0 65-160
2-Methyl-1-butene 300 — 70 77.7 52-113
2-Methyl-2-butene 431 24 93 77.9 61-102
3-Methyl-1-butene 158 — 79 89.5 60-154
Isobutene 318 50 77 64.3 58-76
Isoprene 515 — 121 — –

Acetylene 10.4 82 6.8 16.8 10-42

Benzene 5.7 71 5.3 18.9 11-45
Toluene 23.4 218 34 56.3 41-83
o-Xylene 48.3 38 87 66.6 41-97
m-Xylene 80.2 53 109 99.3 78-135
p-Xylene 49.7 53 89 88.8 63-180
Ethylbenzene 25 32 36 59.3 35-114
1,2,3-Trimethyl benzene 89 — 119 117 76-175
1,2,4-Trimethyl benzene 107 44 119 120 86-176
1,3,5-Trimethyl benzene 159 — 140 115 74-174
o-Ethyltoluene 35 — 96 66.8 31-130
m-Ethyltoluene 50 — 96 79.4 41-140
p-Ethyltoluene 33 — 96 72.5 36-135
n-Propylbenzene 17 — 28 49.2 25-110
i-Propylbenzene 18 — 30 56.5 35-105

Formaldehyde 104 — 117 42.1 22-58
Acetaldehyde 128 — 72 52.7 33-122
Proprionaldehyde 117 — 87 60.3 28-160
Butyraldehyde 124 — — 56.8 16-160
i-Butyraldehyde 144 — — 63.1 38-128
Valeraldehyde 112 — — 68.6 0-268
Acrolein — — — — —
Benzaldehyde 43 — -10 -33.4 -82-(-12)
—————————————————————————->

[TABLE 3 continued]

<———————————————————————–
Sweden EMEP LOTOS
VOC max. diff. 0-4 days
[f] [g] [h] [i]
<————————————————————————

Methane — — — —
Ethane 17.3 12.6 5-24 6-25
Propane 60.4 50.3 — —
n-Butane 55.4 46.7 22-85 25-87
i-Butane 33.1 41.1 — —
n-Pentane 61.2 29.8 — —
i-Pentane 36.0 31.4 — —
n-Hexane 78.4 45.2 — —
2-Methylpentane 71.2 52.9 — —
3-Methylpentane 64.7 40.9 — —
2,2-Dimethylbutane — — — —
2,3-Dimethylbutane — — — —
n-Heptane 79.1 51.8 — —
2-Methylhexane — — — —
3-Methylhexane — — — —
n-Octane 69.8 46.1 — —
2-Methylheptane 69.1 45.7 — —
n-Nonane 63.3 35.1 — —
2-Methyloctane 66.9 45.4 — —
n-Decane 71.9 42.2 — —
2-Methylnonane 71.9 42.3 — —
n-Undecane 66.2 38.6 — —
n-Duodecane 57.6 31.1 — —
Methylcyclohexane 40.3 38.6 — —
Methylene chloride 0 0 — —
Chloroform 0.7 0.4 — —
Methyl chloroform 0.2 0.2 — —
Trichloroethylene 8.6 11.1 — —
Tetrachloroethylene 1.4 1.4 — —
Allyl chloride 56.1 48.3 — —
Methanol 16.5 21.3 — —
Ethanol 44.6 22.5 9-58 20-71
i-Propanol 17.3 20.3 — —
Butanol 65.5 21.4 — —
i-Butanol 38.8 25.5 — —
Ethylene glycol — — — —
Propylene glycol — — — —
But-2-diol 28.8 6.6 — —
Dimethyl ether 28.8 34.3 — —
Methyl-t-butyl ether — — — —
Ethyl-t-butyl ether — — — —

Acetone 17.3 12.4 — —
Methyl ethyl ketone 38.8 17.8 — —
Methyl-i-butyl ketone 67.6 31.8 — —

Methyl acetate 5.8 6.7 — —
Ethyl acetate 29.5 29.4 — —
i-Propyl acetate — — — —
n-Butyl acetate 43.9 32.0 — —
i-Butyl acetate 28.8 35.3 — —

Propylene glycol methyl
Ether 77.0 49.1 — —
Propylene glycol methyl
Ether acetate 30.9 15.7 — —

Ethylene 100 100 100 100
Propylene 73.4 59.9 69-138 55-120
1-Butene 79.9 49.5 — —
2-Butene 78.4 43.6 — —
1-Pentene 72.7 42.4 — —
2-Pentene 77.0 38.1 — —
2-Methyl-1-butene 69.1 18.1 — —
2-Methyl-2-butene 93.5 45.3 — —
3-Methyl-1-butene — — — —
Isobutene 79.1 58.0 — —
Isoprene 53.2 58.3 — —
Acetylene 27.3 36.8 — —
Benzene 31.7 40.2 — —
Toluene 44.6 47.0 — —
o-Xylene 42.4 16.7 54-112 26-67
m-Xylene 58.3 47.4 — —
p-Xylene 61.2 47.2 — —
Ethylbenzene 53.2 50.4 — —
1,2,3-Trimethyl benzene 69.8 29.2 — —
1,2,4-Trimethyl benzene 68.3 33.0 — —
1,3,5-Trimethyl benzene 69.1 33.0 — —
o-Ethyltoluene 59.7 40.8 — —
m-Ethyltoluene 62.6 40.1 — —
p-Ethyltoluene 62.6 44.3 — —
n-Propylbenzene 51.1 45.4 — —
i-Propylbenzene 51.1 52.3 — —
Formaldehyde 42.4 26.1 — —
Acetaldehyde 53.2 18.6 — —
Proprionaldehyde 65.5 17.0 — —
Butyraldehyde 64.0 17.1 — —
i-Butyraldehyde 58.3 30.0 — —
Valeraldehyde 61.2 32.1 — —
Acrolein 120.1 82.3 — —
Benzaldehyde — — — —
<———————————————————————-

[a] OH + VOC rate coefficient divided by molecular weight.
[b] Ambient VOC concentrations at 18 sites in Canada expressed on mass
basics.
[c] Maximum Incremental Reactivity (MIR) based on California scenarios;
Statewide Air Pollution Research Centre, Los Angeles, USA.
[d] Average POCP based on three scenarios and 9 days; FRG-Ireland,
France-Sweden and UK.
[e] Range of POCPs based on three scenarios and 11 days.
[f] POCPs calculated for a single source in Sweden producing maximum ozone
difference.
[g] POCPs calculated for a single source in Sweden using average difference
in ozone over 4 days.
[h] Range (5th-95th percentile) of POCPs calculated over EMEP grid.
[i] Range (20th-80th percentile) of POCPs calculated over LOTOS grid.

a/b
POCP = — x 100
c/d

where (a) – Change in photochemical oxidant formation due to a change in a VOC
emission
(b) – Integrated VOC emission up to that time
(c) – Change in photochemical oxidant formation due to a change in
ethylene emissions
(d) – Integrated ethylene emission up to that time

It is a quantity derived from a photochemical ozone model by following the
photochemical ozone production with and without the presence of an individual
hydrocarbon. The difference in ozone concentrations between such pairs of
model calculations is a measure of the contribution that VOC makes in ozone

Volatile Organic Compounds, 1991

Volatile Organic Compounds, 1991 in United States

Volatile Organic Compounds, 1991

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