Tio2 Simplification Report Iss3

Analysis of the Simplification of
the Titanium Dioxide Directives
Report to European Commission DG ENV.G.1

Restricted Commercial
ED05640
AEAT/ENV/R/2506 Issue Number 3
December 2007
AEAT/ENV/R/2506/Issue 3
Analysis of the simplification

of the TiO2 Directives
Title
Analysis of the Simplification of the Titanium Dioxide Directives
Customer
European Commission DG Environment Sustainable Development and

Economic Analysis Unit
Customer reference
ENV.G.1/FRA/2006/0073
Confidentiality,
copyright and
reproduction
This document has been prepared by AEA Technology plc in connection

with a contract to supply goods and/or services and is submitted only on
the basis of strict confidentiality. The contents must not be disclosed to
third parties other than in accordance with the terms of the contract.
File reference
ED05640
Reference number
AEA Energy & Environment

The Gemini Building
Fermi Avenue
Harwell International Business Centre
Didcot
OX11 0QR
Phone: +44 (0) 870 190 6575
Fax: +44 (0) 870 190 6318
AEA Energy & Environment is a business name of
AEA Technology plc
AEA Energy & Environment is certificated to ISO9001
and ISO14001
Author
Name
R. Stewart, H. Lawrence, A. Leonard (AEA Energy and

Environment)
M. Holland (EMRC)
A. van Hyfte, A. Algoet and L. de Smet (Arcadis Ecloas)
Approved by
Name
D. Forster
Signature
Date
December 2007
iii

iv
AEA/ED05458/Issue 3

Executive Summary
The overall objective of this contract is to support the Commission in the simplification and
rationalisation of the Titanium Dioxide (TiO2) Directives, taking into consideration the review of
Directive 96/61/EC on Integrated Pollution Prevention and Control (IPPC). The costs and benefits of
different scenarios for setting emission limit values for the TiO2 manufacturing industry are assessed.
In addition, consideration is given to the simplification of monitoring requirements for releases to water
and air, bearing in mind that any simplification must meet the objective of ensuring no reduction of
environmental protection.
The objective of this study required three linked tasks:
1. Data gathering
2. Emission limit analysis
3. Options for simplification of monitoring and changes in frequency
Two processes are used for TiO2 manufacture, the chloride and sulphate processes. Both take ore
containing TiO2, convert it to other compounds enabling impurities to be removed, and then re-form
TiO2. Naturally, each process has its own set of burdens to health and the environment via pollutants
generated in the process.
Questionnaires designed to supplement information obtained through an earlier consultation led by the
European Commission have been sent to all operators of TiO2 manufacturing plant and to regulators
in all relevant Member States. Responses have been received from several Member States (Belgium,
Czech Republic, Finland, Germany, the Netherlands, Slovenia and the UK).
Responses to the questionnaire indicate that there is a view in several Member States that much of
the content of the TiO2 Directives is now redundant, largely because of the role of other Directives (the
IPPC Directive in particular). The response of industry to the questionnaire has been low, but it has
been indicated by the TDMA (Titanium Dioxide Manufacturers Association) that they are reluctant for
the emission limit values specified in the 1992 TiO2 Directive to be removed.
The latest emissions data available show broad ranges for emissions per tonne of pollution. In some
cases plant barely meet the Directive limits, whilst in others plant meet the lower range defined for
1
BAT (Best Available Techniques) in the sectors BREF note .
The costs and benefits of tightening the emission limit values given in the Directives to the ranges
defined under the LVIC-S BREF for the TiO2 industry have been considered to the extent possible.
Scenarios were defined as follows:
Table i. Emission limit values for each scenario
Scenario 1
Directive
Sulphate process
3
Dust to air
50 mg/m
SO2 to air
10 kg/t TiO2
SO4 to water
800 kg/t TiO2
Chloride process
3
Dust to air
50 mg/m
SO2 to air
Not given
3
Cl2 to air
5 mg/m (daily)
3
40 mg/m (instant)
Cl to water
130-450 kg/t TiO2
1
Scenario 2
Upper BAT
Scenario 3
Lower BAT
Scenario 4
Between S1
and S2
Scenario 5
Between S2
and S3
0.45 kg/t TiO2

3
20 mg/m
6 kg/t TiO2
550 kg/t TiO2
0.004 kg/t TiO2

3
5 mg/m
1 kg/t TiO2
100 kg/t TiO2
0.7 kg/t TiO2
0.25 kg/t TiO2
9 kg/t TiO2
785 kg/t TiO2
4 kg/t TiO2
300 kg/t TiO2
0.2 kg/t TiO2

1.7 kg/t TiO2
Not given
0.1 kg/t TiO2

1.3 kg/t TiO2
Not given
0.4 kg/t TiO2

No data
No data
0.15 kg/t TiO2

No data
No data
330 kg/t TiO2
38 kg/t TiO2
330 kg/t TiO2
150 kg/t TiO2
The Large Volume Solid Inorganic Chemicals (LVIC-S) BAT Refernce (BREF) note.

AEA/ED05458/Issue 3
The emissions data provided by the industry to the Commission earlier in 2007 enabled assessment of
the extent to which these limit values were met on a plant by plant (though anonymous) basis. Where
they were not met, estimates were made of the emission reductions required and associated costs
2
and benefits, where possible. Results are summarised in Tables (ii) and (iii), the two tables
representing the range of results arising from uncertainty in the way that emission limit values and
emissions data are expressed (whether per tonne of pure TiO2 or per tonne TiO2 pigment).
1
Table ii. Costs and benefits of moving to within the emission limit values defined for each scenario
based on assumptions that minimise the number of plant exceeding limit values (emissions
expressed against TiO2, ELVs against TiO2 pigment).
Scenario 2
Additional abatement costs (M/year)
Dust
1.3
SO2
6.4
Chlorine
No data
Sulphate
2.2
Chloride
0
4
Quantified costs
9.9
Scenario 3
Scenario 4
Scenario 5
6.4
17
No data
12
No data
34
0
0
No data
0
0
0
2.2
9.6
No data
4.4
No data
16
0
0
Not quantified
0
3.2
17
Not quantified
20
2, 3
Benefits from additional abatement (M/year)

Dust
1.3
10
SO2
14
25
Other pollutants
Not quantified
Not quantified
4
Quantified benefits
15
35
Notes: 1) So far as simplification of the TiO2 Directives is concerned, there are no costs or benefits relating to the attainment of
the current Directive (i.e. the Scenario 1 limit values). 2) Damage cost data are available only for emissions of dust and SO2,
but not for emissions of sulphate, chloride or chlorine. 3) Benefits shown are based on damage costs at the lower end of the
range given in the BREF on Economics and Cross Media Effects. Use of the upper end of the range would make these benefits
roughly three times larger. 4) The total quantified costs shown here omit the costs of any further abatement of chlorine (if it is
necessary) and in some cases, further controls on chlorides. Quantified benefits are less complete still, with no benefits
quantified for sulphates, chlorides or chlorine. This needs to be considered when comparing the totals shown for costs and
benefits.
1
Table iii. Costs and benefits of moving to within the emission limit values defined for each scenario
based on assumptions that maximise the number of plant exceeding limit values (emissions
expressed against TiO2 pigment, ELVs against TiO2).
Scenario 2
Additional abatement costs (M/year)
Dust
1.8
SO2
9.6
Chlorine
No data
Sulphate
4.4
Chloride
no data
4
Quantified costs
16
Scenario 3
Scenario 4
Scenario 5
6.4
19
No data
13
No data
39
1.3
4.8
No data
0
0
6.1
3.9
16
No data
6.6
No data
27
0.5
11
Not quantified
12
4.5
20
Not quantified
25
2, 3
Benefits from additional abatement (M/year)

Dust
2.5
11
SO2
17
25
Other pollutants
Not quantified
Not quantified
4
Quantified benefits
20
36
Notes: See notes to Table (ii).
Updated emissions data were sent by the TDMA to the Commission at the end of the project, but unfortunately too late for inclusion in the full
analysis carried out under the contract. However, it has been concluded that they are unlikely to significantly change the conclusions reached in
this report (see Section 6.4 and Appendix 5).
vi

The results shown in the two tables are subject to various uncertainties further to questions about how
emission limit values and emissions data are expressed and the magnitude of benefits per unit
emission of SO2 and dust (see note 3 to Table ii). The most significant include:
a) Changes in emissions through switching to alternative sources of ore and to different fuels.
b) Uncertainties in the extent to which emissions can be reduced. This brings into question the
achievability of the Scenario 3 limits in particular.
c) Uncertainties in the costs of reducing emissions. This contains biases in both directions
estimated costs are largely based on installation of new equipment rather than the upgrading
of existing plant. This is unlikely to be necessary in all cases. On the other hand, some plant
may require significant adaptation to fit in necessary equipment. Costs are most uncertain for
attainment of the Scenario 3 (lower BAT-AEL) limits - there is little information in the LVIC-S
BREF on how these are achieved.
d) Uncertainties in the response of industry to a tightening of emission levels. It is possible that
cheaper solutions could be found than those proposed (e.g. changing the type of ore used).
At the other extreme, operators could decide to close plant rather than upgrade them
industry sources have said that 2 plant could close if dust emission limits were reduced to
3
5 mg/Nm , though have provided no supporting evidence for this view.
e) There is potential to generate significant additional environmental burdens by moving to the
lowest emission control scenarios. The effects of these burdens (greenhouse gas and other
air emissions, solid wastes, etc.) are not accounted for here.
Overall, no evidence has been made available under the contract that demonstrates that the analysis
presented here has a significant bias in any direction. At the same time, information that would allow
more detailed analysis of the effects of these uncertainties on the cost-benefit analysis is not available.
With this in mind, and irrespective of the way that a future directive might express ELVs, it is
recommended that most attention be given to the results shown in Table (iii) where it is assumed that
emissions data available for the analysis are expressed per unit TiO2 pigment and ELVs are
expressed per unit pure TiO2,. This is the most pessimistic case of the three listed above so far as
possible exceedance of limit values and hence additional costs of abatement are concerned. As the
most pessimistic case, it is also the one that provides the most robust rationale for a reduction in
emission limit values.
It has not been possible to assess compliance of chlorine emissions with the Directive through a lack
of data in the format necessary. However, releases of chlorine to the environment should be tightly
controlled as a result of the Seveso II directive, which applies to chloride process TiO2 plant. It is
noted that emissions of chlorine from one plant seem significantly higher than from the other four
chloride process plant.
The effects of pollutant releases to air and to water are dependent on the site of release. However,
this is much more important for emissions to water, as pollutant movement is more constrained and
receiving environments are extremely variable with respect to chemical composition, flow rates,
ecology and so on. When setting emission limits for liquid discharges it is therefore much more
important to take account of the site of release than it is when setting limits for aerial discharges. A
further issue is that this variability means that generic estimates of damage per tonne emission are not
available for releases to water in the same way that they are available via the BREF on Economics
and Cross Media Effects for certain air pollutants, and hence for sulphate and chloride emissions no
estimate of the benefits of additional control has been made (explaining the lack of information on their
effects in Tables (ii) and (iii)).
The monitoring requirements of the TiO2 Directives have been reviewed and considered alongside
other legislation (e.g. the Air and Water Framework Directives and the IPPC Directive). CEN, ISO and
other monitoring standards have been identified and are listed in the report.
It is acknowledged that, historically, the requirement for environmental monitoring around TiO2
manufacturing sites made good sense, though given improvements in the performance of TiO2 plant in
the last 30 years it is not clear that this remains the case. On this basis (and others detailed in the
report, such as the requirements of the air quality and water framework Directives, agreed since the
last of the current TiO2 came into force) there may be a rationale for abandoning much of the wider
environmental monitoring required specifically in relation to the TiO2 industry. Associated costs are
estimated, with a commentary on whether they are likely to be paid for by the operator or the
vii

AEA/ED05458/Issue 3
regulator. However, it is noted that Directive 82/883/EEC already provides for simplification of
monitoring to meet local conditions (via Article 4.3) once it is established that emissions from TiO2
manufacture are not causing significant environmental damage.
It would be possible to simplify the 1992 Directive by reference to the process discharge monitoring
requirements of the IPPC Directive. However, given that the monitoring would need to be done
anyway this simplification would have no effect, other than a minor easing of the regulatory burden
for reporting on the TiO2 regulations to the European Commission.
viii

Table of contents
1
Introduction ...................................................................................................... 1
1.1
Objectives of this Report.................................................................................................... 1
1.2
Environmental Regulation of the TiO2 Industry ................................................................. 1
1.3
Consultation on Simplification of the TiO2 Directives ........................................................ 2
1.4
Overview of Study Methodology ........................................................................................ 2
The TiO2 Industry in Europe............................................................................ 6

2.1
Overview ............................................................................................................................ 6
2.2
Chloride Process ............................................................................................................... 7
2.3
Sulphate Process............................................................................................................... 9
2.4
Pollution Control Techniques for Air Emissions............................................................... 11
2.5
Pollution Control Techniques for Liquid Effluents............................................................ 12
2.6
Control of Solid Wastes ................................................................................................... 13
2.7
TiO2 Content of Pigment as Sold..................................................................................... 14
Data Collection from the Industry and Regulators...................................... 16

3.1
Approach.......................................................................................................................... 16
3.2
Responses to Survey Sent to Plant Operators................................................................ 16
3.3
Responses to Surveys Sent to Member State Regulators .............................................. 16
Emission Scenario Analysis of Social, Economic and Environmental
Impacts .................................................................................................................... 18
4.1
Impacts Associated with the Sector................................................................................. 18
4.2
Scenario Development .................................................................................................... 19
4.3
Analysis............................................................................................................................ 21
4.4
Effects on competitiveness and employment .................................................................. 33
Analysis on Monitoring of the Environment ................................................ 38

5.1
Introduction ...................................................................................................................... 38
5.2
Summary of monitoring requirements in the TiO2 Directives........................................... 38
5.3
Current monitoring in relation to TiO2 manufacture: ........................................................ 41
5.4
Monitoring Standards....................................................................................................... 44
5.5
Potential for simplification of monitoring .......................................................................... 46
5.6
Analysis of the impacts of simplifications of monitoring requirements ............................ 49
Conclusions and Recommendations ........................................................... 52

6.1
Emission limit values ....................................................................................................... 52
6.2
Monitoring ........................................................................................................................ 54
6.3
Definitions ........................................................................................................................ 55
6.4
Further analysis ............................................................................................................... 55
ix

AEA/ED05458/Issue 3
Appendices
Appendix 1: References
Appendix 2: Questionnaire sent to Plant Operators
Appendix 3: Questionnaire sent to Member States
Appendix 4: Background information on impacts associated with pollutants emitted from TiO2
manufacture
Appendix 5: Emissions data
Appendix 6: Emission control methods and costs
Appendix 7: Trends in Emissions According to EPER, 2001-2004
Appendix 8: Monitoring standards for relevant air pollutants

1 Introduction
1.1 Objectives of this Report
The overall objective of this contract is to support the Commission in the simplification and
rationalisation of the Titanium Dioxide (TiO2) Directives, taking into consideration the review of
Directive 96/61/EC on Integrated Pollution Prevention and Control (IPPC). The costs and benefits of
different scenarios for setting emission limit values for the TiO2 manufacturing industry are assessed.
In addition, consideration is given to the simplification of monitoring requirements for releases to water
and air, bearing in mind that any simplification must meet the objective of ensuring no reduction of
environmental protection.
1.2 Environmental Regulation of the TiO2 Industry

At present there are three Directives in place which set out controls including monitoring requirements
for TiO2 manufacture. The Directives are summarised in Table 1-1.
Table 1-1 : Summary of titanium dioxide Directives
Directive
78/176/EEC
Title
Council Directive on waste from the
Titanium Dioxide Industry
82/883/EEC
Council Directive on procedures for

the surveillance and monitoring of
environments concerned by waste
from the Titanium Dioxide industry
Council directive on procedures for
harmonising the programmes for
the
reduction
and
eventual
elimination of pollution caused by
waste from the Titanium Dioxide
industry.
92/112/EEC
Main Provisions
Minimum permitting requirements, monitoring
and requirement for Member State progress
reports.
Defines
the frequency, locations, and
parameters to be monitored at and around TiO2
facilities
Specifies emission limit values for waste
streams discharged to water and discharges to
air.
The TiO2 Directives include requirements for Member States to provide reports to the Commission on
progress towards objectives and the ongoing monitoring of the receiving environments. However, little
information was available on this.
Other Community legislation is also relevant; in particular the Directive 96/61/EC (IPPC) and the
Directive 2006/12/EC on waste, Directive 2000/60/EC (the Water Framework Directive) and Directive
96/62/EC on air quality.
The industry is also affected by the Euratom Directive (96/29/EEC) as a result of the presence of trace
levels of NORMs (Naturally Occurring Radioactive Materials) in some ores and the Seveso II Directive
from use of chlorine in plant that follow the chloride process for TiO2 manufacture.
Use of sector-specific Directives to control the environmental impact of industrial activities is not
common (other directives include 2000/76/EC on incineration of waste and 2001/80/EC on large
combustion plant), the main Community mechanism for control of industrial activities is the IPPC
Directive, which requires consideration of releases to all media. However, the IPPC Directive was not
in place when the need for a Community measure to control TiO2 manufacture was identified.

AEA/ED05458/Issue 3
1.3 Consultation on Simplification of the TiO2 Directives

1.3.1 Stakeholder consultation
The Commission started to consult Member States in 2004, with a questionnaire relating to
simplification of specific measures in the TiO2 Directives. A second stakeholder consultation was
carried out in 2006 including a questionnaire and a paper showing potential simplifications to the TiO2
3
Directive . The proposals for the simplified Directive essentially merged the requirements of the three
existing TiO2 Directives into a single Directive. The questionnaire offered stakeholders the opportunity
to comment on the proposed changes. Stakeholders were also invited to comment and provide
suggestions for further potential simplification; in particular in those areas, such as permitting and
monitoring, where other Community legislation (including IPPC, waste and water Directives) provides
some overlap in controls.
The Titanium Dioxide Manufacturers Association (TDMA) provided a detailed response to the
Commission, including specific suggestions for reduction of monitoring and comments on wastes and
by-products. Two other organisations provided comments on the consultation.
Kronos (a TiO2 manufacturer) and,

RIZA (the Netherlands Institute for Inland Water Management and Waste Water Treatment)
The RIZA response provided comments on waste definition, consistency with the BREF (Best
Available Techniques Reference) note on the Large Volume Inorganic Chemical Solids (LVIC-S) IPPC
sector and questioned whether there was still a need for a separate Directive for TiO2. However,
Kronos recommended retention of the TiO2 Directives emission limit values and did not consider that
regulation under the IPPC Directive alone was appropriate.
1.3.2 Further consultation with Member States
Following the Stakeholder consultation the Commission sought additional information from Member
States in early 2007. Seven Member States with TiO2 plant in their territories provided responses and
these all considered that simplification of the monitoring requirements of the Directives was possible
but only a few provided any detail of proposed simplifications and changes.
The suggestions included:
Reducing monitoring frequency (to once every five years),
Basing water monitoring on the requirements of the Water Framework Directive,
Using CEN Standards where available,
Monitoring effluent toxicity directly rather than monitoring the effect of emissions in the broader
environment, and
Targeting monitoring to address the most important components.
1.4 Overview of Study Methodology

The objective of this study required three linked tasks:
1. Data gathering
2. Emission limit analysis
3. Options for simplification of monitoring and changes in frequency
These tasks are described in the following sections.
Consultation document on a simplification of the Titanium Dioxide Directives available on the European Commission DG Environment website
at http://ec.europa.eu/environment/waste/titanium.htm

1.4.1 Data gathering

Information from the Commissions consultation and information gathering exercise was reviewed with
LVIC-S BREF note and selected IPPC permits for TiO2 installations.
Questionnaires were developed for the environmental regulatory authorities in Member States
responsible for the TiO2 industry. A separate questionnaire was developed for the operators of the
TiO2 installations. The questionnaires are provided in Appendix 2 and Appendix 3 and were developed
to address gaps (and potential changes) in data from the earlier stakeholder and Member State
consultation and the BREF document for the sector.
The timescale for data collection was very short and a low response was anticipated. Initial contact
with the manufacturers association (TDMA) had indicated that data for the manufacturing sites could
be obtained from this organisation. Following a meeting with the TDMA however, it was agreed that
the level of detail and timescale required contact with the individual manufacturers.
Although the time for response was very short several Member States (Belgium, Czech Republic,
Finland, Germany, the Netherlands, Slovenia, Spain and the UK) provided responses. Of the
manufacturers only Kemira Pigments has so far responded to the questionnaire, though some other
information has been provided on behalf of the industry by the TDMA in response to some further
questions raised in the course of this work.
1.4.2 Cost-benefit analysis
A cost-benefit analysis has been carried out against different limit values, to the extent possible. The
existing TiO2 Directives provide the baseline, with further scenarios based on the upper and lower
ends of ranges specified in the relevant BREF note. Changes in emissions from reported data to the
alternative limits were considered. Quantification through to monetised values of (primarily) health
benefits was possible for dust and SO2 using reference data on costs per tonne emission from the
BREF on Economics and Cross Media Effects. Similar analysis is not possible for pollutants
discharged to water as such reference values do not yet exist, largely because of the complexity of
exposure pathway characterisation. Data on the costs of further abatement were taken from sources
including the LVIC-S BREF note, responses to the questionnaires and the US Environmental
Protection Agency (USEPA).
1.4.3 Potential monitoring changes
The monitoring requirements of the TiO2 Directives were reviewed. The TiO2 Directives include
mandatory and optional monitoring with guidance on frequency and measurement technique. The
purpose of the monitoring was assessed; in particular those parameters which provide a potential
input to assessment of environmental deterioration and those parameters which have limit values
identified.
The monitoring requirements of the TiO2 Directives were compared with monitoring requirements
implemented by regulatory authorities in operating permits and additional monitoring by regulators and
other agencies (where available).
The availability of EN, ISO and national standards for the monitoring parameters in the TiO2 Directives
was assessed (the Directives provide little information on measurement standards).
The responses from earlier consultations were reviewed for potential simplifications in monitoring
scope. In addition the monitoring requirements were assessed for coherence with BAT guidance on
monitoring and the sector.

AEA/ED05458/Issue 3

AEA/ED05458/Issue 3
2 The TiO2 Industry in Europe

2.1 Overview
At a European level the TiO2 industry is represented by the Titanium Dioxide Manufacturers
Association (TDMA), part of CEFIC (the Council of the European Chemical Industry). TDMA
membership is as follows:
Cinkarna Celje.d.d. (SI)
Degussa (DE)
Huntsman Tioxide Europe (GB, ES, FR, IT)
Kemira Pigments Oy (FI)
Kronos Worldwide Inc. (BE, DE, NO)
Millennium Chemicals (GB, FR)
Precheza AS (CZ)
Sachtleben Chemie GmbH (DE)
Tronox Pigments International GmbH (DE, NL)
Zaklady Chemiczne POLICE S.A. (PL)
Associate members:
DuPont de Nemours (USA)
Ishihara Sangyo Kaisha, Ltd. (Japan)
Titanium dioxide (TiO2) pigments are used in a variety of products ranging from printing inks to plastics
to food. Annual production in Europe is around 1.5 million tonnes, spread across 19 factories
operating in 12 countries (Table 2-1). There are two processes used to manufacture TiO2, the chloride
process and the sulphate process. Each leads to different environmental burdens with respect to the
types and quantity of pollution released, as shown in the following sections. The plant at Leverkusen
uses both processes, with a capacity of 100 kt for the chloride process and 30 kt for the sulphate
process.
Table 2-1. Production capacity of TiO2 facilities in the European Union in 2002 (Source LVIC-S
BREF).
Country
Belgium
Czech Rep
Finland
France
France
France
Germany
Germany
Germany
Germany
Italy
Netherlands
Poland
Slovenia
Spain
UK
UK
UK
Company
Kronos Europe
Precheza
Kemira Pigments
Tioxide Europe
Millenium Chemicals
Millenium Chemicals
Sachtleben
Tronox
Kronos Titan
Kronos Titan
Huntsman Tioxide
Tronox
Zaklady Cemiczne
Cinkarna
Tioxide Europe
Tioxide Europe
Tioxide Europe
Millennium Chemicals
Location
Langerbrugge
Prerov
Pori
Calais
Le Havre
Thann
Duisburg-Homberg
Krefeld-Uerdingen
Leverkusen
Nordenham
Scarlino
Rotterdam-Botlek
Police
Celje
Huelva
Greatham
Grimsby
Grimsby/Stallingborough
Process
Chloride
Sulphate
Sulphate
Sulphate
Sulphate
Sulphate
Sulphate
Sulphate
Both
Sulphate
Sulphate
Chloride
Sulphate
Sulphate
Sulphate
Chloride
Sulphate
Chloride
Capacity (t)
60,000
41,000
130,000
100,000
95,000
30,000
100,000
107,000
130,000
62,000
80,000
55,000
40,000
44,000
80,000
100,000
80,000
150,000

As in other sectors, the TiO2 industry has made major investment (in excess of 1.4 billion) to reduce
its burden on the environment since the early 1980s and emissions have undoubtedly fallen
significantly as a result. However, there has as yet been no formal appraisal of costs and benefits to
determine whether current emission levels are at a societal optimum. An important feature of both the
chloride and sulphate processes is the extent to which waste materials are recycled within process, or
sold as by-products, avoiding unnecessary releases and generating revenue or avoiding material
costs for the companies involved.
2.2 Chloride Process

The chloride process is shown in Figure 2-1, which is followed by a list of material inputs and, for each
stage of the process a list of the main burdens arising to health and the environment, and brief details
of how they are controlled (Table 2-2).
Figure 2-1. Outline process diagram for manufacture of TiO2 via the chloride process (Source:
LVIC-S BREF)
The main inputs to the process, in addition to water and energy, are as follows, by process stage:
Chlorination: Ore containing TiO2, chlorine and coke
Solids separation and waste solid metal chlorides treatment: Lime and coal
TiCl4 purification (removal of vanadium): Oil
Oxidation: Oxygen, toluene
Cooling and separation: Abrasive solids (e.g. silica sand, rock salt or granular TiO2)

AEA/ED05458/Issue 3
Waste gas cleaning: Caustic soda

Liquid effluent cleaning: Lime
Table 2-2. Main burdens and risks arising from each stage of the chloride process and their
control.
Stage
Chlorination: Reaction of
TiO2 with chlorine to form
TiCl4.
Main burdens
Use of chlorine
Some impurities such as

silica and zirconium removed
Solids separation
Further removal of impurities,

generating waste
Neutralisation of waste solid

metal chlorides using lime
Condensation of TiCl4, jet
scrubbing of gas stream with
cold TiCl4
Distillation, further
purification of TiCl4
Vanadium oxychloride
removal using oil

generating solid waste
generating waste
Oxidation at 900-2000C,
converting back to TiO2 and
controlling final crystal size
Use of oxygen
Emissions associated with
energy use
Generation of chlorine
Presence of chlorine
Cooling and separation

generating waste
Generation of sludge
containing complexed VOCl2
Adsorption / desorption
process, TiO2 slurried in
water
Presence of chlorine
Finishing via milling and

coating with additives to
improve pigment properties
Waste gas treatment
Generation of dust
CO, COS
HCl
Treatment of solid wastes,

via neutralisation using chalk
or lime, precipitation and
stabilisation of metals
Treatment of liquid effluents
Cl2
Use of caustic reagents
Generation of liquid effluent
Production of filter cake
requiring disposal
Transfer of pollutants from

liquid to solid media
Control
Seveso II Directive requires enclosure
and high integrity of process and
detailed hazard assessment to
minimise Cl emissions to environment
Solid wastes either recycled or
destined for appropriate landfill
disposal
Solid wastes either recycled or
destined for appropriate landfill
disposal
Some sale of FeCl2, most metal
chlorides sent to appropriate landfill
Gas stream passed for waste gas
treatment (see below)
See below
Sludge recycled back to solids
separation where it is removed from
the process stream and disposed of
as appropriate
Energy efficiency measures
See next stage
Chlorine recycled to chlorination
stage
Chlorine absorbed in liquid TiCl4 and
recycled to chlorination stage, though
some remains for waste gas
treatment
Removal using bag filters
May be removed by thermal oxidiser,

generation of less hazardous CO2
and SO2, possibility of selling sulphur
as a co-product
Absorbed using aqueous scrubbers,
may produce sale grade HCl acid
Removed by caustic scrubbing
Containment, safe handling, etc.
See below
Some generation of by-products.
Residual solid wastes disposed of to
appropriate landfill.
Consent limits for effluent composition
will reflect the nature of the receiving
medium
The term main burdens as given in the above table needs some clarification. It refers to the main
burdens of the process before control. Hence, although containment of chlorine gas is a major

consideration at plant using the chloride process, the process technology is designed to prevent
significant emissions of chlorine to the wider environment.
2.3 Sulphate Process

The sulphate process is shown in Figure 2-2, which is followed by a list of material inputs and, for
each stage of the process a list of the main burdens arising to health and the environment, and brief
details of how they are controlled (Table 2-3).
Figure 2-2. Outline process diagram for manufacture of TiO2 via the sulphate process (Source:
LVIC-S BREF)
The main inputs to the process, in addition to water and energy, are as follows:
Digestion: Ore containing TiO2, sulphuric acid
Reduction: Scrap iron
Clarification and crystallisation: Small amounts of filter aid and lime
Hydrolysis, filtration and washing: No significant material usage
Calcination: Small amounts of mineral salts such as KCl
Finishing: Inorganic metal sulphates and caustic soda
Waste gas cleaning: Caustic soda and peroxide

AEA/ED05458/Issue 3
Liquid effluent cleaning: Lime and limestone, particularly if neutralisation is the chosen
abatement system
Table 2-3. Burdens arising from each stage of the sulphate process, and their control.
Stage
Digestion
Reduction (when primary ore

is ilmenite)
Clarification and
crystallisation using
flocculation and filtration
Hydrolysis
Filtration and washing
Calcination
Finishing via milling and

coating with additives to
improve pigment properties
Waste gas treatment
Treatment of solid wastes,

via neutralisation using chalk
or lime, precipitation and
stabilisation of metals
Abatement of aqueous
emissions
Main burdens
Use of concentrated (8095%) sulphuric acid
Off-gases containing SOx,
dust, H2S
Generation of hydrogen
Solid residue

energy use
Spent acid
Acidic filtrate
Residual solid metals (Fe, Cr,

Mn, V)
energy use
SO3
SO2
TiO2 dust
Generation of dust
Dust
H2S, SO2
Use of caustic reagents
Generation of liquid effluent
Production of filter cake
requiring disposal
Transfer of pollutants from

liquid to solid media
Control
Normal or multi-stage scrubbing
Discharged to air avoiding explosive
hazard
Limited re-use, most neutralised then
sent for landfill
Acid is recycled or neutralised with
lime or limestone to form gypsum,
which is sold or land filled
Acid is recycled or neutralised with
lime or limestone to form gypsum,
which is sold or land filled

Removed by ESPs
Scrubbed or oxidised to SO3 and
absorbed to form sulphuric acid which
can be recycled
Removed by scrubbing, recycled
Removal using bag filters
Removed using bag filters and

cyclones
Removed by scrubbing
See below
Some generation of by-products.
Residual solid wastes disposed of to
appropriate landfill.
Acid recycling
Neutralisation
Consent limits for effluent composition
will reflect the nature of the receiving
medium
An important feature of the sulphate process is that the digestion process is carried out batch wise
rather than continually. One consequence of this is that the gas cleaning systems need to be able to
handle large volumes of gas for relatively short periods in the order of minutes, followed by lower
volumes during a bake period that lasts for several hours.
10

2.4 Pollution Control Techniques for Air Emissions4

2.4.1 Sulphate process
The LVIC-S BREF indicates that the main emissions to air from the sulphate process arise from the
digestion and calcination sections. The key emissions are oxides of sulphur (SO2 and SO3) and
hydrogen sulphide (H2S). Other emissions from the process including particulate matter (PM) from
materials handling, storage/packing and milling. Off-gas treatment from the digestion stage are simple
scrubbing processes or, in common with the calcination process, are designed to suit opportunities for
recovery of materials on site.
In some digestion plant (only plant dealing with natural ore rather than slag) the off-gases are
scrubbed with waste water which then passes for treatment before discharge. In other processes, offgases can be quenched and scrubbed with caustic soda; the resulting scrubber liquor can either be
decomposed to SO2 and S for further use in an acid plant or, is passed for treatment before discharge.
Alternatively; gases are quenched and passed through an electrostatic precipitator to remove acid
mist. The SO2 fraction is then oxidised to SO3 and absorbed in dilute sulphuric acid and recovered.
The LVIC-S BREF provides the following summary of costs for digestion and calcination off-gas
treatment.
Table 2-4 : LVIC-S Costs of acid gas abatement for digestion and calcination
Costs /tonne
TiO2 produced
Capital
Operating
Digestion (installations)
Slag (3)
Ilmenite (8)
85
10
75
5
Calcination (installations)
std catalyst
hp catalyst
Scrubbing
(6)
(1)
(3)
70
140
170
5
10
9
The average SO2 concentrations discharged to atmosphere in 1999 for digestion and calcination in
3
the BREF were 87 and 713 mg/m respectively. The average SO2 emission concentration for
digestion is comparatively low and the scope for improvement is limited. However, it is interesting to
note the BAT range for AELs (as a daily average) for sulphuric acid manufacture from contact and
3
absorption which is between 100 and 680 mg/m . The BAT range for sulphuric acid plant suggests
that there is scope for up to 85% reduction based on 1999 emission levels.
The LVIC-S BREF indicates that particulate emission controls are fabric filters or cyclones and these
technologies are able to meet the ELVs specified in the TiO2 Directives. However the indicated
3
average concentrations (12-39 mg/m for various activities in 1999) appear high for fabric filters which
3
can achieve concentrations <<5 mg/m . An account of why the filters used at TiO2 plant perform to a
lower standard is absent from the BREF.
2.4.2 Chloride process
CO and COS generated in the system may be removed using thermal oxidisers, generating CO2 and
SO2 which are less hazardous. There is also the possibility of selling sulphur as a by-product. HCl is
readily absorbed using aqueous scrubbers and this may generate sale grade hydrochloric acid.
Chlorine gas is removed by aqueous scrubbing. Specific controls are present via the Seveso II
Directive to prevent significant escape of chlorine.
Dust is captured either by cyclones or bag filters. However, it is again noted that the capture rates for
bag filters cited in the LVIC-S BREF for TiO2 manufacture seem low compared to the efficiency of this
technology elsewhere, for example at waste incinerators (see the next section).
Further information relevant to this section is given in Appendix 6, particularly with respect to the costs of abatement.
11

AEA/ED05458/Issue 3
2.5 Pollution Control Techniques for Liquid Effluents5

2.5.1 Wastewater composition
Based on the information found in the LVIC-S BREF (2006) and the answers to questionnaires from
Member States (including e.g. general and specific permit conditions) the wastewater of a titanium
dioxide plant contains the following substances:
For the chloride route: chlorides (hydrochloric acid (HCl)), suspended solids (SS), metals (Mn, Fe,
V, Cr, Zn, Ni, Pb, Cu, As, Cd, Hg), chlorinated organic compounds
For the sulphate route: sulphate, suspended solids (SS), metals (Fe, Cd, Hg, others)
2.5.2 Effluent treatment techniques
Based on the wastewater composition, it can be concluded that effluent treatment techniques should
be considered for chlorides, sulphates, suspended solids and metals. In the following sections, a brief
description is given for some techniques.
2.5.2.1
Chlorides
Inorganic chlorides contained in a waste water stream are generally not abated, but released into the
environment [CEFIC, 2002 in LVIC-S BREF, 2006, BREF Common WWT and GT, 2003]. However,
this is strongly dependent on the receiving environment and the compound emitted [85, EIPPCB,
2004-2005 in LVIC-S BREF, 2006].
2.5.2.2
Sulphates
Part of the sulphates can be removed by, e.g. precipitation with lime (or limestone to form gypsum
which can be sold as a co-product). An excess of lime allows a reduction in the release of sulphates,
but this obviously leads to an increased usage of lime [6, CEFIC, 2002 in LVIC-S BREF, 2006].
2.5.2.3
Suspended solids
There are many ways, used individually or in combination, to eliminate suspended matters from waste
water streams:
Flocculation
Natural or mechanical-aided decantation
Air-flotation
Filtration
Etc.
are the most widely used techniques [CEFIC, 2002 in LVIC-S BREF, 2006, BREF Common WWT and
GT, 2003].
2.5.2.4
Metals
Metals are usually contaminants (such as Fe(II) to Fe(III)) of the feedstock and they end up with the
product, as solid waste, or dissolved in waste water streams. In this latter case, and when it is
necessary to avoid rejecting them into the water body, the conventional process consists of
precipitating and separating insoluble metal hydroxides, sulphides or phosphates. The metal release
depends on many factors, such as the metal itself; the nature of the precipitating agent and the
presence of other metals or organics. Also an excess of reactant allows the reduction in the release of
metal, but this then leads to an increased release of the reactant itself [CEFIC, 2002 in LVIC-S BREF,
2006].
Further information relevant to this section is given in Appendix 6, particularly with respect to the costs of abatement.
12
2.5.3

Description of most relevant techniques
2.5.3.1
2.5.3.1.1
Primary treatment
Oxidation
Oxidation of contaminants can be achieved by the addition of a variety of reagents. For example,
ozone, hydrogen peroxide, and sodium hypochlorite can be used. Other schemes involve pure
oxygen, and proprietary catalyst systems.
2.5.3.1.2
Neutralisation
If possible, the first step of neutralisation should be to merge the acidic and alkaline waste water
streams, in order to avoid additional salt load. Effluents should be dosed with an appropriate acid or
alkali to achieve a neutral solution. As dosing systems cannot cope with effluents of extreme pH, an
intermediate facility capable of storing strongly acidic or alkaline effluents should be installed with
automatic control.
2.5.3.1.3
Solids removal
The removal of particulate matter from effluents can be hindered by flow fluctuations. The removal of
finely divided suspended solids can be enhanced by the addition of chemical coagulants/flocculants.
These substances can also aid the removal of emulsions and grease. Techniques for the removal of
solids include: settlement, flotation, precipitation, dewatering and filtration.
Precipitation can be described as the altering of dissolved compounds to insoluble or badly soluble
compounds, in order to be able to remove the compounds by means of filtration.
Filtration is the separation of a solid and a liquid by using a porous substance that only lets the liquid
pass through.
2.5.3.2
2.5.3.2.1
Secondary/tertiary systems
Ion exchange resins
Ion exchange can be employed for the removal of undesirable anions and cations from waste water.
Cations are exchanged for hydrogen or sodium, and anions for hydroxyl ions. Removal of the fine
particles containing metal prior to ion exchange may be necessary. Special selective ion exchange
resins are used to selectively remove trace amounts of e.g. metals from the other ions in the solution.
2.5.3.2.2
Membrane processes
Membrane processes include: ultrafiltration, reverse osmosis, and membrane filtration. These systems
concentrate solutions by selective filtration and usually produce a purified filtrate stream and a
concentrate stream. These types of processes can be used either to clean up the waste water for reuse, or to recover material for recycling.
2.5.3.2.3
Biological treatment
In specific conditions, biological treatment can be used to remove the compounds of nitrogen,
phosphorus and sulphur from waste waters.
2.5.3.2.4
Electromechanical techniques
Metals can be extracted from aqueous streams by sacrificial exchange. This process would result in
the release of another metal into the aqueous stream.
2.6 Control of Solid Wastes

To the extent considered possible by the industry, waste streams associated with the industry,
whether gaseous, liquid or solid are processed to remove materials that can be extracted with
sufficient quality for use elsewhere. Residual solid wastes (filter cake, etc.) will be sent to landfill.
Controlled disposal at landfill sites requires that account be taken of the hazard posed by waste
materials. In the case that hazardous wastes are disposed of the landfill concerned must have
adequate leachate collection, etc., to prevent the escape of hazardous substances.
13

AEA/ED05458/Issue 3
2.7 TiO2 Content of Pigment as Sold

The Titanium Dioxide Directives do not define titanium dioxide, presumably because there seemed at
the time that they were written not to be any need to define beyond the chemical formulation. In
contrast, the BREF gives AELs per unit TiO2 pigment produced. This leads to some uncertainty in
how emissions, normalised per unit of production (i.e. expressed as kg per tonne TiO2) have been
calculated, whether against the actual quantity of TiO2 produced, or the quantity of pigment labelled as
TiO2 leaving the factory. The issue arises chiefly as a result of the finishing stage where additives are
used to improve the properties of the TiO2. Information provided on the internet gives the following
data on TiO2 content of the marketed product for six of the European producers, with figures ranging
from 80 to 99%. This suggests that any bias introduced by different assumptions to the meaning of a
tonne of TiO2 is at most 25%, and typically less (possibly much less).
Table 2-5. Titanium dioxide content of pigments as sold
Manufacturer
Product name
or brand
Product applications
Pigment TiO2
content (%)
Huntsman Pigments
TIOXIDE
Decorative and industrial coatings,

plastics, inks, paper and ceramics
80 97.5
Tiona
Surface coatings, plastics, paper
80 99
Kemira Pigments Oy
Kemira
Paints and coatings, packaging inks,

paper and plastics
82 99
Kronos
KRONOS
Coatings, plastics and paper laminates
82 99
Tronox Pigments International

GmbH
TRONOX
Coatings, paper, plastics and printing

inks
Paints, plastics, rubber, textile, ceramic
and paper
Millennium Chemicals Ltd
Zakady Chemiczne POLICE S.A
TYTANPOL
86 99
88 98.5
Note: No data were found on the internet for the products of Degussa, Cinkarna, Precheza and Sachtleben
The TDMAs interpretation is that the directive expresses sulphate and chloride discharge limits as per
tonne of 100% TiO2 which is typically equivalent to the uncoated product that arises either from
calcination (sulphate process) or oxidation (chloride process). The ecolabel criteria for paints refer to
the directive so it is necessary to back calculate from the coated product to the limits based on pure
TiO2. So far as the BREF was concerned it was felt that it would be simpler to express limits related to
the actual product sold (i.e. per tonne pigment), to avoid the need for additional calculation.
However, there remains uncertainty concerning the emissions data used below, and on which
discussions relating to the development of the BREF were based. Whilst labeled as being per tonne
TiO2 the figures provided in several cases match those given per tonne pigment in the BREF. One
option for addressing this issue whilst the question remains open is to run sensitivity analysis in the
assessment of possible changes to emission limit values, considering reported emissions to be per
tonne TiO2 and per tonne TiO2 pigment. A value of 85% TiO2 content looks a suitable lower bound
from the information given in Table 2-5. Lower values are given in the table, but the analysis is
concerned not with products at the extremes of ranges, but with likely average values for any plant.
14

15

AEA/ED05458/Issue 3
3 Data Collection from the Industry and

Regulators
3.1 Approach
Questionnaires were developed for the environmental regulatory authorities in Member States
responsible for the TiO2 industry. A separate questionnaire was developed for the operators of the
TiO2 installations. The questionnaires were developed to address gaps (and potential changes) in
data from the earlier stakeholder and Member State consultation and the BREF document for the
sector.
3.2 Responses to Survey Sent to Plant Operators

Only limited response was received during the contract period from operators. These provided some
useful information for the analysis, but a more complete response would have enabled the analysis to
be performed with a higher level of confidence. However, response was received from the TDMA on a
series of specific questions raised during the course of the contract in relation to:
1. How industry defines TiO2 for the purpose of the Directive (i.e. as 100% pure TiO2, or following
coating etc. to make the marketed pigment). For the purpose of the Directive the industry
seems to consider the weight of uncoated TiO2, in other words, the material at the end of the
calcinations step (for the sulphate process) or the oxidation step (for the chloride process). It
was felt to be simpler in the BREF to define limits against the amount of material sold.
2. Performance of gas cleaning equipment. It is noted below that the emitted concentration of
dust for TiO2 plant is higher than that achieved using similar technologies for gas control
3
3
elsewhere. The TDMA respond that Although values below 50mg/m are obtainable 5mg/m
is not realistic. One of the TDMA member companies has indicated that the required increase
in filter area to get near this would result in the need for new buildings and closure of 2 plants.
3. Performance of liquid effluent cleaning equipment. Again, questions have been raised as to
whether the existing TDMA plant are operating optimally with respect to chloride and sulphate
emissions. TDMAs response is that emissions are site specific reflecting the sensitivity of the
receiving environment and also reflect the ore used for input.
Emissions data were submitted by the TDMA to the European Commission for European operators
prior to the start of the contract (the data on which analysis presented in the BREF was based, with
6
some updates to fill in gaps) .
3.3 Responses to Surveys Sent to Member State

Regulators
Responses were received from the Regulatory Authorities in 8 Member States. Several commented
that the European Commission had requested similar information in its questionnaire of March 2007
and were unable to go far beyond that on the short timescale of this contract. However, it was noted
that some Regulatory Authorities were able to provide much more detailed information than others, for
example, permits were made available for only about half of the plant in the countries covered by
respondents.
As noted elsewhere, further data (specific to 2006) were provided by TDMA at the end of the contract, too late for inclusion in the main analysis.
These data are presented in Appendix 5.
16

3.3.1 Releases to Air and Water

Responses to these questions varied considerably in depth, ranging from no response, to a simple
reference to compliance with the Directives, to more detailed description of emissions and their
monitoring and how plant specific limits were derived. Most respondents confirmed whether
discharges to water were released to rivers, estuaries or the sea.
3.3.2 Discharges to Land
Five Member States provided information on this topic, confirming that solid wastes were being sent to
landfills of appropriate design for the materials concerned, and that monitoring was done to guard
against environmental harm.
3.3.3 Environmental Monitoring
An overview of the answers given in relation to monitoring can be found under section 5.
3.3.4 Monitoring Organisations and Costs
A summary of the monitoring practice in the different Member States, based on the answers received
from the different authorities, is given in Table 3-1.
Table 3-1 Monitoring practice
Member State
Belgium
Monitoring
Surface water quality (Ti)
Wastewater (emissions)
NR
Czech Republic
Spain
Plant emission monitoring
Any additional monitoring
carried out by authority
NR
Germany
NR
The Netherlands
Slovenia
National monitoring
Emission monitoring
UK
Emission monitoring
Environmental monitoring
NR = No Response received
Estimated yearly cost ()

2,400
1,500-2,000 (+ 1 man-day)
NR
NR
NR
Payer
Authority
Authority
NR
Operator
Authority
NR
NR
NR
75,000
NR
In excess of 21,000
NR
NR
Authority
Operators
Operator
Authority
3.3.5 TiO2 Directives Reporting Costs

Three responses indicated that the preparation of centralised reports took about 1 week per year.
However, additional regional reporting costs equivalent to 5,000/plant were reported by one Member
State.
3.3.6 Costs for Emissions Control
Only 2 Member States responded with any information on the costs for emissions control, though this
was far from complete. Most usefully, one regulator stated that for one plant, reduction of sulphate
(from current level) to 550kg/t TiO2 would cost in the region of 735,000 capital plus an additional
15/te operating cost.
3.3.7 Issues from Removal of TiO2 Directives
The environmental authorities in Member States considered that removal of the TiO2 Directives would
not lead to environmental harm. This was partly a result of the fact that the plant concerned are
covered in any case by the IPPC Directive, and that the BAT-AELs indicate tighter emission limits than
the Directive.
However, it was recognised that the Titanium Dioxide directives specify particular requirements that
might not be covered by IPPC e.g. monitoring of receiving environments. Concern was expressed,
for example, over groundwater monitoring. To maintain continuity of these controls, one regulator saw
benefit in transcribing appropriate monitoring requirements into a TiO2 Technical Annex in a revised
IPPC Directive. It was also said that such monitoring would be useful in confirming the effectiveness
of IPPC in protecting the environment.
17

AEA/ED05458/Issue 3
4 Emission Scenario Analysis of Social,

Economic and Environmental Impacts
4.1 Impacts Associated with the Sector
4.1.1 Environmental and Health Impacts
Impacts on environment and health are considered together, as many of the pollutants with which this
assessment is concerned are capable, at sufficient concentration, of having effects on both. This
section provides a summary with more detail being given in Appendix 4.
Titanium Dioxide is considered sufficiently non-toxic that it is used in products including some foods
and toothpaste, as well as plastics and paints. Indeed, it has largely replaced the use of white lead in
paints, and hence, as a product, has had a significant benefit to health. Evidence for health effects of
TiO2 dust in air have been reviewed by the National Institute of Occupational Safety and Health
7
(NIOSH) in the US . The review concluded that TiO2 poses a negligible risk of lung cancer through
workplace exposures. The review, did, however, also find that TiO2 was capable of causing
inflammation of the lung, and of causing cancer in rats when exposure levels were high. Effects
appear to be unrelated to the chemical nature of TiO2. Given that this establishes that TiO2 particles
can affect health, and given the sub-micron size of TiO2 particles it seems appropriate to treat TiO2 as
falling in the PM2.5 fraction. Health impacts of non-specific PM2.5 have been reviewed by WHO for the
ECs Clean Air For Europe (CAFE) Programme. Whilst WHO did not identify specific causes of death
linked to fine particle exposure they did recommend quantification of various impacts, including
mortality.
CAFE also considered it appropriate to treat sulphate aerosols generated in the atmosphere following
emissions of SO2 as PM2.5 for the purposes of health impact assessment. SO2 emission also has
significant effects on ecosystems in acid-sensitive areas, particularly in NW Europe.
Chlorine is well known as a poisonous gas. However, its use for the chloride process for TiO2
manufacture is controlled through the Seveso II Directive. Automatic monitoring for chlorine, with shut
down should significant levels of the gas be detected, is now a standard part of process control at
chloride process plants.
Pollutants in liquid effluents, such as chlorides, HCl, iron compounds, sulphate and suspended solids
are mainly a risk factor for the health of aquatic organisms. Effects will differ significantly with the type
and quality of the receiving environment, with risks much higher for freshwaters than marine or
systems. Acidity (when input at sufficiently high levels) can interact with other pollutants, for example
increasing the solubility of harmful metals
Various carcinogenic elements are also present in liquid effluents from TiO2 plant (e.g. arsenic, lead,
nickel). However, to damage health with any degree of certainty, these pollutants need to enter a
pathway where human exposure will occur, at a sufficiently high concentration.
4.1.2 Social Impacts

The main social impacts of the sector are likely to be through the effects of pollutant emissions on
health (covered above under environmental impacts) and on employment (covered below under
economic impacts).
4.1.3 Economic Impacts

The economic impacts of the sector, and hence of any changes to its regulation that have an
economic impact, exist at various scales, ranging from the local economy (e.g. employment effects
and the competitiveness of specific installations) to the competitiveness of the national and European
economies.
7
http://0-www.cdc.gov.mill1.sjlibrary.org/niosh/review/public/TIo2/pdfs/TIO2Draft.pdf
18

4.2 Scenario Development

Specification of required levels of emission controls needs to account for several factors:
Protection of health and the environment, accounting for the nature of the receiving media.
Composition of input materials, noting in particular variability between TiO2 ores
Process characteristics (e.g. whether the chloride or sulphate process is used)
Cost of improvement
Time scales for emission control, accounting for costs and damage done to the environment
A strength of the IPPC process is that it is sufficiently flexible to take such factors into account. This
flexibility can, however, also be a weakness, as it is difficult to define what exactly constitutes Best
Available Techniques at any site.
The specification for this contract stated that the following scenarios should be considered:
Scenario 1: Directive 92/112/EEC (S1)
8
Scenario 2: Upper limits for emissions for TiO2 production according to the LVIC-S BREF (S2)
8
Scenario 3: Lower limits for emissions for TiO2 production according to the LVIC-S BREF (S3)
Scenario 4: An otherwise undefined position between S1 and S2 (S4)
Scenario 5: The likely position following implementation of the IPPC Directive for the sector (S5)
Emission limits for the first three scenarios are shown in Table 4-1. It is assumed that all plant already
meet the limit values of the TiO2 Directives. As well as being a legal requirement this is also a
requirement of membership of the TDMA (all producers in the EU are members of the association).
Any costs incurred to meet the TiO2 directive limits are not relevant here as they are a function of
previous legislation.
The baseline emission scenario for this analysis is based on the latest set of emissions data provided
to the European Commission by Peter Thompson, on behalf of the TDMA. This is based on the
information that was used in the development of the section of the LVIC-S BREF that deals with TiO2
manufacture, supplemented with additional information to fill in some of the gaps in that dataset.
9
Much of the data therefore dates back to 1999 . It is also anonymised so that emissions data cannot
be linked to specific plant, preventing integration of more recent information that has been obtained for
a small number of cases. The fact that the analysis is based on rather old information may not be too
problematic for the results, as it post-dates the most recent Directive by 7 years. It is therefore quite
possible that plant will have been adapted to meet the requirements of the Directive before 1999, and
in most cases may not have been altered since, given the lack of further legislative pressure specific
10
to the sector as a whole .
Consideration was given to applying two versions of Scenario 1. One version would be based on
available emissions data, representing business as usual. With all plant meeting the Directive limits,
costs and benefits for this scenario are both zero. The second version would take the view that
emissions at all plant could increase up to the limits specified in the 1992 Directive. However, this is
not realistic and so was not applied in the analysis. Scenario 1 was therefore based on current
emissions, which reflect not just the limit values specified in the Directive but also the concerns of local
regulators. A similar logic has been applied to the other scenarios also, with performance of plant that
currently meet the limit values assumed to remain constant rather than increase up to the emission
limit value.
Scenarios 2 and 3 are based on the upper and lower BAT-AELs from the BREF. It is assumed that
these scenarios only affect those plant whose emissions for any pollutant are not already at or below
the appropriate BAT-AEL.
Scenario 4 takes limit values based on the plant with highest emissions that meet the limit values of
the Directive. This is very similar to scenario 1, but would avoid the potential for the highest emitting
plant in the future producing more pollution than they currently do.
8
BAT upper limit = the upper end of the range specified for emissions from the TiO2 industry in the LVIC-S BREF (least restrictive case). BAT
lower limit = the lower end of the range specified for emissions from the TiO2 industry in the LVIC-S BREF (most restrictive case).
9
The TDMA is collecting more up to date information in response to the questionnaire sent to operators in August 2007. However, no new
information had been received by the deadline required for this report.
10
As noted elsewhere in this report, emissions data for 2006 for all plant was supplied by the TDMA at the end of the contract (see Appendix 5),
too late for full inclusion in the analysis presented here.
19

AEA/ED05458/Issue 3
Table 4-1. Emission limit values from Directive 92/112/EEC and the BREF
Emission
Sulphate process
Weak Acid / neutralised waste
SO4 total to water
Suspended solids to water
Iron compounds to water
Mercury to water
Cadmium to water
V, Zn, Cr, Pb, Ni, Cu, As, Ti, Mn
Dust to air, major sources
Dust to air, other sources
Dust to air, total
Dust to air, emission rate
SO2 to air
SO2 to air from plant for
concentration of waste acid
Acid droplets
NO2
H2S
Plants for roasting salts generated
by waste treatment
Waste
Chloride process
Weak Acid / neutralised waste,
neutral rutile
synthetic rutile
slag
HCl to water
Chlorides to water
Suspended solids to water
Iron compounds to water
Hg, Cd, V, Zn, Cr, Pb, Ni, Cu, As,
Ti, Mn
Dust to air, major sources
Dust to air, other sources
Dust, total emission
SO2, total emission
Cl2 daily average
Cl2 at any time
HCl, total emission
Waste
Directive
1
92/112/EEC
BAT upper limit
BAT lower limit
800 kg tot SO4 /

t TiO2
550 kg / t TiO2
100 kg / t TiO2
40 kg / t TiO2
1 kg / t TiO2
125 kg / t TiO2
0.3 kg / t TiO2
1.5 g / t TiO2
0.32 mg / t TiO2
2 g / t TiO2
1 mg / t TiO2
No techniques identified - lack of data
3
50 mg/Nm
3
150 mg/Nm
10 kg/t TiO2
0.45 kg / t TiO2
3
20 mg / Nm
6 kg/t TiO2
0.004 kg / t TiO2
3
<5 mg / Nm
1 kg/t TiO2
500 mg/Nm
0
Monitor NOx from Calciner
0.05 kg/t TiO2
0.003 kg/t TiO2
To have BAT
Avoid, reduce,
etc.
130 kg Cl / t TiO2
228 kg Cl / t TiO2
450 kg Cl / t TiO2
14 kg / t TiO2
330 kg / t TiO2
2.5 kg / t TiO2
0.6 kg / t TiO2
10 kg / t TiO2
38 kg / t TiO2
0.5 kg / t TiO2
0.01 kg / t TiO2
No techniques identified - lack of data

3
50 mg/Nm
3
150 mg/Nm
0.2 kg / t TiO2
1.7 kg / t TiO2
0.1 kg / t TiO2
1.3 kg / t TiO2
0.1 kg / t TiO2
0.03 kg / t TiO2
5 mg / Nm
3
40 mg / Ng
Avoid, reduce,
etc.
Note 1) Directive limit specified per tonne TiO2, BAT limits defined per tonne TiO2 pigment.
Scenario 5 is based on Scenario 3 (lower BAT-AEL), but assumes that control technologies do not
work so well for the TiO2 sector as for others. During discussion of this work the industry has
commented that sector-specific factors mean that they cannot meet the tightest standards at all plant.
The result is that the costs of the scenario are the same as for Scenario 3, but the benefits are lower.
20

Emission limit values for each scenario are summarised for the pollutants of most concern in Table
4-2. In all cases the Scenario 4 limits are close to the existing Directive limits, and the Scenario 5
limits are roughly midway between the upper and lower BAT-AELs.
Table 4-2. Emission limit values for each scenario
Scenario 1
Sulphate process
3
Dust to air
50 mg/m
SO2 to air
10 kg/t TiO2
SO4 to water
800 kg/t TiO2
Chloride process
3
Dust to air
50 mg/m
SO2 to air
Not given
3
Cl2 to air
5 mg/m (daily)
3
40 mg/m (instant)
Cl to water
130-450 kg/t TiO2
Scenario 2
Scenario 3
Scenario 4
Scenario 5
0.45 kg/t TiO2

3
20 mg/m
6 kg/t TiO2
550 kg/t TiO2
0.004 kg/t TiO2

3
5 mg/m
1 kg/t TiO2
100 kg/t TiO2
0.7 kg/t TiO2
0.25 kg/t TiO2
9 kg/t TiO2
785 kg/t TiO2
4 kg/t TiO2
300 kg/t TiO2
0.2 kg/t TiO2

1.7 kg/t TiO2
Not given
0.1 kg/t TiO2

1.3 kg/t TiO2
Not given
0.4 kg/t TiO2

No data
No data
0.15 kg/t TiO2

No data
No data
330 kg/t TiO2
38 kg/t TiO2
330 kg/t TiO2
150 kg/t TiO2
Questions arise as to whether emission limits are best described in terms of:
3
Emission rates per unit of flow (mg/Nm ) or per unit of production (kg/t product), and if the latter
Against production of pure TiO2 or TiO2 pigment.
These are addressed in the analysis that follows.
4.3 Analysis
This section describes the costs and benefits for the sector of moving to different possible emission
limit values. It proceeds through the following stages:
Definition of boundaries for quantification of emissions and consideration of abatement
technologies.
Quantification of emissions and a preliminary assessment of performance against the scenario
emission limit values.
Quantification of the costs of damage caused by pollutants emitted from the sector. For those
pollutants of main interest these costs can be quantified for SO2 and dust only.
Identification of pollution abatement techniques and associated costs.
Comparison of the costs and benefits of meeting scenario emission limit values.
Discussion of uncertainties in the results.
Consideration of trends since the late 1990s in other pollutants emitted by the sector.
4.3.1 Boundaries
The operational boundary considered for the impacts of the sector relevant to this analysis is restricted
to operations at the European TiO2 manufacturing plant, in line with the boundary set under the TiO2
Directives. It therefore excludes impacts from ore extraction, manufacture of certain reagents and
additives manufactured off-site, transport and use of materials.
Geographical boundaries are set to the EU level, in terms of the plants considered and the effects of
air pollutants. Effects of liquid effluents and solid wastes are considered at a local to regional level,
depending on the specific pollutant concerned.
The temporal boundary for environmental impacts is set to the period over which the emissions (for
pollutants for which ELVs exist under the Directives) from one years operation by the sector will be
active in the environment and on health.
4.3.2 Emissions data
Emissions data for individual plant (referred to by number rather than name) are presented in
11
Appendix 5 to the extent that they are available. It is not clear whether the data are reported as pure
11
Appendix 5 contains the original dataset supplied by TDMA to the European Commission prior to the start of this contract, on which analysis in
this chapter is based. It also includes more up to date information (specific to 2006 and referred to as the new dataset), though this was received
too late to be included in the main assessment.
21

AEA/ED05458/Issue 3
TiO2 or TiO2 pigment, or whether this is reported consistently between locations. Recognition of this is
given in sensitivity analysis in the CBA that follows.
A broad indication of performance against the ELVs of each scenario is given in Table 4-3. Most
appear to have met the requirements not just of the TiO2 Directives but also the upper end of the BAT
AELs (as shown by the figures S2 upper BAT-AEL, S3 lower BAT-AEL and S5 intermediate
position between the AELs, in the table). In these cases there will be no costs or benefits of meeting
the upper BREF limits.
Table 4-3. Scenario targets met by each plant, based on the BREF data, supplemented with additional
information supplied by TDMA. It is assumed that the emissions data available for the
analysis that follows are directly comparable with emission limit values (i.e. that both are
expressed as kg/t TiO2, or kg/t TiO2 pigment).
1
Plant
Dust
Sulphate process
2
S2
1
S2
2
S4
3
S4
4
S3
5
S5
6
S5
7
S5
8
S5
9
S5
10
S5
11
S2+?
12
S2+?
13
Chloride process
S2
1
S3
2
S4
3
S5
4
S3
5
SO2
Sulphate
S5
S5
S4
S4
S2
S3
S5
S5
X
S5
S3
S4
S4
S4
S5
S3
S5
S5
S5
S5
S5
S5
S5
S3
S4
S5
Cl2
?
?
?
?
?
Chloride
S3
S5
S5
?
S2
Notes:
1) These data were not available with the specific plant identified, other than by number.
2) The numbers in the table show which scenarios emissions used for the development of the BREF agree with. Hence S1
means that a plant meets the limit values set for Scenario 1 (the baseline as specified in the TiO2 Directives), whilst S2 or S3
correspond to the limit values under scenarios 2 and 3 respectively. X signifies that a plant did not meet the requirements of
the baseline. ? means that data were either absent or unavailable in a form that permitted direct comparison with the scenario
limits.
3) Data supplied for chlorine emissions were not given in the same format as the Directive limit. The BREF does not give limit
values for chlorine.
4.3.3 Monetised damage factors for pollutant emissions

12
Figures presented in the BREF on Economics and Cross Media Effects give monetary values for
national average damage linked to emissions to air of SO2 and fine particles (PM2.5), accounting for
trans-boundary impacts. The methods of calculation were subject to extensive debate and
13
independent peer review under the ECs CAFE Programme .
Accounting for different methodological assumptions, chiefly linked to the approach for quantifying and
monetising mortality effects gives roughly a factor 3 range in unit damage costs. Damage factors for
dust and SO2 from chloride and sulphate process plant (averaged across the countries that contain
chloride or sulphate plant) are shown in Table 4-4. Further information on the calculation of the
14
averaged damage factors is given in Appendix 4.
12
http://www.jrc.es/pub/english.cgi/d1254319/18%20Reference%20Document%20on%20Economic%20and%20Cross%20Media%20Effects%20%2
8adopted%20July%202006%29%20-%201.8%20Mb
13
http://cafe-cba.aeat.com/html/reports.htm
14
The BREF provides country specific damage factors. However, the emissions data supplied for this contract were anonymised, and so it is not
possible to apply country-specific data to them.
22

Table 4-4. Averaged damage factors for estimating the costs of PM2.5 and SO2 emissions from chloride
and sulphate plant on health
Process
Chloride plant
Sulphate plant
Pollutant
1
PM2.5
1
PM2.5
SO2
/t low
46,000
35,500
7,500
/t high
134,000
104,000
21,700
Note 1) The difference in the damage factors for dust between chloride and sulphate process plant arises because analysis
accounts for variation in location. Higher damages are quantified for countries towards the centre of Europe than for those at
the fringes because of differences in the extent to which people will be exposed.
The BREF on Economics and Cross Media Effects takes the position followed in the CAFE
Programme and does not assign preference to any point in the range of PM2.5 damage costs. The
authors of this report have a preference for the lower end of the range for the following reasons:
A belief that mortality associated with air pollution exposure should be quantified against loss of life
expectancy and valued in terms of the value of a lost life year rather than deaths valued in terms
of the value of statistical life, partly because it is unlikely that deaths from exposure to particles
generally (rather than, e.g. known carcinogens) could ever be ascribed to air pollution from a
specific source within the current regulatory framework.
The coastal location of many of the plant will limit particle impacts to some degree. The effect of
this is, however, more limited than may at first sight appear to be the case as a result of the
extended distances over which particles and SO2 are carried on the air, and the no-threshold
position recommended by WHO and expert groups elsewhere.
Whilst our own preference is for the lower end of the range, we recognise that others have a different
view, and so include here the full range given from the data in the BREF on Economics and Cross
Media Effects.
The LVIC-S BREF provides average figures for emissions of SO2 and dust from each stage of
production of TiO2 for chloride and sulphate process plant. These emissions data can be combined
with the damage/tonne estimates from Table 4-4 to estimate total damage attributable to emissions of
the two pollutants from TiO2 manufacture
Table 4-5. Total dust and SO2 related damage from European TiO2 manufacture.
Process
Pollutant
Chloride
Sulphate
Sulphate
PM2.5
PM2.5
SO2
Average emission
Total emission
0.159 kg/t TiO2

0.28 kg/t TiO2
4.97 kg/t TiO2
120 t/year
289 t/year
5,130 t/year
Lower bound
damage
5.5 M/year
10 M/year
38M/year
Upper bound
damage
16 M/year
30 M/year
111 M/year
It is clear for dust and for SO2 that emissions from TiO2 plant cause an appreciable level of damage (in
total estimated at between 54 and 157 million/year), and so it is reasonable to consider whether
further emission reductions should be sought.
Monetised damage factors are not available for any of the other pollutants of principal interest to this
report. However, it should be noted that the impact of the discharge of (e.g.) sulphate or chloride rich
waste water depends not only on the discharge rate and concentration, but also on the characteristics
of the receiving water with respect to factors such as:
Flow rate in the receiving environment
Nature and state of the receiving environment
Use of waters in the receiving environment
It may therefore be appropriate to vary the level of control according to the site of emission and the
likely harm caused to the environment for aquatic discharges.
4.3.4 Costs of pollution abatement measures for the sector
The estimated costs of abating emissions of dust, SO2 and chlorine to air and sulphate and chloride to
water are presented in Table 4-6. A more complete discussion of the derivation of the data in the
table is provided in Appendix 6.
Table 4-6. Techniques and annualised costs for various pollutant abatement techniques.
Pollutant
Process
Technique
Annualised
Performance
Source of data
23

AEA/ED05458/Issue 3
1
Dust
Chlorine
Sulphate
Chloride
Sulphate
Sulphate
Sulphate
Sulphate
Chloride
Sulphate
Chloride
Chloride
SO2
Fabric filter
Fabric filter
Standard catalyst
High performance catalyst
Scrubber
No data
Not specified, presumed
4
upgrade
No data
cost/plant
2
483k/year
2
412k/year
0.8M/year
1.6M/year
1.7M/year
1.1M/year
See note 3
See note 3
8 kg/t TiO2
2 kg/t TiO2
1 kg/t TiO2
550 kg/t TiO2
USEPA
USEPA
LVIC-S BREF
LVIC-S BREF
LVIC-S BREF
UK Environment
Agency
-
Notes: 1) The costs cited for dust and SO2 control are for new facilities. The costs for sulphate control are considered to be for
plant upgrade. 2) The cost difference reflects variation in the average size of chloride and sulphate process plants. 3) The
potential performance of dust abatement equipment at TiO2 plant is open to question. Fabric filters in other applications
routinely attain <5 mg/Nm3, though the TDMA has stated that the TiO2 sector would have great difficulty attaining such levels.
No further information has been supplied to justify this view. 4) Cited costs may underestimate through omission of the costs of
additional waste disposal.
The cost assessment made below is hampered by the lack of site specific data made available to the
project. Ideally, an assessment would have been made of which plant required current equipment
simply to be upgraded and which would require existing equipment to be removed and new facilities
installed. However, there was neither the time nor data available for analysis at this level. The
assumptions made for abatement of emissions to air are likely to provide an upper bound of costs as
they deal with new facilities, provided that there is room on site.
However, if new equipment is needed and there is not currently room on site there are two
possibilities:
Costs could increase through the need to undertake a significant restructuring of the plant; or
The plant could close if it was considered uneconomic to carry out the significant restructuring.
The TDMA has stated that the second possibility applies to at least 2 plants with respect to additional
dust abatement equipment needed to achieve the lower BAT AEL. but have not provided supporting
information.
There are thus potential biases in either direction so far as the abatement cost assessment is
concerned. Consideration of these biases needs to be carried through to the comparison of costs and
benefits in the next section.
4.3.5
Comparison of the costs and benefits of meeting scenario ELVs
Overall structure of the analysis

The cost-benefit analysis (CBA) proceeds through the following steps leading to the quantification of:
a) The number of plant exceeding the limit value.
b) The reduction in emissions required to meet the ELVs.
c) The costs of abatement.
d) The benefits of the quantified emission reductions.
e) The ratio of costs to benefits.
f) Consideration of uncertainties.
Costs and benefits of reaching specified emission limit values are only quantified for plant that do not
currently meet them (though see the discussion of uncertainties below).
In most cases the reduction in emissions required to meet the ELVs (step [b]) assumes that emissions
are reduced to meet the ELVs exactly, based on the following rationale.
For dust, the TiO2 industry appears to have problems in achieving similar efficiencies using fabric
filters to those seen in some other sectors. For each scenario it is therefore assumed that it is only
just feasible to meet the ELVs. This raises an obvious inconsistency with the same technology at
the same cost being assumed to meet different levels of emission control in different scenarios.
However, within the scope of the current contract it was not possible to resolve with the industry
what level of control is possible.
The level of abatement for liquid effluents can be varied by (e.g.) changing levels of reagents such
as lime. On this basis systems can be designed to meet specific emission limits.
24

For SO2, however, a series of abatement measures (standard catalyst, high performance catalyst and
scrubbers) were given in Table 3.53 of the LVIC-S BREF (reproduced in this report as Table A6.2 in
Appendix 6). The BREF specifies different levels of abatement for each of these measures. For SO2
it is therefore assumed that where these technologies are fitted the plant concerned would operate to
the levels defined in the BREF. However, it is assumed that only emissions of SO2 from the
calcination stage are treated, where necessary, as this is the stage that emits most SO2 and for which
the LVIC-S BREF states that the cost-effectiveness data reported therein apply.
The costs of further abatement of emissions are quantified by application of the data provided in
Section 4.3.4 for each pollutant.
The benefits of emission controls are quantified for dust and SO2 abatement by multiplying emission
reductions by the damage per tonne data provided in Section 4.3.3. This is applied for dust and SO2
only as unit damage costs are not available for other pollutants.
Uncertainties
Scenario emission limit values were defined in Table 4-2. Those specified in the Directive are given
as emissions per unit TiO2 production, whereas limit values from the BREF are defined per unit
TiO2 pigment production. Turning to emissions, the discussion in Section 4.3.2 noted uncertainty as to
whether reported data per unit of production are expressed:
per unit of pure TiO2,
per unit of TiO2 pigment, or
a mix of the two, varying from plant to plant.
Taking a pragmatic approach to these issues, this report investigates the balance of costs and
benefits under all possible combinations, with numerical values for ELVs in each scenario held
constant whether or not they are expressed per unit pure TiO2 or per unit TiO2 pigment:
1. Emissions per unit pure TiO2, ELVs per unit pure TiO2. So far as results are concerned this of
course gives the same result as when both emissions and ELVs are expressed per unit TiO2
pigment.
2. Emissions per unit pure TiO2, ELVs per unit TiO2 pigment.
3. Emissions per unit TiO2 pigment, ELVs per unit pure TiO2.
From an industry perspective, option [2] gives the most optimistic result in terms of the number of plant
exceeding possible limit values and option [3] the most pessimistic.
Further uncertainties are as follows:
f) Changes in emissions as a result of significant changes to plant or process since the
data provided were originally collected. Whilst some of the data are recent, others are
older and changes may have occurred in the intervening years. However, the fact that the
TiO2 Directives were last revised in 1992 suggests that there may have been little drive more
recently to reduce emissions below levels achieved in the early 1990s, with the result that the
figures provided are reasonably reliable for current use.
g) Changes in emissions through switching to alternative sources of ore and to different
fuels. These could push emissions either up or down.
h) Uncertainties in the benefits of reducing emissions. These are addressed using ranges
taken from the BREF on Economics and Cross Media Effects (see Section 4.3.3). There will
also be uncertainty resulting from the fact that the figures taken are national average damages
per tonne emission, rather than figures specific to the location and dispersion parameters of
individual TiO2 plant. However, assessment of variation in damage per tonne figures between
neighbouring countries suggests that associated uncertainty is relatively small for SO2, largely
because health damage associated with SO2 emissions is quantified via exposure to one of its
reaction products in the atmosphere, sulphate aerosol. The time taken for aerosol formation
to take place reduces the dependence of damage on the exact location of a plant. There is
greater potential for uncertainty in damages associated with PM emissions, though it should
be noted that these total only about half of the damage associated with releases of SO2 (Table
4-5). The fact that results are generated for groups of plant, rather than individual facilities,
means that location-specific errors should to some extent cancel out.
25

AEA/ED05458/Issue 3
Uncertainties in the extent to which emissions can be reduced. This problem has been
identified elsewhere in this report, particularly with respect to the abatement of dust emissions,
where industry sources have said that there are (unspecified) problems for achieving similar
levels of abatement using bag filters to those seen in other sectors. Given a lack of evidence
for this view, however, it is simply raised here as a possible problem.
j) Uncertainties in the costs of reducing emissions. This uncertainty, like several others,
could go either way. If for example, it is possible to upgrade dust controls rather than replace
them with new equipment, costs could be overestimated. Some options not considered in this
report, such as changing raw materials, may also provide the required improvement but at
lower cost. However, if it is necessary to significantly alter the layout of a plant to allow
incorporation of new emission control equipment the costs given here may be underestimated.
k) Uncertainties in the response of industry to a tightening of emission levels. Companies
could decide to act differently, e.g. close plant rather than upgrade them. This is discussed
below in Section 4.4.
i)
Overall, no evidence has been made available under the contract that demonstrates that the analysis
presented below has a significant bias in any direction. At the same time, information that would allow
more detailed analysis of the effects of some of these uncertainties (a, b, d, e) on the cost-benefit
analysis is not available. With this in mind it is recommended that most attention be given to the
case where it is assumed that emissions data available for the analysis are expressed per unit
TiO2 pigment and ELVs are expressed per unit pure TiO2, irrespective of the way that a future
directive might express ELVs. This is the most pessimistic case of the three listed above so
far as possible exceedance of limit values and hence additional costs of abatement are
concerned. As the most pessimistic case, it is also the one that could demonstrate the most
robust rationale for a reduction in emission limit values given the uncertainties listed above.
4.3.5.1
CBA for further control of dust
Data on dust emissions were available for all but 2 sulphate plant in the required (kg/t) format for
comparison with the BAT-AELs. However, emissions data for these two plant at the finishing stage
3
expressed in mg/m suggest that they would perform well in comparison to others, and are only likely
to demonstrate exceedance against the lower BAT-AEL limits (S3). Sensitivity to the setting of limit
values vs. TiO2/TiO2 pigment has been assessed as follows:
First, by assuming that emissions data are reported in a format that is consistent with emission limit
values.
Second, assuming that emissions are reported per tonne TiO2 pigment and ELVs are expressed
per tonne TiO2.
Third, assuming emissions are reported per tonne TiO2 and ELVs are expressed per tonne TiO2
pigment.
The second and third options are investigated by varying ELVs by +15% or -15% respectively, in line
with the assumption given above about the average TiO2 content of TiO2 pigment. The results of
analysis are presented in Table 4-7, based on:
Emissions calculated as the difference between reported emission levels and scenario limit values.
The range for emissions abated for each scenario addresses uncertainty in the definition of
emissions/limits in terms of TiO2 and TiO2 pigment.
Costs calculated by multiplying the number of plant showing exceedance for any scenario by the
costs per plant given above (Table 4-6).
Benefits calculated by multiplying the change in emissions by the damage per tonne estimates
shown in Table 4-4.
Benefit:cost ratios calculated by dividing benefits by costs.
Table 4-7. Change in emissions and costs and benefits of moving to scenario limit values for dust
arisings.
Scenario 2
Scenario 3
Scenario 4
Scenario 5
Limit values and ELVs expressed relative to the same unit of production (t TiO2 or TiO2 pigment)
N plant exceeding limit value
3
15
0
6
Emission change (t)
49
281
0
99
Cost (M/year)
1.3
6.4
2.6
Benefit Low (M/year)
1.9
10.4
3.8
Benefit High (M/year)
5.6
30.5
11.1
26

Benefit:cost ratio low

1.5
1.6
Benefit:cost ratio high
4.3
4.8
Limit values expressed per unit TiO2 pigment, emissions in tonnes TiO2
N plant exceeding
3
15
Emission change (t)
33
276
Cost (M/year)
1.3
6.4
1.3
10.2
3.9
29.7
1.0
1.6
3.0
4.7
Limit values expressed per unit TiO2, emissions in tonnes TiO2 pigment
N plant exceeding
4
15
Emission change (t)
64
286
Cost (M/year)
1.8
6.4
2.5
10.6
7.4
31.1
1.4
1.7
4.1
4.9
1.4
4.2
0
0
5
83
2.2
3.2
9.3
1.5
4.2
3
13
1.3
0.5
1.5
0.4
1.2
9
118
3.9
4.5
13.2
1.2
3.4
Results show benefits exceeding costs (i.e. benefit cost ratios in excess of 1) in all cases except for
Scenario 4 with limit values expressed per tonne TiO2 and emissions per tonne TiO2 pigment. This
may seem surprising given that Scenario 4 has the weakest limit values, but it arises because the
difference between current performance and limit value for the plant that exceed the limit value is
small, and the assumption that the use of bag filters is sufficient only to just meet the limit value of any
scenario. The results for Scenario 3 may be questioned on the grounds of the feasibility of all plant
meeting the limit values used (noting the comments of the TDMA). Given that many plant already
meet the limit values for Scenarios 2 and 5, the levels set under those scenarios appear feasible and
likely to return a net benefit.
One (unnamed) plant is reported in the BREF as having an emission of 0.5 kg/t TiO2 associated with
waste solid metal chloride neutralisation and that no abatement method is applied to control this
emission. It is possible that this part of the process has been or will be decommissioned as it is
reported that it is technically very problematic and under close examination. Taking an average
sized chloride process plant (with capacity 93 kt TiO2 per year) suggests an emission linked to this
process of 46.5 tonnes of dust per year. Assuming a significant proportion of the particles to be in the
sub-micron range, effective control (95%) would require either the use of electrostatic precipitators or
15
bag filters . Assuming a 95% efficiency would reduce emissions from this part of the process by
16
44 tonnes, with resulting benefits of 2.0 to 4.6 million per year against annualised costs estimated
to be in the region of 483,000.
As already noted, the results are subject to additional uncertainties of which the following seem most
important:
1. The precise extent of particle abatement achieved using upgraded filters. Here, it is assumed that
additional abatement, where applied, just achieves the scenario limit values. For the upper BAT
AEL in particular it seems possible that emissions could be reduced well below the limit. This
would increase the benefits for that case.
2. The assumption that totally new filters are needed, rather than that improvements can be made to
existing equipment at lower cost.
3. The assumption that improved filters can be fitted without significant effects on other parts of the
plants concerned. If this is incorrect costs could be higher. As noted elsewhere, one company
states that it could lead to the closure of 2 plant, though no evidence is provided to back up this
statement.
15
Higher efficiencies, closer to 100% should be achieved using the technologies mentioned. However, this makes little difference (at most 5%) to
tbe benefit estimates given. In the absence of more detailed information on constraints that could affect abatement at this part of the process 95%
is therefore a reasonable figure to take.
16
The range given here reflects the difference between the upper and lower estimates of damage per tonne shown inTable 4-4. However, there
is other uncertainty given that the name of the plant and hence its location are not provided in the BREF. The actual damage caused will be
dependent on location in line with the variation seen in estimated damage per tonne PM2.5 in Table A4.2 in Appendix 4. This is less important for
other estimates made in this chapter, as they deal with several plant, not just one, and location-related error can be expected to cancel itself out to
a large degree.
27

4.3.5.2
AEA/ED05458/Issue 3
Costs and benefits of further abatement of SO2 emissions
The analysis is now repeated for SO2 emissions. The analysis of possible changes in dust limits took
emissions only so far as the limits themselves, a conservative approach based on the view of the
TDMA that dust control in the industry is more difficult than for other sectors. However, the same
need not apply to control of SO2 emissions given the performance figures cited in Table 4-6, based on
information from the LVIC-S BREF. Hence the analysis for SO2 assumes that all plant requiring
additional abatement to meet scenario limit values move to the emission values cited in the table, at
least for the calcination stage, rather than to the scenario limits.
Results show benefits exceeding costs (i.e. benefit cost ratios in excess of 1) in all cases irrespective
of whether the low or high estimate of damage per tonne SO2 is applied. The Scenario 3 (lower BATAEL) limit values would be exceeded for many plant based on available emission data and the
assumption that the abatement techniques used can reduce emissions only down to 1 kg/t TiO2 and
apply only to emissions from calcination. However, two plant already perform within the Scenario 3
ELV, and it may be assumed that this performance could be matched by others.
28

Table 4-8. Change in emissions and costs and benefits of moving to scenario limit values for SO2
emissions.
Scenario 2
Scenario 3
Scenario 4
Scenario 5
N plant exceeding limit value
5
11
0
6
Emission change (t)
2,198
3,345
0
2,304
1
Cost (M/year)
8.0
19
9.6
17
25
17
48
73
50
2.1
1.3
1.8
6.0
3.9
5.2
N plant exceeding
4
10
0
6
Emission change (t)
1818
3,337
0
2304
1
Cost (M/year)
6.4
17.0
9.6
14
25
17
40
72
50
2.1
1.5
1.8
6.2
4.3
5.2
N plant exceeding
6
11
3
10
Emission change (t)
2,304
3,345
1,421
2,673
1
Cost (M/year)
9.6
19
4.8
16.0
17
25
11
20
50
73
31
58
1.8
1.3
2.2
1.3
5.2
3.9
6.4
3.6
Notes: 1) The BREF cites a 30% uncertainty in capital costs, which make up about 50% of the total annual cost
for both the high performance catalysts and the scrubbers. No uncertainty is cited for the operating costs.
Assuming that these uncertainties represent variation between plant, associated errors seem likely to cancel out
when several plant require additional controls. 2) Initial analysis for Scenario 3 indicated lower emission
reductions, of 2,747 tonnes per year with benefits of 20 to 60 million per year. Revised estimates reflect use of
an improved approach for dealing with assessment of emission reductions from 2 plant for which available data
were not disaggregated between digestion and calcination.
4.3.5.3
Costs of further abatement of chlorine emissions
The use of chlorine in the industry is regulated through the Seveso II Directive, which should lead to
minimal emission levels, and so further analysis is not presented here. Emissions at one of the 5
European chloride process plant do, however, appear to be significantly higher than at the others and
17
may warrant further consideration. This plant also has the highest emissions of chloride, and so may
be in need of more general updating.
4.3.5.4
Costs of further abatement of sulphates
Only the sulphate process gives significant emissions of sulphates to water. As a consequence, this
section only concerns the sulphate process. Estimated reductions in emissions required for plant to
meet the scenario limit values are given in Table 4-9, together with estimated costs of further control.
In view of the potential need for additional expenditure for disposal of solid wastes this figure may be
biased downwards. The absence of estimates of damage per tonne of sulphate prevents direct
comparison of these costs with the benefits of abatement.
17
The updated emissions information received at the end of the contract showed this still to be the case in 2006.
29

AEA/ED05458/Issue 3
Table 4-9. Overall emission change for sulphate released from sulphate process plant, required to meet
the scenario limit values.
S2
S3
S4
S5
Limit value, kg/t TiO2
550 kg/t TiO2
100 kg/t TiO2
785 kg/t TiO2
300 kg/t TiO2
N plant exceeding
4
11
0
4
Emission change (t)
43,055
238,114
0
122,055
Cost (M/year)
4.4
12.1
0
4.4
N plant exceeding
2
10
0
4
Emission change (t)
17,450
222,853
105,326
Cost (M/year)
2.2
11
0
4.4
N plant exceeding
4
12
2
6
Emission change (t)
69,125
252,176
14,260
143,385
Cost (M/year)
4.4
13.2
0
6.6
The cost data used here are taken for a specific case, estimating the costs of meeting the upper BAT
AEL of Scenario 2 (see Appendix 6). Whilst it seems reasonable to use the estimate for assessment
for Scenario 2 compliance in the absence of better data, its application to other scenarios is open to a
higher level of uncertainty. It is most problematic for Scenario 3 (lower BAT AEL) as this takes
emissions furthest from the case for which data are quoted. Indeed, even from the BREF, it is not
clear how the lower BAT AEL level of 100 kg/t TiO2 can be reached the lowest figure cited being
300 kg/t TiO2. However, levels lower than 300 kg/t are reached by no fewer than 7 sulphate process
plant, according to the data behind the BREF. Theoretically, further reductions in emission should be
possible by adding more lime so as to reach a higher pH. The sulphate concentration is determined
by the solubility of the sulphate salts such as CaSO4 and FeSO4. The solubility diminishes with a
higher pH. This will result in a higher amount of SO4 precipitated as CaSO4 and hence lower SO4
emissions. A subsequent neutralisation of liquid effluents will be necessary in these cases prior to
release to the environment.
As a note of caution, one of the footnotes to Table 3.55 in the BREF (reproduced in appendix 6 to this
report as Table A6.3) states that further abatement from acid recycling beyond a level of 500 kg/t TiO2
would require significant energy inputs for evaporating the weak acid. In addition to the costs of such
action this would also pose additional environmental burden through the release of global and regional
air pollutants.
A more detailed cost analysis of all plant for meeting the Scenario limit values for sulphate is not
possible, given the limited amount of information made available under the contract.
4.3.5.5
Costs of further abatement of chlorides
Only the chloride process gives rise to the emission of significant amounts of chloride to water. As a
consequence, this section only concerns the chloride process.
Estimated emission reductions necessary for chloride process plant in the EU to meet the Scenario
limits for chloride emissions to water are given in Table 4-10. Data were available for 4 of the 5
chloride process plant. Of these, only one exceeds the upper BAT AEL though only under the most
pessimistic assumptions.
30

Table 4-10. Emission reductions for chlorides for moving to the scenario emission levels.
No of plant in exceedance
Additional tonnes abated to

reach Scenario limit
Limit values and ELVs expressed relative to the same unit of production
(t TiO2 or TiO2 pigment)
Scenario 2
0
0
Scenario 3
3
47,000
Scenario 4
0
0
Scenario 5
1
16,700
Scenario 2
0
0
Scenario 3
3
45,000
Scenario 4
0
0
Scenario 5
1
14,000
Scenario 2
1
4,600
Scenario 3
4
49,000
Scenario 4
0
0
Scenario 5
3
22,000
Note: this analysis takes account of 4 of the 5 chloride process plant in the EU.
The BREF does not indicate how the lower AEL level can be reached. Reverse osmosis could be
considered, but this results in the production of a waste water stream that is enriched in chlorides that
needs to be disposed of. Therefore this technique is not really considered a solution for waste water
with a high chloride concentration.
The need to take further action is dependent on the nature of the water body into which the chloride
process plant discharge their effluent. Clearly, water in the sea or in tidal estuaries can cope with
higher chloride inputs than freshwaters. The anonymised nature of the data provided mean that it is
possible only to assume that plant with the lowest emissions discharge to freshwater and the plant
with the highest emissions discharge to the sea or to tidal estuaries. Assuming this to be the case,
and assuming that monitoring has not established significant effects of discharges of chloride to the
ecology of the water bodies concerned, the benefits of further control may be minimal. Disbenefits
associated not just with the costs of additional control but also the supply of additional reagent may
well outweigh any benefit from further control.
There is possibly a question to be asked when the BREF is reviewed as to whether all plant truly meet
BAT, given the factor 10 range between the least and most polluting plant and the fact that the range
seems to include all plant for which data were available. It is noted that the plant with the highest
18
chloride emissions also has the highest chlorine emissions, and so may be somewhat dated.
4.3.6 Trends in emissions of other pollutants
The emissions data provided under the contract do not include a number of pollutants (heavy metals,
etc.) though some additional information is provided by the EPER database (European Pollutant
Emission Register). Trends in emissions from each plant based on EPER data for 2001 and 2004 are
summarised in Table 4-11. Further detail is provided in Appendix 7. The data held on EPER are
more complete for some plant than others. This will be due in part to emissions for some
plant/pollutant combinations being below the thresholds set for reporting to EPER. However, this does
not seem to explain all of the gaps in the database. Over the full set of pollutants there is some
indication of a general tendency towards reduced emissions, though significant increases are evident
for some pollutants. Changes in emissions at any specific plant as listed in EPER may arise for a
variety of reasons:
Variation in efficiency of environmental controls
Variation in operating efficiencies against one or more inputs
Changes in plant capacity, either through commissioning new production lines or decommissioning
old ones, or through changes in plant availability, for example through improved maintenance
regimes
18
The 2006 dataset received at the end of the contract add weight to the issues raised in this paragraph (see data in Appendix 5). Data for all 5
plant were available. The highest emission for any plant is now 199 kg/t, substantially lower than the upper BAT AEL of 330 kg/t/. One plant
continues to emit chlorine at a higher level than the others. The new data suggest that differentiation of ELVs according to the type of ore used is
no longer necessary.
31

AEA/ED05458/Issue 3
Alterations to plant operation

Differences in input materials (such as ore or coke, e.g. with respect to heavy metal content)
Any of the above, but with respect to activities unrelated to TiO2 manufacture (i.e. related to the
production of other chemicals at the same site, as at the Zaklady plant at Police in Poland).
Table 4-11. Trends in emissions between 2001 and 2004 from EPER. Figures show the number of plant in
each change category for which data were available for both 2001 and 2004.
Pollutant
Significant
reduction
(20%)
Emissions to water
As
Cd
2
Cr
2
Cu
1
Hg
1
Ni
2
Pb
3
Zn
6
TOC
1
Emissions to air
CO
2
CO2
NOx
2
TOTALS
22
Small
reduction
(<20%)
Neutral
( 5%)
Small
increase
(<20%)
Significant
increase
(20%)
1
2
1
-
2
1
1
2
1
1
2
1
-
2
1
1
2
1
-
1
1
2
-
3
-
10
It is necessary to ask whether, on the basis of these trend data for 2001-4, the performance against
the scenarios and environmental performance more generally (i.e. for pollutants for which specific
limits do not exist under the scenarios) will have improved or worsened. The largest % increases are
as follows:
Thann, 58% increase in arsenic emissions.
Calais, 105% increase in copper emissions.
Grimsby, 65% increase in mercury emissions.
Stallingborough, 90% increase in nickel emissions.
Scarlino, 131% increase in SO2 emissions.
Whilst any increase in emissions is regrettable, in no case do these increases in emission affect plant
that are already in the highest emitting category for the pollutant in question, or move a plant into the
19
highest emitting group . For example, whilst there is a large percentage increase in SO2 emissions
from the Scarlino plant in 2004 compared to 2001, Scarlino remains in a cluster of plant with the
lowest SO2 emissions. Similarly, Grimsby remains the lowest emitter of mercury of those plant
reporting their mercury emissions, despite the increase in emission rate.
However, reductions in emissions at some plant appear more significant, particularly for the following:
Rotterdam and Duisburg for a number of pollutants discharged to water
Le Havre for emissions of zinc to water
Huelva for NOx to air
Calais for SO2 emissions.
These reductions suggest some improvement in performance against the scenario limits compared to
the data used to develop the BREF, but not a major change across the board. This can be explained
by the schedule for implementation of IPPC for the industry and the existence of sector-specific limit
values dating back to the 1992 Directive. A constraint for the EPER data is that it refers to total
emission, rather than emission normalised per unit output. Differences from year to year may thus be
due at least in part to changes in production.
19
This statement should be read with some caution given that the data presented on EPER do not cover all pollutants for all plant.
32

4.4 Effects on competitiveness and employment

A macroeconomic assessment was performed using the GEM-E3 model for the DG Environment
CAFE (Clean Air For Europe) Programme, for which the costs of pollution abatement were many times
greater than those considered here. Even in that case, it was concluded that the macroeconomic
consequences of emissions control were small, less than the uncertainty in the modelling. From this
we can conclude that the macroeconomic (Europe-wide) consequences of action to further control
emissions from European TiO2 manufacturers is likely to be negligible. However, it is still necessary to
consider possible consequences for the industry at the sector level.
20
It is worth noting the views of Vercaemst who suggests that a detailed affordability assessment is not
necessary if:
There is consensus of what constitutes BAT in the relevant Technical Working Group,
If the measure with the best overall environmental performance is actually proposed by operators
in the sector, and
If the pollution prevention measure is already applied by many operators in the sector.
On this basis, affordability is already established for Scenarios 1, 2 and 4, as these deal with positions
that go only so far as the upper BAT-AEL from the BREF, given the industrys involvement in
development of the BREF and the fact that many TiO2 manufacturers already meet the upper BATAEL.
The sensitivity of the sector to added cost is dependent to a significant degree on the extent to which it
is able to pass these costs onto consumers, rather than absorb them via reduced profitability. Initial
consideration is given to various factors in Table 4-12, with more discussion following the table.
Table 4-12. Performance of the sector against determinants of cost pass-through.
Factor
Geographical extent of the market
Rating
Global
Price elasticity of demand and supply
Low
Degree of competition between

products / threat of substitute
products or services
Rivalry among existing firms in
sector
Low
Medium
Bargaining power of customers and

suppliers
Threat of new entrants
Medium-high
Low medium
Degree of international competition
High
Comment
The TDMA has expressed concern that
cheap imports from China have depressed
prices.
The market seems to have resisted
attempts to increase prices (see below).
TiO2 has a number of physical and chemical
characteristics that favour it over
alternatives.
Rivalry certainly exists within the market,
but not at the extremes of some other
sectors that have the ability to modify
product lines more easily.
Customers seem to have resisted price
increases, whilst the cost of some supplies
(e.g. energy) are driven by factors outside
of the TiO2 sector.
Standards required of plant operating in the
EU may discourage new entrants. Capacity
increases in recent years have been
through expansion of existing plant and
reducing downtime.
Competition from China is said to be
capturing some market share in the EU.
21
Several manufacturers (Millennium , Tronox and Huntsman and possibly others) have announced
price increases recently of between 4% and 7%, against a price of around 2,000/tonne achieved by
the European manufacturers. From other information on the internet it appears that the industry has
sought to increase prices for some time, but with limited success. This could be taken to mean that
the industry is under significant pressure (Huntsman refers to price increases for materials, energy
and freight), or that the industry believes that the market for TiO2 is strong enough to take price
20
21
P. Vercaemst (2001) BAT: When do Best Available Techniques Become barely affordable technology? BAT-Centre, VITO, Mol, Belgium.
http://www.millenniumchem.com/News+and+Events/_News/PriceIncreasePressReleaseGlobalJune2007fin.htm
33

AEA/ED05458/Issue 3
increases of this order. The truth may well of course be a mix of the two extremes. However, the
markets apparent reluctance to pass costs on to consumers implies that the businesses concerned
may well have to absorb costs themselves, affecting profitability.
According to the TDMA, 2 sulphate plants have recently come up for sale, but have so far not been
able to find buyers. The selling price of TiO2 in real terms has dropped since the eighties so the TiO2
business cannot sustain investment in new plants but has been able to carry out some expansions at
chloride facilities. Cheap imports from China are now helping to keep prices depressed.
With respect to plant being unable to find new buyers, Tronox has concluded the evaluation of
strategic options for its Uerdingen plant and has made the decision to retain it because the business
and financial market assessments did not accurately reflect the long-term value of this world-class
sulfate-process TiO2 facility. They go on to say that With the strong European economic conditions,
our recent investments in the facility and our strategic plans for the future, we believe the Uerdingen
asset will provide better long-term value for our shareholders as part of our portfolio. To maximize its
value, we will continue to focus on our strategy to drive costs out of the business through
improvements in our operations and processes.
TDMAs reference to cheap imports from China keeping prices depressed perhaps provides only a
temporary perspective. Given the rate of economic growth in China, and its demonstrated demand for
other products (e.g. steel, oil), it seems that there may be potential in the longer term for the market
pressure from China to be reversed. Detailed analysis of this is, however, outside the remit of the
present assessment.
TDMA have also stated that a reduction in the dust emission limit to the lower BAT AEL level (5
3
mg/m ) could lead to the possible closure of 2 plants (though it is unclear whether this is for the
European industry as a whole, or for one company). Questioned on this, the TDMA has said that it
3
would result from the increased filter area required to achieve something close to 5mg/m dust levels.
For the plant concerned dust abatement is housed inside, so new buildings would be required, the
cost of which could not be sustained by the plants. It remains unknown, however, whether this would
3
3
apply were the limits set higher than 5 mg/m (the BREF range for sulphate plant is 5-20 mg/m ) or the
extent to which suppliers of bag filter technologies have been consulted to see whether improved
efficiency of abatement can be achieved without such major change.
There are thus mixed signals from the industry, with some reference to strong European economic
conditions (e.g. Tronox, in explaining its decision to retain the Uerdingen plant) and others implying
that the industry is currently very sensitive to additional pressure on costs.
Assessment of the financial health of the industry is complicated for several reasons. Many plant are
operated by international companies, and it has proved impossible to obtain annual accounting data at
a plant specific level in many cases. Also, many plant manufacture other products on site, so splitting
out the relative contributions of the different product streams is again not possible from data typically
provided in annual reports. However, from annual reports available for four companies, overall
profitability of the TiO2 business would appear to be in the region of 3.5% to 10% of sales. This full
range is used in the analysis that follows, though the lower end of the range may be more accurate for
the industry as a whole, given increased costs for energy, etc., in recent times, and the apparent
difficulty in pushing through price increases to consumers.
Taking a price of 2,000/t TiO2, an capacity of 1.5 million tonnes/year and an 85% availability of plant
implies total annual production of 1.3 million tonnes and sales of 2.6 billion. Additional annual costs
of abatement are compared with sales revenues and profits in Table 4-13.
34

Table 4-13. Comparison of estimated additional annual costs of abatement with sales and profits.
Scenario 2
Scenario 3
Scenario 4
Scenario 5
Limit values and ELVs expressed relative to the same unit of production (t TiO2 or TiO2
pigment)
Dust (M/year)
1.3
6.4
0
2.6
SO2 (M/year)
8
19
0
9.6
Sulphate (M/year)
4.4
12
0
4.4
Chloride (M/year)
0
nd
0
nd
Cl2 (M/year)
nd
nd
nd
nd
Total (M/year)
13.7
37.2
0
16.6
% sales
1%
1%
0%
1%
% low estimate of profit
15%
41%
0%
18%
% high estimate of profit
5%
14%
0%
6%
Dust (M/year)
1.3
6.4
0
2.2
SO2 (M/year)
6.4
17
0
9.6
Sulphate (M/year)
2.2
11
0
4.4
Chloride (M/year)
0
nd
0
nd
Cl2 (M/year)
nd
nd
nd
nd
Total (M/year)
9.9
34.4
0
16.2
% sales
0%
1%
0%
1%
11%
38%
0%
18%
4%
13%
0%
6%
Dust (M/year)
1.8
6.4
1.3
3.9
SO2 (M/year)
9.6
19
4.8
16
Sulphate (M/year)
4.4
13.2
0
6.6
Chloride (M/year)
nd
nd
0
nd
Cl2 (M/year)
nd
nd
nd
nd
Total (M/year)
15.8
38.6
6.1
26.5
% sales
1%
1%
0%
1%
17%
42%
7%
29%
6%
15%
2%
10%
nd = no data
Scenario 4, being based on plant performance has a very low impact on profitability. The effects of
Scenario 3, in particular, and to a slightly lesser extent Scenario 5, look significant, especially at the
lower end profitability. Costs for these two scenarios would of course increase if estimates of the
additional costs of chloride control were added in.
An important caveat to consider when looking at Table 4-13 is that the table assumes that for each
scenario efforts would be made to bring all emissions in line with the respective scenario emission
limits. However, as noted in the text above, there may be good reasons for selecting emission limits
from different scenarios for different pollutants for specific plant. The most obvious example concerns
emission limits for chloride, which can very justifiably vary to achieve similar levels of environmental
protection depending on whether a plant discharges to the sea or to a river.
There are competing effects of tightened emission limits on employment. On the one hand, the need
to manufacture and install additional abatement equipment and to supply reagents and other materials
for pollution control facilities generates additional job opportunity (alongside the reduction in pollution
this provides a double dividend). On the other hand, jobs may be lost, either because impacts on
profitability reduce investment over time, or because plant cannot meet the emission limits and have to
close. The example cited by the industry in relation to this work concerns reducing emissions of dust
3
to 5 mg/m , which one company has claimed would lead to the closure of 2 plant (it is not clear
whether this is 2 plant owned by a single company, or 2 plant from all 18 of those operating in the
European Union). Around 800 jobs could be lost by the closure of the two plant. A caveat to this
estimate as noted elsewhere is that the estimate of 2 plant requiring closure is purely anecdotal, no
evidence having been supplied to indicate how it was reached, and in particular, what alternatives
were considered.
The robustness of the conclusions drawn here is limited, reflecting the extent to which data has been
available to the assessment. Of particular concern is the feasibility of some measures at some plant
35

AEA/ED05458/Issue 3
further guidance from the industry on this issue, backed up with a firm rationale where it was
considered that measures were not feasible would have been extremely useful.
36

37

AEA/ED05458/Issue 3
5 Analysis on Monitoring of the Environment

5.1 Introduction
With respect to environmental monitoring, the following questions were raised in the Technical Annex
for this contract:
The potential for simplification of the requirements for monitoring air and water set out in the
Annexes of Directive 82/883/EEC, accounting for existing legislation, for example under the Air and
Water Framework Directives.
Appropriate monitoring requirements for water and air emissions for pollutants regulated under
Directive 92/112/EEC, based on current practice, with reference to the frequency and method to be
used for monitoring.
The extent to which further monitoring of the environment is necessary if appropriate emission
monitoring for water and air is established.
Whether the frequency of monitoring of the environment, as set out in Directive 82/833/EEC can be
simplified or altered based on the present state of the environment potentially affected by waste
from TiO2 production.
The costs and benefits (economic, social, and environmental) of changes to the environmental
monitoring specified in Directive 82/883/EEC.
Key to the considerations made here is the fact that since 1982 there has been a great deal of
environmental legislation made by the EU and by Member States. For example, the monitoring and
assessment of air quality and water quality have both expanded greatly throughout the EU in the last
25 years as a result of the framework directives on air quality and on waters. The requirements of the
TiO2 Directives are therefore partly replicated by other legislation.
A further factor to consider is that whilst simplification of the existing requirements is desirable, it
should not cause a worsening of environmental quality.
5.2 Summary of monitoring requirements in the TiO2

Directives
5.2.1 Monitoring of emissions to air
The TiO2 directives set minimum requirements for the measurement of emissions to air from TiO2
manufacturing plants (Table 5-1).
Table 5-1 : Summary of monitoring of emissions to air in TiO2 Directives
Directive
Component
82/883/EEC
SO2
Cl2
PM
(optional)
92/112/EEC
PM, SOx,
acid
droplets, Cl2
Emission/
Air quality
Air quality
Emission
Limit Value
None stated
Emission
See Table 4-1
Comment
Concerns monitoring of air quality around TiO2
plant. Continuous air quality monitoring where
existing network in place otherwise monthly.
SO2 where sulphate process and Cl2 where
chlorine process. SO2 monitoring in
accordance with Directive 80/779/EEC.
Continuous Cl2 monitoring when monitoring
technology developed.
Variation in requirements according to process
used and whether emissions are released from
major or minor sources on-site. Monitoring
time period only defined for Cl2.
The Council Directive 82/883/EEC on surveillance and monitoring of environments concerned by the
waste from the TiO2 industry requires mandatory air quality measurement of SO2 in the vicinity of
sulphate process plant and measurement of chlorine around chlorine processes. There is a
derogation for the measurement of chlorine this is to be undertaken when there is a suitable
38

measuring technology available. The continuous measurement of ambient dust is optional under this
Directive.
The air quality monitoring required by Directive 82/883/EEC concerns monitoring of the receiving
environment. Assessment is notionally with monitoring at a neighbouring control location; though
there are no criteria within the Directive which assess the extent to which the TiO2 facility is impacting
the receiving environment.
Under Directive 92/112/EEC harmonizing programmes for the reduction and elimination of waste from
the TiO2 industry emission limit values (ELV) are set for the main species emitted to air that is, dust,
oxides of sulphur (SOX) and chlorine (Cl2) (see Table 4-1). All emission limit concentrations are for
existing plant and were to be achieved 15 June 1993. They are expressed at STP (273 K, 101.3 kPa)
with no correction for moisture or oxygen content of exhaust gases.
No information is provided on the methodology, frequency or duration of emission monitoring. Apart
from the chlorine ELVs no detail is provided on the averaging period for the ELV. In addition, (and in
contrast to, for example, Directive 2000/76/EC on incineration of waste) there is no consideration of
measurement uncertainty.
The Air Quality Framework Directive 96/62/EC (and daughter directives) defines requirements for air
quality management including air quality standards (but not for chlorine). The IPPC Directive includes
use of emission monitoring as part of BAT.
5.2.2 Monitoring of emissions to water
The requirements of the TO2 Directives with respect to the monitoring of emissions to water are
summarised in Table 5-2. The requirements shown in the table need to be considered against more
recent legislation:
the Water Framework Directive (2000/60/EC);
the IPPC Directive (96/61/EC)
The Landfill Directive (1999/31/EC)
The Water Framework Directive (WFD) (2000/60/EC): Article 8 of the WFD deals with Monitoring of
surface water status, groundwater status and protected areas This article states that:
1. Member States shall ensure the establishment of programmes for the monitoring of water
status in order to establish a coherent and comprehensive overview of water status within
each river basin district:
For surface waters such programmes shall cover the volume and level or rate of flow to the extent
relevant for ecological and chemical status and ecological potential, and the ecological and
chemical status and ecological potential.
For groundwaters such programmes shall cover monitoring of the chemical and quantitative status.
For protected areas the above programmes shall be supplemented by those specifications
contained in Community legislation under which the individual protected areas have been
established.
2. These programmes shall be operational at the latest six years after the date of entry into force
of this Directive unless otherwise specified in the legislation concerned. Such monitoring shall
be in accordance with the requirements of Annex V.
3. Technical specifications and standardised methods for analysis and monitoring of water status
shall be laid down in accordance with the procedure laid down in Article 21.
39

AEA/ED05458/Issue 3
Table 5-2: Summary of non-air mandatory monitoring in TiO2 Directives

Directive
Component
78/176/EEC
Acute toxicity
pH, dissolved O2
,turbidity, hydrated
iron oxides and
hydroxides in
suspension, toxic
metals, suspended
solids
toxic metals
diversity,
abundance
toxic metals
Acidity, iron
content, calcium,
toxic metals
Soil structure
82/883/EEC
(Salt water)
Ecology
assessment
Temperature,
salinity, pH, O2 ,
turbidity, Fe, Ti
Fe
Fe, Iron oxides and

hydroxides
Ti, Fe, Iron oxides
and hydroxides
(Fresh
water)
Ti, Cr, Fe, Ni, Zn,

Pb
Diversity,
abundance, lesions
Temperature
conductivity, pH, O2
, turbidity, Fe, Ti
Fe
Fe, Iron oxides and

hydroxides
(Storage on
land)
Ti, Fe, Iron oxides

and hydroxides
Ti, Cr, Fe, Ni, Zn,
Pb
Diversity,
abundance
pH, SO4 , Ti, Fe,
Ca, Cl
Site management,
Subsoil, ecology,
92/112/EEC
40
Sulphate, chloride
Emission/
Environment
Emission
(effluent)
Emission
Limit Value
20% Mortality
Environment
(water column)
Environment
(living matter)
Selected benthic and Pelagic organisms
Flora and fauna
Environment
(sediment)
Environment
(surface and
ground waters)
Environment
(subsoil)
Environment
Comment
Over 36 hours exposure at 1/5000 dilution on certain
species preferably those commonly found in
discharge area and brine shrimp; limit applies to
adult exposure, Larval mortality not to exceed a
control group.
Periodic checks on area affected by discharges to
follow development of the receiving environments.
In the case of storage, tipping or injection of waste.
Where necessary to monitor adverse effects
General assessment around storage, tipping or

injection point.
Minimum frequency 3 times per year,.
Environment
(water column,
filtered)
Environment
(suspended
solids)
Environment
(sediment)
Minimum frequency 3 times per year.
Minimum frequency 3 times per year.
Environment
(organisms)
Minimum frequency once per year. In the top layer

of sediment as near surface as possible, metals to
be determined for a range of particle sizes.
Minimum frequency once per year. Specifications
on parts of creatures used for extraction.
Benthic fauna, lesions on fish selected for metal
analysis
Environment
(water column)
Environment
(water column)
Environment
(water column,
filtered)
Environment
(suspended
solids)
Environment
(sediment)
Environment
(organisms)
Environment
(surface water/
groundwater)
Environment
(topography,
soil)
Emission
(effluent)
See Table 4-1
No information on frequency of measurement

For surface waters three types of monitoring are required by the WFD:
Surveillance to validate the characterisation pressure and impact assessments, detect long-term
trends;
Operational to help classify those water bodies which are at risk of failing to meet good status;
and
Investigative to ascertain the cause and effects of a failure to meet good status where it is not
clear.
For each surface water body, the Competent Authorities will assess as appropriate:
Biology (plankton/phytobenthos, macrophytes, invertebrates and fish);
Hydro-morphology ;
Physico-chemical (including organic pollutants);
Priority and priority-hazardous substances.
Priority substances should be monitored every 3 months and other substances every month (so more
frequently than under the TiO2 Directives). No mention is made of specific monitoring around TiO2
facilities. It may be expected that this would be done under the WFD in cases where TiO2 plant
remained a specific concern in a given river basin. However, given the relatively long history of
regulation of the industry this may not be done. Withdrawal of a requirement to monitor around TiO2
plant could have contrasting effects:
Reducing protection around TiO2 plant
Enabling resources devoted to monitoring around TiO2 plant to be used to monitor in other places
where need is greater
Enabling resources currently devoted to environmental monitoring to be allocated to quite different
purposes.
For groundwaters, the monitoring requirements cover:
Groundwater resources through a water level monitoring network;
Surveillance and operational monitoring of chemical status
The IPPC (Integrated Pollution Prevention and Control) Directive: sets out the principle that
industrial operators are responsible for carrying out monitoring of emissions from installations falling
under IPPC. To support the implementation of the Directive the European IPPC Bureau in Seville has
prepared a reference document (BREF) on the principles of monitoring under IPPC. The document
recognises that wherever possible emissions should be monitored using standards produced by
recognised standard making organisations and sets down a hierarchy of standards making
organisations. While the BREF is a useful reference document on monitoring generally, in the area of
monitoring discharges to water, experience has shown that the applicability of standard methods
should never be taken for granted. The operator should always ensure that the laboratory undertaking
the analysis is able to verify that the degree of validation of a particular method is adequate to ensure
that the results reported are fit for purpose.
Directive 1999/31/EC on the landfill of waste: requires that landfill operators monitor leachate to
ensure that no significant harm arises to the environment surounding the landfill.
5.3 Current monitoring in relation to TiO2 manufacture:

The following data have been collated from questionnaire responses by some Member States and
some TiO2 producers. Cost data are available in some cases but not others. The data that are
available from these sources represent the total costs of monitoring, rather than the costs for
application of individual methods.
5.3.1 Belgium
For most of the relevant environmental aspects for the activities of Kronos Europe, a good monitoring
system is already in place, following the current legal obligations. The Environmental Inspectorate
Division (EID) is in the Flemish Region responsible for the enforcement of the environmental
legislation in which the TiO2 Directives are transposed. During the routine inspections of the EID, the
wastewater of the company is also monitored: each year at least 4 samples of the wastewater were
taken and analysed (at least 2 spot samples and two 24 hour flow proportional samples, within every
sampling campaign also a sample of the surface water that is used in the company is analysed.
41

AEA/ED05458/Issue 3
The company also has set up a detailed action plan to limit their potential environmental impacts.
Therefore, the authorities do not propose additional monitoring or post evaluation.
For the landfill, a working plan is submitted by the company to monitor the quality of the groundwater.
The quality of the groundwater is assessed every 6 months and shows that the landfill does not have
any effect on the environment.
In Flanders the Flemish Environmental Agency (VMM) is responsible for the monitoring of surface
water. Ti is measured in surface water, monthly, near the TiO2 -production sites. The monitoring of
surface water is estimated at 100/site/sample. Taking into account the monitoring of two sites in
Flanders (till end 2006), with a frequency of 12 samples per year, a total cost for the Flemish
government of 2400/year is estimated.
The total cost for the monitoring by the EID is roughly estimated as 1,500 2,000 for the sampling
and the analysis of the water samples. There is also an extra cost of 1 day (total) for the
environmental inspector of the EID. The operators do not pay for this type of monitoring.
The costs or time required for supervision and reporting requirements of the TiO2 Directives is
estimated to be two days work for the VMM to report data on quality of surface water and another two
days for supervision and reporting by the EID.
5.3.2 Czech Republic
The ELVs set in the Directive 92/112/EEC and IPPC legislation is used to control emissions. There is
a requirement for the measurements to be made by accredited personnel and organisations. BREF
notes were not used as the reference to decide the monitoring requirements. According to legislative
requirements of the Czech Republic, the monitoring is carried out regularly. All values are monitored
by accredited persons and accredited laboratories. The yearly average cost of monitoring according
to Directive 82/883/EEC is approximately 70,000. This cost is however paid by the operators.
5.3.3 Finland
The ELVs set in the Directive 92/112/EEC are used to control the emissions. An IPPC approach is
being developed but not currently employed. CEN methods have to be used to measure the
emissions from the plant where available. Comprehensive environmental monitoring is undertaken
overseen by South Western Finland Environmental centre.
5.3.4 Germany
The plants in Germany operate under IPPC permitting with ELVs compliant with the requirements of
the directive 92/112/EEC. The ELVs applied across the sector are currently between those of the
92/112/EEC and 2006/12/EEC (for water) levels. Environmental monitoring is undertaken at multiple
sites with a variety of different frequencies and analysing for different analyses.
5.3.5 Netherlands
In the Netherlands, the environments possibly effected by the emissions of the titanium dioxide
installations are monitored by:
Individual controls by the Authorities and
Continuous monitoring by the organization
There is no specific information on costs related to environmental monitoring. It is however so that in
the Netherlands all costs for monitoring are paid by the authorities.
The monitoring operations, referring to art. 7.2 of Directive 78/176/EEC, are carried out regularly by
the regional competent authority in the Netherlands (especially DCMR Milieudienst Rijnmond and
Rijkswaterstaat directie Zuid-Holland).
5.3.6 Poland
Operates under IPPC complying with the 92/112/EEC ELVs.
5.3.7 Slovenia
For water emission monitoring discontinuous measurements are used, with frequency and sampling
period dependent of the yearly quantity of discharged water. If the amount of discharged water is less
than 50.000 m per year it is obligatory to sample 6-hours, and for more than 50.000 m discharged
per year, a 24-hours sampling is obligatory.
42

National monitoring of ambient air and surface water quality is performed either continuously or
periodically on a limited number of locations.
Operators have to carry out environmental monitoring programs on both waste tipping sites (closed
and active). The monitoring program is approved by the competent body and is in line with provisions
of directive 82/883/EEC. National monitoring is covered by a budget from the national authorities and
can not be attributed to individual operators.
Operators have to perform an official monitoring of discharges into the air, water and noise at its own
costs once a year. According to operators, the related costs are about 75,000/year.
Monitoring of discharges is entirely covered by the operator.
All reporting requirements done by the competent authority, are estimated on about 1 man/week
approximately. Emissions to air comply with the 92/112/EEC directive requirements.
5.3.8 Spain
All discharges to air are monitored by the installation within a routine analysis plan. In general, water
discharge is monitored by the installation, again within a routine monitoring plan. The authorities
check discharges to air and water periodically.
5.3.9 United Kingdom
Within the UK there are some variations in the monitoring requirements placed upon the three TiO2
installations. The IPPC Directive is implemented under Pollution Prevention and Control Regulations
(PPC) via the operating permits. These permits define the monitoring requirements considered to be
necessary by the Environment Agency of England & Wales acting as the regulatory body (the three
installations are all in England). These include additional monitoring over that required in the TiO2
Directives and are summarised in the following table;
Table 5-3 : Summary of the Air Emission Monitoring Required for UK Installations
Site
Component
Frequency
Oxides of Nitrogen
Hydrogen Chloride
Chlorine
Hydrogen Sulphide
Sulphur Dioxide
Particulate
Oxides of Nitrogen
Hydrogen Chloride
Chlorine
Hydrogen Sulphide
Sulphur Dioxide
Sulphur Dioxide
Particulate
Particulate
Carbon Monoxide
Carbonyl Sulphide
Oxides of Nitrogen
Oxides of Nitrogen
Hydrogen Chloride
Sulphur Dioxide
Sulphur Dioxide
Sulphur Dioxide
Particulate
Particulate
Particulate
Particulate
Quarterly
Quarterly
Continuous
Quarterly
Quarterly
Quarterly
Monthly
Monthly
Continuous
Monthly
Monthly
Continuous
Monthly
Continuous
Continuous
Monthly
Bi-annual
Continuous
Bi-annual
Quarterly
Bi-annual
Continuous
Annual
Bi-annual
Quarterly
Continuous
Standard method
used
ISO 10849
EN 1911
Colorimetry
BS 6069-4.4:1993
ISO 9096
ISO 10849
EN 1911
BS 6069:4.4
BS 6069:4.4
EN 13284-1
EN 13284-2
ISO 12039
Electrochemical
Colorimetrically
NaOH/Glycerol
NaOH/Glycerol
ISO 9096:2003
ISO 9096:2003
ISO 9096:2003
43

AEA/ED05458/Issue 3
5.4 Monitoring Standards

5.4.1 Air monitoring
This section describes standards that are listed for the measurement of species listed in the process
directives, BREF Notes and permits to operate. The standards are referenced in accordance with the
hierarchy of standards used within the EU that is. EN, ISO, national and other standards. Where CEN
and ISO standards are not available national and other standards have been searched.
Recently a number of CEN standards have been devised with the objective of ensuring compliance
with published EU directives and as such can be considered best practice.
CEN, ISO or EU national standards exist for the measurement of the main emissions to air from all
stages of the processes identified in the BREF with the exception of H2S, Cl2 and COS. However,
there are continuous automated monitoring systems (AMS) available for chlorine measurement which
should be considered best practice when used in conjunction with other CEN and ISO standards
applicable for AMS. The use of large volumes of chlorine necessitates a high standard of continuous
monitoring in the sector through the requirements of the Seveso II Directive. There are also other
established methods for the periodic measurement of Cl2, H2S and COS that enable a BAT approach
to be adopted using these as the basis of measurement.
Further details on methods for measuring these air pollutants are given in Appendix 8.
Table 5-4 : Summary of standards applicable to air emission monitoring for TiO2 Directives
Pollutant
Particulate matter
Continuous or
Periodic
Continuous
Standard
Comment
EN13284 Pt 2
For determination of mass concentration of

dust using automated measuring systems (for
lower concentrations)
dust using automated measuring systems (for
lower concentrations)
Manual sampling procedure for particulate for
concentrations <50 mg/m3
Manual sampling procedure for particulate for
concentrations >50 mg/m3
SO2 using automated measuring systems
Integrated sample collection followed by
chemical analysis.
analysis, use of multiple collection media to
collect SO2 and SO3
chemical analysis, use of multiple collection
media to determine HCl and Cl2 separately.
Continuous method
ISO 10155
Periodic
EN13284-1
ISO 9096
SO2
Continuous
ISO 7935
Periodic
EN 14791, ISO11632
SO2 + SO3
Periodic
USEPA Method 8
Cl2
Periodic
USEPA Method
26/26A
Continuous
Continuous
ISO14164
ISO 10396
Flow
General use of
automated measuring
systems
Sampling for the automated determination of

gas concentrations. Can be applied to
continuous Cl2 measuring systems
5.4.2 Water monitoring

Table 5-5 summarises relevant water analysis standards produced by the CEN Technical Committee
on Water Quality. Note that many of these standards may not be applicable to monitoring effluent
discharges.
44

Table 5-5 : CEN/TC 230- Published standards on water sampling and analysis
Component
Standard reference
Title
Cr
EN 1233:1996
Hg
EN 12338:1998
Hg
EN 13506:2001
Organisms
EN 13946:2003
Organisms
Organisms
EN 14011:2003
EN 14184:2003
Organisms
EN 14407:2004
Other
EN 14614:2004
Organisms
Hg
EN 14757:2005
EN 1483:2007
Organisms
EN 14962:2006
QA aquatic
sampling
Organisms
EN 14996:2006
Organisms
EN 15196:2006
Dissolved O2
EN 25813:1992
Dissolved O2
EN 25814:1992
As
EN 26595:1992
As
EN 26595:1992/AC:1992
Water quality - Determination of chromium - Atomic absorption spectrometric

methods
Water quality - Determination of mercury - Enrichment methods by
amalgamation
Water quality - Determination of mercury by atomic fluorescence
spectrometry
Water quality - Guidance standard for the routine sampling and pre-treatment
of benthic diatoms from rivers
Water quality - Sampling of fish with electricity
Water quality - Guidance standard for the surveying of aquatic macrophytes
in running waters
Water quality - Guidance standard for the identification, enumeration and
interpretation of benthic diatom samples from running waters
Water Quality - Guidance standard for assessing the hydromorphological
features of rivers
Water quality - Sampling of fish with multi-mesh gillnets
Water quality - Determination of mercury - Method using atomic absorption
spectrometry
Water quality - Guidance on the scope and selection of fish sampling
methods
Water quality - Guidance on assuring the quality of biological and ecological
assessments in the aquatic environment
Water quality - Guidance standard for the sampling of zooplankton from
standing waters
Water quality - Guidance on sampling and processing of the pupal exuviae of
Chironomidae (Order Diptera) for ecological assessment
Water quality - Determination of dissolved oxygen - Iodometric method (ISO
5813:1983)
Water quality - Determination of dissolved oxygen - Electrotechnical probe
method (ISO 5814:1990)
Water quality - Determination of total arsenic - Silver diethyldithiocarbamate
spectrophotometric method (ISO 6595:1982)
Water quality - Determination of total arsenic - Silver diethyldithiocarbamate
spectrophotometric method (ISO 6595:1982)
Water quality - Methods of biological sampling - Guidance on handnet
sampling of aquatic benthic macro-invertebrates (ISO 7828:1985)
Water quality - Determination of electrical conductivity (ISO 7888:1985)
Water quality - Design and use of quantitative samplers for benthic macroinvertebrates on stony substrata in shallow freshwaters (ISO 8265:1988)
Water quality - Determination of suspended solids - Method by filtration
through glass fibre filters
Water quality - Determination of dissolved anions by liquid chromatography of
ions - Part 2: Determination of bromide, chloride, nitrate, nitrite,
orthophosphate and sulfate in waste water (ISO 10304-2:1995)
Water quality - Determination of 33 elements by inductively coupled plasma
atomic emission spectroscopy (ISO 11885:1996)
Water quality - Determination of arsenic - Atomic absorption spectrometric
method (hydride technique) (ISO 11969:1996)
Water quality - Determination of dissolved Li+, Na+, NH4+, K+, Mn2+, Ca2+,
Mg2+, Sr2+ and Ba2+ using ion chromatography - Method for water and
waste water (ISO 14911:1998)
Water quality - Determination of trace elements using atomic absorption
spectrometry with graphite furnace (ISO 15586:2003)
Water quality - Digestion for the determination of selected elements in water Part 1: Aqua regia digestion (ISO 15587-1:2002)
Water quality - Digestion for the determination of selected elements in water Part 2: Nitric acid digestion (ISO 15587-2:2002)
Water quality - Determination of chloride by flow analysis (CFA and FIA) and
photometric or potentiometric detection (ISO 15682:2000)
Water quality - On-line sensors/analysing equipment for water Specifications and performance tests (ISO 15839:2003)
Water quality - Guidelines for quantitative sampling and sample processing of
marine soft-bottom macrofauna (ISO 16665:2005)
Water quality - Determination of acute toxicity of marine or estuarine
sediment to amphipods (ISO 16712:2005)
Water quality - Application of inductively coupled plasma mass spectrometry
(ICP-MS) - Part 1: General guidelines (ISO 17294-1:2004)
Water quality - Application of inductively coupled plasma mass spectrometry
(ICP-MS) - Part 2: Determination of 62 elements (ISO 17294-2:2003)
Water quality - Guidance on marine biological surveys of hard-substrate
communities (ISO 19493:2007)
EN 15110:2006
Organism
EN 27828:1994
sampling
Conductivity
EN 27888:1993
Organism
EN 28265:1994
sampling
Suspended solids EN 872:2005
Chloride
EN ISO 10304-2:1996
Metals
EN ISO 11885:1997
As
EN ISO 11969:1996
Ca
EN ISO 14911:1999
Metals
EN ISO 15586:2003
Metals
EN ISO 15587-1:2002
Metals
EN ISO 15587-2:2002
Cl
EN ISO 15682:2001
On-line sensors
EN ISO 15839:2006
Fauna
EN ISO 16665:2005
Acute toxicity
EN ISO 16712:2006
General ICP-MS EN ISO 17294-1:2006

Elements
EN ISO 17294-2:2004
Sampling
sediment
EN ISO 19493:2007
45

Component
Standard reference
Sampling
programmes
EN ISO 5667-1:2006
Cd
Turbidity
Acute toxicity
Sulphate
Chlorine
Ca
Ecology
Sampling
QA
AEA/ED05458/Issue 3
Title
Water quality - Sampling - Part 1: Guidance on the design of sampling

programmes and sampling techniques (ISO 5667-1:2006)
EN ISO 5667-1:2006/AC:2007 Water quality - Sampling - Part 1: Guidance on the design of sampling
programmes and sampling techniques (ISO 5667-1:2006)
EN ISO 5667-16:1998
Water quality - Sampling - Part 16: Guidance on biotesting of samples (ISO
5667-16:1998)
EN ISO 5667-19:2004
Water quality - Sampling - Part 19: Guidance on sampling in marine
sediments (ISO 5667-19:2004)
EN ISO 5667-3:2003
Water quality - Sampling - Part 3: Guidance on the preservation and handling
of water samples (ISO 5667-3:2003)
EN ISO 5667-3:2003/AC:2007 Water quality - Sampling - Part 3: Guidance on the preservation and handling
of water samples (ISO 5667-3:2003)
EN ISO 5961:1995
Water quality - Determination of cadmium by atomic absorption spectrometry
(ISO 5961:1994)
EN ISO 7027:1999
Water quality - Determination of turbidity (ISO 7027:1999)
EN ISO 7346-1:1997
Water quality - Determination of the acute lethal toxicity of substances to a
freshwater fish (Brachydanio rerio Hamilton-Buchanan (Teleostei,
Cyprinidae)) - Part 1: Static method (ISO 7346-1:1996)
EN ISO 7346-2:1997
Cyprinidae)) - Part 2: Semi-static method (ISO 7346-2:1996)
EN ISO 7346-3:1997
Cyprinidae)) - Part 3: Flow-through method (ISO 7346-3:1996)
EN ISO 10304:2-1995
Water quality -- Determination of dissolved anions by liquid chromatography
of ions -- Part 2: Determination of bromide, chloride, nitrate, nitrite,
orthophosphate and sulfate in waste water
EN ISO 22743:2006
Water quality Determination of Sulphates Method by Continuous Flow
Analysis (CFA)
EN ISO 7393-1:2000
Water quality - Determination of free chlorine and total chlorine - Part 1:
Titrimetric method using N, N-diethyl-1,4-phenylenediamine (ISO 73931:1985)
EN ISO 7393-2:2000
Colorimetric method using N, N-diethyl-1, 4-phenylenediamine, for routine
control purposes (ISO 7393-2:1985)
EN ISO 7393-3:2000
Iodometric titration method for the determination of total chlorine (ISO 73933:1990)
EN ISO 7980:2000
Water quality - Determination of calcium and magnesium - Atomic absorption
spectrometric method (ISO 7980:1986)
EN ISO 8689-1:2000
Water quality - Biological classification of rivers - Part 1: Guidance on the
interpretation of biological quality data from surveys of benthic
macroinvertebrates (ISO 8689-1:2000)
EN ISO 8689-2:2000
Water quality - Biological classification of rivers - Part 2: Guidance on the
presentation of biological quality data from surveys of benthic
macroinvertebrates (ISO 8689-2:2000)
EN ISO 9391:1995
Water quality - Sampling in deep waters for macro-invertebrates - Guidance
on the use of colonization, qualitative and quantitative samplers (ISO
9391:1993)
ENV ISO 13530:1998
Water quality - Guide to analytical quality control for water analysis (ISO/TR
13530:1997)
5.5 Potential for simplification of monitoring

Various simplifications are possible to reduce the monitoring requirements of the TiO2 Directives.
They include:
Reduction in the number of chemicals to be measured
Reduction in the frequency of monitoring
Reduction in the variety of media to be tested (currently, air, water, sediments, living organisms,
etc.)
More detailed specification of methods to ensure consistency in interpretation
Replacement of obligations for monitoring around TiO2 plant through reference to environmental
monitoring required under other EU Directives.
A complication to any simplification is that it should not lead to a reduction in environmental quality.
46

5.5.1 Stakeholder responses

The TDMA considered that infrequent analysis of water quality around TiO2 plant provided little useful
information due to the potential for large (and natural) fluctuations in the samples taken. Similarly
occasional sampling of large aquatic organisms at specific locations is likely to produce very variable
results. However, the TDMA considered that monitoring of benthic species provided a better
indication of biological activity but could be reduced to a frequency of once in five years. Comments
from one operator suggest a reduction in frequency for certain analysis from annual to 3-yearly
although biological monitoring was proposed for autumn and spring (to cover the initial and late stages
of biological activity).
Another respondent commented that the fish lesion analysis was of limited benefit. Respondents
commented that the TiO2 Directives could be entirely replaced by IPPC although at least one Member
State commented that retention of the wider environmental monitoring included in the TiO2 Directives
could be of benefit. This is particularly worthy of note as it implies that at least one Member State
considers that the requirements of Directive 82/883/EC are not duplicated by other legislation.
5.5.2 Process discharge monitoring
Process discharge monitoring (to ensure compliance with ELVs) should be covered within an IPPC
permit and hence could be removed from a simplified Directive, though given that the monitoring
would need to be done anyway this simplification would have no effect, other than a minor easing of
the regulatory burden for reporting on the TiO2 regulations to the European Commission.
IPPC requires that The permit shall contain suitable release monitoring requirements, specifying
measurement methodology and frequency, evaluation procedure and an obligation to supply the
competent authority with data required for checking compliance with the permit.
The IPPC guidance indicates that monitoring should be in accordance with recognised standards (as
given in Section 5.4) and the level of monitoring should be consistent with the potential impact to the
environment. For example this could be implemented as continuous quantitative monitoring of the
major discharges with periodic monitoring of minor discharges.
Averaging periods for monitoring are not specified in the TiO2 Directives, with the exception of chlorine
which has a daily average and absolute maximum. Sampling is up to three times per year for liquid
wastes but this is unlikely to represent BAT under IPPC (for example for installations in the UK,
monitoring is generally specified as continuous flow proportional samplers providing daily samples
albeit with some analysis specified on a combined sample over several days) .
It can be argued that retention of the TiO2 Directives monitoring specifications as a minimum standard
may not maintain the current degree of environmental protection if regulators and operators arbitrarily
change the frequency of monitoring. With this in mind it is appropriate to define the time period to
which the limit values refer. For any emission that is monitored continuously a requirement for ELVs
to be complied with on an hourly, or at least daily, basis seems at first sight to be appropriate.
However, a problem with this approach is that the limit values given in the BREF are defined on the
basis of kg/tonne of product. Whilst this approach is very useful for assessing the consistency of
environmental performance in operation between different plant, it is an unusual way to define
emission limits for regulation of industrial facilities. Existing kg/tonne_production emission figures are
presumably quantified on an annual average basis, meaning that we currently have no information on
how variable emissions are over any given time period. Direct application of an ELV derived from
annual average emissions data to a time period of an hour or a day is incorrect, as it would inevitably
mean that many readings were above the limit, even though there may be compliance on an annual
basis.
5.5.3 Wider environmental monitoring
The TiO2 Directives include a wide range of monitoring requirements that are intended to show
development or deterioration of the receiving environments. This monitoring does not necessarily
include assessment against environmental quality standards (EQS) such as those for air quality or
water quality. This would seem to be a straightforward extension of the assessment linked to
monitoring requirements, though of course, any exceedance of quality standards should be addressed
under other legislation and so extension of the Directive requirements seems unnecessary. Sampling
parameters and frequencies from Directive 82/883/EEC are shown in Table 5-6.
47

AEA/ED05458/Issue 3
Table 5-6. Annual frequency of sampling and measurement as specified in Directive 82/83/EC.
Disposal
route
Salt water
and fresh
surface
water
Medium
Parameter
Water column
Water column
Water column
Water column
Water column
Water column
Organisms
Benthic fauna
Benthic fauna
Fish
Temperature
Salinity
pH
Dissolved O2
Turbidity
Iron (soluble and
particulate)
Ti
Iron (soluble)
Iron (total)
Hydrated iron oxides and
hydroxides
Ti, Fe
Hydrated iron oxides and
hydroxides
Ti, Cr, Fe, Ni, Zn, Zn, Pb
Diversity
Abundance
Lesions
Water column
Water column
Water column
Water column
Water column
Water column
Environment
Environment
Environment
Environment
Water column
Water column
Water column
Water column
Water column
Water column
Environment
Environment
Environment
Air
Air
Air
pH
SO4
Ti
Fe
Ca
Chloride
Topography
Management
Subsoil
Ecology
pH
SO4
Ti
Fe
Ca
Chloride
Stability
Permeability
Porosity
SO2
Chlorine
Dust
Water column
Filtered water
Susp. solids
Susp. solids
Sediment
Sediment
Storage &
dumping on
land
Injection into
soil
Air
Annual frequency of
sampling, measurement
3
3
3
3
3
3
Comments
3
3
3
3
1
1
1
1
1
1
Optional for
freshwater
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Continuously
Continuously
Continuously
12/year where no
network exists
Optional
Article 4.3 of Directive 82/883/EEC permits some simplification of monitoring regimes already, where it
states that:
For the monitoring and inspection of the environments affected, Member States shall determine the
frequency of sampling and analysis for each parameter listed in the Annexes. For parameters where
determination is mandatory, the frequency of sampling and analysis must not be less than the
minimum frequencies indicated in the Annexes. However, once the behaviour, fate and effects of the
waste have, as far as possible, been established, and provided that there is no significant deterioration
in the quality of the environment, Member States may provide for a frequency of sampling and
analysis below these frequencies. Should there subsequently be any significant deterioration in the
quality of the environment as a result of the waste or of any change in the disposal operation, the
Member States shall revert to the sampling and analysis at a frequency not less than that specified in
the Annexes. If a Member State considers it necessary or advisable, it may distinguish between
different parameters, applying this subparagraph to those parameters where no significant
deterioration in the quality of the environment has been recorded.
48

The existing Directive therefore already provides Member States with a substantial amount of
discretion in determining the frequency of monitoring. Given the age of the 1982 Directive it is to be
expected that the monitoring frequency for existing plant should already have been adjusted to reflect
the potential for harm caused by waste from TiO2 manufacture for plant in EU15 Member States and
possibly those that joined the EU later on. The age of the Directive also opens a possibility that the
rationale for current monitoring arrangements in each Member State may no longer be well
understood.
The 1982 Directive requires comparison of the samples from the area affected by the installation with
a control sample in a neighbouring area unaffected by the installation. However, with a sampling
frequency of as little as once per year and limited guidance on the sampling and analysis protocol, the
value of such monitoring to assess compliance with an EQS or the impact of an individual industrial
facility is limited. This is particularly so given that TiO2 installations are frequently located near other
industrial installations that may contribute to the local pollution burden, making interpretation of data
collected extremely difficult with respect to the role of the TiO2 plant.
Although the samples collected for TiO2 Directives provide a record of the receiving environments, the
benefit to regulatory control is unclear, particularly given the requirements of other Directives such as
the IPPC Directive and the air and water quality framework Directives. In the absence of a clear
environmental need for continuing the wider environmental monitoring, there may appear to be limited
benefit in retaining the requirement. It is therefore recommended that this be reconsidered with a view
to establishing more clearly its regulatory benefit. If this cannot be shown it may be appropriate to
remove the requirement, but it is necessary first to be sure that this would not lead to a reduction in
environmental protection. A pragmatic solution could be that Member States be allowed in a simplified
Directive to drop the requirement for environmental monitoring under the TiO2 Directives if they can
demonstrate monitoring activities outside of TiO2 regulation are sufficient to detect damage to the
receiving environment.
Linkage can also be made with the emission monitoring carried out at the plant. If it is established that
emissions are not having a significant effect on the environment it may be considered sufficient to drop
the environmental monitoring provided that there is no increase in the release of one or more
pollutants from the plant in question. A weakness in this argument is that it treats the plant in isolation
from other activities in the area being considered, though this is not a problem if other environmental
monitoring is being carried out.
5.6 Analysis of the impacts of simplifications of monitoring

requirements
Data received during the course of the contract on the costs of monitoring were given above in Section
5.3, and are summarized in Table 5-7. Further to that, relevant data for specific monitoring
requirements are available for only a small number of cases, raising questions as to how
representative they are. An alternative approach to costing the simplifications listed above would be
to make a bottom up assessment, providing a cost for each sample required. However, this is unlikely
to give a final result that is of any better quality than the top down approach of using the cost data
provided by some operators and Member States given the way that monitoring work is typically
contracted. Turning to the data in Table 5-7, information is not supplied in an ideal level of detail, for
example, with respect to what has been measured at each site, though it seems clear that there is
variability between Member States in the amount of monitoring carried out and the allocation of
responsibility for monitoring between regulators and operators. In general it appears that regulators
pay for much of the environmental monitoring and operators for emissions testing, though there are
exceptions to this. Operator costs seem reasonably consistent, between 50k and 100k, with a
cluster of plant at 70k.
49

AEA/ED05458/Issue 3
Table 5-7. Reported pollution monitoring costs for TiO2 manufacturing plant.
Site(s)
1 and 2
3
4
5
6
7
8
9
Monitoring
Brown shrimp toxicity survey (2 plant)
Water sampling and chemical analysis
(2 plant)
Benthic survey
Water sampling and analysis
Sediment/biota sampling and analysis
Water
Air
All operator monitoring
Liquid effluent test (assumed to be
check measurements)
Testing for Ti in surface waters
Cost to
Regulator
Regulator
Annual cost
2,625
16,875
Regulator
Regulator
Regulator
Operator
Operator
Operator
Operator
Operator
Operator
Regulator
52,500
5,250
21,000
82,500
22,500
70,000
52,830
75,000
70,000
2,000
Regulator
2,400
The costs incurred by regulators are more variable, ranging from 2k to 50k, though this reflects
differences in what is being monitored (the range just given being for simple chemical analysis at one
end to benthic surveying at the upper end). The data from plants 1, 2 and 3 in Table 5-7 suggest that
the costs of environmental monitoring are of the order 15k to 30k/plant/year. The costs of a full
benthic survey increase this to between 67k and 92k/plant/year. It is, however, questionable
whether a full benthic survey as costed here would be required. The costs shown may be for a more
sophisticated level of analysis than is needed for compliance with the TiO2 Directives, reflecting the
regulators wider remit for monitoring the health of water systems in the area in question.
Combing the operator costs, taken here as relating largely to emissions monitoring of 50k to 100k
with the regulator costs, taken here as relating mainly to monitoring of environmental quality (including
full benthic survey) of 67k to 92k gives a range for monitoring costs per plant of 117k to 192k per
year. These figures do not account for two important elements:
1. Monitoring of pollutant levels in ambient air, giving some bias to underestimation of costs.
However, this would now be covered in most Member States through the monitoring
requirements of the Air Quality Framework Directive.
2. The potential for regulators to have reduced monitoring frequency reflecting Article 4.3 of
Directive 82/883/EEC, which would bias towards overestimation of costs.
Given that these two uncertainties act in different directions, the range for annual costs of 117k to
192k per plant per year seems reasonably robust (not least because of the breadth of the range).
Drawing on the preceding sections, the main simplifications with respect to monitoring arrangements
identified here are as follows:
i.
To reduce the frequency of monitoring of benthic species, possibly down to one year in five as
suggested by some industrial stakeholders
ii.
To eliminate the requirements for monitoring around plant
iii.
To leave emissions monitoring to IPPC permitting.
Options (i) and (ii) may already be covered under Article 4.3 of Directive 82/883/EEC in cases where it
is shown that there is unlikely to be a negative effect of emissions from the Ti plant in question.
However, cost savings are possible in cases where a case has not been made for reducing monitoring
requirements. A failure to present such a case does not necessarily mean that the plant in question is
having a significant negative impact on the environment. Instead, those responsible for the monitoring
may feel that it is a justifiable use of resource. Option (iii) is covered by IPPC legislation, and as such
would not have any impact, economic or otherwise provided that the same pollutants are sampled as
required by the TiO2 Directives. Assuming that options (i) and (ii) are not currently implemented, the
change in costs under different scenarios is summarized in Table 5-8. Environmental and social
implications of these changes in monitoring are likely to be insignificant given the extent to which
environmental quality is monitored under other legislation.
50

Table 5-8. Annual monitoring costs per plant and the effects of options (i) and (ii) for simplification of
monitoring requirements
On-site monitoring of emissions

Total monitoring costs
Total costs under option (i)
Total costs under option (ii)
Low
50k
67k
117k
75k
50k
High
100k
92k
192k
150k
100k
The importance of these costs can be assessed against turnover in the industry and profitability. This
is done taking the following parameters:
A range in plant size of 30 to 150 kt TiO2 capacity per year (the extremes amongst the European
plant)
A load factor for each plant of 85%
A price per tonne of TiO2 of 2000
A range for profitability of plant of 3.5% to 10% against turnover
Total monitoring costs of 192k
A potential reduction in monitoring costs of 92k
Table 5-9. Monitoring costs incurred by operators and regulators relative to estimated sales and profits
for TiO2 plant in Europe
30 kt plant
51,000,000
1,785,000
5,100,000
150 kt plant
255,000,000
8,925,000
25,500,000
Relative to total monitoring costs of 192k/year

192k as % of sales
0.4%
192k as % of profits (low)
10.8%
192k as % of profits (high)
3.8%
0.1%
2.2%
0.8%
Sales
Profit (low)
Profit (high)
Relative to potential reduction in monitoring costs of 92k/year

92k as % of sales
0.2%
0.0%
92k as % of profits (low)
5.2%
1.0%
92k as % of profits (high)
1.8%
0.4%
Monitoring costs are only a small share of turnover and profits for the larger plant. Assuming similar
costs for the smaller plant they naturally make up a larger share relative to turnover and profits, though
of course, costs tend to be shared between the operator and the regulator which will reduce the
impact on the industry of the total monitoring burden.
51

AEA/ED05458/Issue 3
6 Conclusions and Recommendations

6.1 Emission limit values
There are three options open with respect to emission limit values in the simplification of the TiO2
Directives:
Leave them as they are
Remove them and refer simply to application of BAT
Reduce them, considering information on feasibility and costs and benefits presented here.
By demonstrating that costs are likely to be less than benefits for most of the cases considered here,
this report clearly makes a case for reducing limit values (though of course policy makers need to be
content that this case is sufficiently robust). The second option leaves open the potential for a
worsening of emissions in cases where local regulators interpret BAT differently (for whatever reason)
to BAT as defined in the LVIC-S BREF. On this basis, removing emission limit values altogether
would remove the existing safety net, and the change to regulation would not ensure that no additional
damage to health and the environment. Accordingly, it is concluded that the third option is to be
preferred.
6.1.1 Emissions of dust
So far as improvements to dust control are concerned, the TDMA has stated that:
3
3
Although values below 50mg/m are obtainable 5mg/m is not realistic. One of the TDMA member
companies has indicated that the required increase in filter area to get near this would result in the
need for new buildings and closure of 2 plants.
There are several problems with this statement:
The section of the LVIC-S BREF that deals with the TiO2 industry does not refer to other
industries where these lower values are reached to explain why the TiO2 industry is different.
No evidence is provided to back up the statement that 2 plants would have to close.
Some TiO2 plant attain dust emission rates that are much lower than others.
3
If there are good reasons why the industry cannot move to 5 mg/m it would still be useful for the
industry to state how far it believes it can improve and at what cost.
It is possible that one reason for the industrys reluctance to consider further control of dust arises
from research that shows that TiO2 per se is not toxic, and hence it may be thought that there is no
rationale for further control. Evidence for health effects of TiO2 dust in air has been reviewed by the
22
National Institute of Occupational Safety and Health (NIOSH) in the US . The review concluded that
TiO2 poses a negligible risk of lung cancer through workplace exposures. This may give a perception
that this means that it has no effect on health. However, the review also found that TiO2 was capable
23
of causing inflammation of the lung and that this effect appears to be unrelated to the chemical
nature of TiO2. This ties in with other research on the health effects of particles in the atmosphere
over the last 10 years that has shown them to pose a significant risk to health. Analysis undertaken
for the ECs CAFE (Clean Air For Europe) Programme, based on response functions reviewed and
approved by a working group set up by WHO, estimated the loss of 3.6 million life years annually
across the EU through exposure to fine particles at ambient levels in 2000 (this is equivalent to a
shortening of life by several months per person on average). Some types of particle have specific
mechanisms of impact through either chemical or physical properties. However, WHOs advice to
CAFE was to quantify effects against overall particle mass, and not to disaggregate effects to specific
components of the atmospheric particle mix. In addition to effects on mortality, WHO agreed to
quantification of various morbidity impacts, including bronchitis, hospital admissions and various minor
symptoms, and recommended the position of no-threshold of concentration for effect.
22
The review also found that TiO2 was capable of causing cancer in rats when exposure levels were high. However, this is of very little relevance
here as such levels are not likely to be experienced around the plant concerned.
23
52

On this basis there is a need to consider whether further control of dust emissions is warranted. A
cost-benefit analysis is presented in this report, based on monetised estimates of damage per tonne
PM2.5 contained in the BREF on Economics and Cross Media Effects and data on the costs of dust
abatement from USEPA. That analysis concludes that there is a probable excess of benefit of further
particle abatement over costs. A review of uncertainties that cannot currently be quantified shows
some going in either direction, suggesting that there is not overall a systematic bias to this conclusion
provided that the core recommendations of WHO are correct.
6.1.2 Emissions of SO2
With SO2 it is possible to perform a similar analysis to that carried out for dust, estimating both the
costs and benefits of actions to reduce emissions. Like PM2.5, the effects of SO2 emissions on health
have been reviewed by WHO under the CAFE Programme, and health damage costs per tonne
emission are available from the BREF on Economics and Cross Media Effects (note that these
estimates exclude damage to ecosystems from acidification).
Attention in this analysis focussed mainly on the calcination stage as this gives rise to the greatest
SO2 emissions.
There are important questions concerning the quantification of the costs of further SO2 controls. The
first concerns the extent to which existing controls can be pushed to further reduce emissions, rather
than requiring new abatement equipment to be fitted. The second is from the perspective of IPPC,
with SO2 removed from flue gases potentially being transferred to the liquid effluent and making it
more difficult to meet the sulphate AELs.
The BREF provides data on the costs and performance of high performance catalysts that appear able
to reduce emissions of SO2 down to 2 kg/t TiO2 (easily sufficient to meet the upper BAT AEL), and
scrubbers that can reduce emissions further to 1 kg/t (which may be sufficient to meet the lower BAT
AEL, if emissions from digestion (the other stage important for SO2 release) are very low. Comparison
of estimated costs and benefits suggests that benefits exceed costs for the use of both improved
catalysts and scrubbers.
6.1.3 Emissions of chlorine
Insufficient data were available to permit analysis of the costs or benefits of further control of chlorine.
However, this may not be necessary given that the use of chlorine at chloride process plant is covered
by the Seveso II Directive. This should ensure that the process is shut-down if chlorine is detected in
significant concentration outside the area in which it is used.
6.1.4 Emissions of sulphate
Of the 13 sulphate process plant in the EU, emissions from between two and four exceed the upper
BAT AEL (depending on assumptions as to how emissions data and limit values are defined), and
almost all exceeded the lower AEL. A detailed cost analysis of all plant for meeting the BAT AELs is
not possible, given the limited amount of information available. However, information from the UK
Environment Agency was used to give an estimate that costs to take all four plant below the upper
BAT AEL are in the region of 4.4 million/year. Using data given in the BREF would provide a higher
figure, though the BREF data look high, particularly when considering that many plant may not need
new control equipment, but simply an upgrading of existing facilities. Robust cost data for meeting the
lower BAT AEL have not been identified, but as a minimum, costs might be expected to be of the
order of 12 million/year based simply on scaling up the figures for meeting the upper BAT AEL from 4
plant to 11. This estimate has to be regarded as highly uncertain. The need to move to the lower BAT
AEL in particular clearly needs to be considered against the characteristics of the receiving
environment for any plant.
6.1.5 Emissions of chloride
24
A maximum of one plant was found to exceed the upper BAT AEL . There is a question to be asked
when the BREF is reviewed as to whether all plant truly meet BAT, especially given the factor 10
range between the least and most polluting plant. Also, as was noted above, the plant with the
highest chloride emissions also has the highest chlorine emissions, and so may be somewhat dated.
The reason for the extensive variation in emissions between plant may of course concern the
24
The revised information on emissions received at the end of the contract (see Appendix 5) shows that all chloride process plant would easily
meet the upper BAT AEL. However, none would meet the lower BAT AEL.
53

AEA/ED05458/Issue 3
difference between freshwater and marine receiving environments. No estimates are provided for the
costs of meeting the lower BAT AEL for chlorides that is exceeded by 3 of the 4 plant for which data
were available. As was the case for sulphates, there are no estimates of the benefits of further control
of chloride emissions as generic data on damage per tonne emission are only available for air
pollutants. Any damage done will of course be a function of the nature and quality of the receiving
environment, with marine systems clearly able to handle a lot more chloride than freshwaters.
6.1.6 Recommendations on emission limit values for a simplified TiO2 Directive
The existing Directive limits are of course based on the performance of abatement equipment at the
time that the 1992 Directive came into force. The far more widespread implementation of advanced
pollution abatement techniques since that time across industry generally has led to improvements in
performance and reductions in cost that mean that the Directive limits seem outdated. Some
tendency has been noted in IPPC permitting for use to be made of the emission limit values given in
the TiO2 Directives in preference to the ranges defined in the BREF. As shown above, there is a case
based on cost-benefit analysis for moving to the ranges given for BAT in the BREF and serious
consideration should be given to amending the limit values given in the Directive to the upper BAT
AELs.
The analysis for SO2 and dust suggests that it may be appropriate to go further than the upper BAT
AEL. This may be considered to contradict the development of the ranges specified for BAT in the
BREF, though this brings in questions of how these ranges were set in the first place and whether or
not they are too internally focussed on the existing performance of plant in the TiO2 sector. We ask
whether the TiO2 industry may have been too ready to reject experience from other sectors based on
an assumption that they already generally operate at an optimum for emissions. However, it may be
appropriate to wait until future revision of the BREF and the definition of BAT for the sector before
requiring an emission level that is below the upper end of the range currently defined as BAT.
Some recognition needs to be given to the different configurations of TiO2 plant. Designs differ from
plant to plant, particularly with respect to integration with other processes that may be able to take
advantage of waste streams from TiO2 manufacture and hence reduce emission levels. However, the
simple existence of such differences should clearly not be seen as a rationale for no further abatement
without close consideration, particularly where analysis suggests that benefits are likely to exceed
costs. Any argument made by the industry against a tightening of the limit values therefore needs to
be backed up by a greater amount of documented evidence than is currently the case.
6.2 Monitoring
The monitoring requirements of the TiO2 Directives have been reviewed and considered alongside
other legislation (e.g. the Air and Water Framework Directives and the IPPC Directive). It is
recommended that emission limit values and acute toxicity requirements are retained as minimum
standards (this is consistent with the approach adopted for large combustion plant and waste
incinerators) but that specification for monitoring of discharges be defined on a site-specific basis
through the IPPC Directive provisions.
It is acknowledged that, historically, the requirement for environmental monitoring around TiO2
manufacturing sites made good sense, though given improvements in the performance of TiO2 plant in
the last 30 years it is not clear that this remains the case. On this basis there appears to be a
rationale for abandoning much of the wider environmental monitoring. Other justifications for this line
of argument are:
The sampling frequency for some variables is too low to be used for meaningful trend
analysis;
Other legislation (e.g. the air and water quality framework Directives) developed since the
TiO2 Directives also includes environmental sampling on a more systematic basis the
inclusion of such sampling in the TiO2 Directives may therefore be redundant;
The attribution of an environmental impact to a specific industrial site is difficult or impossible
in an environment where there are many sources of pollution. Most, if not all, TiO2 plant in
Europe are sited in general industrial areas, so separating out their impact from the effects of
other plant would be extremely complex.
54

Proposals for simplification of the monitoring requirements are therefore focused on the environmental
monitoring requirements of Directive 82/883/EEC. They include a reduced sampling frequency for
benthic organisms and dropping wider environmental monitoring altogether. The second option does
not mean that there would be no monitoring of environmental quality this would still be required
under the air quality and water framework Directives. However, there would be no requirement to
focus attention on TiO2 manufacturing facilities. It is estimated that these simplifications would reduce
monitoring costs of 192k/year by up to 92k. In many countries much of this saving would go to the
regulators rather than the industry. However, if the regulators have designed broader environmental
monitoring networks around TiO2 plant they may decide not to change existing arrangements. In this
case the monitoring costs of the 1982 Directive can now be considered to fall under other legislation
and there would be no saving. It was also noted that there is a mechanism for simplification of
monitoring requirements already provided in Article 4.3 of Directive 82/883/EEC where it is stated that:
For the monitoring and inspection of the environments affected, Member States shall determine the
frequency of sampling and analysis for each parameter listed in the Annexes. For parameters where
determination is mandatory, the frequency of sampling and analysis must not be less than the
minimum frequencies indicated in the Annexes. However, once the behaviour, fate and effects of the
waste have, as far as possible, been established, and provided that there is no significant deterioration
in the quality of the environment, Member States may provide for a frequency of sampling and
analysis below these frequencies.
Given incomplete response to the questionnaires distributed as part of this work it is not clear to what
extent this provision is currently applied.
Chapter 5 of this report provides details of CEN, ISO and other standards for monitoring pollutants. It
is note that the 1992 Directive does not define time periods over which emission limit values should be
met, except for chlorine. For any pollutant monitored continuously it would seem appropriate to
express limit values on an hourly or daily basis. However, the TiO2 limit values are unusual in that
they define limits not against pollutant concentration in the emitted waste stream, but against
production (i.e. emissions expressed as kg per tonne TiO2). Assuming that these data are currently
calculated from consideration of annual mass emission of pollutants relative to annual production, it
would be wrong to require that the limit values be met for shorter periods as the annual averaging
period naturally takes out the inevitable fluctuations in emissions over time.
In any case, process discharge monitoring (to ensure compliance with ELVs) should be covered within
an IPPC permit and hence detailed specification of what monitoring should be done could be removed
from a simplified Directive. Given that the monitoring would need to be done anyway this
simplification would have no effect, other than a minor easing of the regulatory burden for reporting
on the TiO2 regulations to the European Commission.
6.3 Definitions
In the course of this contract, problems of definition have been identified with the TiO2 Directives, as
follows:
Emission limits per unit TiO2 production do not specify whether they are against production of
pure TiO2 or finished TiO2 product.
Time periods relevant to emission limits are not specified.
Sampling and measurement methods are not specified in such a way as to ensure
consistency in application throughout the EU. Such consistency would improve understanding
of variation from site to site and help to inform future changes in ELVs and monitoring
requirements.
Clarification of these issues would promote consistency in the application of the TiO2 legislation.
6.4 Further analysis

The TDMA provided further data on emissions at the end of the contract, too late for full inclusion in
the analysis carried out in Section 4. The following were noted from the new dataset, the main
differences concerning liquid effluents:
55

AEA/ED05458/Issue 3
25
Overall, results for SO2 and dust appear similar to those of the original dataset , though there is some
3
reduction in SO2 emissions. For chlorine most values in the new dataset are the same (1 mg/Nm for
all but one plant, irrespective of whether the figures are daily or instantaneous). They are clearly not
measured values but are instead likely to reflect criteria for compliance with the Seveso II Directive.
One plant stands out as a clear anomaly, with daily average figures given as <5 and instantaneous
3
values as <33 mg/Nm .
For sulphates there appear to be significant increases in emission at 6 plant. On the other hand,
whilst previously 4 plant exceeded the upper BAT-AEL, now only 2 plant do so (one of which exceeds
the Directive limit as well), which would reduce estimated costs by half. In contrast, the scenario 5
position is now exceeded by 8 plant, not the 4 previously, so costs for that scenario increase.
For chlorides the lowest emission in the original dataset was 38 kg/t product and the highest, 330 kg/t.
The range is now much reduced, with the lower end increasing to 93 kg/t and the upper end falling to
199 kg/t. The differential chloride limit values set under the Directive for different ore types appear
unnecessary for the current emission performance. For example, the plant using slag have emissions
lower than 50% of the Directive limit of 450 kg/t. Indeed, the new figures have one plant using slag
having emissions that are less than one plant using natural rutile, even though the latter is below the
natural rutile Directive limit of 130 kg/t. On this basis the new data do not make a good case for
differentiating chloride emission limits according to the type of ore.
It is concluded that the new dataset is unlikely to give results that are substantially different to the
original information. For some releases the new data suggest the original data to have been
pessimistic, for others, optimistic. Overall, it is anticipated that they would generate results within the
envelope defined in the analysis made in Section 4 of this report.
25
Direct comparison is difficult as a result of differences in presentation between the old and new dataset and the anonymisation of data. Some of
the changes in presentation are useful, for example, specification of chloride emissions against different types of ore. Some create difficulty in
interpretation of data, for example restriction of reported dust emissions to mg/Nm3 and a lack of disaggregation for emissions of SO2 by process
step. To illustrate, the new dataset notes for one plant that whilst the concentration of dust in the flue gas has increased, the flow rate has gone
down. It is not known whether this means that overall the annual emission has increased, decreased or remained the same.
56

57
Appendices
Appendix 2: Questionnaire sent to Plant Operators
Appendix 3: Questionnaire sent to Member States
Appendix 4: Background information on impacts associated with
pollutants emitted from TiO2 manufacture
Appendix 6: Emission control methods and costs
Appendix 7: Trends in Emissions According to EPER, 2001-2004
Appendix 8: Monitoring standards for relevant air pollutants
List of companies with EPER links
Cinkarna Celje.d.d. (Slovenia, Celje)
2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=151377&year=2001&CountryCode=SL
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=151377&year=2004&CountryCode=SI
Huntsman Tioxide Europe
Italy (Scarlino):
2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=187621&year=2001&CountryCode=IT
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=189971&year=2004&CountryCode=IT
Spain (Huelva):
2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=210254&year=2001&CountryCode=ES
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=211760&year=2004&CountryCode=ES
France (Calais):
2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=170742&year=2001&CountryCode=FR
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=214064&year=2004&CountryCode=FR
UK1 (Greatham):
2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=186367&year=2001&CountryCode=UK
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=191480&year=2004&CountryCode=UK
UK2 (Grimsby):
Kemira Pigments Oy (Finland, Pori)
2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=114575&year=2001&CountryCode=FI
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=196434&year=2004&CountryCode=FI
Kronos Worldwide Inc.
Belgium (Langerbrugge):
2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=110864&year=2001&CountryCode=BE
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=200581&year=2004&CountryCode=BE
Germany 1 (Nordenham):
2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=205955&year=2001&CountryCode=DE
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=207772&year=2004&CountryCode=DE
Germany 2 (Leverkusen):
Norway (Fredrikstad):
2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=156057&year=2001&CountryCode=NO
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=156057&year=2004&CountryCode=NO
Millennium Chemicals
France1 (Thann) :
France2 (Le Havre):
UK (Stallingborough):
Precheza AS (CZ)
2001: Not found
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=205642&year=2004&CountryCode=CZ
Sachtleben Chemie GmbH (Germany, Duisburg)

Tronox Pigments International GmbH (DE, NL)
Netherlands (Rotterdam, operated in 2001 by Kerr McGee Pigments):
2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=115688&year=2001&CountryCode=NL
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=190195&year=2004&CountryCode=NL
Germany (operated in 2001 and 2004 by Kerr McGee Pigments):
Zaklady Chemiczne POLICE S.A. (PL)
2001: Not found
2004: http://eper.cec.eu.int/eper/facility_details.asp?id=215325&year=2004&CountryCode=PL
Sources for TiO2 content in pigments

Kemira:
http://www.kemira.com/Specialty/English/Businesses+and+products/Titanium+dioxide/Pigmentary+tita
nium+dioxide/
Millennium Chemicals:
http://www.millenniumchem.com/Products+and+Services/Products+by+Type/Titanium+Dioxide++Paint+and+Coatings/Product+Stewardship/Titanium+Dioxide++Paint+and+Coatings+Product+Stewardship_EN.htm
Huntsman Tioxide:
http://www.huntsman.com/pigments/eng/Home/Titanium_Dioxide_Pigments/Brochures__Europe/index.cfm?PageID=6722
Kronos: http://www.kronostio2.com/
Precheza: http://www.precheza.cz/www/english/vyrobky.htm
Tronox: http://www.tronox.com/products/tio2/applications/coatings/index.htm
Zaklady: http://www.zchpolice.pl/uk/produkty.php?gr=biel
Appendix 2: Questionnaire sent to Plant

Operators
Dear <contact name>
EC project to assess benefit of simplification of Titanium Dioxide Directives
The European Commission needs information to assess the impacts of simplifying the Titanium
Dioxide Directives. Stakeholders have already been consulted on potential simplifications but further
information is needed for a short term study led by AEA Energy and Environment, supported by
Ecolas. A letter from the European Commission describing the project is attached, together with a
questionnaire listing the information needed for this study.
We have discussed the project with Greg McNulty of Huntsman, in his role as representative of the
Titanium Dioxide Manufacturers Association. We feel that it is in the best interests of the industry to
respond to this questionnaire on a plant by plant basis in order that any revision of the Directives can
take account of factors specific to titanium dioxide manufacture. An alternative, in the absence of
good recent data from the industry, would be to define future emission limits in terms of what can be
achieved in other industries. We are concerned that this could create future difficulties as it may not
take into account the variation possible in TiO2 manufacture, e.g. through use of different ores.
We will be happy to treat any data provided as confidential, to the extent that information provided
would not be attributable to specific plant in the project report. I am sure that the Commission would
be happy to make the report available to you at the end of the contract.
th
Responses are needed by Tuesday 29 August which we appreciate is a very short time, particularly
during the holiday period.
We would be very grateful if you could inform us by return if you or one of your colleagues will respond
to this information request and, which information can be provided on this timescale. A two stage
submission, with a first response containing the most easily accessible information and the second
response providing further data would of course be acceptable to us if a full response is not
immediately possible.
Please contact <Ecolas or AEA contact> if you have any queries.
Yours sincerely,
Attached :
MS Questionnaire
Letter from the European Commission
TiO2 Directive Questionnaires for operators

Where multiple TiO2 production plant exist on a single installation please provide separate information
for each plant (if possible).
Supplementary or detailed information can be provided in a spreadsheet or separate table.
No.
Information needed
General
1
Installation and production capacity (Tonnes TiO2 per year)
Actual/typical recent production (Tonnes TiO2 )
Any general comment on recent (post 2000 ?) measures undertaken specifically for
improvement to environmental releases
Releases to air :
4
General description of in-process, abatement or other techniques used for control of
releases to air.
For example techniques and equipment for sulphur removal, particulate abatement,
chlorine abatement
Describe current discharges to air.

Discharge points, discharge flows, pollutant concentrations (please note any
standardisation of concentration and flow).
Describe the frequency of monitoring undertaken at present to air.

Pollutants monitored, whether continuous or periodic (if periodic please provide
frequency).
Which monitoring methods are used to monitor discharges to air?

For example EN/ISO/National Standards, industry or in-house methods. Are
laboratories/monitoring organisations accredited to EN17025.
No.
8
Information needed
How has regulatory authority applied emission limit values in operating permit?
Hourly, Daily or annual limits or perhaps high short-term controls with more stringent
longer-term averages
Releases to water :
9
General description of in-process, treatment or other techniques for control of releases
to water.
For example effluent reduction and treatment
10
Where are liquid effluents transferred to environment ?

Inland waterway, Estuary, Sea
(please comment if further treatment offsite)
11
Describe current discharges to water.

Discharge points, discharge flows, pollutant concentrations, effluent flow rate).
12
Describe the frequency of monitoring undertaken at present of liquid effluents.

Pollutants monitoring and whether continuous, proportional samplers or periodic (if
proportional and periodic please describe frequency).
13
Which monitoring methods are used to monitor effluent discharges.

For example EN/ISO/National Standards, industry or in-house methods. Are
laboratories and monitoring organisations accredited to EN17025.
14
How has regulatory authority applied emission limit values in operating permit? Please
provide us with the emission limit values.
Hourly, daily or annual limits or perhaps high short-term controls with more stringent
longer-term averages.
Discharges to land
15
Describe any discharge to land.
Where relevant.
No.
16
Information needed
Describe any broader environmental monitoring undertaken.
For example monitoring of flora and fauna, air quality monitoring, any other offsite
monitoring
17
Monitoring organisations and costs

Which monitoring is undertaken or commissioned by the installation and, which
monitoring is undertaken by regulatory authorities?
Are any other organisations involved ?
18
How much does monitoring of effluent and stack discharges cost operators?
For example sampling systems, sampling personnel (man days), analysis costs. How
much for other monitoring. Do operators pay for monitoring undertaken by competent
authorities.
TiO2 Directives reporting costs

19
Estimate the cost or time required for supervision and reporting requirements of the
TiO2 Directives for operators.
Where these are considered to be additional to other environmental reporting
requirements.
Costs for emission control

20
Can you provide any information on capital expenditure and operating costs for
equipment to control air emissions and liquid effluent? Please specify equipment and
costs.
For example any recent work undertaken on the installation.
Issues from removal of TiO2 Directives

21
If the TiO2 Directives were ended, what concerns would you have for regulation of
releases to the environment from the industry?
Are there any areas which would not be considered by IPPC, Waste and water
framework directives? Would there be a reduction in protection of the environment?
Appendix 3: Questionnaire sent to Member

States
Dear <contact name>
EC project to assess benefit of simplification of Titanium Dioxide Directives
The European Commission needs information to assess the impacts of simplifying the Titanium
Dioxide Directives. Member States have already been consulted on potential simplifications but
further information is needed particularly regarding emission and environmental monitoring. The
attached questionnaire requests the information needed for this study.
A letter from the Commission describing the project is attached.
Responses are needed by Friday 24 August which I appreciate is a very short time, Earlier response
for certain information (the IPPC permit document for the Titanium Dioxide installations) would be very
helpful.
It is important that you inform us by return, if you or one of your colleagues will respond to this
information request and, which information can be provided in this timescale.
Please contact <Ecolas contact> if you have any queries.
Regards.....
Attached :
MS Questionnaire
TiO2 Directive Questionnaires for Member States

Supplementary or detailed information can be provided in a spreadsheet or separate table if preferred.
No.
Information needed
General
1
Please summarise installations and production capacity (Tonnes TiO2 per year)
Please provide a copy of the IPPC or other relevant Authorisations for each installation
Releases to air :
What measures are in place to assess air quality impact of TiO2 installations, is air
3
quality monitoring undertaken around each installation.
How has the regulatory authority applied emission limit values for discharges to air in
operating permit.
longer-term averages
Releases to water :
5
Where are liquid effluents transferred to environment ?
Inland waterway, Estuary, Sea
(please comment if further treatment offsite)
How has regulatory authority applied emission limit values in operating permit.
longer-term averages.
Discharges to land
7
Describe any discharge to land.
8
Describe any broader environmental monitoring undertaken.
For example monitoring of flora and fauna, air quality monitoring, any other offsite
monitoring.
Monitoring organisations and costs
No.
9
Information needed
Which monitoring is undertaken or commissioned by the regulatory authorities or other
regional or national government organisations ?
10
How much does monitoring of water, sediment and other monitoring cost the Member
State,
For example sampling systems, sampling personnel (man days), analysis costs. How
much for other monitoring. Do operators pay for monitoring undertaken by competent
authorities.
TiO2 Directives reporting costs

11
Estimate the cost or time required for supervision and reporting requirements of the
TiO2 Directives for the Member State.
Where these are considered to be additional to other environmental reporting
requirements.
Costs for emission control

12
Can you provide any information on capital expenditure and operating costs for
equipment to control air emissions and liquid effluent in the TiO2 industry.
For example any recent work undertaken on the installations.
Issues from potential removal of TiO2 Directives

13
If the TiO2 Directives were ended, what concerns would you have for regulation of
releases to the environment from the industry.
Are there any areas which would not be considered by IPPC, Waste and water
framework directives. Would there be a reduction in protection of the environment.
Appendix 4: Background information on

impacts associated with pollutants emitted
from TiO2 manufacture
Table A4.1
Pollutant
To air
TiO2 dust
Other dust
SO2
NO2
H2S
Chlorine
26
Pollutants associated with the manufacture of TiO2 and their effects on health and the
environment. Note that some of these pollutants can be beneficial to health at low dose (e.g.
zinc, copper, manganese). Note also that impact will be dependent on concentration in the
environment, exposure routes, etc.
Effects
Evidence for health effects of TiO2 dust in air have been reviewed by
26
National Institute of Occupational Safety and Health (NIOSH) in the US .
The review concluded that TiO2 poses a negligible risk of lung cancer
through workplace exposures. The review, did, however, also find that
TiO2 was capable of causing inflammation of the lung, and of causing
cancer in rats when exposure levels were high. Effects appear to be
unrelated to the chemical nature of TiO2, and so it seems appropriate to
treat TiO2 as other dust rather than recognising it to have any specific
impact.
The main effects of dust, generally defined as PM2.5 or PM10 are on human
health. Analysis undertaken for the ECs CAFE (Clean Air For Europe)
Programme estimated the loss of 3.6 million life years annually through
exposure to particles at ambient levels in 2000. Some types of particle
have specific mechanisms of impact through either chemical or physical
properties. However, WHOs advice to CAFE was to quantify effects
against overall particle mass, and not to disaggregate effects to specific
components of the atmospheric particle mix. In addition to effects on
mortality, WHO agreed to quantification of various morbidity impacts,
including bronchitis, hospital admissions and various minor symptoms, and
recommended the position of no-threshold for effect.
SO2 emissions affect both health and the environment. Health effects are
considered by WHO to be mediated in part through the formation of
sulphate aerosols which then act as particulate matter. There is evidence
of direct effects of SO2 at levels near to those that currently exist in parts of
Europe. However, these were not quantified in the CAFE work through
concern over the potential for double counting of impacts.
Whilst current levels of SO2 across the EU25 are not high enough to cause
significant ecological damage (as shown by the widespread return of
lichens following continent-wide reductions in SO2 over the last 30 years),
SO2 released into the atmosphere forms acids and remains a major
contributor to exceedance of critical loads for acidity to terrestrial and
freshwater aquatic ecosystems, particularly in NW Europe.
Similar to SO2, though evidence of direct health impacts at ambient levels
is limited. The TiO2 industry does not pose a specific threat to health or
the environment via the release of NOx.
Although H2S is a poisonous gas, it is unlikely to be present at harmful
concentrations. It is a pungent gas with an odour threshold below 1ppm
(http://www.safetydirectory.com/hazardous_substances/hydrogen_sulfide/fact_sheet.htm).
This is well below the concentrations known to cause health damage
(http://www.epa.gov/iris/toxreviews/0061-tr.pdf). Its release from a TiO2
plant is likely to be noticed before reaching such a level that it has an
effect on the population.
Like H2S, chlorine is unlikely to be present at harmful levels. Its use for the
chloride process for TiO2 manufacture is controlled through the Seveso II
Directive. Automatic monitoring for chlorine with shut down should
Pollutant
HCl
To water
Chlorides, HCl, iron
compounds, sulphate,
suspended solids
As (arsenic)
Cd (cadmium)
Cr (chromium)
Cu (copper)
Hg (mercury)
Mn (manganese)
Ni (nickel)
Pb (lead)
Ti (titanium)
V (vanadium)
Zn (zinc)
To land
Various, as above
Effects
significant levels of the gas be detected is now a standard part of process
control at chloride process plants,
There is limited evidence for human health effects of HCl
(http://www.epa.gov/IRIS/subst/0396.htm). In any case, it is readily
soluble in water and hence easy to remove from effluent gas streams.
The main impacts of these pollutants are on the health of aquatic
organisms. Effects will differ significantly with the type and quality of the
receiving environment, with risks much higher for freshwaters than marine
or systems. Acidity (when input at sufficiently high levels) can interact with
other pollutants, for example increasing the solubility of harmful metals.
Human carcinogen, with various other effects on human health
(http://cfpub.epa.gov/iris/quickview.cfm?substance_nmbr=0278).
Various effects on human health. Carcinogenicity proven in animals but
not in humans, though considered as a probable human carcinogen
(http://www.epa.gov/iris/subst/0141.htm).
Chromium VI is a known human carcinogen via inhalation though it is not
known if it is carcinogenic via other exposure routes
Chromium III is not known to have carcinogenic properties via inhalation or
ingestion (http://cfpub.epa.gov/iris/quickview.cfm?substance_nmbr=0028).
Copper is an essential nutrient, though like others can have effects on
health if consumed to excess. Higher concentrations can also affect
aquatic life, for example fish and other creatures may experience damage
to gills, liver, kidneys, and the nervous system.
Various effects on health identified depending on mercury compound.
Some regarded as possible human carcinogens.
Carcinogenicity not established. Capable of effects on nervous system
Nickel refinery dust is a known human carcinogen
(http://cfpub.epa.gov/iris/quickview.cfm?substance_nmbr=0272), as is
nickel subsulphide. Nickel carbonyl is a probable human carcinogen.
However, evidence on soluble salts of nickel, presumably of most
relevance here, is inconclusive.
Lead has a number of effects on health, ranging from effects on learning
development to hypertension and being a probable human carcinogen
(http://www.epa.gov/IRIS/subst/0277.htm). It is bioaccumulative and can
affect the health of aquatic organisms.
Titanium is non-toxic, most of that ingested to the human body passes
through without being absorbed. Its environmental effects also seem
insignificant, some plants (e.g. nettles) may use Ti to stimulate growth.
The toxicity of vanadium compounds increases with oxidative state the
most toxic being considered as vanadium pentoxide.
There seems more concern amongst health professionals about the
potential for zinc deficiency in the population than exposure to excess
levels of zinc (http://www.ehponline.org/members/1994/Suppl-2/walshfull.html). Zinc can have effects on the wider environment, though again
the potential for negative effects will be a function of concentration.
European legislation against uncontrolled dumping of materials, and on
landfill regulation should ensure that waste sent for disposal to land does
not pose a threat to health or the environment. Available data show most
solid waste generated by TiO2 manufacture (96%) to be non-hazardous.
It is important to put the effects shown in the table, as they relate to the TiO2 industry, into context. Thresholds exist for some
pollutant/effect combinations (though not all), and effects will not be observed below those thresholds. Environmental
thresholds will vary from place to place. For example, the release of chloride to a marine or tidal estuary habitat within reason
should have little or no effect given the high chloride content of marine waters. Similarly, whilst deposition of acidifying
pollutants (acid rain) such as NOx or SO2 to land is important in some parts of Europe such as Scotland and Scandinavia, but
unimportant in areas where soils on softer bedrock have a high capacity to buffer incoming acidity.
For the purpose of impact assessment it is necessary to know the size of particles emitted from the
industry as this will affect their ability to penetrate the airways deep into the lung. The following figure
shows that TiO2 particles used for pigments are less than 1 m in size, and therefore contribute to the
PM2.5 size fraction. Such particles are able to penetrate deep into the lung. Without more specific
data relative to the different stages of production and different types of particle emitted at each stage it
is assumed here that all emissions are in the sub-2.5 m fraction (PM2.5). This assumption permits
direct application of reference values for damage per tonne of particle emission expressed as PM2.5
cited in the BREF on Economics and Cross Media Effects.
Figure A4.1. TiO2 particle size distribution relative to pigmentary properties (Source:
http://www.millenniumchem.com/NR/rdonlyres/09E9AAC0-5A44-4D9B-A55F3304A169AA1A/0/Figure53TiO2F.pdf).
27
Figures presented in the BREF on Economics and Cross Media Effects give national average
damage linked to emissions, accounting for trans-boundary impacts. The methods of calculation were
28
subject to independent peer review under the ECs CAFE Programme . Accounting for different
methodological assumptions, chiefly linked to the approach for quantifying and monetising mortality
effects gives roughly a factor 3 range in unit damage costs. Data for the 4 countries that contain
chloride process TiO2 plant are shown in the following table. Capacity weighted averages for the low
and high ends of the damage factor range have been taken for the countries that contain TiO2
29
factories that use the chloride process .
27
http://www.jrc.es/pub/english.cgi/d1254319/18%20Reference%20Document%20on%20Economic%20and%20Cross%20Media%20Effects%20%2
8adopted%20July%202006%29%20-%201.8%20Mb
28
http://cafe-cba.aeat.com/html/reports.htm
29
The analysis presented here is based on averaged figures, as a result of the lack of availability of emissions data by named plant. It is intended
that analysis be done on a plant by plant basis following response by operators to the questionnaire that has been sent to them. However, the
results provided here give a reasonable indication of the overall magnitude of benefits.
Table A4.2. Averaged damage factors for estimating the costs of PM2.5 emissions from chloride process
plant on health
Belgium
Germany
Netherlands
UK
Total / averages
Capacity (kt)
60
100
55
250
465
PM2.5 damage (/t) low

61,000
48,000
55,000
37,000
46,000
PM2.5 damage (/t) high

180,000
140,000
180,000
110,000
134,000
Estimates of damage per tonne PM2.5 are shown in table A4.3 for the countries that contain sulphate
process TiO2, with the averages in the last row of the table weighted by production in each country.
Table A4.3. Averaged damage factors for estimating the costs of PM2.5 emissions from sulphate process
plant on health
Czech Republic
Finland
France
Germany
Italy
Poland
Slovenia
Spain
UK
Total / averages
Capacity (kt)
41
120
225
322
80
40
44
80
80
1,032
PM2.5 damage (/t) low

32,000
5,400
44,000
48,000
34,000
29,000
22,000
19,000
37,000
35,508
PM2.5 damage (/t) high

91,000
16,000
130,000
140,000
97,000
83,000
64,000
54,000
110,000
103,679
Damage per tonne SO2 estimates are shown in Table A4.4 for the countries that contain sulphate
process TiO2, with the averages in the last row of the table weighted by production in each country.
Table A4.4. Averaged damage factors for estimating the costs of SO2 emissions from sulphate process
plant on health
Czech Republic
Finland
France
Germany
Italy
Poland
Slovenia
Spain
UK
Total / averages
Capacity (kt)
41
120
225
322
80
40
44
80
80
1,032
SO2 damage (/t) low

8,000
1,800
8,000
11,000
6,100
5,600
6,200
4,300
6,600
7,503
SO2 damage (/t) high

23,000
5,100
23,000
32,000
18,000
16,000
18,000
12,000
19,000
21,692

The emissions data from 1999 used in the BREF, supplemented with some more recent information
for some plant, are shown in Tables A5.1 and A5.2 (for dust emissions), Table A5.3 (for SO2
emissions), Table A5.4 (for sulphate emissions to water) and Table A5.5 (for chlorine emissions to air
and chloride to water). These data were provided to the European Commission by Peter Thompson
on behalf of the TDMA. For those tables expressing emission per unit of product it is not clear
whether rates are based on pure TiO2 or pigment. This uncertainty has been taken into account in the
analysis of Section 4.
3
Table A5.1. Dust emission rate (mg/Nm ) by site and process step (original dataset).
Sulphate process
Chloride Process
Scenario limits
Site
1
2
3
4
5
6
7
8
9
10
11
12
13
Ore prep
1
17.25
37
27
16
19
16
7
1
2
3
4
5
<50
Directive
BAT AEL
50
5-20
Calcination
0.0
<10
28
25
<1
<1
0
<1
23
0
0
9
8
Milling
Finishing
<50
<50
<28
<50
6.5
<20
<14
<20
60
14.00
18.00
5
3.2
12
20
16
6.2
18
18
<5
28
50
5-20
50
5-20
50
5-20
Table A5.2. Dust emissions (kg/t TiO2) by site and process step (original dataset).
Sulphate process
Site
1
2
3
4
5
6
7
8
9
10
11
12
13
Ore prep
0.002
0.002
0.03
0.04
0.0002
0.076
0.04
0.08
0.06
0.019
0.05
Calcination
0
0.36
0.22
0.0001
0.0035
0
0
0.15
0
0
Milling
0
0.017
0.003
0.002
0.02
Finishing
0.37
0.25
0.30
0.30
0.049
0.05
0.15
0.003
0.12
0.002
Directive
BAT AEL
Total dust
0.372
0.252
0.685
0.597
0.00025
0.1455
0.09
0.23
0.216
0.141
0.072
Not specified
0.004 - 0.045
Chloride Process
1
2
3
4
5
0.005
0.0002
0.186
0.0023
0.4
0.143
0.06
Directive
BAT AEL
0.191
0.0025
0.4
0.143
0.06
Not specified
0.1 - 0.2
Table A5.3. SO2 emissions to air (kg/t TiO2) by site and process step (sulphate process plant only,
original dataset).
Site
1
2
3
4
5
6
7
8
9
10
11
12
13
Digestion
0.04
0.99
0.96
0.03
1.91
0.12
0.00
1.03
0.04
0.0001
0.0001
Directive
BATAEL
Calcination
3.85
2.42
7.79
7.03
3.35
0.84
4.00
2.40
12.10
1.10
0.53
Total SOx
3.89
3.41
8.75
7.06
5.26
0.96
4.00
3.43
12.14
1.10
0.53
6.80
8.20
10
1.0 - 6.0
Table A5.4. Sulphate emissions to water (kg/t TiO2) by site (sulphate process plant only, original dataset).
Site
1
2
3
4
5
6
7
8
9
10
11
12
13
Total sulphate emission (kg/t TiO2)

730
183
98
630
600
300
140
170
117
~300
36
1030 (785)
159
Directive
BATAEL
800
100-550
Table A5.5. Chlorine emissions to air and chloride emissions to water by site (chloride process plant
only, original dataset).
Site
1
2
3
4
5
Directive
BATAEL
Cl2 g/t TiO2
Cl2 mg/Nm (daily average)
0.41
0.1
8
Chloride kg/t TiO2

38
140
150
330
130-450
38-330
With respect to Table A5.5 it is noted that emission from site 5 of both chlorine and chloride are
significantly higher than for the other plant (a factor of 20 to 80 for chlorine and a factor a little higher
than 2 for chloride). This may indicate that the control systems at this plant are more dated than
elsewhere.
The new data provided at the end of the contract by TDMA are presented in the following tables,
though were not used for the analysis presented in the main text. Some differences in the format of
the data create difficulty in repeating the analysis for example, dust emissions are given only in
3
terms of mg/Nm . SO2 emissions are given as aggregates across all process steps, whereas in the
original dataset they were separated for the digestion and calcination stages. It is not clear whether
the numbering of plant is consistent between the two datasets.
Table A5.6. Dust emission rate (mg/Nm ) by site and process step (new dataset).
Sulphate process
Site
1
2
3
4
5
6
7
8
9
10
11
12
13
Ore prep
0
1
17
3
1
<30
20
<10
47
15
46
16
7
Chloride Process
1
2
3
4
5
Scenario limits
Directive
BAT AEL
Calcination
0.93
11
<6
42
NA
<5
20
NA
3
5
5
NA
4
NA
16
15
NA
1
50
5-20
50
5-20
Milling
3.75
<5
28.5
<5
13
<20
20
<1
40
9.0
17.0
12.2
22
Drying
15.50
25
NA
26
NA
<20
20
10
10
10.0
17.0
32.5
9
Max 21
10
NA
<5
4
Max 22
6
17
<5
4
50
5-20
50
5-20
Table A5.7. SO2 emissions to air and sulphate emissions to water (both kg/t TiO2) by site and process
step (sulphate process plant only, new dataset).
Site
1
2
3
4
5
6
7
8
9
10
11
12
13
SO2 kg/t TiO2 (average)

2.96
6.2
6.92
5.7
7
2
0.11
4.8
4
2.3
3.8
6.8
0.9
Sulphate kg/t TiO2 (average)

472
400
98
650
345
399
405
239
127
441
257
1030
136
10.00
1.0-6.0
800
100-550
Directive
BAT AEL
Table A5.8. Chlorine emissions to air and chloride emissions to water by site (chloride process plant
only, new dataset).
Site
Cl2 daily
average
3
5mg/Nm
Cl2 <40
3
mg/Nm at
any time
Chloride
using natural
rutile (kg/t)
1
2
3
4
5
<5
1
1
1
<1
Max 33
1
1
1
<1
93
Directive
BAT AEL
<5
<40
120
Chloride
using
synthetic
rutile (kg/t)
Chloride
using slag
(kg/t)
Not used
161
100.8
120
199
130
38-330
228
38-330
450
38-330
Appendix 6: Emission control methods and

costs
Abatement of dust emissions
The most effective technique for abating particles is the use of fabric (also called bag) filters. Use of
such filters is already widespread in the TiO2 industry, though discussion with the TDMA suggests that
those factories and parts of the process that generate the greatest particle emissions may be using
alternative techniques (e.g. cyclones or electrostatic precipitators). When asked why performance of
3
fabric filters in the TiO2 industry (emission rates in many cases are around 50 mg/Nm ) seems not as
3
good as elsewhere (fabric filters typically achieve emission rates of 5 mg/Nm and lower) the TDMA
has said that the industry has experienced problems in use of the technology when pushing it to very
low emission rates. The reason for this is unclear as fabric filters are known to work well for particles
of similar size (0.1 to 0.5 micron) to TiO2 particles. Also, the data provided in Appendix 5 show some
3
sites already achieving much lower emission rates than others, close to the figure of 5 mg/Nm . It is
unknown whether this reflects specific factors affecting the industry, or whether performance could be
improved by (e.g.) better management of dust handling systems. If that is the case, associated costs
for further abatement of dust from the industry could be very low and may even generate additional
benefit, for example, through reduced downtime as a result of improved maintenance regimes.
Despite the reservations of the TDMA it is assumed here that the best approach to address
exceedances of limit values for any scenario would be through the use of fabric filters, either replacing
existing dust abatement equipment or used behind it. The USEPA has published cost estimates for
3
30
fabric filters equivalent to 13,000 to 78,000 /m /s flow rate . Estimated flow rates calculated from
information given in the BREF regarding the dustiest stages (ore preparation and finishing) of TiO2
3
manufacture gives very broad ranges, 944 to 8,828 m /t TiO2. Cost estimates based on these ranges
are shown in Table A6.1. Analysis is based on 20 year lifetimes for equipment and 4% discount rate
to generate annualised cost estimates. Mid-point estimates of the cost to an average plant (used in
the analysis that follows) are 483,000/year for the chloride process and 412,000/year for the
sulphate process.
Table A6.1. Estimated ranges for the costs of fabric filters for average sized chloride and sulphate
process plant
Chloride process
Sulphate process
Cost (/year) based on lower

bound flow rate
93,000
79,000
Cost (/year) based on

upper bound flow rate
872,000
744,000
The precise level of performance achieved by the bag filters is open to question, given on the one
hand the statements made by the TDMA about the difficulties of dust abatement in the sector, and on
the other, a lack of data to show what precisely the problems are.
Abatement of SO2 emissions
There are two stages that generate significant emissions of SO2 from the sulphate process. The first
of these is digestion, which leads to the release of 0.47 kg SO2 / t TiO2 on average for the EU plant.
The second, calcination, is more polluting with emissions on average of 3.5 kg SO2 / t TiO2. In cases
where emission levels exceed limit values it seems likely therefore that the calcination step would be
targeted for further control. Some very effective techniques are already in place at some sites for
reducing SO2 emissions. At one site calciner gases are fed directly to a plant for sulphuric acid
manufacture. The case study for the Grimsby plant given in the BREF highlights a reduction in SO2
emissions of 84% in 2002. The sulphur does not appear to have been transferred to other
environmental media as sulphate discharged to water remained constant and the quantity of gypsum
generated fell by about half for the year.
30
http://www.epa.gov/ttn/catc/cica/atech_e.html#1c
There are important questions concerning the quantification of the costs of further SO2 controls. The
first concerns the extent to which existing controls can be pushed to further reduce emissions, rather
than requiring new abatement equipment to be fitted. The second is from the perspective of IPPC,
with SO2 removed from flue gases potentially being transferred to the liquid effluent and making it
more difficult to meet the sulphate AELs.
The BREF contains the following information on gaseous emissions treatment performance and costs
for calcination (Table A6.2). The high performance catalyst appears able to reduce emissions of SO2
down to 2 kg/t TiO2 (easily sufficient to meet the upper BAT AEL), whilst scrubbing can reduce
emissions further to 1 kg/t (sufficient to meet the lower BAT AEL).
Table A6.2 Gaseous emissions treatment performance and costs for calcination (Source: LVIC-S BREF)
It is assumed that plant that do not meet the limits of scenarios 2, 4 and 5 would need to be equipped
with the high performance catalyst. For those plant that do not meet the lower BAT AEL of Scenario 3
it is assumed that scrubbing would be required. 20 year lifetimes and 4% discount rates are used to
annualise capital costs. For an average sized sulphate plant with capacity of 79,000 t/year these data
equate to total annualised costs of 1.6 M/plant for the high performance catalyst and 1.7 M/plant for
the scrubber.
Abatement of chlorine emissions
Analysis of further abatement of chlorine emissions was not possible because:
The BREF does not provide AELs for chlorine
Emissions data were not provided in the right format for comparison with the Directive limits.
However, this is unlikely to be of any great significance. The use of chlorine in TiO2 manufacture is
regulated via the Seveso II Directive. To meet the requirements of the Directive it is understood that
the industry applies monitoring so that systems are shut down should an escape of chlorine be
detected. This should lead to minimal emission levels.
One caveat on chlorine releases arises from the emissions data provided to the Commission by
TDMA, in which variation from 0.1 to 8 g/t TiO2 is noted. This demonstrates some plant to be
operating to much tighter standards than others. Data received for 2006 emissions suggests that all
plant except one operate to a similar standard. The one exception has emissions up to 5 times higher
(as a daily average) and 33 times higher (limit to be complied with at all times).
Abatement of sulphate emissions
Only the sulphate process gives significant emissions of sulphates to water. According to the BAT
reference document the upper BREF AEL can be reached by acid recycling or neutralisation. Acid
recycling would reduce the sulphate emission to 500 kg/t TiO2, whereas a lower emission of 300 400
kg SO4/t TiO2 is possible through neutralisation. In the latter process, the emission depends on the
effluent pH: the higher the pH the lower the emission, but the higher the waste production. Table A6.3
summarises the costs and performances of the different treatment processes. The capital costs seem
high, but the treatment costs look acceptable. For the recycling process the treatment cost is mainly
determined by the high energy consumption, whereas for the neutralisation process the treatment cost
is mainly determined by the waste treatment costs.
Table A6.3. Costs and efficiency of techniques for sulphate abatement (Source: LVIC-S BREF).
Applying the capital costs shown in Table A6.3 to each of the plant listed enables comparison with the
total capital expenditure figures for each plant shown in Table 3.6 of the BREF. In all but three cases
the capital costs of sulphate equipment, based on the figures shown in Table A6.3 exceed the total
capital costs given in the BREF. This implies either that the capital costs given above or in Table 3.6
of the BREF are wrong, or that facilities have been upgraded at lower cost, rather than being replaced.
Assuming the latter, the costs provided in the BREF do not help in determining the costs of further
improvements at existing TiO2 plant.
The cited costs are also much higher than what was reported by the UK Environment Agency in its
response to the questionnaire sent to regulators states. The reduction of sulphate from its current
level to 550 kg/t TiO2 (the upper BAT AEL) for one plant with a capacity of 80 kt TiO2 would be of the
order 700,000 capital cost and 14/t TiO2 operating cost. This equates to an annual cost per plant of
1.1 million/year, annualising against a 20 year lifetime for the additional equipment and a discount
rate of 4%. However, a possible explanation for the low investment cost given by the UK Environment
Agency is that their analysis only considers extension of an existing treatment plant (which seems the
most likely response by the industry), whereas the BREF data account for all plant costs. Still the
capital cost given in the BREF seems extremely high. It is possible that the operating costs cited by
the UK Environment Agency are underestimated, possibly through the exclusion of landfill costs.
These costs will depend on the fate of residual wastes, in particular whether they can be sold on as a
by-product. In the event that there is no market for these wastes disposal costs can amount to 60 /t,
depending on the country under consideration. Waste production depends on the degree of
neutralisation and is estimated to be 1,000 5,000 kg/t TiO2 for a reduction of the sulphate emission
from 800 to 550 kg/t TiO2.
From the BREF, it is not clear how the lower BAT AEL level of 100 kg/t TiO2 can be reached the
lowest figure cited being 300 kg/t TiO2. However, lower levels, are reached by no fewer than 7
sulphate process plant, according to the data behind the BREF. Theoretically, further reductions in
emission should be possible by adding more lime so as to reach a higher pH. The sulphate
concentration is determined by the solubility of the sulphate salts such as CaSO4 and FeSO4. The
solubility diminishes with a higher pH. This will result in a higher amount of SO4 precipitated as
CaSO4 and hence lower SO4 emissions. A subsequent neutralisation of liquid effluents will be
necessary in these cases prior to release to the environment. Cost data for meeting the lower BAT
AEL have not been identified.
As a note of caution, one of the footnotes to Table A6.3 states that further abatement from acid
recycling beyond a level of 500 kg/t TiO2 would require significant energy inputs for evaporating the
weak acid. In addition to the costs of such action this would also pose additional environmental
burden through the release of global and regional air pollutants.
Abatement of chloride emissions
Only the chloride process gives rise to the emission of significant amounts of chloride to water. From
the baseline emission data provided by TDMA all plant meet the upper BAT-AEL, so consideration of
the costs and benefits of reaching that level is immaterial here. The BREF does not indicate how the
lower AEL level can be reached. Reverse osmosis could be considered, but this results in the
production of a waste water stream that is enriched in chlorides that needs to be disposed of.
Therefore this technique is not really considered a solution for waste water with a high chloride
concentration.
The need to take action is dependent on the nature of the water body into which the chloride process
plant discharge their effluent. Clearly, water in the sea or in tidal estuaries can cope with much higher
chloride inputs than freshwaters. The anonymised nature of the emissions data provided mean that it
is possible only to assume that the lowest emissions are sent to freshwater and the highest emissions
to sea- or estuarine-water. Assuming this to be the case, and assuming that monitoring has not
established significant effects of discharges of chloride to the ecology of the water bodies concerned,
the benefits of further control are likely to be minimal. Dis-benefits associated not just with the costs of
additional control but also the supply of additional reagent may well outweigh any benefit from further
control.
When the BREF is reviewed it should be asked whether all plant truly meet BAT, given the factor 10
range between the least and most polluting plant and the fact that the range seems to include all plant
for which data were available. It is noted that the plant with the highest chloride emissions also has
the highest chlorine emissions, and so may be somewhat dated.
Abatement of metal emissions
For the sulphate process the Fe emission can be reduced by neutralisation or basification to a higher
pH. Adding lime to a pH of 9 would be sufficient to reach the lower BAT AEL level. The
corresponding costs have been discussed above. For the other metals considered, no such
information is available, neither does the BREF indicate how the specified upper and lower limits can
be reached.
For the chloride process the waste water treatment consists of a neutralisation process. No
information is available on the effect of the neutralisation process on the emission of metals. It is
expected that some precipitation takes place, but to what extend and how it can further be influenced
is not clear.
After-treatment processes (such as membrane filtration processes) that can guarantee extremely low
metals concentrations in the effluent do exist, but are not referred to in the BREF. As these
techniques are apparently not considered to be BAT, they are not considered here.
Abatement of emissions of suspended solids
The upper BAT AEL level for the sulphate process corresponds with a suspended solids concentration
3
of 800 mg/l (sulphate process with a reference volume of 50 m waste water per ton TiO2). This can
easily be reached in a standard precipitation process. Therefore it can be assumed that most plants
comply with the upper BAT AEL level (S2) and that no further costs are necessary. The lower BAT
AEL level for sulphate plants corresponds with a suspended solids concentration of 20 mg/l In this
case a simple precipitation process would not be sufficient and a sand filtration would be necessary as
a final treatment step. For a typical plant with a production capacity of 70,000 tTiO2/year and a waste
3
water production of 50 m /t TiO2, the investment cost is estimated to be 400,000 and the operational
cost 175,000 /year (Vito, techniekbladen).
For the chloride process the BAT AEL levels are considerably lower than for the sulphate process.
Again no information is available on the actual emission levels and on the processes used to reach the
specified BAT levels. The upper BAT AEL level can still be reached with a standard precipitation
process, whereas for the lower level sand filtration will be necessary, with resulting higher costs.
Appendix 7. Trends in emissions from EPER,

2001-2004
The following should be noted:
1. Emissions are not reported for all pollutants for all plant in the EPER database. So, for PM10, trend
data are only available for one plant, whilst for SO2 data are available for 12 plants for both 2001 and
2004.
2. The trend data for the Fredrikstad and Celje plants appear to show constant emissions. However,
inspection of the database found in both cases that the link to the 2001 data leads to the 2004 data
instead. Hence the information presented in this appendix for these 2 plant should be ignored.
3. Note that slight increases in emissions may be due to increased production, rather than a
worsened environmental performance per unit of TiO2 production.
4. Whilst some plant are dedicated solely to TiO2 production others are not. Therefore attribution of
all emissions shown to TiO2 will overestimate the burdens relevant to the present analysis.
30,000
Chloride emission, t/year
25,000
20,000
15,000
10,000
5,000
2001
Duisburg
Stallingborough
2004
Langerbrugge
Rotterdam-Botlek
Figure A7.1. Changes in emissions of chloride to water for TiO2 plant, 2001-4, as reported by EPER
350
TOC emission, t/year
300
250
200
150
100
50
1
2
Calais
Rotterdam-Botlek
Figure A7.2. Changes in emissions of TOC to water for TiO2 plant, 2001-4, as reported by EPER
0.06
Arsenic emission, t/year
0.05
0.04
0.03
0.02
0.01
2001
Grimsby
2004
Calais
Thann
Rotterdam-Botlek
Figure A7.3. Changes in emissions of arsenic to water for TiO2 plant, 2001-4, as reported by EPER
0.030
Cadmium emission, t/year
0.025
0.020
0.015
0.010
0.005
2001
2004
Grimsby
Calais
Figure A7.4. Changes in emissions of cadmium to water for TiO2 plant, 2001-4, as reported by EPER
Chromium emission, t/year
30
25
20
15
10
5
-
Duisburg
Calais
Nordenham
Pori
Le Havre
Stallingborough
Grimsby
Fredrikstad
Rotterdam-Botlek
Figure A7.5. Changes in emissions of chromium to water for TiO2 plant, 2001-4, as reported by EPER
1.4
Copper emission, t/year
1.2
1.0
0.8
0.6
0.4
0.2
2001
2004
Duisburg
Grimsby
Calais
Fredrikstad
Figure A7.6. Changes in emissions of copper to water for TiO2 plant, 2001-4, as reported by EPER
0.025
Mercury emission, t/year
0.020
0.015
0.010
0.005
2001
2004
Duisburg
Grimsby
Fredrikstad
Figure A7.7. Changes in emissions of mercury to water for TiO2 plant, 2001-4, as reported by EPER
1.0
0.9
Nickel emission, t/year
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
2001
Duisburg
Fredrikstad
2004
Pori
Rotterdam-Botlek
Grimsby
Greatham
Calais
Stallingborough
Figure A7.8 Changes in emissions of nickel to water for TiO2 plant, 2001-4, as reported by EPER
0.7
Lead emission, t/year
0.6
0.5
0.4
0.3
0.2
0.1
2001
Duisburg
Calais
2004
Huelva
Rotterdam-Botlek
Grimsby
Stallingborough
Figure A7.9. Changes in emissions of lead to water for TiO2 plant, 2001-4, as reported by EPER
20
18
Zinc emission, t/year
16
14
12
10
8
6
4
2
2001
Duisburg
Thann
Greatham
2004
Pori
Le Havre
Rotterdam-Botlek
Grimsby
Fredrikstad
Calais
Celje
Figure A7.10. Changes in emissions of zinc to water for TiO2 plant, 2001-4, as reported by EPER
10,000
9,000
CO emission, t/year
8,000
7,000
6,000
5,000
4,000
3,000
2,000
1,000
2001
2004
Greatham
Stallingborough
Figure A7.11. Changes in emissions of CO to air for TiO2 plant, 2001-4, as reported by EPER
600,000
CO2 emission, t/year
500,000
400,000
300,000
200,000
100,000
2001
Nordenham
Duisburg
2004
Greatham
Le Havre
Pori
Huelva
Figure A7.12 Changes in emissions of CO2 to air for TiO2 plant, 2001-4, as reported by EPER
700
NOx emission, t/year
600
500
400
300
200
100
2001
Duisburg
2004
Uerdingen
Pori
Huelva
Figure A7.13. Changes in emissions of NOx to air for TiO2 plant, 2001-4, as reported by EPER
80
PM10 emission, t/year
70
60
50
40
30
20
10
2001
2004
Pori
Figure A7.14. Changes in emissions of PM10 to air for TiO2 plant, 2001-4, as reported by EPER
2,000
1,800
SO2 emission, t/year
1,600
1,400
1,200
1,000
800
600
400
200
2001
Duisburg
Leverkusen
Le Havre
2004
Uerdingen
Grimsby
Scarlino
Pori
Calais
Fredrikstad
Huelva
Thann
Celje
Figure A7.15. Changes in emissions of SO2 to air for TiO2 plant, 2001-4, as reported by EPER
Appendix 8: Monitoring standards for relevant

air pollutants
A8.1 Chlorine
Currently there are no CEN or ISO standards available for the measurement of chlorine. There are,
however, German VDI and USEPA standards for periodic measurements that can be applied.
VDI 3488 Blatt 1:1979-12
Messen gasfrmiger Emissionen; Messen der Chlorkonzentration; Methylorange-Verfahren
Gaseous emission measurement; measurement of chlorine and oxides of chlorine;
methyl orange method
VDI 3488 Blatt 2:1980-11
Messen gasfrmiger Emissionen; Messen der Chlorkonzentration; Bromid-Jodid-Verfahren
Gaseous emission measurement; measurement of chlorine concentration;
bromide iodide method
USEPA Method 26 Determination of Hydrogen Halide and Halogen Emissions from Stationary
Source
This method involves the sampling of an integrated sample into dilute sulphuric acid and sodium
hydroxide solutions. The halogens, including chlorine, have a low solubility in acidic solutions
therefore is not retained in the sulphuric acid solution but is retained in the sodium hydroxide solution.
Which is then analysed by ion chromatography for the halide ions in this case Cl thus enabling the
measurement of the chlorine present in the sample. One assumption made is that each chlorine gas
molecule dissociated in solution to give two Cl ions.
In addition to these periodic methods there are a number of continuous measurement techniques that
are capable of measuring chlorine. In addition these technologies can be specific to the measurement
of chlorine. Detection principles listed as being applicable to the measurement of chlorine include ion
mobility analysers, continuous flow analysers using ion chromatography and Ion selective electrode,
mass spectrometry, Differential optical absorption spectroscopy (DOAS) and tuneable diode laser
analysers.
However, there are no published standards that relate specifically to the use of systems to measure
chlorine. The principles of other CEN and ISO standards provide the basis of best practice. In
addition, ISO 10396 Stationary source-emissions- Sampling for the automated determination of gas
concentrations provides general specifications. The aim of the measurement is to provide a result
representative of the process. To this end, Standards define general sampling systems, performance
parameters such as linearity, response time and detection limit, they define a procedure for the
selection of sample plane and points. So a combination of these technologies and existing standards
can provide a representative measurement of the emission of chlorine from TiO2 processes.
A8.2 Particulates
There are CEN and ISO standards available for the measurement of particulate material both
periodically and continuously.
EN 13284-1 Stationary Source emissions- Determination of low range mass concentration of
dust- Part 1: Manual gravimetric method.
This prescribes the methodology to be adopted including equipment performance, sample plane
position, both the position and number of sample points and the procedure to be used. A stream of
the gas is collected isokinetically (that is at the same velocity as the gas stream) extracted at
representative points across the profile of the duct. This is filtered out of the sample by use of a preweighed dry plane filter. The gain in weight of this paper and the volume sampled are used to
determine the concentration in the duct.
-3
This standard is applicable to concentrations of below 50 mg m with special emphasis around

-3
5 mg m .
EN 13284-2 Stationary Source emissions- Determination of low range mass concentration of

dust- Part 2: Automated measuring systems.
This standard specifies test criteria for the certification of continuous dust monitors used to
-3
demonstrate compliance with emission limit values of below 50 mg m . In addition calibration and ongoing control procedures are described. The calibration procedure uses BS EN 13284-1 as the
reference method against which the response of the analyser is correlated to give a calibration
function. It is accepted that particulate monitors using a surrogate parameter i.e. light attenuation,
light scattering or charge to determine the mass concentration of particulate present must be
calibrated against a gravimetric method once installed onto the process. This is due to materials
produced by a process will have specific physical characteristics of colour or composition that will
affect the response of the analysers.
ISO Standards
-3
ISO 9096:2003 (20 mg m ) Stationary source emissions Manual determination of mass
concentration of particulate matter
-3
-3
This method is applicable in the range of 20 mg m to 1000 mg m . A representative sample of the
gas stream is withdrawn isokinetically and the particulate material is collected on a pre-weighed and
dried flat filter.
ISO 12141:2002 Stationary source emissions Determination of particulate matter (dust) at low
concentrations Manual gravimetric method
This standard was developed in close liaison with the CEN working group responsible for EN13284-1
and gives procedures for extending the range of ISO 9096. This is applicable in the same range as
-3
EN 13284-1 i.e. below 50 mg m
A8.3 Oxides of sulphur

CEN Standards
EN14791: 2005 Stationary Source emissions - Determination of mass concentration of sulphur
dioxide Reference method.
This method involves the sampling of a representative sample from the stack or duct via a heated and
temperature controlled probe and filter assembly. The sample is taken for a specific time and at a
controlled flow rate to ensure that limits of detection and absorption efficiencies are achieved. The
sample is collected in 0.3% hydrogen peroxide. Oxides of sulphur are absorbed and oxidised to the
sulphate ion, which is retained in solution. The solutions are then analysed by using ion
chromatography analysing for sulphate ion or titration with a barium perchlorate solution and thorin
indicator.
ISO Standards
ISO 7935:1992 Characterization of air quality. Stationary source emissions - Determination of
the mass concentration of sulfur dioxide. Performance characteristics of automated measuring
methods.
This standard defines the performance characteristics that an automated monitoring system must
meet so as to ensure a measurement inaccuracy of less than 10% related to the upper limit of
measurement. This standard must be used in conjunction with ISO 10396 Stationary source
emissions Sampling for the automated determination of gas concentrations.
ISO 11632:1998 Stationary source emissions Determination of mass concentration of sulphur
dioxide Ion chromatography
This is periodic methodology, and involves the taking a representative sample in a measured volume
of the gas stream through a solution of hydrogen peroxide. In which the oxides of sulphur are oxidised
to sulphate ions. The solutions are subsequently analysed of the sulphate ions using ion
chromatography.
A8.4 Carbon monoxide

EN 15058:2006 Stationary Source emissions Determination of the mass concentration of
carbon monoxide (CO) Reference method: Non-dispersive infrared spectrometry (NDIR).
This method is applicable to both periodic and continuous measurement. Overall uncertainties in this
method are quoted as less than 6.0% relative to the ELV if its requirements are met. The quoted
-3
range operation range is 0 to 740 mg m . The standard describes the components of the system, the
procedure and defines minimum performance characteristics.
ISO 12039:2001 Stationary source emissions Determination of carbon monoxide, carbon

dioxide and oxygen Performance characteristics and calibration of automated measuring
systems.
This method prescribes minimum performance characteristics for measurement principles used to
determine the concentration of CO listing both electrochemical and NDIR detection methods for its
measurement. This standard should be used in conjunction with ISO 10396 that describes the
principle of using these analysers to obtain a representative sample.
A8.5 Carbonyl sulphide (COS)

There are no CEN or ISO standards applicable to the measurement of COS. There is a USEPA
method that can be used.
USEPA method 15
A Gas sample is extracted from the emission source and analysed by gas chromatograph and flame
photometric detector. The sample can be diluted with clean dried air to avoid problems with moisture
blocking the column. This method is suitable for periodic measurement use.
A8.6 Oxides of nitrogen (NOx)

There are CEN and ISO methods for the measurement of oxides of nitrogen (defined as nitric oxide,
NO, and nitrogen dioxide, NO2, but excluding others such as nitrous oxide, N2O) for stationary
sources.
The following CEN has been devised as a reference method with the aim of ensuring compliance with
emission measurement uncertainty requirements in Waste Incineration and Large combustion plant
Directives. Both the CEN and ISO standards describe procedures that can be used for continuous
and period of measurement of NOX
EN 14792:2005 Stationary source emissions Determination of mass concentration of nitrogen
oxides (NOX) Reference method: Chemiluminescence.
This method can be used for the measurement of oxides of nitrogen, defined as nitric oxide (NO) and
nitrogen dioxide (NO2) and has been validated for minimum sampling periods of 30mins in the range
-3
of 0 -1300 mg as NO2.
A representative volume of flue gas is extracted from the source, passed through a filter and
conditioning system and present the analyser with a sample with interferences such as particulate and
moisture removed or controlled so that the effect of these are reduced to a minimum.
The standard describes a number of configurations for the systems but in all cases uses
chemiluminescence as the detection principle. Minimum performance criteria is set for the systems
used and requires that the overall uncertainty be less than 10% relative to process ELVs.
ISO 10849:1996 Stationary Source emission Determination of the mass concentration of
nitrogen oxides Performance characteristics of automated measuring systems.
This standard defines performance characteristics for systems measuring these species such as
linearity, response time, detection limit and effect of inerferent species. A number of different
detection principles are listed i.e. chemiluminescence, non-dispersive infrared spectroscopy, nondispersive ultraviolet spectroscopy and differential optical absorption spectrometry. Brief descriptions
of the sample system are given. However, this standard must be used in conjunction with
ISO 10396 Stationary source-emissions- Sampling for the automated determination of gas
concentrations which prescribes a sampling methodology, giving requirements for the sampling
position and guidelines on obtaining representative samples from a stack or duct
A8.7 Hydrogen chloride (HCl)

A CEN standard that has been developed for the measurement of hydrogen chloride
EN 1911 Stationary source emissions Manual method of determination of HCl:1998 Parts 1

Sampling, Part 2 Gaseous compounds absorption and Part 3 Absorption solutions analysis
and calculation.
This standard involves the extraction of a representative sample from a stack or duct via a heated
probe and filter assembly before the gaseous chlorides are collected in chloride free water. The
standard describes the use of three different methods for the subsequent analyses of the collected
samples.
A8.8 Hydrogen sulphide

There are no CEN or ISO standards applicable to the measurement of hydrogen sulphide emissions.
However, there are USEPA methods.
USEPA Method 11
This method involves the collection of H2S in cadmium sulphate with iodometric analysis to determine
the concentration present.

Tio2 Simplification Report Iss3

Diunggah oleh

Informasi Dokumen

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

Tio2 Simplification Report Iss3

Diunggah oleh

Hak Cipta:

Format Tersedia

Analysis of the Simplification of

the Titanium Dioxide Directives

Report to European Commission DG ENV.G.1

Analysis of the simplification

Analysis of the Simplification of the Titanium Dioxide Directives

European Commission DG Environment Sustainable Development and

This document has been prepared by AEA Technology plc in connection

AEA Energy & Environment

R. Stewart, H. Lawrence, A. Leonard (AEA Energy and

AEA Energy & Environment

Analysis of the simplification

AEA Energy & Environment

Analysis of the simplification

0.45 kg/t TiO2

0.004 kg/t TiO2

0.7 kg/t TiO2

0.25 kg/t TiO2

0.2 kg/t TiO2

0.1 kg/t TiO2

0.4 kg/t TiO2

0.15 kg/t TiO2

330 kg/t TiO2

330 kg/t TiO2

150 kg/t TiO2

AEA Energy & Environment

Analysis of the simplification

Benefits from additional abatement (M/year)

Benefits from additional abatement (M/year)

AEA Energy & Environment

Analysis of the simplification

AEA Energy & Environment

Analysis of the simplification

AEA Energy & Environment

Analysis of the simplification

Objectives of this Report.................................................................................................... 1

Environmental Regulation of the TiO2 Industry ................................................................. 1

Consultation on Simplification of the TiO2 Directives ........................................................ 2

Overview of Study Methodology ........................................................................................ 2

The TiO2 Industry in Europe............................................................................ 6

Chloride Process ............................................................................................................... 7

Pollution Control Techniques for Air Emissions............................................................... 11

Pollution Control Techniques for Liquid Effluents............................................................ 12

Control of Solid Wastes ................................................................................................... 13

TiO2 Content of Pigment as Sold..................................................................................... 14

Data Collection from the Industry and Regulators...................................... 16

Responses to Survey Sent to Plant Operators................................................................ 16

Responses to Surveys Sent to Member State Regulators .............................................. 16

Emission Scenario Analysis of Social, Economic and Environmental

Impacts Associated with the Sector................................................................................. 18

Scenario Development .................................................................................................... 19

Effects on competitiveness and employment .................................................................. 33

Analysis on Monitoring of the Environment ................................................ 38

Summary of monitoring requirements in the TiO2 Directives........................................... 38

Current monitoring in relation to TiO2 manufacture: ........................................................ 41

Potential for simplification of monitoring .......................................................................... 46

Analysis of the impacts of simplifications of monitoring requirements ............................ 49

Conclusions and Recommendations ........................................................... 52

Emission limit values ....................................................................................................... 52

Further analysis ............................................................................................................... 55

AEA Energy & Environment

Analysis of the simplification

AEA Energy & Environment

Analysis of the simplification

1.2 Environmental Regulation of the TiO2 Industry