Analysis of the Simplification of the Titanium Dioxide Directives

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

Restricted – Commercial Analysis of the simplification AEAT/ENV/R/2506/Issue 3 of the TiO2 Directives

AEA Energy & Environment iii

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 AEAT/ENV/R/2506/Issue 3

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Analysis of the simplification Restricted – Commercial of the TiO2 Directives AEA/ED05458/Issue 3

iv AEA Energy & Environment


AEA Energy & Environment v

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 BAT (Best Available Techniques) in the sector’s BREF note

1.

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 Scenario 2 Scenario 3 Scenario 4 Scenario 5

Directive Upper BAT Lower BAT Between S1 and S2

Between S2 and S3

Sulphate process

Dust to air 50 mg/m3

0.45 kg/t TiO2

20 mg/m3

0.004 kg/t TiO2

5 mg/m3

0.7 kg/t TiO2 0.25 kg/t TiO2

SO2 to air 10 kg/t TiO2 6 kg/t TiO2 1 kg/t TiO2 9 kg/t TiO2 4 kg/t TiO2

SO4 to water 800 kg/t TiO2 550 kg/t TiO2 100 kg/t TiO2 785 kg/t TiO2 300 kg/t TiO2

Chloride process


0.2 kg/t TiO2 0.1 kg/t TiO2 0.4 kg/t TiO2 0.15 kg/t TiO2

SO2 to air Not given 1.7 kg/t TiO2 1.3 kg/t TiO2 No data No data

Cl2 to air 5 mg/m3 (daily)

40 mg/m3 (instant)

Not given Not given No data No data

Cl to water 130-450 kg/t TiO2 330 kg/t TiO2 38 kg/t TiO2 330 kg/t TiO2 150 kg/t TiO2

1 The Large Volume Solid Inorganic Chemicals (LVIC-S) BAT Refernce (BREF) note.


vi AEA Energy & Environment

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 and benefits, where possible.

2 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).

Table ii. Costs and benefits of moving to within the emission limit values defined for each scenario1

based on assumptions that minimise the number of plant exceeding limit values (emissions expressed against TiO2, ELVs against TiO2 pigment).

Scenario 2 Scenario 3 Scenario 4 Scenario 5

Additional abatement costs (€M/year)

Dust 1.3 6.4 0 2.2

SO2 6.4 17 0 9.6

Chlorine No data No data No data No data

Sulphate 2.2 12 0 4.4

Chloride 0 No data 0 No data

Quantified costs 4

9.9 34 0 16

Benefits from additional abatement (€M/year) 2, 3

Dust 1.3 10 0 3.2

SO2 14 25 0 17

Other pollutants Not quantified Not quantified Not quantified Not quantified

Quantified benefits 4

15 35 0 20

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.

Table iii. Costs and benefits of moving to within the emission limit values defined for each scenario1

based on assumptions that maximise the number of plant exceeding limit values (emissions expressed against TiO2 pigment, ELVs against TiO2).

Scenario 2 Scenario 3 Scenario 4 Scenario 5

Additional abatement costs (€M/year)

Dust 1.8 6.4 1.3 3.9

SO2 9.6 19 4.8 16

Chlorine No data No data No data No data

Sulphate 4.4 13 0 6.6 Chloride no data No data 0 No data

Quantified costs 4

16 39 6.1 27

Benefits from additional abatement (€M/year) 2, 3

Dust 2.5 11 0.5 4.5

SO2 17 25 11 20

Other pollutants Not quantified Not quantified Not quantified Not quantified

Quantified benefits 4

20 36 12 25

Notes: See notes to Table (ii).

2 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).


AEA Energy & Environment vii

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 5 mg/Nm

3, 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


viii AEA Energy & Environment

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.


AEA Energy & Environment ix

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

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

3 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

4 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

5 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

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

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

6.2 Monitoring ........................................................................................................................ 54

6.3 Definitions ........................................................................................................................ 55

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


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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


AEA Energy & Environment 1

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 Title Main Provisions

78/176/EEC Council Directive on waste from the

Titanium Dioxide Industry

Minimum permitting requirements, monitoring

and requirement for Member State progress

reports.

82/883/EEC Council Directive on procedures for

the surveillance and monitoring of

environments concerned by waste

from the Titanium Dioxide industry

Defines the frequency, locations, and

parameters to be monitored at and around TiO2

facilities

92/112/EEC Council directive on procedures for

harmonising the programmes for

the reduction and eventual

elimination of pollution caused by

waste from the Titanium Dioxide

industry.

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.


2 AEA Energy & Environment

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

Directive3. 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.

3 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 Commission’s 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.



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 Company Location Process Capacity (t)

Belgium Kronos Europe Langerbrugge Chloride 60,000

Czech Rep Precheza Prerov Sulphate 41,000

Finland Kemira Pigments Pori Sulphate 130,000

France Tioxide Europe Calais Sulphate 100,000

France Millenium Chemicals Le Havre Sulphate 95,000

France Millenium Chemicals Thann Sulphate 30,000

Germany Sachtleben Duisburg-Homberg Sulphate 100,000

Germany Tronox Krefeld-Uerdingen Sulphate 107,000

Germany Kronos Titan Leverkusen Both 130,000

Germany Kronos Titan Nordenham Sulphate 62,000

Italy Huntsman Tioxide Scarlino Sulphate 80,000

Netherlands Tronox Rotterdam-Botlek Chloride 55,000

Poland Zaklady Cemiczne Police Sulphate 40,000

Slovenia Cinkarna Celje Sulphate 44,000

Spain Tioxide Europe Huelva Sulphate 80,000

UK Tioxide Europe Greatham Chloride 100,000

UK Tioxide Europe Grimsby Sulphate 80,000

UK Millennium Chemicals Grimsby/Stallingborough Chloride 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)



• 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 Main burdens Control

Chlorination: Reaction of TiO2 with chlorine to form TiCl4.

Use of chlorine Some impurities such as silica and zirconium removed

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

Solids separation Further removal of impurities, generating waste

Solid wastes either recycled or destined for appropriate landfill disposal

Neutralisation of waste solid metal chlorides using lime

Further removal of impurities, generating solid waste

Some sale of FeCl2, most metal chlorides sent to appropriate landfill

Condensation of TiCl4, jet scrubbing of gas stream with cold TiCl4

Further removal of impurities, generating waste

Gas stream passed for waste gas treatment (see below)

Distillation, further purification of TiCl4

Further removal of impurities, generating waste

See below

Vanadium oxychloride removal using oil

Generation of sludge containing complexed VOCl2

Sludge recycled back to solids separation where it is removed from the process stream and disposed of as appropriate

Oxidation at 900-2000°C, converting back to TiO2 and controlling final crystal size

Use of oxygen Emissions associated with energy use Generation of chlorine

Energy efficiency measures See next stage

Cooling and separation Presence of chlorine Chlorine recycled to chlorination stage

Adsorption / desorption process, TiO2 slurried in water

Presence of chlorine Chlorine absorbed in liquid TiCl4 and recycled to chlorination stage, though some remains for waste gas treatment

Finishing via milling and coating with additives to improve pigment properties

Generation of dust Removal using bag filters

Waste gas treatment CO, COS HCl Cl2 Use of caustic reagents Generation of liquid effluent

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

Treatment of solid wastes, via neutralisation using chalk or lime, precipitation and stabilisation of metals

Production of filter cake requiring disposal

Some generation of by-products. Residual solid wastes disposed of to appropriate landfill.

Treatment of liquid effluents Transfer of pollutants from liquid to solid media

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



• 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 Main burdens Control

Digestion Use of concentrated (80-95%) sulphuric acid Off-gases containing SOx, dust, H2S

Containment, safe handling, etc. Normal or multi-stage scrubbing

Reduction (when primary ore is ilmenite)

Generation of hydrogen Discharged to air avoiding explosive hazard

Clarification and crystallisation using flocculation and filtration

Solid residue Limited re-use, most neutralised then sent for landfill

Hydrolysis Emissions associated with energy use Spent acid

Energy efficiency measures Acid is recycled or neutralised with lime or limestone to form gypsum, which is sold or land filled

Filtration and washing Acidic filtrate Residual solid metals (Fe, Cr, Mn, V)

Acid is recycled or neutralised with lime or limestone to form gypsum, which is sold or land filled

Calcination Emissions associated with energy use SO3 SO2 TiO2 dust

Energy efficiency measures Removed by ESPs Scrubbed or oxidised to SO3 and absorbed to form sulphuric acid which can be recycled Removed by scrubbing, recycled

Finishing via milling and coating with additives to improve pigment properties

Generation of dust Removal using bag filters

Waste gas treatment Dust H2S, SO2

Use of caustic reagents Generation of liquid effluent

Removed using bag filters and cyclones Removed by scrubbing Containment, safe handling, etc. See below

Treatment of solid wastes, via neutralisation using chalk or lime, precipitation and stabilisation of metals

Production of filter cake requiring disposal

Some generation of by-products. Residual solid wastes disposed of to appropriate landfill.

Abatement of aqueous emissions

Transfer of pollutants from liquid to solid media

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.



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, off-gases 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

Digestion (installations) Calcination (installations) Costs €/tonne TiO2 produced

Slag (3) Ilmenite (8) std catalyst (6)

hp catalyst (1)

Scrubbing (3)

Capital 85 75 70 140 170

Operating 10 5 5 10 9

The average SO2 concentrations discharged to atmosphere in 1999 for digestion and calcination in the BREF were 87 and 713 mg/m

3 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 absorption which is between 100 and 680 mg/m

3. 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 average concentrations (12-39 mg/m

3 for various activities in 1999) appear high for fabric filters which

can achieve concentrations <<5 mg/m3. 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).

4 Further information relevant to this section is given in Appendix 6, particularly with respect to the costs of abatement.



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].

5 Further information relevant to this section is given in Appendix 6, particularly with respect to the costs of abatement.



2.5.3 Description of most relevant techniques

2.5.3.1 Primary treatment

2.5.3.1.1 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 Secondary/tertiary systems

2.5.3.2.1 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 re-use, 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.



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

Millennium Chemicals Ltd 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

86 – 99

Zakłady Chemiczne POLICE S.A TYTANPOL®

Paints, plastics, rubber, textile, ceramic and paper

88 – 98.5

Note: No data were found on the internet for the products of Degussa, Cinkarna, Precheza and Sachtleben

The TDMA’s 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.



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 elsewhere. The TDMA respond that “Although values below 50mg/m

3 are obtainable 5mg/m

3

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. TDMA’s 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 some updates to fill in gaps)

6.

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.

6 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.



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 Monitoring Estimated yearly cost (€) Payer

Belgium Surface water quality (Ti) 2,400 Authority

Wastewater (emissions) 1,500-2,000 (+ 1 man-day) Authority

Czech Republic NR NR NR

Spain Plant emission monitoring NR Operator

Any additional monitoring carried out by authority

NR Authority

Germany NR NR NR

The Netherlands NR NR NR

Slovenia National monitoring NR Authority

Emission monitoring 75,000 Operators

UK Emission monitoring NR Operator

Environmental monitoring In excess of 21,000 Authority

NR = No Response received 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.



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 (NIOSH) in the US

7. 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 EC’s 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



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) Scenario 2: Upper limits

8 for emissions for TiO2 production according to the LVIC-S BREF (S2)

Scenario 3: Lower limits8 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. Much of the data therefore dates back to 1999

9. 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 to the sector as a whole

10.

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.



Table 4-1. Emission limit values from Directive 92/112/EEC and the BREF

Emission Directive

92/112/EEC 1

BAT upper limit 1 BAT lower limit

1

Sulphate process

Weak Acid / neutralised waste 800 kg tot SO4 /

t TiO2

SO4 total to water 550 kg / t TiO2 100 kg / t TiO2

Suspended solids to water 40 kg / t TiO2 1 kg / t TiO2

Iron compounds to water 125 kg / t TiO2 0.3 kg / t TiO2

Mercury to water 1.5 g / t TiO2 0.32 mg / t TiO2

Cadmium to water 2 g / t TiO2 1 mg / t TiO2

V, Zn, Cr, Pb, Ni, Cu, As, Ti, Mn No techniques identified - lack of data

Dust to air, major sources 50 mg/Nm3

Dust to air, other sources 150 mg/Nm3

Dust to air, total 0.45 kg / t TiO2 0.004 kg / t TiO2

Dust to air, emission rate 20 mg / Nm3 <5 mg / Nm

3

SO2 to air 10 kg/t TiO2 6 kg/t TiO2 1 kg/t TiO2 SO2 to air from plant for concentration of waste acid 500 mg/Nm

3

Acid droplets 0

NO2 Monitor NOx from Calciner

H2S 0.05 kg/t TiO2 0.003 kg/t TiO2 Plants for roasting salts generated by waste treatment To have BAT Waste Avoid, reduce,

etc.

Chloride process

Weak Acid / neutralised waste, neutral rutile 130 kg Cl / t TiO2 Weak Acid / neutralised waste, synthetic rutile 228 kg Cl / t TiO2 Weak Acid / neutralised waste, slag 450 kg Cl / t TiO2

HCl to water 14 kg / t TiO2 10 kg / t TiO2

Chlorides to water 330 kg / t TiO2 38 kg / t TiO2

Suspended solids to water 2.5 kg / t TiO2 0.5 kg / t TiO2

Iron compounds to water 0.6 kg / t TiO2 0.01 kg / t TiO2 Hg, Cd, V, Zn, Cr, Pb, Ni, Cu, As, Ti, Mn No techniques identified - lack of data

Dust to air, major sources 50 mg/Nm3

Dust to air, other sources 150 mg/Nm3

Dust, total emission 0.2 kg / t TiO2 0.1 kg / t TiO2

SO2, total emission 1.7 kg / t TiO2 1.3 kg / t TiO2

Cl2 daily average 5 mg / Nm3

Cl2 at any time 40 mg / Ng3

HCl, total emission 0.1 kg / t TiO2 0.03 kg / t TiO2

Waste 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.



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 Scenario 2 Scenario 3 Scenario 4 Scenario 5

Sulphate process


0.45 kg/t TiO2

20 mg/m3

0.004 kg/t TiO2

5 mg/m3

0.7 kg/t TiO2 0.25 kg/t TiO2

SO2 to air 10 kg/t TiO2 6 kg/t TiO2 1 kg/t TiO2 9 kg/t TiO2 4 kg/t TiO2

SO4 to water 800 kg/t TiO2 550 kg/t TiO2 100 kg/t TiO2 785 kg/t TiO2 300 kg/t TiO2

Chloride process


0.2 kg/t TiO2 0.1 kg/t TiO2 0.4 kg/t TiO2 0.15 kg/t TiO2

SO2 to air Not given 1.7 kg/t TiO2 1.3 kg/t TiO2 No data No data

Cl2 to air 5 mg/m3 (daily)

40 mg/m3 (instant)

Not given Not given No data No data

Cl to water 130-450 kg/t TiO2 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:

• Emission rates per unit of flow (mg/Nm3) 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 year’s 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 Appendix 5 to the extent that they are available.

11 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.



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).

Plant1

Dust SO2 Sulphate Cl2 3

Chloride

Sulphate process

1 S2 2

S5 S4

2 S2 S5 S5

3 S4 S4 S3

4 S4 S4 S5

5 S3 S2 S5

6 S5 S3 S5

7 S5 S5 S5

8 S5 S5 S5

9 S5 X S5

10 S5 S5 S5

11 S5 S3 S3

12 S2+? S4 S4

13 S2+? S4 S5

Chloride process

1 S2 ? S3

2 S3 ? S5

3 S4 ? S5

4 S5 ? ?

5 S3 ? 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 Figures presented in the BREF on Economics and Cross Media Effects

12 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 independent peer review under the EC’s CAFE Programme

13.

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 averaged damage factors is given in Appendix 4.

14

12

http://www.jrc.es/pub/english.cgi/d1254319/18%20Reference%20Document%20on%20Economic%20and%20Cross%20Media%20Effects%20%28adopted%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.



Table 4-4. Averaged damage factors for estimating the costs of PM2.5 and SO2 emissions from chloride and sulphate plant on health

Process Pollutant €/t low €/t high

Chloride plant PM2.5 1

46,000 134,000

Sulphate plant PM2.5 1

35,500 104,000

SO2 7,500 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 Average emission Total emission Lower bound damage

Upper bound damage

Chloride PM2.5 0.159 kg/t TiO2 120 t/year €5.5 M/year €16 M/year

Sulphate PM2.5 0.28 kg/t TiO2 289 t/year €10 M/year €30 M/year

Sulphate SO2 4.97 kg/t TiO2 5,130 t/year €38M/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 1

Annualised 1

Performance Source of data



cost/plant 1

Dust Chloride Fabric filter €483k/year 2

See note 3 USEPA

Sulphate Fabric filter €412k/year 2 See note 3 USEPA

SO2 Sulphate Standard catalyst €0.8M/year 8 kg/t TiO2 LVIC-S BREF

Sulphate High performance catalyst €1.6M/year 2 kg/t TiO2 LVIC-S BREF

Sulphate Scrubber €1.7M/year 1 kg/t TiO2 LVIC-S BREF

Chlorine Chloride No data - - -

Sulphate Sulphate Not specified, presumed upgrade

4 €1.1M/year 550 kg/t TiO2 UK Environment

Agency

Chloride Chloride No data - - - 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/Nm

3, 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.



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.



i) 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.

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 expressed in mg/m

3 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



Benefit:cost ratio low 1.5 1.6 1.4 Benefit:cost ratio high 4.3 4.8 4.2 Limit values expressed per unit TiO2 pigment, emissions in tonnes TiO2 N plant exceeding 3 15 0 5 Emission change (t) 33 276 0 83 Cost (€M/year) 1.3 6.4 2.2 Benefit Low (€M/year) 1.3 10.2 3.2 Benefit High (€M/year) 3.9 29.7 9.3 Benefit:cost ratio low 1.0 1.6 1.5 Benefit:cost ratio high 3.0 4.7 4.2 Limit values expressed per unit TiO2, emissions in tonnes TiO2 pigment N plant exceeding 4 15 3 9 Emission change (t) 64 286 13 118 Cost (€M/year) 1.8 6.4 1.3 3.9 Benefit Low (€M/year) 2.5 10.6 0.5 4.5 Benefit High (€M/year) 7.4 31.1 1.5 13.2 Benefit:cost ratio low 1.4 1.7 0.4 1.2 Benefit:cost ratio high 4.1 4.9 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 bag filters

15. Assuming a 95% efficiency would reduce emissions from this part of the process by

44 tonnes, with resulting benefits of €2.0 to 4.6 million per year16

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.



4.3.5.2 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 BAT-AEL) 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.



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 Limit values and ELVs expressed relative to the same unit of production (t TiO2 or TiO2 pigment) N plant exceeding limit value 5 11 0 6 Emission change (t) 2,198 3,345 0 2,304 Cost (€M/year)

1 8.0 19 9.6

Benefit Low (€M/year) 17 25 17 Benefit High (€M/year) 48 73 50 Benefit:cost ratio low 2.1 1.3 1.8 Benefit:cost ratio high 6.0 3.9 5.2 Limit values expressed per unit TiO2 pigment, emissions in tonnes TiO2 N plant exceeding 4 10 0 6 Emission change (t) 1818 3,337 0 2304 Cost (€M/year)

1 6.4 17.0 9.6

Benefit Low (€M/year) 14 25 17 Benefit High (€M/year) 40 72 50 Benefit:cost ratio low 2.1 1.5 1.8 Benefit:cost ratio high 6.2 4.3 5.2 Limit values expressed per unit TiO2, emissions in tonnes TiO2 pigment N plant exceeding 6 11 3 10 Emission change (t) 2,304 3,345 1,421 2,673 Cost (€M/year)

1 9.6 19 4.8 16.0

Benefit Low (€M/year) 17 25 11 20 Benefit High (€M/year) 50 73 31 58 Benefit:cost ratio low 1.8 1.3 2.2 1.3 Benefit:cost ratio high 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 may warrant further consideration.

17 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.



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

Limit values and ELVs expressed relative to the same unit of production (t TiO2 or TiO2 pigment) 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 Limit values expressed per unit TiO2 pigment, emissions in tonnes TiO2 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 Limit values expressed per unit TiO2, emissions in tonnes TiO2 pigment 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.



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 Limit values expressed per unit TiO2 pigment, emissions in tonnes TiO2

Scenario 2 0 0 Scenario 3 3 45,000 Scenario 4 0 0 Scenario 5 1 14,000 Limit values expressed per unit TiO2, emissions in tonnes TiO2 pigment

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 chloride emissions also has the highest chlorine emissions, and so may be somewhat dated.

18

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.



• 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%)

Small reduction (<20%)

Neutral (± 5%)

Small increase (<20%)

Significant increase (≥20%)

Emissions to water

As - 1 - - 2

Cd 2 - - - -

Cr 2 2 2 1 -

Cu 1 1 - - 1

Hg 1 - - - 1

Ni 2 - 1 2 2

Pb 3 - 1 1 1

Zn 6 - 2 - -

TOC 1 - 1 - -

Emissions to air

CO 2 - - - -

CO2 - 1 - 2 3

NOx 2 1 1 - -

TOTALS 22 6 8 6 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 highest emitting group

19. 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.



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. It is worth noting the views of Vercaemst

20 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 industry’s involvement in development of the BREF and the fact that many TiO2 manufacturers already meet the upper BAT-AEL. 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 Rating Comment

Geographical extent of the market Global The TDMA has expressed concern that cheap imports from China have depressed prices.

Price elasticity of demand and supply Low The market seems to have resisted attempts to increase prices (see below).

Degree of competition between products / threat of substitute products or services

Low TiO2 has a number of physical and chemical characteristics that favour it over alternatives.

Rivalry among existing firms in sector

Medium 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.

Bargaining power of customers and suppliers

Medium-high 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.

Threat of new entrants Low – medium 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.

Degree of international competition High Competition from China is said to be capturing some market share in the EU.

Several manufacturers (Millennium

21, 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

P. Vercaemst (2001) BAT: When do Best Available Techniques Become barely affordable technology? BAT-Centre, VITO, Mol, Belgium. 21

http://www.millenniumchem.com/News+and+Events/_News/PriceIncreasePressReleaseGlobalJune2007fin.htm



increases of this order. The truth may well of course be a mix of the two extremes. However, the market’s 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.” TDMA’s 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 mg/m

3) 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 would result from the increased filter area required to achieve something close to 5mg/m

3 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 apply were the limits set higher than 5 mg/m

3 (the BREF range for sulphate plant is 5-20 mg/m

3) 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.



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% Limit values expressed per unit TiO2 pigment, emissions in tonnes TiO2 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% % low estimate of profit 11% 38% 0% 18% % high estimate of profit 4% 13% 0% 6% Limit values expressed per unit TiO2, emissions in tonnes TiO2 pigment 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% % low estimate of profit 17% 42% 7% 29% % high estimate of profit 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 to 5 mg/m

3, 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 –



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.



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 Emission/ Air quality

Emission Limit Value

Comment

82/883/EEC SO2 Air quality None stated

Cl2

PM (optional)

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.

92/112/EEC PM, SOx, acid droplets, Cl2

Emission See Table 4-1 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



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.



Table 5-2: Summary of non-air mandatory monitoring in TiO2 Directives Directive Component Emission/

Environment Emission Limit Value

Comment

78/176/EEC Acute toxicity Emission (effluent)

20% Mortality 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.

pH, dissolved O2 ,turbidity, hydrated iron oxides and hydroxides in suspension, toxic metals, suspended solids

Environment (water column)

- Periodic checks on area affected by discharges to follow development of the receiving environments.

toxic metals Environment (living matter)

- Selected benthic and Pelagic organisms

diversity, abundance

- Flora and fauna

toxic metals Environment (sediment)

-

Acidity, iron content, calcium, toxic metals

Environment (surface and ground waters)

- In the case of storage, tipping or injection of waste.

Soil structure Environment (subsoil)

- Where necessary to monitor adverse effects

Ecology assessment

Environment - General assessment around storage, tipping or injection point.

82/883/EEC (Salt water)

Temperature, salinity, pH, O2 , turbidity, Fe, Ti


- Minimum frequency 3 times per year,.

Fe Environment (water column, filtered)

- Minimum frequency 3 times per year.

Fe, Iron oxides and hydroxides

Environment (suspended solids)

- Minimum frequency 3 times per year.

Ti, Fe, Iron oxides and hydroxides

Environment (sediment)

- 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.

Ti, Cr, Fe, Ni, Zn, Pb

Environment (organisms)

- Minimum frequency once per year. Specifications on parts of creatures used for extraction.

Diversity, abundance, lesions

- Benthic fauna, lesions on fish selected for metal analysis

(Fresh water)

Temperature conductivity, pH, O2 , turbidity, Fe, Ti


-

Fe Environment (water column, filtered)

-

Fe, Iron oxides and hydroxides

Environment (suspended solids)

-

Ti, Fe, Iron oxides and hydroxides

Environment (sediment)

-

Ti, Cr, Fe, Ni, Zn, Pb

Environment (organisms)

-

Diversity, abundance

-

(Storage on land)

pH, SO4 , Ti, Fe, Ca, Cl

Environment (surface water/ groundwater)

-

Site management, Subsoil, ecology,

Environment (topography, soil)

-

92/112/EEC Sulphate, chloride 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.



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 m³ per year it is obligatory to sample 6-hours, and for more than 50.000 m² discharged per year, a 24-hours sampling is obligatory.



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 Standard method used

1 Oxides of Nitrogen Quarterly ISO 10849

Hydrogen Chloride Quarterly EN 1911

Chlorine Continuous Colorimetry

Hydrogen Sulphide Quarterly

Sulphur Dioxide Quarterly BS 6069-4.4:1993

Particulate Quarterly ISO 9096

2 Oxides of Nitrogen Monthly ISO 10849

Hydrogen Chloride Monthly EN 1911

Chlorine Continuous

Hydrogen Sulphide Monthly

Sulphur Dioxide Monthly BS 6069:4.4

Sulphur Dioxide Continuous BS 6069:4.4

Particulate Monthly EN 13284-1

Particulate Continuous EN 13284-2

Carbon Monoxide Continuous ISO 12039

Carbonyl Sulphide Monthly

3 Oxides of Nitrogen Bi-annual Electrochemical

Oxides of Nitrogen Continuous

Hydrogen Chloride Bi-annual Colorimetrically

Sulphur Dioxide Quarterly NaOH/Glycerol

Sulphur Dioxide Bi-annual NaOH/Glycerol

Sulphur Dioxide Continuous

Particulate Annual ISO 9096:2003

Particulate Bi-annual ISO 9096:2003

Particulate Quarterly ISO 9096:2003

Particulate Continuous



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

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.

Pollutant Continuous or Periodic

Standard Comment

Particulate matter Continuous EN13284 Pt 2 For determination of mass concentration of dust using automated measuring systems (for lower concentrations)

ISO 10155 For determination of mass concentration of dust using automated measuring systems (for lower concentrations)

Periodic EN13284-1 Manual sampling procedure for particulate for concentrations <50 mg/m

3

ISO 9096 Manual sampling procedure for particulate for concentrations >50 mg/m

3

SO2 Continuous ISO 7935 For determination of mass concentration of SO2 using automated measuring systems

Periodic EN 14791, ISO11632 Integrated sample collection followed by chemical analysis.

SO2 + SO3 Periodic USEPA Method 8 Integrated sample collection followed by analysis, use of multiple collection media to collect SO2 and SO3

Cl2 Periodic USEPA Method 26/26A

Integrated sample collection followed by chemical analysis, use of multiple collection media to determine HCl and Cl2 separately.

Flow Continuous ISO14164 Continuous method

General use of automated measuring

systems

Continuous ISO 10396 Sampling for the automated determination of gas concentrations. Can be applied to continuous Cl2 measuring systems



Table 5-5 : CEN/TC 230- Published standards on water sampling and analysis Component Standard reference Title

Cr EN 1233:1996 Water quality - Determination of chromium - Atomic absorption spectrometric methods

Hg EN 12338:1998 Water quality - Determination of mercury - Enrichment methods by amalgamation

Hg EN 13506:2001 Water quality - Determination of mercury by atomic fluorescence spectrometry

Organisms EN 13946:2003 Water quality - Guidance standard for the routine sampling and pre-treatment of benthic diatoms from rivers

Organisms EN 14011:2003 Water quality - Sampling of fish with electricity

Organisms EN 14184:2003 Water quality - Guidance standard for the surveying of aquatic macrophytes in running waters

Organisms EN 14407:2004 Water quality - Guidance standard for the identification, enumeration and interpretation of benthic diatom samples from running waters

Other EN 14614:2004 Water Quality - Guidance standard for assessing the hydromorphological features of rivers

Organisms EN 14757:2005 Water quality - Sampling of fish with multi-mesh gillnets

Hg EN 1483:2007 Water quality - Determination of mercury - Method using atomic absorption spectrometry

Organisms EN 14962:2006 Water quality - Guidance on the scope and selection of fish sampling methods

QA aquatic sampling

EN 14996:2006 Water quality - Guidance on assuring the quality of biological and ecological assessments in the aquatic environment

Organisms EN 15110:2006 Water quality - Guidance standard for the sampling of zooplankton from standing waters

Organisms EN 15196:2006 Water quality - Guidance on sampling and processing of the pupal exuviae of Chironomidae (Order Diptera) for ecological assessment

Dissolved O2 EN 25813:1992 Water quality - Determination of dissolved oxygen - Iodometric method (ISO 5813:1983)

Dissolved O2 EN 25814:1992 Water quality - Determination of dissolved oxygen - Electrotechnical probe method (ISO 5814:1990)

As EN 26595:1992 Water quality - Determination of total arsenic - Silver diethyldithiocarbamate spectrophotometric method (ISO 6595:1982)

As EN 26595:1992/AC:1992 Water quality - Determination of total arsenic - Silver diethyldithiocarbamate spectrophotometric method (ISO 6595:1982)

Organism sampling

EN 27828:1994 Water quality - Methods of biological sampling - Guidance on handnet sampling of aquatic benthic macro-invertebrates (ISO 7828:1985)

Conductivity EN 27888:1993 Water quality - Determination of electrical conductivity (ISO 7888:1985)

Organism sampling

EN 28265:1994 Water quality - Design and use of quantitative samplers for benthic macro-invertebrates on stony substrata in shallow freshwaters (ISO 8265:1988)

Suspended solids EN 872:2005 Water quality - Determination of suspended solids - Method by filtration through glass fibre filters

Chloride EN ISO 10304-2:1996 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)

Metals EN ISO 11885:1997 Water quality - Determination of 33 elements by inductively coupled plasma atomic emission spectroscopy (ISO 11885:1996)

As EN ISO 11969:1996 Water quality - Determination of arsenic - Atomic absorption spectrometric method (hydride technique) (ISO 11969:1996)

Ca EN ISO 14911:1999 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)

Metals EN ISO 15586:2003 Water quality - Determination of trace elements using atomic absorption spectrometry with graphite furnace (ISO 15586:2003)

Metals EN ISO 15587-1:2002 Water quality - Digestion for the determination of selected elements in water - Part 1: Aqua regia digestion (ISO 15587-1:2002)

Metals EN ISO 15587-2:2002 Water quality - Digestion for the determination of selected elements in water - Part 2: Nitric acid digestion (ISO 15587-2:2002)

Cl EN ISO 15682:2001 Water quality - Determination of chloride by flow analysis (CFA and FIA) and photometric or potentiometric detection (ISO 15682:2000)

On-line sensors EN ISO 15839:2006 Water quality - On-line sensors/analysing equipment for water - Specifications and performance tests (ISO 15839:2003)

Fauna EN ISO 16665:2005 Water quality - Guidelines for quantitative sampling and sample processing of marine soft-bottom macrofauna (ISO 16665:2005)

Acute toxicity EN ISO 16712:2006 Water quality - Determination of acute toxicity of marine or estuarine sediment to amphipods (ISO 16712:2005)

General ICP-MS EN ISO 17294-1:2006 Water quality - Application of inductively coupled plasma mass spectrometry (ICP-MS) - Part 1: General guidelines (ISO 17294-1:2004)

Elements EN ISO 17294-2:2004 Water quality - Application of inductively coupled plasma mass spectrometry (ICP-MS) - Part 2: Determination of 62 elements (ISO 17294-2:2003)

Sampling sediment

EN ISO 19493:2007 Water quality - Guidance on marine biological surveys of hard-substrate communities (ISO 19493:2007)



Component Standard reference Title

Sampling programmes

EN ISO 5667-1:2006 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)

Cd EN ISO 5961:1995 Water quality - Determination of cadmium by atomic absorption spectrometry (ISO 5961:1994)

Turbidity EN ISO 7027:1999 Water quality - Determination of turbidity (ISO 7027:1999)

Acute toxicity 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 Water quality - Determination of the acute lethal toxicity of substances to a freshwater fish (Brachydanio rerio Hamilton-Buchanan (Teleostei, Cyprinidae)) - Part 2: Semi-static method (ISO 7346-2:1996)

EN ISO 7346-3:1997 Water quality - Determination of the acute lethal toxicity of substances to a freshwater fish (Brachydanio rerio Hamilton-Buchanan (Teleostei, Cyprinidae)) - Part 3: Flow-through method (ISO 7346-3:1996)

Sulphate 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)

Chlorine 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 7393-1:1985)

EN ISO 7393-2:2000 Water quality - Determination of free chlorine and total chlorine - Part 2: Colorimetric method using N, N-diethyl-1, 4-phenylenediamine, for routine control purposes (ISO 7393-2:1985)

EN ISO 7393-3:2000 Water quality - Determination of free chlorine and total chlorine - Part 3: Iodometric titration method for the determination of total chlorine (ISO 7393-3:1990)

Ca EN ISO 7980:2000 Water quality - Determination of calcium and magnesium - Atomic absorption spectrometric method (ISO 7980:1986)

Ecology 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)

Sampling 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)

QA 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.



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.



Table 5-6. Annual frequency of sampling and measurement as specified in Directive 82/83/EC.

Disposal route

Medium Parameter Annual frequency of sampling, measurement

Comments

Water column Temperature 3 Water column Salinity 3

Water column pH 3 Water column Dissolved O2 3

Water column Turbidity 3 Water column Iron (soluble and

particulate) 3

Water column Ti 3 Filtered water Iron (soluble) 3

Susp. solids Iron (total) 3

Susp. solids Hydrated iron oxides and hydroxides

3

Sediment Ti, Fe 1 Sediment Hydrated iron oxides and

hydroxides 1

Organisms Ti, Cr, Fe, Ni, Zn, Zn, Pb 1 Benthic fauna Diversity 1

Benthic fauna Abundance 1

Salt water and fresh surface water

Fish Lesions 1 Optional for freshwater

Water column pH 1

Water column SO4 1 Water column Ti 1

Water column Fe 1

Water column Ca 1

Water column Chloride 1

Environment Topography 1 Environment Management 1

Environment Subsoil 1

Storage & dumping on land

Environment Ecology 1

Water column pH 1 Water column SO4 1

Water column Ti 1

Water column Fe 1

Water column Ca 1

Water column Chloride 1 Environment Stability 1

Environment Permeability 1

Injection into soil

Environment Porosity 1 Air SO2 Continuously

Air Chlorine Continuously

12/year where no network exists

Air

Air Dust Continuously 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.”



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.



Table 5-7. Reported pollution monitoring costs for TiO2 manufacturing plant.

Site(s) Monitoring Cost to Annual cost

1 and 2 Brown shrimp toxicity survey (2 plant) Regulator € 2,625

Water sampling and chemical analysis (2 plant)

Regulator € 16,875

Benthic survey Regulator € 52,500

3 Water sampling and analysis Regulator € 5,250

Sediment/biota sampling and analysis Regulator € 21,000

4 Water Operator € 82,500

Air Operator € 22,500

5 All operator monitoring Operator € 70,000




9 Liquid effluent test (assumed to be check measurements)

Regulator € 2,000

Testing for Ti in surface waters 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.



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

Low High

On-site monitoring of emissions €50k €100k

Environmental monitoring €67k €92k

Total monitoring costs €117k €192k

Total costs under option (i) €75k €150k

Total costs under option (ii) €50k €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 150 kt plant

Sales 51,000,000 255,000,000

Profit (low) 1,785,000 8,925,000

Profit (high) 5,100,000 25,500,000 Relative to total monitoring costs of €192k/year

€192k as % of sales 0.4% 0.1%

€192k as % of profits (low) 10.8% 2.2%

€192k as % of profits (high) 3.8% 0.8%

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.



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: “Although values below 50mg/m

3 are obtainable 5mg/m

3 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. If there are good reasons why the industry cannot move to 5 mg/m

3 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 industry’s 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 National Institute of Occupational Safety and Health (NIOSH) in the US

22. 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 of causing inflammation of the lung

23 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 EC’s 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, WHO’s 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

http://0-www.cdc.gov.mill1.sjlibrary.org/niosh/review/public/TIo2/pdfs/TIO2Draft.pdf 23

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.



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 A maximum of one plant was found to exceed the upper BAT AEL

24. 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.



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.



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:



Overall, results for SO2 and dust appear similar to those of the original dataset25

, though there is some

reduction in SO2 emissions. For chlorine most values in the new dataset are the same (1 mg/Nm3 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

values as “<33 mg/Nm3”.

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/Nm

3 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.

Appendices

Appendix 1: References

Appendix 2: Questionnaire sent to Plant Operators

Appendix 3: Questionnaire sent to Member States


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

Appendix 1: References 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): 2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=186368&year=2001&CountryCode=UK 2004: http://eper.cec.eu.int/eper/facility_details.asp?id=191481&year=2004&CountryCode=UK 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): 2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=206221&year=2001&CountryCode=DE 2004: http://eper.cec.eu.int/eper/facility_details.asp?id=207997&year=2004&CountryCode=DE 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) : 2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=170603&year=2001&CountryCode=FR 2004: http://eper.cec.eu.int/eper/facility_details.asp?id=213910&year=2004&CountryCode=FR France2 (Le Havre): 2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=169930&year=2001&CountryCode=FR 2004: http://eper.cec.eu.int/eper/facility_details.asp?id=213224&year=2004&CountryCode=FR UK (Stallingborough): 2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=186144&year=2001&CountryCode=UK 2004: http://eper.cec.eu.int/eper/facility_details.asp?id=191271&year=2004&CountryCode=UK 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) 2001: http://www.eper.cec.eu.int/eper/facility_details.asp?id=206155&year=2001&CountryCode=DE 2004: http://eper.cec.eu.int/eper/facility_details.asp?id=207918&year=2004&CountryCode=DE 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): 2001: http://eper.cec.eu.int/eper/facility_details.asp?id=206189&year=2001&CountryCode=DE 2004: http://www.eper.cec.eu.int/eper/facility_details.asp?id=207961&year=2004&CountryCode=DE 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+titanium+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. Responses are needed by Tuesday 29

th 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)

2 Actual/typical recent production (Tonnes TiO2 )

3 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

5 Describe current discharges to air. Discharge points, discharge flows, pollutant concentrations (please note any standardisation of concentration and flow).

6 Describe the frequency of monitoring undertaken at present to air. Pollutants monitored, whether continuous or periodic (if periodic please provide frequency).

7 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. Information needed

8 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.

Environmental monitoring



16 Describe any broader environmental monitoring undertaken. For example monitoring of flora and fauna, air quality monitoring, any other offsite monitoring

Monitoring organisations and costs

17 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)

2 Please provide a copy of the IPPC or other relevant Authorisations for each installation

Releases to air :

3 What measures are in place to assess air quality impact of TiO2 installations, is air quality monitoring undertaken around each installation.

4 How has the regulatory authority applied emission limit values for discharges to air in operating permit. Hourly, Daily or annual limits or perhaps high short-term controls with more stringent longer-term averages

Releases to water :

5 Where are liquid effluents transferred to environment ? Inland waterway, Estuary, Sea (please comment if further treatment offsite)

6 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.

Discharges to land

7 Describe any discharge to land.

Environmental monitoring

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


9 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.


Table A4.1 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.

Pollutant Effects

To air

TiO2 dust Evidence for health effects of TiO2 dust in air have been reviewed by National Institute of Occupational Safety and Health (NIOSH) in the US

26.

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.

Other dust The main effects of dust, generally defined as PM2.5 or PM10 are on human health. Analysis undertaken for the EC’s 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, WHO’s 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 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.

NO2 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.

H2S 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.

Chlorine 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

26

http://0-www.cdc.gov.mill1.sjlibrary.org/niosh/review/public/TIo2/pdfs/TIO2Draft.pdf


Pollutant Effects

significant levels of the gas be detected is now a standard part of process control at chloride process plants,

HCl 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.

To water

Chlorides, HCl, iron compounds, sulphate, suspended solids

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.

As (arsenic) Human carcinogen, with various other effects on human health (http://cfpub.epa.gov/iris/quickview.cfm?substance_nmbr=0278).

Cd (cadmium) 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).

Cr (chromium) Chromium VI is a known human carcinogen via inhalation though it is not known if it is carcinogenic via other exposure routes (http://cfpub.epa.gov/iris/quickview.cfm?substance_nmbr=0144). Chromium III is not known to have carcinogenic properties via inhalation or ingestion (http://cfpub.epa.gov/iris/quickview.cfm?substance_nmbr=0028).

Cu (copper) 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.

Hg (mercury) Various effects on health identified depending on mercury compound. Some regarded as possible human carcinogens.

Mn (manganese) Carcinogenicity not established. Capable of effects on nervous system (http://cfpub.epa.gov/iris/quickview.cfm?substance_nmbr=0373).

Ni (nickel) 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.

Pb (lead) 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.

Ti (titanium) 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.

V (vanadium) The toxicity of vanadium compounds increases with oxidative state – the most toxic being considered as vanadium pentoxide.

Zn (zinc) 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/walsh-full.html). Zinc can have effects on the wider environment, though again the potential for negative effects will be a function of concentration.

To land

Various, as above 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 µm 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 µm 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-A55F-3304A169AA1A/0/Figure53TiO2F.pdf).

Figures presented in the BREF on Economics and Cross Media Effects

27 give national average

damage linked to emissions, accounting for trans-boundary impacts. The methods of calculation were subject to independent peer review under the EC’s CAFE Programme

28. 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 factories that use the chloride process

29.

27

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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

Capacity (kt) PM2.5 damage (€/t) low PM2.5 damage (€/t) high

Belgium 60 61,000 180,000

Germany 100 48,000 140,000

Netherlands 55 55,000 180,000

UK 250 37,000 110,000 Total / averages 465 46,000 134,000

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

Capacity (kt) PM2.5 damage (€/t) low PM2.5 damage (€/t) high

Czech Republic 41 32,000 91,000

Finland 120 5,400 16,000

France 225 44,000 130,000

Germany 322 48,000 140,000

Italy 80 34,000 97,000

Poland 40 29,000 83,000

Slovenia 44 22,000 64,000

Spain 80 19,000 54,000

UK 80 37,000 110,000

Total / averages 1,032 35,508 103,679

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

Capacity (kt) SO2 damage (€/t) low SO2 damage (€/t) high

Czech Republic 41 8,000 23,000

Finland 120 1,800 5,100

France 225 8,000 23,000

Germany 322 11,000 32,000

Italy 80 6,100 18,000

Poland 40 5,600 16,000

Slovenia 44 6,200 18,000

Spain 80 4,300 12,000

UK 80 6,600 19,000

Total / averages 1,032 7,503 21,692

Appendix 5: Emissions data 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.

Table A5.1. Dust emission rate (mg/Nm3) by site and process step (original dataset).

Site Ore prep Calcination Milling Finishing

Sulphate process 1 1 0.0 <50 2 <10 <50 3 28 <28 4 25 <50 5 <1 6 17.25 <1 6.5 <14 7 0 <20 8 37 <1 <20 60 9 27 23 10 16 0 14.00 12 11 19 0 18.00 20 12 16 9 5 16 13 7 8 3.2 6.2 Chloride Process 1 18 2 18 3 <50 <5 4 28 5 Scenario limits Directive 50 50 50 50

BAT AEL 5-20 5-20 5-20 5-20


Table A5.2. Dust emissions (kg/t TiO2) by site and process step (original dataset).

Site Ore prep Calcination Milling Finishing Total dust

Sulphate process 1 0.002 0 0.37 0.372 2 0.002 0.25 0.252 3 0.03 0.36 0.30 0.685 4 0.04 0.22 0 0.30 0.597 5 0.0002 0.0001 0.00025 6 0.076 0.0035 0.017 0.049 0.1455 7 0.04 0 0.05 0.09 8 0.08 0 0.15 0.23 9 0.06 0.15 0.003 0.003 0.216 10 0.019 0 0.002 0.12 0.141 11 0.05 0 0.02 0.002 0.072 12 13 Directive Not specified BAT AEL 0.004 - 0.045 Chloride Process 1 0.005 0.186 0.191 2 0.0002 0.0023 0.0025 3 0.4 0.4 4 0.143 0.143 5 0.06 0.06 Directive Not specified BAT AEL 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 Digestion Calcination Total SOx

1 0.04 3.85 3.89 2 0.99 2.42 3.41

3 0.96 7.79 8.75

4 0.03 7.03 7.06

5 1.91 3.35 5.26

6 0.12 0.84 0.96

7 0.00 4.00 4.00

8 1.03 2.40 3.43

9 0.04 12.10 12.14

10 0.0001 1.10 1.10

11 0.0001 0.53 0.53

12 6.80

13 8.20

Directive 10

BATAEL 1.0 - 6.0

Table A5.4. Sulphate emissions to water (kg/t TiO2) by site (sulphate process plant only, original dataset).

Site Total sulphate emission (kg/t TiO2)

1 730

2 183

3 98

4 630

5 600

6 300

7 140

8 170

9 117

10 ~300

11 36

12 1030 (785)

13 159

Directive 800

BATAEL 100-550

Table A5.5. Chlorine emissions to air and chloride emissions to water by site (chloride process plant only, original dataset).

Site Cl2 g/t TiO2 Cl2 mg/Nm3 (daily average) Chloride kg/t TiO2

1 38

2 140

3 0.41 0 150

4 0.1

5 8 330

Directive 5 130-450

BATAEL 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 terms of mg/Nm

3. 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/Nm3) by site and process step (new dataset).

Site Ore prep Calcination Milling Drying

Sulphate process 1 0 0.93 3.75 15.50 2 1 11 <5 25 3 17 <6 28.5 NA 4 3 42 <5 26 5 1 NA 13 NA 6 <30 <5 <20 <20 7 20 20 20 20 8 <10 NA <1 10 9 47 3 40 10 10 15 5 9.0 10.0 11 46 5 17.0 17.0 12 16 NA 12.2 32.5 13 7 4 22 9 Chloride Process 1 NA Max 21 Max 22 2 16 10 6 3 15 NA 17 4 NA <5 <5 5 1 4 4 Scenario limits Directive 50 50 50 50 BAT AEL 5-20 5-20 5-20 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 SO2 kg/t TiO2 (average) Sulphate kg/t TiO2 (average)

1 2.96 472

2 6.2 400 3 6.92 98

4 5.7 650

5 7 345

6 2 399

7 0.11 405

8 4.8 239

9 4 127

10 2.3 441

11 3.8 257

12 6.8 1030

13 0.9 136

Directive 10.00 800

BAT AEL 1.0-6.0 100-550

Table A5.8. Chlorine emissions to air and chloride emissions to water by site (chloride process plant only, new dataset).

Site Cl2 daily average 5mg/Nm

3

Cl2 <40 mg/Nm

3 at

any time

Chloride using natural rutile (kg/t)

Chloride using

synthetic rutile (kg/t)

Chloride using slag

(kg/t)

1 <5 Max 33 93 Not used

2 1 1 161

3 1 1 100.8

4 1 1 120 120

5 <1 <1 199

Directive <5 <40 130 228 450

BAT AEL 38-330 38-330 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 fabric filters in the TiO2 industry (emission rates in many cases are around 50 mg/Nm

3) seems not as

good as elsewhere (fabric filters typically achieve emission rates of 5 mg/Nm3 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 sites already achieving much lower emission rates than others, close to the figure of 5 mg/Nm

3. 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 fabric filters equivalent to €13,000 to 78,000 /m

3/s flow rate

30. Estimated flow rates calculated from

information given in the BREF regarding the dustiest stages (ore preparation and finishing) of TiO2 manufacture gives very broad ranges, 944 to 8,828 m

3/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

Cost (€/year) based on lower bound flow rate

Cost (€/year) based on upper bound flow rate

Chloride process 93,000 872,000

Sulphate process 79,000 744,000

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 SO 2 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

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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 of 800 mg/l (sulphate process with a reference volume of 50 m

3 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 water production of 50 m

3/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.

-

5,000

10,000

15,000

20,000

25,000

30,000

2001 2004

Chlo

ride e

mis

sio

n,

t/year

Duisburg Stallingborough Langerbrugge Rotterdam-Botlek

Figure A7.1. Changes in emissions of chloride to water for TiO2 plant, 2001-4, as reported by EPER


-

50

100

150

200

250

300

350

1 2

TO

C e

mis

sio

n,

t/year

Calais Rotterdam-Botlek

Figure A7.2. Changes in emissions of TOC to water for TiO2 plant, 2001-4, as reported by EPER

-

0.01

0.02

0.03

0.04

0.05

0.06

2001 2004

Ars

enic

em

issio

n, t/

year

Grimsby Calais Thann Rotterdam-Botlek

Figure A7.3. Changes in emissions of arsenic to water for TiO2 plant, 2001-4, as reported by EPER

-

0.005

0.010

0.015

0.020

0.025

0.030

2001 2004

Cadm

ium

em

issio

n,

t/year

Grimsby Calais

Figure A7.4. Changes in emissions of cadmium to water for TiO2 plant, 2001-4, as reported by EPER

-

5

10

15

20

25

30

Chro

miu

m e

mis

sio

n,

t/year

Duisburg Pori Grimsby

Calais Le Havre Fredrikstad

Nordenham Stallingborough Rotterdam-Botlek

Figure A7.5. Changes in emissions of chromium to water for TiO2 plant, 2001-4, as reported by EPER


-

0.2

0.4

0.6

0.8

1.0

1.2

1.4

2001 2004

Copper

em

issio

n,

t/year

Duisburg Grimsby Calais Fredrikstad

Figure A7.6. Changes in emissions of copper to water for TiO2 plant, 2001-4, as reported by EPER

-

0.005

0.010

0.015

0.020

0.025

2001 2004

Merc

ury

em

issio

n,

t/year

Duisburg Grimsby Fredrikstad

Figure A7.7. Changes in emissions of mercury to water for TiO2 plant, 2001-4, as reported by EPER

-

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

2001 2004

Nic

kel em

issio

n,

t/year

Duisburg Pori Grimsby Calais

Fredrikstad Rotterdam-Botlek Greatham Stallingborough

Figure A7.8 Changes in emissions of nickel to water for TiO2 plant, 2001-4, as reported by EPER

-

0.1

0.2

0.3

0.4

0.5

0.6

0.7

2001 2004

Lead e

mis

sio

n,

t/year

Duisburg Huelva Grimsby

Calais Rotterdam-Botlek Stallingborough

Figure A7.9. Changes in emissions of lead to water for TiO2 plant, 2001-4, as reported by EPER


-

2

4

6

8

10

12

14

16

18

20

2001 2004

Zin

c e

mis

sio

n,

t/year

Duisburg Pori Grimsby Calais

Thann Le Havre Fredrikstad Celje

Greatham Rotterdam-Botlek

Figure A7.10. Changes in emissions of zinc to water for TiO2 plant, 2001-4, as reported by EPER

-

1,000

2,000

3,000

4,000

5,000

6,000

7,000

8,000

9,000

10,000

2001 2004

CO

em

issio

n,

t/year

Greatham Stallingborough

Figure A7.11. Changes in emissions of CO to air for TiO2 plant, 2001-4, as reported by EPER

-

100,000

200,000

300,000

400,000

500,000

600,000

2001 2004

CO

2 e

mis

sio

n,

t/year

Nordenham Duisburg Greatham Le Havre Pori Huelva

Figure A7.12 Changes in emissions of CO2 to air for TiO2 plant, 2001-4, as reported by EPER

-

100

200

300

400

500

600

700

2001 2004

NO

x e

mis

sio

n,

t/year

Duisburg Uerdingen Pori Huelva

Figure A7.13. Changes in emissions of NOx to air for TiO2 plant, 2001-4, as reported by EPER


-

10

20

30

40

50

60

70

80

2001 2004

PM

10 e

mis

sio

n,

t/year

Pori

Figure A7.14. Changes in emissions of PM10 to air for TiO2 plant, 2001-4, as reported by EPER

-

200

400

600

800

1,000

1,200

1,400

1,600

1,800

2,000

2001 2004

SO

2 e

mis

sio

n,

t/year

Duisburg Uerdingen Pori Huelva

Leverkusen Grimsby Calais Thann

Le Havre Scarlino Fredrikstad 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 gasförmiger 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 gasförmiger 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 pre-weighed dry plane filter. The gain in weight of this paper and the volume sampled are used to determine the concentration in the duct. This standard is applicable to concentrations of below 50 mg m

-3 with special emphasis around

5 mg m-3

.


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 demonstrate compliance with emission limit values of below 50 mg m

-3. In addition calibration and on-

going 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 ISO 9096:2003 (20 mg m

-3) Stationary source emissions – Manual determination of mass

concentration of particulate matter This method is applicable in the range of 20 mg m

-3 to 1000 mg m

-3. 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 EN 13284-1 i.e. below 50 mg m

-3

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 range operation range is 0 to 740 mg m

-3. 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 of 0 -1300 mg

-3 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, non-dispersive 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.

Analysis of the Simplification of the Titanium Dioxide Directives

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