Priority-setting regarding offshore substances and preparations

Table of Content

List of abbreviations

1. Introduction
1.1 Background
1.2 Purpose
1.3 Organisation of the project

2. OSPAR regulation of offshore chemicals
2.1 Background
2.2 HOCNF
2.3 The CHARM model

3. Pre-screening of offshore chemicals
3.1 Procedures for pre-screening
3.1.1 Purpose
3.1.2 General procedure for pre-screening
3.1.3 Criteria for grouping of substances
3.1.4 Criteria for grouping of preparations
3.1.5 Final grouping of preparations
3.1.6 Example of grouping of a preparation
3.2 Data collection
3.3 Development of database
3.4 Results of the pre-screening
3.4.1 Substances
3.4.2 Preparations

4. Substitution of offshore chemicals
4.1 Criteria for substitution
4.1.1 Substitution criteria # 1: P3 for P1
4.1.2 Substitution criteria # 2: P2 for P1
4.1.3 Substitution criteria # 3: Different P1 preparations
4.2 Identification of possibilities of substitution
4.3 Evaluation of environmental hazards of preparations by CHARM
4.4 Comparison of preparations with the same technical function
4.5 Comparison of original and alternative preparations
4.6 Comparison of evaluation methods

5. Conclusions
5.1 Pre-screening procedures
5.2 Possibilities of substitution
5.3 Comparison of PROSPECT and CHARM

6. References

Appendix 1

Appendix 2 Data Collection

Appendix 3 Preparations grouped in category P1(E)

Appendix 4 Evaluation of two preparation groups by use of the principles of PROSPECT (Confidential)

List of abbreviations

1. Introduction

1.1 Background

The offshore industry uses a relatively large number of chemicals for the production of oil and gas, for transport through pipe-lines, for maintenance of installations and equipment, and in laboratories.

In the OSPAR area, about 1 million tons of offshore chemicals are used annually, covering a range from large volumes of more or less harmless chemicals to lower volumes of black-listed substances as e.g. heavy metals and halogenated organics. The knowledge on the contents of the chemicals and their environmental and occupational hazards was at the start of the project very limited. Moreover, it is the general policy of the Danish Environmental Protection Agency (EPA) and the Danish Energy Agency (DEA) that industrial use of chemicals should be evaluated with the purpose of identifying possibilities for substituting hazardous chemicals with less hazardous chemicals.

Therefore, the Danish EPA initiated the present project in 1994.

1.2 Purpose

The objective of the project is to establish principles and knowledge for evaluation and prioritisation of offshore chemicals regarding their risks to environment and human health in order to identify candidates for substitution.

The objective is obtained by accomplishment of the following activities:

	establishment of a database on offshore chemicals including composition, use pattern and the physico-chemical, human health and environmental properties of preparations and substances contained herein
	development of criteria for pre-screening of offshore chemicals
	development of criteria for substitution evaluation of offshore chemicals

1.3 Organisation of the project

The project was prepared in co-operation between the Danish Environmental Protection Agency, the Danish Energy Agency, the North Sea Operators Committee, Denmark (NSOC-D), the Danish Products Registration Office and a project group.

Steering group

A steering group followed and guided the project. Members of the steering group were:

Eva Lise Bendixen, Danish EPA (chairman)
Peter Györkös, Danish EPA
Lone Schou, Danish EPA (until 31 December 1997)
Hanneke Tibosch, Danish EPA (until 31 March 1996)
Søren Strange, Danish Energy Agency (until 31 March 1997)
Hans Erik Christensen, Danish Energy Agency (from 1 April 1997)
Graca Gosk, Danish Products Registration Office
John Douglas Petersen, NSOC-D (observer - until 30 November 1997)
Mike Robson, NSOC-D (observer)
Lisbeth Mygind, DTC
Anders Schmidt, dk-TEKNIK
Preben Kristensen, VKI (until 30 April 1997)
Finn Pedersen, VKI

Project group

The project group consisted of VKI, dk-TEKNIK, DTC Danish Toxicology Centre and the Danish EPA. The criteria for pre-screening of offshore chemicals were developed by the project group. VKI has been responsible for the development of the PROSPECT database, the testing of the pre-screening criteria, the ecotoxicological evaluation of the chemicals a.o. via the CHARM model. dk-TEKNIK and DTC have been responsible for the evaluation of human toxicology. The Danish EPA has been responsible for the contact to NSOC-D and the suppliers, for the collection of data on the offshore chemicals and entering data into the database. Finally, VKI has prepared the report and co-ordinated the project.

Members of the project group were Finn Pedersen (VKI), Axel Damborg (VKI), Preben Kristensen (VKI), Arne Hurup Nielsen (VKI), Dorte Rasmussen (VKI), Anders Schmidt (dk-TEKNIK), Lisbeth Mygind (DTC) and Hanneke Tibosch (Danish EPA).

2. OSPAR regulation of offshore chemicals

2.1 Background

At the Third International Conference on the protection of the North Sea (the Hague 1990), the ministers of the North Sea States requested the Paris Commission to develop and adopt a harmonised mandatory control system for the discharge and use of chemicals offshore. This was further confirmed by the ministers at the first ministerial meeting of the Oslo and Paris Commissions (Paris 1992) who agreed upon an action plan which among other things called for a reduction of the discharge of noxious chemicals taking into account the best environmental practice. In order to fulfil these requirements, two main activities were initiated: the development of a Harmonised Offshore Chemicals Notification Format (HOCNF), and the development of a Chemical Hazard Assessment and Risk Management model (the CHARM model). In 1996, the Paris Commission agreed on PARCOM Decision 96/3 on the use and discharge of offshore chemicals, which prescribes a pre-screening step and encompasses the use of HOCNF and the CHARM model or similar models.

The present project is intended to build upon and support these initiatives and they are therefore described briefly below. For detailed information please refer to the references cited. It should be noted that, at the initiation of the project, there was a general lack of knowledge on the chemicals used offshore. Today, it is mandatory that operators must supply information to the competent authorities before use.

2.2 HOCNF

In order to harmonise the data that are to be submitted to the different national authorities responsible for the environment of the North Sea, PARCOM has prepared the Harmonised Offshore Chemicals Notification Format 1995 (HOCNF). In this format, data must be submitted on general aspects (e.g. supplier, use, discharge, composition, hazard labelling, physico-chemical properties) and on ecotoxicological properties (e.g. log P_ow, bioconcentration and biodegradability of the deliberately added substances, and aquatic and sediment toxicity of the preparation).

2.3 The CHARM model

In 1992, Norway and the Netherlands initiated a common project on development of a model (the CHARM model) for environmental hazard assessment and risk management of offshore chemicals. The project was carried out by TNO (the Netherlands) and Aquateam (Norway). The model is intended to be used as a tool for the harmonised regulation of the use of chemicals in the offshore industry in the North Sea.

The CHARM model, version 3, is described in Karman et al. (1996) and Karman & Vik (1996). The basic principle of the hazard assessment part of the model is that it calculates the discharge of an offshore chemical and the resulting Predicted Environmental Concentrations (PECs) in different environmental compartments. The PEC is then compared with a predicted No-Effect-Concentration (PNEC) thus establishing the PEC:PNEC ratio (Hazard Quotient) for each of the environmental compartments considered. The hazard assessment, which is in fact a generic risk assessment, is conducted in a scenario with a standard platform.

A pre-screening module, which is relatively vaguely developed, is included in the CHARM model. The model finally includes a local risk assessment module in which a user-defined scenario is applied and a risk management module. The Danish EPA intends to use the CHARM hazard assessment/generic risk assessment module except in special cases, in which for instance a local site assessment would imply a stricter regulation than the generic risk assessment.

3. Pre-screening of offshore chemicals

3.1 Procedures for pre-screening

In this chapter, the procedures developed for pre-screening of offshore chemicals are described.

3.1.1 Purpose

The purpose of the pre-screening is to divide the offshore chemicals into three groups. The three groups are defined as:

	Group 1. Chemicals having an unacceptable impact on the environment or on human health and which should therefore be considered for phasing out or substitution
	Group 2. Chemicals that may have a deleterious impact on the environment or on human health and which should therefore be further evaluated (e.g. by using the CHARM-model or other suitable procedures)
	Group 3. Chemicals that are considered to be of low hazard to the environment and to human health. The chemicals in this group are regarded as acceptable alternatives for chemicals that should be phased out (group 1 chemicals

3.1.2 General procedure for pre-screening

The PROSPECT pre-screening process is a stepwise procedure with focus on the environmental and occupational health aspects. The pre-screening is based solely on the inherent properties of the chemicals.

The primary information used is the classification of the substances and preparations regarding physico-chemical, human health and environmental hazards. Throughout the present report, the definition of preparations specified in the EU Classification Directive (67/548/EEC) applies, i.e. "preparations" means mixtures or solutions composed of two or more substances.

No criteria for classifying preparations with regard to environmental hazards are yet implemented and therefore, the hazards of the individual substances in the preparations are considered. The evaluation of the occupational health hazards is based on the human health hazard classification of the preparations. The classification of the preparations is based on the human health hazards (classification) of the individual substances in the preparations. Suppliers of chemical preparations are responsible for their correct classification.

An offshore chemical is usually composed of several different substances. These substances cannot be expected to distribute similarly in the environment and to have the same effects on the organisms. Therefore, the first step in the procedure is to evaluate the individual substances in the chemical. Substances are evaluated according to environmental criteria only and are placed in one of the following groups:

	Group S1
	Group S2
	Group S3

Substances that cannot be evaluated because of shortage of data, are placed on a waiting list. If more data on environmental hazards become available, the substances on the waiting list may be evaluated further.

The environmental hazards of preparations are evaluated according to the content of hazardous substances in the preparation. The preparation is placed in one of the following groups:

	Group P1 (E)
	Group P2 (E)
	Group P3 (E)

Waiting list

Preparations that cannot be evaluated because of shortage of data on the environmental properties of the individual substances, will be placed on a waiting list. If more data on their environmental hazards are obtained, the preparations may be evaluated further.

The occupational health hazards are also considered in the evaluation of preparations for substitution possibilities, resulting in the final placement in one of the following groups:

	Group P1 (H)
	Group P2 (H)
	Group P3 (H)

3.1.3 Criteria for grouping of substances

The criteria are based on information on the inclusion of the substances in a high priority list and on the inherent properties of the substances as expressed by the EU hazard classification system regarding the aquatic environment.

Substances belonging to group S1 are those included in high priority lists of very hazardous substances or those which are considered very hazardous to the aquatic environment according to their inherent properties. Substances fulfilling one of the criteria below should be considered for phasing out from actual use in offshore activities.

	Substances included in high priority lists of very hazardous substances (e.g. the EU list I, North Sea list 1A, Esbjerg declaration list, Helsinki Commission and Convention lists, cf. Appendix 1, Danish EPA’s List of Undesirable Substances).
	Substances classified as dangerous to the aquatic environment and assigned one of the following risk phrases (cf. Annex I to Directive 67/578/EEC):
	R50 (very toxic to aquatic organisms)
	R50/R53 (very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment)

or which according to the formal criteria for environmental hazard classification (cf. Annex VI to Directive 67/548/EEC (EC 1996)) should be assigned one of these risk phrases.

Substances that are considered to be of low hazard to the aquatic environment according to information on their inherent properties, are placed in group S3 according to either of the following criteria:

	Substances that according to the criteria for environmental hazard classification shall not be classified as dangerous to the aquatic environment.
	Substances on the list of substances/preparations used and discharged offshore (PARCOM offshore list A).

Placement of substances in group S2

Substances, for which available data indicate that they do not belong to either group S1 or group S3, are placed in group S2.

Substances for which sufficient information on inherent environmental properties is not available, are placed on a waiting list. Additional data must be obtained before a further evaluation and grouping can take place.

3.1.4 Criteria for grouping of preparations

Preparations are grouped into one of 3 groups during a two step procedure comprising an evaluation of their environmental hazards and an evaluation of their occupational health hazards. The specific criteria for grouping of the preparations are outlined below.

Placement of preparations in group P1(E)

Preparations are placed in group P1(E) according to the criterion below. These preparations are regarded as very harmful to the aquatic environment.

Preparations containing one or more group S1 substances

Placement of preparations in group P3(E)

Preparations fulfilling the below criterion are placed in group P3(E). These preparations are considered to be of low hazard to the aquatic environment.

Preparations only containing group S3(E) substances

Placement of preparations in group P2(E)

Preparations, for which data on environmental hazards indicate that they do not belong to either group P1(E) or P3(E), are placed in group P2(E).

Placement of preparations on a waiting list

Preparations that cannot be evaluated because of lack of data on one or more of the substances contained therein, are placed on a waiting list until enough relevant data are obtained.

Placement of preparations in group P1(H)

Preparations belonging to group P1(H) are those which are considered very hazardous to human health according to their inherent properties. Preparations fulfilling one of the criteria below should be considered for inclusion in group P1(H).

Preparations that have chronic or severe occupational health effects according to the EU classification system (EC 1996). The following classification/labelling applies:
Carcinogenic:	T;R45 or R49 or Xn;R40
Reproduction toxic:	T;R60 or R61 or Xn;R62 or R63
Mutagenic:	T;R46 or Xn;R40
Acutely toxic effects:	Tx;R26 or R27 or R28 or R39
T; R23 or R24 or R25 or R39 or R48

Placement of preparations in group P3(H)

Preparations fulfilling the below criterion are placed in group P3(H). These preparations are considered to be of low hazard to human health.

Preparations that according to the criteria for human health hazard classification shall not be classified as dangerous.

Placement of preparations in group P2(H)

Preparations, for which data on human toxicity indicate that they do not belong to either group P1(H) or P3(H), are placed in group P2(H).

For human health effects, this means that preparations that are or should be classified with the following risk phrases are placed in group P2(H):

3.1.5 Final grouping of preparations

The final grouping of preparations is based on a balancing of the environmental hazards with the occupational health hazards. In this assessment, possible precautions to be made to protect humans to exposure of the substance or preparation are included.

In general, the most severe grouping of the preparation will be decisive for the balanced placement of the preparation in one of the groups P1, P2 or P3. For example, a preparation grouped as P1(E) and P3(H) will be placed in group P1. However, considering that many preparations cannot be grouped on the basis of the environmental hazard criteria and therefore are placed on a waiting list, such preparations need to be handled separately. If a waiting list preparation is grouped in P1(H), it will be grouped as P1. If it is grouped in P2(H), it will be preliminarily grouped in a special group P2* in order to indicate that when more data on environmental properties become available, a more severe grouping may be necessary. Finally, if the waiting list preparation is grouped in P3(H), it is retained on a waiting list until more data become available. An overview of this grouping system is given in Table 3.1.

3.1.6 Example of grouping of a preparation

In order to illustrate the basic principles for grouping of preparations, the evaluation of a theoretical corrosion inhibitor is described. The theoretical composition of the preparation is given in Table 3.2 below:

Ethylene glycol

Ethylene glycol is readily biodegradable, has a log P_ow of about 0 although a bioconcentration factor of 190 has been determined with algae, and has a very low toxicity (LC50 > 1000 mg/l) towards aquatic organisms. The substance shall not be classified as dangerous for the aquatic environment and consequently, it is placed in group S3.

Tall oil

Tall oil is readily biodegradable, has a log P_ow of 0.3-5.5 and is therefore potentially bioaccumulative, and has a very low toxicity (LC50 > 1000 mg/l) towards aquatic organisms. The substance shall not be classified as dangerous for the aquatic environment and consequently, it is placed in group S3.

Hydrotreated light petroleum distillates are not readily biodegradable, are potentially bioaccumulative with a log P_ow of 1.5-5.7, and are toxic to various fish species with LC50 values in the range 2.4-5.9 mg/l. The data correspond to an environmental hazard classification of N; R51/53 (toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment) and the substance is therefore grouped in S2.

NPEO

Nonylphenol ethoxylate is not readily biodegradable and have acute toxicities towards various aquatic organisms in the range 1-1000 mg/l. The data correspond to an environmental hazard classification of N; R51/53 (toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment) and the substance should therefore be grouped in S2. However, because of the hormone-like effects of the substance, it is included in the Esbjerg Declaration list of substances that shall be substituted by less hazardous substances. It is therefore grouped in S1.

As the preparation contains a S1 substance, namely nonylphenol ethoxylate, it is placed in preparation group P1(E) covering chemicals that should be considered for phasing out or substitution.

Human health effects

Hydrotreated light petroleum distillates are classified as Xn;R65 (Harmful: may cause lung damage if swallowed). None of the other substances should be classified regarding human health hazards. As the kinematic viscosity of the preparation is probably above 7 mm²/sec, the preparation shall not be classified as dangerous to the human health. The preparation is therefore placed in group P3 (H).

Because of the placement in group P1(E), the final grouping will be P1.

3.2 Data collection

Data on offshore chemicals used in the Danish sector of the North Sea were obtained from the suppliers via the NSOC-D and from the Danish Products Registration Office. In general, the data from the suppliers were submitted in the HOCNF but very often additional information on composition as well as on the properties of the chemicals was requested because the submitted data were incomplete.

Additional information on the ecotoxicological properties of the substances contained in the offshore chemicals was collected from a few relatively easily available data sources. A list of the data sources is given in Table 3.3 and additional data sources are listed in Appendix 2:

3.3 Development of database

The PROSPECT database was established in order to facilitate the data handling. The database system was developed in the database program Paradox.

An overview of the structure of the PROSPECT database is given in Figure 3.1.

A User Manual has been prepared in which the facilities of the program are described.

The database contains confidential information on formulation of offshore chemicals and is therefore not available to the public but only for the Danish EPA and the Danish Products Registration Office. For further information, please contact the Danish EPA.

3.4 Results of the pre-screening

In total, 273 offshore preparations containing 306 substances were evaluated by use of the pre-screening criteria described in Section 3.1.

3.4.1 Substances

The pre-screening was initiated by evaluating the environmental properties of the individual substances present in the offshore preparations. The number of substances grouped into the 4 categories (S1, S2, S3, WL) according to the above criteria regarding hazard to the aquatic environment is shown in Table 3.4.

Category S1

24 substances have been grouped into category S1:

	13 of the 24 substances are proposed to be classified with the risk phases N;R50 or N;R50/53 with regard to environmental danger
	8 of the 24 substances are on the Esbjerg declaration lists on substances to be phased out (alkylphenol or alkylphenol ethoxylates which shall probably be classified with N;R51/53 but which are additionally suspected to have estrogen-like effects on reproduction)
	3 of the 24 substances are on the EU list I although they should be classified with N;R51/53, R52/53 and not classified with regard to environmental danger, respectively, according to the formal criteria for environmental hazard classification (EC 1996).

Category S2

31 substances were grouped into S2:

	12 of the 31 are proposed to be classified with N;R51/53 with regard to environmental danger
	17 of the 31 substances are proposed to be classified with R52/53 with regard to environmental danger
	2 of the 31 substances are proposed to be classified with R53 with regard to environmental danger

Substance waiting list

For a relatively large proportion of the substances (40 %), an evaluation was not possible due to lack of data on one or more of the properties. However, as only a few relatively easily available data sources were consulted, a more thorough data collection would probably move several of the substances on the WL into one of the 3 categories S1, S2 or S3. It was, however, not the intention of the project to make a thorough data collection on ecotoxicological properties of all chemicals identified in offshore preparations.

3.4.2 Preparations

Based on the grouping of the substances into the 4 categories, the preparations were grouped according to the criteria regarding hazard to the aquatic environment (cf. Section 3.1.4). Based on their health hazard classification, the preparations were also grouped according to the criteria specified in Section 3.1.4. An overview of the grouping of the preparations is given in Table 3.5.

Based on this grouping, the final placement of each preparation is made according to the criteria described in Section 3.1.5, i.e. the most severe category determines the grouping. When a preparation is placed in P2 due to health criteria, but WL due to lack of data on environmental properties, it is placed in P2* to indicate that new data on environmental properties might result in a severe grouping. The resulting final placement is shown in Table 3.6 in which also the reason for the grouping is shown.

P2*: Substances assigned P2 (health) and WL (environment)

Despite the relatively large number of substances that could not be grouped regarding environmental hazard due to lack of data (40%), most of the preparations (240 corresponding to 88%) could be assigned a category. Of these, however, 33 (12%) were preliminarily placed in P2* based solely on human health hazards as no sufficient data on environmental hazards were available. For 32 preparations (12%), the hazard to the environment was decisive for the placement, for 114 preparations (42%), the human health hazards were decisive, and for 94 preparations (34%), both environmental and human health properties were decisive. These aspects are described in more detail below.

It follows from the above Table 3.6 that 35 preparations (13%) are placed in the most severe group (P1). The health hazard classification was only decisive for grouping of 7 of those chemicals.

Category P1

Of the 28 preparations grouped in category P1 due to environmental hazards, 20 preparations contain substances that are grouped into S1 because they should be classified with N;R50 or N;R50/53, 11 contain substances covered by the Esbjerg declaration, and 2 contain substances included in the EU list I. Note that some of the preparations contain more than one substance from S1.

13 preparations are grouped in P1 due to health hazards. One is to be classified with R45 (carcinogenic), 5 are classified R40 (carcinogenic or mutagenic) and 9 are classified with R23, R24, R25, R48 or combinations thereof (acutely toxic).

A list of the P1 preparations and information on the reason for the placing in group P1 are given in Appendix 3.

In principle, all P1 preparations should be subjects for phasing out plans. However, if a prioritisation is necessary, it should be based upon a more precise assessment of the risks to human health and the environment.

The human health risk assessment should combine the above hazard (effect) assessment and an exposure assessment. The latter should focus on the actual offshore use of the preparation, i.e. an assessment of the volume used, the risk of contact with the preparation, how a contact will take place, etc.

The environmental risk assessment could be an initial one where both the content of S1 substances in the preparation and the volume used could be taken into account. The content of S1 substances varies between the preparations from less than 1% to substantial amounts (more than 30-50%) and for one preparation 100% (zinc oxide). No information was collected on the volume used in the offshore industry of the category P1 preparations.

Category P2 and P2*

129 preparations corresponding to 48% of the preparations are placed in P2 and P2*. Of these, 33 are preliminarily grouped in P2* as only sufficient data on human health hazards are available. Only 22 preparations are included in P2 and P2* due to environmental hazards. 11 preparations contain substances proposed to be classified with N;R51/53 in amounts from 10 to 100%, and 11 preparations contain substances proposed to be classified with R52/53 or R53 in amounts from 16 to 100%.

119 preparations are grouped in P2 and P2* due to human health hazards (incl. 12 preparations that are also P2 due to environmental hazards). The classification of these are shown in Table 3.7 below. A relatively large number of these are classified due to more than one human health hazard. These preparations are represented more than once in Table 3.7.

It is evident that many of the preparations used offshore are corrosive and/or irritating as many are acids or bases.

4. Substitution of offshore chemicals

4.1 Criteria for substitution

For preparations that required to be phased out (P1 preparations), two possibilities are available:

1. reformulation of the preparation to eliminate the undesirable substances or properties giving rise to the P1 grouping, or
2. substitution by an existing alternative preparation.

Alternative preparations discussed in this chapter comprise both of these possibilities. For the evaluation of possibilities of substitution, three sets of criteria are proposed.

4.1.1 Substitution criteria # 1: P3 for P1

The highest priority is given to possibilities of replacing P1 preparations by P3 preparations which are regarded to be of low risks to the environment and to human health.

4.1.2 Substitution criteria # 2: P2 for P1

If substitution criteria # 1 cannot be fulfilled, the replacement of P1 preparations by P2 preparations should be considered. In most cases, P2 preparations will be better than P1. However, if the use of higher volumes is necessary, the improvement must be evaluated further. For preparations placed in P2(E) (due to environmental hazards), the evaluation should be confirmed by e.g. the CHARM model (when possible), because the model also includes the volumes used. For preparations placed in P2 (due to occupational health hazards), the use and handling should be evaluated further.

4.1.3 Substitution criteria # 3: Different P1 preparations

If neither P3 nor P2 preparations with the same technical properties can be found, it might for a limited period of time be acceptable to choose between different P1 preparations. Preparations are placed in group P1 due to a content of S1 substances (environmental properties)(resulting in the placement in P1(E)) and/or a classification regarding health hazards (resulting in the placement in P1(H)). It is not possible to deem one of the two hazards (to environment or health) as worse than the other. This will under any circumstances depend on a concrete assessment of the actual hazards. However, within each of the two types of hazards a ranking may be possible. The following criteria for these two considerations are proposed:

Environmental properties

The S1 substances in each of the P1(E) preparations are evaluated and the potential new preparation may be preferred if the following criteria for improvement are fulfilled:

The environmental performance is improved with respect to the following properties:

	acute toxicity: The sum of the toxic units1 in the alternative preparation is > 10 times less than in the original preparation
	bioaccumulation: The sum of the bioaccumulative units2 in the alternative preparation is 1 unit lower than in the original preparation
	biodegradation: The amount of readily biodegradable substances is greater in the alternative preparation than in the original preparation

CHARM evaluation

When it is possible to conduct a CHARM evaluation: The risk quotient of the alternative preparation is > 10 times lower than the risk quotient of the original preparation. When a CHARM evaluation is not possible, the percentage of the S1 substances in the preparation(s) must not increase.

To discriminate between different preparations, at least one of the above parameters should be fulfilled and none should be worse.

Occupational health (P1)

For comparing P1 preparations according to occupational health hazards, the following criteria for evaluation are proposed:

	Long-term effects (carcinogenecity, reproduction toxicity, mutagenicity) are worse than short-term toxicity (very toxic, toxic, acutely toxic) and imminent hazards (E, Fx, O)
	Carcinogenicity is worse than mutagenicity
	Toxicity: Tx is worse than T

At least one of the above parameters should be fulfilled and none of them should be worse.

Evaluation of preparations

As a minimum for deeming one preparation better than another, this preparation must be improved with regard to one of the environmental hazard properties or to one of the occupational health hazard properties. This assessment include the possibility of introducing technical measures to avoid human exposure to the preparation.

4.2 Identification of possibilities of substitution

In order to identify possibilities of substitution, the function of each of the preparations was identified. The function groups are those defined by OSPAR for reporting on offshore chemicals discharges, and it is important to bear in mind that preparations in the same function group may not necessarily be interchangeable, since a preparation may have been developed for specific use in one particular situation, or for use together with a suite of other preparations from the same supplier. The function groups are rather ambiguous and also overlap.

For function groups, in which relatively many different preparations from different preparation hazard categories are present, the number of preparations from each of the categories are shown in Table 4.1. Preparations from other function groups, in which no direct possibilities for substitution considerations are seen, are not included.

The above grouping of preparations describes the main technical functions, which may be further subdivided depending on the specific technical function of each of the preparations. It is not within the frame of the present project to make a detailed assessment of actual possibilities for substitution. This will require a detailed technical knowledge that is only available among operators and suppliers. In stead, the basic principle of substitution considerations are presented.

It is, however, obvious from the above table that for some of the function groups, preparations of different hazard (i.e. from different categories) are used. Especially for the function groups Nos. 5, 19, 27, 33 and 35, it seems obvious that the technical possibilities of substituting P1 and/or P2 preparations with P3 preparations should be further evaluated.

4.3 Evaluation of environmental hazards of preparations by CHARM

In order to demonstrate the principles for comparing preparations from the different categories, a generic environmental risk assessment was performed using the hazard assessment module in the CHARM model (Karman et al. 1996, Karman & Vik 1996). As examples, the environmental hazard of offshore chemicals with the same main technical function, but placed in different preparation categories (P1(E), P2(E) or P3(E)), is compared (cf. Section 4.4). Also the environmental hazard of alternative offshore chemicals that have already replaced chemicals considered more hazardous, was compared with the environmental hazard of the chemicals originally used (cf. Section 4.5).

Although the CHARM model is proposed to be used for evaluation of both offshore preparations and offshore substances, the basic principles in the model for estimating emission to the aquatic environment and the subsequent distribution between environmental compartments (i.e. the PEC estimate) and for estimating the PNEC are based on the international experience gained by evaluating single substances. This means that the use of preparation data on toxicity in the CHARM model is in principle not scientifically valid as for instance toxicity data related to preparations cannot be compared to exposure data for substances. As a trial, the CHARM model was, however, run also with preparation data.

In general, no information on the typical amounts of the chemicals used was available and consequently, it is not possible to estimate the PECs for the chemicals. Instead, a so-called "critical dosage" was estimated for each chemical. The "critical dosage" is defined as the dosage of the preparation resulting in the PEC of the most critical substance equalling the PNEC of the substance for the most critical of the environmental compartments included in the CHARM model, i.e. water phase, sediment and biota. Thus, if a dosage greater than the critical dosage is used, the estimated PEC will - at least in the most critical compartment - be higher than the PNEC. The critical dosage is estimated for each of the preparations based on preparation data or on the basis of data on the most critical substance, respectively.

4.4 Comparison of preparations with the same technical function

The comparison of preparations with the same main technical function was prepared by use of the CHARM model although they in practice may not be directly exchangeable. Each of the function groups 19 (gelling agents) and 35 (well stimulation fluids) contains a relatively high number of different preparations and among them both P1(E), P2(E) and P3(E) preparations. Obviously, the technical possibilities of replacing P1(E) and P2(E) preparations with P3(E) preparations should therefore be evaluated. Only the environmental hazards of the preparations are compared here and the actual technical possibilities for substitution are not considered.

In general, no comparison based on the preparations data could be performed as sufficient data are only available for 2 out of 21 gelling agents and 3 out of 28 well stimulation fluids. Therefore, only comparisons based on the most critical substances in the preparations are discussed and evaluated. More detailed results of the comparisons are presented in Appendix 4. An overview of the results based on the most critical substances is given below.

3 of the gelling agents are placed in group P1(E). One because it contains an EU list I substance, and two because they contain a substance on the Esbjerg Declaration list. The critical dosages of the preparations based on the most critical substances are very different ranging from 0.0001 mg/l for two of the preparations to 226 mg/l (cf. Appendix 3). However, neither the list I substance nor the substances on the Esbjerg Declaration list are the most critical substances in the preparation. This is probably due to a combination of the content of the substances in the preparations, the estimated emission with the produced water, the fate in the aquatic environment and the intrinsic ecotoxicological properties. It should moreover be mentioned that the EU list I substance is not very toxic and the present inclusion in the EU list I might be reconsidered by the European Commission.

3 gelling agents are placed in group P2(E). The critical dosages range from 0.25 mg/l to 25 mg/l. Finally, the 15 preparations, which are grouped in P3, have critical dosages ranging from 1.4 to 1000 mg/l.

Of the well stimulation fluids, 3 are placed in group P1(E) and the estimated critical dosages range from 0.08 mg/l for two preparations to 18000 mg/l for the last preparation. The reason for this great difference is that the latter contains a substance on the Esbjerg Declaration list. As no toxicity data are available on this substance, it is not taken into account in the calculation of the critical dosage.

5 preparations are placed in group P2(E) with estimated levels of critical dosages ranging from 0.00003 mg/l (for two preparations) to 30 mg/l. 20 preparations are placed in group P3(E) and the estimated critical dosages for these preparations range from 7.7 to 10000 mg/l.

The comparison is hampered by lack of data on the environmental properties of both the preparations and the substances contained in the preparations. When data on the most hazardous of the substances in a preparation are missing, the critical dosage is estimated for one of the less hazardous substances, which will most likely result in an overestimation of the critical dosage and thus an underestimation of the hazard. It should, moreover, be noted that the substance with the most hazardous intrinsic ecotoxicological properties does not necessarily need to be the most critical substance. If the most hazardous substance is used in the preparation in a low concentration or if it is retained in the oil phase due to its lipophilic properties and therefore not discharged to the environment with the produced water, another substance that is used in a higher concentration in the preparation or is more water soluble may be the most critical substance.

4.5 Comparison of original and alternative preparations

7 pairs of original and alternative preparations were evaluated covering corrosion inhibitors, gelling agents, defoamers and well stimulation fluids. The comparison was made applying both the PROSPECT environmental pre-screening method, the total content of toxic and bioaccumulative substances in the preparations (toxic units and bioaccumulative units, respectively) and the modified CHARM generic risk assessment model (calculation of critical dosage). The evaluation by use of the CHARM model is described in more details in Rasmussen & Pedersen (1997).

An overview of the results of the evaluation exercise is presented in Table 4.2. For some of the substances in the preparations, basic data are missing and consequently, the estimated critical dosage of the substance is not necessarily referring to the most critical substance. The grouping of the substances for which data are missing, is shown in the table as well.

PROSPECT pre-screening

Only for two of the preparation pairs, it was possible to compare the PROSPECT environmental pre-screening grouping of the original preparation with the grouping of the alternative preparation. For these two preparation pairs, it is seen that none of the alternatives can be evaluated as less hazardous than the original preparation as one P1(E) preparation is used in stead of another P1(E) preparation. For the remaining substitutions, all of the alternative preparations are placed on the waiting list due to lack of data of the inherent properties of the constituents, and the possible improvement of the environmental performance can therefore not be evaluated.

Comparison based on TU

The content of toxic substances, defined as the sum of the toxic units (S TU), were estimated for all substances contained in the preparations with an estimated PNEC < 0.1 mg/l. As seen in Table 4.2, only for one of the alternative preparations the S TU is lower than for the original preparation. For 3 of the remaining 6 preparations, the S TU of the alternative preparation is equal to the original, and for the other 3 preparations the S TU of the alternative is greater than of the original. Thus, in general the content of toxic substances in the alternative preparations is greater than or equal to the content in the original preparations and the alternatives can therefore not be regarded to have a better environmental performance than the original preparations. However, for most of the preparations data are lacking for some of the substances contained therein which hampers the comparison.

Comparison based on BU

Similarly, the content of bioaccumulative substances, defined as the sum of the bioaccumulative units (S BU), were estimated for all substances with a log P_ow > 3. Only for two of the alternative preparations, the S BU was reduced compared to the original preparations. For 4 of the preparations, the S BU was increased. As for the content of toxic substances, the alternative preparations do not seem to have a better environmental performance than the original.

Results of comparison of offshore preparations (p) and alternative preparations (a)

n.a. Not available due to lack of data.

The comparison by use of the CHARM generic risk assessment model based on preparation data was only possible for 3 pairs of preparations. For the remaining preparations, the estimates of the critical dose for one or both of the preparations could not be performed due to lack of data. 2 of the comparisons showed that the critical dosage for the alternative preparation was considerably higher than for the original preparation and therefore, the alternative preparation may be considered less hazardous for the environment than the original preparation. However, none of these two alternatives can be evaluated thoroughly as data for some of the substances are missing. Therefore, the critical dosage might have been lower. However, this is also the case for the original preparations. For one pair of preparations, the critical dosage for the alternative was lower than for the original and the alternative preparation is therefore considered more hazardous than the original preparation. Both of these preparations are grouped as P1 preparations and for both, data are missing for some of the substances.

CHARM - substance data

When the comparison by use of the CHARM model was based on data on the most hazardous of the substances in the preparations that could be evaluated and assigned to one of the groups (S1, S2, S3), the comparison could be made for 5 of the pairs of preparations. One of the comparisons showed that the alternative was considerably less hazardous than the original, 2 showed that the alternatives were slightly less hazardous (but probably not significantly), 1 showed that the alternative was slightly more hazardous, and 1 showed no difference between the 2 preparations.

For only 3 pairs of preparations, the comparison using the CHARM model could be prepared on both preparation and substance data. 2 of the comparisons showed the same result, namely that the alternative preparation was less hazardous than the original preparation, while the remaining comparison showed no difference when it was based on the critical component, but when the preparation data was used the alternative was evaluated as more hazardous than the original preparation.

For all preparations but Optiflo AP, data are missing for some of the substances. If one of these substances is the critical substance of the preparation, the estimated critical dosage will be too high. For three of the preparations, substance data are missing for S1-substances, which may be the critical substances of the preparation.

Lack of data

It should, however, be noted that only for one of the preparations, sufficient data on all of the substances were available so they could be grouped correctly into one of the 3 substance groups. This has almost certainly influenced the results of the comparisons of the preparations and the most hazardous substances.

Based on the above comparison it must be concluded that, despite the thorough search for data on the ingredients in the offshore chemicals, the comparison is hampered by a lack of data on the ecotoxicological properties of the substances contained in the preparations as well as of the preparations themselves.

4.6 Comparison of evaluation methods

In the above Section 4.5, 7 pairs of original and alternative preparations were compared by use of 5 different evaluation methods (PROSPECT environmental pre-screening, sum of toxic units, sum of bioaccumulative units, CHARM generic risk assessment of preparations and of substances). In the present section, the results obtained by the various methods are compared. An overview of the results is given in Table 4.3.

n.a. Comparison result not available, - alternative more hazardous than original, + alternative less hazardous than original, ~ no difference between original and alternative.

In general, only for two preparation pairs the different methods resulted in the same conclusions regarding the comparison of original and alternative preparations. This was the case for the two HAI preparations and the two J preparations for which the substitutions were evaluated to result in an improvement of the environmental performance and no significant change, respectively. For the remaining preparation pairs, the various evaluation methods gave different results.

As mentioned above the lack of data seriously hampers the comparison both of the individual pairs of preparations and also of the various evaluation methods. However, it should also be considered that the PROSPECT evaluation methods (environmental pre-screening and toxic and bioaccumulative units) are based upon the inherent properties of the individual substances contained in the preparations, while the CHARM method is based on a generic risk assessment where both the potential emission to the aquatic environment and the resulting effects are taken into account. Especially, the log P_ow of the substances is an important parameter as substances with a high log P_ow result in a high S BU, but on the same time, the CHARM model estimates these to be more or less retained in the oil phase and therefore, only a limited amount of the substances is estimated to be emitted with the produced water.

Thus, as the PROSPECT and CHARM methods are applying different approaches, different results of the evaluations may be expected. On the one hand it is tempting to use the CHARM generic risk assessment method, despite its conceptual limitations as previously discussed, as it intents to simulate the actual use and emission pattern - at least for production chemicals. On the other hand there is no evaluation of the potential hazards of the part of the chemicals that remains in the oil phase and might be emitted later in the life-cycle of the oil. Moreover, in general the CHARM model does not take into account the biodegradability of the substances in the preparations (only in estimating concentrations in the sediment compartment). Thus, the CHARM model can not be used directly for prioritising the substances with the highest intrinsic hazard.

1 Toxic unit (TU) is a quantitative measure for the content of toxic substances in a preparation or in a waste water. The following definition of the sum of TU is used in the present work:

C_i is the content of substance i in the preparation

PNEC_i is the Predicted No Effect Concentration for substance i in the aquatic environment. Only substances with PNEC_i < 0.1 mg/l are included.

2 Bioaccumulative unit (BU) is a quantitative measure of the content of bioaccumulative substances in a preparation or in a waste water. The following definition of the sum of BU has been used in this project:

log P_ow is the logarithm to the octanol-water partition coefficient. Only substances with log P_ow > 3 are included.

5. Conclusions

5.1 Pre-screening procedures

The pre-screening procedures developed in the present project are based on an evaluation of the intrinsic environmental and occupational health hazards of the individual substances present in the preparations and on the placement of these substances on lists of hazardous substances that are subject to phasing-out or cleaner technology considerations. The pre-screening procedure with regard to the environmental hazards does not take into account the amount of the substances used, the relative content in the preparation or the preparation itself whereas the pre-screening procedure with regard to the occupational health hazards is based on the classification of the preparation, in which information on both the human health classification of the individual substances and on their content in the preparation is taken into consideration.

Preparation groups

In the pre-screening, offshore preparations are grouped into one of four groups. For environmental hazards: P1(E), P2(E), P3(E) or WL(E) with P1(E) being the group of preparations containing the most hazardous substances, P2(E) the group of preparations with less hazardous properties, P3(E) the group of preparations considered to be of low risk to the aquatic environment, and WL(E) a waiting list of preparations that cannot be grouped due to lack of data on the hazard of at least some of the substances. Similarly, a grouping is made for preparations according to occupational health hazards: P1(H), P2(H) and P3(H). Finally, the various preparations are placed in groups taking into account both environmental and occupational hazards, P1, P2, P3 and WL. Additionally, a preliminary group P2* is made for preparations that can be evaluated only with regard to health hazards (P2(H)) but not environmental hazards (WL(E)). Further data on environmental properties may place the preparations in either P1 or P2. It is the intention that offshore preparations grouped in P1 should be considered for cleaner technology measures or phasing-out and that preparations grouped in P2 should be further evaluated for their hazard or risk to the aquatic environment, e.g. according to the principles laid down in the CHARM model, or to health in the working environment.

Evaluation of preparations

273 offshore preparations containing 306 different substances were evaluated by use of the pre-screening criteria. Although the environmental hazard of 40% of the substances contained in the preparations could not be assessed due to lack of data, 10% of the preparations were grouped in P1(E), 8% in P2(E), 56% in P3(E), and only 26% could not be grouped due to lack of data on the environmental hazard of the substances. However, a more thorough data collection might have revealed more data resulting in fewer preparations on the waiting list.

Similarly, a grouping based on human health classification was performed resulting in 4% of the preparations placed in P1(H), 51% in P2(H) and 45% in P3(H). By combining the two criteria, 12% were grouped in P1, 35% in P2 and 28% in P3. Preliminarily, 12% were placed in P2* based on human health hazards but lacking data on environmental properties, and 12% were retained on a waiting list.

Conclusions

The use of the pre-screening procedures on 273 preparations has clearly demonstrated the applicability of the procedures for identifying the most hazardous offshore chemicals based on their intrinsic properties. The pre-screening requires that a data set is available corresponding to the HOCNF supplemented with a minimal data search for aquatic toxicity data of substances in the preparations.

5.2 Possibilities of substitution

Basic criteria for evaluation of possibilities for substitution were elaborated. The general rule is that P3 preparations are of low hazard and that they therefore whenever technically possible may replace P1 and P2 preparations. Similarly, P2 preparations may replace P1 preparations although differences in the used amounts should also be taken into account. Finally, specific criteria for comparison of two P1 preparations have been developed.

Candidates for substitution

Preparations with identical main technical functions were compared according to their placing in the 3 environmental hazard groups. For some technical functions, both hazardous preparations and non-hazardous preparations are used in the offshore industry. Although no detailed comparison of the technical possibilities for substitution was possible, there might be some possibilities of substitution and these should be further evaluated. This is especially the case for preparations used as cementing chemicals and cement additives, gelling agents, viscosifiers and filtrate reducers, water-based muds and additives, weighting agents, and well stimulation fluids.

5.3 Comparison of PROSPECT and CHARM

The result of the PROSPECT environmental pre-screening of the preparations was compared with a generic risk assessment (i.e. environmental hazard assessment) following the principles of the CHARM model. Two comparisons were made:

1. A comparison of preparations with identical technical function (gelling agents and well stimulation fluids were selected)
2. A comparison of preparations that have already been replaced by other anticipated less environmentally hazardous preparations (7 pairs of preparations were selected).

In the latter comparison also the estimated sums of toxic units and bioaccumulative units were included in the evaluation.

Lack of data

Some general conclusions could be made from this comparison. In general, both the PROSPECT and the CHARM evaluations were hampered by lack of data on the ecotoxicological properties of both the preparations and of the substances contained in the preparations. The intention of the CHARM model is to use toxicity data for the preparations for predicting no-effect-concentrations for the various environmental compartments. Despite the criticism of this approach for not being scientifically valid, the use was evaluated but due to lack of those toxicity data, it was only possible to perform this assessment for very few of the preparations.

Critical substance - Critical dosage

In stead, the evaluation was based on the most critical substance in the preparations, i.e. a combination of the intrinsic hazard of the substance, the content in the preparation and the estimated release of the substance. As no information on the recommended dosage was available, the so-called "critical dosage" was estimated for the preparations based on the content of the most critical substance. The comparison showed that even within the groups (P1(E), P2(E), P3(E)) very large differences in critical dosages were found.

The model requires aquatic toxicity data on either the preparations itself (although this approach as mentioned has some scientific limitations) or at least on the most hazardous substances contained in the preparations. However, for many of the preparations, information on the preparation or on the most critical substance was not available. Consequently, the estimated critical dosages of the preparations were not always based on the most critical substances and the critical dosages were therefore not directly comparable between the preparations.

Moreover, the CHARM model is only based on data on the immediate aquatic toxicity of the preparations/substances. This means that additional information on the environmental hazards of the chemicals is not taken into account. This is the case for alkylphenol ethoxylates, which are not as acutely toxic as some of the other substances used but which due to their potential long-term estrogenic effects are placed on the Esbjerg Declaration list of substances that should be phased out of actual use. This is also the case for some of the substances placed on the proposed EU list I. Some of these substances are not very toxic (and their placing on the list I might therefore be questioned) but as they are presently on the list, they are subject to cleaner technology considerations.

Applicability of  PROSPECT and CHARM

The present comparison of the PROSPECT pre-screening and the CHARM hazard assessment thus demonstrates that the pre-screening regarding environmental hazards was possible for the majority (74%) of the offshore chemicals despite the lack of data on 40% of the substances contained in the preparations while a precise CHARM hazard assessment could not be performed due to the lack of data. The CHARM model must therefore be considered more sensitive to lack of data than the PROSPECT environmental pre-screening model. This highlights the intention of the PROSPECT model as a pre-screening tool to be used for grouping of offshore chemicals in a group that should be considered for substitution (P1(E)), a group that can be used without further assessment (P3(E)), and a group that should be further evaluated (P2(E)). For the latter group, a more thorough evaluation could be made, for instance by use of the CHARM model.

Finally, it can be concluded that the PROSPECT and CHARM evaluation models are applying two different approaches. The PROSPECT approach (both in pre-screening and content of toxic and bioaccumulative substances) is focusing on the intrinsic hazard of the substances contained in the preparations, while the CHARM approach is focusing on a generic risk assessment of the use at a platform in the North Sea.

The two different approaches give different priority to some of the intrinsic properties of the substances. A high bioaccumulation potential, as determined by a high log P_ow, is negative in the PROSPECT approach, but in the CHARM evaluation (of production chemicals) these substances are estimated to be retained in the oil phase and they are therefore not considered to be of high risk for the aquatic environment. Similarly, substances of a low biodegradability are negative in the PROSPECT approach, but this is only considered in one compartment in the CHARM model, namely the hazard to the sediment compartment. Such substances might, however, cause a long-term risk for the aquatic environment.

Which of the two approaches that is most appropriate may of course be debated, but if priority is given to the phasing-out of the substances with the most hazardous environmental properties, the use of the PROSPECT approach for identifying such preparations seems more appropriate.

6. References

EC (1996). Classification, packaging and labelling of dangerous substances in the European Union. European Commission.

Esbjerg Declaration. 4th International Conference on the Protection of the North Sea, Esbjerg, Denmark, 8-9 June 1995.

Karman C.C. & E.A. Vik (1996). CHARM III. Technical background report. TNO-MEP-R 96/354.

Karman C.C., E.A. Vik, H.P.M. Schobben, G.D. Øfjord and H.P. van Dokkum (1996). Charm III. Main Report. TNO-MEP-R96/355.

Rasmussen D. & F. Pedersen (1997). Evaluation of off-shore chemicals by use of the PROSPECT and CHARM models. VKI 10037. Report to the Danish EPA.

Schobben H.P.M., C.C. Karman, M.C.Th. Scholten, E.A. Vik, S. Bakke & G.D. Øfjord (1994). CHARM 2.1: Chemical hazard assessment and risk management of offshore exploration & production chemicals. TNO-MW - R 94/315.

Appendix 1

Table A.1   List of priority environmentally hazardous substances

Substance	CAS No.
Acrylonitrile	107-13-1				x
Aldrin	309-00-2	x			x	x
2-Amino-4-chlorophenol	95-85-2					x
Anthracene	120-12-7					x
Aramite	140-57-8				x
Arsenic and compounds	7440-38-2	x		x		x
Atrazine	1912-24-9	x		x		x
Azinphos-ethyl	2642-71-9	x		x		x
Azinphos-methyl	86-50-0	x		x		x
Bentazone	25057-89-0					x
Benzene	71-43-2					x
Benzidine	92-87-5					x
Benzyl chloride (Alpha-chlorotoluene)	100-44-7					x
Benzylidene chloride (Alpha, alpha-dichlorotoluene)	98-87-3					x
Biphenyl	95-52-4					x
Brominated flame retardants			x
Cadmium and compounds	7440-43-9	x	x	x	x	x
Carbon tetrachloride	56-23-5	x		x		x
Chloral hydrate	302-17-0					x
Chlordane	57-74-9				x	x
Chlordecone	143-50-0				x
Chlordimeform	6164-98-3				x
Chloroacetic acid	79-11-8					x
2-Chloroaniline	95-51-2					x
3-Chloroaniline	108-42-9					x
4-Chloroaniline	106-47-8					x
Chlorobenzene	108-90-7					x
1-Chloro-2,4-dinitrobenzene	97-00-7					x
2-Chloroethanol	107-07-3					x
Chloroform	67-66-3	x		x	x	x
4-Chloro-3-methylphenol	59-50-7					x
1-Chloronaphtalene	90-13-1					x
Chloronaphtalenes (technical mixture)	-					x
4-Chloro-2-nitroaniline	89-63-4					x
1-Chloro-2-nitrobenzene	88-73-3					x
1-Chloro-3-nitrobenzene	121-73-3					x
1-Chloro-4-nitrobenzene	100-00-5					x
4-Chloro-2-nitrotoluene	89-59-8					x
Chloronitrotoluenes (other than 4-Chloro-2-nitrotoluene)	-					x
2-Chlorophenol	95-57-8					x
3-Chlorophenol	108-43-0					x
4-Chlorophenol	106-48-9					x
Chloroprene (2-Chlorobuta-1,3-diene)	126-99-8					x
3-Chloropropene (Allyl chloride)	107-05-1					x
2-Chlorotoluene	95-49-8					x
3-Chlorotoluene	108-41-8					x
4-Chlorotoluene	106-43-4					x
2-Chloro-p-toluidine	615-65-6					x
Chlorotoluidines (other than 2-Chloro-p-toluidine)						x
Chlorpicrin	76-06-2			x
Chromium	7440-47-3	x		x
Coumaphos	56-72-4					x
Copper and compounds	7440-50-8	x		x
Cyanuric cloride (2,4,6-Trichloro-1,3,5-triazine)	108-77-0					x
2,4-D (including 2,4-D-salts and 2,4-D-esters)	94-75-7					x
DDT (DDD & DDE)	50-29-3	x			x	x
Demeton (including Demeton-o, Demeton-s, Demeton-s-methyl and Demeton-s-methylsulphone)	298-03-3					x
Dibromoethane 1,2-	106-93-4				x	x
Dibutyltin dichloride	683-18-1					x
Dibutyltin oxide	818-08-6					x
Dibutyltin salts (other than Dibutyltin dichloride and Dibutyltin oxide)	-					x
Dichloroanilines	-					x
Dichlorobenzene 1,2-	95-50-1					x
Dichlorobenzene 1,3-	541-73-1					x
Dichlorobenzene 1,4-	106-46-7					x
Dichlorobenzidines	-					x
Dichlorodiisopropyl ether	108-60-1					x
Dichloroethane 1,1-	75-34-3					x
Dichloroethane 1,2-	107-06-2	x		x		x
Dichloroethylene 1,1- (Vinylidene chloride)	75-35-4					x
Dichloroethylene 1,2-	540-59-0					x
Dichloromethane	75-09-2					x
Dichlorobenzenes	-					x
Dichlorophenol 2,4-	120-83-2					x
Dichloropropane 1,2-	78-87-5					x
Dichloropropane-2-ol 1,3-	96-23-1					x
Dichloropropene 1,3-	542-75-6					x
Dichloropropene 2,3-	78-88-6					x
Dichlorprop	120-36-5					x
Dichlorvos	62-73-7	x		x		x
Dieldrin	60-57-1	x			x	x
Diethylamine	109-89-7					x
Dimethoate	60-51-5					x
Dimethylamine	124-40-3					x
Dioxins	n.a.	x	x	x
Disulfoton	115-29-7					x
Endosulfan	115-29-7	x		x		x
Endrin	72-20-8	x			x	x
Epichlorohydrin	106-89-8					x
Ethylbenzene	100-41-4					x
Fenitrothion	122-14-5	x		x		x
Fenthion	55-38-9	x		x		x
Fluoroacetic acid and derivatives	7664-39-3, 144-49-0				x
Halogenated organic substances measured as AOX				x
Heptachlor (including Heptachlorepoxide)	76-44-8				x	x
Hexachlorobenzene	118-74-1	x		x		x
Hexachlorobutadiene	87-68-3	x		x		x
Hexachlorocyclohexane (including all isomers and Lindane)	608-73-1 58-89-9	x		x		x
Hexachloroethane	67-72-1					x
Highly chlorinated, short chained paraffins (10-13 carbon atoms)			x
Isobenzane	297-78-9				x
Isodrine	465-73-6	x			x	x
Isopropylbenzene	98-82-8					x
Kelevan	4234-79-1				x
Lead and compounds	7439-92-1	x		x
Malathion	121-75-5	x		x		x
MCPA	94-74-6					x
Mecoprop	93-65-2					x
Mercury and compounds	7439-97-6	x	x	x	x	x
Methamidophos	10265-92-6					x
Mevinphos	7786-34-7					x
Monolinuron	1746-81-2					x
Morfamquat	4636-83-3				x
Musk xylenes			x
Naphtalene	91-20-3					x
Nickel	7440-02-0	x		x
Nitrophen	1836-75-5				x
Nonylphenols and nonylphenol ethoxylates and related substances			x	x
Omethoate	1113-02-6					x
Organotin compounds					x
Oxydemeton-methyl	301-12-2					x
PAHs			x	x		x
Parathion	56-38-2	x		x		x
Parathion-methyl	298-00-0	x		x		x
PCBs and PCTs					x	x
Pentachlorophenol	87-86-5	x		x	x	x
Phoxim	14816-18-3					x
Polychlorinated terpenes	8001-50-1				x
Propanil	709-98-8					x
Pyrazon	1698-60-8					x
Quintozene	82-68-8				x
Selenium-compounds	(7782-49-2)				x
Simazine	122-34-9	x		x		x
2,4,5-T	93-76-5				x	x
Tetrabutyltin	1461-25-2					x
Tetrachlorobenzene 1,2,4,5-	95-94-3					x
Tetrachloroethane 1,1,2,2-	79-34-5					x
Tetrachloroethylene	127-18-4	x		x		x
Toluene	108-88-3					x
Toxaphene	8001-35-2				x
Triazaphos	24017-47-8					x
Tributyltin-compounds	-	x		x
Trichlorobenzene	-	x	x	x
Trichloroethane 1,1,1-	71-55-6	x		x
Trichloroethylene	79-01-6	x		x
Trifluralin	1582-09-8	x		x
Tributyl phosphate	126-73-8					x
Tributyltin oxide	56-35-9					x
Trichlorfon	52-68-6					x
Trichlorobenzene (technical mixture)	-					x
Trichlorobenzene 1,2,4-	120-82-1					x
Trichloroethane 1,1,1-	71-55-6					x
Trichloroethane 1,1,2-	79-00-5					x
Trichloroethylene	79-01-6-					x
Trichlorophenols	-					x
Trichlorotrifluoroethane 1,1,2-	76-13-1					x
Trifluralin	158-09-8					x
Triphenyltin-compounds	-	x		x		x
Vinyl chloride (Chloroethylene)	75-01-4					x
Xylenes	-			x		x
Zinc and zinc compounds	7440-66-6	x		x

Appendix 2 Data collection

The environmental pre-screening is primarily based on information provided by the chemical suppliers and entered into the PROSPECT database. In addition to this information, relevant data has been obtained from the following data sources:

Ecotoxicity:

Relevant databases and handbooks specified in the Nordic data collection strategy (Nordic Council of Ministers TemaNord 1994:589) Danish Ministry of Environment and Energy: Statutory Order 921/ 1996 on Quality objectives for the aquatic environment and demands to discharge of certain dangerous substances to rivers, lakes and the sea. Other compilations of water quality criteria (e.g. from the Netherlands, US-EPA, Canada, new Danish proposals) EU list of dangerous substances (Annex I of Directive 67/548/EEC) Different EU working lists containing "proposals" for environmental hazard classification of chemicals (e.g. reports or working documents from Nordic Council of Ministers, TemaNord 1994:643, bkh Consulting Engineers - substances in group 1 to 8, UBA)

If enough data on ecotoxicological properties cannot be obtained from the above data sources, they may be estimated by using one or more of the quantitative structure-activity relationship (QSAR) programs:

	ECOSAR for estimating toxicity to aquatic organisms
	BIODEG Probability Program for estimating biodegradability
	LOGKOW for estimating the octanol-water partition coefficient

Human health:

EU list of dangerous substances (Annex I of Directive 67/548/EEC) IARC: Monographs on the evaluation of carcinogenic risks to humans (60 volumes) Johnsen H. et al.: Occupational neurotoxicity: Criteria document for evaluation of existing data. Copenhagen, 1992 Hass U. et al.: Reproduktionsskadende stoffer i arbejdsmiljøet. AMI-rapport nr. 35, Copenhagen, 1990 EU: International Chemical Safety Cards. Compiler's Guide. International Programme on Chemical Safety. Commission of the European Communities. 1990 PARCOM lists Flyvholm, M.: Allergirapporter fra AMI

If the information on human toxicology obtained from these data sources does not yield satisfactory results, additional information may be obtained from the following books and databases:

General Handbooks	Special Handbooks	Databases
RTECS Merck Sax Patty's Industrial Hygiene Gosselin Kühn-Birett Hommel MAK-Kommision ACGIH ECETOX DOSAGE Martindale	Irritation/allergy: Grant Cronin Fischer Fousseraud Nervous system: Ethel Browning Arlien-Søborg Reproduction:: Shepard Schradein Norpoth & Waschinsky Barlov & Sullivan	General databases: RTECS HSDB ECDIN Toxicology: TOXLINE TOXLIT Medicine: MEDLINE EMBASE Cancer: Cancerlit

Appendix 3 Preparations grouped in category P1

Product	Function Group	Function Group	Reason for categorisation
ID	No.		EHC	ED	EU1	HHH
1	4	Carrier solvents				+
35	3	Biocides	+			+
59	7	Corrosion inhibitor	+
1324	35	Well stimulation fluids		+
1352	38	H2S scavenger	+
1387	7	Corrosion inhibitor				+
1603	7	Corrosion inhibitor		+
1781	10	Demulsifiers	+	+	+
1814	1	Antifoam	+	+
1870	7	Corrosion inhibitor		+		+
1883	0	?	+			+
1898	13	Drilling lubricant		+
1901	3	Biocides	+
1960	35	Well stimulation fluids	+
1963	19	Gel			+
2133	35	Well stimulation fluids	+			+
2216	?					+
2355	19	Gel		+
2391	10	Demulsifiers	+	+		+
2516	?					+
2518	7	Corrosion inhibitor				+
2638	3	Biocides	+
2667	3	Biocides	+
2718	?					+
2735	27	Polymeric viscosifiers and filtrate reducers	+
2737	7	Corrosion inhibitor	+	+		+
2804	33	Water-based mud and additives	+
2923	19	Gel		+
2993	40	?	+
3061	?		+
3066	?		+
9002	?			+
9003	?		+
9007	?		+
9013	?					+

Reason for categorisation: EHC: Environmental Hazard Classification; ED: Esbjerg Declaration; EU1: EU List 1, HHH: Human Health Hazards.

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