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«EUROPEAN COMMISSION Integrated Pollution Prevention and Control (IPPC) Reference Document on Best Available Techniques for the Textiles Industry July 2003 ...»

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(exposure); how much of, how long and how is the substance present in the aquatic environment. A influences the effect of B and C, while B influences the effect of C. The total score, which is obtained by multiplying the score for A, B and C, is called the exposure score.

Effects of chemical exposure depend on the toxicity of the chemical. The toxicity (D) should be evaluated concurrently in proportion to the exposure.

Each parameter is given a numerical value between 1 and 4 with 4 indicating the most critical environmental impact. Missing information involves highest score. The result is that each substance can be given a score as to exposure (A x B x C), and independent of this, a score as to toxicity (D). Subsequently, it will be possible to make a ranking of the chemicals.

Application of the system implies that the system is worked into the waste water permits or environmental approvals of the companies. Hereafter, the companies should send in information on consumption of chemicals as well as environmental data. The first time, information on all chemicals employed should be submitted, but following, reporting of new chemicals may take place concurrently with the employment of these. At least once a year, the statement of consumption should be updated.

The Federation of Danish Textile and Clothing Industries is prepared to act as "consultant" for the individual companies, and it has established a data base management system for storing of information on chemicals and calculation of score. By means of the data base facilities, it will thus be possible to print out a list of the employed chemicals and the calculated score (a Score Report) specifically for each company. This list could subsequently be supplemented with a detailed analysis of the chemicals, which were given a high score.

The information now available should form the basis of the environmental authority's (municipality/county) evaluation as to possible "interventions".

2. DESCRIPTION OF THE SCORE SYSTEM

The score system is an administrative method of sorting chemicals on the basis of information especially from the chemical supplier's specification sheets. The sorting permits a priority selection of those chemicals, which should be subject to closer examination because of actual consumption and environmental behaviour.

The score system is based on the parameters usually considered to be the most interesting in connection with characterisation of substances injurious to the environment of industrial sewage.

–  –  –

A-score is based on estimatet amount of chemical, which is discharged into enviroment as waste water. B-score is based on biodegradability and C-score on bioaccumulation.

Together the parameters A, B and C indicate the potential presence of the substance (exposure) in the environment; how much of, how long and where is the substance present in the aquatic environment. A influences the effect of B and C, while B influences the effect of C. Thus, exposure score is obtained by multiplying A, B and C.

The effect of presence of a substance in the environment depends on its toxicity (D). The toxicity score should be evaluated concurrently and independently in proportion to the exposure score.

The exposure score (AxBxC) and toxicity score (D) are estimated for each chemical.

Subsequently it will be possible to make a ranking of the chemicals.

How to use the score system?

On basis of information from especially the chemical supplier's specification sheets each parameter is given a numerical value between 1 and 4 with 4 indicating the most critical environmental impact. Missing information involves highest score.

It is advisable that the data used as score basis have been obtained according to internationally approved methods of examination.

Within the parameters B and C and D, data on different levels are used. The highest level represents data generated on basis of examination conditions, which are most comparable with a natural aquatic environment. As regards the parameter C, data obtained from standardised bioaccumulation tests with fish are thus more realistic than data from examinations based on determination of the distribution of the substance in a two-phased mixture of octanol and water (Pow -data). However, Pow has a more direct correlation with bioaccumulation than solubility data.

–  –  –

Implementation Application of the system implies that the system is worked into the waste water permits or environmental approvals of the companies. Hereafter the companies should send in information on consumption of chemicals as well as environmental data.The first time, information on all chemicals employed should be submitted, but following, reporting of new chemicals may take place concurrently with the employment of these. At least once a year, the statement of consumption should be updated.

The Federation of Danish Textile and Clothing is prepared to act as "consultant" for the individual companies, and it has established a data base management system for storing of information on chemicals and calculation of score. By means of the data base facilities, it will thus be possible to print out a list of the employed chemicals and the calculated score (a Score Report) specifically for each company. This list could subsequently be supplemented with a detailed analysis of the chemicals, which were given a high score.





The Score Report forms the basis of the erivironmental authority’s (municipality and county) dialog with the companies and evaluation as to possible interventions.

–  –  –

Information The Score System is worked out by a working group representing the municipalities in Ringkøbing County, Ringkøbing County and Federation of Danish Textile and Clothing in Denmark.

The Score System was implemented in 1992 in Ringkøbing County, it was worked into the waste water permits or environmental approvals of the companies. The reader is wellcome to contact Ringkøbing County, Damstræde 2, 6950 Ringkøbing, Denmark for further information about the system and experiences from the use of the system.

Information including The Compendium with Guidelines to the Sorting System for sorting af Chemicals can also be found on the web site.

–  –  –

13.3 Dutch General Policy Scheme Summary The lead-up to the grant of a permit under the Dutch Pollution of Surface Waters Act comprises three phases: information provision, establishing measures to be taken to control emissions, and assessing any residual emissions. The assessment of substances and preparations relates mainly to the 'information provision' phase. However, the data required to assess a substance or preparation are equally relevant to the assessment of residual emissions (immission assessment).

The implementation of the Pollution of Surface Waters Act demands an understanding of the toxicity of individual substances and preparations to the aquatic environment.

This report describes both the general method of assessment and the procedure for informing the competent authority (via the user) of the water toxicity of individual substances and preparations. The general method of assessment is designed to apply to direct and indirect discharges under the Pollution of Surface Waters Act, but can also be used to assess substances and preparations involved in indirect discharges falling under the Environmental Protection Act.

The method employs parameters and criteria which comply with European regulations regarding the classification and characteristics of substances and preparations, but couples to the properties of substances a set level of effort to limit pollution at source. The method can be used wherever it is necessary to determine the water toxicity of substances and preparations.

This means that companies can use it if they need to supply information on substances and preparations to competent authorities in relation to permit or licence applications under the two aforementioned Acts or, for example, to demonstrate that a decision to use a particular substance or preparation will contribute to the on-going reduction of pressure on the environment.

It should be remembered that the general assessment method is a means of using various properties of substances to categorise them with regard to their toxicity to the aquatic environment. It will not indicate what measures should be taken in a specific case to prevent or reduce emissions. Nor can it be used to assess residual emissions.

With regard to the procedure, it should be stressed that responsibility for supplying information to the competent authority still lies with the applicant for a permit or licence under the relevant Acts. This is a blanket rule and therefore also applies to information about any basic or auxiliary substance, and any intermediate or final product which may find its way into waste water.

However, producers wishing to preserve confidentiality regarding the composition of their preparations do not always provide complete information to users. This means that users are in turn unable to pass it on to the competent authority.

For this reason, and for the sake of efficiency, producers are expected to use the general method of assessment to assess substances and preparations and to supply wholesalers and users with the results of the assessment, together with information about the relevant substances and preparations. The procedure is in line with the widely supported programmes of ’responsible care’ and ’product stewardship’ within the chemical industry. The private sector is launching international programmes to identify the missing data necessary for the assessment of the toxicity of a large number of substances.

The procedure described in this report can be used to resolve the dilemma between the need of applicants for permits under the Pollution of Surface Waters Act to supply information on the toxicity of preparations and the desire of producers to protect information on the composition of their preparations. The description of the procedure is accompanied by a discussion of possible means of monitoring and enforcement.

–  –  –

In addition to describing the general method of assessment and the procedure, the report focuses on points relevant to their application. It ends with conclusions and recommendations.

1 Procedure Assessment of substances and preparations within the context of the implementation of the water discharge policy.

This chapter deals with the procedure for providing the authorities with information about substances and preparations by means of the user.

Key issues are the information that must be provided, the verifiability of this information and the enforceability of the procedure.

1.1 Introduction The Pollution of Surface Waters Act prescribes that anyone applying for a permit under this act is obliged to provide information to enable the competent authorities to review the application.

This obligation also applies to information about raw and auxiliary materials and partly processed and finished products that are used by companies and may be discharged into the surface water. Due to the confidentiality of information about the composition of preparations, producers and suppliers are not always willing to provide this information. In this situation, the customer does not have the exact information. A request to observe secrecy with regard to part of the permit applications by the user does not solve this problem, because in the confidential section of the application the water quality manager cannot be provided with any information about the preparation.

To solve this bottleneck, a procedure has been designed to help users, authorities and third parties to gain sufficient insight into the aquatic harmfulness of a substance or preparation, while guaranteeing the confidentiality of the information vis-à-vis the producer or supplier.

Producers and suppliers of substances and preparations play an important part in the provision of information and the assessment of substances and preparations in accordance with the GAM.

The working group dealing with the effects on the market of the deregulation of legislation concerning permits granted under the Pollution of Surface Waters Act has recommended to encourage that in consultation with the corporate sector a system is set up within certain branches, which will make all standard information about raw and auxiliary materials relating to the permit-application procedure accessible to all parties involved. This working group has proposed to link up with the initiatives taken by the Integrated Water Management Committee.

The Dutch cabinet has adopted this recommendation.

1.2 Procedure

Producers of substances and preparations play an important part in the procedure. In fact, if there are any details available about substances and preparations, it is most likely the producers who have this information. Besides, it is not efficient to have numerous users collect the data of properties of the same substances and preparations. The most obvious approach is to have the producer/supplier collect the data and assess the substances. This is in line with Directive 86/609/EEC, which deals with the protection of animals used for experimental and other scientific purposes. The procedure distinguishes between the submission of a basic set3 and a full set of information about substances and preparations.

The following figure represents the proposed procedure in diagram form.

–  –  –

1.2.1 Full data set The full data set for assessing substances and preparations contains the answers to the questions below, plus the results of the assessment. This information must be made available through the commercial chain to the user, who can pass this on to the authorities dealing with the permits.

Substances

The details of each substance required to carry out the GAM are:

§ Is the substance carcinogenic (R-45), insofar as is known?

§ Is the substance mutagenic (R-46), insofar as is known?

§ What is the acute toxicity to water organisms (LC50), preferably for four trophic levels, but in any case for crustaceans or fish.

§ What is the degree of biodegradability?

§ What is the Log Pow?

§ What is the BCF? (optional) § What is the water solubility if the acute toxicity to water organisms cannot be determined.

Preparations For preparations, the results of the GAM must be given, as well as the exact composition of the preparation and information about the substances of each component.

! Basic set should not be confused with Base-set according to Annex 7 of the Substances Directive.

Assessment of substances and preparations within the context of the implementation of the water discharge policy 1.2.2 Basic data set Producers may provide only a basic set of information about substances or the composition of a preparation, if the substance or preparation is assessed in accordance with the GAM.

–  –  –

Substances If the producer/supplier assesses the substance and provides only a basic set of information, then it is in principle enough to indicate its aquatic harmfulness and the place at which the substance file is available for inspection by the (verifying) authorities. In this case, the authorities will apply a worst-case approach to the water quality test (i.e. assessment of residual discharge after introduction of btm/bpm), based on the most harmful properties that have resulted to this category. In other words: if a substance falls into category {6} of aquatic harmfulness according to the GAM, it is assumed that the substance has an acute toxicity to water organisms of 1 mg/l and is persistent. If this results in additional decontamination measures, then a more accurate water quality test may be carried out if the producer provides more exact data about the properties of the substance.

Preparations

In principle, users must be provided with the following basic data set for preparations:

§ results of assessment of the preparation in accordance with the GAM § components in the category of aquatic harmfulness of 'black-list substance, may cause hereditary damage and/or cancer', as well as the rough quantities of the components that make up the preparation § components with abatement effort A and the rough quantities of these components in the preparation § the place at which the product file is available for inspection by the (verifying) authorities.

The exact composition of the preparation is only known to the producer or supplier.

In the case of preparations, too, the authorities will base the water quality test on the most harmful properties, which have led to the category of aquatic harmfulness, if the producer fails to state the exact composition.

If this results in additional measures, then the producer may ensure that a more accurate water quality test is carried out by providing more exact data about the composition of the preparation.

1.3 Verifiability To assess substances and preparations, information is necessary. But it is impossible to verify whether all the information provided is correct.

Users and authorities must be able to trust that the assessment is based on the correct information and that the assessment itself has been carried out correctly. Those who carry out the assessment, the producers of substances and preparations, are responsible for this. The details of properties of substances may be determined by or under the authority of the producer.

For many existing substances, the information stored in databases may be used. In both cases, the details are preferably verified by certified laboratories (Good Laboratory Practice) in accordance with standardised methods. Any information about properties or substances that may have been assessed before standard test methods and the GLP came into force, may be used if valid conclusions can be drawn on the basis of this information. This is dealt with by the technical guidelines in Directive 93/67/EEC and Regulation 1488/94 for risk assessment of new and existing substances.

To reduce the risk of errors in the assessment, a software application has been made of the GAM. However, both the corporate sector and the government value a form of verification, which may be carried out in various ways.

–  –  –

1.3.1 Verification by authorities In case of doubt (but also simply as a random test), the authorities must be able to verify whether the information provided is correct and whether the assessment is carried out correctly.

It is proposed to use the same procedure as that used in the verification of information for the assessment of effects on humans and the environment. In other words, the authorities (for example, in the shape of the Inspectorate for the Environment) will be permitted to inspect the product file, at their request. Of course, the user and the authorities must know by whom and where the product file is kept. This file must also contain the information that has been used for the assessment of preparations.

1.3.2 Verification by the corporate sector

Apart from the authorities, the corporate sector may organise the verification themselves. For example, an independent, certified body may be designated to carry out or verify the assessment. The assessment may also form part of a section of the business operations that may be certified. This means that in environmental audits within the scope of the certification, the auditor will then verify whether the assessment has been carried out correctly. But the protocols for this will have to be set up first.

1.3.3 Product liability

Apart from this, the producer is at all times responsible for the correctness of information provided. On the other hand, the customer must also verify whether the information is correct, for example, by comparing the properties to those of other products. In this way, the user of a hazardous product that has been incorrectly categorised by the producer may prevent the incorrect use of the product.

However, if the user of a product has been misled by its supplier and the user could not reasonably have known this, then the producer can be held liable. According to criminal law, the user will always be liable. But based on product liability, the user is able to recover any damage from the producer in civil proceedings.

In the Netherlands, the Environment Inspectorate verifies whether the information provided is correct. If misleading information has been provided, steps can be taken. The EU member countries have entered into agreements in the event that companies from EU countries are involved.

1.4 Enforceability

In the permit-application procedure, the information provided must be verified; usually, the body that grants the permits (competent authorities) verifies the information itself. After that, the manner in which the permit is formulated determines its enforceability. For example, the wording of the conditions must provide clear legal grounds to allow for measures to be taken if other substances are discharged than those mentioned in the permit. In enforcing the permit conditions, special attention may be paid, for instance, to the availability of information about raw and auxiliary materials, as well as partly processed and finished products that are used by a company and may be discharged into the waste water.

Enforcers also ought to be alert if the permit allows the holder, for example, to change any raw or auxiliary materials, provided that the authorities are notified, whether in advance or afterwards.

–  –  –

14 ADVANCED OXIDATION PROCESSES (FENTON REACTION)

The Fenton reaction involves an advanced oxidation process. Advanced oxidation processes (which are a particular case of chemical oxidation processes) are oxidation processes that produce active oxygen species that react as powerful and clean oxidants.

The Fenton process is based on the redox oxidation of hydrogen peroxide to produce the OH* radical. Other methods to produce the OH* radical from H2O2 are for example H2O2 and UV, ozone/ H2O2 and ozone/UV.

The Fenton reaction is based on H2O2 and Fe2+ at pH 3. At pH 3, the first hydrolysed form of ferric ion (Fe(OH)++) is in equilibrium with water, thereby controlling the rate of production of free OH* radical from the decomposition of H2O2.

There is evidence from recent research in advanced oxidation processes to assume the following pathway: Fe2+ + HO-OH → Fe(OH)++ + OH*.

In the absence of organics the generated OH* radical slowly further reacts consuming hydrogen

peroxide. However, in the presence of organics (R-H) the following reaction takes place:

1. R-H + OH* → R* + H2O Organic radicals are formed that react further by complex chain mechanisms or become terminated by deactivation and radical-radical combination. This process may occur in the absence or presence of oxygen gas (O2). In the presence of oxygen gas, the alkyl radicals (R*) produced by advanced oxidation, react very rapidly and the formation of the peroxyl radical

occurs:

2. R* + O2 → ROO* (Ground state molecular oxygen is consumed instead of the oxygen from the more expensive hydrogen peroxide).

The peroxyl radical may or may not be stable (which can slow down the oxidation process). In any case, oxygen is chemically introduced into the organic molecule and thus consumed, leading to the oxidation of organic molecules to more hydrophilic and usually more biodegradable intermediates. This is known as a clean route (unlike chlorination where chlorine atoms are introduced into the organic molecule).

The OH* radical is (after fluorine) the most powerful oxidant in nature and reacts in an aspecific way with any substance containing at least one hydrogen atom.

With the Fenton reaction there is no risk of an accumulation of oxygen. Therefore potentially dangerous reactions in the presence of VOCs cannot occur. Moreover as the H2O2 is present in very low concentrations (about 0.1 %) it should never be possible to reach explosive mixtures.

On the contrary O2 is consumed by the reaction in the above-mentioned conditions.

It was stated earlier that OH* is a very powerful oxidant. However, there are some dyes or groups that react more slowly than other groups (e.g. antraquinone dyes react 100 times more slowly than azo dyes because the product of the degradation is regenerated into the original one). However, what is interesting about Fenton is that the dyes that react slowly or not efficiently with the OH* radical are often removable by precipitation or complexation with iron (III), which is a reaction product of the Fenton process. As a result less iron (II) is consumed for nothing!

–  –  –

Moreover, in the enhanced system (the Enhanced Thermal Fenton ETF and the Enhanced Photo Fenton) the intention is to concentrate the reactants and to reactivate the iron(III) by reduction (thermally, via radiation UV-VIS, or via electrochemistry).

In conclusion, the Fenton reaction is a very efficient process for treating highly-loaded segregated streams with a high concentration of non readily biodegradable substances.

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