The flow of biocides from production of biocidal chemicals to consumption of finished goods is illustrated in Figure 2.1.

The flow of the biocides subsequent to the use of the products and the possible exposure of man and the environment will be discussed more within Phase 2 of this project.

The emphasis of the assessment is on the use-phase and the consumption of biocides with finished biocidal products and other products containing biocides. The consumption of biocides for a specific application indicated in the tables in the following sections thus represents the total content of the biocides in finished goods sold on the Danish market in 1998, if nothing else is explicitly indicated.

Figures for the volume of biocidal chemicals used for production of finished goods in Denmark are not represented in the report, except for wood-preservatives, for which the consumption for production in Denmark is registered in the Pesticide Statistics.

Figure 2.1
Initial part of the flow of the biocides through the society

The consumption volumes for the biocides are estimated on the basis of information from the Danish Product Register Database PROBAS, the Danish Pesticide Statistics, Statistics Denmark, the Danish EPA, trade organisations, consumers, and companies producing or trading the products.

Initially a retrieval of biocidal substances registered in PROBAS, the database of the Danish Productregister was carried out. The retrieval was based on the 'List of biocidal substances' of July 1999 from the European Chemical Bureau. The list comprised 1,336 substances with CAS No. Of these, 607 substances were registered in PROBAS as used in Denmark.

For these substances, a more extensive retrieval of turnover by application areas was carried out. The application areas registered in PROBAS are, however, not identical with the application areas defined in this work, and the data from PROBAS are not immediately applicable. In addition, only a part of the biocidal products is registered. Companies only have the obligation to submit information on the turnover of products to PROBAS if the products contain substances classified dangerous (Bek 540). If the products contain dangerous substances, however, all constituents of the products are registered.

As all products are not registered, the data from PROBAS cannot be used directly to estimate the consumption of the biocidal products in Denmark, but the information from the database has been used in combination with information received from the relevant branches of trade. Producers and importers have to submit information on the expected turnover of the products and any changes in this respect. By experience, the turnover volumes are often not updated frequently, and the registered turnover may be quite far from the actual volumes.

The data from PROBAS have been most useful as regards applications within Main Group 2: ‘Preservatives’ and product-type 21: ‘Antifouling products’. For antifouling products, the registering in PROBAS was updated and quality assessed, and turnover volumes have been applied directly in this study.

A total of 144 different compounds are registered in PROBAS as used as preservatives in various products. The PROBAS data supplement the information obtained from the industry, as the information from the industry for most application areas focus on the compounds typically used. The information in PROBAS regarding the specific use of the substances is considered confidential, if the number of registered products and registered users is below three. The detailed lists of preservatives used for different application areas are consequently only included in a confidential unpublished version of this report.

Until now the biocides included in the product-types 8, 10 (partly), 12 (partly), 14, 18, 19 (partly) and 23 have been covered by the Danish Statutory Order No. 241 of 27 April 1998 on Pesticides (Bek 241). According to the regulation only pesticides approved by the Danish EPA are allowed in Denmark, and information about the content of active agents of the approved pesticides is included in 'Survey of approved pesticides' published by the Danish EPA (Danish EPA. 1999 A). The total sale of the pesticides and active agents are registered by the Danish EPA and reported annually in the 'Pesticide Statistics' (Danish EPA. 1999 B). In the tables in this report, the number of approved products for each application area is indicated, but the turnover of some of the approved products on the Danish marked for the year of reference may actually be zero.

The total consumption of biocides for these application areas is estimated on the basis of the Pesticide Statistics. In these instances when the active agents are used for more than one application area, the distribution of the registered biocides on product-types and sub-types is based on information retrieved from the pesticide register of the Danish EPA. In one instance, wood preservatives, the biocidal products are used for production of products containing biocides, and both the Danish consumption of biocidal products for manufacturing of products and the consumption with finished goods are assessed.

For application areas where the biocides are not covered by the Pesticide Statistics, the total consumption of the biocides are predominantly estimated on the basis of information from consumers, trade organisations and companies producing or trading the finished goods. As mentioned above, this information is combined with information retrieved from PROBAS.

For most of the biocides, it is not possible to assess the exact sale of the biocide with finished goods in 1998. The consumption figures will consequently be represented by ranges based on more or less uncertain 'expert judgements'. The basis for the judgements is indicated in the text or notes to the tables. In order to limit the extent of the ranges , the indicated ranges represent a 80% certainty level or in other words: The figures are represented by the range, within which the authors estimate the 'true value' with a 80% certainty can be found. In this way, there is a direct correlation between the uncertainty of the estimates and the width of the ranges. It should be noted that the ‘true value’ of about 20% of the estimates accordingly could be outside the indicated range.

The content of active agents in the products is represented as (weight/weight), if nothing else is indicated.

The group includes biocidal products for disinfection and general biocidal products used for human and veterinary hygiene.

These product-types exclude cleaning products that are not intended to have a biocidal effect, such as washing preparations, powders and similar products.

Producers and suppliers of products for disinfection in Denmark are organised in the trade organisation SPT (Trade Organisation for Soap, Perfume and Toiletries). As part of this project SPT has carried out an inventory of disinfectants in products traded on the Danish market by the members of the organisation. The following chapter is to a large extent based on the results of this inventory. As the members of the trade organisation do not cover 100% of the market, additional information has been gathered from other suppliers, or the total consumption in Denmark is estimated by extrapolation of the SPT inventory results.

It has been attempted to base the estimates of the total consumption on extrapolations of the SPT inventory. The lists of used active agents in the following sections are mainly based on the SPT inventory, and the lists are most likely not comprehensive. The information on the consumption of specific compounds is in the publishedreport only indicated for agents for which the consumption volumes is based on information from more than two suppliers.

The confidential version of this report contains in addition a list of substances registered in PROBAS as used as disinfectants.

3.1 Product-type 1: Human hygiene biocidal products

Products in this group are biocidal products used for human hygiene purposes. Human hygiene biocidal products are mainly used in relation to care, examination and treatment of patients in the public health service sector, in private medical and dental clinics, nursing homes, in the food processing industry and other food handling areas. A limited number of products are used in private homes and workplaces with the purpose of avoiding contamination and preventing infections in relation to cuts, abrasions and the like. Human biocidal products have until now not been covered by any statutory approval procedure.

3.1.1 Skin disinfectants

Skin disinfectants or antiseptics are used for human hygiene purposes in order to destroy microorganisms that could cause infections or have a detrimental effect on human activities, for example spoiling or contaminating food or for general hygiene purposes in the health care sector. Skin disinfectants either inhibit the growth (microbiostatic effect) or kill microorganisms (microbiocidal effect) on the surface of the skin. Disinfectants specifically aimed at treating or preventing disease in human beings and animals are regarded as medicinal products.

Chlorhexidine is one of the most common active ingredients used in human hygiene disinfectants for retail sale and also to a large extent for use in the health care sector. The absence of a Danish approval procedure for chemical disinfectants has resulted in a large number of different products on the market, many of them containing similar ingredients. Skin disinfectants particularly used in the health care sector are generally containing chlorhexidine, iodine or alcohols as active ingredients according to information from Statens Serum Institut (Statens Serum Institut, 1997). Triclosan is found in many antibacterial soap-formulations for both the professional and the private market. If the concentration is less than 0.3%, triclosan will act as a preservative, and the statutory order on cosmetics will apply. In order to achieve a biocidal effect the concentration must be above this limit.

Chlorhexidine is rapidly bactericidal and persistent and is recommended as a relatively non-toxic skin antiseptic for general use. It is most active against Gram-positive organisms and fairly effective against Gram-negative bacteria and many viruses. It is inactivated by soap and organic matter and is therefore used in aqueous or alcoholic solutions for topical application, hand and skin washing. Chlorohexidine and alcohol are often used together for skin disinfection.

Iodine is mostly used in solutions with water and detergents (iodophors) together with alcohol. Iodine complexes with the detergents and exists in equilibrium with a small amount in the water phase. Iodophors are slowly sporicidal but rapidly effective against vegetative organisms including fungi and Trichomonas. The microbiocidal effect, especially against viruses, is however varying.

Iodine in alcohol solutions (tincture of iodine) are powerful and efficient skin disinfectants, but also rather irritant to skin. Free iodine may cause toxic dermatitis and is easily absorbed through injured skin. Previously these tinctures were widely used.

Alcohols like isopropyl alcohol and ethanol are optimally bacteriocidal in aqueous solution at concentrations of 70 to 75%, and have very little bacteriocidal effect outside this range, e.g. when 'absolute' or diluted too much. Alcohols represent the group of substances which most rapidly and efficiently reduces the number of microorganisms on the skin. They are microbiocidal against bacteria including mycobacteria, fungi and especially lipid containing virus. They are not active against spores and non-lipid containing viruses.

Triclosan has been widely used as an antimicrobial agent in consumer goods including cosmetics for many years. Recently it was discovered that triclosan has a very specific mode of action, as is the case for antibiotics. Triclosan is fat-soluble and crosses easily cell-membranes. Once inside the cell, triclosan blocks the active site of an enzyme called enoyl-acyl carrier-protein reductase, preventing the bacteria from producing fatty acids needed for building cell membranes and other vital functions. As a preservative in soaps, triclosan is added in low concentrations (<0.3%). In order to obtain an antiseptic effect, the concentration must typically be up to 3%.

According to information from major Danish hospitals, Statens Seruminstitut and SPT, the most frequently used biocides for skin disinfection are those listed in Table 3.1.

Table 3.1
Biocides used for skin disinfectants in Denmark¹⁾

Skin disinfectants are used in the primary health care sector, the hospital sector, in industry and institutions and in private homes.

According to the Danish Medicines Agency it is not possible to get the full picture of the use of skin disinfectants in the primary health care sector and the hospital sector from the Medicinal Products Statistics in 1998. This statistics includes data submitted by high street (private) pharmacies, hospital pharmacies and Statens Seruminstitut. As of 1 July 1995, it became compulsory for pharmacies to install a special point-of-sale terminal to enable recording of over-the-counter (OTC) sales. Based on this recording the sales of chlorhexidine in 1998 in the primary health care sector amounts to DKK 1,600,000 (pharmacy retail price) and DKK 220,000 in the hospital sector (settling price).

Information from the County Medicine Registration Office in Denmark, which is an office belonging to the Association of County Councils in Denmark, provides an overview of the consumption of SAD (Sygehusapotekerne i Danmark) skin disinfectants in the hospital sector in 1999. The County Medicine Registration Office in Denmark is responsible for registration of SAD-medicines in the Danish Medicines Agency's speciality register and for maintenance of the documentation for medicinal products produced by the hospital pharmacies in Denmark. Apart from the SAD products, which are produced by the hospital pharmacies, the hospitals also purchase skin disinfectants from wholesalers and other companies supplying products to the health care sector. SAD products are estimated to account for only a small fraction of the consumption in the hospital sector according to some of the hospital pharmacies.

Information about the consumption of skin disinfectants in the hospital sector in Copenhagen County was therefore obtained in order to estimate the total consumption of skin disinfectants in this sector in Denmark. Using the number of inhabitants in Copenhagen County and in Denmark, the total consumption of skin disinfectants in Denmark is estimated to be approximately eight times the consumption in Copenhagen County. The same extrapolation is used in relation to the consumption of medicinal products in general (L. Nielsen, 2000). In order to include also the primary health care sector, the amount of skin disinfectants used in Copenhagen County is estimated at 5-10% of the total consumption.

In Table 3.2 the consumption of chlorhexidine, surgical spirit and iodine in the health care sector and triclosan in antibacterial soaps is shown. The table does not provide a full picture of the consumption of skin disinfectants in Denmark, as the private sector is only partly included. Due to a change in the demarcation between the Medicinal Products Directive, the Cosmetics Directive and the Biocides Directive, it has not been possible to provide a full overview within the timeframe of the project.

Table 3.2
Consumption of biocides with skin disinfectants in the health care sector and in antiseptic soap in Denmark 1999

Due to rising concerns about the possible consequences of the increasing use of triclosan, many suppliers are phasing out this substance. . In the mid nineties the industry decided to phase out triclosan in 'high-volume down-the-drain-products'. This decision was taken through their organisation AISE (Association Internationale de la Savonnerie, de la Détergence et des Produits d'Entretien) of which SPT is the Danish division. This resulted in a reduction of triclosan-containing cleaning products for private use. According to members of SPT, it can also be expected that triclosan will be phased out in antibacterial soaps, and several suppliers have already substituted soaps containing e.g. chlorhexidine for these soaps on a voluntary basis.

3.2 Product-type 2: Private area and public health area disinfectants and other biocidal products

Products in this group are used for the disinfection of air, surfaces, materials, equipment and furniture which are not used for direct food or feed contact in private, public and industrial areas, including hospitals. The product-type also includes products used as algicides in these areas.

3.2.1 Disinfectants for private areas

Disinfectants for private areas primarily include chlorine containing products for bleaching, surface disinfection and automatic dishwashing and furthermore disinfectants for toilets.

Information about the active ingredients and the consumption of biocidal products was obtained from the trade organisation SPT, based on both available information about the sodium hypochlorite consumption in Denmark a few years ago and responses to questionnaires sent out by SPT to their members specifically in relation to this project. SPT estimates that their members cover 80-90% of the market for disinfection in Denmark.

As disinfectants for private use do not have to be registered with the Danish Product Register, no relevant information is available from PROBAS.

Table 3.3
Biocides used for private areas in Denmark

The consumption of biocidal active agents with these product groups - based on the information from SPT - is shown in Table 3.3. Main agents for the application area are sodium hypochlorite, phosphoric and sulfamic acid.

Table 3.4
Consumption of biocides for private areas in Denmark 1998

3.2.2 Disinfectants for professional cleaning and industrial use

Professional and industrial use in this context includes industry, institutions, the primary health care sector and the hospital sector. The primary health care sector is here defined as general practitioners (medical and dental clinics), nursing homes and similar institutions.

Disinfectants for professional and industrial use include products for disinfecting surfaces like floors and walls as well as larger pieces of portable equipment and furniture. Disinfectants for food handling areas are not included, as they are covered by product-type 4.

The efficiency of the disinfectant depends on the direct contact between the disinfectant and the surface that need to be disinfected, the concentration of the active ingredient, duration of the contact and on the pH and the temperature of the solution. As most disinfectants act by denaturing or altering proteins or lipids in the cytoplasmic membrane, they will need time to penetrate the outer surface of the microorganisms. The time it takes to kill a certain microorganism depends on the specific biocide.

The main suppliers of biocidal products in Denmark for professionel and industrial use are Henkel Ecolab A/S, Novadan A/S and Diversey Lever A/S.

Suppliers to the primary health care and hospital sector are wholesalers of disinfectants to the pharmacies including Nomeco, K.V. Tjellesen A/S and the joint-stock company Max Jenne. Among suppliers to the wholesalers are Medicteam, ScanMedic and Unichem in Denmark and Galderma in Sweden.

In Denmark, there has been no legal demand for approval of chemical disinfectants for professional and industrial use as defined here. This has resulted in quite a considerable number of different products on the market. Many of these are variations of the same basic constituents. Disinfectants for professional use which are defined as hazardous according to Statutory Order no. 540 on substances and materials from the Danish Working Environment Authority must be notified with the Product Register.

For disinfection of surfaces, the main active ingredients include chlorinated compounds, acids and quaternary ammonium compounds. Quaternary ammonium compounds are not always considered real disinfectants as soap and organic material easily inactivate them, and because they are not very effective against gram-negative bacteria like Pseudomonas. They are also not very efficient against virus. They do however have very god surface active properties and are therefore often used as auxiliary substance in disinfectants with the purpose of dissolving dirt.

Contact to some of the major hospitals in Denmark confirmed that very few chemical disinfectants are used for cleaning of surfaces. In the ‘Hygiene principles’ for the hospitals in Copenhagen County, it is stated that surfaces should be cleaned with surgical spirits (70% v/v). Mixtures of surgical spirits and chlorhexidine are also used for some cleaning tasks, especially for portable equipment. Products based on buffered and stabilised peracid are used only in extreme cases, e.g. when the operating room is heavily contaminated.

Table 3.5
Biocides used for professional cleaning and industrial use in Denmark

The total consumption of disinfectants for the professional and industrial area is estimated at 710-1,140 tonnes based on an assessment carried out by the trade organisation SPT. This estimate is based on answers to questionnaires sent out to all members of the trade organisation, who are expected to cover about 80% of the market.

It should be noted that surgical spirit, which is widely used for mild disinfection in the health care and hospital sector, is not mentioned in the list of biocides. This is probably because surgical spirits are supplied by companies which are not members of SPT. According to information from the hospitals in Copenhagen County, the consumption of surgical spirit in 1998 at these hospitals was 17,500 l (14 tonnes) in 1998. Assuming this amount corresponds to 5-10% of the consumption in the health care sector as a whole, the total consumption of finished product would be 140-280 tonnes. This assumption is based on the same principles for extrapolation as was used for the skin disinfectants.

In PROBAS, there are 64 different active ingredients registered as ‘disinfectants’ in the products. Of these 64 active ingredients, 13 are also included in Table 3.1.

Two products for toilet disinfection containing sodium hypochlorite are registered in PROBAS and 23 products in total for toilet cleaning.

Table 3.6
Consumption of biocides for professional cleaning and industrial use in Denmark 1998

3.2.3 Disinfectants for medical equipment

Multipurpose disinfectants or sterilisation agents are covered by this product group.

Disinfectants specifically intended for use with medical devices (e.g. contact lens care products for disinfecting) fall under the definition ‘accessory’ and are covered by the Medical Devices Directive (93/42/EEC) according to a document from the European Commission, DGIII (The European Commission, March 1998). The document determines the demarcation between Medical Devices Directives and Medicinal Products Directives. These disinfectants are used to enable the device to be used in accordance with its intended purpose or to enhance the performance of the device. This demarcation may however also be changed, so that this type of products will be covered by the Biocides Directive in the furture.

The method for sterilisation, which means that the medical equipment is freed from all living organisms, including viruses, bacteria and their spores and fungi and their spores, both pathogenic and non-pathogenic, is mainly heat. But for disinfecting equipment, which is heat-sensitive, chemical disinfectants are used.

Henkel Ecolab A/S, Novadan A/S, Diversey Lever A/S, Johnson and Johnson and Superfos Biosector are among the main suppliers who are also members of SPT. According to the disinfection booklet from Statens Serum Institut, products are also marketed by a number of other suppliers, who are listed in the booklet.

A typical biocide for chemical disinfection is buffered glutaraldehyde. The efficiency of glutaraldehyde solutions is highly dependent on the correct pH, and they are therefore supplied together with a separate alkaline buffer, which is added before use. The efficiency increases with increasing pH, which at the same time decreases the stability of the disinfectant.

A number of biocides for this application area is listed in the booklet from Statens Seruminstitut giving advice and instructions about disinfection in the health care sector. These suggestions include hypochlorite, chlorine dioxide, chloramine and dichloro isocyanurate. A consumption of these has not been revealed by the assessment carried out by SPT.

Contact to some of the major hospitals in Denmark confirmed that very few chemical disinfectants are used for medical equipment. In the ‘Hygiene principles’ for the hospitals in Copenhagen County, it is stated that heat should be used whenever possible. Glutaraldehyde in a concentration of 2% is used for flexible endoscopes, and heat-sensitive equipment is soaked 60 minutes in a solution containing chlorine and potassium bromide. A typical biocide for chemical disinfection is buffered glutaraldehyde. The efficiency of glutaraldehyde solutions is highly dependent on the correct pH, and they are therefore supplied together with a separate alkaline buffer, which is added before use. The efficiency increases with increasing pH, which at the same time decreases the stability of the disinfectant. Glutaraldehyde is not significantly inactivated by organic material and is active against spores. Aldehydes, including glutaraldehyde, are among the more toxic disinfectants and gluteraldehyde is both irritant and sensitising.

Table 3.7
Identified biocides used for disinfection of medical equipment in Denmark 1998

Information about the consumption of biocides with finished products received from SPT only contains data from one of their member companies. The estimated consumption is therefore subject to quite some uncertainty.

3.2.4 Disinfectants for laundries

Laundry disinfectants can be used for laundry from the primary and secondary health care sector, hotels, nursing homes and other areas where disinfection is needed.

Typical biocides for this application area are chlorine, hypochlorite, peroxide and peracetic acid. The disinfectants which are used have a combined effect as both disinfectants and bleaching agents.

Main suppliers of bleaching agents and disinfectants are Henkel Ecolab A/S, Diversey Lever A/S and Novadan A/S (Larsen et al., 1998).

Table 3.9
Biocides used for laundry disinfection in Denmark

Estimates of the consumption from Larsen, 1998, is shown in Table 3.1. The total consumption is estimated at 277 tonnes.

Table 3.10
Consumption of biocides disinfectants for laundries in Denmark 1996

3.2.5 Disinfectants for air-conditioning system

Disinfectants can be applied to air-conditioning systems with the purpose of preserving the cooling liquid or disinfecting the system. Contamination of the cooling liquid is most likely to happen in open or semi-open systems, e.g. for control of Legionella and other pathogenic bacteria in cooling water in hospitals.

Contact to suppliers of cooling liquids showed that biocides used for liquid-cooling and processing systems and biocides for air-conditioning systems were very much the same. In this report, the biocides used for air-conditioning systems are therefore included in the description of product-type 11, preservatives for liquid-cooling and processing systems.

3.2.6 Disinfectants for chemical toilets

Disinfectants for chemical toilets are added with the purpose of cleaning and controlling possible growth of bacteria.

Chemical toilets are typically mobile and mostly found in boats, busses and campers with no connection to the sewer system.

Main importers and suppliers of biocides for chemical toilets in Denmark are Camper and DCT, both located in Jutland. Camper markets Thetford products and DCT markets Italian products. Neither of these companies are members of the trade-organisation SPT.

Among the SPT members only one company is registered.

A large number of biocides for toilet cleaning and disinfection is registered in the Product Register. It is however not possible to distinguish between ordinary toilet disinfectants and disinfectants for chemical toilets, but most likely some of the registered products are for chemical toilets.

According to a main supplier, who is not a member of SPT, his products only contain biocides as preservation and only in very small amounts (<0.1%). Table 3.1 therefore only contains data from SPT and cannot be considered representative to all biocides for this application area.

Table 3.11
Identified biocides used for chemical toilets in Denmark

According to the assessment carried out by SPT about 15 tonnes biocidal products was used for chemical toilets in 1998. The assessment, however, is estimated only to cover a part of the market, as the main suppliers are not members of the organisation.

It has not been possible to obtain detailed information of the rest of the market, and the total consumption will here be roughly estimated on the basis of the following assumptions.

According to the Statistics Denmark, the number of registered caravans is around 100,000. Most caravans have a toilet, but not all of the toilets are used regularly. Typically, 150 ml of the biocidal product is used for 20 l of water. Based on the experience of a few interviewed campers, it is assumed that on average 0.3-1.5 litres of biocidal product are used per caravan per year.

The total consumption will based on these assumptions be approximately 30-150 tonnes. Quaternary ammonium compounds seem to be the biocides of choice in concentrations around 10%.

Table 3.12
Consumption of biocides for chemical toilets in Denmark 1998

3.2.7 Disinfectants for swimming pools

The quality of water in swimming pools is regulated through the Statutory Order No. 195 of 5 April 1998 that is under revision. This order covers swimming pools, which are intended to be used by a larger number of people, e.g. in schools, hotels, camping grounds, holiday camps, etc.

In order to ensure a low level of microbes and thereby protect the bathers from getting sick, swimming pool water is disinfected with chlorine gas or hypochlorite. Sodium hypochlorite is the main disinfectant for this application area, whereas calcium hypochlorite and chlorine gas are only used in smaller amounts and not very often.

Main suppliers of sodium hypochlorite for swimming pools include Henkel Ecolab A/S, Novadan A/S, and Diversey Lever A/S.

Table 3.13
Biocides used for swimming pools in Denmark

In 1981 the consumption of disinfectants for swimming pools was estimated in a report from the Danish Environmental Protection Agency /Bidsted et al, 1981/. At that time, the consumption of sodium hypochlorite was estimated at 3,250 tonnes, the consumption of chlorine gas at 5 tonnes and the consumption of calcium hypochlorite at 13 tonnes. Since 1981 the number of swimming pools has increased but the consumption of disinfectants has decreased at the same time. According to the Danish Techological Instute, Swimming Pool Technology /Ole Bidsted, 2000/ it must be expected that the consumption of sodium hypochlorite in 1998 should be lower than in 1981.

Based on an assessment made by SPT a few years ago, the consumption of sodium hypochlorite for swimming pools is estimated at 500-1,000 tonnes (Table 3.1).

Table 3.14
Consumption of biocides for swimming pools in Denmark 1998

3.2.8 Disinfectants for wastewater and hospital waste

Five major hospitals in Denmark, including the hospitals in Copenhagen County, have been asked about the use of disinfectants for waste and wastewater. None of the hospitals used disinfectants for this purpose, and it is assumed that this is the general picture all over the country.

There are no longer any approved products for soil disinfection on the Danish market according to the Danish Plant Protection Association.

Based on this information, the total consumption for these application areas is estimated to be zero.

3.3 Product-type 3: Veterinary hygiene biocidal products

Veterinary hygiene biocidal products are biocidal products used for veterinary hygiene purposes including products used in areas in which animals are housed, kept or transported.

The product-type can be subdivided into the following sub-types:

	Disinfectants applied directly to domestic animals
	Disinfectants for areas in which animals are housed, kept or transported
	Disinfectants for milking equipment

Biocidal products used for cleaning of teats and udder, for animals' footbaths, for disinfection of equipment for feeding and feed areas as well as products for disinfection of milking equipment are included in this section.

The estimates of consumption in this section include entries in the inventory from SPT, which could be positively correlated to use for veterinary purposes, i.e. entries like ‘udder cleaning’, ‘animal stables’ and ‘milking machines’. Entries in the inventory, which are described solely by wording like ‘cleaning’, ‘disinfection’, ‘surfaces’, ‘equipment’, ‘tubing’ or ‘containers’, are included in section 3.2.

3.3.1 Disinfectants applied directly to domestic animals

Disinfectants applied directly to domestic animals are used for the control or prevention of diseases, for cleaning the animals’ feet and for udder cleaning. The substances used for disease control or prevention are covered by the Veterinary Medicinal Products Directive (81/851/EEC as last amended by Directive 93/40/EEC). Products used to kill and/or repel arthropods are included in Main Group 3: Pest Control, product-type 18.

Disinfectants in products for cleaning the animals’ feet are considered biocides. Products used for teats and udder cleaning are considered biocides in the EU regulation (EU Biocidal Group, 1999). In Denmark, these products are covered by the Veterinary and Food legislation, but results regarding their use are included in Table 3.1 and Table 3.1.

For stocks of cattle, pigs and sheep, in which infectious skin diseases are a problem (e.g. digital dermatitis), disinfectants may be used in hoof baths, which the animals are forced to walk through regularly, e.g. on their way to the stable in which the milking takes place. According to the Danish advisory service for cattle (Landskontoret for Kvæg), the main use of disinfectants for cleaning the animals’ feet takes place in cattle farms and is at present increasing due to an increase in the problems.

Disinfectants for teats and udder are used before milking and for teats after milking. The products may be applied by means of cloths, by dipping or as sprays.

Two Danish suppliers of products for disinfection of animals’ feet have been identified: Vittfoss and Danish Genetics. The main suppliers of agricultural chemicals in general are not marketing products, specifically for hoof baths, but they state that some of the products sold for general disinfection in stables are also used for this purpose. The amounts should thus be included in section 3.3.2.

Danish producers and suppliers of disinfecting products for cleaning of teats and udder are Alfa Laval Agri, Ciba Geigy A/S, DiverseyLever, Medimerc A/S, Novadan A/S, Henkel-Ecolab A/S, Hypred Danmark A/S, Superfos Biosector A/S, B.S. ApS, S.A. Christensen, Danish Genetics A/S, J.P. Hansen Ltd., Jettadam Fabrikker A/S, Linds Handelsselskab, Manus Agroteknik, MW-cleantrade ApS, Nardos og S. Sørensen. Among these, Alfa Laval Agri, DiverseyLever, Novadan A/S and Henkel-Ecolab A/S are the dominating suppliers.

Biocides used for the application area are shown in Table 3.1. The list is based on the inventory of SPT supplemented by additional information (CuSO₄, chlorhexidine-digluconate and isopropanol)

The disinfectants used for hoofs are formaldehyde and CuSO₄. Due to the strong irritant and carcinogenic properties of formaldehyde, products containing this substance are not recommended by the advisory service. No information is available regarding the use of this substance for this purpose. Possible use of formaldehyde for hoof baths may be included in the consumption for stables, i.e. in section 3.2.2. According to the advisory service, the consumption of products for hoof baths is very limited, and it is not included in the consumption volumes below.

One of the biocides used for udder and teats cleaning is dodecylbenzene sulfonic acid (LAS). However, even if LAS is included in the EU-list of biocides for type 3 products, its classification as a biocide may be questioned, as it is mainly used as a detergent.

Sodium dichloroisocyanurat, which is frequently used for the cleaning of teats, is not mentioned for this use in the SPT-inventory. However, it is included under the heading ‘milking equipment’, and the use for cleaning of teats is supposedly covered by the consumption described in section 3.3.3.

Table 3.15
Biocides used for application directly to domestic animals (udder and teats) in Denmark

The total consumption of biocides for cleaning udder and teats in Denmark is estimated to be 19-22 tonnes per year (Table 3.1)

Table 3.16
Consumption of disinfectants applied directly to domestic animals in Denmark 1998

3.3.2 Disinfectants for areas in which animals are housed, kept or transported

Areas in which animals are housed, kept and transported are most often cleaned and disinfected on a regular basis in order to prevent the build up and/or dispersal of pests and/or diseases among the animals.

‘Disinfectants for areas in which animals are housed’ are used for disinfection of the entire stable, including disinfection of containers, consumption utensils, surfaces and pipe work for transport, storage and consumption of feed and drinking water. Such disinfection may be carried out, when a section of a stable is closed down, e.g. every 6 weeks by slaughtering of chickens, in case of heavy infections with e.g. salmonella, or occasionally after emptying the stables. Normally, a disinfection process is very extensive and comprises the whole interior of the building, including all equipment.

Furthermore, disinfectants may be used for the footwear of people working in the stables in the form of containers in which the footwear is cleaned before entering into the stables. According to the Danish advisory service, this practise is limited in Denmark, and the consumption is not included in the assessment.

The number of disinfectants used in pig and cattle farming is limited, as most cleaning is based on the use of high-pressure water and lime.

The principal Danish producers and suppliers are Alfa Laval Agri, DiverseyLever, Novadan A/S and Henkel-Ecolab A/S.

Disinfectants used for cleaning areas in which animals are housed, kept and transported are shown in table 3.17.

Table 3.17
Biocides used for application in areas in which animals are housed, kept or transported, including feed areas in Denmark

The total consumption of biocides for areas in which animals are housed, kept or transported in Denmark amounts to 4-5 tonnes per year, of which formaldehyde, glutaraldehyde and hydrogen peroxide are the dominant, sold in amounts of one tonne per year of each.

Sodium dichloroisocyanurate is not mentioned for this use in the inventory of SPT, but the use for disinfection in stables is expected to be covered by the consumption volumes in section 3.3.1.

Table 3.18
Consumption of biocides for disinfection around domestic animals in Denmark 1998

3.3.3 Disinfectants for milking equipment

Disinfectants for milking equipment may be covered by Directive 92/46/EEC (production and placing on the market of milk). However, as the products used for this purpose are used in the same production process as the remaining veterinary products, the available data on the use of disinfectants for milking equipment are presented here.

Disinfection of milking equipment includes the milking machines, pipework and containers used for the milk. Typically, these are disinfected after each batch of milk by flushing the system with the disinfectant followed by clean water to remove possible residues of the product.

The Danish market for agricultural, biocidal products is dominated by four producers and suppliers: Alfa Laval Agri, DiverseyLever, Novadan A/S and Henkel-Ecolab A/S.

The use of disinfectants for milking equipment is dominated by chloride and acid compounds.

Table 3.19
Biocides used for the application area milking equipment in Denmark

3.3.3.3 Consumption of biocides with finished products

The total, annual consumption of disinfectants for milking equipment in Denmark is estimated to be 71-83 tonnes of which the chloride compounds account for 25-30 tonnes and the acid compounds for 43-51 tonnes.

Table 3.20
Consumption of disinfectants for milking equipment in Denmark 1998

3.4 Product-type 4: Food and feed area disinfectants

Food and feed area disinfectants are used for disinfection of equipment, containers, consumption utensils, surfaces or pipe work associated with production, transport, storage or consumption of food, feed or drink (including drinking water) for humans and animals.

The product-type can be organised into the following application areas:

	Food and feed area disinfectants used in agriculture
	Disinfectants used in the food-processing industry
	Disinfectants used for food handling in retail shops or other food handling areas

Food and feed area disinfectants are used to secure a high standard of hygiene in order to interrupt potential sources of infection and contamination of food and feed, and thereby minimising the risk of foodborne diseases.

3.4.1 Food and feed area disinfectants used in agriculture

Disinfectants are used in agriculture for disinfection of containers, consumption utensils, surfaces and pipe work for transport, storage and consumption of feed and drinking water. Feed area disinfectants are not used on a routine basis. Disinfection may be carried out when a section of a stable is closed down, e.g. every 6 weeks by chicken slaughtering, in case of heavy infections with e.g. salmonella, or occasionally after emptying the equipment. The feed system will not be disinfected separately. In practice, a disinfection process is very extensive and comprises the complete interior of the building including all equipment.

Disinfection of the feed system is therefore integrated in the disinfection process for veterinarian hygiene purposes. It is not possible to estimate the biocide consumption specifically with regard to disinfection of feed systems. The biocides used for this application are the same as used for veterinarian hygiene purposes. According to the industry, the consumption is included in the figures for veterinarian hygiene purposes (in section 3.3).

Under certain circumstances, e.g. by private well-borings with varying water quality, or when drinking water is stored in open systems, biocides are used for disinfection of drinking water. In these cases, disinfectants approved for the food industry are used. According to the industry, the consumption for this application is included in the figures for the food-processing industry (section 3.4.2.).

3.4.2 Disinfectants used in the food-processing industry

Disinfectants intended for use in the food-processing industry are mainly defined or within the scope of other directives e.g. 89/109/EEC (materials and articles intended to come into contact with foodstuffs), 92/46/EEC (production and placing on the market of milk), 89/437/EEC (production and placing on the market of egg products), 89/1107/EEC, 88/388/EEC and 95/2EC (food additives and flavourings), 91/493/EEC (production and placing on the market of fishery products), 95/5/EC (production and marketing of certain products of animal origin). This means that products comprised by these directives are excluded from the Biocide Directive.

The Biocide Directive applies to products intended for hand disinfection. The Biocide Directive also applies to products intended for disinfection in food retail shops and other food handling areas, e.g. cafeterias and canteens.

In Denmark, the national legislation does not discriminate between disinfectants used in the food-processing industry or in retail shops and other food handling areas. This means that all disinfectants, which may come into contact with foodstuffs, must be approved by the Danish Veterinary and Food Administration. The suppliers do not categorise the consumption of disinfectants, and in the light of this, it is not possible to estimate the consumption exclusively for the retail area and other food handling areas.

The estimate of consumption covers disinfectants used for the whole food handling area in Denmark.

Disinfectants are typically used after clean-up processes for disinfection of equipment, containers, consumption utensils, surfaces or pipework associated with the production, transport, storage or consumption of food or beverages. After application of the disinfectant, the treated area/equipment is washed with water.

The Danish main producers of disinfectants or the food industry are Henkel-Ecolab and Novadan, and the main suppliers are Henkel-Ecolab, Diversey-Lever, Novadan, SFK a.m.b.a. and Nopa-Nordisk Parfumerivarefabrik A/S.

Producers and suppliers of disinfectants for foodstuffs are organised in the trade organisation SPT (Soap, Perfume and Toiletware).

All disinfectants, which may come into contact with foodstuffs, must be approved by the Danish Veterinary and Food Administration. The identity of active biocidal compounds is therefore well known. The approval is based on the concept that residues do not cause acute or chronically harmful effects to the consumer. Furthermore, in order to secure that food will not be contaminated by biocides, all disinfected equipment must be washed with water before use.

A list of approved active ingredients in disinfectants (of 9 October 1998) is shown in the table.

Table 3.21
Biocides approved by the Danish Veterinary and Food Administration ¹⁾

1) List of approved active ingredients in disinfectants for the food area, 9 October 1998

Approximately 200 biocides are registered as disinfectants in PROBAS. The application areas are not indicated, and consequently it is not possible to pick out those intended for the food and feed area. According to the industry, only a limited number of the biocides accounts for the main part of the consumption for food area disinfection.

Chlorine in the form of liquid Sodium hypochlorite is the most well-known and used disinfectant in the food industry. Sodium hypochlorite causes irreversible oxidative attacks on the cells in microorganisms. A powdered organic chlorine-releasing compound like sodium dichloroisocyanurate is used in small amounts. Chlorine itself is very sensitive to organic material and will suddenly be reduced by ‘dirt’ leading to ineffectiveness.

Hydrogen peroxide and peracetic acid are oxidising disinfectants like chlorine.

Quaternary ammonium compounds (benzalkonium chloride and didecyl dimethyl ammonium chloride) are surfactants that disturb the permeability of the cell membrane resulting in cell death.

Table 3.22
Identified biocides used as disinfectants for food handling areas ¹⁾

1) Biocides that are used for food area disinfection according to the industry.

The total consumption of disinfectants for the food handling area is shown in Table 3.1 based on an inventory carried out by the trade organisation SPT. This estimate is subject to some uncertainty, because the figures do not include the total consumption of disinfectants used in other food handling areas than the food-processing industry. Some companies have divisions for the industrial market and the retail market. The consumption of disinfectants for other food handling areas, e.g. cafeterias and canteens will often be regarded as a part of the retail market, and as such reported under product-type 2: Private area and public health area disinfectants and other biocidal products.

Table 3.23
Consumption of biocides for disinfection of food handling areas in Denmark 1998

3.4.3 Disinfectants used for food handling in retail shops or other food handling areas

Disinfectant are used for food handling areas other than the food-processing industry, e.g. retail shops as butchers, bakeries, cafeterias, canteens and other catering activities to secure a satisfactory hygienic standard. As mentioned in section 3.4.2, the biocides for these application areas must be approved in Denmark by the authorities. In the light of this, the suppliers do not split the consumption of biocides for the food-processing industry and other food handling areas. The consumption for other food handling areas than the food-processing industry is included in the figures shown in section 3.4.2 and in some cases reported under product-type 2: Private area and public health area disinfectants and other biocidal products. The estimate of the consumption is subject to some uncertainty, because disinfectants intended for other applications, e.g. private cleaning, may be used professionally for disinfection in food handling areas.

Disinfectants are typically used after clean-up processes for the disinfection of equipment, containers, consumption utensils, surfaces or pipework associated with production, transport, storage or consumption of food or beverages in food handling retail shops or other food handling areas, e.g. cafeterias and canteens. After application of the disinfectant, the treated area/equipment is washed with water.

Actors of the market will also be covered by the description in section 1.2.2.

3.5 Product-type 5: Drinking water disinfectants

Drinking water disinfectants are primarily used for the disinfection of drinking water at the waterworks. The product-type includes disinfectants used by the waterworks and disinfectants used locally by the user before drinking low quality water.

Drinking water disinfectants are used at the waterworks to control the microbiological quality of the water before it is supplied to the distribution network. The intention is to destroy pathogenic and infectious micro-organisms and to reduce the total counts of micro-organisms to an acceptable level.

Disinfectants for cleaning of the drinking water distribution network are used only occasionally when laying down new drinking water mains, and only if flushing with drinking water is not sufficient to secure low content of germs.

Drinking water disinfectants can be used locally for disinfection of drinking water in case of bad sanitary conditions, e.g. during travelling and temporary stays in developing countries. These products are not used in Denmark.

Chlorine for disinfection of drinking water at the waterworks is supplied by common suppliers of industrial chemical compounds.

The chlorine is also used as ingredient for site production of monochloroamine disinfectants by the waterworks themselves.

Harmful microorganisms are not allowed in water for human consumption. The content of total microorganisms, measured as total count at 22 and 37°C, must be below 50 and 5 per ml, respectively.

In Denmark, it is not the drinking water policy to add disinfectants except in areas where ground water of good bacteriological quality cannot be achieved, or in areas where surface water is used for drinking water.

Addition of disinfectants to drinking water can only be carried out at a waterworks, if the Regional County finds it acceptable and intends to approve the disinfection product according to the § 21 in the Water Supply Act. Normally, the Danish EPA is asked to carry out an assessment of the disinfection product and to set up purity criteria for the product.

Until now, only chlorine products like chlorine and sodium hypochlorite and substances produced from them, e.g. monochloroamine, are used as disinfectants for drinking water. The same disinfectants are used for surface water during the treatment process at present, but ozone has been used in a newly closed plant. Disinfection must be carried out in such a way that formation of disinfection by-products is minimised. Therefore, chlorination is only accepted after the flocculation and sedimentation step of the water treatment process.

The biocidal properties are based on the strong oxidizing effect of the chlorine and chlorinated compounds.

Disinfection at drinking water supply plants is primarily carried out when drinking water production is based on surface water. Only one of Copenhagen’s seven waterworks produces water from surface waters and only in short periods of the year - mainly the summer season.

The Copenhagen Water Supply uses chlorine as a third step in the surface water treatment process in amounts of approximately 18 mg/l. The fourth step is to remove all residual chlorine. The last step before the water leaves the waterworks is to add monochloroamine in amounts of approximately 0.35 mg monochloro-amine/litre drinking water.

Gentofte Water Services has stopped using surface water, but treats the ground water with monochloroamine to secure the biological quality of the water, before it leaves the waterworks. The dosing of 0.20 mg/l results in approximately 0.15 mg monochloroamine/litre drinking water leaving the plant.

The waterworks prepare the monochloroamine by adding hypochlorite to an aqueous solution of ammonium sulphate at adequate pH.

Some minor waterworks, Christiansø, Skagen and Rørvig treat their drinking water with sodium hypochlorite before supplying water to the pipe system. The resulting concentration of free chlorine for Skagen is below 0.05 mg/litre drinking water and for Christiansø approximately 0.1 mg/litre drinking water.

Table 3.24
Biocides used for water disinfection in Denmark

3.5.1.3 Consumption of biocides with finished products

The total consumption of biocides for this application area is based on information from the waterworks. The annual consumption of drinking water disinfectants in 1998 is shown in table Table 3.1. Even though detailed figures from Skagen and Rørvig waterworks are not included, the estimate is assessed to cover 95% of the consumption. The great variation in annual consumption is caused by the fluctuating amount of surface water used for production of drinking water each year.

Table 3.25
Consumption of biocides for drinking water disinfection in Denmark 1998

4. Main group 2: Preservatives

4.1 Product-type 6: In-can preservatives

In-can preservatives are biocidal-products used for the preservation of manufactured products, other than foodstuff or feedingstuff, in containers by the control of microbial deterioration to ensure their shelf life.

In-can preservatives are used in virtually all water-based non-food products.

The product-type can based on application areas be organised into four application areas:

	In-can preservatives for paints
	In-can preservatives for inks, fountain water, adhesives and sealants
	In-can preservatives for cleaning materials
	In-can preservatives for other products

In-can preservatives for medicine, toys, cosmetics and human hygiene products are not included, as these products are covered by other directives.

There is a large number of in-can preservatives in use in many different products, and in this project it has not been possible to carry out a comprehensive assessment of all preservatives and applications.

In PROBAS, 236 different CAS No’s are registered as used as preservatives. As many of the water-based products are not registered in PROBAS, the actual number of preservatives may be higher.

It is in PROBAS not possible to distinguish between in-can preservatives and other preservatives. In total, 144 CAS No’s are registered as preservatives in the following product groups: Paint, inks, dyes, binders, adhesives, maintenance products, photographic products, cleaning agents and sealants. The preservatives in these products will either be in-can preservatives covered by this section or film preservatives covered by the next section. In-can preservatives may also be used in other product groups, and the list is consequently not comprehensive.

Of the 144 CAS No’s, 75 is used in less than 3 registered products and are not shown due to confidentiality. The remaining 68 preservatives are shown in Table 4.1 with the number of registered products indicated.

It should be noted that the preservatives registered in a large number of products are not necessarily the preservatives used in largest quantities. As mentioned, most water-based products as paint and cleaning agents are not registered in PROBAS.

The table, however, gives an indication of the large number of preservatives in use, and indicates some of the most widespread. Of the upper 12 compounds as regards product groups, the isothiazolones(4), 1,3-,2-bromo-2-nitro-propanediol and quaternary ammonium compounds (2) are some of the preservatives estimated to account for the major part of the consumption. As regards formaldehyde, the current inventory indicates that formaldehyde is not very widespread as in-can preservative today.

The consumption figures for the different application areas are assessed in the following sections.

Table 4.1
Preservatives registered in >2 products in PROBAS under the product groups: Paint, inks, dyes, binders, adhesives, maintenance products, photographic products, cleaning agents and sealants

4.1.1 In-can preservatives for paints

In-can preservatives are used for preservation of all types of water-based paints.

4.1.1.1 Actors on the market

There is no Danish production of in-can preservatives for paints. The main suppliers of the preservatives are Thor Chemie GmbH and Rohm & Haas; both without Danish offices.

Producers and suppliers of paints containing in-can preservatives are organised in the trade organisation 'The Danish Paintmakers Association' ('Foreningen for Danmarks Lak- og Farveindustri').

The content of biocides in paints has as a part of another ongoing project supported by the Danish EPA been assessed by a panel of experts from the paint industry. The following information on in-can preservatives in paint is based on this work, if nothing else is mentioned.

The main biocides registered in PROBAS for the application is listed in Table 4.2. According to the industry only a limited number of the biocides (indicated in the table) accounts for the main part of the consumption. Basically, the same biocides are used for both indoor and outdoor water-based paints for both masonry and wood.

There are more than 39 biocides registered as preservatives in paints in PROBAS. The list of preservatives is not shown due to confidentiality. For most water-based paints, there is no obligation to declare the products to PROBAS, and the register cannot be used for estimation of the total content of biocides in paint.

Table 4.2
Main biocides used as in-can preservatives for paint in Denmark ¹⁾

1) The list includes the main biocides registered in PROBAS for the application. Some of the biocides may, however, not be in use today. According to the industry a limited number of biocides accounts for the main part of the consumption (indicated as most common).

2) Concentrations in the paint according to PROBAS. The average concentrations in common products are shown in the next table.

The total consumption of water-based paints in Denmark is 33,000-36,300 tonnes. The estimated total consumption of in-can preservatives with paint is shown in Table 4.3. The estimate is based on the typical content of the preservatives and the consumption of the relevant types of paint. The basis for the estimate is indicated in the notes to the table. According to the industry a typical water-based paint contain either 200 ppm BIT, 30 ppm CIT/MIT or 0,1% Bronopol. The biocides may be used in combination and if so used in proportionally lower concentrations.

Table 4.3
Consumption of in-can preservatives with paint in Denmark 1998

4.1.2 In-can preservatives for inks, fountain water, sealants and adhesives

In-can preservatives are used in water-based inks, fountain water for offset printing, and water-based sealants and adhesives.

Concerning adhesives, in-can preservatives are present in most types; among others: Adhesives based on natural polymers, polymer dispersions/emulsions and adhesives based on water-soluble polymers. In sealants, preservatives are used in latex acrylic sealants that only account for a small part of the total consumption of sealants.

Producers and suppliers of inks, sealant and adhesives are organised in the trade organisation 'The Danish Paintmakers Association' ('Foreningen for Danmarks Lak- og Farveindustri'). Fountain water is usually supplied by the same business as supply the inks.

The main suppliers of inks are Akzo Nobel Inks A/S, BASF Tryksystemer A/S, Coates Lorilleux A/S, Zeller & Gmelin A/S, Resino Trykfarver A/S, Sicpa Denmark A/S, Sun Chemical Hartmann A/S.

Main suppliers of adhesives and sealant are Casco A/S, Aaffa A/S, Bostik A/S, Dana Lim A/S, Wacker-hemie Danmark, C Ljungdal A/S, Sika Danmark A/S, Dafa A/S, but there are several other actors on the market.

4.1.2.2 Biocides used in Denmark for the application area

Identified biocides used for preservation of inks, fountain water, sealants and adhesives in Denmark are shown in Table 4.4. A large number of different products are marketed and the list is probably not comprehensive. The data are based on an inventory carried out by the Danish Paintmakers Association concerning sealant and adhesives, in combination with information obtained by means of a questionnaire to suppliers of inks and fountain water. Less than half of the suppliers answered the questionnaire.

Table 4.4
Preservatives used for inks, fountain water, sealants and adhesives in Denmark

1) Typical concentration in the products. The agents are often used in combinations.

2) In some semi-manufactures for adhesives the compounds exist on hydrochloride form in acid solution as 3(2H)-Isothiazolone, 5-chloro-2methyl-, hydrochloride (CAS No. 26530-03-0) and 2-methyl-2H-isothiazol-3-one hydrochloride (CAS No. 26172-54-3).

In PROBAS, there are 29 biocides registered as preservatives in dyes, 13 in dyes, 17 in sealants and 25 in adhesives. The list of preservatives is not shown due to confidentiality.

The estimated total consumption of preservatives with these product groups is shown in Table 4.1.

According to the trade statistics from Statistics Denmark, the total consumption of inks in 1998 was 16,000 tonnes. Based on information from suppliers, it is estimated that only about 2,500 tonnes of this is water-based and contains preservatives. The consumption of fountain water containing preservatives is based on information from suppliers estimated at about 500 tonnes.

According to the trade statistics from Statistics Denmark, the total consumption of sealant and fillers in 1998 was about 34,000 tonnes. According to statistics of the trade organisation FDLP, water-based products containing preservatives only accounted for a relatively small part of this. Based on an assessment done by the organisation at the beginning of 2000 covering suppliers of sealants and fillers, it is estimated that only about 200-500 tonnes of these products should contain preservatives.

The total consumption of adhesives in 1998 was approximately 10,000 tonnes according to the trade statistics. The main part of this seems to be preserved and the assessment by the trade organisation revealed that an amount of the same magnitude was preserved with in-can preservatives.

Table 4.5
Consumption of preservatives with inks, fountain water, sealant and adhesives in Denmark 1998

4.1.3 In-can preservatives for cleaning materials

In can preservatives are added to virtually all water containing cleaning materials except cleaning materials with a very high or low pH or cleaning materials which are preserved by the content of disinfectants (see Main Group 1).

The producers of cleaning materials are organised in SPT, the Trade Organisation for Soap, Perfume and Toiletware.

The Danish main producers of food area disinfectants are Henkel-Ecolab and Novadan, and the main suppliers are Henkel-Ecolab, Diversey-Lever, Novadan, SFK a.m.b.a. and Nopa-Nordisk Parfumerivarefabrik A/S. The main suppliers of disinfectants for private areas are Reckitt Benckiser A/S, A/S Blumøller, Colgate Palmolive and Lever Fabergé Danmark A/S whereas the main suppliers of biocidal products for professional and industrial use are Henkel Ecolab A/S, Novadan A/S and Diversey Lever A/S.

There are 96 different biocides registered as preservatives in cleaning materials in PROBAS. The list of preservatives is not shown due to confidentiality.

It seems, however, only to be relatively few preservatives which account for the main part of the consumption. The main biocides used for preservation of cleaning materials according to general experience of the trade organisation SPT are shown in Table 4.6.

Table 4.6
Main biocides used for preservation of cleaning materials in Denmark

The total consumption of water-based cleaning materials in Denmark is estimated at 40,000-60,000 tonnes based on information from the trade organisation SPT.

The exact distribution between the different preservatives is not known. As the different preservatives are used in concentrations ranging from 0.02 to 0.7%, the total consumption of preservatives with the cleaning materials can only be estimated with high uncertainties (Table 4.7).

Table 4.7
Consumption of in-can preservatives with cleaning materials in Denmark 1998

4.1.4 In-can preservatives for other products

In-can preservatives are used for a large number of other product types, among others:

	Dyes and textile processing fluids
	Maintenance products (polishes, wax emulsions, car maintenance agents, etc.)
	Photographic process fluids
	Additives to concrete
	Lubricants and machine oils
	Water bed fluids
	Industrial fluids (e.g enzyme solutions)

For textile processing, biocides may be used in dyes and fluids for sizing and finishing (Laursen et al., 1997). Sizing is the protection of threads during weaving because of mechanical actions. Often the protecting agent is starch, which is degradable for microorganisms. But biocides are not necessarily used for this purpose though.

‘Other products’ covers a wide range of products, and it has not been attempted to obtain market information.

It has not been possible to make a comprehensive inventory of the preservatives used in other products. Preservatives identified by direct information from suppliers are shown in Table 4.8. The preservatives are the same as used for other technical purposes.

Table 4.8
Identified in-can preservatives for other products

As shown in Table 4.1, the number of different biocides is very high, and it cannot based on the obtained information be concluded that the biocides shown in Table 4.8 are the most used for ‘other applications’. The number of different biocides registered as preservatives in PROBAS is 36 for maintenance products (wax and polish among others) and 20 for photographic processing fluids. The list of preservatives is not shown due to confidentiality.

4.1.4.3 Consumption of biocides with finished products

The consumption of preservatives with ‘other products’ has not been assessed in detail, but the total consumption may be significant compared to the application areas covered by the previous chapters. For example, the total supply of wax and polish was according to the trade statistics about 6,000 tonnes of which some may not contain preservatives.

It is roughly estimated that the consumption of preservatives with ‘other applications’ is in the order of magnitude of 10-100 tonnes.

4.2 Product-type 7: Film preservatives

Film preservatives are used for the preservation of films or coatings by the control of microbial deterioration in order to protect the initial properties of the surface of materials or objects such as paint, plastic, sealants, adhesives, paper and art works.

The product-type can be organised into three sub-types:

	Film preservatives for paints
	Film preservatives for plastics
	Film preservatives for sealants, fillers and other products

4.2.1 Film preservatives for paints

Film preservatives are used for preservation of most types of topcoat paints used for outdoor applications by the control of microbial (mainly fungal) deterioration of the paint film.

Biocides used in priming wood-care products, for which the main function is a protection of the wood agaist microbial detoriation, are included in product-type 8: 'Wood preservatives'.

The content of biocides in paints has as a part of another ongoing project supported by the Danish EPA been assessed by a panel of experts from the paint industry. The following information on film preservatives in paint is based on this work, if nothing else is mentioned.

The main suppliers of film preservatives for paint on the Danish market are Troy chemical corp. (IPBC), Bayer A/S (dichlorfluanid, tolyfluanid) and Jansen Pharmaceuticals (Propiconazol), but there a several other suppliers.

Actors on the paint market mentioned in section 4.1.1 also apply to film-preservatives in paint.

Biocides registered in PROBAS for the application is listed in Table 4.1. Except for Di-butyl-p-cresol the use of the biocides has been confirmed by the industry as actually used today.

In some linseed oil paints for outdoor use an extract of grapefruit-seed, Citricidal, is used as fungicide (Henriksen, 2000). The active component of Citricidal is a quaternary ammonium chloride (a diphenol hydroxybenzene reacted with ammonium chloride) (Nutriteam, 2000). Also zinc-sulfate (7733-22-0) may be used for linseed oil paints.

Table 4.9
Main biocides used as film preservatives for paint in Denmark 1)

1) The list includes the main biocides registered in PROBAS for the application except bis(tributyltinoxid), which is still registered, but today not allowed for this application. Except for Di-butyl-p-cresol the use of the biocides has been confirmed by the industry.

2) Concentrations according to PROBAS. The average concentrations in common products are shown in the next table.

According to the industry, different film-preservatives are typically used for different applications as shown in Table 4.10.

Table 4.10
Typical concentration of film preservatives in outdoor paints according to the industry

1) According to PROBAS; the concentration is not indicated by the industry.

The estimated total consumption of film-preservatives with paint is shown in Table 4.11.

The estimate is based on the typical content of the preservatives and the consumption of the relevant types of paint. The basis for the estimate is indicated in the notes to the table.

Table 4.11
Consumption of film-preservatives with paint in Denmark 1998

4.2.2 Film preservatives for plastics

Plastic products are in general not preserved against microbial degradation, but biocides may be added to plastics containing plasticisers to prevent microbial growth at the surface. During use of the plastic product, the plasticiser will diffuse to the surface and in moist environment, the plasticiser will be attached by microorganisms, especially fungi, which use the plasticiser as carbon source. In some flooring products, the biocide is added for antiseptic reasons to prevent growth of undesirable bacteria at the surface.

Plasticisers and other degradable additives may be added to different plastics, but soft PVC seems to account for the main part of preserved plastic.

The main application areas for soft PVC containing fungicides are roof foils, tarpaulins, bathroom curtains and tents of PVC coated fabric or reinforced PVC foil, (see section 4.4.1) and some types of PVC flooring (vinyl flooring) for bathrooms, busses and institutions.

The range of plastic products that may be preserved with fungicides appears from catalogues from producers of biocides. The catalogues from Rohm and Haas and Ackros Chemicals, some of the leading producers of preservatives for this application, mention the following application areas: Swimming pools (pool liners, accessories and furniture), boats (seat cushions, boat bumpers, canopies), geomembranes, grill covers, lawn furniture, wire insulation, wall coverings, kitchen products (cutting boards, countertops, cooking utensils, refrigerator and appliance gaskets), bathroom products (shower safety mats, toilet seats and covers, soap and lotion dispensers), automotive gaskets, shoes and cleaning products (trash cans, scrub and mop buckets, dustpans). According to suppliers of biocides, biocides seem not to be used in Denmark for production of these products, but imported products may contain biocides.

The only identified supplier of biocides for plastic in Denmark is Akcros Chemicals Nordic A/S. The only identified Danish producer of preserved PVC is Duratex A/S.

Roofing membranes and PVC flooring are imported, mainly from other Nordic countries.

It has not been possible to make a comprehensive assessment of biocides in all products within this application area, as most of the products are imported. Table 4.1 includes biocides in some of the main product groups: PVC roofing and flooring and PVC-coated fabric for tarpaulins and tents. OBPA seems to be the main biocide of choice for products produced in Northern Europe, but it has not been possible to obtain specific information on biocides in PVC produced in other parts of the world.

Table 4.12
Identified film preservatives used for plastics in Denmark

4.2.2.3 Consumption of biocides with finished products

As mentioned above it has not been possible to cover all applications of biocide preserved plastics. The estimate of the total consumption of biocides with roofing membranes is based on information from one main supplier. The estimate regarding PVC flooring and PVC coated tents and tarpaulins are based on new information from suppliers of the products. It should be noted that only a minor part of PVC flooring contains biocides.

In total, these applications correspond to a PVC consumption of 2000-3000 tonnes.

The biocide consumption with PVC and other plastics for other applications has not been assessed in detail. The order of magnitude can, however, be indicated by the amount of PVC used for these other applications. It is not known to what extent biocides are used for these applications if used at all. In the most resent assessment of the PVC consumption in Denmark from 1996, the following consumption figures were estimated:

	Fenders and other maritime equipment: 65 tonnes
	Water beds: 12 tonnes
	Shower curtains <50 tonnes
	Boots and waders: 380 tonnes
	Cars: 3,160 tonnes (including PVC for undersealing which must be expected to be without biocides)

Cars could potentially account for a significant part of the film preservatives for plastic. There is no Danish production of cars, and it has been beyond the limits of this project to gather information on biocides in imported cars.

The remaining applications are estimated to account for <1000 tonnes PVC, which is significantly less than the applications covered in Table 4.1. The total content of biocides for other applications is roughly estimated to be <2 tonnes.

Table 4.13
Consumption of film preservatives with plastic products in Denmark 1998

4.2.3 Film preservatives for sealant, fillers and other products

Film preservatives may also be used in sealant, fillers, glues and adhesives.

Fungicides are added as film preservatives to sealants and fillers for application in wet rooms. According to Danish suppliers sealants for outdoor use around windows, between concrete panels, around sheeting, etc. in general do not contain fungicides.

Film preservatives are in general not added to glues and adhesives. In some instances, however, they are added to prevent mould growth.

Producers and suppliers of sealants are organised in the Danish Adhesives and Sealants Association and the suppliers will be the same as mentioned in section 4.1.

An assessment made by the trade organisation the Danish Adhesives and Sealants Association revealed rather few film preservatives used in products on the Danish market (see Table 4.14). The list cannot be considered comprehensive, as other film preservatives may be present in products not covered by the assessment.

Table 4.14
Film preservatives used for sealants, fillers and other products in Denmark

4.2.3.3 Consumption of biocides with finished products

The total consumption of sealants and fillers was according to Statistics Denmark in 1998 about 22,000 tonnes (see section 4.1.4). According to the assessment made by the trade organisation, only a relatively small amount of oil-based fillers, solvent-based acrylic sealants, silicone sealants and ‘other’ sealants contain fungicides. In total these fillers and sealants account for about 111 tonnes. The assessment may not be comprehensive, and the total amount of sealants and fillers with fungicides is here roughly estimated to be 120-500 tonnes.

The exact distribution between the different film preservatives is not known. The estimated total consumption of fungicides, based on an average concentration of the fungicides of 0.2-0.4%, is shown in Table 4.15. The estimate on the total consumption is very uncertain, but compared to the consumption of film preservatives with paint, the consumption with sealant and fillers is certainly rather small.

Table 4.15
Consumption of film preservatives with sealants and other products in Denmark 1998

4.3 Product-type 8: Wood preservatives

The product-type includes products used for the preservation of wood or wood products by the control of wood-destroying or wood-disfiguring organisms. The product-type includes both preventive and curative products. Treatment of wood before the sawmill stage is not covered by the Biocide Directive.

The consumption of biocides with wood preservatives for control of wood-destroying organisms is registered in the Danish Pesticide Statistics (Danish EPA, 1999 A).

The product-type can be organised into two sub-types:

	Vacuum preservatives and pressure preservatives
	Preservatives for surface treatment

The first sub-type includes preservatives used in industrial processes, whereas preservatives for surface treatment are used mainly by craftsmen and private persons.

The product-type does not include biocides for preservation of paints, where the effect of the biocide is to preserve the paint itself. These are included in product-type 6 'In-can preservatives' and product-type 7 'Film preservatives'.

It should be noted that the term ‘wood preservatives’ in Danish is often used as synonym of all ‘wood-care products’. In this context, ‘wood preservatives’ only cover wood-care products for priming.

4.3.1 Vacuum and pressure preservatives

Pressure preservatives are used for wood for exterior use with a high risk of degradation, i.e. wood in contact with water or soil. A specific method is used for preservation of poles.

Vacuum preservation is mainly used for preservation of wooden doors and window frames.

Producers and suppliers of vacuum and pressure preservatives are organised in the trade organisation 'The Danish Paintmakers Association' ('Foreningen for Danmarks Lak- og Farveindustri' ).

Main Danish producers of these preservatives in 1998 were Rentokil Initial A/S, S.Dyrup & Co A/S, Sadolin Woodcare, A/S Hygæa, Tanaco Danmark A/S, and Akzo Nobel Industrial Coating A/S.

Main suppliers of these preservatives in 1998 were (apart from producers) BASF Danmark A/S, Beta DK Aps, Kai R. Spangenbergs Eftfl. I/S, and Hickson Timber Protection.

Biocidal products used for control of wood destroying organisms of wood in Denmark have to be approved by the Danish EPA and are described in the survey of approved pesticides (Danish EPA 1999 B).

The consumption of active agent in preservatives for vacuum and pressure preservation in Denmark in 1998 is listed in Table 4.16 and Table 4.17.

Of the total consumption of pesticides in Denmark in 1998, wood preservatives accounted for 7% corresponding to 297 tonnes (Danish EPA 1999 A).

Of the total production of industrial-preserved wood in Denmark in 1998, 87.1% was preserved by a pressure process, and 12.7% by a vacuum process. The last 0.2% of the production was production of poles using CKB-agents (copper, chromium, boron). In 1998, 87 plants were approved by Danish Impregnation Control. Of these plants, 64 produced vacuum-treated wood, 21 pressure-treated wood, and 2 plants produced masts and poles (Dansk Imprægneringsstatistik, 1998).

Table 4.16 Se her!
Consumption of biocides for production of pressure-preserved wood in Denmark 1998 ¹⁾

Table 4.17 Se her!
Consumption of biocides for production of vacuum-preserved wood in Denmark 1998 ¹⁾

The consumption of biocides with finished wood products in Denmark differs from the consumption for production as import and export of preserved wood alter the figures. In Table 4.18, the estimate on the consumption of active agents in preserved wood used in Denmark in 1998 is shown.

Production, import and export of chromium and creosote with preserved wood have recently been assessed by Hansen et al. (2000 a,b), and the consumption of chromium and creosote is derived from these analyses.

Figures for production of vacuum-preserved and pressure-preserved wood were found in the Danish Statistics of Preserved Wood (Dansk Imprægneringsstatistik, 1998). Statistics Denmark has figures for import and export of different wood products, but the products are not grouped to preservation method (Statistics Denmark 1999a). The statistics on import/export seem only to include a minor part of the actual import/export of preserved wood, and figures on import/export have been derived from Hansen et al. (2000 b) (see appendix 2).

For the estimate of the total import/export of biocides with wood products, it is necessary to make some assumptions regarding the content of biocides in imported/exported products. The basis for the estimates can be found in Appendix 2.

It is by Hansen et al. (2000 b) estimated that the net import of pressure-preserved wood is about 90% of the Danish production for Cr-containing wood and about 20% for Cr-free wood (see appendix 2) thereby increasing the consumption of biocides for this purpose compared to the Danish production. The main import is from the other Nordic countries.

The consumption of biocides with vacuum-preserved wood products is slightly smaller than the consumption for production of these products in Denmark due to a net export of preserved windows and doors, but there is a considerable uncertainty regarding the biocides that are actually imported/exported.

Both production and import of wood preserved with arsenic is now prohibited, but chromium and creosote are still allowed in imported wood.

Table 4.18
Consumption of biocides with vacuum-preserved and pressure-preserved wood in Denmark 1998

The range between minimum and maximum values reflects the uncertainty of the preservation method of the products covered by the different commodity numbers in the trade statistics (see appendix 2).

Organotin compounds were not permitted after October 2000.

4.3.2 Preservatives for surface treatment

Preservatives for surface treatment are used for protection of wood constructions, which are only exposed to moistness at the surface and dry easily. The biocides used and the application areas are in many ways the same as for vacuum treatment, but surface application is cheaper and more suitable for larger constructions.

The preservatives are most often used as primers and covered by one or more layers of wood grain fillers and topcoats. In-can preservatives and film preservatives in wood grain fillers and topcoats are included in product-types 6 and 7.

The methods of surface treatment can be divided into:

	Immersion of the wood products into preservative baths
	Application by machinery
	Brush painting
	Spray painting.

4.3.2.1 Actors on the market

Suppliers of approved wood preservatives are listed in (Danish EPA 1999 B).

Producers and suppliers of wood preservatives are organised in the trade organisation 'The Danish Paintmakers Association' ('Foreningen for Danmarks Lak- og Farveindustri').

Main Danish producers of these preservatives in 1998 were Rentokil Initial A/S, S. Dyrup & Co A/S, Sadolin Woodcare, A/S Hygæa, Tanaco Danmark A/S, and Akzo Nobel Industrial Coating A/S.

Main suppliers of these preservatives in 1998 were (apart from producers) BASF Danmark A/S, Beta DK Aps, Kai R. Spangenbergs Eftfl. I/S, Hickson Timber Protection. Color Dragon A/S, Profa Amba, and Borup Kemi A/S.

The consumption of active agents in biocidal products used for surface preservation is shown in Table 4.19. The figures are derived from the Danish EPA. Some of the agents may as well be used for control of wood-destroying fungi in masonry.

The biocides are a very diverse group including boron, organotin, and other organic compounds. Both waterborne preservatives and preservatives based on organic solvents are used.

Table 4.19 Se her!
Consumption of biocides for surface preservation of wood in Denmark 1998 ¹⁾

Wood preservatives that contain propiconazol (CAS No 60207-90-1), boron acid (CAS No 10043-35-3) and disodium octaborate (CAS No 12008-41-2) are also approved for control of wood-destroying fungi in masonry, and a part of the consumption may in fact be used for masonry.

4.3.2.3 Consumption of biocides with finished products

The import/export of surface preservatives with wooden products is estimated to be quite small compared to the total consumption of preservatives for surface treatment in Denmark.

The relevant wooden products are not easily identified in the trade statistics, and due to the uncertainty the net import of surface-treated wood is estimated to range between 5,000 and 13,000 tonnes. See appendix 2 for the basis for the estimate. The biocides used for imported wood is roughly estimated under the assumption that the biocide content per tonne resembles the amount typically used for this application in Denmark.

The total consumption including import/export with wood products is shown in Table 4.20.

Table 4.20
Consumption of biocides for surface treatment of wood in Denmark 1998 including net import with surface treated wood

4.4 Product-type 9: Fibre, leather, rubber and polymerised materials preservatives

The group includes products used for the preservation of fibrous or polymerised materials, such as leather, rubber, paper and textiles by the control of microbiological deterioration of the material itself.

4.4.1 Preservatives for textiles

Biocides may be used for preservation of textiles during storage, transport and use of the textiles.

Liquids used during the production of the textiles (e.g. for sizing and finishing) and inks used for textile printing may also be preserved by biocides. The purpose of the use of these biocides is, however, to preserve the processing fluids or inks and not the finished textiles, and these agents are included in product-type 6: In-can preservatives.

The main application of preservatives for textiles is for preservation of textiles for outdoor applications. Preserved textiles are used for tents, tarpaulins, awnings, sunblinds, parasols, sails, waterproof clothing, etc. Virtually all textiles used for outdoor applications except clothing seem to be preserved by biocides. For in-door applications only shower curtains and in some instances mattress ticking are preserved.

Most of the textiles are made of synthetic materials like acrylic, polyester and PVC or is coated with PVC. The boundary between this sub-type and the sub-type 'Film preservatives for plastics' in section 4.2.2 is not clear-cut. For example bathroom curtains and tarpaulins are mainly made from reinforced soft PVC, whereas the function of the biocides is to prevent microbial growth on the surface. It has been chosen to include the PVC products in section 4.2.2 together with other uses of PVC and include the remaining textile products in this section, although the primary function of the biocides on synthetic textiles is also film preservative.

It is actually only for cotton textiles that the primary function of the preservatives is to preserve the fibres itself. Today cotton seems mostly (apart form clothing) to be used for garden furniture fabric, whereas it has been replaced by synthetic fibres for other applications. According to the producers of tents, awnings, etc. one of the reasons for this substitution is that the biocides on the market today do not provide the necessary protection of the cotton fabric. Cotton fabric was formerly preserved with pentachlorophenol (PCP), which is now prohibited in Denmark, but is still used for fabric in some other EU countries, especially the UK.

Biocides are not used for protection of textiles during storage and transport in Denmark, but textiles and clothing imported from sub-tropical and tropical areas, especially from Eastern Asia, may contain small amounts of biocides applied for preservation of the textiles during transport and storage in the humid and warm climate. The biocides are applied by spraying the biocides into the containers (Eksportrådet, 1996) and can be found in trace amount in textiles. Among the biocides, PCP seems still to be used to some extent in Asia for this purpose.

Clothing, especially for sport, may be preserved with biocides to prevent odour producing microbial growth on the sweat. One example is the use of tributyltin in some t-shirts. No examples have been found as regards the use of biocides for clothing for outdoor applications. It has within this project not been possible to assess these application areas further.

Table 4.21
Biocides used for textile products produced in Denmark ¹⁾

1) Most of the fabrics are produced abroad, but are used for production of tents and other products in Denmark

Imported tents, awnings, etc. are predominantly produced in Asia. It has been difficult to receive information on the biocides used for preservation of the fabric.

The total consumption of biocides with textile products can only be estimated with very high uncertainty. The total consumption of cotton textiles for outdoor use has by 1983 been estimated at 500-600 tonnes, which were all preserved with pentachlorophenol (Tørslev, 1985). The total supply of tents, tarpaulins, awnings and sails in 1988 can based on the trade statistics be estimated at 5,000-7,000 tonnes (inclusive non-textile parts of the products). Only a part of this is the fabric and only a part of the fabric is preserved. The tarpaulins are virtually all produced of PVC and are included in section 4.2.2.

Based on the present information it is estimated that approximately 600-1,400 tonnes preserved textile is annually used in Denmark. Cotton seems only to be used for garden furniture, whereas the rest of the textiles are made of polyester, acrylic and other synthetic materials.

The estimated total consumption of biocides with textiles is shown in Table 4.22.

Table 4.22
Consumption of biocides with textile products in Denmark 1998

4.4.2 Preservatives for leather

Biocides are applied to leather during the tanning process for life-time preservation of the leather.

The only large Danish producer of leather is Swewi Svendborg A/S, but tanning also takes place in small scale at Mønsters Garveri. The biocides for tanning are directly imported by the users from suppliers abroad. Leather and leather products are imported by a large number of companies.

Biocides used for tanning in Denmark are shown in Table 4.23. Some of the other chemicals used for tanning may also have a biocidal effect, although the primary function of the chemicals in the tanning process is another.

Table 4.23
Biocides used for tanning in Denmark

Leather and leather products used in Denmark are, however, mainly imported, and the Danish production only accounts for a small percentage of the consumption with finished products. The main biocides that can be expected to be present in imported leather products are listed in Table 4.24 (Frendrup, 2000).

Table 4.24 Se her!
Main biocides in imported leather and leather products ¹⁾

Chromium salts are widely used for tanning of leather. In 1998, about 80% of leather tanned worldwide was tanned with chromium salts (USGS, 1999). Chromium is not used any more for tanning in Denmark. The chromium salts may have a biocidal effect, but the main function of the chromium in the tanning process is not as a biocide, and chromium salts are consequently not included as biocide in this assessment. To give an impression of the magnitude of the chromium consumption with leather products, the consumption of chromium with leather products in Stockholm, Sweden, in 1995 has been estimated at about 6 tonnes (Lohm et al., 1997). Upscaled to the Danish population, it corresponds to some 20-30 tonnes chromium.

The total consumption of biocides for tanning in Denmark is considered confidential.

No assessment of the content of biocides in imported leather products is available. The average concentration of the biocides in the leather is estimated to be 200-300 ppm (Frendrup, 2000), but will vary by agent. The expected most common biocides in imported leather are indicated in Table 4.24.

The main application areas for leather are furniture, clothing, bags, shoes and riding gear. The total consumption of leather products cannot be estimated exactly from the trade statistics; e.g. leather furniture is not registered under specific commodity numbers, and the production of leather products is not registered in terms of weight. The total consumption of leather products in Denmark in 1998 is roughly estimated at 3,000-8,000 tonnes.

Table 4.25
Consumption of biocides with leather in Denmark 1998

4.4.3 Preservatives for rubber and other polymerised materials

Preservatives may be used for rubber products for two reasons:

	Preservation of liquid latex raw materials
	Preservation of the finished rubber products

Liquid latex is preserved for control of microbial growth in the liquid before polymerisation of the latex. The preservatives used for this application may instead be considered ‘In-can preservatives’.

Rubber products are in general not explicitly preserved against microbial degradation, but many of the chemicals used for manufacturing of rubber products may, however, have a biocidal effect as well. Product catalogues from leading suppliers of chemicals for the rubber industry includes in general no preservatives, but a few biocides are marketed for use in latex products (natural rubbers).

The only identified application where biocides are explicitly added to control microbial deterioration of the rubber is applications where the rubber is in permanent contact with soil, e.g. rubber in seal rings for tubes in soil. However, no specific information on the biocides in such products has been obtained.

Other polymerised materials include linoleum made from linseed oil. Linoleum has an inherent capability of preventing microbial degradation and growth at the surface due to some components of the linseed oil and is in general not added preservatives.

Polymerised materials like plastics, paints and fillers are added preservatives that are included in the product-types ‘In-can preservatives’ and ‘Film preservatives’. It has not been possible to identify applications where the preservatives are added to protect the polymers itself.

Enquiries to the main producers of rubber products in Denmark did not reveal any use of biocides for production of rubber products in Denmark.

To stabilise liquid latex and prevent coagulation, ammonia (CAS no. 7664-41-7) is added to the latex at concentrations of about 0.2-0.6%. The ammonia may as well have a biocidal effect by increasing the pH and is included in the 'List of biocidal substances' of July 1999 from the European Chemical Bureau. It will, however, not be considered a biocide in this report. Liquid latex, e.g. used for rubber under sides of carpets, was formerly preserved with formaldehyde, but this is no longer used in Danish produced carpets. According to a leading Danish producer of carpets and a supplier of latex, the same is presumed to be true for most imported carpets. In cannot, however, be excluded that some imported carpets or other products made from liquid latex may contain preservatives in the rubber.

As mentioned above, many of the chemicals used for manufacturing of rubber products may as well have a biocidal effect. The following list includes chemicals placed on the global market by some of the leading suppliers of chemicals for the rubber industry (the list may not be complete). The listed chemicals are all included in the 'List of biocidal substances' of July 1999 from the European Chemical Bureau, but is used in the processing of rubber as accelerators, antioxidants, vulcanising agents etc.

Formaldehyde (CAS No. 50-00-0)
Thioperoxydicarbonic diamide (CAS No. 97-77-8)
Carbamodithioic acid, dimethyl-, sodium salt (CAS No. 128-04-1)
Tetramethyl thiuramidisulfide (CAS No. 137-26-8)
Thioperoxydicarbonic diamide ([(H2N)C(S)]2S2), tetramethyl- (CAS No. 137-26-8)
Zinc, bis(dimethylcarbamodithioato-S,S')- (T-4)- (CAS No. 137-30-4)
2-Mercaptobenzothiazole, zinc salt (CAS No.155-04-4)
2(3H)-benzothiazolethione (CAS No. 149-30-4)
Zinc oxide (CAS No. 1314-13-2)
2(3H)-benzothiazolethione, sodium salt (CAS No. 2492-26-4)

Most of these chemicals can be expected to be present in products produced in or imported to Denmark.

It has not been possible to identify any use of biocides for production of synthetic rubbers. Product catalogues from suppliers of chemicals for the rubber industry (globally) contain in some instances biocides for use for preservation of latex and natural rubber products. It has not been possible within the boundaries of this project to try obtaining specific information of biocides in imported rubber products and in this way confirm the presence of these chemicals in products marketed in Denmark. The list, which may not be comprehensive, is shown in Table 4.1.

Table 4.26
Biocides that may be present in imported latex products ¹⁾

1) The list may not be comprehensive. The chemicals are in March 2000 marketed at the Internet as preservatives for latex.

4.4.3.3 Consumption of biocides with finished products

Due to lack of data it has not been possible to estimate the consumption of biocides with finished products of rubber and other polymeric materials.

4.4.4 Preservatives for insulating materials of organic fibres

Insulating materials of organic fibre materials like paper, cellulose, wool and flax (Linum) contain preservatives for control of microbial degradation of the fibres during use.

The preservatives are mixed up with the fibre materials before the insulation material is blown into the walls of the houses or placed above the ceiling. The used agents have both a biocidal effect and a flame retarding effect.

Insulation materials of organic fibres are produced in Denmark by Isodan Danmark A/S and Miljøisolering Aps.

The main suppliers of insulation materials of organic fibres are Miljøisolering Aps, Isodan Danmark A/S, Borry Henriksen ApS and Holbæk Byggemateriale Compagni A/S.

The main biocides used for this application area are boric acid and borax, which are used in insulation materials made of paper, cellulose fibres and wool. The boron compounds also have a flame retarding effect. Beside the boron compounds, the insulation materials may also contain aluminium hydroxide. The main function of the aluminium hydroxide is flame retardancy, but the compound may also have a biocidal effect by increasing the alkalinity of the material. Aluminium hydroxide will, however, not be considered a biocide in this context.

In flax, the main preservative seems to be ammonium sulphate, but ammonium phosphate may be used as well.

Table 4.27
Biocides used for preservation of insulation materials of organic fibres in Denmark

1) In the list of biocidal substances from the EU, ‘Borax’ is used as chemical name for CAS no. 12267-73-1, tetraboron disodium heptaoxide, hydrate.

2) The totals of borax and boric acid vary from 5-25%.

Insulating materials of paper account for the main part of the consumption of insulating materials of organic fibres (Table 4.28). The total content of boric acid and borax vary between 5% and 25% of the products dependent on whether the products are added other flame retardants (e.g. aluminium hydroxide). Based on information from suppliers, it is roughly estimated that the paper insulation on average contains 6-9% borax and boron acid with a 1:2 ratio between the two compounds. The consumption of insulation materials of wool is very close to 0 tonnes.

One of the main insulation materials of flax contains about 8% ammonium sulphate, and it is roughly estimated that the products on average contain 6-10% ammonium sulphate or ammonium phosphate.

Table 4.28
Consumption of preservatives for insulation materials of organic fibres in Denmark 1999

4.4.5 Preservatives for paper and other materials

‘Paper and other materials’ include:

	Paper and cardboard (other than insulating materials)
	Art and archaeological artefacts

Biocides used for prevention of slime formation during production of paper and cardboards are included in product-type 12: 'Slimicides'. Besides these preservatives may be used during the production process to control microbial growth in the wet paper, if it is stored before drying. According to the Danish paper factories, preservatives are not used for this purpose in Denmark.

Paper for applications where the paper can be exposed to moisture may be preserved. One example of use of preservatives for paper is preservation of library books that have been stored under moist conditions. No use of preservatives for this application in Denmark has been identified.

According to information from two museums in Denmark, biocides are not used for preservation of art, archaeological artefacts or other items in these two museums, but insecticides (included in section 5.5) are used for control of insects in the stores.

It has not been possible to identify any use of preservatives in Denmark for this application area.

4.5 Product-type 10: Masonry preservatives

Masonry preservatives are products used for preservation and remedial treatment of masonry or construction materials other than wood by the control of microbiological and algal attack.

The product-type does not include biocides for preservation of insulation materials, which are included in product-type 9.

Some of the wood preservatives are also approved for use on masonry. By attack of wood destroying fungi both wood and masonry may be preserved to control the fungi. These preservatives are included in section 4.3: 'Wood preservatives’. Apart from this, the only masonry preservatives identified are agents for treatment of algal attack on masonry.

Mortar, which is moist when stored, is not added preservatives, as the high pH prevents microbial growth during storage.

Producers and suppliers of products for cleaning of masonry are organised in the Danish Paintmakers Association (FDLF) and/or the trade organisation Soap, Perfume and Toiletware (SPT).

Suppliers of products containing masonry preservatives are S. Dyrup & Co. A/S, BN Skaderenovering I/S, Sadolin Farver A/S, Superfos A/S and Profa amba among others.

Biocides for prevention of algal attack (algicides) are to be approved by the Danish EPA. According to the ‘Survey of Approved Pesticides’ no algicides were approved in 1998. In 1999, only one product containing quinoclamine in horticulture was approved for use.

For use as masonry preservatives, two products containing fatty acids (C8-C18, main fraction: decanoic acid) were according to the Danish EPA approved in 1998 and 1999, but the products are not included in the ‘Survey of Approved Pesticides’.

A few years ago a number of products were approved for use as algicide (20 products in 1994). The most common active agents in the approved algicides were benzalkonium chloride and sodium hypochlorite. These agents are today not approved as algicides, but are allowed in cleaning materials. As a consequence, algae are today removed, and algal attack is prevented by use of ‘masonry cleaners’ instead of algicides.

Information on masonry cleaners from six of the main suppliers of formerly approved algicides has been obtained. The masonry cleaners from these all contain benzalkonium chloride or sodium hypochlorite, and the products in general have the same trade names as the formerly approved algicides.

Biocides used in products for cleaning of masonry is listed in Table 4.29.

Table 4.29
Biocides used for preservation and remedial treatment of masonry in Denmark 1998 ¹⁾

1) Wood preservatives containing propiconazol (CAS No 12008-41-2), boron acid (CAS No 12008-41-2) and disodium octaborate (CAS No 60207-90-1) are also approved for control of wood-destroying fungi in masonry.

2) ‘Benzalkonium chloride’ is also used as trivial name for CAS no. 8001-54-5 and CAS no. 959-55-7.

According to the Pesticide Statistics, the consumption of approved algicides in 1998 was 0 tonnes.

As mentioned above algicides are not used for prevention of algal attack on masonry anymore. As the same products are used today, the former use of algicides is assumed to give a good indication of the consumption of the active agents with 'masonry cleaners' today. The consumption trend from 1992 to 1996 is shown in Table 4.1.

Table 4.30
Consumption of active agents with algicides 1992-1996

1) Benzalkonium chloride was also active agent in some wood preservatives, which explains that the total consumption of the two agents is larger than the consumption of algicides.

Beside the consumption of sodium hypochlorite in approved algicides there has presumably in addition been some consumption of sodium hypochlorite in all-round cleaning materials applied for cleaning of masonry. Consequently the amount of sodium hypochlorite in approved products will somewhat underestimate the actual consumption.

The annual consumption will vary with higher consumption after mild winters. Based on information from suppliers the consumption has more likely increased than decreased since the mid-nineties.

Based on this information, the total consumption of biocides with 'masonry cleaners' in 1998 is estimated at 11-25 tonnes (Table 4.2). Some of the products may also be used as algicides indoors, but it is presumed to be a minor part of the total consumption.

Table 4.31
Consumption of biocides with products for preservation and remedial treatment of masonry in Denmark 1998 ¹⁾

4.6 Product-type 11: Preservatives for liquid-cooling and processing systems

Products of this product-type are used for the preservation of water or other liquids used in cooling, heating or processing systems by the control of harmful organisms such as microbes, algae and mussels. District heating systems are neither liquid-cooling systems nor processing systems, but are included here, as they do not fit into any other product-type.

The product-type does not include slimicides (product-type 12) and products used for the disinfection of drinking water (product-type 5), drinking water drainwork (product-type 4), preservation of metalworking-fluids (product-type 13) and moisteners used in the printing process (product-type 6, section 4.1.4).

Biocides are applied to the systems either to preserve the liquids (control of microorganisms) or to disinfect the systems (kill the microorganisms) (Dokkum et al., 1998).

Biocides used for preservation of the liquid cooling system or air-conditioning systems are included here although the biocides in semi-open systems may serve as both preservatives and disinfectants. Microbial growth in the systems leads to biofilm mediated corrosion, and the formation of biofilms increases the heat exchange resistance of the systems.

The liquid systems can be organised into three types (Dokkum et al., 1998):

	Once-through cooling systems
	Open recirculation systems
	Closed recirculation systems

Once-through systems can be used when plenty of cheap cool water is available and adequate facilities for disposal of warm waterare available. Once-through cooling systems may be used for power plants and industrial installations. No use of biocides has specifically been identified for these systems, but biocides may be used in the systems.

Open recirculation systems are mainly used for cooling water in the food-processing and pharmaceutical industry and in large air-conditioning systems. The water in these systems is cooled down in open cooling towers. In these systems, the biocides are applied by shock dosage at a frequency of usually once or twice a week. To prevent development of resistant bacteria usually two biocides are used alternately. The water in the semi-open systems is changed continuously, and the average residence time of the water may be down to a few hours.

Closed systems include first of all district heating systems, but also liquid systems of air-conditioning systems. The biocides are added continuously. The control of microbial growth in district heating systems has thoroughly been described by Smidt et al. 1998.

Open processing systems are used for pressure founding and wash of semi-manufactures and tolls. Microbial growth may as well be a problem in these systems, but the use of biocides for control of the growth in these systems is not as widespread as in the food-processing and pharmaceutical industry.

In air-conditioning systems with open recirculating cooling water, the biocides may as well be applied for control of pathogenic bacteria; especially some species of Legionella. Some of the applied biocides are particularly efficient in the control of these organisms and are often used in air-conditioning systems of hospitals. The bacteria in the cooling water may be released with aerosols from the cooling towers and expose patients via e.g. windows. The content of Legionella in the cooling water is not a hospital specific phenomenon, but patients may be more liable to infection than the main population.

Main suppliers of biocidal products for preservation of water used in cooling, heating or processing systems are Hydro-X A/S, Ashland Denmark A/S and Aqua-Sur A/S.

Biocides used in Denmark for the application area are shown in Table 4.1.

The main biocides of choice for district heating system are quaternary ammonium compounds. According to a study on microbial corrosion in district heating systems, four groups of biocides are proposed by suppliers for use in district heating systems: Hydrogen peroxide, glutaraldehyde, quaternary ammonium compounds and isothiazolones, but only the use of quaternary ammonium compounds and isothiazolones is evident (Schmidt & Frølund, 1998). According to a survey from 1994, about 8% of the district heating stations used biocides.

For cooling water in air-conditioning systems and for the food processing and pharmaceutical industry, a number of biocides is used.

Table 4.32
Biocides used for preservation of water for cooling, heating and processing systems in Denmark

1) Particularly applied for control of pathogenic bacteria in air-conditioning systems.

The total consumption of biocides for this application area is estimated on the basis of a questionnaire estimated to cover more than 80% of the market (see Table 4.1).

The market for biocides for cooling water and processing water is increasing, as it becomes more evident that corrosion and other operational problems of the systems are microbially mediated.

Table 4.33
Consumption of preservatives for cooling, heating and processing systems in Denmark 1999

4.7 Product-type 12: Slimicides

Slimicides are used for the prevention or control of slime growth on materials, equipment and structures used in industrial processes.

The product-type can be organised into two sub-types:

	Slimicides for wood and paper pulp
	Slimicides used by oil extraction and fuel storage

4.7.1 Slimicides for wood and paper pulp

Slimicides are added to paper pulp to prevent the formation of slime during the pulping process by biocidal control of bacteria in the pulp. The slime formation may also be controlled by other agents as enzymes, and there seems to be a trend toward the use of these other agents.

Suppliers of approved slimicides (1999) are Flemming Zwicky Aps., Chr. Krogh A/S and BetzDearborn AB (Sweden).

The main Danish producers of paper and paper products are Dalum Papir A/S, Skjern Papirfabrik A/S, Grenaa Papir A/S, Drewsen Silkeborg Papirfabrik A/S and Brødrene Hartmann A/S. Paper pulp is used in small scale by a few additional users.

Biocides for control of slime in paper pulp have to be approved by the Danish EPA and aredescribed in the survey of approved pesticides (Danish EPA 1999 B).

The consumption of slimicides in Denmark in 1998 is listed in Table 4.34.

Table 4.34
Consumption of slimicides for pulp and paper in Denmark 1998 ¹⁾

1) Consumption according to the Danish Pesticide Statistics 1998 (Danish EPA 1999 A).

2) According to the Danish survey of approved pesticides 1998 (Danish EPA 1999 B). Includes only the number of products for this application.

3) Was not permitted after December 31, 1998.

4) Used for prevention of microbial growth in paper-pulp (not paper manufacturing). Not approved as slimicide.

According to two paper producers, the content of the biocides in the finished paper is expected to be insignificant, but no analysis is available (Hoed, 2000; Tang, 2000). The biocides are water-soluble and are expected to follow the process water to the wastewater treatment system. The trace amounts following the fibre fraction are expected to be decomposed during the subsequent paper production processes.

A British report regarding pentachlorophenol (PCP) in paper and cardboard indicates that PCP may be present in paper and cardboard in trace amounts (MAFF, 1997). PCP has previously been widely used as slimicide in paper pulp and may still be in use in some countries out of Europe. In 36 out of 403 samples, PCP was found in concentrations above 0.008 ppm, with 0.7 ppm as the highest value. PCP is, however, a relatively stable compound.

On this basis, the content of biocides in the finished paper is assumed to be low, and no attempt has been done to estimate the content of biocides in the finished paper.

Paper pulp with copper sulphate is mixed with other raw materials and ends up in finished building materials.

4.7.2 Slimicides and other biocides used at oil extraction and fuel storage

Biocides are used at oil extraction for three purposes:

	Control of slime forming microorganisms in water-based drilling mud during storage (when necessary)
	Control of hydrogen sulphide formation by sulphate reducing bacteria by oil extraction
	Control of microbial growth and hydrogen sulphide formation in oil pipelines

Actually only biocides used for control of slime formation by preserving the drilling mud should be included in the product-type 'Slimicides', but for the sake of the clearness all biocides used by oil extraction and storage of oil are included here.

The biocides are added to flows pumped into the reservoir (drilling processes, injection and reinjection water) and to the transportation flow of produced oil and gas before transportation by either pipeline or tanker to shore.

The biocides are generally used in the offshore industry in very large quantities and are therefore supplied to the rig/platform in bulk containers. Chemicals from bulk containers are usually added to the drilling mud, the water injection or production flows through closed systems.

When the used drilling mud reappears at the surface, cuttings are separated from the mud in a shaker system, and the drilling mud is discharged to the sea.

Based on information from one Danish refinery, it is estimated that biocides are not added to the crude oil or oil products at the refineries. Microbial growth is prevented by avoidance of water in the tanks with crude oil and oil products.

During storage of fuels, especially diesel and fuel oil, slime formation by microorganisms may take place if water finds it ways into the tanks. The phenomenon is in Denmark known as 'diesel plaque' (in Danish: 'diesel pest'). The biocides are not preventively added to the fuel, but preventive addition of biocides is to some extent done by the owners of fuel tanks; for example on ferries. Biocides are most commonly only used when an infected tank is to be disinfected. Diesel plaque was formerly a more widespread phenomenon, but is today reduced by avoidance of water in the tanks.

Beside this, biocides may be used in antifouling paint for oilrigs, but according to the reports from the contractors to the Danish EPA, antifouling paints are not used for this purpose in the Danish oilfields.

Suppliers of biocides for offshore activities have not been surveyed.

All emissions from offshore activities in the Danish part of the North Sea are reported by the operators to the Danish EPA. For this assessment, the Danish EPA has asked for more specific information on the used biocides in 1998. The results are shown in Table 4.1 and Table 4.1.

Isothiazolones are used for disinfection and preventive control of microorganisms in fuel tanks. The compounds used, CIT an MIT, are also used as in-can preservatives for paint, fillers and other products.

Table 4.35
Biocides used for control of microbial growth by oil extraction and fuel storage in Denmark

4.7.2.3 Consumption of biocides with finished products

The consumption of biocides by oil extraction and fuel storage is shown in Table 4.36. Due to confidentiality, only the total consumption of slimicides in drilling mud and biocides for other offshore activities respectively, is given.

Table 4.36

Consumption of biocides for control of microbial growth by oil extraction and fuel storage in Denmark 1988

4.8 Product-type 13: Metalworking-fluid preservatives

Metalworking-fluid preservatives are used for control of microbial deterioration of metalworking fluids.

Metalworking fluids are a very diverse group of products. An assessment of metalworking fluids marketed in Denmark 1987 includes more than 300 different products of which 133 products contain preservatives (Brandorf & Fries, 1987).

The main objectives of metalworking fluids are reduction of friction, removal of heat and flushing away chips. The fluids are nearly always used in closed or semi-open systems where the fluids are recirculated and filtered to remove chips.

Biocides are added as preservatives to metalworking fluids based on emulsions, synthetic or semi-synthetic fluids and fluids based on pure vegetable oils. Metalworking fluids based on pure mineral oils and solvent-based liquids contain in general no biocides.

Besides the use as preservatives, biocides are also used for thorough disinfection of the systems by maintenance of the systems and changing of the fluids. The biocides are for this application strictly speaking not used as preservatives but as disinfectants, but will nevertheless be included here.

The main Danish producer of metalworking-fluids is Castrol A/S. The main suppliers of metalworking-fluids are Castrol A/S, Fuchs & Sidal A/S, Rocol Scandinavia A/S, A/S Dansk Shell and Houghton Danmark A/S, but there is a large number of minor suppliers.

Biocides identified as used for metalworking fluids in Denmark are listed in Table 4.37.

Table 4.37
Identified biocides used for metalworking-fluid in Denmark

There are 30 biocides registered as preservatives in metalworking fluids in PROBAS. The list of preservatives is not shown due to confidentiality.

4.8.1.3 Consumption of biocides with finished products

The consumption of biocides with metalworking fluids in Denmark is estimated from information from suppliers covering approximately 70% of the market. The biocides have been organised into three groups: Quaternary ammonium compounds, isothiazolones and 'Other' (Table 4.38).

Table 4.38
Consumption of biocides for preservation of metalworking fluids in Denmark 1999