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Mapping and release of chemical substances from products made of chloroprene

2 Mapping phase

• 2.1 Method
• 2.2 Results
  • 2.2.1 The Internet
  • 2.2.2 Contact via phone
  • 2.2.3 Contact to wholesalers and retailers
  • 2.2.4 Personal interviews
  • 2.2.5 Visits to shops
  • 2.2.6 Literature
• 2.3 Conclusion/Summary
  • 2.3.1 Consumption pattern and exposure
  • 2.3.2 Which environmentally problematic substances can appear in chloroprene products
  • 2.3.3 Which products should be included in the screening phase

In this phase, the market has been mapped for chloroprene products with which consumers get into contact.

2.1 Method

Information has been searched via:

• The Internet
• Contact via phone
• Personal contact
• Visits to shops
• Literature

A detailed description of mapping procedure and the result from the Internet search is to be found in annex A.

2.2 Results

2.2.1 The Internet

The result of the search for chloroprene in relation to recipes, health and migration was disappointing since no information about recipes appeared in addition to what we already knew. However, a single, completely new monograph was identified as being of interest in terms of chloroprene formularies and it was acquired (R.N. Datta). Search on the combination of health and migration did not result in any usefull information.

Search on chloroprene/neoprene and wetsuits gave a row of hits on which products based on chloroprene one can buy via the Internet.

Search on web sites in relation to chains of sportsshops, health products and leisure activities gave no usefull information.

On the web site for the Sports Confederation of Denmark (DIF) www.dif.dk it is possible to get information about the number of members of the different special national confederations.

2.2.2 Contact via phone

2.2.2.1 Contact to federations and agencies

The results of the direct contact via phone to the national federations under DIF appear from the table 2.1 below. In those case where it was impossible to contact a federation over the phone, the number of members was taken from the statistics available at www.dif.dk.

Table 2.1 Number of organised sportsmen broken down by national federations

It should be pointed out that not all sportsmen are members of the Sports Confederation of Denmark and that quite a lot of consumers are simply engaged in the relevant sports activities to keep fit. On the other hand, it is to be expected that consumers who are members of the national federations under the Sports Confederation of Denmark are much more often in contact with chloroprene-based garments.

The websites www.fd.dk (the Danish Directorate of Fisheries), www.lystfiskeren.dk, www.sportsfiskeren.dk and www.jaegerforbundet.dk have been visited to record the number of anglers and hunters in Denmark. Hunters and anglers are not considered as real sportsmen.

Table 2.2 Number of hunters and anglers

2.2.3 Contact to wholesalers and retailers

We contacted wholesalers and retailers dealing in chloroprene-based consumer products for leisure activities to record the consumption of chloroprene-based garments. The results appear from Table 2.3 made anonymous.

Table2.3 Various wholesalers and dealers

2.2.4 Personal interviews

The results of interviewing participants in sports in which garments based on chloroprene are used are summarised below. The following sports are involved:

• Triathlon
• Canoeing, kayaking and rowing
• Dinghy sailing, windsurfing and kitesurfing
• Diving
• Waterskiing
• Other sports (ball games, athletics, gymnastics, running, swimming, skiing)

2.2.4.1 Triathlon

Triathlon includes the sportive disciplines swimming, biking and running. A full ironman distance involves a 3.8 km swim. But triathlon also involves shorter swimming distances.

We have been informed that participants typically swims about 2 km wearing wetsuits and that they swim for about 40 minutes and rest for about 20 minutes. According to the literature (Terje Nordberg), elite athletes typically swim 3km twice weekly in addition to running and cycling training.

2.2.4.2 Canoeing, kayaking and rowing

Chloroprene garments are primarily used in sea kayaking. In the sea kayak, a chloroprene cover is used around the cockpit and the paddler. Only a relatively few people are engaged in sea kayaking but the sport is gradually becoming more popular. Very few persons are considered to be using chloroprene garments for ordinary kayaking and rowing since these sports are typical summer sports.

2.2.4.3 Dinghy sailing, windsurfing and kitesurfing

For optimist dinghy sailing, we were informed that children who are very active may wear chloroprene suits for up to 10 hours at a time. The Danish Sailing Association estimates that the optimist sailors typically sail for two hours when training and 5-6 hours when competing. All sailors are wearing chloroprene gloves when it is cold.

The Danish Sailing Association informed us that a suit used for sailing optimist dinghies lasts for max. one year as the seat of the suit is exposed to a high degree of wear due to the rough surface which the sailor sits on and which is necessary on account of the friction.

According to information provided, active windsurfers and kite surfers can spend up to 3-4 hours a day all week windsurfing and even more in connection with competitions. They wear wetsuits very much all year since they often fall into the water.

Surf suits made of chloroprene last longer than suits used for sailing dinghies. Typically 3-5 years. However, suits are known to last up to ten years if maintained well and if the user is experienced, knowing how to avoid tearing the suit.

2.2.4.4 Diving

Divers can dive max. 30 minutes at a time at a depth of 20-25 m and based on interviews, it has to be concluded that a diver is wearing his diver's suit for at total of 2-4 hours at a time, and four hours has to be considered as the max. period of time. It is possible only to dive for a period of max. 1½ hours at a time at shallower depths before the cylinder is emptied of air so four hours correspond to diving twice and a break of one hour ashore.

We were informed that the "old", 7mm thick types were able to last for up to 10 years (Scubatech) but that the tendency is towards greater use of 3mm and 5mm suits. Their service lives are estimated at 3-5 years.

The difference between a wetsuit and semi-wet suit is that the latter has rubber seals on the inside that prevent significant water replacement. This means that you keep warm better in the semi-wet suit due to insignificant water replacement.

2.2.4.5 Waterskiing

No special information has been collected about waterskiing. There are very few waterskiers and they are assumed to wear their wetsuits for a limited period of time compared to wind- and kitesurfers.

2.2.4.6 Other sports

In other sports, such as ball games, athletics, gymnastics, running and cycling, the participants can get into contact with primarily supports made of chloroprene. The contact time will typically be for the duration of a run or a competition/match. So the participant will rarely be in contact with chloroprene for more than a couple of hours at a time.

2.2.5 Visits to shops

The following different types of shops were visited in the mapping phase:

• A hunting and angling shop
• A surgical appliance shop
• A diving shop

The truss and bandage shop was interviewed about chloroprene supports. They do not recommend using chloroprene supports if they are to be worn all day since the skin cannot breathe through the material. So in that case the shop recommends its customers to buy alternative materials even though they do not provide as efficient support as chloroprene supports. Since this shop is a surgical appliance shop, its customers are not necessarily sportsmen but also people suffering from a physical impairment that requires support of a weak joint. These consumers are expected to use their supports for a longer period of time each day than is the case for sportsmen.

At the Bandagist – Centret which was visited in the purchase phase for supports the firm was interviewed with regard to supports in chloroprene. Danish Technological Institute was informed that patients which had permanent problems with their junctions easily could be in direct skin contact with the support for more than twelve hours a day.

The diving shop deals in a range of products used for diving activities. The shop has several different types of suits. The owner informed us that no customers had complained about chloroprene suits having caused inconvenience but in connection with a dry suit a customer had once had rashes caused by the wrist and neck seals manufactured from another rubber material and that this material had been replaced with chloroprene to remove the inconvenience.

2.2.6 Literature

In connection with the mapping, information has been gathered from two types of literature. One type discussed the various sports in which chloroprene garments are known to be used. The other type of literature contained information about chloroprene and the composition of chloroprene recipes. As for the latter, literature also comprised information collected from the websites of the raw material suppliers.

2.2.6.1 Sports literature

The specialist books consulted on sports concerned sailing, windsurfing, diving and running. The books on sailing, windsurfing and diving were the only books that contained information about the clothing used for these sport activities, i.e. wetsuits used for all three sports and the dry suit for diving. The latter is used in the cold season of the year because of its thicker insulation (7mm). Besides the suit, gloves, socks and hoods are used in diving. In the warm season, windsurfers have bare feet. But when it gets colder, shoes with chloroprene uppers, etc. are used whereas, according to the book, chloroprene socks are unfit for use since they wear too soon. Chloroprene gloves are recommended for use only in the winter season because it is difficult to hold on to things properly when sailing.

2.2.6.2 Chloroprene literature

Information has been collected about the availability of types of raw chloroprene rubber on the market as well as the additives which may be used in a chloroprene recipe. Details of the results of this search and the visits to the websites of three raw material suppliers (DuPont Dow Elastomers, Tosoh and Bayer) are available in Annex B. The next section points to the types of chemical substances and elements which the literature on chloroprene recipes gives rise to look into in the analysis phase.

2.3 Conclusion/Summary

2.3.1 Consumption pattern and exposure

The results of the mapping phase regarding the number of consumers getting into contact with chloroprene products, exposure conditions and estimated duration of contact each week are summed up in the table 2.4. Despite the comprehensive search for information, the figures are to a high degree based on very rough estimates. For the number of consumers using waders, it was estimated that at least half of those active in inshore fishing and angling are wearing waders. For rubber boots, 108,000 Danish hunters are known to go hunting and they all wear rubber boots, however, not necessarily boots made of chloroprene. The reason why the figure is estimated to be higher than 100,000 is that consumers, who do not go hunting, are expected to wear chloroprene rubber boots to some extent because they are comfortable. As far as these two product groups are concerned, the consumer usually wears a suit underneath so direct contact with the skin does not occur. However, a certain degree of contact will occur if the user wears ankle socks or short trousers underneath.

The number of consumers using wetsuits or semi-wet suits is based on information obtained from the national federations under the Sports Confederation of Denmark. All people who are active in diving, windsurfing, kitesurfing and triathlon are indicated as wearing chloroprene suits. For kayaking and rowing, it is assumed that only those active in sea kayaking wear wetsuits. For sailing, it is very difficult to give an exact figure. In this connection, approx. two-thirds of the 10,000 dinghy sailors are assumed to wear wetsuits and it is assumed that there is a similar number of windsurfers (windsurfers also belong under the Danish Sailing Association). The Danish Sailing Association informs that 3.000 – 4.000 wind- and kitesurfers are members of the association. The Association guess that further 5 – 7.000 consumers are active at exercise level, but it is a pure guess.

The number of persons wearing dry suits is according to a telephone interview with the daily manager of the magazine “DYK” estimated to 5000. The suits are primarily worn in the cold autumn and winter periods. They are quite expensive. Clothing is always worn underneath the dry wetsuits. It should be added that the sport in the wet element reaches its peak in the summer season and that the use of chloroprene products above and below water culminates in that period, however, this does not include holidays under warmer skies in the winter season. In summer the use of wet suits dominates.

The number of consumers wearing chloroprene gloves is considered to be about 40,000 since we learned that this type of glove is used widely among all sailors of whom 60,000 are members of the Danish Sailing Association alone. The figure was found by estimating that approx. 50% of the sailors wear chloroprene gloves, except windsurfers. This type of glove prevents windsurfers from holding properly on to the sail.

For socks and boots made of chloroprene, the number of consumers using these products is estimated to be equal to the number of users of wet and semi-wet suits as it is assumed that all users of suits also use socks and boots.

The daily manager of the magazine “DYK” informs that besides leisure divers organised in The Danish Sport Diving Federation further 4.500 divers is educated by PADI (Professional Association of Diving Instructors). The Manager estimates that the total amount of leisure divers in Denmark is around 10.000. Many leaves the sport after 3 years but newcomers balance the figure. It might be that the amount based on the figures from the retailers with regard to sales of diving suits is too low an estimate. However it is difficult to etimate how many diving suits are sold via the Internet. However many internet web sides have been recognised in the mapping phase.

For supports, it is very difficult to determine how many consumers get into contact with supports made of chloroprene. In principle, any consumer risks having to wear a support; however, in the great majority of cases the consumer will have to wear it only for a short period of time until he/she has recovered from a sports injury. However, consumers suffering from weak joints may have to wear supports more or less permanently. This group is probably the one most severely exposed to nuisance due to repeated and daily contact all year.

The contact time column is based on the most enthusiastic persons in the various sports. It is not unusual for an angler, who is on a fishing holiday for a week, to wear his waders for more the 10 hours each day. Wind- and kitesurfers also often wear their suits all day; they just strip off the upper part when on shore. For supports, the lower limit is estimated at 15 hours for normal sportsmen and the upper limit at 60 hours for consumers suffering from joint impairments. This is of course a rough estimate.

The contact conditions are divided into direct and indirect contact. As previously mentioned, waders and chloroprene boots can to some extent be in contact with the user's legs when he is wearing ankle socks or short trousers. No temperature has been indicated for the contact, but since the body temperature is typically 37°C, a temperature of about 30°C does not seem unrealistic. The temperature underneath a support may be higher when running or playing ball due to the high activity level.

Table 2.4 Consumption pattern for chloroprene products

2.3.2 Which environmentally problematic substances can appear in chloroprene products

A detailed review of slightly older as well as the most recent literature on chloroprene and chloroprene formularies indicates that it would be relevant to screen the products to be selected for the analysis phase. The chemical substances to screen are to be found within the following groups:

• Heavy metals (particularly lead)
• Plasticisers (particularly phthalates and chlorinated paraffines)
• Accelerators (a wide group of nitrogenous organic sulphur compounds)
• Anti-aging agents (aromatic amines or diamine compounds).

As for accelerators, ETU (ethylene-thio-urea/imidazoline-2-thione) will receive special attention since it is a constituent in the great majority of published chloroprene recipes and is included on the list of hazardous substances class 2; R 45 “Might cause cancer”". Attention should also be paid to thiuram compounds or their breakdown products since they can give rise to nitrosamine formation.

Degradation products from the classes of chemical substances above should also be part of the screening study.

In annex B a more detailed information is given with regard to chloroprene and recipes for chloroprene.

2.3.3 Which products should be included in the screening phase

Based on the exposure conditions expected for the different types of chloroprene products with which consumers get into contact, it was suggested to select the following product types for the initial screening study:

• Two types of supports
• Two types of gloves
• One type of socks
• One type of dive hood
• One type of waders
• A semi-wet suit

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Version 1.0 September 2005, © Danish Environmental Protection Agency