EU Derogation Application Form for Copper CAS No 7440-50-8

EU Derogation Application Form For Copper CAS No 7440-50-8

Appendix F Alternative Substances and Essential Use

Appendix F

Preamble:

The use of alternative substances to copper silver ionisation is widespread. The main agents or products used are:

Chlorine and various chlorine compounds

As the majority of the above are broad-spectrum disinfectants, with uses in a range of areas, it is important to detail the exact use of each in the areas where copper silver is similarly used. All of the uses for copper silver ionisation detailed in this application relate directly to water treatment and under the product types 2 and 11. Thus a more detailed view of each, relating to these product types, is detailed in this appendix.

All of the above agents are generally effective within limits for disinfection but in specific instances each has qualities far below copper silver ionisation

Chlorine (Product Type 2):

Chlorine is one of the most widely used disinfectants available. Its uses spread from the bleaching of textiles to surface disinfection. In the area of swimming pool sanitation it is used under product type 2 in Europe.

Chlorine is a chemical element of atomic number 17. Similar to other disinfectants it is a halogen. In elemental form Chlorine exists at ambient temperatures as a gas. In swimming pool disinfection it is used in the form of: Sodium hypochlorite, hypochlorite solutions, Sodium dichloroisocyanurate, Trichloroisocyanuric acid and other forms.

As a gaseous element Chlorine is generally introduced as a swimming pool disinfectant as part of a compound, which when dissolved in water, releases Chlorine as the disinfecting agent.

Health Issues:

As swimming pools have become more numerous and their use by the public more frequent so too has the awareness of swimming pool water quality and its effects on health. Swimming pools are, for all intents and purposes, a large body of stored water, into which pathogenic and toxic substances are introduced by their users. As such disinfection of these pools is critical to ensuring the safety of users and the public at large. Chlorine has a residual effect which is required in such applications, but in open vessels it evaporates quickly, is affected by sunlight and thus requires continuous introduction into the pool.

Such constant dosing has been much studied in recent years. Chlorine is a powerful oxidising agent and will readily combine with organic compounds and these compounds and disinfection by-products have been raised as an area for concern.

A recent study into the number of disinfection by-product compounds in chlorinated swimming pools identified over 100 DBP (disinfection by-products) and further indicated that the tested swimming pool water was mutagenic (1). Prior to this study DBPs resulting from chlorine use had been widely acknowledged. Various chlorine formed compounds have been studied in relation to the health effects they have on swimming pool users and industry workers. A study involving swimming pool attendance in three schools in Belgium found that “our findings show that CPA (Chlorinated pool attendance) during childhood interacts with atopic status to increase the risk of asthma, hay fever and allergic rhinitis”This risk of increased respiratory health issues was noted only in adolescents with atopy but interestingly also found that “Such associations were not found among adolescents without atopy or with copper-silver pool attendance” (2).

A Swiss study from 2011 assessed the occupational and public exposure to trichloramine is Swiss indoor pools. Trichloramine is formed in swimming pools by the reaction of ammonia introduced by bathers and free Chlorinepresent as a disinfectant. This paper firstly noted that “asthma caused by trichloramine has been recognized as a professional disease in France.” and further stated that “Our results demonstrate an increasing risk of irritative symptoms up to a level of 0.2–0.3 mg m23 of trichloramine. The health data in our study, as well as the review of the literature, strongly suggest fixing the trichloramine occupational exposure limit at 0.3 mg / m -3.” (3). As trichloramine formation is directly linked to chlorine use and as a constant dosing of chlorine is required to ensure safe bacterial water quality it is difficult to see how trichloramine levels can be reduced practically without lower chlorine levels below what is required to ensure bacterial contamination is controlled. Copper silver ionisation does present a method of disinfection which can minimise the production of such DBP’s.

In a further study into the effects of infants swimming in chlorinated pools a study from 2009 found that “Among children with no parental antecedents of atopic disease or no day-care attendance, odds ratios for bronchiolitis amounted to 4.45 (1.82–10.9; p50.001) and 4.44 (1.88–10.5; p50.007) after .20 h spent in chlorinated pools during infancy. Infant swimmers who developed bronchiolitis also showed higher risks of asthma and respiratory allergies later in childhood” (4)

Importantly, apart from swimmers themselves, further research has highlighted the risk of health effects of DBP and chlorine on workers involved in the swimming pool sector. It is now accepted that “lifeguards can develop asthma as an occupational disease“ and further that “In the case of coaches, instructors, lifeguards or maintenance staff, DBPs inhalation is not negligible and after an hour’s exposure in a ‘typical’ 100 μg/m3 atmosphere, a THM concentration of 30 μg is found in alveolar air” (5).

Due to the growing body of research available on the health effects of swimming in chlorinated pools a so called “Chlorine Hypothesis” has been subject of public and academic discussion. This hypothesis proposes that swimming pool attendance is directly linked to an increase in childhood asthma and allergic diseases in developed countries. In a study involving 226 children the researchers concluded “We therefore postulate that the increasing exposure of children to chlorination products in indoor pools might be an important cause of the rising incidence of childhood asthma and allergic diseases in industrialised countries.” (6) This study has led to further and longer term studies on the same topic and all point to the same conclusion as the above. In a case study from Spain a 13 year old elite swimmer was diagnosed as suffering from”chlorine-induced asthma” (7). In general there is a growing body of information which links chlorination of swimming pool water to respiratory health issues.

Links to other health issues are now being studied and a recent example which concluded that “our study found strong inverse relationships between testicular hormones and the attendance of indoor chlorinated pools during childhood, which suggests that this type of pool contains substances detrimental to the testes” (8).

Other studies into DBP’s in chlorinated swimming pools detail the increased risk of bladder cancer in those exposed such compounds in the long term. Bladder cancer is the 7th most common cancer in men and the 17th most common cancer in women and has a higher incidence in Europe and America than Asia or developing nations.(9)

A study from conducted on drinking water found that “The consistency of these findings with experimental observations of GSTT1, GSTZ1, and CYP2E1 activity strengthens the hypothesis that DBPs cause bladder cancer” and while DPS’s in chlorinated drinking water are similar to these formed in swimming pools the concentrations are likely to be higher in pool water. Further while volumes of water ingested during swimming are far lower than those from potable sources, pools present addition absorption methods via respiration and dermal exposure.

Another study into the increased risk of bladder cancer from DBP’s in swimming pools found that long term exposure to trihalomethanes, one of the most commonly formed DBP’s in chlorinated pools, resulted in a two fold increase in bladder cancer risk. The same study went on to state that” Subjects who had ever swum in a pool showed an increased risk of bladder cancer compared with those who had never swum in pools” (10) while an earlier study from 2004 concluded that “These findings strengthen the hypothesis that the risk of bladder cancer is increased with long-term exposure to disinfection by-products at levels currently observed in many industrialized countries” (11).

DPB’s found in chlorinated pools include compounds that have been highlighted as possible carcinogens. Some of the compounds identified in a 2010 study (1) carried out jointly in the USA and Europe includes:

In both Water and Air:

Chloroform: “Reasonably anticipated to be a human carcinogen First listed in the Second Annual Report on Carcinogens (1981)” (12)

Bromodichloromethane: “Reasonably anticipated to be a human carcinogen. First listed in the Sixth Annual Report on Carcinogens (1991)” (12)

Bromoform: Classification — B2; probable human carcinogen (13)

Dichloromethane: Probable human carcinogen (14)

In Water only

Trichloroethylene: characterized as “carcinogenic to humans” by all routes of exposure (15)

Many of the other DPB’s identified are not yet classified as regards toxic or carcinogenic effects but overall DPB’s must be considered a risk to public health when formed due to chlorination in swimming pools.

Copper as an agent used for treating pool water is released in ionic form and while this is not as reactive as chlorine it will combine with organic compounds and chemicals. In the case of copper however the U.S. Department of Health and Human Services Public Health Service National Toxicology Program “Report on Carcinogens” Twelfth Edition 2011 mentions only certain copper alloys such as copper beryllium and compounds such as chromated copper arsenate as carcinogenic or potentially carcinogenic. The occurrence of such compounds or alloys in swimming pool water as result of copper treatment is negligible at best.

Swimming in chlorinated water has been long known to affect the skin. More recent studies have shown a link between prolonged exposure to chlorinated water and contact dermatitis. One such study concluded that “contact dermatitis should be recognized as an occupational disease in hydrotherapists.” (16)

Other Issues:

Copper ionisation involves the electrical generation at low voltages of copper ions. The precursor to these ions is metallic copper. In terms of transport and storage metallic copper presents little risk outside of manual handling issues.

Chemical treatment of swimming pool water requires the handling, transport and storage of several hazardous chemicals. As chlorine is pH dependant its use requires the addition of acids to regulate the pH of the water. In addition flocculants such as aluminium sulphate are required to ensure water quality. Ionic copper acts both as a biocide and a flocculants.

Chemical storage and the hazard of these chemicals being inadvertently combined incorrectly has long been an issue in the swimming pool industry. Statistics from the HSE in the UK show that in the years between 1992 and 1998 267 reportable dangerous occurrences involving chlorine were reported. Of these 59 involved swimming pools. (17) A more recent report confirmed that 13 cases of chlorine incidents were recorded in a five month period between June and October 2007. Of these some involved the evacuation of up to 210 persons and the treatment of up to 19 and in the majority of cases “The most common causes of chemical release in the incident were chemical tank or pipe leaks (responsible for five (42%) of the incidents), followed by the incorrect mixing of chemicals (responsible for four (33%) of the incidents) (Table 1). Sodium hypochlorite was one of the chemicals involved in all 10 of the incidents for which specific chemical information was available. This was mixed with an acid (hydrochloric acid or sulphuric acid) in three incidents, and combined with sodium bisulphate in two incidents, resulting in the release of chlorine gas.” (18) Thusly chlorine use in the swimming pool sector required special precautions but as such precautions should by now be well established it is reasonable to conclude that chlorine is not entirely suitable as a safe method of disinfection in terms of safe usage.

Chlorine Product Type 11:

Product type 11 details uses such as cooling towers and water storages systems. Chlorine is an effective bacterial control agent but is temperature dependant. Dissolved, subject to conditions can dissipate from water at temperatures below 30 deg C. Thus in many cooling towers it is of limited use. Further as chlorine is a corrosive agent it is well known to damage piping and other parts of cooling equipment.

Bromine and Iodine:

Neither bromine nor Iodine are frequently used in either PT 2 or PT 11 applications due to health concerns.

Ultra Violet:

Ultra Violet is an effective bacterial control measure but only deals with contamination at point of contact. Thus at best it can only be considered as an auxiliary measure and is not suitable for store water or continuous control.

References:

1. Susan D. Richardson, David M. DeMarini, Manolis Kogevinas, Pilar Fernandez, Esther Marco, Carolina Lourencetti, Clara Ballesté, Dick Heederik, Kees Meliefste,A. Bruce McKague, Ricard Marcos, Laia Font-Ribera, Joan O. Grimalt, and Cristina M. Villanueva “What’s in the Pool? A Comprehensive Identification of Disinfection By-products and Assessment of Mutagenicity of Chlorinated and Brominated Swimming Pool Water” Environmental Health Perspectives Vol 118 No 1 November 2010
2. Alfred Bernard, Marc Nickmilder, Catherine Voisin and Antonia Sardella “Impact of Chlorinated Swimming Pool Attendance on the Respiratory Health of Adolescents” Pediatrics 2009;124;1110
3. JEAN PARRAT, GE´ RARD DONZE, CHRISTOPHE ISELI, DANIEL PERRET5, CATHERINE TOMICIC and OLIVIER SCHENK “Assessment of Occupational and Public Exposure to Trichloramine in Swiss Indoor Swimming Pools: A Proposal for an Occupational Exposure Limit” Ann. Occup. Hyg., pp. 1–14
4. C. Voisin, A. Sardella, F. Marcucci and A. Bernard “Infant swimming in chlorinated pools and the risks of bronchiolitis, asthma and allergy” EUROPEAN RESPIRATORY JOURNAL VOLUME 36 NUMBER 1 41
5. Zarzoso M., Llana S., Pérez-Soriano P. “POTENTIAL NEGATIVE EFFECTS OF CHLORINATED SWIMMING POOL ATTENDANCE ON HEALTH OF SWIMMERS AND ASSOCIATED STAFF” Biology of Sport, Vol. 27 No4, 2010
6. A Bernard, S Carbonnelle, O Michel, S Higuet, C de Burbure, J-P Buchet, C Hermans,X Dumont, I Doyle “Lung hyperpermeability and asthma prevalence in schoolchildren unexpected associations with the attendance at indoor chlorinated swimming pools” Occup Environ Med 2003;60:385–394
7. S Beretta, T Vivaldo, M Morelli, P Carlucci, GV Zuccotti “Swimming Pool–Induced Asthma” J Investig Allergol Clin Immunol 2011; Vol. 21(3): 240-241
8. M. Nickmilder and A. Bernard “Associations between testicular hormones at adolescence and attendance at chlorinated swimming pools during childhood” International Journal of Andrology 2011 European Academy of Andrology, 34, e446–e458
9. Marco Grasso “Bladder Cancer: A Major Public Health Issue” Ruropean urology supplements 7 (2008 510–515
10. Cristina M. Villanueva, Kenneth P. Cantor, Joan O. Grimalt, Nuria Malats, Debra Silverman,

Adonina Tardon, Reina Garcia-Closas, Consol Serra, Alfredo Carrato, Gemma Castan˜ o-Vinyals, Ricard Marcos, Nathaniel Rothman, Francisco X. Real, Mustafa Dosemeci, and Manolis Kogevinas. “Bladder Cancer and Exposure to Water Disinfection By-Products throughIngestion, Bathing, Showering, and Swimming in Pools” American Journal of EpidemiologyVol. 165, No. 2 2006

1. Cristina M. Villanueva, Kenneth P. Cantor, Sylvaine Cordier, Jouni J. K. Jaakkola, Will D. King, Charles F. Lynch, Stefano Porru, and Manolis Kogevinas “Disinfection Byproducts and Bladder Cancer A Pooled Analysis” Epidemiology Volume 15, Number 3, May 2004
2. U.S. Department of Health and Human Services Public Health Service National Toxicology Program “Report on Carcinogens” Twelfth Edition 2011
3. US Environmental Protection Agency Integrated Risk Information System web page accessed 5/01/2013
4. US Environmental Protection Agency Integrated Risk Information System web page accessed 5/01/2013
5. US Environmental Protection Agency Integrated Risk Information System web page accessed 5/01/2013
6. Lazarov A., Nevo K., Pardo A. et al. Self-reported skin disease in hydrotherapists working in swimming pools. Contact Dermatitis 2005;53:327-331.
7. Health and Safety Executive web site accessed 8/01/2013
8. H. Lucy Thomas, Virginia Murray “Review of acute chemical incidents involving exposure to chlorine associated with swimming pools in England and Wales, June–October 2007”