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

EU Derogation Application Form For Copper
Appendix F Alternative Substances and Essential Use
Appendix F
CAS No 7440-50-8
EU Derogation Application Form For Copper
Appendix F Alternative Substances and Essential Use
CAS No 7440-50-8
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
EU Derogation Application Form For Copper
Appendix F Alternative Substances and Essential Use
CAS No 7440-50-8
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 byproducts 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 Chlorine present 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
EU Derogation Application Form For Copper
Appendix F Alternative Substances and Essential Use
CAS No 7440-50-8
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 ”chlorineinduced 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.
EU Derogation Application Form For Copper
Appendix F Alternative Substances and Essential Use
CAS No 7440-50-8
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)
EU Derogation Application Form For Copper
Appendix F Alternative Substances and Essential Use
CAS No 7440-50-8
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.
EU Derogation Application Form For Copper
Appendix F Alternative Substances and Essential Use
CAS No 7440-50-8
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.
EU Derogation Application Form For Copper
Appendix F Alternative Substances and Essential Use
CAS No 7440-50-8
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 No 4, 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˜ oVinyals, Ricard Marcos, Nathaniel Rothman, Francisco X. Real, Mustafa Dosemeci, and
Manolis Kogevinas. “Bladder Cancer and Exposure to Water Disinfection By-Products through
Ingestion, Bathing, Showering, and Swimming in Pools” American Journal of Epidemiology
Vol. 165, No. 2 2006
11. 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
12. U.S. Department of Health and Human Services Public Health Service National Toxicology
Program “Report on Carcinogens” Twelfth Edition 2011
13. US Environmental Protection Agency Integrated Risk Information System web page
http://www.epa.gov/iris/subst/0214.htm#quaoral accessed 5/01/2013
EU Derogation Application Form For Copper
Appendix F Alternative Substances and Essential Use
CAS No 7440-50-8
14. US Environmental Protection Agency Integrated Risk Information System web page
http://www.epa.gov/iris/subst/0070.htm#evid accessed 5/01/2013
15. US Environmental Protection Agency Integrated Risk Information System web page
http://www.epa.gov/iris/subst/0199.htm#carc accessed 5/01/2013
16. Lazarov A., Nevo K., Pardo A. et al. Self-reported skin disease in hydrotherapists working in
swimming pools. Contact Dermatitis 2005;53:327-331.
17. Health and Safety Executive web site http://www.hse.gov.uk/foi/internalops/td_din/othergas/td5_027.htm accessed 8/01/2013
18. 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”