# Water chlorination

Water chlorination is the process of adding chlorine (Cl
2
) to water as a method of water purification to make it fit for human consumption as drinking water. Water that has been treated with chlorine is effective in preventing the spread of waterborne disease.

## Technology

As a halogen, chlorine is a highly efficient disinfectant, and is added to public water supplies to kill disease-causing pathogens, such as bacteria, viruses and protozoans, that commonly grow in water supply reservoirs, on the walls of water mains and in storage tanks.[1] The microscopic agents of many diseases such as cholera, typhoid fever, and dysentery killed countless people annually before disinfection methods were employed routinely.[1]

Chlorine is obtained from salt (NaCl). It is a gas at atmospheric pressures but liquifies under pressure. The liquified gas is transported and used as such.

As a strong oxidizing agent, chlorine kills via the oxidation of organic molecules.[1] Chlorine and its hydrolysis product hypochlorous acid are neutrally charged and therefore easily penetrate the negatively charged surface of pathogens. It is able to disintegrate the lipids that compose the cell wall and react with intracellular enzymes and proteins, making them nonfunctional. Microorganisms then either die or are no longer able to multiply.[2]

### Principles

When dissolved in water, chlorine converts to an equilibrium mixture of chlorine, hypochlorous acid (HOCl), and hydrochloric acid (HCl):

Cl2 + H2O $\overrightarrow{\leftarrow}$ HOCl + HCl

In acidic solution, the major species are Cl2 and HOCl while in alkaline solution effectively only ClO- is present. Very small concentrations of ClO2-, ClO3-, ClO4- are also found.[3]

### Shock chlorination

Shock chlorination is a process used in many swimming pools, water wells, springs, and other water sources to reduce the bacterial and algal residue in the water. Shock chlorination is performed by mixing a large amount of sodium hypochlorite, which can be in the form of a powder or a liquid such as chlorine bleach, into the water. Water that is being shock chlorinated should not be swum in or drunk until the sodium hypochlorite count in the water goes down to three ppm or less.

## Drawbacks to water chlorination

Disinfection by chlorination can be problematic, in some circumstances. Chlorine can react with naturally occurring organic compounds found in the water supply to produce compounds known as disinfection byproducts (DBPs). The most common DBPs are trihalomethanes (THMs) and haloacetic acids (HAAs). Trihalomethanes are the main disinfectant by-products created from chlorination with two different types, bromoform and dibromochloromethane, which are mainly responsible for health hazards. Their effects depend strictly on the duration of their exposure to the chemicals and the amount ingested into the body. In high doses, bromoform mainly slows down regular brain activity, which is manifested by symptoms such as sleepiness or sedation. Chronic exposure of both bromoform and dibromochloromethane can cause liver and kidney cancer, as well as heart disease, unconsciousness or death in high doses.[4] Due to the potential carcinogenicity of these compounds, drinking water regulations across the developed world require regular monitoring of the concentration of these compounds in the distribution systems of municipal water systems. The World Health Organization has stated that the "risks to health from these by-products are extremely small in comparison with the risks associated with inadequate disinfection" [5] There are also other concerns regarding chlorine, including its volatile nature which causes it to disappear too quickly from the water system, and aesthetic concerns such as taste and odour. Chlorination of swimming pools can have adverse effects on the skin and hair of swimmers due to chlorine's oxidizing properties; various remedies have been developed, most recently an antioxidant formulation of Vitamin C.[citation needed]

## History

In a paper published in 1894, Moritz Traube proposed the addition of chloride of lime (calcium hypochlorite) to water to render it “germ-free.” Two other investigators confirmed Traube’s findings and published their papers in 1895.[6] Three years later, a full-scale test of Traube’s laboratory work was conducted at Maidstone, England. In the midst of a typhoid fever epidemic, Dr. Sims Woodhead applied (on a one-time basis) about 4,200 ppm of chlorine in the form of chloride of lime to a drinking water reservoir and the distribution system.[7]

Two early chlorination episodes in Belgium advanced the science and practicality of water disinfection. In Ostende, disinfection by what was most likely chlorine dioxide took place about 1900 for a short period of time. Middlekerke, Belgium is sometimes referred to as the first continuous application of chlorine in a drinking water supply. Chlorine in the form of a mixture of chloride of lime and chloride of iron was added to a highly colored water supply over the period of 1902 to 1921.[8][9]

Improper operation of a slow sand filter and a contaminated water supply led to a serious typhoid fever epidemic in Lincoln, England in 1905. Dr. Alexander Cruickshank Houston used chlorination of the water to stem the epidemic. His installation fed a concentrated solution of chloride of lime to the water being treated. The chlorination of the water supply helped stop the epidemic and as a precaution, the chlorination was continued until 1911 when a new water supply was instituted.[10]

In the United States, the first use of chlorine for continuous disinfection of a drinking water supply took place in 1908 at Boonton Reservoir (on the Rockaway River), which served as the supply for Jersey City, New Jersey.[11] Chlorination was achieved by controlled additions of dilute solutions of chloride of lime (calcium hypochlorite) at doses of 0.2 to 0.35 ppm. The treatment process was conceived by Dr. John L. Leal and the chlorination plant was designed by George Warren Fuller.[12] Over the next few years, chlorine disinfection using chloride of lime was rapidly installed in U.S. drinking water systems.[13]

The technique of purification of drinking water by use of compressed liquefied chlorine gas was developed in 1910 in the U.S. by Major (later Brigadier General) Carl Rogers Darnall (1867–1941), Professor of Chemistry at the Army Medical School.[14] Shortly thereafter, Major (later Colonel) William J. L. Lyster (1869–1947) of the Army Medical Department used a solution of calcium hypochlorite in a linen bag to treat water. For many decades, Lyster's method remained the standard for U.S. ground forces in the field and in camps, implemented in the form of the familiar Lyster Bag (also spelled Lister Bag).

Chlorine gas was first used on a continuing basis to disinfect the water supply at the Belmont filter plant, Philadelphia, Pennsylvania beginning in 1913. Darnall's work and the technological innovations by Dr. George Ornstein and the Wallace & Tiernan Company became the basis for present day systems of chlorination of municipal water supplies. By 1941, disinfection of U.S. drinking water by chlorine gas had largely replaced the use of chloride of lime.[15][16]

## Alternatives methods for water disinfection

Chlorine in water is over three times more effective as a disinfectant against Escherichia coli than an equivalent concentration of bromine, and over six times more effective than an equivalent concentration of iodine.[17]

### Ozone

Ozonation is used by many European countries and also in a few municipalities in the United States and Canada. This alternative is more cost effective and energy-intensive. It involves ozone being bubbled through the water, breaking down all parasites, bacteria, and all other harmful organic substances. However, this method leaves no residual ozone to control contamination of the water after the process has been completed.[18] Due to current regulations, systems employing ozonation in the United States still must maintain chlorine residuals comparable to systems without ozonation.

The advantage of chlorine in comparison to ozone is that the residual persists in the water for an extended period of time. This feature allows the chlorine to travel through the water supply system, effectively controlling pathogenic backflow contamination. In a large system this may not be adequate, and so chlorine levels may be boosted at points in the distribution system, or chloramine may be used, which remains in the water for longer before reacting or dissipating.

### Chloramine

Disinfection with chloramine is also becoming increasingly common. Unlike chlorine, chloramine has a longer half life in the distribution system and still maintains effective protection against pathogens. The reason chloramines persist in the distribution is due to the relatively lower redox potential in comparison to free chlorine. Chloramine is formed by the addition of ammonia into drinking water to form mono-, di-, and trichloramines. Whereas Helicobacter pylori can be many times more resistant to chlorine than Escherichia coli, both organisms are about equally susceptible to the disinfecting effect of chloramine.[19]

### Home filtration

Water treated by filtration and home filtration may not need further disinfection; a very high proportion of pathogens are removed by materials in the filter bed. Filtered water must be used soon after it is filtered, as the low amount of remaining microbes may proliferate over time. In general, these home filters remove over 90% of the chlorine available to a glass of treated water. These filters must be periodically replaced otherwise the bacterial content of the water may actually increase due to the growth of bacteria within the filter unit.[18]

Another method which is gaining popularity is UV disinfection. UV treatment leaves no residue in the water due to use of light instead of chemical disinfectants. However, this method alone (as well as chlorination alone) will not remove toxins from bacteria, pesticides, heavy metals, etc. from water.

## References

1. ^ a b c Calderon, R. L. (2000). "The Epidemiology of Chemical Contaminants of Drinking Water". Food and Chemical Toxicology 38 (1 Suppl): S13–S20. doi:10.1016/S0278-6915(99)00133-7. PMID 10717366.
2. ^ Kleijnen, R.G. (2011). The Chlorine Dilemma. Eindhoven University of Technology. pp. 3–49.
3. ^ Shunji Nakagawara, Takeshi Goto, Masayuki Nara, Youichi Ozaqa, Kunimoto Hotta and Yoji Arata (1998). "Spectroscopic Characterization and the pH Dependence of Bactericidal Activity of the Aqueous Chlorine Solution". Analytical Sciences 14 (4): 691–698. doi:10.2116/analsci.14.691.
4. ^ Public Health Statement: Bromoform & Dibromochloromethane. ATSDR. 2011.[full citation needed]
5. ^ . Guidelines for drinking-water quality Vol. 1, Recommendations. – 3rd ed. World Health Organization. 2006 http://www.who.int/water_sanitation_health/dwq/gdwq0506.pdf Missing or empty `|title=` (help)
6. ^ Turneaure, F.E., and H.L. Russell (1901). Public Water-Supplies: Requirements, Resources, and the Construction of Works (1st ed.). New York: John Wiley & Sons. p. 493.
7. ^ "Typhoid Epidemic at Maidstone". Journal of the Sanitary Institute 18: 388. October 1897.
8. ^ Whipple, George C (1906). "Disinfection as a Means of Water Purification". Proceedings AWWA: 266–280.
9. ^ Baker, Moses N. (1981). The Quest for Pure Water: the History of Water Purification from the Earliest Records to the Twentieth Century 1 (2nd ed.). Denver: American Water Works Association. p. 336.
10. ^ Reece, R.J. (1907). “Report on the Epidemic of Enteric Fever in the City of Lincoln, 1904-5.” In Thirty-Fifth Annual Report of the Local Government Board, 1905-6: Supplement Containing the Report of the Medical Officer for 1905-6. London:Local Government Board.
11. ^ Leal, John L. (1909). “The Sterilization Plant of the Jersey City Water Supply Company at Boonton, N.J.” Proceedings American Water Works Association. pp. 100-9.
12. ^ Fuller, George W. (1909). “Description of the Process and Plant of the Jersey City Water Supply Company for the Sterilization of the Water of the Boonton Reservoir.” Proceedings AWWA. pp. 110-34.
13. ^ Hazen, Allen. (1916). Clean Water and How to Get It. New York:Wiley. p. 102.
14. ^ Darnall C.R. (1911), "The Purification of Water by Anhydrous Chlorine", American Journal of Public Health; 1: 783–97.
15. ^ Hodges, L. (1977). Environmental Pollution (2nd ed.). New York: Rinehart and Winston. p. 189.
16. ^ Baker, Moses N. (1981). The Quest for Pure Water: the History of Water Purification from the Earliest Records to the Twentieth Century. 2nd Edition. Vol. 1. Denver: American Water Works Association. p. 341-342.
17. ^ Koski TA, Stuart LS, Ortenzio LF (1 March 1966). "Comparison of Chlorine, Bromine, and Iodine as Disinfectants for Swimming Pool Water". Applied Microbiology 14 (2): 276–279. PMC 546668. PMID 4959984.
18. ^ a b Neumann, H. (1981). Bacteriological safety of hot tapwater in developing countries. Public Health Rep.84:812-814
19. ^ Baker KH, Hegarty JP, Redmond B, Reed NA, Herson DS (2002). "Effect of Oxidizing Disinfectants (Chlorine, Monochloramine, and Ozone) on Helicobacter pylori" (PDF). Applied and Environmental Microbiology 68 (2): 981–984. doi:10.1128/AEM.68.2.981-984.2002. PMC 126689. PMID 11823249.