Water chlorination is the process of adding chlorine (Cl
2) or hypochlorite to water. This method is used to kill certain bacteria and other microbes in tap water as chlorine is highly toxic. In particular, chlorination is used to prevent the spread of waterborne diseases such as cholera, dysentery, typhoid etc.
In a paper published in 1894, it was formally proposed to add chlorine to water to render it "germ-free". Two other authorities endorsed this proposal and published it in many other papers in 1895. Early attempts at implementing water chlorination at a water treatment plant were made in 1893 in Hamburg, Germany, and in 1897 the town of Maidstone, England was the first to have its entire water supply treated with chlorine.
Permanent water chlorination began in 1905, when a faulty slow sand filter and a contaminated water supply caused a serious typhoid fever epidemic in Lincoln, England. Dr. Alexander Cruickshank Houston used chlorination of the water to stop the epidemic. His installation fed a concentrated solution of so-called chloride of lime to the water being treated. This was not simply modern calcium chloride, but contained chlorine gas dissolved in lime-water (dilute calcium hydroxide) to form calcium hypochlorite (chlorinated lime). 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.
The first continuous use of chlorine in the United States for disinfection took place in 1908 at Boonton Reservoir (on the Rockaway River), which served as the supply for Jersey City, New Jersey. 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. Over the next few years, chlorine disinfection using chloride of lime (calcium hypochlorite) were rapidly installed in drinking water systems around the world.
The technique of purification of drinking water by use of compressed liquefied chlorine gas was developed by a British officer in the Indian Medical Service, Vincent B. Nesfield, in 1903. According to his own account, "It occurred to me that chlorine gas might be found satisfactory ... if suitable means could be found for using it.... The next important question was how to render the gas portable. This might be accomplished in two ways: By liquefying it, and storing it in lead-lined iron vessels, having a jet with a very fine capillary canal, and fitted with a tap or a screw cap. The tap is turned on, and the cylinder placed in the amount of water required. The chlorine bubbles out, and in ten to fifteen minutes the water is absolutely safe. This method would be of use on a large scale, as for service water carts."
Major Carl Rogers Darnall, Professor of Chemistry at the Army Medical School, gave the first practical demonstration of this in 1910. This work became the basis for present day systems of municipal water purification. Shortly after Darnall's demonstration, Major William J. L. Lyster 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). The canvas "bag, water, sterilizing" was a common component of field kitchens, issued one per 100 persons, of a standard 36-gallon capacity that hung from an often-improvised tripod in the field. In use from World War I through the Vietnam War, it has been replaced by reverse osmosis systems that produce potable water by pressure straining local water through microscopic-level filters: the Reverse Osmosis Water Purification Unit (1980) and the Tactical Water Purification System (2007) for large-scale production, and the Light Water Purifier unit for smaller-scale needs that includes ultrafiltration technology to produce potable water from any source and uses automated backwash cycles every 15 minutes to simplify cleaning operations.
Chlorine gas was first used on a continuing basis to disinfect the water supply at the Belmont filter plant, Philadelphia, Pennsylvania by using a machine invented by Charles Frederick Wallace who dubbed it the Chlorinator. It was manufactured by the Wallace & Tiernan company beginning in 1913. By 1941, disinfection of U.S. drinking water by chlorine gas had largely replaced the use of chloride of lime.
Chlorination can also be practiced using sodium hypochlorite or various other chemicals.
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. The microscopic agents of many diseases such as cholera, typhoid fever, and dysentery killed countless people annually before disinfection methods were employed routinely.
Chlorine is manufactured from salt by electrolysis or other methods. It is a gas at atmospheric pressures but liquefies under pressure. The liquefied gas is transported and used as such.
As a strong oxidizing agent, chlorine kills via the oxidation of organic molecules. Chlorine and 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.
When dissolved in water, chlorine converts to an equilibrium mixture of chlorine, hypochlorous acid (HOCl), and hydrochloric acid (HCl):Cl2 + H2O ⇌ HOCl + HCl
In acidic solution, the major species are Cl
2 and HOCl, whereas in alkaline solution, effectively only ClO− (hypochlorite ion) is present. Very small concentrations of ClO2−, ClO3−, ClO4− are also found.
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 hypochlorite into the water. The hypochlorite can be in the form of a powder or a liquid such as chlorine bleach (solution of sodium hypochlorite in 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 parts per million (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 by-products (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. 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".
There are also other concerns regarding chlorine, including its volatile nature which causes it to disappear too quickly from the water system, and organoleptic concerns such as taste and odor.
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.
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.
Chloramination is also becoming increasingly common. Disinfection with chloramine produces less undesirable byproducts than chlorine (gas or hypochlorite). Chloramine has a longer half-life in the distribution system, and maintains effective protection against pathogens. Chloramines persist in the distribution because of their lower redox potential in comparison to free chlorine. Chloramine is formed by adding ammonia and chlorine into drinking water to form monochloramine and/or dichloramine. 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.
Bromination and iodinization
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.
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.
UV disinfection is gaining popularity. UV treatment leaves minimal residue in the water. In water UV generates ozone in situ and thus has many of the advantages of ozone disinfection. However, ultraviolet germicidal irradiation alone (as well as chlorination alone) will not remove toxins from bacteria, pesticides, heavy metals, etc. from water.
Like UV, ionizing radiation (X-rays, gamma rays, and electron beams) has been used to sterilize water.