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Group C: nthony rtono 021111007 021111008 021111009 021111043 021111045 021111079
Dicky Daruanggono Primarizka Ayunda W. Viera Ananda Duatri S. Endah Sih Wilujeng Cornelia Melinda Adi S.
Nayu Nur Annisa Sholikhin 021111080 Irina Fardhani Zahrah Musthofani Aprillia Sonya Federika Febria Rosana Satya Devi Siti Atikah Nadjwa 021111117 021111119 021111118 021111152 021111153 021111154
Faculty of Dentistry Airlangga University 2012 i
We are deeply praising and thankful to our Lord ALLAH SWT. Because of His mercy, this paper can be finished as we are expected. In this paper, we discuss about chlorinated water effects to human health, which is always a problem for people who experienced less use of the environment with good holistic resulting in decreased. This paper was made in order to deepen understanding of chlorine water issues and its effect on the human body with the hope of getting adequate health and excellent balance. In the process of discussing and deepening of the issue, we get the guidance, direction, correction and advice, so we deeply thanks to: 1. Titik Bernianti, drg.,M.Kes, as our responsible person and lecturer in 3rd Problem Based Learning. 2. Sri Yogyarti, drg., M.S as our responsible tutor and lecturer in Group I 3rd Problem Based Learning. We realize that there are still many shortcomings of this paper, both of material and presentation techniques, given our lack of knowledge and experience. So, criticism and suggestions are expected to improve this paper. Hopefully this paper is useful for the readers.
Surabaya, 8rd of April 2012 Editor
COVER ............................................................................................................. PREFACE .........................................................................................................
CONTENTS ..................................................................................................... iii ABSTRACT ..................................................................................................... v CHAPTER 1 FOREWORD ........................................................................... 1 1.1 Background .............................................................................................. 1 1.2 Learning Issues ........................................................................................ 2 1.3 Purpose ..................................................................................................... 2 1.4 Benefits .................................................................................................... 3 CHAPTER 2 THEORITICAL REVIEW. ..................................................... 4 2.1 Definition of Chlorine .............................................................................. 4 2.2 Characteristic of Chlorine ........................................................................ 4 2.2.1 2.2.2 Physical ........................................................................................ 4 Chemical ...................................................................................... 4
2.3 Kind of Chlorine Compound and The Applications ................................ 6 2.3.1 2.3.2 2.3.3 2.3.4 2.3.5 2.3.6 Hydrochloric Acid (HCl) ............................................................. 6 Liquid Calcium Chloride (CaCl2 .................................................. 6 Calcium Hypochlorite (Ca(ClO)2) .............................................. 7 Sodium Chlorate (NaClO3) ......................................................... 7 Chlorine Perchlorate (Cl2O4) ...................................................... 8 Organochlorine Compound .......................................................... 8
2.4 Chlorinated Water ..................................................................................... 9 2.4.1 2.4.2 2.4.3 Environment Factors .................................................................... 9 Good Effect .................................................................................. 9 Bad Effects ................................................................................... 11 126.96.36.199 Effect on Plants and Animals ........................................... 11 iii
188.8.131.52 Effect on Human Health .................................................. 12 184.108.40.206.1 220.127.116.11.2 Short Term Effects ......................................... 13 Long Term Effects …………………………… 14
2.5 Host Factors Supporting Chlorine Exposure ........................................... 21 2.5.1 Habits ........................................................................................... 21 18.104.22.168 Eating or drinking ............................................................ 21 22.214.171.124 Showering ......................................................................... 21 126.96.36.199 Washing ........................................................................... 22 2.5.2 Activities ...................................................................................... 22 188.8.131.52 Swimming ........................................................................ 22 184.108.40.206 Fishing .............................................................................. 23 220.127.116.11 Farming ............................................................................ 23 2.6 Solutions .................................................................................................. 24 2.6.1 2.6.2 2.6.3 Controlling Host Habits ............................................................... 24 Maintaining Chlorine Percentage in Water .................................. 24 Alternative Ways of Water Treatment Systems ........................... 25 18.104.22.168 Ozone Disinfectants ......................................................... 26 22.214.171.124 UV Disinfectants .............................................................. 28 126.96.36.199 Carbon Treatment Method ............................................... 31 188.8.131.52 Dechlorination .................................................................. 32 CHAPTER 3 CONCEPT MAPPING ........................................................... 37 CHAPTER 4 DISCUSSION ........................................................................... 39 CHAPTER 5 CLOSING ................................................................................. 44 5.1 Conclusion ................................................................................................. 44 5.2 Recommendation ....................................................................................... 44 REFERENCES ................................................................................................. 45
There are many factors cause available water contaminated by excessive chlorine. Geographical conditions or lack of caring clean environment can decrease fresh water supply in an area. Bad water sources require the region drinking water company to do water treatment system, called chlorination. Industrial area, using and wasting chlorine, also contaminate the ground water with excessive chlorine. Water is an essential matter for life; human habits and activities always contact with water, so it is difficult to avoid the available water perfectly. Host socio-culture aspects interact with agent (chlorine in water) and exacerbate effects of chlorinated water. Characteristic of chlorine is bound with other element easily, it can produces some harmful substances such as acid and THM that effects to human skin, hair, inhale, and teeth health. Chronic disease like cancer and heart disease is potentially happen. High intensity of chlorinated water exposure effects on short and long term diseases. Keywords: Chlorinated water, environment, human lifestyle, effect on human health.
CHAPTER 1 FOREWORD
1.1 BACKGROUND Chlorine is one of elements that exists on earth and are rarely found in free form. It is a yellow-green, noncombustible gas with a pungent, irritating odor. It is a chemical substance, which has been used in many industries for a long time, especially in the pulp and paper industry and drinking water treatment. It has also been used in making dye, medicine, plastic, solvent, and dry clean. In the sector of energy and electricity, chlorine is used in the cooling water system. Besides, it is also used in household for disinfectant and bleach. In agriculture chlorine, in a form of organochlorine, is also used for pesticide. Although it has many benefits for many aspects of life, chlorine also has adverse effects for human and environment. In industry, due to the lack of condition of chlorine‘s stor ge, it will le d to the le k ge of chlorine g s, which will endanger environment and health. Waste from industrial or household activity containing chlorine has also a potential to damage environment. If it is discharged into the waters, it will pollute the waters and its ecosystems. Moreover, the use of chlorine in agriculture for pesticide, such as dichlorodiphenyl-trichloroethan, can cause accumulation of residues on food chains. Due to gas leaks, bad disposal and handling of waste containing chlorine, it can cause high levels of chlorine in the areas. Waters can also be contaminated by chlorine, resulting in high levels of chlorine in the water supply in the areas. Although chlorine has a good effect as disinfectant for water treatment systems, it can be harmful for human health. Chlorine can also easily react with many compounds because of its character as a strong oxidator. In the chlorination process, chlorine is also able to bind with organic compounds in water to form organochlorine compounds, such as trihalomethanes, which are carcinogens in the body.
Chlorinated water itself can cause bad effect on human health, which the level of severity depends on these three factors. They are the amount of chlorine is exposed to, the route of exposure, and the length of time of the exposure. Human can be exposed by chlorine through their daily activities, such as drinking chlorinated water, using it for cooking, showering, et cetera. As a result of this chlorine exposure, it can cause short term and long term disease. Therefore, in this paper, we will discuss further on the relationship between host (humans), agent (chlorine), and the environment, which influence each other and play an integral part in the effects of the overall disease system. It also outlines the solution to decrease high level of chlorine in the water supply, regarding to those epidemiologic triangle.
1.2 LEARNING ISSUES 1. How is the interaction between host (humans), agent (chlorine), and the environment in the process of diseases? 2. How is the effect of chlorine on animal and plants? 3. What are the short term and long term effects of chlorine on human health? 4. How is the influence of human lifestyle that supports the occurrence of chlorine exposure? 5. How to cope the excessive chlorine content in water?
1.3 PURPOSE 1. To understand the interaction between host (humans), agent (chlorine), and the environment in the process of diseases. 2. To understand the effect of chlorine on animal and plants. 3. To understand the short term and long term effects of chlorine on human health? 4. To understand the influence of human lifestyle that supports the occurrence of chlorine exposure 5. To find out how to cope the excessive chlorine content in water
BENEFITS From these problems we can get many benefits. As we know, the
interaction between host (human), agent (chlorine), and environment play an integral part in the effects of the overall disease system. From this we not only gain some knowledge, but also good information to prevent and overcome the occurrence of disease, based on the epidemiologic triangle.
CHAPTER 2 THEORITICAL REVIEW 2.1 DEFINITION OF CHLORINE Chlorine (Cl2) is one of the most reactive elements; it easily binds to other elements. Because of its reactivity, chlorine gas is almost never found in nature. Approximately 2% of the e rth‘s surf ce m teri ls is chlorine which is mostly in the form of sodium chloride in sea water and in natural deposits as carnallite (KMgCl3.6H2O) and as sylvite (KCl). (The Chlorine Institute Inc., 2000) Active volcanoes emit some chlorine, and it has been detected coming from the decomposition of sea salt. It was first prepared in pure form by the Swedish chemist Carl Wilhelm Scheele in 1774. Scheele heated brown stone (manganese dioxide; MnO2) with hydrochloric acid (HCl). When these substances are heated the bonds are broken, causing manganese chloride (MnCl2), water (H2O) and chlorine gas (Cl2) to form. (Hasan A, 2006) 2.2 CHARACTERISTIC OF CHLORINE 2.2.1 Physical Characteristic Chlorine is greenish-yellow diatomic gas, a liquid, or in rhombic crystals. The pungent odor is suffocating and very irritating by inhalation. It is soluble in water, alcohols, and alkalis, and evaporates into the air very quickly. At standard temperature and pressure, two chlorine atoms form the diatomic molecule Cl2. This is a yellow-green gas that has a distinctive strong odor, familiar to most from common household bleach. The bonding between the two atoms is relatively weak (only 242.580 ± 0.004 kJ/mol), which makes the Cl2 molecule highly reactive. The boiling point at regul r tmosphere is round −34˚C, but it c n be liquefied t room temperature with pressures above 740 kPa. (National Pollutant Inventory, 2010) 2.2.2 Chemical Characteristic Along with fluorine, bromine, iodine, and astatine, chlorine is a member of the halogen series that forms the group 17 (formerly VII, VIIA, or VIIB) of the periodic table. Chlorine forms compounds with almost all of the elements to give
compounds that are usually called chlorides. Chlorine gas reacts with most organic compounds, and will even sluggishly support the combustion of hydrocarbons. (Hammond, 2000) At 25 °C and atmospheric pressure, one liter of water dissolves 3.26 g or 1.02 L of gaseous chlorine. Solutions of chlorine in water contain chlorine (Cl2), hydrochloric acid, and hypochlorous acid: Cl2 + H2O is in equilibrium with HCl + HClO This conversion to the right is called disproportionation, because the ingredient chlorine both increases and decreases in formal oxidation state. The solubility of chlorine in water is increased if the water contains dissolved alkali hydroxide, and in this way, chlorine bleach is produced. Cl2 + 2OH– → ClO– + Cl– + H2O Chlorine gas only exists in a neutral or acidic solution. (Ophardt, 2003) Chlorinated water should be protected from sunlight. Chlorine is broken down under the influence of sunlight. UV radiation in sunlight provides energy which aids the break-down of underchloric acid (HOCl) molecules. First, the water molecule (H2O) is broken down, causing electrons to be released which reduce the chlorine atom of underchloric acid to chloride (Cl-). During this reaction an oxygen atom is released, which will be converted into an oxygen molecule: 2HOCl 2H+ + 2Cl- + O2 Chlorine is produced from chlorine bonds by means of electrolytic or chemical oxidation. This is often attained by electrolysis of seawater or rock salt. The salts are dissolved in water, forming brine. Brine can conduct a powerful direct current in an electolytic cell. Because of this current chlorine ions (which originate from salt dissolving in water) are transformed to chlorine atoms. Salt and water are divided up in sodium hydroxide (NaOH) and hydrogen gas (H2) on the cathode and chlorine gas on the anode. These cathode and anode products should be separated, because hydrogen gas reacts with chlorine gas very aggressively. (Agriculture and Agri-Food Canada, 2012)
2.3 KINDS OF CHLORINE COMPOUNDS AND THE APPLICATIONS 2.3.1 Hydrochloric Acid (HCl) Hydrochloric acid is included in a strong acid compound. Hydrochloric acid is made by reacting chlorine and hydrogen gas at high temperatures. Gaseous hydrochloric acid dissolved in water to obtain a solution of hydrochloric acid with a concentration of about 36%. In industrial activities, hydrochloric acid is used as a solvent in metal industry, chemical, food, and petroleum processing. In the human body, hydrochloric acid is one important component of gastric acid that acidify the gastric function. Acidity of the stomach is needed to activate pepsinogen into pepsin enzyme as well break down protein. Hydrochloric acid in the stomach is useful to kill the seeds of diseases carried by food. However, the excess of hydrochloric acid in gastric fluid can damage the mucous membranes of the stomach and even intestines. Hydrochloric acid is included in a strong acid, which is in excessive levels can injure the walls of the stomach and intestines. (Salocks and Kaley, 2004) 2.3.2 Liquid calcium chloride (CaCl2)
Liquid calcium chloride (CaCl2) is an ionic compound consisting of the elements calcium (alkaline earth metal) and chlorine. It is odorless, colorless, nontoxic solution, which is used extensively in various industries and applications worldwide. This compound can be found most often in seawater and mineral springs. Ability of calcium chloride to absorb a lot of fluids is one quality that makes it so versatile. For example, these products work much more efficient than rock salt when it comes to clearing snow and ice from sidewalks, roads, and highways. This is especially true at lower temperatures. There are some drawbacks with this application, because there is some evidence that the product may be harmful to plant life than rock salt. Besides, calcium chloride can serve as a source of calcium ions in the solution, not as a source of calcium ions in solution. Unlike most other calcium compounds, calcium chloride is dissolved. These properties are useful to replace the ions from the solution. Liquid calcium chloride can be electrolyzed to give
calcium metal and chlorine gas. Many pools using products that contain calcium chloride, especially in areas where there is relatively little calcium is found in the water. The use of these products help increase water calcium levels, which in turn minimizes the potential for corrosion of the pump. Also limit the corrosion products with different types of swimming pool equipment, pool and completeness of any decisions made with metal. Calcium chloride is also used in a number of other applications. For example, the splashing of products on the streets in a dry climate, especially the desert, can help to minimize the amount of dust being kicked up because of traffic. This product can be used to dry the seaweed, which helps in the production of soda ash. It can be used as an ingredient in many kinds of plastic products, and help thin liquid fabric softener. Common applications include cooling brine for plants, ice and dust control on roads. Due to its nature hygroscopic, anhydrous calcium chloride should be stored in an airtight container tightly closed. (Flinn Scientific, Inc., 2002) 2.3.3 Calcium Hypochlorite (Ca(ClO)2)
Calcium hypochlorite is a chlorine or chemical compound that has the chemical formula Ca(ClO)2 and available in a variety of forms, including powder, granules, briquettes, and teblets. All these delivery forms contain solid calcium hypochlorite with 65%-70% available chlorine. These products differ only in their physical delivery form. Calcium hypochlorite is a white solid which is decomposed in water, then it release oxygen and chlorine. These compounds are not found freely in nature. Primarily, this substance is used as a water purifier or a disinfectant. Typically used in commercial bleach, cleaning solvents, pool water purifier, drinking water and disinfectants. As a disinfectant, chlorine can kill the microbes. (Black, 2010) 2.3.4 Sodium Chlorate (NaClO3) Sodium Chlorate is a chemical compound with the chemical formula (NaClO3). When pure, it is a white crystalline powder that is readily soluble in water. It is hygroscopic. It decomposes above 250 °C to release oxygen and leave sodium chloride. Sodium chlorate is used in papermaking in textile industry, and 7
as a cheap, if unselective, weed killer. There are many electrolytic plants for its production, usually on the 5000-20000 ton/year. The electrolytic formation of chlorate is dependent on complex solution chemistry coupled to a simple electrontransfer process. In simplified terms, the overall cell reaction is: NaCl+3H2O NaClO3+3H2 The majority of chlorate cells involve a relatively high external circulation rate of electrolyte. The Kreb cells technology provides one example of this type of cell. (Derek, 2010) 2.3.5 Chlorine Perchlorate (Cl2O4) Chlorine perchlorate is the chemical compound with the formula Cl2O4. This chlorine oxide is an asymmetric oxide, with one chlorine atom in oxidation state +1 and the other +7, with proper formula ClOClO3. It is produced by the photolysis of chlorine dioxide at room temperature with 436 nm ultraviolet light. (Pletcher and Walsh, 2010) 2.3.6 Organochlorine Compound Chlorine is used extensively in organic chemistry in substitution and addition reactions. Chlorine often imparts many desired properties to an organic compound, in part owing to its electro negativity. Organochlorine compounds usually use as side products of industrial processes or as persistent pesticides. Many important industrial products are produced via organochlorine intermediates. Examples include polycarbonates, polyurethanes, silicones, polytetrafluoroethylene, carboxymethyl cellulose, and propylene oxide.
Organochlorine is also used as a pesticide, such as dikloro difenil trikloro etana, metokskhlor, aldrin, and dieldrin. However, some of pesticide from organochlorin compound can cause accumulation of residues on food chains, which is bad for health and environment. In the chlorination process, chlorine is also able to bind with organic compounds in water to form organochlorine compounds, such as trihalomethanes, which are carcinogens in the body. (Department of Environmental Services New Hampshire, 2006)
2.4 CHLORINATED WATER 2.4.1 Environment Factors Chlorine contamination in the environment can be caused due to gas leak nd industry‘s w stes which re not tre ted properly. V rious industries using chlorine in the process of its activities will generate waste containing chlorine. Waste may contain solid, liquid, or gas. Industries using chlorine as their raw materials, such as plastics, solvents, cement, pulp and paper, pesticides, metals, power generation, and other chemical industries. Chlorine-containing waste is also generated by the activity or drinking water treatment, waste of human activity (multiple waste), and hospital waste. Therefore, in environments, especially industrial environments which use chlorine, are usually encountered high level of chlorine contaminating their neighborhood. Chlorine-containing wastes can pollute the environment, including water, resulting in high levels of chlorine in the water supply in the areas. Chlorine pollution case ever happened in America. Kalamazoo River in Michigan, America was polluted by waste containing PCBs (poly chlorinated byphenyls) from paper industry. Another cause of high level of chlorine in the water supply is the water treatment system itself. In the process of chlorination, chlorine is used as a disinfectant to kill microorganisms effectively. However, water treatment system, which uses too much chlorine in the chlorination process, can also cause high levels of chlorine in the water supply. (Hasan A, 2006) 2.4.2 Good Effect The Use of Chlorine as Disinfectant Chlorine is a very effective disinfectant, relatively easy to handle, cost effective, simple to dose, measure and control, and it has a relatively good residual effect. Chlorine disinfection is generally carried out using one of three forms of chlorine or it can be generated on site. For small water treatment plants, calcium hypochlorite in the form of a dry powder or proprietary tablet-type dispenser can be used. This is more expensive than gaseous chlorine or
hypochlorite solution, but can offer advantages in terms of convenience and low installation costs. On a cost per mass of active chlorine basis, chlorine in the form of a liquefied gas is the most cost effective option, but is better suited to larger, more sophisticated works (Freese and Nozaic, 2004) Chlorine kills pathogens such as bacteria and viruses by breaking the chemical bonds in their molecules. Disinfectants that are used for this purpose consist of chlorine compounds which can exchange atoms with other compounds, such as enzymes in bacteria and other cells. When enzymes come in contact with chlorine, one or more of the hydrogen atoms in the molecule are replaced by chlorine. This causes the entire molecule to change shape or fall apart. When enzymes do not function properly, a cell or bacterium will die. When chlorine is added to water, underchloric acids form: Cl2 + H2O HOCl + H+ + ClDepending on the pH value, underchloric acid partly expires to hypochlorite ions Cl2 + 2H2O HOCl + H3O + C-HOCl + H2O H3O+ + OClThis falls apart to chlorine and oxygen atoms: OCl- Cl- + O Underchloric acid (HOCl, which is electrically neutral) and hypochlorite ions (OCl-, electrically negative) will form free chlorine when bound together. This results in disinfection. Both substances have very distinctive behavior. Underchloric acid is more reactive and is a stronger disinfectant than hypochlorite. Underchloric acid is split into hydrochloric acid (HCl) and oxygen atom (O). The oxygen atom is a powerful disinfectant. The disinfecting properties of chlorine in water are based on the oxidizing power of the free oxygen atoms and on chlorine substitution reactions. The cell wall of pathogenic microorganisms is negatively charged by nature. As such, it can be penetrated by the neutral underchloric acid, rather than by the negatively charged hypochlorite ion. Underchloric acid can penetrate slime layers, cell walls and protective layers of microorganisms and effectively kills pathogens as a result. The microorganisms will either die or suffer from reproductive failure.
The effectiveness of disinfection is determined by the pH of the water. Disinfection using chlorine will take place optimally when the pH is between 5,5 and 7,5. Underchloric acid (HOCl) reacts faster than hypochlorite ions (OCl-); it is 80-100% more effective. The level of underchloric acid will decrease when the pH value is higher. With a pH value of 6 the level of underchloric acid is 80%, whereas the concentration of hypochlorite ions is 20%. When the pH value is 8, this is the other way around. When the pH value is 7,5, concentrations of underchloric acid and hypochlorite ions are equally high (Cook, et al, 2010). Beside the use of chlorine as disinfectants in drinking-water and swimming pool, it can be used for household bleach and controlling bacteria and odours in the food industry. Chlorine enters the body breathed in with contaminated air or when consumed with contaminated food or water. It does not remain in the body, due to its reactivity. Effects of chlorine on human health depend on how the amount of chlorine that is present, and the length and frequency of exposure. Effects also depend on the health of a person or condition of the environment when exposure occurs. (Department of Community Health, 2004) 2.4.3 Bad Effects 184.108.40.206 Effect on plants and animals Chlorine in water can affect plants which are growing under water, such as phytoplankton. It makes the water acidic which over time can change soil pH. Plants do not thrive as well on chlorinated as on unchlorinated water. Phytoplankton was no recovery of photosynthetic activity when residual chlorine had fallen to undetectable levels on it. Chlorine dioxide (ClO2) is being evaluated for treatment of water to kill pathogens in recirculation systems in greenhouses and in water pumped from catchment ponds to irrigate nursery stock. The percentage of ClO2 may result in nutrient tie-upand can affect many symptoms in plants. Phytotoxicity symptoms, which application of ClO2 ranged from necrotic tips and margins, necrotic spots and blotches, and death. Predominant symptoms resulting from ClO2 were necrosis of leaf and flower tissue as spots between and across veins, and marginal necrosis. Early symptoms could start as a yellowing of the margin or tip of leaf or
flower. Lesions could have darkened borders. All plant species were damaged by 1000 and 2000 ppm ClO2. At 1000 and 2000 ppm ClO2, a mean toxicity rating >4% occurred (Copes, et al, 2003). Too much percentage of chlorine can make the pH of water decrease. The animals can get the bad effects of chlorinated. Wild animals do not develop atherosclerosis until they drink chlorinated water in zoos. Animals in freely life eat their food not selected by people, they caught their food their self. So, animals which drink chlorinated water can cause atherosclerosis. Animals that live under water such as, frog and fish can also get the bad effect of chlorinated water. Scientist in Minnesota propagated embryos from healthy frogs in plain tap water. Some of the frogs had no legs or six legs, or an eye in the middle of the throat (Hattersley JG, 2000) Fish can tolerate chlorine extremely high, acute doses of ascorbic acid without injury. Live channel catfish were able to withstand concentrations of ascorbate with levels ranging from 10 to 3,000 milligrams per liter over a 24-hour period. Additional research results are consistent with these findings. Changes in pH are also an important concern for fish in receiving waters. Ascorbic acid will lower pH under extreme conditions (low alkalinity water) during flushing operations. If there are so many chlorinated water absorbed by the fish more than 24 hour it can affected the fishes mass and make the fish being killed (Peterka G, 2002). 220.127.116.11 Effects on human health At least, the body has a standard how much that chlorine can enters and be acceptable. Table 1. The standard reference ranges of chloride for humans (in mmol/L) (Bergman, 2010) Normal Value 95–110 mmol/L Abnormal value Less than 90 mmol/L and greater than 115 mmol/L Less than 20 mmol/L and greater than 60 mmol/L
Chloride in serum / plasma Chloride in urine Chloride in sweat
110–250 mmol/24 hours 5–40 mmol/L 12
Chlorine in solution at the concentrations recommended is considered to be toxicologically acceptable even for drinking-water. The WHO health-based guideline value for chlorine in drinking-water is 5 mg/L (WHO, 2004). However, high levels of chlorine make the water smell and give it a bad taste, which will discourage people from drinking it. The higher level will be close to the disinfection point and the lower level at the far extremities of the supply network. The effects of various levels of chlorine inhalation vary with the individuals involved. The following list is a compilation of chlorine exposure thresholds and reported responses in humans: Table 2. The effects of various levels of chlorine inhalation on human health (The Chlorine Institute Inc., 2000) Level of Chlorine 0.2-0.4 ppm Effect on Health threshold of odor perception with considerable variation among subjects (a decrease in odor perception occurs over time) mild, mucous membrane irritation, tolerated for up to one hour moderate irritation of the respiratory tract immediate chest pain, vomiting, dyspnea, and cough toxic pneumonitis and pulmonary edema lethal over 30 minutes fatal within a few minutes
1-3 ppm 5-15 ppm 30 ppm 40-60 ppm 430 ppm 1000 ppm
To receive a lethal exposure, a person would have to remain near a leak source, within a chlorine cloud, and without respiratory protection (The Chlorine Institute Inc., 2000). 18.104.22.168.1 Short-term (acute) effects:
1. Short-term exposures to low levels of chlorine in the air rarely lead to any long-lasting lung changes. Any exposure from smelling appropriately treated drinking water or swimming pool water is not harmful. 2. Acute exposure to high concentrations of chlorine can lead to a build-up of fluid in the lungs (pulmonary edema) and severe shortness of breath that could
lead to death if untreated. Immediately or within a few hours after breathing chlorine gas, the lungs can become irritated, causing coughing and/or shortness of breath. The amount of time before these symptoms occur is dependent on the amount of chlorine to which one is exposed. (The higher the amount one is exposed to, the shorter the amount of time before symptoms are seen.) Exposure may result in nose and throat irritation, watery eyes, coughing, bloody nose, nausea, vomiting, chest pain, and/or lightheadedness. 3. Drinking a chlorine solution can cause vomiting, nausea, and throat and stomach irritation. The vomit is likely to have a chlorine smell to it. 4. Contact with chlorine gas can severely burn and irritate the eyes and skin upon contact, possibly causing permanent damage. Liquid chlorine solutions (such as bleach) can have vapors that are irritating to the eyes, nose and throat. Chlorine bleach can cause irritation to exposed skin. 5. When chlorine vapor or solution comes into contact with moist tissues (such as those found in the nose, eyes, throat, and lungs), it forms an acid (hydrochloric acid) and can damage the exposed tissue. 6. Contact with chlorine liquid (gas kept under pressure) can cause frostbite and chemical burns to the skin. 7. The elderly, smokers, and persons with chronic pulmonary disease may be at greatest risk for breathing problems following acute exposure.
Long-term (chronic) effects:
1. Long-term exposure to low levels of chlorine gas is potentially linked to diseases of the lung (bronchitis, shortness of breath, possible permanent damage) and tooth corrosion. 2. Chronic exposure to chlorine also has possible link to cancers. (Department of Community Health, 2004) Those short-terms and long-term effects can be described as follows according to the organ affected by exposure to chlorine
Skin and hair Chlorine in shower water also has a very negative effect that is omitting the moisture and elasticity of skin and hair. Anyone who has ever swum in chlorinated pool can relate to the harsh effect that chlorine has on the skin and hair. However, levels of chlorine are found higher in tap water than in the swimming pools. (Chopra, 2006) Chlorine destroys protein in bodies and cause adverse effects on skin and h ir. Chlorine softens the h ir‘s protective outer shell, its sc ly cuticle. In f ct, under an electron microscope, the cuticle can be seen to have melted or worn away. It can also damage the hair follicle itself. (Sigler, 2011) The morphology of the cuticle cells does not reveal any fibrous components under the transmission electron microscope (TEM). Inside the bounding surface membrane (the outer surface) resides a layer, which has a constant width and contains high amount of sulfur. This layer protects the cuticle from negative effects of physical and chemical environmental factors. The next two layers are the exocuticle and the endocuticle, vary in width. The endocuticle firstly suffers the effect of chlorinated water and fungal invasion. Access to this part of the cell is at the chipped border of the free cuticle edge occurring above the skin surf ce s n effect of wh t is c lled ―we thering‖. (Forslind, et al, 2003) Weathering is rare in children and common after puberty, particularly in women with long hair. Natural weathering covers the cumulative effects of climatic exposure, sunlight, wind, and water (both sea and chlorinated). Accelerated weathering occurs with the physiochemical procedures that the owner inflicts: oxidation by bleaching or coloring with permanent dyes. Weathered hair may have loss of sheen, dryness or a brittle feel, increased porosity, lower disruption point as a result of disruption of cystine linkages, decreased sulfur content, amino acid degradation, focal disruption (trichorrhexis nodosa), or split ends (Baron, 2005). Taking long, hot showers is a health risk. The problem is that chloroform and chlorine, formed in a hot steamy shower. The heat causes these toxic gases to vaporize. The poisonous gases are then inhaled and absorbed through your skin.
Not only is chlorine toxic to the body, other chemicals may lurk in tap water (Sigler, 2011). Pool chemicals such as chlorine have a more profound effect on hair. With prolonged exposure, chlorine can act as a bleaching agent on the hair. This is a similar to the effects of prolonged exposure to the sun. The hair can lighten in color and may become brittle. These effects are usually minor and are directly proportional to the amount of time spent in the pool (Grootenhuis, 2002). Washing in heavily chlorinated water is very harmful for skin. The destruction of protein in bodies by chlorine can cause skin and hair become very dry and unmanageable. Chlorine also strips the natural protective oils from skin and hair, causing excess dryness. After clinical studies were carried out for over a year at the Department of Dermatology, Toyama Medical Pharmaceutical University in Japan, the researchers stated that residual chlorine in bathing water reduces the water-holding capacity of the top layer of our skin, which results in the skin drying out more e sily, compromising the skin‘s b rrier nd potenti lly leading to infections and irritation. (Grace, 2010). Heart Disease There is an undeniable connection between the practice of chlorinating water supplies and arteriosclerosis, in which a plaque composed mainly of cholesterol builds up inside arteries, resulting eventually in heart attacks and strokes. When chlorinated water is run through a hose or carried in a pail followed by milk as in a dairy, very tenacious, yellowish deposits chemically similar to arterial plaque are form; with unchlorin ted w ter this doesn‘t h ppen. (Hattersley, 2000) Cholesterol is a lipid (fatty) substance present in organism cells and essential to life, it's a precursor for many common bio chemical compounds. But when excess chlorine has been absorbed from drinking chlorinated water, it reacts 'with some of the cholesterol in the blood, forming the yellowish fatty deposits that accumulate along artery walls, narrowing and hardening them, and often causing ruptures. The result is plaque formation that causes Atherosclerosis. Atherosclerosis is a condition in which an artery wall thickens as a result of the
accumulation of fatty materials such as cholesterol. It is commonly referred to as a hardening or furring of the arteries. It is caused by the formation of multiple plaques within the arteries.
Figure 1. Atherosclerosis (National Heart Lung and Blood Institute, 2011) A study using chickens as test subjects, in which two groups of several hundred birds were observed throughout their span to maturity. One group was given water with chlorine and the other water without chlorine. The group raised with chlorine, when autopsied, showed some level of heart or circulatory disease in every specimen; the group without had no incidence of disease. (Hattersley, 2000) Cancer Chlorination of drinking water throughout the world has been recognized. Where water is effectively chlorinated infection by waterborne diseases such as cholera, typhoid fever and dysentery has ceased to pose a risk to public health. However, chlorination of drinking water may produce by-products such as a group of chemicals known as trihalomethanes (T M‘s). T M‘s m y be formed when chlorine reacts with natural organic matter that can be found in some water sources. There re m ny forms of T M‘s, such s chloroform, bromoform,
bromodichloromethane and dibromochloromethane. If the levels of disinfection by-products are not controlled, they may pose a risk to health. For several years a number of researchers around the world have been concerned th t T M‘s could be c use of some forms of c ncer in the liver,
kidneys, colon, bladder, rectum and reproductive areas of the body. People living in households with an average household water trihalomethanes (THM) level of more than 49 micrograms per liter had double the bladder cancer risks of those living in households where water trihalomethanes (THM) concentration was below 8 micrograms per liter, the researchers found. (Hattersley, 2000). T M‘s c n be e sily bsorbed by the body when (Department of Health Western Australia, 2009): 1. water containing high levels comes into contact with the skin, or 2. if they are consumed in food prepared in water; or 3. they are inhaled during showering or bathing. Inhale Most high-level exposure occurs in workplaces where chlorine is used. People may inhale chlorine by using chlorine bleach or by living near an industry that uses chlorine. The smell from treated drinking water or swimming pools may be irrit ting but isn‘t usu lly h rmful. (Wisconsin Department of Health Services, 2010) Chlorine in swimming pools reacts with organic matter such as sweat, urine, blood, feces, and mucus and skin cells to form more chloramines. Chloroform risk can be 70 to 240 times higher in the air over indoor pools than over outdoor pools. Canadian researchers found that after an hour of swimming in a chlorinated pool, chloroform concentrations in the swimmers‘ blood r nged from 100 to 1,093 ppb. Taking a warm shower or lounging in a tub filled with hot chlorinated water, one inhales chloroform. Researchers recorded increases in chloroform concentr tion in b thers‘ lungs of bout 2.7 ppb fter 10-minute shower. Worse, warm water causes the skin to act like a sponge; and so one will absorb and inhale
more chlorine in a ten-minute shower than by drinking eight glasses of the same water. This irritates the eyes, the sinuses, throat, skin and lungs, dries the hair and scalp, worsening dandruff. It can also weaken immunity. A window from the shower room open to the outdoors would release chloroform from the shower room air, but to prevent its absorption through the skin requires a showerhead that removes chlorine. (Hattersley, 2000) Genetics Studies in Belgium have related development of deadly malignant melanoma to consumption of chlorinated water. Drinking and swimming in chlorinated water can cause melanoma. Sodium hypochlorite, used in chlorination of water for swimming pools, is mutagenic in the Ames test and other mutagenicity tests. Redheads and blonds are disproportionately melanomaprone; their skin contains a relative excess of pheomelanins compared to darker people. It was reported that pollution of rivers and oceans and chlorination of swimming pool water have led to an increase in melanoma. (Hattersley, 2000) Long-term risks of consuming chlorinated water include excessive free radical formation, which accelerates aging, increases vulnerability to genetic mutation and cancer development, hinders cholesterol metabolism, and promotes hardening of arteries. Excess free radicals created by chlorinated water also generate dangerous toxins in the body. These have been directly linked to liver malfunction, weakening of the immune system and pre-arteriosclerotic changes in arteries. Excessive free radicals have been linked also to alterations of cellular DNA. Chlorine also destroys antioxidant vitamin E, which is needed to counteract excess oxysterol or free radicals for cardiac and anti-cancer protection. A study also found that chlorinated water appears to increase the risk of g strointestin l c ncer over person‘s lifetime by 50 to 100 percent. l ter met -
analysis found chlorinated water is associated each year in America with about 4,200 cases of bladder cancer and 6,500 cases of rectal cancer. Chlorine is estimated to account for 9% of bladder cancer cases and 18% of rectal cancers. Those cancers develop because the bladder and rectum store waste products for periods of time. Chlorinated water is also associated with higher total risk of
combined cancers. Recent research has found a new hazard in chlorinated water: a byproduct called MX. A research team from the National Public Health Institute in Finland discovered that, by causing genetic mutations, MX initiates cancer in laboratory animals. Also, DCA (dichloroacedic acid) in chlorinated water alters cholesterol metabolism, changing HDL to LDL cholesterol and causes liver cancer in laboratory animals. (Hattersley, 2000) Teeth Erosion Chlorine is the chemical most often used to keep swimming pools free of bacteria. When chlorine was added into water, it produced hypochlorous acid (HOCl) and hypochloride ion (OCl-). Therefore, extremely high levels of chlorine in the water caused decreasing of the pH level in swimming pool water. Meanwhile, a pH of 5.5 is considered to be the critical pH for enamel dissolution. Dental erosion is a painful, costly, irreversible condition which can be caused by low pH water of inadequately maintained chlorinated swimming pools. There was a study to evaluate enamel erosion due to immersion in low pH swimming pool water. Tooth enamel specimens were immersed in low pH swimming pool water for a 4 hours period. Enamel loss was measured by using a focusing method of a measuring microscope and Vickers microhardness of enamel was measured with a microhardness tester. After immersion for 4 h, pool water with pH of 3.85 and titratable acidity of 1.4 ml of 0.1 N NaOH eroded 5.1 μm of en mel nd resulted in h rdness v lue of en mel decre sed by 23.2%, whereas pool water with pH of 2.91 and titratable acidity of 9.5 ml of 0.1 N NaOH eroded 31.3 μm of en mel nd resulted in h rdness v lue of en mel decreased by 19.3%. Therefore, increase in enamel loss related to the lower pH of water and increase in exposure time. (Chuenarrom, et al, 2010)
Figure 2. Erosive potential of swimming pool water with different pH on tooth enamel over a 4 hours period. (Chuenarrom, et al, 2010)
HOST FACTORS SUPPORTING CHLORINE EXPOSURE 2.5.1 Habits (eating/drinking, showering, washing) 22.214.171.124 Eating or Drinking If human consume chlorinated drinking water daily, it turns out people
who drink water containing chlorine are more likely to get cancer of the bladder, rectum or colon. As for pregnant women, chlorine can cause birth defects with abnormalities of the brain or spinal cord, low birth weight, premature birth or even miscarriage experience. The effect of drinking chlorinated water is also the same as using it as substance in cooking the food. (Hattersley, 2000) 126.96.36.199 Showering Using chlorinated water for taking shower daily can also cause bad effects on hum n‘s he lth. Exposure to chlorine is through v por inh l tion nd
absorption through the skin when take a bath using a shower. The warm water from shower will open the skin pores and lead to increased absorption of chlorine and other chemicals in that water. Inhalation of chlorine gas is very dangerous because it can be inhaled directly into the bloodstream. (Department of Community Health, 2004)
188.8.131.52 Washing Using chlorinated water for washing may cause chlorine to contact with skins and have almost similar effects with using it for showering. The skin does not absorb chlorine well, but small amounts can pass through the skin when people are exposed to chlorine gas, bleach, or come into contact with water containing high levels of chlorine. Small amounts of chlorine can pass through the skin into human bodies. Chlorine may irritate or burn the skin, especially moist areas. (Department of Community Health, 2004) 2.5.2 Activities (swimming, fishing, farming) 184.108.40.206 Swimming The present study of short term exposure to chlorine for swimmers can cause significant immediate morbidity in most exposed people and potential lung damage after 15–30 days affected. Swimming park or water park in a closed pace is more dangerous than outdoors. The immediate clinical manifestation in most people was predominantly due to the irritant effect of chlorine gas on the lachrymal, nasal, oral, and tracheobronchial tree. Inhalation of chlorine gas can damage both the airways and the alveolarcapillary structures because of its solubility. At physiological pH on most surfaces, chlorine gas combines with tissue water to form hydrochloric and hypochlorous acids which diffuse into cells to react with the amino groups of cytoplasm proteins, forming N-chloral derivatives. A study found restrictive ventilator function with reduced diffusing capacity and some obstruction in small but not in large airways 14–16 hours after the exposure of four healthy men in a swimming pool. Lung function deficit in asymptomatic subjects is accidentally exposed 14 days after the exposure. Although the exact pathological change is not known, bronchiolitis obliterans has been proposed as a lesion occurring after some toxic gas inhalation. It has been hypothesized that low background levels of the respiratory irritants among swimmers cause a chronic inflammatory response in the small airways that may enhance the effects of a single acute gassing episode with a higher possibility of long term squealed than in other settings. A case of asthma, persisting 2 years
after the inhalation of a mixture of sodium hypochlorite and hydrochloric acid, is also found. (Agabiti, et al, 2001) 220.127.116.11 Fishing On the average of water pH, about 7.8-8.0, is the ideal pH for fish to life normally. On the higher pH and increased chlorine level up to 40% for about 28 days, fish would show the increasing frequency of operculum significantly. The normal operculum movement is 140-143 per minutes meanwhile the fish which are putted inside of chlorinated water will have the increase operculum movement up to 140-153 per minutes. That increase of operculum movement is caused by hinder diffusion of oxygen inside of fish gills, so the absorption of the oxygen become down dramatically. As a response fish will increase operculum movement for loaded the amount of oxygen inside of fish body. Increased operculum movement in a long period can affect the damage of the fish gills which impact to the death because of the weak muscle which are used to moved the operculum. The compound of this increased operculum cannot be known certainly because the components of the chlorinated water are heterogeneous. But the compound estimated as an organochlorine which have lipophilic characteristic and reserved on the fish body easily. That organochlorine can disturb the oxidative phosphorilation on the cell respiratory which can block the ATP forming. The increasing of the operculum movement can cause the decrease of the addition of fish mass. That process will happen after 16 days in chlorinated water (Peterka, 2002). 18.104.22.168 Farming An accidental release of approximately 15 tons of chlorine has been described. Vegetation on farms and roadsides in the affected areas suffered from damage from the chlorine gas. Leaves on trees were darkened and coniferous trees were affected to the degree that the needles dropped. Feed samples, although of generally poor quality because of difficult harvesting conditions, showed no significant changes in pH or chloride ion content when compared with samples collected elsewhere in the province. Soil
analyses showed no chlorine accumulation and no differences which could be attributed to chlorine exposure. A limited feeding trial on three calves with forage from the affected area showed no harmful effects in a three-week feeding period and no observable loss of palatability. Eggs, milk and cream samples showed no abnormalities when examined by a taste panel. Farm livestock including pets became sick and in some cases died following exposure. Several cattle died and post mortem lesions consisting primarily of edema and emphysema of the lungs were observed. Pigs were sick, but seemingly recovered in most cases. Pet animals and poultry appeared to recover fairly quickly. Horses were more severely affected clinically and permanent damage to the lungs may have resulted. (MacDonald, et al, 2000)
2.6 SOLUTIONS 2.6.1 Controlling Host Habit
Controlling host habit can be done by using shower filter to remove the chlorine and soften the bathing water (Grace, 2010). The chlorine filter only removes chlorine from the water supply, nothing else. The gaseous shower odor from toxic chloroform was eliminated. Moreover our skin, where the hair is made, is no longer dry and brittle (Sigler, 2011). Here are three ways to avoid releasing chlorine gas in and around the home: When using a dry, chlorine-based swimming pool sanitizer, always add the sanitizer to the pool water. Never mix water into pool treatment chemicals. Never mix different types of swimming pool treatment chemicals together. Never mix household chlorine compounds (bleach, cleansers) with ammonia or with acidbased household chemicals like toilet-bowl cleaners 2.6.2 Maintaining Chlorine Percentage in Water
The required chlorine dose can be calculated by determining the desired residual, the volume of flow, and chlorine demand. For example, to treat 1 million gallons per day (MGD) of water and produce a chlorine residual of 0.6 mg/L with
water having a 1.0 mg/L chlorine demand, the chlorine dose rate in pounds per day would be calculated as follows: Chlorine, pounds/day = Vol. MGD x 8.34 lbs/gal x total concentration, mg/L = 1.0 MGD x 8.34 lbs/gal x 1.6 mg/L = 13.3 lbs per day Using this example, the chlorination feed equipment should be calibrated to provide a dose of 13.3 pounds of chlorine per day. When gaseous chlorine is used, the chlorine cylinder should be set up on a scale, and the total pounds per day should be recorded. When using a solution tank of calcium hypochlorite or sodium hypochlorite, the equation above must be modified because the amount of chemical used is not 100 percent chlorine. In the case of a hypochlorite solution that is 65 percent available chlorine, the dose of hypochlorite needed to produce 13.3 pounds per day of chlorine would be 20.5 pounds per day (13.3 pounds per day/0.65). The hypochlorinator must be calibrated to feed 20.5 pounds of calcium hypochlorite per day. The contact time and dose are extremely important to achieve good disinfection. A contact time of 30 minutes is a minimum, and the contact time may need to be increased at low temperatures or higher pH to achieve the same level of disinfection if the dose remains constant. A higher chlorine dose may allow for a shorter contact time, but that may not be the best way to optimize the disinfection process. (Lindsay L, 2005) 2.6.3 Alternative Ways of Water Treatment System
Table 3. The Advantages and Disadvantages of Disinfectants (Department of Environmental Health Washington State, 2004) Disinfectant Chlorine Applied as gas or liquid (hypochlorite) Principal Advantages Principal Disadvantages Effective for most Forms DBP when organic microorganisms. substances are present Can oxidize iron and manganese Not effective against (makes them easier to remove) Cryptosporidium protozoa Keeps a residual in distribution Can cause taste and odor system problem Technology well understood Relatively easy to use in a hypochlorite form 25
Chloramines Formed by combining chlorine and ammonia
Chlorine Dioxide Produced by reacting sodium chlorite with chlorine or hydrochloric acid
Forms more stable residual than Less effective than chlorine chlorine alone against microorganisms, viruses and Forms less DBBPs than especially protozoa chlorine Forms less taste and odor Poorly oxidizes iron and manganese causing compounds in water Usually requires a more Technology well understood powerful disinfectant for primary disinfection More effective than chlorine or Must be produced on site chloramines as disinfectant Forms additional DBPs such against microorganisms as Controls taste and odor better chlorite and chlorate than chlorine in some cases Requires daily chlorite and Forms less THMs and HAAs chlorine dioxide monitoring than chlorine Costs more for equipment and chemicals than chlorine Takes more technical skill to use Most powerful disinfectant used in drinking water treatment More effective than chlorine dioxide Effective against Giardia and Cryptosporidium protozoa Must be produced on site Takes more technical skill to use Forms bromate and other DBP Compounds Requires bromate monitoring Does not provide residual protection Effective against bacteria, Disinfection effectiveness Giardia, and Cryptosporidium and efficiency are affected by turbidity and dissolved Does not form DBPs substances Less effective against certain Viruses Technically complex, requires training to operate equipment Does not provide residual protection (may need secondary disinfectant) Does not reduce DBP formation by secondary disinfectant
Ozone Produced by electrical discharge through air or oxygen
Ultraviolet Radiation Non-chemical disinfection by using ultraviolet radiation at certain wavelengths
22.214.171.124 Ozone Disinfection Applicability Ozone disinfection is generally used at medium to large sized plants after at least secondary treatment. In addition to disinfection, another common use for ozone in wastewater treatment is odor control. Ozone disinfection is the least used method in the U.S., although this technology has been widely accepted in Europe for decades. Ozone treatment has the ability to achieve higher levels of disinfection than either chlorine or UV, however, the capital costs as well as maintenance expenditures are not competitive with available alternatives. Ozone is therefore used only sparingly, primarily in special cases where alternatives are not effective.
Figure 3. Ozone Process Schematic Diagram (EPA, 2000) Advantages 1. Ozone is more effective than chlorine in destroying viruses and bacteria. C The ozonation process utilizes a short contact time (approximately 10 to 30 minutes). 2. There are no harmful residuals that need to be removed after ozonation because ozone decomposes rapidly. 3. After ozonation, there is no regrowth of microorganisms, except for those protected by the particulates in the wastewater stream.
Ozone is generated onsite, and thus, there are fewer safety problems associated with shipping and handling.
Ozonation elevates the dissolved oxygen (DO) concentration of the effluent. The increase in DO can eliminate the need for reaeration and also raise the level of DO in the receiving stream.
Disadvantages 1. Low dosage may not effectively inactivate some viruses, spores, and cysts. 2. Ozonation is a more complex technology than is chlorine or UV disinfection, requiring complicated equipment and efficient contacting systems. 3. Ozone is very reactive and corrosive, thus requiring corrosion-resistant material such as stainless steel. 4. Ozonation is not economical for wastewater with high levels of suspended solids (SS), biochemical oxygen demand (BOD), chemical oxygen demand, or total organic carbon. 5. Ozone is extremely irritating and possibly toxic, so off-gases from the contactor must be destroyed to prevent worker exposure. 6. The cost of treatment can be relatively high in capital and in power intensiveness. (EPA, 2000)
126.96.36.199 UV Disinfectant Description UV light, which continues to be a reliable means of disinfection, involves exposing contaminated water to radiation from UV light. The treatment works bec use UV light penetr tes n org nism‘s cell w lls nd disrupts the cell‘s genetic material, making reproduction impossible. A special lamp generates the radiation that creates UV light by striking an electric arc through low-pressure mercury vapor. This lamp emits a broad spectrum of radiation with intense peaks t UV wavelengths of 253.7 nanometers (nm) and a lesser peak at 184.9 nm. Research has shown that the optimum UV wavelength range to destroy bacteria is between 250 nm and 270 nm. At shorter 28
wavelengths (e.g.185 nm), UV light is powerful enough to produce ozone, hydroxyl, and other free radicals that destroy bacteria. The U.S. Department of Health, Education, and Welfare set guidelines for UV light disinfection. These guidelines require a minimum dose of 16 mWs/cm2 [milliwatt seconds per square centimeter] at all points throughout the water disinfection unit. However, the American National Standards Institute and the National Sanitation Foundation International set the minimum UV light requirement at 38 mWs/cm2 for class A point of use (POU) and point of entry (POE) devices that treat visually clear water. The U.S. Environmental Protection Agency (EPA) lists UV disinfection as an approved technology for small public water systems. In addition, EPA is considering the following variations of convention l UV tre tment s ―emerging‖ technologies: pulsed UV, mediumpressure UV, and UV oxidation.
Figure 4. Closed Vessel Ultraviolet Reactor (National Drinking Water Clearing House USA, 2000) Advantages 1. Generally, UV is simple to install and requires little supervision, maintenance, or space. Improved safety, minimum service time, low operation 2. and maintenance costs, and the absence of a chemical smell or taste in finished water are primary factors for selecting UV technology rather than traditional disinfection technologies. 29
3. UV treatment breaks down or removes some organic contaminants. UV achieves 1-log reduction of Giardia lamblia at an intensity of 80-120 mWs/cm2, and 4-log reduction of viruses at an intensity of 90-140 mWs/cm2. Only recently has the scientific community begun to accept UV as a highly effective tool for Cryptosporidium control. 4. UV light disinfection does not form any significant disinfection byproducts, nor does it cause any significant increase in assimilable organic carbon (AOC). 5. Research has confirmed that UV effectiveness is relatively insensitive to temperature and PH differences. In addition, researchers found that UV application does not convert nitrates to nitrites, or bromide to bromines or bromates. 6. Recent pilot studies show that UV-treated drinking water inhibits bacterial growth and replication in the distribution system; however, conditions within distribution systems, such as leaks, still require additional residual disinfection (e.g., free chlorine). 7. The advantages of using UV, rather than chemical disinfection, include: 8. Has no known toxic or significant nontoxic byproducts; 9. Has no danger of overdosing; 10. Removes some organic contaminants; 11. Has no volatile organic compound (VOC) emissions or toxic air emissions; 12. Has no onsite smell and no smell in the final water product; 13. Requires very little contact time (seconds versus minutes for chemical disinfection); 14. Does not require storage of hazardous material; 15. Requires minimal space for equipment and contact chamber; 16. Improves the taste of water because of some organic contaminants and nuisance microorganisms are destroyed; 17. Does not affect minerals in water; and 18. Has little or no impact on the environment, except for disposing of used lamps or obsolete equipment.
Limitations 1. Microbial and chemical characteristics are two major water quality factors that affect the UV unit performance. Microbial characteristics of water include type, source, age, and density. Chemical water characteristics include nitrites, sulfites, iron, hardness, and aromatic organic levels. 2. UV radiation is not suitable for water with high levels of suspended solids, turbidity, color, or soluble organic matter. These materials can react with UV radiation, and reduce disinfection performance. Turbidity makes it difficult for radiation to penetrate water. 3. Disadvantages of UV disinfection include: 4. No disinfection residual; 5. No technical database exists on how well UV systems perform for various water quality conditions; and 6. No standardized mechanism measures, calibrates, or certifies how well equipment works before or after installation. 7. Systems also should consider using different kinds of microbial testing. Laboratories typically test for total coliform to judge microbiological activity in drinking water—but coliforms are sensitive to UV light. Because of this sensitivity, microbial tests for UV treated finished water should include a Heterotrophic Plate Count (HPC) test. HPC microorganisms may provide a better disinfection assessment than the UV sensitive coliforms. (National Drinking Water Clearing House, 2000) 188.8.131.52 Carbon Treatment Method Trace concentration of phenol from wastewater from CO & BP can be removed by adsorption on granulated carbon. This process can be directly applied to undiluted effluents from the ammonia still, final cooler blow down, light oil decanter liquor and fractional ion condensate without previous biological treatment. In addition, all the streams which have been bio-treated and diluted can further be carbon treated. Therefore, carbon treatment is either an alternative or an adjunct to biological treatment Efficiency of carbon treatment in comparison to bio-treatment is furnished in Table 5.
Table 4. Efficiency of Carbon Treatment to bio-treatment (Sirajuddin, et al, 2008)
The secondary residuals from this treatment process are particulate and sulphur dioxide from carbon regeneration in the reactivation of carbon by burning off the adsorbed residuals. (Sirajuddin, et al, 2008) 184.108.40.206 Dechlorination Applicability Chlorination has been used widely to disinfect wastewater prior to discharge since passage of the 1972 Federal Water Pollution Control Act (WPCA). In the first years following the WPCA, disinfected wastewater with significant levels of residual chlorine was routinely discharged into the receiving waters. It became clear, however, that residual chlorine is toxic to many kinds of aquatic life. Moreover, the reaction of chlorine with organic materials in the water formed carcinogenic trihalomethanes and organochlorines. As a result, dechlorination was instituted to remove residual chlorine from wastewater prior to discharge into sensitive aquatic waters. Dechlorination minimizes the effect of potentially toxic disinfection byproducts by removing the free or total combined chlorine residual remaining after chlorination. Typically, dechlorination is accomplished by adding sulfur dioxide or sulfite salts (i.e., sodium sulfite, sodium bisulfite, or sodium metabisulfite). Carbon adsorption is also an effective dechlorination method, but is expensive compared to other methods. Carbon adsorption is usually implemented when total dechlorination is desired. (EPA, 2000)
Advantages 1. Protects aquatic life from toxic effects of residual chlorine. 2. Prevents formation of harmful chlorinated compounds in drinking water through reaction of residual chlorine with waterborn organic materials. (EPA, 2000) Disadvantages 1. Chemical dechlorination can be difficult to control when near zero levels of residual chlorine are required. 2. Significant overdosing of sulfite can lead to sulfate formation, suppressed dissolved oxygen content, and lower pH of the finished effluent. (EPA, 2000) Design Criteria 1. Chemistry of Dechlorination by Sulfonation Sulfur dioxide (SO2) is a corrosive, nonflammable gas with a characteristic pungent odor. At atmospheric temperature and pressure, it is a colorless vapor. When compressed and cooled, it forms a colorless liquid. Sulfur dioxide is supplied as liquefied gas under pressure in 100 or 150 pound containers and oneton cylinders. As an alternative to sulfur dioxide gas, various dry chemicals are available which form sulfur dioxide in solution. These include sodium sulfite (Na2SO3), sodium metabisulfite (Na2S2O5), sodium bisulfite (NaHSO3), a 38% aqueous solution of sodium metabisulfite, and sodium thiosulfate (Na2S2O3), among others. When dissolved in water, chlorine hydrolyzes to form hypochlorous acid (HOCl) and hypochlorite ions (OClG) which, taken together, are referred to as ―free chlorine.‖ It is rarely found in wastewater since the conditions of formation are relatively extreme. Once formed, the free chlorine reacts with natural organic matter in water and wastewater to form chlorinated organic compounds. The free chlorine also combines with ammonia to form mono-, di-, and trichloramines in quantities dependent on the ratio of chlorine to ammonia nitrogen.
When either sulfur dioxide or sulfite salts are dissolved in water, aqueous sulfur compounds in the +4 oxidation state are produced, often notated S(IV). The S(IV) species, such as the sulfite ion (SO3 -2), reacts with both free and combined forms of chlorine, as illustrated in equations (1) and (2): (1) SO3-2 + HOCl SO4-2 + Cl- + H+ (2) SO3-2 + NH2Cl + H20 SO4 -2 + Cl- + NH4+ Since free chlorine and inorganic chloramines react rapidly with S(IV), a short contact time of one to five minutes is considered to be sufficient; nevertheless, complete blending at the point of application is essential for effective dechlorination. Proper dosage is critical to produce a nondetectable chlorine residual. On a mass basis, 0.9 parts sulfur dioxide (or 1.46 parts NaHSO3 or 1.34 parts Na2S2O5) is required to dechlorinate 1.0 part residual chlorine. In practice, approximately a oneto- one ratio is used. Dosing in excess must be avoided because excess sulfite can react with dissolved oxygen (four parts sulfite to one part oxygen) in the wastewater to produce sulfates, potentially leading to reduced dissolved oxygen concentrations and low pH levels in the finished effluent for high levels of overdose. Careful process control will help prevent overdosing. 2. Equipment for gaseous sulfonation Equipment required for gaseous sulfonation using SO2 is similar in design to that used for chlorination, except that the materials are chosen for their application-specific chemical resistance. The four basic components of the system include: sufficient gas supply with automatic switch-over between cylinders; a metering system, usually consisting of a vacuum regulator and a rotameter for feed rate control; one or more injectors with check valves; and a residual analyzer to measure and transmit a continuous signal proportional to the chlorine residual in the sample stream. In small concentrations, exposure to SO2 can cause eye and throat irritation. In high concentrations, exposure can produce a suffocating effect caused by irritation to the upper respiratory tract. Therefore, facility design should include features for safe storage, handling, and use of sulfur dioxide. The chlorine and sulfur dioxide cylinders should be located in separate rooms and stored in a
well ventilated, temperature-controlled area so that their temperature never drops below 18 or exceeds 70 degrees Celsius. Gas leak detectors are necessary in the storage area and the sulfonator area. An emergency eyewash shower and selfcontained breathing apparatus should also be provided. All personnel should receive emergency response training. Facilities with more than 1,000 pounds of SO2 stored on-site must abide by the Process Management Safety Standard in the OSHA regulations. 3. Effect of Temperature on Gas Withdrawal Rate The room temperature where the gas supply is located should be maintained around 70 degrees F to ensure optimal gas withdrawal rates. At this temperature, the maximum safe sulfur dioxide gas withdrawal rate is approximately 2 lb/hr for a 150 lb container, or 25 lb/hr for a ton container. Higher temperatures are required to achieve higher continuous gas withdrawal rates. Strip heaters or liquid baths may be used for this purpose. 4. Injector Selection Proper selection of the injector is critical for proper system operation. The injector produces a vacuum that draws sulfur dioxide gas through the sulfonator. It then mixes the gas with dilution water supply and injects the solution into the wastewater. To properly size the injector, the back pressure on the injector at the point of application and the water supply pressure required at the injector must be determined. The injector can either be installed in a pipe or an open channel. As an alternative to the typical vacuum regulator with injector system, a chemical induction system may be used to introduce the sulfur dioxide directly as a gas. (EPA, 2000) Performance Sulfonation has been widely considered effective for removal of chlorine compounds in disinfected wastewater and reduction of toxicity for aquatic life. Nevertheless, two studies have suggested that disinfected/sulfonated wastewater poses a hazard to some sensitive aquatic species. Furthermore, one estimation of
chlorine removal efficiency is from 87 to 98 %, leaving the actual residual chlorine following sulfonation above most regulatory limits. Chloramines tend to be longer lived and less reactive than other chlorinated species in wastewater. While hydrophilic organic chloramines have been thought of as generally nontoxic, Helz and Nweke have found that the S(IV) fraction resistant to dechlorination may be composed of hydrophobic secondary amines and peptides, including chloramines, suggesting possible toxicity for aquatic organisms in receiving streams. The authors note that this fraction of S(IV)-resistant chlorine has been overlooked because the dechlorinating agent interferes with standard analytical methods for total chlorine. Continued testing is underway to further characterize the dechlorination-resistant fraction and its effects on aquatic organisms. (EPA, 2000)
CHAPTER III CONCEPT MAPPING
CHAPTER IV DISCUSSION Issue A woman move to a city in which the consume of pure water is gotten from the chlorinated water. The woman really takes care of the effect of chlorine upon health; despite she has never sick caused by that water yet. She also does not like the taste of water. If the woman is not severely sick cause of the water, what kind of negative effect that may happen, if you want learn further about the long term effect of the chlorinated water consume, what do you need to know? Is that going trigger any problem?
It is said on the issue that the wom n doesn‘t like the t ste, so we analyzed that the water taste is not good; it was the sign that chlorine level is high. From the issue, we also know the woman has a good comprehension about her health. She knows that chlorinated water will effects badly to her body. As we know before, chlorine is needed as disinfectant in the water. There are so many risks that we will get if the water is not free from virus and bacteria. Chlorine is beneficial for human for that matter, but if the level is over, then many bad effects will appear. The exposure of high level chlorine results in bad effects on human health. Chlorinated water is important matter for a human. Same with the air, no one can life without water. It also happen to the woman in the issue above, it will be so difficult to avoid the chlorinated water perfectly. Because she still lived in the area with chlorinated water being the one water sources. From the socioculture angle, there are many activities of people which is always contact water, fishing, farming, swimming, etc. The farming activities will use the available water in watering crops and plants, also the fishing activity will use the available water to fill the fishpond. So, the chlorine still effects to the plants and fishes, when the products consumed by the woman, so chlorine is effects to her 39
indirectly. Chlorinated water is also detected in pool, because calcium hypochlorite is used as pool water purifier. Therefore, the chlorinated water still has effects to her, as we know it will exposure to her skin, hair, teeth directly. Chlorinated water has a conjunction with many effects that occur on human's life such as farming and fishing. Fishing is an activity that finds some animal which life in the water like sea, lake, river and etcetera. Besides, farming is kind of activity that usually doing by group of people to process the area for planted by certain plant. In this case, if chlorinated water exposure are used to farm sector, this water can be infect the plant that are planted and watered by the water which contaminated in the chlorine. If the plants eaten by the woman without any good treatment of washing and cooking, it can bring the negative effect for the woman in case, for example affect her body organ like liver, mouth cavity, trachea, digestive system and so on. Because of the contents of chlorine reserved by fish or animals water, it can cause the damages for the animal, and if the fish consumed by the woman, it can damage the woman's life like the effect that she gets if she does not washed or cooked plant. People, who may use the chlorine water, may have effect to their hair and skin. The chlorinated water will rob our skin and hair moisture and elasticity. And it destroys protein in our bodies. On hair, the chlorinated water can soften the hair's protective outer shell, its scaly cuticle and causes weathering of hair. Weathered hair may have loss of sheen, dryness or a brittle feel, increased porosity, lower disruption point as a result of disruption of cystine linkages, decreased sulfur content, amino acid degradation, focal disruption (trichorrhexis nodosa), or split ends. Beside that, with prolonged exposure, chlorine may become a bleaching agent on hair. This is a similar to the effects of prolonged exposure to the sun. The hair can lighten in color and may become brittle. On skin, the chlorinated water can cause skin drying out more easily, compromising the skin‘s b rrier nd potenti lly le ding to infections nd irrit tion. Shower filter can be used to remove the chlorine and soften the bathing water. The chlorine filter can remove chlorine from the water supply. The gaseous
shower odor from toxic chloroform was eliminated. Moreover, our skin, where the hair is made, is no longer dry and brittle. Chlorine is an effective treatment for disinfecting water and is used in swimming pools. It has negative effect for the human especially on teeth (dental enamel). Exposure to excessive levels of chlorine, which cause the pH level of the pool to fall, has been shown to cause the erosion of dental enamel. The pool water with pH 2.91 had six times higher erosive potential on enamel than the pool water with pH 3.85, indicated that an increase in enamel loss related to the lower pH of water and increasing contact time. Low pH caused by excessive chlorination causes the enamel to erode or wear away. Enamel is the hard protective coating of the tooth, which protects the sensitive, softer and darker yellow dentin underneath. When the enamel is eroded, the dentin underneath is exposed. Prevention of tooth erosion cause by low pH of pool water starts with keeping your pool water properly balanced. Over chlorinated pools that produce excessively elevated levels of acidity can contribute to dental enamel erosion. A swimming pool should have a neutral pH level between 7.2 and 7.8. Chlorine levels should be maintained between 1.0 to 3.0 ppm (parts per million). Pool chemistry should be checked regularly. It is not recommended to allow any pool water into the mouth. Keep consuming the chlorinated water in the long term will lead to several diseases. One of them is atherosclerosis that will lead to heart attack and stroke. In addition, consuming chlorinated water also increase the risk of cancer. Chlorine content in the water that we drink later will go into the blood vessels. Other than drinking, chlorine can also enter the body through the skin when showering. In the blood vessels, chlorine reacts with various substances. Among them is cholesterol. The reaction of chlorine with cholesterol makes the cholesterol to settle / precipitate in the veins, which later will clog and interfere the blood flow, characterized by thickening of blood vessel wall. This commonly referred to atherosclerosis, which became the beginning of heart attack and stroke. If atherosclerosis occurs in the blood vessels leading to the brain, it will cause stroke. If leading to the heart it will cause heart attack.
Chlorinated water is also a factor increasing the risk of cancer. The presence of compounds called Trihalomethanes (THMs) as by-product of disinfection with chlorine compound. Trihalomethanes are formed when chlorine reacts with the organic substances which naturally occur in raw water. The most common THM components formed during chlorination include chloroform, bromoform, bromodichloromethane, and chlorodibromomethane. THMs are carcinogenic, long term consumption of water contain THMs may damage the kidney and intestine and cause cancer. Prevention of water that contains chlorine can be minimized if done properly water quality treatment. In addition, important follow-up activities are outreach efforts to educate the user or chlorinated water. Education is the process of learning, from not knowing about the effects of chlorine to knowing, from not being able to overcoming the idea of prevention. The purpose of this education is to improve the health status, prevent the onset of disease and increased health problems, maintain existing health status, maximize function and role of the patient during the illness, and help patients and families to address health problems on the dangers of chlorine that can enter the body humans and can be bad for health if the life depending on chlorinated water. In carrying out the process of water purification, one medium that can be used is ctiv ted c rbon. It‘s better to use ctiv ted c rbon th n chlorine bec use it has some interested chemical properties and physical properties, that one of them is possibility to absorb organic and anorganic substance and being a catalyst for some reactions. Activated carbon can be used to absorbing gases, absorbing metal, eliminate micro pollutants like organic substance, detergen, smell, phenol, etc. Characteristic of activated carbon depending on the materials used, example is coconut shell produce smooth carbon and it suits for water purification. There are advantages from using an activated carbon for water purifying: a. easy to use because the water flow in carbon medium, b. quick prosses bec use the c rbon‘s p rticle h s bigger size, and
c. c rbon doesn‘t mix with mud so it c n be regener ted Most of small water system use only groundwater, so they have low levels of dissolved organic substances, DBP levels are usually not a major concern. If water systems use hypochlorite, they can use inexpensive equipment and widely available chemicals, and they will need no special technical skills to operate and maintain the equipment. Most small systems find that disinfection using chlorine, especially when added in hypochlorite form, to be the best method of disinfection of their water supply. However, in this case the woman complained that the w ter‘s t ste is not good, so it means it has high level of chlorine in it. As a result, it is recommend to use dechlorination system by using sulfur dioxide which is common in use and consider to be the safest chemical kinds for dechlorination. This process can reduce the negative effect of chorine residual which is give bad effect for human body. To produce the best water quality, it needs to use ozone disinfectant, because it is the most powerful disinfectant, but it cost high, so it can be applicable at metropolitan city such as Jakarta, Surabaya, etc. It is not to applicable at small city which has few professional, so it is better to use UV which is has moderate level of disinfectant and usually combined with chlorine. The addition of free chlorine (at a concentration of 0.25 mg/L free chlorine for 1 minute of contact time) can provide the desired 4-log inactivation of adenovirus.
CHAPTER V CLOSING
5.1 CONCLUSSION Though chlorine has a big role in disinfect the bacteria and virus from water, the excessive chlorine is very harmful to human health. There are some factors that correlate one and others in exacerbating the impacts of chlorine in human health. Chlorinated water has potential to the long term and short term diseases. However, there are some solutions that can minimize the impacts of chlorine.
5.2 RECCOMENDATION Migration is the most effective way to avoid the impacts perfectly for people who live in the chlorinated water area. However, the most important is to keep healthy life and maintain our habit especially in consuming water. We can do some solutions above to minimize the impacts of chlorine, for example using filter with active carbon to neutralize excessive chlorine. The region drinking water company also must pay attention to the level of chlorine used in their water treatment system.
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