Analysis of Factors Influencing the Action of Disinfectants In applying the disinfection agents or means that have been described,

the following factors must be considered: (1) contact time, (2) concentration and type of chemical agent, (3) intensity and nature of physical agent, (4) temperature, (5) number of organisms, (6) types of organisms, and (7) nature of suspending liquid. Contact Time It is one of the most important variables in the disinfection process. In general, it has been observed that for a given concentration of disinfectant, the longer the contact time, the greater the kill. This observation was first formalized in the literature by Chick. In differential form, Chicks law is

Where: Nt = number of organisms at time t t= time k= constant, time -1 If No is the number of organisms when t equals 0, the equation can be integrated to

Or

Departures from this rate law are common. Rates of kill have been found to increase with time in some cases and to decrease with time in other cases. To formulate a valid relationship for the kill of organisms under a variety of conditions, an assumption often made is that

where m is a constant. If m is less than 1, the rate of kill decreases with time, and, if m is greater than 1, the rate of kill increases with time. The constants can be obtained by plotting ln (N/No) versus the contact time t on log- log paper. The straight- line form of the equation is

Another formulation that has been used to describe the observed effects of contact time is

This equation results from the analysis of chlorination data that have been found to plot as straight lines on log- log paper. Concentration and Type of Chemical Agent Depending on the type of chemical agent, it has been observed that, within this limits, disinfection effectiveness is related to concentration. The effect of concentration has been formulated empirically:

Where: C= concentration of disinfectant n= constant tp= time required to effect a constant percentage kill

 Intensity and Nature of Physical Agent Heat and light are physical agents that have been used from time to time in the disinfection of wastewater. It has been found that their effectiveness is a function of intensity. For example, if the decay of organisms can be described with a first order reaction such as

Where: N= number of organisms t= time k= reaction velocity of constant, 1/ min

then the effect of the intensity of the physical disinfectant is reflected in the constant k through some functional relationship.

Temperature The effect of temperature on the rate of kill can be represented by a form of the vant HoffArrhenius relationship. Increasing the temperature results in a more rapid kill. In terms of the time t required to effect a given percentage kill, the relationship is

Where: t1, t2 = time for given percentage kill at temperatures T1 and T2, K, respectively

E= activation energy, J/mol (cal/mol) R= gas constant, 8.314 J/mol-K (1.99 cal/ K- mol) Since typical values for the activation energy for various chlorine compounds at different pH values are reported below.

Activation Energies for Aqueous Chlorine and Chloramines at Normal Temperatures Compound Aqueous chlorine pH 7.0 8.5 9.8 10.7 Chloramines 7.0 8.5 9.5 E, cal/mol 8,200 6,400 12,000 15,000 12,000 14,000 20,000

Number of Organisms The effectiveness of various disinfectants will be influenced by the nature and condition of the microorganisms. For example, viable growing bacteria cells are killed easily. In contrast, bacterial spores are extremely resistant, and many of the chemical disinfectants normally used will have little or no effect. Other disinfecting agents, such as heat, may have to be used.

 Nature of Suspending Liquid In addition to the foregoing factors, the nature of the suspending liquid must be evaluated carefully. For example, extraneous organic material will react with most oxidizing disinfectants and reduce their effectiveness. Turbidity will reduce the effectiveness of disinfectants by absorption and by protecting entrapped bacteria.

CHLORINE DISINFECTION
The most common form of disinfection regarding wastewaters is the use of Chlorine compounds since chlorine is the only substance able to capture all the requirements and properties of a disinfectant. Widely used chlorinated compounds include chlorine (Cl2), sodium hypochlorite (NaOCl), calcium hypochlorite (Ca(OCl)2), and chlorine dioxide (ClO2). Properties of Chlorinated Compounds for Disinfection A. Chlorine (Cl2)

This substance may be present in gaseous or liquid form. Gaseous form is greenish yellow in color and is 2.48 times heavier than air while liquid chlorine is amber colored and is 1.44 times heavier than water. Unconfined liquid chlorine rapidly vaporizes to a gas at standard temperature and pressure with 1 liter of liquid yielding 450 liters of gas.

Chlorine is moderately soluble in water with a maximum solubility of about 1 percent at 10C or 50F. Chlorine is supplied as a liquefied gas under high pressure in containers varying in size from 45 kg (100 lb) and 68 kg (150 lb) cylinders, 908 kg (1 ton) containers, multiunit railcars containing fifteen 908 kg (1 ton) containers, and railcars with capacities of 14.5, 27.2, and 49.9 Mg (16, 30, and 55 tons).

Properties of Chlorine, Chlorine Dioxide, and Sulfur Dioxide

Important considerations for the continued use of Chlorine Compounds

1. Chlorine is a highly toxic substance that is transported by accident-prone means like trucks and rails. 2. Accident release of the substance may pose health risk exposure to the plant operator and general public. 3. Due to toxicity, proper implementation of the stringent requirements and for containment and neutralization according to Uniform Fire Code (UFC) should be done. 4. Upon reaction to organic compounds, chlorine produces odorous substance.

5. Upon reaction to organic compounds, it forms by-products known to be carcinogenic and/or mutagenic. 6. Residual chlorine in treated wastewater effluent is toxic to aquatic life. 7. Concerns exist pertaining to the discharge of organo-chloride compounds to the environment which long-term effects remain unknown.

B. Sodium Hypochlorite

Many of the safety concern regarding handling and containment of chlorine is eliminated by the use of sodium hypochlorite and calcium hypochlorite. Sodium hypochlorite is also known as liquid bleach with the chemical formula NaOCl and has the following distinctions: Only available in liquid Contains 12.5 to 17% available chlorine upon manufacture In bulk purchasing, it can have 12-15% available chlorine

However, sodium hypochlorite decomposes more readily in high concentrations and is highly affected by light and heat. For example, a 16.7% solution contained at 26.7C (80F) will lose in 10 days, 10% of its strength, 20% in 25 days, and 30% in the next 45 days therefore storage in a cool and corrosive-resistant tank is a must. Other disadvantages include: High chemical cost (NaOCl costs 150-200% more than liquid chlorine) Design considerations due to corrosiveness and chlorine fumes formation

C. Calcium Hypochlorite This substance, with chemical formula Ca(OCl)2, is commercially available in dry or wet form. High-test calcium hypochlorite contains at least 70% available chlorine. In dry form it is available in off-white powder, or as granules, compressed tablets and pellets. Granular or

pelleted forms are readily soluble in water from about 21.5g/100ml at 0C (32F) to 23.4g/100ml at 40C (104F). Due to high oxidative potential, these should be stored in cool, dry location away from other chemicals in corrosion-resistant containers but with proper storage conditions, the granular Ca(OCl)2 is relatively stable. This chlorinated compound is used most commonly at small installations. On the other hand, hypochlorite is more expensive than liquid chlorine, loses its available strength in storage, and maybe difficult to handle. Calcium hypochlorite tends to crystallize thereby clogging metering pumps, piping, and valves.

Chemical Reactions of Chlorinated Compounds A. Chemistry of Chlorine in Water Upon application of either liquid or gaseous form of chlorine to water, two chemical reactions take place: hydrolysis and ionization. Hydrolysis is defined as the reaction between chlorine and water producing hypochlorous acid (HOCl)

Cl2 + H2O

HOCl + H+ + Cl-

This reaction has an equilibrium constant KH equivalent to:

KH= [HOCl] [H+] [Cl-] / [Cl2] = 4.5 x 104 (mol/L)2 at 25C

An equilibrium constant of this magnitude means that large amount of Cl2 can be dissolved in water. Ionization is defined as the formation of hydrogen (H+) and hypochlorite (OCl- )ions from hypochlorous acid (HOCl)

HOCl

H+ + OCl-

Ionization constant, KI, is equivalent to:

KI= [H+] [OCl-] / [HOCl] = 3 x 10-8 mol/L at 25C

The total HOCl and OCl- present in water is known in the collective term free available chlorine. It is very important that HOCl amount be monitored as compared to OCl- since the previous has a killing efficiency of around 40-80 times that of the latter. The percentage distribution of HOCl can be computed together with the values of KI and the pH of the sample:

[HOCl] / [HOCl] + [OCl-] = 1/ 1 + KI10pH Values of KI at different temperatures

B. Hypochlorite Reactions with Water Free available chlorine can also be added to water in the form of hypochlorite salts. Both sodium and calcium hypochlorite form hypochlorous acid in the following mechanism which would then be disassociated further in the earlier discussed reactions:

C. Chlorine Reactions with Ammonia Untreated wastewater contains nitrogen in the form of ammonia and various combined organic forms. The effluent from most treatment plants also contains significant amount of

ammonia or nitrate if the plant is designed to achieve nitrification. Due to the very oxidative nature of hypochlorous acid, it will readily form 3 types of chloramines.

The reactions and their products are highly dependent of the pH, temperature, contact time, and ratio of ammonia to chlorine. Only two components are predominant in the reactions namely monochloramine and dichloramine while trichloramine is negligible up to the chlorine-nitrogen ratio of 2.0. Chlorine contents of these compounds are termed combined available chlorine. Chloramines are also considered disinfectants however these are relatively slower than those with free available chlorines. When these chloramines are solely used as the disinfectant, the measured residual chlorine, is then called combined chlorine residual while for hypochlorous acid and hypochlorite it is called free chlorine residual.

DECHLORINATION
Chlorination is one of the most commonly used methods for the destruction of pathogenic and other harmful organisms that may endanger human health. However, certain organic constituents and compounds may react with chlorine to form toxic compounds that can have long term adverse effects on the beneficial uses of the waters to which they are discharged. To minimize the effects of these potentially toxic chlorine residuals on the environment, dechlorination of the wastewater is necessary.

Dechlorination is a practice used to reduce or remove the chlorine discharge levels. Free and combined chlorine residuals are reduced by sulfur dioxide, sulfites and other dechlorinating agents. The most cost effective dechlorinating agent is sulfur dioxide. Stoichiometrically, 0.9 parts of sulfur dioxide

are required to remove one part chlorine. In actual practice, at least 10% excess may be required for complete dechlorination. 1. Dechlorination with Sulfur Dioxide

Sulfur dioxide is handled in equipment very similar to standard chlorine systems. When added to water, sulfur dioxide reacts to form sulfurous acid (H2SO3-), a strong reducing agent. In turn, the sulfurous dissociates to form HSO3- that will react with free and combined chlorine, resulting in formation of chloride and sulfate ions. Sulfur dioxide successively removes free-chlorine, monochloramine, dichloramine, nitrogen trichloride, and poly-n-chlor compounds.

Reactions between sulfur dioxide and free chlorine: HSO3- + H+ Cl- +SO42- + 2H+ Cl- + SO42- + 3H+

SO2 + H2O HOCl + HSO3SO2 + HOCl + H2O

Sulfur dioxide is the most common dechlorinating agent for the following reasons:

1. Removes free or combined chlorine residual 2. Cost effective 3. Similar to chlorine feeding apparatus design 4. Simple to control

Sulfur dioxide dechlorination is a very reliable unit process in wastewater treatment, provided that the precision of the combined chlorine residual monitoring service is adequate. Excess sulfur dioxide dosages should be avoided, not only because of the chemical wastage but also because of the oxygen demand exreted by the excess sulfur dioxide.

A. Disinfection with Ozone

Ozone (O3), or trioxygen, is a triatomic molecule, consisting of three oxygen atoms. It is an allotrope of oxygen that is much less stable than the diatomicallotrope (O2). Ozone in the lower atmosphere is an air pollutant with harmful effects on the respiratory systems of animals and will burn sensitive plants; however, the ozone layer in the upper atmosphere is beneficial, preventing potentially damaging ultraviolet light from reaching the Earth's surface. Ozone is present in low concentrations throughout the Earth's atmosphere. It has many industrial and consumer applications. Although historically used primarily for the disinfection of water, recent advances in ozone generation and solution technology have made the use of ozone economically more competitive for wastewater disinfection. Ozone can also be used in wastewater treatment for odor control and in advanced wastewater treatment for the removal of soluble refractory organics, in lieu of the carbonadsorption process.

Steps in Ozone Disinfection

1 Computer animation of a bacterial cell 2 Close-up of an ozone molecule on the bacterial cell wall 3 Ozone penetrates the cell wall and causes corrosion 4 Close-up of the effect of ozone on the cell wall 5 Bacterial cell after it has come in contact with a number of ozone molecules 6 Cell destruction (lysis)

Ozone as Disinfectant

Ozone functions as both an oxidant and disinfectant in the treatment of drinking (potable) water and wastewater. This is similar to chlorine. Chlorine and Ozone, however, operate by different mechanisms when disinfecting water. As a result, ozone and chlorine can act synergistically. Ozone's germicidal properties are associated with its high oxidation potential. Disinfection by ozone is a direct result of bacterial cell wall disintegration, also known as cell lysis. This mechanism is different than that by chlorine. Although the exact chemical action of chlorine is not clear, it is believed that the chlorine residual in aqueous solution diffuses through the cell wall of the microorganisms and attacks the enzyme group which results in the destruction of the microorganism.

Advantages and Disadvantages of Ozone:

Pros

Cons

- Extremely powerful disinfectant

- Expensive option

- Does not form trihalomethanes

- Can form other hazardous disinfection-by-products such as

bromated

- Requires relatively short contact time

- Requires high level of technology

- Reduces taste, odor, and color in water by oxidizing the algea and - Requires another disinfectant to

humic material which causes these achieve residual disinfection levels problems

- Forms microfloc upon contact therefore improving coagulation and reducing the required coagulant dose - Unstable - must be generated on-site

- Can improve filtration rates. With improved coagulation, more material settles in the sedimentation basin. Hence, less material reaches the filters and the filters can be run longer before backwashing. - Climate control needed to maintain solubility

Ozone vs. Chlorine

ACTION IN WATER Oxidation Potential (Volts)Disinfection:

CHLORINE 1.36

OZONE 2.07

Bacteria Viruses Environmentally Friendly Color Removal Carcinogen Formation Organics Oxidation Micro flocculation pH Effect Water Half-Life Operation Hazards: Skin Toxicity Inhalation Toxicity Complexity Capital Cost Monthly Use Cost Air Pre-treatment

Moderate Moderate No Good Likely Moderate None Variable 2-3 hours

Excellent Excellent Yes Excellent Unlikely High Moderate Lowers 20 min.

High High Low Low Moderate-High None

Moderate High High High Low Filer and dehumidify air