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DISINFECTION (3rd DC 240; 4th DC 294) Definition Disinfection - Killing or inactivating pathogens
- To destroy organisms that cause diseases in humans and domestic animals.

Pathogens: Disease-producing microorganisms Sterilization: destruction of all living organisms - Drinking water need not be sterile Purpose of Disinfection - To protect public health by preventing the spread of water born diseases by disinfecting drinking and wastewater to an acceptable level. Three categories of human enteric pathogens: 1) Bacteria 2) Viruses 3) Protozoa (amebic cysts) - Purposeful disinfection must be capable of destroying all three. Diseases and Pathogens (Examples) Water Born Disease Typhoid Bacillary dysentery Cholera Giardiasis Cryptosporidiosis Amoebiasis Adenovirus infection Gastroenteritis Gastroenteritis Pathogens Salmonella typhi Shigella dysenteriae Vibrio cholera Giardia lambia Cryptosporidium parvumis Naglaria Adenovirus Astrovirus Parvovirus Note Bacteria Bacteria Bacteria Protozoa Protozoa Protozoa Virus Virus Virus

Removal of Pathogenic Microorganisms by Water Treatment Processes

- Removal of pathogenic microorganisms and other microorganisms in conventional water treatment processes include:

a. Coagulation/flocculation b. Sedimentation c. Filtration d. Inactivation by chemicals, (e.g., lime, soda ash) e. Natural die-away of organisms in an unfavorable environment
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Disinfection by chemical disinfectants Considerations as a water disinfectant 1) Effectiveness - ability to kill the types and numbers of organisms within reasonable (practicable): a) contact time b) temperature (over an expected range) c) water quality variations 2) Availability
- constant and readily available supply of disinfectant at reasonable cost and in form conveniently, safely and accurately applied.

a) b) c) d) 3) Toxicity

reasonable cost ($) readily, safely available constant supply convenient form

- cannot render the water toxic or objectionable (aesthetically or otherwise) for human consumption

a) non-toxic to humans and domestic animals b) palatable, non-objectionable 4) Handling a) convenient, safe, and easy to store, transport, and handle. b) conveniently, safely, easy, and accurately apply 5) Persistency (maintaining killing power) a) persist in residual concentrations as safeguard against recontamination 6) Assay technique (for process control) a) practical, easy, reproducible b) reasonable cost c) rapid and accurate

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Disinfectants 1) Chlorine, Cl2 C hypochlorous acid, HOCl C hypochlorite, OCl2) Chloramine C monochloramine, NH2Cl C dichloramine, NHCl2 3) Chlorine dioxide, ClO2 4) Ozone, O3 5) Others C Bromine (Br), Iodine (I2), Iodide (I -)

Chemistry of Chlorination Chlorine a. Chlorine gas is soluble in water

solubility = 7160 mg/L at 20 C, 1 atm

b. Chlorine reacts with: 1) Water 2) Ammonia and 3) Other compounds:

a) b) c) d) e) Organic nitrogen Organic compounds (phenol, humic substances) Nitrites Iron and manganese Hydrogen sulfide and cyanide.

Basic reactions with water Formation of Hypochlorous acid, HOCl

- Chlorine gas hydrolizes in water rapidly, almost completely, to form hypochlorous acid: - Hypochlorous acid is a weak acid and dissociate poorly at pH< 6.

Cl2(g) + H2O

HOCl + H+ + Cl-

(1) (2)

{HOCl} {H+} {Cl-} Keq = ------------------------ = 4 x 10-14 {Cl2} {H2O}

{ } = [ ] { } = activity [ ] =M = activity coefficient

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{HOCl} 4 x 10-14 ---------- = -------------{Cl2} {H+} {Cl} {HOCl}/{Cl2} increases, as {H+} decreases Note: pH = - log {H+} Formation of Hypochlorite ion, OCl - Hypochlorous acid ionizes to (dissociates into) hypochlorite ion and hydrogen ions in the reversible reaction: HOCl H+ + OCl (3) (4)

{H+} {OCl} Ka = ----------------- = 2.7 x 10-8 = 107.5 {HOCl} 2.7 x 108 {OCl} ---------- = ----------------{HOCl} {H+} {OCl } / {HOCl} decreases, as {H+} increases,

- HOCl is approximately 80100 times as effective as OCl. - Chlorine exists predominantly as HOCl at pH 4 - 6.

Chloramines
- Chloramine can be formed by first adding a small quantity of ammonia to the water, then adding chlorine.

1. Reaction with ammonia

- Ammonium ion exists in equilibrium with ammonia and hydrogen ion

NH4+

NH3

+ H+

2. Chlorine reacts with ammonia in water to form chloramines NH3 NH2Cl NHCl2 + + + HOCl HOCl HOCl NH2Cl NHCl2
dichloramine

+ H2O + H2O + H2O

(3) (4) (5)

monochloramine

NCl3

trichloramine (nitrogen trichloride) 4

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3. Chlorine Residuals and Chlorine Demand a. Free available chlorine residual (FAR): HOCl, OCl- Residual chlorine existing in water as hypochlorous acid or hypochlorite ion. - Hypochlorous acid is primary disinfectant, hypochlorite ion is somewhat less effective. Thus the power of free chlorine residual decreases with increasing pH.

b. Combined available chlorine residual (CAR): NH2Cl, NHCl2, NCl3, organic N-Cl
- Residual existing in chemical combination with ammonia (chloramine) or organic nitrogen compounds. - Effectiveness of CAR is significantly less than that of FAR.

c. Total Available Chlorine Residual (TAR):

TAR = FAR + CAR

d. Chlorine demand - is the amount of chlorine that reacts with inorganics (Fe2+, Mn2+, NO2-, and NO3 -) and organic impurities. Chlorine Demand = (Chlorine added to water) - (TAR)
- This amount must be satisfied before free available chlorine is formed. - Difference between the amount of Cl2 added to a water and the quantity of free and combined available chlorine remaining at the end of a specified contact period.

Example (Sato): Chlorine added to water (chlorine dosage) is 7 mg/L, free chlorine residual is 0.1 mg/L, monochloramine is 0.3 mg/L, and dichloramine is 0.2 mg/L. 1) What is total available chlorine residual (TAR)? 2) What is the chlorine demand? Solution Total Available Chlorine Residual (TAR) = FAR + CAR = 0.1 mg/L + (0.3 + 0.2) mg/L = 0.6 mg/L Chlorine Demand = (Chlorine added to water) - (TAR) = 7 mg/L 0.6 mg/L = 6.4 mg/L

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Removal of microbes (or spores) in a treatment plant a) Log removal (LR) in a plant is given by Influent concentrations LR = log (----------------------------------) Effluent concentrations b) Percent (%) removal in a treatment plant is 100 % removal = 100 - ---------10LR Example 4-29 (4th DC 297) A city measured the concentration of aerobic spores in its raw and finished water as an indicator of plant performance. Spores are often plentiful in water supplies and are conservative indicators of how well a plant is able to remove Cryptosporidium. The city data are as follows:
(Spores/L) Raw Finished 200,000 16 145,000 4 170,000 2 150,000 8 170,000 10 180,000 2 180,000 3

Day of Week Sunday Monday Tuesday Wednesday Thursday Friday Saturday

(Solution) 1) Calculate weekly average: (Spores/L) Day of Week Raw Finished Sunday 200,000 16 Monday 145,000 4 Tuesday 170,000 2 Wednesday 150,000 8 Thursday 170,000 10 Friday 180,000 2 Saturday 180,000 3 AVERAGE 170,714 6.43
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170,714 Log Removal (LR) = log (--------------- ) = 4.42 6.43 100 % Removal = 100 - --------- = 99.996 104.42 Example (Sato): What is the equivalent percent reduction for a 3 log reduction of E. coli? (Solution) 100 % removal = 100 - -------10LR 100 % removal = 100 - -------- = 99.90 % 103 Example (Sato): What is the log reduction of E. coli that is equivalent to 99.90% reduction? (Solution) 100 % removal = 100 - --------- = 99.90 % 10LR Solve for LR, LR = 3 There is a 3 log inactivation of E. coli.

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Disinfection Kinetics (4th DC 295)

- Under ideal conditions, when an exposed microorganism contains a single site vulnerable to a single unit of disinfectant, the rate of die-off follows Chick's law.

Chicks law (Chick, 1908) - the number of organisms destroyed in a unit time is proportional to the number of organisms remaining (First-order reaction).

N N t

dN = kN dt

where N = the number of organisms k = rate constant, time-1 (1st order rate constant) Factors affecting the kill 1) Form of chlorine 2) pH 3) Concentration 4) Contact time 5) Type of organism 6) Temperature - Chlorine concentration and contact time relationship can be expressed by: Cn tp = constant where C = concentration of chlorine, mg/L n = constant for a given system (experimentally derived), dependent on type of disinfectant species being used, related to its power to kill. tp = time required for given percent kill, min. constant = constant for a given system (experimentally derived), which is specific for type of microorganisms being killed.
For example, Polio melitus would have a much higher constant value than E. coli.

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Water Disinfection (Chlorine Disinfection)

(3 DC 243; 4 DC 296)
- Microorganisms kill by disinfectants appears to follow the CT concept.
rd th

The CT concept - The product of disinfectant concentration (C) and contact time (T) yields a constant. - widely used in the Surface Water Treatment Rule (SWTR) as a criteria for cyst and virus disinfection. Empirical expression: CT = 0.9847 C0.1758 pH 2.7519 temp -0.1467 where C = disinfectant concentration (mg/L) T = contact time between the microorganism and the disinfectant (min) pH = - log {H+} temp = temperature, C
- The relationship in Eqn 114 means that the combination of concentration and time (CT) required to produce a 3-log reduction in Giardia cysts by free chlorine can be estimated if the free chlorine concentration, pH, and water temperature are known.

(114) (3rd DC 243; 4th DC 296)

Table 3-20 (3rd DC 244); Table 4-20 (4th DC 298) Table 3-20 (3rd DC 244) or Table 4-20 (4th DC 244) presents the required CT values (in mg/L min) for inactivation of Giardia cysts by free chlorine at 10 C.

- If the free chlorine concentration, pH, and water temperature are known, the combination of concentration and time (CT) required to produce a 3-log reduction in Giardia cysts by free chlorine can be estimated.

EPA used empirical data and a safety factor to develop the table. Therefore, the numbers in the table do not exactly match Eq. 114.
for a conventional coagulation plant, 0.5-log inactivation of Giardia is required for an untreated surface water, 3-log inactivation is required

Generally,

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Example : Determine the required residual chlorine concentration? Given: Water treatment for the disinfection of Giardia At Peak hourly flow rate, Q = 5.0 MGD, Contact ontact time = 50 min, pH = 7, temperature = 10 10 C. -------------------------------------------------------Approach C Use the CT (concentration time) concept: C Apply Surface Water Treatment Rule (SWTR): C For disinfection of Giardia, a) 3 log inactivation required (plant efficiency). b) 2.5 log inactivation is allowed for treatment prior to disinfection. C The chlorine dosage must not exceed 1.8 mg/L to minimize THM formation. Steps 1) Determine log inactivation required by disinfection nactivation 3 - 2.5 = 0.5 log inactivation 2) Determine contact time At a peak hourly flow rate = 5 MGD contact time T = 50 min

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3) Determine CT from Table 420 (4th DC 298) Noting that the chlorine dosage must not exceed 1.8 mg/L to minimize THM formation, CT = 20 (mg/L)(min) at pH = 7 4) Determine chlorine dosage C = CT / T = 20 (mg/L)(min) / (50 min) = 0.4 0.40 mg/L The residual chlorine concentration needed is 0.4 0.40 mg/L. Breakpoint chlorination Definition: - The application of chlorine to water to the point where free residual chlorine is available.
- Chlorination of a water to the extent that all the ammonia is converted to N2 (or a higher oxidation state).

Breakpoint chlorination is required - to obtain a free chlorine residual for better disinfection (if ammonia is present in a water supply) Breakpoint chlorination Curve (3rd DC247; 4th DC 302)
When chlorine is added to water containing reducing agents and ammonia, you yield a curve similar to Figure 11-13 11 (3rd DC, p.247), Fig. th 4-47 (4 DC 302), or Fig. 11.16 : VH, p. 400).

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Zone I, A-B: a. Chlorine reacts first with reducing agents present and develops no measurable residual. b. Reducing agents (those common to water and wastewater include nitrites, ferrous ions, hydrogen sulfide, cyanide, manganese ions) c. The chlorine dosage at B is the amount required to meet the demand exerted by the reducing agents. Zone II, B-C: a. The addition of chlorine in excess of that required up to point C results in the formation of chloramines. b. Chloramines established show an available chlorine residual and are effective as disinfectants. c. When all the ammonia has been reacted with, a free available chlorine residual begins to develop (point C on the curve). Zone III, C-D: a. As the free available chlorine residual increases, the previously produced chloramines are oxidized. b. This results in the creation of oxidized nitrogen compounds (e.g., nitrous oxide, nitrogen, nitrogen trichloride), which in turn reduce the chlorine residual. c. At D (Break Point) - Once most of the chloramines are oxidized, additional chlorine applied to the water creates an equal residual (as indicated by the rising curve at point D) Zone IV, D-E: a. Beyond the breakpoint, all added residual is free available chlorine. - some resistant chloramine can still be present beyond D, but their relative importance is small.

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Chemical Reactions of Chlorine in Natural Waters ================================================================= Rxn No. Reaction ------------------------------------------------------------------------------------------------------------------Zone I, A - B: 2Fe(HCO3)2 + Ca(HCO3 -)2 + Cl2 2Fe(OH)3 + CaCl2 + 6CO2 MnSO4 + 4NaOH + Cl2 MnO2 + 2Na2SO4 + 2NaCl + 2H2O H2S + Cl2 S + 2H+ + 2Cl Zone II, B - C: NH3 + HOCl NH2Cl + H2O Zone III, C - D: NH2Cl + HOCl NHCl2 + H2O NH2Cl + NHCl2 N2(g) + 3H+ + 3Cl NHCl2 + 2HOCl + H2O NO3 - + 5H + + 3Cl Zone IV, D - E: Cl 2(g) + H2O HOCl + H + + Cl HOCl + H2O OCl- + H3O+ hypochlorous acid hypochlorite N-trichloride ammonia formation dichloramine N removal nitrate formation monochloramine

NHCl2 + HOCl NCl3 + H2O NH2Cl + NH2Cl NH3 + NHCl2 -----------------------------------------------------------

Reference: Saunier, B.M. and Selleck, R.E. Kinetics of Breakpoint Chlorination in Continuous flow systems. Paper presented at 96th Annual Conference AWWA, New Orleans, LO (June, 1976).

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Chloraminated Potable Water Storage Tanks (Opflow, p.14-16, December 2008) Problem: Ammonia-Oxidizing Bacteria (AOB) Trouble arises when AOB converts free ammonia to nitrite and then to nitrate. When chloraminated water reaches 15C (59F), AOB start growing rapidly. AOB consume nearly all of the free ammonia in the tank, causing an acceleration of chloramines into chlorine and more free ammonia (by auto-decomposition). NH3 + 2 O2 NH3 + HOCl NO3- + H+ + H2O NH2Cl + H2O

As the AOB continue to consume free ammonia, most of the residual chloramine in the tank can be destroyed in just a few days.

Solution: 1) Fast response - Interrupting the rapid formation of nitrite and corresponding chloramine loss as soon as possible - Twice-weekly water testing when water temperature reach 15C or higher (on total chlorine, free chlorine, ammonia, nitrite, nitrate, pH, DO). 2) Boost the chlorine dosage
- e.g., to boost 1 Mgal of water by 0.5 mg/L of chlorine requires 3.3 gal of 12.5 % sodium hypochlorite

3) Adequate mixing throughout the tank

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Trihalomethanes (THMs) - Disinfection Byproducts (DBP) Common THMs: CHCl3 chloroform CHBr3 bromoform CHCl2Br bromodichloromethane CHClBr2 dibromochlormethane Formation and Control of Trihalomethanes Formation - THMs are formed by the reaction between chlorine and dissolved organics (humic substances) during the chlorination of surface waters.
- Chlorine reacts with humic substances commonly found in raw surface waters to forms trihalomethanes (principally, chloroform and bromodichloromethane).

Precursor

HOCl time*

THMs * reaction time (detention time)

Precursors Dissolved organics; e.g., humic acids, fulvic acids

- Decaying vegetation produces the humic substances, i.e., humic and fulvic acids, referred to as precursors.

Water Quality Standard (MCL) Total trihalomethanes (THMs), 0.1 mg/L (interim) (Source: Safe Drinking Water Act of 1996) 2. Control of THM Formation (Remedial Actions)
- Alternatives for reducing the production of THMs

1) Change the point of chlorine application - Moving the point of chlorine application to later stages in water treatment (the easiest method for reducing THM formation) - Not before coagulation process
- Breakpoint chlorination prior to chemical coagulation is no longer common practice (bacause of trihalomethane formation.)

2) Improve the removal of precursors prior to chlorination, by aeration, adsorption using activated carbon.
- If necessary, activated carbon can be applied during early treatment stages to adsorb humic substances, in addition, improved coagulation can be implemented to enhance the removal of organic substances.

3) Use an alternative disinfectant, e.g., UV, O3

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Wastewater Disinfection (Chlorine Disinfection)

Plot of

Nt No

vs.

(1+0.23 Ct t )

where No = number of coliform organisms at time t = o N t = number of coliform organisms at time t C t = total (amperometric) chlorine residual at time t, mg/L t = residence time, min

( log10 slope =
Therefore,

-6

- log1

( log100 - log1)

) = 6 0 = 3
20

log

Nt = ( 3) log(1 + 0.23 Ct t ) No

Nt = (1 + 0.23 Ct t ) 3 No

- The reductions of coliform organisms in a chlorinated primary treated effluent can be expressed by the relationship:
Nt = (1 + 0.23 Ct t ) 3 No

where No = number of coliform organisms at time t = o N t = number of coliform organisms at time t C t = total (amperometric) chlorine residual at time t, mg/L t = residence time, min

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Example: What is the required total chlorine residual (mg/L)? Given: No = 10,000 org/100 mL N t = 200 org/100 mL t = 15 min (Solution)

Nt = (1 + 0.23 Ct t ) 3 No
solve for Ct
1/ 3 Nt 200 1 1 No 10,000 Ct = = = 0.78 mg / L 0.23 t 0.23 (15) 1/ 3

Pocatello WWTP Chlorine contact basin --------------------------------------------------------------------------Chlorine dose 8 mg/L Chlorine demand 5 mg/L At the end of the chlorine contact basin 1 mg/L Discharge to the Portneuf River after dechlorination using SO2 <0.1 mg/L ---------------------------------------------------------------------------

Chlorine contact basin in Pocatello WWTP (2011)

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Calculating Chlorine Dosage 1. The chlorine dosage at a water treatment plant is 2.0 mg/L. The flow rate at the plant is 700,000 gpd. How many pounds per day of chlorine are required to disinfect the plants water supply? Conversion formula is: (mg/L)(MGD)(8.34) = lb/d (2.0 mg/L)(0.7 MGD)(8.34) = 11.68 lb/d Thus, 11.68 lb/d of chlorine required. 2. Disinfection at a treatment plant requires 280 lb/d of chlorine. If calcium hypochlorite (65 percent available chlorine) is used, how many pounds per day of calcium hypochlorite will be required? (0.65)(X lb/d) = 280 lb/d 280 lb/d X lb/d = ------------- = 430.77 lb/d 0.65 Thus, 430.77 lb/d of calcium hypochlorite required. 3. A water supply requires 30 lb/d of chlorine for disinfection. If sodium hypochlorite with 10 percent available chlorine is used, how many pounds per day of sodium hypochlorite are required? (0.1)(X lb/d) = 30 lb/d 30 lb/d X lb/d = ------------- = 300 lb/d 0.1 Thus, 300 lb/d of sodium hypochlorite is required.

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Dechlorination a. Dechlorination is required to detoxify a discharge after chlorination. b. Usually accomplished by adding sulfur dioxide, SO2 in aqueous solution
- added at the discharge end of the chlorination chamber. - the oxidation-reduction reaction between the monochloramine residual and sulfur dioxide is very rapid.

For free chlorine residual SO 2(g) + H2O HSO3 - + H+

HOCl + HSO3Cl- + SO4 2- + 2H + -----------------------------------------------------------------------SO2 + HOCl + H2O Cl- + SO42- + 3H+

For monochloramine SO2(g + H2O HSO3 - + H +

NH2Cl + HSO3 - + H2O Cl- + SO4 2- + NH4 + + H + ----------------------------------------------------------------------------------NH2Cl + SO2(g) + 2H2O NH4 + + SO42- + Cl- + 2H+

- Any excess sulfur dioxide applied reduces dissolved oxygen as: 2SO2 + O2 + 2H2O
c. Other dechlorination compounds: C sulfite, sodium metabisulfite

2SO4 2- + 4 H+

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Ultraviolet Radiation (4th DC 303)

Source: http://www.wedeco.com/us/index.php?id=91294

Source: http://www.wedeco.com/us/index.php?id=91294

Table 4-22 (4th DC 304): Spectral ranges of interest in photochemistry

Range name Near infrared Visible Ultraviolet UVA UVB UVC Vacuum ultraviolet (VUV)

Wavelength range (nm) 700 - 1,000 400 - 700 315 - 400 280 - 315 200 - 280 100 - 200

UVA: causes changes to the skin that lead to tanning UVB: can cause skin burning and is prone to induce skin cancer UVC: is extremely dangerous since it is absorbed by proteins and can lead to cell mutations or cell death

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Note: Ozone absorbs UV radiation in the 220-330 nm region. UV light is most strongly absorbed by DNA at 253.7 nm (primarily between 200 nm and 300 nm). Low-pressure Hg arcs at 253.7 nm, disinfection UV has been found to be very effective for the disinfection of Cryptosporidium, Giardia, and viruses. U.S. EPA has established UV dose requirements See Table 4-23 (4th DC 305) shows the U.S. EPA requirements.

UV dose - The inactivation of microorganisms by UV is directly related to UV dose. The average UV dose is calculated by: D=It where D = UV dose I = average intensity, mW/cm2 t = average exposure time, s

Satos experimental unit

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Survival Fraction (similar to Log removal, LR) The survival fraction is calculated by: Survival fraction = log (N / No) where N = organism concentration after inactivation No = organism concentration before inactivation The major factor affecting the performance of UV disinfection systems is influent water quality: 1) Particles, turbidity, and suspended solids
- can shield pathogens from UV light or scatter UV light to prevent it from reaching the target microorganisms, thus reducing its effectiveness as a disinfectant.

2) Organic and inorganic compounds

Some organic compounds and inorganic compounds (such as iron and permanganate) can reduce UV transmittance by absorbing UV energy, requiring higher levels of UV to achieve the same dose.

Thus, it is recommended that UV systems be installed downstream of the filters.

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UV application to Combined Sewer Overflow (CSOs)

Source: Muller et al. Water Environment & Technology, p. 36-39 (2011)

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Ozone (Journal AWWA, Vol. 100, No. 11, p.100-111 (2008). Ozone (O3) - is a highly reactive (unstable, strong oxidant), odorous, colorless gas. - must be generated onsite via air or oxygen electrolytic processes. - is used as a disinfectant to kill bacteria, viruses, and protozoa (including Giardia and Cryptosporidium) . - is also used to control manganese, iron, and naturally occurring taste-and-order substances. Ozonation: does not form THMs (or HAASs, Haloacetic acids) can form bromate if source waters contain bromide. o Bromate is regulated at 10 ug/L (due to cancer risk) o http://www.epa.gov/enviro/html/icr/gloss_dbp.html http://water.epa.gov/drink/contaminants/basicinformation/disinfectionbyproducts.cfm Ozone reacts with natural organics in source waters, converting natural organics to smaller assimilable organic carbon (AOC) molecules that can be bacterial nutrients. Thus the systems using ozone often include biologically active filters (BAFs) or other biologically active processes to reduce AOC levels prior to entering the distribution system in order to prevent biological re-growth in the distribution system.

Example of O3 treatment - Murano Water Treatment Plant, Osaka, Japan - Chlorine is added after ozonation

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