Disinfection

Disinfection
Definition:
the selective destruction of disease causing organisms

History:
1881: Koch demonstrated that chlorine could kill bacteria
in lab
1905: London England first chlorination of a public water
supply following typhoid fever outbreak
1912: Large scale chlorination facilities installed at
Niagara Falls, N.Y.

Disinfection
Chlorine
Historically, dominant methods of disinfection
Chloramines
Strictly a secondary disinfectant for drinking water
Ozone
Used widely in France, Germany
Some popularity in USA, Canada
Chlorine Dioxide
Used to some extent in Europe, rare in USA and Canada
Ultraviolet Light (UV)
Has become very popular in last 15 years

Disinfection
Disinfection Terminology
(in drinking water treatment)
Primary Disinfection
Disinfectant applied in a water treatment plant to control
microorganismsmakes the water safe to drink
Secondary Disinfection
Disinfectant applied to water leaving the treatment plant to
protect against intrusion in the distribution system,
suppress biofilm on pipes
Inactivation
Rendering a pathogen harmless (not necessarily killing it)




Disinfection
Disinfection Characteristics

Toxic to microorganisms
Soluble in water and cell tissues
Stable can be stored prior to use
Non-toxic to higher forms of life (at dose and residual
used
Effective over the range of temperature and pH
Should be able to penetrate surfaces (e.g. biofilm)
Should be available in large amounts, reasonable $$
Safe to handle
Leave a measurable residual

Disinfection
An ideal substance does not exist, but some that are used
include:

Conventional:
Chlorine
Chloramines
Chlorine Dioxide
Ozone
UV

Alternatives:
Bromine (swimming pools)
Mixed oxidants (MIOX)
Iodine (small applications)
Disinfection
Microorganism Characteristics
Pathogens may be divided into four common groups:
1. bacterial spores
2. protozoan spores
resistance to disinfection is f(cell wall properties)
3. viruses
4. vegetative bacteria
easy to kill
respiration takes place at cell surface


Decreasing
order
according
to chemical
disinfection
resistance
(not UV!)
Disinfection
Chemical Disinfection
Disinfection with Chlorine (Chlorination):
Disinfectant capabilities depend on its chemical form in
water
f (temperature, pH, organic content of water)
Gaseous chlorine (Cl
2
) when added to water rapidly
hydrolyzes to hypochlorous acid (HOCl)

-
2 2
Cl H HOCl O H Cl + + +
+
Disinfection
Reaction proceeds essentially to completion @ pH> 4
Hypochlorous acid subjected to additional reactions:
disinfection, reaction with organics, dissociation to
hypochlorite ions (OCl
-
), etc.




Between pH 6 and 9, HOCl decreases, OCl
-
increases
Dissociation of HOCl also temperature dependant

Hypochlorous
acid
Hypochlorite
ion
+
+ H OCl HOCl
-
20
o
C
0
o
C
Disinfection
Chemical Disinfection


HOCl much more effective than OCl
-
at killing
microorganisms
Maintain pH at 6 to 7 for optimum disinfection with Cl
2
Chlorine usually added as:
Chlorine gas
Sodium hypochlorite (NaOCl) (liquid)
more expensive
better safety
poorer stability (loss of approximately 1% per month)
used in smaller plants
5% to 15% available Cl
2
Chlorine Free ] [OCl [HOCl]
-
= +
Disinfection

Disinfection

Disinfection

Disinfection
Chloramines
When chlorine (Cl
2
) is added to water and ammonia
(NH
4
+
) is present, react to form chloramines
Chloramines
also referred to as combined chlorine
poor disinfectants

HOCl + NH
3
H
2
O + NH
2
Cl (monochloramine)
HOCl + NH
2
Cl H
2
O + NHCl
2
(dichloramine)
HOCl + NHCl
2
H
2
O + NCl
3
(trichloramine or
nitrogen trichloride)


chloramines
Disinfection
Chloramine formation
Species is a f(ammonia, pH, temperature)

pH 4.5-8.5 monochloramines + dichloramines
pH > 8.5 monochloramine alone
pH < 4.5 trichloramine

Disinfection
Note
Free chlorine = residual chlorine existing in water as
HOCl and OCl
-
Combined chlorine = residual existing in combination with
ammonia. i.e. chloramines)
Total chlorine = free + combined chlorine
Chlorine demand = the difference between amount
added to a water and the amount remaining after a
period of time


Disinfection
Breakpoint Chlorination

In many natural waters, a graph of total residual chlorine
vs. applied chlorine looks like this:









This is referred to as the chlorine breakpoint curve
22
Chlorine Residual Curve for Breakpoint Chlorination
Rxns with easily oxidizable substances
A B
Formation of Chloramines
C
D
E
Destruction of Chloramines
Formation of Free residual
Breakpoint
Free
Residual
Combined Residual
1
1
Disinfection
Breakpoint Chlorination




4 phenomena occurring as you increase Cl
2
dose:

1. A-B
Chlorine reacts with immediately with oxidizable substances
such as Fe
2+
(ferrous ion), H
2
S (hydrogen sulfide), nitrite,
organic compounds
as a result, chlorine is converted to chloride which has no
disinfecting power
there is little or no measured residual total chlorine despite
the applied chlorine dose.
23
Chlorine Residual Curve for Breakpoint Chlorination
Rxns with easily oxidizable substances
A B
Formation of Chloramines
C
D
E
Destruction of Chloramines
Formation of Free residual
Breakpoint
Free
Residual
Combined Residual
1
1
Disinfection
4 Steps (Contd):

2. B-C
Formation of mono- and dichloramines (assuming ammonia is
present!)
Every molecule of free chlorine you add reacts with
ammonia to form a molecule of combined chlorine
Chloramine species formed is a f (pH, N:Cl
2
ratio)
> pH 8.5 mono
pH 4.5-8.5 mono and di
Also some formation of chloro-organic compounds (e.g.
THMs) (usually < 1% at this point. The reaction with ammonia
is much faster, and is preferred.)

23
Chlorine Residual Curve for Breakpoint Chlorination
Rxns with easily oxidizable substances
A B
Formation of Chloramines
C
D
E
Destruction of Chloramines
Formation of Free residual
Breakpoint
Free
Residual
Combined Residual
1
1
Disinfection
4 Steps (Contd):

3. C-D
Once all the ammonia has been used up in forming
chloramines, additional free chlorine oxidizes and destroys
the chloramines (products = nitrogen, nitrate, chloride, and
other products)
reduces the total chlorine residual

Cl
2
+ chloramines Cl
-
, N
2
, others

23
Chlorine Residual Curve for Breakpoint Chlorination
Rxns with easily oxidizable substances
A B
Formation of Chloramines
C
D
E
Destruction of Chloramines
Formation of Free residual
Breakpoint
Free
Residual
Combined Residual
1
1
Disinfection
4 Steps (Contd):

4. D-E
Once most of the chloramines are oxidized (Point D),
additional chlorine added creates an equal free chlorine
residual
free chlorine residual = [HOCl] + [OCl
-
]
D known as breakpoint
some chloramines may also be present at low
concentration
The presence of free chlorine provides
Effective disinfection
Some chloro-organic by-product formation
23
Chlorine Residual Curve for Breakpoint Chlorination
Rxns with easily oxidizable substances
A B
Formation of Chloramines
C
D
E
Destruction of Chloramines
Formation of Free residual
Breakpoint
Free
Residual
Combined Residual
1
1
Disinfection
Chlorine Dioxide (ClO
2
)

Historically had limited application as a disinfectant in
North America
Applied for taste and odour (T&O) control (historically)
However, in certain circumstances (especially for
Giardia control) excellent choice as disinfectant
Effective in destroying phenols
Does not form THMs in significant amounts
Pulp & paper industry: largely replaced chlorine for
bleaching of paper products in North America
Less environmental impact than Cl
2


Disinfection
Chlorine Dioxide (ClO
2
) Generation

1 method: mix sodium chlorite and chlorine in controlled
proportions to form ClO
2




yields 85% - 90% ClO
2
(typical)
want to minimize unreacted chlorine and chlorite
resulting solution concentration of ClO
2
500-2,000
mg/L
slowly add to water to dose at 0.5-1.0 mg/L (typical)

NaCl 2 2ClO Cl 2NaClO
2 2 2
+ +
sodium
chlorite
chlorine
dioxide
sodium
chloride
Disinfection
Advantages and Disadvantages

Advantages
does not react with ammonia
much stronger disinfectant than chlorine no strong
disinfection efficiency dependence on pH
strong chemical oxidant taste and odour control, colour
does not form THMs (unless excess chlorine present)

Disinfection
Advantages and Disadvantages

Disadvantages
must be generated on site (unstable)
generation system must be well controlled to minimize
excess free chlorine
produces byproducts
chlorite (ClO
2
-
), chlorate (ClO
3
-
)
may cause health problems
U.S. limits: ClO
2
-
- 0.8 mg/L; ClO
3
-
- 1.0 mg/L
Ontario limit: ClO
2
-
- 0.8 mg/L
costs more than Cl
2


Disinfection
Ozone

Unstable gas, must be generated onsite, used
immediately
Strong oxidizing gas (strongest common oxidizing agent
in water treatment)
reacts with many organic, inorganic molecules
More reactive than chlorine, however ozone does not
leave a residual
must add an additional chemical for secondary disinfection
Reactions rapidly inactivate organisms
Can use it for simultaneous disinfection and oxidation
(flocculation aid, taste and odour control, colour removal,
etc.)

Disinfection
Chemistry of Ozone

Air or oxygen flows between 2 electrodes and electrical
spark produces ozone (O
3
)
1 to 3.5% by weight if ambient air is used
2 to 8% by weight if oxygen is used

Disinfection

Disinfection

Disinfection

Disinfection

Disinfection

Disinfection
Ozone is capable of reacting by 2 mechanisms:
Direct reaction of ozone molecule (O
3
) (pH 6-8)
As hydroxyl free radical (OH

)
at pH 9+, ozone added to water rapidly decomposes to form
the OH

radical
OH

much more powerful than ozone itself, but scavenged
by carbonate and bicarbonate ions & natural organic matter
Half life of O
3
approximately minutes 1 hour
Half life of (OH

) approximately microseconds

Disinfection
Method of Application

Apply ozone gas to water in ozone contactor
Use porous diffusers to make small bubbles (maximize
contact)

40
Disinfection
Method of Application

Old Rule of thumb application:
Try to maintain 0.4 mg/L O
3
(C) contact for 4 minutes (T)
CT = 1.6 mg/L
.
min
We now dose ozone according to CT requirements
(discussed later)
Must destroy any unused offgas since its toxic

Disinfection
Advantages and Disadvantages

Advantages
strongest common chemical disinfectant and strongest
oxidant
does not form halogenated byproducts (unless bromide
ion is present bromate formation)


can oxidize many inorganic and organic molecules
taste and odour, colour
can enhance oxidation by increasing pH to form hydroxyl
free radicals

-
3
-
3
BrO Br O +
Disinfection
Advantages (contd)
Organic by-products produced by ozone are easily
biologically degradable

incorporate biological filtration following ozonation to allow
mineralization of assimilable organic carbon (AOC)

instead of allowing this material to be discharged into
distribution system (= regrowth)
O
3
+ biological filtration becoming common in Quebec
excellent combination of disinfection, organics destruction
Ozone known to inactivate Cryptosporidium cysts
UV is usually more cost-effective for this
GAC
to CO
2
and H
2
O
Disinfection
Advantages and Disadvantages

Disadvantages
most complex disinfection technology
cannot be employed as secondary disinfectant due to very
short half-life (no residual)
cannot be purchased in bulk and stored until use
generation equipment is capital cost expensive
secondary disinfectant should be withheld until after
biological filtration to allow AOC to be converted to CO
2

and water

Disinfection
Disinfection (Chlorination) By-Products (DBPs)
Chlorine + organic matter DBPs
DBPs are mostly organochlorine (organohalide)
compounds
Organic precursors
e.g. humic or fulvic acids from soil, decaying vegetation,
algae
Trihalomethanes (THMs)
chloroform, bromodichloromethane,
dibromochloromethane, bromoform
Disinfection
Haloacetic Acids (HAAs)
Five common HAAs:
Monochloroacetic Acid
Dichloroacetic Acid
Trichloroacetic Acid
Monobromoacetic Acid
Dibromoacetic Acid
THMs and HAAs some used to be suspected
carcinogens. Current evidence suggests not, but
regulations remain.
Reducing THMs/HAAs likely lowers other DBPs that are
suspected carcinogens

Disinfection
DBPs regulated in Ontario:
THMs: 100 g/L (soon to be 80 g/L?)
Bromate (BrO
3
-
): 10 g/L
Chlorite (ClO
2
-
): 1.0 mg/L
HAAs: none, but soon to be 60 g/L?
United States:
THMs, bromate, HAAs, chlorite, chlorate
World Health Organization (WHO):
Also includes cyanogen halides, aldehydes, several others

Disinfection
Formation of DBPs is function of:
Type of disinfectant
Cl
2
= THMs, HAAs, other organochlorine compounds
O
3
= bromate, AOC
ClO
2
= chlorite, chlorate
NH
2
Cl = no THMs, HAAs, so satisfies regulations
recent research shows formation of nitrosamines,
nitromethanes, which may be more toxic than THMs/HAAs
Precursor type and concentration
humic acid fraction, fulvic acid, algae, etc.
Disinfectant dose
pH
Contact time
Temperature

Disinfection
Control of DBPs (Trihalomethanes)
Chlorine reacts with natural organic matter (NOM) to form
THMs (NOM measured as total organic carbon TOC)
Alternatives to reduce formation of THMs:
Improve removal of precursors prior to chlorination (or
change location of chlorine addition)
Use alternative disinfectant
Remove DBPs after formation

Only if no other alternative
available.
- can use activated
carbon
- aeration in reservoirs
for volatile THMs
(dubious health benefit)
Disinfection
Improve Removal of Precursors Prior to
Chlorination
Optimize chemical coagulation
possible to reduce THM Formation Potential (THMFP) by
20-70% (typically 30-50%)
Examples:
optimize alum dose for TOC removal, not turbidity (may
require increased dose) = enhanced coagulation
Maybe change to optimum coagulant for TOC removal
e.g. alum ferric chloride
add powdered activated carbon (PAC) to adsorb
precursors (remove PAC in subsequent coag/flocc/filtration)


Disinfection
Examples (contd):
change location of Cl
2
addition until after sedimentation
and filtration
if possible (e.g. zebra mussel control)
But MUST ensure sufficient CT

Disinfection
Use Alternative Disinfectant to Reduce DBPs
Must identify advantages/disadvantages for alternative
disinfectants
Factors to consider:
Potential to form different DBPs (e.g. ClO
2
-
, ClO
3
-
)
Disinfection effectiveness
Cost
Operational issues (more complexity, etc.)
Disinfection
Alternatives to chlorine include:
Chlorine dioxide (forms chlorite, chlorate)
Ozone (may form bromate, AOC)
Chloramines (only for secondary disinfection)
UV (doesnt form THMs/HAAs)

Disinfection
Drinking Water Disinfection Rules
General Concepts:
Disinfection requirements are based on sufficiently
inactivating some target pathogen
target should be most resistant pathogen likely to be in
water
Targets
Cryptosporidium parvum oocysts
Giardia lamblia cysts
viruses (typically hepatitis A and rotavirus)

Cryptosporidium Giardia
Disinfection
General Concepts (contd):
Monitoring for such target pathogens is impractical (too
expensive, time-consuming)
Instead, monitor disinfectant concentration and contact
time to ensure pathogen control based on inactivation
kinetics

Disinfection
General Concepts (contd):
Its impossible to inactivate all organisms
Chick-Watson Inactivation Kinetics:


N = number of surviving organisms
C = disinfectant concentrations
T = time
k = inactivation kinetic constant

kCT
N
o
N
= log
Disinfection



Lets talk in terms of log inactivation
1-log means 10% are surviving (90% inactivation)
2-log means 1% are surviving (99% inactivation)
3-log means 0.1% are surviving (99.9% inactivation)
etc.

Therefore Log inactivation = -kCT
Log inactivation directly proportional to CT

kCT
N
o
N
= log
Disinfection



The value of k is a function of the organism, so use the
k for the target organisms

Regulations specify the CT that is required for a minimum
log inactivation needed, based on surveys of ambient
concentrations of pathogens

kCT
N
o
N
= log
Disinfection
General Concepts (contd):
Common Requirements:
2-log Cryptosporidium reduction
3-log Giardia reduction
4-log virus reduction
Note: reduction = removal + inactivation, where removal is
physical removal via sedimentation/filtration, and
inactivation is disinfection
*Read the Ontario Procedure for Disinfection

Tables of CT needed to achieve the above under
different conditions (pH, temperature) are given.
Engineers design for adequate CT (i.e. dose and contact
time)

Disinfection
Ontario Drinking Water Requirements Surface Waters

Requires surface water treatment facilities to achieve:
99% (2-log) removal/inactivation of Cryptosporidium
99.9% (3-log) removal/inactivation of Giardia lamblia
99.99% (4-log) removal/inactivation of viruses

Assume well operated plants that practice
coagulation/flocculation/filtration achieve:
2.5-log removal of Giardia
2.0-log removal of viruses
2.0 log removal of Cryptosporidium
Disinfection
Disinfection must therefore supply:
0.5-log inactivation of Giardia (= 3.0-2.5 log)
2.0-log inactivation of viruses (= 4.0-2.0 log)

Impractical and costly for water treatment plants to
monitor for Giardia and viruses
Use tables of CT values corresponding to inactivation

See example following next slide.

CT values (mg/L

min) for 90% (1 log) Inactivation of
Giardia


Water Temp
pH
Free Cl
2

0.5 C 5 C 10 C 15 C
6
7
8
9
49
70
101
146
35
50
72
104
26
37
54
78
19
28
36
59
Chloramines 1300 730 620 500
Chlorine Dioxide
21 8.4 7.4 6.3
Ozone
0.97 0.63 0.48 0.32
6-9
6-9
6-9
Example:
0.5 mg/L free chlorine
10
o
C, pH 7.5
How much contact time is needed to meet Ontario
disinfection requirements in a conventional plant
(i.e. coag/flocc/sed/filtration) treating surface water?
Answer: need 3-log Giardia and 4-log virus reduction.
Physical removal gets 2.5/2-log removal credit for Giardia
and viruses, respectively. Need remaining 0.5-log/2-log
Giardia/virus inactivation by chlorine.


CT for 0.5-log Giardia inactivation
(0.5 mg/L Cl
2
, pH 7.5, 10
o
C)
CT for 2-log virus inactivation
(any Cl
2
, pH 7.5, 10
o
C)
22 mgmin/L 3 mgmin/L
CT for 0.5-log Giardia inactivation
(0.5 mg/L Cl
2
, pH 7.5, 10
o
C)
CT for 2-log virus inactivation
(any Cl
2
, pH 7.5, 10
o
C)
22 mgmin/L 3 mgmin/L
The Giardia requirement controls (for Cl
2
, it always does!)
Given: 0.5 mg/L Cl
2

Need: CT = 22 mg/L
Therefore contact time = 22/0.5 = 44 minutes
COMPLICATION #1: Chlorine decays. We almost always
use the effluent concentration from the process as C.
But, if you know the decay rate, you are allowed to
integrate (see following)
Disinfection
C
h
l
o
r
i
n
e

C
o
n
c
.

Time in the tank
Area under the decay curve is CT
C
effluent

Hydraulic
retention time
You get more CT if you consider decay
in your CT calculation
COMPLICATION #2: Not every element of water spends
44 minutes in the tank (there is a residence time
distribution).
Solution: use the t
10
(time representing the 10
th
percentile
fastest water through the process. i.e. 90% of the water
spends more than this time)
t
10
obtained from tracer tests, computational fluid dynamics,
or conservative baffle factors (below).
Superior baffling (t
10
maybe 70% hydraulic residence time)
Poor baffling (t
10
maybe 10% hydraulic residence time)
So in previous question, if required t = 44 minutes, and
Q = 10 MLD (6.94 m
3
/min)
Baseline volume required =6.94

3

44 = 305
3

Assuming baffle factor of 0.7:
Actual tank volume needed = 305 m
3
0.7 = 436 m
3


COMPLICATION #3: For chlorine (only), CT requirements
are a function of C (see example 11.10).
Disinfection






Use CT tables to select an appropriate CT value
Disinfection

assume
2.0
mg/L
initially
Disinfection





At pH =7, Temperature = 5
o
C, assuming C = 2.0 mg/L:
CT for 0.5 log inactivation = 28 mg/Lmin

Disinfection
Determine t
10
for the peak hourly flowrate

Disinfection

90
Disinfection
Determine t
10
for the peak hourly flowrate
From Fig. 1.17(b) t
10
= 90 min @ 3.0 MGD



But we assumed C = 2.0 mg/L, so iterate using C = 0.31 as
the new guess.

mg/L 0.31
min 90
min mg/L 28
C =

=
Disinfection

assume
0.31
as new
guess
Disinfection
t
10
= 90 min (this doesnt change!)



The new answer (0.25) is close to the previous iterated
answer (0.31), so we have converged on our solution.
We need 0.25 mg/L of chlorine after 90 minutes to disinfect
the water.
(We then need to figure out what chlorine dose will provide
0.25 mg/L after 90 minutes!) How?

mg/L 0.25
min 90
min mg/L 23
C =

=
Disinfection
Groundwater Disinfection for Drinking Water
Primary pathogens of concern are fecal viruses
larger pathogens (e.g. Giardia cysts) removed by natural
filtration
In Ontario, there are 2 classes of groundwaters:
protected groundwaters
groundwaters under the direct influence of surface waters
(GUDI)
GUDI waters are identified using a long list of criteria
Proximity to surface sources
Evidence of contamination (coliform, turbidity, etc.)
Others (see Disinfection Procedure in supplemental notes)

Disinfection
GUDI waters are treated as surface waters
require 2-log Crypto, 3-log Giardia and 4-log virus
control
CT concept may be applied to groundwaters
for pure groundwaters, must disinfect for 2-log virus
inactivation
for GUDI, need same total reductions as for surface
waters (2/3/4-log Crypto/Giardia/viruses)

End of Disinfection