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Cooling Water
Microbial Control
Webinar
Why Biofouling Control is Important

Oxidizing Biocides

Non-Oxidizing Biocides

Biodispersants

Monitoring Microbiological Control

Programs
 How Does Biofilm
Affect your Operation?
l Energy Losses – Biofilm (slime) is highly insulating
l Same order of magnitude as most scales

l Corrosion - Premature Equipment Replacement

l Unscheduled Maintenance or Downtime

l Reduced Cooling at Heat Exchangers

l Quality Control Problems in Process Streams

l Health and Safety Related Issues

Biofouling Increases Risk of Microbiologically
Induced Corrosion (MIC)
• Accelerated localized corrosion (pitting) caused either directly
or indirectly by microbial metabolic processes.

• Almost always associated with deposits.

– Sulfate reducing bacteria (SRBs)
– Acid producing bacteria
– Microbiologically catalyzed metal
precipitating bacteria.
– Slime-forming bacteria
Cooling Tower Biofilm Control Challenges

l Operational pH that favors growth

l Nutrient and organism contamination is constant

l Water reuse (greywater) has become more common

l Biocide handling is a safety concern

l Environmental impact of using Biocides

Diversity – Many kinds of Organisms
• Aerobic • Nitrogen transformation
• Anaerobic • Sulfur transformation
• Facultative anaerobic • Iron depositing
• Acid producing • Mold and Fungus
• Legionella • Cyst and Spore forming -
thick cell walls
Many types can be found in an industrial cooling system:

• including Legionella, which can be inhaled and grows

best at human body temperature
• Including Pseudomonas, the most common slime former
which can Denitrify in closed loops consuming NO2,
producing N2 that gases off.
• Including Anaerobes which produce corrosion and black iron
deposits, such as desulfovibrio (SRB)
• Highly diverse microbial populations (especially with higher
life forms) are typically indicative of a system under poor
control
Protozoa are Strong Indicators of
Poor Microbial Control

Protozoa consume
bacteria. Protozoa
Protozoa
contamination is
indicative that
biofilms are present
in the system.

Bacteria Bacteria
Oxidizing Biocides: Halogens
• Chlorine Gas
• Sodium Hypochlorite (Bleach)
• Activated Bromide (Bleach + NaBr
presursor)
• Stabilized Bromine
• Bleach/Bromide plus Stabilizer
• BCDMH (solid stabilized chlorine and
free bromine)
• Solid Chlorine + NaBr
Products that consist of an active (oxidized) species (Cl, Br);
indiscriminately destroy microorganism essential cell
components.
Halogens: Chlorine Gas, Bleach & Bromine

y Chlorine gas
Cl2 + H2O → HOCl + HCl

y Chlorine bleach
NaOCl + H20 → HOCl + NaOH

y Activated bromide
HOCl + NaBr- → HOBr + NaCl
Halogen Chemistry

Dissociation

HOCl H+ + OCl -

HOBr H+ + OBr -

Formation of Haloamines

HOCl + NH3 H2NCl + H2O

HOBr + NH3 H2NBr + H2O

pH Effect on Oxidizing Biocides

Bromine provide much better kill at pH > 8

Activated Bromine
Activated bromine 1:1 Molar Ratio Bleach: Bromide
100% Conversion

NaOCl + H2O HOCl + Na+ + OH-

74.5 lb/lbmol
Bleach @ 12.5% NaOCl
596 lbs. Of Bleach
Bleach @ 10.01 lb/gal
59 gallons

HOCl + NaBr HOBr + Na+ + Cl-

102.9 lb/lbmol
Nalco 1318 @ 43% NaBr
239 lbs.Nalco 1318
Nalco 1318 @ 12.25 lb/gal
19.5 gallons

Volume : Volume ratio

59 gallons Bleach / 19.5 gallons Nalco 1318

3:1 Bleach : Nalco 1318

Activated Bromine - Conversion to HOBr
• 100% Conversion - 1:1 Molar – Highest Ratio
• 3:1 :: Bleach:1318 by Volume
• Fastest kill - Kills at Lower free residual than chlorine
• HOBr less volatile than HOCl (up to 8.0pH)
• More Aggressive to phosphonates
• Higher cost
• Reacts faster (depletes HOBr) when organics High
• typical concern at > 400 ppm COD

• 50% Conversion - 2:1 Molar

• 6:1 :: Bleach:1318 by Volume
• Lower Cost

• 25% Conversion - 4:1 Molar – Typical Starting Ratio

• 12:1 :: Bleach:1318 by Volume
• More Economical
• More HOCl present to consume organics, as
HOBr depletes (faster)
• Above 8.0 pH less important
• Slower Acting
Oxidizing Biocides: Chlorine

• 7341 (12.5% NaOCl) (not for potable)

• 7360 (12.5% NaOCl) (NSF60 - New)

• YECL - XY-12 (8.4% NaOCl) (mainly F&B)

• YECL7000 (3” Tablet)

Bleach, Calcium Hypochlorite, or Cl2 Gas - Hypochlorous Acid

• Advantages: • Disadvantages:
~ Effective for bacteria, fungi ~ Reduced effectiveness alone at
and algae > 7.5 pH, higher feed required
~ Fast acting ~ Reacts with amines, sulfide
~ Breaks down rapidly ~ Volatile
(environmental) ~ Chloride accelerates corrosion
~ Useful in short and long HTI ~ Contribution to AOX and THM
cooling systems
~ Usually a commodity
~ Inexpensive
~ Bleach Storage is unstable
~ 3D TRASAR compatible

Oxidizes cell components

and quickly stops
metabolism
Activated Bromine – Hypobromous Acid
• Advantages:
~ Effective for bacteria, fungi and
algae
~ Effective over 7.5 pH
~ Fast acting
~ E.g. Once –Through systems
~ Breaks down rapidly
~ Less volatile below 8.0 pH
~ Useful in short and long HTI
cooling systems
~ Inexpensive (Chlorine :
Bromine ratio can be adjusted)
~ 3D TRASAR compatible
• Disadvantages:
~ Requires a chlorine source to
activate
~ Reacts with amines, sulfides
~ Bromide accelerates corrosion
~ Contribution to AOX and THM
~ But bromamines biocidal
~ Bromine more aggressive on
phosphonates especially HEDP
than Chlorine
~ NaBr nearly a commodity
~ Depends on geography
~ Bleach Storage unstable
Oxidizes cell components
and quickly stops
metabolism
Oxidizing Biocides: Bromine & Stabilized Bromine

• ACTI-BROM® 1318 (NaBr)

ACTI-BROM® 1338 (NaBr plus surfactant)
(non-stabilized)

• STA·BR·EX® ST-70 (stabilized bromine)

• ControlBrom® CB-70 (NaBr + stabilizer)

• 7346 TAB (tablet)

(BCDMH, stabilized chlorine / bromine)

• Towerbrom® 960 and 961 (solid chlorine +

NaBr)
Liquid Stabilized Bromine - STA•BR•EX ST70
y Blend of monobromo and dibromo Sulfamate

Br2NSO3- Na+ + H20 HOBr + HBrNSO3- Na+

HBrNSO3- Na+ + H20 HOBr + H2NSO3- Na+

y Hypobromous acid and sulfamate residual are ultimately produced

y Shown to Penetration Biofilm
y Bromine – Improved Effectivenes compared to chlorine, over 7.5 pH
y Moderate Halogen Demand Systems
y Moderate HTI
y Low to Moderate free residual required
y Control to FRO3 (three minute FRO)
STA•BR•EX ST70 Risk of Overstabilization

§ As more StaBrEx fed, HOBr can be consumed, but sulfamate concentration

increases
- High Cycles / Low blowdown / High HTI
- High biological demand
- High organic demand
- Overfeed
§ Timer Settings
§ ORP control (not recommended)

§ Normal Dissociation Reaction Reverses

- HBrNSO3- Na+ + H20 HOBr + H2NSO3- Na+
- Typically Significant at Sulfamate / FRO(3) residual > 20
- Test Sulfamate residual, compare to FRO(3)
- e.g. Sulfamate > 5 ppm / FRO3 = 0.25 Ratio >20

-
Stabilized Halogen - Controlbrom CB70
y Blend of Sodium Bromide and Sulfamate Stabilizer
§ Like ActiBrom with Stabilizer
§ Like ST70 with greater control of stabilizer levels

y Good for systems over 7.5 pH

y Requires Chlorine or Bleach feed
y Shown to Penetration Biofilm
y Bromine/Chlorine
§ Effective over 7.5 pH
§ Can Control Ratio of Chlorine : Bromine

y Good for Moderate - Higher Halogen Demand Systems

§ Still Low - Moderate HTI

y Low to Moderate free residual required

Liquid Stabilized Halogen - ST70 & CB70
• Advantages:
~ Bromine Control • Disadvantages:
~ Effective for bacteria ~ Potential for Overstabilization
~ Very High Demand Systems
~ Effective at pH >7.5
~ Very Long HTI
~ Penetrates biofilms
~ Less effective for algae
~ Phosphonate compatible
~ Expensive in large systems
~ Less AOX formation
~ Not for once-through systems
~ 3D TRASAR compatible
~ Difficult to keep high residuals

Chemically oxidize
nitrogenous organic
components of the
cell
Dry Stabilized Halogen
y Towerbrom 960 (NaDCC - Sodium Dichloroisocyanurate - Granular + NaBr)

y Towerbrom 991 (TCCA - Trichloroisocyanurate - Tablet + NaBr)

y Reduced Risk of overstabilization

y Easy to Slug feed – Equipment Selection is Based on Volume of

System
§ Feed to about 1 ppm free residual for at least 5 minutes
§ Feed is 0.5 X the lbs compared to BCDMH
§ Feed is about 0.1(lbs.) X bleach(gallons) slugged

y Good for systems over 7.5 pH

y Good for Higher Demand Systems
Stabilized Halogen –Towerbrom
• Advantages:
• Disadvantages:
~ Dry stable halogen product
~ Slug feed only
~ Slug dose to meet demand
~ Not stabilized in use
~ Suitable for Once-Through
~ Dry feeder needed
~ Effective above pH 7.5
~ Mix of dry chlorine and
Bromide-
~ Towerbrom is compatible with
3D TRASAR

• Products:
–Towerbrom 960 (90% NaDCC, granular) Oxidizes nitrogenous
–Towerbrom 991 (93% TCCA, tablets) organics in cells
Dry Stabilized Halogen - BCDMH
y Dry Blend of Stabilized Chlorine and Sodium Bromide
§ Nalco 7346 TAB (BCDMH, DCDMH, DCMH)
§ H-901G (granular)

y Chlorine and bromine on dimethylhydantoin (DMH)

§ Slow release of HOBr
§ Very Slow Release of HOCl
§ Continuous Feed with Brominator (Spec-309)
§ Feed to about 0.5 to 1.0 Total residual

y Good for systems over 7.5 pH

y Feed to systems < 5.0 ppm Ammonia

Feeding 7346 – Bypass Feeder

Dry Stabilized Halogen - BCDMH
•Advantages:
~ Effective for bacteria
~ Dry halogen product
~ Dual oxidant (HOCl / HOBr)
~ 7346TAB Continuous feed
with feeder
~ Can be slug fed – but
less efffective
~ H-901G Can be broadcast
onto deck
• Disadvantages:
~ Less effective - fungi and algae
~ Slowly soluble, slug feed is
difficult
~ Near-commodity material
~ Special feeder needed
~ Not good with elevated ammonia
Oxidizes nitrogenous
organics in cells
Chlorine Dioxide - ClO2

y Excellent biocide at low dosage for Rapid Kill

y Present as dissolved ClO2 Gas in Water
§ Volatile, but some residual can persist over the tower

y Effective over wide pH range (5 – 10 pH)

y Low Oxidation Strength / High Oxidation Capacity
§ Fewer disinfection by-products – Low AOX
§ Selective toward microorganisms
§ Effective on Viruses

y Helps reduce Biofilm

§ Penetrates Biofilm
Oxidizing Biocides: Chlorine Dioxide

–HYG-25 (25% NaClO2)

Precursor for Envirox (Electrochemical)Systems)

–Accucide 101A (25% NaCLO2)

–Accuvator 100A (sulfuric/phosphoric Acid Blend)

–Accucide and Accuvator used in Accucide Chlorine Dioxide

Generator Systems
Oxidizing Biocides – Accucide / Envirox
• Advantages: • Disadvantages:
~ Effective for bacteria, ~ Very volatile
fungi, and algae
~ On-site generation required
~ Very fast acting
~ Acid required for generation
~ Breaks down rapidly (Accucide)
~ No AOX formation
~ Not pH dependent
~ Penetrates biofilms
~ 3D TRASAR compatible

Oxidizes aromatic
components of cells
Free Oxidant Demand Test

Cooling water samples dosed with known amount of oxidants

1 ppm FRO 2 ppm FRO 3 ppm FRO 4 ppm FRO

15 min

Demand =
2.5 ppm
0 ppm FRO 0 ppm FRO 0.5 ppm FRO 1.5 ppm FRO
 Non-Oxidizing Biocides
§ They are Organic Compounds engineered for a specific function.
§ In general, Non-Oxidizing Biocides are not consumed in reactions with non-
living organisms where as Oxidizers attack and degrade most oxidizable
organic compounds.
§ Fed at higher concentrations than oxidizers
§ minimum amount of contact time required to kill.
§ Usually fed intermittently rather than continuously.
§ Dosage Requirements - CPP generally shows a range for the product
dosage.
§ Resistance/tolerance patterns to Non-Oxidizing Biocides can develop at low
doses.
ØWhen microorganisms are threatened by a toxic substance, their natural survival
response is to increase their metabolism rate.
If the biocide is fed at too low of a concentration, this can actually stimulate population
growth. .
 Biocide Program Selection

y Selectacide Test is used to screen for Non-Oxidizing

Biocide Choice
§ For Initial Selection
§ To Establish Continuing Effectiveness

y Other determining factors include:

§ Presence of sulfides, ammonia, oxidizers
§ whether you have automated feed control
§ method of monitoring the program
§ discharge points and permits
§ types of organisms to control
Biocide Program Selection
 Persistence and Half-Life
§ Persistence
§ ability to remain in an environment in an unchanged form
§ the biocides ability to resist degradation..

§ Biocide Product Half-Life.

§ the amount of time required for 50% of the active biocide to be
degraded to the point where it is no longer effective.
§ affected by many factors (pH, temp, sunlight, existence of other
compounds, etc.).
 System Holding Time Index (HTI)

§ The Cooling System Holding Time Index (HTI) is not to be confused with
the Biocide Product Half-Life.
The Cooling System Holding Time Index (HTI) is defined as the amount of time
it takes for an applied dosage to decrease to 50% of its initial ppm value by
removal from the system through blowdown.
Non-Oxidizing Biocides
Organic compounds that can react with cell components: disrupt
cell walls, metabolism, or reproduction.
üDBNPA
üIsothiazolone
üGlutaraldehyde
üQuaternary Ammonium Compounds (Quats)
üCarbamates
üBronopol
• Methylene Bisthiocyanate (MBT)
• Tetrakis (Hydroxymethyl) Phosphonium Sulfate (THPS)
• Dodecylguanidine Hydrochloride (DGH)
• Terbuthylazine
Non-Oxidizing Biocides - DBNPA
• Mode of Action:
~ Reacts with sulfhydryl groups present in bacterial
enzymes which interferes with cellular respiration
and metabolism.
Non-Oxidizing Biocides - DBNPA
DBNPA decomposition by hydrolysis in DI water (Product Half-Life in hours)

At pH 9 & Temp of 77 °F, Product Half-Life is 0.35 hours which is 21 minutes.

 Non-Oxidizing Biocides - DBNPA
2,2-Dibromo-3-nitrilopropionamide (DBNPA)

• Advantages: • Disadvantages:
~ Effective for bacteria ~ Less effective - fungi and algae
~ Very fast acting ~ Not Persistent
Contact Time (< 1 hour) ~ Not UV Stable
~ Breaks down rapidly ~ Degrades quickly above pH 8.5
(Environmental Acceptability) (half-life at pH 9 is 15 to 30 min)
~ Useful in short HTI cooling ~ Deactivated by sulfide
systems
~ Compatible with most system
additives
~ Some synergism with
halogen biocides
Non-Oxidizing Biocides - Isothiazolone
• Mode of Action:
~ Reacts with enzymes in the cell, which disrupts the
cell metabolism and repair systems. This inhibits
cell growth, respiration, and food transport through
the cell wall.
 Non-Oxidizing Biocide - Isothiazolone
• Advantages:
~Effective for bacteria & fungi
~Persistent
~Wide pH range of activity
(pH 4.5 to pH 9)
~Compatible with most
system additives
~Synergistic with oxidizers
~Often Used in Closed loops
• Disadvantages:
~ Slower acting - requires contact
time of 6 to 8 hours
~ Skin sensitizer (special handling)
- Eductor feeder recommended
~ Copper stabilizer may promote
galvanic corrosion
~ Copper free formulation available
for closed loops
~ Deactivated by sulfide
 40

Non-Oxidizing Biocides - Glutaraldehyde

• Mode of Action:
~ Reacts with amino acids in cell walls in a crosslinking reaction
deforming it which hinders nutrient flow in and waste flow out of the
cell, leading to cell death.

Glutaraldehyde, or 1,5-pentanedial, is a
linear five-carbon dialdehyde
CAS # 111-30-8
 41

Non-Oxidizing Biocides - Glutaraldehyde

• Advantages:
~ Broad-Spectrum Biocide
~ Effective against
Anaerobic Bacteria –
notably SRB’s
~ Persistent (about 12 hr half
life)
• Disadvantages:
~ Reacts with ammonia, and primary
and secondary amines
(but not quaternary amines)
~ Reacts with oxidizing biocides -
consumes oxidizer residual first
before active glut is available

~ Relatively fast acting

(Minimum 4 hour contact
time required)
~ Effective pH range between
5 and 10
~ Ideal for closed water loop
systems
~ Compatible with most
system additives
Non-Oxidizing Biocides – Quaternary
Ammonium Compounds (Quats)
• Mode of Action:
~ Reacts with components of the cell wall and cell membrane,
disrupting transport and cell integrity.
 Non-Oxidizing Biocides – Quaternary
Ammonium Compounds (Quats)
• Advantages:
~ Effective against bacteria
and algae
~ Contact Time typically 4 to 6
hours
~ Broad pH range of activity
(pH 6.5 to 9.5)
• Disadvantages:
~ Activity is lost by adsorption
(hardness, salinity, dirt, silt, etc.)
~ Foaming Tendency- (surface-active
dispersing properties)
~ Quats do not discriminate between
living and non-living surfaces.
Their cationic charge reacts with
anionic species including anionic
scale and corrosion control
polymers
Non-Oxidizing Biocides – Carbamates
• Mode of Action:
~ Chelates metallic ions essential to a cell’s metabolism.
Non-Oxidizing Biocides – Carbamates
Principal Type:
Sodium Dimethyldithiocarbamate
Nabam (Disodium Ethylene Bis-dithiocarbamate)

• Anionic Broad Spectrum Bactericide and Fungicide.

• Typically, used at 20 to 40 ppm, at 30% activity.
• Contact Time (6 to 8 hours).
• Effective pH range 7.0 to 8.5.
• Not compatible with cationic materials such as quats.
• Precipitation may occur in the presence of significant levels of
dissolved iron or zinc.
Non-Oxidizing Biocides – Bronopol
• Mode of Action:
~ Attacks the bacterial cell’s nucleophilic centers, primarily by
reactions with thiol containing enzymes which results in inhibition
of respiration and metabolism.
 Non-Oxidizing Biocides – Bronopol
2-Bromo-2-nitropropane-1,3-diol (Organo-Bromine Group)

• Broad Spectrum Biocide.

• Effective against aerobic and anaerobic bacteria including slime-forming
bacteria and sulfate-reducing bacteria (SRB’s).
• Good compatibility with most other biocides.
• Typically, used at 25 to 100 ppm (active basis).
• Effective pH range 5.0 to 9.0.
• Slow biocidal effect – can take as long as 24 hours to kill.
• Compatible with most system additives.
• Sensitive to strong reducing agents such as bisulfite > 50 ppm and
oxidizing agents such as free chlorine residual > 5 ppm.
Biodispersants/Biodetergents

y Disperse clumps of bacteria floating in the bulk phase;

so they don’t settle on surfaces.
y Remove soft foulant (biofilm-enmeshed mud, silt or
clay) deposit from water system surfaces by
Detergency.
y Do not require US EPA registration for usage
Fouled Film Fills in a Power Plant

Before After Biodetergent

About 73550…...
y Nonionic liquid blend of alkyl polyglycoside (50% a.i.)
y pH 7.5~8.5
y No odor
y Viscosity 1520 cps @ 32 oF
y Tolerant to water hardness
y Has complete freeze-thaw recovery
y Compatible with oxidizing and non-oxidizing biocides
y Compatible with corrosion and scale inhibitors
y Patented technology
y Good oil and silt dispersant
How to Monitor and Control Biocide Programs
y Visual and Physical Conditions

y 3D Bio Control

y AND by “Counts” (cfu / ml) (Dipslides, PetriFilms, Agar)

§ Colony Forming Units per milliliter

y Open Towers
§ Best Practice Control 103 - 105 (Typical Action Level)

y Closed Systems
§ Best Practice Control 100 - 103 (Typical Action Level)

y Or Any 2 log (102) Increase

3D Bio-Control Principle

Microbial
enzyme
activity

3D Bio-Reporter 3D Bio-Product
Rz Rs

Enzymes present in
living microbes react
with Bio-Reporter

Microbial Rs
Activity = Rz
=
3D Bio-Control Automation
Automatic oxidizing biocide control - demand based dosing

Bio-Reporter
Bio-Product
3D TRASAR Microbe
Fluorometer

Rs
> 1.82
Rz
Bleach ON

Oxidizing
Biocide

Rs
< 1.82
Rz
Bleach OFF
 54
Bio Index Upper Control
Ratio
6 hour moving average value of the ratio
relative to the control band
Averaged
(+) Averaged Ratio above Lower Fixed Ratio Ratio
(- ) Averaged Ratio below Lower Fixed Ratio
>100 Averaged Ratio Above Upper Fixed Ratio
(Both fixed ratios are empirically determined for each Lower Control
biocide) Ratio
Bio-Index Control

AvgRatio – LoRatio <-20 At startup(first 48 hrs). If

Bio-Index = X 100 persistent with no other
HiRatio – LoRatio alarm, call 3D TRASAR
Support
-999: Ox Slug in progress -20 to +10 Normal control

+10 to +30 Responding to

0: No 3D Bio-Bio Control
Moderate Stress
+30 to +80 Responding to High
Stress
>80 Alarm
 Field Test - Dipslides
• Advantages: • Disadvantages:
~ Simple estimate by colony ~ Results in two days
density ~ Doesn’t detect all types
~ Results in two days ~ Doesn’t differentiate types
~ Economical ~$2.50-4.50/test ~ Must be checked min. 48 hours
~ No instrument needed or at the same time every time
~ Separate estimations of ~ Must keep constant incubation
bacteria, fungi, SRBs temperature
~ Wide range of detection
Testing Range = 102- 107 CFU/ml
Control Range = 103 - 105 CFU/ml
Any 2-log increase in counts
should be a warning sign
Aerobic 500-P1673.88
Anaerobic 500-P3053.88
Total Bact & Fungi 500-P3054.88

Weekly to Monthly - Estimate of total count

 Field Test – ATP Test
• ATP (Adenosine Tri-Phosphate) is the biological energy currency
• Higher ATP numbers means more organisms
• ATP results expressed as Relative Light Units (RLU)

• Advantages:
~ Rapid field test for total of
all types of microorganisms
~ Very sensitive over a wide
range
3M - FREE pens 500-SPO126.88
3M – TOTAL pens 500-SPO124.88
•Disadvantages:
~ Need to Correlate to cfu/mL
~ No differentiation of microbial types
~ Free and total ATP distinction
necessary
~ Expensive ~$5.50/test

BioTrace Meter 460-SPO120.88 Extract

ATP Luciferin/Luciferase
(approx. $3,000) ATP

ATP ATP

ATP
ATP
ATP
ATP

Microbes
Biofilm Monitoring

Use Surface Microbial Monitoring Test Kit

Collect samples with sterile swabs

Submit the test tube to Lab with test code
BIOSWB

Less than 106 CFU/cm2 indicates a

monolayer of biofilm

Look for trends in diversity and counts

Test Kit 420-C0243.88

Swabs 500-P3065.88
Tubes 500-P3066.88
AP Sheet AP-105
Fouling in 3DT Strainer