The Use of Phosphates in Water Treatment for

Corrosion Control & Sequestration

Maine Water Utilities Association

April 13, 2017
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 Agenda

• US EPA Lead and Copper Rule

• Corrosion Definition
• Chemical Factors Influencing Corrosion and Corrosion Control
• Factors to Reduce Corrosion
• Phosphates in Water Treatment
• Chemical Inhibitors
• Dosage Rates
• Selection of Phosphates/Benefits of Phosphates
• Case Studies
• Monitoring Corrosion Control Success

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 Lead and Copper Rule

June 7, 1991 EPA Document in Effect

Current Action Level 1991 MCLG

Lead 0.015 mg/L 0 mg/L

Copper 1.30 mg/L 1.30 mg/L

Health Effects:
Lead: Delays in physical and mental development of children,
kidney problems, & high blood pressure

Copper: Gastrointestinal/liver/kidney problems

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 Lead and Copper Rule

90th percentile is the value to determine compliance with

the action level

All customers samples are arranged from lowest to

highest in a list, the value at 9/10 of the way up is the
value to determine compliance with action level.

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 Lead and Copper Rule

Monitoring is based on the size of the distribution system and

high risk sites (lead service lines).
Frequency is every 6 months for initial monitoring.
Systems consistently meeting the Action Level can reduce
monitoring to once a year and half of the samples.
Finally to once every three years.

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 Lead and Copper Rule

Sampling of “First Draw”

1-Liter of water from a cold water tap that has not
been used for at least 6 hours.
No upper limit on stagnation time.

2016 Recommendations
No pre-flush
Use wide mouth bottles
Higher flow rate
Don’t remove faucet aerators

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 Lead and Copper Rule

Actions Required after an exceedance occurs

Distribution of Public Education
Increased Monitoring of Consumer Taps
Develop and Submit a Corrosion Control Plan
Adjust pH, Alkalinity, Hardness, or Corrosion
Inhibitor
Lead Service Line Replacement
7% per year

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 Lead and Copper Rule - References

• Lead and Copper Rule

➢ https://www.epa.gov/dwreginfo/lead-and-copper-rule
• Water Research Foundation – Fact Sheet – Dist. Syst. Mgmt. –
“Impacts from Lead and Copper Corrosion”
➢ http://www.waterrf.org/knowledge/distribution-system-
management/FactSheets/DistributionSystemMgmt_LeadCopper
_FactSheet.pdf
• Optimal Corrosion Control Treatment Evaluation Technical
Recommendations for Primacy Agency and Public Water Systems –
March 2016
➢ https://www.epa.gov/sites/production/files/2016-
03/documents/occtmarch2016.pdf

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 Corrosion

Destructive attack of a material by a chemical or

electrochemical reaction with its environment.

• Electrochemical

• Chemical

• Microbiological

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 Electrochemical Corrosion
Galvanic Series

Magnesium (Base Metals)

Anode (Most Active)
Zinc
Aluminum
Steel
Cast Iron
Lead - Tin Solder
Lead
Nickel
Brass
Copper
Stainless Steel
Silver
Gold

Cathode (Least Active) (Noble Metals)

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 Cast Iron Pipe Corrosion

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 Corrosion – Tuberculation

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 Corrosion

• Oxidation Fe Fe++ + 2e-

Cu Cu++ + 2e-
Pb Pb++ + 2e-

•Reduction 2H2O + 2e- H2 + 2OH-

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 Electrochemical Corrosion
• Is an electrochemical process in which electrons flow from one site on the
metal pipe surface to another
• Metal is oxidized to form positive ions (cations) while other chemical
species either in the pipe or water are reduced.

•The anode is the place where the oxidation occurs (electrons lost)
•The cathode is where the reduction occurs (electrons accepted)

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 Chemical factors influencing corrosion and
corrosion control

Factor Effect
pH Low pH increase corrosion, High pH protects

Alkalinity Help form protective CaCO3 coating, controls pH

D.O. Increases rate of corrosion

Chlorine residual Increases metallic corrosion

TDS High TDS increases conductivity and corrosion

Hardness Ca may precipitate as CaCO3 provide protection

Chloride, sulfate High levels increase corrosion in iron, copper,and steel

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 CSMR

Reference:
Lead Solder or Partially
NO
Replaced Lead Pipes in No Concern Chloride-to-Sulfate Mass Ratio and
the Distribution System Lead Leaching to Water (PDF)
YES Author(s): Edwards, Marc; Triantafyllidou,
YES
Simoni
CSMR < 0.2 Publications: Journal - American Water
NO Works Association
Significant Issue Date: July 2007
CSMR > 0.2 Concern Volume / Number: 99, Number 7
YES

NO

NO

CSMR > 0.5, and

Alkalinity < 50 mg/L as
CaCO3

Serious
YES
Concern

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 Corrosion Effects

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 Corrosion Increases. . .

Tuberculation & Deposits

Cost to Pump Water
Fire Insurance Ratings
Chlorine Demand
Bacterial Re-Growth
Flushing Frequency
Leaks & Main Breaks
Water Heater
Replacement
Decay of Water Quality
Customer Complaints

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 Factors to Reduce Corrosion

• pH Adjustment
• Passivation Techniques
Carbonate Adjustment
Calcium Adjustment
• Inhibitors – orthophosphate or blends
• Reduction of DIC
Aeration
Lime Softening
Ion Exchange

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 Stabilization

• An Increase in pH + Alkalinity can prevent

corrosion
• Lime-Increases both and adds hardness
Soda Ash- increase Alkalinity
• Both use for protective coatings
• DIC is a very important parameter,
• pH + ALK + DIC are better indicators of
corrosion control effectiveness
• Reference: https://www.epa.gov/sites/production/files/2016-03/documents/occtmarch2016.pdf

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 pH-Alkalinity Contribution

Alkalinity Increase per mg/L

Chemical Feed Rate mg/L
1.35 mg/L (adds calcium and
Lime-Ca(OH)2
1-20 mg/L (8-170 lb/MG) hydroxide alkalinity)

Caustic Soda NaOH

1-30 mg/L (8-250 lb/MG) 1.25 mg/L (hydroxide alk)
(50% sol)

1-40 mg/L (8-330 lb/MG) 0.94 mg/L (carbonate alk

Soda Ash Na2CO3
depending on pH)

Sodium Bicarbonate
5-30 mg/L (40-250 lb/MG) 0.59 mg/L (carbonate alk
NaHCO3
depending on pH)
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 Buffer Intensity

• Increasing the buffer intensity in low alkalinity waters

stabilizes pH. A stable pH is an important factor for
maintaining a low corrosion rate and low metal release.

• A stable pH is important in controlling lead solubility for

the long term.

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Calcium Carbonate Precipitation Potential

• The CCPP measures the amount of carbonate

precipitation that will deposit on the pipes
• The optimal range for treatment is 5-10 mg/L
• Controlling Calcium Carbonate is difficult because ;

Calcium Carbonate films rarely adhere to lead and copper

pipe walls and are not considered an effective form of
corrosion control.
• (Schock and Lytle, 2011; Hill and Cantor, 2011).

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 Calcium Carbonate Precipitation

• Is Achieved by taking pH/AlK adjustment too far

CO2 +Ca(OH)2 2HCO3- + Ca 2+
LIME BICARBONATE

Ca(HCO3) + Ca(OH)2 2CaCO3 + 2H2O

Calcium Carbonate
• Caustic Soda
CO2 + NaOH HCO3- + Na+

Ca(HCO3)2 + NaOH CaCO3 + 2H20

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 Corrosion Inhibitor and Sequestering agents

• Used if water cannot achieve CaCO3 coating

• Sequestering Agents - prevent scale formation, prevent
red water and pprecipitation of (Fe, Mn, Ca) preventing
corrosion by-products

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 Galvanic Corrosion
Prevention

• Use of DIELECTRIC couplings

» Plastic
» Ceramic
» Non-conductive

• SACRIFICIAL ANODES
» Zinc
» Magnesium

• CORROSION INHIBITORS
» Slow the rate of corrosion

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 Phosphates in Water Treatment

1887 First recognized use of phosphates in water treatment.

“Threshold Treatment”- use of few ppm sodium

1930’s hexa-metaphosphate powder to potable water for control
of calcium carbonate scale.

1970’s Zinc phosphates introduced for the treatment of low

hardness aggressive water supplies (Murray AWWA 1969)

Lead & Copper Rule: Set limitations on the amount of

1990’s permissible lead and copper in drinking water

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 Phosphates in Water Treatment

• Potable Water Treatment

• Corrosion Control (Lead & Copper)
• Sequestration: Color Control/Scale Control
• 2001 Used by 56% of water utilities
• AWWARF (corrosion control): $200 million spent
annually on phosphate products
➢ Resulted in $4 billion in savings (20 fold ROI)
• Cost range $0.30 - $2.00/lb
➢ or 1¢ - 10¢ thousand gallons

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 Chemical Inhibitors

•Anodic film formers

• orthophosphates
• zinc orthophosphates
•Cathodic inhibitors
• calcium carbonate
• polyphosphates
• zinc orthophosphate

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 Phosphate Classes

• Two distinct classes

➢ Each has different properties
• Orthophosphate
➢ Contains one PO4 unit
• Condensed (poly) phosphate
➢ Contains several PO4 units “chained” together

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 Phosphate Classes

Orthophosphate
➢ Contains one PO4 unit

0 P 0

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 Phosphate Classes

Polyphosphate
➢ Contains two or more PO4 units

0 0

0 P 0 P 0

0 0

➢ Metaphosphate: contains 3 or more PO4 units in a ring

structure
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 Corrosion Control Mechanism

• Phosphate forms film over pipes or metals

➢ Anodic film formers
➢ Cathodic inhibitors- Cationic complex provides a
diffusion barrier for oxygen
• Microscopic Film
➢ Very insoluble compounds- phosphate salts
➢ Mechanisms are still being researched

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 Orthophosphate Research

• Precipitates with 2+ valence metals

➢ Ca, Mg, Pb, Fe, Mn, Cu [Fe3(P04)2* H20]
• Formation of insoluble film (Schock, 1989 et al)
• P04 with two Fe3+ ions forming Fe-P04-Fe linkages
(Stumm, 1996 et al)
• May bond directly with pipe or soluble ions (Vik, 1996 et
al)
➢ 0.5 –1.0 mg/L P04 reduced Fe release two-thirds
• Reduce corrosion in distribution system

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 Chemical Inhibitors - Orthophosphates

• Orthophosphate
• Do not sequester
• pH important - Ideal for lead control pH 7.2 -7.8
• It is polyprotic acid - adds 3 H+
• DIC/Alkalinity important for its use
• Anodic inhibitor
• Applicable for lead control with pH adjustment

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 Chemical Inhibitors Phosphates

• Orthophosphate
• Lead can form several orthophosphate solids that are
less soluble than lead carbonates
• Most likely form is hydroxypromorphite (Pb5[PO4] 3OH)
• Other likely form is tertiary lead orthophosphate
Pb3(PO4)

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 Optimal Orthophosphate

• Typically >0.5 mg/L PO4 may reduce Pb

solubility in pH range 7- 9
• Excess of 3 mg/L PO4 yields little change
• Low DIC waters - even 1 mg/L is sufficient
• pH 7: Pb decreases with higher PO4
• Maintenance levels typically >1.0 mg/L

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 Zinc Orthophosphate (ZOP)

• Orthophosphate & Zinc Salt

• Corrosion Control Only
➢ Cannot sequester metals
• Quick to form film on pipes
➢ ‘Passivation’ can take place in weeks
• Doses range: 0.10 to 0.25 mg/L as Zinc
0.50 to 2.00 mg/L as P04
• Zinc loading limit in wastewater

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 Optimal Zinc Dose

• Typically >0.5 mg/L as Zinc

• Excess of 2 mg/L Zinc yields little change
• Low DIC waters - even 1 mg/L is sufficient
• pH 6.5 – 8.2 ideal range
• Maintenance levels typically 0.25 mg/L as Zinc

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 Poly/Ortho Blended Phosphate

• Became very popular in 1990’s

➢ Promulgation of Lead and Copper Rule
• Sequesters ( Fe2+, Mn2+, Ca2+)
• Moderate Corrosion Control
➢ Provides Lead and Copper Control
• Prevents and Removes Scale Deposits
• Improves Disinfection
➢ Chlorine doesn’t react with dissolved metals

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 Optimal Poly/Ortho Blended Phosphate Dosing

• Doses range: 0.20 to 1.50 mg/L as Ortho- P04

• Doses range: 0.50 to 4.00 mg/L as Total- P04
• Dose is dependent on water quality or equation
• Objective may also determine dosing
➢Sequestering: higher dose
➢Flushing: higher dose
➢Corrosion Control: lower dose

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 Iron & Manganese Sequestration

 “Sequestering is a chemical combination of a

sequestrant and metal ions in which soluble
complexes are formed… ... Sequestrants
function as chelating agents, they donate
electrons to form a “coordinate bond” with iron
and manganese ions.

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 Sequestering Mechanism

• Bonding of polyphosphate to metals

• Prevents chlorine from oxidizing metal
➢ Typically, iron and manganese
• Result is clear water
➢ Prior water was rusty orange (Fe3+)
➢ Prior water was black or brown (Mn02)
• “Threshold Treatment”
➢ calcium & bicarbonate ions-”ion-pairs”
➢ phosphate attracted to these clusters
➢ inhibit/retard crystal growth

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 Polyphosphate Research

• Sequestering of metals depends on water chemistry (Klueh

& Robinson, 1988)
• Reduces apparent color and turbidity in Fe3+ colloids (Lytle,
2002)
• Polyphosphates improve disinfection (LeChevallier, 1990)
➢ Application results in 1,000 fold decrease in biofilm
counts
• Revert to ortho over time (Thilo, Chem, 1957)
➢ Change to ortho as they age

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 Polyphosphate Sequestering Total Hardness

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 Chemical Inhibitors - Polyphosphates

• Polyphosphates
• In general strongest complexing agent for iron and
manganese of the phosphates.
• Sequester calcium
• Cathodic inhibitor
• Degrades to orthophosphate
• Polyprotic acid (4 H+) in water will become P2O7-3
• Wide pH range for it effective use

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 Iron & Manganese Sequestration

Polyphosphates – “Condensed Phosphates” – Threshold Treatment

Tripolyphosphate

TKPP
SHMP

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 Optimal Polyphosphate Dosing

• Doses range 0.50 to 4.00 mg/L as Total-P04

• Dose is dependent on soluble cations in water
• Objective may also determine dosing
➢ Sequestering: higher dose
➢ Flushing: higher dose

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 Typical Well Water Application

SEQUESTERING IRON & MANGANESE

SEQUESTERING
Chlorine
AGENT pH Adjustment
Treated
Water
1 Ft for every 1” diameter pipe
Groundwater
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 Flushing Process – Water Quality

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 Flushing Process – Water Quality

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 SPRING & FALL - FLUSHING SEQUENCE TO REMOVE
PARTICULATE MATTER

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 Iron & Manganese Oxidation

When iron and manganese are present in high

concentrations the recommendation is Oxidation and
Filtration.

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 Oxidation Process

PERMANGANATE

Corrosion Control
Agent and pH
Adjustment

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 Typical Well Water Application

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 Choice of Phosphate

• Which phosphate to use? Choice can be as critical as

dosing
➢ What is the water quality leaving the plant and in the
distribution system?
➢ What types of problems are you having in the
distribution system?
➢ What are your treatment goals?

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 Product Selection & Dose

• Need to Determine
➢ Hardness
➢ Soluble Fe & Mn (after filtration)
• The Fe SMCL is 0.30 mg/L for potable water
• The Mn SMCL is 0.05 mg/L for potable water
➢ Orthophosphate
• Background ortho does not aid corrosion
➢ pH
• Ortho/poly phosphate 6.0 - 9.0 with 7.0 - 8.0 optimal
• Zinc orthophosphate 6.7 - 8.2 with 7.3 - 7.8 optimal

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 Selection of Phosphates

High
Fe/Mn Carus 1000
2.0mg/L/0.3mg/L
Series

SMCL
0.3 mg/L Fe
Aqua Mag
0.05 mg/L Mn Carus 8000 Series

Carus 3000 Series

Low Carus 4000 Series
Fe/Mn
0.1mg/L/0.02mg/L

Corrosive Scale forming

water water
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 Case Study 1
Carus 4105

• Background:
• Eliminate pH adjustment for corrosion control
(soda ash combined with calcium chloride)
• Eliminate bad taste caused by pH adjustment
• Reduce periodic dirty water (red water)
• Reduce lead and copper levels below action levels

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 Case Study 1
Carus 4105

• Plant Operation
• Ground Water Filtration Plant
• 1.5 MGD
• Water Quality

Fe 0.04 mg/L TDS 200 mg/L

Mn 0.01 mg/L Alkalinity 68 mg/L
pH 8.40 Hardness 24 mg/L

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 Case Study 1
Carus 4105

• Treatment
• 100% Orthophosphate
• Dosage: 1.0 mg/L as Ortho-PO4
• Feed Rate: 23 lbs per MGD
• Results
• Improved Taste
• Reduced pH to 7.5 saved 37% in soda ash costs
• Replaced calcium chloride saved 50% in costs
• Lead Levels < 2 ppb
• Copper Levels < 0.05 mg/L (after 2 yrs)

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 Case Study 2
Carus 8500 Blended Phosphate

• Background:
• Reduce Lead Below Action Level
➢Current Action Level of 22 ppb
• Reduce Discoloration in Households
• Reduce Long Hydrant Flushing Times
➢Greater than 30 minutes

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 Case Study 2
Carus 8500 Blended Phosphate

• Plant Operation
• Ground Water Filtration Plant/3 Wells
• Radium Removal with HMO
• 1.1 MGD (7,500 Customers)
• Water Quality

pH 7.3-7.5
Fe 0.1-0.5 mg/L Mn 0.01-0.05 mg/L
Hardness 280-340 mg/L Alkalinity 288 mg/L

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 Case Study 2
Carus 8500 Blended Phosphate

• Treatment
• Blended Phosphate (50/50 Ratio Poly/Ortho)
• Dosage: 1.5 mg/L as Total PO4
• Feed Rate: 35 lbs per MGD
• Results Within 90 Days
• Lead Levels from 22 ppb to 7.5 ppb
• Hydrant Flushing Times from 30 minutes to less
than 5 minutes
• Customer Complaints Reduced

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 Case Study 3
Aqua Mag Blended Phosphate

• Background:
• Heavy Tuberculation
• Reduced Flows
• Periodic Dirty Water (Red Water)
• 90th Percentile Copper Levels:
2.25 mg/L

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 Case Study 3
Aqua Mag Blended Phosphate

• Plant Operation
• Iron Removal (aeration), Gravity Filtration
• 2.5 MGD
• Water Quality

Fe 0.1 –0.3 mg/L TDS 350 mg/L

Mn 0.01 mg/L Alkalinity 340 mg/L
pH 7.6 – 7.9 Hardness 180 mg/L

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 Case Study 3
Aqua Mag Blended Phosphate

• Treatment
• Blended Phosphate (70/30 Ratio Poly/Ortho)
• Dosage: 1.50 mg/L as Total PO4
• Feed Rate: 38 lbs per MGD
• Results
• Average Flow Improvement by 10-40%
• Reduced Customer Complaints
• Copper Levels Decreased 65% to 0.79 mg/L

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 Phosphate Injection Applications

• Inject Phosphate solution using a corporation stop in

main prior to chlorination for sequestering
-Inject neat or with carry water, static mixer can be used
-Peristaltic or Membrane chemical feed pump
Flow paced, SCADA controlled recommended

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 Phosphate Injection Applications

• Typical Phosphate Feed Rate Measurements

• Calibration of Metering Pump (mLs/min or gals/hr)
• Weigh Scale for Day Tank (pounds used per day)
• Level Indicator for Day Tank (gallons used per day)

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 How Do I Monitor Phosphate?

• USEPA Approved Ascorbic method 8048

• Measures orthophosphate residual in mg/L
• Two minute reaction – turns light blue

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 Monitoring a Phosphate Product?

Test at Finished Water Tap,

Distribution System, & Dead
1
Ends
 Results should be at or above
2 the target level throughout the
distribution system

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 Coupon Testing Design

• Coupon Based Monitoring (NACE Protocol)

• Test Exposed Coupons for MPY
“Mils penetration per year”
▪ Test Duration (90 days exposed)
▪ Need non-treated, treated and distribution loops
▪ Focus on “trend of data” not numerical data

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 Coupon Testing Rack

Effluent

Influent

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 Coupon Testing Results

Coupon Exposure:
90 Days

Matrix:
Surface Water

No Treatment 50:50 Blend Treated

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 Personal Protection Equipment (PPE)

PPE required for phosphoric acid and zinc orthophosphate

• pH is < 1 (corrosive inorganic liquid)

➢ Goggles and/or face shield
➢ Rubber or appropriate polymer gloves
➢ Rubber apron
➢ Complete acid resistant suit
➢ Rubber boots
• DOT hazardous for shipping

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 Personal Protection Equipment (PPE)

PPE required for pH adjusted orthophosphates and

blended phosphates

• pH is typically neutral
➢ Safety glasses or goggles
➢ Rubber or appropriate polymer gloves
• Not DOT hazardous for shipping

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 Summary of Phosphates Uses

•Phosphate use is extensive in US

•Very small systems to very large
•Benefits are worth the cost
•Reduced lead and copper corrosion
•Clearer water (sequestering)
•Reduced flushing times
•Reduced disinfectant demand
•Overall better water quality

CARUS CORPORATION
 Questions

Carus Corporation Switchboard: 815-223-1500

Luis Hernandez
North East Regional Manager
[email protected]
Mobile Phone: 518-423-8635

Carus Corporation
315 Fifth Street
P.O.Box 599
Peru, IL 61354-0599
CARUS CORPORATION 78