Examples of Iron and

Manganese Treatment
CEE 483
February 25, 2009
Russell Porter, P.E.
 Objectives

Brief Summary of Fe and Mn

Treatment Theory

Two Design Examples

Existing Fe and Mn Plant Retrofit to

Fe/Mn/As Treatment

Existing Ion Exchange Plant

Retrofit to Fe/Mn Treatment

CEE 483 February 25, 2009

 Fe and Mn Treatment Theory

Fe/Mn Treatment by several methods

Lime softening

Conventional treatment (coagulation,

flocculation, settling, filtration)

Membranes

Fe and Mn removal by
oxidation/filtration

CEE 483 February 25, 2009

 Fe and Mn Oxidation/Filtration Theory

First Step - Oxidation

Natural form in groundwater-soluble

Fe+2
Mn+2
Oxidized form insoluble

Fe+3 - Fe2O3 or Fe(OH)3 Rust

Mn+4 - MnO2 Black Precipitate
CEE 483 February 25, 2009
 Fe and Mn Oxidation/Filtration Theory

Oxidation of Fe - Rapid
2Fe+2 + 1/2O2 + 5H2O 2Fe(OH)3 + 4H+

Oxidation of Mn - Slow
Mn+2 + 1/2O2 + H2O MnO2 + 2H+
Catalyzed Oxidation of Mn - Rapid

Mn+2 + 1/2O2 + H2O MnO

MnO2 + 2H+
2

MnO2 is Mn Oxidation Catalyst.

CEE 483 February 25, 2009

 Fe and Mn Oxidation/Filtration Theory

Several Oxidants are Used.

Ozone

Chlorine
Cl2 gas

Hypochlorite

KMnO4

Air (Oxygen)

CEE 483 February 25, 2009

 Fe and Mn Oxidation/Filtration Theory
Second Step - Filtration

Theoretically Similar to Other Types of

Filtration

Special Media - MnO2 Surface 2 Types

Core Glauconite, Dolomite, Silica Solid MnO2 Mineral

(Mn Ore)
Manufactured MnO2
Surface

Manufactured Media Mined and Processed

Greensand, Birm Media - Pyrolusite
CEE 483 February 25, 2009
 Fe and Mn Oxidation/Filtration Theory
Second Step - Filtration

Theoretically Similar to Other Types

of Filtration

Special Media - MnO2 Surface

CEE 483 February 25, 2009

CEE 483 February 25, 2009
CEE 483 February 25, 2009
 CASE STUDY 1
BACKGROUND

Existing Iron and Manganese

Treatment Facility

Served by Three Wells

1,100 gpm

Startup in 1997

Planned Expansion to 1,650 gpm

CEE 483 February 25, 2009

 RAW WATER QUALITY

Water Quality Average MCL Range of Values

Parameter Value
Manganese 0.143 mg/L 0.05 mg/L 0.117 0.191 mg/L
Ammonia 0.19 mg/L NA NA
Iron 0.128 mg/L 0.3 mg/L 0.069 0.199 mg/L
Arsenic 0.013 mg/L 0.010 mg/L 0.011 0.015 mg/L

CEE 483 February 25, 2009

 EXISTING PLANT

Degassers

Air Ozone BIRM

Dryer Generator FILTER
#1

From To
Wells OZONE System
BIRM
CONTACT FILTER
Venturi TANKS #2
Inductor

NaOCl
Injection

CEE 483 February 25, 2009

 DESIGN PARAMETERS FOR EXISTING PLANT

Parameter Value
Ozone Dose 0.65 mg/L
Ozone Contact Tanks per Train 2
Total Ozone Contact Time 6.5 minutes
Filter Media Birm
Number of Filter Tanks per Train 2
Filter Loading Rate 3.5 gpm/square foot

CEE 483 February 25, 2009

EXISTING PLANT

Ozone Venturi
Inductor

CEE 483 February 25, 2009

EXISTING PLANT

Ozone Contact
Tanks

CEE 483 February 25, 2009

EXISTING PLANT

Filter Units

CEE 483 February 25, 2009

 TASTE AND ODOR ISSUES
Large Number of Customer Complaints

Survey Data - Unsatisfactory Taste and Smell

over 50% of the Time

Description of Tastes
Dirty
Sour

Description of Odors
Earthy
Algae-like
Chlorinous

CEE 483 February 25, 2009

 TASTE AND ODOR ISSUES

Staff noted musty backwash odor.

Biofilm noted in ozone contact tanks and filters.

Lab analysis confirmed presence.

Iron Bacteria (Gallionella ferruginea)
Sulfur Bacteria (Thiodendron mucosum)
Protozoa
Larval Crustaceans
Nematodes

CEE 483 February 25, 2009

BIOFILM GROWTH

CEE 483 February 25, 2009

 INITIAL INVESTIGATION

Initial investigation focused on ozone performance.

Ozone Nameplate Capacity 0.65 mg/L

Post Injector Ozone Concentration 0.1 mg/L

Post Ozone Contactor Concentration 0 mg/L

Hypothesis: Insufficient ozone dose in ozone contact tanks

allowed biogrowth to occur.

CEE 483 February 25, 2009

 BENCH-SCALE OZONE INVESTIGATION

Bench-scale Testing Goal: What dose of ozone would

produce a measurable concentration after ozone
contact tanks (6.5 minutes)?

Bench-scale test used a comparison between ozone

behavior in distilled and raw water to determine ozone
demand.

Bench-scale test compared ozone doses of 0.9 mg/L,

1.6 mg/L, and 1.9 mg/L.

CEE 483 February 25, 2009

 RESULTS OF BENCH SCALE TESTS

1.4
Bench Test, Dose = 0.9 mg/l
1.2
Bench Test, Dose = 1.6 mg/l
Measured O 3 , mg/L

1 Bench Test, Dose = 1.9 mg/l

0.8

0.6

0.4

0.2

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Time, Minutes From End of Sparging

CEE 483 February 25, 2009

 BENCH-SCALE OZONE INVESTIGATION

Bench-scale test indicated that there is an immediate

demand of 0.6-0.7 mg/L.

Bench-scale test indicated that dosing at approximately

1.1 mg/L would provide a trace of ozone after 6.5
minutes.

CEE 483 February 25, 2009

 FULL-SCALE OZONE INVESTIGATION

Additional Ozone Equipment Rented

Ozone Dose 1.1 mg/L (0.65 mg/L Pre-test)

Post Injector Ozone Concentration 0.4 mg/L (0.1 mg/L)

Post Ozone Contactor Concentration 0.1 mg/L (0 mg/L)

CEE 483 February 25, 2009

 RESULTS OF FULL SCALE TEST

1.4
Bench Test, Dose = 0.9 mg/l
1.2 Bench Test, Dose = 1.6 mg/l
Measured O 3 , mg/L

Bench Test, Dose = 1.9 mg/l

1 Full Scale Test, Dose = 1.1 mg/L

0.8

0.6

0.4

0.2

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Time, Minutes From End of Sparging

CEE 483 February 25, 2009

 FULL-SCALE OZONE INVESTIGATION

Increased Ozone Improved Water Quality

Fewer Customer Complaints Not Totally

Eliminated

No Biofilm Present

Staff Noted Backwash Musty Odor Diminished

CEE 483 February 25, 2009

 ADDITIONAL FULL-SCALE INVESTIGATION
Ambient air injected at venturi instead of ozone.

Degassers

BIRM
FILTER
Ambient #1
Air

From To
Wells OZONE System
BIRM
CONTACT FILTER
Venturi TANKS #2
Inductor

CEE 483 February 25, 2009

 ADDITIONAL FULL-SCALE INVESTIGATION

Results of Ambient Air Injection Test

Customer complaints decreased compared with

ozone.

Biofilm present but no musty odor.

Iron and manganese removal same as with ozone.

CEE 483 February 25, 2009

 OTHER PILOT WORK

Plant expansion provided opportunity for review of other

technology.

Hypochlorite oxidation and pyrolusite filtration chosen

based on preliminary cost analysis.

City was interested in discontinuing ozone due to

maintenance burden.

CEE 483 February 25, 2009

 PYROLUSITE TREATMENT SCHEMATIC
NaOCl
Injection

From
Wells

PYROLUSITE PYROLUSITE PYROLUSITE PYROLUSITE

FILTER #1 FILTER #2 FILTER #3 FILTER #4

To
System

CEE 483 February 25, 2009

 PILOT STUDY PARAMETERS

Parameter Value
Oxidant Sodium Hypochlorite
Average Oxidant Dose 2.1 mg/L
Number of Pilot Filters 4
Filter Diameter 6 inches
Filter Surface Area (1 Filter) 0.196 ft2
Total Filter Surface Area 0.785 ft2
Media AS-741 M Pyrolusite
Grain Size (US Mesh) 20-40 Mesh
Media Depth 36 inches
Hydraulic Loading 4.65-9.91 gpm/ft2

CEE 483 February 25, 2009

 PERFORMANCE OF PYROLUSITE

Contaminant Average Raw Water Average Treated Average

Concentration, Water Removal
mg/L (Range) Concentration,
mg/L (Range)
Iron 0.128 (0.069 0.199) 0.001 (ND 0.005) 99.2 %
Manganese 0.143 (0.117 0.191) 0.001 (ND 0.001) 99.3 %
Ammonia 0.19 ND 100 %

CEE 483 February 25, 2009

COMPARISON OF TREATMENT TECHNOLOGIES

Process Manganese
Removal
Hypochlorite and Pyrolusite (Pilot) 99.3 %
1.1 mg/L Ozone and Birm (Full Scale Pilot) 93 %
Ambient Air Injection and Birm (Full Scale Pilot) 93 %

Hypochlorite and pyrolusite provided best Mn removal.

Significant Cost Advantage with Hypochlorite and Pyrolusite.

CEE 483 February 25, 2009

 ARSENIC REMOVAL

DOH decreased MCL from 50 g/L to 10 g/L in January

2006.

Raw Water Arsenic -11-15 g/L Requires Treatment

As BATs for Small Systems

Adsorption (generally Fe Oxide Media)
Ion Exchange
Oxidation/Filtration

Oxidation/Filtration is an As BAT.

CEE 483 February 25, 2009

ARSENIC REMOVAL OXIDATION/FILTRATION

First Step Oxidation of Arsenite (As III) to Arsenate (As V)

OCl- + H3AsO3 Cl- + H3AsO4

Second Step Filtration

Arsenate must complex to form a solid to be filtered out.

Arsenate has an affinity for ferric oxides.

Ability to remove As by Ox./Filt. is dependent upon iron

content of water. Iron can be added as FeCl3.

CEE 483 February 25, 2009

 ARSENIC REMOVAL

Arsenic removal tested as part of chlorination/pyrolusite

filtration pilot.

FeCl3 added to determine optimal dose.

Field test kit (Industrial Test Systems) and commercial lab

samples were used to measure As.

CEE 483 February 25, 2009

 ARSENIC REMOVAL PILOT WORK
Arsenic in Treated Water, mg/L ' 0.016

0.014

0.012

0.01

0.008
Field Tests
0.006
Lab Tests
0.004 MCL
0.002

0
0 1 2 3 4 5 6

Ferric Chloride Dose, mg/L as Fe

CEE 483 February 25, 2009
 TREATMENT PLANT DESIGN CRITERIA

Parameter Value
Oxidant Sodium Hypochlorite
Average Oxidant Dose 2.1 mg/L
Average FeCl3 Dose ~3 mg/L as Fe
Number of Filters 18
Filter Diameter 36 inches
Filter Surface Area (1 Filter) 7.07 ft2
Total Filter Surface Area 127 ft2
Media AS-741 M Pyrolusite
Grain Size (US Mesh) 20-40 Mesh
Media Depth 36 inches
Hydraulic Loading 12.9 gpm/ft2

CEE 483 February 25, 2009

New Filters

CEE 483 February 25, 2009

New Filters

CEE 483 February 25, 2009

New Onsite Hypochlorite System

CEE 483 February 25, 2009

 TREATMENT PLANT PERFORMANCE

Contaminant Raw Water Finished Water Percent

Average (Range), Average (Range), Removal
mg/L mg/L
Mn 0.14 (0.12-0.40) 0.007 (0-0.035) 95%
Fe 0.34 (0.12-1.73) 0.01 (0-0.05) 97%
As 0.014 <0.002 >86%

CEE 483 February 25, 2009

 TREATMENT PLANT PERFORMANCE
14

12 Field Data
Lab Data
Arsenic in Treated Water, ug/L

MCL
10

0
0 1 2 3 4 5 6 7

Total Iron (Raw plus added), mg/L as Fe

CEE 483 February 25, 2009
 ARSENIC REMOVAL

Initial start-up testing indicated that 2-3 mg/L

as Fe would remove As below MCL to the 6-
8 g/L range.

First compliance sample - <2 g/L

Future optimization testing will investigate

improved As during filter runs.

CEE 483 February 25, 2009

 CONCLUSIONS
Initial taste and odor issues possibly caused by ozone
interactions with organic material and accumulated biofilm.

Ambient air and ozone showed no difference in Mn removal

for the Birm system.

Chlorine oxidation and pyrolusite filtration performed better

at Mn and Fe removal than ozone and Birm.

Chlorine oxidation and pyrolusite filtration appear to have

greatly improved taste and odor issues. Chlorine injection
prior to filtration limits biofilm.

FeCl3 addition to chlorine oxidation/pyrolusite filtration can

remove As below MCL.

CEE 483 February 25, 2009

 Case Study No. 2
Klickitat - Unincorporated Community
Served By Klickitat PUD
450 Residents

Klickitat River Source until 1990

Two Groundwater Wells/Softener since 1990

CEE 483 February 25, 2009

 Well Raw Water Quality
Parameter Value
Fe 2.2 2.9 mg/l (0.3 MCL)
Mn <0.015 0.06 mg/l (0.05 MCL)
pH 5.5 7.5 generally 6.5 6.9
Hardness 50 350 mg/l as CaCO3
Alkalinity 290 350 mg/l as CaCO3
H2 S Present at times

CEE 483 February 25, 2009

Water Quality Issues
Iron and Manganese

Low pH

Hardness

Hydrogen Sulfide

CEE 483 February 25, 2009

 Initial Situation
Treatment since 1990
Ion Exchange Softener
Bulk 12.5% Sodium Hypochlorite
250 gpm Capacity
High Number of Customer Complaints
Rusty, chlorinous, bitter, metallic, cloudy, salty, septic
69% of customer surveyed bought bottled water.
Corrosion of WTP Equipment
Frequent Wastewater Plant Disruptions

CEE 483 February 25, 2009

Decision Factors
Pending Failure
EPA Grant
Test Well 3000 Ft. Away
Fe/Mn Present
H2S Present
Higher pH
Lower Hardness
WWTF Discharge Issues
Operations & Maintenance

CEE 483 February 25, 2009

Plant Corrosion

CEE 483 February 25, 2009

Plant Corrosion

CEE 483 February 25, 2009

 Project Parameters
Iron/Manganese Targeted

Pilot Study

Treat Existing Wells

pH Not Treated

Future Options for Test Well and

Other Treatment Left Open

CEE 483 February 25, 2009

 Modifications
Remove Softener System

Install Iron Oxidation/Filtration

Bulk Hypochlorite

Pyrolusite Filtration

Repair Existing Building

CEE 483 February 25, 2009

Pyrolusite Design Parameters

Parameter Value
Total Capacity 250 gpm
Pressure 100 psi
Number of Filters 4
Filter Diameter 36 inches
Loading Rate 8.8 gpm/ft2
Backwash Rate 30 gpm/ft2
Chlorine Residual 0.6 mg/l

CEE 483 February 25, 2009

Installation And Startup

CEE 483 February 25, 2009

 Comparison Of Processes
Parameter (MCL) Raw Softener Fe/Mn Oxidation/Filtration

Fe (0.3 mg/L) 2.2 2.9 mg/l <0.05-1.1 .01-.05

Mn (0.05 mg/L) <0.015 0.06 mg/l 0.03 ND

pH 6.5 6.9 6.5 6.9 6.4 6.8

Hardness 50 350 mg/l as 1.0-6.0 mg/l as 270 mg/l as CaCO3

CaCO3 CaCO3

CEE 483 February 25, 2009

CEE 483 February 25, 2009
Ventilated Hypochlorite Closet

CEE 483 February 25, 2009

 Existing Lixator
Becomes A..

Site Plan

CEE 483 February 25, 2009

 New Backwash
Settling Basin

Flow Control Outlet

CEE 483 February 25, 2009

 Improvement Results
Finished Water Improvements
No Fe/Mn or H2S
Hardness Present
Low pH
Customer Satisfaction Initially High
Customer Complaints Have Not
Disappeared Altogether
Metallic Taste
Additional Work in Future Phases
CEE 483 February 25, 2009
 Questions ?

CEE 483 February 25, 2009