5 Epa As Course Coag and PPT Processes Yujungchang

Arsenic Removal by Coagulation &
Precipitation Processes
Presentation Prepared by:
Joe Chwirka - Camp Dresser & McKee
(chwirkajd@cdm.com)
Bruce Thomson - University of New Mexico
(bthomson@unm.edu)
Presented by: YuJung Chang HDR Engineering, Inc.
Coagulation-Filtration - Chwirka & Thomson
Introduction
Arsenic removal by coagulation & filtration is effective for
many applications
Presentation will discuss:
Chemistry of the process
Variables affecting process performance (especially pH
& coagulant dose)
Process variations
Coagulation & granular media filtration
Coagulation & membrane filtration
Design considerations
Acid-Base Chemistry of As(V)
1.2
1.0
H3AsO4
Fraction
0.8
2-
HAsO4
H2AsO4
3-
AsO4
0.6
0.4
0.2
0.0
0
10
12
14
pH
Acid-Base Chemistry of As(III)
1.2
AsO 3
1.0
3-
H3AsO3
Fraction
0.8
H2 AsO3
0.6
HAsO3
2-
0.4
0.2
0.0
0
10
12
14
pH
Redox Chemistry of As
20
1 .0
15
H 3A sO
H 2A sO
10
.5
5
H A sO
pe
H 3A sO
2-
E h (v o lts )
A sO
34
A s 2 S 3 (s )
-5
-.5
H 2A sO
-1 0
H A sO
23
A sO
33
-1 5
0
Coagulation-Filtrationp H-
10
12
Chwirka & Thomson
14
Solubility of As(III) Compounds
0
-1
log Concentration
-2
Arsenolite (As2O3)
-3
Claudetite (As2O3)
-4
Orpiment (As2S3)
-5
-6
-7
-8
-9
-10
0
10
12
14
pH
Solubility of As(V) Species

0
Ca3(AsO4)2
-2
log Concentration
-4
Fe3(AsO4)2
-6
Mn3(AsO4)2
AlAsO4
Ca3(AsO4)2
CrAsO4
Cu3(AsO4)2
Fe3(AsO4)2
FeAsO4
Mn3(AsO4)2
LaAsO4
-8
-10
-12
-14
0
FeAsO4
Cu3(AsO4)2
AlAsO4
CrAsO4
LaAsO4
6
10
12
14
pH
Important Points
As has two oxidation states - As(III) & As(V)
As(III)
Non-ionic (H3AsO3) at neutral pH
High solubility
More toxic to many organisms
As(V)
Ionic (H2AsO4-/HAsO42-) at neutral pH
Some phases are less soluble
More reactive in solution:
Membranes
IX
Adsorption
Coprecipitation
Coprecipitation involves removal of two or more
constituents by a precipitation reaction. Coprecipitation of
As with Fe(OH)3 is an effective treatment process:
FeCl3 + 3H2O = Fe(OH)3(s) + 3H+ + 3ClPoints:
Produces HCl which will lower pH
Typical Fe dose ~10-4 M, whereas As conc. ~10-7 M, hence
As is minor component within precipitate
As likely removed by adsorption onto Fe(OH)3 surface with
subsequent enmeshment as floc particle grows
Al(OH)3 also effective
Solubility of Fe(OH)3
0
-2
Solubility of Fe(OH)3
log Conc.
-4
-6
Fe(OH)4-
-8
Fe3+
-10
-12
Fe(OH)2+
FeOH2+
-14
0
10
12
14
pH
10
Effect of pH on Surface Charge of Fe(OH)3
1.2
+
FeOH2
1.0
FeO
o
FeOH
0.8
Fraction
0.6
0.4
0.2
0.0
0
10
12
14
pH
11
Covalent Bond Formation

(Grossl et al., 1997)
Fe
O H
O
Fe
As
O
O H
O H
k1
G o e t h it e S u rf a c e
k -1
O H
Fe
As
O
O
k2
Fe
Fe
k -2
As
Fe
O H
O H
+ H 2O
M o n o d e n ta te
S u r f a c e C o m p le x
+ O H-
B id e n ta t e
S u r f a c e C o m p le x
12
pH of Zero Point of Charge

Electrostatic attraction is important first step in adsorption
pHzpc = pH at which net surface charge = 0
Surface is positive at pH < pHzpc
Most clay minerals have pHzpc < 6
Hence poor adsorption
Clays dominate surface chemistry of soils
Fe(OH)3 and Al2O3 have relatively high pHzpc
Good adsorbents of As(V)
13
As Removal by Conventional Treatment

(McNeill & Edwards 1997)
Survey of conventional coagulation-flocculation water
treatment plants
Correlate As removal to removal of Fe, Mn, & Al
K[Fe]
As Fraction Removed
1 K[Fe]
[Fe] = Iron Precip. Formed (mM)
14
As Removal by Conventional Trt. - 2
100
90
As Removal (% )
80
70
60
50
40
30
[Fe]
20
[Fe]+[Al]
10
0
0
0.02
0.04
0.06
0.08
0.1
Precipitate Formed (mM)

15
As Removal by Conventional Trt. - 3

Strong correlation to removal of Fe & use of FeCl3 as
coagulant
Weaker correlation to removal of Al & use of Alum
Possible sorption onto colloidal Al(OH)3 which passes
through granular media filters
Improved As removal achieved by minimizing effluent
total Al concentration
Note the importance of particulate As
16
Arsenic Removal vs FeCl3 Dose, Albuquerque NM
50
10
9.5
40
30
8
7.5
20
Filtrate pH
Residual As, ug/L
8.5
Residual Arsenic
Filtrate pH
6.5
10
6
5.5
5
0
10
15
20
FeCl3 Dose, mg Fe/L
17
100.0
10.00
90.0
9.00
80.0
8.00
70.0
7.00
60.0
6.00
50.0
5.00
40.0
4.00
30.0
3.00
20.0
2.00
10.0
1.00
0.0
0.00
0
20
40
60
80
100
As
pH
Arsenic, ug/L
Ambient pH: FeCl3 vs As Leakage, NAS Fallon
pH
120
FeCl3, mg/L
18
El Paso Jar Testing
25
8.5
Arsenic
pH
8
7.5
15
7
10
pH
Arsenic Leakage, ug/L
20
6.5
6
5.5
0
0
10
15
20
25
30
35
40
FeCl3 Dose, m g/L
19
pH Adjustment with CO2, NAS Fallon, NV
pH Reduction with CO2

100
90
R esidual As, ug/L
80
70
60
pH 6.0
pH 6.8
50
40
30
20
10
0
0
10
12
14
16
FeCl3 Dose, mg/L
20
Silica Impacts Arsenic Removal

at pH 7.0 and Above
As Removal as a Function of Silicate and pH
Effluent As, ug/L
25
pH 8.5
20
15
pH 6.5
pH 7.5
pH 8.5
pH 7.5
10
5
pH 6.5
0
0
10
20
30
40
50
60
Silicate, mg/L
FeCl3 Dose: 4 mg/L

After Clifford and Ghurye
21
Silica Speciation with pH

1.2
H4SiO4
1.0
H3SiO4-
Fraction
0.8
0.6
H2SiO420.4
0.2
0.0
0
10
12
14
pH
22
Silica in US Water Supplies (NAOS)
Cumulative Percentage (%)
100
80
60
Surface Waters
40
Ground Waters
20
0
0
10
20
30
40
50
60
70
Soluble SiO2 (mg/L)
After Davis and Edwards

23
Polymeric Silica
[Si]polym er/[Si]total (%)
100
80
50 mg/L
60
17 mg/L
40
5 mg/L
20
0
5.0
5.5
6.0
6.5
7.0 7.5
pH
8.0
8.5
9.0
9.5
After Davis and Edwards
24
Coagulation/ Filtration
Use pressure filters
Direct Filtration frequently used for iron and manganese
removal.
Limited to low ferric dose applications.
High coagulant dose will result in frequent backwash
requirements
Increased residuals production & handling costs
Increased production of wastewater
25
Schematic of Coagulation/ Filtration

FeCl3
Pressure Filter
CO2
CO2
Treated
Water
Raw Water
Aeration
Rapid Mix
Solids to
Dewatering
Solids to Landfill
26
Calculation of Filter Loading Limitation

Rule of Thumb, no more than 10 mg/L of FeCl3
Limit Solids Loading to 0.1 lbs/SF
May need to add sedimentation
27
Vertical Pressure Filter
28
Direct Filtration Performance

(Based on 0.1 lbs Solids/sf)
Filter Run Time, Hrs
Filter Performance at 3 gpm/sf

130
120
110
100
90
80
70
60
50
40
30
20
10
0
1
10
11
12
13
14
15
Ferric Chloride, mg/L
29
Backwash Water as Percent of Production

(Based on 250 gal/sf)
Wastewater Production at 3 gpm/sf
16.0%
14.0%
Wastewater, %
12.0%
10.0%
8.0%
6.0%
4.0%
2.0%
0.0%
0
10
12
14
16
Ferric Chloride Dose, mg/L
30
C/F O&M Issues

Large backwash volume (20 gpm/sf for 10 minutes)
Tanks may need internal painting, 10 yr intervals. Use 316
SST.
Standby filters, typically provided, but need to evaluate.
Pneumatic or electric valve operators.
31
Coagulation/ Pressure Filtration
Particle size
Particle breakthrough
backwash requirements
filter ripening
Backup Filters
32
Coagulation/ Microfiltration
Pilot tested in Albuquerque, 1998
Pilot tested in NAS Fallon, NV, 2001
Pilot tested in El Paso, TX, 2001/2002
Fallon Paiute Shoshone Tribe: 0.5 mgd
City of Albuquerque: 2.3 mgd
33
Microfiltration General Concepts
Low Operating Pressure, 5 - 30 psi

0.1 to 0.2 micron pore size
Water flow from Outside to the Inside
Air-Water Backwash
Backwash Every 25 to 30 minutes (95% recovery)
Flux rate defined as Gallons/SF/Day (GFD)
Chemical Cleaning Frequency > 30 days
34
What is C/MF?
FeCl3
Microfiltration
Unit
CO2
CO2
Treated
Water
Raw Water
Aeration
Rapid Mix
Solids to
Dewatering
Solids to Landfill
35
Pressure Driven Membranes

0.001
0.01
0. 1
1.0
10
100
1000
Sand
Dissolved Organics
Bacteria
Viruses
Salts
Colloids
Cysts
Media Filtration
Microfiltration
Ultrafiltration
Nanofiltration
Reverse Osmosis
36
MF Process Operates in
Direct Filtration Mode
Filtrate
Feed
Feedwater
(with
contaminants)
Filtrate
37
Solids are Removed from Module

by an Air-Water Backwash
Air
Air
(100
psig)
Feedwater
3
38
Coagulation/ Microfiltration
Pilot tested in Albuquerque, 1998
Pilot tested in NAS Fallon, NV, 2001
Pilot tested in El Paso, TX, 2001/2002
Fallon Paiute Shoshone Tribe: 0.5 mgd
City of Albuquerque: 2.3 mgd
39
What is C/MF?
FeCl3
Microfiltration
Unit
CO2
CO2
Treated
Water
Raw Water
Aeration
Rapid Mix
Solids to
Dewatering
Solids to Landfill
41
Pressure Driven Membranes

0.001
0.01
0. 1
1.0
10
100
1000
Sand
Dissolved Organics
Bacteria
Viruses
Salts
Colloids
Cysts
Media Filtration
Microfiltration
Ultrafiltration
Nanofiltration
Reverse Osmosis
42
MF Process Operates in
Direct Filtration Mode
Filtrate
Feed
Feedwater
(with
contaminants)
Filtrate
43
Solids are Removed from Module

by an Air-Water Backwash
Air
Air
(100
psig)
Feedwater
3
44
Pall Microfilter
45
Memcor Performance
NAS Fallon, 15 mg/L FeCl3
Transmembrane Pressure
25
32 GFD
20
15
psi
27 GFD
27 GFD
38 GFD
(No FeCl3)
10
25 GFD (No FeCl3)
0
0
20
40
60
80
Elapsed Time [days]
100
120
46
Memcor Cleaning Efficiency

NAS Fallon, Citric Acid
TMP vs. Normalized Flux
9
8
TM P [psi]
7
6
5
Start-Up
Post Clean
3
2
1
0
0
10
20
30
40
50
Normalized Flux [gfd @ 20C]
47
Pall Performance
NAS Fallon, FeCl3 45 mg/L
20
54 GFD
TMP, psi
15
54 GFD
42GFD
10
5
0
0
10
20
30
40
50
60
70
80
90
Elapsed Time, Days
48
El Paso C/MF Pilot Studies
49
El Paso Pilot Studies

Only Pall MF tested
Ferric dose 10 mg/L
pH lowered to 6.8 with CO2
50
El Paso
Pall Performance
24
20
Well Shutdown for
Repair
TMP (psi)
16
15 mg/L FeCl3, pH 6.8,

89.8 gfd, >100 Day CIP
12

0
0
500
1000
1500
2000
2500
Operational Hours
3000
3500
4000
51
Fallon Paiute Shoshone Tribe C/MF PFD

CO2
Cl2
Treated
Water to
Distribution
System
Rapid Mix
M
CO2
Well 1
Microfilter
Well 2
Static Mixer
Lowry
Aeration
System
Ferric
Chloride
Finished
Water
Sump
Solids
Recycle
Recycle
Sump
Lamella
Plate
Thickener
Liquids to
Sewer
Dewatered
Solids to
Landfill
Filter
Bottom
Dumpster
52
Fallon Paiute Shoshone Tribe C/MF
53
Fallon Paiute Shoshone Tribe As Treatment

Faciliy
54
Fallon Paiute Shoshone Tribe Start-up

December 2004
55
C/MF Summary
Emerging Technology for Arsenic Treatment
Can be designed for high flux rates with Low TOC
groundwater
Optimize solids loading by pH pre-treatment
Cost competitive with other technologies
56
Recent Studies on Particle Size Filtration and

Arsenic Removal
57
C/MF O&M Issues

Membrane Replacement: Pall warrantees membranes for
10 years, prorated.
Chemical cleaning with citric acid, can not be recycled,
must be disposed of.
Provide sufficient replacement parts, not system
redundancy.
58
Comparison of C/MF to Pressure Filters at the Fallon

Paiute Shoshone Tribe
Capital Cost Summary

Total Estimated C/MF Facility Cost
Summary of Annual O&M Costs
Total Estimateded O&M for Treatment, $/yr
Unit O&M Costs for C/MF
Present Worth Analysis
Total Present Value of Facitlities
Annual Amortized Cost of Capital & O&M
Total Unit Cost of Water Produced, $/1,000 gals
Pressure Filters
$1,252,998
C/MF
$987,898
$71,436
$0.77
$82,392
$0.89
$2,087,000
$125,220
1.38
$1,948,000
$116,880
1.29
59
Residuals Characteristics for C/MF and C/F
C/MF around 4% to 5 % Backwash.

C/F around 5% to 10% Backwash.
Recycle the backwash water to minimize wastewater.
Ferric residuals will pass TCLP, however, may not pass the
Cal WET.
60
Residuals Handling
Mechanical dewatering will be complicated: Ferric sludge is
difficult to dewater
Need body additives, Diatomaceous Earth
Filter Bottom Dumpsters and polymer for small applications.
Solids drying ponds:
Ponds need to be lined.
Anaerobic conditions may release the As.
Provide access for sludge removal equipment.
61
Concurrent Iron, Manganese, and Arsenic

Drinking Water Standards
Fe: Secondary Standard of 0.30 mg/L
Mn: Secondary Standard of 0.05 mg/L
62
Iron and Arsenic Removal

Oxidize Fe with Cl2 or O3
Adsorb As onto Fe(OH)3 precipitate
pH needs to be around 7.3
63
Manganese and Arsenic Removal
As requires low pH for adsorption

Mn requires high pH (>10) for oxidation with Cl2
Mn oxidation by ClO2 is rapid & appears to be
independent of pH
ClO2 reported to be ineffective for As(III) oxidation.
May need to add Cl2 in addition
64

5 Epa As Course Coag and PPT Processes Yujungchang

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Arsenic Removal by Coagulation &

Coagulation-Filtration - Chwirka & Thomson

Coagulation-Filtration - Chwirka & Thomson

Acid-Base Chemistry of As(V)

Acid-Base Chemistry of As(III)

Chwirka & Thomson

Solubility of As(III) Compounds

Coagulation-Filtration - Chwirka & Thomson

Solubility of As(V) Species

Coagulation-Filtration - Chwirka & Thomson

Coagulation-Filtration - Chwirka & Thomson

Effect of pH on Surface Charge of Fe(OH)3

Coagulation-Filtration - Chwirka & Thomson

Covalent Bond Formation

pH of Zero Point of Charge

Coagulation-Filtration - Chwirka & Thomson

As Removal by Conventional Treatment

Coagulation-Filtration - Chwirka & Thomson

As Removal by Conventional Trt. - 2

Precipitate Formed (mM)

As Removal by Conventional Trt. - 3

Coagulation-Filtration - Chwirka & Thomson

Arsenic Removal vs FeCl3 Dose, Albuquerque NM

Residual As, ug/L

FeCl3 Dose, mg Fe/L

Coagulation-Filtration - Chwirka & Thomson

Ambient pH: FeCl3 vs As Leakage, NAS Fallon

Coagulation-Filtration - Chwirka & Thomson

El Paso Jar Testing

Arsenic Leakage, ug/L

FeCl3 Dose, m g/L

Coagulation-Filtration - Chwirka & Thomson

pH Adjustment with CO2, NAS Fallon, NV

pH Reduction with CO2

R esidual As, ug/L

FeCl3 Dose, mg/L

Coagulation-Filtration - Chwirka & Thomson

Silica Impacts Arsenic Removal

Effluent As, ug/L

FeCl3 Dose: 4 mg/L

Coagulation-Filtration - Chwirka & Thomson

Silica Speciation with pH

Coagulation-Filtration - Chwirka & Thomson

Silica in US Water Supplies (NAOS)

Cumulative Percentage (%)

Soluble SiO2 (mg/L)

After Davis and Edwards

[Si]polym er/[Si]total (%)

After Davis and Edwards

Coagulation-Filtration - Chwirka & Thomson

Coagulation-Filtration - Chwirka & Thomson

Schematic of Coagulation/ Filtration

Coagulation-Filtration - Chwirka & Thomson

Calculation of Filter Loading Limitation

Coagulation-Filtration - Chwirka & Thomson

Vertical Pressure Filter

Coagulation-Filtration - Chwirka & Thomson

Direct Filtration Performance

Filter Run Time, Hrs

Filter Performance at 3 gpm/sf

Ferric Chloride, mg/L

Coagulation-Filtration - Chwirka & Thomson

Backwash Water as Percent of Production