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In-Situ PFAS Remediation Using Colloidal Activated...
Transcript of In-Situ PFAS Remediation Using Colloidal Activated...
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In-Situ PFAS Remediation Using Colloidal Activated Carbon
Copyright Porewater Solutions (2019) 1
Presented By Grant R. Carey, Ph.D.
Ottawa, Ontario, Canada [email protected]
CACBarrier
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Co-Author Acknowledgement
Copyright Porewater Solutions (2019) 2
Seyfollah Gilak Hakimabadi Dr. Anh Pham Rick McGregor Dr. Brent Sleep
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Agenda
1. Colloidal Activated Carbon (CAC) Concepts
2. Canadian Site – PFOS Longevity Modeling 3. AFFF Site Longevity Assessment
• Groundwater plumes (PFOS, PFOA, PFHxS)
• Isotherm Results
• CAC Longevity modeling
Copyright Porewater Solutions (2019) 3
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Colloidal Activated Carbon Concepts
4 Copyright Porewater Solutions (2019)
Section 1
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Activated Carbon
Copyright Porewater Solutions (2019) 5
GAC 0.5-1 mm
Granular Activated Carbon 0.5 to 1 mm
Powdered Activated Carbon 0.01 to 0.1 mm
Colloidal Activated Carbon 0.001 to 0.002 mm
750 microns 25 microns 1.5 microns
GAC
PAC
CAC
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In-Situ Colloidal Activated Carbon (CAC)
Copyright Porewater Solutions (2019) 6
SEM Image of CAC attached to sand grains.
Courtesy of Regenesis
• Polymer enables distribution and prevents clogging
• Polymer biodegrades/ flushed downgradient
• Low-pressure injections minimize preferential pathways and enhanced distribution (Rick McGregor, 2018)
Courtesy of Rick McGregor, IRSL
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Conceptual Cross-Section
Copyright Porewater Solutions (2019) 7
Flow
PFAS Plume
Ground Surface
Vadose Zone
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PFAS Mass Flux Reduction Using CAC Injection
Copyright Porewater Solutions (2019) 8
Flow
Injection Wells
CAC Zone PFAS Plume
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PFAS Mass Flux Reduction Using CAC Injection
Copyright Porewater Solutions (2019) 9
Flow
CAC Zone PFAS Plume Detachment
PFAS Plume
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PFAS Mass Flux Reduction Using CAC Injection
Copyright Porewater Solutions (2019) 10
Flow
CAC Zone PFAS Plume Detachment
PFAS Plume
Longevity depends on:
• fCAC
• CAC zone length
• Regulated PFAAs
• Co, velocity
• Isotherms
• Competitive effects
After CAC saturation:
• Additional injection or new alternative
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Canada Site Case Study: CAC Longevity Modeling
Section 3
11 Copyright Porewater Solutions (2019)
Remediation Journal, 2018 Remediation Journal, 2019
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Central Canada Site: Furniture Manufacturer • Petroleum hydrocarbons, & PFOS-PFOA at low
ug/L
• Remedy implemented by Rick McGregor (2016) • CAC injected with ORC
• Low-pressure injections to avoid fracturing soil
• 3 m well spacing
• Single injection event over one week period
• Total treatment cost: $100,000
• Two years of monitoring data indicate that PFAS remain below target criteria
Rick McGregor, President InSitu Remediation Services Limited
12 Copyright Porewater Solutions (2019)
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PFOS Concentrations versus Time
Copyright Porewater Solutions (2019) 13
W-1 MW-1MW-11
MW-2
MW-4
MW-5
MW-7
MW-8
0 5 10
Scale, in meters
CAC Zone
0
200
400
600
800
1000
1200
1400
Jan-16 Jul-16 Dec-16 Jul-17 Dec-17 Jul-18
Conc
entr
atio
n (n
g/L)
Date
MW-1
0
200
400
600
800
1000
1200
1400
Jan-16 Jul-16 Dec-16 Jul-17 Dec-17 Jul-18
Conc
entr
atio
n (n
g/L)
Date
MW-2
0
200
400
600
800
1000
1200
1400
Jan-16 Jul-16 Dec-16 Jul-17 Dec-17 Jul-18
Conc
entr
atio
n (n
g/L)
Date
MW-5
0
200
400
600
800
1000
1200
1400
Jan-16 Jul-16 Dec-16 Jul-17 Dec-17 Jul-18Co
ncen
trat
ion
(ng/
L)Date
MW-8
Pre-injection Pre-injection
Pre-injection Pre-injection
Source Zone
MW-90 5 10
Scale, in metersScale, in meters
0 5 10 Flow
N
Detected
Non-detect
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PFSA Radial Diagrams (2017)
Copyright Porewater Solutions (2019) 14
MW-1
MW-2
MW-5
MW-8
MW-90 5 10
Scale, in meters
101001,00010,000
PFOSA
PFDS
PFOS
PFHxS
PFBS
October 2017
Spring 2016
March 2018: all ND at MW-1, MW-8
CAC Zone
Source Zone
Flow
N
Concentrations in ng/L
Non-detect (plotted at one-half of the detection limit)
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PFCA Radial Diagrams (2017)
Copyright Porewater Solutions (2019) 15
MW-1
MW-2
MW-5
MW-8
MW-90 5 10
Scale, in meters
101001,00010,000
PFDoA
PFUnA
PFDAPFNA
PFOA
PFHpA
PFHxAPFPeA
PFBA
Concentrations in ng/L
Non-detect (plotted at one-half of the detection limit)
October 2017
Spring 2016
March 2018: all ND at MW-1, MW-8
CAC Zone
Source Zone
Flow
N
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ISR-MT3DMS Model: PFOS Mass Balance in CAC Zone
Copyright Porewater Solutions (2019) 16
Tota
l PFO
S M
ass
On-
Site
(mg)
a) Prior to CAC Injection b) Immediately after CAC Injection
0
100
200
300
400
500
1 20
100
200
300
400
500
Carey et al. (2019)
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PFAS-CAC Isotherms
17 Copyright Porewater Solutions (2019)
15 mL plastic test tube Rotate for 1-3 day
Polycarbonate ultracentrifuge tube
Centrifugation
mass-labelled standard
& methanol
HPLC vial
Plumestop®PFAS 1 – 1000 ug/L
Courtesy of Dr. Anh Pham, University of Waterloo
Note: Site-specific isotherms and pilot tests are recommended.
Seyfollah Gilak Hakimabadi
Dr. Anh Pham [email protected]
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Isotherms: AFFF Site Groundwater Sample
18
AnalyteResult(ug/L)
PFBS 2.71PFPeS 2.46PFHxS 65.5PFHpS 3.13PFOS 208PFDS <0.020
Total PFSAs: 281.8
AnalyteResult(ug/L)
PFBA 1.14PFPeA 10PFHxA 11.6PFHpA 2.73PFOA 20.8PFNA 0.552PFDA 0.092
PFUnDA <0.020PFDoDA <0.020PFTrDA <0.050PFTeDA <0.050Total PFCAs: 46.9
AnalyteResult(ug/L)
FOSA 2.04MeFOSA <0.050EtFOSA <0.050MeFOSE <0.050EtFOSE <0.020
MeFOSAA <0.020EtFOSAA <0.0204:2 FtS 0.226
6:2 FtS 40.48:2 FtS 17.5
10:2 FtS <0.020Total Precursors: 60.2
PFSAs PFCAs Precursors
Copyright Porewater Solutions (2019)
TOC: 23.8 mg/L
Note: GW sample was provided by Dr. Charles Schaeffer (CDM).
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PFAS-CAC Isotherms
19 Copyright Porewater Solutions (2019)
𝑆𝑆 = 𝐾𝐾𝑓𝑓𝐶𝐶𝑎𝑎 Freundlich Isotherm:
In-situ Retardation Coefficient: 𝑅𝑅𝐶𝐶𝐶𝐶𝐶𝐶 = 1 +ρ𝐵𝐵θ
𝑓𝑓𝐶𝐶𝐶𝐶𝐶𝐶𝐾𝐾𝑓𝑓𝑎𝑎𝐶𝐶𝑎𝑎−1
Seyfollah Gilak Hakimabadi
Dr. Anh Pham [email protected]
0
5
10
15
20
25
30
35
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
Soil
Conc
entr
atio
n (m
g/g)
Aqueous Concentration (mg/L)
Solution type: PFOS-only AFFF site sampleKf (mg1-a La / g): 143 4.9
a (dimensionless): 0.59 0.24
GW sample from AFFF site
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Simulated PFOS Plume Detachment
20 Copyright Porewater Solutions (2019)
0.97 1.45
<0.02
0.780.37
<0.02
<0.02
0.28
<0.02
<0.02
0.57
0 10 20
Scale, in meters
PFOS (ug/L)
a) Prior to CAC injection
Source area
b) 180 days after CAC injection
N
Source area CAC Zone
Flow
Flow
Carey et al. (2019)
PFOS Md = 0.6 g/y
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Simulated PFOS Plume versus Time
Copyright Porewater Solutions (2019) 21
a) t=1 year
a) t=10 years
a) t=20 years
a) t=30 years
a) t=40 years
a) t=50 years
0 10 20
Scale, in meters
PFOS (ug/L)
CAC Zone Source Area
N
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AFFF Site Model
22 Copyright Porewater Solutions (2019)
Section 3
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Groundwater Plumes
23
0 500 1000
Scale, in feet
PFOA PFOS PFHxS
N N N
GV to 10 ug/L
GV: Guidance Value
10 to 100 ug/L
100 to 1,000 ug/L
>1,000 ug/L
Copyright Porewater Solutions (2019)
GV = 0.07 ug/L GV = 0.07 ug/L GV = 0.56 ug/L
Former FTA Former FTA Former FTA
Note: plumes based on GW samples collected in 2011 through 2015
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Plume Characteristics
24 Copyright Porewater Solutions (2019)
PFHxS PFOS PFOAA 992 321 213B 92 43 32C 74 42 32D 90 54 41E 0.9 n/a n/a
Mass Discharge (g/y)Transect
0 500 1000
Scale, in feet
A
N
B
C
D
E
0.07 to 10 ug/L
10 to 100 ug/L
100 to 1,000 ug/L
>1,000 ug/L
PFHxS PFOS PFOAA 617 345 206B 106 46 74C 70* 40* 35*D 60* 35* 35*E 0.44 0.008 0.05
Maximum Concentration (ug/L)Transect
* Conservative Estimate
Groundwater velocity ~ 30 m/year
PFHxS
x = 150 ft
x = 700 ft
x = 1300 ft
x = 2100 ft
Former FTA
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Preliminary PFAS-CAC Isotherms
25 Copyright Porewater Solutions (2019)
Kf : mg1-a La / g; a: dimensionless
Seyfollah Gilak Hakimabadi
Dr. Anh Pham [email protected]
K f a K f aPFOS 143 0.59 4.9 0.24PFOA 25 0.56 0.5 0.22PFHxS 41 0.42 1.2 0.22PFBS 12 0.68PFBA
PFPeAPFHxA
Single Species AFFF Site GW SampleAnalyte
IN PROGRESS
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1-D PFAS CAC Longevity Model
Copyright Porewater Solutions (2019) 26
Co*
Velocity: 30 m/year
CAC Zone Breakthrough Time?
12 to 24 m
* Based on Transect D concentrations PFOA: 35 ug/L PFHxS: 60 ug/L
Note: PFOS longevity longer than PFHxS and PFOA, so was not modeled.
fCAC: 0.02% to 0.2%
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0
10
20
30
40
50
60
70
CAC
Long
evity
(yea
rs)
PFOA PFHxS
CAC Longevity for PFOA and PFHxS at AFFF Site
Copyright Porewater Solutions (2019) 27
4 y 6 y 10 y
15 y 20 y
30 y
40 y
60 y
fcac = 0.02% fcac = 0.05% fcac = 0.10% fcac = 0.20%
Longevity α fcac and LENGTH of sorption zone
Canadian Site
Potentially Attainable
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Conclusions and Recommendations • CAC is viable as an interim remedy for PFAS mass flux
reduction at some sites, but not all sites • May be able to offset longer term costs until more
regulatory and technological certainty • Additional laboratory and field-scale testing are needed,
and in progress • Variation in sorption capacity at range of PFAS sites? • Performance with shorter-chain PFAAs? • Attainable fCAC? • Competitive sorption effects?
Copyright Porewater Solutions (2019) 28
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• PFAS isotherms • PFCAs, PFSAs, FtS • Sensitivity to various conditions
• CAC colloidal transport • Fate and transport model development • Field-scale pilot tests • Site characterization & visualization methods • Seeking GW samples
PFAS Remediation Research Group
• Univsersity of Waterloo (Dr. Anh Pham) • University of Toronto (Dr. Brent Sleep) • Carleton University (Dr. Paul Van Geel) • Porewater Solutions (Dr. Grant Carey) • IRSL (Rick McGregor)
29 Copyright Porewater Solutions (2019)
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Questions?
30
Grant Carey, Ph.D. Porewater Solutions
613-270-9458
[email protected] www.porewater.com
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Copyright Porewater Solutions (2018)
PFOS Sorption Isotherms: GAC, PAC, and CAC
0
1
10
100
1,000
10,000
100,000
1,000,000
0.0000001 0.000001 0.00001 0.0001 0.001 0.01 0.1 1 10 100 1000
Batc
h Te
st S
orbe
d Co
ncen
trat
ion
(mg/
Kg)
Aqueous Concentration (mg/L)
CAC-Pham & Gilak (2018) CAC-Regenesis
GAC-Yu et al (2009) PAC-Yu et al (2009)
GAC-Senevirathna et al (2010) GAC-Hansen et al (2010)
PAC-Hansen et al (2010) Ochoa-Herrera & Sierra-Alvarez (2008) - high Cw
Ochoa-Herrera & Sierra-Alvarez (2008)-lower Cw CAC-extrapolated
Carleton U. (AFFF site GW)
Regenesis (pure solution)
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Copyright Porewater Solutions (2019) 32
GAC Bench-Scale Test (Based on McCleaf et al., 2017)
y = 0.9466e-2E-05x R² = 0.9033
y = 0.9939e-1E-05x R² = 0.9251
y = 1.0027e-8E-06x R² = 0.9593
y = 1.0154e-7E-06x R² = 0.9578
y = 1.2437e-7E-05x R² = 0.9014
y = 0.9897e-3E-05x R² = 0.8716
-20%
0%
20%
40%
60%
80%
100%
0 20,000 40,000 60,000 80,000 100,000 120,000 140,000
Rem
oval
Effi
cien
cy
Pore Volumes
Removal Efficiency Decline Rates: PFCAs (shorter chained)
PFBA PFPeA PFHxA PFHpA
PFOA PFNA PFBA-Trend PFPeA
Expon. (PFHxA) Expon. (PFHpA) Expon. (PFOA) Expon. (PFNA)
Expon. (PFBA-Trend) Expon. (PFPeA)
Source: McCleaf et al. (2017)
0.1 m
0.05 m
Velocity = 61 m/day Retention time = 2 minutes
Length = 0.1 m Mass flux = 0.002 g/m2/day
Desorption
Carey et al. (2019, in preparation)
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y = 1.011e-4E-06x R² = 0.9539
y = 1.0074e-1E-05x R² = 0.9058
y = 1.0258e-7E-06x R² = 0.9653
y = 1.0255e-4E-06x R² = 0.9454
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 20,000 40,000 60,000 80,000 100,000 120,000 140,000
Rem
oval
Effi
cide
ncy
Pore Volumes
FOSA
PFBS
PFOS
PFHxS
GAC Bench-Scale Test (Based on McCleaf et al., 2017)
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Copyright Porewater Solutions (2019) 34
GAC Full-Scale Pilot Test (Appleman et al., 2014)
0%
20%
40%
60%
80%
100%
0 50,000 100,000 150,000 200,000Co
ncen
tratio
n (u
g/L)
nPV
PFOS
Lead Effluent Lead Effluent - ND Lag Effluent Lag Effluent ND
0%
20%
40%
60%
80%
100%
0 50,000 100,000 150,000 200,000
Conc
entra
tion
(ug/
L)
nPV
PFOA
Lead Effluent Lead Effluent - ND Lag Effluent Lag Effluent ND
-20%
0%
20%
40%
60%
80%
100%
0 50,000 100,000 150,000 200,000
Conc
entra
tion
(ug/
L)
nPV
PFHxA
Lead Effluent Lead Effluent - ND Lag Effluent Lag Effluent ND
-80%-60%-40%-20%
0%20%40%60%80%
100%
0 50,000 100,000 150,000 200,000
Conc
entra
tion
(ug/
L)
nPV
PFBA
Lead Effluent Lead Effluent - ND Lag Effluent
Carey et al. (2019, in preparation)
LEAD VESSEL
LAG VESSEL
1 2
Velocity = 500 m/day Retention time = 7 minutes
Length = 2.7 m Mass flux = 0.2 g/m2/day
Breakthrough Lag Period
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Copyright Porewater Solutions (2019) 35
Influence of Activated Carbon Size on PFOS Sorption
10,000
100,000
1,000,000
10,000,000
100,000,000
1,000,000,000
1 10 100 1000
Effe
ctiv
e K
d (L
/Kg)
Activated Carbon Particle Size (um)
? PAC-GAC Data from Xiao et al. (2017)
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0 10 20
Scale, in meters
PFOS (ug/L)
0.6 0.8 1 1.2 1.4
Injection Well Locations and Vertical Carbon Distribution
36 (Modified from McGregor, 2018)
CAC Zone PFOS Source Area
Radius of influence: >4 m Average fCAC: 0.02%
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Redox Radial Diagrams
Copyright Porewater Solutions (2019) 37
-300-200-1000100200300
0.1
1
10
0.1 1 101
10
100
ORP(mV)
DO (mg/L)
Nitrate(mg/L)
Sulfate (mg/L)
MW-1
MW-2
MW-5
MW-8
MW-1
MW-2
MW-4
MW-5
MW-7
MW-8
MW-11
MW-1
MW-2
MW-5
MW-8
a) Spring 2016 (pre-injection)
b) April 2017 (13 months after injection)
c) Oct. 2017 (19 months after injection)
Aerobic Anaerobic
CAC Zone
CAC Zone
N