anaged by UT-Battelle

EPA/GWPC Workshop on MMV	 New Orleans, January 16, 2008 

Monitoring and Verification 

of Geologically Sequestered 

CO2 using Suites of 

Perfluorocarbons and other 

Inert Tracers 

T.J. Phelps and D.R. Cole 

Oak Ridge National Laboratory, Oak Ridge, TN, 37831 

(phelpstj@ornl.gov) 

1	 Managed by UT-Battelle 

for the Department of Energy Presentation_name 

Frio Geochemical Investigation Objectives 

(a carbon sequestration pilot study funded by DOE-FE and TBEG) 

•	 Determine chemical (organic and inorganic) and isotopic 

compositions of water and gases in the Frio Sandstone– baseline, 

during and post injection. 

• Determine behavior of multiple suites of perfluorcarbon tracers. 

•	 Delineate CO2 front using on-line probes to monitor pH and 

conductance complemented by PFT’s and isotopes. 

• Assess water-mineral-CO2 interactions 

• Investigate environmental implications of post injection results. 

•	 Develop procedures for use on carbon sequestration 

demonstrations for monitoring, modeling and verification
 

2 M 

for the Department of Energy Presentation_name 

Monitoring and Verification of Geologically 

Sequestered CO2 using Suites of 

Perfluorocarbons and other Inert Tracers 1 
 

 

 

EPA/GWPC Workshop on MMV	 New Orleans, January 16, 2008 

Fresh water (USDW) zone 

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Injection zones: 

First experiment 

2004: Frio 2004: Frio “C ”

2006 Frio “Blue”	 

Frio Brine Pilot Site 

Fresh water (USDW) zone 

protected by surface casing 

•	 Injection intervals: Oligocene 

fluvial and reworked 

sandstones, porosity 34-24%, 

permeability 4.4-2.5 Darcys 

• Dipping 11 to 16 Dipping o 11 to 16

Second experiment 

•	 Seals − several thick shales 

• Depth 1,500 and 1,657 m 

• 150 and 165 bar, 53 -60°C, 

Hovorka, 2007 

Oil production supercritical CO2

Benefits of PFTs and isotopic tracers for 

modeling, monitoring, and verification 

• PFT’s sensitive at pg-fg quantities and isotopes at ppt fractions 

• PFT’s easy and cheap to add and natural isotopes vary with source 

• Non -hazardous complemented by geochemistry providing multiple hazardous, complemented by geochemistry providing multiple 

lines of evidence for measurement, monitoring and verification. 

• Can be analyzed in the field or the lab 

• Specific PFT suites provide signatures of multiple CO2 injections 

• Proven and established procedures 

• Scalable – readily scaled to thousands of samples 

• Directly applicable for modeling or model verification 

• Identification of multiple breakthroughs or serial lot numbers 

• Applicable for near-surface analysis of potential leakage 

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for the Department of Energy Presentation_name 

Monitoring and Verification of Geologically 

Sequestered CO2 using Suites of 

Perfluorocarbons and other Inert Tracers 2 
PFT Injection

•

•

•

 

•

•

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•

•

PFTs Used at Frio Pilot Test and sample collection

 

 

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EPA/GWPC Workshop on MMV New Orleans, January 16, 2008 

Stepwise paired PFT injections 

Injection 1 

– 900 mL PMCH &860 mL PTCH 

Injection 2 

– 100 L PMCP & 100 L PDCH 100 mL PMCP & 100 mL PDCH 

Injection 3 

– 90 mL PMCH & 85 mL PTCH 

HPLC pump and solutions were 

housed inside a waterproof tool box 

with a fan 

Multiple check valves prevented

back flow 

PFTs injected through 1/8 inch 

tubing at 6-8 mL/min for 0.5 to 4 

hour durations at ~1800 psi 

r _ 

PMCP 

F F

F

FF F F

F F CF3

F F 

F 

FF F F

F F CF3 

Deployed multiple-tracer suites (others available) 

Different molecular weights, solubilities, and phys-chemical 

attributes enable chromatographic separation in reservoir 

High pressure cylinders were used to capture samples 

PMCH 

PDCH 

F

F F F

F

F F F F F 

F 

F 

CF3 F

F

F

F F F

F

F

F

F CF3 CF3 F 

F 

F 

F F F 

F 

F 

F 

F CF3 

gp y p p 

from the sampling apparatus at the well head 

Analyses performed in the field or preserved 

r _ 

PTCH 

CF3 F

F

F

F

F

F

CF3 F F

F 

F 

F

F 

F 

F 

CF3

CF3 F

F

F

F F F

F

F

F CF3

CF3 

CF3 F

F 

F 

F F F 

F 

F 

F C 

F 

3 

Monitoring and Verification of Geologically 

Sequestered CO2 using Suites of 

Perfluorocarbons and other Inert Tracers 3 
 

EPA/GWPC Workshop on MMV	 New Orleans, January 16, 2008 

PFT Sample Collection (II) 

•	 Serum vials (58 ml) were 

filled using sample loops
 

•	 2 mL of H2O was added to 

the serum vial to assist in 

septa sealing
 

•	 Serum vials crimp sealed 

with Teflon coated septa 

for storage and transport
 

•	 Used sample loops were 

flushed with > 20 volumes 

of H2O and air for > 10 

minutes
 

7	 Managed by UT-Battelle 

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PFT Sample Analysis 

•	 Serum vials warmed to 85°C 

for ~2 hours prior to analysis 

•	 Samples analyzed using HP 

5890 gas chromatograph with 

Rt-alumina column and an 

electron capture detector 

•	 Gas chromatographic

separation of PFTs shown at 

right 

•	 GC provided detection of PFTs 

at the picogram level 

•	 BNL ( R. Dietz) has 1000-fold

better detection 

•	 NETL soon to have improved 

detection 

8	 Managed by UT-Battelle 

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Monitoring and Verification of Geologically 

Sequestered CO2 using Suites of 

Perfluorocarbons and other Inert Tracers 4 
C d C

 

EPA/GWPC Workshop on MMV New Orleans, January 16, 2008 

PFT Travel Time 

• Travel time nearly constant (50.5 ±1.6 hours) 

• Well developed CO2 flow path 

PFT Peak Broadness 

Peak broadness increased with time implying; 

PFT injection values for samples analyzed using GC and MS 

0.5 

0.8 

1.0 

C/Cmax 

PMCP 

PMCH 

3rd ORNL PFT 

Breakthrough 

2nd ORNL PFT 

Breakthrough 

Injection # 

Injection

time (hours 

after CO2 

start) 

Injection

Duration 

(hours) 

Peak 

Arrival 

Time 

(hours) 

PFT Travel 

Time 

(hours) 

(GC) 

PFT Travel 

Time 

(hours) 

(MS) 

PFT Peak 

Broadness 

(hours) (GC 

and MS) 

p y g; 

– The PFTs were dispersing in the CO2 

throughout the experiment 

– That minor flow paths continued to 

develop as the CO2 injection progressed 0.0 

0.3 

Time 

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#1 

PMCH/PTCH 2 4 54 50 49 14 

#2 

PMCP/PDCH 103 0.6 157 52 49 20 

#3 

PMCH/PTCH 120 0.5 173 51 53 24 

Results of 2nd Injection 

• Breakthrough of

PMCP and PDCH 10 

tracers 

• Breakthrough time

was at 156.6 hrs 

• Travel time was 51.5 

hrs 

• PECH breakthrough 

0.3 

0.5 

0.8 

1.0 

C/Cmax 

PMCP 

PDCH 

Calculated PECH 

NETL's PECH 

Breakthrough 

2nd Breakthrough of 

ORNL PFT Injection 

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PECH breakthrough 

0.0 

115 120 125 130 135 140 145 150 155 160 165 

Time (hours after 1st CO2 injection) 

Monitoring and Verification of Geologically 

Sequestered CO2 using Suites of 

Perfluorocarbons and other Inert Tracers 5 
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EPA/GWPC Workshop on MMV New Orleans, January 16, 2008 

Frio II - Observation Well; U-tube 

6.5 

7.0 

7.5 

700 

800 

900 

1000 

e (PSIA) 

5.0 

5.5 

6.0 

pH 

300 

400 

500 

600 

700 

on Well Tubing Pressure 

-

r _ 

3.5 

4.0 

4.5 

9/25/06 9/26/06 9/27/06 9/28/06 9/29/06 9/30/06 10/1/06 10/2/06 10/3/06 

0 

100 

200 

300 

Observatio 

in-line pH 

bench pH 

Tubing pressure Kharaka et al 

Carbon Isotope Compositions 

of Carbon Dioxide 

Carbon Isotope Compositions of 

Dissolved Inorganic Carbon (DIC) 

Stable isotope and chemistry, Kharaka and Cole et al. 

C CO2 (vs PDB in per mil) 

-14 

-12 

-10 

-8 

-6 

-4 

-2 

Pre-injection reservoir CO2 

CO2 injectate 

Obs. well CO2 

Frio II 

of Carbon Dioxide 

δ13 

 C DIC (in per mil) 

-15 

-10 

-5 

0 

5 

Pre-injection; obs. well 

Pre-injection; injection well 

Post-injection; obs. well 

CO 

Frio II 

g ( ) 

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0 50 100 150 200 

δ13 

 C 

-18 

-16

 Hours Relative to Start of CO2 Injection 

(sampled at -458 hrs) 

Hours Relative to Start of CO2 Injection 

-500 -400 -300 -100 0 100 200 

-20 

15 CO2 

break through 

Monitoring and Verification of Geologically 

Sequestered CO2 using Suites of 

Perfluorocarbons and other Inert Tracers 6 
8

(by vol.) versus Time

 

20

 

 

EPA/GWPC Workshop on MMV New Orleans, January 16, 2008 

CO2 / CH4 Ratios

Oxygen Isotope 

Compositions of Brine 

Stable isotope and chemistry, Kharaka and Cole et al 

CO2 / CH4 Ratios 

CO2 / CH4 

0.1 

1 

10 

100 

Obs. well 

I j ti ll 

Frio II 

-457 to -345 

e (vs VSMOW in per mil)

-8 hrs prior to 

-6 

-4 

-2 

0 

2 

Pre-injection - obs. well 

Pre-injection - injection well 

Observation well 

Frio II 

Compositions of Brine 

13 Managed by UT-Battelle 

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- 0 20 40 60 80 100 120 140 

0.001 

0.01 Injection well 

Obs. well

 Hours Relative to Start of CO2 Injection 

p

 injection 

Hours Relative to Start of CO2 Injection 

-500 -400 -300 0 100 200 

δ18 

 O brin -12 

-10 Injection 

stopped 

Simple Radial Flow Model 

• Preliminary estimate of CO2 • CO2 saturation calculated using saturation the equation: 

SCO2 = (Q t)/(πr2lφf

) • Saturation remains nearly constant Where: 

• Nearly constant saturation values ‘SCO2’ is percent saturation 

of CO2 imply the rapid establishment of well imply the rapid establishment of well ‘Q’ is volumetric flow developed flow paths between the ‘t’ is travel time injection and monitoring well ‘r’ is distance from well to 

• Flow path analysis is important for well 

‘l’ is formation thickness understanding the storage efficiency of ‘φf

’ is percent porosity CO2 sequestration sites 

Injection Peak Time Travel Time % CO2 Saturation Injection # Injection # time (hrs) (hrs) (hrs) (SCO2) 

#1 (PMCH/PTCH) 1.9 54.1 50.3 17 

#2 (PMCP/PDCH) 102.8 156.6 51.7 17 

#3 (PMCH/PTCH) 120.1 173.4 51.2 17 

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Monitoring and Verification of Geologically 

Sequestered CO2 using Suites of 

Perfluorocarbons and other Inert Tracers 7 
 

– -

 

 

EPA/GWPC Workshop on MMV	 New Orleans, January 16, 2008 

Laboratory Test Systems 

High Pressure Flow ORNL Enhanced Coal Bed 

through System (HPFS) Methane Simulator 

HPFS characterizes fluid T: <500C 

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HPFS characterizes fluid 

flow through lithologic media 

at pressure (< 34 MPa) and 

temperature (< 100°C) 

Can deteremine 

sorption,desorption, 

displacement or reactions at 

in situ T, P and flows 

T: 500C 

P: <3000 psi 

Mixed gases: 

CO2; CH4, N2, He 

Adsorption/desorption 

isotherms & flow rates 

Intact/crushed coal core 

Summary and Conclusions 

–	 Breakthrough data with identification of multiple tracers 

–	 Breakthrough data for models and flow path analyses 

–	 Worked well collecting ~200 samples and is readily scalable 

–	 Sensitivity and selectivity (PFT detection upon diluting 12 Sensitivity and selectivity (PFT detection upon diluting 12 -15 orders 15 orders 

of magnitude) 

–	 Monitoring and verification at monitoring wells as well as 

applicability for near-surface applications 

–	 Alkalinity, pH and gas-composition determinations are excellent 

and rapid field methods for tracking injected CO2. 

–	 PFTs, geochemistry and isotopes give multiple indicators of MMV 

–	 Low pH CO2 injection mobilized Fe, other metals and organics. 

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We acknowledge the collaborative support of the entire Frio Project team, especially the 

Texas Bureau of Economic Geology. Phelps and Cole were supported by the DOE-FECarbon Sequestration program. 

Acknowledgements 

Monitoring and Verification of Geologically 

Sequestered CO2 using Suites of 

Perfluorocarbons and other Inert Tracers 8