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



# Monitoring and Verification of Geologically Sequestered CO 2 

# usin g 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 )

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# 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, durin g and p ost in j ection.
• Determine behavior of multiple suites of perfluorcarbon tracers.
• Delineate CO 2 

## front using on-line probes to monitor pH and conductance complemented by PFT’s and isotopes.
• Assess water-mineral-CO 2 

## interactions
• Investigate environmental implications of post injection results.
• Develop procedures for use on carbon sequestration demonstrations for monitori ng, 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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for the Department of Energy Presentation_name Injection zones: First experiment

2004: Frio “ C ” 2004: Frio 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 o 

## Dipping 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 supercritical CO 2 

### Oil production



# Benefits of PFTs and isotopic tracers for modeling, monitori ng, 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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# 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 m L PMCP & 100 m L 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 CF 3 F F F FF F F F F CF 3 

## Deployed multiple-tracer suites (others available) Different molecular weights, solubilities, and phys-chemical attributes enable chromatographi c separation in reservoir Hi g h p ressure c y linders were used to ca p ture sam p les

PMCH PDCH

F F F F F F F F F F F F CF

3 F F F F F F F F F F CF

3 CF

3 F F F F F F F F F F CF

3 

### gp y p p from the sampling apparatus at the well head Analyses performed in the field or preserved

r _ 

### PTCH CF 3 F F F F F F F CF 3 F F F F F F F

CF 3 CF 3 F F F F F F F F F CF

3 CF 3 CF 3 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 H 2 

## O and air for > 10 minutes

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# PFT Sample Analysis

• Serum vials warmed to 85°C for ~2 hours prior to analysis • Samples analyzed using HP 5890 g as chromato g ra p h 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

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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 im p l y in g; 

# PFT injection values for samples analyzed using GC and MS

0.5 0.8 1.0C/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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for the Department of Energy Presentation_name #1 PMCH/PTCH 2 4 5 4 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 2 nd 

# Injection

• Breakthrough of PM C P an d PD C H 10 

## tracers
• Breakthrough time was at 156.6 hrs
• Travel time was 51.5 hrs
• PECH breakthrough 0.3 0.5 0.8 1 . 0C/Cmax PMCP PDCH Calculated PEC H

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 CO 2 injection)



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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 1000e(PSIA)

5.0 5.5 6.0pH

300 400 500 600 700on 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 300Observatio 

### in-line pH bench pH Tubing pressure 

# Kharaka et al

Carbon Isotope Compositions of Carbon Dioxide Carbon Isotope Compositions of Dissolved Inor g anic Carbon ( DIC ) 

# Stable isotope and chemistry, 

# Kharaka and Cole et 

# al.CCO2(vs PDB in per mil)

-14 -12 -10 -8 -6 -4 -2

Pre-injection reservoir CO 2 CO 2 injectate Obs. well CO 2 Frio II 

### of Carbon Dioxideδ13CDIC(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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for the Department of Energy Presentation_name 0 50 100 150 200δ13C -18 -16
Hours Relative to Start of CO 2 Injection (sampled at -458 hrs)
Hours Relative to Start of CO 2 Injection -500 -400 -300 -100 0 100 200 -20 15 CO 2 break through



# Monitoring and Verification of Geologically Sequestered CO2 using Suites of Perfluorocarbons and other Inert Tracers 68 

### (by vol.) versus Time

20 

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

CO 2 

### / CH 4 

### Ratios Oxygen Isotope Compositions of Brine 

# Stable isotope and chemistr y, Kharaka and Cole et al

CO 2 

### / CH 4 

### RatiosCO2/ CH4 0.1 1 10 100

Obs. well I j ti ll Frio II -457 to -345 hrs p rior toe (vs VSMOW in per mil)

- 8 -6 -4 -2 0 2

Pre-injection - obs. well Pre-injection - injection well Observation well Frio II 

### Compositions of Brine

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Hours Relative to Start of CO 2 Injection p injection

Hours Relative to Start of CO 2 Injection -500 -400 -300 0 100 200δ18O brin
-12 -10 Injection stopped



# Simple Radial Flow Model
• Preliminary estimate of CO 2 • CO2 saturation calculated using 

## saturation the equation: S CO2 = (Q t)/( π r 2 l φ f ) 

## • Saturation remains nearly constant Where: 

## • Nearly constant saturation values ‘S CO2 ’ is percent saturation of CO 2 

## 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 ‘ φ f ’ is percent porosity 

## CO 2 

## sequestration sites
In j ection Peak Time Travel Time % CO 2 Saturation Injection # Injection # time (hrs) (hrs) (hrs) (S CO2 ) #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 14 Managed by UT-Battelle

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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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for the Department of Energy Presentation_name 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 - 15 orders Sensitivity and selectivity (PFT detection upon diluting 12 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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for the Department of Energy Presentation_name We acknowledge the collaborative support of the entire Frio Project team, especially theTexas 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