Carbon Dioxide Sealing Capacity: Textural or Compositional Controls?

Project Narrative Project Objectives: This project will investigate the role of textural and compositional parameters that control the carbon dioxide (CO2) sealing capacity of cap rocks Merit evie! Criterion Discussion: ! Scienti"ic and Tec#nical Merit

Carbon dioxide (CO2) is a major compound identified as affecting the stability of the "arth#s climate $ significant reduction in the volume of greenhouse gas emissions (mainly CO 2) to the atmosphere is a key parameter for mitigating climate change To meet mid% and long%term targets in reducing either CO 2 emissions or their intensity& various mitigations approaches need to be considered& foremost among them being CO2 capture and se'uestration (C()& which will play an important role at least in the first half of this century if reduction targets are to be met ()"$& 2**+) C( is the removal of CO2 directly from large anthropogenic sources and its injection and retention in geological media or in oceans for significant periods of time (centuries to millennia) CO 2 se'uestration in geological media appears to currently be the best available option for the long%term se'uestration of CO2& and indeed this option is being actively pursued in the ,nited (tates (-lara et al & 2**.)& but also in Canada (/enion and /achu& 2**0)& northern "urope (12rster et al & 2**0) and $ustralia (3arma et al & 2**4) 1urthermore& for landlocked regions that are major energy and power producers& such as the Ohio 3alley in the ,nited (tates or $lberta in Canada& se'uestration in geological media is the best and likely only option currently available for increasing CO 2 sinks /y making possible the continued use of coal as fuel for power generation& C( is a technology that contributes to the stability and security of energy systems in 5orth $merica and elsewhere& and provides a bridge from the current fossil%fuel based energy systems to a hydrogen%based economy for late this century (-lara et al & 2**.) )n the mid !66*s& (tatoil pioneered the first C( project at (leipner 7est in the 5orth (ea 5early ! 88mt CO29year is removed from natural gas and injected into a salt%water filled sandstone formation
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deep under the 5orth (ea (/enson& 2**:a) $nother example is the 7eyburn reservoir (Canada)& where& until 2**+& ! 6 88mt CO29year have been injected (7hite et al & 2**+) ;lobal se'uestration capacity in depleted oil and gas fields is estimated between <+:*&*** 88tm CO2 (/enson& 2**:b) and <62.&*** 88mt CO2 (8oritis& 2**:) =epartment of "nergy is expecting that reductions of CO2 by capture and se'uestration will reach almost :&*** 88mt CO 29year by 2*:* (=O"& 2**:) $lthough C( is technically feasible& additional scientific challenges are raised by long%term se'uestration To prevent the injected CO 2 from leaking into adjacent layers above the storage formation& the sealing pressure of a seal rock has to be determined in order to choose an injection pressure that ensures the differential pressure across the seal rock is smaller than the sealing pressure or breakthrough pressure (/erg& !64:> (chowalter& !646> ?ildebrand et al & 2**2& 2**+> @i et al & 2**:& 2**0> Chi'uet et al & 2**4) Otherwise& the seal (cap) rock will leak& the injected CO 2 will penetrate into seal rock& forming a continuous gas phase in the interconnected channels& will migrate into upper layers& and will finally escape back into atmosphere )nvestigations of gas leakage through cap rocks have been reported in the literature (e g & 7ollenweber et al & 2**4> ?ildenbrand et al & 2**2& 2**+> -roos et al & !662& 2**:) )t is widely accepted that retention for relatively long periods of time (thousands of years) of carbon dioxide se'uestrated in an underground reservoir is affected and controlled by permeability (both absolute and relative) and capillary sealing capacity of cap rocks Our proposal is largely focused on studying the capillary sealing capacity of most common seal%rocks& such as shales and anhydrites& that can represent the cap rock of a CO 2 se'uestration reservoir (The permeability study will be carried out later) )t is hypothesiAed that seal

capacity is controlled by textural and9or compositional parameters of cap rocks The capillary sealing capacity of cap rocks is mainly controlled by textural parametersB (e g & the pore%throat siAe& distribution& geometry& and sorting& grain siAe& degree of bioturbation& specific surface area& preferred orientation of matrix clay minerals& and orientation and aspect of ratio of organic particles) and compositional parameters (e g & silt content& ductility& compaction& mineralogical content& proportion
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of soft& deformable mineral grains to rigid grains& cementation& organic matter content& carbonate content& and ash content) (;ruber& !66:> -rushin& !664> =awson and $lmon& !666> "dwards et al & !666> (utton et al & 2**+& 2**0) )n this proposal& we seek to differentiate between the relative importance of textural and compositional parameters mentioned above The conceptual framework involves two testable end%

member hypotheses concerning the sealing capacity of carbon reservoir cap rocksB $ypot#esis %: The sealing capacity of cap rocks is mainly controlled by their textural parameters $ypot#esis &: The sealing capacity of cap rocks is mainly controlled by their compositional parameters These two end%member hypotheses are not mutually exclusive& nor are they intended to be exhaustive 1or example& it may be possible to find cap rocks whose sealing capacity is due e'ually to both types of parameters approach the problem ?owever& these end%member hypotheses constitute a useful concept to

To differentiate between these two hypotheses& geological& petrophysical& and

geochemical data will be collected and used to constrain the predominant factor(s) of sealing capacity The following 'uestions will be addressedB 7hat is the height of a CO 2 column for a given pore% throat siAeC 7hat are the influences of pore%throat shape& distribution or sorting on sealing capacityC )s the degree of bioturbation increasing or decreasing the sealing capacityC 7hat orientation of matrix clays provides the greatest sealing (parallel or perpendicular to bedding)C )s silt content or cementation or ductility a major factor controlling the sealing capacityC 7hat influence specific surface area of grains has on sealing capacityC =oes organic matter content correlate with sealing capacityC Can higher carbonate content be associated with excellent seals or poor sealsC )f all other factors e'ual& is the mineralogical difference between shales and anhydrates producing different seal 'ualityC 7hat are relationships (if any) between preferred orientation of matrix& total organic content& and grain siAeC /etween matrix and the type of cementC )s there an overall control of se'uence stratigraphic on both texture and compositional parameters or only on one of themC 1or a given cap rock& what are the

supercritical CO2 seal retention columnsC Can we assert& for a given cap rock& what is the main control factor& the texture or the compositionC Overall& the proposed research will fill a gap in our national database regarding the sealing capacity of the most known cap rocks (shales and anhydrites)& with special reference to existing and potential carbon se'uestration reservoirs 2 Tec#nical 'pproac# and (nderstanding

The =epartment of "nergy officially announced in 2**4 a multi%million award for large%scale carbon se'uestration projects to four (out of seven) Carbon (e'uestration Degional Eartnerships Conse'uently& our study will be tied%in with these projects by collecting representative samples from sites that are or will be used for carbon se'uestration (e g & )llinois /asin& Ohio Diver 3alley Degion& 7illiston /asin& (an Foa'uin /asin& or 7est Eermian /asin in Texas) Proposed esearc#: $ypot#esis Testing ) Textural Parameters The pore-throat size, distribution, sorting& and the grain size will be determined using our state%of% the art mercury intrusion porosimeter (8)E) $utoEore 6:**& along with our (edigraph ))) :!2* $utomatic Earticle (iAe $nalyAer (both manufactured by 8icromeritics) =etails of the procedure are

found in our previous works (=eming et al & 2**2> Cranganu& 2**+> Cranganu and 3illa& 2**:& 3illa& 2**:) 7e will collect about :* representative seal rocks from various basins that are or will be used as CO2 se'uestration reservoirs (e g & the )llinois /asin& Ohio Diver 3alley Degion& 7est Eermian /asin in Texas& 7illiston /asin) The 8)E data are obtained by forcing mercury at pressures up to <+!+ x !* 0 Ea (0*&*** psi) into small voids and pore throats within the rock sample Eore throats control the access to larger voids (pores) because greater pressures are re'uired to force mercury& or other nonwetting fluid& into smaller spaces (Eurcell& !6+6> -eighin& !664) Thus pore throats are bottlenecks in the system& and it is necessary to exceed their critical capillary pressure in order to inject mercury into pores The step

pressure increase is plotted against the mercury saturation (1igure !) The parameter derived from 8)E curves (1igure !) is the displacement or sealing or breakthrough pressure (Pd)& which is defined as the minimum pressure re'uired to begin saturating the rock sample with the nonwetting phase (mercury)
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The magnitude of the displacement (breakthrough) Pd pressure is determined by the highest capillary pressure of an interconnected network of pore throats that are first invaded by a nonwetting fluid (?ildebrand et al & 2**2> @i et al & 2**:> 2**0) Pd (Ea) is expressed as
2 P = cos d r

where r (m) is the pore throat radius& (59m%!) is the interfacial tension ()1T) of the mercury%air system> (degree) is the air%mercury%solid contact angle> and Pd (Ea) is the pressure necessary for mercury to displace air from the rock pores ;raphically& Pd is obtained by extending the slope of the plateau to Aero percent mercury saturation (-rushin& !664) (1igure !) ,sually& the conventional mercury injection porosimetry (8)E) is used to estimate the magnitude of sealing pressure The measured displacement capillary curve of mercury9air system is converted to the gas breakthrough pressure of a gas 9water system (/erg& !64:> (chowalter& !646> 7atts& !6G4> (chlHmer and -ross& !664) 7hen Pd is difficult to obtain graphically because the curve plateau is missing or

poorly defined& a proxy for the capillary sealing capacity of shales is the displacement pressure at 10% mercury saturation Pd @10% ((chowalter& !646> (utton et al & 2**+> 5abawi et al & 2**6) (1igure !) 1igure ! suggests that that the displacement pressure at !*I mercury saturation is much less than the graphically determined Pd.

1igure ! =isplacement pressure (Pd)& in Ea& and displacement pressure at !*I ?g saturation (Pd@10%) for sample JG* from (cott%! well The well is located in the $nadarko /asin& .: *22o5& 64 664o7 (ample depth is .&.!0 m =ata are taken from 3illa& 2**:

Figure 2 8aximum Threshold "ntry Dadius (8T"D) (in microns) for sample JG* from (cott%! well The well is located in the $nadarko /asin& .: *22o5& 64 664o7 (ample depth is .&.!0 m =ata are taken from 3illa& 2**:

=ifferent rocks with different pore throat siAes will have different displacement pressures and different saturation as a function of height (h) above the free water level (17@) Thus& in any given reservoir

section& the lowest indication of live (vs residual) CO 2 in a particular rock type approximates the displacement pressure (Pd) for that rock The Pd can thus be considered as the CO 2 K water contact for that particular rock type (=aniel& 2**4) The height h (in ft) of CO2 column above 17@ can be calculated from the following formulaB

Pd = h ( b CO2 ) 0.433
where Pd is the displacement pressure (psi) of reservoir brine9 CO 2 system> b L brine density (g9cm.)& and CO L CO2 supercritical density (g9cm.) $pplying the above formula& =aniel (2**4) calculated supercritical CO2 seal retention columns with heights between 00. and !!60 m in two locations from $ustralia

Tanguay and 1riedman (2**!) defined the !a"imum #hreshold $ntry %adius (8T"D) as the pore radius at which significant invasion of a sample with mercury occurs On the capillary pressure curve (1igure 2)& they interpret it as indicating the largest radius of the largest population of ubi'uitous pore throat siAes in the sample The recognition of this parameter is based on a histogram (1igure 2) created with the incremental percentage of intrusion (times !* to emphasiAe the values) and the siAe of the pore throat radius to which it is e'uivalent The peak or peaks on the histogram reflect the distribution of the different pore throat radius populations in a rock sample One peak represents a unimodal distribution> two peaks represent a bimodal distribution& and multiple peaks represent a multiple (no mode) distribution (1igure 2) These distributions are linked to the locations of voids in the rock and they are important in determining if one& two& or more pore throat systems dominate the pore geometry of a geologic formation )n turn& this determination has conse'uences in recogniAing the presence of one significant fluid invasion (unimodal distribution)& two significant fluid invasions (bimodal distribution)& or no significant fluid invasion (no mode distribution) 7e will attempt to integrate 8T"D data with the other parameters

defining the sealing capacity of cap rocks Pore throat geometry will be analyAed by using our ?itachi T8%!*** ("8 ((canning "lectron 8icroscope) The degree of bioturbation, pre&erred orientation o& matri" clay minerals, and orientation and aspect o& ratio o& organic particles will be performed using our polariAed microscopes& capable of working with both transmitted and reflected light 'rain size distribution up to 0. m will be measured using our 8icromeritics (edigraph ;rain siAes greater than 0. m will be determined by sieving (peci&ic sur&ace area (single%point& multi%point /"T& or @angmuir surface area) will be measured using our 8icromeritics ;emini Ehysisorption $nalyAer

7e will study the influence of each of these parameters on Pd values as determined according to "' ! and will infer the relative importance of each parameter with respect to Pd )f cap rock samples with similar compositional parameters show no discernible variations in their sealing capacity as revealed by Pd values& then the textural hypothesis may be disproved Proposed esearc#: $ypot#esis Testing ) Compositional Parameters "nergy =ispersive M%Day (pectrometer ("=() will be used to both determine the bulk and individual component mineralogy as well as their content These analyAes will be performed using our ?itachi T8%!*** "=( instrument )uctility of shale is affected by the expandability of the clay and kerogen content *erogen content will be estimated by measuring TOC9TC (Total Organic Carbon9Total Carbon) These analyAes will be performed outside /rooklyn College by a professional laboratory /ulk density will be used to determine the compaction /ulk densities& as well as porosities& will be determined using our $utoEore 6:** The cement and te"ture of the seal rocks will be concluded through optical petrography Our

department has two EolariAed @ight 8icroscopes (E@8)& capable of working with both transmitted and reflected light 7e will study the influence of each of these parameters on Pd values as determined according to "' ! and will infer the relative importance of each parameter with respect to Pd Testing this hypothesis

would imply a significant correlation between various compositional parameters and the sealing capacity of the sample& provided that the textural parameters are more or less constant )f this situation does not occur& then the compositional hypothesis may be disproved Proposed esearc#: $ypot#esis Testing ) Textural vs* Compositional Parameters 1inally& we will be able to assess the relative importance of each of these two groups of parameters by studying their respective influence on the same cap rock samples The group of parameters& either textural or compositional& that display the largest influence on sealing capacity would be considered the primary control factor of sealing capacity for those specific cap rock samples
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'pplicant+Team Capabilities, Organi-ation and .acilities Project Management Plan /see appendix0

elevance and Outcomes+1mpacts: a* 1ntellectual merits o" t#e proposed activity The proposed research project will advance our knowledge of the sealing capacity of rocks such as shales and anhydrites and& in turn& we will better understand the processes taking place in geologic reservoirs subject to CO 2 injection $ database containing detailed sets of textural and compositional

parameters controlling sealing capacity of cap rocks from existing and potential carbon se'uestration sites in the ,($ will represent a major asset for companies managing those sites )mportant 'uestions about textural and compositional controls of the cap rock sealing capacity will be answered The findings from the proposed research will be geared to expand the maximum capacity of potential global reservoirs& project economic benefits& attract the energy sector or governmental agencies to participate in future feasibility assessments of CO2 geose'uestration )n most scenarios for stabiliAation of atmospheric greenhouse gas concentrations between +:* and 4:* ppmv CO2 and in a least%cost portfolio of mitigation options& the economic potential of C( would amount to 22*K 2&2** ;tCO2 (0*K0** ;tC) cumulatively& which would mean that C( contributes !:K ::I to the cumulative mitigation effort worldwide until 2!**& averaged over a range of baseline scenarios ()ECC& 2**:) The results of the proposed research will be relevant to a variety of fields& including ;eologic (e'uestration of CO2> 7ater9)ndustrial (@i'uid) 7aste =isposal> Oil and ;as exploration> and ;eologic ?aAards $nalysis The newly ac'uired information will be of interest to multiple parties& including )ndustry workers> (tate& @ocal& and 5ational governments> academia> and the public )t will be e'ually important because risk 'uantification (for long term storage of fluids) is currently poorly understood by the public and hard to clearly demonstrate for "arth scientists (e g & Nucca 8ountain) The proposed research has also potential value9relevance in other (unanticipated) areas of studying& includingB
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i) (hale ;as9 /asin%Centered (hale evaluation (a semi%unconventional source of energy)> ii) =evelopment of relationships between old (traditional) core data& which is widely available& and the more rigorous and complete analysis proposed by this study& which may allow for O'uick%lookP or screening evaluation of potential storage sites based on existing core analysis data b* 2roader impacts o" t#e proposed activity $dvancing scientific discovery and understanding through proposed activity will be intimately related to promoting teaching& training and learning activities at /rooklyn College "very semester& Erof Cranganu will teach an upper tier core course& titled OClimate Change K Torn between 8yth and 1actP =uring course lectures and practice activities& undergraduate students from various departments will learn about the most important environmental issues raised by increased concentration of CO 2 in the atmosphere and the efforts taken by many countries& including ,($& to reduce the amount of CO 2 One of the efforts& namely carbon dioxide se'uestration& will be exemplified by our anticipated results (tudents will also be trained in incorporating new data from our database in existing databases that will be provided to them during the course and practice activities /ased on the high concentration of underrepresented minority students (various races& ethnicities& and geographic origins) at /rooklyn College& the proposed research project will offer the opportunity for some of them to work with E) in various stages of the three%year long project timeframe One

undergraduate and two graduate students (one 8$ and one Eh=) will work under the supervision of E) ,pon successful completion of the proposed research activity& the opportunities for collaboration and partnership with similar institutions within the City ,niversity of 5ew Nork or outside the university will most likely occur They will enhance the infrastructure for research and education at /rooklyn College by offering new possibilities to attract more students to research and better tools for teaching courses in geology& environmental studies& or health sciences departments The results of the proposed research will be disseminated broadly by publications in peer%reviewed journals and presentations at scientific meetings and workshops related to global warming mitigation processes ($;,& $$E;& (";& (E") The aims of dissemination will be focused on enhancing scientific
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and technological knowledge and understanding of the carbon dioxide se'uestration process and importance of determining the sealing capacity of the cap rocks )t is our intention to cooperate with

other academic& governmental and industry groups involved in carbon dioxide se'uestration (e g & =O" Carbon (e'uestration Degional Eartnerships& Carbon 8itigation )nitiative at Erinceton "nvironmental )nstitute& 8idwest Carbon (e'uestration Erogram& ;ulf Coast Carbon Center in Texas& Cooperative Desearch Center for ;reenhouse Technology in $ustralia& "uropean Desearch Eroject CO 2()5- in Eotsdam& ;ermany& etc ) 7e also intend to share our results with a broader audience& represented mainly by non%scientists (students& colleagues& educators& policymakers& etc ) in order to make them aware that there is a constant preoccupation and on%going research focused on various ways of mitigation the conse'uences of global warming due to increased levels of carbon dioxide concentration model produced at the end of our research will illustrate our claim $s a whole& our society will gain more information and data about the possibility of reducing the effects on climate of a harmful greenhouse gas (carbon dioxide) by se'uestering it in a depleted9underpressured oil or gas reservoir "nvironmental impacts of a safe underground CO 2 The database and the petrophysical

se'uestration will positively reverberate through multiple domains& currently affected by global warming& such asB public health& water supply& energy demands& sea%level rise and coastal environments& etc )ntegrating the results of our proposed research into educational process will be done in a continuous manner by discussing& during the lectures of our course OClimate Change K Torn between 8yth and 1actP& the implications for climate change of reducing the amount of CO 2 released into atmosphere The students will have to work on class projects (midterm and final exams) dealing with representing and interpreting climate data (temperature& carbon dioxide concentration& methane concentration& etc ) $s a part of the scenario involving possible mitigation of global warming& they will be re'uired to integrate our database and petrophysical model into their solutions Desearch students working on the project will

present their work to their peers& explaining what they are doing and answering 'uestions from the student audience
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7ith over !0&*** students& /rooklyn College has an impressive racial& ethnic& religious& and minority diversity 1rom its founding seventy%six years ago& the College has offered men and women K immigrants or the children of immigrants& often the first in their families to go to college K the opportunity to receive a first%rate education that leads to productive careers and satisfying lives $s

researchers and educators at /rooklyn College& we are committed to broaden opportunities and enable participation of all students in research projects& as an essential way to maintain the health and vitality of science and engineering The current proposal will support the Eh= research of 8rs (adi'ua $Aad from )ndia and the 8$ research of 8r 8ichael Damsaroop from Trinidad and Tobago undergraduate student will get her first research skills Multiple Principal 1nvestigators: This proposal will be carried out by a single E) (Erof Constantin Cranganu) Statement o" Project Objectives /SOPO0 T)T@" O1 T?" 7OD- TO /" E"D1OD8"= Carbon =ioxide (ealing CapacityB Textural or Compositional ControlsC
$ O/F"CT)3"(

$dditionally& one

This research will try to determine the role of te"tural (e g & the pore%throat siAe& distribution& geometry& and sorting& grain siAe& degree of bioturbation& specific surface area& preferred orientation of matrix clay minerals& and orientation and aspect of ratio of organic particles) and compositional parameters (e g & silt content& ductility& compaction& mineralogical content& proportion of soft& deformable mineral grains to rigid grains& cementation& organic matter content& carbonate content& and ash content) controlling the carbon dioxide sealing capacity of cap rocks Ehase ) will achieve the collection of

samples =uring Ehase )) textural measurements will be conducted =uring Ehase ))) compositional measurements will be performed& as well as testing the hypotheses about the role of textural and compositional controls over carbon dioxide sealing capacity of cap rocks
/ (COE" O1 7OD-

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)n this proposal& we seek to differentiate between the relative importance of textural and compositional parameters mentioned above The conceptual framework involves two testable end%

member hypotheses concerning the sealing capacity of carbon reservoir cap rocksB $ypot#esis %: The sealing capacity of cap rocks is mainly controlled by their textural parameters $ypot#esis &: The sealing capacity of cap rocks is mainly controlled by their compositional parameters These two end%member hypotheses are not mutually exclusive& nor are they intended to be exhaustive 1or example& it may be possible to find cap rocks whose sealing capacity is due e'ually to both types of parameters approach the problem ?owever& these end%member hypotheses constitute a useful concept to

To differentiate between these two hypotheses& geological& petrophysical& and

geochemical data will be collected and used to constrain the predominant factor(s) of sealing capacity C T$(-( TO /" E"D1OD8"= P$'S3 1 Tas4 %*5 ) Project Management and Planning

A detailed project plan with duties or each student will !e created. A plan or constant "onitorin# and re$ision o the %roject %lan will !e esta!lished to support the chan#es necessar& as the results lead to new in or"ation.
(ubtask 1.1 Collect about :* representative samples of cap rock (mainly shales and anhydrites) from core libraries and9or geological services implied in =O" Carbon (e'uestration Degional Eartnerships E?$(" )) Tas4 &*56 Data Collecting (ubtask .1. Conduct 8)E measurements and construct capillary K pressure curves "stimate the pore%throat siAe& pore%throat distribution& pore%throat geometry& pore%throat sorting& and grain siAe
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(ubtask . . Conduct other textural measurements& including degree of bioturbation& specific surface area& preferred orientation of matrix clay minerals& and orientation and aspect of ratio of organic particles (ubtask .+. Conduct compositional measurements& including "=(& TOC& and microscopy P$'S3 111 Tas4 7*5 Testing #ypot#eses ,se data collected to test either hypothesis "stablish relationships between sealing capacity of cap rocks and both textural and compositional parameters = ="@)3$D$/@"( #ask 1.1 K $bout :* samples of representative cap rocks (mainly shales and anhydrites) will be collected from sites that are or will be used by =O" for carbon dioxide se'uestration (e g & )llinois /asin& Ohio Diver 3alley Degion& 7illiston /asin& (an Foa'uin /asin& or 7est Eermian /asin in Texas) #ask .1 1or each sample& a capillary Kpressure curve will be produced& along with data regarding the pore%throat siAe& pore%throat distribution& pore%throat geometry& pore%throat sorting& and grain siAe #ask . 1or each sample& measurements of degree of bioturbation& specific surface area&

preferred orientation of matrix clay minerals& and orientation and aspect of ratio of organic particles will be performed #ask .+ 1or each sample& compositional measurements ("=(& TOC& and microscopy) will be conducted #ask +.0 $ssessment of the relative importance of each group of parameters on sealing capacity of cap rocks will be done by studying their respective influence on the same rock sample The group of parameters& either textural or compositional& that display the largest influence on sealing

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capacity would be considered the primary control factor of sealing capacity for those specific cap rock samples ("nd of (OEO)

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