A 3D study of the CO2 naturally stocked: the case of Minero-Florida block in the Sabinas basin, north of Mexico

J. C. Gallardo , L. Martinez , G. Caumon , L. F. Camacho-Ortegon , N. Piedad- anchez , J. au""e

1. #M$ CN$ %&''-G2$, Nanc( #ni)er"it*, +P-2!,, &4&-' .andoeu)re Cede/, France 2. C$PG-CN$ , Nanc( #ni)er"it*, $ue du 0o(en Marcel $ou1ault, &4&-1 .andoeu)re Cede/, France !. 2 3, #ni)er"idad 4ut5noma de Coahuila, Nue)a $o"ita, Coahuila, C.P. 2'6--, M*/ico 4. CO3M72C, La" Choa8a" !-', +ella)i"ta, alamanca Gto, C.P. !'%!-, M*/ico
1,4 1 2 1 ! 1

Abstract 9e 8re"ent a method to calculate the !0 di"tri1ution o: CO2 :ormed and;or "toc<ed in the 1loc< Minero-Florida =MF> o: the a1ina" 1a"in. 7hi" 1a"in i" located in the northern 8art o: Me/ico, 16- <m :rom the 1order ?ith the # 4. 3t i" a 1a"in 8roducer o: natural C@4 ga" ?hich contain" more than &<m o: Me"ozoic "edimentar( roc<" de8o"ited in a marine en)ironment. 7he con"truction o: the "8atial di"tri1ution ma8" o: CO2 i" "u88orted 1( the !0 "ei"mic inter8retation o: the 1loc< MF and it" inter8retation a" a !0 "tructural model 1uilt ?ith GOC40 geomodeling "o:t?are. CO2 data con"i"t o: 8unctual mea"urement" in :i)e ?ell", geochemical model re"ult" and o: the CO2 re"ulting :rom the te"t" carried out on geochemi"tr( and 8etrogra8hic characterization o: roc<" :rom )ariou" "edimentar( :ormation" and their :luid". 7he CO2 and C@4 )olumetric ma8" ?ere generated a"A a> in-"itu ga" anal("i", 1> o1tained 1( arti:icial maturation la1orator(, c> generated :rom the theorical .an Bre)elen, d> re"ulting :rom the "am8le anal("i" on $oc<-2)al 8(rol("i", e> calculated ?ith geochemical Petromod "o:t?are. $e"ult" ?e al"o conducted an a""e""ment o: the 1e"t e/8loitation location to drill to ne? ?ell" in the area, con"idering the CO2 a""ociated ?ith the C@4. 7hi" ?or< ?ill "u88ort meaning:ull( the deci"ion-ma<ing o: e/8loration o: geochemical engineering, in )ie? o: the location o: :uture drilling o: ?ell". Our methodolog( can 1e ada8ted al"o to other area" o: oil e/8loration.

ntroduction 7he a1ina" 1a"in i" located in the northern 8art o: Me/ico in the "tate o: Coahuila, 180 km

from the border with the USA =Figure 1>, ?ith an area o: a1out !%,--- <m 2. 7hi" 1a"in ha"
initiall( e)ol)ed a" a ri:t 1a"in :ollo?ed 1( a decelerating "u1"idence =Goldhammer and John"on, 2--1>. 3t ?a" de)elo8ed on the margin o: North 4merican craton during the earl( Me"ozoic o8ening o: the Gul: o: Me/ico ?ith a 8re:erential direction N9- 2 =e/ten"ional 8ha"e>, and then it :olded during the Laramide Orogen( =com8re""ional 8ha"e> =4l"aa1, 2--%>. 7he "edimentar( :ill reache" a thic<ne"" o: &--- meter" and i" mainl( Me"ozoic. 2guiluz de 4tuCano =2--1> and Menetrier =2--&> "ho? that there are three main "ource roc<" in the a1ina" 1a"inA La Ca"ita Formation =late Jura""ic> ?ith "ediment" ?ith a high

car1on content =7otal Organic Car1on D 7OC> ?hich range" 1et?een -.& and !E, and a high organic maturit( =)itrinite re:lectance F$r G 2 EH>, La PeCa Formation =earl( Cretaceou"I -.4 to 2., E o: 7OC> and the 2agle Ford Formation =late Cretaceou"I -.' to 2.& E o: 7OC>. 7he"e "ource roc<" are "ometime" al"o diagenetic re"er)oir" ?ith 7 $, + $ mineral tran":ormation" and contain continental organic matter mi/ed ?ith lo? 8ro8ortion" o: marine organic matter. 7he main re"er)oir roc<" identi:ied in the a1ina" 1a"in are La Gloria =#88er Jura""ic>, La Ca"ita =#88er Jura""ic>, Padilla =@auteri)ian>, La .irgen =+arremian>, Gorge 7o?n =4l1ian>, and 4u"tin =Cam8anian> Formation" =2guiluz de 4tuCano, 2--1>. 7he"e re"er)oir roc<" re"ult" :reJuentl( o: the :luid" circulation ?ith diagenetic calcite-dolomite mineral tran":ormation".

Figure 1. Location of the block Minero-Florida (part of Pirineo block) into the Sabinas basin, Mexico.

7he +loc< Pirineo i" an area o: !64- <m and i" located & <m "outh o:

a1ina" Coahuila and

4- <m North 2a"t o: Monclo)a, Coahuila =Figure 1>. 7he +loc< i" con"idered a" an im8ortant region o: Ga" 8roduction in Me/ico. 7he "tud( area called Minero-Florida =Figure1> i" located north o: +loc< Pririneo and i" an area o: 42% <m . 0uring the 8a"t decade", in the Minero-Florida area, Petroleum indu"trie" drilled ?ell" that "ho?ed e)idence o: @2 drilling 8ro"8ect". and CO2 =7a1le 1>. 3t i" o: maKor im8ortance to <no? the CO2 origin and it" di"tri1ution, ?ith regard to the :ormation" to decide a1out the 8lanning o: ne?
2

4 num1er o: geological "tudie" ha)e 1een made on the

a1inaL" 1a"in due to the 8re"ence

o: no metallic and metallic de8o"it", "uch a" :luorite-1arite mineral", coal and ga" :ield". @o?e)er, no "tud( ha" e)er :ocu"ed on the CO2 di"tri1ution and origin.

7a1le 1. Shares of CO2 and H2S as anal!sis in-sit" in the #ells of the block Minero-Florida$

!ell
Florida-!1 Florida-!1 Florida-11 Florida-1 Florida-! Florida-1-1 Florida-1-1 @ulla-1 Cacana8o-1 Cacana8o-1 Cacana8o-1-1 Minero 1 Minero 1

CO2 "#$
4% 1-!2 !&.! ,%.'1 --1.%' --%1 -.&4 --2%.21 2%.21

%2S "&&'$
----------!--4------------

For'ation
Padilla La Ca"ita Padilla Padilla Padilla La .irgen La Ca"ita --Padilla La Ca"ita La Ca"ita Padilla La Ca"ita

(OCAD MOD)** +( 7he !0 "8atial di"tri1ution" o: CO2 and 8etro8h("ical 8ro8ertie" at the 1loc< Minero-Florida ?ere carried out u"ing the GOC40 geomodeling "o:t?are. 9e de"igned a method 1a"ed on the e/i"ting data o: the area o: "tud(. 9e u"ed the :ollo?ing in8ut" to our GOC40 modelA

#7M coordinate" o: the 1loc< Minero-Florida ei"mic inter8reted line" =inline and cro""line> and it" #7M coordinate" 2/i"ting ?ell" and it" coordinate" #7M 0ata o: each o: the e/i"ting and under de)elo8ment ?ell"A 8oro"it(, 8ermea1ilit(, ?ater "aturation, in-"itu ga" mea"urement" =CO2, C@4 and @2 >, de8th" o: each :ormation, etc.

CO2 and C@4 )alue" calculated ?ith a geochemical cali1rated model ?ith the geochemical Petromod model Pro8ert( )alue" o1tained :rom 8etrochemical and anal("i" =$o<-2)al ', arti:icial =)itrinite maturation, M-ra( di::raction, etc.> micro"co8ic mea"urement"

re:lectance and canning 2lectron Micro"co8(>, "ee 7a1le 2.

7a1le 2. Properties %al"es (in &ocad for'at) obtained fro' petroche'ical and 'icroscop! anal!sis, Minero-Florida area$
POZO Cacanapo-1 Cacanapo-1 Cacanapo-1 Cacanapo-1 Cacanapo-1 Cacanapo-1 Cacanapo-101 Cacanapo-101 Cacanapo-101 Cacanapo-101 Cacanapo-101 %#ori"a -1 %#ori"a -1 %#ori"a -1 %#ori"a -101 %#ori"a -101 %#ori"a -101 & ##a - 1 & ##a - 1 & ##a - 1 & ##a - 1 & ##a - 1 & ##a - 1 )inero -1 )inero -1 )inero -1 )inero -1 FORMACION La Pea La Virgen s p La Virgen !! La Virgen ! Pa"i##a La casi$a La Pea La Virgen s p La Virgen ! Pa"i##a La casi$a La Pea La Virgen s p Pa"i##a La Pea La Virgen s p Pa"i##a La Pea La Virgen s p La Virgen ! Pa"i##a 'arri# Vie(o-)enc*aca La Casi$a La Pea Pa"i##a 'arri# Vie(o-)enc*aca La Casi$a PUNTO PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX PVRTX Numero 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 X 276606 276606 276606 276606 276606 276606 276091 276091 276091 276091 276091 266347 266347 266347 267186 267186 267186 273789 273789 273789 273789 273789 273789 277673 277673 277673 277673 Y 3063515 3063515 3063515 3063515 3063515 3063515 3063252 3063252 3063252 3063252 3063252 3064777 3064777 3064777 3062500 3062500 3062500 3066200 3066200 3066200 3066200 3066200 3066200 3062519 3062519 3062519 3062519 Z -1710 -2200 -2570 -2820 -2920 -3395 -1765 -1935 -2760 -3000 -3390 -1410 -2000 -2660 -1450 -2000 -2790 -1500 -1880 -2480 -2690 -3080 -3140 -1595 -2850 -3265 -3700 Anhy 0 32.10 48.80 13.80 0.45 0 0 0.50 1.30 0.28 0 0 1.93 4.45 0 5.97 0.90 0 0.40 5.50 7.10 0 0 0 0 0 0 Qz 8 6 6 17 11 20 9.77 1.83 7.00 20.73 36.30 6.05 3.23 6.52 1.75 1.67 10.07 4.20 1.73 3.80 42.90 63.50 63.98 1.65 13.20 35.80 48.20 Calci 77.8 31.25 5.90 6.60 46.20 59.20 72.66 87.97 42.30 65.17 31.00 80.95 76.47 2.40 93.45 68.45 69.43 88.80 80.93 75.60 22.30 4.40 8.78 92.80 38.98 5.60 23.22 Dolom Pyrite Ro_ itri 1 0.07 -999 34 0.40 1.07 47 0.55 -999 46 0.90 -999 35 0.90 1.98 2 0.90 -999 0.66 1.46 -999 6.10 0.17 -999 31.80 0.60 -999 10.55 0.65 -999 10.08 2.38 2.36 0.20 1.35 1.78 14.73 0.36 1.90 74.75 0.82 2.11 2.10 0.50 0.95 11.77 0.12 1.85 12.98 1.19 -999 0.30 1.10 1.21 16.53 0.43 -999 8.40 0.07 -999 17.60 0.15 -999 25.40 0.90 2.26 3.64 0.52 3.69 1.90 0.45 1.76 37.56 1.08 2.84 0.40 0.30 3.88 13.00 0.60 3.55 Poro !at"#O TOC "I OI $%&C_calci $%'O_calci 3.3 -999 1.15 15 40 -999 -999 2 -999 -999 -999 -999 -999 -999 3 -999 -999 -999 -999 -999 -999 2 -999 0.16 99.19 239.34 -999 -999 1 -999 -999 -999 -999 -999 -999 3 -999 0.49 34.14 83.78 -999 -999 1.34 11 32 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 1.6 56.3 0.49 14 160 -999 -999 2.28 2.22 15.63 2.2 30.2 -999 -999 3.2 27.6 -999 -999 -999 -999 -999 2.5 36.0 -999 -999 -999 -0.5 -1.3 4.1 30.1 -999 -999 -999 -999 -999 2.3 32.8 0.15 48 180 -2.70 -2.06 2.2 -3.47 0.15 76 189 2.5 39.4 -999 -999 1.11 2 35 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -999 -1.15 -9.2 -999 -999 -999 -999 -999 -999 -999 2.3 26.7 0.15 37 188 -999 -999 2.1 26.2 -999 -999 -999 1.94 -4.2 3.7 22.7 -999 -999 -999 -999 -999 -2.16 -11.4 0.07 14 235 5.7 7.4

"

Figure 2. Se%eral sta es of the &OC() 'ethod (applied to the Minero-Florida st"d!).

Modelin, in (ocad 3n thi" "ection ?e de"cri1e our general method to 1uilt a !0 "8atial di"tri1ution o: CO2 at the Minero-Florida 1loc< =Figure !> u"ing Gocad.

Fir"t, a Gocad 8roKect ?a" de:ined u"ing #7M coordinate" :or the geogra8hical area o: "tud( =Figure 2a>. econd, the image" =)o/et t(8e> o: each o: 1oth inline and cro""line inter8reted , "ee Figure !1> ?ere im8orted and geore:erenced. 7he"e 3 line" ?ere ?ith "ei"mic "ection" =3

"u88lied 1( a Me/ican com8an( =MPG - Monclo)a Pirinero" Ga"> and generated u"ing the Landmar< "o:t?are and the "ei"mic cu1e o: Minero-Florida. 4n o8tion to ha)e 3 geochemical Petromod model to calculate the"e 8ro8ertie" :or each 3 =Figure !d>. 8h("ical 8ro8ertie" =8oro"it(, 8ermea1ilit(, tem8erature, 8re""ure, etc> i" a88l(ing the #n:ortunatel(, ?e did not ha)e acce"" to the original "ei"mic cu1e, "o much o: the inter8retation ?or< had no 1e re8eated :rom the "ection" 1( manuall( 8ic<ing the la(er 1oundarie". Man( la(er" con"idered in thi" "tud( ?ere tho"e o: the re"er)oir roc<" =La .irgen and Padilla> and the "ource roc<" =La PeCa and La Ca"ita>. Pic<ing ?a" al"o nece""ar( to inter8ret 1! :ault" cutting the "edimentar( :ormation" =Figure !e>. 7he F tructural ModelingH ?or<:lo? ?a" u"ed to generate a con"i"tent :rame?or< o: triangulated "ur:ace" re8re"enting the horizon" and :ault" =Figure 2: and 2g>. 4 Jualit( control =NC> ?a" 8er:ormed in order to re:ine the triangulation o: the "ur:ace and correct the "tructural model ?hen 8oorl( con"trained 1( the cro"" "ection data e"8eciall( at the contact 1et?een horizon" and :ault". +ecau"e o: an incon"i"tenc( o: de8th" 1et?een the horizon" de:ined on the 3 and the horizon" identi:ied ?ith the ?ell data, ?e a88lied "e)eral "cri8t" to adKu"t the "ei"mic horizon" to ?ell data in the "ame :a"hion a" :or time to de8th con)er"ion. 4 correction :actor ?a" inter8olated in )olume u"ing <riging, "o that 1oth horizon" and :ault" could 1e de:ormed )erticall( to honor ?ell mar<er". 7he re"er)oir" model" allo? calculate the )olume o: roc< o: each o: them. From the "tructural model, ?e generated "tratigra8hic grid" =Figure 2i and 2K> :or 1oth "ource and re"er)oir roc<" u"ing the !0 $e"er)oir Grid +uilder. ince the :ault net?or< to8olog( a1ina" 1a"in )arie" )erticall(, ?e created one grid 8er la(erI the grid orientation ?a" cho"en to :ollo? the a)erage orientation o: the h(drocar1on migration de:ined a" N9- 2 :or the =4l"aa1, 2--%>. 4:ter the re"er)oir model" ?a" created, the F$e"er)oir Pro8ertie"H ?or<:lo? ?a" a88lied to ge1erate !0 di"tri1ution ma8" o: the CO2, C@4, and 8etro8h("ical 8ro8ertie" :or each o: the :our re"er)oir" generated in thi" "tud(. For thi", ?e u"ed ordinar( <riging to inter8olate a?a( :rom the ?ell", u"ing a )ariogram to Juanti:( the "8atial )aria1ilit( =Gringarten and 0eut"ch, 2--1>. ince no )ariogram range could rea"ona1l( 1e determinate :orm the e/8erimental )ariogram, ?e ar1itraril( u"ed an areall( i"otro8ic Gau""ian )ariogram o: &--- m range, ?hich i" con"i"tent ?ith the "8atial )aria1ilit( 8ro)ided 1( Petromod "imulation. 4l"o, t?o ne? ?ell" =Picota and Li1eria to drill during the 2--%-2--6 8eriod, "ee Figure !> ?ill "oon 1e located into the Minero-Florida 1loc<. Once the"e ?ell" are re:erenced ?ithin the Minero-Florida domain, ?e ?ill o1tain, :or each ?ell, the o1"er)ed )alue" o: CO2, C@4 and the corre"8onding "imulated or inter8olated 8ro8ertie" to carr( out an e)aluation o: the

8roduction o: C@4 relati)e to the Juantit( o: CO2. Moreo)er, it ?ill 1e 8o""i1le to e)aluate the ne?" ?ell" 8o"ition" =geogra8hic location> and their dee8ne"". 4l"o, to 1e a1le to 8ro8o"e 8o""i1le relocation o: the"e ?ell" in the ca"e o: ha)ing high oil 8roduction in other 8lace o: the Minero-Florida 1loc<. 9hen ?e o1tain the oil 8roduction and 8ro8ertie" in:ormation =mea"ure"> :or Picota and Li1eria ?ell", the"e ?ill 1e u"ed to )alidate the Gocad re"ult" 1( 8er:orming a com8ari"on 1et?een the mea"ure" and the Gocad model. 3n other" ?ord", thi" ne? data acJui"ition ?ill 8ro)ide a critical NC o: our "tructural and re"er)oir model :or the 1loc< Minero-Florida. Gi)en the ca"e o: an incorrect )alidation, ?e could 8ro8o"e di::erent "olution" "uch a" the direct u"e o: the !0 "ei"mic cu1e =?ithout inter8retation> in Gocad to generate 1etter inter8retation o: all the horizon" and :ault" 8re"ent in the "ei"mic. 7hi" o8tion ?ould ne)erthele"" greatl( increa"e the Jualit( o: our Gocad model.

2alidation of the results: structural & reservoir model

Definition of study area .enerate properties for each ne' 'ell e0ploration .enerate spatial distri1ution maps for each property

.eographical location of seismic lines

Seismic lines interpreted ( "SLI " - inline & crossline): -*etromod -Landmar(

Location of futures 'ells &pply the 'or( flo' ")eservoir *roperties" Data properties !"# $%# porosity#///

Digitalize curves that represent the horizons and faults

reate horizons and faults surfaces

-C

&pply the 'or( flo' "Structural +odeling" to generate the structural model
-C

3ell mar(er information &d,ust the structural model 'ith 'ell mar(ers

&pply the 'or( flo' "-D )eservoir .rid" to generate the reservoir model

-C

Figure !. )ia ra' sho#in the 'ethod &ocad applied to the Minero-Florida st"d!.

First results 0ue to the earl( "tage o: the 8roKect and the lac< o: data, "im8le 1ut re8re"entati)e "(nthetic ca"e" are 8re"ented a" illu"tration" o: the 8otential o: the 8ro8o"ed methodolog(. +e:ore 8re"enting the re"ult" o: the "8atial di"tri1ution 20 and !0 o1tained ?ith Gocad i" im8ortant to "ho? a "ummar( o: the e/8erimental re"ult" =8etrogra8hic anal("i" and micro"co8(>, "ince the"e e/8erimental data ?ere u"ed a" in8ut" to Gocad. Microscop! (*itrinite reflectance)+

7he re"ult" o: micro"co8( =.itrinite re:lectance,E$r> indicate that man( o: the "am8le" 8re"ented organic matter di"8er"ed, "ometime" in "mall 8article". 7he 8re"ence o: )itrinite, inertinite and rarel( li8tinite, i" in greater a1undance in :ormation" La Ca"ita and La PeCa, and much lo?er in Padilla and La .irgen. La Ca"ita, ?ith organic matter t(8e 333 =and a minorit( o: t(8e 33>, i" the "ource roc< mo"t im8ortant :or hi" marine 8etroleum 8otential, hi" thic<ne"" and hi" re"er)oir ca8acit(. 7he h(drocar1on" generated ?ere e""entiall( ga"e" a" the re"ult o: thermal organic diagene"i" =7 G 16- OC>, and almo"t all the oil ?a" tran":ormed. E$r )alue" are )er( high relati)e to the )alue" re8orted in the literature ?hich ?ould indicate a high :ormation o: C@4 and a lo? oil content in the Minero-Florida area. Petrogra8hic anal("i" and geochemical modeli"ation are in accord ?ith thi" inter8retation and "ho?" :reJuentl( "econdar( crac<ing and 8iro1itumen" in oil migration 8hath?a(".

Scannin ,lectron Microscop! (S,M)+ 7he canning 2lectron Micro"co8( = 2M> ?a" u"ed ?ith "am8le" :rom di::erent ?ell", :or the La Ca"ita and Padilla Formation". 9e o1"er)ed the 8re"ence o: mineral" that :a)or the reaction" o: CO2 8roduction. 4l"o the 8re"ence o: calcite =CaCO!> and dolomite =CaMg =CO!> 2> ?a" o1"er)ed in mo"t o: the "am8le", and rarel( Juartz = iO2> in lo?er Juantitie". am8le" 8re"ented a matri/ lime"tone 8redominant, ?ith 8re"ence o: "e)eral cr("tal", including anh(drite =Ca O4>, calcite, 1arite =+a O4>, cele"tite = r O4>, 8(rite =Fe > and elemental "ul8hur = >. 7hi" techniJue con:irm" the 8oro"it( re"er)oir 8otential o: :ormation" =Figure 4, Martinez et al., 2--6> La Ca"ita, Padilla and La .irgen to generate organic and inorganic CO2 :rom reaction" "uch a" 1acteria "ul:ate reduction =+ $>, thermochemical "ul:ate reduction =7 $> and the thermal decom8o"ition o: car1onate" =Machel, 2--1I 7rilla et al., 2--4>.

Figure 4. Sa'ple of Florida--.- #ell sho#in a 'atrix li'estone #ith calcite, dolo'ite and p!rite (obser%ed #ith the Scannin ,lectron Microscop!$

/ock ,%al 0+

7he techniJue o: 8(rol("i" $oc< 2)al ' i" a88lied to determine the 8otential o: CO2 generated :rom the organic matter 8re"ent in the 1loc< Miner--Florida. 7he re"ult" "ho? )alue" o: 7OC and 3@ =mg @C;g 7OC> )er( lo? :or all the anal(zed "am8le". @o?e)er the 8otential :or inorganic and organic CO2 i" )aria1le. For e/am8le, La Ca"ita ha" an inorganic 8otential o: -.1' mg CO2;g roc<, Padilla o: -.11 CO2;g roc< and La PeCa o: -.2' mg CO2;g o: roc<. $e"ult" indicate too a )er( lo? 8otential o: CO2 organic. Moreo)er, it "ugge"ted a "trong migration in relation ?ith the ma/imum tem8erature" reached during the 8(rol("i" 1ecau"e anal("i" "ho?" CO2 in relation ?ith oil roc< im8regnation = 1 8ic<, Pmg @C;gQ>.

1-ra! diffraction+ 7he re"ult" o: the M-ra( di::raction =0$M> indicate that the "am8le" ha)e "u::ered the in:luence o: diagenetic 8roce""e" and o: the 8re"ence o: calcite, dolomite and "ul:ate" =e"8eciall( anh(drite>. am8le" indicate a mi/ture o: "ea and continental ?ater" = urdam et al., 1,6,>. 7he relati)e high content" o: Juartz, 1arite and cele"tite at de8th 8romote reaction" in the inorganic 8art o: the"e roc<" to 8roduce CO2.

*an 2re%elen dia ra'+ Numerical "imulation" ?ere conducted to determine the 8otential o: CO2 organic :ollo?ing the trend 8ro8o"ed 1( the .an Bre)elen diagram :or organic matter o: t(8e 333 and com8aring ?ith numerical "imulation" o: 8roduct" o1tained ?ith arti:icial maturation =4l"aa1, 2--%>. +oth "imulation" ?ere conducted u"ing the E$r a" a thermal mar<er ?ith McCartne( R 7eichmuller eJuation. E $r S 12 e/8 =-!.!=@;C>>-O;C 7he re"ult" o: t?o "imulation" indicate that man( o: the "ource roc<" "tudied ha)e e/hau"ted their thermal organic 8otential o: CO2 at ma/imal de8th a:ter Laramide #8 li:t =Menetrier, 2--&>.

Fl"ids incl"sions+ 0i::erent "am8le" o: :ormation" La Ca"ita, Padilla and La .irgen ?ere o1"er)ed to :ind :luid" inclu"ion" that could hel8 determine the initial concentration" o: CO2, C@4 and @2 in the anal(zed roc<" and the e)olution o: the"e concentration". 7he "tudied "am8le" 8re"ent :luid inclu"ion" in the matri/ a" in the :racture", in mineral" o: calcite, Juartz and anh(drite =Figure &>. 7he o1"er)ed :luid" inclu"ion" ?ere in one-8ha"e, t?o-8ha"e and three-8ha"e in relation ?ith L3# 0ehan et al., =2--'> reaction =in Martinez et al., 2--6>. Ca O4 T @C @2 T CO2 T CaCO! T 1itumen T ga"eou" @C =12- UC D 16- UC>

7he :luid" inclu"ion" indicate that the CO2 8re"ent in the Minero-Florida 1loc< ha" in addition an e/ternal "ource di::erent :rom the + $-7 $ organic-inorganic interaction" o: the "tudied roc<". 7here ?ere o1"er)ed more :luid" inclu"ion" ?ith @2 circulation". in the Padilla and La .irgen :ormation" that in La Ca"ita :ormation, that con:irm 7 $ diagenetic reaction" in relation ?ith :luid"

Figure &. /elation bet#een the CO2 and CH3 in the fl"ids incl"sions of Minero, 4arroteran, Florida and H"lla #ells$

5sotop!+ am8le" anal(zed 1( i"oto8( o: car1onate =calcite, dolomite and "iderite> allo?ed to determine their in:luence on the diagenetic e)olution o: the "tudied roc<". 7he re"ult" o: the i"oto8e" al"o indicate that the organic-inorganic CO2 contri1ution i" not onl( organic ?ith + $-7 $ reaction" 1ut 8ro1a1l( al"o e/ternal, a" magmatic =Camacho et al., 2--6>.

&eoche'ical 'odel (PetroMod)+ 7he 10 PetroMod model ?a" u"ed to recon"truct the hi"tor( o: "edimentation in "ome ?ell" o: the Minero-Florida 1loc<. 3n 8arallel, it ?a" 8o""i1le to "imulate the e)olution o: the tem8erature at ?hich the geological :ormation" ?ere "u1Kected. 3n general, 10 modeling i" con"i"tent ?ith tho"e re8orted in the literature, ?here the area Minero-Florida re"ult" a" a mature 1a"in ?ith a 8otential to 8roduce C@4. 10 cali1rated model" ?ere u"ed to generate 20 PetroMod model" in order to calculate the generation o: organic CO2 in the :ormation" La Ca"ita, Padilla, La .irgen and La PeCa along t?o 3 A 3 1 =inline> and 3 +-+V =cro""line>. 7he re"ult" indicate that a "trong migration o: :luid" could 1e the cau"e o: that toda( =zero million" o: (ear" F-MaH> the large"t accumulation" o: CO2 =)alue" 1et?een 1'E and !%E :or 3 1 and 3 +-+V re"8ecti)el(> occur in the Padilla :ormation.

2) Maps of CO2+ 20 and !0 "8atial di"tri1ution ma8" o: CO2 and 8etro8h("ical 8ro8ertie" ?ere al"o generated ?ith Gocad. 7he 20 ma8" re8re"ent the di"tri1ution o: CO2A a> o1"er)ed in hi"torical mea"urement" Win "ituW, 1> calculated 1( arti:icial maturation c> generated 1( "imulation :ollo?ing .an Bre)elen diagram d> o1tained :rom the $oc< 2)al and e> calculated ?ith Petromod. 7he "8atial di"tri1ution o: CO2 ?a" 8er:ormed 1( a88l(ing a method o: inter8olation - e/tra8olation 1et?een the )alue" o: CO2. Figure ', "ho?" the 20 "8atial di"tri1ution o: CO2 organic generated 1( the 8(rol("i" $oc< 2)al '. 7a1le !, "ho?" a "ummar( o: the )alue" generated 1( 20 inter8olation :or Picota =Pic> and Li1eria =Li1> ?ell" and :or La Ca"ita and Padilla Formation". 7he"e t?o ?ell" are actuall( in drilling "tate. 7he re"ult" :rom 20 "8atial di"tri1ution "ho? that the area Miner-Florida i" )er( "u"ce8ti1le to contain CO2, :ocu"ing on the area 1et?een Picota and Li1eria ?ell". 2/8erimental data o: CO2 organic ha)e "imilar trend", ?hile the CO2 mea"ured data "ho? a high )aria1ilit( o: CO2, ?hich "ugge"t" an e/ternal "u88l( o: CO2 to the "("tem that doe" not ta<e into account the di"tri1ution o: geological :ormation".

7a1le !. S"''ar! of CO2 %al"es for Liberia and Picota (obtained b! se%eral 2) distrib"tion 'ethods), in the block Minero-Florida (&allardo et al$, 2..6)$

!ell
Li1eria Picota Li1eria Picota Li1eria Picota Li1eria Picota Li1eria Picota Li1eria Picota Li1eria Picota Li1eria Picota Li1eria

For'ation
La Ca"ita La Ca"ita La Ca"ita La Ca"ita Padilla Padilla Padilla Padilla Padilla Padilla La Ca"ita La Ca"ita Padilla Padilla La Ca"ita La Ca"ita Padilla

CO2 .alue
'-E 6'E '-E 66E ,-E !-E ,1E 1%E '1 mg CO2;g 7OC 41 mg CO2;g 7OC ,' mg CO2;g 7OC ,6 mg CO2;g 7OC !', mg CO2;g 7OC !2% mg CO2;g 7OC 414 mg CO2;g 7OC 4-1 mg CO2;g 7OC -.2,! mg CO2;g

Distribution 'ethod
3n-"itu mea"urement"A "cenario 1 3n-"itu-mea"urement"A "cenario 1 3n-"itu mea"urement"A "cenario 2 3n-"itu mea"urement"A "cenario 2 3n-"itu mea"urement"A "cenario 1 3n-"itu mea"urement"A "cenario 1 3n-"itu mea"urement"A "cenario 2 3n-"itu mea"urement"A "cenario 2 Organic CO2 D 4rti:icial maturation Organic CO2 D 4rti:icial maturation Organic CO2 D 4rti:icial maturation Organic CO2 D 4rti:icial maturation Organic CO2 D .an Bre)elen Organic CO2 D .an Bre)elen Organic CO2 D .an Bre)elen Organic CO2 D .an Bre)elen Organic CO2 D $oc< 2)al '

7OC Picota Padilla -.!-! mg CO2;g 7OC Li1eria Picota La Ca"ita La Ca"ita -.2& mg CO2;g 7OC -.2'% mg CO2;g 7OC Organic CO2 D $oc< 2)al ' Organic CO2 D $oc< 2)al ' Organic CO2 D $oc< 2)al '

7) 'aps of CO2 and petroph!sical properties+ +e"ide" the"e 20 "8atial di"tri1ution ma8", !0 di"tri1ution ma8" o: CO2 ?ere generated u"ing the Gocad method de)elo8ed in thi" ?or< =Figure !>. Figure % "ho?" the !0 "8atial di"tri1ution o: CO2 mea"ured in-"itu, a" ?ell a" the 8oro"it( )alue" in the Padilla re"er)oir. For the !0 "8atial di"tri1ution a Gau""ian )ariogram ?a" a88lied to mimic the "t(le o: "8atial continuit( 8ro)ided 1( the 20 ma8". For a 1etter !0 "8atial di"tri1ution ?e "hould o1)iou"l( u"e a )ariogram re8re"entati)e o: each 8ro8ert( "imulated in the re"er)oir. 7he )ariogram ha" an e/tremel( im8ortant role to 8la( in the a88earance and 1eha)ior o: the re"ulting !0 model" =Gringarten and 0eut"ch, 2--1>. 7he detailed anal("i" o: the !0 "8atial di"tri1ution o: CO2 and 8etro8h("ical 8ro8ertie" i" "till in 8rogre"", "o the di"cu""ion o: the"e re"ult" are not 8re"ented in thi" 8a8er.

Figure '. 2) spatial distrib"tion of CO2 or anic enerated b! the p!rol!sis /ock-,%al$ Picota #ell (Pic) and Liberia #ell (Lib)$

Figure %. 7) spatial distrib"tions co'p"ted fro' () CO2 'eas"red in-sit" and, 4) porosit! 'eas"red insit" for the Padilla For'ation$

Figure 6 "ho?" the re"er)oir" !0 La Ca"ita, Padilla-Menchaca, La Mula, La .irgen and La PeCa, a" ?ell a" their re"8ecti)e )olume" o: roc< in the area Florida-Minero. 7he"e )olume" o: roc< "er)e to calculate the )olume" o: h(drocar1on", CO2 and @2 "tud(. 8re"ent in the area o:

Figure 6. *ol"'es of La Pe8a, La *ir en, La M"la, Padilla-Menchaca and La Casita For'ations in the block Minero-Florida$

Conclusions 7he e/8erimental re"ult" "ho? that the Minero-Florida area re8re"ent" a 1a"in mature that 8roduce C@4, ?ith a lithological "eJuence ?ith ?ater circulation ca8a1le to 8roduce CO2 organic and inorganic ?ith 8roce""e" "uch a" 1acteria and thermochemical "ul:ate reduction =+ $ and 7 $>. @o?e)er, the CO2 8roduced 1( the"e reaction" i" not "u::icient to e/8lain the )olume" re8orted in the "tud( area. 7he"e e/8erimental re"ult" can onl( 8ro)ide a 8unctual idea o: the origin o: CO2 in the Miner-Florida area. 7he re"ult" o: our 8reliminar( !0 "8atial di"tri1ution o: CO2 and 8etro8h("ical 8ro8ertie" ha)e 1een o1tained u"ing the :e? a)aila1le data. 7he "tructural modeling and the !0 model Jualit( ?ould greatl( 1ene:it :rom an e/hau"ti)e !0 "ei"mic data, "ince the current inter8retation :rom "ection" "till lea)e" "ome area" highl( uncertain. 7he 8etro8h("ical and ga" content modeling ?ere 8er:ormed u"ing <riging ?ith a Gau""ian )ariogram :or all )aria1le". 3n order to 1etter e/8lain the origin and di"tri1ution o: CO2 in the Minero-Florida area, it ?ould 1e nece""ar( to o1tain more data to 1etter con"train )ariogram" model" and range" :or each 8etro8h("ical 8ro8ert(. #ltimatel(, ga" com8o"ition" could 1e modeled u"ing thermal and chemical modeling con"i"tentl( ?ith the !0 model geometr( and it" e)olution through time. @o?e)er, the methodolog( 8ro8o"ed in thi" 8a8er ha" a good 8otential in oil e/8loration. 3t ?ill meaning:ull( "u88ort the deci"ion-ma<ing at Peme/, in )ie? o: the location o: :uture drilling o: ?ell". Our methodolog( can 1e ada8ted to other area" o: oil e/8loration. 7hi" method ?ill 1e im8ro)ed 1( adding the direct u"e o: !0 "ei"mic data and doing a lin< 1et?een Gocad and Petromod "o:t?areL".

Ackno/led,e'ents 9e ?i"h to than< man( colleague", e"8eciall( JacJue" Pironon, 3"1ael uXrez $uiz, 0anielle +artier and Judith 0u8la( :or acce8ting in their re"8ecti)e la1oratorie" :or the anal("i" o: "am8le" u"ed in thi" ?or<. 9e ?ant to than< too the Me/ican Com8an( MPG ?hom 8ro)ided in:ormation, "am8le" and 8art o: the :unding :or thi" 8ha"e o: the "tud(. Paradigm i" al"o ac<no?ledged :or 8ro)iding the Gocad "o:t?are.

0eferences 4l"aa1 0., 2--%. 2tude" de la 8roduction et de la migration de" h(drocar1ure" dan" le 1a""in de a1ina" au Me/iJue et de 0onet" en #<raine =4"8ect *conomiJue et 2/8loitation>, 7hY"e de lL#ni)er"it* @enri Poincar*, Nanc( 3. Camacho-Ortegon L.F., Martinez L., Piedad- anchez N., Pironon J., Monte"-@ernandez G., Gallardo J.C., uarez $uiz 3., 2--6. Modeling o: the CO2 and C@4 :ormation in Me"ozoic tud( o: geochemical im8lication in relation ?ith "ediment" o: the Mi""i""i8i .alle( t(8eA

heat :lo? e)olution in the Pirineo 1loc< o: the

a1ina" 1a"in o: Northea"tern Me/ico.

22eme $eunion de" ciencie" de la 7erre, Nanc( =Fr>. Machel @. G., 2--1. +acterial and thermochemical "ul:ate reduction in diagenetic "etting"A old and ne? in"ight", edimentar( Geolog( 14- 8814!-1%&. Martinez L., Gallardo Garcia J.C., Camacho-Ortegon L.F., Piedad- anchez N., Monte" G., uarez-$uiz 3., +artier 0., 0u8la( J., 0elgado @uerta", 2--6. et @2 toc<age naturel de C@4, CO2 dan" le" "*diment" car1onat*" de t(8e Mi""i""i88i .alle(A *tude" g*ochimiJue et

8*trogra8hiJue de la di"tri1ution "8atiale de" r*action" 7 $ et + $ dan" le +a"in de a1ina" au Nord du Me/iJue. 22eme $eunion de" ciencie" de la 7erre, Nanc( =Fr>. M*n*trier C., 2--&. Mod*li"ation thermiJue a88liJu*e au/ 1a""in" "*dimentaire" A +a""in de Pari" =France> et, +a""in de a1ina" =Me/iJue>, 7hY"e de lL#ni)er"it* @enri Poincar*, Nanc( 3. 22&8. 2guiluz de 4ntunano, ., 2--1. Geologic e)olution and ga" re"ource" o: the a1ina" +a"in in northea"tern Me/ico, 44PG Memoir %&, 88. 241-2%-. Gallardo J.C., Martinez L., Caumon G., Camacho-Ortegon L.F., Monte"-@ernandez G., Piedadanchez N., au""e J., =2--6>. !0 0i"tri1ution o: the CO2 Naturall( toc<ed and;or Formed into the Minero-Florida +loc< in the ciencie" de la 7erre, Nanc( =F$>. Godhammer, $. B. and John"on, C. 4., 2--1. Middle Jura""ic-#88er Cretaceou" Paleogeogra8hic 2)olution and eJuence-"tratigra8hic Frame?or< o: the North?e"t Gul: o: Me/ico $im. ((P&. Memoir %&, 88. 4&-61. Gringarten 2mmanuel and 0eut"ch Cla(ton .., 2--1. 7eacherL" 4ideA .ariogram 3nter8retation and Modeling. Mathematical Geolog(, !!, &-%-&!4. Gallardo J.C., Martinez L., Caumon G., Camacho-Ortegon L.F., Monte"-@ernandez G., Piedadanchez N., au""e J., 2--6. !0 0i"tri1ution o: the CO2 Naturall( toc<ed and;or Formed into the Minero-Florida +loc< in the ciencie" de la 7erre, Nanc( =F$>. urdam $.C., MacGo?an 0.+., 0unn 7.L., 1,6,. 0iagenetic 8ath?a(" o: "and"tone and "hale "eJuence". Contri1ution" to Geolog(, #ni)er"it( o: 9(oming. 7rilla J., Gonzalez-Partida 2., Le)re""ea G.,+an<" 0., Pironon J., 2--!. Fluorite de8o"it" at 2ncantada-+uena)i"ta, Me/icoA 8roduct" o: Mi""i""i88i .alle( t(8e 8roce""e", POre Geol. $e). 2!, 1-%D124QZa re8l(. a1ina" +a"in, North o: Me/ico. 22eme $eunion de" a1ina" +a"in, North o: Me/ico. 22eme $eunion de"