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Home My WebLink AboutGMC Data Report No. 008SHELL OIL COMPANY P.O. BOX 527 HOUSTON, TEXAS 77001 July 25, 1974 · Subject: Gulf of Alaska Samples Mr. Thomas Marshall Chief Petroleum Geologist Alaska Department of Natural Resources Division of Oil and Gas 3001 Porcupine Anchorage, AK 99504 Dear Mr. Marshall: Attached are copies of analytical work performed by Shell on samples collected from the Division of Oil and Gas sample laboratory by ~ir. Clif Jordan before his resignation. The analyses performed were Pyrolysis-Fluorescence and Vitrinite Reflectance. In order to aid you in understanding the results, we have attached additional text and illustrations defining the proc edur e s. We greatly appreciate the opportunity to perform the analyses and trust that the attachments are satisfactory documentation. Please sign and return one copy of the enclosed Transmittal of Data. PTL: SAH Attachments Very truly yours, PYROLYSIS-FLUORESCENCE AND VITRINITE REFLECTANCE STUDY TENNECO MIDDLETON ISL~D NO. 1, SECTION 28 T28S, R6W, C.R.B.M. GULF OF ALASKA PROVINCE, ALASKA Pyro1ffsis-Fluorescence Study Ditch samples from the Tenneco Middleton Island No. 1 well were examined for source rock potential using the pyrolysis-fluorescence method. The results are summarized on the attached source rock log and data sheet. Because of the very small size of available material, we composited a number of ditch samples to make up a single "p-f" sample. For this reason, we used 0.2 gram for the 30 samples examined, but the results were Plotted according to the standard size of 0.1 gram. The attached Patent Disclosure by R. L. Heacock, et al., "Process for Measuring the Live Carbon Content of Organic Samples" provides the background needed to interpret the basic data. The pyrolysis-fluorescence technique differs from the non-carbonate carbon content in that p-f measures only the thermally reactive organic matter. On the data sheet and source rock log is the notation "STD = 37 /~ 2." A glass rod having a fluorescence of 37 · 2 units is used to staEdardize the fluorome.ters; the values shown in the Patent Disclosure and in the current study are calibrated in this manner. Vitrinite Reflectance Study A total of ten composited ditch samples were prepared for vitrinite reflectance study. The vitrinite was concentrated by non-oxidative acid solution of the inorganic matrix. Standard A.S.T.M. procedures are followed for polishing and examining the specimens. The results of the examination are sunn~arized on the individual sample histograms and in the table presented below. On the histograms, each vitrinite reflectance reading is shown to thc nearest 0.01 percent reflectance in oil (% Ro), and the values are summed up for each 0.1 percent Ro group, i.e., 0.30 to 0.39, 0.40 to 0.49, etc. In the table, the maximum and minimum reflectance values give the range in readings; the (arithmetic) mean Ro is given with the limits of uncertainty calculated for 95 percent confidence limits. Where the confidence limits are broad, such as in the first sample, the results are con- sidered to be poor; where the limits are narrow, such as in the 7500-9000 foot sam. pie, the results are good. Inasmuch as these are ditch samples, there is apt to be a certain amount of cavings present; further interpretation would be required to discriminate between cavings and in-place material. Depth,_f.t_ M__~ax Ro% Min, Ro% 195-1350 1.75 0.72 1635-2025 1.50 0.57 2].00-3250 0.95 0.28 3250-4500 0.57 0.21 4500-6000 0.37 0.20 6000-7500 0.52 0.23 7500-9000 0.45 0.34 8900-10500 0.74 0.2]. 10500-11500 0.89 0.20 11500-12000 1.05 0.24 Mean Ro ~: 95% Confidence Limits · 1.32 + O. 15 1.02 -+ 0.16 O. 53 ± O. 07 0.29 ~ 0.02 ~',,~ ~, , 0 34 · 0 03 ~'"' . ~ ,~/,:i. 0.41 · 0.O2 0.37 ~ 0.04 0.37 · 0.03 ,~.~ :~.:.i 0.49 · O. 10 Some of ti ethods used to determine the burial metamorphic history are summarized in the attached table taken from a forthcoming publication by Hood and Castano. These methods are related through the use of the LOM (level of organic metamorphism) scale reported by Hood, et al. (in press). The tech- niques for measuring the level of organic metamorphism reflect tile irreversible effects of temperature and time--hence, of thermal history. Therefore, the reflectance data presented above can be readily tied into LOM or the coal rank scale, which for many years has been the standard for changes in organic matter during burial. .- , :.- ...~ ~, ~ PYROLYSIS-FLUORESCENCE D'~:~, SPL. 2X 4X SX 16X ,-,j;~'~-.~. ,.'~ ,,o. s,,,,.,.,~,~,.,.. ,~.o.o~¥ ,.,,.,.,,.,~ ~,., ..fl( ~.:,,,,:~: .- 5ML 12ML 24ML 48ML U~) , '/ / /~'- ~0;' ,,. q. ~ 0 ,, ,p..~/o---.~ola o o o ..... ~ l&~-~-/.~_~~ ~ I e._.l "'. e,,t J 00 ~.ff.,/o.~-/~oc l.e-_..I o "o ~ . . 6 /J&~-/5~.~., .. o_ o .... t ........ o o ~ /¢~-:.,~.,.~ .. % ~ o o . .. ¥ ,p:'c: .... "_ :.l .. ~ o_..s ~ ~ ,pp..~-,~ ,.'~o ..o o ... /~ ..... ~..~ . ~] , , , ,~ {~, ........... ' ~ "' ~ ~ ,.- t j . '~ ~x ' '~ ~ ' " ~ ' ., , ,, '.. ' ~ ..' . . . ~ ' , , .~., . '. ~ ,, , ; ~, .- .. C~I~,;~©ANY - TE~;qECB ','fELL ~R BUTCRBP - ~.,EOOLETE~I'..~ IS.-I,~ DEPTH DR S,~},?IPLE i.:~g;.':'.'.-.:.. 1SS 1350 LAB I-,lO,. - V8875 LDCATIDd- 28 2dS STATE -. ^LS 17. 2, ' I I I I t I I I I I d 6 6 6 6 IT O --, N 6 ' PERCENT { ' , { ~ETRZNITE REFLECTANCE HISTEESRAM CE.~WPAN] - TEFI, qECB. ~'~ELL ~R @UTCROP - WIOOLETBN IS IqE,) 1 DEPTH @R SAWPLE ~";-,.-.- 1835 2025 LAB lqt9 - ,, 8~,, ~ L~CATIE',N- 28 o,~o STATE- ALS 17. Z < ~o. · 2. I. 6 · I ' I" l' i 6 6 ,,, I 6 6 d d d d d .-. .-; .~ · PERCF~',,IT i I I ! "! brJ]TRTNTTE REFi_EDTANCE H]]ST~DGRAM . : . ESk,1, ANY - TENNEP. B VtELL E~R BUTCRDP - MIOOLETFJN IS. N@ l' E£PTH eR SAI~P..L..E..-r,~;?-=-'-: '2tOO 3250 L,,",,B Nfg. - VS877 LBCATZ@N- 28 255 STATE- ALS · lC~ 18 * 1.'/ 15. IS. 14. 13. 11. '7'. .4. :2. I. d d d d '1 ~_ PERCENT '~¢-r"r~-rNI'rTk- p, FFi._E~T,~N~E:'i HZS'I"EJ, ISRAM 18. 17. IS. > 12. FIIl. ~] 3. Cg)WPAN"f - TENNECB ',','ELL '~R .EIUTCRE~P - WII]OLETBN IS. I'qB 1 DEPTH ,~R S&WPLE NE'~" . 3250 4500 LAB ND. - V8878 LDCATIDN - 2B 28S '.STATE- ALS d d 6 6 6 6 6 6 PERCENT VITRINiTE REFLECTANCE HIST~GR/~M CI~.,,IP,~N'f - TENI',EC@ t'IELL ~R DUTCRDP - t,,,'IIOOLETi"']N IS. N@ 1 DEPTH DR S,A, WPLE ND.'- qSO0 8000 LAB NB. - VB87q LDCATI~iN- 28 285 ' D,'t STATE - ALS ~1. 20. 1~i. 18. 1G, 1~. 14. 13. 1~. 11 10 8 ? S 3 1 d d d d d d d 6 6 6 .... PERCENT -'. b~J]TR]]NZ[TE REFLECTANCE HIST~]R^M 18. 17. Z [] 3. 2. CBWPANY - TENNECEI ~18o~.0 LAB Ng3. -' ~','ELL ~R @UTCRBP - MIDOLETEN IS. N@ 1 LQCATIBN- 28 285 lB'It · OEPTH ~R SABPLE. ~I~7:'..- 8000 7500 .STATE - ALS · '~ . PER£ENT ~,rlTRTN]]_TI-- REFLEE';T^NCE HI"STI~GR^M CBk,'~P,nI"~Y - TENNECB LAB NS. - V8881 2'2. 20. 18. 0 ,'3 >'12. 3. · ','~ELL I~R BUTCREP- MII3OLETIgN' IS. NB 1 ., DEPTH eR SAI,,,i.P.~. ~>':--'- -. 7BOEI qOEO d d d d d d- 'd d ,~ . LBC, ,TIEIN 28 28S B',',' STATE - ALS ,j PERCENT bC[TRZNiETE REFLEE;T,&NCE HZST[gGRF, M LAB hiD. -'v ','TELL ['ER' BUTCRE.':P -MiODLETSN' IS. DEPTH · :22. ~1. L"E4. L.,'",,TiW,J- 28-.- c,c, STATE- ALS 17. 'd d d d d 5 6 5 d d ~ ; ..... ~ - - ~ PERCENT .. ,, V.-[TRTNTTE F:,'EFI_EBTANE;E H]]ST~GRAM " E.'I~MPAI'q'f' - TEI',II',IECi~ '~ELL ~R @dTCR~P -WIODLcTFa,I !S. I',!9 1 22. DEPTH 8R SAWPLE h,.~f~...L'~:_.IC6LO 11SO0 STATE- ALS 21. 20. lcd. 18. 17. 14. 13. 12. 11. I0. 8. 7. 3. I. O. 0 N ~] ~' 6 d d d d PERCENT l i' V]]TRZNTTE REFLEE;TANCE HZSTEc.3. RAM ' LAB h,tt~ _ · ¥ LbTCATIFJN '28 285 ',STATE- ALS 17. 1~. IS - Oo i I 6 6 6 6 6 6 6 6 ~ PERCENT .__ I · V]]TRTI-,ITTE F~EFLEIZTAI',,IIZE F-I.T_STIDGRAM , , ' ' ' ' ' SPORE THERMAL VITRINITE COAL - CARBON- ALTERATION REFLECTANCE LOM RAN~' BTU IZATION INDEX '~ % VM SUGGATE -3 .STAPLIN (1969, 1973).,j 0 ~ (1959) X ]0 GUTJAHR (1966) SEE ALSO CORREIA('GT)J! _ · -.- "" INTERNAT. CASTA~O, 1 - N 0 N E HDBX. OF THIS PUBL. COAL (R O~,~Ax) - (YELLOW) PETROGR., 2- l Ro,, ~,,,, ) LIGN. - 2-SLIGHT 4-- (BROWN- - 8 YELLOW) , SuB_C -9 -.- ' BIT. B--10 -- ~.. - -- 11 - --2.5 8- C Z_. 12Z-(45) YELLOW 0.5 - HIGH__13 z - -VOL. B__ Z_ 14 ~--('4 O) ..... - 10--BIT' A - - YELLOW _ - - _15 '---(35) TO DARK 1.0 1.0 _ - -, --=- 30 BROWN - 3-MODERATE- - 12,MV BIT. _B.-25 3.5 (BROWN)- 1.5 1.5 - - ~~. - LV BIT. z._ 15 3.7 .... ,.,,~..f,,~,.x_ Z - - 2.0 2.0 _ 14- -_ - ~ SEMI- -10 - - - ANTH. - - 2.5L" _ BLACK - +_ 4- STRONG ,,,2.5 -- 16-- _ (BLACK)- ----- - 3.0 ,, . ANTH. 5 3.5- - 18- 4.0'= · · · ,, ~ O/'1 .......... 74. 105'2 ~ . .. .< April 2"o, 1970 R. L, HEACOCK ET AL 3,508,877 I'ROCESS FOR MEASURING TtlE LIVE CARBON COHTENT OF ORGANIC SAgFLE$ Filed Nov. 15. 1967 Sheets-Sheet 1 I000 800 ~00 400 200 / 0.4 0.6 1.0 2.0 ¢),0 6.0 10TAL 0~CAI!IC CAR~0,~, FIG. ! 20O .. ~ L___..L,__I I 1LJJ. ,50 10 I00 200 400 GOO 10O0 [ XTRACT/,BL[ IIEAV¥ HYDROCAR~OtlS,PPH FIG. 4 200 0.6 0.~ 1.0 2.0 '~.0 G.O 8.0 IOIAL ORGAIIIC CARBO[t, % FIG..2 INVENTORS: ROBERT L. HEACOCK ARCHIE ItOOD t~Y' ~~-,~/3 a~~' THEIR ATTORNEY Aprll 28, 1970 r~. L, HE^COCK ET At. %.;[¢~;i'&~ FF, OCES5 FOR }41.3ASURING IllE LIVE C^i~BOlt CoN'r?HT OF O,~O^:l;i;X; :~::,,,,tl~ Filed Nov. 15. 1967 iNVENTORS' A R C H ! E BY; ~~ $l~'~~ ~o April 28, 1970 R.I._. HEACOCK F-T AL 3,508,877 ['R.3CESS FOR t.:E,\SURII:G TIlE LIVE CAREON CO:ITEN? OF ORGANIC SA:,;FLES Filed [~o'l. 13. 1967 3 Shccts-Shee% 3 A !000 2000 ..%000 ~ooo ~o~ ,°o o I00 2OO lA · 2620 3070 JC 3290 421~ I ~. E j [ 4465 ~00 (; FLUOROgEIER UNIIS FIG. 6 INVENTORS'. ROBERT L.'liEACOCK ARCHIE HOOD BY: THEIR ATTORNEY 3,508,877 Patented Apt'. 28~ 1970 i . 3.Sfl~1,877 l l,,,q~,,~, irs.. u,,i::m~rs I, Mu.~t (Iii ('Omlmny, New l.ilcd N~. 13. l'}bT, Sur. N,. 682.466 Inf. ('1. (;0In 2i/24, .~1/12, 33/2.1 U.S. Cl. 23~23~ 8 Gl:thus AllST[,'.~.(:I' {11r '1'111.; I)ISCI,OSUI~F, A process for m."a,.u~h~?, lite live carl,on content of an orp:~nic, sample bv. Jwalin,'. Ih.: .,,a.'uplc lo pyrolyzing tem- perature so that vapm's are :.iron oil. The vapors arc co:l- 15 dcn.:cd, tit,: fluorc-ccncc lhc~o.,f i_s ntc::,.urcd and the live carbon cea[on! of the ~.nmFle merle, rial is d.:'lermincd by correlating thc IVlcastlred liuo;e:,,:cl~e xx ith thc fluorescence from a n:atcrial c,f kr.ov.n c:u b~)n content. .... 20 I1ACKGROUND OF TIIF. INVF!N'FION Field of the inventiun T],is invention rekltcs to a process for measuring the 25 live carbo:~ con~cnt of Ol'~itlliC samF!cs a~xl, ii,ore par- fict:l:trly, thc live c:~rbon co,dent of bit cuttings obtained iu orilling a well ia subterranean ca~lh formations so as to map thc dist~butiou of live org:~nic ca, hen content of lhc subterranean formations. 30 l),~cripfien of the prior a~t Varhms geochemical mcth'ods have been suggcslcd prcv[ous!y for dctcrmin~n~: the locntion of underground pelvok,~;m rc-ervcirs. 'l'hcsc m~thu,ls are iutcndcd to tlc- 35 lcct the pre,once of petroleum con~lhucmg in surface or l~ndc:'~zrot~nd formations in ~,rcatcr II~an normal quantity. Such anomalies arc'taken as an imlic,~tion of the prox- imhy of a petroleum reservoir or other concentration of ~21rolcum-lypc hydro-carbon~. It i:~ thus possible, by dc- d0 tcciing the pre,once of t,ctroDum con, titucnts in earth loc:etlon and proxi:nity of petroleum dope>its by cot're- lati~g il~e relative amotmts of lx'trolcum constituents pre,.cnl in the earth ~am?;e~ with tl~c locations from which .!5 It has been st ?.to-,ted previously that file presence pctro]cunl ctm~lit~cnt~ in an earth samt*l~ may be tcclcd by ext~ac:ing or?.:~nic conqituculs from the earth s:~mi, le and then er:flu:fling the llmuc:.ccnce of the ex- 50 tract or a concenlralion t}lercof u~}dcr hilt:ri'lo!ct light. co, lain i'ctrolcum constitut-nts, c~q~ccial!y inlcrmcdiale nrom,ttics. ();}e such mclhod i~ d~s:ril)cd in t].S. Patent No. 2/151.883. }loxvcvcr, such prior art techniques arc' 55 rdativcly elaborate and complex. SUSISIARY el: TIIE INVENTION It is an object of Ibis inx cnti,m lo rapidly and cco- n0mically dclcrmine thc live ca,ben contour of an organic sample. It is a further el,itel of ll~is invcntion to rapidly and cct>m):nic;tlly m.,p It)c di,llil,~,ion of live erg:talc c:u'btm con( c~ltl'ali~,ll in ~:tml,lCx. s~l~Jl an bit cullings released in d~illing a wc!l. rlo:n stfl,lcrrancan earth formations. G5 sample lo :t ~clcclcd lD'~olyzing lCml'cratt~rc :it tent. In one application of the invention, a pluralily of such.s:~ml'Ics, prt. fcrablv comprihir~g bit cuttings ~ctcascd I,y drilling a p!u~ality of x,.'cll horcholc% arc mc,tsuicd so as Io map t}lu live tarbell contents of thc cm th format/ohs. IIRll[l: DESCRIPTION OF 'DIE DRAWING FIGL!I(I[S I through 6 arc graphical prcscnlations comparing the resulls obtained by thc process of tl~e 10 vcmion with knoxxn tests, DESCRIPTION OF TtlI[ PREFERRED EMBODI~IKNT There are lhrce types of carbon of org:u~[c mallet. Total c:ubon includes all of the organic (i.e., noncar- bonale) carl~on ia a sample. I.ivc carbon is flint portion of thc fetal crabon which, on pyrolysis at 500° C. in the labor:dory or du~ing future burial Io grcaler depths and Icmpcratures in the sub~tu'l'acc, yields apprcc[ai)lc (lu~nti- l~cs of hydrocarbcms and ether volatile organic matter.. l)cad ca,ben is thc remaining.. Fro'lion of total carbon, i.e., that xx hich, on heating, yields essentially no hydtocarbonfi or other volatile or[:anic matter. In earth form:~tions, nfixtu:'e t)f both dead and live carbon commonly occur. It is mainly th~ live ca~bon fincfi:rained rocks with which we are concerned in instant disclosure, since it rcl~rescnts the source of the carboa of petroleum mokcules. After exposure to labora- tory temperatures of about 500* C. or to subsurface temperatures of about 250° to 300~ C., thc live carbon is dc;t~oycd thcrn~aily, and Ibc remaining carbon is dead carbon. The or/anic live c:ttl,on contel!Iq of subterranean earth formations arc determined by sampling bit cuttings Ica~cd by drilling at knov,'n dcptl,s ami location~ within the earth formations. A sample of the bit cuttings preferably boated in a small container, such as a glass test tube, hcl,l over the flame of a h~ating ,levite, such as a 13un<ch burner, until thc closed end of the test tube reaches ;t se!coted pyrolyzing temperature and vapors are given off. This tcml'~raturc is approximately 500° C. or Ibc poinl when the closed end tff the test tube turns rcd (i.e.. "red heal"). Such a tcm?cr:tlurcs insures the pyrof )'sis of suJ,sl:tnti:tllv all of the erg:lille mat:er within a relatively short treatment time. 'l'hc amount of bit cuttin:;s p!~ccd in ll~e lest lube for sampling is rchxlivelT ~m:tll, as. for example, about Ion small drill cutlin:'.s or approxhm~tcly one-tenth of a gram. 'lbo lest tube is hchl ?,ct:ally horizontally xkhi!e being heated, w/th the closed end over the hc:tting des ice. The open end of ll~c lube rcm:dns cool and tiros the pyrolytic v;tpo~x from lhe cultings l.:nd Io ctmdunst~ on the walls of the tube. When the sample is cool, a small qu:ultity so!vent is :tddcd to obtain a nearly transparcut solution. For example, three ~nitliliters of chlorothc~te i,; added Ibc et;c-tenth gram sample, and thc solution obtahlcd ttam[crred Io a clean tc~,t tube. The test tube containing lite solution is lhen lq:Iced in ;t convent{onal l]t~oromctcr (for example, a Tu~ nor Model O0 11(} lh~oromcter, pzclc~ably mo,tilicd by thc addi;h,n a 99C~. opaque neutral dcn,lty iiltcr Io bring the 5cn,itivity of tl~e fiuoromclcr wilhin lhe range typically uccdcd for 0.1 g~'am samples) for measuring the light intensity the solution. As discussed above, the solulion musl be nearly It:ms- s:imp!ch j'.ixiiut a fluore,cence reading Frcatcr Ihan 2(} on Iht m~lilicd 'l'urncr llumomclcr~ or havin~: a 1,~o,~ colmcd s~dl~l-itm, may, t,l Itlllhcl thlulion xviih gixc lar}'cr meter rcadin,,,~ of Ilu,~rc,,ccncc I~r I~nil original ~.mHqc (Ihis i-, b:[{cvcd lO be due to lil'hl sorp~itm by lhe lelativcl7 conccnHalcd solution~ of 3,505, S77 3 taincd. '1 h.' Ik:~.~l :c.;di~? f,,r thc diluted sample is muhi- plied by Ih: dili:t{o:l f.,.clt,r to obtain the corrected ql~c :tp:,roxima:c 5C0" C. pyrolyzing tempera!utc con,ider:d, ly F~ca~cr th.~n lite temperature ;tt ~bich oil is formed from o:'g.~n/c m:tllor ill %-(limenls ig thc sub- organic :;~;::l.:r t,f ;t linc-g~aincd szdiment may I'c postu- lated a~ f,4k, ws: l:i~,t, part of the o~g:mic matter convcr:,.,l t,, a nonxclatilc. Cltl'bOlldciotls roiduc (i.e., dead c;::'!'{.:l~. Scdolld. simt:ltancously, the other part of the otga,~c n:atlcr is COgVCl'It'd [O VOl;tl[]C hy..l;oc:~rk'ons and ~'clat,'d conll'ot~gdx x~h;ch ;lle rapLlly db;tilled from the rock. The highcr-Ndli[;g products arc condcuscd on the cool walls of thc test tut'c. Third. thc diwtribution of molcct:!c~ by s;/e aad IS'pc in the volatile pyrolysis l~roducls m:ty differ co::,Llcrably from thc tot:il dis- triL',ut[o;1 of molccu!cs which xvotdd be released fro:n the rock u::.Icr natural conditions cfi increasing dcpLh of burial xx'ifi:h~ ~hc carth. !Ivwcvcr, although tl~2 l-roporlion of x'o~a!ile l,Yrols'sN l,ro,h:cl5 exhibiting fluorescence is probably small, the fluorescence of thc volatile pyrolysis product; is ~clatcd lo li:.2 s,m of (a) thc small amount of heavy hydrocarbons in 1!~,2 rock before pyrol)'~is and (b) the addhional oil x~h[ch could be generated in the rock undor ,a~ura! condi~k,ns of incre:t~;~ng ten~pornlure. The fo!!owisg discussion of thc figures or the drawing will l,ri,,: oul Ibis rcl2~ion,hip more clc[:rly. Sam?cs tzced in developing and checking lhe method discu,,.cd above :~n,i ~l:c int.:rprc~ations following were taken flo:n central Wyomi?g core holes dri!!cd in 1963. The~e snmples a~c all Cretaceous rocks that have not been cx;'o,.c,! Io h~j:h lcn;pcr:m~res and are immature odd-c~'o:~-nunfi'crcd no;'mM parafl~ns, Iow naFhthcne ring iptl:z and Iow ratio of extractable hydrec:~rbons to to[al o;Tanic c:M-on. I'-'IGkJRE 1 shows the relation- ship of cxtr.ts~,~Nc hc::vv hydrocarbons lo lolal organic careen comcms in the qVyoming core holes. 'I'bcse sulls v.'crc obtained by routine source rock analysis. The dca:l carbon cements of the Wyoming core hole samplss arc ;n all ca~s close ~o 1% wt. lie,ce lhe rcla- tion41~p invol;ing total organic carbon in I:IGURES 1 through 3 can l-e convcllc,l approximately lh'c ¢arboa simply by co:;~klcring live cant, on !o ke .1% wt. Ic% l'.l:~n ~he tolal organic earl'on. Thc coracle!ion bclv.'ccn lolal organic carbon concnt and pyro!y4x-fiut,rcsscncc values is shown in IrlGURI~S 2 and 3. f:IGURE 2 shows Iht relation,hip cf pyrolysis- flilOfec2ClldC values to tot21 oruanic cart'on contents in the W>o~a;n7 core l,olcs of I'tGURE 1. FIGURIL 3 is a str:digraph~: co:hD.:ri-on of lhe fetal erg.mit carbon con- lents and pyrolv-iq Ihmr:~<ccnce yahoos in the WSoming core holes. 'Iht r~ght-hand portion of the gr:~ph includes data for san:rlcs analyzed by thc test lul-c pyrolysis- fluoresced,cc i, rccsss of thc invention: the left-hand For- lion of the graph includdq tt:d:t analyzed for total or- ganic ca,ben. Thc l)'iw~ of formations lrax'crqcd by thc wcH l,o:chole arc indka~cd I,v thc Ic~crs to thc cxtrcmc right cf lhc graph of I"IGURIL 3. These formations are as follows: A--Steele shale B~Niobr.~ra limy shale C~C:trlilc shale l)--Frtmli;'r form:dion E--.Xlowry shale 70 1:~1.. 'l'lwrn,opolN shale O~Clovct ly 1'ol,nation I.IGIJRI~ 4 shmvs a comparison of pyrolyG,-lhmtcs- c¢nc¢ xalt:cs lo cxtracl;d,lc heavy hydtuc:ffl,ol~5 in tho 75 \\'yomi~g core h{dcs. As ii: l:IGIYl,'l". 3, thc right-h;::M portion of l:ILikJl{l( 5 includes data for sample'; ::inly,cd by the to4 lul'c plyr(dy~N.Iluorcsccncc process of. lbo in- x'cntion; the Icft.h.~nd l'Ortioa of thc Fr.tl:h d:pict.; thc con!chi of cxtr,~ct.tblc he:try [~v,lrtw:~rbtms.. 'Ilk' 5 of formations llaxcr>cd by th~ well l~orcl:nlc ;-c indi- ] ](.;URI~ 5 a,d corrcslX)lld to Iht ]cllcr~ dcscHlsscd xvi~h rc',~ct to I"I(iURIi 3. I:I(;UILE 6 i, a sm:ti!~r:~phic distribulion of pyrt,ly~ix- l0 l]t~o:'c::ccncc x';t'.uc~ comparin:: st;,,; :cs from th,: hole (ff ]:I(;URI'% 1 throu!:h 5 x~irl~ drill cultii~F'; from :: n,:arbv, well (approxim:itclv, I0 mi!0saw::v). .'l'he ri."'~.,~,- hand Forlion of thc graph cot'~cspom{~ to ll~e dr;ll lfi tings; thc left-hand ?trion of the core hole ~amplc~. 'Iht typ~s of fom~:tl[on,, cucougltqcd arc Ih.tel to lbo cxlremc ;iTht of FIGURI5 6 and s~mil:tr lc~t.:rs correq~ml tho'~c lihlcd above wi~h rcs,.wct to I'.'I(';URt~ 3. Thi~ gral,h shows that thole is a Food correlation belwcctl thc core 20 hole samples and li~z drill cutting~ f:om Ibc nearby borcho!c. I:I(;URIL 6 also shoxvs tlmt pyroly~.is-fluorcs- ccnce data for good cuttings can l)e t)scd intcrcb:tn~c;dqy. 5~ iih lite r,trcly avail.tbl~ data for co:'cs' in tl~c of Ibc hydroc;trbon l~otcntiz:l of a source formation. 25 In summ:zry, the test It)be py~ols'sis l]l~orcsccncc method of our i:wcntkm gives good cerrcl:¢ions xkil[1 el:al,orate chemical mclhoJs f(')]' dc:crm[ning iions of live crg:tn~c carbon and cxlract:d,!e he?.vy carbons ~n a subtcrrcan form:~t[on. It provides ov~ way 30 of con Jutting a sampling and map;qn? procedure utilizes wells that nmv bc drilled for 2urpo::es o:bcr mapi~ing procedure. Thc sami'!{ng and mnpph~g pro,c- dure comr, r~scs: sam?ling thc bit cuttings from conclata- ble depths in a ph~r:dity of well~: py~olyzing s::mFh:s 35 of ~he cuttings at a common sclectol le~nFcraturc: uring a common selected prOl,Crty of each pyro!3'zate- lJmt is indicnt~v2 of the live orm~qc c::rhgn contra,! of the lilt cutth:g malcr[al' and in,licating 1)~e varia~km v. hh the :weal location of 1he live o~ganic carb~m.co~tcnt 4{I ear[Ii formations fi'om which bh ct~ttinl,.s ~cre Thc pyrob'zing amt measuriag Froccdurcs can be of any of a v. ide vafic:y of proceduccs, such as c!cct~ic rum:we pyrolysis, flame ionizntion delector an:dys[s, sFcc~ro- metric analysis or thc like, that provide :,dcquate rapidhy' and economy with adequnte nccuracy. 45 The method of Our invention has the advaut:~e:~ excellent rcprod~mibility of rcqult% spce,l and sim:qiciw of OFCration, small size requiremcn!, :md low cost. On~ nF, l'!~c:~lion of ot,r invcnlkm would bca process' rork" map~. 'llms. our method is especially uscfu} identifying and cvahl:tt/ng Ibc tlt)::lily of both oil shah's 5~ ' · time. For cxaml,le, {!;eI }:ischcr As<~y method 60-granl samples and in excess el two hours analytical time. The p>rolysis-liuorcsccnce analvGq of our invcu- I[on rC¢lu[rcs oaly 0.[ grams of snmp[c and three to four 60 I~igtlle:; t~[ analysis. Ahho~q:h our inx'cnt{on ba~ t~ecn described xvi~h tria- l{oil to live orPallic c;~'l,og in stfl~torr;t~l¢;tn e3ri]l forg~a- lious, sttbst3ntially any mate~i:d having a pyrolyzable of 65 gan{c earl'oh content eau be analyzed by our mcth,,d, as, for example, resins, paint~, etc. In respect to mapping the distributhm of snblerrancnn live organic carbon comcnts, the tiara obta;ncd f~om a ph~ralily of wclN in :t given location can be il,cd Io indi- cate bolh Iht vcrtlcal and areal distribution of live x~h!~in the location. Of course, other mclhods for healhq~ a'sanqqe may occur Io one skilled in the ntt. l:or example, I:trFcr c{mlalrtcr~ and olhcr 15'l~:S of hc:~ti:~g tlcvi¢cs m.ty u'cd. lltmcver, o~r method gix'c, excellent rc~ult~ .% , I 10 5 for fl~:tlwr Jn¢;',',u[cm,.:nl,L if desired. We claim as our i,v,.'mion: I. ,5, p~o¢¢ss fc, r inc::,,~in:: thc carl..o,~ content of :tn orL'.:,nic s:tmFIc ¢o:~p, jxln!: tile :.tops of: Ilc:tli.,g said ,q,ililplt' 10 it sclectctl pyrolyzi,g lem{,cra- lille until F)'rcdyl;c va?ors al'e £ixcn o'.[ by s:sid sample; ,llClt',411'i:l:t thc llUOrescem, e th:ti is cxilil',iled by d¢IcFn'lil~i:l.',, tli~: c.trb,',n coatenl cH' :;.lid ~:tmpl.z by cor- I'¢{;!lil]g thc IllCa'.tl,¢d {]t,o,'¢'.;.'ellcc v.'ilh lhlOl'CSC¢,lt ¥:1!1!c5 Of ,ll;ttc,'{a['~ whose (.,[~',;tl]}C Caf[COil COlltCllt i~ known. 2. Thc l:roccss of ok, ira 1 incluilhl.?., p~ior to heating said s;tml,le, t'h¢ nlcl) of: t~iSl:O~.i,l.'.'. ,2{'~proXilll;ltcl.V O:~c-t¢llth of a .,.'ran~ of said snmplc in thc cl,.'~,.:d end of :~n o?cn ended test tribe. 3. 'l J:'2 F,,'OCCg5 O1' cl:,inl 2 whclcJil I1,¢ step of heating said :..'.mi,lc includes holt!ing said ~:'sl It,be subst:tnlialiy htu'i,',~::t:,.lly over Ibc li,i;ne of a hcatin?, device, ll~e closed end ~q' s:tkl test tube containing said s:,inplc being directly in ct,,:;~cl wi:h said flame. ,- 4. '11,,: p;ocess of claiitl 3 '" "' ~nc,uwn:...', :it'.er condensing ltl,.', t'i,]",t); .?, I}:e stcl:q of: co,~{i~'..!: said sa:'nl;lc; addiu?. :t tolvent lo s:lkl san:pie until said sample is $=,:. ,t,tnlially t, a!','q:.tlottt; and lra:,.fcrz'in:3 said cook.:l , ' S:ll]l?l,.2 Io ;t second test $. 'l'hc process of clai:u -; ,.\'{,crotn Ibc slep of measur- in?. ~h.:' ll,oresc,:nce includes the step of p{:~c.i;~g lhe sec- o,ld ;c:.t ti,be contai,fing Ibc cooled saint~l¢ in a light- intc;~,ity measuring d,:vicc. 35 6. 1he p!o.:css of ::~:~?ping Ibc didrR;t!lion of organic c:trb:m cent,tnt of bit c,ttings released in drilling a well ill a st,bterranean l'orm:d!on co;nprising tile stops Of: rcl,:o;'ing :t sitlnp!c {.~1' :,:lid bit cuilin.,.:s at ;t known depth and location x~ i;hin said subterranean formation; 40 he:~ting said s:llnplc Io a selected pyrtdyzing tempera- lure until pyrolytic vapors arc gi\'en off by said sample; coI:dcn.~ing thc ;,yrolytk x'al.'ors; mea<,ring thc liuo:'csccnce that is exhib{:ed by thc con- d,lnfied vapor.q of :l unit of said s:tmpl¢; dc!crmiui~,g Ill:' c:llbon conical of said sample by cot ~elating lite n~e:,surtd · litloicscence whh lll,orescent values of nlatc:'ial:; :'.'ho~¢ organic cart:on content is k IIOWll; 3 cor~'cl::ting linc r¢l:llionshil~ bc't',VO¢l~ lbo known depth ;!,;d ]o.2;lliull or .~;1!,.[ s;l:q{)le with lbo t!cternti~:cd car- boll cO~:lt'~lt Of sa/ti samp!e, l}~t,s determining both II,e dcpll~ itt u l~icll live orgat..ic mallet disapt~ars ;:lid 2U 25 30 6 tile depth at which so,rcc rocks for liquid h)dro- ca:'t, ons can be f{,und in a {fivcn area. 7. Thc pro:ess of claim 6 incluJi,~g the .steps determining the carbtm conical of a plurality (~f ,arm pies of bit cutting~ removed :ti a pl,ralily of kuosvn depths and }ocations uithin ~aid subtclri, ncan for. m;tti,)~:q ami rcco=,ling ~he carbon con~ent of said samplc~ with ~cla. ilea to thc depth :tilt{ ]oc;t:Jotl of said samples ma,~ thc distribution of all t,f s:,id s.tmplc', xvithiu said sublcirancan form;ilion. 8. A process for meast.'ing the carbon content of a rc!:uivc!y ~m;tll l,o:-tion of :tn ors,trait s:~mple, in:lmling heafi,¢ ,levite l~;tvillg a l]anlc Io heat said p,~lion, a seco;M lest lube bavinR an oFen cn.I and :t clmcd end. and a litdmintcnshy~ measuring device, said process inc't,d the steps di~{,osin~: said po, lion in the closed cml of saki first les: it, be; holding sakl first test tube substan!i:~lly t:ori;'on~al[y with the closed emi of sam ill'St test lube }:yin!: di- rectly in contact with thc llanic of said heating dc- vice' he:sting said porl[on to a selected pa~olyzing lem;,cra- tm'e unli!.~'"rols'ti:. vapors are =.-;yen c~[ by sai.l For- lion; eo,~dcnsing lbo pyrol'.,'tic vapors on the walls of said first lest tube; ct~vling sakl {-orlion within smd fir~.t test tube; ad.ti,U a solvent to said cooleJ Fortion until snkt porl}on is a sub.4antially tranMx, rcnt solution; transferrinlr said solution 1o li:c closed end of the sec. end le~t tube; measm'ing the Iluorescence !hat is exhibhed by the con- densed vapors of a ,~nit of s:dd p,,'ih',,~ t,:' pi:wing said second test tube in said light-intcnshy Jag device: and detcr,~ining the carbon content of sakl sample by cot relating the measured fluorescence with lluo~cscc~t values of materials whoso organic c:,rbon content is known. Refere,ces CRed . ' UNITED STATF. S PATENTS 2,!~3.564 12/I939 lforvitz. 2.45 l.$?~3 1{')/19.18 Squires. 3,322,50-1 5/1967 Capuano. 50 ""O"~ ,,l,'lS O. ",VOLi(, l'rimary Examiner R(31H:ICI' Xl. III:il:SI:., Assislant l.:xaminer U.S. Cl. X.R. r o t o/~o0 ,',- z o rr o · C RM-100 (4-71) ~"~"~='~'+-, ,.- ;;;;t, SHELI~-"_ cOMPANY I"=~c:o" SOURC,.. ROCK LOG STATE OR PROV COUNTY COMPANY FIELD OR AREA ELEV. SURVEY BLK. COMM. COMP. m.D. ELEC, LOG RADIOACTIVE MICROLOG LATEROLOG PRODUCTION SAMPLED BY: DATE P LOTTED BY: C~~-~:~ DATE .0 ',r I- TOTAL F LUO R ESCE NT UN ITS SCALE o o o o o o DEPTH AND REMARKS t O