QUANTIFYING KEROGEN, TOC

Slide 0
Quantification of Total Organic Carbon
• Reservoir quality indictor

• Quantify adsorbed gas in

conjunction with Langmuir
isotherm, pressure and temperature

• Estimate kerogen volume and

porosity
 Slide 1

Conversion of TOC to Kerogen Volume

Kerogen (vol%) ~ TOC( wt %) 

 b

 K vr
ker ogen

K vr
 M aturityConstant

• Kerogen contains Carbon, Hydrogen and

Oxygen
• As kerogen matures, carbon
concentration increases (Hydrogens and
Oxygens convert to Hydrocarbon)
• Kvr ~ 1.1 to 1.2, maturity constant,
function of thermal maturity
 Slide 2

Conversion of TOC to Kerogen Volume

(dry weight)

1) Grain density which includes kerogen 3) Bulk Density

1 K  TOC (1  K  TOC) b   gx (1  Vk   )  kVk   f 
 
g k  gx

2) Total porosity Where

ρg – grain density
  ρk – kerogen density
g b ρgx –rock matrix density
  ρb –bulk density
  ρf – fluid density
g f
Φ – total porosity

TOC – dry weight fraction of organic

carbon in kerogen
4) Kerogen Volume K – maturity constant

K  TOC   gx ( b   f )
Vk 
 k (  gx   f )  K  TOC   f (  gx   k )
 Slide 3

TOC Estimation (Core or Cuttings)

LECO
Sediment treated with phosphoric acid to dissolve away inorganic carbon

The remainder of carbon in the sample is oxidized to carbon dioxide which is then measured
with an IR detector.

Standard for TOC

Rock Eval Pyrolysis

Identify type and maturity of organic matter
Programmed heating of sample in inert gas (no O2)
3 minutes at 300C (VOLATIZN)
• Free hydrocarbons are volatilized and measured with FID – S1 peak

Heated from 300 to 500C at 25C/minute

• Volatilization of heavy hydrocarbons (>C40) and cracking of
nonvolatile organic matter - S2 peak
• Temperature of S2 peak is Tmax (fc of nature and maturity of
hydrocarbon
• CO2 issued from kerogen cracking is trapped in 300 to 390C range - S3
peak

The residual portion of the TOC is obtained from the oxidation of the sample in
a second oven following pyrolysis
.
 Slide 4

Total Organic Carbon Analysis

In-Situ NMR

Overlap
Kerogen Bitumen Light Oil
S2 S1

Core or Cuttings (Non Extracted)

• TOC (in-situ) is an
excellent proxy for

Overlap
Residual Oil
Kerogen Bitumen and OBM kerogen volume in gas
S2 S1 reservoirs.

• TOC can include bitumen

Core or Cuttings (Extracted) and oil in liquid bearing
reservoirs.
Kerogen
• Core measured TOC can
S2
depend on sample
preparation.
* S1 and S2 from Pyrolysis
 Slide 5

Example of sample
preparation impacting
TOC estimation in shale
oil well
 Slide 6

Estimation of bound/adsorbed hydrocarbon

via combination of Dean Starks and Pyrolysis
RHO_O (g/cc) 0.8
S1 (mg/g) S1 wt S1 PU OFP HFP Bnd Bnd:HFP
0.31 0.00031 0.1023 1.7922 2.8922 1.6899 0.584295692
0.41 0.00041 0.134788 1.064 1.864 0.929213 0.49850456
0.39 0.00039 0.12675 1.608 2.308 1.48125 0.641789428
0.47 0.00047 0.151575 1.9266 2.6266 1.775025 0.675788091 Adsorbed Oil as Fraction
0.36 0.00036 0.1161 1.1427 2.1427 1.0266 0.479115135
0.45 0.00045 0.147375 0.9455 1.7455 0.798125 0.457247207 of Total Hydocarbon
0.43 0.00043 0.139213 0.9 1.7 0.760788 0.447522059
0.47 0.00047 0.154513 0.9856 1.6856 0.831088 0.493051436 3.5
0.34 0.00034 0.11135 1.0257 1.7257 0.91435 0.529842962 3 y = 0.5621x - 0.0996
0.48 0.00048 0.1536 1.3578 2.1578 1.2042 0.558068403

Soluble Oil in S2
0.77 0.00077 0.253138 0.6732 1.1732 0.420063 0.3580485
2.5
0.15 0.00015 0.047438 1.9635 3.2635 1.916063 0.587118891 2
1.02 0.00102 0.330225 1.9366 2.4366 1.606375 0.659269063
1.5
1.35 0.00135 0.423563 3.0291 4.3291 2.605538 0.601865861
1.85 0.00185 0.592 2.5767 3.6767 1.9847 0.539804716 1
2.44 0.00244 0.77775 2.7864 4.1864 2.00865 0.47980365 0.5
2.64 0.00264 0.8349 3.2785 4.9785 2.4436 0.490830571
2.2 0.0022 0.70125 2.982 3.982 2.28075 0.572764942
0
3.47 0.00347 1.097388 2.772 3.972 1.674613 0.421604355 0 1 2 3 4 5 6
1.97 0.00197 0.627938 2.6376 4.0376 2.009663 0.497736898 Hydrocarbon Filled Porosity from Dean Starks
1.22 0.00122 0.382775 2.0384 3.3384 1.655625 0.495933681 Gas + Oil Filled Porosity
1.51 0.00151 0.479425 1.886 2.586 1.406575 0.54391918
0.69 0.00069 0.228563 0.6846 1.6846 0.456038 0.270709664
1.16 0.00116 0.3683 2.015 3.015 1.6467 0.546169154
1.33 0.00133 0.415625 1.9981 2.9981 1.582475 0.527825956
2.71 0.00271 0.85365 2.2825 3.5825 1.42885 0.398841591
1.78 0.00178 0.5696 2.6312 3.6312 2.0616 0.5677462
0.97 0.00097 0.314038 2.2458 4.1458 1.931763 0.46595651
1.14 0.00114 0.36195 3.48 4.48 3.11805 0.695993304

Soluble Oil in S2 = Oil Filled Porosity – S1 converted to PU

 Slide 7

TOC Estimation Methods from Logs

Empirical Methods

• Regression to bulk density

• Correlation to uranium content
• DeltaLogR – Resistivity porosity overlay method

Direct Methods

• Carbon subtraction method

• NMR porosity deficit method
TOC is traditionally used as proxy for kerogen volume in gas shale.
TOC is also important so adsorbed gas can be estimated in gas shale.
 Slide 8

Schmoker Model
• Kerogen from bulk
density
• Does take matrix
variation into account
• Clay vs. carbonate grain
density
• Weak with very mature
shales
• Kerogen conversion
 157 
  58.3 
 
TOC( wt / wt )   b 
100
 Slide 9

Uranium vs. Core TOC

Barnett Shale

SPE 114925
 Slide 10

Passey Methodology for TOC

 log R  log10  R   0.02  t  t
 baseline
 Rbaseline 

TOC (wt/wt)   log R  10 


2.297-0.1688  LOM 

100

R  Log resistivity (ohm - m)

R  Baseline resistivity (ohm - m)

baseline
t  Log compressio nal slowness(sec/ft)

t  Baseline compressio nal slowness (sec/ft)

baseline
LOM  Level of maturity Passey et al. (1990)
Correlation of Vitrinite Reflectance to LOM

http://www.henersonpetrophysics.com/tocp_html#LOMvsTOCP
 Estimation of Thermal Maturity
Passey Delta T Log R Methodology

GR Resistivity Porosity ELAN 2 200

125 05 15

1.5
1.8
1.9
2.0
2.1
DTCO 2.4

Deep
Resistivity
 Geochemical Spectroscopy:
Measurement Principles
Spectral
Stripping Oxides Interpretation
Acquistion (Relative Yields) Closure (Spectrolith)
(Dry Weights)
Si Ca Fe Mg S Al K Na Mn Ti Gd C
Counts

Energy
 TOC from Spectroscopy Log in Shale Gas
Depth
(ft)

TOC from Spectroscopy

 TOC = Total Carbon – Inorganic Carbon
(TC) (TIC)

 TOC is representative of TOC from Kerogen.

Oil-Base Mud
 NMR Porosity Deficit Method
SGR Deep Resistivity DPHI
CGR Ro TCMR
0…….150 0.2……….2000 CMFF > 3ms
(GAPI) (ohmm) 0.2…………. ELAN
…0 The separation between
matrix adjusted density
porosity (DPHI) and Magnetic
Resonance Porosity (TCMR) is
due to kerogen volume, which
NMR does not detect.
Lower EF Upper EF

The most viscous of bitumen

320ft may not be seen by the NMR.

Separation between SGR

and CGR reflects uranium
content
 Case Study – Eagle Ford

• Core TOC Extracted is the lowest as it

represents only TOC from kerogen
while Spectroscopy TOC sees all in-situ
TOC

• Core TOC Non-Extracted contains

residual hydrocarbon and bitumen but
is less than Spectroscopy Scanner TOC
due to some expelled oil

• NMR Porosity Deficit TOC matches

TOC Extracted as the NMR “sees” all
the bitumen.

1
MINERALOGY
 Common Minerals in Organic Shale

• Clay • Organics
• Illite • Kerogen
• Smectite • Bitumen
• Chlorite • Others
• Kaolinite
• Pyrite
• Quartz-Feldspar-Mica • Marcasite
• Quartz • Siderite
• Orthoclase • Barite
• Plagioclase
• Carbonate
• Calcite
• Dolomite
• Fe-Dolomite, Ankerite
• Phosphate
 Woodford Barnett Fayetteville Haynesville Marcellus Eagle Ford

Gas Shale
Lithology

Kerogen

Gas-filled porosity
Slide 123
 Source of Mineralogy
• Core / Cuttings
• XRD
• FTIR
• XRF
• DRIFTS

• Log
• Geochemical logs (LithoScanner and ECS)
• Mineral Model
 XRD (X-Ray Diffraction)
• Purpose
• Used to measure mineralogy
• Distinguish clay maturity based on
smectite interlayers
• Good for reservoir sensitivity
• Function: X-ray beam scatters based
on the lattice structure of minerals
• Disadvantages:
• Needs to be a well-defined crystal
http://pubs.usgs.gov/of/2001/of01-041/htmldocs/xrpd.htm
structure (ie. no organic or
amorphous quartz)
• Can not distinguish crystallography
similar minerals (ie. illite and certain From C. Calvin (2014)
micas)
 Slide 128

Core Data
X-Ray Diffraction (XRD)

Total Expandable Clay = Illite/Smectite * % I/S Expandability / 100

Units in wt%
 Calculation of Expandable Clay from XRD

Wtexp andable  Wtsmectite 

Wtillite / smectite  EI 
100
Wtillite  Wtillite / mica 
Wtillite / smectite  100  EI 
100

W texp andable  Expandable clay (wt/wt)

W tsmectite  Separate phase Smectite (wt/wt)

W tillite / smectite  Mixed layer illite- smectite (wt/wt)

W tillite / mica  Illite- mica (wt/wt)

EI  Expandability Index
 Smectite Group
A0.3 D2-3 [T4O10] Z 2 · nH2O

Aliettite Ca0.2Mg6(Si,Al)8O20(OH)4 · 4H2O

Beidellite (Na,Ca0.5)0.3Al2(Si,Al)4O10(OH)2 · nH2O
Hectorite Na0.3(Mg,Li)3Si4O10(F,OH)2
Montmorillonite (Na,Ca)0.33(Al,Mg)2Si4O10(OH)2 · nH2O
Nontronite Na0.3Fe2(Si,Al)4O10(OH)2 · nH2O
Saponite Ca0.25(Mg,Fe)3(Si,Al)4O10(OH)2· nH2O
Sauconite Na0.3Zn3(Si,Al)4O10(OH)2 · 4H2O
Stevensite (Ca,Na)xMg3Si4O10(OH)2
Swinefordite Li(Al,Li,Mg)4(Si,Al)8O20,(OH,F)4 ·nH2O
Volkonskoite Ca0.3(Cr,Mg,Fe)2(Si,Al)4O10(OH)2 · 4H2O
Yakhontovite (Ca,Na)0.5(Cu,Fe,Mg)2Si4O10(OH)2 · 3H2O
Zincsilite Zn 3Si4O10(OH)2 · 4H2O
Temperature vs. Maturation and Illitization

Pollastro1993
Smectite to Illite Equation

Elliott and Matisoff 1996

 FTIR
(Fourier Transform Infra-Red spectroscopy)
• Function: Infrared radiation is passed
through the sample –
• Some light is absorbed by the sample
before reaching the detector – each
material has a unique spectra
• Size of peaks is directly related to
amount of material in the sample
• Purpose:
• Measures mineralogy and
organic
• Can distinguish crystal phases
• Able to determine organic
• Disadvantages
• Sample prep is longer than mmrc.caltech.edu/FTIR/FTIRintro.pdf
XRD
• Not currently giving clay
maturity numbers with FTIR data

From C. Calvin (2014)

 XRD vs. FTIR mineralogy
XRD
WHOLE ROCK MINERALOGY
SAMPLE ID
DEPTH (ft)
1
n.a.
2
n.a.
3
n.a.
4
n.a.
5
n.a.
6
n.a.
7
n.a.
8
n.a.
9
n.a.
10
n.a.
FTIR
QUARTZ 45 65 54 62 69 48 46 64 40 56

K-FELDSPAR 4 1 2 2 1 2 3 5 7 4

PLAGIOCLASE 3 1 5 5 4 6 4 3 2 4

CALCITE 2 16 3 6 9 3 3 3 4 3
ANKERITE/ FE-DOLOMITE 0 1 0 0 0 0 0 0 0 0

DOLOMITE 35 9 10 7 7 11 33 10 34 11

PYRITE 0 0 1 1 0 0 0 0 0 0

BARITE 0 1 1 0 0 0 0 0 0 0

TOTAL NON-CLAY 89 95 77 84 90 69 89 85 86 78

SMECTITE 0 0 1 0 0 1 0 0 0 1
ILLITE/SMECTITE (I/S) 4 0 6 3 1 6 0 5 5 8

ILLITE+MICA 6 4 12 9 6 20 9 7 6 11

KAOLINITE 2 1 2 2 1 3 1 2 2 1

CHLORITE 0 1 2 2 2 2 1 1 1 2

TOTAL CLAY 11 5 23 17 10 31 11 15 14 23

GRAND TOTAL 100 100 100 100 100 100 100 100 100 100

RELATIVE CLAY ABUNDANCE IN BULK SAMPLE

% I/S EXPANDABILITY 25 15 40 45 45 45 45 45 45 50

SMECTITE 0 0 2 2 1 2 0 3 1 3
ILLITE/SMECTITE (I/S) 34 0 26 21 13 21 0 33 34 34
ILLITE+MICA 52 67 53 55 64 63 82 49 46 49
KAOLINITE 14 11 9 12 5 8 7 10 14 5
CHLORITE 0 22 10 10 16 6 11 5 4 10
TOTAL EXPANDABLE CLAY 1 0 3 2 1 3 0 3 2 4

RELATIVE CLAY ABUNDANCE (LESS THAN 4 MICRON SIZE FRACTION)

% I/S EXPANDABILITY 25 15 40 45 45 45 45 45 45 50

SMECTITE 0 0 4 4 3 5 3 3 2 4
ILLITE/SMECTITE (I/S) 24 16 49 46 41 60 46 39 38 46
ILLITE 45 25 30 22 23 16 31 30 34 30
KAOLINITE 22 43 9 19 19 16 12 17 16 12
CHLORITE 9 17 8 9 14 4 9 11 10 9

TOTAL CLAY 100 100 100 100 100 100 100 100 100 100

From C. Calvin (2014)

 XRF (X-Ray Fluorescence)
• Purpose: Used for bulk chemical analyses of
trace elements (>1 ppm; Ba, Ce, Co, Cr, Cu, Ga,
La, Nb, Ni, Rb, Sc, Sr, Rh, U, V, Y, Zr, Zn)
• Function: Sample is irradiated with
x-ray beam, which causes emission of
fluorescent x-rays at specific wave-
lengths
• Portable vs. benchtop
• Benchtop
» Higher accuracy over more elements
» Larger samples required
» More sample prep
• Portable
» Can be perfomed in situ
» Non-destructive
» Lower accuracy
geology.uprm.edu/facilities/Class%20Forms/xrf.pdf

From C. Calvin (2014)

Comparing Geochemical Techniques
XRD XRF XRF FTIR
(Benchtop) (Portable)
Mineralogy X X
Trace Element X X
Cuttings X X X X
Core X X X X
Destructive* X X X

*Indicates sample may need to be crushed or more

to be analyzed.

From C. Calvin (2014)

 Mineralogy from Log
• Neutron
• Gamma Ray
• Spectral Gamma Ray
• Geochemical
Life of Neutron
 Vclay vs. Neutron Phi

• Hydrogen index
50

• Clay
45

• Pore water
40

• Gas
35

• Kerogen
30

• Bitumen
VTCLYX
25

• Thermal absorbers
20

• Reconnaissance
15
10
5
0

0.45 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0 -0.05 -0.1 -0.15
TNPH
WELL: BRITT RANCH G 4-44
ZONE: 10000.000 - 13670.000 FT
DATE: 29 Jan 2004 @ 9:33
GR for Clay Quantification • GR activity sum of K, Th and U
• Clay content sum of K and Th
• U reflects redox potential

Gas Shale

Gamma Ray
 Spectral Gamma Log Summary

• Robust, passive gamma ray tool that provides significantly more information
than gross gamma
• The tool deconvolves gross gamma signature into K, Th and U
• Use CGR (K + Th) for clay content
Poor vertical resolution (20”) and good depth of investigation (9.5”)
• Useful precision requires slow logging speed (<800 ft/hr)
• Assumes secular equilibria for U and Th
• Different activities for different clay types
• Invaluable for quantifying kaolinite
• Open or cased-hole
• Water and air-filled
 Smectite
GR Resistivity Porosity ELAN ELAN Porosity

• Swelling clay
– High bound water
• Completion design
– Fluid sensitive
– Ductile
– Higher stress (elevated
PR)

• Problematic > 3 to 4 wt%

Smectite
 How to Quantify Different Clays
• Illite
– Assumed clay
• Chlorite
– Fe-rich
– Pe
– Bulk density
• Smectite
– High-neutron
– Low-resistivity
– Caliper
– Variable petrophysical properties
• Kaolinite
– Th-rich
• Core
– XRD beneficial
– Not necessarily quantitative
 Pyrite
 Reduction of sulfate to sulfide
– Generally highest in zones with
high GR activity
– Most abundant in Paleozoic
shales
– Low concentrations in
lacustrine shales
 Properties
– Dense (4.99 g/cm3)
– Electrically conductive
– Acid sensitive
– Difficult to drill
 Concentrations up to 50 wt%,
commonly < 10 wt%