high-definition spectroscopy—determining mineralogic complexity

17
34 Oilfield Review High-Definition Spectroscopy—Determining Mineralogic Complexity Neutron-induced capture spectroscopy tools measure the concentrations of specific elements in downhole rocks. From these data, petrophysicists can derive mineralogic, lithologic and matrix properties. Early spectroscopy tools lacked the spectral sensitivity to derive total organic carbon—an important measurement for understanding unconventional resource plays. A new tool delivers total carbon, from which organic carbon concentrations can be determined. This tool also has the ability to resolve complex lithology with a degree of accuracy never before possible. Manuel Aboud Rob Badry Calgary, Alberta, Canada Jim Grau Susan Herron Cambridge, Massachusetts, USA Farid Hamichi Jack Horkowitz Sugar Land, Texas, USA James Hemingway Houston, Texas Robin MacDonald Saudi Aramco Al-Khobar, Saudi Arabia Pablo Saldungaray Al-Khobar, Saudi Arabia Don Stachiw Northern Cross (Yukon) Ltd. Calgary, Alberta Christian Stoller Princeton Junction, New Jersey, USA Richard E. Williams BHP Billiton Houston, Texas Oilfield Review Spring 2014: 26, no. 1. Copyright © 2014 Schlumberger. CMR-Plus, ECS, ELANPlus, GST, Litho-Density, Litho Scanner, Minitron, Platform Express, RST, SpectroLith and TerraTek HRA are marks of Schlumberger. LECO is a mark of the LECO Corporation. Rocks comprise an assortment of minerals and fluids. Many processes combine to form the com- plex mixtures found in the subsurface, including the transport mechanisms that delivered sedi- ments and rock fragments to their current rest- ing place, heat and pressure applied during burial and subsequent lithification and a myriad of internal and external forces acting on the rocks. Using downhole spectroscopy tools, also referred to as geochemical tools, geologists can unravel the composition of sedimentary, meta- morphic and igneous formations and better understand their stratigraphy, mineralogy, dia- genesis and hydrocarbon potential. In the early days of well logging, geologists and petrophysicists developed models to help identify the presence of hydrocarbons, estimate their quantities and determine production poten- tial. Saturation models such as those described in equations proposed by Gus Archie, later modified to account for the influence of shale, usually assume homogeneous, isotropic formations. 1 These methods provide reasonable results when computing hydrocarbon saturations in conven- tional reservoirs; however, to determine the oil and gas potential in complex reservoirs and unconventional resource plays, petrophysicists have replaced simple models with techniques

Upload: others

Post on 07-Apr-2022

24 views

Category:

Documents


0 download

TRANSCRIPT

Page 1: High-Definition Spectroscopy—Determining Mineralogic Complexity

34 Oilfield Review

High-Definition Spectroscopy—Determining Mineralogic Complexity

Neutron-induced capture spectroscopy tools measure the concentrations of specific

elements in downhole rocks. From these data, petrophysicists can derive mineralogic,

lithologic and matrix properties. Early spectroscopy tools lacked the spectral sensitivity

to derive total organic carbon—an important measurement for understanding

unconventional resource plays. A new tool delivers total carbon, from which organic

carbon concentrations can be determined. This tool also has the ability to resolve

complex lithology with a degree of accuracy never before possible.

Manuel AboudRob BadryCalgary, Alberta, Canada

Jim GrauSusan HerronCambridge, Massachusetts, USA

Farid HamichiJack HorkowitzSugar Land, Texas, USA

James HemingwayHouston, Texas

Robin MacDonaldSaudi AramcoAl-Khobar, Saudi Arabia

Pablo SaldungarayAl-Khobar, Saudi Arabia

Don StachiwNorthern Cross (Yukon) Ltd.Calgary, Alberta

Christian StollerPrinceton Junction, New Jersey, USA

Richard E. WilliamsBHP BillitonHouston, Texas

Oilfield Review Spring 2014: 26, no. 1. Copyright © 2014 Schlumberger.CMR-Plus, ECS, ELANPlus, GST, Litho-Density, Litho Scanner, Minitron, Platform Express, RST, SpectroLith and TerraTek HRA are marks of Schlumberger.LECO is a mark of the LECO Corporation.

Rocks comprise an assortment of minerals and fluids. Many processes combine to form the com-plex mixtures found in the subsurface, including the transport mechanisms that delivered sedi-ments and rock fragments to their current rest-ing place, heat and pressure applied during burial and subsequent lithification and a myriad of internal and external forces acting on the rocks. Using downhole spectroscopy tools, also referred to as geochemical tools, geologists can unravel the composition of sedimentary, meta-morphic and igneous formations and better understand their stratigraphy, mineralogy, dia-genesis and hydrocarbon potential.

In the early days of well logging, geologists and petrophysicists developed models to help identify the presence of hydrocarbons, estimate their quantities and determine production poten-tial. Saturation models such as those described in equations proposed by Gus Archie, later modified to account for the influence of shale, usually assume homogeneous, isotropic formations.1 These methods provide reasonable results when computing hydrocarbon saturations in conven-tional reservoirs; however, to determine the oil and gas potential in complex reservoirs and unconventional resource plays, petrophysicists have replaced simple models with techniques

Page 2: High-Definition Spectroscopy—Determining Mineralogic Complexity

Spring 2014 3535

that require greater understanding of the compo-sition and mineralogy of the rocks.

In the laboratory, scientists have an array of instruments at their disposal to peer into the rock structure. Using these tools, they can deter-mine the chemical and mineral composition of the rocks, hypothesize about their origins and diagenesis and establish empirical relationships of rock properties that affect generation, accu-mulation and production of hydrocarbons. In the downhole environment and in words familiar to most petrophysicists, “All interpretations are opinions based on inferences from electrical or other measurements.” 2 However, as technologies and techniques advance, service companies are providing a number of laboratory-grade measure-ments from tools at the end of a wireline cable or attached to drillpipe.

Spectroscopy measurements, which are cru-cial to understanding complex reservoir rocks and unconventional resource plays, have been used by scientists in the laboratory for several decades. Downhole spectroscopy tools have been available since their introduction in the 1980s, but the recently introduced Litho Scanner high-definition spectroscopy service delivers geo-chemical data at a level of precision and accuracy that has never before been available downhole. The tool acquires measurements of a greater number of elements than were available from earlier tools and includes an accurate measure-ment of carbon, from which total organic carbon (TOC) can be derived. For understanding uncon-ventional resources such as oil- and gas-bearing shales, TOC is crucial.

This article reviews the basic theory of spec-troscopy measurements and the development of neutron-induced capture spectroscopy tools, including advances in spectroscopy measure-ments introduced by the Litho Scanner tool. Case studies from an Arctic wildcat well, an oil-bear-ing resource play in the US and an unconven-tional resource play with complex lithology in the Middle East demonstrate various applications of spectroscopy data.

Spectroscopy—Capturing ComplexityTwo families of downhole spectroscopy tools are used in the oil and gas industry: spectral natural gamma ray tools and neutron-induced gamma ray spectroscopy services. Geoscientists primarily use spectral gamma ray tools to quantify the con-centrations of naturally occurring thorium, potassium and uranium in rocks by measuring the energy level of gamma rays emitted as these radioactive elements decay. From these data, log analysts can estimate clay type, quantify radioac-tive mineral effects on natural gamma ray mea-surements and identify radioactive deposits.

Neutron-induced gamma ray spectroscopy, which is a more comprehensive measurement technique than that of spectral gamma ray tools, delivers concentrations of the most common ele-ments found in the minerals and fluids of reservoir and source rocks. A neutron-induced spectroscopy tool records transitory effects—lasting a few microseconds to a few milliseconds—from forma-tions bombarded with neutrons from a source: either an electronic pulsed neutron generator

(PNG) or an americium [241Am] and beryllium [9Be] radioisotopic source [AmBe] (above).3 The AmBe chemical sources used for downhole logging output a relatively stable number of neutrons with a predictable energy level. Compared with AmBe sources, PNGs generate many more neutrons and at much higher energy levels, but their output can vary with temperature, tool power and PNG age. Unlike AmBe sources that are always generating neutrons, when electrical power is removed from PNGs, neutron generation ceases.

Laboratory spectroscopy tools such as X-ray diffraction (XRD) and X-ray fluorescence (XRF) spectrometers bombard rock samples with X-rays or gamma rays and measure the resulting emis-sions. To determine mineralogy, technicians use XRD devices; to perform elemental analysis, they use XRF equipment. The XRF equipment in the laboratory can measure more elements than can downhole tools. However, the subset of elements measured downhole includes the common min-eral-forming elements, which are sufficient for geologists to determine the mineralogic composi-tion of most reservoir and source rocks.

1. For more on the Archie water saturation equation: Archie GE: “The Electrical Resistivity Log as an Aid in Determining Some Reservoir Characteristics,” Petroleum Transactions of AIME 146 (1942): 54–62.

2. For many years, these words, or a similar statement, appeared on the printed logs provided by most service companies.

3. For more on PNGs used as neutron sources: Allioli F, Cretoiu V, Mauborgne M-L, Evans M, Griffiths R, Haranger F, Stoller C, Murray D and Reichel N: “Formation Density from a Cloud, While Drilling,” Oilfield Review 25, no. 2 (Summer 2013): 4–15.

>Neutrons from a pulsed neutron generator (PNG) and an americium beryllium [AmBe] radioisotopic source. PNGs (top left) are self-contained particle accelerators that produce neutrons from a fusion reaction (bottom left). The neutrons leave with high kinetic energy of approximately 14 MeV of the total 17.6 MeV released. Typical PNG output is 3 × 108 neutron/s. AmBe sources, on the other hand, generate neutrons as by-products of nuclear reactions (right). The AmBe source contains a mixture of americium [ 241Am] and beryllium [9Be]. When 241Am decays to an excited state of neptunium [237Np*]—the * denotes an excited state—it emits 5.5-MeV alpha particles (α). To reach its final ground state, the excited 237Np* emits a 60-keV gamma ray (γ). A small fraction of the alpha particles from the 241Am react with the 9Be, resulting in the formation of an excited state of carbon [13C*], which emits 4-MeV neutrons (n) to reach an excited state of 12C*. The 12C* reaches its stable state through the emission of a high-energy gamma ray (approximately 4.4 MeV). A typical AmBe source generates 4 × 107 neutron/s.

n (4 MeV, average)

Americium-Beryllium Source Reaction

Target

High- voltagesupplyControls

Mainpower

On-Offswitch

Ion source

Pulsed Neutron Generatorn

Deuterium2H

Tritium3H 4He

Heliumn

Neutron E (17.6 MeV)

nnp+

n np+

n np+ p++ + + Kinetic

energy

241Am

9Be 13C* 12C* 12C

237Np* 237Np

γ (60 keV)

γ (4.4 MeV) α (5.5 MeV)

Page 3: High-Definition Spectroscopy—Determining Mineralogic Complexity

36 Oilfield Review

The first geochemical logs were created by combining measurements from several existing tools. In the late 1980s, scientists at the Schlumberger Houston Product Center, sup-ported by researchers at the Schlumberger-Doll Research Center in Ridgefield, Connecticut, USA, combined the data from an NGT natural gamma ray tool, a GST gamma ray spectrometer tool and an AACT aluminum activation clay tool.4 From these data, they computed simple elemental con-centrations for the following: aluminum [Al], cal-cium [Ca], iron [Fe], gadolinium [Gd], potassium [K], sulfur [S], silicon [Si], thorium [Th], tita-nium [Ti] and uranium [U]. These elemental concentrations provided information about min-eralogy and rock composition.

Although early geochemical tools provided geologists with information about the geochemis-try of the rocks, first-generation tools suffered from some inherent limitations. These limitations include slow logging speeds, lack of combinability with other logging tools, degradation of both qual-ity and resolution of the measurements in down-hole environments, an inability to differentiate organic carbon from inorganic carbon and a lack of sensitivity for some elements that are essential for understanding complex lithology. For instance,

geologists use magnesium [Mg] to differentiate dolomite from calcite, and an accurate Mg mea-surement was difficult to obtain with older gen-eration tools.

Many geologists and petrophysicists consider geochemical logging data crucial for accurately characterizing reservoir rocks, but the tools were not universally included in traditional evaluation suites for many reasons. Among these were the facts that the tools were long, could not be com-bined with other services and had to be run slowly; also, the information could be obtained from core data. The application of the ECS ele-mental capture spectroscopy tool for shale gas exploration revolutionized the service.5 Because of its ability to provide the mineralogic composi-tion of the rocks, a geochemical tool was fre-quently included in logging programs for unconventional reservoir evaluation and comple-tion design.

Elements of Neutron Capture SpectroscopyOf the many types of nuclear radiation, two are of particular interest for spectroscopy measure-ments—gamma rays and neutrons. Gamma rays are similar to X-rays and visible light and are the highest energy form of electromagnetic radia-tion. Visible light has a wavelength range of about

400 to 700 nm; gamma rays, with wavelengths much smaller than 1 nm, have a range of frequen-cies. Wavelengths typically encountered in down-hole measurements are roughly 0.001 nm. However, gamma rays are not usually described by their wavelength, but by their energy level, expressed in electron volts (eV) or the larger units of keV (thousand eV) and MeV (million eV).

Induced neutron spectroscopy tools count gamma rays over a range of discrete energy bins—the gamma ray spectrum. In essence, they measure the energies of artificially induced gamma rays emitted by elements in the forma-tion that have been bombarded by high-energy fast neutrons supplied by the tool. These neu-trons collide with other particles and rapidly lose energy until they eventually reach thermal energy level of about 0.025 eV. Because neutrons are similar in mass to hydrogen’s single proton, the maximum energy transfer and the neutron’s most rapid slowing occur from collisions between neutrons and hydrogen atoms (above).6

Thermal neutrons are eventually absorbed—captured—by the atomic nuclei of various ele-ments found in the formation, the borehole and the tool. These now excited nuclei emit gamma

> Life of a neutron and neutron scattering. Both electronic (PNG) and traditional (radioisotopic) sources emit high-energy neutrons. Neutrons from the PNG used in the Litho Scanner tool have approximately 14 MeV initial kinetic energy, whereas AmBe sources emit neutrons with around 4.4 MeV (left). These fast neutrons rapidly reach thermal energy level (approximately 0.025 eV). During those first few microseconds, before their energy falls below about 1 MeV, the neutrons experience inelastic interactions (top right). Inelastic neutron scattering occurs when high-energy, fast neutrons collide with, pass closely by or are absorbed by atomic nuclei. The now excited nucleus emits inelastic gamma rays to return to a deexcited state. Neutron capture (bottom right) occurs when thermal neutrons are absorbed by atomic nuclei. The capturing atom generates gamma rays to return to a deexcited state.

102

104

106

100

200 40010–2

Neu

tron

ener

gy, e

V

Electronic source

High energy

Epithermal energy

Intermediate energy

Traditional source

Neutron energy leaving source

Inelastic region

Neutrons with thermal energy

Capture gamma ray

emitted

Deexcitednucleus

Deexcitednucleus

Averagethermalenergy

0.025 eV

Time, μs

Capturegamma ray

Thermalneutron

Neutron Capture

n

Excited nucleus

Excited nucleus

n

n

Inelastic Neutron Scattering

Inelasticgamma rays

Page 4: High-Definition Spectroscopy—Determining Mineralogic Complexity

Spring 2014 37

rays—referred to as capture gamma rays because they are a product of neutron capture— to return to their lowest stable energy state. Capture gamma rays have energy levels that are characteristic of the element from which they are emitted. Elastic scattering and eventual capture can take place over a few tens to hundreds of microseconds. Most downhole neutron capture spectroscopy tools rely on neutron-induced cap-ture gamma rays for their measurements.

Prior to reaching thermal energy level, high-energy neutrons that have not yet been signifi-cantly slowed may cause inelastic reactions. Inelastic reactions differ from elastic scattering and occur in about a microsecond after neutron bombardment. These interactions are character-ized by atomic nuclei that become excited by encounters with neutrons with energy levels above 1 MeV. During inelastic interactions, neu-trons may collide with an atomic nucleus, trans-fer energy to that nucleus and then emerge with reduced energy, or the fast neutron may be absorbed after first knocking a subatomic parti-cle from the nucleus. As in neutron capture, nuclei become excited by these encounters and emit one or more gamma rays to return to a deex-cited state; however, the gamma rays resulting from inelastic reactions have specific energy lev-els that differ from those of neutron-induced cap-ture gamma rays for the same element (right).

Only PNG-based tools can accurately distin-guish between the effects of capture and inelas-tic neutron interactions, but not all PNG-based tools can make this measurement. To measure inelastic interactions, the neutron generator must be turned on and off rapidly, emitting pulses of high-energy neutrons. Furthermore, for accu-rate measurements, the pulse must have a well-defined, repeatable burst shape, meaning the neutron emissions have a constant and identical output for each pulse of neutrons. Most spectros-copy tools, including the ECS tool, detect gamma rays from inelastic reactions but cannot accu-rately determine elemental yields from these measurements. Some downhole logging tools may offer qualitative inelastic scatter data, but with-out hardware and measurement techniques to take advantage of the inelastic interactions, quantitative measurements are not possible.

Measurements from inelastic interactions are less sensitive to environmental effects than those from capture interactions. For instance, chlorine [Cl] has a high thermal neutron capture cross section and can significantly reduce the number of thermal neutrons available for capture by other elements.7 Reducing the pool of available

thermal neutrons for capture increases the sta-tistical variability of the measurement. Because the inelastic measurements are not affected by neutron absorbers, they can serve to enhance the resolution or precision of some capture data in the presence of high Cl levels.

The Litho Scanner tool utilizes capture gamma rays to determine concentrations of Al, Ca, Fe, Gd, K, S, Si and Ti, as other tools have done, but also quantifies concentrations of bar-ium [Ba], Cl, hydrogen [H], Mg, manganese [Mn], sodium [Na] and metals such as copper [Cu]

4. Hertzog R, Colson L, Seeman B, O’Brien M, Scott H, McKeon D, Wraight P, Grau J, Ellis D, Schweitzer J and Herron M: “Geochemical Logging with Spectrometry Tools,” SPE Formation Evaluation 4, no. 2 (June 1989): 153–162.

5. For more on the ECS tool: Barson D, Christensen R, Decoster E, Grau J, Herron M, Herron S, Guru UK, Jordán M, Maher TM, Rylander E and White J: “Spectroscopy: The Key to Rapid, Reliable Petrophysical Answers,” Oilfield Review 17, no. 2 (Summer 2005): 14–33.

6. Radioisotopic neutron sources emit neutrons with energy levels on the order of 4 million eV and typically output 4 × 107 neutron/s. PNGs emit neutrons with energies

> Gamma ray spectra. Most neutron capture gamma ray spectroscopy logging tools rely on capture gamma rays to determine elemental yields. After absorbing thermal neutrons, atomic nuclei emit capture gamma rays with characteristic energies. For example, silicon [Si] (top left ) emits gamma rays with several emission energies, but the highest probabilities are approximately 3.5 and 4.8 MeV. The full capture gamma ray spectrum (bottom left ) is the combination of contributions from all the elements generally found downhole. Inelastic gamma rays are generated when fast neutrons—those with energies above 1 MeV—interact with nuclei in the formation, mud and the tool and result in the emission of gamma rays. These inelastic gamma rays have an energy spectrum (bottom right ) that looks similar to the capture gamma ray spectrum, but the characteristic energies differ. The Si inelastic gamma ray energy (top right ) is about 1.8 MeV. The Litho Scanner tool takes advantage of both spectra, which gives enhanced resolution to some elements, such as Mg and Fe, and adds others such as C, which is not available from the capture spectrum. Capture tool background (CTB, bottom left ) and inelastic tool background (ITB, bottom right ) are contributions to the measurement from the tool and the borehole environment detected during spectral acquisition.

C

Al

Gamma ray energy

Gamma ray energy, MeV Gamma ray energy, MeV0 2 4 6 8 100 2 4 6 8 10

Inelastic Gamma Ray SpectrumCapture Gamma Ray Spectrum

Si Capture Si Inelastic

Gamma ray energy

Ca

Mg MgS Ti

O

Si

Al Ca Fe S ITBFeKGdH Cl Si CTBCo

unts

Prob

abili

ty

around 14 million eV and typically output 30 × 107 neutron/s and higher. Thermal neutrons are defined as those with energy of 0.025 eV.

7. Neutron capture cross section is a relative measurement of the probability of a nucleus capturing a neutron and has the unit of barns (1 barn = 10–24 cm2). Of the elements commonly encountered downhole, Cl is one of the most receptive for absorbing thermal neutrons, thus has a high capture cross section of 35 barns. Thermal neutron capture cross section is low for most other common downhole elements such as O (0.00019 barns), C (0.0035 barns), Si (0.17 barns) and Ca (0.43 barns). Its low capture cross section is one reason C concentrations are determined using inelastic interactions.

Page 5: High-Definition Spectroscopy—Determining Mineralogic Complexity

38 Oilfield Review

and nickel [Ni]. The tool uses inelastic data pri-marily to quantify carbon [C] and Mg (above). With an accurate Mg measurement, petrophysi-cists can differentiate calcite [CaCO3] from dolo-mite [CaMg(CO3)2]. The accurate C measurement is crucial for determining TOC levels.

Hidden in the SpectraMost downhole gamma ray logging tools use scin-tillation crystal detectors. When a gamma ray encounters the detector crystal, the energy of that

gamma ray is converted into a flash of light—hence the name scintillation—and the magni-tude of the light pulse is proportional to the energy transferred to the crystal by the incident gamma ray. A photomultiplier tube converts the flash of light to a current, which it amplifies many times before sending it to additional electronics, where the analog signal is further amplified and con-verted to a digital value. The amplitude of the sig-nal is determined by a pulse height analyzer, and these data are combined with all the other pulses

that arrive at the detector to produce a gamma ray spectrum (below left).

Sodium iodide [NaI] crystals doped with thal-lium [Tl] are used as detectors in most conventional gamma ray logging tools, including some neutron-induced spectroscopy tools. Although the NaI crys-tal is robust, it is not efficient enough, nor is its resolution great enough to separate the spectra of all the desired elements. The ECS tool uses a bis-muth germanate [Bi4Ge3O12], or BGO, crystal, which, because of its high density and atomic num-ber, produces a unique gamma ray spectrum. However, the BGO scintillator is temperature sensi-tive; its spectral response broadens and loses defini-tion or resolution, at elevated temperatures. The Litho Scanner tool uses a cerium-doped lanthanum bromide [LaBr3:Ce] crystal, which has a fast decay time that permits high counting rates as well as stable yields up to 200°C [400°F]. The light output of the crystal is 50% brighter than that of NaI crys-tals, the benchmark for scintillation crystals; at room temperature, its brightness is an order of mag-nitude higher than that of BGO crystals. The use of the LaBr3:Ce scintillator marks a significant increase in the ability to detect and count gamma rays, and thus when combined with the high neu-tron output of a PNG, constitutes a major advance in spectroscopy logging.

To be useful to petrophysicists, the gamma ray spectrum measured by spectroscopy tools must be translated into relevant mineralogy, a multi-step process. The first step is the acquisition of the gamma ray spectrum, which is a measure of gamma ray counts versus energy bins as deter-mined by the scintillation detector. After the spectral response has been recorded, the spec-trum must be converted to elemental yields.

Each element detected by the tool has a unique signature, or elemental standard (next page, top).

8. Sedimentary minerals contain single or multiple oxides. Examples are quartz [SiO2], calcite [CaCO3] and dolomite [CaMg(CO3)2]. Clay minerals can also be treated as complex mixtures of oxides. Examples are illite {(K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O)]} and montmorillonite [(Na,Ca)0.33(Al,Mg)2(Si4O10)(OH)2·nH2O]. Concentrations are expressed in weight %; the mass and not the volume of any given element contributes to the spectrum.

For more information about the oxide closure method: Grau JA, Schweitzer JS, Ellis DV and Hertzog RC: “A Geological Model for Gamma-Ray Spectroscopy Logging Measurements,” Nuclear Geophysics 3, no. 4 (1989): 351–359.

9. Radtke RJ, Lorente M, Adolph B, Berheide M, Fricke S, Grau J, Herron S, Horkowitz J, Jorion B, Madio D, May D, Miles J, Perkins L, Philip O, Roscoe B, Rose D and Stoller C: “A New Capture and Inelastic Spectroscopy Tool Takes Geochemical Logging to the Next Level,” Transactions of the SPWLA 53rd Annual Logging Symposium, Cartagena, Colombia, June 16–20, 2012, paper AAA.

10. Radtke et al, reference 9.

> Elements determined through capture and inelastic gamma ray spectroscopy. (Adapted from Radtke et al, reference 9.)

Element Element Name Capture Inelastic

Aluminum

Barium

Carbon

Calcium

Chlorine

Copper

Iron

Gadolinium

Hydrogen

Potassium

Magnesium

Manganese

Sodium

Nickel

Oxygen

Sulfur

Silicon

Titanium

Al

Ba

C

Ca

Cl

Cu

Fe

Gd

H

K

Mg

Mn

Na

Ni

O

S

Si

Ti

> Scintillation detector. Gamma rays enter the scintillation crystal (top left ) causing a flash of light. The intensity of the flash is directly related to the energy transferred to the crystal by the incident gamma ray. The photomultiplier tube receives the light, converts it to a current, amplifies the current through a series of dynodes and passes the signal along for additional amplification, shaping and pulse height analysis (top right ). The information from all the gamma rays is combined, and counts are plotted versus discrete energy levels (bottom right ).

Amplification,pulse shaping and

pulse height analyzer

Photomultipliertube (PMT)

Photo cathode Dynodes Anode

Gamma ray energy, MeV0

0.01

0.1

1

10

100

2 4 6 8

Gam

ma

ray

coun

ts

LightoutputScintillation crystalGamma rays

Page 6: High-Definition Spectroscopy—Determining Mineralogic Complexity

Spring 2014 39

> From acquisition to interpretation. Capture gamma ray and inelastic data (left ) are acquired with the Litho Scanner tool. Using elemental standards established for the tool, spectral stripping converts data to elemental yields (center left ). Software computes elemental weight fractions from these elemental yields based on the oxide closure model (center right ). Elemental analysis programs convert the yields or weight fractions to mineralogy (right, Track 1). The Litho Scanner tool also directly measures carbon, from which TOC is computed (Track 2). Petrophysicists can use matrix density computed from the elemental weight fractions and corrected for TOC (Track 3) to improve computed properties such as density porosity.

C

Al

Nor

mal

ized

coun

tsN

orm

alize

d co

unts

Energy channel

TOC

Matrix Density

CorrectedDensity

IlliteSi Ca Fe Mg S Al K Na Mn Ti Gd C

Quar

tzK-

feld

spar

Na-

feld

spar

Calc

iteDo

lom

iteAn

hydr

itePy

rite

Kero

gen

2 3g/cm3

2 3g/cm3

Capture

Inelastic

Capture

Inelastic

Energy channelEnergy channel

Energy channel

Nor

mal

ized

coun

tsN

orm

alize

d co

unts

Ca

Mg

Mg

S Ti

O

Si

Al Ca Fe S ITB

FeKGdH Cl Si CTB

Spectral Stripping• Elemental yields

Oxide Closure• Elemental weight fractions

C t d

Interpretation• Minerals• Total organic carbon (TOC)• Matrix properties

Spectral Acquisition• Inelastic• Capture

These elemental signatures can be used to decompose the total measured spectra—which are first corrected for environmental and elec-tronic factors that distort them—into the contri-butions from the elemental standards. In the case of the Litho Scanner tool, these standards were established in test formations at the Schlumberger Environmental Effects Calibration Facility in Houston.

To obtain elemental weight fractions and produce realistic mineralogic models of the formation, scien-

tists apply the oxide closure model to the dataset.8 The closure model assumes that dry rock consists of a set of oxides or compounds, and the sum of the pro-portions of all the oxides must equal 100%, or unity. This closure requirement produces a unique normal-ization factor at each depth level, which in turn is applied to the relative spectral yields to produce the dry weight concentrations of specific elements.9

Dry weight elemental yields are then con-verted to mineralogy and lithology using software modeling programs. SpectroLith lithology pro-

cessing for spectroscopy tools is one example. It is an empirical model developed from hundreds of laboratory measurements in known rock types.10 ELANPlus advanced multimineral log analysis is another technique. This analysis pro-gram computes the most probable formation mineralogy and pore volume based on inputs from several tools, including Litho Scanner yields (below). Geologists may use knowledge of expected rock types to guide the modeling soft-ware toward the correct mineralogic solution.

> Elemental standards and tool calibration. Engineers characterized the Litho Scanner tool at the Schlumberger Environmental Effects Calibration Facility in Houston. The tool was placed in slabs of formation rocks (left ) and laboratory-prepared, simulated formations (right ) with known geochemical and lithologic composition. Standards were derived for 18 elements using capture spectroscopy and 13 elements using inelastic spectroscopy (center, not all shown). These standards are the basis for computing elemental yields.

Coun

ts, a

rbitr

ary

log

scal

e

Gamma ray energy, MeV Gamma ray energy, MeV Gamma ray energy, MeV

Capture Standards Capture Standards Inelastic Standards

Fe

Fe

Si

Si

Ba

Ti

Cl

Mg

Mg

Mn

Al

AlCa

Ca

Gd

Na

S

S

C

K

O

H

Page 7: High-Definition Spectroscopy—Determining Mineralogic Complexity

40 Oilfield Review

Litho Scanner DevelopmentNeutron-induced capture spectroscopy data have proved their value in characterization of complex lithologies in both conventional reservoirs and unconventional resource plays. However, petro-physicists who use these data have recognized some of the limitations of early spectroscopy tools. Engineers and scientists at Schlumberger worked for many years to develop a spectroscopy tool to address these concerns and correct issues that affect data accuracy and precision.

Since the raw spectra measured by the tool are the foundation upon which all other infor-mation is based, engineers searched for an alternative to BGO detectors used in the ECS tool, the gadolinium orthosilicate (GSO) [Gd2SiO5] detector used in the RST reservoir saturation tool and NaI detectors used in many other tools. One of the major operational reasons for replacing BGO detectors is their temperature sensitivity. BGO crystals are sealed in a Dewar flask and cooled with carbon dioxide [CO2] to keep the

tool internal temperature below 60°C [140°F] for the entire logging operation. The BGO crys-tal output drops dramatically with tempera-ture—light output when the crystal temperature is greater than 60°C is too low to make accept-able logging measurements. This severely limits the use of the ECS tool for long duration logging such as drillpipe-conveyed or tractoring operations.

Schlumberger design engineers chose a large-diameter LaBr3:Ce gamma ray detector for use in the Litho Scanner tool. Compared with NaI and

> Crystal scintillator comparisons. Several types of scintillation crystals are used in gamma ray logging tools; the NaI crystal is the most common because of its ruggedness and low cost. A BGO scintillator is used in the ECS tool. For the Litho Scanner tool, engineers chose the LaBr3:Ce scintillator because of its superior qualities compared with those of other scintillators. The quick response time of the LaBr3:Ce scintillator—based on primary decay time—compared with that of other detectors (top left ) translates into greater efficiency and much higher counting capability. The relative light yield is stable from 0°C to 175°C [32°F to 350°F] (bottom left ), a clear improvement over the BGO scintillator, which can operate up to only about 60°C [140°F] before the output drops below a usable level. The light yield of the LaBr3:Ce detector is higher than that of either the NaI or BGO crystals. The LaBr3:Ce crystal detector is also more immune to thermal degradation than other detectors (right ). The clearly defined peaks for elemental standards at room temperature (top right, green) are similar to those at 150°C (bottom right ). The elemental standards response for the BGO crystal used in the ECS tool (red) broadens and loses definition at 60°C.

Property BGO

BGO

LaBr3:Ce

LaBr3:Ce

Nal (Tl)

Nal (Tl)

3.67

50.8

230

43.0

7.13

75.2

300

8.2

5.29

46.9

25

61

Density, g/cm3

Effective atomic number

Primary decay time, ns

Light yield, photon/keV

Rela

tive

light

yie

ld

0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

Temperature, °C0 50 100 150 200

Gam

ma

ray

coun

ts

Room Temperature

Gam

ma

ray

coun

ts

Gamma ray energy, MeV

Fe

Si

Ca

S

H

Fe

Si

Ca

S

H

0 2 4 6 8 10

Litho Scanner tool standardECS tool standard

LaBr3:Ce at 150°C, BGO at 60°C

Page 8: High-Definition Spectroscopy—Determining Mineralogic Complexity

Spring 2014 41

11. Pileup occurs when more gamma rays arrive at the detector than can be resolved by the system. Because of the high output of the PNG used in the Litho Scanner tool, pileup can be problematic during inelastic processing. If the response of the system to pileup can be characterized, the condition may be correctable.

12. Alexander T, Baihly J, Boyer C, Clark B, Waters G, Jochen V, Le Calvez J, Lewis R, Miller CK, Thaeler J and Toelle BE: “Shale Gas Revolution,” Oilfield Review 23, no. 3 (Autumn 2011): 40–55.

BGO crystals, this scintillator has an order of magnitude faster response time. The faster response enables high counting rates, improving the tool’s precision compared with that of other devices. The brighter output compared with that of NaI and BGO scintillators translates to improved spectral resolution. The LaBr3:Ce scin-tillator has a stable response from 0°C to 150°C [32°F to 300°F], and even above 150°C, the light yield is not significantly reduced (previous page).

The engineers also focused on the neutron source when developing the Litho Scanner tool. The PNG in the Litho Scanner tool includes a Minitron PNG tube that uses a proprietary hot cathode technology to produce crisp 8-μs bursts with 400-ns rise and fall times (above). The rapid response of this neutron generator allows precise separation of inelastic and capture interactions. Rated to 175°C [350°F], the PNG is capable of producing 3 × 108 neutron/s; this high output makes full use of the LaBr3:Ce scintillator’s fast counting capabilities, as the count rate can exceed 2.5 million count/s.

Engineers designed a new state-of-the-art photomultiplier tube that is able to handle the output from the high count rates now possible from combining the LaBr3:Ce scintillator and the new PNG. The Litho Scanner tool also incorpo-rates specialized electronics to process the high rate signals to avoid pileup, a condition in which more counts arrive than can be separated by the detector or the electronics (above right).11 Using fast signal processors to handle the load avoids spectral distortion caused by nearly coincident

gamma ray arrivals. Unprecedented spectral reso-lution and precision are attained with the cou-pling of the scintillator, PNG, downhole electronics and signal processing. The combination of these enhancements results in the Litho Scanner tool as a high-definition, third-generation neutron cap-ture gamma ray spectroscopy service.

Spectroscopy, Rocks and TOCBecause of the increased development of uncon-ventional resources, the ability to quantify TOC in organic-rich rocks may be one of the most important features of the new tool. TOC is the weight % of organic carbon that resides within the pore space of rocks. TOC includes carbon in kerogen, bitumen and other solid, volatile and liquid hydrocarbons trapped within the pore space. Kerogen is the insoluble organic matter from which hydrocarbons are generated.

Kerogen density is slightly higher than that of fluids that fill the pore space; using only bulk density measurements, petrophysicists have dif-ficulty differentiating between liquid-filled pore volume and the presence of immovable bitumen in pores or kerogen in the rock framework. Computing the true porosity of organic-rich

shales requires the removal of solid hydrocarbon from the porosity measurement, which can be accomplished with accurate TOC data combined with other measurements such as those from magnetic resonance tools.

For organic-rich shale exploration, geologists and petrophysicists target formations that have TOC values between 1.5 and 10 weight %. Rocks with more than 10 weight % TOC from kerogen only are usually considered too immature for development.12 TOC values are typically derived from core samples using a combustion technique in which inorganic carbon is removed using phos-phoric acid. The remaining sample material is combusted in an oxygen-rich environment, and the resulting CO2 is measured in an infrared detection cell such as the LECO carbon analyzer. A limitation of determining TOC from cores is that

> Stable and rapid neutron output. The hot cathode method used by the Minitron PNG delivers a rapid response when current is applied to the PNG and an even faster decay when power is switched off. This repeatable, controlled output allowed design engineers to develop the inelastic measurement that complements traditional neutron capture gamma ray spectroscopy.

Neu

tron

outp

ut, r

elat

ive

coun

ts

Time, μs-2 0 2 4 6 8 10

> Pileup distortion. When more gamma rays arrive at the detector than can be counted, pileup occurs, and the result is spectral distortion. The problem is more evident during high count rates (red) than low count rates (blue). Because the Litho Scanner tool utilizes a high neutron output PNG and an efficient LaBr3:Ce detector, pileup is most pronounced during inelastic spectrum measurements. Algorithms have been developed to remove the pileup degradation from the field spectrum based on the count rate (purple).

Gamma ray energy, MeV

High count rateLow count ratePileup corrected

Litho Scanner Tool, Zero-Porosity Limestone Example

Gam

ma

ray

coun

t, ar

bitra

ry s

cale

0 1 2 3 4 5 6 7 98 10

Page 9: High-Definition Spectroscopy—Determining Mineralogic Complexity

42 Oilfield Review

the core sample may not be representative of the rest of the reservoir; TOC can vary considerably across a reservoir section, which can be tens or even hundreds of meters thick.

The Litho Scanner tool offers a continuous carbon measurement from which TOC data can be computed. A continuous dataset of TOC is a more cost-effective and statistically accurate option than measuring TOC on hundreds of core

samples. Many log-derived techniques—such as the Schmoker and ΔlogR methods—have been used to estimate TOC.13 The uncertainty can be high for the various indirect measurement techniques and most require calibration to core data (above).

Log analysts use the carbon component from the Litho Scanner inelastic spectral measure-ments to quantify TOC. The carbon measurement from the formation includes both inorganic (car-

bon in minerals) and organic carbon. The inor-ganic carbon can be quantified by assigning it to the calcium and magnesium measurements, which are associated with calcite and dolomite; the amount of carbon bound up in these rocks can be computed by first quantifying these ele-mental weight fractions. Some calcium and mag-nesium may be associated with minerals other than carbonates. To address this situation, an

13. Gonzalez J, Lewis R, Hemingway J, Grau J, Rylander E and Schmitt R: “Determination of Formation Organic Carbon Content Using a New Neutron-Induced Gamma Ray Spectroscopy Service That Directly Measures Carbon,” Transactions of the SPWLA 54th Annual Logging Symposium, New Orleans, June 22–26, 2013, paper GG.

For more on the Schmoker technique: Schmoker JW: “Determination of Organic-Matter Content of Appalachian Devonian Shales from Gamma-Ray Logs,” AAPG Bulletin 65, no. 7 (July 1981): 1285–1298.

For more on the ΔlogR method: Passey QR, Bohacs KM, Esch WL, Klimentidis R and Sinha S: “From Oil-Prone Source Rocks to Gas-Producing Shale Reservoir—

> Comparison of methods to determine TOC. Several techniques have been developed to quantify organic carbon indirectly from well logs. The Schmoker method utilizes density logs, and ΔlogR is based on sonic and resistivity data. The logs (left ) compare continuous outputs for Schmoker TOC (Track 1, blue), Litho Scanner TOC (Track 2, purple) and ΔlogR TOC (Track 3, tan) with core-derived TOC values (red dots). The three methods are shown together for direct comparison (Track 4). The crossplots (right ) compare calculated TOC weight % with core-derived TOC weight % values. The TOC data from the Litho Scanner tool (center right ) compared most favorably with core-derived TOC values, especially in rocks with high TOC weight %.

0

Schmoker TOC

Core TOC Core TOC Core TOC

Litho Scanner TOC

Litho Scanner TOC

ΔLogR TOCΔLogR TOC

Schmoker TOCSchmoker TOC

Litho Scanner TOC

ΔLogR TOC

Schmoker TOC

Litho Scanner TOC ΔLogR TOC

20

20

15

10

5

-5

0

0 10Core TOC, weight %

Calc

ulat

ed T

OC, w

eigh

t %Ca

lcul

ated

TOC

, wei

ght %

Mea

sure

d TO

C, w

eigh

t %

Core TOC, weight %

Core TOC, weight %

20

20

15

10

5

-5

0

0 10 20

20

15

10

5

-5

0

0 10 20

% 0 20% 0 20%

0 20%

0 20%

0 20%

0 20% 0 20% 0 20%

Depth, m

XX,000

XX,025

XX,050

Geologic and Petrophysical Characterization of Unconventional Shale-Gas Reservoirs,” paper SPE 131350, presented at the CPS/SPE International Oil and Gas Conference and Exhibition in China, Beijing, June 8–10, 2010.

14. Gonzalez et al, reference 13.

15. Several varieties of calipers are used to measure borehole diameter. An X-Y caliper measures the borehole diameter with two sets of arms positioned 90° apart and can more accurately describe the borehole geometry than can single-axis calipers.

16. “Canada’s Arctic,” Alberta Online Encyclopedia, Canada’s Petroleum Heritage, http://www.albertasource.ca/petroleum/industry/historic_dev_canada_arctic.html (accessed March 24, 2014).

17. Some historians consider Norman Wells—discovered around 1910—at 65° 16’ 52” N latitude in Northwest Territory, the first arctic oil field in Canada; however, it is located just south of the Arctic Circle, which is the defining line of the Canadian Arctic at 66° 33’ 44” N latitude. For reference, the Eagle Plain basin, located in Yukon, Canada, straddles the Arctic Circle.

18. For more on Arctic exploration: Bishop A, Bremner C, Laake A, Strobbia C, Parno P and Utskot G: “Petroleum Potential of the Arctic: Challenges and Solutions,” Oilfield Review 22, no. 4 (Winter 2010/2011): 36–49.

Page 10: High-Definition Spectroscopy—Determining Mineralogic Complexity

Spring 2014 43

extensive set of Litho Scanner rock matrix measurements has been developed. Other less common minerals with inorganic carbon that might be encountered in oil and gas exploration include siderite [FeCO3], rhodochrosite [MnCO3] and ankerite [Ca(Fe, Mg, Mn)(CO3)]. Litho Scanner tools measure the elemental concentrations neces-sary to correct for the presence of these carbon-bearing minerals.14

Remaining carbon can then be considered organic in nature and is equivalent to TOC. The organic carbon determined using this tech-nique includes carbon in the kerogen, bitumen and any hydrocarbons—solid, oil and natural gas—in the pore volume.

Correcting for Borehole FluidsBorehole fluids are another potential contributor of carbon to computed TOC. Determining TOC in wells drilled with water-base mud (WBM) sys-tems is fairly straightforward. In the absence of organic-based additives, the organic carbon com-puted from tool measurements can be associated with solid, liquid or gaseous hydrocarbons. Additives in a WBM system may contribute to the total carbon measurement, and a constant cor-rection is often applied to compensate for it. Oil-base mud (OBM) systems present a different challenge, and applying a constant offset may not always account for the borehole contribution, which is sensitive to borehole size and shape and to environmental effects.

Scientists at Schlumberger-Doll Research, working in collaboration with engineers in the field for a solution to the OBM contribution to TOC, discovered that the correlation between the borehole carbon contribution and TOC is not a simple linear relationship. Because the composi-tion of mud in the borehole can vary considerably from TD to surface, application of a simple offset correction may not be valid. The researchers were, however, able to develop a correction algo-rithm that has been successfully tested in both OBM and WBM systems.

This new method computes an empirical car-bon offset from the Litho Scanner carbon mea-surement as a function of borehole geometry determined from caliper data. Software then determines a correction factor to normalize results for the specific mud system. For the pur-pose of computing this final correction, an X-Y caliper is preferred, especially in hole sections prone to ovality or enlargement.15 The correction is applied at each depth frame (right). This tech-nique recently proved its value in an Arctic explo-ration well in Yukon, Canada.

Arctic ExplorationIndigenous peoples in the Canadian Arctic were aware of oil seeps in that region for centuries and used pitch from these seeps to waterproof their fishing boats.16 But it wasn’t until 1974 that the

first Canadian Arctic oil field was discovered.17 In the recent past, oil, rather than natural gas, has often been the target of exploration in the Arctic because of oil’s portability; today, however, both natural gas and oil are viewed as targets.18

> TOC correction for borehole contribution. Early methods of compensating for borehole fluid TOC contributions applied a constant offset to the TOC output; however, this method is sensitive to changes in borehole geometry. For example, the TOC computed with a constant offset (Track 1, black) generally follows the effective borehole size (magenta) when the hole is washed out. Because borehole integrity is often difficult to maintain while drilling in shales, data quality problems may be encountered. Recognizing this limitation, Schlumberger scientists developed a more effective method to compensate for TOC contributions from the mud system. This method computes the TOC contribution in an in-gauge hole section, uses X-Y axis calipers to model enlarged boreholes more accurately and applies a realistic depth-by-depth offset. The TOC computed with the new method (Track 2, blue) no longer reflects borehole geometry. The yellow shading indicates the difference between the constant offset correction (gray curve) and the borehole offset correction (blue curve) methods.

Depth, m Correction Difference

X,X00

X,X50

X,Y00

Core TOC

Litho Scanner TOC (Constant Offset)

Litho Scanner TOC (Borehole Offset)

0 % 20

0 % 20

0 % 20

Effective Hole Size

Litho Scanner TOC (Constant Offset)

200 mm 325

–2.5 % 20

Page 11: High-Definition Spectroscopy—Determining Mineralogic Complexity

44 Oilfield Review

Northern Cross (Yukon) Ltd. has recently begun a campaign to actively explore the Eagle Plain region in northern Yukon, Canada, a basin cover-ing more than 5,000 km2 [2,000 mi2] (above). Northern Cross speculates that Eagle Plain has the largest oil and gas potential of any onshore basin in the Yukon.

The Arctic region is a harsh environment for drilling and exploration operations. Unlike loca-tions in more temperate climates, vast areas in the Arctic have seen little to no drilling activity because of logistical difficulties. Across the expanse of the Eagle Plain basin, only 34 wells had been drilled prior to the Northern Cross exploration campaign, and these were drilled mostly in the 1960s and 1970s. The existing seis-mic data were 2D legacy surveys acquired before many of the recent advances in high-resolution 3D techniques. From previous drilling programs, engineers with Northern Cross knew that the basin was geologically complex, and drilling through some sections, including organic-rich shales, posed operational difficulties.

Northern Cross targeted formations that include conventional reservoirs and unconven-tional resource plays. A strong potential for struc-tural and stratigraphic traps in the basin exists,

and these traps may provide opportunities for conventional hydrocarbon production. For the initial exploration phase, the operator planned six wells, of which four had been drilled by the end of 2013. Because of their close proximity to the Dempster Highway, three wells are accessible year-round and have been drilled. Typical of many wells drilled in northern Canada, the other three locations are accessible only during winter months; one of these locations was drilled during the 2012–2013 drilling season.

In addition to the logistical problems attrib-uted to weather, operators exploring in the Arctic face other challenges. In developing petrophysi-cal analysis programs, geologists must decide which tools and techniques should be utilized to best evaluate exploratory wells. These geologists face a daunting task, especially in complex reser-voirs such as those of the Eagle Plain basin because there are few wells with legacy datasets for correlation and little state-of-the-art informa-tion about subsurface geology. Acquiring as much data as is economically feasible is the norm, which often includes taking conventional core.19 However, these are rank wildcat wells, and there are no offset wells to offer guidance in determin-ing which intervals to core. To avoid the expense

of coring rock that has no production potential, engineers with Schlumberger suggested a tradi-tional logging suite augmented with data from the Litho Scanner tool. These data could then be processed using the TerraTek HRA heteroge-neous rock analysis service to determine optimal sidewall core points, which could be taken using a rotary coring tool.20

The output of the TerraTek HRA software is commonly used for determining geomechanical rock properties, but it also groups similar rock types.21 Engineers and geologists used the rock-typing feature to pick rotary core depths, thus ensuring desired rock types were represented in the sampling program while avoiding oversam-pling in rocks with similar properties. The geolo-gists also used TOC data from the Litho Scanner tool to help further define core points. Because the wells were drilled with a water-base mud system, any conventional zones that displayed elevated TOC values should correspond to hydrocarbons in the pore space and be further evaluated.

Because the processing was conducted in real time, the geologists were able to cross-reference rocks identified from Litho Scanner data as hav-ing high TOC content with superior reservoir

> Exploration in Arctic regions. Northern Cross (Yukon) Ltd. is exploring an area near the Arctic Circle in Yukon, Canada. Only 34 wells had been drilled in the company’s 5,000-km2 lease in the Eagle Plain basin prior to the operator’s recent activity. Harsh conditions in and around the Arctic Circle limit the drilling season and can potentially increase exploration and development costs. (Photograph courtesy of Don Stachiw.)

C A N A D A

Y u k o n

Eagle Plain

A r c t i c C i r c l e

A r c t i c C i r c l e

Page 12: High-Definition Spectroscopy—Determining Mineralogic Complexity

Spring 2014 45

19. For more on conventional coring: Andersen MA, Duncan B and McLin R: “Core Truth in Formation Evaluation,” Oilfield Review 25, no. 2 (Summer 2013): 16–25.

20. For more on rotary sidewall coring: Agarwal A, Laronga R and Walker L: “Rotary Sidewall Coring— Size Matters,” Oilfield Review 25, no. 4 (Winter 2013/2014): 30–39.

21. For more on the TerraTek HRA technique: Suarez- Rivera R, Deenadayalu C, Chertov M, Hartanto RN,

quality rock types identified from TerraTek HRA software (right). Rotary sidewall cores were taken, and recovery was considered excellent in both quality and quantity. Data from the high-graded rotary coring program helped confirm results from the Litho Scanner tool and provided lithol-ogy information similar in quality to that obtain-able from whole core without the expense and operational inefficiencies associated with cutting conventional core. In addition, the operator avoided costly conventional coring over intervals of little interest.

While processing the Litho Scanner data dur-ing the initial log evaluation, petrophysicists observed some puzzling results; a few intervals exhibited elevated TOC values where none were expected. These intervals generally corresponded to borehole washouts, pointing to the mud system as the source of the organic carbon. A review of the mud report revealed the culprit of the ele-vated TOCs. In some wells, the mud engineer occasionally used a lignite-based additive to improve drilling performance. Lignite, a low-rank coal, is a source of organic carbon, and its pres-ence explained the elevated readings. The addi-tive was not uniformly dispersed in the wells and was not present across all intervals. Schlumberger researchers had developed a borehole correction technique to account for organic carbon in oil-base mud systems. Engineers used the technique to correct for the presence of lignite, resolving the problem.

In addition to the effects of mud additives encountered by log analysts evaluating these Arctic wells, operational issues related to drilling affected the logging programs. During the course of drilling two of the exploration wells, openhole logs were acquired prior to a planned casing point. Drilling deeper, the operator encountered difficulties in a shale section that necessitated drilling with a technique referred to as casing drilling, in which the drill bit and mud motor are attached to the casing. The interval is drilled, and rather than being pulled from the well when the rig reaches TD, the casing is cemented in place.22

Schlumberger and Northern Cross petrophys-icists and geologists acquired Litho Scanner data in the cased section. Although spectroscopy data can be acquired in cased hole, the influence of the steel and cement behind the casing create data offsets that require corrections. No open-hole logs over the casing-drilled section existed for comparison, but portions of the cased section overlapped some previously logged openhole intervals. By comparing openhole data to well logs obtained inside the casing, engineers were

> The Litho Scanner tool as an alternative to conventional coring. Because of cost and drilling efficiency, conventional coring may not be an ideal choice for Arctic exploration wells; sparse offset well data may provide little guidance for determining coring intervals. Northern Cross geologists used the continuous mineralogy data from the Litho Scanner tool (Track 1) and TOC content computed from carbon data (Track 2, gray shading) to identify zones with hydrocarbon potential. They then applied TerraTek HRA software to identify similar rock types (Track 4) and determine the best depths for rotary sidewall coring (Track 5, black dots). TOC measurements from those cores (Track 2, red dots) compare favorably with Litho Scanner TOC measurements. The integration of these various data types resulted in sampling that provided representative cores without needless oversampling. Neutron porosity (Track 3, blue), density porosity (red) and Litho Scanner corrected porosity (black) computed using the true mineralogy are also presented; the lithology-corrected porosity demonstrates how Litho Scanner data can enhance petrophysical measurements.

Clay TOC

Calcite

Dolomite

Pyrite

Siderite

Anhydrite

Litho Scanner Mineralogy

Quartz+Feldspar+MicaDepth, m

Density Porosity

TerraTek HRA Rock Types

RotaryCore

Depth

Neutron Porosity

Corrected PorosityLitho Scanner TOC

Core TOC

0 12%

0 12%

X,700

X,750

30 –10%

30 –10%

30 –10%

Gathogo P and Kunjir R: “Improving Horizontal Completions on Heterogeneous Tight Shales,” paper CSUG/SPE 146998, presented at the Canadian Unconventional Resources Conference, Calgary, November 15–17, 2011.

22. For more on the casing drilling technique: Fontenot KR, Lesso B, Strickler RD and Warren TM: “Using Casing to Drill Directional Wells,” Oilfield Review 17, no. 2 (Summer 2005): 44–61.

Page 13: High-Definition Spectroscopy—Determining Mineralogic Complexity

46 Oilfield Review

able to apply offsets and correct for the contribu-tions from the steel and cement (above). Satisfied with the comparison of data from the previously logged openhole section and logs from the now cased section, Northern Cross had confidence that the data faithfully represented the lithology and TOC in the newly drilled portion.

Northern Cross plans to continue its explora-tion program in the Yukon and is in the process of acquiring 3D seismic data across its lease posi-tion. Interpretation of log data indicates both oil and natural gas potential in the basin.

What’s in a Name?When referring to resource plays, some industry professionals broadly apply the term shale to unconventional reservoirs. Although many uncon-ventional reservoirs may not necessarily meet the

standard geologic definition of shale, the term is used to describe reservoir rocks that are often rich in clay and have very low permeability.23 The targets for exploration are generally referred to as organic-rich shales because they have rela-tively high volumes of kerogen, a source of hydro-carbons. To have the potential for hydrocarbon production, these rocks must possess the proper mineralogy, porosity, hydrocarbon saturation, organic content and thermal maturity.24 One other aspect of most successful plays is the pres-ence of large volumetric quantities of nonclay components such as quartz, feldspar and carbon-ate. In contrast to clay, which tends to possess low strength and may be highly ductile, these nonclay minerals have high strength and contrib-ute to a rock’s ease of fracture.

Most shale developments, such as the Barnett Shale, the Marcellus Shale and the Haynesville Shale, focus on rocks with a large proportion of quartz, feldspar and mica (QFM)—an assem-blage of silicate minerals common in sedimen-tary rocks. An abundance of these minerals within the shale matrix may translate into suc-cessful unconventional wells. An exception to the QFM-rich reservoir model is the Eagle Ford Formation—or Eagle Ford shale—in south Texas, USA. This formation, which is the source rock for the prolific Austin Chalk formation, has produced both liquids and gas in relatively large volumes. The Eagle Ford Formation differs from many other shale plays because of its high carbonate content. As a result, the formation is amenable to hydraulic fracture stimulation.25

The Eagle Ford Formation extends from south Texas into northeast Mexico and is roughly 80 km [50 mi] wide and 644 km [400 mi] long (next page, top left). The average thickness is 76 m [250 ft] at reservoir depth, which is approxi-mately 1,220 to 3,660 m [4,000 to 12,000 ft] deep. The Eagle Ford is sandwiched geologically between the Austin Chalk and the Buda Limestone formations. In some areas, the Maness Shale may lie between the Eagle Ford and the Buda Limestone.

Results from a well recently drilled by BHP Billiton demonstrate the value of spectroscopy data for evaluating the complex mineralogy of the Eagle Ford Formation, especially when these data are combined with information from the CMR-Plus combinable magnetic resonance tool. The CMR-Plus tool was operated in a newly devel-oped 50-burst enhanced precision mode that resolves small pores typically found in unconven-tional reservoir rocks.26 The TOC computed from

> Spectroscopy data from inside casing. While drilling an exploration well in the Eagle Plain basin in Yukon, Canada, Northern Cross drilling engineers encountered hole problems that necessitated drilling with casing to reach TD. The cased interval included sections previously logged in open hole and sections not logged before setting casing. Geologists decided to acquire data inside casing with the Litho Scanner tool and compare it with the data from openhole runs. The gamma ray logs (Track 1) from the openhole (magenta) and cased hole (black) passes were corrected for casing and cement effects. Lithology and mineralogy data from the Litho Scanner tool run in open hole (Track 2) and cased hole (Track 3) have good agreement. The TOC data from openhole (Track 4, magenta) and cased hole (black curve, gray shading) measurements differ to some degree but are within the statistical limits of the measurement precision.

TOCClay

Calcite

Dolomite

Pyrite

Anhydrite

Openhole Mineralogy

Quartz+Feldspar+Mica

Clay

Calcite

Dolomite

Pyrite

Anhydrite

Quartz+Feldspar+MicaDepth, m

Openhole Gamma Ray

Cased Hole Gamma Ray

0 100%Cased Hole Mineralogy

0 100%

0 150gAPI

0 150

X,600

X,650

gAPIOpenhole

Litho Scanner TOC

Cased HoleLitho Scanner TOC

–3 12%

–3 12%

23. Shales are fine-grained rocks that form from the compaction of silt and clay-sized particles. Because they are formed from mud, they are also referred to as mudstones. Shales are differentiated from other claystones and mudstones in that they are laminated—finely layered—and fissile, which means they can be broken or split into sheets along their laminations.

For more on shales and shale exploration: Alexander et al, reference 12.

24. For more on characteristics for targeting organic shale: Glaser KS, Miller CK, Johnson GM, Toelle B, Kleinberg RL, Miller P and Pennington WD: “Seeking the Sweet Spot: Reservoir and Completion Quality in Organic Shales,” Oilfield Review 25, no. 4 (Winter 2013/2014): 16–29.

25. For more on oil-prone source rocks and their evaluation: Passey et al, reference 13.

26. For more on the 50-burst enhanced precision mode: Hook P, Fairhurst D, Rylander E, Badry R, Bachman N, Crary S, Chatawanich K and Taylor T: “Improved Precision Magnetic Resonance Acquisition: Application to Shale Evaluation,” paper SPE 146883, presented at the SPE Annual Technical Conference and Exhibition, Denver, October 30−November 2, 2011.

Page 14: High-Definition Spectroscopy—Determining Mineralogic Complexity

Spring 2014 47

> The Eagle Ford Formation. The Eagle Ford Formation is the oil and gas source rock for the prolific Austin Chalk formation. In Mexico, it lies along the Mexican border with the US (red) and then extends north through central South Texas (green). Several E&P companies are evaluating the Eagle Ford for both oil and gas production.

M E X I C O

300

km0 300

miles0

T e x a s

Eagle Ford

Formation

U N I T E D S T A T E S

. Optimizing liquids production from the Eagle Ford Formation. Operators developing the Eagle Ford (blue shaded interval) have found that oil can be produced economically. Based on the SpectroLith mineralogy data (Track 1), the Eagle Ford Formation is rich in calcite (light blue), unlike the clay-rich (tan shading) Maness Shale that lies below it; the Austin Chalk that lies above it is almost pure calcite. The calcite in the Eagle Ford facilitates hydraulic stimulation treatments. As seen in the ELANPlus mineralogy data (Track 2), the Eagle Ford has significant TOC content (Track 2, maroon shading)—the source of its oil; the TOC is composed of both oil and kerogen—the nonproductive solid hydrocarbon portion. Petrophysicists used the results from a combination of tools to determine the optimal interval for landing the lateral, locating the well in the better rock type for stimulation while also taking advantage of the liquids-rich section. For example, the clay component of the Eagle Ford is composed of varying amounts of montmorillonite, kaolinite and illite (Track 2); illite may be less ductile than other clay types and thus a target for fracture stimulation. Engineers also landed the lateral in the intervals with stiffer rocks such as the calcite-rich sections. To determine oil-bearing intervals, the density porosity was first corrected for matrix density from Litho Scanner mineralogy. This porosity (Track 3) is the sum of the volumes of all liquids and the solid hydrocarbons (kerogen). The CMR-Plus total porosity (Track 3, thick black curve) is the sum of all liquid volumes—clay-bound water (light blue), free water (blue) and oil (green). The difference between the CMR-Plus total porosity and the mineralogy-corrected density porosity is the unproductive kerogen portion of the TOC volume (Track 3, maroon shading). The remaining TOC volume, not associated with kerogen, must be the liquid oil volume.

the Litho Scanner tool’s carbon measurements consists of all forms of organic carbon, including kerogen, bitumen, coal and oil. Magnetic resonance measurements are sensitive only to liquids. The integration of fluid property mea-surements from the CMR-Plus tool with TOC data from the Litho Scanner tool allows geologists to distinguish between solid and liquid hydrocar-bons and quantify oil potential for the reservoir.

Operators can use this information to plan the placement of lateral sections and make comple-tion decisions.

For the formation evaluation program, BHP conventionally cored the Eagle Ford section; sam-ple plugs were taken at 1- to 5-ft [0.3- to 1.5-m] intervals and analyzed for TOC weight % using a LECO carbon analyzer. The wireline logging program included a traditional Platform Express

triple combo suite along with the CMR-Plus and Litho Scanner tools.

Litho Scanner mineralogy data clearly differ-entiate the compositions of the Maness Shale and the Eagle Ford Formation (above). Compared with that of the Eagle Ford, the Maness section has a large volume of illite and smectite, which are ductile clays not suitable for hydraulic fracture stimulation. However, the most telling difference

Depth,ft

X,450

X,475

X,500

X,525

X,550

X,575

X,600

X,625

Clay IlliteKaolinite

Montmorillonite

TOCOil

Water

Bound WaterFree Water

OilKerogen

Bound Water

Quartz+Feldspar+Mica

Quartz+Feldspar+Mica

Calcite

Calcite

Dolomite

DolomitePyrite

Pyrite 0 25%

Total CMR-PlusPorosity

Form

atio

n Na

me

Aust

in C

halk

Eagl

e Fo

rdM

anes

s Sha

le

Page 15: High-Definition Spectroscopy—Determining Mineralogic Complexity

48 Oilfield Review

between the two formations is the high TOC volume in the Eagle Ford, which is absent in the Maness. High organic carbon volume in the Eagle Ford Formation makes it a target for exploration.

In the Eagle Ford Formation, TOC weight % from core analysis and from the Litho Scanner pro-cessed data ranges from 2 to 7 weight %. Organic carbon may be associated with both kerogen and oil in the formation; therefore, without more infor-mation about the composition of the TOC, fully evaluating the resource potential of this reser-voir would be difficult. Nuclear magnetic reso-nance (NMR) data from the CMR-Plus tool helped resolve this uncertainty.

NMR tools respond to liquids in formation rocks. If the pore space is filled with oil or water, the NMR porosity should replicate the porosity determined from the Litho-Density tool. Because gas has a low density and kerogen is a solid, the NMR porosity measured in rocks containing these substances will be lower than that com-puted from density tools.

Pores in unconventional reservoirs such as the Eagle Ford Formation are small, and there-fore most NMR tools are incapable of properly measuring the total liquid volume. The CMR-Plus tool has the shortest echo spacing in the industry, which translates into the ability to resolve small pores and compute a more accurate liquid vol-ume than other tools can in similar environ-ments, especially when the tool is operating in the enhanced precision mode. The NMR porosity measurement includes water—both free and bound—and oil. In clay-rich rocks, most of the water measured by the CMR-Plus tool is bound water associated with the clays.

For liquids-rich unconventional resource plays such as the Eagle Ford, petrophysicists can compare fluid volumes computed from CMR-Plus data with the Litho Scanner TOC volume and derive a volumetric oil component. Reservoir engineers can then use this information to determine the

volume of oil in place, estimate the oil production potential and make better informed decisions on where to land the lateral.

Saudi Arabia Unconventional ReservoirSaudi Aramco utilized the Litho Scanner tool to evaluate formations in the Nafud basin and deter-mine their potential as unconventional resource plays.27 The basin is characterized by a thick sequence of Paleozoic rocks from the Cambrian through Devonian periods. The Silurian-aged Qusaiba Shale—the target for these wells—is a member of the Qalibah Formation (below left). The organic-rich Qusaiba Shale is a prolific source of hydrocarbons, generating an estimated 90% of the Paleozoic light oil and gas found in the Middle East, and it is the source rock for many major oil and gas fields.

The Qusaiba Shale is characterized by high gamma ray readings, which result from precipi-tated uranium in the reducing environment where the shale was deposited. The deepest shale intervals are Rhuddanian stage and typi-cally have 8 to 9 weight % TOC on average. Younger Aeronian- and Telychian-aged intervals have lower TOC values.

To evaluate the Litho Scanner tool’s ability to characterize the mineralogy of the formation and quantify TOC, Saudi Aramco ran the tool in two wells, one drilled with 10-lbm/galUS [1,200-kg/m3] OBM and another with 9.2-lbm/galUS [1,100-kg/m3] WBM. Saudi Aramco did not cut a conventional core in the first well drilled with OBM because LECO TOC core data were avail-able from a well located about a mile away. These data compared favorably with TOC from the Litho Scanner tool run in the new OBM well.

For a more direct comparison between log data and core measurements, the operator ran the Litho Scanner tool in a second well and cut core over the kerogen-rich zone of interest. The target formation in this case was the Rhuddanian hot shale. The operator conducted a special study on core samples. To minimize the effects of rock heterogeneity on core measurements and obtain measurements more representative of the vol-ume probed by the spectroscopy tool, technicians took 1 ft [0.3 m] long trim core slabs. These sam-ples were then crushed into a homogenized pow-der for analysis.

Technicians used XRF to analyze a portion of the powder for elemental concentrations and a LECO total carbon analyzer to determine TOC.28 Schmoker TOC was computed from the formation

>Nafud basin stratigraphic column. Geologists consider the organic- rich Qusaiba Shale member of the Silurian-period Qalibah Formation the hydrocarbon source rock for many Middle East oil and gas fields. Because the gamma ray logs from the Qusaiba Shale have very high counts, the shale is considered a “hot shale.” High gamma ray counts indicate organic-rich shales, and geologists target these formations for exploration. (Adapted from Al-Salim et al, reference 27.)

Chronostratigraphy

Nafud Basin Stratigraphic Column

Qalib

ah F

orm

atio

nQa

sim

For

mat

ion

Lithostratigraphy

Sharawramember

Sarah Formation

Zarqa facies

Quwarahmember

Ra’anmember

Kahfahmember

Hanadirmember

Qusaibamember Hot

shale

Hot shale

Homerian

Sheinwoodian

Telychian

Aeronian

Rhuddanian

Himantian

Katian

Sandbian

Darriwilian

Dapingian

Floian

TremadocianSaq Formation

Silu

rian

Ordo

vici

an

Wenlockian

StagePeriod Epoch

Llandoverian

Caradocian

Llandeilian

Llanvirnian

Arenigian

Tremadocian

Ashgillian

Page 16: High-Definition Spectroscopy—Determining Mineralogic Complexity

Spring 2014 49

27. Al-Salim A, Meridji Y, Musharfi N, Al-Waheed H, Saldungaray P, Herron S and Polyakov M: “Using a New Spectroscopy Tool to Quantify Elemental Concentrations and TOC in an Unconventional Shale Gas Reservoir: Case Studies from Saudi Arabia,” paper SPE-SAS-312, presented at the SPE Annual Technical Symposium and Exhibition, Al-Khobar, Saudi Arabia, April 21–24, 2014.

28. X-ray fluorescence is a measurement technique that bombards materials with X-rays to ionize the atoms. Ionization results in the emission of characteristic fluorescent radiation in a manner similar to the element-specific gamma ray emissions from neutron capture. Individual elements in complex mixtures can be accurately measured in the laboratory using this technique.

29. Schmoker, reference 13.

density log as a third source for comparison.29 The results of the core laboratory measurements compared favorably with the Litho Scanner ele-mental dry weights and TOC data (above). Petrophysicists combined the Litho Scanner dry weight data with other logging data and com-puted the reservoir mineralogy; these data were then compared with dual range Fourier trans-form infrared (FTIR) spectroscopy measure-ments from the core (next page). The mineralogy analysis is a model-dependent computation, and application of the appropriate model is crucial for correct results.

Engineers with Saudi Aramco and Schlumberger made several findings from the analysis of data from the Litho Scanner tool. The Litho Scanner TOC data closely matched core TOC data without empirical calibration. Using core-derived TOC values as the baseline for com-parison, they determined that the Schmoker

technique TOC was not as accurate as the TOC computed from the Litho Scanner carbon output. Because the Schmoker technique was developed specifically for Appalachian Devonian shales and the Bakken Formation, whose characterizations differ from those of the Nafud basin, the results are not surprising. Further refinement or calibra-tion is necessary to apply this technique in for-mations other than the ones for which it was developed.

The Litho Scanner tool provides reliable information for developing or refining petrophys-ical models in formations with complex litholo-gies. The improved accuracy in measuring certain elements allows petrophysicists to include more minerals in formation evaluation models to describe the reservoir rocks and better under-stand depositional environments. Correctly char-acterized mineralogy translates into more accurate matrix properties and, consequently,

more accurate porosity and water saturation computations. These benefits may be achieved in a fraction of the time and at a fraction of the cost of cutting and analyzing whole core. This infor-mation is especially important during explora-tion and early development stages when core data may be scarce or cover a limited area of a new prospect.

> Dry weight yields and TOC from a Middle East well. To confirm the quality of downhole spectroscopy data, Saudi Aramco petrophysicists compared core-derived elemental yields from XRF measurements (Tracks 2 to 9, black dots) with Litho Scanner dry weight yields (red curves). The elemental concentrations show good agreement, except around X,600 ft, where there are high concentrations of pyrite (Track 1, orange) and TOC (Track 10). The recovered core from that zone was fractured and fragmented, possibly causing some depth mismatch when the core was analyzed. TOC computed from the Litho Scanner data (Track 10, red) was compared with core TOC (black dots) and TOC computed from the Schmoker technique (blue); Litho Scanner TOC matched core results better than did the Schmoker technique. (Adapted from Al-Salim et al, reference 27.)

Clay

Calcite

Dolomite

Pyrite

Quartz+Feldspar+Mica

X,600

6 16in.

X,650

X,700

X,750

Depth,ft

Caliper

Al from Core

0 20%

0 20%

Litho ScannerDry Weight Al

Si from Core

0 50%

0 50%

Litho ScannerDry Weight Si

Fe from Core

0 20%

0 20%

Litho ScannerDry Weight Fe

S from Core

0 10%

0 10%

Litho Scanner Dry Weight S

Ca from Core

0 20%

0 20%

Litho ScannerDry Weight Ca

Mg from Core

0 10%

0 10%

Litho ScannerDry Weight Mg

Na from Core

0 5%

0 5%

Litho ScannerDry Weight Na

K from Core

0 5%

0 5%

Litho ScannerDry Weight K

TOC from Core

0 20%

0 20%

0 20%

Schmoker TOC

Litho ScannerTOC

Mineralogy

Page 17: High-Definition Spectroscopy—Determining Mineralogic Complexity

50 Oilfield Review

Ultimate AnswersDownhole spectroscopy is just one method petro-physicists use to determine the complex nature of reservoir rocks. Spectroscopy tools provide bulk measurements but are not able to deter-mine rock fabric. For instance, the Litho Scanner tool can identify zones with pyrite but cannot determine how the mineral is dispersed. Similarly, the percentage of clay in one zone may be identical to that in another, but the tool can-not determine spatial distribution of the clay

particles, specifically whether they are struc-tural, laminated or pore filling. Certain questions about mineral composition can be answered only from core analysis. Many mineralogic and litho-logic conditions affect log responses, especially those of resistivity and nuclear tools. In this age of unconventional reservoir development, petro-physicists must rely on the integration of multi-ple data sources to understand the rock composition and fabric.

In earlier times, simple models sufficed to identify hydrocarbon productive zones and quan-tify production potential. Wells in which simple conditions prevail are becoming more uncom-mon. To characterize hydrocarbons in complex rocks and reservoirs, petrophysicists now have more and better tools and techniques at their dis-posal. Geologists and petrophysicists are using these new tools and techniques to help operators find and produce more oil and gas from increas-ingly complex plays. —TS

>Mineralogy comparison. Scientists at the Schlumberger-Doll Research Center performed FTIR spectroscopy analysis on cores from a well drilled with WBM and compared the XRD-derived core mineralogy (Track 1) with the mineralogy computed from Litho Scanner data and other log inputs (Track 2). Accurate mineralogy data are crucial for computing many petrophysical properties such as porosity and fluid saturations. In this well, mineralogy data helped petrophysicists make proper analyses; for instance, high K levels in sands can be attributed to orthoclase (K-feldspar) or muscovite (K-mica) (Track 7). The matrix density values of these minerals are 2.57 g/cm3 and 2.76 g/cm3, respectively. In this case, geologists have local knowledge of the rock types, and all the K was attributed to muscovite. The correct mineralogy results in a more accurate matrix density and, consequently, more accurate density porosity and water saturation computations. In addition, a better quality Na measurement from the Litho Scanner tool can be used to quantify concentrations of Na-bearing minerals such as albite—Na-plagioclase feldspar (Track 6)—with less uncertainty. (Adapted from Al-Salim et al, reference 27.)

Depth,ft

X,000

X,100

X,200

0 % 100 0 % 100 0 % 100 0 % 50 0 % 50 0 % 500 % 20 0 % 25

0 % 100 0 % 100 0 % 100 0 % 50 0 % 50 0 % 500 % 20 0 % 25

Illite Quartz Muscovite Siderite PyriteKaolinite DolomiteNa-Feldspar

Litho ScannerDry Weight Illite

Chlorite Chlorite

Kaolinite Kaolinite

Na-Feldspar Na-FeldsparAnkerite AnkeriteCalcite Calcite

Dolomite DolomiteMuscovite Muscovite

Pyrite PyriteSiderite Siderite

OrthoclaseCa-Feldspar

Biotite

Smectite SmectiteQuartz Quartz

Illite Illite

Litho ScannerDry Weight Kaolinite

Litho ScannerDry Weight Quartz

Litho ScannerDry Weight Feldspar

Litho ScannerDry Weight Muscovite

Litho ScannerDry Weight Siderite

Litho ScannerDry Weight Pyrite

Litho ScannerDry Weight Dolomite

Illitefrom Core

XRD-DerivedMineralogy

Litho ScannerMineralogy

Kaolinitefrom Core

Quartzfrom Core

Na-Feldsparfrom Core

Muscovitefrom Core

Sideritefrom Core

Pyritefrom Core

Dolomitefrom Core

Calcite