Mass Spec Chemical Mass Spec Chemical Profiling of Gas Profiling of Gas

Composition in Real Time Composition in Real Time at Wellsite with the at Wellsite with the

Dq1000 Divining QuadDq1000 Divining Quad

Fluid Inclusion Technologies

Mass Spec Chemical Mass Spec Chemical Profiling with the Dq1000Profiling with the Dq1000TMTM

The Dq1000 is a portable quadrapole mass analyzer for use on drilling wells. It replaces all conventional gas detectors. It analyzes C1-C10 petroleum species, and inorganic compounds such as CO2, He, N2, O2 and sulfur bearing volatiles. It can discriminate among paraffins, naphthenes and aromatics, as well as contributions from the drilling fluid.

The Dq1000 is capable of delineating charged zones, petroleum type, compartmentalization, fluid contacts and seals to a much greater extent than conventional instrumentation. Interpretation of data follows from our 18 years of experience with subsurface fluid chemistry

Gas Fraction

Inorganics

Oil Fraction

Source RockMaturityBurial History

A petroleum deposit is the cumulative product of original composition and post- expulsion readjustments along route. Recognizing these processes results in more informed and successful exploration

MigrationFractionationSolubilityBiodegradationThermal Alteration

Gas ComponentsGas Components

Normal Paraffins

Cyclo-Paraffins

Asp

hal

ten

es

ResinsNaphtheno-Arom

Aromatic

s

Iso-paraffins

C1 C10 C30+

Sch

emat

ic V

olu

me

Per

cen

t o

f F

ract

ion

Largest chemical variability in petroleumRecorded in PNA fraction

WSGC

Fluid Inclusion Technologies, Dq1000

Analytical Limitations of Analytical Limitations of Conventional Gas Equipment Conventional Gas Equipment TGD records total combustible hydrocarbons without TGD records total combustible hydrocarbons without

compound specificitycompound specificity GC generally analyzes gas-range alkanes (paraffins), GC generally analyzes gas-range alkanes (paraffins),

which react similarly to subsurface processes. Other two which react similarly to subsurface processes. Other two major classes of hydrocarbons (naphthenes and major classes of hydrocarbons (naphthenes and aromatics) not recordedaromatics) not recorded

Generally poor performance on C5+ at low concentrationGenerally poor performance on C5+ at low concentration Analysis of inorganic compounds (e.g., COAnalysis of inorganic compounds (e.g., CO22, sulfur , sulfur

species, He) requires special equipmentspecies, He) requires special equipment Difficult to account for drilling additives and/or OBMDifficult to account for drilling additives and/or OBM Infexible to specific needs of individual wells Infexible to specific needs of individual wells

Species Analyzed by the Species Analyzed by the Dq1000Dq1000

CC11-C-C1010 organic speciesorganic species Discriminates among paraffins, Discriminates among paraffins,

naphthenes and aromaticsnaphthenes and aromatics BTEX compounds and organic acidsBTEX compounds and organic acids Inorganic volatiles such as COInorganic volatiles such as CO22, He, N, He, N22

and other atmospherics, sulfur species, and other atmospherics, sulfur species, HH22, etc., etc.

Identifies contribution from mud system Identifies contribution from mud system and organic additivesand organic additives

Why Analyze these Why Analyze these Additional Compounds?Additional Compounds?

Better estimates of petroleum type and Better estimates of petroleum type and qualityquality

Identifying fluid contactsIdentifying fluid contacts Delineating porosity/permeability trendsDelineating porosity/permeability trends Inferring nearby charge in wet reservoirsInferring nearby charge in wet reservoirs Establishing reservoir and basin Establishing reservoir and basin

compartmentalizationcompartmentalization

Dq1000 Mass Spectra Examples Dq1000 Mass Spectra Examples

1.00E+00

1.00E+01

1.00E+02

1.00E+03

1.00E+04

1.00E+05

1.00E+06

1 11 21 31 41 51 61 71 81 91 101 111 121 131

1.00E+00

1.00E+01

1.00E+02

1.00E+03

1.00E+04

1.00E+05

1.00E+06

1 11 21 31 41 51 61 71 81 91 101 111 121 131

1.00E+00

1.00E+01

1.00E+02

1.00E+03

1.00E+04

1.00E+05

1.00E+06

1 11 21 31 41 51 61 71 81 91 101 111 121 131

1.00E+00

1.00E+01

1.00E+02

1.00E+03

1.00E+04

1.00E+05

1.00E+06

1 11 21 31 41 51 61 71 81 91 101 111 121 131

1.00E+00

1.00E+01

1.00E+02

1.00E+03

1.00E+04

1.00E+05

1.00E+06

1 11 21 31 41 51 61 71 81 91 101 111 121 131

1.00E+00

1.00E+01

1.00E+02

1.00E+03

1.00E+04

1.00E+05

1.00E+06

1 9 17 25 33 41 49 57 65 73 81 89 97 105 113 121 129 137

Mostly atmosphere; minor dry gas

HC’s to C7

HC’s to C7 with aromatics

HC’s to C8

HC’s to C8;

wetter

HC’s to C10; wetter; aromatic rich; coal sourced

BB

TT

X

P/N

P/N

0.01

0.1

1

10

100

1000

10000

100000

1000000

1 11 21 31 41 51 61 71 81 91 101 111 121 131

CS2

COS

C5C4

N2

O2

Ar

CO2

C3C2

C1

C6

Benzene

H2

m/z

ppm

“Aromatic”

Dq1000 Mass Spectrum of Interpreted Dq1000 Mass Spectrum of Interpreted Mixed Thermogenic and Biogenic Gas at Mixed Thermogenic and Biogenic Gas at High SwHigh Sw

0.01

0.1

1

10

100

1000

10000

100000

1000000

1 11 21 31 41 51 61 71 81 91 101 111 121 131

C5C4

N2

O2

ArC3

C2

C1

C6

Benzene

H2

m/z

ppm

Toluene

XylenesC7

C8C9

C10

Dq1000 Mass Spectrum of Atmosphere Dq1000 Mass Spectrum of Atmosphere over Stock Tank Oil at Room over Stock Tank Oil at Room Temperature (Low Sw)Temperature (Low Sw)

Interpretation of Dq1000 Interpretation of Dq1000 DataData

Based on Fluid Inclusion Stratigraphy Based on Fluid Inclusion Stratigraphy (FIS, cuttings volatile analysis) of (FIS, cuttings volatile analysis) of thousands of wells worldwide over the thousands of wells worldwide over the last 18 yrslast 18 yrs

FIS SchematicFIS Schematic

FIS DataFIS Data

Lith

Log

E-lo

gsBlack = Inorganic speciesRed = Gas-range HC’sBlue = Water-soluble speciesGreen = liquid-range HC’s

CO

2H 2

S

C1

C7

Ben

zene

Org

anic

Aci

d

CS 2

SEAL ZONE

BYPASSED PAY ZONE

SEAL ZONE

PAY ZONE

THIN MIGRATION ZONESAND SEALS

GAS-OIL CONTACTOIL-WATER CONTACT

FIS Fluid Contact FIS Fluid Contact ExampleExample

FIS Pay Delineation and FIS Pay Delineation and Reservoir CompartmentsReservoir Compartments

8525

8575

8625

8675

8725

8775

8825

0.E+00 2.E+04 4.E+04 6.E+04 8.E+04 1.E+05

8525

8575

8625

8675

8725

8775

8825

0.E+00 5.E-02 1.E-01 2.E-01 2.E-01

8525

8575

8625

8675

8725

8775

8825

0.E+00 5.E+06 1.E+07 2.E+07 2.E+07 3.E+07

8525.0

8575.0

8625.0

8675.0

8725.0

8775.0

8825.0

0.7090 0.7090 0.7091 0.7091 0.7092

8525

8575

8625

8675

8725

8775

8825

9.E+04 9.E+04 1.E+05 1.E+05 1.E+05 1.E+05

C7 Acetic Acid CO2 Sr-RSA FI Salinity

OWC

Barrier

Barrier

Decrease in C7 and concomitant increase in AA demarcates the OWC. Detailed C7 response in oil leg reflects poroperm. CO2 shows position of carbonate cemented zones, which act as intra-reservoir seals or baffles. SrRSA and fluid inclusion salinity also show major compartment boundaries

Dq1000 Fluid Contact Dq1000 Fluid Contact ExampleExample

Oil-Water Contact; Dq1000 Data Oil-Water Contact; Dq1000 Data

Hi abundance of visible moderate gravity oil inclusions in thin section suggests Zone A may be a bypassed pay interval.

Probable OWC

Production-Depleted Zone; Dq1000 Data Production-Depleted Zone; Dq1000 Data

FIS FIS Compartmentalization Compartmentalization ExampleExample

Seal Definition and Reservoir Seal Definition and Reservoir Compartments; FIS DataCompartments; FIS Data

SEAL

SEAL

A

B

MethaneFIS methane response indicates effectiveness of top seal and inter-reservoir seal. Fluid inclusions in the two reservoirs have discrete chemistries. Biomarker work indicates a separate source for the two fluids.

Dq1000 Dq1000 Compartmentalization Compartmentalization ExampleExample

Reservoir Compartmentalization; Dq1000 Reservoir Compartmentalization; Dq1000 Data Data

SHOW #1 compartmentalized. SHOW #2 wetter; chemically distinct; better porosity; out of communication with SHOW #1.

SHOW #1

SHOW #2

Elevated Ben/Tol in Seals overlying showsCompartment indicators

Top Show #1

Base Show #1

Top Show #2

Base Show #2

Increased porosity with depth in SHOW #2

HyHeANP

C3C1

C7

C5

C10

C9

BenTol CO2B/T

Barrett 5-21-36 BTR

02

00

00

04

00

00

06

00

00

08

00

00

01

00

00

00

12

00

00

0

0 10000 20000 30000 40000 50000 60000 70000

AMU26

AM

U15

Show 1A Show 1B Show 1C Show 2 Show 3A Show 3B

Increased Wetness

Different Slopes = DifferentChemical Compartments

Methane vs. Ethane

Compartmentalization from Cross PlotsCompartmentalization from Cross Plots

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

4 14 24 34 44

Helium

Me

tha

ne

shalegas

gsa

gsb

tripa

gsc

gsd

tripb

show1a

show1b

tripc

show2

Trend 1 Trend 2

Trend 3

Data from Anomalies in

Well “A”

Trip gas composition correlates to zone (s) from which it is derived

Differences among trends are primarily related to fluid source and migration history. Differences along trend are primarily related to porosity. Secondary porosity effects (e.g., in tight rock) may contribute to scatter around trends

Compartmentalization from Cross PlotsCompartmentalization from Cross Plots

FIS Proximity to Pay FIS Proximity to Pay ExampleExample

Proximity to Pay: FIS DataProximity to Pay: FIS Data

BTEX and organic acid anomalies in reservoir equivalent section across fault

BTEX and organic acid anomalies in water leg to updip oil reservoir.

C7

Ben

zene

Ben

zene A

cetic Acid

FIS data document diffusion of BTEX and organic acid across lateral fault seal at reservoir depth. Similar anomalies are seen in the water leg. Presence of these features significantly enlarges exploration target and extends view well beyond the limits of the borehole

Oil indications in reservoir

= diffusion of water soluble species

Dq1000 Proximity to Pay Dq1000 Proximity to Pay ExampleExample

Proximity to Pay; Dq1000 DataProximity to Pay; Dq1000 Data

Two wells drilled into adjacent fault blocks. PTP interpreted as lateral diffusion from Prospect 2 identified during drilling of Prospect 1. Confirmed by subsequent oil discovery. Perfect analogy to FIS data mentioned in previous slide.

Prospect 1 Prospect 2

~ TVD crest of Prospect 2 reservoir

Application to Shale Plays, Application to Shale Plays, Tight Reservoirs and Horizontal Tight Reservoirs and Horizontal WellsWells

Predict sweet spots along lateralPredict sweet spots along lateral Identify faults and fractures Identify faults and fractures Assess water saturationAssess water saturation Evaluate source rock maturity and Evaluate source rock maturity and

compositioncomposition Aid well completionAid well completion

Observations in ShaleObservations in Shale Shales can be very heterogeneous even Shales can be very heterogeneous even

within a single horizonwithin a single horizon Heterogeneity, whatever the source Heterogeneity, whatever the source

(fracture systems, diagenetic variations) (fracture systems, diagenetic variations) affect gas production significantlyaffect gas production significantly

The Dq1000 can characterize the most The Dq1000 can characterize the most production portions of the lateral and production portions of the lateral and define compartmentalizationdefine compartmentalization

Completion programs that implement Completion programs that implement these data are more effective.these data are more effective.

Schematic Shale Dq1000 Schematic Shale Dq1000 ResponseResponse

BASELINEBASELINE BASELINEENHANCED

DEPLETEDEnhanced features represent the most productive portions of the lateral

Depletions may represent dissipated gas zones and may cause production problems

Horizontal Borehole Trajectory

Gas

Res

pons

e(N

orm

aliz

ed)

Ligh

t/H

eavy

or

Baseline gas response is intrinsic to mature shale. Positive deviations suggest added gas from fracture system (or diagenetically enhanced porosity). Negative deviations suggest depletion of intrinsic gas response by communication with another fluid compartment

Completion Completion ConsiderationsConsiderations

F F FF

Potential Sw problems

Possible Thief Zones

Potentially Higher Sulfur

F FF

Poor

Moderate

Good

Higher Sw

Sulfur Species

Helium Hydrogen

Ben/TolBenzene

C1 NormC4 Norm

Total GasC1/C4

Best Overall

FFF Fractures

More hydrogen could indicate greater amount of mature oil-prone kerogen

Designing Frac Stages in Horiz. Shale Designing Frac Stages in Horiz. Shale WellsWells

From the Bill Barrett Corporation Website

Application to Fractured ReservoirsApplication to Fractured ReservoirsOil Indicators

Oil filled fracture zones

Low Sw gas-cond filled fractures

High Sw gas-cond filled fractures

Dq1000 Application ConclusionsDq1000 Application Conclusions

Effective single-instrument replacement for the Effective single-instrument replacement for the TGD and GCTGD and GC

Better measurement of wet-gas and liquid-range Better measurement of wet-gas and liquid-range organic species even at low TGorganic species even at low TG

Superior chemical characterization from Superior chemical characterization from measurement of wide range of compoundsmeasurement of wide range of compounds

Data used to infer petroleum type and quality, Data used to infer petroleum type and quality, fluid contacts, proximity to pay, porosity, fluid contacts, proximity to pay, porosity, compartmentalization compartmentalization

Mass Spec Mass Spec

in the in the FieldField Like conventional gas Like conventional gas

detection equipment, detection equipment, the Dq1000 deploys the Dq1000 deploys using a gas trap and using a gas trap and sample flow systemsample flow system

Continuous gas sampleContinuous gas sample Depth and circulation Depth and circulation

input from WITSinput from WITS More-or-less stable More-or-less stable

electrical power supplyelectrical power supply

Hardware OverviewHardware Overview Scanning quadrupole mass spectrometer yields Scanning quadrupole mass spectrometer yields

dynamic range of 7+ orders of magnitude.dynamic range of 7+ orders of magnitude. No carrier or oxidizer gasses.No carrier or oxidizer gasses. Standard issue PC/laptop computer.Standard issue PC/laptop computer. Field serviceable - most routine maintenance Field serviceable - most routine maintenance

operations can be performed on-site by logger.operations can be performed on-site by logger. Full Electronic Isolation provides uninterrupted Full Electronic Isolation provides uninterrupted

service in extremely hostile environments.service in extremely hostile environments. International Deployment - electrical power International Deployment - electrical power

requirements are 90-240 VAC, 50-60 Hz.requirements are 90-240 VAC, 50-60 Hz.

Software OverviewSoftware Overview FIT’s Dq1000 Divining Quad Chemical Profiler FIT’s Dq1000 Divining Quad Chemical Profiler

uses a proprietary, Windows-based software driver uses a proprietary, Windows-based software driver designed to optimize the application of mass designed to optimize the application of mass spectrometry to well site geochemistry, spectrometry to well site geochemistry, incorporating real-time gas analyses with essential incorporating real-time gas analyses with essential drilling parameters monitored by dq1000’s internal drilling parameters monitored by dq1000’s internal circuitry into LAS-format digital output suitable for circuitry into LAS-format digital output suitable for display, data transfer and archival.display, data transfer and archival.

Together with FIT’s proprietary server software and Together with FIT’s proprietary server software and a satellite uplink, real time data are available a satellite uplink, real time data are available virtually anytime, anywhere….virtually anytime, anywhere….

Dq1000 Driver SoftwareDq1000 Driver Software

Dq1000 Depth ProfileDq1000 Depth Profile

Dq1000 Mass SpectraDq1000 Mass Spectra

Dq1000 Time ProfileDq1000 Time Profile

CrossplotsCrossplots

Network SoftwareNetwork Software Dq1000dvr Driver Software Dq1000dvr Driver Software on the FIT-supplied on the FIT-supplied

Laptop computer operates the portable unit in the Laptop computer operates the portable unit in the field, locally archiving gas chemistry and drilling field, locally archiving gas chemistry and drilling parameters, and providing an operator interface parameters, and providing an operator interface for stand-alone deployment.for stand-alone deployment.

Dq1000svr Server Software Dq1000svr Server Software automatically automatically retrieves and archives chemical and drilling data retrieves and archives chemical and drilling data from rig, storing it in a secure location offsitefrom rig, storing it in a secure location offsite

Dq1000mon Monitor Software Dq1000mon Monitor Software installs on any installs on any Windows-based PC allowing secure, real-time Windows-based PC allowing secure, real-time monitoring of gas chemistries and various drilling monitoring of gas chemistries and various drilling parameters from remote locations.parameters from remote locations.

Dq1000 Server SoftwareDq1000 Server Software

Dq1000 Monitor SoftwareDq1000 Monitor Software

Analytical OverviewAnalytical Overview Unit Mass Discrimination from AMU = 1 - 140 Unit Mass Discrimination from AMU = 1 - 140 Analytical cycle time is adjustable between 15 Analytical cycle time is adjustable between 15

seconds and 6 minutes (nominally ~1.5 min/cycle)seconds and 6 minutes (nominally ~1.5 min/cycle) Dynamic analytical range of 7+ orders of magnitudeDynamic analytical range of 7+ orders of magnitude Fully temperature compensatedFully temperature compensated Calibrate with standard test gases (minimal drift Calibrate with standard test gases (minimal drift

requiring infrequent calibration)requiring infrequent calibration) Discriminates paraffins, naphthenes, aromatics, Discriminates paraffins, naphthenes, aromatics,

organic acids, COorganic acids, CO22, He, N, He, N22, O, O22, H, H22, various sulphur , various sulphur species andspecies and mud additivesmud additives

Dq1000 SpecificationsDq1000 Specifications Dimensions:Dimensions: 26in x 7.5in x 15in26in x 7.5in x 15in Weight:Weight: 54 lbs (portable)54 lbs (portable) Power:Power: 85-264 VAC (3.0-1.5 Amp)85-264 VAC (3.0-1.5 Amp)

47-63 Hz (international)47-63 Hz (international) Network:Network: LAN, Internet, SatelliteLAN, Internet, Satellite Sensors:Sensors: Mud Circulation, Pump Strokes,Mud Circulation, Pump Strokes,

Depth, Gas Extraction Line FlowDepth, Gas Extraction Line Flow Cycle Time:Cycle Time: 15 sec – 6 min15 sec – 6 min

(~1.5 min nominal)(~1.5 min nominal) Modes:Modes: Dual (differential) orDual (differential) or

Single Port Gas StreamSingle Port Gas Stream

Dq1000 Divining QuadDq1000 Divining QuadWellsite Gas AnalyzerWellsite Gas Analyzer

Dq1000 DistributorsDq1000 Distributors Crown Geochemistry:Crown Geochemistry: Domestic US, inc OKDomestic US, inc OK

Bruce WarrenBruce Warren EPOCH Well Services:EPOCH Well Services: Domestic US, GOMDomestic US, GOM

Kevin RomeyKevin Romey EPOCH Well Services:EPOCH Well Services: AKAK

Jim CarsonJim Carson King Canyon Buffalo:King Canyon Buffalo: Domestic USDomestic US

Chris NerudChris Nerud Halliburton (Sperry):Halliburton (Sperry): International, GOM, AKInternational, GOM, AK

Ian MitchellIan Mitchell Stratochem Services:Stratochem Services: Egypt, MEEgypt, ME

Mohamed SaidMohamed Said