Grant agreement No. 640979

ShaleXenvironmenT

Maximizing the EU shale gas potential by minimizing its environmental footprint

H2020-LCE-2014-1

Competitive low-carbon energy

D2.1 Report on PTx properties of shale rock samples

WP 2 – Shale Core Acquisition and HTHP Handling Capabilities Due date of deliverable 28/02/2018 (Month 30) Actual submission date 03/05/2018 (Month 33) Start date of project September 1st 2015 Duration 36 months Lead beneficiary Halliburton Last editor Jabraan Ahmed (UCL) Contributors UCL, Halliburton, GFZ, UoM Dissemination level Public (PU)

This Project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 640979.

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History of the changes

Version Date Released by Comments

1.0 14-03-18 Jabraan Ahmed First draft circulated internally to WP2 members

1.1 23-04-18 Jabraan Ahmed Second draft circulated internally to WP2 members

1.2 30-04-18 Jabraan Ahmed Final Draft

1.3 01-05-18 Jabraan Ahmed Submission Version

Table of contents

History of the changes .......................................................................................................................... 2

Key word list .......................................................................................................................................... 3

Definitions and acronyms ..................................................................................................................... 3

1. Introduction ............................................................................................................................. 4

1.1 General context ............................................................................................................. 4 1.2 Deliverable objectives ................................................................................................... 4

2. Methodology ............................................................................................................................ 5

2.1 Compositional Data ....................................................................................................... 5 2.2 PT Conditions ................................................................................................................ 6

3. Summary of activities and research findings ........................................................................... 7

3.1 Composition Data ......................................................................................................... 7 3.2 HPHT Data & Handling Capabilities ............................................................................. 12

4. Conclusions and future steps ................................................................................................. 12

5. Publications resulting from the work described .................................................................... 12

6. Bibliographical references ...................................................................................................... 13

List of tables Table 2.1 – Experimental techniques used in the determination of composition parameters. XRD - X-ray diffraction, QemScan - quantitative evaluation of minerals by scanning, EDS – energy dispersive spectroctrscopy, ICP – inductively coupled plasma, MS – mass spectrometry, AES - atomic emission spectroscopy, OES - optical emission spectrometry and SEM – scanning electron microscopy. ........... 5

Table 3.1 – Interpretations of compositional data detailed in table 3.2. ............................................... 7

Table 3.2 – Compositional data of Bowland Shale Samples as conducted by SXT members. (References given in §5) Compositional parameters are given in wt%. ..................................................................... 9

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Key word list Shale rock library, European shale gas basins, Pressure – Temperature conditions, Shale Composition, Total organic carbon range, Maturity range, Exploration target areas

Definitions and acronyms

Acronyms Definitions

BGS British Geological Survey

BSF Bowland Shale Formation

D Deliverable

EIA U.S. Energy Information Administration

HB Halliburton

HPHT High Pressure High Temperature

MPa Mega pascal (pressure)

OM Organic Matter

PTx Pressure – temperature – composition

Ro Vitrinite reflectance (%); measure of thermal maturity

SXT ShaleXenvironmenT European Consortium

Tcf Trillion cubic feet (for gas reservoir estimates)

TOC Total organic carbon, measured in volume percent (%)

UCL University College London

USGS United States Geological Survey

WP Work Package

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1. Introduction

1.1 General context

WP2 has the main task of providing shale core samples for experimental characterization. The specific objectives as part of WP2 include:

1. Provide shale rock samples (some at reservoir pressure) for scientific research.

2. Develop capability for laboratory exchange and analysis of pressurised samples recovered from depth.

3. Provide pressure, temperature & composition (PTx) properties of shale rocks to be used in physical, chemical, thermodynamic models and mechanical experiments.

1.2 Deliverable objectives

This deliverable (D2.1) focusses on the latter objective by summarising PTx data on shale rock samples which have either been determined experimentally by consortium partners, or derived from the literature. Due to the nature of the data presented herein, there is some overlap in content between the deliverables of WP2. However, D2.2 and D2.3 are more generalised in their nature and report insitu reservoir conditions of shale gas bearing basins across Europe. Within this report, we focus on:

Providing compositional data on shale rock samples including: bulk mineralogy, clay mineralogy, elemental geochemistry, total organic carbon (TOC), organic matter (OM) composition/type/maturity and porosity.

The development of high pressure high temperature (HPHT) Laboratory handling capabilities and results of HPHT experiments.

In addition to PTx data being invaluable in its own right, these measurements form the basis parameters input into experiments, technical analyses and models covered by the SXT research consortium.

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2. Methodology

2.1 Compositional Data

Due to the myriad of variables involved in resource characterisation, the consortium has focussed its efforts by considering one prospective shale-gas play in particular: the Bowland Shale Formation (BSF) located in Lancashire, N.England. Thus, we report the compositional properties of the BSF in detail herein and summaries for other European basins can be found in D2.2 and D2.3 (month 36). The experimental techniques used to determine the compositional parameters are given in table 2.1. Details regarding the instrumentation of each procedure are beyond the scope of this report and the reader is referred to the journal articles (§6.) where they are discussed in depth. Table 2.1 – Experimental techniques used in the determination of composition parameters. XRD - X-ray diffraction, QemScan - quantitative evaluation of minerals by scanning, EDS – energy dispersive spectroctrscopy, ICP – inductively coupled plasma, MS – mass spectrometry, AES - atomic emission spectroscopy, OES - optical emission spectrometry and SEM – scanning electron microscopy.

x Parameter Technique

Bulk Mineralogy XRD + QemScan

Clay Mineralogy Oriented >2μm + heating

Elemental Geochemistry QemScan + EDS + ICP-

MS/AES/OES

Maturity RE + Vitrinite Reflectance

TOC RE+ LECO

OM composition RE + δ13C

Porosity SEM + QemScan + Gas

Pycnometry + Permeametry

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2.2 PT Conditions

PT conditions of prospective European shale gas basins from literature data are discussed in D2.2 and will be augmented in D2.3 (month 36). Development of insitu HPHT measurement and handling capabilities are discussed in §3.

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3. Summary of activities and research findings

3.1 Composition Data

A summary of composition data derived from experimental works and literature are given below:

Table 3.1 – Interpretations of compositional data detailed in table 3.2.

x Parameter Findings

Bulk Mineralogy

Generally low clay contents (<20%) with the lower part of the formation being carbonate rich whilst the upper part switches to being dominated by quartz.

Presence of framboidal pyrite is indicative of deposition in an environment persistently depleted in oxygen.

Mg-rich carbonate phases (ankerite-dolomite etc) indicative of significant diagenetic alterations having taken place post-burial

Clay Mineralogy

Kaolinite and Illite are the dominant clay minerals.

The lack of a 2:1 structured expanding clay (i.e. smectite) is favourable from a hydraulic fracturing perspective.

Elemental Geochemistry

QemScan analyses correlate well with XRD data where BSF has a grain size in excess of 10 microns.

Redox proxies indicating high degrees of anoxia correlate well with high TOC intervals.

Zr and Ti correlate well with detrial quartz and thus are a good indicator of detrital influx into the Bowland Basin.

Maturity

The BSF has been buried and uplifted asymmetrically, like many US shales.

Burial was most severe in the West as evidenced in the PH1 borehole where maturities are well into the gas window (Tmax ~485 C)

Time equivalent sections from the basin East are marginally less mature (Tmax ~450 C) however they have been uplifted to the surface.

From the literature, the BSF has been shown to be highly mature in wells further south (ie. Formby)

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TOC

TOC is highly variable but correlates reasonably well with proposed sea-level curves.

TOC is highest (~5 wt%) in the locally termed “marine bands” intervals which were deposited at times of high sea-level.

However, non-marine band sections of the BSF can also show elevated TOC contents, the geological controls on this are currently unknown. One theory is that this OM has a terrestrial source (type III) and so despite being abundant, is of a lower quality.

OM composition

The BSF is dominated by type II/III OM.

Marine band intervals have δ13C values of ~-27.9 ‰ which is indicative of a predominately marine type II source (much more favourable for hydrocarbon generation)

Non-marine band intervals have more type III OM (less conducive to hydrocarbon generation) however the proportions of type II/III in this strata have yet to be quantified.

Low hydrogen indices indicate some hydrocarbon expulsion from the source rock. This may also be an issue of sample preparation procedures however.

Porosity Total and effective porosities are highly variable.

Average values from gas pycnometry experiments indicate values ~4 and 2 % respectively.

Permeability + Compressibility

This work is ongoing, preliminary experiments suggest permeabilities in the range of 10-18 to 10-22 m2 at ambient pressures.

One experiment conducted at reservoir pressures saw effective porosity in a BSF from the PH1 well sample drop from 4 to 2.5 %.

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Table 3.2 – Compositional data of Bowland Shale Samples as conducted by SXT members. (References given in §5) Compositional parameters are given in wt%.

UCL_SXT sample code sample no. Quartz Feldspar Calite Ankerite Pyrite Muscovite

Preese Hall-1

SXT1_BS_15 B1-1 57 3 15 13 2 9

SXT1_BS_01 1 21 3 65 6 1 4

SXT2_BS_30 NB_05

SXT1_BS_02 2

SXT1_BS_03 3 29 2 60 3 2 4

SXT1_BS_04 4

SXT1_BS_16 B2-2 53 0 17 1 8 11

SXT1_BS_05 5

SXT1_BS_17 B4-2 65 6 4 4 4 11

SXT1_BS_18 B5-2 56 5 12 6 6 10

SXT1_BS_06 6

SXT1_BS_07 7

SXT2_BS_33 NB_08

SXT1_BS_19 B6-2 71 4 6 2 1 10

SXT1_BS_20 B7-2 68 4 10 3 2 9

SXT1_BS_08 10 56 2 26 0 2 11

SXT1_BS_21 B8-2 52 9 4 11 2 5

SXT1_BS_22 B9-2 52 5 21 3 5 9

SXT1_BS_23 B10-2 56 5 18 1 5 11

SXT1_BS_24 B11-2 23 2 69 2 1 2

SXT1_BS_25 B13-2 73 4 5 0 1 11

SXT1_BS_10 8 31 2 42 21 1 3

Marl Hill Moor

MHD13

SXT1_BS_11 11

SXT1_BS_13 13

SXT1_BS_14 14 84 0 3 8 0.5 0.5

SXT2_BS_38 NB_13

SXT2_BS_39 NB_14

SXT2_BS_41 NB_16

SXT2_BS_42 NB_17

SXT2_BS_43 NB_18

SXT2_BS_46 NB_21

Blue Scar

SXT3_BS_59 BF04

SXT3_BS_60 BF05

SXT3_BS_61 BF06

Walmsley Bridge

SXT3_BS_65 BF10

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UCL_SXT sample code sample no. Chlorite Kaolinite Illite Smectite Clays

(unclassified) TOC

(wt%)

Preese Hall-1

SXT1_BS_15 B1-1 1.4

SXT1_BS_01 1 0.9

SXT2_BS_30 NB_05

SXT1_BS_02 2 1.2

SXT1_BS_03 3 1.2

SXT1_BS_04 4 0.9

SXT1_BS_16 B2-2 5 4.1

SXT1_BS_05 5 0.9

SXT1_BS_17 B4-2 5 1.7

SXT1_BS_18 B5-2 6 3.2

SXT1_BS_06 6 1.5

SXT1_BS_07 7 0.6

SXT2_BS_33 NB_08

SXT1_BS_19 B6-2 7 6.1

SXT1_BS_20 B7-2 3 1.5

SXT1_BS_08 10 3 1.2

SXT1_BS_21 B8-2 18 1.1

SXT1_BS_22 B9-2 6 2.1

SXT1_BS_23 B10-2 5 2.0

SXT1_BS_24 B11-2 1 0.5

SXT1_BS_25 B13-2 6 5.6

SXT1_BS_10 8 0.9

Marl Hill Moor

MHD13

SXT1_BS_11 11 5.6

SXT1_BS_13 13 0.1

SXT1_BS_14 14 4 0 0 0 0 1.9

SXT2_BS_38 NB_13

SXT2_BS_39 NB_14

SXT2_BS_41 NB_16

SXT2_BS_42 NB_17

SXT2_BS_43 NB_18

SXT2_BS_46 NB_21

Blue Scar

SXT3_BS_59 BF04 3.0

SXT3_BS_60 BF05 3.0

SXT3_BS_61 BF06 2.8

Walmsley Bridge

SXT3_BS_65 BF10 1.9

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Normalisd Ternary wt%

UCL_SXT sample code

sample no. Qtz + Fsp + Py Clay

content Carbonates

Permeability (m2)

Nano-darcy (nD)

Preese Hall-1

SXT1_BS_15 B1-1 69 0 31

SXT1_BS_01 1 26 0 74

SXT2_BS_30 NB_05 2.0E-22 0.2

SXT1_BS_02 2

SXT1_BS_03 3 34 0 66

SXT1_BS_04 4

SXT1_BS_16 B2-2 73 6 21

SXT1_BS_05 5

SXT1_BS_17 B4-2 84 6 10

SXT1_BS_18 B5-2 74 6 20

SXT1_BS_06 6

SXT1_BS_07 7

SXT2_BS_33 NB_08 2.5E-22 0.3

SXT1_BS_19 B6-2 83 8 9

SXT1_BS_20 B7-2 83 4 14

SXT1_BS_08 10 67 3 29

SXT1_BS_21 B8-2 65 19 15 6.9E-18 6967.9

SXT1_BS_22 B9-2 68 6 26

SXT1_BS_23 B10-2 74 6 21

SXT1_BS_24 B11-2 27 1 72

SXT1_BS_25 B13-2 88 6 5

SXT1_BS_10 8 35 0 65

Marl Hill Moor

MHD13

SXT1_BS_11 11

SXT1_BS_13 13

SXT1_BS_14 14 88 0 12

SXT2_BS_38 NB_13

SXT2_BS_39 NB_14

SXT2_BS_41 NB_16

SXT2_BS_42 NB_17

SXT2_BS_43 NB_18

SXT2_BS_46 NB_21

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3.2 HPHT Data & Handling Capabilities

Efforts toward acquiring insitu measurements and downhole sub-sample are ongoing. UCL and Halliburton are currently seeking suitable locations to deploy the novel CoreVault technology whereby samples can be taken and held at reservoir conditions. We are in current discussions with various operators (Eni, iGas, Cuadrilla) regarding a trial of CoreVault in a European test borehole with meetings planned in June/July. Developments of HPHT laboratory handling capability have been made in the meantime, which will allow for UCL Earth Science laboratories to be able to receive and load pressurised samples into pre-existing rock deformation apparatus. These designs do require some further refinement and will be revisited once confirmation of a test-site is finalised. HPHT experiments are currently being conducted on BSF samples from the SXT rock library to measure for mechanical and petrophysical properties. The aim of this study is to compare the differences between borehole and outcrop material sampling the same geological intervals. Ultimately, once combined with data from CoreVault samples, comparisons and best-practices can be suggested for shale-play characterisation. Furthermore, these results can be used to tie into the modelling and experimental efforts of the other consortium members.

4. Conclusions and future steps

The BSF has been compositionally characterised and the data disseminated to the various consortium members to facilitate their experimental and modelling works. The majority of this data is summarised in table 3.1 and the raw values given in table 3.2. UCL are currently conducting further compositional analyses which will be made available in a similar fashion.

Developments have been made in the acquisition and processing of HPHT shale-core samples. We hope for positive discussions with oil and gas operators in the coming months for the deployment of CoreVault and additionally, will disseminate the results of any HPHT tests (ongoing) before the project end in August 2018.

5. Publications resulting from the work described

Fauchille, Ma, Rutter, Chandler, Lee & Taylor (2017). An enhanced understanding of the Basinal Bowland shale in Lancashire (UK), through microtextural and mineralogical observations. Marine and Petroleum Geology. 86. p.1374–1390.

Herrmann et al. (submitted 2018 – pending review).

Ahmed, Mitchell & Jones. Petrophysical and mechanical comparisons between Borehole and Outcrop material sampling time-equivalent mudstones deposits from the Bowland Basin. (ongoing – expected submission 08/18)

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6. Bibliographical references

1. Ahmed, Thurow, Meredith, Wood, Jourdan & Jones. (in prep) Lateral heterogeneity of the Bowland Shale Formation, Carboniferous, UK.

2. Ahmed, Thurow, Meredith, Mitchell & Jones. (in prep) Petrophysical Properties of the Bowland Shale Formation.

3. Andrews (2013). The Carboniferous Bowland Shale gas study: geology and resource estimation. British Geological Survey for Department of Energy and Climate Change.

4. Clarke, Bustin & Turner (2014). Unlocking the Resource Potential of the Bowland Basin, NW England.

5. Emmings, Davies, Vane, Leng, Moss-Hayes, Stephenson & Jenkin (2017). Stream and slope weathering effects on organic-rich mudstone geochemistry and implications for hydrocarbon source rock assessment: A Bowland Shale case study. Chemical Geology. 471. p.74–91.

6. Fauchille, Ma, Rutter, Chandler, Lee & Taylor (2017). An enhanced understanding of the Basinal Bowland shale in Lancashire (UK), through microtextural and mineralogical observations. Marine and Petroleum Geology. 86. p.1374–1390.

7. Gawthorpe (1987). Tectono-sedimentary evolution of the Bowland Basin, N England, during the Dinantian. Journal of the Geological Society of London. 144 (1). p.59–71.

8. Hough, Vane, Smith & Moss-Hayes (2014). The Bowland Shale in the Roosecote Borehole of the Lancaster Fells Sub-Basin, Craven Basin, UK: A Potential UK Shale gas Play? DOI 10.2118/167696-MS

9. Slatt & Rodriguez (2012). Comparative sequence stratigraphy and organic geochemistry of gas shales: Commonality or coincidence? Journal of Natural Gas Science and Engineering. 8. p.68–84.

10. Smith, Turner & Williams (2012). UK data and analysis for shale gas prospectivity. Geological Society, London, Petroleum Geology Conference series. 7 (1).

11. Smith, Vane, Moss-Hayes & Andrews (2012). Rock-Eval geochemical analysis of 109 samples from the Carboniferous of the Pennine Basin, including the Bowland-Hodder unit. Appendix B to DECC final report (Andrews, 2013). p.8.