Interaction of dissolved CO2, SOx and NOx with the

Moolayember Formation underlying the Precipice Sandstone

J.K. a*
Pearce , G.K.W. a
Dawson , and S.D. Golding a
a j.pearce2@uq.edu.au, School of Earth and Environmental Sciences, University of Queensland, Australia

1238.95 – 1238.83 m

Motivation
1238.45 – 1238.57 m 1239.77 – 1239.85 m

Methods
1237.94 – 1238 m

Fig. 2: Examples of drill

Fig. 1: Map of the Surat core and slabbed
Basin and Bowen Basin with samples from the top of
the West Wandoan 1 well the Moolayember
marked in red, and Formation (Bowen Basin), 1240.11 – 1240.22 m
generalised stratigraphy. West Wandoan 1 well.
The Precipice Sandstone 1240.82 – 1240.92 m
reservoir (Surat Basin)
unconformably overlies the 1249.18 – 1249.33 m
Moolayember Formation
(Bowen Basin) at the site.

Moolayember Formation

• The Precipice Sandstone in the Surat Basin, Australia, is a low salinity target reservoir for CO2
storage. It is also part of the Great Artesian Basin.
• The Surat CCS project proposes to perform a demonstration-scale injection test of 60,000
tonnes per year, for 3 years, of a green house gas (GHG) stream captured from black coal PCC
into the quartz rich Lower Precipice Sandstone. The dissolved GHG stream is expected to
interact with the Lower and Upper Precipice Sandstone and sink to interact with the underlying
Moolayember Formation of the Bowen Basin.
• Previous studies have characterised the reservoir and cap-rocks at the site (e.g. 1-3). However
little was known about the lithologies of the Moolayember Formation which unconformably
underlies the projects proposed injection site, or its response to a GHG stream.
• The West Wandoan 1 well was drilled in the Glenhaven site for a feasibility study, with the top ~
11 m of the Moolayember Formation cored.
• QEMSCAN, scanning electron microscopy (SEM-EDS), X-ray diffraction (XRD), petrography, acid
digestions on different sections of core.
• Kinetic geochemical modelling using Geochemist Workbench version 9 with characterization data
as input, mineral scripts for acid, neutral, basic mechanisms and existing kinetic and
thermodynamic data. Reactive surface areas were based on (4) modified for mineral observations
in the core (e.g. carbonates were cementing phases with low accessible surface areas), then
subject to a scaling factor. Further details on methods are in the paper and (2,5).
• Dissolved CO2 –low salinity formation water reaction (+/- 100 ppm SO2 and NO) for 30 years with
key Moolayember Formation lithologies, 60 °C and a fugacity for 120 bar CO2 (or additionally a
low fugacity assuming only a portion of dissolved CO2 will sink, where resulting predicted pH is ~
0.3 units higher).

Core characterisation and geochemical modelling A 1238.45 m CO2 B 1238.45 m CO2

A 1237.94 m B 1238.45 m
A
Sd

Lower Py
Precipice Ss
Sp
Coal Kln

Opl
Moolayember
Fm C D
1238.45 m CO2 1238.45 m SO2-NO-CO2

C 1238.45 m D 1245.85 m

Sd
Sd Ank/Fe-Dol
Coal

1238.45 m 1239.77 m 1240.82 m

MineralVariety
Quartz Sd
B
K-feldspar
Plagioclase
Muscovite/Illite
Kaolinite
Chlorite
Biotite
Zircon
Calcite Fig. 5: Kinetic geochemical models: Predicted change in pH,
Siderite Coal layers
Dolomite E 1245.85 m F 1245.85 m minerals, and water chemistry of siderite cemented 1238.45 m
Ankerite
Apatite 1249.18 m with (A)-(C) CO2; (D) SO2-NO-CO2
Pyrite Kfs
Fe-Oxides
Rutile Sd Ank/Fe-Dol
*
Ank/Fe-Dol
Siderite cement Clay Quartz A B
1239.77 m CO2 1239.77 m CO2
matrix
Kln

Fig. 3: (A) Minerals by depth in the Moolayember Formation

characterised by QEMSCAN, and minerals in the Lower Fig. 4: SEM (BSE) images of Moolayember Formation, West Wandoan 1
Precipice Sandstone of West Wandoan 1 (1). well. Py = pyrite, Sd = siderite, Sp = sphalerite, Kln = kaolinite,
(B) Example QEMSCAN images of thin sections. Kfs = K-feldspar, Opl = opal/chalcedony, Ank = ankerite, Dol = dolomite
*
• Slight siderite dissolution and re-precipitation was predicted with CO2 reaction of the
1238.45 m siderite cemented lithology (Fig. 5). Chlorite altered to siderite trapping C
D
• The lithologies of the Moolayember Formation are CO2, with kaolinite, chalcedony, and smectite also precipitating. The pH was buffered
1239.77 m CO2 1239.77 m SO2-NO-CO2

generally very different to the overlying quartz-rich
Lower Precipice Sandstone reservoir (Fig. 3A).
• Several drill cores e.g. 1245.85 or 1249.18 m also
contain fracture fills, corroded feldspar, sulphide
cements, and complex carbonate mineral
assemblages consistent with that expected from
previous interaction with natural CO2 (Fig. 4).
by carbonate dissolution after 30 yrs to 4.7.
• 1238.45 m reacted with CO2, SO2 and NO: After 30 yrs reaction pH was 4.6 only
very slightly lower than the pure CO2 case. Minerals dissolving and precipitating
were similar to the pure CO2 case (Figure 5D). Dissolved sulphate from SO2
increased, no S-bearing mineral precipitation was predicted.
• The 1237.94 m shale (not shown), and 1239.77 m conglomerate (Fig 6) had
predicted low reactivity to pure CO2 and a lower generated pH. With SO2 and NO in
the GHG stream, alunite sequestered S. For 1239.77 m reacted with CO2, SO2 and Fig. 6: Predicted change in pH, minerals, and water chemistry of
NO the pH was lower (3.52) after 30 years than with pure CO2. conglomerate 1239.77 m with (A)-(C) CO2; (D) SO2-NO-CO2

Geochemical modelling (Cont.) Conclusions

• Core sampled from the Moolayember Fm (West Wandoan 1 well) has a diverse mineralogy compared to the
A B
proposed overlying Lower Precipice Sandstone reservoir.
1240.11 m CO2 1240.11 m CO2
Precipitation • The Moolayember Fm may represent a valuable natural analogue of previous CO2 interaction, with the
presence of complex carbonate assemblages and secondary mineral textures. Further work is needed on
Dissolution
natural analogues as they can give long term insights to validate geochemical model predictions.
• In kinetic geochemical models the predicted pH tended to be controlled by the mineralogy rather than by the
addition of a low concentration of SO2 and NO, however these impurities may accumulate near the injection
zone and impact pH (see D. Kirste poster).
• Precipitation of ankerite or siderite was predicted to occur in some cases mineral trapping CO2.
C D
1245.85 m CO2 1245.85 m CO2 • The predicted alteration of chlorite to siderite and kaolinite is consistent with natural analogue studies.
Precipitation of pyrite, and alunite in the presence of co-injected SO2 is a reasonable model outcome given its
observations in the shallow parts of magmatic hydrothermal systems.
• Net predicted changes in mineral volume or porosity were negligible, which would be favorable.
• Future research will include GHG stream-water-rock experimental reactions at reservoir conditions for the site,
sequential leaching, and high resolution X-ray fluorescence mapping of metals in specific minerals (Australian
Synchrotron). These will allow validation and improvement of model predictions, and insights into long term
sequestration of CO2 and metals in a natural analogue. Further studies on well core in deeper areas of the
central Surat basin are suggested, additionally including isotopic and porosity/permeability studies.
Fig. 7: Predicted change in pH, and minerals of (A)-(B) 1240.11 m with CO2;
(C) – (D) 1245.85 m with CO2.
• Drill core from 1240.11 m contained traces of siderite and chlorite predicted to dissolve.
Siderite re-precipitated, kaolinite and smectite precipitated. Chlorite was altered to Acknowledgements
additional siderite mineral trapping CO2. The predicted pH was buffered to 4.84 by 30 • The authors wish to acknowledge financial assistance provided through Australian National Low Emissions Coal Research and Development (ANLEC R&D).
ANLEC R&D is supported by Australian Coal Association Low Emissions Technology Limited and the Australian Government through the Clean Energy
years. Initiative.
• With SO2 and NO, the pH was buffered to the same value (4.84) after 30 years. No • D. Kirste is acknowledged for providing script files, and helpful discussions.
• A. Golab and S. Sommacal of Thermo Fisher/FEI Australia are thanked for QEMSCAN analyses. R. Heath, N. Hall, D. Greer and CTSCo Pty Ltd. are also
sulphate minerals were predicted to precipitate, and dissolved sulphate cpncentration thanked for access to drill core and data, and valuable discussions. We acknowledge assistance from M. Mostert of the Environmental Geochemistry
increased over time. Laboratory, School of Earth and Environmental Sciences, UQ, and the UQ Centre for Microscopy and Microanalysis.
• Sandstone from 1245.85 m contained the carbonate minerals ankerite, siderite, and
dolomite. With pure CO2 the predicted pH was quickly buffered, and 4.81 after 30 years. References:
• (1) Golab A., et al., 2015. FEI-Lithicon, Report for ANLEC R&D. (2) Pearce, J.K. et al., 2015. Chemical Geology, 399, p65-86. (3) Pearce et al., 2016. Applied
Ankerite was the main mineral precipitated. With SO2 and NO, the predicted pH was the Geochemistry, 75, p152-168. (4) White, A.F., 1995. Reviews in Mineralogy and Geochemistry 31, 407-461. (5) Kirste, D., et al., 2017. Procedia Earth and Planetary
same as for the pure CO2 case after 30 years. Science 17, 606-609.