Applied Geochemistry 109 (2019) 104400

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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Geochemical modelling of experimental O2–SO2–CO2 reactions of reservoir, T

cap-rock, and overlying cores
Julie K. Pearcea, , Dirk M. Kirsteb, Grant K.W. Dawsona, Victor Rudolphc, Suzanne D. Goldinga
⁎

a
School of Earth and Environmental Sciences, University of Queensland, QLD, 4072, Australia
b
Department of Earth Sciences, Simon Fraser University, Vancouver, Canada
c
School of Chemical Engineering, University of Queensland, QLD, 4072, Australia

ARTICLE INFO ABSTRACT

Editorial handling by Dr D. Wolff-Boenisch Carbon dioxide streams stored geologically from industrial sources e.g. coal oxy-fuel firing sources, steel or
Keywords: cement processing, may contain gas impurities including O2, NOx and SOX which may have higher reactivity to
CO2 geosequestration rock than pure CO2. Supercritical CO2 with O2 and SO2 impurities (0.16 and 2% respectively) was reacted with
Oxygen and sulphur dioxide impurity core from the Precipice Sandstone, Evergreen Formation, and Hutton Sandstone of the Surat Basin, Australia.
Precipice sandstone The Precipice Sandstone is a low salinity target reservoir for CO2 storage, where the Evergreen Formation would
Evergreen formation be the overlying cap-rock, and the Hutton Sandstone is an overlying aquifer. High and low water regimes were
Hutton sandstone investigated with core sections either submerged in bulk gas saturated water, or suspended in the water satu-
rated supercritical gas head at reservoir in situ conditions of 60 °C and 12 MPa. During O2–SO2–CO2 water rock
reactions in bulk solution, a low solution pH (~1–2) was measured owing to the relatively high gas impurity
concentrations used. Dissolution of reactive minerals from the core including Fe-chlorite, ankerite, siderite, and
plagioclase was directly observed. The Evergreen Formation cap-rock and Hutton Sandstone cores reacted here
contained ~ 5–10 times higher total concentrations of elements such as Fe, Al, Ti, Ba than the Precipice
Sandstone core. Several cations were mobilised to solution including Mn, Co, Zn, Sr, Si, and Mg. Increasing
dissolved concentrations of Mn, and Co were strongly correlated with Fe (R2 = 0.99) during reaction of the
Precipice Sandstone core. Dissolved Co and Sr were strongly correlated with Fe during reaction of the Evergreen
Formation core. Dissolved Mn was somewhat correlated with Fe (R2 = 0.99) from reaction of the Hutton
Sandstone core, from both carbonate and chlorite dissolution. During gas-water reaction with the Hutton
Sandstone core, dissolved element concentrations subsequently decreased, by incorporation into newly formed
Fe oxide precipitates observed with Cr and Ni signatures. Geochemical models were built and validated with
good agreement attained with experiments, predicting Fe-chlorite and minor carbonate minerals were the main
minerals dissolving. Reactive surface areas initially estimated by a modified geometric method needed sub-
stantial increases for example in the case of chlorite (up to 2000x), and decreases for carbonates (2–10x) to
match experimental data. A 30 year simulation of reservoir rock reactivity showed that the lowered pH was
buffered by mineral dissolution. Compared to previously published pure CO2-water-rock reactions, the con-
centrations of ions such as Si generally were initially higher through reaction of more silicate minerals at the
lower generated pH, and the oxidation of sulphides. Compared to SO2–CO2-water reactions, the concentrations
of cations were similar, but with O2 present dissolved Fe subsequently decreased as Fe-oxide, sulphate and clay
minerals precipitated. Cap-rock showed reactivity to wet supercritical O2–SO2–CO2 fluid in the supercritical gas
headspace. Corrosion of minerals including ankerite and Fe-chlorite were observed, along with precipitation of
oxide, sulphate and silicate minerals on rock surfaces. These results have implications for impacts in CO2 storage
sites where gas impurities may be co-injected with CO2 and accumulate in the near wellbore region.

1. Introduction or cement processing. Separation and purification of CO2 from high

concentrations of inert gases such as N2, Ar can introduce high costs.
Carbon capture and storage (CCS) involves the capture of CO2 Coal oxy-fuel firing can produce a flue gas with a high proportion of
streams from point sources such as coal fired power stations, steel, gas, CO2, reducing the need for extensive purification, and is an option for

⁎
Corresponding author. UQ Centre for Coal Seam Gas and School of Earth and Environmental Sciences, University of Queensland, QLD, 4072, Australia.
E-mail address: j.pearce2@uq.edu.au (J.K. Pearce).

https://doi.org/10.1016/j.apgeochem.2019.104400
Received 16 May 2019; Received in revised form 9 August 2019; Accepted 13 August 2019
Available online 13 August 2019
0883-2927/ © 2019 Elsevier Ltd. All rights reserved.
J.K. Pearce, et al.
CO2 capture and storage. Several oxy-fuel firing plants have been as-
sessed or trialled in Australia (e.g. The Calide Oxy-fuel Project)(Spiro,
2014) and internationally (e.g. Vattenfall Oxy-fuel Pilot Program,
Germany, and the White Rose Project, UK) (Ting et al., 2014). CO2
streams from coal oxy-fuel firing or cement and lime processing may
contain up to a few percent of impurities including O2, SOx and NOx
which have reactivity to minerals such as carbonates, pyrite, plagio-
clase and clays when in contact with formation water (Wang et al.,
2012). Oxygen content in injected CO2 streams generally from different
capture sources is expected to range from ~30 ppm to ~5 vol%, with an
upper limit of 4% suggested by European regulations (de Visser et al.,
2008; IEAGHG, 2011; Jia et al., 2009; Jia et al., 2007). Injection and
storage of impure CO2 streams geologically has been suggested to
provide potential economic benefits through lower capture and pur-
ification costs, however, relatively less is understood of the geochemical
impacts compared to pure CO2 (Gaus, 2010; Glezakou et al., 2012;
Thaysen et al., 2017).
Storing CO2 subsurface has implications for the redox potential and
water chemistry of storage reservoirs and overlying aquifers, an im-
portant consideration for monitoring efforts (Humez et al., 2014). CO2-
water-rock reactions may also change the porosity and permeability of
reservoir and cap-rock through dissolution and precipitation processes
with implications for CO2 stream migration and containment (Dávila
et al., 2016; Farquhar et al., 2015; Kummerow and Spangenberg, 2011;
Pearce et al., 2019). Experimental studies allow the collection of data to
validate and improve geochemical models for longer term predictions
of impacts to water chemistry and rock properties. There is however
generally relatively little data on the geochemical effects of co-injection
of O2 in stored CO2 streams (de Visser et al., 2008; Kather, 2009). The
overwhelming majority of water-rock interaction studies at CO2 storage
conditions have been performed with pure CO2, with an increasing
number of studies including co-injected SO2 +/− traces of O2 from air
e.g. (Dawson et al., 2015; Kirste et al., 2017; Palandri et al., 2005;
Pearce et al., 2015, 2016a; Wilke et al., 2012). In addition recently a
portion of SO2 (~60% at equilibrium) has been shown to remain in the
supercritical gas head in SO2–CO2- water or brine dissolution experi-
ments (Amshoff et al., 2018).
Co-injected oxygen has received even less attention, even though
most injected streams will contain traces of O2 from air. Pyrite oxida-
tion caused water acidification and element mobilisation from Gothic
shale with gypsum and Fe oxide formation when reacted in the pre-
sence of 1–8% O2 in CO2 (Jung et al., 2013). A gas mixture containing
4% SO2 and 4% O2 in CO2 was also reacted with Mano Dolostone in
high salinity brine (Renard et al., 2011). The dissolution of calcite and
clays, and precipitation of Ca sulphate and barite were attributed to
inclusion of the co-injected gases. Both authors observed oxygen to be a
reactive component, as have others investigating the reactivity of well
materials such as steel (Choi et al., 2010). Wet basalt cores reacted with
1% SO2 and 1% O2 in CO2 also resulted in formation of the sulphate
minerals jarosite, alunite and gypsum (Schaef et al., 2014). Calcite
cemented cap-rock was recently reacted with O2 and SO2 in CO2 with
calcite dissolution increasing overall porosity but precipitation of
gypsum observed which may decrease porosity or permeability over
longer time scales (Pearce and Dawson, 2018; Pearce et al., 2016b).
Clay rich cap-rock was also reacted, with precipitation of Fe-oxides
observed to close nanoscale pores (Pearce et al., 2016a, 2018).
SO2 acidifies formation water and may induce reactive rock dis-
solution with subsequent potential changes to water quality and rock
porosity/permeability. The additional presence of O2 can drive the
formation of sulphuric acid (Equ. 1) (Palandri et al., 2005).
SO2 (g) + H2O + ½O2 ↔ HSO4− + H+ 1
As the mobility of some elements (e.g. Fe) released from rock into
formation water is affected by redox processes, the addition of co-in-
jected gases such as O2 to a CO2 stream could be expected to either
2
Applied Geochemistry 109 (2019) 104400
increase or decrease element mobility with implications for water
chemistry and mineral trapping of CO2 (Little and Jackson, 2010; Lu
et al., 2010). The subsequent precipitation of oxides such as hematite or
Fe oxyhydroxides can, however, beneficially incorporate dissolved
trace metals.
Storage in high salinity aquifers has generally been considered
worldwide, however, CO2 storage in low salinity aquifers is proposed in
Queensland, Australia (Hodgkinson and Grigorescu, 2012). A storage
site in the Gippsland Basin, Victoria, Australia also has a fresh water
intrusion in the proposed injection site (Michael, 2014). Although the
majority of CCS studies focus on deep saline aquifers, several authors
have performed low salinity experimental studies (at pressure and
temperature relevant to shallow aquifers) mainly to determine likely
changes to water quality in the case of a pure CO2 leak to overlying
freshwater aquifers. Reduced pH from carbonic acid formation, and
subsequent dissolution of reactive minerals (mainly carbonates) were
observed to increase the concentration of dissolved elements including
Ca, Mn (Little and Jackson, 2010). The concentration in solution of
major and trace elements including Fe, Al, U, As, Cr was also reported
to be affected by redox changes causing desorption from rock core,
although vessel corrosion may be a source (Lu et al., 2010). The in-
creasing dissolved concentrations of several elements (Sr, Co, Mn, Ni,
Tl, Zn) in CO2-water-rock experiments with carbonate cores have been
attributed to carbonate rather than sulphide dissolution (Humez et al.,
2014; Wunsch et al., 2013, 2014). Dissolved cations are however site
and mineralogy specific, and the element sources from sandstones are
not well understood. A recent experimental study on Surat Basin core
reactivity to pure CO2 reported mobilised concentrations of dissolved
Co, Zn, and Mn with Co and Zn showing a correlation with increasing
CO2 pressure up to 3.8 MPa at 45 °C though no mineral sources were
discussed (Horner et al., 2014).
Two complementary experimental and modelling studies on the
reactivity of pure CO2 or CO2 with SO2 impurities at low salinity in situ
conditions (12 MPa and 60 °C) with similar sections of Surat Basin core
from Queensland, Australia, as those reacted here also indicated po-
tential changes to near well bore water chemistry (Farquhar et al.,
2015; Pearce et al., 2015). Dissolved elements including Fe and Ca,
were mobilised to solution at generally higher concentrations from seal
core in comparison to reservoir core. In the presence of SO2 a lower pH
was generated and dissolved Fe concentrations from reactive silicates
was elevated up to 20 times.
Supercritical (sc)CO2 has historically been thought to have little
reactivity with rock except when dissolved in formation water to form
carbonic acid (Gaus, 2010). However, formation water can also dissolve
into the scCO2 phase (Spycher et al., 2003). Buoyant scCO2 may ac-
cumulate under cap-rock (structural trapping) and become water sa-
turated (Shao et al., 2011). The reactivity of water saturated (wet)
scCO2 (pure CO2 or with H2S or SO2 impurities) with wetted or non-
wetted rock and well materials has been recently observed, however
relatively little experimental work has been performed compared to
experiments with rock submerged in brine or formation water. With
work on the wet supercritical phase or gas head mostly focussed on
pure mineral studies mainly with pure CO2 (Choi et al., 2010; Felmy
et al., 2010; Glezakou et al., 2012; Loring et al., 2011). Further in-
vestigation of this phase was suggested owing to its potential reactivity
with cap-rock (Gaus, 2010). Indeed recent studies of reservoirs with
naturally high concentrations of CO2 have revealed high rock reactivity
in the gas-leg with precipitation of carbonates and chlorite conversion
to kaolinite (Higgs et al., 2015). As oxygen has a low relative solubility,
accumulation in the near well bore region in the buoyant supercritical
gas phase has been predicted (Jung et al., 2013). In certain storage
sites, contact of an impure wet scCO2 phase with the sealing cap-rock
may take place; hence the potential for reactivity of this phase with cap-
rock should also be assessed (Black et al., 2014).
In this work, CO2 with SO2 and O2 impurity gases has been ex-
perimentally reacted with reservoir and cap-rock core from a potential
J.K. Pearce, et al. Applied Geochemistry 109 (2019) 104400

CO2 storage site. Both core submerged in water with the dissolved gas siltstone-fine sandstone, generally contained quartz, kaolin, k-feldspar,
mixture, or suspended in the wet scCO2 phase are investigated experi- ankerite, chlorite, Fe-oxide, and siderite. H 279 contained quartz with
mentally through changes to water chemistry and rock. Geochemical feldspars, chlorite, siderite (Table 1), with organic matter present, and
modelling of experiments with core reacted submerged in water was Fe-oxides.
also performed to identify dissolving or potentially precipitating mi-
nerals on the time scale of experiments. Similar core depth sections and 2.2. Experimental procedure
conditions were used to previous studies to allow comparison to pure
CO2 or CO2–SO2 water rock reactivity (Farquhar et al., 2015; Pearce Experiments were conducted in an apparatus based on unstirred
et al., 2015). Parr® reactors with custom built thermoplastic liners as described in
detail previously (Pearce et al., 2015). Reactions were performed at
60 °C and 12 MPa to simulate conditions in the Surat Basin, Australia
2. Method (Raza et al., 2009). The Precipice Sandstone in the Surat Basin has fresh
to brackish formation water, although a reliable composition at the
2.1. Materials study wellbore has not been determined (Hodgkinson and Grigorescu,
2012). Formation water measurements from nearby bores indicate
CO2 storage has been proposed in the Precipice sandstone of the measured pH of 6.7–6.9, conductivity in the range 200–5000 μS/cm
Surat Basin, Queensland, Australia, with the low permeability and alkalinity 90–1100 mg/L as CaCO3, with Cl concentrations of
Evergreen formation to act as the sealing cap-rock (Hodgkinson et al., 8–1170 mg/kg (Feitz et al., 2014). Milli Q water was used in the ex-
2010). The overlying Hutton sandstone could act as a secondary seal, or periments with an initial water-rock equilibration in N2 to allow com-
has been suggested to provide a region for subsurface monitoring of parison to previous SO2–CO2-water-rock and CO2-water-rock reactions
CO2 leakage. Four core sections from the three formations were tested. with similar core sections, and to simplify interpretation and prevent
The Precipice Sandstone hosts fresh to brackish water, unlike the ma- masking of dissolved analytes (Pearce et al., 2015).
jority of sites investigated for CO2 storage internationally (Hodgkinson Three sets of experiments were performed with the rock cores;
and Grigorescu, 2012; Hodgkinson et al., 2010).
Sub-sample blocks were used from the GSQ Chinchilla-4 well core of 1) Deoxygenated MQ water (70 mL) was added to the reactor, with the
the Precipice Sandstone, referred to here after as P 386 sampled at a solid core blocks suspended in a thermoplastic basket immersed in
depth of 1193 m, the Evergreen Formation E 368 sampled at 1138 m the water. Heated vessels were purged of residual air with a low
and E 289 sampled at 898 m, and the Hutton Sandstone H 279 sampled pressure N2 flush. A Teledyne ISCO syringe pump (500HP) was used
at 868 m. These general core sections have been previously miner- to pressurise vessels to 12 ± 0.5 MPa, initially with N2 gas.
alogically characterised in detail (Farquhar et al., 2013, 2015). These Following the initial baseline water – rock reaction period to ob-
sub-sample sections were similar but not adjacent to those reacted in serve any initial release from water-rock interaction, as in previous
SO2–CO2 –water and pure CO2 – water at similar conditions by our studies, water samples were obtained. N2 gas was subsequently re-
group as described in detail previously (Pearce et al., 2015). The GSQ placed with a gas mixture of 0.16% SO2, and 2% O2 in a balance of
Chinchilla-4 well is approximately 10 km south-south east of Miles in CO2 (Coregas) using the syringe pump. The concentration of SO2
Queensland, Australia, at a latitude of 26.72722 and longitude of and O2 gas was chosen to simulate a simplified potential average
150.2014. Note that the E 368 sample from the Evergreen Formation at composition of industrially captured CO2 from oxy-fuel fired power
1138 m may also be classified as part of the upper Precipice Sandstone plants (Kather, 2009; Notz et al., 2011). The potential average
by other authors. Briefly, P 386 contained generally low reactivity composition used does not necessarily reflect likely concentrations
minerals, major quartz with kaolinite, smectite, and illite, and addi- expected to be injected into the Surat Basin. Excess supercritical
tional trace minerals (including calcite) based on previous QEMSCAN fluid was maintained during experiments, with a supercritical fluid
and XRD adjusted by SEM observations of the blocks reacted here gas head in the reactors above the water line. Fluid was sampled
(Table 1). More reactive minerals were present in the reacted core from periodically over ~16 days reaction for analysis, before depressur-
the Evergreen Formation and Hutton Sandstone; these cores were more isation and collection of rock material.
heterogeneous in nature, with some minerals in trace quantities only 2) Additional experiments were separately performed with wet solid
detectable by SEM-EDS of the sub-samples reacted here. E 368 con- core blocks suspended in the supercritical fluid at the top of reactors
tained quartz, k-feldspar, kaolinite and plagioclase feldspar, as well as in a thermoplastic basket with core not in direct contact with the
Fe-chlorite, calcite and illite and biotite. E 289, an interlaminated 40 mL of MQ water initially added to the bottom of the reactor. The
rectors were heated, and then the same gas mixture (Coregas;
Table 1 O2–SO2–CO2) was used to pressurise the reactors to 12 MPa at 60 °C.
Initial model input mineral volume % based on data from Pearce et al. (2015) A portion of water (~0.58%) would subsequently be expected to
and Farquhar et al. (2015), modified for core sub-sample observations (e.g.
dissolve into the supercritical phase on heating and pressurisation
trace calcite observed in P 386 sample reacted here). The core depths are given
(Duan and Sun, 2003). Bulk water was periodically sampled for
in brackets.
analysis over ~28 days via a dip tube into a small sampler volume
P 386 E 368 E 289 H 279 (described in Pearce et al., 2015) to avoid pressure loss. Reaction
(1193 m) (1138 m) (898 m) (868 m)
conditions were otherwise generally the same as the first set of ex-
Quartz 94.0 45.50 43.00 50.90 periments.
k-Feldspar 0.10 27.00 10.00 6.00 3) Blank tests were also conducted at the conditions of both experiment
Plagioclase Feldspar 0.10 8.00 4.00 7.00 sets 1 and 2, but without rock material present to identify any po-
Kaolin 2.55 12.4 18.00 7.00
tential cation contamination from corrosion of connections in the
Illite/Muscovite 2.70 20.00 3.00 9.00
Smectite 0.20 0.40 0.50 reaction vessel.
Biotite 0.50 2.00 8.00
Fe–Mg Chlorite 0.20 3.10 4.00 7.00 2.3. Analytical methods
Calcite 0.05 1.10
Ankerite 10.00 4.00
Adjacent core sections to the sub-samples used in reactions were
Siderite 0.05 4.00 0.10
Fe Oxide 0.05 2.00 0.50 subject to whole rock analysis. Whole rock fusions and elemental ana-
lysis by inductively coupled plasma optical emission spectroscopy (ICP-

3
J.K. Pearce, et al.
OES) was performed to determine major elemental compositions of the
core sub-samples reported as percentage oxides with an error of less
than 5% (PerkinElmer Optima 3300 DV ICP-OES instrument with a 3σ
detection limit of 0.001 mg/L) by methods described previously (Pearce
et al., 2015). Loss on ignition was also determined, along with trace
element analysis by acid digestion (HCl–HNO3) and inductively coupled
plasma mass spectrometry (ICP-MS) on a Thermo Fisher Series Xi
quadropole ICP-MS (RSD error less than 10%, for most elements less
than 5%). Two portions of both rock samples E 289 and H 279 were
analysed owing to the rock sample heterogeneity. Rock elemental
analyses were also performed on the rock samples post O2–SO2–CO2
-water-reaction. Pore size distributions of separate subsamples of the
cores were measured by mercury intrusion with the method described
previously (Farquhar et al., 2015).
Scanning Electron Microscopy with Energy Dispersive Spectrometry
(SEM-EDS) was performed on rock sample surfaces pre and post reac-
tion (low-vacuum JEOL6460LA environmental SEM with an EDS de-
tector) to detect corrosion effects and formation of new precipitates, by
methods described previously (Dawson et al., 2015). In most cases the
same position could be imaged before and after reaction, avoiding
ambiguity between previous diagenetic alteration, and dissolution/
precipitation occurring during gas-water-rock reactions. Prior to, and
post reaction, rock sample skeletal density was also determined via
helium pycnometry (Micromeritics AccuPyc 1330) on selected samples
to detect physical changes. Core sample E 368 was crushed and ana-
lysed by XRD (UQ CMM) post reaction to attempt to identify newly
formed precipitates. Other samples were mainly used up in digestions
post-reaction to identify changes to elemental composition (or changes
deemed likely too small to detect by XRD).
Solution pH and conductivity were immediately measured after
sampling from batch reactors with ex situ probes (TPS WP81,
error ± 0.01), the pH represents maximum values as CO2 may have
degassed from solution. A portion of solution was filtered (0.45 μm),
diluted 10 times, and acidified to 2% HNO3 which preserved the sam-
ples prior to element analysis by ICP-OES. Further portions of solution
(prior to O2–SO2–CO2 gas injection and at the termination of experi-
ments) were also filtered, diluted and acidified with ultrapure HNO3
prior to trace element analysis by ICP-MS. Selected unacidified samples
were analysed for sulphate, chloride and alkalinity by ALS
Environmental by methods described in detail previously (Pearce et al.,
2015).
2.4. Geochemical modelling
Experiments with rock core submerged in water with dissolved
O2–SO2–CO2 gas were modelled with the React module of the
Geochemist's Work Bench (GWB), with methods described in detail
previously (Pearce et al., 2015). Initial mineral input volume % are
given in Table 1, which were based on previous core characterisation
adjusted slightly according to SEM observations of minerals on the sub-
samples reacted here. A lower Evergreen Formation calcite-cemented
sample E 368 (Table 1) was additionally modelled to investigate likely
pH buffering above the reservoir at the contact with the Evergreen
Formation. Mineral kinetic parameters are given in Table 2, the ther-
modynamic database for mineral and aqueous species is based on the
EQ3/6 database with modifications as described previously (Delany
and Lundeen, 1989; Pearce et al., 2015). Mineral data is from the
compilation of (Palandri and Kharaka, 2004), except for chlorite from
(Lowson et al., 2005, 2007), siderite and ankerite from (Steefel, 2001),
and illite from (Köhler et al., 2003). Input water chemistry was based
on experimentally measured values after the water-rock soak at 60 °C
and 120 bar N2 prior to O2–SO2–CO2 gas injection. A mass of SO2 gas
was added to replicate experimentally observed concentrations, as de-
scribed previously, and a fixed fugacity of O2 was used (tested values
increased from −40 to use a value of −10 to match experimental pH
values and precipitation profiles of experimental ion concentrations).
4
Applied Geochemistry 109 (2019) 104400
CO2 fugacity was calculated based on a solubility model at the ex-
perimental PT conditions (Duan and Sun, 2003). Initial values of mi-
neral reactive surface areas are given in Table 2, calculated as described
previously in (Pearce et al., 2015) based on the grain size determined
through SEM and modified for spheres or clay plate morphology by the
method of (White, 1995). Mineral reactive surface areas were subse-
quently adjusted to reach a fluid compositional match with experi-
mental data. These values varied by rock experiment and the final va-
lues used are given in the results section.
Subsequently, 30 year geochemical models were built using the
mineral content of the rocks but with an equilibrated formation water
chemistry from (Feitz et al., 2014). The volume of water used was based
on the rock porosity, and the O2 fugacity was not fixed. The experi-
mentally fitted reactive surface area final values were generally sub-
sequently upscaled for the reservoir by a factor of 0.1, and for carbo-
nates were 0.05 cm2/g (Kirste et al., 2017).
3. Results and discussion
3.1. Rock elemental compositions
Whole rock major elemental analysis as oxides and loss on ignition
(LOI) are shown in Table 3 for specific sub-sections of core. These were
generally in good agreement with those measured previously for non-
adjacent sections of core (Farquhar et al., 2015). The H 279 rock sample
reacted in this study was observed to contain visibly more organic
matter and Fe bearing phases (mainly Fe oxides, biotite, and siderite),
as reflected in the higher LOI and Fe oxide content of rock sample H
279b (Table 3). In general the P346 sample has the highest Si content
and lowest Ca, consistent with the mineral content in Table 1 showing
the highest quartz content and lowest calcite or ankerite content. E368
has the highest K content consistent with the highest K-feldspar content.
Whole rock trace element analysis of the core sections by digestion
indicated approximately 5–10 times higher concentrations of most trace
elements in the Evergreen Formation and Hutton Sandstone cores when
compared to the Precipice Sandstone core, as shown in Table 4. Pre-
vious microprobe analysis of these cores indicated chlorite is Fe-rich,
and also contains Mg and less Mn. Calcite contains Mg and Mn, with Sr
in both the calcite and clays. Ti was mainly present in ilmenite, and also
chlorite and muscovite.
Organic matter, oxides and carbonate cements were generally ob-
served to be sporadic and spatially variable in the cores and may re-
present sources of trace elements, especially in Evergreen Formation
and Hutton Sandstone core sections, as shown in Table 4. Trace
amounts of phosphate, sulphide and fine-grained Cu containing mi-
nerals were also observed in cores occasionally.
3.2. Porosity and pore throats
Mercury intrusion and micro CT porosities of the cores and sub-
plugs were reported previously (Farquhar et al., 2015). The Precipice
Sandstone sample P 386 had the highest porosities of 15.2% and 18.4%
by mercury intrusion and micro CT (with a resolution of 2.2 μm) re-
spectively. Evergreen Formation core containing calcite cement, E 368,
had mercury and resolvable micro CT porosities of 8.8% and 0.2% re-
spectively. The fine-grained E 289 had mercury and micro CT porosities
of 6.1%, and 2% including organic content. H279 had porosities of
7.9% and 1.9% respectively, and the calcite cemented H256 10.1% and
1.1%. The μCT characterisation was performed on sub-plugs, and the
mercury intrusion on separate core offcut material. This may have in-
troduced some heterogeneity. Since the μCT characterisation is a cal-
culated porosity and had a resolution of 2.2 μm in this case it was
reasonable for the reservoir sandstone P346, but less useful for fine-
grained clay-rich rocks containing a lot of small pores below the re-
solution. For the cap-rocks and overlying aquifer cores the mercury
intrusion porosities were likely more reliable.
J.K. Pearce, et al. Applied Geochemistry 109 (2019) 104400

Table 2
Kinetic parameters for modelling as described in detail in (Pearce et al., 2015) As are initial reactive surface areas used to model experiments, and subsequently
adjusted with the final values used defined for each experiment in the results section. Γ is the pre-exponential factor for nucleation.
Mineral k25(acid) Ea(acid) kJ/mol n k25(neut) mol/cm2/s Ea(neut) kJ/mol Asa cm2/g K(precip) mol/cm2/s Γ
mol/cm2/s

Chalcedony 1.70E-17 68.70 10 K(diss) 2E+10

K-feldspar 8.71E-15 51.7 0.500 3.89E-17 38.00 10 K(diss) 2E+10
Albite 6.92E-15 65.0 0.457 2.75E-17 69.80 10 K(diss) 2E+10
Kaolinite 4.90E-16 65.9 0.777 6.61E-18 22.20 70 K(diss)/10 2E+10
Illite/Muscovite 1.91E-16 46.0 0.600 8.91E-20 14.00 70 K(diss) 2E+10
Smectite 1.05E-15 23.6 0.340 1.66E-17 35.00 150 K(diss) 2E+10
Biotite 1.45E-14 22.0 0.525 2.82E-17 22.00 70 K(diss) 2E+10
Fe–Mg-Chlorite 1.62E-14 25.1 0.490 1.00E-17 94.30 70 K(diss) 2E+10
Calcite 5.01E-05 14.4 1.000 1.55E-10 23.50 10 K(diss) 1E+10
Ankerite 1.59E-08 45.0 0.900 1.26E-13 62.76 10 K(diss)/1e5 3E+10
Siderite 1.59E-08 45.0 0.900 1.26E-13 62.76 10 K(diss) 2E+10
Fe-oxide 4.07E-14 66.2 1.000 2.51E-19 66.20 70 K(diss) 1E+10

a
Initial.

Pore throat size distributions for the four core sub-sections de-
scribed here and additionally a calcite cemented Hutton Sandstone
sampled from 799 m depth of the same well core (H256) are shown in
Fig. 1. The Precipice Sandstone (reservoir) sample P386 has the highest
population of large pores with the majority in the macro pore range, in
agreement with the observation of open porosity in SEM. The Evergreen
Formation (seal or cap-rock) samples have the highest occurrence of
smaller pores in the mesopore range. The Evergreen E298 fine-grained
shale has the majority of its pore throats below 1000 Å, likely asso-
ciated with clays and organic matter. The Hutton Sandstone (overlying
aquifer) samples have intermediate pore throat distributions variable
over a wide size range. The high proportion of small pore throats as-
sociated with clays in the cap-rocks and overlying aquifer core is con-
sistent with the lower porosities reported by micro CT where the ma-
jority of pores are below the technique resolution in that case.
3.3. Dissolved gas-water-rock reactions
3.3.1. Rock changes
3.3.1.1. Precipice. SEM-EDS surveys of the mineral surfaces were
performed. Where possible the same area probed pre-reaction was
returned to post-reaction to observe mineral surfaces and EDS
signatures. This allowed more confident assignment of changes owing
to reaction rather than previous diagenetic changes of the rock.
The Precipice P 386 sample had variable grain size, with trace
amounts of Fe bearing mineral phases. These included Fe-oxide cements
and grain coatings (also identified previously in petrography) Ti–Fe-
oxide previously identified as ilmenite and siderite (Fig. 2A) (Farquhar
et al., 2013, 2015). Ca signatures associated with trace calcite on
kaolinite were observed in SEM-EDS. EDS signatures also indicated a
trace amount of fine grained Ca-phosphate and an occasional NaCl
signature. Trace amounts of albite were also identified. Occasional fine
grained pyrite, sphalerite, and Cu–Sn oxide/carbonate were also pre-
sent in the reacted sub-section (Fig. 2G and H, and supplementary
material).
The minor amounts of siderite (e.g. bright spot in the centre of
Fig. 2A) were corroded post-reaction (Fig. 2B) with the quartz grain
surfaces generally unchanged. Kaolin and Ti–Fe oxides observed on the
sample surface pre-reaction, showed only minor corrosion post reaction
(Fig. 2C–F). Some minor movement of kaolin booklets appeared to have
occurred. Ca signatures observed pre-reaction were absent post-reac-
tion as were NaCl, and Ca-phosphate suggesting they dissolved during
the reaction. In general significant mineral surface changes were
however not observed for this sample.
Corrosion of kaolin from P 386 was not observed in previous reac-
tions at similar conditions with either pure CO2 or SO2–CO2 gas streams
(Farquhar et al., 2015; Pearce et al., 2015).
3.3.1.2. Evergreen. The E289 core sample had a relatively fine grain
size, with organic matter present (Fig. 3A). Some siderite and ankerite
present on this E 289 sub-sample surface tended to have no Mg content
unlike sub-samples reacted previously (Farquhar et al., 2015; Pearce
et al., 2015). The rock sample mass used was 1.4823 g.
Fine grained siderite and ankerite were observed, with EDS in-
dicating ankerite contained Ca, Fe and also some Mn ± Mg (supple-
mentary material). Siderite also sometimes contained Mg ± trace sig-
natures of Mn. These carbonates were often associated with chlorite or
occasional biotite and chloritized biotite both Fe-rich ± Mg signatures.
Occasional zircon grains were observed and a monazite (supplementary
material). Also trace amounts of Ti–Fe-oxides sphalerite, pyrite, and
plagioclase solid series. K-feldspar and plagioclase grains were not fresh
surfaces pre-reaction, and had relatively high surface areas through
previous diagenetic changes (Fig. 3C and inset, and E).
Siderite and ankerite on the surface of E 289 was observed to be
completely corroded post-reaction (Fig. 3A and B). Post-reaction, minor
pitting of K-feldspar surfaces (Fig. 3D), and more significant pitting of
albite and Ca–Na-plagioclase surfaces (Fig. 3F) were observed. Chlorite
was also corroded, although some residual chlorite remained. Occa-
sional chlorite and chloritized biotite booklets appeared to have totally
dissolved or dislodged from the surface during reaction (Fig. 3G)
especially where they were associated with carbonates that dissolved.
Organic matter appeared to still be present after reaction, and the

Table 3
Whole rock elemental composition of adjacent core sections reported as element (%) oxides from fusions and ICP-OES, and loss on ignition (%). H 279b indicates the
sub-sample with greater visible organic matter (coal) content.
Al2O3 CaO Fe2O3 K2O MgO MnO Na2O P2O5 SiO2 TiO2 Total LOI

P 386 3.24 0.00 0.12 0.31 0.01 0.00 0.68 0.02 98.48 0.08 102.95 0.73
E 368 15.30 0.77 2.65 4.48 0.78 0.02 1.32 0.11 72.03 0.64 98.12 5.56
E 289 15.96 0.22 3.40 2.76 0.70 0.04 1.46 0.06 68.52 0.88 94.00 7.71
H 279 10.15 0.02 3.79 1.60 0.37 0.05 1.19 0.03 79.33 0.48 97.02 3.14
H 279b 11.47 0.04 4.30 1.81 0.46 0.04 1.23 0.04 80.18 0.63 100.21 3.99

5
J.K. Pearce, et al. Applied Geochemistry 109 (2019) 104400

Table 4
Whole rock trace elemental composition (mg/kg), two sections of E 289 and H 279 were analysed owing to the rocks heterogeneous nature, H 279b sub-sample had
visibly greater organic matter (coal) content.
Li Be B Sc Ti V Cr Co Ni Cu Zn

P 386 2.5 0.1 12.9 0.6 455.5 3.9 6.5 2.3 3.8 41.0 15.4
E 368 15.4 1.2 20.4 4.4 3065.4 41.7 15.9 7.5 7.8 20.3 52.7
E 289 30.0 1.9 32.5 10.8 4830.6 70.1 53.1 9.7 19.0 16.6 75.2
E 289b 12.0 0.6 148.0 5.4 333.8 40.9 104.5 2.5 5.7 14.3 25.5
H 279 21.7 1.1 40.9 6.6 2824.8 48.2 31.1 7.4 14.1 9.2 56.2
H 279b 24.3 1.3 28.5 8.1 3668.5 61.4 43.1 9.4 16.3 50.6 88.7

As Se Rb Sr Zr Nb Mo Cd Ba Pb U

P 386 0.8 0.1 2.5 10.4 27.3 184.0 0.2 0.0 24.0 2.9 0.4
E 368 5.5 0.3 98.6 108.6 112.7 760.3 0.6 0.1 714.1 14.6 1.3
E 289 3.5 0.8 108.4 141.7 249.2 1552.6 0.6 0.3 524.2 17.8 2.8
E 289b 25.9 1.5 23.2 310.6 27.0 359.4 1.1 13.1 93.9 7.7 1.9
H 279 3.4 0.4 53.0 56.7 115.1 999.3 0.5 0.1 288.6 10.7 1.2
H 279b 4.2 0.5 67.7 73.0 143.6 1329.3 0.8 0.2 330.3 13.1 1.5

Fig. 1. Pore throat size distributions (mercury intrusion) of the four cores described here, and also a calcite cemented Hutton Sandstone.

surface of the rock appeared rougher. (Farquhar et al., 2015).

Corrosion of ankerite and chlorite appeared to be more extensive in
the current study than in previous studies of similar rock sample re-
activity with pure CO2 or SO2–CO2 and water (Pearce et al., 2015).
Elemental S signatures were not observed post O2–SO2–CO2 reaction on
the E 289 sample likely owing to oxidation by co-injected oxygen. In
previous reaction with SO2–CO2-water in the absence of oxygen, ele-
mental S formation was observed.
3.3.1.3. Hutton. The Hutton 279 sub-sample reacted here appeared to
contain a relatively higher organic matter, Fe-oxide, and siderite
content (Fig. 4A, and supplementary material) when compared with
sub-samples previously reacted from this depth section of core. Siderite
was observed in SEM-EDS to be variable with Fe and also Fe–Mg
signatures ± Mn and occasional associated trace signatures of Ca.
Biotite was occasionally observed often chloritized. The Ca content
(Table 3) was lower for this core sub-section than for similar sub-
sections reacted previously (Farquhar et al., 2015). Trace signatures of
Ca-phosphate, Cu–Fe-sulphide, apatite, barite cements, Cu–Sn oxide/
carbonate, zircon and plagioclase solid series were observed. Generally
more Ti–Fe oxide cement (Fig. 4B, inset), identified as illmenite in
previous microprobe analysis, was observed in this sub-sample
Post reaction, chlorite and siderite were corroded (Fig. 4A, B, C, D).
Post-reaction, some areas of the rock sample surface had an orange-
brown colouration, and in these areas fine-grained Fe ± Mn bearing
phases with EDS signatures suggesting oxides were observed by SEM to
have been precipitated. Sulphate Fe, O and S signatures were also ob-
served (Fig. 4E). Kaolin did not show obvious corrosion post reaction
(e.g. Fig. 4D, F (6)). Minor pitting on k-feldspar, albite and Na–Ca-
plagioclase surfaces was observed (Fig. 4F).
The surface corrosion on H 279 observed in this study appeared
visibly more extensive than in previously published reactions with pure
CO2 or SO2–CO2 (Pearce et al., 2015).
3.3.2. Water chemistry and geochemical modelling
3.3.2.1. Precipice. Changes in measured ex-situ pH, conductivity, and
dissolved element concentrations during P 386 O2–SO2–CO2 water rock
reaction are detailed in Table 5a, b, and Supplementary Information.
After O2–SO2–CO2 gas injection, solution pH sharply decreased to 1.23.
Conductivity increased coincident with an increase in the concentration
of total S in solution (Table 5 b). The dissolved concentration of S
continued to increase gradually until the termination of the experiment,
and pH generally continued to decrease to ~1.13. On depressurisation

6
J.K. Pearce, et al.
Fig. 2. P 386 SEM pre and post gas-water-rock reaction. A) Surface view of
quartz grains, note central bright siderite spec, upper left bright rutile spot, and
B) surface view post-reaction. C) Kaolin pre-reaction and D) kaolin post-reac-
tion with minor corrosion (1). E) Pre-reaction Ti–Fe oxide surrounded by
quartz, and F) post-reaction showing only very minor corrosion. G) Pre-reac-
tion, pyrite (2) on kaolin. H) Pre-reaction, Cu–Sn signatures (3) on kaolin.
the pH of the quench fluid was higher at 1.26, with residual fluids near
the core sample having a pH of ~1.5. Solution conductivity increased to
20.49 ms/cm3 by experiment termination. This indicates dissolution
and conversion of SO2 gas to form sulphuric acid. The measured
dissolved S is assumed to exist mainly as measurable dissolved
sulphate through oxidation including by co-injected oxygen, and
additionally by oxide minerals when rock was present.
The concentration of elements in solution from silicate and trace
carbonate dissolution generally increased over 384 h. However, Fe
concentration increased to 120 mg/kg then subsequently decreased
after ~120 h. This decrease was likely due to precipitation of Fe bearing
phases such as hematite, goethite or Fe-oxyhydroxide. Dissolved Fe
measured during reaction was correlated with Mn (R2 = 0.99), and
with Co with an R2 of 0.99. Concentrations of elements including As,
Co, Rb and V were higher at the termination of experiments as shown in
Table 5 and Supplementary Information An initial alkalinity of
~149 mg/kg as CaCO3 before mixed gas injection was measured and
used for modelling input, with subsequent measured alkalinity below
detection, the dissolved Cl concentration was below 1 mg/kg.
Element concentrations in solution during the P 386 (and other rock
samples) experiments were generally higher indicating the main con-
tribution from rock reaction. The concentration of dissolved Zn and Co
were slightly higher than might be expected from the rock content of an
7
Applied Geochemistry 109 (2019) 104400
Fig. 3. E 289 SEM images pre and post gas-water-rock reaction. A) Surface view
pre-reaction, with bright fine grained ankerite and chlorite (1), next to dark
organic matter, inset view (500x) of ankerite and chlorite. B) Surface view post-
reaction with ankerite corroded. C) K-feldspar pre-reaction with inset view
(2000x) of a sanidine surface showing the high surface area. D) K-feldspar post-
reaction with minor pitting on surface. E) Ca–Na-plagioclase surface pre-reac-
tion, and F) post-reaction with the Ca–Na-plagioclase surface corrosion. G)
Fine-grained ankerite/siderite and chlorite pre-reaction, and H) post-reaction
with ankerite dissolved and chlorite dissolved or detached from the surface.
adjacent sub-section, indicting either some contribution from the re-
actor or from oxidative dissolution of trace amounts of sulphide mi-
nerals such as sphalerite, or carbonates, both present in higher con-
centrations in the reacted sub-sample. The blank experiment with no
rock or minerals present indicated some contribution of elements in
solution from reactor corrosion including up to 17 mg/kg of Fe,
2.66 mg/kg Ni and 2.19 mg/kg Cr (Table 5). The pH in the blank ex-
periment was slightly higher than the P 386 experiment, with dissolved
S concentration lower. Dissolved S in the blank experiment originated
from SO2 dissolution and oxidation by co-injected O2. A gas head ex-
isted above the aqueous phase containing excess O2–SO2–CO2 gas. Fe
oxide minerals present in the P 386 rock sample were available to
further oxidise SO2 generating more sulphuric acid (lower pH) and a
higher measurable sulphate concentration in solution. Oxidation of SO2
likely fixed S in solution as sulphate which was measurable ex-situ,
unlike dissolved gases such as H2S which could be desorbed on sam-
pling and depressurisation (measured dissolved total S was therefore
assumed to be sulphate).
Previous reactions of P 386 with SO2–CO2 gas indicated lower levels
of sulphate in solution likely owing to the generation of both sulphate
J.K. Pearce, et al.
Fig. 4. H 279 SEM pre and post gas-water-rock reaction. A) Surface view pre-
reaction with bright areas including siderite (1), Fe-chlorite, and Fe-oxides, and
darker kaolin and organic matter. B) Surface view post-reaction with some
bright chlorite and siderite corroded. Inset bright Ti–Fe-oxide, and dark organic
matter still present post-reaction. C) Fine grained siderite on chlorite (2), and
kaolinite (3) pre-reaction. D) Post-reaction view from C), siderite and chlorite
were corroded. E) Fine grained Fe-oxides (4) observed to be formed post-re-
action. F) Post-reaction, minor pitting on albite surfaces (5), bright Ti-oxide,
and kaolinite mainly appears unaltered (6). G) Pre-reaction Cu-sulphide (7) on
chlorite. H) Cu–Sn signatures (8) on clay.
and H2S under more reducing conditions (Pearce et al., 2015). Higher
Fe-oxide content (oxidising capacity) was also observed in SEM on the P
386 rock subsample surface reacted in experiments here, and is ex-
pected to have contributed to oxidation of SO2.
Experimentally measured dissolved S and Si concentrations were
subsequently converted assuming they were SO42− and SiO2 respec-
tively for comparison to model outputs. Increases in sulphate con-
centration through gradual SO2 conversion in experiments could not be
modelled as further addition of SO2 was not possible during the model.
Geochemical modelling of the P 386 experiment is shown in Fig. 5
(lines). A reasonable match with experimental dissolved element con-
centrations (icons in Fig. 5 A, B) was obtained by increasing reactive
surface areas of several silicates and decreasing those of carbonates.
The reactive surface area of chalcedony was increased from 10 to
1000 cm2/g, chlorite from 70 to 10000, kaolinite from 70 to 700, and
anorthite from 10 to 20 cm2/g. This is consistent with the fine grain
sizes of these clays, and initially altered/weathered nature of the sur-
faces of plagioclase and quartz resulting in higher initial surface areas.
In addition colloidal silica/chalcedony has been reported in sections of
8
Applied Geochemistry 109 (2019) 104400
this core likely contributing to the higher reactive surface areas needed
(Farquhar et al., 2015). For siderite, surface areas were decreased from
10 to 5, for ankerite from 10 to 3, and hematite from 70 to 0.01 cm2/g.
This is consistent with the cementing nature of these minerals.
Simulated in situ pH was in good agreement with experimentally
measured ex situ values (Fig. 5C). Trace amounts of siderite, chlorite,
calcite, and chalcedony (note amorphous silica has been generally ob-
served in this depth section of Precipice core), were the most reactive
phases, with additionally some dissolution of kaolinite, illite, albite,
and k-feldspar predicted (Fig. 5D). Precipitation of 0.01 g of hematite
matched the decrease in Fe observed experimentally (Fig. 5B, D).
3.3.2.2. Evergreen. During reaction of the E 289 rock sample, solution
pH sharply decreased after O2–SO2–CO2 gas injection, however, some
mineral buffering is evident though the subsequent slight increase from
pH 1.57 to 1.62 (Table 5). A higher pH of 1.79 was measured after
depressurisation on quench fluid, and residual fluid near the core
sample had a pH of ~2.3. Solution conductivity was lower than during
P 386 reaction, increasing up to 7.37 ms/cm3. The concentration of
most elements in solution continued to increase during the experiment,
with dissolved S, Fe, Al and Si the most abundant (Table 5). The
concentration of sulphate was measured for selected samples, and
increased from initially 9 mg/kg ( ± 10%), to 2446 mg/kg at 216 h and
4175 mg/kg at 408 h indicating the majority of measured dissolved S
existed as sulphate. Fe, Al and Mg likely partly originated from the Fe
and Mg rich chlorite observed in SEM to be leached of Fe. Ca and some
component of the Fe and Mg were also likely from ankerite and siderite
dissolution. Mn content in the unreacted rock was observed in EDS
analysis to be mainly associated with carbonates ankerite and siderite,
and also chlorite. Dissolved Co and Sr were correlated with Fe (with R2
of 0.997 and 0.994, respectively). The initial concentration of Cl was
below 1 mg/kg, with alkalinity before mixed gas injection ~229 mg/kg
CaCO3 and subsequently below detection. Trace elements in solution
including Pb, As, V, Rb generally had increased after 408 h reaction,
except for Sn which showed a decrease in concentration
(Supplementary Information Table S5). The majority of trace
elements in solution are expected to originate from mineral
dissolution or surface desorption as the concentrations were above
blank reaction levels (Table S5).
The concentration of total S in solution was lower than for the P 386
reaction (Figs. 5a and 7a), and similar to the blank experiment level
without rock. The lower mass of the E 289 rock sample and lower
amount of Fe oxides available (Fe-oxides were not observed in SEM) for
further dissolved SO2 oxidation (Equ. 1) to measurable sulphate sub-
sequent to initial oxidation by O2 gas (Equ 2) could be one reason.
Previous work has indicated surface mediated reactions (hence greater
with higher mass/surface area of rock) acting as a proton sink could be
the reason for increased CO2 gas dissolution and higher than expected
dissolved inorganic carbon content in CO2 water rock experiments
(Humez et al., 2014). Although SO2 dissolution mechanisms are not
well understood, the generation of bicarbonate in mineral buffering
reactions (e.g. Equ. 3) could remove protons and shift the solution
equilibrium of Equ. 2 to conversion of more SO2 producing more sul-
phate/sulphuric acid. This process would be controlled by the amount
of available minerals (carbonates and possibly oxides) and hence mi-
neral mass in the system. This was also reported separately for a Marl
cap-rock reaction, where an initial presence of sulphate yielded HSO4
deprotonation (~1% of the total sulphate) (Dávila et al., 2017).
SO2 + Fe2O3 + 4H+ ↔ H2SO4 + 2Fe2+ + H2O (2)
SO2 + H2O +½O2 ↔ HSO4- + H+ ↔ SO42− + 2H +
(3)
CaCO3 +H+ → HCO3− + Ca 2+
(4)
The O2–SO2–CO2 water reaction of the lower Evergreen (E 368)
core, although not reacted experimentally here (owing to limited
J.K. Pearce, et al. Applied Geochemistry 109 (2019) 104400

Table 5
a, b and c: Water chemistry during O2–SO2–CO2 water rock reaction; pH, conductivity (mS/cm3), major and minor elements in solution by ICP-OES (mg/kg),
DL = detection limit. * Ni and Cr concentrations are higher than expected, as described in the text.
DL Time/h pH Cond. mS/cm3 Al Ba Ca Fe K

5.40E-03 1.12E-04 2.74E-03 1.49E-02 5.99E-04

Blank 384 1.35 9.68 0.20 0.00 1.18 17.27 0.31

P 386 0 4.55 0.03 0.04 0.01 16.55 1.41 0.11

48 1.23 15.23 4.15 0.04 21.96 20.97 0.38
120 1.19 17.66 4.87 0.07 51.46 120.05 0.47
216 1.23 18.43 5.33 0.05 46.77 97.44 0.53
288 1.13 19.41 5.71 0.05 41.42 89.39 ND
384 1.13 20.49 6.38 0.05 36.89 40.07 0.59

E 289 0 5.60 0.08 0.05 0.00 13.27 1.97 0.31

48 1.57 4.86 29.18 0.11 58.42 185.41 6.57
120 1.48 4.60 58.57 0.11 65.91 326.75 4.62
216 1.56 4.61 88.55 0.09 54.74 421.86 6.14
288 1.61 6.99 114.77 0.08 41.61 440.02 ND
384 1.62 7.37 98.51 0.07 42.09 447.74 7.15

H 279 0 6.01 0.16 0.36 0.02 62.69 2.32 0.49

72 1.61 10.24 183.66 0.13 73.45 555.09 2.20
168 1.70 8.31 229.12 0.08 47.30 700.01 8.07
240 1.82 6.98 267.20 0.03 44.20 793.68 8.57
336 1.86 7.46 351.58 0.01 54.26 950.99 4.49
408 1.84 7.31 343.28 0.01 65.27 817.43 0.20

DL Time/h Mg Mn Na P S Si Sr

4.10E-04 1.96E-04 1.80E-02 5.12E-03 1.09E-01 1.32E-02 2.16E-04

Blank 384 0.10 0.38 1.78 0.11 1233.85 0.70 0.00

P 386 0 0.28 0.08 1.29 0.16 3.70 0.70 0.02

48 1.51 0.36 2.90 0.42 1398.95 8.17 0.08
120 1.94 2.74 5.48 0.13 1448.88 11.09 0.10
216 1.87 2.39 2.51 0.20 1604.24 11.83 0.10
288 1.98 2.21 2.45 0.29 1707.70 12.78 0.10
384 1.95 1.04 6.40 0.66 1697.15 13.33 0.11

E 289 0 0.15 0.08 22.28 0.10 3.54 2.03 0.01

48 10.79 4.45 43.01 ND 894.42 28.41 1.03
120 20.90 7.57 47.60 0.64 1033.65 53.41 1.61
216 30.52 8.69 51.96 1.03 1101.80 80.36 1.99
288 35.56 8.61 52.02 ND ND 88.16 2.09
384 35.03 8.48 53.21 1.15 1139.61 97.05 2.09

H 279 0 0.67 0.00 25.22 0.40 11.88 3.54 0.05

72 37.57 0.01 25.86 ND 1412.19 124.34 0.61
168 47.25 0.01 25.37 1.52 1424.18 153.75 0.72
240 55.91 0.01 26.04 0.71 1492.66 172.41 0.85
336 74.99 0.01 32.00 0.85 1760.70 205.35 1.13
408 75.16 0.01 30.64 0.84 1595.15 196.26 1.17

DL Time/h Ni* Cr* Zn Co Cu

8.21E-04 3.35E-04 6.08E-04 5.24E-04 5.58E-04

Blank 384 2.66 2.19 0.08 0.05 0.23

P386 0 0.23 0.15 0.1 0.01 0.05

48 0.65 1.16 0.75 0.06 0.31
120 17.03 23.86 0.52 0.42 0.41
216 14.04 18.65 0.54 0.34 0.42
288 12.10 16.82 0.57 0.32 0.34
384 3.80 5.86 0.57 0.12 0.76

E289 0 0.39 0.29 0.05 0.02 0.01

48 1.90 5.12 1.24 0.76 0.66
120 2.51 5.88 2.08 1.36 0.80
216 1.42 3.53 2.63 1.65 0.68
288 1.69 2.98 – – 0.71
384 1.09 1.31 1.90 1.76 0.56

H279 0 0.30 0.16 0.14 < DL 0.07

(continued on next page)

9
J.K. Pearce, et al. Applied Geochemistry 109 (2019) 104400

Table 5 (continued)

DL Time/h Ni* Cr* Zn Co Cu

8.21E-04 3.35E-04 6.08E-04 5.24E-04 5.58E-04

Blank 384 2.66 2.19 0.08 0.05 0.23

72 3.30 4.83 2.75 0.36 0.73

168 3.65 3.75 2.77 0.42 1.01
240 4.60 4.54 3.18 0.45 1.05
336 5.23 4.90 4.04 0.59 1.16
408 4.22 3.31 3.91 0.59 0.86

available core), was modelled to investigate likely pH buffering at the
interface or reservoir rock and seal. Baffling of acidified formation
water could be expected to occur in the reactive lower Evergreen core
where horizontal permeability is higher than vertical permeability
(Farquhar et al., 2015). A previously determined mineralogy was used
as input with an initial formation water chemistry from previous water-
rock equilibration of E 368 samples (unpublished data)(Farquhar et al.,
2015). Rock sample total mass and surface areas from the H 279 model
were generally used. Model outputs are shown in Fig. 6, with a high
concentration of dissolved sulphate (Fig. 6A), Fe and Ca (Fig. 6B)
predicted. The solution pH was predicted to be buffered to ~2 after
408 h reaction. Calcite and chlorite were the most reactive minerals
present, with 90% of chlorite and 100% calcite predicted to react
(Fig. 7D). Minor illite (0.003 g) and chalcedony precipitation was pre-
dicted, with chalcedony precipitation likely indicating the incongruent
dissolution of chlorite as described below. Smectite (nontronite), he-
matite, jarosite, and goethite were saturated in the model; gypsum and
anhydrite were not saturated.
A good match with experimental element concentrations (icons
Fig. 7) was obtained in geochemical modelling of E 289 reaction (lines
Fig. 7). The surface area of chalcedony was increased from 10 to
10,000, K-feldspar from 10 to 7000, albite from 10 to 9000, and
chlorite from 70 to 200,000 cm2/g to match the experimental ion re-
lease. This is consistent with the initially altered/weathered appearance
of these grains and mineral surfaces, resulting in initially higher surface
areas. The surface area of illite was however decreased from 70 to
0.1 cm2/g (note on the rock surface illite was generally not easily ob-
served and may have been covered by other minerals). The surface
areas of siderite were decreased from 10 to 5, and ankerite from 10 to
0.1 cm2/g, consistent with their cementing morphology. Solution pH
was in reasonable agreement, with a slightly higher predicted pH ~2
likely reflecting the inability to model additional SO2 dissolution during
the reaction which maintained a slightly lower experimental pH
(Fig. 7C). Chlorite and ankerite were the main minerals dissolving and
contributing to dissolved elements with also K-feldspar, albite, and illite
dissolution (Fig. 7D). In the model of E 289 reaction, 87% of the
chlorite present in the rock sample reacted. Chalcedony precipitation
was included in the model to match experimental observations of SiO2

Fig. 5. Model outputs from P 386 O2–SO2–CO2 water reaction (lines) with experimental data as icons: A) and B) Concentration (mg/kg) of fluid components in
solution over 384 h's reaction, note the different scales in the y axis. C) Solution pH, D) minerals (g) dissolved and precipitated (chalcedony not shown).

10
J.K. Pearce, et al. Applied Geochemistry 109 (2019) 104400

Fig. 6. Model outputs from E 368 O2–SO2–CO2 water reaction (lines): A) and B) Concentration (mg/kg) of fluid components in solution over 384 h's reaction, note the
different Y axis scales. C) Solution pH, D) minerals (g) dissolved (chalcedony not shown).

Fig. 7. Model outputs from E 289 O2–SO2–CO2 water reaction (lines) with experimental data as icons: A) and B) Concentration (mg/kg) of fluid components in
solution over 384 h's reaction, note the different Y axis scales. C) Solution pH, D) minerals (g) dissolved (chalcedony not shown).

11
J.K. Pearce, et al. Applied Geochemistry 109 (2019) 104400

Fig. 8. Correlation of dissolved concentrations (mg/kg) in solution during O2–SO2–CO2 water reaction. A) Co and Sr during reaction of E289 core. B) Fe and Sr during
reaction of E289 core. C) Fe and Al during reaction of E289 core. D) Sr and Mg during reaction of H279.

concentration. However, this likely reflects the incongruent dissolution
of Fe rich chlorite. Under acidic conditions the dissolution of chlorite
has been shown elsewhere to be incongruent with preferential leaching
of Fe and Al to leave a silica rich layer (Brandt et al., 2003). The pre-
cipitation of secondary silica phases was not observed in experiments
here, and has not been observed during chlorite dissolution experi-
ments performed elsewhere (Black and Haese, 2014; Smith et al.,
2013). Hence, the precipitation of chalcedony in models was used as a
proxy for the silica-rich chlorite structure remaining after leaching of
the Fe and Al ions to correct the aqueous silica concentrations. Smectite
(nontronite), hematite, jarosite, and goethite were saturated in the
model, however allowing their precipitation could not be reconciled
with matching the experimentally observed water chemistries, also
observable quantities of these minerals were not observed to be formed
on mineral surfaces in SEM.

Fig. 9. Model outputs from H 279 O2–SO2–CO2 water reaction (lines) with experimental data as icons: A) and B) Concentration (mg/kg) of fluid components over
408 h's reaction, note the different Y axis scales. C) Solution pH, D) minerals (g) dissolved (chalcedony not shown).

12
J.K. Pearce, et al. Applied Geochemistry 109 (2019) 104400

Fig. 10. E 368 pre- and post- O2–SO2–CO2 wet supercritical fluid reaction. A) Surface view pre-reaction indicating the courser grain size compared to the E 289
Evergreen core. B) (Ca–Mg) Fe-aluminosilicate (amphibole) surrounded by degraded k-feldspar present pre-reaction. C) Fe–Mg-chlorite (1) and k-feldspar (2) grains
pre-reaction. D) Colloidal silica (3), Ti oxide (4) and k-feldspar (5) pre-reaction. E) Post reaction, a disaggregated silicate grain with Fe oxide coating, including Mg
and Ba elemental signatures, surrounded by Ca-sulphate flat bladed crystals (6). F) EDS spectrum of Ca-sulphate shown in E formed during reaction.

3.3.2.3. Hutton. Experimental pH decreased sharply after mixed gas
injection during H 279 reaction; subsequently it was buffered to pH
1.84 by reaction termination (Table 5a). Residual fluid near the core
sample had a higher pH on depressurisation of ~2.2. Solution
conductivity increased to 10.24 ms/cm3 after mixed gas injection and
subsequently decreased slightly to 7.31 ms/cm3. Fe concentration
reached 951 mg/kg then decreased slightly to 817 mg/kg by
experiment termination. Dissolved Fe likely originated from chlorite
and siderite, with subsequent precipitation of Fe oxides (observed in
SEM) contributing to the slight reduction in dissolved Fe concentration
after 336 h. Element concentrations including Mg, were generally
higher in solution compared to the E 289 and P 386 experiment,
likely partly owing to the larger mass of this core sample, however, Mn
and Na concentrations were lower (Table 5b). Although Sr only
increased to ~1 mg/kg, it had a strong correlation with Mg with an
R2 of 0.998 (Fig. 8). The correlation of Mg with Sr indicates potentially
a similar source for these elements. Previous microprobe analysis of
similar H 279 sections indicated Mg content in illmenite (Ti–Fe oxide)
and muscovite as well as chlorite (Farquhar et al., 2015). Dissolved Mn
was somewhat correlated with Fe (R2 = 0.99). Fe was also correlated
with Si (R2 = 0.99). On reaction, bicarbonate alkalinity was initially
~510 mg/kg as CaCO3 in good agreement with previous experimental
work on other sections of the Hutton core (Horner et al., 2014), and
subsequently fell below detection after mixed gas injection. Trace
element concentrations in solution were generally higher compared to
the Precipice Sandstone and Evergreen Formation core experiments
prior to gas mixture injection. However many dissolved trace element
concentrations including Ti, V, Cu, As, Pb appeared to have decreased
by the experiment termination (Supplementary Information Table S5).
This indicates their co-precipitation with the observed precipitated Fe-
oxides, or adsorption onto precipitated mineral surfaces. Adsorption on
organic matter surfaces is also possible as this sample contained coal.
The concentration of S measured in solution was generally high,
reaching 1760 mg/kg at 336 h with a subsequent slight decrease by the
end of the experiment (Table 5b). Again mineral buffering removing
acidity likely caused the conversion of further SO2 to sulphate/sul-
phuric acid in solution. The relatively high Fe-oxide content of this
rock, as for the P 386 core, likely contributed to further SO2 oxidation
(with oxidation by co-injected O2) to reach a similar sulphate con-
centration in solution as observed during P 386 reaction. The sub-
sequent slight decrease in sulphate concentration could indicate pre-
cipitation of S bearing phases (Fe sulphates) in agreement with Fe and S
signatures observed in post-reaction SEM on the rock surface.
Modelled Fe, Al, Na, Ca and K concentration in solution (lines;
Fig. 9A and B) were in good agreement with experimental observations
(icons Fig. 9A and B). The surface area of chalcedony was increased

13
J.K. Pearce, et al. Applied Geochemistry 109 (2019) 104400

Fig. 11. E 289 pre- and post- O2–SO2–CO2 wet supercritical fluid reaction. A) Chlorite (1), and muscovite/biotite (2) pre-reaction. B) Ankerite pre-reaction. C) K-
feldspar (3) and sphalerite (4) pre-reaction. D) Albite grain (5), muscovite/biotite (6), ankerite (7), and quartz (8) pre-reaction. E) Post reaction surface covered by
fine-grained precipitates with Fe S and O signatures in EDS. F) Magnified view of fine grained euhedral Fe–Na–K–Al-sulfate and Fe-sulphate precipitates.

from 10 to 1000 cm2/g, K-feldspar from 10 to 50, and chlorite from 70
to 200,000 cm2/g (consistent with the fine-grained nature of the
chlorite). Predicted Mg was high and likely reflects a lower Mg content
present in chlorite in the rock than that used in the model. Ankerite
surface area was decreased from 10 to 0.5 cm2/g, with siderite at
10 cm2/g. Very little ankerite was observed on the rock surface,
therefore the lower needed surface area may represent ankerite being
covered by other minerals and not accessible to fluids. Predicted solu-
tion pH was ~1.7 at 55 h in good agreement with experimental values
(Fig. 9C), but was subsequently up to 1 pH unit higher than measured
values. This likely reflects the inability of adding further SO2 to the
model during reaction. Chlorite and siderite were the most reactive
minerals, with K-feldspar and albite also dissolving. Loss of 75% of the
chlorite was predicted after 408 h. The precipitation of chalcedony and
very minor illite (0.0003 g) were predicted, however chalcedony pre-
cipitation likely reflects the incongruent dissolution of chlorite as in the
E 289 model. Saturated phases in the model were nontronite (smectite),
glauconite, hematite, jarosite and alunite.
3.4. Wet supercritical fluid-rock reactions
3.4.1. Rock changes
3.4.1.1. Evergreen wet supercritical fluid reaction. A lower Evergreen
formation core sample, E 368, was reacted in the wet O2–SO2–CO2 sc
fluid. The E 368 sample was previously characterised to contain
reactive phases including calcite and chlorite as detailed in Table 1.
Smectite was previously identified as saponite (Farquhar et al., 2013).
This lower Evergreen core section has a courser grain size than E 289,
an SEM image of the surface is shown in Fig. 10A. K-feldspar and Fe-
chlorite were observed pre-reaction to have high surface areas owing to
previous diagenetic changes (Fig. 10 B, C). Both Fe-chlorite, and
chlorite containing mainly Fe with also some Mg were identified.
Traces of biotite and a Fe–Ti phyllosilicate (possibly oxy phlogopite)
were present. Amorphous silica and Ti oxides (Fig. 10 D) were also
observed pre-reaction, in addition to the major minerals listed in
Table 1. Sphalerite, FeS/pyrite, phosphate, garnet, and Cu–Sn
minerals were additionally observed.
After reaction, rock disaggregation had occurred (owing to the
presence of swelling clays) and grains had a greenish colouration. Flat
bladed crystals of precipitated Ca sulphate with a gypsum morphology
were observed around grains replacing calcite cement, with Fe oxide
coatings on grain surfaces and barite traces (Fig. 10 E, F). XRD analysis
of the rock sample post-reaction (Supplementary Information Table S6)
identified abundant quartz, major orthoclase, minor kaolinite, albite,
illite, Na-anorthite, and trace chlorite/montmorillonite. Ca-sulphate
minerals, however, were not detected and were certainly below the

14
J.K. Pearce, et al.
XRD detection limit (~5%).
The E 289 wet supercritical fluid (WS) reacted core sample, referred
to as E 289WS, was similar before reaction to the E 289 sub-sample
described in section 3.2.1.2 and Fig. 2, containing reactive silicates
including Fe-chlorite (Fig. 11A), and carbonates including pore-filling
and fine-grained ankerite (Fig. 11B). Ankerite and siderite contained
Mg and Mn signatures in EDS. K-feldspar and albite surfaces were not
pristine pre-reaction (Fig. 11 C, D). Occasional grains of Na–Ca-plagi-
oclase, rutile and Ti–Fe phlogopite were observed along with organic
matter. Trace sphalerite was also observed, along with occasional S and
Ni signatures or Ca and S signatures on chlorite (Fig. 11C).
After reaction, the E 289WS rock sample surface was covered in
fine-grained precipitates (Fig. 11 E) making observations of underlying
mineral corrosion impossible. Precipitates were generally ~2 μm size
euhedral crystals with Fe–Na–K(Al) sulphate signatures in EDS, poten-
tially jarosite (Fig. 11F). Some precipitates had Fe, S and O signatures of
a Fe-sulphate.
3.4.1.2. Hutton Sandstone wet supercritical fluid reaction. The H 279 WS
sub-sample contained similar amounts of organic matter and Fe-oxides
as the H 279 rock sub-sample described in section 3.2.3.1 and Fig. 4.
Albite and K feldspar grains were again not pristine with rough
surfaces. Occasional Fe–Ca-silicate and rutile grains were present. Fe
(Mn) oxides existed as cements and grain coatings. Trace amounts of
Zn–Fe-sulphide and Ca-phosphate were also observed. Some clay and
oxide surfaces had Ca and S signatures in EDS. Fe-chlorite and siderite
containing Mn and trace Ca signatures were also present pre-reaction
15
Applied Geochemistry 109 (2019) 104400
Fig. 12. H 279 pre- and post-wet O2–SO2–CO2 su-
percritical fluid reaction. A) Pre-reaction mixed
Fe–Mg-chlorite (1) with fine grained siderite, k-
feldspar (2), siderite traces (3). B) Post-reaction
view in A) showing Fe-chlorite and carbonates cor-
roded, with inset magnified view (700x). C) Pre-
reaction Ti-oxide, and D) post-reaction view of C
with precipitates covering pre-existing Ti-oxide
with Fe, O, K and S signatures (4) and fine grained
Fe oxides (5). E) Magnified view of D (4) showing
fine grained booklets of silicate and/or sulphate
precipitates (6) and Fe oxides (7). F) Post-reaction
surface view of long radiating crystals of Al–Fe –K-
sulphate precipitates (8).
(Fig. 12A).
Fe-chlorite and siderite were corroded post-reaction (Fig. 12B) ap-
pearing to increase porosity and open up fine cracks around grains in
some areas. Fine grained precipitates with an Fe-(Na–K-)Al-sulfate
signature covered the majority of the sample surface, which was visibly
orange/brown in areas. Fine-grained Fe-sulphate signatures had also
precipitated on biotite with occasional Cr, Ni, Cu and Mn signatures in
EDS. Some precipitated Fe oxides also had Cr and Ni signatures. Ti-
oxides present pre-reaction (Fig. 12C), had thin mats of fine-grained
precipitates covering their surfaces post reaction (Fig. 12D). Some
precipitates had the appearance of micron-sized clay booklets. Long
radiating crystals were also observed to have been formed during re-
action, with an EDS signature suggesting an Al–Fe–K sulphate such as
alunite (Fig. 12F). The rock sample mass used was 0.8295 g. Alunite
precipitation has been predicted elsewhere in geochemical model re-
actions of CO2 and SO2 with saline brine and feldspar rich reservoir
rock (Xu et al., 2007).
3.5. 30 y geochemical model
The P346 sample mineralogy was used as input for a 30 year
CO2–SO2–O2 model. The reactive surface areas determined from the
model of the gas-water-rock experiment were decreased for reservoir
scale (as described in the methods) and used for input. The predicted
change in minerals and the pH are shown in Fig. 13. The trace amount
of calcite was included in the mineral input, and this dissolved along
with chlorite mainly. Precipitation of goethite was an initial transitory
J.K. Pearce, et al.
Fig. 13. Predicted change in minerals and pH over 30 year CO2–SO2–O2 reaction using the reservoir P346 mineral input including the trace amount of calcite.
phase consuming O2, and subsequently anhydrite, ankerite, kaolinite
and traces of siderite, and pyrite precipitated. Overall for this low re-
activity rock, rock volume decreased very slightly with no impact on
porosity. The lowered pH was buffered after 30 years to 4.77 by mineral
dissolution and the groundwater.
3.6. Comparison to pure CO2 and other reactions
Compared to previous experiments with pure CO2 where pH was
~4.5–6, the pH generated is much lower with SO2 and O2 gases present
and small amounts of carbonates in the reacted rock (Farquhar et al.,
2015). The generated pH with O2–SO2–CO2 gas is slightly lower than
with SO2–CO2 gas (~2–3), likely due to additional oxidation of the SO2
gas (and potentially oxidation of sulphides present in the rock) (Pearce
et al., 2015). The Surat Basin is a very large area, with variation in the
formation properties across the basin, and some areas with little data.
In the area studied here in the North region, the Precipice Sandstone
aquifer has a reported pH range at depth of 6.7–8.2, with the Evergreen
Formation reported pH range 7.7–7.9, and Hutton Sandstone 7.5–8.1
(Feitz et al., 2014). All are within the recommended pH 6.5–8.5 for
groundwater resources (NHMRC and NRMMC, 2011). Bicarbonate al-
kalinity in the three formations is variable, reported from ~50 to
1260 mg/kg in the region and generally higher in the Hutton Sand-
stone. Lowered pH through gas injection could be expected to be buf-
fered by reservoir alkalinity over longer timescales, especially in car-
bonate cemented zones, as predicted in the longer simulations
performed here. The experiments performed here were at initial low
alkalinities in the range of the reservoir, and with low carbonate con-
tent cores. Pure CO2 experiments (Farquhar et al., 2015), and SO2–CO2
reactions of the same core sections have been reported elsewhere
(Pearce et al., 2015). Table 6 compares the observations from the
current study with those other gas stream experiments.
Mineral precipitation was, generally, not observed in pure CO2 re-
actions of the same or similar cores from the same well (Farquhar et al.,
2015; Horner et al., 2014). Compared to pure CO2 experiments, the
dissolved concentration of Fe was ~10–30 times, Si ~5–15 times, Al
~10–100 times, Mg 2–4 times, and Mn 2–15 times higher in
O2–SO2–CO2 experiments (Farquhar et al., 2015). This is consistent
Table 6
Comparison of experiment observations from this study and the published pure CO2 or SO2–CO2 reactions of the same core. Observations differed with core type but
are generalised here.
Gas stream pH Dissolution
CO2 4.5–6 Traces of carbonates, chlorite
SO2–CO2 2–3 Carbonates, chlorite, albite, K-feldspar, kaolinite
O2–SO2–CO2 1.1–1.9 Carbonates, chlorite, albite, K-feldspar, kaolinite, ilmenite. Generally stronger corrosion and
clay collapse
Wet gas head Carbonates, note precipitates obscured observations of corrosion
O2–SO2–CO2
16
Applied Geochemistry 109 (2019) 104400
with the observation of increased silicate mineral dissolution at the
lower pH generated in O2–SO2–CO2 experiments. The concentrations of
dissolved Zn, Co, Ni and Cr are also higher in the O2–SO2–CO2 ex-
periments compared to pure CO2 experiments by ~2–20 times. This is
likely owing to oxidation of small amounts of sulphides including
sphalerite and pyrite and increased dissolution of clays, although the
core heterogeneity may have also played a role. Mobilised concentra-
tions of As, Cr, Co, Ni and Zn were also reported in experimental re-
actions of different cores from the Surat Basin with up to 38 bar pure
CO2 at 45 °C although the potential source minerals were not discussed
(Horner et al., 2014). Compared to previous SO2–CO2 experiments the
dissolved concentration of Al is ~0–5 times higher, Si is similar or
slightly higher in the O2–SO2–CO2 experiments, Sr, Mg, and Mn con-
centrations are also similar except for H279 with a much lower Mn
(Pearce et al., 2015). Here, concentrations of dissolved Fe appeared
however to subsequently decrease with time in O2–SO2–CO2 experi-
ments, especially for Hutton H279 as Fe was incorporated into Fe-oxide
and sulphate minerals. Note changes to water chemistry are expected to
be higher in experiments than in aquifers where higher alkalinities,
dilution and transport may minimise changes (Kharaka et al., 2010).
Dissolved sulphate concentration was high in all O2–SO2–CO2 ex-
periments. Compared to the equivalent SO2–CO2 experiments, total S
was 3–5 times higher in O2–SO2–CO2 experiments from the co-injected
O2 oxidising SO2 to sulphate which is not desorbed on sampling. The
concentration of SO2 present in the injection gas would partly control
the concentration of dissolved sulphate. Lower concentrations of SO2
than used here could be expected to be injected subsurface owing to
pipeline regulations. Although accumulation of impurity gases in the
near well bore have the potential to increase concentrations initially
during CO2 injection, the precipitation of sulphates and S bearing mi-
nerals over longer time periods may subsequently decrease dissolved
sulphate concentration.
A previous experimental study reacted 0–8% O2 in CO2 with gothic
shale and observed the initial increase and subsequent decrease of
dissolved Fe (and Ni) concentration as Fe oxides were precipitated.
Lower dissolved U concentrations with higher injected O2 were also
attributed to co-precipitation with Fe oxides (Jung et al., 2013). The
precipitation of Fe oxides and Ca sulphate were observed in the current
Precipitation
S, gypsum
Fe oxide + Cr, Fe-sulphate
Gypsum, Fe oxide + Cr,Ni, Fe-sulphate, alunite,
jarosite
J.K. Pearce, et al.
study. Fe oxide and gypsum formation have been reported in a previous
study on O2–CO2 brine reaction of Gothic shale cap-rock containing
pyrite, with gypsum also formed in O2–SO2–CO2 reaction of basalt and
in SO2–CO2 water reaction with calcite cemented Hutton Sandstone
(Jung et al., 2013; Pearce et al., 2015).
If all the 1% calcite in the lower Evergreen sample E 368WS reacted
here were converted during wet sc fluid reaction to gypsum, this would
result in a 1% volume increase of the rock (by mass balance), or 0.3%
volume increase if the calcite were converted to anhydrite. If 50% of the
calcite present were converted, with the other ~50% transferred to
solution and transported away (as suggested by experiments), the vo-
lume increase would be 0.3% with formation of gypsum, or 0.1% vo-
lume increase with anhydrite formation potentially reducing CO2 mi-
gration. Measurements of changes to core porosity and permeability
through experiments and natural analogue studies are needed in future
to validate predictions and models. There is longer-term potential for
self-sealing of cap-rock, however in the time scales of the experiments
and models performed here rock mass decreased after impure CO2-
water or wet supercritical fluid reaction indicating initial corrosion. The
Precipice Sandstone sample reacted with O2–SO2–CO2 gas dissolved in
water lost 0.5% mass, with the Evergreen and Hutton samples losing up
to 2.4% mass. The H 279 WS and E 289 WS samples reacted in wet
supercritical fluid lost 1.3 and 1.7% of their original masses respec-
tively.
Park et al., reacted sandstone containing chlorite with CO2–SO2 at
0–1% impurity concentrations, and subsequently modelled the
CO2–SO2 reactions over 25 days (Park et al., 2018). They also found an
overall decrease in rock mass owing to a generated low pH and dis-
solution of chlorite mainly in agreement with this study. The low
content of calcite in their case resulted in no precipitation of gypsum or
anhydrite. In the 30 year simulation of reaction of the Precipice
Sandstone core performed here, the rock volume also decreased slightly
overall with essentially no effect on porosity. This was owing to the low
amount of reactive minerals present. The small amount of calcite was
converted to anhydrite, however the volume change was too small to
affect the porosity. Bacon et al., built a reactive transport model for CO2
and CO2 with 1% SO2 reacting with the saline Rose Run Sandstone or
Copper Ridge dolomite for 10 years (Bacon et al., 2009). They predicted
dissolution of calcite and to some extent dolomite, and precipitation of
anhydrite close to the injector, however the volumes were not sig-
nificant enough to change the reservoir properties. In contrast Xu et al.,
predicted increases to porosity in the near well bore acidified zone with
CO2 and SO2 reaction of a plagioclase rich sandstone over 10–10,000
years (Xu et al., 2007). Precipitation of alunite and anhydrite decreased
porosity further from the injector, with ankerite, silica, Na-smectite,
dawsonite, siderite and magnesite precipitation also predicted. Com-
paring model outcomes with alteration observed in natural analogue
data from basins with natural occurrences of CO2 is vital for validation
of the predictions. Kaszuba et al., studied the Madison Limestone as a
natural analogue for carbon and sulphur co-sequestration (Kaszuba
et al., 2011). With sources of Ca and Fe from calcite and dolomite,
anhydrite trapped sulphate, and subsequently pyrite, and carbonates re-
precipitated. In our case calcite and chlorite are the main mineral
sources of Ca and Fe but the predicted minerals precipitated are con-
sistent with the findings of Kaszuba. The alteration of chlorite to side-
rite or ankerite and kaolinite has been observed in other natural ana-
logue situations (Higgs et al., 2015; Watson et al., 2004). Reactivity of
silicates including Fe-chlorite and plagioclase were observed in current
experiments to release Fe and Ca cations, a source of ions for mineral
trapping of CO2 as siderite, ankerite or calcite. Sulphate has ad-
ditionally been shown elsewhere to increase the dissolution rates of
silicates such as plagioclase, hence SO2 co-injection could potentially
enhance mineral trapping of CO2 (Min et al., 2015).
17
Applied Geochemistry 109 (2019) 104400
4. Conclusions
With the presence of both 0.016% SO2 and 2% O2 impurities in CO2-
water-rock reactions, sulphuric acid generation resulted in a low solu-
tion pH (~1–2) in experiments. Relatively low reactivity quartzose
reservoir rock from the Precipice Sandstone had minimal pH buffering
capacity, although Fe–Ti oxides (ilmenite) and Fe-oxide grain coatings
likely contributed to oxidation of co-injected SO2. Dissolution of re-
active minerals from Hutton Sandstone and Evergreen Formation core
was directly observed including mainly Fe-chlorite, ankerite, siderite,
and also albite and K-feldspar. The initially low solution pH was buf-
fered to a greater extent in these experiments. Increases in concentra-
tions of several cations were observed. Dissolved Mn, Co, +/− Sr, Mg,
and Si were correlated with Fe. Precipitation of minerals including Ca-
or Fe-sulphates and Fe oxides appeared to subsequently reduce some
dissolved element concentrations, with Cr and Ni signatures occasion-
ally observed trapped in new mineral precipitates. Compared to pre-
vious pure CO2 experiments, stronger clay, plagioclase and K-feldspar
mineral dissolution was observed through mineral surface corrosion
features in SEM, and higher concentrations of ions such as Al, Fe, and Si
at the lower pH. Higher concentrations of dissolved cations associated
with oxidative dissolution of sulphides, including Zn, were also mea-
sured. The stronger clay and plagioclase dissolution can provide more
cations for precipitation of carbonate, sulphate, clay and sulphide mi-
nerals especially in the more reactive cap-rocks at the gas water in-
terface. This may help self-seal cap-rocks over longer timescales. The
potential for oxidative dissolution of sulphides however should be
further investigated as they could release heavy metals.
Longer term experiments with lower gas impurity concentrations
including NOx to replicate expected PCC or oxyfuel capture gases are
recommended in future work to investigate likely reactions resulting
from injection of CO2 from coal combustion sources. Investigating the
impacts to rock porosity and permeability which impact CO2 migration
are also suggested.
Geochemical models were in good agreement with experiments,
indicating Fe-chlorite and minor carbonates were the most reactive
minerals, with prediction of Fe oxide precipitation. Initial predictions of
solution pH were in good agreement, although experimentally further
SO2 likely dissolved from a supercritical gas head during the experi-
ments further reducing pH which could not be modelled using the
current method. Incorporating the correct (or best possible) mineral
stoichiometry's, and calculating the initial reactive surface areas mod-
ified based on observed grain size and mineral habit improves model
predictions. Parameterising with experimental data further improves
predictive capacity. Surface areas had to be generally increased for si-
licates and fine grain size clays, and decreased for cementing carbo-
nates to match experimental data in this study. Using the parameterised
upscaled reactive surface areas in a 30 year simulation predicted that
porosity and pH would not be significantly impacted in a low reactivity
sandstone with co-injection of O2 and SO2. Further work should include
the building of a reactive transport model for co-injection including the
overlying formation to determine if continued co-injection can strip
impurity gases in close proximity to the injector and further decrease
pH.
Observable reactivity of siltstone and sandstone (cap-rock) core to
wet supercritical O2–SO2–CO2 fluid indicated further work is needed to
determine likely changes to storage cap-rock integrity in contact with
buoyant supercritical CO2. Corrosion of reactive minerals including
ankerite and chlorite, and precipitation of new (Fe) oxide and sulphate
phases were observed on rock surfaces. Future work investigating
changes to cap-rock porosity and permeability through reaction of
impure wet supercritical CO2 (low water availability regime) is sug-
gested to determine if reactions will result in self-sealing.
J.K. Pearce, et al.
Acknowledgements
The authors acknowledge the funding provided by the
Commonwealth of Australia and industry sponsors through the
CO2CRC Program "Reactive Rocks" (Australia) for part of this work, and
Ralf Haese for management and technical feedback in the Reactive
Rocks program. The University of Queensland, Australia, is acknowl-
edged for financial support for part of this project through a new staff
research start-up fund. Susan Farquhar is thanked for access to rock
core samples.
Special thanks to Dean Biddle for technical assistance with the high
pressure and temperature experiments. Marietjie Mostert of the
Environmental Geochemistry Laboratory, CGMS, University of
Queensland, is acknowledged for her assistance with chemical analyses,
as is Alison Law. We acknowledge the facilities, and the scientific and
technical assistance, of the Australian Microscopy and Microanalysis
Research Facility at the Centre for Microscopy and Microanalysis, The
University of Queensland. Three reviewers are thanked for their con-
structive comments that improved this manuscript.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apgeochem.2019.104400.
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