One of the most challenging goals of flooded chalk analyses used in Enhanced Oil Recovery (EOR) is to reach high-resolution mineralogical data, in order to detect the composition of new crystals grown after brine injections, with ≤1 μm grain size. Understanding how flooding affects chemical induced compaction, mechanical strength permeability, and porosity is paramount in EOR related investigations. Magnesite formation is the most pervasive process when MgCl2 is injected into chalk, and the submicrometric grain size of the new minerals requires a high performing imaging technique and a new methodological approach: in our study, we present the first attempt of applying Tip-Enhanced Raman Spectroscopy (TERS) to rock and mineral samples. It is a new frontier technique that couples Raman Spectroscopy with Atomic Force Microscopy, allowing impressively high-resolution topography and mineralogical maps. Two long term experiments have been analyzed, where chalk cores were flooded for 718 days and 1072 days, at reservoir conditions comparable to hydrocarbon reservoirs in chalk at the Norwegian continental shelf. Few microns squared areas have been imaged by Atomic Force Microscopy using ultra-polished thin sections. First analyses identified a less pervasive secondary growth of magnesite in the 718 days test and an almost pure magnesite composition in the 1072 days test. Transmission Electron Microscopy (TEM) has been employed to confirm the results of TERS and add dark and bright field grain imaging to the investigations. This confirms the need for high-resolution methodologies such as TERS and TEM to fully understand the EOR effects at submicron-scale.
References
1
Andersen
, P. Ø.
, Wang
, W.
, Madland
, M. V.
, Zimmermann
, U.
, Korsnes
, R. I.
, Bertolino
, S. R. A.
, Minde
, M.
, Schulz
, B.
, and Gilbricht
, S.
, “Comparative study of five outcrop chalks flooded at reservoir conditions: Chemo-mechanical behaviour and profiles of compositional alteration
,” Transp. Porous Media
121
(1
), 135
–181
(2018
). 2
Andò
, S.
and Garzanti
, E.
, “Raman spectroscopy in heavy-mineral studies
,” in Sediment Provenance Studies in Hydrocarbon Exploration and Production
, edited by R. A.
Scott
, H. R.
Smyth
, A. C.
Morton
, and N.
Richardson
(Geological Society
, London
, England
, 2013
), Special Publications, p. 386
.3
Bailo
, E.
and Deckert
, V.
, “Tip-enhanced Raman scattering
,” Chem. Soc. Rev.
37
, 921
–930
(2008
). 4
Bischoff
, W. D.
, Sharma
, S. K.
, and MacKenzie
, F. T.
, “Carbonate ion disorder in synthetic and biogenic magnesian calcites: A Raman spectral study
,” Am. Mineral.
70
(5–6
), 581
–589
(1985
).5
Borromeo
, L.
, Zimmermann
, U.
, Andò
, S.
, Coletti
, G.
, Bersani
, D.
, Basso
, D.
, Gentile
, P.
, Schulz
, B.
, and Garzanti
, E.
, “Raman spectroscopy as a tool for magnesium estimation in Mg-calcite
,” J. Raman Spectrosc.
48
(7
), 983
–992
(2017
). 6
Borromeo
, L.
, Egeland
, N.
, Minde
, M. W.
, Zimmermann
, U.
, Andò
, S.
, Madland
, M. V.
, and Korsnes
, R. I.
“Quick, easy and economic mineralogical studies of flooded chalk for EOR experiments using Raman spectroscopy
,” Minerals
(to be published).7
Dandeu
, A.
, Humbert
, B.
, Carteret
, C.
, Muhr
, H.
, Plasari
, E.
, and Bossoutrot
, J. M.
, “Raman spectroscopy—A powerful tool for the quantitative determination of the composition of polymorph mixtures: Application to CaCO3 polymorph mixtures
,” Chem. Eng. Technol.
29
(2
), 221
–225
(2006
). 8
De La Pierre
, M.
, Carteret
, C.
, Maschio
, L.
, André
, E.
, Orlando
, R.
, and Dovesi
, R.
, “The Raman spectrum of CaCO3 polymorphs calcite and aragonite: A combined experimental and computational study
,” J. Chem. Phys.
140
(16
), 164509
(2014
). 9
Edwards
, H.
, Villar
, S.
, Jehlicka
, J.
, and Munshi
, T.
, “FT–Raman spectroscopic study of calcium-rich and magnesium-rich carbonate minerals
,” Spectrochim. Acta A
61
, 2273
(2005
). 10
Egeland
, N.
, Minde
, M. W.
, Kobayashi
, K.
, Ota
, T.
, Nakamura
, E.
, Zimmermann
, U.
, Madland
, M. W.
, and Korsnes
, R. I.
, “Quantification of mineralogical changes in flooded carbonate under reservoir conditions,
” in IOR 2017—19th European Symposium on Improved Oil Recovery
(EAGE
, 2017
).11
Griffith
, W. P.
, “Raman spectroscopy of minerals
,” Nature
224
, 264
–266
(1969
). 12
Hattin
, D. E.
and Siemers
, C. T.
, Upper Cretaceous Stratigraphy and Depositional Environments of Western Kansas
(Kansas Geological Survey
, 1987
), Guidebook 3.13
Heggheim
, T.
, Madland
, M. V.
, Risnes
, R.
, and Austad
, T.
, “A chemical induced enhanced weakening of chalk by seawater
,” J. Petroleum Sci. Eng.
46
(3
), 171
–184
(2005
). 14
Herman
, R. G.
, Bogdan
, C. E.
, Sommer
, A. J.
, and Simpson
, D. R.
, “Discrimination among carbonate minerals by Raman spectroscopy using the laser microprobe
,” Appl. Spectrosc.
41
(3
), 437
–440
(1987
). 15
Hiorth
, A.
, Jettestuen
, E.
, Lawrence
, C. M.
, and Madland
, M. V.
, “Precipitation, dissolution, and ion exchange processes coupled with a lattice Boltzmann advection diffusion solver
,” Geochim. Cosmochim. Acta
104
, 99
–110
(2013
). 16
Hjuler
, M. L.
and Fabricius
, I. L.
, “Engineering properties of chalk related to diagenetic variations of Upper Cretaceous onshore and offshore chalk in the North Sea area
,” J. Petroleum Sci. Eng.
68
(3
), 151
–170
(2009
). 17
Korsnes
, R. I.
, Strand
, S.
, Hoff
, Ø
, Pedersen
, T.
, Madland
, M. V.
, and Austad
, T.
, “Does the chemical interaction between seawater and chalk affect the mechanical properties of chalk
,” in Multiphysics Coupling and Long Term Behaviour in Rock Mechanics
, edited by A. V.
Cottheim
, R.
Charlier
, J. F.
Thimus
, and J. P.
Tshibangu
(Taylor & Francis
, London
, 2006
), pp. 427
–434
. 18
Korsnes
, R. I.
, Madland
, M. V.
, Austad
, T.
, Haver
, S.
, and Rosland
, G.
, “The effects of temperature on the water weakening of chalk by seawater
,” J. Petroleum Sci. Eng.
60
, 183
–193
(2008
). 19
Krishnamurti
, D.
, “Raman spectrum of magnesite
,” Proc. Indian Acad. Sci., Sec. A
, 43
(4
), 210
–2012
(1956
). 20
Kuebler
, K.
, Wang
, A.
, Abbott
, K.
, and Haskin
, L. A.
, “Can we detect carbonate and sulfate minerals on the surface of Mars by Raman spectroscopy?
” in Lunar and Planetary Science XXXII n. 1889
(Lunar and Planetary Inst., Houston, TX
, 2001
).21
Kumar
, N.
, Su
, W.
, Veselý
, M.
, Weckhuysen
, B. M.
, Pollard
, A. J.
, and Wain
, A. J.
, “Nanoscale chemical imaging of solid–liquid interfaces using tip-enhanced Raman spectroscopy
,” Nanoscale
10
(4
), 1815
–1824
(2018
). 22
Langelüddecke
, L.
, Singh
, P.
, and Deckert
, V.
, “Exploring the nanoscale: Fifteen years of tip-enhanced Raman spectroscopy
,” Appl. Spectrosc. OA
69
(12
), 1357
–1371
(2015
). 23
Li
, L.
, Liu
, K.
, Suen
, B.
, Liu
, Q.
, King
, A.
, and Talke
, F. E.
, “Numerical and experimental study of near-field heating using Tip-Enhanced Raman Spectroscopy (TERS)
,” Tribology Lett.
66
(1
), 26
(2018
). 24
Madland
, M. V.
, Finsnes
, A.
, Alkafadgi
, A.
, Risnes
, R.
, and Austad
, T.
, “The influence of CO2 gas and carbonate water on the mechanical stability of chalk
,” J. Petroleum Sci. Eng.
51
, 149
–168
(2006
). 25
Madland
, M. V.
, Midtgarden
, K.
, Manafov
, R.
, Korsnes
, R. I.
, Kristiansen
, T.
, and Hiorth
, A.
, “The effect of temperature and brine composition on the mechanical strength of Kansas chalk
,” in International Symposium of the Society of Core Analysts
(SCA
, Abu Dhabi
, 2008
)
, pp. 1
–6
.26
Madland
, M. V.
, “Rock-fluid interactions in chalk exposed to seawater, MgCl₂, and NaCl brines with equal ionic strength
,” in 15th European Symposium on Improved Oil Recovery
(EAGE
, Paris
, 2009
), pp. 27
–29
.27
Madland
, M. V.
, Hiorth
, A.
, Omdal
, E.
, Megawati
, M.
, Hildebrand-Habel
, T.
, Korsnes
, I. R.
, Evje
, S.
, and Cathles
, M. L.
, “Chemical alterations induced by rock-fluid interactions when injecting brines in high porosity chalks
,” Transp. Porous Media
87
, 679
–702
(2011
). 28
Madland
, M. V.
, Zimmermann
, U.
, Haser
, S.
, Audinot
, J. N.
, Gysan
, P.
, Korsnes
, R. I.
, Schulz
, B.
, Gutzmer
, J.
, and Hiorth
, A.
, “Neoformed dolomite in flooded chalk for EOR processes
”, in 75th EAGE Conference & Exhibition Incorporating SPE EUROPEC 2013
(EAGE
, 2013
).29
Meyer
, R.
, Yao
, X.
, and Deckert
, V.
, “Latest instrumental developments and bioanalytical applications in tip-enhanced Raman spectroscopy
,” Trends Analyt. Chem.
102
, 250
–258
(2018
). 30
Minde
, M. W.
, Haser
, S.
, Korsnes
, R. I.
, Zimmermann
, U.
, and Madland
, M. V.
, “Comparative studies of mineralogical alterations of three ultra-long-term tests of onshore chalk at reservoir conditions
,” in IOR 2017—19th European Symposium on Improved Oil Recovery 2017
(EAGE
, 2017
).31
Molenaar
, N.
and Zijlstra
, J. J. P.
, “Differential early diagenetic low-Mg calcite cementation and rhythmic hardground development in Campanian-Maastrichtian chalk
,” Sediment. Geol.
109
(3–4
), 261
–281
(1997
). 32
Nermoen
, A.
, Korsnes
, R. I.
, Hiorth
, A.
, and Madland
, M. V.
, “Porosity and permeability development in compacting chalks during flooding of nonequilibrium brines: Insights from long-term experiment
,” J. Geophys. Res.: Solid Earth
120
(5
), 2935
–2960
(2015
). 33
Ossikovski
, R.
, Nguyen
, Q.
, and Picardi
, G.
, “Simple model for the polarization effects in tip-enhanced Raman spectroscopy
,” Phys. Rev. B
75
(4
), 045412
(2007
). 34
Park
, J. Y.
, Maier
, S.
, Hendriksen
, B.
, and Salmeron
, M.
, “Sensing current and forces with SPM
,” Mater. Today
13
(10
), 38
–45
(2010
). 35
Pettinger
, B.
, Ren
, B.
, Picardi
, G.
, Schuster
, R.
, and Ertl
, G.
, “Nanoscale probing of adsorbed species by tip-enhanced Raman spectroscopy
,” Phys. Rev. Lett.
92
(9
), 096101
(2004
). 36
Picardi
, G.
, Chaigneau
, M.
, Ossikovski
, R.
, Licitra
, C.
, and De La Pierre
, G.
, “Tip enhanced Raman spectroscopy on azobenzene thiol self-assembled monolayers on Au (111)
,” J. Raman Spectrosc.
40
(10
), 1407
–1412
(2009a
). 37
Picardi
, G.
, Chaigneau
, M.
, and Ossikovski
, R.
, “High resolution probing of multiwall carbon nanotubes by tip enhanced Raman spectroscopy in gap-mode
,” Chem. Phys. Lett.
469
, 161
–165
(2009b
). 38
Picardi
, G.
, Kròlikowska
, A.
, Yasukuni
, R.
, Chaigneau
, M.
, Escude
, M.
, Mourier
, V.
, Licitra
, C.
, and Ossikovski
, R.
, “Exchange of methyl and azobenzene terminated alkanethiol on polycrystalline gold studied by tip enhanced Raman mapping
,” Chem. Phys. Chem.
15
, 276
–282
(2014
). 39
Purgstaller
, B.
, Mavromatis
, V.
, Immenhauser
, A.
, and Dietzel
, M.
, “Transformation of Mg-bearing amorphous calcium carbonate to Mg-calcite—in situ monitoring
,” Geochim. Cosmochim. Acta
174
, 180
–195
(2016
). 40
Pyne
, A.
, Thompson
, R.
, Leung
, C.
, Roy
, D.
, and Hoogenboom
, B. W.
, “Single-molecule reconstruction of oligonucleotide secondary structure by atomic force microscopy
,” Small
10
(16
), 3257
–3261
(2014
). 41
42
Ren
, B.
, Picardi
, G.
, and Pettinger
, B.
, “Preparation of gold tips suitable for tip-enhanced Raman Spectroscopy and light emission by electrochemical etching
,” Rev. Sci. Instrum.
75
, 837
–841
(2004
). 43
Risnes
, R.
, Madland
, M. V.
, Hole
, M.
, and Kwabiah
, N. K.
, “Water weakening of chalk—mechanical effects of water-glycol mixtures
,” J. Petroleum Sci. Eng.
48
, 21
–36
(2005
). 44
Robaszynski
, F.
, Dhondt
, A. V.
, and John
, W. M.
, “Cretaceous lithostratigraphic units (Belgium)
,” Geol. Belg.
4
(1–2
), 121
–134
(2001
).45
Rutt
, H. N.
and Nicola
, J. H.
, “Raman spectra of carbonates of calcite structure
,” J. Phy. C: Solid State Phys.
7
(24
), 4522
–4528
(1974
). 46
Schultz
, Z. D.
, Marr
, J. M.
, and Wang
, H.
, “Tip enhanced Raman scattering: Plasmonic enhancements for nanoscale chemical analysis
,” Nanophotonics
3
(1–2
), 91
–104
(2014
). 47
Slimani
, H.
, “New species of dinoflagellate cysts from the Campanian-Danian chalks at Hallembaye and Turnhout (Belgium) and at Beutenaken (the Netherlands)
,” J. Micropalaeontol.
20
(1
), 1
–11
(2001
). 48
Stadler
, J.
, Schmid
, T.
, and Zenobi
, R.
, “Nanoscale chemical imaging of single-layer graphene
,” ACS Nano
5
(10
), 8442
–8448
(2011
). 49
Strand
, S.
, Standnes
, D. C.
, and Austad
, T.
, “Spontaneous imbibition of aqueous surfactant solutions into neutral to oil-wet carbonate cores: Effects of brine salinity and composition
,” Energy Fuels
17
(5
), 1133
–1144
(2003
). 50
Strand
, S.
, Hjuler
, M. L.
, Torsvik
, R.
, Pedersen
, J. I.
, Madland
, M. V.
, and Austad
, T.
, “Wettability of chalk: Impact of silica, clay content and mechanical properties
,” Petroleum Geosci.
13
(1
), 69
–80
(2007
). 51
Sun
, J.
, Wu
, Z.
, Cheng
, H.
, Zhang
, Z.
, and Frost
, R. L.
, “A Raman spectroscopic comparison of calcite and dolomite
,” Spectrochim. Acta Part A Mol. Biomol. Spectrosc.
117
, 158
–162
(2014
). 52
Tang
, G. Q.
and Firoozabadi
, A.
, “Effect of pressure gradient and initial water saturation on water injection in water-wet and mixed-wet fractured porous media
,” SPE Res. Eval. Eng.
4
, 516
–524
(2001
). 53
Toccafondi
, C.
, Picardi
, G.
, and Ossikovski
, R.
, “Molecular bending at the nanoscale evidenced by tip-enhanced Raman spectroscopy in tunneling mode on thiol self-assembled monolayers
,” J. Phys. Chem. C
120
(32
), 18209
–18219
(2016
). 54
Unvros
, J.
, Sharma
, S.
, and Mackenzie
, F.
, “Characterization of some biogenic carbonates with Raman spectroscopy
,” Am. Mineral.
76
, 641
–646
(1991
).55
Vanacore
, G. M.
, Chaigneau
, M.
, Barrett
, N.
, Bollani
, M.
, Boioli
, F.
, Salvalaglio
, M.
, Montalenti
, F.
, Manini
, N.
, Caramella
, L.
, Biagioni
, P.
, Chrastina
, D.
, Isella
, G.
, Renault
, O.
, Zani
, M.
, Sordan
, R.
, Onida
, G.
, Ossikovski
, R.
, Drouhin
, H.-J.
, and Tagliaferri
, A.
, “Hydrostatic strain enhancement in laterally confined SiGe nano-stripes
,” Phys. Rev. B
88
, 115309
(2013
). 56
Wang
, W.
, Madland
, M. V.
, Zimmermann
, U.
, Nermoen
, A.
, Reidar
, I.
, Korsnes
, R.
, Bertolino
, S. R. A.
, and Hildebrand-Habel
, T.
, “Evaluation of porosity change during chemo-mechanical compaction in flooding experiments on Liege outcrop chalk
,” in Reservoir Quality of Clastic and Carbonate Rocks: Analysis, Modelling and Prediction
, edited by P. J.
Armitage
, A. R.
Butcher
, J. M.
Churchill
, A. E.
Csoma
, C.
Hollis
, R. H.
Lander
, J. E.
Omma
, and R. H.
Worden
(Geological Society
, London
, 2016
), Special Publications, 435-10.57
Yang
, Z.
, Aizpurua
, J.
, and Xu
, H.
, “Electromagnetic field enhancement in TERS configurations
,” J. Raman Spectrosc.
40
(10
), 1343
–1348
(2009
). 58
Zangiabadi
, B.
, Korsnes
, R. I.
, Hildebrand-Habel
, T.
, Hiorth
, A.
, Surtarjana
, I. K.
, Lian
, A.
, and Madland
, M. V.
, “Chemical water weakening of various outcrop chalks at elevated temperature
,” in Poromechanics IV
, edited by H. I.
Ling
, A.
Smyth
, and R.
Betti
(DEStech Publications, Inc.
, Lancaster
, 2009
), pp. 543
–548
.59
Zimmermann
, U.
, Madland
, M. V.
, Nermoen
, A.
, Hildebrand-Habel
, T.
, Bertolino
, S. A. R.
, Hiorth
, A.
, Korsnes
, R. I.
, Audinot
, J. N.
, and Grysan
, P.
, “Evaluation of the compositional changes during flooding of reactive fluids using scanning electron microscopy, nano-secondary ion mass spectroscopy, x-ray diffraction, and whole-rock geochemistry
,” Am. Assoc. Petroleum Geol. Bull.
99
, 791
–805
(2015
). 60
Zimmermann
, U.
, Madland
, M.
, Minde
, M.
, Borromeo
, L.
, and Egeland
, N.
, “Tools to determine and quantify mineralogical changes during EOR flooding experiments on chalk
,” in SPE Abu Dhabi International Petroleum Exhibition & Conference. Society of Petroleum Engineers
(SPE
, 2017
).61
Zhang
, P.
, Tweheyo
, M. T.
, and Austad
, T.
, “Wettability alteration and improved oil recovery in chalk: The effect of calcium in the presence of sulfate
,” Energy Fuels
20
(5
), 2056
–2062
(2006
). © 2018 Author(s).
2018
Author(s)
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