Impacts of hydrothermal AUTHORS

dolomitization and Bianca C. Biehl ~ Energy and Mineral

Resources Group, Geological Institute, RWTH
Aachen University, Wüllnerstraße 2, 52056
thermochemical sulfate Aachen, Germany; [Link]@[Link]-
[Link]
reduction on secondary porosity Bianca C. Biehl received her [Link]. degree in
applied geosciences from RWTH Aachen
creation in deeply buried University in 2011. Her research interests
include carbonate sedimentology and
carbonates: A case study from diagenesis, as well as salt tectonics. She is
currently working at the Geological Institute in
the Lower Saxony Basin, Aachen on her Ph.D. thesis, which will be
completed in 2016.

northwest Germany Lars Reuning ~ Energy and Mineral

Resources Group, Geological Institute, RWTH
Bianca C. Biehl, Lars Reuning, Johannes Schoenherr, Aachen University, Wüllnerstraße 2, 52056
Aachen, Germany; [Link]@[Link]-
Volker Lüders, and Peter A. Kukla
[Link]
Lars Reuning worked at the GEOMAR Centre for
Ocean Research and received a Ph.D. from the
ABSTRACT University of Kiel, Germany. In 2005, he joined
RWTH Aachen University, where he is currently
The role of deep-burial dissolution in the creation of porosity in working as senior lecturer. His main research
carbonates has been discussed controversially in the recent past. interests are carbonate diagenesis,
We present a case study from the Upper Permian Zechstein carbonate–evaporate interactions, and three-
2 carbonate reservoirs of the Lower Saxony Basin in northwest dimensional seismic geometries in carbonates.
Germany. These reservoirs are locally characterized by high
Johannes Schoenherr ~ ExxonMobil
amounts of carbon dioxide (CO2) and variable amounts of hy-
Production Germany, Riethorst 12, 30659
drogen sulfide (H2S), which are derived from thermochemical Hannover, Germany; [Link]@
sulfate reduction (TSR) and inorganic sources. To study the [Link]
contribution of these effects on porosity development, we com-
Johannes Schoenherr received his [Link]. in
bine petrography, stable isotope, and rare earth and yttrium (REY) structural geology from Technical University of
analyses of fracture cements with Raman spectroscopy and d 13C Darmstadt, Germany, and his Ph.D. in
analyses of fluid inclusions. It is shown that fluid migration along carbonate reservoir quality and salt tectonics
deep fault zones created and redistributed porosity. Fluid in- from RWTH Aachen University, Germany. He is
clusion analyses of vein cements demonstrate that hydrothermal currently working with ExxonMobil Production
fluids transported inorganic CO2 into the reservoir, where it Germany as a hydrocarbon geologist on
mixed with minor amounts of TSR-derived organic CO2. The Zechstein carbonate reservoirs. Johannes’
research interests encompass basic and applied
likely source of inorganic CO2 is the thermal decomposition
aspects of hydrocarbon systems geology in
of deeply buried Devonian carbonates. The REY distribution carbonate–evaporite settings.
patterns support a hydrothermal origin of ascending iron- and
CO2-rich fluids causing dolomitization of calcite and increasing Volker Lüders ~ GeoForschungsZentrum
porosity by 10%–16% along fractures. This porosity increase Potsdam, Telegrafenberg, 14473 Potsdam,
Germany; volue@[Link]
Volker Lüders is a senior research scientist at
Copyright ©2016. The American Association of Petroleum Geologists. All rights reserved.
the Helmholtz Centre Potsdam. He received his
Manuscript received March 27, 2015; provisional acceptance October 13, 2015; revised manuscript received
Ph.D. in geochemistry from the Free University
November 17, 2015; final acceptance January 14, 2016. Berlin in 1988. His fields of research are fluid
DOI:10.1306/01141615055

AAPG Bulletin, v. 100, no. 4 (April 2016), pp. 597–621 597

 inclusions, stable isotopes, and trace elements results from hydrothermal dolomitization and dissolution by
in hydrothermal systems, including fluid and acids generated from the reaction of Fe2+ with H2S to pre-
oil/gas migration in sedimentary basins. cipitate pyrite. In contrast, hydrothermal dolomite cements
Peter A. Kukla ~ Energy and Mineral reduced early diagenetic porosity in dolomitic intervals by
Resources Group, Geological Institute, RWTH approximately 17%. However, the carbonate dissolution in the
Aachen University, Wüllnerstraße 2, 52056 predominantly calcitic host rock results in a net increase in
Aachen, Germany; [Link]@[Link]- porosity and permeability in the vicinity of the fracture walls,
[Link] which has to be considered for modeling reservoir properties
Peter A. Kukla has been a professor of geology and fluid migration pathways.
at RWTH Aachen University since 2000. He has
worked for Shell International (1991–2000) in
The Netherlands and Australia. Peter graduated
with degrees in geology from Wuerzburg
University, Germany, and Witwatersrand
INTRODUCTION
University, South Africa (Ph.D., 1991). His
research interests include basin analysis, The concept of carbonate dissolution in the deep-burial realm has
reservoir characterization, unconventional gas, been widely applied in the interpretation of carbonate reservoir
geodynamics of salt basins, and pore pressures. quality. Different mechanisms for mesogenetic porosity creation
(Choquette and Pray, 1970) have been proposed, including
ACKNOWLEDGMENTS
thermochemical sulfate reduction (TSR) (Ma et al., 2007),
dissolution by CO2-rich formation waters (Beavington-Penney
We would like to thank ExxonMobil et al., 2008), and burial dolomitization (Davies and Smith,
Production Deutschland GmbH for
2006). In contrast, Ehrenberg et al. (2012) claimed that porosity
supporting us with core samples and thin
creation during deep burial lacks supporting quantitative data. The
sections and for the opportunity to publish
the data, Philipp Binger (Energy and Mineral authors argued that burial dissolution in carbonates would not
Resources Group) for preparing further thin contribute significantly to a net increase in carbonate reservoir
sections for transmitted light microscopy and porosity. Furthermore, they stated that pore waters highly un-
cathodoluminescence, Uwe Wollenberg dersaturated with respect to calcite would in most cases be neu-
(Energy and Mineral Resources Group) for tralized very rapidly during migration before reaching carbonate
the help with the cathodoluminescence reservoirs. Therefore, dissolution would be limited to narrow re-
microscope, Stefan Krüger (Leipzig action fronts in case acidic waters would reach the reservoir level.
University) for the measurements of carbon
Many previous studies on porosity creation during burial focused
and oxygen isotopes, Harald Strauss
(Muenster University) for the sulfur isotope on petrographic evidence (Elliott, 1982; Mazzullo and Harris,
analyses, Maike Leupold for help in drafting 1992; Beavington-Penney et al., 2008; Zampetti, 2010), which
figures, and Anna Lewin for helpful showed that it is challenging to distinguish deep-burial pores from
discussions and her support. We thank our shallow-burial pores. Furthermore, Ehrenberg et al. (2012) sug-
reviewers Cathy Hollis and James (Jim) gested that fluids causing carbonate dissolution during burial could
Markello for their comments and suggestions in many cases be surface derived and migrated downward along
that greatly improved the quality of our deep-reaching faults and fractures.
manuscript.
To evaluate porosity creation in deep-burial settings, we present
new data from an upper Permian (Zechstein) carbonate reservoir
EDITOR’S NOTE in the Lower Saxony Basin, one of Germany’s most important gas
A color version of Figure 2 can be seen in the provinces. The reservoir gas in the Zechstein 2 (Z2) carbonate is
online version of this paper. locally characterized by very large amounts of CO2, which is
thought to be derived from a mixture of organic and inorganic
sources (Fischer et al., 2006) and variable amounts of TSR-derived
hydrogen sulfide (H2S) (Mittag-Brendel, 2000). Nonfractured parts
of the studied reservoir are characterized by alternating porous
dolomitic and tight calcitic intervals. The almost complete loss of
primary and near-surface porosity in the calcitic intervals is

598 Secondary Porosity Creation in Deeply Buried Carbonates

resulting from calcite cementation and dedolomitiza- et al., 2010). The evaporite sedimentation began
tion during shallow burial (Clark, 1980; Strohmenger when the dry basins were flooded from the Boreal Sea
et al., 1996). This early burial porosity reduction helps in the north by a combination of rifting and a rise in sea
to define the creation of late-burial vuggy pores level. Thick rock salt series are regionally interlayered
caused by dolomitizing fluids ascending along with thin sulfate beds occupying the basin center
fractures from deeper parts of the basin. A con- (Biehl et al., 2014), with anhydrites and carbonates
tribution of descending surface-derived fluids can be deposited at the basin margins (Taylor, 1998). Cy-
ruled out, as the carbonate reservoir is sealed by a thick clical, sea-level fluctuations controlled sedimentation
rock salt succession. This geological setting of the study patterns in the Southern Permian Basin during the
area makes it ideal to study modifications on burial Zechstein. In total, five to seven carbonate–evaporite
porosity development in carbonate reservoir systems. cycles are identified for the Southern Permian Basin,
Supported by empirical data, this study combines whereof each transgression phase marks the base of a
classical carbonate petrography with geochemical new cycle (Peryt et al., 2010). In northern Germany,
analyses, in particular carbon and oxygen stable iso- the Zechstein Group comprises seven evaporite cycles
tope analysis of matrix and fracture-filling minerals, of formation rank. All cycles were described in detail
and the analysis of fluid inclusions trapped in vein by Taylor (1998) and Peryt et al. (2010). The focus
cements. Additional information is provided for of this study is the second Zechstein cycle, which is
mineral precipitation conditions and different gas composed of a basal carbonate unit (Z2 carbonate;
phases (methane [CH4], CO2, H2S) generated during Stassfurt Carbonate), followed by anhydrite (A2), and
diagenesis. Information on fluorite formation is given a thick halite interval (Figure 1B). The platform facies
by analysis of rare earth and yttrium (REY) distribution of the Z2 carbonate hosts northwest Germany’s most
patterns. We aim to demonstrate that deep-burial, prolific gas play (Strohmenger et al., 1996). The Z2
fracture-controlled dissolution of carbonates can be carbonates are situated between two anhydrite layers
significant enough to convert a carbonate matrix res- (A1 and A2), have a thickness of 20–80 m (66–262 ft)
ervoir with low porosity and permeability into a pro- on the platform, and show variation in the platform
ductive reservoir rock with moderate-to-good quality. facies from shallow subtidal to supratidal (Strohmenger
et al., 1996). In this study, core material from one
GEOLOGICAL SETTING well of the Lower Saxony Basin was extensively
studied regarding rock types, diagenetic processes,
The study area is located in northwest Germany, and the precipitation conditions of vein cements
west of the city of Hannover and south of Bremen within the Z2 carbonate, which was deposited in
(Figure 1A), and belongs structurally to the central intertidal (tidal flat) to shallow subtidal (oolite in-
part of the Lower Saxony Basin, an intraplate terbar; oolite bar) environments. The platform sub-
crustal segment in northwest Germany with a length facies types were described in detail by Steinhoff and
of 300 km (186 mi) and a width of 65 km (40 mi). Strohmenger (1999). The studied well is located close
It represents a west–east striking trough and is to a deep-reaching fault system (Figure 2), which
bordered by the Pompeckj block in the north and most likely formed during a phase of rapid subsidence
the Rhenish Massif and the Harz Mountains in the during the Early Cretaceous and was reactivated
south. The sediments in the Lower Saxony Basin during Late Cretaceous inversion. The Zechstein
experienced maximum burial and therefore max- layers are underlain by lower Permian (Rotliegende)
imum temperatures during the Early Cretaceous, volcanics, siliciclastic red beds, and Carboniferous
whereas a major inversion phase caused uplift of coals, which are the main source rocks for gas ac-
the sediments during the Late Cretaceous (Betz cumulations in the Lower Saxony Basin (Magri et al.,
et al., 1987; Kockel et al., 1994; Petmecky et al., 2008; Kombrink et al., 2010).
1999; Maystrenko et al., 2008). The Lower Saxony
Basin is part of the Southern Permian Basin, a land- MATERIALS AND METHODS
locked depression that developed because of high
subsidence rates and underwent several flooding For this study, 27 core samples of the Z2 carbonate
periods in the Late Permian (Zechstein) (Pharaoh member were collected in the core repository of

Biehl et al. 599

Figure 1. (A) Map of the study area in the Lower Saxony Basin between the cities of Hannover (H) and Bremen (B) in northwest Germany
with locations of gas fields and wells. The black circle indicates the location of the studied well for this study; black dots show the locations of
neighboring wells. (B) Stratigraphy of the lower Zechstein cycles and the underlying Rotliegende Formation. The studied carbonates belong
to the second Zechstein cycle (Z2) and are underlain and overlain by anhydrite deposits. Thick rock salt layers are present above the Z2
carbonate in the second and third Zechstein cycles. Z1 = first Zechstein cycle; Z3 = third Zechstein cycle.

ExxonMobil Production GmbH (EMPG), Nienhagen, apparatus HC1-LM mounted on an Olympus po-
Germany. Thin sections for transmitted light micro- larizing microscope. The device was tuned to an
scopy were prepared from all core samples and further electron beam current of approximately 0.6 mA, an
103 thin sections, as well as the reservoir gas compo- excitation voltage of 14 kV, and a filament current of
sition and its carbon isotopy were provided by EMPG. 2.5 A at 0.001 mbar vacuum.
All thin sections and all core samples were stained Point counting on four samples was performed
with Alizarin red-S and potassium ferricyanide with the software JMicroVision 1.2.7 with 1000
where calcite is stained red, ferroan dolomite is points each to evaluate the porosity evolution in
stained blue, and nonferroan dolomite remains dolomitic and calcitic host rock samples.
unstained. Cathodoluminescence microscopy was ap- Oxygen and carbon stable isotopes were mea-
plied to 12 polished thin sections and was performed sured for 41 samples. The measurements were carried
using a hot cathode Lumic cathodoluminescence out at the Institute for Geophysics and Geology,

600 Secondary Porosity Creation in Deeply Buried Carbonates

 Figure 2. Geologic cross sec-
tion based on seismic profile,
showing how close the studied
well is to deep-reaching, east–
west striking fault systems. A1 =
anhydrite layer of first Zechstein
cycle; A2 = anhydrite layer of
second Zechstein cycle; Ca1 =
carbonate layer of first Zechstein
cycle; Ca2 = carbonate layer of
second Zechstein cycle; TVDSS =
true vertical depth subsea.

Leipzig University, Germany. Carbonate powders were garnet laser (100 mW). For internal calibration, silicon
reacted with 105% phosphoric acid at 70°C (158°F) (520 cm-1) and diamond (1332 cm-1) were used.
using a Kiel IV online carbonate preparation line con- Raman spectra of gaseous inclusions were collected
nected to a MAT 253 mass spectrometer. All carbonate in the spectral range between 1200 and 3000 cm-1
values are reported in per mil, relative to Vienna with a Peltier cooled charge-coupled device collector.
Peedee belemnite (VPDB). Reproducibility was A 2 · 45 sec acquisition time was used for all
checked by replicate analysis of standard NBS19 and CO2–CH4–bearing inclusions; CO2–CH4–nitrogen
was better than –0.023‰ (1s) for carbon (d 13C) and (N2)–bearing inclusions were measured 3 · 60 sec to
better than –0.055‰ (1s) for oxygen isotopes (d 18O). improve the signal-to-noise ratio.
Sulfur isotope analysis (d 34S) was applied to four The carbon isotopic compositions of CH4 and
pyrite samples. The measurements were carried out at CO2 in fluid inclusions were measured using a
the Institute for Geology and Paleontology, Münster sample crusher connected via a gas chromatography
University, Germany, using a ThermoFinnigan Delta column to an elemental analyzer isotope ratio mass
Plus equipped with an elemental analyzer isotope ratio spectrometry system. This analytical setup allows
mass spectrometry. Approximately 100 mg of pyrite online simultaneous measurements of stable isotope
powder were homogenously mixed with the same ratios of N2, CH4, and CO2 in natural gas mixtures
amount of vanadium pentoxid and placed in a tin released by crushing of fluid inclusions (Lüders
capsule for subsequent automated combustion and et al., 2012; Plessen and Lüders, 2012).
isotope analyses. All pyrite values are reported in per The REY measurements were performed on two
mil, relative to Vienna Cañon Diablo troilite (V–CDT). fluorite samples. Approximately 0.1 g of sample
Reproducibility was checked by lab standards and powder was dissolved in 0.5 m nitric acid (HNO3)
international reference material (IAEA S1, S2, S3, and filled up to 50 ml volume with 0.5 mol-1 hy-
NBS 127) and was better than 0.3‰ V–CDT. drogen chloride (HCl). Inductively coupled plasma
Gas-bearing fluid inclusions hosted in anhydrite, (ICP) mass spectrometry measurements were per-
ferroan saddle dolomite, and fluorite were measured formed with an ELAN 5000A quadrupole ICP mass
in doubly polished thick sections for gas composi- spectrometer (Perkin–Elmer/SCIEX, Canada). The
tions. A Jobin–Yvon LabRam confocal Raman mi- precision of the method was checked by replicate
crospectrometer equipped with an Olympus optical analyses of fluorite in-house standard C5-FL and was
microscope was used. The excitation radiation used better than 3% for REY (except for europium [Eu],
was a 532.6 nm neodymium-doped yttrium aluminum which was better than 5%).

Biehl et al. 601

RESULTS AND INTERPRETATION 2895 m (9483–9498 ft) and from 2909 to 2915 m
(9544–9564 ft) depth. Because of the staining with
Petrography Alizarin red-S and potassium ferricyanide, calcite
and dolomite can be easily distinguished on all core
Core Description samples (Figure 4). The dolomite matrix was in-
The studied core section consists of alternating calcitic terpreted by Clark (1980) to be a result of reflux
and dolomitic intervals (Figure 3). Calcitic intervals dolomitization. The lower part of the core section
dominate, whereas pure dolomitic intervals are only (2923–2936 m [9588–9633 ft]) is classified as
found from 2898 to 2899 m (9508–9511 ft) and from packstone, whereas the upper part (2878–2923 m
2926 to 2935 m (9600–9628 ft) depth. Two thicker [9442–9588 ft]) is classified as grainstone. The
layers of dolomitic calcite are present from 2891 to dominant grain types are ooids and peloids. Fractures

Figure 3. Lithology of the

Zechstein 2 carbonate of the
studied well, displaying the al-
ternating layers of calcite, dolo-
mite, and dolomitic calcite. Zones
with abundant pyrite mineraliza-
tions and zones with abundant
horizontal and vertical stylolites
are indicated. The major particles
are ooids and peloids. The posi-
tions of samples taken at the core
repository are shown with cross
reference to (micro)photographs
of samples. Fig = figure; G =
grainstone; M = mudstone; P =
packstone; W = wackestone.

602 Secondary Porosity Creation in Deeply Buried Carbonates

are very abundant in the studied core section (Figure 3) during basin inversion or folding phases (Breesch
and have widths of up to 3 cm (1 in.) and lengths of et al., 2007). In contrast to the horizontal stylolites,
several decimeters. Fractures with pyrite mineralization large veins are crosscut by vertical stylolites, in-
occur in all intervals (Figure 4C–E). The fractures are dicating that these veins formed during late burial,
either completely cemented (veins) or partly open. after horizontal stylolitization had stopped but before
Several veins show significant dolomitic halos with or simultaneously to the formation of vertical stylo-
vuggy porosity in otherwise calcitic matrix (Figure 4B). lites. Calcite-filled tension gashes originated along
Abundant pressure solution features such as high- vertical stylolites, such as in Figure 4D. Crack-seal
amplitude horizontal and vertical stylolites are pres- structures with inclusion trails are visible inside the
ent in all core intervals. Horizontal stylolites are tension gashes, indicating that the cementation oc-
commonly thought to form at burial depths greater curred contemporaneously with the formation of the
than 500 m (1640 ft; Machel, 2005) and are crosscut tension gashes. Triaxial stresses are responsible for
by larger fractures. Vertical stylolites can either occur the formation of tension gashes perpendicular to the

Figure 4. Core samples stained with Alizarin red-S and potassium ferricyanide to distinguish calcite (red) from dolomite (white to gray) and
ferroan dolomite (blue). (A) Dolomite matrix (blue) shows large secondary vuggy pores and pyrite (arrow) along small fractures, compared
with tight calcite matrix (red). (B) A small fracture cemented with saddle dolomite (arrow) is surrounded by a zone where significant
dolomitization (blue) and pyrite mineralization occurred, in accordance with the creation of secondary vuggy pores (circle) along the fracture in
otherwise calcitic matrix (red). (C) Fracture filled with (1) nonferroan saddle dolomite (SD) (white), (2) ferroan saddle dolomite (blue), and (3)
ferroan calcite (CC) in the center (purple). Early moldic porosity in dolomite matrix is cemented with saddle dolomite and pyrite. (D) Calcite
cement-filled tension gash (arrow) along vertical stylolite with pyrite mineralization (P). (E) Interval of massive P alternating with saddle
dolomite 1. (F) Former anhydrite nodule, cemented with calcite 1 and pyrite (arrow) in dolomite matrix 1 (gray).

Biehl et al. 603

minimum principal stress axis s3, whereas vertical mosaic containing corroded dolomite inclusions
stylolites develop perpendicular to the maximum (calcite matrix). Plug measurements of nonfractured
principal stress axis s1. This indicates that tension samples show matrix porosities between 1% and 4%
gashes and vertical stylolites are typical for a com- in dominantly calcitic intervals and porosities up to
pressional regime and developed at the same time 23% in dolomitic intervals (Figure 6). The dolomite
(Sibson, 1994). The burial and thermal history matrix 1 shows abundant moldic and intercrystal
(Figure 5), modeled by Petmecky et al. (1999) for a porosity, whereas the calcite matrix is tightly packed,
neighboring well, shows that the Zechstein layers and former molds (Figure 7A) are cemented with an
were deeply buried during the Early Cretaceous and early calcite generation (calcite 1; Figure 7B). Because
underwent considerable uplift and cooling during the of abundant dolomitic inclusions in calcite, we
Late Cretaceous. assume the calcite matrix to be a replacement of
dolomite matrix 1 and refer to this replacement
Matrix Petrography calcite as dedolomite in the sense of Evamy (1967).
The matrix is either composed of finely to medium– The same calcite generation also cements former molds.
crystalline, sub- to euhedral dolomite (dolomite matrix Under cathodoluminescence, the dolomite matrix 1
1) or of an anhedral, coarse-crystalline, calcite crystal appears bright red, whereas the calcite matrix is

Figure 5. Burial and temper-

ature history modeled for a well
approximately 4 km (2 mi)
southwest of the studied well. The
Zechstein layer is colored in gray.
The burial model is based on
borehole temperature and vitri-
nite reflectance data (modified
from Petmecky et al., 1999).
Neog. = Neogene; TDC = thermal
decomposition of carbonate;
TSR = thermochemical sulfate
reduction.

604 Secondary Porosity Creation in Deeply Buried Carbonates

 Figure 6. Helium porosity and
permeability measured for matrix
plug samples. The diagram shows
much higher porosities and per-
meabilities in dolomitic intervals
(grain density 2.9 g/cm3) than in
pure calcitic intervals (grain den-
sity 2.71 g/cm3). Plug samples
with grain densities greater than
3 g/cm3 probably contain pyrite
derived from thermochemical
sulfate reduction.

nonluminescent. Such matrix types are typical for the approximately 17%. Former anhydrite nodules have
Z2 carbonate in the Southern Permian Basin and are been completely replaced by calcite 1 (Figure 4F) and
thought to be of early diagenetic origin, predating the are found in dolomitic and calcitic intervals.
onset of burial stylolitization (Clark, 1980; Reijers,
2012). Large fractures crosscut horizontal stylolites,
indicating that those fractures formed after burial to at Vein Petrography
least 500 m (1640 ft). Adjacent to larger fractures, the Extensive fracturing occurs throughout the core
calcite matrix is replaced by dolomite matrix 2, as in- section. All mineral phases occurring in larger veins
dicated by halos visible on core sections (Figure 4A, B). are either cements or partial replacement products.
During burial, the matrix is affected by dolomitizing Saddle dolomite and ferroan calcite (calcite 2) are the
fluids migrating through the extensive fracture system. two most important vein cements. Saddle dolomite
The dolomite matrix 1 and calcite matrix were thus (Figure 8A) is either present as rare, milky-white
affected in different ways. As shown in Figure 7C, the nonferroan saddle dolomite (saddle dolomite 1) or
moldic porosity in dolomite matrix 1 is partly cemented abundant ferroan saddle dolomite (saddle dolomite
with pyrite and coarse crystalline ferroan dolomite (see 2), as revealed by the blue staining with potassium
also Figure 4C) that is interpreted as saddle dolomite ferricyanide (Figure 4C). Saddle dolomite 1 predates
based on its curved crystal boundaries and sweeping saddle dolomite 2, if both types are present. Under
extinction under cross-polarized light. The dolomitic cathodoluminescence, saddle dolomite 2 is nearly
crystals within the matrix, however, have not been nonluminescent, whereas saddle dolomite 1 shows a
altered by the late-burial dolomitizing fluids. In con- dull red color (Figure 8B). The coarse saddle dolomite
trast, the calcite matrix is affected by the late-burial crystals with a size up to 2000 mm host many aqueous
dolomitization process, leading to a replacement of and gaseous fluid inclusions and solid mineral phases
former dedolomite by subhedral-to-anhedral, coarse- such as calcite, anhydrite, pyrite, or bitumen along
crystalline dolomite matrix 2 and pyrite. Additionally, crystal growth zones, probably indicating alternating
secondary intercrystal and vuggy porosity is created mineral precipitation (Figure 8C, D), in which a
(Figures 4, 7D). This replacement typically affects phase of saddle dolomite growth is followed by
several centimeters of the dolomite matrix 1 adjacent other mineral phases. Saddle dolomite 2 is abundant
to the veins (Figure 4A, B), creating secondary vuggy in veins and occurs either as a single mineral phase or
porosity. Point counting of the dolomite matrix 2 with pyrite and calcite 2 (Figure 8C). Calcite 2
revealed a porosity increase between 10% and 16% in replaces or postdates saddle dolomite 2 and occurs
the former calcite matrix. In contrast, saddle dolomite simultaneously with pyrite. Staining reveals a purple
cements reduced primary porosity in dolomite by color with partly extensive zonation of the crystal

Biehl et al. 605

Figure 7. Microphotographs of
different matrix types under plane
polarized light. Pores appear blue
due to blue epoxy. (A) Dolomitic
matrix 1 with intercrystal porosity
between euhedral crystals and
oomoldic porosity. Coarser do-
lomite cements are present in the
molds (arrow). (B) Calcite matrix
with anhedral calcite crystals,
corroded dolomite inclusions
(dedolomite), and oomolds ce-
mented with calcite 1. (C) Ce-
mentation of oomoldic porosity
with saddle dolomite 2 (SD).
Porosity is reduced by approx-
imately 17% (see Figure 4C). (D)
Former calcite matrix replaced by
dolomite matrix 2 and pyrite (P)
under creation of secondary
vuggy pores (Figure 4B). Simul-
taneously, some porosity is ce-
mented again by SD. However,
porosity is increased by
10%–16% in these intervals.

(Figure 8E). Calcite 2 shows bright yellow to bright Because of the high number of fluid inclusions, a well-
orange colors in cathodoluminescence (Figure 8F), with defined classification of a primary or secondary origin
well-developed zonation in some crystals (Figure 9B, C). of the fluid inclusions using the criteria of Roedder
Fluorite postdates saddle dolomite 2 and pyrite (1984) is often vague or even impossible (see
(Figure 9D), and it shows clear uniaxial crystals with Table 1). Primary fluid inclusions are often orientated
fluid inclusions of primary and secondary origin parallel to the crystal planes. Raman spectroscopic
(Figure 9E). Fluorite is known to precipitate from analyses revealed different molecular compositions of
cooling fluids (Richardson and Holland, 1979; gaseous inclusions, which can be grouped as follows:
Esteban and Taberner, 2003) and is therefore as- (1) CH4-rich inclusions with CH4 content greater
sumed to be the youngest vein mineral phase of the than 66 mol % and similar CO2 and N2 content
Z2 carbonate; however, the relationship to calcite 2 is (sample 4), (2) CO2-rich inclusions with CO2 contents
uncertain. In addition to the mineral phases men- ranging from 60 to 100 mol % (samples 1, 2, and 6), and
tioned above, minor amounts of anhydrite occur, (3) N2-rich inclusions with N2 content greater than
hosting abundant fluid inclusions (Figure 9F). 42 mol % with still-high CO2 and CH4 contents
All observations regarding the matrix evolution (sample 3). All studied gas inclusions show no or only
and vein cements are summarized in the paragenetic low H2S contents (maximum 2.3 mol % in sample 3B).
sequence shown in Figure 10. Inclusions rich in H2S were reported from other
Zechstein carbonates in the northern part of the
Lower Saxony Basin (Gerling et al., 1997) but were not
Fluid Inclusion Analyses observed in the studied samples. The results show
that primary inclusions hosted in saddle dolomite 2
Gaseous inclusions are contained in studied samples are CO2 rich and contain no H2S (samples 1 and 2)
of saddle dolomite 2, anhydrite, and fluorite. As compared with fluorite (samples 3 and 4) and that
shown in Figure 9F, the inclusions have a rounded the CO2 concentrations decrease in younger min-
or rectangular shape with a size less than 20 mm. eral phases (Table 1; Figure 11A). Secondary fluid

606 Secondary Porosity Creation in Deeply Buried Carbonates

Figure 8. Microphotographs of veins and vein cements taken under plane polarized light and cathodoluminescence (CL). (A) Picture of
polished section (plane polarized light) showing large saddle dolomite crystals, which are nonferroan in the center (saddle dolomite 1). The
outer zone (arrow) is ferroan and shows small pyrite inclusions (saddle dolomite 2). Note that the polished section is unstained (Figure 4C).
(B) CL picture of Figure 8A reveals zonation of saddle dolomite. The outer zones are nonluminescent, reflecting higher iron concentrations.
The dashed line shows the transition between outer crystal zone and pore (Figure 4C). (C) Saddle dolomite 2 (SD) with curved crystal
boundaries postdated by calcite 2 (Cc). (D) Saddle dolomite 2 under crossed polarized light showing anhydrite inclusions along growth bands
(arrow). (E) Fracture cemented with zoned calcite 2. The intense purple staining in the crystal center reflects higher iron concentrations. (F) CL
picture of vein cements with bright-orange luminescent calcite 2 in the center postdating nonluminescent saddle dolomite 2 at rims.

Biehl et al. 607

Figure 9. Microphotographs of
veins and vein cements taken
under plane polarized light and
cathodoluminescence (CL). (A)
Tension gash filled with calcite 2
and an inclusion band indicating a
crack-seal structure (arrow) in
dolomite matrix 1. The tension
gash is syngenetic with a vertical
stylolite (Figure 4D), and the
crack-seal structure shows that
cementation was simultaneous
with crack opening and stylolite
formation. (B) CL picture of
coarse crystalline calcite 2 vein
cement in dolomite matrix 1. (C)
CL picture of calcite 2 (Cc)
postdating nonluminescent sad-
dle dolomite 2 (SD). Non-
luminescent zones in calcite 2
(arrow) are associated with fluid
inclusion trails. (D) Saddle dolo-
mite 2 (SD) with pyrite (P) and
calcite 1 (arrow) inclusions pre-
dating fluorite (F). The pyrite
occurs both as inclusions in sad-
dle dolomite 2 and as stand-alone
crystals postdating saddle dolo-
mite 2. (E) Picture of fluorite with
fluid inclusion trails (arrow)
postdating pyrite and calcite 1. (F)
Fluid inclusion trails with gas
bubbles in anhydrite.

inclusions measured in fluorite (sample 4) reflect saddle dolomite 2, dolomite matrix 2, and calcite 2
the composition of the wells’ reservoir gas, which is (Table 3; Figure 12). Saddle dolomite 2 and calcite 2
63.8% CH4, 20.4% CO2, 14.3% N2, and 2.3% H2S. show d 13C values that range between +0.9‰
The d 13CCO2 and d 13CCH4 values of fluid in- and -6‰ VPDB and d 18O values that range be-
clusion gases were measured in two samples of saddle tween -8.8‰ and -13‰ VPDB. In contrast, the
dolomite 2 and four samples of fluorite, and they calcite matrix and dolomite matrix 1 have positive
range from -4.2‰ to -0.8‰ VPDB for CO2 and d 13C values, ranging from +2.8‰ to +6.1‰ VPDB
from -20‰ to -11‰ VPDB for CH4 (Figure 11B; (Figure 12). Dolomite matrix 1 displays d 18O values
Table 2). The reservoir gas has a d 13CCO2 of -1.4‰ between -5.6‰ and -2.9‰ VPDB.
VPDB. The d 13C values for CO2 in fluid inclusions Sulfur isotopes (d 34S) were determined for four
are in the range of d 13C values for saddle dolomite 2 pyrite samples (Table 4). The measured values show
and calcite 2 (Figures 11, 12). a range from +0.1‰ to +10.2‰ V–CDT. The
lowest d 34S value of 0.1‰ V–CDT was measured
Stable Isotopes of Carbonates for the massive pyrite mineralization occurring to-
gether with saddle dolomite 2, as shown in Figure 4E.
Stable oxygen and carbon isotopes were measured for The highest d 34S value of 10.2‰ V–CDT was
dolomite matrix 1, calcite matrix, saddle dolomite 1, measured for pyrite associated with calcite 2.

608 Secondary Porosity Creation in Deeply Buried Carbonates

Figure 10. Paragenetic sequence of observed mineral phases for the studied well. Dashed lines indicate an uncertain timing or a long-
term event.

Rare Earth and Yttrium Pattern of Fluorite DISCUSSION

Rare earth elements (REE) were determined for Effects of Thermochemical Sulfate Reduction
two fluorite samples. Since there is a close associ- and Hydrothermal Fluids
ation between REE and yttrium (Y), the normal-
ized REE patterns are extended to the normalized It has been proposed that TSR is a process causing
REY pattern, where Y is inserted between dys- dissolution of carbonates and a net increase in porosity
prosium (Dy) and holmium (Ho). The parts per (Ma et al., 2007; Cai et al., 2014), but many case
million concentrations (Table 5) were normalized to studies do not indicate such significant changes in
porosity (Machel, 2001). In the Lower Saxony Basin,
post-Archaean Australian Shale after McLennan
TSR took place in reservoirs that have experienced
(1989). The fluorite samples show bell-shaped pat-
burial temperatures greater than 125°C (257°F),
terns with high-middle REE (MREE; samarium,
whereas the contribution of bacterial sulfate reduc-
Eu, gadolinium, terbium) compared with light REE
tion (BSR) to H2S generation was shown to be
(LREE; lanthanum, cerium (Ce), praseodymium, negligible (Mittag-Brendel, 2000). The well used in
neodymium) and heavy REE (Dy, Ho, erbium, thu- this study reached burial temperatures exceeding
lium, ytterbium, lutetium). The LREE especially 125°C (257°F) at the end of the Jurassic (~150–140
show very low concentrations, with a strong in- Ma) and experienced a maximum burial temperature
crease toward MREE. Both samples display a of up to 270°C (518°F) during the Late Cretaceous
strong positive normalized-Y anomaly (Figure 13) (ca. 90 Ma; Figure 5). Independent evidence for TSR
but no normalized-Eu anomaly. is given by relatively small differences in the sulfur

Biehl et al. 609

Table 1. Molecular Compositions of Primary and Secondary 100°C and 200°C (212°F and 392°F) during TSR
Gaseous Inclusions Hosted by the Vein Cements Saddle Dolomite and some degree of Rayleigh fractionation (Machel
2, Anhydrite, and Fluorite et al., 1995). A stronger separation of up to 65‰
between the d 34S values of anhydrite and pyrite
Gas Phase (mol %)
would be expected for BSR (Ohmoto and Rye,
Sample Mineral CH4 CO2 N2 H2S Type 1979; Machel et al., 1995). The complete replace-
ment of all anhydrite nodules by calcite and pyrite
1A SDol 2 0 100 0 0 n.p.
(Figure 4F) demonstrates that TSR has been ex-
1B 0 100 0 0 n.p.
1C 0 100 0 0 n.p.
tensive (Worden and Smalley, 1996). The high
1D 0 100 0 0 n.p. dryness coefficient (C1/C1–3) of 0.998 in the res-
2A SDol 2 36.3 49.5 14.2 0 P ervoir gas is also consistent with extensive TSR, be-
2B 26.8 73.2 0 0 P cause high-carbon-number hydrocarbon molecules,
2C 21.6 64.6 13.8 0 P such as ethane or propane, are preferentially removed
2D 24.9 72.6 2.5 0 P during TSR (Krouse et al., 1988). Once these heavier
2E 20.1 69.1 10.8 0 P hydrocarbons are almost depleted in the reservoir and
2F 28.4 58.7 12.9 0 P the dryness coefficient is greater than 0.95, methane
3A Fluorite 20.9 35.2 42.3 1.6 P becomes involved in TSR. The relatively high d 13CCH4
3B 17.5 36.7 43.5 2.3 P values of up to -11‰ VPDB of fluid inclusion gases
3C 19.3 34.9 43.7 2.1 P (Figure 11B) confirm that methane was involved in
3D 18.5 36.5 43 2 P TSR, because lighter carbon isotopes are preferentially
3E 20.1 34.9 43.2 1.8 P consumed during TSR, leading to a 13C-rich residual
3F 19.5 36.1 42.5 1.9 P carbon pool. The first methane generated from type III
4A Fluorite 67.4 15.9 14.9 1.8 S kerogen in the Carboniferous source rock of the
4B 66.5 16.6 14.9 2 S Lower Saxony Basin can be assumed to have d 13C
4C 66.9 15.7 15.8 1.6 S values of -30‰ VPDB (Lüders et al., 2012). With
4D 67 16 15.2 1.8 S increasing maturity during burial, the isotopic com-
4E 66.8 16.3 14.9 2 S position of methane shifts toward less negative values.
5A Anhydrite 45.5 35.5 17 2 P Considering a vitrinite reflectance between 3.5 and 4
5B 45.1 38.2 14.8 1.9 P for the studied well (Petmecky et al., 1999), methane
5C 45.4 38 14.6 2 P with d 13CCH4 values between -23‰ and -20‰
5D 45.6 38.2 14.3 1.9 P VPDB can be expected for late gas being generated
5E 45.3 37.1 16.6 2 P during maximum burial (Lüders et al., 2012;
6A Anhydrite 27 66 7 0 S Figure 6). The difference between these d 13CCH4
6B 39.9 60.1 0 0 S
values and the measured d 13CCH4 values of fluid in-
6C 40 60 0 0 S
clusion gases in the studied well amounts to 9‰–19‰.
6D 27.2 64.4 7.9 0.5 S
Such a positive shift of the d 13CCH4 values can be at-
6E 33.4 62.9 3.2 0.5 S
tributed to TSR and has also been described by several
6F 37.5 60.5 2 0 S
other authors (Krouse et al., 1988; Worden and Smalley,
Abbreviations: CH4 = methane; CO2 = carbon dioxide; H2S = hydrogen sulfide; N2 = 1996; Heydari, 1997; Worden et al., 2000; Cai et al.,
nitrogen; n.p. = not possible to distinguish between primary and secondary fluid 2004). A calculation introduced by Cai et al. (2013)
inclusions (see Figure 11A); P = primary; S = secondary; SDol 2 = saddle dolomite 2.
using the above d 13CCH4 values shows that approx-
imately 17%–50% of reactive methane was used during
isotope composition between pyrite and anhydrite. TSR. Lu et al. (2012) showed that, besides a 13C en-
The typical d 34S value for sedimentary anhydrite richment in methane, 13C-depleted CO2 is also diag-
above and below the carbonate reservoir is 10‰–12‰ nostic of TSR production, because 13C-depleted CO2 is
V–CDT (Mittag-Brendel, 2000), which is 2%–12% formed by the oxidation of isotopically light methane.
higher than the measured isotopic composition of Consequently, the residual methane should be isotopi-
the pyrite samples (Table 4). This is consistent with cally less negative than newly generated CO2. Our re-
a typical fractionation of only 20‰–10‰ between sults, however, show a 13C enrichment in CH4 but less

610 Secondary Porosity Creation in Deeply Buried Carbonates

 Figure 11. (A) Crossplot
showing relationship between
carbon dioxide (CO2) and hydro-
gen sulfide (H2S) gas composition
(in percent) measured in fluid
inclusions hosted by saddle do-
lomite 2, anhydrite, and fluorite.
Secondary fluorite inclusions
show a comparable gas compo-
sition to present-day reservoir gas.
(B) Carbon isotope ratios (d 13C)
of CO2 and methane (CH4) (in ‰
VPDB) measured in fluid in-
clusions hosted by saddle dolo-
mite 2 and fluorite. Carbon
isotopes of CH4 indicate thermo-
chemical sulfate reduction, domi-
nated by CH4. The carbon isotopes
of CO2 reflect a mixing of organic
and inorganic CO2. VPDB = Vienna
Peedee belemnite.

negative d 13C values for CO2 compared with methane massive pyrite mineralizations are present in the
(Figure 11B), indicating that the CO2 was not ex- studied well (Figure 4E), and we assume that large
clusively derived from TSR but also derived from an amounts of H2S were removed from the reservoir
additional source. during pyrite formation. This process has also been
Fracture filling calcite 2 cement shows d 13C described by Orr (1977). Pyrite is often included in
values as depleted as -6‰ VPDB (Figure 12). vein cements, such as saddle dolomite 2 and calcite 2,
Comparing these with the host-rock depleted carbon indicating that iron-rich fluids ascended along fractures
isotope values points to an incorporation of TSR- into the reservoir, where Fe2+ reacted with TSR-
derived carbon during calcite cement formation. derived H2S to form pyrite. Further evidence for as-
Despite this evidence for extensive TSR, the cending fluids is given by the REY analyses of two
reservoir gas of the studied well only shows 2.3% fluorite samples. The fluorites show enrichment in
H2S, and the concentrations of H2S in fluid inclusions intermediate REE, resulting in bell-shaped patterns
do not exceed 2.3%, either. In particular, fracture with strong positive normalized-yttrium anomalies
cements, such as saddle dolomite 2, do not contain H2S (Figure 13), which are typical for pore waters that
in fluid inclusions (Table 1). Typically, TSR is asso- mobilized REE from clay minerals, biogenic phos-
ciated with H2S concentrations greater than 3% (Orr, phates, and/or iron–manganese (Fe–Mn) oxides from
1977). However, it is known that the H2S accumu- siltstones or shales. Bell-shaped REE patterns are
lation in a reservoir can be limited by the presence of typically observed in biogenic phosphate debris that
metal ions, such as Fe2+ (Machel, 2001). Veins with derived MREE-enrichment from post-depositional

Biehl et al. 611

Figure 12. Crossplot showing
relationship between d13C and
d 18O isotopic ratio values of do-
lomite matrix 1, calcite matrix,
dolomite matrix 2, and vein ce-
ments. VPDB = Vienna Peedee
belemnite.

alteration (i.e., diagenesis; Lécuyer et al., 1998; which commonly is the result of episodic crack
Reynard et al., 1999). Fluorites that originate from opening, where the cracks are rapidly cemented with
marine carbonate source rocks are characterized by crystalline material before the next cracking and
inherited negative Ce anomalies (Bau et al., 2003). closing phase follows (Ramsay, 1980; Urai et al.,
The fluorite samples have Y/Ho ratios of 140 for 1991). The observed tension gash textures are in-
fluorite sample 1 and 196 for fluorite sample 2. Ac- terpreted to be formed during basin inversion, si-
cording to Bau and Dulski (1995), fluorites with multaneously with the cementation by calcite 2.
Y/Ho ratios ranging from 40 to 200 are of hy- The isotopic signature of the calcite 2 cementing the
drothermal origin. The absence of negative Eu tension gash is in the same range as all other calcite 2
anomalies in the REY patterns of fluorite indicates that cements (Table 3; Figure 12), indicating a formation
the fluorite-forming fluids have not experienced tem- from similar fluids and under similar temperatures.
peratures above 250°C (482°F; Bau and Möller, 1992) Calcite 2 often appears together with saddle dolomite
and also excludes fluid origin and/or significant fluid- 2 and pyrite, so we assume that this mineral assem-
rock interaction with felsic magmatic rocks (Lüders blage precipitated during tectonic inversion in the
et al., 1993). In addition to our data, Fischer et al. Late Cretaceous (ca. 70–60 Ma), as they occur in
(2006) measured REY for calcite cements of the same tension gashes associated with vertical stylolites. This
well, which also show a bell-shaped pattern with high is supported by the study of Fischer et al. (2006),
MREE and depleted LREE concentrations, reflecting who determined absolute ages based on rubidium/
carbonate formation under hydrothermal conditions.

Table 2. Carbon Isotopic Compositions of Methane and Carbon

Timing of Vein Formation Dioxide Trapped in Fluid Inclusions Hosted by Saddle Dolomite 2
and Fluorite
The studied well shows a great degree of fracturing, in
which several veins crosscut horizontal stylolites but Mineral d 13CCH4 (‰VPDB) d 13CCO2 (‰VPDB)
predate vertical stylolites (Figure 14). This observation SDol 2 -12.5 -4.2
restricts the vein formation to a minimum burial depth SDol 2 -11 -2
of 500 m (1640 ft) and the end of basin inversion. Fluorite -20 -0.8
Further petrographic evidence for the timing of Fluorite -17.1 -2.4
vein formation is given in Figure 4D, where a calcite Fluorite -12.6 -0.8
2–cemented tension gash originates at a vertical sty- Fluorite -11.7 -2
lolite, indicating that they formed at the same time
See Figure 11B.
(Sibson, 1994). The calcite 2 cements within the Abbreviations: CH4 = methane; CO2 = carbon dioxide; d 13C = carbon isotopic ratio;
tension gash show a crack-seal structure (Figure 9A), SDol 2 = saddle dolomite 2; VPDB = Vienna Peedee belemnite.

612 Secondary Porosity Creation in Deeply Buried Carbonates

Table 3. Results of Carbon and Oxygen Stable Isotope Analyses of Matrix and Vein Filling Minerals

Sample Sample Type Mineralogy d 13C (‰ VPDB) d18O (‰ VPDB)

2-I Fracture Saddle dolomite 2 0.878 -8.819
2-II Matrix Dolomite matrix 2 1.445 -8.236
2-III Matrix Calcite matrix 4.372 -11.920
2-IV Matrix Dolomite matrix 2 1.587 -7.754
2-V Matrix Dolomite matrix 2 1.152 -8.160
4-II Fracture Saddle dolomite 1 -1.741 -9.357
6-I Fracture Calcite 2 -4.150 -13.011
6-II Fracture Saddle dolomite 2 -1.594 -11.073
6-III Matrix Calcite matrix 5.028 -11.509
6-IV Fracture Calcite 2 0.141 -9.311
7-II Fracture Calcite 2 -3.346 -12.568
7-III Fracture Calcite 2 -4.765 -12.602
8-I Fracture Calcite 2 -5.967 -12.946
9-I Fracture Calcite 2 -0.821 -9.448
11-I Fracture Saddle dolomite 2 -1.741 -9.357
11-II Matrix Dolomite matrix 2 -0.067 -8.199
11-MI Matrix Calcite matrix 4.848 -6.673
12-I Fracture Saddle dolomite 2 -0.347 -9.542
12-II Fracture Saddle dolomite 2 -0.558 -9.767
14-I Fracture Saddle dolomite 2 -0.658 -10.376
14-II Matrix Dolomite matrix 1 2.815 -5.582
15-I Fracture Saddle dolomite 2 -1.335 -10.707
15-II Matrix Dolomite matrix 2 -0.058 -9.409
15-III Matrix Calcite matrix 5.197 -9.488
16-I Fracture Saddle dolomite 2 -1.415 -9.172
16-II Matrix Dolomite matrix 2 -1.305 -9.174
16-III Matrix Dolomite matrix 2 -0.364 -8.409
16-IV Matrix Dolomite matrix 2 -1.109 -8.944
17-I Concretion Mix of calcite 1 + 2 -0.125 -9.202
17-II Concretion Mix of calcite 1 + 2 0.179 -9.083
17-III Concretion Mix of calcite 1 + 2 0.113 -9.332
17-IV Matrix Calcite matrix 6.089 -7.983
17-V Matrix Dolomite matrix 1 5.029 -4.758
20-II Fracture Saddle dolomite 2 -0.444 -9.699
21-I Matrix Calcite matrix 5.309 -8.906
21-II Matrix Dolomite matrix 2 0.334 -9.182
22-I Fracture Saddle dolomite 2 0.421 -8.865
26-II Fracture Calcite 2 -2.250 -12.486
27-I Fracture Saddle dolomite 2 -1.264 -10.488
27-II Fracture Saddle dolomite 2 -0.361 -9.612
27-III Matrix Dolomite matrix 1 5.342 -2.909
27-IV Matrix Dolomite matrix 2 0.401 -8.710
See Figure 12.
Abbreviation: VPDB = Vienna Peedee belemnite.

Biehl et al. 613

Table 4. Results of Sulfur Stable Isotope Analyses of Pyrite of pyrite. Iron-depleted saddle dolomites 1 are
directly bound to massive pyrite mineralization zones
Sample Sample Type Mineralogy d 34S (‰ V–CDT)
(Figure 4E). Here, we assume that iron is incorporated
4-I Fracture Pyrite 0.1 in the pyrite crystals. In contrast, less pyrite is present in
10-I Fracture Pyrite 7.2 samples with saddle dolomite 2. Calcite 2 postdates
20-I Fracture Pyrite 8.5 saddle dolomite 2 and shows less variation in iron
26-I Fracture Pyrite 10.2 concentration. The high amounts of iron were prob-
ably derived from fluids migrating upward through
Abbreviation: V-CDT = Vienna Cañon Diablo troilite.
underlying Carboniferous clays and Rotliegende
(lower Permian) volcanic and siliciclastic red beds
strontium (Rb/Sr) and uranium/lead (U/Pb) isotope into Zechstein reservoirs. Iron-rich minerals present
analyses of fracture-hosted carbonates, sphalerite, in Rotliegende intervals are, among others, chlorite,
and galena as Late Cretaceous. The burial history ankerite, and siderite, which have released iron dur-
(Figure 5) shows temperatures of approximately ing diagenetic processes (Gaupp et al., 1993). Over-
270°C (518°F) prevailing at the onset of inversion pressures in these clastic successions could control
(ca. 80 Ma), with temperatures decreasing to ap- the upward flow of basinal fluids (Davies and Smith,
proximately 100°C (212°F) at the end of inversion 2006). Downward-migrating fluids seem very un-
(ca. 60 Ma). This temperature range is consistent likely in the case of the Z2 carbonate, because it is
with saddle dolomite as the main vein cement, which overlain by more than 150 m (492 ft) of salt
is known to precipitate from fluids with temperatures (Figure 1B) that acts as a seal for reservoir gases and
ranging from 80°C to 235°C (176°F to 455°F; Davies lacks brittle fractures. Therefore, the system can be
and Smith, 2006). Variations in the iron content of regarded as closed, prohibiting a further ascent of
saddle dolomite can be correlated to the abundance fluids, as well. As shown in Figure 2, the studied well
is located near a deep-reaching fault system. Con-
Table 5. Results of Rare Earth and Yttrium Analyses of Two sidering the burial history (Figure 5) and the results of
Fluorite Samples and Values Used for Post-Archaean Australian REY analysis, it is evident that fluid mobilization oc-
Shale Normalization curred after the maximum burial and during basin in-
version between 6500 and 2000 m (21,325 to 6562 ft).
REY Fluorite 1 (ppm) Fluorite 2 (ppm) PAAS (ppm)*
La 0.006 0.006 38.2
Ce 0.028 0.013 79.6 Sources of Carbon Dioxide
Pr 0.013 0.005 8.83
Nd 0.155 0.058 33.9 The isotopic composition of CO2 measured in fluid
Sm 0.223 0.107 5.55 inclusions suggests that the high amount of CO2 in
Eu 0.104 0.056 1.08 reservoir gas and fluid inclusions has been mixed from
Gd 0.609 0.376 4.66 at least two sources. The carbon isotope values of
Tb 0.074 0.049 0.774 CO 2 measured in fluid inclusions range between
Dy 0.378 0.274 4.68 -4‰ and -1‰ VPDB (Table 2; Figure 12), and the
Y 7.910 8.790 27 d 13CCO2 value for reservoir gas is in the same range
Ho 0.056 0.045 0.991 (-1.4‰ VPDB). Such carbon isotope values are
Er 0.098 0.081 2.85 known for CO2 originating from inorganic sources,
Tm 0.006 0.004 0.405 such as volcanic origins, mantle degassing, or carbo-
Yb 0.022 0.016 2.82 nate decomposition processes (Clayton et al., 1990;
Lu 0.002 0.001 0.433 Wycherley et al., 1999). Dai et al. (1996) showed
Abbreviations: Ce = cerium; Dy = dysprosium; Er = erbium; Eu = europium; that CO2 derived from a magmatic source or meta-
Fe = iron; Gd = gadolinium; Ho = holmium; La = lanthanum; Lu = lutetium; morphism of carbonate rocks is a likely origin for
Nd = neodymium; PAAS = Post-Archaean Australian Shale; Pm = promethium; inorganic CO2 in sedimentary basins and should not
Pr = praseodymium; REY = rare earth and yttrium; Sm = samarium; Tb = terbium;
Tm = thulium; Y = yttrium; Yb = ytterbium. be neglected. The Permian strata is underlain by
*After McLennan (1989); see Figure 13. Devonian carbonates (Kombrink et al., 2010), which

614 Secondary Porosity Creation in Deeply Buried Carbonates

 Figure 13. Post-Archaean Aus-
tralian Shale (PAAS)-normalized
rare earth and yttrium (REY)
pattern of two fluorite samples
displaying a bell-shaped pattern.
Ce = cerium; Dy = dysprosium;
Er = erbium; Eu = europium;
Fe = iron; Gd = gadolinium; Ho =
holmium; La = lanthanum;
Lu = lutetium; Nd = neodymium;
Pm = promethium; Pr = praseo-
dymium; Sm = samarium; Tb =
terbium; Tm = thulium; Y =
yttrium; Yb = ytterbium.

experienced much higher temperatures resulting CO2 found in fluid inclusions and reservoir gas. Fluid
from a greater burial depth (>310°C [590°F] for inclusions measured from the Upper Carboniferous
Carboniferous; Figure 5) than the Z2 carbonate. in one of the neighboring wells show CO2 concen-
Temperatures greater than 330°C (626°F) are suffi- trations up to 88 mol %, supporting the idea of ex-
cient to produce CO2 from thermogenic breakdown ternally derived CO2-rich fluids. The d 13C values of
of carbonates, as modeled by Cathles and Schoell CO2 measured in fluid inclusions in this study, as well
(2007). Devonian carbonates have d 13C values be- as in the reservoir gas, are much more depleted than
tween 1‰ and 4‰ (Buggisch and Joachimski, 2006), would be expected by decarbonation. We therefore
and the d 13C values of the produced CO2 should be suggest that the inorganic CO2 derived from the
similar (Sharp et al., 2003) or slightly heavier thermal decomposition of carbonates was mixed with
compared with the precursor carbonate (Santos isotopically more negative organic CO2 derived from
et al., 2009). Nevertheless, CO2 derived from a TSR, resulting in the d 13C values of fluid inclusions
volcanic source cannot be ruled out completely, and reservoir gas.
because vitrinite reflectances up to 6% Ro for the Fluid inclusions trapped in saddle dolomite 2 show
Carboniferous observed for other wells in the study high CO2 concentrations (49.5–100 mol %) but no H2S
area were interpreted to result from a deep-seated content (Table 1). In contrast, fluid inclusions trapped
magmatic intrusion (Stadler and Teichmüller, 1971). in younger vein cements, such as fluorite, show higher
In contrast, Petmecky et al. (1999) stated that the CH4 concentrations (17.5–67.4 mol %) and moderate
extremely deep subsidence in the Lower Saxony Basin CO2 concentrations (15.7–36.7 mol %; Figure 11A),
is responsible for high vitrinite reflectances, which was likely indicating that ascending CO2-rich fluids mixed
confirmed by recent modeling studies (Bruns et al., with reservoir gases containing H2S and methane.
2013). Alternatively, Fischer et al. (2006) suggested
that the high amounts of CO2 could also be derived
from pressure solution within the Z2 carbonate itself. Fluid Drive Mechanisms
Frequent high-amplitude stylolites are observed in
the studied core. However, we do not assume that The migration of externally derived fluids was facili-
13
C-rich CO2 generated by pressure solution is tated by the deep faults and associated dense frac-
sufficient enough to explain the high amounts of ture system (Figure 2). The studied well is situated

Biehl et al. 615

Figure 14. Idealized three-step
sketch of matrix and vein para-
genesis for dolomite matrix 1
(left) and calcite matrix (right) to
display porosity creation and re-
distribution, fluid migration, and
the fracture–stylolite relationship.
Veins are partially cemented with
saddle dolomite 2, pyrite, and
calcite 2. Fluorite is the youngest
vein cement precipitating in ac-
cordance with falling temper-
atures (T). Hydrothermal
dolomitizing fluids cause ce-
mentation of former molds in
dolomite matrix 1, whereas sec-
ondary porosity is created in tight
calcite matrix. CO2 = carbon di-
oxide; CH4 = methane; H2S =
hydrogen sulfide.

approximately 500 m (1640 ft) away from a deep evaporitic seal, followed by a rapid increase during
reaching, east–west striking fault system. We assume burial. Due to the impermeable evaporitic Zechstein
that these faults and associated fracture networks, units above the Z2 carbonate, overpressures could be
which are below seismic resolution, acted as preferred maintained for a long time period. Local pressure release
pathways for CO2-bearing fluids ascending into the as a result of basin inversion triggered the ascent of CO2-
Z2 carbonate reservoir. Baldschuhn et al. (1991) and rich fluids and carbonate precipitation resulting from
Urai et al. (2008) have shown that basement-hosted CO2 degassing in open fractures (Leach et al., 1991).
faults in the Lower Saxony Basin can be open and thus
act as fluid conduits for deep-reaching fluid flow. It is
assumed that overpressures developed due to the rapid Creation of Secondary Porosity
subsidence and sedimentation during the Early Cre-
taceous. This is also confirmed by a pore-pressure and In intervals with the highly porous dolomite matrix 1,
overpressure calculation made by Fischer et al. (2006), the dominantly moldic pores are partly cemented by
which shows that overpressure developed directly saddle dolomite 2 (Figure 7C). In the tight calcite
after precipitation of the Zechstein, due to the good matrix (dedolomite), the almost complete loss of

616 Secondary Porosity Creation in Deeply Buried Carbonates

primary and near-surface porosity caused by calcite causes a later supersaturation of the pore water with
cementation and dedolomitization during shallow respect to calcite, leading to a phase of calcite ce-
burial (Clark, 1980; Strohmenger et al., 1996) helps mentation (Leach et al., 1991; Figure 5), which is in
to differentiate the fracture-related dolomitization accordance with our petrographic observations. The
from its associated vuggy porosity. Many veins are rapid ascent of the CO2-rich fluids therefore facili-
surrounded by a dolomitic, chemically blue-stained tated the vuggy porosity creation in calcitic intervals;
halo (Figure 4), indicating a significant influence of however, it also led to cementation of some of the
the ascending basinal brines into the host rock, with vuggy and fracture porosity by saddle dolomite 2,
different effects on porosity depending on matrix pyrite, and calcite 2.
mineralogy. Point counting reveals an overall porosity It has been proposed that TSR creates late burial
increase of 10%–16% in the former calcite matrix porosity in carbonate reservoirs either directly
after late dolomitization and a porosity reduction of through the generation of H2S (Ma et al., 2007) or
17% in dolomite matrix 1 from a few millimeters up through TSR reactions involving magnesium sulfate
to several centimeters along the fractures. However, formed previously by the reaction of dolomite with
the dominance of calcite matrix in the studied core anhydrite (Cai et al., 2014). However, despite clear
section (Figure 3) results in a net increase in porosity evidence of TSR, there is no indication of deep-burial
around fractures. Porosity was increased only in de- porosity increase in the host rock unaffected by
dolomitic layers affected by hydrothermal alteration fractures. On the other hand, a significant porosity
(Figure 14). Davies and Smith (2006) pointed out increase has been observed associated with burial
that hydrothermal dolomitization is often accom- dolomitization and pyrite formation (Figure 6). Sig-
panied by a porosity increase. A porosity increase up nificant volumes of pyrite crystals occur in areas
to 13% could be expected if the dolomitization fol- where the matrix has been affected by hydrothermal
lows mole-per-mole replacement of calcite by dolo- fluids (Figures 4B; 7C, D). The pyrites are particularly
mite (Machel, 2004). However, the presence of abundant at the boundary of the calcite matrix and
saddle dolomite 2 cements within the vuggy pores the zone of fracture-related dolomitization (Figure
indicates that some of the newly created porosity was 14), because pyrite is precipitated along the sta-
closed again by a continuous supply of fluids capa- tionary reaction front by diffusion of Fe2+ from the
ble of precipitating saddle dolomite 2 in open vugs dolomitizing fluid and H2S from the reservoir gas.
(Figure 14). However, because not all porosity is Acidification of fluids by metal sulfide deposition is an
closed and the porosity increase lies between 10% and accepted mechanism for deep-burial dissolution of
16% after dolomitization of the former calcite matrix, carbonates and the creation of secondary porosity,
other processes likely contributed in combination with which has been reported from Mississippi Valley type
the dolomitization to the creation of burial porosity. deposits (Moore and Druckman, 1981; Qing and
Fluid inclusion analyses revealed high CO2 con- Mountjoy, 1994) and was modeled by Corbella et al.
centrations of 50%–100% in primary inclusions (2004). Carbonates are dissolved under acidic con-
hosted by saddle dolomite 2. Retrograde dissolution ditions when metal sulfides are precipitated and H+ is
of carbonates resulting from cooling of CO2-rich released from TSR-derived H2S. For the presented
brines during the ascent of hydrothermal fluids or study, the reaction would be the following:
uplift could contribute to porosity creation (Davies
2H2 S + Fe2 + →FeS2 + 4H+
and Smith, 2006). However, this seems unlikely, as
no dissolution of vein carbonates such as saddle do- Machel (2001) claimed that this process is often
lomite 2 and calcite 2 was observed petrographically. negligible in deep-burial carbonates because metal
Instead, dolomitization to form dolomite matrix 2 ions, such as Fe2+, are limited and that the removal of
was favored by such high initial CO2 concentrations, H2S by Fe2+ is more typical of BSR settings. However, in
as proposed by Leach et al. (1991), who stated that a the studied well, the high volumes of ferroan carbonate
sudden release of initially high amounts of CO2 cements and pyrite provide evidence of a high Fe2+
(“CO2 effervescence”) leads to high dolomitization concentration, which was introduced into the system
rates and dissolution of calcite. They demonstrated by from the underlying clastic strata. Consequently, the
geochemical modeling that continued dolomitization formation of pyrite by removal of TSR-derived H2S

Biehl et al. 617

likely contributed to the creation of secondary vuggy CONCLUSIONS
porosity in the studied carbonates. The dissolved
material is partially incorporated into newly formed 1. The Z2 carbonate in the studied well consists of
dolomite cements in veins and pores. Due to acid- alternating porous dolomitic and tight calcitic
ification by the formation of pyrite, additional cal- (dedolomitic) intervals, which have been affected
cium carbonate can be absorbed in the fluid of the by late diagenetic, iron-rich hydrothermal fluids.
closed reservoir system. Ehrenberg et al. (2012) ar- The fluids ascended along a deep-reaching fault
gued that the rapid kinetics of carbonate dissolution system into the reservoir, which is covered by
would cause the nearly instantaneous buffering of anhydrites and thick rock salt layers. These layers
undersaturated water chemistry during upward flow, prohibit a fluid descent from shallower strati-
leaving virtually no potential for porosity creation. graphic units into the reservoir.
However, the above reaction would generate the 2. Sudden release of CO2 from the ascending fluids
acidity necessary for calcite dissolution within facilitated fracture-controlled burial dolomitization
the reservoir itself, without the need to assume mi- of the calcite matrix. The CO2 was mainly sourced
gration of undersaturated waters from below. The from an inorganic origin, most likely from the ther-
ascent of iron-rich, dolomitizing, basinal fluids into mal decomposition of carbonates, such as underlying
carbonate reservoirs affected by TSR is not un- deeply buried Devonian carbonates. The d 13C values
common and therefore has to be considered as an of CO2 gas within fluid inclusions of saddle dolomite
important setting for deep-burial porosity creation and fluorite and reservoir gas reflect a mixture of
(Gregg, 1985; Davies and Smith, 2006). Thus, CO2- inorganic CO2 and TSR-derived, organic CO2.
rich fluids in combination with hydrothermal dolo- 3. Calcitized anhydrite nodules and abundant pyrite
mitization of the calcite matrix and the reaction of mineralizations indicate that TSR occurred to a
H2S with Fe2+ to produce pyrite are the processes great extent in the studied well. High-carbon-
leading to the creation of secondary burial pores in number hydrocarbons and up to 50% of reactive
the calcite matrix and to partial cementation of moldic methane were consumed during TSR, as evidenced
pores in dolomite matrix 1 and fractures (Figure 14). by the positive shift in the d 13C values of methane.
In accordance with Ehrenberg et al. (2012), the net 4. The TSR-derived H2S reacting with Fe2+ from
increase in porosity is limited to a relatively narrow iron-rich, ascending fluids led to the precipitation
reaction zone along the length of the fractures, of pyrite and acidification of formation waters.
likely exerting a stronger control on permeability than This, in combination with hydrothermal dolo-
total net porosity. More than 80% of matrix per-
mitization, caused the replacement of the calcite
meability measurements from plugs of the studied
matrix with dolomite, accompanied by a 10%–16%
well range between 0.003 and 0.7 mD, with an
increase in porosity in a several-centimeter-wide
average value of 0.03 mD (Figure 6). However,
halo around fractures. In contrast, hydrothermal
production inflow performance tests from the same
saddle dolomite cements reduced moldic po-
well indicate a much higher average dynamic perme-
rosity in the early diagenetic dolomite matrix by
ability (calculated at 2 mD), representing the in situ
effective flow capacity for fluids averaged over the entire approximately 17% and led to partial-to-complete
reservoir away from the wellbore. It is likely that this cementation of fractures. However, the carbonate
dynamic permeability better displays an additional dissolution in the dominantly calcite matrix in the
contribution to reservoir performance from a hydro- reservoir results in a net increase in porosity and
thermally altered carbonate matrix, which often shows permeability in the vicinity of the fracture walls,
permeabilities greater than 1 mD (Figure 6) close to which has to be considered for modeling reservoir
the conduit faults. Small volumes in the direct vicinity properties and fluid migration pathways. This
of fractures therefore influence reservoir permeabilities process generates the acidity necessary for calcite
to a large extent, despite their small effect on total reservoir dissolution within the reservoir itself, without the
porosity. Such an increase in permeability and redis- need to assume migration of undersaturated wa-
tribution in porosity have to be considered for mode- ters from below. The co-occurrence of TSR with
ling reservoir properties and fluid migration pathways. hydrothermal alteration is reported for many

618 Secondary Porosity Creation in Deeply Buried Carbonates

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