ELSEVIER Sedimentary Geology 126 (1999) 205–222

Bacterially mediated formation of diagenetic aragonite and native

sulfur in Zechstein carbonates (Upper Permian, Central Germany)
J. Peckmann a,Ł , J. Paul a , V. Thiel b
a Institut und Museum für Geologie und Paläontologie, Georg-August-Universität, Goldschmidtstrasse 3, D-37077 Göttingen, Germany
b Institut für Biogeochemie und Meereschemie, Universität Hamburg, Bundesstrasse 55, D-20146 Hamburg, Germany

Received 9 March 1998; accepted 3 March 1999

Abstract

Neoformed diagenetic aragonite associated with organic-rich aggregations and native sulfur occur within cavities of the
Ca2 and Ca3 Zechstein carbonates in Central Germany. The cavities were formerly filled with gypsum. Bacterial sulfate
reduction favored the precipitation of the carbonate phase. This can be attributed to an increase in alkalinity accompanied
with sulfate reduction. The high Sr concentrations of the neoformed aragonites compared to the low concentrations in
the carbonate host rocks point to sulfate dissolution as the cation supplying process for the precipitation of aragonite.
Low δ13 C values ( 10‰ PDB) of the aragonite indicate that some of its carbon is derived from organic matter that
has been oxidized by bacterial sulfate reduction. Aragonite inclusions bear rhomb-shaped crystals of calcite, replacing
former dolomite. Elevated Mg=Ca ratios due to this dedolomitization may have promoted the precipitation of aragonite
instead of calcite. The aragonite precipitated in the near-surface meteoric–vadose zone in recent times. Aragonite crystals
display a platy habit. SEM analyses show that two types of micro-rods are associated with these plates. The mineralized
micro-rods are interpreted to be fossilized bacteria. Aragonite inclusions, most of which contain organic-rich aggregations,
yield a distinctive biomarker pattern. High concentrations of specific unsaturated fatty acids are clearly indicative of newly
produced organic matter and reflect the presence of a discrete microbial community being associated with the formation
of the aragonite. At one of the studied localities the aragonite is accompanied by native sulfur. The formation of sulfur
was mediated by H2 S-oxidizing bacteria. This is corroborated by the presence of densely packed curved rods representing
permineralized bacterial cells on and within the sulfur.  1999 Elsevier Science B.V. All rights reserved.

Keywords: aragonite; sulfur; bacteria; gypsum replacement; Zechstein; Germany

1. Introduction known example are the carbonates recognized in the

A strong link between gypsum deposits and neo-
formed carbonate minerals is well established in the
literature. Diagenetic carbonates have been reported
from sulfate-dominated host rocks and soils. A well
Ł Corresponding
author. Fax: C49 551 397918; E-mail:
jpeckma@gwdg.de
Permian evaporites of the Castile and Salado For-
mations from the Delaware Basin. These carbonates
have been interpreted as replacing gypsum and an-
hydrite (Davis and Kirkland, 1979; Kirkland and
Evans, 1976) and are associated with biogenic sul-
fur (Hentz and Henry, 1989). Similar associations of
diagenetic carbonates (calcite, aragonite, dolomite,
and magnesite) and sulfur deposits like these Amer-

0037-0738/99/$ – see front matter  1999 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 7 - 0 7 3 8 ( 9 9 ) 0 0 0 4 1 - X
206 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222
ican examples occur on the Gemsa Peninsula on the
west coast of the Gulf of Suez in a cap rock of
a diapir (Pierre and Rouchy, 1988; Youssef, 1989).
The δ18 O values of the carbonates indicate that the
replacement of sulfate minerals by carbonates took
place at both an early and late diagenetic stage
(Pierre and Rouchy, 1988; Youssef, 1989). In the
case of the Tripoli Formation in Sicily, replacement
occurred very soon after deposition (McKenzie et al.,
1979/1980; McKenzie, 1985). Sulfur within lagoonal
evaporite–carbonate sequences in Sicily has been in-
terpreted to be of biogenic origin (Dessau et al.,
1962). The process of transforming sulfate minerals
in the presence of petroleum to carbonate miner-
als and native sulfur is attributed to sulfate-reducing
bacteria (Thode et al., 1954).
Carbonate replacement of gypsum is not restricted
to marine sediments, but occurs likewise in lacustrine
environments. Calcite and dolomite pseudomorphs
after aragonite crystals occur embedded in paleo–
lacustrine sediments of the rift basins on the east
coast of North America (Triassic–Jurassic; Riccioni
et al., 1996). Much of the original crystal form is
still preserved. Formation of aragonite is attributed
to the release of CO2 by bacterial decomposition of
organic matter. Elevated Mg=Ca ratios were found to
be crucial for the preferential formation of aragonite
over calcite (Riccioni et al., 1996). In the lacustrine
deposits of the Miocene Teruel and Cabriel Basins,
gypsum is replaced by aragonite and calcite (Anadón
et al., 1992). Replacement occurred soon after de-
position in the Libros gypsum (Teruel Graben), re-
spectively at shallow burial depths in contact with
meteoric waters (Cabriel Basin). Sulfate reduction is
believed to be the driving mechanism for carbonate
precipitation in the Libros gypsum, which is sup-
ported by the high content of organic matter and the
associated native sulfur (Anadón et al., 1992).
Sulfate-rich soils are another reactor for the neo-
formation of carbonates. In soils derived from gyp-
sum-bearing Keuper strata in east-central Spain, fi-
brous radial aragonite nodules are common (Laya
et al., 1992). The quality of preservation of the
nodules decreases downward, indicating that arago-
nite formation is a very recent near-surface process.
Within gypsum-bearing horizons in soil profiles in
the Tamoa Valley on the western coast of New Cale-
donia, calcite (in situ pseudomorphs after lenticular
gypsum) and aragonite are forming (Podwojewski,
1995). However, Laya et al. (1992) and Podwojew-
ski (1995) do not presume that carbonate precipita-
tion might be mediated by soil bacteria. Both soil
bacteria and soil fungi were found to precipitate cal-
cite when cultured on a Ca-rich medium (Boquet
et al., 1973; Monger et al., 1991). Applying the
‘biomarker-concept’, Newman et al. (1997) demon-
strated that calcites formed in fractures in the vadose
zone were derived from microbial activity. The au-
thors suppose that the precipitation of other types of
pedogenic calcites is also controlled biologically.
Aragonite aggregations within Zechstein carbon-
ates are known as ‘Schaumspat’ (Köhler, 1930). It
is described as a leafy and loose pseudomorphism
of aragonite after gypsum. Köhler suggested that
the aragonite formed during burial diagenesis with
enhanced pressure and temperature. In this paper
we report on neoformed aragonite and native sulfur
in a vadose–meteoric environment within Zechstein
carbonates. Petrographic and stable isotope analyses
indicate that diagenesis was mediated by biologi-
cal processes involving sulfate-reducing and sulfur
bacteria.
2. Geological setting and stratigraphy
Sediments of the Upper Permian Zechstein Group
crop out in a small belt south of the Variscan Harz
Mountains in Central Germany (Fig. 1). The Zech-
stein Basin is a giant evaporite–carbonate basin in
which huge masses of rocksalt and sulfate (anhy-
drite and gypsum), and smaller amounts of carbonate
were deposited. Evaporitic cycles, which document
the changing conditions within the basin, were used
to establish a stratigraphic division of the Zechstein
(Richter-Bernburg, 1955). Each cycle starts with ei-
ther a clay (T) or carbonate (Ca) horizon, both
deposited under normal marine conditions. These
horizons are overlain by sulfate (A) and rocksalt
(Na) deposits, which precipitated from hypersaline
waters more or less isolated from the open sea.
During the Mesozoic, an overburden of several kilo-
meters of clastic and carbonate rocks accumulated
in this area. This resulted in the conversion of the
gypsum deposits to anhydrite. Beginning in the Late
Cretaceous, the evaporites were uplifted and exposed
 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222
Fig. 1. Geological sketch map of the Harz Mountains in Central Germany with the localities of aragonite occurrences.
to surface conditions. The humid climate of Central
Europe favors the dissolution of the rocksalt to a
depth of several hundred meters and the near-surface
reconversion of anhydrite to gypsum.
During the deposition of evaporites, the central
part of the Zechstein belt south of the Harz Moun-
tains was influenced by a palaeo-high, the Eichsfeld
High (Paul, 1993). The evaporite accumulation from
the first cycle (A1) is strongly influenced by this
high. Here, a thick succession of shallow water gyp-
sum was deposited, generating a sulfate platform
(Fig. 2). The carbonates of the second cycle (Ca2)
draped this platform. The Ca2 oolitic grain- and
packstones on the platform, which reach more than
50 m in thickness, pass basinward into thin-bedded
mud- and wackestones. The edge of the platform is
characterized by an intense brecciation of the carbon-
ate, due to early slumping and sliding processes. The
pre-existing differences in the platform and basin
facies were intensified by variable diagenesis and
resulted in two different lithologies. The Ca2 unit of
the platform is preferentially dolomitic, whereas the
basinal facies was converted to dedolomite (Clark,
1980; Huttel and Mausfeld, 1991).
The sulfate of the second cycle (A2) is up to 50
m thick in the basin and wedges out on top of the
207
platform. The rocksalt of this cycle (Na2), which
once filled up the basin, has been dissolved in the
study area. The third evaporitic cycle starts with
claystones and thin carbonate beds (Ca3), which
have a uniform thickness, like the overlaying sulfate
(A3) which terminates the evaporite sequence south
of the Harz Mountains.
2.1. Walkenried
Aragonitic inclusions within the second cycle car-
bonate (Ca2) were collected 3 km southwest of the
village of Walkenried. Unfortunately, these strata are
not well exposed; therefore the exact position of the
inclusions in the carbonate sequence is not clear.
Palaeogeographically, the rocks were deposited on
top of the Eichsfeld High (Fig. 2). They consist
of about 50 m of oolitic and oncolitic grain- and
packstones (dolomites and dedolomites).
2.2. Mühlberg
Aragonite occurrences of the Mühlberg locality
are found near the top of an abandoned quarry at
the northwestern margin of the village of Nieder-
sachswerfen, north of Nordhausen. They are also
208 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222
Walkenried
A B
0
200
400
m 5 km
Fig. 2. Stratigraphic and palaeogeographic position of the host rocks containing neoformed aragonite on the eastern slope of the Eichsfeld
Palaeo-High. Ca1 D first cycle carbonate; A1 D first cycle sulfate; Ca2 D second cycle carbonate; A2 D second cycle sulfate; T3 D third
cycle clay; Ca3 D third cycle carbonate; A3 D third cycle sulfate.
embedded in second cycle carbonates (Ca2), which
were deposited at the steep eastern slope of the
Eichsfeld High. As a consequence of this, the car-
bonate sequence consists of sedimentary breccias
in the lower part, followed by fossiliferous wacke-
stones, which are overlain by oncolitic and peloidal
dolomite bearing the aragonite inclusions. Today the
Ca2 crops out in a steep slope of 50 m in height with
the Bere Creek at its base, indicating that the recent
water table is almost 50 m below the occurrences of
neoformed aragonite.
2.3. Alter Stolberg
The aragonite inclusions of the Alter Stolberg area
were found between the villages of Steigerthal and
Stempeda, northeast of Nordhausen. In contrast to
the other occurrences, aragonite is hosted in carbon-
ates of the third evaporite cycle (Ca3). The Ca3 has
a thickness of a few meters and consists of alternat-
ing well-bedded grayish, platy calcitic mudstones,
massive limestones and grayish marly claystones.
The limestones are porous due to the dissolution
of gypsum nodules. The aragonite occurs in these
dissolution cavities.
3. Methods
Thin sections (15 ð 10 cm) and polished thin sec-
tions (48 ð 28 mm) were studied petrographically.
Mühlberg
Alter
Stolberg
Fluorescence microscopy was carried out on a Zeiss
Axiolab (lamp: HBO 50; filter: BP 450-490 FT 510
LP 520). Thin sections and polished rocks were
stained with combined potassium ferricyanide and
alizarin red, dissolved in 0.1% HCl solution (Fücht-
bauer, 1988, pp. 240–241), and with Feigl’s solution
to stain aragonite (Feigl, 1958). SEM analyses were
performed with gold-coated samples using a Hitachi
S-2300. A LEO 1530 Gemini was used for field-
emission (FE)–SEM analyses on uncoated samples.
Mineralogy was determined by X-ray diffraction on
unoriented slurries using a diffractometer with CuKa
radiation (Philips PW 1800). Chemical composition
was measured by atomic absorption spectrometry
(AAS) on a Philips PU 9200X. Samples for car-
bon and oxygen stable isotope ratios were taken
from polished slabs using a hand-held microdrill.
CO2 was liberated by the standard phosphoric acid
technique (McCrea, 1950) at 75ºC. Isotope mea-
surements were made with a Finnigan Mat 252
mass spectrometer, using a Carbo-Kiel carbonate
preparation technique, at the University of Erlan-
gen. The δ13 C and δ18 O results are reported rela-
tive to the PDB standard and appropriate correction
factors were applied (Craig, 1957). The standard
deviation ranges for carbon and oxygen from 0.01
to 0.04‰. A correction factor for δ18 O values of
0.7‰ (Grossman and Ku, 1986) was added to the
aragonite samples and a correction factor of 0.8‰
(Sharma and Clayton, 1965) was added to the δ18 O
ratios of dolomitic samples. 3.7 g of aragonite were
 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222
mechanically prepared and subjected to biomarker
analysis. After saponification of the ground sam-
ple in 6% KOH in methanol (60ºC, 2 h), the su-
pernatant was decanted and the sample was ultra-
sonically extracted with dichloromethane=methanol
(3 : 1; v=v). The combined supernatants were acid-
ified to pH2 and extracted with dichloromethane.
The resulting organic phase was fractionated by sil-
ica gel column chromatography into hydrocarbons,
alcohols (not discussed here) and an acidic fraction
(elution with dichloromethane=methanol; 3 : 1, v=v).
Methyl esters of the organic acids were prepared by
treatment with 1 ml methanol=trimethylchlorosilane
(8 : 1, v=v; 60ºC, 2 h). After filtration over silica
gel, the hydrocarbon and methyl ester fractions were
subjected to gas chromatography (GC) and com-
bined gas chromatography–mass spectrometry (GC–
MS). GC analyses were run on a Carlo Erba Frac-
tovap 4160 gas chromatograph, using ‘on-column’
injection and a flame ionization detector. The GC
was equipped with a 30-m DB5 column (0.3 mm
i.d., 0.25 µm film thickness; carrier gas H2 ). The
GC–MS system was a Finnigan Mat CH7A mass
spectrometer interfaced to a Carlo Erba 4160 GC
(60 m XLB, 0.25 mm i.d., 0.32 µm film thick-
ness, carrier gas He, ‘on-column’ injection). The
identification of the compounds was based on a com-
parison of their mass spectra and of GC retention
times with those of published data or with reference
compounds. Quantification was carried out by GC-
peak area integration (Bruker Chromstar software)
and comparison with an internal standard of known
concentration.
4. Carbonate petrography
4.1. The host rocks (Ca2 and Ca3)
The host rocks consist of a crystal mosaic of
carbonate, gypsum and anhydrite. The carbonate is
calcite at the localities Walkenried and Alter Stolberg
and dolomite at the Mühlberg locality. Neomorphic
fabrics prevail. Carbonate crystals mostly exhibit
irregular crystal boundaries typical for a neomor-
phic spar. Their crystal size distribution is patchy
with a mean of about 20 µm. At Mühlberg rhomb-
shaped dolomite crystals, which are about 150 µm
209
in diameter, are common. Occasionally remains of a
dark-gray, homogenous micrite are preserved within
the neomorphic fabric (Alter Stolberg) or the primary
fabric of a former oolitic limestone is still obvious
(Mühlberg). Acicular gypsum lines the ooids. Lo-
cally granular gypsum may be volumetrically even
more important than carbonate. Its crystal sizes range
from 10 to 150 µm. Less common than gypsum is
anhydrite, the crystal size of which may reach 1.2
mm. Gypsification of some of the anhydrite crys-
tals is obvious with transformation directed from the
crystal surface to the center. Veins crosscutting the
rock consist dominantly of anhydrite and to a lesser
extent of gypsum. Framboidal pyrite is locally abun-
dant. The only fossils found in the thin sections are
foraminifera of the genus Nodosaria (Mühlberg).
4.2. Aragonite and native sulfur
Aragonite inclusions occur in voids of the host
rocks, which were formerly filled with gypsum.
These inclusions of white aragonite may reach 3
cm in diameter (Fig. 4a). Joint surfaces may also be
covered by aragonite over areas of about 10 cm2 .
The aragonite is not indurated and is always closely
associated with gypsum. Internally the aragonite in-
clusions are formed of platy crystals (Fig. 4b). Plates
may exhibit the same general orientation in one in-
clusion (Fig. 4c) or may be arranged in bundles with
the orientation of the plates changing from one bun-
dle to the other (Fig. 4d). Perfectly preserved arag-
onite crystals also occur on heavily weathered joint
surfaces (Fig. 4e). Only one example has been found
of fibrous aragonite crystals (Fig. 4f). Some arag-
onite inclusions enclose rhomb-shaped crystals of
calcite replacing former dolomite (Fig. 4g). Within
some veins there is a sequence from acicular gypsum
to granular gypsum to aragonite towards the center
of the vein. Aragonite crystals are oriented orthogo-
nally or at an obtuse angle to solution fronts on the
gypsum crystals (Fig. 4h). Replacement of gypsum
by aragonite is obvious from these solution fronts
along gypsum crystals (Fig. 5a,b). Acicular gypsum
appears to be less affected by replacement than the
granular gypsum.
Two types of micro-rods are associated with the
aragonite plates (Fig. 5c). The first type of micro-rod
is about 0.1 µm in diameter and 1 µm in length. Rods
210 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222

Fig. 3. Gas chromatograms of the total hydrocarbons (a) and the fatty acids (b) extracted from neoformed aragonite (Alter Stolberg).

of this type are frequent. Often these rods were found
to be arranged in nest-like structures (Fig. 5d). They
are cylindrical in cross section, have rounded termi-
nations, and may be straight or curved along their
length. The second type of micro-rod is less common.
Rods with larger dimensions of about 0.8 µm in di-
ameter and 4 µm in length are attached to the crystal
surfaces or even appear to be slightly embedded in
depressions on the crystal surfaces (Fig. 5e).
Both at the margins of the aragonite inclusions
and between the bundles of aragonite, dark-brown to
black organic-rich aggregations occur. These very
characteristic residues are restricted to the arag-
onite. Within the host rocks nothing similar was
 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222 211

found. The organic-rich aggregations have an irreg- Table 1

ular shape and may reach 1 mm in diameter. Half Mineralogy and chemical composition of host rocks (Müh-B,
Sto-C) and aragonite inclusions
of the volume of some aragonite inclusion may be
composed of these organic residues. Their fabric is Sample Mineralogy Ca2C Mg2C Sr2C Fe2C Mn2C
peloidal, and at their margins it becomes obvious (%) (%) (ppm) (ppm) (ppm)
that they are formed of accumulations of globules Müh-A aragonite 38.7 0.374 2800 20 20
(Fig. 5f). The diameters of globules show a contin- Müh-B dolomite 22.5 13.3 90 310 250
uous spectrum from 3 µm to smaller sizes. Epiflu- Sto-A aragonite 37.6 0.190 820 2820 730
orescence-microscopy applied on these thin sections Sto-B aragonite 36.7 0.051 1620 140 85
Sto-C calcite 34.9 0.093 80 980 920
is a useful tool to prove the organic composition of
these aggregations within the aragonite. Irradiation
with ultraviolet light causes an intense fluorescence the occurrence of Fe–Mn-oxy-hydroxides within the
of the organic residues (Fig. 5g,h and Fig. 6a,b). aragonite inclusion analyzed. XRD studies indicate
Another feature of the Ca3 from the locality Al- that the black phases associated with aragonite are
ter Stolberg is the local occurrence of native sulfur X-ray amorphous. The Fe–Mn minerals were found
within micro-cavities. The latter is found associated in association with only one aragonite inclusion,
with aragonite, but more commonly it occurs in cav- whereas the overwhelming majority of the aragonite
ities without any aragonite phases (Fig. 6c). Where inclusions contained no additional mineral phase,
aragonite and sulfur are associated, the formation except for rhomb-shaped calcites. The high Mg con-
of sulfur postdates the former. Globular aggregates tent (0.051–0.374 wt.%) of the aragonite samples is
consisting of microcrystalline sulfur reach 800 µm probably related to these dedolomite rhombs.
in diameter. The surfaces of sulfur are densely cov-
ered with mineralized curved rods (Fig. 6d). These
5.2. Stable isotopes
rods are about 7 µm in length and 3 µm in width.
Their size and shape are extremely constant. Many of Carbon and oxygen isotopes of Zechstein carbon-
them exhibit small depressions on their outer surface ates and the aragonite inclusions are given in Table 2.
(Fig. 6d). With ongoing precipitation of sulfur, the The δ13 C differ significantly from host rock to arago-
rods become enveloped (Fig. 6e). Associated with nite at the localities Mühlberg and Alter Stolberg. The
them are coccoid-shaped bodies. The latter have a host rock is slightly enriched in 13 C at the Mühlberg
diameter of about 0.4 µm (Fig. 6d). (C0.96 to C0.97‰) and depleted at Alter Stolberg
At the locality Walkenried some aragonite inclu- ( 5.28 to 5.63‰). At both localities δ13 C values of
sions exhibit a small central cavity caused by the aragonite ( 9.67 to 10.20‰) are lower than those
solution of aragonite. These cavities are lined with of the surrounding rock. The aragonite from Walken-
microcrystalline gypsum growing on the aragonite ried yielded similar δ13 C values, ranging from 9.24
and partially replacing the carbonate. to 9.64‰. In contrast to the other localities, the host
rock here does not differ significantly from the arag-
onite values ( 9.45 to 9.99‰).
5. Geochemistry Oxygen isotope measurements from aragonite in-
clusions yield rather uniform values, ranging from
5.1. Mineralogy and chemical composition 6.17 to 7.21‰. The host rocks exhibit a broader
range, with values for Mühlberg of 3.66 to
Chemical analyses of the host rocks and the arag- 4.84‰, for Walkenried of 6.64 to 6.66‰, and
onite inclusions are shown in Table 1. Measured for Alter Stolberg of 6.60 to 6.63‰.
Sr concentrations in the samples of the host rock
are smaller than 100 ppm, whereas the aragonite 5.3. Organic geochemistry
inclusions exhibit elevated Sr concentrations rang-
ing from 820 to 2800 ppm. The high concentrations A gas chromatogram of the total hydrocarbon
of Fe and Mn in the sample Sto-A are related to fraction is shown in Fig. 3a. The aragonite with or-
212 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222
 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222 213

Table 2 Table 3
Stable carbon (δ13 C) and corrected oxygen (δ18 O) isotope analy- Concentrations of selected molecular markers present in the
ses of Zechstein carbonates and aragonite inclusions hydrocarbon and fatty acid fractions of the neoformed aragonite
(Alter Stolberg) cements
Sample Carbonate phase δ13 C δ18 O
(‰ PDB) (‰ PDB) Compound (ng=g cement)
Wal-1 calcitic matrix 9.45 6.64 Hydrocarbons
Wal-2 calcitic matrix 9.99 6.66 n-C21 92
Wal-3 aragonite inclusion 9.24 7.21 n-C28 70
Wal-4 aragonite inclusion 9.64 7.02
Fatty acids
Müh-1 dolomitic matrix C0.96 3.66
16 : 1ω7c 750
Müh-2 dolomitic matrix C0.97 3.68
16 : 1ω7t 430
Müh-3 dolomitic matrix C0.97 4.84
16 : 1ω5c 16780
Müh-4 aragonite inclusion 9.67 6.69
16 7880
Müh-5 aragonite inclusion 9.97 6.17
18 : 2ω9 1240
Müh-6 aragonite inclusion 9.98 6.54
18 : 1ω9c 3340
Sto-1 calcitic matrix 5.28 6.63
18 : 1ω7c 1840
Sto-2 calcitic matrix 5.63 6.60
18 2250
Sto-3 aragonite inclusion 10.08 6.56
Sto-4 aragonite inclusion 10.16 6.75 Fatty acids: c, t refer to cis- and trans-configuration of the
Sto-5 aragonite inclusion 10.20 6.26 (terminal) double bond, respectively.

ganic-rich aggregations shows a simple compound
pattern comprising a modal n-alkane distribution
with a first concentration maximum at n-heneicosane
(n-C21 , 92 ng=g dry sample). Such pattern may de-
rive from a petroleum source and=or microbial re-
working of organic matter rather than from a specific
input. A conspicuous feature of the hydrocarbon
fraction is the presence of a second, more distinc-
tive concentration maximum at n-octacosane (n-C28 ,
70 ng=g) and the occurrence of an unusual suite of
terminally (2- and 3-methyl- D iso- and anteiso-)
branched alkanes in the range of C21 to C25 . Al-
though no information on biomarker significance,
age and=or the biological function of these com-
pounds is available, they are likely to reflect a pri-
mary contribution of lipids from discrete microbial
sources.
The fatty acid pattern of the aragonite is shown
in Fig. 3b. Fatty acids act as building blocks of
the cell membranes in most living organisms. In the
sample studied, the compounds are present in re-
markably high concentrations which exceed those of
individual hydrocarbons by more than two orders of
magnitude. The fraction contains mainly even-chain
saturated and monoenoic n-acids with chain lengths
from 14 to 18 carbon atoms (C16 predominant, see
Table 3). The pattern found yields some valuable im-
plications on the nature and the source of the organic
inclusions present in the neoformed aragonite: (1)
The prominent concentrations and the high relative
amounts of comparably unstable, unsaturated fatty
acids are clearly indicative of fresh, newly produced
organic matter. (2) The simple fatty acid pattern
points to a single organism, or a simple consortium

Fig. 4. (a) Polished slab of the Ca3 from the locality Alter Stolberg with several bright inclusions of aragonite embedded in the dark
matrix of the host rock. Scale bar D 2 cm. (b) SEM image of aragonite plates. The arrow points to a nest-like aggregation of M
micro-rods. Ca3, Alter Stolberg. Scale bar D 20 µm. (c) Sharp transition between the granular, calcitic host rock and an aragonite
inclusion (stained with Feigl’s solution). Ca3, Alter Stolberg. Scale bar D 200 µm. (d) Arrangement of bundles of plates in groups with
the orientation of the plates changing from one bundle to the other. Ca2, Walkenried. Scale bar D 200 µm. (e) Aragonite on a weathered
joint surface. Ca3, Alter Stolberg. Scale bar D 1 cm. (f) Aragonite inclusion made of fibrous crystals. Ca3, Alter Stolberg. Scale bar D
1 mm. (g) Rhomb-shaped crystals of calcite replacing former dolomite within an aragonite inclusion. The bright object on the left is an
organic inclusion. Thin section excited with ultraviolet light. Ca3, Alter Stolberg. Scale bar D 200 µm. (h) Gypsum crystals (left) and
platy aragonite. Center: aragonite crystals are oriented at an obtuse angle to the solution front along the gypsum crystal below the center.
Ca2, Mühlberg. Scale bar D 100 µm.
214 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222
 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222 215

of organisms as the key biota associated with the for-
mation of the aragonite cements. (3) The molecular
characteristics of the acids found strongly suggest
a bacterial source input, since all of them have
been observed as bacterial lipid constituents, or from
recent sediments showing a pronounced microbial
activity (e.g., Volkman et al., 1980; Nichols et al.,
1986 and refs. cited therein). Notably, the 18 : 1ω7
fatty acid was previously reported by Russell et al.
(1997) from diagenetic carbonates replacing gypsum
and was interpreted as a marker of bacterial activ-
ity.
6. Discussion
6.1. Diagenesis of the host rocks
A general scheme of successive diagenetic pro-
cesses of Zechstein carbonates and anhydrites was
proposed by Clark (1980) and Huttel and Mausfeld
(1991). Their model is also valid for the carbonates
of the Eichsfeld High. They assume an early perva-
sive dolomitization of carbonates in response to the
reflux of brines from sabkhas and playas. Due to this
process, microcrystalline dolomites were formed and
later recrystallized. During burial diagenesis anhy-
dritization of gypsum formations, pressure solution,
leaching and calcitization of dolomite due to the gen-
eration of CO2 from microbial oxidation of organic
matter occurred. The latter process took place prefer-
entially at basinal sites, where the available amount
of organic matter was higher than on top of the plat-
forms, resulting in present-day calcitic lithologies in
the basinal settings and in dolomitic lithologies on
the platforms. In addition, uplifting, erosion, and ac-
cess of water enriched in Ca-ions due to the leaching
of anhydrite led to calcification of former dolomites
under near-surface, meteoric conditions.
6.2. Diagenetic aragonite
The delicate aragonite crystals are not affected by
weathering. This is surprising, as they are directly
exposed to the changing conditions at the surface in-
cluding episodic soaking by rainfall. Even aragonite
crystals originating on weathered joint surfaces were
found. This indicates that the aragonite formation
postdates at least part of the weathering. All inclu-
sions are not indurated and the crystal aggregates
readily disintegrate. Taking the metastability of arag-
onite under surface conditions into account, the Re-
cent formation of this mineral phase is likely. Arag-
onite deposits, that were formed in pre-Holocene
times and still preserve their primary mineralogy, are
not uncommon. However, to the best of our knowl-
edge, all of these aragonite deposits were protected
from alterations by the surrounding rock or mineral
phases.
Comparing the development at the three localities,
the process of aragonite formation is least advanced
in the Ca2 from the Mühlberg locality. Here the
aragonite is growing in cavities and veins which
are still partly filled with gypsum. Aragonite crys-
tals are found to protrude into both granular and
fibrous gypsum crystals, replacing the sulfate min-
erals. The granular gypsum crystals are significantly
more affected by this process. The interface between
the gypsum crystals and aragonite is very irregu-
lar, indicating the dissolution of gypsum. The plates
of aragonite are probably directly related to the re-
placement of the gypsum. This is indicated by an
almost constant angle of the aragonite plates to the
dissolution fronts along the gypsum crystals and the
circumstance that aragonite is always in direct con-
tact with these fronts. If the aragonite formation did
not occur immediately after dissolution of gypsum,
a more indiscriminate infill of the cavities should be
expected.

Fig. 5. (a) Aragonite (dark) growing in a micro-cavity surrounded by acicular gypsum. Ca2, Mühlberg. Scale bar D 250 µm. (b) Detail
from Fig. 4a. Solution front on a gypsum crystal with aragonite crystals orientated orthogonally to this surface. (c) SEM image of two
types of micro-rods attached to aragonite plates. Ca3, Alter Stolberg. Scale bar D 6 µm. (d) Detail from Fig. 4c. M micro-rods arranged
in a nest-like cluster. Scale bar D 5 µm. (e) FE–SEM image of a micro-rod. Ca3, Alter Stolberg. Scale bar D 4 µm. (f) Organic-rich
aggregations (bright) within an aragonite inclusion. Note the flaky fabric of the organic aggregate in the center. Excited with ultraviolet
light. Ca3, Alter Stolberg. Scale bar D 100 µm. (g) Aragonite inclusion containing several organic-rich aggregations (dark). The long
axes of organic-rich aggregations are parallel to the orientation of aragonite plates. Ca3, Alter Stolberg. Scale bar D 200 µm. (h) Same
view as Fig. 4c now excited with ultraviolet light, causing the organic-rich inclusions to emit an intense fluorescence.
216 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222

Fig. 6. (a) Organic-rich aragonite replacing gypsum crystals (right). Ca3, Alter Stolberg. Scale bar D 100 µm. (b) Same view as Fig. 5a
now excited with ultraviolet light. Organic compounds cause an intense fluorescence. (c) Globular aggregation of native sulfur within a
micro-cavity. Ca3, Alter Stolberg. Scale bar D 500 µm. (d) SEM image of native sulfur with curved rods (arrows) and coccoid-shaped
bodies. Ca3, Alter Stolberg. Scale bar D 10 µm. (e) SEM image of native sulfur. Curved rods (arrow) become enveloped by extracellular
precipitation of sulfur. Ca3, Alter Stolberg. Scale bar D 10 µm.

These processes are most advanced in Walkenried,
where the return to oxidizing conditions caused some
aragonite to be replaced by secondary gypsum. At
the contact surface between aragonite and gypsum,
which is very irregular, microcrystalline gypsum pro-
trudes into the laminated aragonite fabric. The process
of secondary replacement of aragonite by diagenetic
gypsum under aerobic conditions was already de-
scribed by Anadón et al. (1992) from a similar setting.
6.3. Aragonite vs. calcite precipitation
Several factors such as the presence of bacteria
and organic matter, the magnesium concentration of
 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222
the solution, high temperature and the degree of
carbonate supersaturation have been suggested to fa-
vor aragonite precipitation instead of calcite. The
relationship between microbial activity and the for-
mation of aragonite or calcite still remains unclear.
Buczynski and Chafetz (1991) found that media with
the same bacterial composition yield aragonite or
calcite precipitates dependent on the viscosity of the
media. Oppenheimer (1961) noted the formation of
aragonite in the presence of bacteria, whereas several
others report on microbially-derived calcites (Boquet
et al., 1973; Monger et al., 1991; Newman et al.,
1997). Bacteria may not be able to influence the
mineralogy of the precipitate, but calcifying organic
substances derived from the decay of bacteria might
trigger matrix-mediated precipitation as described
for microbialites from Lizard Island (Reitner, 1993).
Rising Mg=Ca ratios have been demonstrated to
promote the precipitation of aragonite instead of cal-
cite (Riccioni et al., 1996; Laya et al., 1992). Kitano
et al. (1962) found that the presence of MgCl2 in
Ca(HCO3 )2 solutions favors the formation of arago-
nite. This is supported by Berner (1975), who stud-
ied the crystal growth of aragonite and calcite in
sea water, magnesium-depleted sea water, and mag-
nesium-free sea water. He reported that dissolved
magnesium at sea water levels reduces the crystal
growth of calcite. The process which supplies excess
magnesium in the Zechstein carbonates is suggested
to be dolomite replacement. This is corroborated by
the presence of calcitized dolomite crystals within
the aragonite inclusions.
High temperature has been demonstrated to pro-
mote precipitation of aragonite relative to calcite
(Kitano et al., 1962), but is very unlikely to be
responsible for the aragonite formation in the near-
surface setting as discussed here.
The degree of carbonate supersaturation predeter-
mines the mineralogy of the precipitates, with very
high supersaturation levels promoting aragonite for-
mation (Chafetz et al., 1991). In the case of our
example high degrees of supersaturation in Ca2C
(due to the solution of gypsum), and an elevated
PCO2 (due to microbial activity), cannot be proven,
but may have occurred.
217
6.4. Implications on the elemental composition
The contents of Sr in subsurface Zechstein car-
bonates vary from less than 100 ppm to some hun-
dred ppm, with extremely rare values above 1000
ppm (Clark, 1980; Huttel and Mausfeld, 1991). Car-
bonates from outcrops exhibit concentrations up to
110 ppm. Limestones have higher Sr contents than
dolomites, whereas Fe and Mn are enriched in micro-
crystalline dolomites indicating reducing conditions
and saline solutions favoring the transport of Fe and
Mn as metal complexes. The values in subsurface
samples are between 200 and 1000 ppm for Mn and
300–2000 ppm for Fe, for both dolomite and calcite.
Ranging from 820 to 2800 ppm, the neoformed
aragonites exhibit lower Sr concentrations than ma-
rine aragonites, which exhibit values of about 10,000
ppm (Veizer, 1983). The host rocks analyzed in this
study yield much lower Sr concentrations, ranging
from 80 to 90 ppm. This indicates that the neoformed
aragonites have sources of cations other than the cal-
citic or dolomitic matrices. Botz and Müller (1981)
report Sr concentrations in the range of 1300–1700
ppm of the gypsum-rich transition horizons below
and above the Zechstein carbonates. Local enrich-
ment of Sr is obvious from celestite crystals which
occur within gypsificated anhydrite deposits (Lang-
bein, 1968). Jung and Knitzschke (1961) report that
the A2 contains up to 5300 ppm Sr. The distribution
of Sr in carbonates and sulfates elucidates the crucial
part of sulfate dissolution as the process supplying
cations for the precipitation of aragonite.
6.5. Implications on the stable isotope compositions
The aragonite that replaces gypsum is character-
ized by distinctly lower δ13 C values than the host
rocks, except for the Ca2 from Walkenried. The nar-
row range of the δ13 C values of aragonite suggests
that precipitation at the different locations was trig-
gered by the same process. The values reported here
of about 10‰ indicate two different carbon sources.
δ13 C values of about 25‰ are typically associated
with bacterial sulfate reduction and depend on the
composition of the organic matter that becomes ox-
idized (Irwin et al., 1977). Accordingly, the isotopic
composition of the aragonites studied implies a mix-
ing with a less depleted carbon source, probably the
218 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222
carbonate host rocks. The sulfate sources for the bac-
terial sulfate reduction are the minerals gypsum and
anhydrite. The organic matter that became oxidized
was probably derived from the Ca2 and Ca3 and not
from deeper strata. Indeed, the basinal facies of the
Ca2 contains up to 1.75% organic carbon (Botz and
Müller, 1981) and has thus been discussed for its oil
and gas potential (Botz et al., 1981).
The negative δ18 O values of aragonite of about 6
to 7‰ indicate that precipitation occurred under
the influence of meteoric waters. Today, all outcrops
are above the ground water table, implying that
aragonite formation occurs in the vadose–meteoric
zone.
Data from Botz and Müller (1981) regarding the
δ13 C values of the Zechstein carbonates show a range
from C7 to C4‰. Only those samples which contain
considerable amounts of sulfate yielded values that
range from C2 to 0‰. These positive δ13 C values
of Zechstein carbonates are interpreted by Huttel
and Mausfeld (1991) to be derived from the relative
enrichment of 13 C in the seawater. This is due to the
preferential fixation of 12 C in the anoxic sediments
as organic carbon (Magaritz et al., 1983).
In comparison with the data from Botz and Müller
(1981) and Huttel and Mausfeld (1991), the deple-
tion of 13 C in the host rocks of this study indicates
a higher carbon content that was derived by the oxi-
dation of organic matter. Only the dolomitic Ca2 of
the Mühlberg is slightly enriched in 13 C (¾C1‰),
whereas the matrices at the other localities are de-
pleted in this isotope. Studies on the isotopic com-
position of co-existing dolomites and calcites have
revealed that dolomites are slightly enriched in 13 C
with respect to associated calcites (Fritz and Smith,
1970; Tan and Hudson, 1971). However, this en-
richment is not sufficient to explain the offset in
the δ13 C values between the Mühlberg-Ca2 and the
other calcitic host rocks. The 13 C isotopic compo-
sition of the Mühlberg-Ca2 indicates precipitation
from marine sources. At Walkenried the calcitic host
rock exhibits a similar depletion in 13 C of about
10‰ like the aragonite inclusions. This low value
indicates that some carbonate carbon was derived
from the oxidation of organic matter. Probably the
host rock at Walkenried has also been affected by
bacterial sulfate reduction. This implies that similar
processes account for formation of aragonite as well
as the alteration of the host rock in earlier times. To
a lesser extent, this also holds true for the locality
Alter Stolberg (δ13 C 5 to 6‰).
For subsurface samples Huttel and Mausfeld
(1991) report δ18 O values in the range of C4 to
4‰ in Zechstein carbonates. The δ18 O values of
the dolomite host rock from Mühlberg have to be
lowered by 3–7‰, because of the differential oxy-
gen isotope fractionation during crystallization of
calcite with respect to dolomite (O’Neil and Epstein,
1966; Fritz and Smith, 1970; Tan and Hudson, 1971;
Land, 1980). The low temperature precipitation of
protodolomite yields an enrichment in 18 O by 3–
4‰ relative to coexisting calcite (Fritz and Smith,
1970), which corresponds well with the data of Irwin
et al. (1977). Taking this into account, all the host
rocks described here exhibit δ18 O values of about 6
to 7‰, indicating an exchange with isotopically
light meteoric waters during diagenesis (cf. Tan and
Hudson, 1971).
6.6. Bacterial mediation
The bacterial mediation in the diagenetic pro-
cesses taking place within Zechstein carbonates is
evidenced by the co-occurrence of characteristic
phenomena. These are carbonate replacement of
gypsum, low δ13 C values of the replacing carbon-
ates, and the presence of native sulfur. The crucial
role of bacteria is further corroborated by bacterial
body- and chemo-fossils associated with the diage-
netic phases.
The smaller micro-rods attached to the aragonite
plates are organized in nest-like accumulations, lack
any crystallographic form or indication of cleavage,
and their form exhibits similarities to bacteria. This
indicates a biotic origin. They correspond to the M
micro-rods described by Verrecchia and Verrecchia
(1994). These M micro-rods are thought to be calci-
fied bacteria or physicochemical nuclei. Phillips and
Self (1987) interpret them as calcified rod-shaped
bacteria and notice their frequent association with
organic matter. They also have been attributed to
bacteria by their form and their types of organiza-
tion (Chafetz et al., 1998). Micro-rods of the second
type (about 4 µm in length) found on the aragonite
plates exhibit the typical size and form of rod-shaped
bacteria and are probably also calcified bacteria.
 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222
Biomarker studies on aragonite including organic-
rich aggregations yielded high concentrations of spe-
cific unsaturated fatty acids, which are clearly indica-
tive of newly produced organic matter and reflect the
presence of a discrete microbial community being
associated with aragonite formation.
Bacterial sulfate reduction leads to the produc-
tion of H2 S, which might be converted to native
sulfur under aerobic conditions or by the reaction
with Fe–Mn–oxy-hydroxides even under anaerobic
conditions (Jørgensen, 1987). However, as iron and
manganese primarily occur in reduced state in Zech-
stein carbonates, an exposure to oxygen is required
anyway. A shift from anaerobic conditions during
aragonite formation to an aerobic micro-environ-
ment during sulfur formation within some cavities
is most likely related to an exposure to oxygen due
to progressive weathering of the sulfate-rich carbon-
ate rocks. As sulfate-reducing bacteria are obligate
anaerobes, the oxidation of H2 S probably did not
occur at the same time as the sulfate reduction and
aragonite precipitation at the locality Alter Stol-
berg. Formation of native sulfur might have taken
place at a later stage, when H2 S, trapped in cav-
ities, came into contact with oxidizing waters. A
contemporaneous formation of aragonite and sulfur
due to the upward seepage of H2 S into an aero-
bic environment cannot be excluded, but is con-
sidered to be unlikely as cavities represent rather
isolated traps. The process of sulfur formation is
also bacterially mediated. Several groups of bac-
teria are able to use H2 S as an electron donor.
We interpret the curved rods which are associated
with the native sulfur as fossilized bacterial bodies.
The small depressions on their outer surface indi-
cate that shrinkage of the bacterial bodies occurred
at a low extent before they were completely min-
eralized. The permineralization of bacterial bodies
is followed by an extracellular mode of precipita-
tion enveloping the rods. The coccoid-shaped bodies
in the sulfur deposits may also represent fossilized
bacteria. With a diameter of 0.4 µm, these bodies
exceed the size of nannobacteria described by Folk
(1993). Apart from chemolithotrophic sulfur-oxidiz-
ing bacteria, purple sulfur bacteria are also able to
oxidize H2 S to elemental sulfur. However, as the
anoxigenic purple bacteria are phototrophic, it is
highly unlikely that they formed the sulfur deposits
219
in the completely dark cavities within Zechstein car-
bonates.
The following processes of gypsum solution
(Eq. 1), reduction of sulfate ions (Eq. 2), aragonite
precipitation (Eq. 3), and sulfur formation (Eq. 4) are
envisaged:
CaSO4 ð 2H2 O ! Ca2C C SO24 C 2H2 O (1)
The gypsum involved here comes from the nod-
ules embedded in the carbonate host rocks. The
widespread dissolution of the sulfate deposits of the
A1, A2 and A3 may generate additional sources of
Ca2C and SO4 ions.
SO24 C 2CH2 O ! 2HCO3 C H2 S (2)
Due to the utilization of organic material by
sulfate-reducing bacteria, alkalinity increases (see
Eq. 2). Together with the availability of Ca2C ions
(see Eq. 1), precipitation of aragonite will be induced
(Eq. 3):
Ca2C C 2HCO3 ! CaCO3.ara/ C H2 O C CO2 (3)
If the product of sulfate reduction, H2 S, gets
trapped in the aerobic zone for a sufficient length of
time, it can be oxidized to sulfur and sulfur-oxides
(Eq. 4):
3H2 S C 4O2 ! S0 C 3H2 O C SO2 C SO3 (4)
The latter process can accumulate sulfur to de-
posits of commercial value, such as in the Permian
anhydrite formations of West Texas (cf. Davis and
Kirkland, 1979), as well as in the Tertiary of the
Mediterranean area (Dessau et al., 1962), and in the
Middle Miocene of the Gulf of Suez (Pierre and
Rouchy, 1988).
7. Conclusions
Bacterial mediation is a widespread phenomenon
in the formation of diagenetic minerals in different
sedimentary environments. Neoformed aragonite and
native sulfur in the Zechstein carbonates from Cen-
tral Germany described here, highlight the influence
of microbial activity on diagenesis. The precipitation
of diagenetic aragonite and sulfur within cavities of
the carbonates was mediated by bacteria. All occur-
rences of the neoformed, metastable aragonite and of
220 J. Peckmann et al. / Sedimentary Geology 126 (1999) 205–222
sulfur are located far above the watertable, indicat-
ing that aragonite formation occurred in the vadose–
meteoric zone.
The processes which led to the formation of arag-
onite started with the dissolution of sulfate nodules
embedded in the carbonate host rocks. Solution of
gypsum provided both Ca ions for the precipitation
of aragonite and sulfate ions for the metabolic pro-
cesses of sulfate-reducing bacteria. The substrate for
these bacteria was organic matter, probably derived
from the carbonate host rocks. The oxidation of or-
ganic matter was coupled with sulfate reduction in
an anaerobic micro-environment. Aragonite forms as
a consequence of the increase in alkalinity accompa-
nied with bacterial sulfate reduction. The importance
of this process is corroborated by the low δ13 C val-
ues of the aragonite, which indicate that some of its
carbon is derived from organic matter. The bacterial
oxidation of H2 S (product of sulfate reduction) re-
sulted in the formation of native sulfur, which occurs
as globular aggregates at one of the study localities.
Aragonite crystals exhibit a platy habit. SEM
analyses show that two types of micro-rods are asso-
ciated with the plates. The smaller type (1 µm long
and 0.1 µm in diameter) corresponds to the M micro-
rods described by Verrecchia and Verrecchia (1994).
This type and a larger type of mineralized rods (4
µm long and 0.8 µm in diameter) are interpreted
to be bacterial fossils. The volumetrically important
aggregations of organic-rich material, which are lim-
ited to the aragonite inclusions, are derived from
bacterial sources. This is indicated by biomarker
analyses which evidenced molecular characteristics
of a microbial community. SEM analyses show that
bacterial bodies are densely packed on and within
the sulfur. With ongoing sulfur formation, the per-
mineralized curved rods (7 µm long and 3 µm
in diameter) become enveloped by an extracellular
mode of precipitation.
High Sr concentrations in sulfate deposits and
aragonite precipitates indicate that sulfate dissolu-
tion, and not the dissolution of the carbonate host
rocks, was the cation supplying process. On a mi-
croscale, solution fronts on the gypsum crystals ap-
pear to be the interfaces where these processes take
place. The platy aragonite crystals, which replace the
gypsum, are oriented orthogonally or at an obtuse
angle to the solution fronts. This and the ubiqui-
tous loose and platy appearance of the aragonite
inclusions are believed to be caused by the replace-
ment of gypsum by aragonite. The crucial factor for
the precipitation of aragonite instead of calcite was
probably an elevated Mg=Ca ratio.
Acknowledgements
We are indebted to M. Plache, A. Quast and K.
Träger, who discovered the rocks which are the
subject of this study. We thank H. Becker and
K.-H. Faber for the preparation of thin sections.
M. Joachimski is acknowledged for stable isotope
analyses and H. Huckriede and C. Gross for their
comments. Special thanks to I. Harding for a care-
ful review of an earlier version of the manuscript
and to H. Lehnert and K. Techmer for their electron
microscope support. We acknowledge the logisti-
cal support provided by the IMGP, Göttingen (AG
Reitner) and the IfBM, Hamburg (AG Michaelis).
Comments by J.M. Rouchy and an anonymous re-
viewer greatly improved the manuscript. This paper
is a contribution to the SFB 468 ‘Wechselwirkungen
an geologischen Grenzflächen’ (publ. no. 8) at the
University of Göttingen.
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