Physicochemical characteristics of drip waters: Inuence

on mineralogy and crystal morphology of recent cave

carbonate precipitates
Sylvia Riechelmann
a,
, Andrea Schro der-Ritzrau
b
, Jasper A. Wassenburg
a,c
,
Ju rgen Schreuer
a
, Detlev K. Richter
a
, Dana F.C. Riechelmann
c
, Mihai Terente
d
,
Silviu Constantin
d
, Augusto Mangini
b
, Adrian Immenhauser
a
a
Ruhr-University Bochum, Institute of Geology, Mineralogy and Geophysics, Universita tsstrae 150, D-44801 Bochum, Germany
b
Ruprecht-Karls-University Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany
c
Johannes Gutenberg-University Mainz, Institute for Geoscience, Johann-Joachim-Becher-Weg 21, D-55128 Mainz, Germany
d
Department of Geospeleology and Paleontology, Emil Racovita Institute of Speleology, Strada Frumoasa 31,
R-010986 Bucharest 12, Romania
Received 6 May 2014; accepted in revised form 8 September 2014; Available online 18 September 2014
Abstract
Speleothems are one of the most intensively explored continental archives for palaeoclimate variability. The parameters,
however, that control speleothem petrography and its changes with time and space, specically calcite crystal morphology and
carbonate mineralogy, are still poorly understood. In order to shed light on processes and their products, precipitation exper-
iments of recent carbonate crystals on watch glasses and glass plates were performed in seven selected caves. Drip water sites
were analysed for their uid Mg/Ca molar ratio, pH, degree of saturation for calcite and aragonite and drip rates. Corre-
sponding precipitates were analysed with respect to their mineralogy, calcite crystal morphology and Mg/Ca molar ratio
of calcite. The following results are found: High uid Mg/Ca ratios are found only for caves situated in dolostone, thus
the hostrock lithology indirectly controls the carbonate mineralogy and calcite crystal morphology of speleothems. The pre-
cipitation of aragonite in place of calcite occurred only in dolostone caves and is bound to very specic conditions. These are:
high uid Mg/Ca ratios (P0.5), high uid pH (>8.2) and low uid saturation indices for calcite (<0.8). These specic condi-
tions are induced by slow drip rates of <0.2 ml/min as often under more arid conditions, causing the precipitation of calcite/
aragonite prior to reaching the stalagmite top. Due to this, uid chemistry is altered, which in turn leads to changes in car-
bonate mineralogy and geochemistry on the stalagmite top. Calcite growth is inhibited at high uid Mg/Ca ratios and hence,
aragonite precipitation is kinetically stabilised. An increase of the drip water Mg/Ca ratio leads to an increased incorporation
of Mg
2+
into the calcite crystal lattice and thus, to a change in calcite crystal morphology. Four distinctive changes occur with
increasing Mg
2+
incorporation: (i) development of new forms (steeper rhombohedra and base pinacoid) at the edges and cor-
ners of the crystal seed, (ii) crystal habit tend to elongate along [001] due to slower growth of faces with high Mg
2+
densities,
(iii) reconstitution of crystal faces with low Mg
2+
densities, and (iv) occurrence of calcite crystals with bended faces and edges
due to very high Mg
2+
(Mg/Ca ratios of 0.0090.051) incorporation. Growth rates and possibly also organic compounds,
however, may also aect the morphology of calcite crystals. Based on the data shown here, the relation of Mg
2+
incorporation
and the resulting changes in calcite crystal morphologies as well as the conditions of aragonite precipitation are now clearly
http://dx.doi.org/10.1016/j.gca.2014.09.019
0016-7037/ 2014 Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +49 (0)234 32 23256.

E-mail address: Sylvia.Riechelmann@rub.de (S. Riechelmann).
www.elsevier.com/locate/gca
Available online at www.sciencedirect.com
ScienceDirect
Geochimica et Cosmochimica Acta 145 (2014) 1329
better understood. Further work should aim at linking the calcite crystal morphology of watch glass precipitates with calcite
crystal fabrics in speleothems in order to exploit the petrographic archive of speleothem deposits.
2014 Elsevier Ltd. All rights reserved.
1. INTRODUCTION
Speleothems (minerals formed in caves and in particular
stalagmites and owstones) are amongst the most inten-
sively explored archives of past climate change in continen-
tal settings (e.g., Fairchild and Baker, 2012). Considerable
advances with respect to climatic and cave forcing of drip
characteristics and related speleothem proxy data have been
made over the last years (e.g., Cruz et al., 2005; Mattey
et al., 2008; Wassenburg et al., 2013). In contrast to this
variety of geochemical and isotopic studies of speleothems,
the issue of speleothem petrography, and specically calcite
crystal morphologies is less addressed (e.g., Kendall and
Broughton, 1978; Gonzalez et al., 1992; Railsback et al.,
1994; Frisia and Borsato, 2010). The processes determining
the internal structure of speleothems, such as mineralogy
and crystal fabrics are seldom used when interpreting spele-
othem geochemical proxies (Fairchild and Baker, 2012).
Especially their relation to carbonate geochemistry and drip
water properties including Mg/Ca ratios, pH, drip rates,
and super saturation has received comparably little atten-
tion (Fairchild and Baker, 2012).
Given the complexity of cave depositional environ-
ments, crystal fabrics in speleothems, if properly inter-
preted, arguably bear evidence on past drip site specics
(Kendall and Broughton, 1978; Gonzalez et al., 1992;
Frisia et al., 2000; Fairchild et al., 2007; Frisia and
Borsato, 2010). Thus, it is here suggested that an advanced
understanding of the intra-cave variability of past drip
sites in turn, leads to an improved interpretation of dier-
ential crystal fabrics. Another insuciently explored aspect
refers to temporal and spatial changes in speleothem min-
eralogy, specically alternating aragonite and calcite pre-
cipitation (Railsback et al., 1994; Frisia et al., 2002;
Caddeo et al., 2011; Wassenburg et al., 2012). Problems
include the physico-chemical controls on speleothem min-
eralogy, the complex role of precursor phases such as
amorphous calcium carbonate (ACC) or vaterite (Spanos
and Koutsoukos, 1998; Loste et al., 2003). The intricate
combination of these factors leads to a wide spectrum of
resulting crystal fabrics (Railsback, 2000; Frisia and
Borsato, 2010).
In order to approach these issues, a new generation of
long term, detailed, multi-parameter cave monitoring stud-
ies are now performed in a series of caves worldwide (e.g.,
Spo tl et al., 2005; Sundqvist et al., 2007; Mattey et al., 2008;
Miorandi et al., 2010; Frisia et al., 2011; Riechelmann et al.,
2011; Tremaine et al., 2011; Tremaine and Froelich, 2013).
The data obtained from these monitoring studies form a
solid foundation and strong motivation to explore the
impact of uid chemistry and drip rate changes on carbon-
ate mineralogy and calcite crystal morphology in natural
cave systems. We emphasise that this aspect (i.e., eld
experiments) is of key signicance as many of the previous
studies are based on laboratory experiments (e.g., Kitano
et al., 1969; Fu chtbauer and Hardie, 1980; Fernandez-
D az et al., 1996; Zhang and Dawe, 2000; Meldrum and
Hyde, 2001; Loste et al., 2003; De Choudens-Sanchez and
Gonzalez, 2009). Giving full credit to the importance of
well constrained experimental work, the physico-chemical
boundary conditions in natural cave and in experimental
settings might dier in many important aspects, a notion
that raises the issue of the applicability of laboratory
experiments.
Here, we present the outcome of a study using recent
carbonate precipitates from seven dierent caves located
in Germany, Morocco and Romania. All of these caves
are explored by sophisticated monitoring programmes
(Riechelmann et al., 2011, 2013; Schro der-Ritzrau et al.,
2011; Wassenburg et al., 2013) and reveal a wide spectrum
of cave parameters and specically drip site characteris-
tics. The focus is on the relation of drip characteristics
to carbonate mineralogy, to calcite crystal morphology
and specically on the signicance of variable amounts
of Mg
2+
, which is possibly incorporated into the calcite
crystal lattice. The following aims have motivated this
study: (i) to explore factors controlling calcite crystal mor-
phologies in cave precipitation experiments, (ii) to assess
parameters leading to spatially and temporally changing
speleothem mineralogy and (iii) to quantify physicochem-
ical tipping points of changes from calcite to aragonite
precipitation. The data are compiled under strict monitor-
ing controls including the full complexity of natural cave
settings. This work is of importance for those concerned
with speleothem palaeoclimate reconstructions and repre-
sents, to the knowledge of the authors, the rst study per-
forming precipitation experiments in diverse caves from
diverse settings and rigorous comparison with drip site
characteristics.
2. METHODS: CAVE MONITORING AND
LABORATORY WORK METHODS
2.1. Case settings
For this study, watch glass and glass plate experiments
were performed in seven caves in Germany, Morocco and
Romania. These include Bunker Cave, Zoolithen Cave
and Kleine Teufels Cave in Germany, Grotte Bab Mafr-
aque, Grotte Prison de Chien and Grotte de Piste in Mor-
occo and Clos ani Cave in Romania. The studied caves were
selected based on their wide range of drip characteristics,
specically uid Mg/Ca ratios. For a detailed overview of
cave parameters see Table 1.
14 S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329
2.2. Field experimental setup, instrumentation and sampling
strategies
Bunker Cave was monitored monthly from 2006 to 2011
and every two months from 2012 to 2013, whereas Clos ani
Cave was always monitored every two months. The Zooli-
then and Kleine Teufels Cave in Germany as well as the
Moroccan caves were monitored in three-monthly intervals.
Drip rates of the monitored drip sites were measured man-
ually with a stop watch during each cave visit. Drip water
samples were collected during cave trips with durations
required for water collection ranging from a few minutes
to several days. Monthly samples were taken at drip sites
TS 6 and TS 8 from Bunker Cave and fortnightly samples
at drip site 2 from Zoolithen Cave in order to collect
enough water for analyses. Cave air temperatures were
measured with the probe HMP 75 connected to a MI70
device (Vaisala; precision 0.2 C at 20 C).
Drip water pH was measured with a pH/mV pocket
device pH 340i (WTW) using the pH-probes InLab 425
and InLab Science Pro (Mettler Toledo; precision 0.05
pH-units) for Bunker, Kleine Teufels and Zoolithen Caves.
In the other caves, drip water pH was measured with the
pH-probe SenTix 41 (WTW; precision 0.05 pH-units).
Due to CO
2
degassing of the drip water reaching the cave
ceiling, the pH value measured of the drip waters collected
at the cave ground is altered to higher values (Dreybrodt,
2011). As a consequence, the data collected do not reect
the conditions of the drip water prior to CO
2
degassing.
Drip water temperatures were measured using a conductiv-
ity pocket device Cond340i and the probe TetraCon 325
(WTW; precision 0.2 C). In the case of Zoolithen Cave
and Kleine Teufels Cave, the air temperature was used to
calculate the saturation indices instead of the uid temper-
ature assuming no major oset.
In order to collect time-series data on carbonate precip-
itates, watch glasses (diameters of 6 or 7 cm) were posi-
tioned beneath dierent drip sites in caves in Germany
and Morocco. Watch glasses were placed with their convex
side up to mimic the shape of a stalagmite top. Glasses were
collected and replaced seasonally (in three-monthly inter-
vals). One watch glass in Bunker Cave was kept in place
over the duration of 12 months in order to accumulate cal-
cite over a prolonged period (U VIII). In the case of
Clos ani Cave (Romania) 1 mm-thin glass plates of
3.7 cm 5 cm were placed on top of drip counters and
replaced every two months.
The inuence of the substratum on crystal morphologies
was tested in Bunker Cave. Watch glasses present an amor-
phous silicate substratum. Other substrata sampled com-
prise the plastic surface of a drip counter, a plastic slab
and a sand sack coated with cotton.
2.3. Analytical methods in the laboratory
Carbonate alkalinity was analysed using the Aquam-
erck

titration kit (Merck; precision 5 mg/l HCO

3

).
These data were required for calculating the saturation
indices of calcite and aragonite. The analyses of the cation
concentrations of drip waters were performed at Heidelberg
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S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329 15
University with a VISTA MXP ICP-OES (Varian) with an
internal 1r-standard deviation of <1% for Ca
2+
and Mg
2+
.
Two external standards, the NIST1643e with a long-term
1r-reproducibility of 3.6% for Ca
2+
and 3.2% for Mg
2+
and the SPS SW2 with a long-term 1r-reproducibility of
4.3% for Ca
2+
and 3.4% for Mg
2+
were used.
The saturation index is dened as:
SI log X 1
where X is the saturation state and is calculated via:
X IAP=K 2
with IAP being the Ion Activity Product and K the solubil-
ity product. For SI > 0 the solution is supersaturated and
for SI < 0 it is undersaturated (Appelo and Postma,
2005). In this study, the saturation indices for calcite (SI
cc
)
and aragonite (SI
ar
) were calculated with the software
PHREEQC (Parkhurst and Appelo, 1999) using pH,
Ca
2+
and HCO
3

concentrations as well as water/air tem-

perature as input parameters.
Element concentrations of the calcite precipitates were
analysed at Ruhr-University Bochum, Germany, with an
ICP-OES device (Thermo Fisher Scientic iCAP 6500
DUO). The internal 1r-reproducibility of the standards
CRM512 and CRM513 are 1.8% and 1.0%, respectively,
for calcium and 1.5% and 1.3%, respectively, for magne-
sium. The Mg/Ca ratios of drip waters and calcite are
expressed as molar ratios. Mg/Ca ratios of the carbonate
were determined for all particular types of crystal morphol-
ogies where possible. In order to mechanically select calcite
morphologies, the specic crystals were sampled under a
binocular stereo microscope from their substrates using a
dissecting scalpel.
Watch glasses were dried after each cave trip and
weighed before they were placed in the cave and after the
cave trip via a Mettler AT261 Delta Range

(1r 0.015 mg) in order to calculate the growth rate of cal-

cite. For watch glasses the growth rate (G) was calculated
using the following equation:
Glm=a W mg 10
3
=Acm
2
=qg=cm
3

10
4
365d=a=zd 3
where W is the weight of the precipitated carbonate on the
watch glass, A is the circular area, q is the density of calcite
(2.7 g/cm
3
) and z is the duration of the experiment in days.
Watch glass at site GC 5 (Grotte Prison de Chien) moved
away from its drip site due to the impact of the drip water,
therefore, the calculated growth rate may be not accurate
for this site. In general, considering seasonal drip rate vari-
ations and site-specic conditions (e.g., splashing, rapid
seeping of water at high drip rates) as well as errors during
weighing, G can be considered as an estimate. A calcite
growth experiment at sites CC 1 and CL 1 in Clos ani Cave
during 20012007 has shown maximum growth rates of
430 lm/a at both sites. Another important point is the
nucleation rate of crystals, which diers most likely for
watch glasses (smooth surface) compared to a stalagmite
surface. Thus, crystals sizes were measured under the scan-
ning electron microscope.
Carbonate crystals on their dierent substrates were
spattered with gold and analysed under a high resolution
scanning electron microscope (SEM) type Zeiss/LEO 1530
Gemini. The focus was on crystal morphologies. Moreover,
angles between crystal faces and edges were measured in
order to perform indexing of the faces.
3. RESULTS
3.1. Cave and drip site characteristics as well as carbonate
mineralogy
Mean cave air temperatures of the Moroccan caves are
generally higher compared to the German and Romanian
caves (Table 1). The lowest temperatures were found for
Zoolithen and Kleine Teufels Caves in Germany (Table 1).
Drip water chemistry diers between drip sites within
one cave and between dierent caves. Below, we summarise
the main results of the monitoring data. Please refer to
Table 2 and Fig. 1 for details. The lowest mean drip water
Mg/Ca ratios (molar; <0.11) are found for limestone caves,
whilst the higher Mg/Ca ratios (>0.4) of drip waters occur
for caves located in hostrock, which is partly or wholly
dolostone.
The lowest pH values measured were observed for drip
waters in limestone caves, whilst the highest pH values
occur for drip waters in dolostone caves. In total, a positive
correlation (r = 0.72, p = 0.001, n = 17) between drip water
Mg/Ca ratio and pH was observed. Analysis of drip water
pH reveals that all uids are, at the time of uid analysis,
supersaturated with regard to calcite and aragonite. There
is no consistent pattern of drip water saturation indices
and the hostrock lithology. The same accounts for drip
water Mg/Ca ratio and drip rate.
Aragonite crystals precipitated on a series of watch
glasses in (i) a seasonal pattern with calcite precipitation
throughout the year and (ii) calcite and aragonite precipita-
tion throughout the annual cycle. Aragonite occurs only on
watch glasses placed in dolostone caves, thus at higher Mg/
Ca ratios (>0.6) and higher pH values (>8.0) of the drip
waters (Fig. 1). The watch glass precipitate related to the
highest drip water Mg/Ca ratio (2.867.79) is composed
of aragonite only. On some watch glasses, isolated
aragonite crystals precipitated (Fig. 3A), whilst on others
aragonite precipitated predominantly as fan-like arrays
(Fig. 3B).
3.2. Morphology types and Mg/Ca ratios of calcite crystals
Based on crystallographic forms, the habit and charac-
teristic appearances including rough faces or curved edges,
six dierent types of calcite crystal morphology are here dis-
tinguished. In the following the Miller indices of the
observed forms refer to the trigonal-hexagonal setting of
calcite with lattice constants a = 4.99 A

and c = 17.06 A

.
The Mg/Ca ratios of calcite crystals of wherever pos-
sible individual morphology types, or where necessary
of composite samples were analysed (Table 3 and Fig. 2).
Due to the relative small number of crystals of the minor
morphology type, their inuence on the elemental composi-
16 S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329
tion can be neglected in rst approximation and the
measured values were taken into account for the dominant
morphology type (Table 3). Composite samples were taken
due to the diculty to extract sucient sampling material
of a specic morphology type from a dense multi-type crys-
tal meshwork. The physical separation of crystal types D
and B/F was feasible on watch glass 2 from Zoolithen Cave,
because the types precipitated separately from each other.
Crystals of morphology type A are found only on watch
glasses placed in limestone caves, whilst the types B, D, E
and F occurred only on watch glasses located in dolostone
caves. Type C crystals are observed both in limestone and
dolostone caves (Table 3).
Type A (Fig. 2A): Calcite crystals of this type show only
the rhombohedron {104} with well-developed smooth
faces (crystal size: 250 lm). This type (Fig. 3CD and
Table 3) occurred only under low mean drip water Mg/
Ca ratio (0.0130.11; Fig. 5). The calcite Mg/Ca ratio is a
mixture of type A and C with type C being the dominant
one. Thus, the Mg/Ca ratio of this mixture ranges from
0.0003 to 0.0022 with a mean value of 0.0013 (Fig. 2A
and Table 3).
Type B (Fig. 2B): This type is characterised by a combi-
nation of the two rhombohedra {104} and {012} (crystal
size: 5280 lm). The at {104} rhombohedron again has
smooth faces, whilst the steeper {012} rhombohedron
shows macrosteps on the faces. The form {104} is best
developed in crystals precipitated on watch glass GP 6,
whilst these faces are poorly developed on crystals from
other watch glasses with higher uid Mg/Ca ratios
(Figs. 3E and 5 and Table 3). The Mg/Ca ratio of this type
is a mixture of types B and F with type F being the domi-
nant one.
Type C (Fig. 2C): The crystals show a combination of the
{104} rhombohedron with smooth faces and the steep
{031} rhombohedron with stepped faces (crystal size: 10
200 lm). On watch glass 5, only a few single crystals (23)
of that type are present (Fig. 4D). The main dierence
between crystals of type C from dierent watch glasses is
their elongation along [001]. Crystals precipitated on watch
glass GC 5 (Grotte Prison de Chien) with higher calcite Mg/
Ca ratios seem to be more elongated (Figs. 3H and 5 and
Table 3) than crystals precipitated on watch glasses with
lower calcite Mg/Ca ratios (Figs. 3G and 5 and Table 3).
In contrast, single type Ccrystals precipitated on watch glass
GP 6 (Grotte de Piste) appear less elongated (Fig. 4A) com-
pared to Bunker and Clos ani Cave crystals (Fig. 3D, FG).
The Mg/Ca ratio of type C ranges between 0.0003 and
0.0105 witha mean value of 0.0031 and thus, represents lower
ratios compared to types D, E and B/F (Fig. 2).
Table 2
Water chemistry data of the drip sites feeding watch glasses. Number of samples used for statistics varies between 6 and 58.
Cave Watch
glass/Drip
site
Mg/Ca water
[molar]
SI
cc
SI
ar
pH Drip rate
[ml/min]
Monitoring
period
Data partly
published in
Bunker Cave U I/TS 1 0.06 0.01 0.68 0.11 0.53 0.11 8.08 0.15 3.85 4.53 20062013 Riechelmann et al.
(2011, 2012a, 2013),
Mu nsterer et al.
(2012)
U IV/TS 8 0.11 0.01 0.33 0.16 0.18 0.16 8.02 0.12 0.002 0.001 20072013 Riechelmann et al.
(2011, 2012a, 2012b,
2013)
U VIII/TS
6
0.08 0.02 0.35 0.14 0.19 0.14 7.76 0.18 0.10 0.09 20062010 Riechelmann et al.
(2011), Mu nsterer
et al. (2012)
Zoolithen Cave 1 0.97 0.08 0.94
a
0.78
a
7.998.01
b
2.68 4.59 20102013
2 1.33 0.08 0.87
a
0.71
a
8.01
a
0.05 0.02 20102013
Kleine Teufels Cave 4 0.91 0.13 0.740.83
b
0.590.68
b
8.088.41
b
1.46 1.69 20102013
5 0.69 0.07 0.88
a
0.72
a
8.26
a
0.35 0.28 20102013
6 1.02 0.13 0.911.03
b
0.760.87
b
8.188.22
b
2.92 2.62 20102013
Grotte Bab
Mafraque
BM 8 1.05 0.09 0.80 0.10 0.65 0.10 8.44 0.13 0.09 0.03 20102012
BM 12 1.301.61
b
0.690.72
b
0.540.57
b
8.468.56
b
0.040.07
b
20102012
Grotte Prison de
Chien
GC 5 0.43 0.02 0.81 0.13 0.66 0.13 7.97 0.12 1.28 0.48 20092012
Grotte de Piste GP 6 0.65 0.08 0.67 0.21 0.53 0.21 8.06 0.25 0.14 0.14 20102012
GP 13 4.37 1.40 0.29 0.19 0.14 0.18 8.44 0.15 0.03 0.02 20102012
GP 14 3.44 1.04 0.56 0.16 0.41 0.16 8.50 0.05 0.07 0.06 20102012 Wassenburg et al.
(2013)
Clos ani Cave CC 1 0.013 0.001 0.54 0.16 0.38 0.16 7.69 0.18 0.42 0.42 20102012
CL 1 0.013 0.001 0.54 0.20 0.39 0.20 7.68 0.18 3.82 3.55 20102012
CL 3 0.014 0.001 0.67 0.23 0.52 0.24 7.81 0.21 2.74 1.54 20102012
a
Only one data point exists.
b
Only two samples exist and both values are given.
S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329 17
Type D (Fig. 2D): The form of type D crystals consist of
the rhombohedron {011} or {021}, the pinacoid {001}
and the rhombohedron {104} ordered according to mor-
phological rank (crystal size: 10340 lm). Similar to the
cases of types A to C, also here {104} usually shows
smooth faces, whereas the other faces are generally
macro-stepped. The crystals possess an elongated habit
along [001], but also aggregates composed of multiple crys-
tallites (i.e., the smallest building block of a composite
crystal; Kendall and Broughton, 1978; Frisia and
Borsato, 2010) or sub-crystals are not uncommon
(Fig. 4CE). The faces of the dominant {011} or {021}
rhombohedron of crystals precipitated on watch glasses 5
and 6 (Fig. 4DE) are more stepped compared to the corre-
sponding faces of crystals on watch glass 2 (Fig. 4C). Fur-
thermore, on watch glass 2 the {104} rhombohedra of the
crystals are smaller compared to crystals precipitated on
watch glasses 5 and 6. This corresponds with higher Mg/
Ca ratios of watch glass 2 precipitates compared to precip-
itates of watch glasses 5 and 6 (Fig. 5). The Mg/Ca ratio of
type D is between 0.008 and 0.029 with a mean value of
0.019 (Fig. 2D).
Type E (Fig. 2E): These crystals with usually elongated
habit along [001] are dominated by a steep rhombohedron,
probably {011} or {021}, capped by the pinacoid {001}
(crystal size: 30250 lm). All faces are very rough, i.e., most
crystals probably represent aggregates of intergrown crys-
tallites (Fig. 4F and Table 3). The Mg/Ca ratio of this type
ranges from 0.011 to 0.014 with a mean value of 0.013 and
thus, lies within the range observed for type D and B/F
crystals (Fig. 2).
Type F (Fig. 2F): Morphology type F (rhombohedron
{012}; Table 3) resembles type B but with bended faces
and edges (crystal size: 5280 lm). Additionally, the faces
are not smooth, but show steps (Fig. 4G). Several of the
rhombohedra that precipitated on watch glasses BM 8
and BM 12 display crystal intergrowth (Fig. 4H). The
Mg/Ca ratios measured represent a mixture of crystals
belonging to types B and F with type F being the dominant
type. They range from 0.008 to 0.051 with a mean value of
0.019 and therefore, overlap with Mg/Ca ratio of types C,
D and E (Fig. 2). Nevertheless, the highest calcite Mg/Ca
ratios are found for this type (Figs. 2 and 5).
An important observation is that no seasonal variation
in calcite crystal morphology or size was observed on watch
glasses from all caves. As could be expected, most growth
rates are highly variable over the year and only in rare
cases, growth rates were found to be more or less constant
(Table 3). Furthermore, calcite crystals precipitated on drip
counter surfaces, plastic slabs or a cotton coated sand sack
in Bunker Cave have similar dimensions and belong to the
same morphology type as those on the corresponding watch
glasses (type C; Fig. 2C; cf. Riechelmann, 2010).
Watch glass U VIII (Bunker Cave) remained stationary
beneath the corresponding drip for the duration of one
year. Here, with time, an increasingly thick layer of calcite
crystals precipitated mimicking the surface of a stalagmite
(Fig. 4B). Crystals in the centre of the watch glass are
attened due to low water lm thickness (Fig. 4BI). In
contrast, crystals at the outer margins of the watch glasses
(Fig. 4BII) are well developed (morphology types A
and C).
4. INTERPRETATION AND DISCUSSION
4.1. Inuence of drip water chemistry and drip rate on
carbonate mineralogy
Cave drip waters analysed in the context of this study
are characterised by elevated Mg/Ca ratios with the excep-
tion of those from limestone caves (Table 2 and Fig. 1).
Therefore, the Mg/Ca ratio of drip waters is mostly con-
trolled by the hostrock lithology (Fig. 1). It thus seems no
surprise that aragonitic mineralogy is absent on watch
glasses placed in limestone caves in contrast to such located
in dolostone caves. This is because enhanced amounts of
Mg
2+
in the water inhibit the nucleation and growth of cal-
cite due to (i) Mg
2+
incorporation into the crystal lattice,
(ii) adsorption of hydrated Mg
2+
on calcite crystal surfaces,
and (iii) a template eect (Astilleros et al., 2010). There-
fore, aragonite precipitation is kinetically favoured (Fig. 1;
e.g., Kitano et al., 1969; Fu chtbauer and Richter, 1975;
Fernandez-D az et al., 1996; Davis et al., 2000; Astilleros
et al., 2010; Frisia and Borsato, 2010; Fairchild and
Baker, 2012; Wassenburg et al., 2012).
Fig. 1. Environmental factors of the drip water sites, which are
subdivided into drip sites located in limestone caves and dolostone
caves. Furthermore, the mineralogy of the precipitates is indicated.
(A) Mean Mg/Ca ratios plotted against mean drip rate of the drip
sites. (B) Mean Mg/Ca ratios plotted against mean pH of the drip
sites.
18 S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329
Despite high uid Mg/Ca ratios of >0.4 (Table 2 and
Fig. 1), no aragonite precipitated on three watch glasses
from caves with dolostone hostrock. Thus, additional fac-
tors are signicant for aragonite precipitation as well.
One of these factors is the availability of CO
3
2
, thus, the
uid pH (Given and Wilkinson, 1985). Below a uid pH
of 8.2, the amount of CO
3
2
tends to zero, while above this
pH level the amount is increasing and HCO
3

and CO
3
2
coexist. Above a uid pH of 10.3, CO
3
2
becomes the dom-
inant species (e.g., Bo gli, 1978; Appelo and Postma, 2005).
Kim et al. (2006) reported aragonite precipitation at pH
values of 8.2 and 10.8 (uid Mg/Ca ratios: 4). Two of the
three drip sites mentioned above are characterised by a uid
pH of 7.97 and 8.01, which is insucient for aragonite pre-
cipitation (Fig. 1B). The third drip site, in contrast, is char-
acterised by uids having mean pH of 8.44 0.13 (Fig. 1B),
a value that is a priori favourable for aragonite precipita-
tion. In this case, an elevated saturation index for calcite
(0.80 0.10) inhibits aragonite nucleation (Table 2; BM
8). A series of previous studies proposed that aragonite pre-
cipitation is favoured when the supersaturation of the uid
with respect to calcite is low for high Mg/Ca ratios (e.g.,
Fu chtbauer and Hardie, 1980; Fernandez-D az et al.,
1996; De Choudens-Sanchez and Gonzalez, 2009; Frisia
and Borsato, 2010).
Watch glasses recording seasonal aragonite and annual
calcite precipitation display a clear pattern regarding drip
water chemistry and drip rate. This was observed for three
watch glasses, which show aragonite precipitation at high
uid Mg/Ca ratios (0.561.23) and high pH values (8.26
8.48), although SI
cc
display high values at times (0.471).
In contrast, at similar Mg/Ca ratios (0.590.99) and low
pH values (7.778.08), no aragonite precipitates occurred.
Thus, pH is the dominant factor in this case. Variations
in pH are best explained by the supply of CO
2
to the karst
water, which depends on the vegetation density, and the
process of prior calcite/aragonite precipitation causing
enhanced uid Mg/Ca ratios, enhanced pH and lower sat-
uration indices. This process is most probably the reason
why the uid Mg/Ca ratio and pH correlate positively
(Fig. 1B). The term prior calcite/aragonite precipitation
refers to precipitation of carbonates from soil, aquifer or
cave drip water prior to reaching the top of the stalagmite
under study and is usually enhanced under drier (arid) con-
ditions (e.g., Fairchild et al., 2006; Stoll et al., 2012;
Wassenburg et al., 2013). Slow drip rates and aragonite pre-
cipitation may indicate arid conditions in speleothems
formed in caves developed in dolomite, where there is
incongruent dissolution and prolonged water/rock interac-
tion (Railsback et al., 1994; Fairchild et al., 2006; Frisia and
Borsato, 2010; Stoll et al., 2012; Wassenburg et al., 2012,
2013). The majority of the drip water sites investigated in
the context of this study displays dierent lines of evidence
for prior calcite/aragonite precipitation (Riechelmann
et al., 2011; Wassenburg et al., 2013). Drip rates of sites
with only seasonal aragonite precipitation are slow during
these times (>00.23 ml/min) and thus, point to enhanced
prior calcite/aragonite precipitation.
Fig. 2. Types of calcite crystal morphologies precipitating on the watch glasses illustrated with Kristall2000 (Klaus Schilling) and their
respective Mg/Ca ratios. Miller indices refer to the trigonal-hexagonal setting of calcite with lattice constants a = 4.99 A

and c = 17.06 A

. The
observed forms are the rhombohedra {104}, {012}, {011}, {021} and {031} and the base pinacoid {001}. From the cleavage
rhombohedron {104} to the steepest observed rhombohedron {031} the angle between the normals of rhombohedron faces and the 3-fold
symmetry axis increase from 44.6 to 85.2. The range as well as the mean value of the Mg/Ca ratios of the dierent morphology types is given
with their numbers used for statistics.
*
Mixture of type A and C measured (Bunker and Clos ani Cave) with type C being the dominant one,
but type A is only occurring on these watch glasses.
#
Mixture of morphology types B and F with type F being the dominant one.
S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329 19
One of these three above mentioned drip sites records
the highest amount of aragonite, a feature that is arguably
related to elevated uid pH (max. 8.48) relative to the other
two drip sites (8.25, 8.26; Given and Wilkinson, 1985) or to
elevated temperatures in this cave of 12.3 C 0.4 com-
pared to the other cave with an annual temperature of
9.1 C 0.5 (Table 1; e.g., Kitano et al., 1969; Burton
and Walter, 1987; De Choudens-Sanchez and Gonzalez,
2009). However, in the present study, aragonite precipitated
both at lower (min. 8.5 C 0.4) and higher cave air tem-
peratures (max. 12.5 C 0.1). Earlier ndings that tem-
perature is a sole factor leading to aragonite precipitation
(e.g., Burton and Walter, 1987) have thus not been con-
rmed. However, it cannot be excluded completely either
as the observed temperature range may not have been large
enough.
At times of aragonite and calcite precipitation, the growth
rate of calcite on one watch glass is slower (on average
Fig. 3. SEM images of carbonate crystal precipitates of morphology types A to C and aragonite. (A) Single aragonite crystals from Kleine
Teufels Cave (4). (B) Aragonite crystals forming fan-like arrays from Grotte Bab Mafraque (BM 12). (C) Calcite crystal morphology type A
from Bunker Cave (U I); (D) Calcite crystal morphology type A from Clos ani Cave indicated by arrows (CL 3). (E) Calcite crystal
morphology type B from Grotte de Piste (GP 6). Note indication of smooth crystal faces by arrows. (FG) Calcite crystal morphology type C
from Bunker Cave (U IV). (H) Calcite crystal morphology type C from Grotte Prison de Chien (GC 5).
20 S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329
42 lm/a) compared to times when only calcite precipitates
(on average 75 lm/a). Possibly, this occurs because the
presence of Mg
2+
in the uid inhibits the growth and nucle-
ation of calcite crystals and thus, aragonite precipitated,
particularly at high Mg/Ca ratios of the drip water (e.g.,
Fu chtbauer and Hardie, 1980; Fernandez-D az et al.,
1996; Davis et al., 2000; Astilleros et al., 2010; Fairchild
and Baker, 2012).
The reason for aragonite precipitation on two out of 17
watch glasses is at present dicult to constrain, because the
uid chemistry as well as drip rates are not favourable for
aragonite precipitation. Given the time interval of three
months between two sampling trips, it is possible that the
uid chemistry as well as the drip rate changed to a degree
that would allow aragonite precipitation during this time
interval. Another interpretation is that the presence of spe-
cic organic macromolecules may act as templates for ara-
gonite precipitation by lowering the Gibbs free energy of
nucleation (Hou and Feng, 2005). Both these watch glasses
display organic compounds, which occurred contempora-
neous to aragonite precipitates. Thus, aragonite precipita-
tion may be triggered by organics in these cases (Hou and
Feng, 2005). The organic compounds found here do not
seem to inhibit aragonite precipitation as suggested for
other organic compounds (e.g., Kitano et al., 1969;
Meldrum and Hyde, 2001; Niedermayr et al., 2013). On
the contrary aragonite, usually characterised by fan-like
crystals, may have been forced into a bundle of elongated
crystals under the inuence of organic matter (Fig. 6A).
Aragonite and calcite coexist on two out of 17 watch
glasses, whose drip sites are characterised by exceptionally
elevated drip water Mg/Ca ratios (1.302.39), high uid
pH (8.448.57) and slow drip rates (>00.20 ml/min)
throughout the year. Interestingly, at one of these two sites
aragonite and calcite coexisted on one watch glass during
spring as the uid Mg/Ca ratio was lower (1.612.39) and
the drip rate was faster (0.10.2 ml/min) compared to the
rest of the year (Mg/Ca: 3.544.42; drip rate: 00.09 ml/
min;), when only aragonite precipitated. Less arid condi-
tions typify the winter and early spring season, reducing
prior calcite/aragonite precipitation and thus, drip water
geochemistry was altered (Wassenburg et al., 2013). Hence,
calcite as well as aragonite co-precipitated.
On the watch glass belonging to the highest drip water
Mg/Ca ratio (Fig. 1) aragonite is the only carbonate phase
precipitated. The main reason arguably include the uncom-
monly high uid Mg/Ca ratio (2.867.79) and the elevated
uid pH (8.368.60) combined with slow drip rates (0
0.06 ml/min). According to De Choudens-Sanchez and
Gonzalez (2009), aragonite is the only mineral phase precip-
itating at high Mg/Ca ratios (>2) and low SI
cc,
. The two
drip sites with the highest uid Mg/Ca ratios (Fig. 1) are
also characterised by very low uid SI
cc
and SI
ar
. This fea-
ture preferentially favours aragonite precipitation. The
main reason for these low saturation indices lies arguably
in substantial prior calcite/aragonite precipitation causing
a decrease of uid supersaturation (Wassenburg et al.,
2013). The presence of sometimes elongated organic objects
(Fig. 6D) on the watch glass with only aragonite precipita-
tion (Fig. 1) seems to inhibit the precipitation of aragonite
in this case. Instead spherulite calcite crystals precipitated
(Fig. 6D). These greatly resemble crystals precipitated
Table 3
Mineralogy, type of calcite crystal morphology, range of calcite growth rates, range of crystal size and Mg/Ca ratio of calcite crystals for the
watch glass precipitates. Number of samples used for statistics varies between 3 and 22. Dominant morphology type is highlighted as bold
font.
Cave Watch glass/
Drip site
Mineral
phases
Types of
observed calcite
morphology
Range of observed
calcite growth
rate [lm/a]
Range of crystal
size [lm]
Mg/Ca calcite
[molar]
Bunker Cave U I/TS 1 Cc A, C 256 A: 220; C: 20200 0.0012 0.0001
U IV/TS 8 Cc A, C 511 A: 220; C: 20201 0.0020 0.0001
U VIII/TS 6 Cc A, C 66
a
A: 220; C: 20202 0.0018
a
Zoolithen Cave 1 Cc, Ar E 0.3329 E: 30250 0.013 0.001
2 Cc B, D, F 953 B/F: 5100; D: 20150 0.024 0.002 /
0.034
a
;
c
Kleine Teufels Cave 4 Cc, Ar B, F 0.151 B/F: 30280 0.016 0.001
5 Cc, Ar C, D 0.3144 C: 1030; D: 10120 0.010 0.002
6 Cc, Ar D 143 D: 10340 0.015 0.003
Grotte Bab Mafraque BM 8 Cc B, F 131 B/F: 20150 0.022 0.001
BM 12 Cc, Ar B, F 27 B/F: 1070 0.0240.027
b
Grotte Prison de Chien GC 5 Cc C 0.1131 C: 10200 0.010 0.001
Grotte de Piste GP 6 Cc, Ar B, C, F 1783 B/F: 1070; C: 30125 0.009 0.002
GP 13 Ar / / / /
GP 14 Cc, Ar F 3
a
F: 1050 0.051
a
Clos ani Cave CC 1 Cc A, C / A: 550; 20200 0.0003
a
CL 1 Cc A, C / A: 550; 20201 0.0004
a
CL 3 Cc A, C / A: 550; 20202 0.0003
a
a
Only one data point exists.
b
Only two samples exist.
c
Calcite morphology type D and F measured.
S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329 21
during laboratory experiments using dierent organic com-
pounds (e.g., Kitano et al., 1969; Meldrum and Hyde, 2001;
Niedermayr et al., 2013).
In summary, aragonite precipitation is favoured under
high uid Mg/Ca ratios (P0.5), high uid pH (>8.2), low
SI
cc
(<0.8) and slow drip rates (<0.2 ml/min). More arid
climate conditions lead to enhanced uid Mg/Ca ratios,
uid pH and lowered saturation indices, features related
to prior calcite/aragonite precipitation. Interestingly, all
of these factors must act in a concerted manner. If not cal-
cite is the dominant crystalline phase. Temperature may
also be a factor triggering aragonite precipitation, how-
ever, the present data set of this study allows no clear
statement. In addition, the uid Mg/Ca ratio at which
only aragonite precipitates is in the order of 2.4. On the
one hand, the occurrence of amorphous organic com-
pounds induces aragonite precipitation, whilst on the
other hand the presence of sometimes elongated organic
Fig. 4. SEM images of carbonate crystal precipitates of morphology types C to F. (A) Calcite crystal morphology type C from Grotte de Piste
(GP 6). (B) Calcite crystal morphology type C from Bunker Cave. Crystals in centre (BI) and crystals at the outer margins of the watch glass U
VIII (BII). (C) Calcite crystal morphology type D from Zoolithen Cave (2) composed of multiple crystallites or sub-crystals. (DE) Calcite
crystal morphology type D from Kleine Teufels Cave as well as a crystal belonging to type C (white arrow). Onset of formation of a new
crystal face is indicated by a white arrow. (F) Calcite crystal morphology type E from Zoolithen Cave (1). (G) Calcite crystal morphology type
F from Kleine Teufels Cave (4). (H) Calcite crystal morphology type F from Grotte Bab Mafraque (BM 8).
22 S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329
objects inhibits aragonite precipitation and thus, forces
calcite precipitation.
4.2. Inuence of drip site and uid characteristics on calcite
crystal morphologies
In the context of this study, increasing Mg/Ca ratios of
calcite crystals are found at drip sites with increased Mg/Ca
ratios of the respective drip waters (r = 0.93, p = 0, n = 54).
This nding is in agreement with previous work (e.g.,
Fu chtbauer and Hardie, 1980; Mucci and Morse, 1983;
De Choudens-Sanchez and Gonzalez, 2009). Increasing
calcite Mg/Ca ratios are accompanied by characteristic
changes of the calcite crystal morphology (e.g., Folk,
1974; Fu chtbauer and Hardie, 1980; Zhang and Dawe,
2000; Meldrum and Hyde, 2001; Loste et al., 2003; De
Choudens-Sanchez and Gonzalez, 2009).
Type A crystal morphology (Figs. 2A and 3CD) is
characterised by the at {104} rhombohedron precipitated
only on watch glasses in limestone caves. There, drip waters
have low Mg/Ca ratios and thus, only small amounts of
Mg
2+
are incorporated (Tables 2 and 3 and Figs. 2 and
5). Similar observations were reported by Folk (1974),
Fu chtbauer and Richter (1975) and Fu chtbauer and
Fig. 5. The Mg/Ca ratio of drip water plotted against the Mg/Ca ratio of calcite of the respective watch glass. Dierent morphology types are
marked.
Fig. 6. SEM images of watch glass precipitates with organic material (arrows). (A) Aragonite with organic compound forming aggregates
(GP 6; Grotte de Piste, Morocco). (B) Carbonate crystals with organic material forming aggregates (GP 6; Grotte de Piste, Morocco). (C)
Organic compounds with a main body and threads on watch glass U IV (Bunker Cave; Germany) showing no relation to crystal
morphology. (D) Elongated organic material on watch glass GP 13 (Grotte de Piste; Morocco) and calcite precipitates with a spherical habit.
S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329 23
Hardie (1980). The dominant type C calcite crystals on
these watch glasses formed due to enhanced incorporation
of Mg
2+
into the crystal lattice of type A crystals, which
is proved by the growth of additional crystal faces, the
steep {031} rhombohedron at the edges and corners of
the {104} rhombohedra (Figs. 3C, 2 and 5; Folk, 1974;
Zhang and Dawe, 2000).
Furthermore, the enhanced incorporation of Mg
2+
into
the crystal lattice is reected by the crystal habit of type C.
This is exemplied by crystals on watch glass GC 5 with
higher calcite Mg/Ca ratios (Figs. 3H and 5) that are more
elongated than those on the other watch glasses showing
type C, which have lower calcite Mg/Ca ratios (Figs. 3D,
FG and 5). The reason for the elongation is that faces with
a higher Mg
2+
density (rough faces; higher density of
defects) grow slower and thus, are larger compared to crys-
tal faces with faster growth rates (e.g., Kleber, 1998; Davis
et al., 2000; Jimenez-Lopez et al., 2003; De Choudens-
Sanchez and Gonzalez, 2009; Astilleros et al., 2010). Conse-
quently, this leads to an elongation along [001] (e.g., Folk,
1974; Fernandez-D az et al., 1996; Meldrum and Hyde,
2001; Loste et al., 2003; Davis et al., 2004; Fairchild and
Baker, 2012).
The development of new faces at the edges of type C
crystals is observed on watch glass 5 (Kleine Teufels Cave;
Fig. 4D). Morphology type C (crystal size: 1030 lm) most
likely changes over to type D (crystal size: 10120 lm) in
the case of crystals precipitated on watch glass 5. The con-
nection of type B (crystal size: 1070 lm) and C (crystal
size: 30125 lm) in the case of watch glass GP 6 (Grotte
de Piste) is unclear at the moment. Since crystals of type
C are bigger in size compared to type B crystals, type C can-
not develop into type B, but more likely the other way
around. Interestingly, crystals on watch glasses 5 and GP
6 incorporated the same amount of Mg
2+
as those on watch
glass GC 5 (type C; Grotte Prison de Chien), despite the
fact that the Mg/Ca ratios of waters are higher (Tables 2
and 3 and Fig. 5). From this it is concluded that drip water
Mg/Ca ratios are not the sole parameter inuencing crystal
morphology. The patterns observed are arguably induced
by higher growth rates (Table 3) on watch glasses 5 and
GP 6 (average values are 61 and 59 lm/a) compared to
those of crystals on watch glass GC 5 (on average 35 lm/
a). This interpretation seems likely as growth rates have a
similar inuence on calcite crystal morphology as Mg
2+
incorporation (e.g., Fernandez-D az et al., 1996; Davis
et al., 2004; De Choudens-Sanchez and Gonzalez, 2009).
However, growth rates are overlapping and are not abso-
lutely accurate for watch glass GC 5 precipitates, hence,
this assumption remains a hypothesis.
Crystals of type D show clearly higher Mg/Ca ratios
than type C crystals (Fig. 2). This increased incorporation
of Mg
2+
into the crystal lattice leads to a reconstitution
of the {104} rhombohedron with smooth faces, which is
because the rough faces with higher Mg
2+
density of the
steep {011} or {021} rhombohedra grow preferentially
(e.g., Kleber, 1998; Davis et al., 2000; Jimenez-Lopez
et al., 2003; De Choudens-Sanchez and Gonzalez, 2009;
Astilleros et al., 2010). Examples for this behaviour are
found on watch glass 2 (Fig. 4C). The ongoing reconstitution
of the at rhombohedron (smooth faces) might lead to mor-
phology type E (Fig. 2DE). The mean Mg/Ca ratio of
0.013 0.001 as found for type E crystals lies within the
range of type D crystals (0.010.024; Table 3 and Figs. 2
and 5). A possible reason for the development of morphol-
ogy type E might be the highly variable growth rate of these
precipitates (0.3329 lm/a) in comparison to the high,
albeit less variable, growth rates of type D crystals (0.3
144 lm/a).
Furthermore, aggregates composed of multiple crystal-
lites or sub-crystals are exclusively present for type D and
E crystals. Aggregates form under enhanced values of
Mg/Ca ratios, growth rates and organic compounds in
the drip water, respectively (e.g., Folk, 1974; Fu chtbauer
and Richter, 1975; Fernandez-D az et al., 1996; Gonzalez-
Mun oz et al., 2000; Meldrum and Hyde, 2001; Loste
et al., 2003; Bosak and Newman, 2005). Cave environments
as all natural systems are exposed to organic material
including fungi, microbial biolms and non-living organic
compounds (e.g., Barton et al., 2001; Contos et al., 2001;
Cacchio et al., 2004; Nieves-Rivera et al., 2009; Frisia and
Borsato, 2010) and similar types of calcite crystal morphol-
ogies to that of laboratory work using dierent organic
compounds were observed in natural systems (Cacchio
et al., 2004; Cuezva et al., 2009). In the case dealt with here,
it can be assumed that organic compounds may have a lar-
ger impact on the formation of aggregated crystals than the
incorporation of Mg
2+
and the growth rate. This is because
no other aggregates at similar Mg
2+
incorporation or
growth rates could be observed. Furthermore, signicant
amounts of organic material were detected in a stalagmite
from Zoolithen Cave under uorescence microscopy
(Wurth, 2002). Here, organic matter was observed under
the SEM on several watch glasses. It must be kept in mind
that watch glasses were neither placed nor sampled under
sterile conditions and thus, living and non-living organic
matter may include such derived from drip waters, from
the cave air (aerosols) or represent an artefact due to
non-sterile handling of watch glasses. A classication of
the type of organic matter (microbial, fungal, non-living
organic compounds) is beyond the scope of this study. An
example for organic matter is present on watch glass GP
6 (Grotte de Piste), where crystals with amorphous organic
compounds are associated with the formation of crystal
aggregates (Fig. 6A and B). Organic matter, however, with
a main body and threads (Fig. 6C) perhaps best
assigned to fungal organisms does not notably aect the
morphology of crystals on watch glasses from Bunker Cave
(Riechelmann, 2010).
A striking observation is that crystals of type B and F
coexist on watch glasses GP 6 (Grotte de Piste), 4 (Kleine
Teufels Cave), BM 8, BM 12 (Grotte Bab Mafraque) and
2 (Zoolithen Cave). The {104} rhombohedron of type B
is best developed on crystals of watch glass GP 6
(Fig. 3E). Nevertheless, these crystals display a reconstitu-
tion of {104} and in some cases, their faces are very small
and are characterised by curved edges. The increase of the
Mg/Ca ratio of drip water leads to increasing Mg
2+
incor-
poration and {104} gradually disappears (Figs. 2 and 5).
On watch glass GP 14 (Grotte de Piste) calcite crystals show
24 S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329
the highest Mg/Ca ratios (0.51) and there, type B cannot be
found anymore (Figs. 2 and 5). The rounded morphology
of type F occurs due to higher incorporation of Mg
2+
as
it is suggested in literature (e.g., Fu chtbauer and Richter,
1975; Fu chtbauer and Hardie, 1980; Fernandez-D az
et al., 1996; Meldrum and Hyde, 2001; Loste et al., 2003)
and display some similarities with saddle dolomites
(Fu chtbauer and Richter, 1988). Crystals of type F display,
in comparison to other calcites studied here, higher incor-
poration of Mg
2+
at lower Mg/Ca ratios of the drip water
(Fig. 5). A particular case is found on watch glass 2 (Zooli-
then Cave) characterised predominantly by type F crystals.
Here, clusters of type F crystals precipitated from the resid-
ual uid on the watch glass. Given that the residual uid is
enriched in Mg
2+
this observation is considered evidence
that type F crystal morphology forms under high Mg/Ca
ratios of the water (Fig. 5).
In summary, the formation of steeper rhombohedra,
such as {012} to {031}, and the development of the base
pinacoid {001} are favoured with increasing Mg/Ca ratio
of the drip water. As a consequence, the crystal habit
changes from near-isometric to strongly elongated along
the threefold axis (Fig. 2CE). At high Mg/Ca ratios,
rounded crystals with bended edges and faces form. Fur-
thermore, it seems that some organic compounds inuence
crystal morphologies, whilst we found no relation between
organic material, perhaps fungi, with a main body and
threads and crystallography.
4.3. Distribution coecient (D
Mg
) of calcite
Parameters aecting D
Mg
calcite include temperature
(e.g., Oomori et al., 1987; Huang and Fairchild, 2001;
Day and Henderson, 2013), uid Mg/Ca ratio (Mucci and
Morse, 1983; De Choudens-Sanchez and Gonzalez, 2009)
and crystal surface structure (Paquette and Reeder, 1995).
Cave air temperatures are generally constant throughout
the year. Therefore, under similar exterior climate condi-
tions and within the same cave, the Mg-content of speleo-
them calcite is not depending on temperature.
Furthermore, cave drip water has very low salinity and
ionic strength; therefore, these factors will not play a role
either (Fairchild and Baker, 2012). However, rough crystal
surfaces are associated with higher Mg densities (e.g.,
Fernandez-D az et al., 1996; Meldrum and Hyde, 2001).
As such, it should be expected that crystals with mainly
rough surfaces will have a higher D
Mg
compared to their
smooth counterparts. However, in contrast to laboratory
controlled precipitation experiments, cave drip water chem-
istry and precipitates can only be monitored with limited
resolution (in this study monthly up to 3 monthly).
In order to derive the partition coecient D
Mg
all Mg/
Ca ratios of the measured calcite precipitates are plotted
against the Mg/Ca ratios of the corresponding drip waters,
including analytical errors or standard deviation of repli-
cate (Fig. 7). In general, the slope of a trend line through
a set of data from the same cave array and the same crystal
type can be regarded as D
Mg
or to be more precise as the
apparent D
Mg.
The trace element partition into calcite is a
Raleigh fractionation process, where the apparent D
Mg
is
increasing with the percentage of precipitated calcite from
a dened droplet, as depicted in the sketch in Fig. 7. Unfor-
tunately, not all data are available to calculate precipitation
rates for each watch glass and cave setting, and hence, to
correct for dierent precipitation rates. In consequence,
the lowest slope is the calculated apparent D
Mg
which is
closest to the D
Mg
for the data set. Due to pronounced var-
iance in the data set all available data were used for a t to
Fig. 7. Mg/Ca ratios of calcite samples plotted against all available drip water ratios recorded during the specic precipitation phase. Number
of plotted data is higher than in Fig. 5, where mean values for drip water ratios are used. Sketch in the lower right corner shows inuence of
precipitation rate on D calculated from Mg/Ca ratios from drip water and calcite. The slope of the grey line indicates the potentially
lowermost apparent D
Mg
for the depicted data set.
S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329 25
estimate the overall apparent D
Mg
(0.0178 0.0005). This
value corresponds to a general D
Mg
reported from other
studies (e.g., Oomori et al., 1987; Railsback, 1999; Huang
and Fairchild, 2001; Fairchild et al., 2010).
A correction for the dierent cave air temperatures can
be calculated following the relationship between D
Mg
and
cave temperature (D
Mg
= 0.01e
0.02[0.006]T
; Day and
Henderson, 2013). For the reported data set with cave tem-
peratures between 8.5 and 14.3 C this correction is within
the error of the t.
4.4. Implications for speleothem-based climate
reconstructions
Previous studies suggested that dierent crystal fabrics
in speleothems form due to specic drip rates, calcite sat-
uration degree of the drip uids (SI), their Mg/Ca ratios
and pH as well as the presence or absence and probably
the type of organic matter (Kendall and Broughton,
1978; Gonzalez et al., 1992; Frisia et al., 2000, 2002;
Fairchild et al., 2007; Frisia and Borsato, 2010). Calcite
saturation and drip rate control the growth rate of the
precipitate (e.g., Riechelmann et al., 2013). Applying these
concepts in a systematic and quantitative manner to a
wide range of dierent caves in several dierent climate
belts, the present study conrms that all of these factors
except uid pH, inuence calcite crystal morphologies
and thus, the crystal fabric. Conversely, uid pH is,
besides uid Mg/Ca ratio, SI
cc
and drip rate, the one cru-
cial factor for aragonite precipitation, which is controlled
by the degree of prior calcite/aragonite precipitation
(PCP/PAP) and supply of CO
2
(depending on vegetation
density) to the karst water. Thus, aragonite in speleothems
indicates palaeo pH conditions of 8.2 and above. Other
proxies such as Mg/Ca ratio and d
13
C have to be used
to identify the process controlling the pH of the drip water
forming aragonitic speleothems.
The main factor controlling changes of calcite crystal
morphology is the incorporation of Mg
2+
into the crystal
lattice. The availability of Mg
2+
in turn depends on the
uid Mg/Ca ratio. The Mg/Ca ratio of speleothems is
widely used for palaeoclimate reconstructions and its var-
iability is interpreted as a hydrological signal forced by
variable degrees in prior calcite precipitation (e.g.,
Fairchild and Treble, 2009; Fohlmeister et al., 2012).
Thus, the application of a multi-proxy approach to cave
archives including coupled crystal fabrics and Mg/Ca ratio
data has a high potential to improve palaeoclimate recon-
structions. Only few studies applied this dual approach
(e.g., Huang et al., 2001; Treble et al., 2005; Borsato
et al., 2007; Hopley et al., 2009; Fohlmeister et al.,
2012). The data shown here represent a clear advance in
our understanding on the parameters controlling specic
crystal fabrics and represent a solid foundation upon
which future research can be built on. The comparison
of recent speleothem crystal fabrics with recent crystal
morphologies of well studied cave drip sites seems to be
the next logical step as well as the research on organic
compounds and their inuence on mineralogy and calcite
crystal morphology.
5. CONCLUSIONS
Based on well constrained eld experiments performed
in seven caves the following main conclusions are drawn:
(1) The initial Mg/Ca ratio of drip water is mostly con-
trolled by the hostrock lithology. Higher Mg/Ca
ratios are only found in drip waters of caves charac-
terised by a hostrock containing dolomite. Thus, the
hostrock lithology indirectly controls the calcite crys-
tal morphology and carbonate mineralogy of the
speleothem.
(2) The precipitation of aragonite is favoured by (i) high
Mg/Ca ratios of the uid (P0.5), (ii) high pH values
(>8.2), (iii) low saturation indices for calcite
(SI
cc
<0.8) and (iv) slow drip rates. Slow drip rates
(<0.2 ml/min) can cause the precipitation of calcite/
aragonite prior to reaching the stalagmite top and
thus, drip water geochemistry is altered leading to
the above mentioned conditions. It is emphasised
that all four factors must act in a concerted manner,
otherwise calcite will precipitate. Precipitation of ara-
gonite may also be favoured by other factors such as
higher temperature. However, the data presented
here do not show a clear temperature dependency
of aragonite precipitation. Calcite nucleation and
growth is inhibited by high Mg/Ca ratios of the drip
water. Hence, under these conditions aragonite is
kinetically favoured over calcite. The threshold of
aragonite precipitation is at uid Mg/Ca ratios >2.4.
(3) Aragonite precipitation is possibly induced by some
types of organic compounds leading to the formation
of aggregates, whilst it is inhibited in other cases.
(4) Changes of calcite crystal morphologies on watch
glasses are predominantly controlled by increasing
incorporation of Mg
2+
into the crystal lattice under
increasing uid Mg/Ca ratios. Four distinctive mor-
phologic/crystallographic features are related to
increasing Mg
2+
incorporation: (i) development of
new forms (steeper rhombohedra and base pinacoid)
at the edges and corners of the crystal seed; (ii) crystal
habits tend to elongate along [001] due to the prefer-
ential growth of faces with high Mg
2+
densities; (iii)
reconstitution of crystal faces with low Mg
2+
densi-
ties and (iv) formation of calcite crystals with bended
faces and edges due to very high Mg
2+
incorporation.
(5) Whilst these results are largely comparable with inor-
ganic laboratory experiments, several important char-
acteristics of the eld experiments performed here shed
light on the complexity of natural systems. These
include (i) seasonal changes in drip rates and (ii) drip
water geochemistry resulting in dierential growth
rates, as well as (iii) the signicance of organic matter
directly aecting crystal morphologies in several cases.
ACKNOWLEDGEMENTS
This is a joint contribution of the collaborative research pro-
jects DAPHNE II (DFG Forschergruppe 668) and CHARON
26 S. Riechelmann et al. / Geochimica et Cosmochimica Acta 145 (2014) 1329
(DFG Forschergruppe 1644) both nanced by the German Science
Foundation (DFG) and the Karsthives Project funded by the
PCCE 31/2010 Grant. We are grateful to the Speleogroup
Letmathe for the permission to monitor Bunker Cave and
C. Kirchmann, M. Lyhs and T. Meyer are thanked for assisting
during the monitoring. The Forschungsgruppe Ho hle und Karst
Franken e.V. is thanked for the permission to monitor Zoolithen
and Kleine Teufels Cave. We would like to thank W. Zwick, M.
Harder and M. Conrad for their assistance during monitoring tours
in Zoolithen Cave and we thank A. and D. Preu for their help with
monitoring Kleine Teufels Cave. We acknowledge the support of
the Moroccan speleoguides H. El Mansouri and T. Echchibi during
cave monitoring in these logistically complex sites. We thank Dr.
R. Neuser for his work at the Scanning Electron Microscope and
Dr. D. Buhl, K. Schauerte and B. Gehnen are thanked for assis-
tance in calcite sample preparation and measurement with the
ICP-OES device. C. Scholz is thanked for assistance with drip
water analyses. Prof. H. Gies is thanked for his help with identify-
ing the calcite crystal morphologies. Our special thanks go to Dr.
Silvia Frisia (University of Newcastle, Australia) for her valuable
comments leading to a greatly improved version of this paper.
We greatly acknowledge the work of associate editor F. McDermott
and the very constructive comments by reviewers B. Railsback and
I. Fairchild.
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