Paleo Climate Reconstruction

ARTICLE IN PRESS
Quaternary Science Reviews 23 (2004) 901918
Palaeo-climate reconstruction from stable isotope variations in

speleothems: a review
Frank McDermott*
Department of Geology, University College Dublin, Belfield, Dublin 4, Ireland
Received 30 April 2003; accepted 13 June 2003
Abstract
Speleothems are now regarded as valuable archives of climatic conditions on the continents, offering a number of advantages
relative to other continental climate proxy recorders such as lake sediments and peat cores. They are ideal materials for precise
U-series dating, yielding ages in calendar years, thereby circumventing the radiocarbon calibration problems associated with most
other continental records. Stable isotope studies in speleothems have shifted away from attempting to provide palaeo-temperature
reconstructions to the attainable goal of providing precise estimates for the timing and duration of major O isotope-dened climatic
events characterised by high signal to noise ratios (e.g. glacial/interglacial transitions, DansgaardOeschger oscillations, the 8200year event). Unlike the marine records, speleothem data sets are not tuned, and their independent chronology offers opportunities
to critically assess leads and lags in the climate system, that in turn can provide important insights into forcing and feedback
mechanisms. Improved procedures for the extraction and measurement of stable isotope ratios in uid inclusions trapped in
speleothems are likely to provide, in the near future, a much enhanced basis for the quantitative interpretation of O isotope ratios in
speleothem calcite. The latter developments open up once again the tantalising prospect of palaeo-temperature estimates, but more
importantly perhaps, provide a direct test for a new generation of general circulation models whose hydrological cycles will
incorporate the water isotopes. The literature is reviewed briey to provide for the reader a sense of the current state-of-the-art, and
to provide some pointers for future research directions.
r 2004 Elsevier Ltd. All rights reserved.
1. Introduction
Increasingly there is a need for well-dated highresolution palaeo-climate records from continental
settings to test and validate general circulation models
(GCMs) at a higher spatial resolution, and to investigate
possible leads and lags between different components of
the climate system. Speleothems are multi-proxy palaeoclimate archives with the potential to provide such data.
In carefully chosen sites they can record key aspects of
climate variability such as mean annual temperature,
rainfall variability, atmospheric circulation changes and
vegetation response in a variety of measurable parameters that include stable isotope ratios, inter-annual
thickness variations of growth laminae, growth-rate
changes, variations in trace element ratios, organic acid
contents and the nature of trapped pollen grains. This
review focuses on the use of stable isotopes in
*Tel.: +353-1-706-2328; fax: +353-1-283-7733.
E-mail address: frank.mcdermott@ucd.ie (F. McDermott).
0277-3791/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.quascirev.2003.06.021
speleothems as palaeo-climatic indicators, and the

emphasis is on developments and data sets that have
been reported since previous reviews of the subject
(Schwarcz, 1986; Gascoyne, 1992). The focus is primarily on oxygen isotopes, but carbon isotopes are included
whenever they have contributed signicantly to palaeoclimatic interpretations. Several unresolved issues remain, but recently there have been important insights
into the interactions between component parts of the
system (e.g. marine sources, isotopic evolution in the
hydrological system and isotopic effects during inltration through the unsaturated zone) that now underpin
the interpretation of O isotopes in speleothems.
Systematic studies of stable isotopes in speleothems
commenced more than three decades ago (Hendy and
Wilson, 1968; Thompson et al., 1974), but progress was
hampered by the need for large samples (ca 10 g) for
alpha-spectrometric U-series dating. The development
of thermal ionisation mass-spectrometry (TIMS) techniques to measure U-series isotope ratios rejuvenated
the subject (Edwards et al., 1988; Li et al., 1989). TIMS
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F. McDermott / Quaternary Science Reviews 23 (2004) 901918
can provide 230Th/U dates that are almost 10 times more

precise than conventional alpha-spectrometry, with a
reduction in sample size by about the same magnitude.
Recently, a new generation of plasma-ionisation magnetic-sector mass spectrometers (PIMMS) characterised
by high ionisation efciency promise further improvements in sample size requirements and analytical
precision relative to TIMS (Shen et al., 2002). The latter
instruments offer vastly improved ionisation efciency
for thorium, and with further renement are likely to
become the method of choice, especially for lowuranium Holocene speleothems that contain relatively
little radiogenic 230Th. With these new technological
developments, speleothems offer advantages over many
other continental palaeo-climate records because they
can be dated in calendar years with a precision
approaching 70.5% (2s), circumventing radiocarbon
age calibration and reservoir correction problems that
hamper other continental climate archives such as lake
sediments and peat records. Indeed it is likely that
speleothem records will increasingly be used to rene the
chronology of the Greenland ice-core records, assuming
that regional synchroneity for the major early Holocene
and last glacial DansgaardOeschger (D/O) O isotope
shifts can be demonstrated (e.g. McDermott et al., 2001;
. and Mangini, 2002; Genty et al.,
Wang et al., 2001; Spotl
2003). It should be noted, however, that U-series dates
depend critically on the accuracy with which the mixed
229
Th/236U spikes have been calibrated with respect to
known secular equilibrium standards, and there is
currently a need to undertake systematic inter-laboratory comparisons to ensure that U-series dates produced
by different laboratories are directly comparable.
Stalagmite growth rates vary by at least two orders of
magnitude (typically in the range 0.011.0 mm/year),
depending on factors such as temperature and the
calcium ion concentration of the drip-waters (Baker
et al., 1998; Genty et al., 2001a, b). Thus, the time
interval represented by individual stable isotope measurements depends critically on the growth rate of the
speleothem chosen for analysis. Using conventional
sampling techniques (e.g. a dental drill to remove
0.5 mm samples), the time interval averaged by stable
isotope measurements would typically range from a few
years to several decades. The detection of short-lived
climatic events and the resolution of low-amplitude
climatic signals therefore require the use of rapidly
deposited speleothems, assuming that conventional
sampling and analytical techniques are employed. In
slowly deposited speleothems serious damping of the
isotope signal may occur, with the result that signicant
but short-lived climatic events (e.g. the 8200-year
cooling event) might not be detected (McDermott
et al., 2001).
A feature of stable isotope studies on speleothems
during the past decade has been efforts to improve the
spatial, and therefore the temporal resolution of

sampling for O and C isotope analyses. McDermott
et al. (2001) employed a laser-ablation gas-chromatography isotope ratio mass spectrometry (LA-GC-IRMS)
system with a 25 W CO2 laser to thermally release CO2
by 400 ms laser bursts. Using a system of forward and
reverse proling along the central growth axis of a
Holocene stalagmite (CC3) a spatial resolution 250 mm
was achieved (see Section 4.2). Analysis of standards
gives similar d13C values to those obtained by conventional acid digestion, but d18O values that are systematically lowered by 2 per mil. Replicate analyses of
standards indicate that the isotope data are reproducible
to better than 0.1% for d13C and 0.2% for d18O.
Following the 2 per mil correction, the laser data
accurately reproduce the rst-order features of a
previously published coarse resolution O isotope record
for this speleothem (McDermott et al., 1999). The
spatial resolution achievable by this system represents
about a four-fold improvement relative to that of
conventional dental drilling methods, but the data
acquisition is rapid and automated, thereby offering
signicant advantages over conventional analyses.
A different approach has been the use of micro-milling
techniques to improve the spatial resolution of sampling.
A recent study by Frappier et al. (2002), for example,
achieved a sampling resolution of just 20 mm, corresponding to a weekly to monthly temporal resolution in a
recently deposited stalagmite from Belize. These highresolution data exhibit high amplitude (11%), rapid (subseasonal) uctuations in d13C that appear to reect
variations in the El Nino/Southern Oscillation (ENSO)
system. A similar spatial resolution (25 mm) was achieved
recently by Kolodny et al. (2003) using an ion microprobe. This method offers excellent spatial resolution, but
the relatively poor analytical precision that characterises
the current generation of instruments (ca 70.5%)
restricts its use to the study of high-amplitude isotopic
events and/or climate transitions.
In principle though, with carefully chosen speleothems it may be possible in the future to reconstruct
the annual hydrological cycle of d18O variability,
offering both a chronological tool (cycle counting) and
new insights into changes in the amplitude of seasonal
d18O variability in rainfall. For the case of a speleothem
growth rate of 0.5 mm/year for example, it should be
possible to obtain a temporal resolution better than 1
month using an ion-probe technique (25 mm spot size),
and such a study would be best carried out in a region
where a relatively large seasonal d18O cycle is anticipated. In cases where the sampling resolution is subannual, but insufcient to resolve a clear seasonal cycle,
care must be taken to avoid unresolved seasonal effects
that could lead to a noisy signal (e.g. comparing winter
calcite in one analysis with summer calcite in an
adjacent analysis).
ARTICLE IN PRESS
A number of issues relating to the interpretation of

stable isotope data in speleothems remain unresolved.
The most challenging of these has been to decipher the
various, usually competing factors that drive oxygen
isotope variations, in order to recover unambiguous
palaeo-climatic signals. An early goal was to reconstruct
absolute changes in mean annual air temperature (e.g.
Gascoyne et al., 1980), but this is increasingly seen as
unrealistic, because of the plethora of effects that
inuence the d18O of cave drip-waters (d18Odw), and
therefore the d18O of the precipitated speleothem calcite
(d18Oct). These effects are discussed below, but recently
there is renewed condence that reliable stable isotope
data can be extracted from speleothem uid inclusions,
albeit at a relatively coarse temporal resolution (e.g.
Matthews et al., 2000; Dennis et al., 2001; Genty et al.,
2002; Sereddin et al., 2002; McGarry et al., 2004, this
volume). In principle, these developments should allow
the original goal of palaeo-temperature estimation to be
attained in situations where it can be demonstrated that
calcite was deposited in isotopic equilibrium with the
cave drip-waters. In addition, the uid inclusion data
can be used to reconstruct temporal and spatial
variability in the d18O of palaeo-meteoric water, and
in the future these data will test the validity of GCMs
that incorporate the water isotopes in their hydrological cycles.
Despite the intricacies of data interpretation, caves
remain attractive targets for palaeo-climate studies
because they preserve relatively pure calcium carbonate
(typically calcite), precipitated from meteoric water in
environments where it is protected from erosion for long
periods of time (often 104106 years). Speleothems
typically consist of macro-crystalline calcite, although
aragonite occurs occasionally, particularly in association with high-Mg calcite or dolomite host-rocks, and/or
associated with relatively dry periods when long water
rock contact times facilitate relatively more dolomite
dissolution in partially dolomitised limestone hostrocks. Petrographic studies of speleothems prior to
analysis are essential to avoid analysing re-crystallised
specimens, to identify possible growth hiatuses (usually
marked by thin detrital-rich layers), to recognise shifts
and offsets in the growth axis and to identify changes in
carbonate mineralogy. The possible palaeo-environmental signicance of the mineralogy and crystal morphology of speleothems has been discussed elsewhere (e.g.
Gonzalez et al., 1992; Frisia et al., 2000; Frisia et al.,
2002), and in well-characterised karst systems these may
provide additional constraints to aid the interpretation
of stable isotope data. Denniston et al. (2000), for
example, interpreted the presence of aragonite layers in
speleothems from a dolomitic cave in central Nepal as
reecting reduced monsoonal precipitation and increased cave aridity. In many cases, petrographic
information such as this aids the interpretation of stable
903
isotope data, but it is important to demonstrate that

petrographic changes are regionally synchronous, to
avoid mis-interpretations that could result from localised cave- or drip-specic hydrological routing effects.
Two features of the cave environment facilitate the
use of stable isotopes in palaeo-climate reconstruction.
First, cave air temperatures remain relatively constant
(typically 71 C) throughout the year, and are similar to
the mean annual air temperature of the region above
the cave. Second, in cool temperate regions, cave
air is characterised by high-humidity levels (typically
9599%), minimising evaporation that might otherwise
cause kinetic isotope fractionation. The mechanisms of
speleothem deposition have been discussed in detail
elsewhere (Schwarcz, 1986; Ford and Williams, 1989),
but a critical point is that, in cave interiors, calcite
deposition typically occurs by degassing of CO2 from
carbonate-saturated drip-waters on entering the cave
atmosphere, and not by evaporation of water. Degassing is driven by the difference between the pCO2 of
the soil and that of the cave air (typically in the ranges
0.13.5% and 0.060.6%, respectively). In high-humidity cave interiors where evaporation is negligible, it can
often be demonstrated that stalagmite calcite is deposited at, or very close to, isotopic equilibrium with the
cave drip-water. Under these conditions, the d18O of the
freshly precipitated calcite reects both the d18O of the
drip-water and the temperature dependent fractionation
between the drip-waters and the deposited calcite. Thus,
in order to interpret correctly the oxygen isotope
uctuations in the calcite, it is critical to understand
the factors that inuence oxygen isotope ratios in the
cave waters of individual drip systems. The hydrological
characteristics (e.g. Smart and Friedrich, 1987) of
individual drip-sites inuence the transfer of the
meteoric water stable isotope signal to the cave dripwater. Ideally, the d18O of cave drip-water should record
the weighted mean d18O of the meteoric water that falls
on the surface above the cave site. The latter requirement is likely to be met by seepage-ow drip-sites in
shallow temperate-zone caves (Young et al., 1985;
McDermott et al., 1999), but in arid and semi-arid sites,
seasonally variable isotopic enrichment may occur as a
result of near-surface evaporative processes (Bar-Matthews et al., 1996; Denniston et al., 1999a). An
additional complication is that soil pCO2 and dripwater Ca contents may vary seasonally, with the result
that calcite deposition rates also vary seasonally (e.g.
Genty et al., 2001a, b). One consequence is that the
recorded d18O and d13C signal in speleothems can
preserve a seasonal bias, but this possibility could be
detected by detailed seasonal monitoring of the chosen
drip sites to understand the factors controlling intraannual variability in growth rates. These issues highlight
the need for detailed site-specic present-day monitoring
studies to understand better the relationship between the
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palaeo-d18O signal preserved in speleothem calcite

(d18Oct) and palaeo-climatic variability.
2. Oxygen isotopes in precipitation

As discussed above, d18O in cave drip-waters reect (i)
the d18O of precipitation (d18Op) and (ii) in arid/semiarid regions, evaporative processes that modify d18Op at
the surface prior to inltration and in the upper part of
the vadose zone. The present-day pattern of spatial and
seasonal variations in d18Op is well documented
(Rozanski et al., 1982, 1993; Gat, 1996) and is a
consequence of several so-called effects (e.g. latitude,
altitude, distance from the sea, amount of precipitation,
surface air temperature). A critical requirement for the
recovery of d18Op from d18Oct is that isotopic equilibrium is maintained between the cave drip-water and
the calcite deposited therefrom. The criteria for recognising conditions of equilibrium deposition have been
discussed previously (Hendy, 1971; Schwarcz, 1986).
Briey, the conditions are (i) that d18O remains constant
along a single growth layer while d13C varies irregularly,
and (ii) that there is no correlation between d18O and
d13C along a growth layer. In practice, consistent
sampling along single growth layers is often difcult to
achieve, not least because visible layers are often thinner
along the anks of stalagmites compared with their
central growth axis. Nonetheless, the so-called Hendy
criteria are used widely by researchers as a check that
calcite was deposited at or close to isotopic equilibrium
with cave drip-waters. In some cases it can be
demonstrated that calcite deposited along the anks of
speleothem exhibit kinetic fractionation effects, but that
the material deposited close to the central growth axis
may have been deposited in isotopic equilibrium with
.
the cave drip-waters (e.g. Talma and Vogel, 1992; Spotl
and Mangini, 2002).
The temperature dependence of d18O in rainfall
(dd18Op/dT) is variable and site dependent. In principle,
dd18Op/dT could be greater than, equal to, or less than
dd18Oct/dT (approximately
0.24% C 1 at 25 C,
ONeill et al., 1969), the equilibrium fractionation that
accompanies calcite deposition from drip-waters inside a
cave. In a review of long-term changes in the O isotopic
composition of precipitation over the mid- to high
latitudes, Rozanski et al. (1993) calculated an average
modern-day dd18Op/dT of approximately 0.6% C 1,
but such averages clearly mask considerable site-specic
variability (e.g. Fricke and ONeill, 1999), and the
relationship may have been different in the past. In
principle therefore, d18Oct could increase, decrease or
fortuitously remain invariant to an increase in mean
annual air temperature. The latter response would
require that dd18Op/dT cancelled out dd18Oct/dT, and
such cases appear to be rare in the literature. A broadly
similar number of cases where dd18Oct/dT is positive

(e.g. Goede et al., 1990; Burns et al., 2001; Onac et al.,
2002) and negative (e.g. Gascoyne, 1992; Hellstrom
et al., 1998; Frumkin et al., 1999a, b) have been
reported. This illustrates the difculty in unambiguously
relating changes in d18Oct to changes in mean annual
temperature, particularly over time intervals where
temperature changes may have been small, and rstorder climate transitions (e.g. glacial to interglacial
transitions) are not represented in the record. These
uncertainties underline the need for additional proxy
information from the same stalagmite (e.g. annual layer
thickness variations, growth-rate changes, uid inclusion data) to underpin the interpretation of d18O.
On centennial to millennial timescales, factors other
than mean annual air temperature may cause temporal
variations in d18Op (e.g. McDermott et al., 1999 for a
discussion). These include: (i) changes in the d18O of the
ocean surface due to changes in continental ice volume
that accompany glaciations and deglaciations; (ii)
changes in the temperature difference between the ocean
surface temperature in the vapour source area and the
air temperature at the site of interest; (iii) long-term
shifts in moisture sources or storm tracks; (iv) changes
in the proportion of precipitation which has been
derived from non-oceanic sources, i.e. recycled from
continental surface waters (Koster et al., 1993); and (v)
the so-called amount effect.
As a result of these ambiguities there has been a shift
from the expectation that speleothem d18Oct might
provide quantitative temperature estimates to the more
attainable goal of providing precise chronological
control on the timing of major rst-order shifts in
d18Op, that can be interpreted in terms of changes in
atmospheric circulation patterns (e.g. Burns et al., 2001;
McDermott et al., 2001; Wang et al., 2001), changes in
the d18O of oceanic vapour sources (e.g. Bar Matthews
et al., 1999) or rst-order climate changes such as D/O
. and Mangini,
events during the last glacial (e.g. Spotl
2002; Genty et al., 2003).
Future technical developments that may allow direct
measurement of d18O in speleothem uid inclusions will
reduce the uncertainties in the interpretation of d18Oct
and may ultimately allow calculation of absolute
temperature changes. Reliable uid inclusion data can
provide invaluable constraints on palaeohydrological
conditions, particularly in regions where speleothem
deposition is continuous through the glacials. Using
independent palaeo-temperature estimates, Matthews
et al. (2000) calculated the d18O of uid inclusions using
the values from coexisting calcite. Combining these
calculated d18O values with D/H measurements carried
out using a vacuum thermal extraction technique
enabled these authors to compare the uid inclusion
data for four fossil speleothems with the present-day
cave waters and meteoric water lines. The most
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signicant result was that uid inclusions from two

speleothems deposited during the glacial period plot
close to the global meteoric water line (MWL), in
contrast with present-day precipitation and cave dripwaters that plot on the Mediterranean meteoric water
line (MMWL). These data highlight the important
insights into climate-driven changes in the operation of
the meteoric water cycle that can be gained from studies
of speleothem uid inclusions. In a study of uid
inclusions from three caves in Israel, McGarry et al.
(2004, this volume) used both the MWL and MMWL to
calculate the d18O of uid inclusions from measured D/
H values. The resulting palaeo-temperature estimates
are in good agreement with alkenone and modern
analogue-based estimates from the eastern Mediterranean Sea for the past 140,000 years. These data also
indicate that whereas the dDd18O relationships for
meteoric water in the region follow the MMWL in the
present-day and the last interglacial there was a strong
short-lived shift towards the MWL during the time
interval corresponding to the last glacial.
In the near future it is likely that there will be further
developments of the uid inclusion extraction and
measurement techniques that will underpin the interpretation of oxygen isotope ratios in speleothems.
Meanwhile, the emphasis is on developing well-dated
high-resolution d18O records that can be correlated with
better understood (but often more poorly dated) records
such as the Greenland ice cores, and on mapping out the
geographical extent of regionally synchronous O isotope
events such as the D/O events and the early Holocene
8200-year event. Many of these events will offer
productive targets for uid inclusion studies in the
future.
3. Carbon isotopes in speleothems

At pH values typical of karst waters, equilibrium
constants for the relevant reactions dictate that bicarbonate is the dominant species in solution, and so the large
(ca 10%) bicarbonate-CO2 fractionation factor dominates the equilibrium fractionation process. Two endmember models, which describe the processes by which
percolating groundwaters acquire calcium carbonate in
the soil and host-rocks above a cave, have been described
(e.g. Hendy, 1971; Salomons and Mook, 1986). In an
open-system model, continuous equilibration occurs
between the seepage water and an innite reservoir of
soil CO2. This drives a monotonic increase in bicarbonate
content as the water progressively acquires more solutes
in the unsaturated zone. Under these conditions, the d13C
of the dissolved species reects the isotopic composition
of the soil CO2, with no detectable isotopic imprint from
the carbonate host-rock. For a C3 plant system, the d13C
of the dissolved inorganic carbon (DIC) in the percolat-
905
ing solution is predicted to be in the range 14% to

18% when the solution reaches saturation with respect
to CaCO3, depending on soil pCO2 and temperature
(Hendy, 1971; Salomons and Mook, 1986; Dulinski and
Rozanski, 1990).
Under closed system conditions by contrast, the
percolating water becomes isolated from the soil CO2
reservoir as soon as carbonate dissolution commences
(Hendy, 1971; Salomons and Mook, 1986), and since
CO2 is consumed in the carbonation reaction
H2O+CO2=H2CO3 the extent of limestone dissolution
is limited by the nite CO2 reservoir. Under these
conditions the isotopic composition of the carbonate
host-rock inuences the isotopic composition of the
DIC. For a C3 system with soil gas d13C of ca 23%
and a host limestone with d13C of +1%, the DIC d13C is
typically ca 11%. In practice most natural systems are
likely to be partially open, and a mathematical description of such variability has been formulated (Dreybrodt,
1988). In arid regions, large shifts in the d13C values of
speleothem calcite have been ascribed to climate-driven
changes in vegetation (e.g. C3 versus C4 dominated
plant assemblages, Dorale et al., 1992; Bar-Matthews
et al., 1997). Data from pedogenic carbonates often
support such interpretations (e.g. Cerling, 1984; Cerling
et al. 1991). In these regions, relatively large shifts in
d13C can occur, because soil respired CO2 in equilibrium
with a C3 dominated plant assemblage has d13C in the
range 26% to 20%, while that in equilibrium with
C4 vegetation is signicantly heavier (d13C of 16% to
10%). These differences are preserved as distinctive
ranges in d13C in secondary carbonates (typically 14%
to 6% for carbonates deposited in equilibrium with
CO2 respired from C3 plants, and 6% to +2% for
that from C4 plants).
However, many temperate-zone speleothems also
exhibit d13C values > 6%. These values are higher
than those predicted to be in equilibrium with the
prevalent C3 vegetation in temperate regions (Baker
et al., 1997). In situations where the soilwater residence
times may be relatively short, complete isotopic
equilibration may not occur between soil CO2 and the
percolating H2O, with the result that the water may
retain a component of (isotopically heavier) atmospheric
CO2 in solution. Experimental studies (e.g. Liu and
Dreybrodt, 1997) have conrmed that the hydration of
CO2 is relatively slow, and that the kinetics of the
reaction CO2+H2O=H2CO=H++HCO3 is controlled by the CO2 hydration step. Other processes
including evaporation, rapid degassing of cave dripwaters, kinetic fractionation, CO2 degassing of dripwaters and consequent calcite precipitation in the
vadose zone above a cave have been offered as possible
explanations for these relatively heavy carbon isotope
signatures (Baker et al., 1997; Genty and Massault,
1997).
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As an example from the recent literature, Genty et al.

(2003) noted that stalagmites deposited during the late
glacial in the south of France exhibit d13C values that
are much higher than in those deposited during the
Holocene. These differences were attributed to changes
in the relative proportions of atmospheric and biogenic
(light) carbon. This interpretation implies that periods
of climatic amelioration promote the production of soil
biogenic CO2, resulting in isotopically lighter carbon
isotope ratios in the speleothem calcite.
In summary, the interpretation of carbon isotopes in
regions where switches in the proportions of C3 and C4
plants can be independently veried (e.g. from pollen
data) is relatively straightforward. In temperate regions
that lack a natural C4 vegetation however, the
interpretation of carbon isotopes in speleothems remains difcult, and the data are often interpreted on an
ad hoc basis. So far, the geochemical criteria for
distinguishing between the processes that might be
responsible for carbon isotope variations have not been
established, yet these are essential if reliable palaeoclimatic information is to be inferred from the d13C
record of temperate-zone speleothems. If, for example,
incomplete equilibration between soil CO2 and percolating water is the primary factor responsible for elevated
d13C in some temperate-zone speleothems, then elevated
d13C should be associated with wetter periods, when the
water/soil gas contact times are shorter. If, on the other
hand, seasonal evaporation of water in the undersaturated zone or perhaps within the cave itself is the
dominant processes, then high d13C should be associated
with drier periods. One promising line of research is to
combine trace element and carbon isotope data, because
depending on the nature of the co-variations, several
possible mechanisms for changes in d13C can be ruled
out. In a study of a 31,000-year-old speleothem from
New Zealand for example, Hellstrom and McCulloch
(2000) were able to rule out a reduction in cave seepage
water ow rates as an explanation for elevated d13C.
Barium concentrations exhibited a strong negative
correlation with d13C, the opposite to that predicted if
high d13C was caused by enhanced prior calcite
precipitation in the ow-path as a result of slower ow
rates. Future research should seek to develop further
these geochemical and petrographic criteria and to
underpin these arguments with theoretical modelling
and with systematic measurements on present-day dripwaters.
studies for which good chronological control (i.e. TIMS

or PIMMS U-series dates) is available are discussed
below.
4.1. Isotope stage 6 and the penultimate deglaciation
Speleothem records from Late Pleistocene mid- to
high-latitude sites are discussed rst, because these are
likely to be sensitive to glacialinterglacial transitions,
and they illustrate an important feature of speleothems,
namely that calcite deposition slows down or ceases
during glacials. Fig. 1 is a compilation of approximately
750 TIMS U-series speleothem dates that have been
published during the past decade, plotted against the
latitude of the relevant cave site. The absence of
speleothem deposition in the mid- to high latitudes of
the Northern Hemisphere during isotope stage 2 is
striking, consistent with results from previous compilations based on less precise alpha-spectrometric dates
(e.g. Gordon et al., 1989; Baker et al., 1993; Hercmann,
2000). By contrast, speleothem deposition appears to
have been essentially continuous through the glacial
periods at lower latitudes in the Northern Hemisphere
(Fig. 1).
Perhaps the best known Late Pleistocene continental
O isotope record is from the Devils Hole calcite vein
(Nevada) that was deposited continuously from 566 to
60 ka (Winograd et al., 1992; Ludwig et al., 1992).
Unlike speleothems (sensu-stricto), the Devils Hole
calcite (DH-11) was deposited in a phreatic open fault
zone by calcite-supersaturated groundwaters. Its O
isotopic composition therefore reects changes in the
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30
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4. Case study review

The following case study review is structured around
the new insights that studies of stable isotopes in
speleothems have provided in some of the key issues in
palaeo-climatology. The major results from those
50
100
150
200
Age kyr B.P.

Fig. 1. Compilation of approximately 750 TIMS U-series speleothem
dates that have been published during the past decade, plotted against
the latitude of the relevant cave site. The timing and duration of the
marine isotope stages (MIS) 16 (Martinson et al., 1987) are also
shown.
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O isotopic composition of regional meteoric water that

recharged the aquifer, in turn reecting changes in the
average winterspring surface temperature in the southern Great Basin. Unlike speleothems there is a
signicant, but poorly constrained transit time between
the recharge zone and the site of calcite deposition. As a
result, the DH-1 record provides minimum estimates for
the timing of climate-driven changes in O isotope ratios.
A comparison of the DH-11 record with the Vostok
(Antarctica) ice-core deuterium record and the SPECMAP record that largely reects Northern Hemisphere
ice volume (Fig. 2) indicates that both clearly record the
rst-order glacialinterglacial transitions. In detail,
however, there are several important differences between the DH-11 and SPECMAP curves (Winograd
et al., 1992), and most attention has focused on the
differences in the timing of Termination II (Fig. 2),
because it is argued that the timing of this termination is
crucial for testing the Milankovitch hypothesis. In the
DH-11 record, Termination II occurs at 14073 ka, predating by some 12 ka the timing of Termination II in the
SPECMAP record (12873 ka). While the interpretation
of the DH-11 record remains controversial, recently
published independent data sets from both the continental and marine realm (see below) appear to
corroborate the inference that Termination II pre-dated
by several ka the timing of maximum insolation at
65 N.
A study from Spannagel Cave in the high Austrian
. et al., 2002) provides compelling new
Alps (Spotl
evidence that climatic conditions had ameliorated
sufciently by 13571.2 ka, to allow owstone deposition to re-commence following the penultimate (Isotope
Stage VI) glaciation. Results from high-altitude continental sites such as this Alpine site are important,
because they are likely to be sensitive to glacial/
interglacial
transitions.
Calcite
deposited
at
13571.2 ka exhibits very low d18O (ca 12.571.5%),
probably indicating that deposition occurred from low
+2
0
VOSTOK
-2
+2
DH-11
0
-2
18O
-2
SPECMAP
0
+2
100
200
300
400
500
600
Age kyr. B.P.

Fig. 2. Devils Hole O isotope, SPECMAP and Vostok ice-core records
compared. The dashed vertical line represents termination II in the
Vostok and the Devils Hole (DH-11) records. Terminations are dened
as the mid-points of deglaciations. The records have been normalised
to standard deviation units for the portions of each record shown.
Diagram redrawn after Winograd et al. (1992).
907
d18O glacial melt-waters. By contrast, calcite deposited

in the interval 122116 ka has d18O values of about
9%, similar to those for Holocene stalagmites from
the site, indicating a switch from glacier derived to
normal meteoric water sources. The critical result is
that liquid water was available for speleothem deposition at this high-altitude Alpine site by 13571.2 ka,
indicating that deglaciation had clearly commenced.
This result corroborates other lines of evidence from the
marine realm (e.g. Esat et al., 1999; Henderson and
Slowey, 2000; Gallup et al., 2002) that the timing of
termination II occurred at least 8000 years before the
65 N insolation maximum at 128 ka. The new result also
corroborates previously published interpretations based
on compilations of alpha-spectrometric U-series dates
for speleothems (Baker et al., 1993) that speleothem
deposition had re-commenced by at least 133 ka, and
support a TIMS U-series date of 13371.2 ka for the
base of a speleothem in N England (Baker et al., 1995).
However, as noted by Baker et al. (1996), site-specic
effects can inuence speleothem growth, and while the
presence of speleothems can be taken to indicate liquid
water availability, their absence at any particular site
does not necessarily imply permafrost conditions.
Data from high-latitude sites can also yield useful
insights into the timing of the penultimate deglaciation.
U-series ages for stalagmite Ham85-2 from Hamarnesgrotta near Rana, 20 km south of the Arctic Circle in
northern Norway (Linge et al., 2001a, b), are relevant
here, because the high latitude of the cave site makes it
sensitive to the onset of periglacial conditions, associated with the accumulation of ice in northern
Scandinavia. TIMS U-series ages show that speleothem
deposition at this high-latitude site occurred during
isotope sub-stages 5e5a (123.573.3 ka). An important
result is that conditions favourable for speleothem
growth existed during isotope stage 5e, and that the
slowdown in calcite precipitation rate marks the
termination of the interglacial climate sometime between
119.5 and 107.7 ka. During isotope stage 5 the growth
rate of the speleothem apparently responded to progressively deteriorating climatic conditions above the
cave site. Thus, the growth rate was relatively rapid in
the period between 123.35 and 119.5 ka (B46 mm/year),
declining to about 0.7 mm/year in the period 119.5
107.7 ka, marking the end of interglacial conditions.
Speleothem growth became exceedingly slow
(B0.07 mm/year) in the period 107.773.3 ka. d18O in
this speleothem exhibited low-amplitude (ca 0.5%)
variability on centennial to millennial timescales during
isotope stage 5, and the values were similar to those for
Holocene speleothems from the region, reecting
relatively stable conditions, with evidence for cooler
conditions between 122.05 and 121.7 ka. Previously
published alpha-spectrometric U-series dates for speleothems from cave sites in northern Norway are critical
ARTICLE IN PRESS
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to the debate about the timing of the penultimate

deglaciation. In particular, a previously reported alphaspectrometric U-series date of 14575 ka (1s) (Lauritzen, 1995) from Okshola, a lowland site close to the
Arctic Circle in northern Norway is pivotal to the
debate, and perhaps should be rened using more
precise TIMS or PIMMS methods.
Evidence for the timing and duration of the last
interglacial was also presented by Zhao et al. (2001)
based on data for an interglacial stalagmite (NEW-B)
from Newdegate Cave in southern Tasmania. The
stalagmite was deposited from approximately 155 to
100 ka and exhibits highest growth rates (B 61.5 mm/
ka) during a relatively short time interval between
129.271.6 and 122.172.0 ka. This time interval coincides with prolic coral growth along the Western
Australian coast and marks the onset and duration of
full interglacial conditions. Since speleothem growth
rates reect precipitation rather than temperature in this
region, it was argued that the highest rates of precipitation on land occurred during the period when full
interglacial sea-levels were attained. Periods of lower
effective precipitation prior to 129.2 ka (lower speleothem growth rates) were attributed to latitudinal
shifts in the location of the subtropical highs and
associated westerly circulation. Based on the pattern of
the growth rate of the speleothem, Zhao et al. (2001)
argued that the penultimate deglaciation was underway
by about 142 ka, but that the full interglacial conditions
(highest coral and speleothem growth rates) coincide
broadly with the 65 N summer insolation peak that
occurred at 128126 ka. Thus, while the maintenance of
full interglacial conditions can be explained by insolation (Milankovitch) forcing, an additional forcing
mechanism is required to trigger the onset of deglaciation at ca 142 ka.
Plagnes et al. (2002) presented stable isotope data for
a stalagmite (Cla4) from Grotte de Clamouse (S France)
that was deposited discontinuously between 189 and
74 ka. Signicantly, all of the growth phases of
stalagmite Cla4 correspond to humid periods during
which sapropels were deposited in the eastern basin of
the Mediterranean, and most of the growth phases
correspond to relatively warm periods of high sea stands
during isotope stages 5 and 7. As discussed by Plagnes
et al. (2002), several European Cave sites show evidence
for speleothem growth during MIS 6 (Fig. 1), indicating
signicant periodic climatic amelioration. Speleothem
deposition between 169.171.5 and 162.3471.5 ka (MIS
sub-stage 6.4) was interpreted to reect the S6 sapropel
event that occurred in the eastern Mediterranean. In a
study that provides additional evidence for the hydrological conditions during MIS 6, Bard et al. (2002)
demonstrated that d18O in a stalagmite from 19 m below
present-day sea-level at Argentarola Cave on the
Tyrrhenian coast of Italy exhibits a 23% shift to lower
values between 180 and 170 ka (MIS sub-stage 6.5).

Approximately 0.81.5% of the observed 23% shift in
d18O could be accounted for by changes in the isotopic
composition of the vapour source, but the remaining
12% was interpreted as reecting the so-called
amount effect, reecting wetter conditions in the region
during MIS 6.5. The inferred change to wetter conditions during sapropel 6 is consistent with the pluvial
events during this and later sapropel events (S1S6)
inferred independently on the basis of decreases in d18O
in speleothems from Israel (Bar-Matthews et al., 2000;
Ayalon et al., 2002). Taken together these results yield
important new insights. In particular, it is clear that
wetter conditions associated with the formation of
sapropel 6 were not conned to the eastern basin of
the Mediterranean through increased Nile discharge.
Instead the western Mediterranean was also apparently
wetter during this part of the penultimate glacial,
although it is noted that there are signicant (ca 10 ka)
unresolved differences in the timing of the O isotope
shifts interpreted to reect sapropel S6 in the studies of
Bard et al. (2002) and Plagnes et al. (2002).
.
Spotl
and Mangini (2002) demonstrated that a
stalagmite from the Austrian Alps, deposited in the
time interval between 57 and 46 ka preserves evidence
for high d18O events that appear to be coeval with the
MIS 3 interstadial events 15a, 15b, 14 and 12, recognised
previously in the Greenland ice cores. This is an
important result because it is the rst time that precisely
dated D/O events have been identied in terrestrial
climate records in the mid-latitudes. The study also
provides evidence that mean annual temperatures at this
high-altitude (2165 m a.s.l.) site remained close to that of
the present-day (2 C) over the 11 ka interval of
speleothem growth during isotope stage 3. Shifts to
higher d18O of approximately 2% centred at 55.4 ka and
between 54.3 and 51.1 ka are interpreted to reect
interstadial events 15b and 14 of the GRIP record,
respectively, with a smaller (o1%) shift at 54.9 ka BP
corresponding to event 15a of the GRIP record (Fig. 3).
These results are in good agreement with data for ve
partially overlapping stalagmites from Hulu Cave in
eastern China (Wang et al., 2001) that appear to show a
strong coherence with O isotope variability in the GRIP
and GISP2 ice cores (Fig. 4). In the latter study oxygen
isotope records from ve stalagmites dene overlapping
O isotope trends, indicating that these speleothem
records preserve a precisely dated signal of changes in
the d18O of precipitation. Taken together these data
indicate that further renements to the Greenland icecore chronology are required. It is clear from revisions
of the GRIP chronology (compare curves B and C in
Fig. 3) that the dating uncertainties in the ice cores now
present a major obstacle in assessing the latitudinal leads
and lags in the timing of the interstadial events of the
last glacial.
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. and Mangini, 2002).

Fig. 3. Lower curve (D) shows d18O variations in stalagmite SPA 49 from Kreegruben Cave in the Austrian Alps (after Spotl
The O isotope records from the GISP2 core (curve A), and two GRIP d18O records using the 1995 timescale (curve B) and the 2001 timescale (curve
C) are also shown. Tentative correlations between the SPA 49 record and the GRIP curve have been suggested by the authors (dashed lines).
Greenland Interstadials (GIS) events 15 and 14 occurred at 55.6 and 54.2 ka, signicantly earlier than in the older (1995) GRIP chronology, and only
slightly later than indicated by the more recent (2001) GRIP chronology. These data illustrate the potential importance of well-dated speleothem
records in rening the chronology of the high-latitude ice cores.
In a signicant recent study, Genty et al. (2003)

argued that D/O events during the last glacial are
recorded by carbon and oxygen isotopes in a well-dated
stalagmite from Villars Cave (Vil9) in south-east France,
deposited between 83 and 32 ka (Fig. 4). This study is
important, because in addition to demonstrating the

occurrence of the D/O events in mid-latitude western
Europe, it offers perhaps the best available chronological control on the timing and occurrence of such events,
and provides an improved chronological framework for
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910
Fig. 4. Comparison of the carbon isotope record from stalagmite Vil9 (Villars Cave, south-west France) with O isotope records from the Hulu Cave
site in China (Wang et al., 2001) and the GISP2 record (after Genty et al., 2003). Vertical stippled boxes in the Villars record denote the presence of
depositional hiatuses (D2D4). Genty et al. (2003) correlate hiatus D3, the so-called Villars cold phase between 67.470.9 and 61.270.6 ka ago, with
Heinrich event H6. Signicantly, d13C values remain high for several millennia after hiatus D3, indicating that this cold phase probably had a severe
impact on local vegetation and soils. The possible correlation of Heinrich events H1H6 in the Hulu Cave record (upper part of the diagram) with the
GISP2 record are from Wang et al. (2001).
the GRIP and GISP2 ice-core records (Fig. 4). The

stalagmite has three growth hiatuses that occurred
between 78.875.5 ka (hiatus D2), 67.461.2 ka (hiatus
D3) and 55.751.8 ka (hiatus D4). Carbon isotope ratios
increase prior to and after hiatus D3 and are interpreted
to reect a cooling event (the Villars Cold Phase)
rather than a localised drip-water or other cave
hydrological effect. Hiatus D3 is also tentatively
correlated with Heinrich event H6 (Fig. 4).
A remarkably coherent picture of continental climate
Late Pleistocene variability with close links to the
oceanic realm has emerged from studies of speleothems
from the eastern margin of the Mediterranean (Fig. 5).
Particularly impressive is the well-dated composite d18O
record for the past 185 ka based on 21 speleothems from
Soreq Cave in Israel (Bar Matthews et al., 1996, 1997,
1999, 2000; Ayalon et al., 1998, 2002; Kaufman et al.,
1998). One of the reasons that robust matches can be

made between different coeval speleothems in this
composite record is that the shifts in d18O are relatively
large (several per mil), indicating a strong climatic signal
in the d18O record. The Soreq d18O record appears to
reect predominantly two effects: (i) changes in the d18O
of the oceanic vapour source and (ii) the amount effect
(Bar Matthews et al., 1996, 1997, 1999, 2000; Kaufman
et al., 1998; Ayalon et al., 1998, 2002). These studies are
important because they establish a critical link between
the oceanic realm and continental climate in this region.
Thus, d18O minima in speleothems from Soreq coincide
exactly with the occurrence of sapropel events in the
Mediterranean Sea, and recently it has been shown that
this is true for glacial as well as for interglacial
conditions (Ayalon et al., 2002). The dominance of the
amount effect on d18O in stalagmites in this region
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-9
-8
18 O (, PDB)
-7
-6
-5
-4
-3
-2
200
150
100
50
Age (ka)
18
Fig. 5. Composite d O curve constructed from 21 overlapping speleothem records for the past 185 ka from Soreq Cave in Israel (after Ayalon et al.,
2002). Filled circles along the top of the diagram illustrate the position of the 95 TIMS U-series dates that provide the chronology for this long
record. Note that speleothem deposition was continuous during the glacials at this eastern Mediterranean site, in contrast with northern latitude sites
where speleothem deposition ceased (Fig. 1).
allows reliable reconstruction of arid and pluvial phases

(Bar Matthews et al., 1996, 1997, 1999, 2000; Ayalon
et al., 2002; Bard et al., 2002).
d18O and deposition rate changes in speleothems from
Hoti Cave in northern Oman (Burns et al., 1998; Burns
et al., 2001) have provided new palaeo-climatic insights
in this part of the tropics. Low d18O in speleothem
calcite associated with episodes of enhanced deposition
during marine isotope stages 5e, 7a and 9 was
interpreted to reect pluvial phases linked to increased
monsoon rainfall. Thus, rapid speleothem growth
occurred during ve well-dated intervals 610.5, 7882,
120135, 180200 and 300325 ka with evidence for
non-deposition of calcite, reecting relatively arid
conditions during the intervening episodes. Each pluvial
episode was characterised by d18O values that are
signicantly lower (by several %) than those of modern
stalagmites, consistent with a northwards shift in the
monsoon rainfall, as a result of a northwards shift in the
inter-tropical convergence zone during peak interglacial
periods.
Holmgren et al. (1995) presented oxygen and carbon
isotope data for a stalagmite from Lobatse II Cave in
southeastern Botswana in which deposition was restricted to two phases. During the rst phase of
deposition (5143 ka), warm humid conditions associated with C3 vegetation were inferred (low d18O, low
d13C), whereas the second phase (2721 ka) was
dominated by drought-adapted C4 plants (higher d13C
and d18O), indicating cooler conditions. Correlations
between the Lobatse II Cave study and that for Cango
Caves (Cape Province, South Africa) are hindered by

problems of imprecise age constraints, but the available
data tentatively indicate that cooling was recorded at
both sites in the period prior to the last glacial maximum
(Holmgren et al., 1995). Further TIMS or PIMMS
U-series dates are clearly required to investigate further
the possible regional signicance of such cooling.
Dorale et al. (1998) presented oxygen and carbon
isotope data for four stalagmites that were deposited in
the interval between 75 and 25 ka at Crevice Cave,
Missouri, USA. The study is signicant because the four
coeval stalagmites exhibit coherent oxygen and carbon
isotope records. High d18O values between 59 and 55 ka
were inferred to reect warm conditions, and this period
coincided high d13C, interpreted to reect the expansion
of the prairie-type C4 vegetation.
4.2. Holocene records
In a study of a Holocene speleothem from S^ylegrotta, northern Norway, Lauritzen and Lundberg
(1999) calibrated the temperature dependence of d18Oc
at this site, using independently derived estimates of
present-day and Little Ice Age (LIA) mean annual
temperatures. Data from other sources (e.g. tree-line
changes at 3700 years, evidence from early to midHolocene diatoms and inferred climatic conditions at
10,000 years BP) are in broad agreement with the
relationship between d18Oct and temperature based on
these two data points, indicating that this calibration
may be robust outside the calibration interval. Another
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912
Holocene stalagmite (SG95) from the same cave system

(Linge et al., 2001a, b) deposited during the past 4000
years exhibits heavier d18O than that of stalagmite
SG93, and the pattern of d18O correlates with that of
SG93 over some intervals of the Holocene only.
Surprisingly, a third stalagmite (SG924) exhibits d18O
variability that correlates remarkably well with that of
SG93, despite the fact that it was collected from close to
the cave entrance and might be expected to have been
affected by a more variable micro-climate. Studies such
as these that employ several coeval stalagmites are
invaluable to assess the reliability of speleothems as
palaeo-climatic recorders and they highlight the danger
of relying on a single stalagmite d18O record. It seems
likely that processes other than climate variability (e.g.
variable water ingress routes and water mixing) can
substantially affect the d18O values recorded in stalagmites, particularly at high temporal resolutions).
McDermott et al. (2001) presented a laser-ablation
high-resolution O isotope time-series record for a
Holocene stalagmite (CC3) from Crag Cave, a coastal
site in SW Ireland. The main result of this study was that
subtle higher frequency (century scale) d18O variations
in the early to mid-Holocene appear to correlate with
those in the GISP2 ice core, suggesting that the latter

reect regional Holocene climate signals. Approximately
1640 laser-ablation d18O measurements were carried out
along the growth axis of this 465 mm long stalagmite,
resulting in an exceptionally high-resolution Holocene
d18O record. The 8200-year cold event was dened by
eight data points centred on 8.3270.12 ka and it
exhibited a very large (ca 8%) decrease in d18O
(Fig. 6). Since the speleothem d18O signal may in part
reect temporal changes in the vapour source and/or
cloud trajectories it was not possible to calculate
temperature changes from these d18O data. The timing
of the 8200-year event in speleothem CC3 is within the
dating uncertainties of the GISP2 core. Thus, the
maximum amplitude occurs at 8.3270.12 ka compared
with 8.2170.10 ka in GISP2, and is coeval with faunal
evidence for cooling at 8.3070.06 ka in core 28-03 from
the Norwegian Channel.
Signicantly, the amplitude of this large shift to lower
d18O was too large to ascribe solely to a reduction in
mean annual air temperature. Instead it was attributed
to freshening of the surface of the adjacent N Atlantic
by isotopically depleted melt-water. The absence of a
clear shift in d18O in the speleothem data during the
Fig. 6. Comparison of the O isotope record from stalagmite CC3 (south-west Ireland) with the GISP2 curve (McDermott et al., 2001). A timing of
the large (ca 8%) shift in d18O in the CC3 record is indistinguishable (within the 2s dating uncertainty) of the 8200-year cold event in the GISP2
record. Other post-8200-year oscillations in d18O in the early part of the Holocene appear to occur synchronously (within dating uncertainties) in the
two records (McDermott et al., 2001 for a discussion). RWP, DACP, MWP and LIA are possible expressions of the Roman Warm Period, Dark
Ages Cold Period, Medieval Warm Period and Little Ice Age, respectively.
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other N Atlantic ice-rafting events at ca 5.9, 4.3, 2.8 and

1.4 ka despite the high resolution of the data (718 years
per analysis) is signicant. It indicates that unlike the
8200-year event, the later Holocene ice-rafting events
failed to trigger large changes in d18O, and by
implication failed to establish a detectable melt-water
cap on the mid-latitude N Atlantic.
In the mid-western United States a coherent picture of
climate-driven vegetation changes in the Holocene is
beginning to emerge from speleothem studies, supplemented by data from pollen records. Dorale et al. (1992)
presented stable isotope data for a TIMS U-series dated
7800-year-old stalagmite (1 s) from Cold Water Cave in
northeast Iowa. The O isotope data were interpreted in
terms of palaeo-temperature changes, while the carbon
isotope data were taken to reect climate-driven changes
in the nature of the vegetation above the cave. A midHolocene warming of about 3 C relative to the early
Holocene, followed by a cooling of 34 C was inferred
for the period between 4 and 1 ka, assuming a simple
relationship between d18Oct and mean annual air
temperature. d13C exhibited strong unidirectional shifts
during the past 6000 years in this record, and in
particular a marked shift to higher d13C between 5.9
and 3.6 ka indicates a replacement of forest by a C4-rich
prairie vegetation, consistent with published pollen
records from the region. The shift from forest to
prairie-type vegetation about 5900 years ago appears
to have occurred rapidly, probably within a century,
offering insights into the rates at which climate-driven
changes in vegetation type can occur in regions close to
ecotone boundaries (Denniston et al., 1999b).
In a follow-up study of two additional Holocene
stalagmites from Cold Water Cave, northeast Iowa,
Denniston et al. (1999) presented O isotope data that
appear to have been inuenced strongly by site-specic
effects. While d13C varied coherently between the three
stalagmites, d18O did not, indicating that local nearsurface evaporative enrichment of 18O had variably
modied the d18O signal prior to inltration. The O
isotope variations in the stalagmite with lowest d18O
(sample 2SS), and therefore the one least affected by
evaporative enrichment effects appear to reect temporal changes in the moisture source region rather than
temperature changes. Thus, the shift to lower d18O
during the mid-Holocene, accompanied by an increase
in stalagmite growth rate, is best explained by a switch
to 18O-depleted moisture sources derived from the Gulf
of Mexico or the Pacic Ocean. The observation that
low d18O was accompanied by enhanced speleothem
growth in the mid-Holocene is puzzling in view of the
overall drier mid-Holocene climate that must have
accompanied the forestprairie transition in the region.
One explanation is that increased inltration was
possible because most of the precipitation occurred
during the cool season (Denniston et al., 1999a).
913
Speleothems such as these represent good candidates

for uid inclusion studies, because if the preferred
interpretation is correct, trapped uids should exhibit
d18O variations similar to the calcite values. The authors
conclude that the previously calculated temperature
estimates, based on stalagmite 1 s from the Cold Water
Cave may have overestimated the amount of midHolocene warming. This study highlights the difculties
inherent in interpreting speleothem d18O as a quantitative palaeo-temperature proxy, particularly in regions
where surface water decits occur seasonally, and
underlines the need to analyse several coeval stalagmites
to ensure that a robust regional climate signal is
recorded.
The data for the Holocene portions of stalagmites
from Hoti Cave in northern Oman (Burns et al., 1998;
Burns et al., 2001) are consistent with inferences from
studies of lake palaeo-levels in the Sahel region of Africa
(Gasse and Street, 1978; Ritchie et al., 1985). The
speleothem results offer enhanced chronological control,
rmly placing the earlymid-Holocene transition from
pluvial to the present arid to semi-arid conditions at
6.2 ka BP. Signicantly, proxies for monsoon strength
derived from marine sediment proxies from the Indian
Ocean and Arabian Sea (e.g. Anderson and Prell, 1993;
Rosteck et al., 1997) that effectively monitor wind
strength rather than monsoon rainfall amount, differ
from the record derived from speleothems. One explanation (Burns et al., 2001) is that speleothems offer a
more direct and reliable signal of monsoon rainfall
signal over the continents, whereas the marine records
primarily record monsoon wind strength variations that
are not necessarily accompanied by increased rainfall.
This arises because factors other than monsoon wind
strength, such as changes in the sea surface temperature
of the tropical Indian Ocean that supplies the moisture,
may strongly inuence moisture transport to the
Arabian Peninsula (Burns et al., 2001). A more detailed
O isotope analysis for a Holocene speleothem from this
cave was presented by Neff et al. (2001). An important
nding of the latter study was that speleothem d18O
correlates with D14C, interpreted as reecting solardriven changes in the monsoon in this region on
centennial to millennial timescales. Thus, while it
appears that on relatively long timescales the northwards transport of moisture to the Arabian Peninsula
may be driven by glacial to interglacial cycles, similar
changes may occur on much shorter timescales in
response to variable insolation. The latter study is one
of the few that has successfully demonstrated a link
between solar variability and climatic conditions in the
Holocene.
In a multi-proxy study, Xia et al. (2001) presented
stable isotope data for a well-dated 1.13 m long
stalagmite that grew continuously from 9180 to 5060
years BP in Lynds Cave, northwestern Tasmania. The
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914
interval between 8000 and 7400 years BP was characterised by high d18O, relatively low growth rates and
high initial (234U/238U) ratios, reecting conditions that
were probably warmer and drier than those of the
present-day. By contrast, calcite deposited in the interval
between 7400 and 6600 years BP exhibited lower d18O,
high growth rates and low initial (234U/238U) ratios.
These characteristics were interpreted to reect relatively wet conditions, and coincide with the so-called
mid-Holocene climatic optimum that had been recognised in earlier studies of pollen sequences and lake
levels in the region. The most recent part of the record,
from 6100 to 5100 years, is characterised by the lowest
growth rates and dramatic uctuations in both O and C
isotopes as a result of kinetic fractionation processes in
response to cooler, drier conditions and a reduction in
the humidity of the cave air.
In a study of a 2.7 m long stalagmite from Cango
Caves, Cape Province, South Africa, Talma and Vogel
(1992) used data for 14C-dated groundwater to estimate
of the d18O of recharge, and therefore of cave drip-water
in the past. On this basis, they calculated that
temperatures were approximately 67 C colder during
the last glacial maximum compared with the present.
Lower temperatures were also inferred for parts of the
mid- to late Holocene, centred on approximately 4500
and 3000 14C years BP. This study is noteworthy
because it is one of the few where an independent
estimate of the d18O of cave drip-waters could be
provided, allowing quantitative temperature estimates.
In the future material such as this would represent an
excellent target for uid inclusion studies as a means
to test the inferences from the isotopic composition of
14
C-dated groundwater.
Repinski et al. (1999) analysed a speleothem from
Cold Air Cave (Northern Province, South Africa) and
attributed the lower d18O values that occurred between
about 800 and 400 years ago to the LIA. Higher d18O
values between about 4400 and 4000 years ago were
interpreted to reect a warmer period, assuming that the
overall positive correlation between temperature and
d18O was valid through the late Holocene. Further work
is clearly required to explore how the inferences drawn
by Repinski et al. (1999) for the period around 4000
years ago in the Northern Province relate in a regional
context to the results of Talma and Vogel (1992) for the
Cape Province.
5. Summary and pointers for future research

So far, the major contribution of stable isotope
studies on speleothems for palaeo-climatic reconstruction has been the development of well-dated highresolution d18O records that can be correlated with
better understood records such as the Greenland ice
cores, thereby dening the geographical extent of

regionally synchronous O isotope events such as the
D/O events, regional pluvial events, and late glacial to
early Holocene oscillations. The major strength of
speleothem studies has been in the provision of robust
chronologies that are independent of both the orbitally
tuned marine records and the ice-core chronologies. In
some regions where speleothem deposition appears to
continue uninterrupted across glacialinterglacial transitions (e.g. Israel), remarkably detailed landsea
correlations have emerged, that in turn provide important new insights into the operation of the hydrological system under different climatic regimes. A
weakness of speleothem stable isotope studies has been
the difculty in providing unambiguous palaeo-climatic
interpretations of the data. The development of reliable
analytical protocols to recover both the D/H and
the O isotope ratios of trapped uid inclusions would
greatly facilitate the interpretation of stable isotope data
and is the subject of ongoing research at several
laboratories. This capability would allow unambiguous
estimation of palaeo-temperatures, and would provide
valuable tests for the output of water-isotope enabled
GCMs. Critically, stable isotope measurements on uid
inclusions may allow, for the rst time, realistic
estimates of the uncertainties associated with reconstructed climate parameters (e.g. palaeo-temperature,
palaeo-precipitation). Many of the O isotope events
that have been dened by recent studies will offer
productive targets for uid inclusion studies in the
future.
In the past decade there has been a trend towards the
provision of ever more detailed, higher-resolution
records (e.g. use of lasers and micro-drilling). Very
high-resolution (e.g. close to annual) data sets may
prove difcult to interpret however, because seasonal
noise may dominate the signal, particularly in Holocene
speleothems where climate variability is likely to be
subtle. Future studies are likely to make further use of
ion-probe instruments to measure O isotope ratios at a
sub-annual resolution, while accepting a reduced analytical precision on individual measurements. In carefully
chosen, rapidly deposited material it may be possible to
dene the annual cycle in d18O in speleothem calcite,
thereby simultaneously providing a chronology for short
intervals and a measure of changes in seasonal cyclicity
as a function of different climate regimes.
A critical aspect of future speleothem-based O isotope
records will be the provision of ever more reliable
chronologies for which realistic uncertainties are explicitly expressed, in order to compare with other
calendar-year-based proxies (e.g. ice cores) and forcing
mechanisms (e.g. insolation). This in turn will require
the use of more realistic and statistically constrained
agedepth relationships in U-series-dated speleothems.
Currently, there is little effort to realistically represent
ARTICLE IN PRESS
and report age uncertainties associated with interpolations between dated intervals of speleothems, and
different models (e.g. linear interpolation, linear regression and polynomial curve-tting) are used without any
rigorous exploration of the chronological consequences
of choosing one model over other equally plausible
models. This is particularly an issue in the case of
Holocene speleothems for which interpolation uncertainties typically exceed the 2s uncertainties associated
with individual U-series age determinations.
Most chronologies are based on U-series dating
techniques and with the advent of different analytical
approaches (e.g. TIMS and PIMMS) it is imperative
that systematic laboratory inter-comparison programmes are carried out in the near future, because
the accuracy of all U-series ages depends ultimately on
the accuracy with which the mixed UTh spikes have
been calibrated in different laboratories. These issues
relating to chronology are increasingly important as
researchers seek to establish correlations between
different speleothem records and with other independently dated archives such as ice cores.
Speleothems offer perhaps the best opportunity to
accurately constrain the timing of clearly dened climate
signals (e.g. glacialinterglacial transitions, D/O oscillations, the 8200-year event). By focusing on these times
of high signal to noise ratio it should be possible to
assess inter-hemispheric and latitudinal leads and lags,
providing that a carefully constructed chronology is
available. It is noteworthy that at present the lowlatitudes in both hemispheres, and the Southern Hemisphere in particular are under-represented in the
currently available database of reliably dated speleothem stable isotope records (Fig. 1).
Increasingly, multi-proxy studies are being undertaken on individual speleothems (e.g. combining
stable isotopes with trace elements, petrographic information and growth-rate information). These approaches help to narrow the uncertainties associated
with the interpretation of stable isotope data from
individual speleothems, but are not a substitute for
replication of records within individual cave sites.
Clearly, a balance must be found between the conicting
requirements to replicate records and to conserve cave
sites for aesthetic purposes and for scientic investigations in the future.
Finally, studies should include more systematic
seasonal monitoring of present-day precipitation and
cave drip-waters. Monitoring is both expensive and time
consuming. It is, nonetheless, essential to provide
constraints on the O isotopic composition of cave
drip-waters, to assess seasonal biases in calcite deposition rates, to investigate the extent to which drip-waters
reect the weighted mean d18O value of precipitation
and to understand better the factors that control the
d13C of the DIC.
915
Acknowledgements
The author thanks Ian Fairchild and an anonymous
reviewer for their constructive comments that helped to
improve the manuscript. Mira Bar-Matthews kindly
provided Fig. 5. Various aspects of the material
presented here have evolved as a result of discussions
with colleagues and acquaintances that include Ian
Fairchild, Andy Baker, Peter Rowe, Tim Atkinson,
Mira Bar-Matthews, Alan Matthews, Chris Hawkesworth, Silvia Frisia, Andrea Borsato, Dominique Genty,
Tim Heaton, Dave Mattey, James and Lisa Baldini.
Melanie Leng is sincerely thanked for her patient
editorial advice.
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ARTICLE IN PRESS

Quaternary Science Reviews 23 (2004) 901918

Palaeo-climate reconstruction from stable isotope variations in

speleothems as palaeo-climatic indicators, and the

F. McDermott / Quaternary Science Reviews 23 (2004) 901918

can provide 230Th/U dates that are almost 10 times more

spatial, and therefore the temporal resolution of

A number of issues relating to the interpretation of

isotope data, but it is important to demonstrate that

F. McDermott / Quaternary Science Reviews 23 (2004) 901918

palaeo-d18O signal preserved in speleothem calcite

2. Oxygen isotopes in precipitation

similar number of cases where dd18Oct/dT is positive

signicant result was that uid inclusions from two

3. Carbon isotopes in speleothems

ing solution is predicted to be in the range 14% to

As an example from the recent literature, Genty et al.

studies for which good chronological control (i.e. TIMS

4. Case study review

Age kyr B.P.

O isotopic composition of regional meteoric water that

Age kyr. B.P.

d18O glacial melt-waters. By contrast, calcite deposited

F. McDermott / Quaternary Science Reviews 23 (2004) 901918

to the debate about the timing of the penultimate

values between 180 and 170 ka (MIS sub-stage 6.5).

. and Mangini, 2002).

In a signicant recent study, Genty et al. (2003)

important, because in addition to demonstrating the

F. McDermott / Quaternary Science Reviews 23 (2004) 901918

the GRIP and GISP2 ice-core records (Fig. 4). The

1998). One of the reasons that robust matches can be

allows reliable reconstruction of arid and pluvial phases

Caves (Cape Province, South Africa) are hindered by

F. McDermott / Quaternary Science Reviews 23 (2004) 901918

Holocene stalagmite (SG95) from the same cave system

those in the GISP2 ice core, suggesting that the latter

other N Atlantic ice-rafting events at ca 5.9, 4.3, 2.8 and

Speleothems such as these represent good candidates

F. McDermott / Quaternary Science Reviews 23 (2004) 901918

5. Summary and pointers for future research

cores, thereby dening the geographical extent of

F. McDermott / Quaternary Science Reviews 23 (2004) 901918

F. McDermott / Quaternary Science Reviews 23 (2004) 901918

Talma, A.S., Vogel, J.C., 1992. Late Quaternary paleotemperature

500,000-year climate record from vein calcite in Devils Hole,

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