The Holocene 14,2 (2004) pp.

194-208

Speleothem master chronologies:

combined Holocene 180 and 13C records
from the North Island of New Zealand and
their palaeoenvironmental interpretation
P.W. Williams,1* D.N.T. King,1 J.-X. Zhao2 and K.D. Collerson2
('School of Geography and Environmental Science, University of Auckland, PB
92019, Auckland, New Zealand; 2Advanced Centre for Queensland University
Isotope Research Excellence (ACQUIRE), University of Queensland, Brisbane,
Queensland, Australia)
Received 2 April 2002; revised manuscript accepted 20 November 2002

Abstract: The stable isotope records of four stalagmites dated by 19 TIMS uranium series ages are combined
to produce master chronologies for 8110 and 81'C. The 81O records display good overall coherence, but
considerable variation in detail. Variability in the b'C records is greater, but general trends can still be dis-
cerned. This implies that too fine an interpretation of the structure of individual isotopic records can be unre-
liable. Speleothem 18(0 values are demonstrated to show a positive relationship with temperature by comparing
trends with other proxy records, but also to respond negatively to rainfall amount. Speleothem 8 C is con-
sidered to be most influenced by rainfall. The postglacial thermal optimum occurred around 10.8 ka BP, which
is similar in timing to Antarctica but up to 2000 years earlier than most Northern Hemisphere sites. Increasingly
negative B'"O values after 7.5 ka BP indicate that temperatures declined to a late mid-Holocene minimum
centred around 3 ka BP, but more positive values followed to mark a warm peak about 750 years ago which
coincided with the 'Mediaeval Warn Period' of Europe. Low fi8O values at 325 years BP suggest cooling
A coincident with the 'Little Ice Age'. A marked feature of the 8lC record is an asymmetric periodicity averaging
HOLOCENE c. 2250 years and amplitude of c. 1.9%o. It is concluded that this is mainly driven by waterbalance variations
RESEARCH with negative swings representing particularly wet intervals. The f'80 record shows a higher-frequency cyclicity
PAPER
with a period of c. 500 years and an amplitude of c. 0.25 %v. This is most likely to be temperature-driven, but
some swings may have been amplified by precipitation.

Key words: Caves, climatic change, palaeoclimate, periodicities, speleothems, stable isotopes, Holocene,
New Zealand.

Introduction
Crystalline deposits found in caves, such as stalactites, stalagmites
and flowstones, are collectively known as speleothems (Hill and
Forti, 1997). They are usually formed of calcite (CaCO3) chemi-
cally precipitated from seepage water that has percolated through
overlying limestone beds. Oxygen isotopes in speleothem calcite
have been used in attempts to estimate temperature at the time of
deposition, because the 18O/16O in calcite during its precipitation
is temperature-dependert (Hendy and Wilson, 1968; Hendy, 1971;
Gascoyne, 1992; Lauritzen and Lundberg, 1999a). The tempera-
ture within the interior of a cave varies very little over the year
*Author for correspondence (e-mail: p.williarns@auckland.ac.nz)
Amold 2004
and is very close to the external mean annual air temperature
(Wigley and Brown, 1976). So, if the external temperature
changes over time, the cave temperature will adjust accordingly,
and this will result in oxygen isotope ratio changes of the calcite
being precipitated. Thus the oxygen isotope ratios of a stalagmite
reflect temperature changes during its growth, provided this
occurred in isotopic equilibrium (Hendy, 1971; Gascoyne, 1992),
which is usually the case in the interior of caves away from the
effects of evaporation. The oxygen isotope ratio may also reflect
changes in rainfall (Bar-Matthews and Ayalon, 1997), because the
ratio in rainwater from which cave dnps are derived may also
alter. This can occur because of changes in the source of water
vapour and in rainfall volume.
The stable isotopic composition of rainwater that infiltrates into
10.1 191/0959683604hl676rp

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 P.W. Wifliams et al.: Speleothem master chronologies from New Zealand 195
karst tends to be homogenized in the soil and epikarst (the weath-
ered limestone zone immediately beneath the soil) and, as a conse-
quence, the oxygen isotope composition of water seeping into
caves shows only minor variation compared to the rainfall from
which it was derived and has an isotopic value very close to the
mean annual isotopic composition of the rainfall (Goede et at.,
1982; Yonge et al., 1985; Williams and Fowler, 2002). Neverthe-
less, differences in residence time and percolation routes in the
epikarst result in imperfect mixing and so a variation of 10-20%
can occur in seepage water oxygen isotope ratios in different parts
of a cave (Yonge et al., 1985; Chapman et al., 1992; Bar-
Matthews et al., 1996; Dennis et al., 2001). This in turn leads to
corresponding variation in the stable isotopic records of different
speleothems in the same cave and in different caves in a small
region (see, for example, Denniston et al., 1999; Linge et al.,
2001), although usually the directions of large-scale fluctuations
are similar (e.g., Dorale et al., 1998). As a consequence, one must
conclude that a palaeoclimate record derived from one speleothem
is not necessarily representative of its region and that it is more
reliable to obtain a generalized picture constructed from the
evidence obtained from several speleothems. The purpose of the
research reported here is to identify the intra-speleothem varia-
bility in a region of New Zealand, to show how representative
records might be constructed, and to discuss their palaeo-
environmental interpretation.
The islands of New Zealand have a particular significance
for palaeoenvironmental studies, because of their mid-latitude
location in a largely oceanic hemisphere between subtropical and
Antarctic influences. It is probable that the palaeoclimatic experi-
ence of the country can be applied to many other mid-latitude
oceanic sites throughout the Southern Hemisphere. The Waitomo
district is located at latitude 38.3S about 35 km inland from the
west coast of the central North Island (Figure 1), where caves are
developed in Oligocene limestones (Williams, 1992).- The area has
a temperate oceanic climate with a mean annual temperature of
about 13C and an annual rainfall averaging 1618 mm, although
it increases to over 2000 mm on higher areas. Podocarp-hardwood
evergreen forest formerly covered the district (Wardle, 1991), but
much has been cleared in the last 100 years. Further background
30 S
" / 7 :
ll 50 S
160 E 170 E E 180 W 170 W
Figure 1 Location in New Zealand of Waitomo and other sites mentioned
in the text (modified from Williams et al., 1999).
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details and information on the regional context of the site are
provided by Williams et al. (1999).
This paper revises and builds on results presented in this journal
by Williams et al. (1999) on stable isotope stratigraphy from
caves at Waitomo. The speleothem record is enhanced by adding
another chronology (Ruakuri-C), increasing the subsample resol-
ution of existing records, and by much improving the temporal
control of all chronologies by basing it entirely on uranium series
TIMS dating. The previous U/Th a-dates and AMS 4C dates with
1 cr dating errors of 5-17% (a-dates ) and zero age errors of up
to 3680 years (14C) are replaced by 19 TIMS uranium series dates
with 2 cr errors of 0.88-14.74%, averaging 3.5% (Table 1).
Methods
The standard for oxygen isotopes in water is Vienna Standard
Mean Ocean Water (vSMOW) and for calcite is a fossil belemnite
vPDB. Friedman and O'Neil (1977) provide an expression that
shows the relationship between the two:
bsmow = 1.03086 bp5- + 30.86 (1)
Changes in the oxygen isotope ratio are reported in delta units
(Coplen, 1994; Kendall and Caldwell, 1998), which are parts per
thousand (per mil) deviations of the isotopic ratio from a
standard; thus
8 (in %o) = ((R,Ae - Rt)fRs) * 1000 (2)
where R is the ratio of the heavy to light isotope. Delta l80p and
b8`0 are with respect to vSMOW, and and B80c
are with5'3cc
respect to vPDB. Subscripts P, w and c refer to isotope ratios of
precipitation, seepage water and calcite, respectively, and
subscripts atm , , and 1t refer to carbon isotope ratios in the
atmosphere, plants, soil and limestone, respectively.
Expressions used to estimate the temperature (T) of deposition
of secondary calcite (or of a cave atmosphere at the time when a
speleothem was deposited) are based on results by O'Neil et al.
(1969) and have been developed by Hays and Grossman (1991):
T (C) = 15.7 - 4.36 (5180c - '880) + 0.12 (818OC - 5180)2
(3)
and Genty et al. (2002):
T (K) = [2780/ (ln [(1+10-3 * 518Oc) / (1 + 10-3 * 5180)]
0.00289}W2 (4)
Stable isotope determinations of speleothem calcite additional to
those reported in Williams etal. (1999) were made in New
Zealand at the National Institute of Water and Atmospheric
Research (NIWA). Internal precision of measurements is 0.03-
0.08%o for 5'8O and 0.01-0.03%o for 5'3C; external precision is
0.05%o for 18`0 and 0.02%o for B53C. Samples were reacted with
3 drops of H3P04 at 75C in an automated individual-carbonate
reaction (Kiel) device coupled with a Finnigan MAT252 mass
spectrometer.
Thermal ionization mass spectrometry (TIMS) dating of
speleothems was conducted at the Department of Earth Sciences,
University of Queensland. The analytical procedures used were
as described in Zhao et al. (2001). All TIMS data are shown in
Table 1. These and other dates cited are in calendar years before
analysis date.
196 The Holocene 14 (2004)

Table 1 U-Th isotopic data for stalagmite growth layers from caves in the Waitomo district

Speleothem Depth U (ppm) `Fh/ "3JI/ +2a 27h/ +2u 'rh age 2u 23rh age 2u Initial 2u
sample (mm) ?X1'h 23.J 238j (ka) (uncorr.) (ka) (corr.) 23U/238j
GGI 64 0.0604 86.8 1.7531 0.0039 0.0389 0.0004 2.439 0.024 2.416 0.027 1.76 0.00
130 0.0784 12.9 1.6853 0.0039 0.0628 0.0005 4.118 0.037 3.860 0.131 1.696 0.004
170 0.0725 6.9 1.7836 0.0052 0.0924 0.0022 5.767 0.143 5.094 0.355 1.804 0.007
260 0.0801 12.9 1.7433 0.0041 0.1505 0.0018 9.760 0.124 9.163 0.306 1.770 0.006
350 0.0980 3.6 1.6231 0.0065 0.1661 0.0021 11.659 0.161 9.104 1.233 1.665 0.015

GG2 40.5 0.0269 3.7 1.4946 0.0095 0.0158 0.0005 1.155 0.041 0.901 0.133 1.498 0.010
150 0.0413 11.1 1.5457 0.0042 0.0247 0.0007 1.751 0.053 1.622 0.083 1.549 0.004
505 0.0485 107.8 1.5769 0.0063 0.0773 0.0011 5.450 0.081 5.410 0.083 1.586 0.006
594 0.0591 65.52 1.6162 0.0025 0.1499 0.0011 10.526 0.081 10.400 0.100 1.636 0.003
700 0.0498 60.8 1.5352 0.0049 0.1501 0.0009 11.129 0.078 10.986 0.103 1.553 0.005
760 0.1057 108.5 1.7511 0.0057 0.1818 0.0013 11.832 0.096 11.747 0.103 1.778 0.006

Max's 17 0.0586 48.4 1.4979 0.0053 0.0425 0.0011 3.127 0.082 3.075 0.086 1.503 0.005
120 0.0596 138.2 1.4992 0.0059 0.0536 0.0012 3.949 0.090 3.926 0.090 1.505 0.006
215 0.0823 142.5 1.4949 0.0056 0.0716 0.0005 5.323 0.045 5.293 0.048 1.503 0.006
326 0.0918 74.1 1.5819 0.0060 0.0883 0.0007 6.229 0.055 6.162 0.064 1.593 0.006

RK-C 35 0.0680 114.0 1.1391 0.0024 0.0780 0.0007 7.700 0.074 7.646 0.078 1.142 0.002
119 0.0477 159.6 1.1463 0.0058 0.0877 0.0017 8.643 0.184 8.600 0.185 1.150 0.006
197.5 0.0833 143.8 1.1248 0.0024 0.1018 0.0010 10.303 0.111 10.247 0.114 1.129 0.002
285 0.0513 15.7 1.1390 0.0028 0.1177 0.0015 11.835 0.161 11.243 0.333 1.144 0.003

Ratios listed in the table refer to activity ratios normalized to the corresponding ratios measured for the secular-equilibrium HU-1 standard (after Ludwig
et al., 1992; see Zhao et al., 2001).
'rh ages are calculated using Isoplot Excel Version.
Decay constants used are those in Edwards et al. (1986/87). Detrital U-Th correction applied assuming detrital component Th/U = 3.8 1.9 (average
crustal value) (equivalent to 2'h/2Fh 0.83 0.41), and 21U, "'U, 2'rh and 'rh are in secular equilibrium. Detrital correction results in large age
error magnification for samples with low 1'hf'Th ratios.

Construction of master chronologies linear extrapolation from the closest part of the interpolated curve.
In the case of GG1, the basal TIMS date (9.104 ka) has a large
Four speleothem stable isotope chronologies were obtained from error because of detrital thorium and so is statistically indis-
stalagmites from caves in the Waitomo district. The cave locations tinguishable from the next youngest date (9.163 ka), which has a
are shown in Williams (1992) and Williams et al. (1999). Two small 2 af error. In order to avoid an apparent age reversal, the
chronologies (GGI and GG2) are from Gardners Gut Cave, one basal date was therefore assigned a value of 9.721 ka, which is
(RK-C) is from Ruakuri Cave and the other from Max's Cave I a greater than the age listed in Table 1 but within the 2 a error
(MAXS). The speleothem sites in Gardners Gut and Ruakuri are term, and the growth curve in Figure 2 was projected through it.
at about the same elevation (c. 60-100 m above sea level), GG1 is a 356 mm stalagmite that grew from c. 9720 years BP
whereas the site in Max's Cave is somewhat higher (c. 325 m until the date of sampling (3 September 1986). Age control is
a.s.l.). Speleothem age data from Table 1 are plotted against provided by five TIMS dates, and 66 subsamples provide an
position along the growth axes of the respective speleothems in average temporal resolution of 138 years for stable isotope data.
Figure 2. The ages of stable isotope subsamples are estimated by GG2 is a 772 mm stalagmite that grew from c. 11 814 years
linear interpolation between neighbouring dates following the BP until the date of sampling (3 September 1986). Age control
curves on Figure 2. Basal ages of speleothems are determined by is provided by six TIMS dates, and 140 subsamples provide an
average temporal resolution of 84 years for stable isotope data,
800 although the variable sampling density and growth rate implies a
GG2 Itll r large variability in resolution.
Max's is a 320 mm stalagmite that grew from c. 6162 to 2559
years BP. Age control is provided by four TIMS dates, and 60
subsamples provide an average temporal resolution of 60 years
for stable isotope data.
RK-C is a 290 mm stalagmite that grew from c. 11 086 to 6125
years BP. Age control is provided by four TIMS dates, and 31
\G1 X * MAXMAXSI
*44
RK-C subsamples provide an average temporal resolution of 160 years
for stable isotope data.
The usual tests for equilibrium deposition (Hendy, 1971;
\ ,w _
Gascoyne, 1992) were performed on each of the speleothems.
e~~~~~)'_1 \6 Those for GG1, GG2 and MAXS are reported in Williams etal.
12 1o 8 6
-~~~~~~~~~~~~
- w-5w --
4
a
-X 0
(1999). Ruakuri-C speleothem was sampled along three growth
Age (ka BP) layers and also proved to have grown in isotopic equilibrium
Figure 2 Growth curves for GGI, GG2, RK-C and Max's stalagmites (Figure 3). Several other speleothems not used in this paper were
from Waitomo. also tested in this way, but were rejected from further consider-

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 P.W. Williams et al.: Speleothem master chronologies from New Zealand 197
8 So%o
) "I0o%
0 10 20
Distance (mm)
Figure 3 Plots along growth layers at 77, 130 and 210 mm along axis of Ruakuri-C stalagmite of B5',O. against VI3C, and Bl0c against distance from
growth axis. Equilibrium deposition is indicated by a lack of significant trend in isotopic ratios towards heavier isotopic values with distance from the
growth axis and by a lack of statistically significant correlation between b8, and VIC,
ation because kinetic fractionation appeared to have occurred
during calcite deposition.
If speleothem stable isotope curves for the same region are
superimposed, it is to be expected that they will not fall precisely
above each other. This is because: (i) even within the same cave,
the oxygen isotope ratios of seepage waters and growing speleo-
them tips vary somewhat from place to place; (ii) speleothems
from other nearby caves at various altitudes will have precipitated
from waters with slightly different 5'Ow values and at somewhat
different equilibrium temperatures; (iii) plotting errors arising
from subsample ages estimated by linear interpolation between
dates can be as large as the errors on the dates from which they
were derived; and (iv) small experimental errors occur in the
determination of 5-values.
Errors associated with an individual speleothem series can be
reduced if several series are used to derive an average record. To
achieve this for the Waitomo speleothems, a procedure was used
that adjusted each record to a common mean. The steps taken
were as follows.
(1) A primary reference series was selected as that from the
speleothem with the longest record and greatest number of
subsamples (GG2 in this case).
(2) The next longest record (GGI) was selected and its mean
stable isotope 8-value calculated.
(3) The mean stable isotope 5-value of the primary reference
series over the same length of record as the secondary series
was calculated and the two means were compared.
(4) The difference in mean 5-value was added to each subsample
from the secondary series in order to equalize the means of
the two series.
(5) The third-longest record was then selected and its mean 8-
value was adjusted in the same way to the primary reference
series, and so on with other series.
(6) The primary reference and means-adjusted records were then
combined by chronologically merging the individual series
into a composite 'master' series.
(7) The mean 8-value of the composite 'master' series was
adjusted to retain the original mean value of the raw
(unmodified) data from which the composite series was
derived by adding the difference in mean values to the com-
posite series.
Figures 4 and 5 present data plots for the four speleothems. They
compare the raw data with the means-adjusted data for 58`O, and
5'3CC respectively. The general coherence of the oxygen curves
reinforces the conclusion that the speleothems grew in isotopic
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30 40 -10 -8 -6
a
13 C%.
equilibrium. Similar trends imply that they are reflecting regional
environmental changes. Although numerous small shifts in plot-
ting position can be seen in the adjusted records, especially in
5'3C C the overall trends remain unchanged. Nevertheless, the
curves display considerable variation and even mismatch in detail.
Mismatches probably arise mainly from the method of estimating
subsample ages as discussed above, but some mismatch (although
it is difficult to evaluate) is related to real differences in the
records. This could be expected to be a consequence of varying
hydrogeochemical history in the epikarst (different recharge his-
tories, residence times, mixing and percolation paths), where
water is stored prior to calcite deposition on speleothems. Mis-
matches are particularly evident in the 5'3Cc series, probably
because of the intervention of site factors affecting local veg-
etation. The lack of conformity of the curves in detail illustrates
the danger of using just one speleothem record to interpret the
nuances of palaeoclimate history (just as one tree-ring core is
inadequate in representing a dendrochronologicd record and
would be insufficient for reliable interpretation of associated
climate history), although general trends can be discerned from
one record.
Figure 6 shows 'master curves' for 5`8O0 and 5'3CQ calculated
from the chronologically merged combined data series. Each
curve was constructed from 301 stable isotope subsamples over an
I I 814-year record (basal age of GG2), giving an average sample
resolution of 39 years, although this varied from an average
resolution of 32 years for the first 6000 years to 42 years there-
after. The master series carry the errors associated with the orig-
inal individual records; so in order to reduce uncertainties it was
generalized by filtering with a five-point running mean, although
this has the disadvantage that it suppresses some real variability.
The master series also has the disadvantage of being variable in
data density and variance along its length, because of variation in
the number and resolution of individual records that were com-
bined in different sections. Consequently, changes in variability
with time along composite series must be interpreted with caution.
Climatic interpretation of the stable
isotope records
Our ability to provide a realistic interpretation of the climate sig-
nal embedded in stable isotope records depends on our under-
standing of the factors to which they respond. Figure 7 illustrates
the main factors that influence the growth of speleothems and
determine their 818Q, composition; and Figure 8 illustrates the
198 The Holocene 14 (2004)
Figure 4 (A) 8`0O. curves for GGI, GG2, Max's and Ruakuri-C stalagmites (raw data). (B) Means-adjusted f8j)ccurves for GGI, GG2, Max's and
Ruakuri-C stalagmites.
main factors that determine their 5'3C, composition. Both assume
equilibrium conditions (i.e., without the effects of evaporation or
kinetic fractionation).
Speleothem growth rates
The Waitomo speleothems discussed here commenced and ter-
minated their growth at different dates (Figure 2). This can be
ascribed to local hydrological factors affecting pathways supply-
ing seepage water. GG1 and GG2 grew throughout most of the
Holocene and had no interruptions to their growth. So one may
conclude that for at least 9.7 and probably 11.8 ka there has
always been sufficient effective rainfall to sustain growth
(although this does not preclude the possibility of water-balance
deficit in some seasons). Interpretation of growth-rate variation is
complex, because Dreybrodt (1996) concluded that such rates are
determined by many parameters operating in often opposing direc-
tions. For example, high growth rates induced by an increase in
soil CO2 could be offset by reduced temperatures or lower effec-
tive rainfall. For stalagmite growth under relatively humid con-
ditions in Europe, Genty et al. (2001) found there to be a good
correlation between growth rate and mean annual temperature and
drip water calcium content, but not drip rate. They suggested that
this is due to soil CO2 production being primarily determined by
surface temperature and soil moisture but, for environments with
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low drip rates, that factor assumes greater importance in con-
trolling growth rate. It is probable that the dominant controls on
speleothem growth vary in relative importance with climate zone,
and that as aridity increases so water supply becomes an increas-
ingly critical control on growth rate. However, at Waitomo
throughout the Holocene, there appears always to have been
sufficient effective rainfall to support forest and to permit un-
interrupted speleothem growth; so growth-rate variations are prob-
ably mainly related to factors influencing the degree of CaCO3
saturation, namely warmth and humidity that promotes biological
activity and high soil PCO2.
Factors affecting speleothem 118Oc composition
The 8 lOc value of speleothems growing under isotopic
equilibrium is determined by two sets of characteristics: the first
represents the thermodynamic fractionation between calcite and
water, the cave temperature effect, and the second relates to
factors influencing the isotopic composition of the feed water,
termed the drip water function by Lauritzen and Lundberg
(1999b). These characteristics have different temperature sensi-
tivities. The former always has a negative response to tempera-
ture, whereas the latter may respond negatively or positively,
depending on regional meteorology and on the scale of climatic
change. The overall outcome depends on their relative magni-
 P.W. Williams et al.: Speleothem master chronologies from New Zealand 199

- GG 2
- GG 1
-5.0 Ma,s
-6.0 -+4- Ruakuri C
-7.0-

-8.0.

a-1.
-10.0

-12.0-
-13.0 1
12000 11000 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0
YEARS (BP)

B
GG2
-5.0 - GG1
*+z Mains
-6.0 - 4-Ruakuri C
-7.0-

.9-9.0

-1620
-13.0
12000 11000 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0
YEARS (BP)

Figure S (A) VI3C, curves for GGI, GG2, Max's and Ruakuri-C stalagmites (raw data). (B) Means-adjusted 8,EC curves for GGI, GG2, Max's and
Ruakuri-C stalagmites.

tudes. In mid-latitude oceanic settings, the resultant can be posi-
tive (see, for example, Gascoyne etal., 1981; Gascoyne, 1992;
Goede etal., 1986; Lauritzen, 1995; McDermott etal., 1999),
because the cave temperature effect can be dominated by the
stable isotopic characteristics of the precipitation. At Waitomo,
Williams et al. (1999) also concluded d8'8OJdT to be positive,
although '8O, variations cannot be ascribed exclusively to tem-
perature changes, because O818p has been found in northern New
Zealand to be influenced by rainfall amount (Williams and
Fowler, 2002).
Using rainfall data from Kaitaia (Figure 1), a meteorological
station 390 km north of Waitomo that has contributed to the
IAEA/WMO Isotopes-in-Precipitatnn Network, Williams and
Fowler (2002) identified a weak but significant positive relation-
ship between average monthly 8'80P and average monthly screen
temperature (R2= 0. 15, n = 237), but a negative exponential
relationship between monthly 8'8Op values and rainfall amount
(R2 = 0.34, n = 238). The positive temperature effect reflects the
temperature-dependert fractionation between liquid and vapour
phases at the oceanic source of the atmospheric moisture and the
positive correlation between 8l80Op and condensation temperature
identified by Dansgaard (1964). The negative relationship of
8180 p value with rainfall amount can probably be accounted for
by low temperatures during condensation at high altitude during
convective thunderstorms that produce heavy rains.
The combined influence of the above rainfall factors determines
the 8-value of water that recharges the soil and influences the
8'O0 value of drip waters from which speleothems are deposited.
If there is significant evaporation loss from the soil or epikarst,
as occurs in summer and especially in semi-arid environments
(Chapman et al., 1992; Bar-Matthews et al., 1996), then enrich-
ment may result in the value of 818Ow being less negative than
mean V8O8. This process may account for the cave seepage
waters at Waitomo being about 0.3%o more positive than the rain-
fall (Williams and Fowler, 2002), although some enrichment may
come from exchange with the bedrock.
For a given site, the resulting 8180w value can be expected to
remain relatively constant provided climatic boundary conditions
do not change, which in New Zealand has probably been the case
since sea level stabilized about 6000 years ago (Gibb, 1986) after
the postglacial transgression. However, if the 8-value of sea water
changes, as occurred during glacio-eustatic lowstands of the
ocean, when sequestering of 160 in ice sheets led to relative
enrichment of sea water with respect to '80, then the average 8-
value of rainfall also changes. This is known as the ice volume
effect.

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200 The Holocene 14 (2004)

A
Waitomo GG2 GG1
-2.5 - . MaXs Ruakuri C
5PRM

-3.0

GO -4.0-

-4.5

-5.0I
12000 11000 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0
YEARS (BP)

B
Waitomo ---- GG2 GG1
-5.0 - 4Maxs Ruakuri C
5PRM
-6.0 -

-8.0
10- -9.0 I i-

-10.0

-12.0
12000 11000 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0

YEARS (BP)

Figure 6 (A) Combined b' O. data with superimposed five-point running mean 'master' curve. (B) Combined ba'C,. data with superimposed five-point
running mean 'master' curve.

isotopc composition -ATMOSPHERIC CO2

Catm
~~lig
~~ ht
C3 / C4 ratio SU RFACE VEGETATION CLIMATIC v-| tatue
PRECIPITCATION
CONDITIONS predpitaikon

temperature effect 6i13c

4- - - 8sO, valLue _. rainfall volume effect
Prainotuteffect litterfal decompositiont _ SOIL ORGANICWAFER
ice volumeeffect respiration MATTER BALANCE
aridity a positive water balance
frozen ground N PERCOLATION Y effectofevaporation 613 Cbi. open tclosed
flooding
t syste
N < PERCOLATION a(
+
13b CARBONATE
NO SPELEOTHEM SPELEOTHEM NO SPELEOTHEM 6tCbb BEDROCK
GROWTH GROWTH GROWTH
b13CIS |
CO2 DEGASSING

SPELEGTHEM
133Cc
degree ofsupersaturation GROWTH 8|O
voume of sepage j-- RATE T,w
Figure 8 The main factors that determine the VICc composition of
speleothems (assuming equilibrium conditions). Note that under bare or
Figure 7 The main factors that determine the 58"O composition of only partly vegetated limestone there could be a small direct input of
speleothems (assuming equilibrium conditions) and influence their atmospheric 'C into the percolation water (A. Baker, personal
growth rate. communication).

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 P.W. Williams et al.: Speleothem master chronologies from New Zealand 201
Separating the relative effects of T and P on 5180 variations
remains a challenge. There are at least six considerations of
relevance, some involving the factors determining the a180C value
and some the 58Op value (and through it the 8180w value).
Comparison of 618O values with other
proxy records such as pollen
The usual first step in establishing the polarity of the 8'80c:T
relationship is to compare 5'8Oc values with other proxy palaeocli-
mate evidence such as that derived from pollen spectra. Palynol-
ogical records in New Zealand indicate that the early Holocene
was the warmest period of the Holocene. McGlone et al. (1993)
inferred from New Zealand-wide pollen records that by around
9.13 ka (10k 14C years) BP annual temperatures were 'at least
equivalent to those of today' and, summarizing data from various
proxies, they concluded that between 9.13 and 6.8 ka BP tempera-
tures were 1-2C above present, but declined after 6.3 ka ago.
Newnham et al. (1989) interpreted an early postglacial period of
maximum warmth (and wetness) from about 11 to 7.5 ka ago in
the Waikato region close to Waitomo, and the oxygen isotope
record presented here shows its least negative values in that inter-
val. This positive polarity implies the dominance of the drip water
function over the cave temperature effect in the Holocene at the
sites investigated because of the strong oceanic influence on pre-
cipitation. So we can confirm the conclusion of Williams et al.
(1999) that at Waitomo during the Holocene there is a positive
relationship between B5'Oc and temperature. However, since the
postglacial sea level transgression was not completed in the region
until about 6 ka BP (Gibb, 1986), some of the early Holocene
rise in 8'80c value must be attributable to the reducing ice volume
effect on the oceanic reservoir.
Change of 8180p with latitude
In an analysis of global data on oxygen isotopes in precipitation,
Bowen and Wilkinson (2002) define a negative correlation
between 8180p and station latitude, which they consider to result
from the cooling and distillation of water vapour during transport
in a polewards direction. Because average temperatures decrease
with latitude, this implies a positive relationship of 5'80p to
station temperature. Two stations in New Zealand, Kaitaia and
Invercargill (Figure 1), are separated by 1 1.3 latitude and have a
mean annual temperature difference of 6.2C. The mean
precipitation-weighted 8180p value at the warmer Kaitaia site is
-4.85%o compared to Invercargill with -7.05%o (Taylor, 1990).
This confirms the negative correlation between 8'80p and latitude
(-0.19%c/degree latitude in this case) and reveals a positive
relationship between 8180p and temperature of +0.35%c/0C, which
is significantly greater than the cave temperature effect and so
helps explain the positive d'8O`JdT relationship observed at
Waitomo.
Relationship of 818pO to temperature
Taylor (1990) noted that New Zealand precipitation shows a sea-
sonal effect with 8'80)P values being less negative in summer than
in winter. This implies a positive relationship of 8180p with tem-
perature, which was evaluated for Kaitaia for the period 1963-
91 (there being no later data) by Williams and Fowler (2002).
Correlation of mean monthly precipitation-weighted 5180p values
against average monthly surface temperature revealed a gradient
of +0.21%d0C, although the R2 statistic indicated that only 15%
of the variance was explained. The positive correlation is still
more marked at Invercargill with a gradient of +0.79%od0C, but
with no greater level of explanation. The low variance explained
is probably because surface air temperature is a poor surrogate
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for condensation temperature, and neither were source area sea
surface temperature, storm track history nor rainfall amount taken
into account. The positive relationship at Kaitaia is not evident if
mean annual rather than mean monthly values are correlated. This
is important, because the homogenization of infiltrating rainwater
in the soil and epikarst suppresses monthly 8-variability
(Figure 9).
Relationship of 8180p to precipitation amount
Taylor (1990) recognized a weak rainfall amount effect, with
5180P value negatively related to precipitation amount. Analysis
of monthly data from Kaitaia by Williams and Fowler (2002) con-
firmed the negative relationship and showed that it can be
described by a third-order polynomial model with a R2 value that
explains about 34% of the variance. The negative relationship is
still evident if data are generalized to an annual level, although
with a lower a R2 value. The rainfall amount effect decreases with
increasing latitude, so that by Invercargill there is no discernible
relationship. Therefore the effect could be expected to be less
marked at Waitomo than at Kaitaia.
Combined influence of temperature and precipitation
on ;180
The foregoing indicates that the relationships of temperature and
precipitation amount to '8Op have opposite signs. Consequently,
at Waitomo potential variation in 8180p values will be tend to be
suppressed if years are both warm and wet or cool and dry, which
is typical of La Ninla and El Nifio conditions respectively in this
part of New Zealand, but will be accentuated in a negative direc-
tion in years that are especially wet and cool, and in a positive
direction in years that are both warm and dry. Multiple regression
of mean monthly precipitation-weighted 51801p at Kaitaia against
log monthly rainfall and mean monthly temperature yields the
expression:
8 l80p = - .1 45421ogP + 0.124081 T - 1.2031 1 (5)
This indicates that a 0.1%o decrease in annual average 8180,p value
could be induced by a 140 mm increase in annual rainfall, but
that it could be offset if there were also a 0.8C increase in mean
annual T. However, with an R2 value of 0.34 most of the variance
remains unexplained. Both the rainfall amount and temperature
effects are weak, although the rainfall amount effect is the
stronger in northern New Zealand.
Change of 8180p with altitude
Just as temperature and 8180p values decrease with latitude, so
they also decrease with altitude but at a faster rate. In addition,
in New Zealand as altitude increases conditions generally also
become wetter. As moisture bearing air ascends when crossing
hills, it cools. This affects the condensation temperature of pre-
cipitation and consequently its resulting 8180p value. Schotterer
et al. (1996) found that the altitudinal effect on 8'80P has a range
of 0.15-0.30%o/100 m. From a global data set Bowen and
Wilkinson (2002) identified it to closely average 2%dkm which,
when scaled for deuterium by a factor of eight (Craig and Gordon,
1965), is comparable to the altitudinal gradient for 8Dsmcw
values of 1.7%d/100 m determined for New Zealand rainfall
(Stewart, 1987).
Change of 6180C with altitude
The environmental lapse rate in New Zealand is about
0.6C/100 m. Thus in principle, a cave at an elevation 1 km above
a lowland site should be 6C cooler and receive percolation
recharge from rainwater with a 8180 smowvalue that is 2%o more
negative. Given the relationships expressed in equations (3) and
(4), speleothem calcite would be deposited with 8180 vpDp values
,. ; Sw
202 The Holocene 14 (2004)

o ........... Waitomo
- Ruakuri Rainfall
-1 _h Dfip A- -1Drip B
-2. -2
-3. -3 P;

e4
-]t74:_t
-5
-6
._,4s 5

6
S

-7.7
8~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~8(
-9 -9
-10 . . . . . . . . . . . . . . . . . . . . . --13
(0 (0CD
( CGX
O o GO
X 0) 0 0 0)
a) X 00m 0) 0)ax 0)
n 00 0 0

(- 0 - N
Q Q( O
Q- 0 0X - LOs e X)
CQ NS 0 O
C>l O s4
a0
CD C14 Cl
N0

Figure 9 Stable isotope composition of rainfall and seepage waters from cave drips at Waitomo, New Zealand. Whereas the 'O value of rainwater
shows considerable variation, the B"1O values of percolation drip waters show little variation and are close to that of the average rainfall value (from
Williams and Fowler, 2002).

0.51 to 0.75%o more negative than in the lowland site. Scaled to level at various times was estimated using Huon Peninsula evi-
an altitudinal range of less than 300 m, as occurs in the Waitomo dence from Ota and Chappell (1999). This indicates that sea level
district, the difference in 818O, value attributable to the altitude rose at a rate of 8 m/ka from a low level of -52 m at the start of
effect would be less than 0.2%o. This is within the range of vari- the Waitomo record (11 814 years BP) until 10000 years BP,
ation of 8-values in newly deposited calcite at Waitomo and so after which it continued at a rate of 11 m/ka till -6500 years BP,
the difference would be difficult to detect without a large sample when it attained its present level. As this occurred the 818O value
size. Nevertheless, the implied change of Bl8c with altitude is of sea-surface water changed. The amount of change can be
about 0.06%dlO00 m, which indicates that the value determined determined from the difference between the 8 18Oc values of plank-
empirically from speleothem samples by Williams et al. (1999) tonic foraminifera in New Zealand waters over the last 6.5 ka
was an overestimate. compared to the LGM and the difference in sea-level position
over the same interval. Using foraminiferal data for Globigerina
Relationship of 8180C to temperature, rainfall and bulloides from Nelson et al. (1993) for DSDP Site 594, which is
source-area variations just south of the Subtropical Convergence on the Chatham Rise
It is clear from the above that some influences bear negatively to the east of the South Island (Figure 2), a 818O value shift of
and others positively on the dBl80JdT relationship. Positive 1 .54%o can be determined, although its representativenessfor con-
influences are the latitude effect and the at-a-site 818Op versus ditions off the western North Island is uncertain. Part of the V8O
temperature relationship. The altitude effect on 8'8Oc is relatively value change in the foraminifera is due to a change in seawater
small. These are offset by negative influences such as the cave temperature. If this temperature influence is excluded, then the 8-
temperature effect, which is constant at all sites, and the rainfall value change due to ice volume alone is less. On a global basis,
amount effect, which in New Zealand becomes less influential Shackleton (2000) concluded that the ice volume contribution to
with increasing latitude. If conditions at Waitomo were similar in the difference between the LGM and the Holocene is -1 .0%o. Fur-
terms of mean temperature and V8Op to Invercargill today, equiv- thermore, since the 5-value change in surface as opposed to deep
alent to an effective latitude shift of 8.40, then substitution in waters may be different and may vary from place to place, it is
equations (3) and (4) suggests that the 8180 value of speleothems clear that significant uncertainty surrounds the most appropriate
at Waitomo would be approximately 1.3-2.0%o more negative. representative figure to adopt for the 8-value change due to the ice
This implies a dbl8'OJT relationship of 0.54 0.12%a/C, which volume effect at specific sites. Nevertheless, a rate of 0.01%dm is
is larger than that estimated previously by Williams et al. (1999). of the right order and is used here. The resulting 8'O. master
Over long periods of time during the deposition of speleothems, curve adjusted for ice volume effect is shown in Figure 10. The
other factors can influence b88p, 8 '80 and therefore 8180c. adjustment yields a correction of 0.62%o at the start of the record.
Changes in source area characteristics of atmospheric moisture are
particularly important. Such changes were especially significant Factors affecting speleothem 813CC composition
during the last glaciation, when sea level was up to 130 m lower Several recent papers have discussed 8'3C values in the atmos-
and ocean water was enriched in 180 because of the ice volume phere, soil and cave environments (Dulinski and Rosanski, 1990;
effect (Shackleton, 2000). Changes in isotopic composition of Baskaran and Krishnamurthy, 1993; Shopov et al., 1997; Baker
atmospheric moisture also arise because source-area character- et al., 1997; Denniston et al., 2000; Genty et al., 2001). Whereas
istics, such as sea-surface temperature and salinity, vary because it was once common to interpret 8'3C0 variations mainly in terms
of changes in prevailing wind direction and strength. During the of vegetation changes, it is now appreciated that such variations
Last Glacial Maximum (LGM), for example, westerly winds are a result of a complex interplay of several variables (Figure 8).
across New Zealand were stronger, and sea-surface temperatures Four factors are especially important: the concentration and iso-
off the west coast of the North Island were 5-6C cooler than topic composition of CO2 in the atmosphere; production of bio-
today (Barrows et al., 2000). genic CO2 by plant and soil processes; inorganic carbon sourced
In order to make adjustments for the ice volume effect in the from karst bedrock; and outgassing (or degassing) of CO2.
early-Holocene section of the Waitomo record, the position of sea Whether the dissolution of calcium carbonate bedrock by the

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 P.W. WiDliams et al.: Speleothem master chronologies from New Zealand 203
-2.0 Waitomo
-2.5
-3.0
-3.5-
-4.5
-5.0
12000 11000 10000 9000 8000
Figure 10 Composite B58O-,pBmaster series for Waitomo showing adjustment for the ice volume effect prior to 6500 years BP.
percolating water occurs under open or closed system conditions
with respect to soil CO2is also important (Hendy, 1971; Salomons
and Mook, 1980; Dulinski and Rosanski, 1990). These points are
discussed below.
(1) During glacial-interglacialcycles, the concentration and iso-
topic composition of atmospheric CO2 changes (Stauffer et al.,
1998; Petit et al., 1999). Concentrations varied from about 200
ppm by volume between 17 and 18 ka BP to about 280 ppm by 10
to 11 ka BP (Sundquist, 1993). This might be termed the glacial
atmosphere effect. During the Holocene, the peak concentration
of CO2 at 11 ka BP was followed by a reversal to -250 ppm by
9 ka BP and then a return to -270 ppm by 7 ka BP. From then
on, concentrations remained relatively stable between 270 and 290
ppm until 1 ka. CO2 concentrations then rose from near 280 ppm
in AD 1750 to just below 290 ppm in 1850 and to about 353 ppm
in 1990 (Sundquist, 1993). For every 100 ppm increase in CO2
there is a -2.0 0.1%o change in the 813C pl of plants (Feng and
Epstein, 1995; Hattd et al., 2001); so plants track CO2 concen-
tration changes in the glacial-interglacial atmosphere. Atmos-
pheric CO2 isotopic data over a glacial cycle are sparse, but
8 a3C,values appear to have been around -6.7%o during the LGM
and about -6.4%o by 10 ka BP (Leuenberger et al., 1992). Stauffer
et al. (1998) found a weak negative correlation between
and CO2 values. Pre-industrial values were about -6.5%o and had
changed to about -5.9%o by AD 1920 and -8.2%o by the early
1990s (Baskaran and Krishnamurthy, 1993).
In New Zealand, the glacial atmosphere effect is well illustrated
in the '3Cc record for Nettlebed Cave in the South Island, where
'3C, values decreased from +l1.58%o 20.6 ka ago during the LGM
to -7.69%o by 14.23 ka ago. A slow but irregular enrichment then
occurred to -5.18%o around 0.13 ka ago (Hellstrom et al., 1998).
Since the postglacial increase in atmospheric CO2 concentration
ceased by about 11 ka BP, the influence of the glacial atmosphere
effect was almost complete by the time the Waitomo records
discussed here commenced.
(2) Photosynthesis preferentially removes '2CO2 from the
atmosphere; so the atmosphere becomes enriched in '3C02 under
interglacial conditions. This has a direct effect on plant 813CPi
values. Carbon assimilated by the vegetation through photosyn-
thesis reaches the soil directly from litterfall, and indirectly
through the roots as soluble exudates, mucilage, dead root
material and CO2. The photosynthetic pathway that plants follow
affects the 8'3Cpa values of their respired C02, which is in the
range of -26 to -20oo for C3 plants and -16 to -10%o for C4
plants (Cerling, 1984). Decomposition and respiration processes
within the soil in turn affect the 813Cog value of soil CO2. Warm
soil temperatures enhance respiratory activity (Tate et al., 1993)
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-5PRM
- Ice Volume Adjusted
7000 6000 5000 4000 3000 2000 1000 0
YEARS (BP)
and there is preferential uptake of '2C during the formation of
plant material and the release of 13C enriched respiration CO2
(Salomons and Mook, 1980). During periods of low plant activity,
soil CO2 has high values of 8'3C, probably due to a greater admix-
ture of atmospheric CO2. The water balance of the soil also affects
5'3CP, with 8-values becoming higher (less negative) as aridity
increases. This effect was illustrated in eastern Australia by Ste-
wart et al. (1995), who measured a decrease of 0.33 0.07%o per
100 mm increase in precipitation.
In New Zealand almost all plants follow the C3 photosynthetic
pathway (Wardle, 1991), so 5'3CP values are low. The outcome
for soil CO2 derived from C3 vegetation cover is about -25%o
5'3C,0, Consequently, water passing from the soil into the under-
lying rock has a composition reflecting biological processes and
exchange with the open atmosphere, although since PCO2is much
greater in the soil than in the open atmosphere, soil influences
dominate.
(3) Percolating water is enriched with dissolved CO2 and there-
fore dissolves limestone bedrock which contains 'dead' carbon,
although dead carbon can also be derived from overlying soil
organic matter such as peat (Genty et al., 2001). Hendy (1971)
showed that under closed-system dissolution 'dead' carbon could
B`3Ca, comprise 35-50% of the carbon in speleothems, thereby
indicating the substantial dilution of modern carbon that can
occur. However, the dead carbon proportion is less under open-
system conditions and the proportion of openklosed dissolution
will vary from place to place. From European examples, Genty
et al. (2001) show a dead carbon proportion range of 10-38%.
Delta 13C,t values of limestone bedrock are relatively high,
ranging from about -0.98 to -1.72%o in the case of the Oligocene
limestones from Waitomo (Williams et al., 1999). Thus the
greater the addition of the inorganic 8-component from the bed-
rock, the higher the resulting 5'3C value of the seepage water
as it approaches the cave where speleothem deposition occurs. If
carbonate dissolution occurs under closed-system conditions, as
is generally the case at Waitomo with its very thick volcanic soils,
resulting 5'3C values will be considerably less negative than under
open-system conditions (Salomons and Mook, 1980). The relative
significance of the bedrock component also varies with the time
that percolating water is in contact with the rock. In periods when
rainfall is relatively high, flushing rate is increased and residence
time of water in the epikarst is decreased; so the opportunity for
inorganic 813C enrichment also decreases (Shopov et al., 1997).
The effect on 8'3CC values operates in the same direction as the
effect of high rainfall on plants which, as noted above, leads to
a decrease in 513CP1. So wet conditions give rise to relatively low
5'3Cc values.
_w S _
204 The Holocene 14 (2004)
(4) When seepage water that was enriched with CO2 in the soil
percolates through the aerated zone, outgassing of CO2 occurs.
This is important in the cave atmosphere, where PCO2 is close to
that found in the open atmosphere. It is also sometimes important
in aerated fissures en route to the cave, where it leads to the criti-
cal supersaturation that results in calcite deposition on speleo-
thems. This process leads to enrichment of the solution in '3C.
Baker et al. (1997) draw attention to the importance of the work
of Dulinski and Rosanski (1990) in modelling the processes that
lead to the formation of '3C/'2C isotope ratios in speleothems, and
point especially to the importance of time since first deposition
of calcite in accounting for variations of 8'3CC.
Key features of the Waitomo
palaeoclimate record
Palaeoecological and lake-level evidence from Lake Maratoto
were used by Green and Lowe (1985) to infer late-Pleistocene to
Holocene climatic change in the Waikato lowlands about 45 km
northeast of Waitomo. A detailed figure updating their con-
clusions was published in Newnham et al. (1999) part of which
is used here to compare to the speleothem stable isotope data from
Waitomo (Figure 1). In the Waitako lowlands, reafforestation
had commenced around 14.5 ka BP and the region was densely
forested by 12 ka BP (Newnham et al., 1989). In the eastern North
Island, an unequivocal cool period has been identified and pre-
cisely dated by Newnham and Lowe (2000) in the lateglacial pol-
len record between c. 13.6 and 12.6 ka BP, after which it warmed
to an early-Holocene optimum. By the start of the speleothem
records from Waitomo, therefore, conditions were already warm
with temperatures close to the maximum encountered in the Holo-
cene and the area was fully forested. After 7 ka BP the decline
of certain drought- and frost-sensitive species indicates cooler
average temperatures and greater seasonal variability.
ed
518oC
Wetter,warming
but cooler Drier and warmer
than present
14 12 10
Figure 11 Comparison of b181c (corrected for ice volume effect) and bl?Cc from Waitomo with an interpretation from Lake Maratoto records of palaeo-
environmental conditions in the Waikato (Lake Maratoto informnation from Newnham et al., 1999). Peaks a-e in the b 'C. record probably represent
relatively dry intervals.
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r
Oxygen isotope records
The 18OC record is corrected for ice volume. The correction of
-0.62%o at the beginning of the record could be in error by
0.1%o, but the correction gradually reduces to zero by 6 ka BP.
The record commences with a trend towards less negative values
that captures the warming that characterized the earliest Holocene.
The overriding characteristic of the 8'8Oc master curve is the grad-
ual decrease in values from a peak value of -3.26%o at 10.8 ka
BP to troughs of -4.39%o at 3.6 ka BP and again at 3 ka BP
followed by a rise to -3.51%o at 0.8 ka BP and a decline to a
present value of about -4.l%o. The period of least negative bi8Oc
values coincides with the warm and wet interval from 11-7.5 ka
BP identified by Newnham et al. (1989) from pollen records in
the nearby Waikato region. So, bearing in mind the rainfall
amount effect, the positive deviation of 818O, would have been
moderated by the wetness rather than accentuated by it. Further
confirmation of warm conditions in that interval is provided by
evidence that: (i) treelines reached their highest Holocene altitudes
in the central North Island between 10 and 7.5 ka ago (Ogden
et al., 1997); (ii) throughout New Zealand there was a rapid con-
traction of glaciers between 12 and 8 ka BP (Gellatly et al., 1988);
and (iii) rates of speleothem growth were also faster in the earlier
part of the record (Figure 2).
After 6.2 ka BP VOc values, although oscillating, generally
become more negative until about 3 ka BP. This implies cooling,
an interpretation that is supported by pollen records, which
indicate cooling to have occurred after 6.3 ka BP (McGlone, 1988;
Newnham et al., 1989). The oscillating decline in &-values also
mirrors the cooling trend identified from Lake Maratoto records
(Figure 11). The Tasman Glacier in the South Island had several
episodes of expansion during this late mid-Holocene interval, as
indicated by the series of moraines dated by Gellatly et al. (1985;
1988), which tends to reinforce conclusions about the coolness of
the interval.
From 3.6 to I ka BP the droughty summers identified from
Lake Maratoto and Waikato pollen records were probably associa-
--6
c a
b
~~~~~-8
.--10
--12
A A . Af A ' -4 %
Very, Graadually cooler ' Droughty summers,
awet
?j
and drier , colder winters
I~~~~~~~~~~~~~~~~~~~~~~~~~~~
8 6 4 2 0
YEARS (ka BP)
 P.W. Willams et al.: Speleothem master chronologies from New Zealand 205
ted with increasing average warmth, judging by the upwards trend
in Bi8Oc values. This culminated in a late-Holocene b18QO peak
from 0.9 to 0.6 ka BP. However, it was short-lived and gave way
to a minor cool interval at about 0.3 ka BP (approximately AD
1675). Delta "8, values and temperatures have since increased.
Superimposed on the general trend of 88O, throughoutthe Hol-
ocene are numerous oscillations with amplitudes of about 0.25%o
that become especially evident after 6 ka BP when sea level
c.
had stabilized. They may have been present earlier, but the lower-
resolution sampling makes detection less certain. These oscil-
lations suggest temperature swings that might be as great as 0.5
C given the latitudinal gradient of around 0.54%o iOJ'C noted
earlier, although all the above points about Holocene temperatures
need to be qualified because of the effect of precipitation on 8 180
values. The amplitude of variation of b18O" will be moderated by
the influence of precipitation amount, with dry years tending to
make VO8c more positive than they would otherwise be, and
vice versa.
Carbon isotope records
The averaged measurements from Waitomo range from -10.67%o
at 10.9 ka BP to -7.04%o at 6.0 ka BP, and a greater variability
is displayed in individual 8i3Cc curves than is evident in the corre-
sponding 8&Oi curves. The start of the a '3Cr master curve (Figure
6B) shows a steep decline in 8-values that may be related to the
increase in concentration of atmospheric CO2 as the glacial
atmosphere adjusted to interglacial conditions. By 11 ka BP,
atmospheric CO2 had attained 280 ppm, fell slightly to 9 ka BP
and increased slowly to 290 ppm by 1 ka BP (Sundquist, 1993).
Throughout the Holocene, 8&3CC values vary considerably, but
instead of displaying an inverse relationship with atmospheric
CO2 concentration they show an oscillating slowly rising (less
negative) trend. This is probably a reflection of drier conditions
and longer residence time of water in the epikarst as well as of
reduced biological activity in the cooler conditions following
the hypsithermal.
From pollen and lake-level evidence in the nearby Waikato
region, Green and Lowe (1985) and Newnham et al. (1989) inter-
pret conditions to have been wet (as well as warm) around 11 ka
BP, becoming drier (as well as cooler) after 8 ka BP, with falling
lake levels and other evidence for drier conditions after 5.5 ka
BP, and a dry period noted around 3.5 ka BP. Comparison of
these proxy indicators of water-balance conditions with the 5i3C,
curve on Figure 11 shows the wet early Holocene to coincide with
the most negative 8'3CC values and the dry episode around 3.5 ka
BP to coincide with peak b between 4.0 and 3.6 ka BP. The drying
trend of the mid- to late Holocene corresponds with gradually less
negative a 13C values. Newnham and Lowe (1991) also identify
lower lake levels after 1.8 ka BP in the Auckland isthmus, and this
coincides in timing with the rising trend of 8i3Cr after 1.2 ka BP.
Superimposed on the overall trend is an asymmetrical zigzag
oscillation with peaks at about 10.6, 8.3, 6, 3.8 and 1.7 ka BP
(marked a-e on Figure 11) and troughs at about 10.9, 9.2, 7.8,
5.4, 3.4 and 1.2 ka BP. These indicate a periodicity in the record
with a wavelength of c. 2250 years. The oscillations have ampli-
tudes averaging about 1.9%o. The absence of such a periodicity
in the Antarctic CO2 data suggests that it does not arise from the
effect of atmospheric CO2 on plants, but from a regional environ-
mental phenomenon. While periodicity is also apparent in the
Bi8Oc record it is of a different (higher) frequency; so the influ-
ence of periodic warming and cooling on biological activity is
unlikely to be the underlying cause of cyclicity in the fi3C" signal.
Consequently, the most plausible explanation would be periodic
changes in the water balance (and hence in epikarstic flushing
rate), which would result in variations in the fi3C :8i3C,a ratio
(Figure 8) and hence in fluctuations in V'3C value at the point
of speleothem deposition. As noted earlier, high precipitation is
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associated with low values of B'3Cp1 as well as with reduced water-
rock contact time. So, in the context of maritime New Zealand in
the Holocene with only C3 vegetation, negative swings are likely
to represent wetter intervals and positive swings drier intervals
(though still always wet enough at Waitomo to support forest).
However, it should be noted that catastrophic disturbances
sometimes occur in New Zealand vegetation and that in the
Waikato pollen record Newnham et al. (1989) recognized regular
c. 3000 year cycles of Dacrydium dominance. Thus, while 8'3CQ
fluctuations are most likely to be driven by variations in effective
precipitation, plant influences probably also play a part.
At times when relatively negative 8'3C, values coincide with
relatively positive B8i8O values, it is likely that high rainfall
results in more negative b88 and so suppresses I8O, peaks. This
was probably the case around 10.8 ka BP. Hence it is likely that
the warmth of the hypsithermal is underestimated by the magni-
tude of the b18Q0 excursion. During the mid-Holocene between
5.4 and 4.25 ka, and at 3.4 ka BP, relatively negative but oscillat-
ing 5i80, values coincided with periods of relatively negative
bl3C, values. These negative excursions imply low but variable
temperatures at a time when it was relatively dry, and so it may
well have been still cooler than implied by the depth of the
negative bi8Oc excursions, because of the inverse relationship of
8 IOp to P.
Discussion
It is interesting to compare the Waitomo record with palaeocli-
mate evidence from elsewhere in the Southern Hemisphere and
to establish whether events in New Zealand are synchronous with
Holocene temperature changes in the Northern Hemisphere.
The early-Holocene thermal optimum from 11 to 8.5 ka BP in
northern New Zealand coincides almost exactly in time with that
in Antarctica, where Masson et al. (2000) found maximum tem-
peratures to prevail between 11.5 and 9 ka BP. This contradicts
the commonly admitted picture of a worldwide mid-Holocene
optimum. It is also contrary to the view of Iriondo (1999), who
suggested that the hypsithermal in the Southern Hemisphere gen-
erally occurred between 7000 and 6000 years ago, although Mas-
son et al. (2000) identified a secondary optimum at about that
time in the Ross Sea sector. The early-Holocene temperature peak
interpreted from Waitomo speleothem records is also strongly
supported in New Zealand by palynological evidence (Newnham
et al., 1989; McGlone et al., 1993). Palaeotemperature interpret-
ation of a speleothem record from Lynds Cave also suggests a
warm interval in the early Holocene prior to about 11 ka BP in
Tasmania (Goede, 1998).
In contrast, speleothem records in the Northern Hemisphere
(McDermott et al., 1999) point to a thermal optimum in NW Italy
between 9.2 and 7.8 ka BP and in SW Ireland between 9 and 6
ka BP; thus agreeing with the idea of a mid-Holocene optimum,
at least in Europe. Therefore speleothem 8'8O chronologies from
around the globe provide a means of testing the timing of the
Holocene temperature optimum. The evidence from Waitomo so
far suggests that the Holocene temperature maximum in the SW
Pacific may have occurred -2000 years earlier than in Europe.
At Waitomo, a mid- to late-Holocene temperature minimum
marks the interval 6 to 2 ka BP. Goede et al. (1996) identified a
cool period in Victoria around 3 ka BP and, in the south-central
Andes, Grosjean et al. (1998) noted a late-Holocene glacial
advance during this period. Late mid-Holocene cool periods have
also been identified in the Northern Hemisphere. For example,
Norway was especially cool for a few centuries centred on 3.7 ka
BP (Lauritzen and Lundberg, 1 999b). From the speleothem record
in North America, Dorale et al. (1992) also identified a cold inter-
val in Iowa from 3.6 to 1.15 ka BP. Thus a late mid-Holocene
206 The Holocene 14 (2004)
cool episode appears to be characteristic of both hemispheres.
Nevertheless, this generally cool interval was also punctuated by
some relatively mild peaks. At Waitomo, relatively high 8l8O,
values suggest that these occurred at 5.1, 4.9, 4.4, 3.9, 3.2, 2.8 and
2.4 ka BP, showing a rough correspondenceto the warm period in
Iowa from 5.7 to 3.6 ka BP when temperatures were interpreted as
being almost 4C above those that followed (Dorale et al., 1992).
The late-Holocene warm peak at Waitomo implied by relatively
high 818Q, values between 0.9 and 0.6 ka BP coincides closely
with a warm episode in some parts of Europe, when around
AD 1200 in England temperatures may have been 1-1.5C
warmer. This is sometimes referred to as the 'Mediaeval Warm
Period', although Jones et al. (1998) found little evidence to sup-
port its general occurrence. In New Zealand this coincided with a
period of Polynesian settlement (McGlone and Wilmshurst, 1999).
Temperatures, as implied by falling b80 values, subsequently
cooled rapidly to a trough about 325 years ago, although at
Waitomo bl8C values were only marginally below present levels.
Jones etal. (1998) noted that the seventeenth century was the
coldest century of the last millennium in the Northern Hemisphere
and that the coldest decade was 1691-1700. This was the culmi-
nation of the 'Little Ice Age' in Europe (Grove, 1988) and it corre-
sponds closely in time with the implied temperature depression at
Waitomo about 325 years ago.
The Holocene record from New Zealand therefore conveys
mixed messages concerning synchronicity with events in the
Northem Hemisphere. Postglacial warming in the early Holocene
in New Zealand occurred about 2000 years earlier than in Europe,
but the late mid-Holocene cool episode about 2-4000 years ago
and a warm interval that may be the equivalent of the 'Mediaeval
Warm Period' appear to broadly coincide.
Conclusions
The research finds the stable isotope records from four speleo-
thems from Waitomo to be broadly consistent, although they show
differences in detail, especially in the case of 8'3C values. The
overall reproducibility of trends is reassuring, but the divergences
highlight the necessity for caution when interpreting the palaeo-
climate record of just one speleothem. A major cause of mismatch
between individual records was probably the errors arising from
interpolating ages between widely spaced dates. Relatively close
dating is required to overcome this problem, which becomes acute
when there is variability in speleothem growth rate. However, the
relatively greater variability and mismatch in individual V'3C
records compared to 818O may be a reflection of the greater
dependency of the V'3C signal on local rather than regional
factors.
The palaeoclimatic interpretation of the j18O trend over the
Holocene was consistent with that deduced previously from the
region's pollen record. A positive relationship was indicated
between 815O and temperature, although 8180 was also found to
respond inversely to precipitation amount. Delta'3C was con-
sidered on theoretical grounds mainly to reflect water-balance
conditions, and although proxy records of effective precipitation
are relatively sparse, this interpretation was consistent with water-
balance data interpreted from lake-level and pollen data.
We conclude that the Holocene thermal optimum in northern
New Zealand occurred from 11 to 8.5 ka BP and that it was fol-
lowed by a mid-Holocene thermal minimum from 6 to 2 ka BP,
culminating around 4-3 ka BP. Effective precipitation varied con-
siderably through the Holocene. From a relatively wet beginning
around 11 ka BP it became gradually drier, although this trend
was marked by periodic oscillations with a wavelength of about
2250 years. The mid-Holocene was not uniformly cold, having
been interrupted by at least seven short mild intervals, as well as
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being marked by some significant swings in effective precipi-
tation. The late Holocene was significantly warmer, especially
from 0.9 to 0.6 ka BP, suggesting a correspondence with the
'Mediaeval Warm Period' as found in parts of Europe. However,
although this implies synchronicity with the Northern
Hemisphere, the much earlier occurrence of the Holocene thermal
optimum contradicts this. It is clear that much more high-resol-
ution palaeoclimate research is required on speleothem records
before the issue of climatic synchronicity between the northern
and southern hemispheres can be resolved.
Acknowledgements
We are grateful to the NZ Foundation for Research, Science and
Technology for funding support under contract UOAXOO1 1 for P.
Williams, and to the Australian Research Council for an
Australian Research Fellowship (No. ARFIF39802775) support-
ing J. Zhao. The final paper benefited considerably from detailed
constructive critical comment on an earlier version of the manu-
script by Andy Baker and another unknown referee.
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