Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200

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Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

A New Zealand record of sea level rise and environmental change during the
Paleocene–Eocene Thermal Maximum
Luke Handley a,⁎, Erica M. Crouch b, Richard D. Pancost a
a
Organic Geochemistry Unit, Bristol Biogeochemistry Research Centre, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK
b
GNS Science, PO Box 30368, Lower Hutt 5040, New Zealand

a r t i c l e i n f o a b s t r a c t

Article history: The global warming associated with the Paleocene–Eocene Thermal Maximum (PETM) ca. 55.5 Myr ago is the
Received 14 May 2010 most dramatic identified short-term temperature increase of the Cenozoic. One direct consequence of a
Received in revised form 2 March 2011 warming world is a rise in sea level, due primarily to the thermal expansion of water as oceans warmed. The
Accepted 7 March 2011
Kumara-2 core, South Island, New Zealand, spans the Paleocene/Eocene transition and provides a rare
Available online 11 March 2011
southern hemisphere continental margin record of the PETM. Lithology, palynology and compound-specific
Keywords:
stable isotope compositions of higher plant leaf wax n-alkanes reveal a 4.85 m PETM and a carbon isotope
Carbon isotope excursion (CIE) of ca. − 4.5‰, larger than the − 2.5 to − 3.5‰ CIEs generally recorded by deep sea
Hydrogen isotope foraminifera. There is a shift from a terrestrial to a marine, potentially anoxic, sedimentary depositional
Plant microfossil assemblage environment at the base of the PETM, interpreted as being the result of a local sea level rise. Coincident with
Palynology the onset of the CIE is the appearance of pollen associated with thermophilic conditions and the development
Organic geochemistry of Nypa mangrove swamps. Moreover, there is a reorganisation of the angiosperm pollen assemblage during
the PETM, and an initial increase in fern spores and decrease in gymnosperms. Crucially, all of these changes
occur below the horizon characterised by the most negative δ13C values, suggesting that: 1) the recorded
negative excursion of 4.5‰ may indeed reflect the shift in atmospheric CO2 isotopic composition; and 2) that
the large input of 13C-depleted carbon into the ocean–atmosphere system was not geologically instantaneous,
with at least some of the added carbon lagging warming, sea level rise and vegetation change. Furthermore,
compound-specific hydrogen isotope analyses show a large degree of variability both directly before and
during the CIE, suggesting that the PETM in New Zealand was characterised by complex and transient changes
in the hydrological regime, similar to those reported in North America, the Arctic and Eastern Africa. Thus, the
new PETM record from Kumara-2 reveals local climatic and biotic responses, driven by a combination of
global warming and the consequential change in local depositional environment induced by sea level rise.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
The Paleocene–Eocene Thermal Maximum (PETM) is one of the most
abrupt climatic events of the Paleogene, characterised by an increase in
global temperatures that remained elevated for ca. 170 kyr (Röhl et al.,
2007). This temperature increase has been estimated to be 4–6 °C for the
deep ocean (Kennett and Stott, 1991; Bralower et al., 1995; Tripati and
Elderfield, 2005), 5 °C for tropical sea surface waters (Bralower et al.,
1995; Thomas et al., 1999; Zachos et al., 2003), 5–8 °C for mid to high
latitude surface waters (Kennett and Stott, 1991; Zachos et al., 2003;
Sluijs et al., 2006; Zachos et al., 2006) and 8 °C for Arctic mean annual air
temperatures (Weijers et al., 2007). The PETM global warming period
was most likely driven by a dramatic increase in atmospheric pCO2 (e.g.
Pagani et al., 2006a; Panchuk et al., 2008), although some recent
⁎ Corresponding author at: address: NIOZ Royal Netherlands Institute for Sea
Research, Department of Marine Organic Biogeochemistry, PO Box 59, 1790 AB Den
Burg, Texel, The Netherlands. Tel.: +31 222369408.
E-mail address: luke.handley@nioz.nl (L. Handley).
modelling studies suggest that such an increase cannot alone account
for the inferred warming such that other unidentified processes and/or
feedbacks must have also contributed to the rise in global temperatures
(Zeebe et al., 2009).
The source of this carbon dioxide remains uncertain, but evidence for
a massive injection of 13C-depleted carbon into the ocean–atmosphere
reservoir comes from the presence of a negative carbon isotope
excursion (CIE) recognised in organic and inorganic carbon. This
decrease in δ13C values is recorded in marine carbonates (Shackleton,
1986; Kennett and Stott, 1991; Bains et al., 1999; Thomas et al., 2002;
Zachos et al., 2003; Zachos et al., 2006), in both marine (Bolle et al., 2000;
Sluijs et al., 2006) and terrestrial total organic carbon (Magioncalda et al.,
2004; Collinson et al., 2007), in paleosol carbonates (Koch et al., 1992;
Koch et al., 1995; Bowen et al., 2002; Schmitz and Pujalte, 2003) and in
individual terrestrial biomarkers (Pagani et al., 2006b; Smith et al., 2007;
Handley et al., 2008).
Sea level change may have been another consequence of PETM
warming. Although Earth in the Early Paleogene is generally believed to
have been ice-free, a number of recent studies (Speijer and Wagner,

0031-0182/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2011.03.001
186 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200
2002; Miller et al., 2005; Hollis et al., 2009) suggest the presence of
ephemeral small ice sheets in Antarctica, and melting of these ice sheets
prior to or during the PETM would result in sea level rise. Moreover, a
global temperature increase of 5 °C would translate into a eustatic rise of
3–5 m through thermal expansion of seawater (using the temperature–
volume relationship of seawater of 1.9 × 10− 4 m3/°C). In coastal regions,
a sea level rise would have a direct impact on both marine and terrestrial
biota, along with the source of organic matter delivered to sediments.
Sluijs et al. (2008a) recently presented evidence for a sea level rise
associated with the PETM. Examining sites from the New Jersey Shelf,
North Sea, Arctic Ocean and New Zealand, they observed palynological
and organic biomarker changes that indicate near-shore marine
sections became located further from the coast during the PETM. The
collective results from their study point towards a eustatic rise with a
maximum flooding surface during the early stages of the PETM, possibly
initiated prior to the associated negative CIE (Sluijs et al., 2008a).
Documenting the magnitude of the CIE and the impact of warming on
local depositional environments is crucial for our understanding of the
quantity of carbon released and the impacts of global warming. The
Kumara-2 core in New Zealand (Fig. 1) spans the Late Paleocene–Early
Eocene, including the PETM; unlike other New Zealand marine records
deposited in an outer shelf-upper slope setting (Kaiho et al., 1996;
Hancock et al., 2003; Hollis et al., 2005) the Kumara-2 core represents one
of the few known Southern Hemisphere continental margin records that
span this time interval. The sequence is characterised by a transient
switch, during the PETM, from a terrestrial to a shallow marine
depositional setting (Sluijs et al., 2008a). The Kumara-2 core contains
well preserved organic matter, which has allowed us to complete a multi-
proxy study of biomarkers and palynomorph assemblages across the
PETM to provide information on the depositional environment and
associated local effects of abrupt global warming. Specifically, the CIE is
documented using n-alkane compound specific δ13C values, to provide a
new record with which to consider the magnitude of carbon release.
Changes in depositional environment, including changes in organic
matter input, and changes in the plant community structure are evaluated
using organic biomarkers and palynomorphs. We use compound-specific
hydrogen isotopes of higher plant leaf wax n-alkanes to constrain
whether environmental changes included variations in the hydrological
cycle and local humidity, as recorded across the PETM at northern mid
latitudes (Smith et al., 2007) and the Arctic (Pagani et al., 2006b).
Moreover, we compare the timing of these changes to that of the n-alkane
recorded CIE in order to evaluate whether environmental change
preceded or lagged the input of 13C-depleted carbon into the ocean–
Fig. 1. Location of the Kumara-2 exploration well in the South Island, New Zealand.
atmosphere reservoir and whether this large input was geologically
instantaneous or not, as has been suggested from some recent studies
(e.g. Sluijs et al., 2007; Sluijs et al., 2008a).
2. Site and sample description
The Kumara-2 exploration well was drilled in 1985 and is located
in central Westland, South Island (NZTopo50 map grid reference
BU19/519 849), ca. 20 km south of the Greymouth township (Fig. 1).
The well was drilled to a total depth of 1756 m, with several intervals
throughout the well being cored. A core interval was taken from 1753
to 1197 m below the surface (mbs), and we have examined sediment
from this interval, spanning 1750 to 1710 mbs (Fig. 2). The lower
40 m of core incorporates Paleocene and Eocene sediments of the
Brunner and Paparoa coal measures (Carter et al., 1986; Raine, 1986).
Terrestrial sediments are predominant in the lower 40 m of core and
consist of a mixture of sandstone, shales, mudstones and coals (Fig. 2),
with the depositional environment interpreted as backswamp, over-
bank and channel fill deposits (Carter et al., 1986). However, marine
sediments occur from 1739.1 to 1734.25 mbs (Carter et al., 1986).
3. Methods
3.1. Palynological analyses
30 samples, from 1749.98 to 1710 mbs, were processed for
palynological analysis. Samples were collected from mudstone, shale,
coal and fine sandstone sediments. Between 6 and 40 g of sediment were
crushed, dried in an oven and treated with hot 10% HCl and 50% HF for
carbonate and siliceous removal, respectively. Oxidation was completed
and due to the variety of sediment types oxidation times ranged from 15
to 70 min. Samples were then sieved over a 6 μm mesh to remove small
organic and mineral particles. To break up clumps of residue, samples
were placed in an ultrasonic bath for a maximum of 3 min during the
sieving process. Well-mixed representative fractions of the N6 μm
residue were mounted on glass slides using a glycerine jelly medium
and analysed. The quantitative examination involved a minimum count
of 200 spores and pollen and, where possible, a minimum of 100
dinoflagellate cysts. Slides were also scanned for additional taxa. In
addition, a count of 100 palynomorphs was completed to calculate the
percentage of terrestrial and marine palynomorphs. Three samples,
1733.97, 1725.15 and 1722.96 mbs, contained very sparse palynomorph
assemblages and are not discussed further.
 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200 187

Fig. 2. Lithological column, n-alkane δ13C records, relative abundance of marine palynomorph and the dinoflagellate genus Apectodinium, total organic carbon (TOC) content, and (Pr + Ph)
concentrations for the Kumara-2 core in New Zealand across the Paleocene/Eocene boundary. (A) Compound specific δ13C values of terrestrial higher plant derived n-alkanes. The error bars
represent one standard deviation based on duplicate analyses; (B) Relative abundance of marine palynomorphs, as a percentage of the total palynomorph assemblage, and Apectodinium
relative abundance as a percentage of the total dinocyst count; (C) TOC content expressed as % of total freeze-dried sediment weight; (D) Total TOC-normalised pristane and phytane (Pr + Ph)
concentrations, expressed as μg per g of sedimentary organic carbon. Sampling horizons are highlighted on the lithological column; Mst: mudstone; Sst: sandstone. The shaded area highlights
the PETM CIE. The arrows and horizontal dashed lines indicate the first occurrences of the angiosperm taxa Cupanieidites orthoteichus and Spinizonocolpites prominatus (☆), which mark the
base of New Zealand miospore zone PM3b and base of the Eocene, and the most abundant occurrence of the dinoflagellate genus Apectodinium (✻).

3.2. Organic and biomarker analyses
3.2.1. Bulk organic analyses
28 samples were gently washed with methanol (MeOH) and
powdered with a Retsch PM100 Ball Mill. Total organic carbon, inorganic
carbon, sulphur, and total nitrogen were measured as a mass% of the total
sediment using a Carlo Erba EA 1108 and a Coulomat 702 (Strohlein).
3.2.2. Lipid biomarker extraction and fractionation
For biomarker analyses, the powdered samples were extracted via
Soxhlet apparatus for 24 h using dichloromethane (DCM)/MeOH (2:1
v/v) as the organic solvent. The total lipid extracts were separated into
two fractions on an aminopropyl solid phase extraction column by
elution with DCM/iso-propanol (3:1 v/v; neutral fraction) and 2% (by
volume) acetic acid in diethyl ether (acid fraction). The neutral
fraction was further split using a column packed with (activated)
alumina by elution with hexane (saturated hydrocarbon fraction),
hexane/DCM (9:1 v/v; aromatic fraction) and DCM/MeOH (1:2 v/v;
polar fraction). n-alkanes were selectively adducted from the
saturated hydrocarbon fraction via urea adduction by adding 200 μl
of urea (saturated in methanol) and 200 μl of acetone, followed by
200 μl of hexane. The resulting urea crystals were washed with
hexane to remove non-adducts and then dissolved in 500 μl MeOH
and 500 μl double distilled water. The adductable hydrocarbons were
then extracted with three consecutive hexane washes.
3.2.3. Gas chromatography and gas chromatography–mass spectrometry
Individual compounds were identified and quantified relative to
internal standards (5α-androstane, apolar fraction; hexadecan-2-ol,
polar fraction; n-C19 alkane, acid fraction) using gas chromatography
(GC) and gas chromatography–mass spectrometry (GC–MS). Typical
error in absolute quantification was ±20%. GC analyses were performed
on a CarloErba Gas Chromatograph equipped with a flame ionisation
detector (FID) and fitted with a Chrompack fused silica capillary column
(50 m × 0.32 mm i.d.) coated with a CP Sil-5CB stationary phase
(dimethylpolysiloxane equivalent, 0.12 μm film thickness). GC–MS
analysis was performed on a Thermoquest Finnigan Trace GC interfaced
with a Thermoquest Finnigan Trace MS operating with an electron
ionisation source at 70 eV and scanning over m/z ranges of 50 to 850 Da.
The GC was fitted with a fused silica capillary column (50 m × 0.32 mm i.
d.) coated with a ZB1 stationary phase (dimethylpolysiloxane equiva-
lent, 0.12 μm film thickness). For both GC and GC–MS, 1 μl of sample was
injected at 50 °C using an on-column injector. The temperature was
increased to 130 °C with an initial ramp of 20 °C/min, then to 300 °C at
4 °C/min, followed by an isothermal for 20 min.
3.2.4. Gas chromatography–combustion–isotope ratio mass
spectrometry
Compound-specific stable carbon isotope ratios were determined for
urea-adducted n-alkanes by gas chromatography–combustion–isotope
ratio mass spectrometry (GC–C–IRMS) using a Varian 3400 GC coupled
to a Finnigan MAT Delta-S IRMS via a modified Finnigan MAT Type I
combustion interface; the combustion furnace comprised Cu and Pt
wires (0.1 mm o.d.) in an alumina reactor (0.5 mm i.d.). GC column and
conditions were the same as described above for GC–MS. Values,
measured in duplicate, are reported in standard per mil notation relative
to Vienna PeeDee Belemnite (VPDB); analytical accuracy, on the basis of
replicate analysis of standards, was typically ±0.3‰ and precision, as
represented by 1 standard deviation, was generally b0.3‰ (see
supplementary material).
3.2.5. Gas chromatography–thermal conversion–isotope ratio mass
spectrometry
Compound-specific stable hydrogen isotope ratios were determined
for urea-adducted n-alkanes by gas chromatography–thermal conver-
sion–isotope ratio mass spectrometry (GC–TC–IRMS) using an Agilent
188 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200
6890 gas chromatograph equipped with an Agilent split/splitless injector
(splitless mode; 300 °C; purge time=2 min) coupled to a ThermoQuest
Finnigan DeltaPlus XL isotope ratio mass spectrometer via a thermal
conversion reactor (300× 0.5 mm i.d.; Al2O3; 1450 °C) and ThermoQuest
Finnigan GC Combustion III interface. An H+3 factor, to correct for H3 ions,
was calculated daily and was consistently lower than 5 ppm V− 1. The GC
column was the same as described above, but the temperature
programme comprised an initial isothermal of 1 min at 40 °C followed
by a ramp of 10 °C/min to 300 °C and a final isothermal for 13 min. The
analytical accuracy and precision of the system were monitored using a
standard suite of 15 n-alkanes (C16–C30; Mixture B, Arndt Schimmel-
mann, Biogeochemical Laboratories, Indiana University), which was
analysed before and after each sample. The root-mean-square error
(RMS) for hydrogen isotopic measurements of the standard mixture was
calculated for each sample analysed to monitor analytical accuracy and
was typically b5‰. Analytical precision, as represented by 1 standard
deviation, was generally b2‰ (see supplementary material). δD values,
based on duplicate analyses and reported in standard per mil notation
relative to Vienna Standard Mean Ocean Water (VSMOW), were
calculated against a calibrated H2 gas.
4. Results
Based on lithological, geochemical and palynological examination,
the onset of the PETM is recorded in the Kumara-2 core between
samples at 1739.76 and 1737.97 mbs, and is placed at the base of the
mudstone interval that begins at 1739.1 mbs (Fig. 2). The n-alkane
compound specific δ13C record clearly shows the shift to 13C-depleted
values, which are characteristic of the PETM negative carbon isotope
excursion, and the mudstone interval coincides with the first evidence
of marine palynomorphs and the dinoflagellate cyst (dinocyst) genus
Apectodinium. The top of the PETM is placed at 1734.25 mbs, at the
unconformity between the mudstone unit and the overlying sandstone-
dominated lithology (Fig. 2). Therefore, the PETM interval recorded in
the Kumara-2 core is 4.85 m thick, here defined as spanning from 1739.1
to 1734.25 mbs (Fig. 2). Lithological, geochemical and palynological
variations associated with the PETM, and pre- and post-PETM, are
discussed in more detail below.
4.1. Lithology and bulk geochemistry
From the base of the examined core, 1749.98 mbs, to 1739.1 mbs, the
sequence is predominantly composed of a non-calcareous shale and
mudstone, interspersed with coal lenses and layers, and silty and fine
sandstone (Fig. 2), which is consistent with a terrestrial depositional
environment (Carter et al., 1986). A 10 cm coal layer is present at the top
of this interval, from 1739.2 to 1739.1 mbs (Fig. 2), and palynomorph
assemblages indicate a terrestrial depositional environment. At
1739.1 mbs, there is a shift to a dark non-calcareous mudstone dominated
lithology with common pyrite, which persists as the dominant facies for
the following 4.85 m upsection (Fig. 2). The first marine dinocysts are
recorded at 1737.97 mbs and are present throughout the mudstone unit.
From 1734.25 to 1718.2 mbs is a hard sandstone dominated interval that
contains carbonaceous laminae and mudstone clasts in the upper part.
Above 1718.2 mbs to the top of the studied section at 1710 mbs, the
sediment consists of interbedded sandstone, shale, mudstone and coal
layers and lenses (Fig. 2), interpreted to represent a terrestrial
depositional environment similar to that in the lower part of the section
(Carter et al., 1986).
Total organic carbon (TOC) content varies throughout, ranging from
0.4 to 36% (Fig. 2). Sediments with very high organic carbon content
contain minor to large amounts of coal (e.g., sample at 1743.26 mbs). In
the dark non-calcareous mudstone layer, between 1739.1 and
1734.25 mbs, TOC contents are uniformly low (b1%) and are much
lower than the rest of the section, which suggests a significant change in
depositional environment from over- and under-lying strata.
4.2. Palynology
Palynomorph assemblages are well-preserved and diverse through-
out most of the interval studied, although they are rare to absent from a
ca. 12.5 m interval within the 16.05 m hard sandstone-dominated unit
that begins at 1734.25 mbs. Only terrestrial palynomorphs were
recorded in the studied core, except for an interval between 1739 and
1733.43 mbs where marine dinocysts are also recorded (Fig. 2). Within
the marine mudstone unit, marine palynomorphs comprise up to 31% (at
1735.92 mbs) of the total palynomorph assemblage (Sluijs et al., 2008a).
Pollen of angiosperm taxa associated with thermophilic conditions,
such as Cupanieidites orthoteichus and Spinizonocolpites prominatus (Nypa
mangrove), are first recorded at 1737.97 mbs (Figs. 2 and 3). These
species are characteristic of New Zealand miospore zone PM3b (Raine,
1984), which is regionally correlated to the base of the New Zealand
Waipawan Stage and equivalent to the base of the Eocene (Hancock et al.,
2003; Cooper, 2004). In addition, the dinocyst genus Apectodinium is
abundant within the marine mudstone (Fig. 2), in agreement with other
coastal marine PETM sequences in New Zealand and other regions of the
world (e.g. Crouch et al., 2001; Sluijs et al., 2008a).
In the lower part of the core (1749.98–1739.21 mbs), angiosperm
taxa are the most abundant terrestrial palynomorphs, with percentages
ranging from 42 to 60% of the assemblage (Fig. 3). Gymnosperm taxa,
such as Phyllocladidites mawsonii, range from 16 to 44% and fern spores
constitute 10–39% of the plant microfossil assemblage. At 1737.97 mbs,
concurrent with the first occurrence of thermophilic angiosperm
species, there is a change in the overall spore/pollen assemblage that
continues in the overlying ca. 3.5 m section. The relative abundance of
gymnosperms declines to 10% in the lower part of the 3.5 m section and
then begins to increase at the top of this interval (Fig. 3). Conversely,
fern spores show an increase in relative abundance (to 45%) in the lower
part and then decrease in the upper part. Angiosperm taxa slightly
decrease in the lower part of the interval (to 41%) but then become more
abundant, up to 60% of the assemblage, in the upper part (Fig. 3). Within
the angiosperm assemblage, there is a notable change in composition
through the 1737.97–1734.5 mbs interval, including a decrease in
Proteaceae and Triorites species and the common presence of several
species that first occur within this interval — Malvacipollis, Myrtaceae,
Cupanieidites orthoteichus and Spinizonocolpites prominatus (Fig. 3).
In samples taken at 1733.43 and 1732.74 mbs, the plant micro-
fossil assemblage returns to a composition similar to that seen in the
latest Paleocene part of the core (1749.98–1739.21 mbs), with more
abundant angiosperms (up to 63%), an increase in gymnosperms
(30%) and lower abundances of fern spores (down to 5%). Moreover,
the relative abundance of angiosperm taxa associated with thermo-
philic conditions, particularly Malvacipollis and Spinizonocolpites
prominatus, is lower than in underlying interval from 1737.97 to
1734.5 mbs (Fig. 3).
In the upper part of the core, from 1721.54 to 1710 mbs,
angiosperm taxa become more abundant, ranging from 61 to 80% of
the spore/pollen assemblage. The abundance of gymnosperm pollen
remains relatively stable (17–33%) and fern spores comprise less than
11% of the assemblage. The most prominent vegetation change
through the entire studied interval occurs at 1712.98 mbs and is
marked by a significant increase in Casuarina (Myricipites harrisii)
pollen (Fig. 3). This change in the plant microfossil record has been
consistently recognised throughout New Zealand in the Early Eocene
and marks a notable long-term shift in vegetation records (e.g. Raine,
1984; Pocknall, 1990; Crouch et al., 2003).
In the lower part of the marine mudstone interval (1737.97–
1737.02 mbs), dinocysts of the genus Spiniferites and Fibrocysta type
species are most common. The dinocyst assemblage is dominated by
Apectodinium (ca. 54%) in the interval with the highest percentage of
marine palynomorphs, from 1735.92 to 1735.5 mbs (Fig. 2). The upper
horizon of the marine mudstone interval (1735.04–1734.5 mbs)
comprises common Operculodinium and Kenleyia species.
 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200
Fig. 3. Relative abundance of selected species and groups of plant microfossils, major plant microfossil groups (fern spores, gymnosperms and angiosperms), along with the n-alkane δ13C
record from the Kumara-2 core. Plant microfossil abundances are shown as a percentage of the total spore and pollen count. The shaded area highlights the PETM CIE.
4.3. Biomarkers
Functionalised compounds are only found in trace amounts
throughout, suggesting the sequence is relatively thermally mature,
likely near the onset of the oil generation window. This is confirmed
by the distribution of steranes and hopanes, as discussed below.
Consequently, only the saturated hydrocarbon fraction contained
compounds detectable in appreciable quantities for analysis using
GC–MS and GC–C–IRMS.
4.3.1. n-alkanes
The saturated fraction is dominated by a homologous n-alkane
series; all samples contain n-C17 to n-C32 alkanes, and some have
measurable quantities of n-C14 to n-C16 and n-C33 to n-C41 (Fig. 4). The
series is dominated by high molecular weight (HMW) odd-carbon-
number homologues, a signature typical of terrestrial higher plant leaf
wax n-alkanes (Eglinton et al., 1962; Eglinton and Hamilton, 1967;
Kolattukudy, 1976). However, the odd-over-even predominance (OEP),
an expression of the preference for odd carbon number n-alkanes
compared to their even carbon number homologues (Scalan and Smith,
1970; OEP = (Cn − 2 + 6 × Cn + Cn + 2) / (4 × Cn − 1 + 4 × Cn + 1), with n
being an odd integer) ranges from 0.6 to 2 (Fig. 5), which is markedly
lower than that found in fresh leaf waxes (Collister et al., 1994b) and
suggests a potential diagenetic or catagenetic overprint of the original
biological signal. The OEP values for n = 27/29/31 all have identical
trends; throughout most of the section, OEP values are N1, which
reflects a predominantly terrestrial source for the n-alkanes. At
1737.97 mbs, coincident with the presence of marine dinocysts, OEP
values decrease dramatically to a minimum of 0.7 and remain lower
than 1 for the overlying 2.5 m before increasing gradually (Fig. 5). Above
1733.97 mbs, OEPs return to near pre-excursion values. The Carbon
Preference Index (CPI; Bray and Evans, 1961), which uses 9 adjacent n-
alkanes from the homologous series, can also be used to express the
preference for odd or even n-alkanes: CPI = 2 × (C25 + C27 + C29 + C31) /
[C24 + 2 × (C26 + C28 + C30) + C32]. As with the OEP, the CPI decreases
from 1.5 to values b1 at 1737.97 mbs and remains low over the marine
189
mudstone interval, before returning to near pre-excursion initial values
above 1733.97 mbs (Fig. 5).
The n-alkane terrigenous to aquatic ratio (TAR = (C27 + C29 + C31)/
(C15 + C17 + C19)) varies throughout the section (Fig. 5). At the base of
the section TARs are generally high, being greater than 7.6 and with a
maximum value of 14.1. Ratios then decrease from 1745.88 to
1743.26 mbs due to a decrease in the concentration of HMW n-
alkanes, before increasing again to values greater than ca. 8 between
1741.75 and 1739.76 mbs. At 1737.97 mbs, ratios decrease to 1.3 and
remain lower than 4.2 up to 1733.97 mbs, with a slight increase at the
upper end of this interval (Fig. 5). The initial decrease is caused by
both a decrease in the concentration of long chain n-alkanes but also
an increase in the concentration of the short chain homologues. Above
the marine mudstone interval, TAR ratios increase once more to an
average value of 5, with a peak value of 10 at 1717.36 mbs (Fig. 5).
4.3.2. n-alkane compound-specific carbon isotopes
δ13C values were measured for C27, C29 and C31 n-alkanes, all
derived primarily from terrestrial higher plant leaf waxes (Eglinton
and Hamilton, 1967). Throughout most of the section there is an offset
in δ13C values between the 3 n-alkanes: C31 is the most 13C-depleted
in all but one sample, with values typically ca. 1‰ lower than C29,
which in turn has values typically ca. 0.5‰ more negative than C27
(Fig. 2). Despite this small offset in isotope composition, the δ13C
values of all three n-alkanes describe almost identical trends
throughout the core.
Below 1737.97 mbs, values fluctuate between − 29.4 and − 31.1‰
for C31, −28.2 and − 29.9‰ for C29 and −27.5 and −29.1‰ for C27
(Fig. 2). At 1737.97 mbs, δ13C values for all three start to shift toward
more negative values. This trend continues in the following 5 sampled
sediments from the marine mudstone interval, culminating in the
most 13C-depleted values recorded for the core between 1735.04 and
1734.5 mbs: − 33.4, − 33.6 and − 35.0‰ for C27, C29 and C31,
respectively (Fig. 2). This negative isotope excursion is interpreted
as the PETM CIE and the magnitude of the excursion is 4.5‰ for all
three n-alkanes. At the peak of the CIE, the offset between n-alkane
190 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200

Fig. 4. Partial m/z 57 mass chromatograms of the saturated hydrocarbon fractions for representative sediments below and within the PETM CIE, highlighting acyclic hydrocarbons.
(A) Sample Kum-4, 1747.1 mbs depth, and (B) sample Kum-13, 1737.0 mbs depth: •, n-alkanes; Pr, pristane; Ph, phytane; IS, internal standard. Numbers indicate the number of
carbon atoms.

records observed in the lower part of the core becomes less
pronounced. At 1733.43 mbs, above the marine mudstone, there is a
sharp positive shift in all δ13C values, with an abrupt return toward
pre-CIE values and the re-establishment of an offset between records.
However, these values are slightly 13C-depleted relative to pre-
excursion values and remain relatively constant throughout the
remainder of the section (Fig. 2).
4.3.3. n-alkane compound-specific hydrogen isotopes
δD values were also measured for the C27 and C29 n-alkanes;
concentrations of the C31 n-alkane were too low for accurate δD
determination. Both n-alkanes have similar values and exhibit similar
trends (Fig. 6). In the lower part of the section (1749.98 to 1739.76 mbs),
prior to the PETM, δD values increase from ca. −160‰ to −140‰ before
decreasing once more to −155‰ (Fig. 6). Samples at 1737.97 and
1737.02 mbs, the first two geochemical samples within the CIE, have δD
values of −165‰, a slight negative shift compared to immediate pre-
excursion values. The sample at 1735.92 mbs records a positive shift of ca.
+20‰, which is followed by a decrease throughout the remainder of the
CIE; δD values reach a PETM minimum at 1734.5 mbs of −166 and
−165‰ for C27 and C29, respectively (Fig. 6). Above the marine mudstone
interval and CIE, with the exception of a sample at 1733.43 mbs, δD
values increase gradually upsection from −169‰ to −137‰ (Fig. 6).
4.3.4. Pristane and phytane
Although the saturated fraction is dominated by n-alkanes, other
biomarkers are present. Pristane (Pr) and phytane (Ph), C19 and C20
isoprenoidal hydrocarbons typically inferred to derive from the phytyl
sidechain in chlorophyll a (e.g. Rowland, 1990; Rontani and Volkman,
2003), are present in all sediments. Concentrations track the TOC
content, but concentrations normalised to TOC vary throughout the core
(Fig. 2). In the lower part (1749.98 to 1739.76 mbs), TOC-normalised
concentrations are highly variable, ranging from 0.82 to 4.1 μg g− 1
TOC.
From 1737.97 to 1734.5 mbs, coinciding with the CIE and marine
mudstone unit, TOC-normalised concentrations are relatively constant
at ca. 1.8 μg g− 1
TOC. Above 1734 mbs, they initially increase but are then
consistently low (b1.5 μg g− 1
TOC) above 1722 mbs (Fig. 2).
The pristane to phytane (Pr/Ph) ratio has been invoked to reflect
depositional conditions, such as changes in salinity and oxicity (Didyk
et al., 1978), but must be used with caution as many factors, such as the
organic matter source and thermal maturity, can also affect the ratio
(Burnham et al., 1982; Ten Haven et al., 1987). Pr/Ph ratios have an
 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200 191

Fig. 5. n-alkane distribution ratios for the Kumara-2 core in New Zealand. (A) n-alkane δ13C values (B) HMW n-alkane odd-over-even predominance (OEP). OEP = (Cn − 2 + 6 × Cn + Cn + 2) /
(4× Cn − 1 + 4 × Cn + 1). (C) HMW n-alkane carbon preference index (CPI). CPI = 2 × (C25 + C27 + C29 + C31) / [C24 + 2 × (C26 + C28 + C30) + C32]. (D) n-alkane terrigenous to aquatic ratio
(TAR). TAR = (C27 + C29 + C31)/(C15 + C17 + C19). The shaded area highlights the PETM CIE and the horizontal dashed lines indicate the first occurrence of thermophilic angiosperm pollen
and the most abundant occurrence of the dinoflagellate genus Apectodinium, respectively. The arrows highlight the inferred increase in terrigenous organic matter input during the CIE,
within the marine interval.

average value of 5.5 for most of the Kumara-2 core (Fig. 7). A marked
decrease occurs at the onset of the CIE, with values ≤2.5 occurring in
the four lowermost samples within the CIE. Values then increase in
the upper part of the recovered CIE and reach a pre-CIE ratio of 6.0
at 1733.4 mbs (Fig. 7). Ratios remain greater than 4.5 for the
remainder of the core except for the topmost sediment at 1710 mbs
(Pr/Ph = 2.8).
4.3.5. Oleananes
Various saturated triterpanes are present in the Kumara sediments,
with oleanane, a diagenetic product of various triterpenoids found in
angiosperm species (Rullkötter et al., 1994), being the predominant
non-hopanoid. It is present in the majority of sediments in both its
18α(H),22β(H) and 18β(H),22α(H) isomeric configurations (Figs. 8
and 9). However, due to low concentrations, the isomer peaks were not
fully resolved in all chromatograms and the two were summed for
Fig. 6. δD values of terrestrial higher plant derived n-alkanes for the Kumara-2 core in
New Zealand. The error bars represent one standard deviation based on duplicate
analyses. The shaded area highlights the PETM CIE and the horizontal dashed lines
indicate the first occurrence of thermophilic angiosperm pollen and the most abundant
occurrence of the dinoflagellate genus Apectodinium, respectively.
quantification. Oleanane concentration varies greatly and parallels
fluctuations in TOC content (Fig. 2). While TOC-normalised oleanane
concentrations are very low in the majority of samples (Fig. 9), there is a
ca. 3 m interval associated with the CIE and marine mudstone unit
where concentrations are notably higher. An initial increase at
1737.97 mbs is followed by a maximum at ca. 1735.92 mbs, which
marks an overall increase of nearly 2 orders of magnitude compared to
background values (Fig. 9). After this spike, concentrations decrease
sharply, returning at 1734.5 mbs to values close to those found in the
lower part of the core.
4.3.6. Hopanes and related indices
Hopanes, diagenetic products of bacterial bacteriohopanepolyols
(Ourisson et al., 1979; Rohmer et al., 1984), occur in all Kumara
sediments. As with other biomarkers, only the fully saturated defunc-
tionalised hopanes were observed. All samples contain a suite of C29–C35
17α(H),21β(H)-hopanes (Fig. 8), and C31 to C35 homohopanes are
present in both their 22R and 22S isomeric configurations. The C27
hopanes, trisnorneohopane and trisnorhopane also occur throughout.
Moretanes, hopanes with the 17β(H),21α(H) isomeric configuration,
are also present, albeit in low concentrations, and hopanes with the
biologically produced ββ configuration were not detected.
The homohopane isomerisation ratio (22R to 22S) for C31
homohopane has an average value of 0.5 with a standard deviation
of 0.02 for the entire study section. Similarly, the ratio of βα to αβ for
the C30 hopane varies between 0.4 and 0.6 with an average value of 0.5
and a standard deviation of 0.07. Such ratios suggest an equivalent
vitrinite reflectance (R0) no greater than 0.5 (Seifert and Moldowan,
1980; Waples and Machihara, 1991; Peters et al., 2005), and the
persistence of an OEP in the n-alkane distribution suggests that the
section has only just entered the oil window. The relatively uniform
values for both thermal maturity indicators show that the degree of
maturity remains unchanged throughout the interval examined in the
Kumara-2 core.
The homohopane index is defined as the ratio of C35 αβ homohopane
to the total C31–35 homohopane concentration (Peters and Moldowan,
1991). Throughout most of the core, the homohopane index is b0.04
(such that the C35 component represents less than 4% of the total
homohopanes), with typical values of 0.02 (2%; Fig. 7). Between 1737.97
192 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200
Fig. 7. Indicators of depositional redox conditions for the Kumara-2 core in New Zealand. (A) n-alkane δ13C excursions. (B) Homohopane index, the ratio of C35 αβ-homohopane to
total C31–35 homohopane concentration. (C) Ratio of trisnorneohopane (Ts) to total C27 hopane (Ts + Tm). (D) Pr/Ph ratio. The shaded area highlights the PETM CIE and the
horizontal dashed lines indicate the first occurrence of thermophilic angiosperm pollen and the most abundant occurrence of the dinoflagellate genus Apectodinium, respectively.
and 1734.5 mbs, however, homohopane indices increase markedly and
abruptly, with a maximum of 28% at ca. 1735.92 mbs before decreasing
upcore to b4% at depths above 1734.5 mbs (Figs. 7 and 8).
17α-22,29,30-trisnorhopane (Tm) and 18α-22,29,30-trisnorneo-
hopane (Ts) are both C27 hopanes that differ with respect to the
position of a D-ring methyl group; Tm is substituted at C-18 and Ts at
C-17. The ratio of Ts to total C27 hopane, (Ts + Tm), varies between
0.86 and 0.96 throughout most of the section. While Ts is the
predominant isomer (Fig. 7), at 1737.97 mbs, the ratio decreases
abruptly to 0.64 and then returns to near pre-excursion values above
1734.5 mbs (Fig. 7).
5. Discussion
5.1. Stratigraphy of the Kumara-2 core
5.1.1. Maturity and implications
As indicated by biomarker distributions, organic matter (OM) in
the Kumara-2 core has just entered the early stages of the oil window.
Hydrogen isotopic enrichments have been shown to occur in
n-alkanes in thermally mature sedimentary OM and oils (Li et al.,
2001; Schimmelmann et al., 2004; Dawson et al., 2005; Radke et al.,
2005; Pedentchouk et al., 2006; Dawson et al., 2007). However,
diagenetic n-alkane hydrogen exchange may only occur significantly
in early to post mature sediments (R0 values of ca. 0.7 to 1.6;
Pedentchouk et al., 2006; Dawson et al., 2007). The effects of
thermal maturation on the carbon isotopic composition of individual
n-alkanes are not believed to be as significant as for hydrogen,
occurring most significantly in the oil generation window, during and
following petroleum formation (e.g. Clayton, 1991; Clayton and
Bjorøy, 1994; Rooney et al., 1998; Harris et al., 2003). With an
inferred R0 value of ca. 0.5, the Kumara-2 sediments are only in the
early stages of thermal maturity and, therefore, the n-alkane carbon
and hydrogen isotope compositions are assumed to record original
values. Furthermore, maturity remains constant throughout the core
and thus trends may be preserved even if absolute values are not.
5.1.2. Bio- and chemostratigraphic recognition of the PETM
One of the defining characteristics of hyperthermals, such as the
PETM, is a pronounced negative CIE. Due to the complex lithological
changes that occur in the Kumara-2 core, along with the inferred co-
occurring changes in organic matter source, the CIE was evaluated using
the C27, C29 and C31 n-alkanes, typically derived from terrestrial higher
plant leaf waxes (Eglinton et al., 1962). The pronounced CIE of 4.5‰,
which is identified in sediment samples taken from 1737.97 to
1734.5 mbs, combined with the plant microfossil zonation and
presence of abundant Apectodinium dinocysts, confirm that the
section spans the Paleocene/Eocene boundary and the PETM. Based
on lithological, geochemical and palynological observation, the
recovered CIE spans 4.85 m (Fig. 2). The CIE is terminated by a very
sharp return to near pre-excursion values at an unconformity
recognised at 1734.25 mbs (Fig. 2). This suggests the PETM is
truncated and the latter part of the interval is missing from the
sedimentary record, as many existing PETM records reveal a more
gradual return (e.g. Kennett and Stott, 1991; Zachos et al., 2003;
Zachos et al., 2005; Sluijs et al., 2006).
The gradual decrease in n-alkane δ13C values at the onset of the
CIE, which is not often observed in PETM records, is interpreted as a
gradual input of 13C-depleted carbon into the earth–atmosphere
system, suggesting that the early stages of the event were recovered
at this site. It is possible that this gradual decrease was caused by the
reworking of pre-CIE n-alkanes, particularly as the transition from a
terrestrial to marine depositional environment could have encour-
aged the resuspension, mixing and redeposition of pre-CIE material,
with the reworked component gradually decreasing into the early
stages of the CIE. However, the onset interval spans more than 2 m of
core and this would therefore require the resuspension of older
material for a significant period of time. Also, there is a significant
negative shift in n-alkane δD values at the onset of the CIE. If pre-CIE
n-alkanes were being extensively reworked then this negative
excursion must have been even larger. This is followed by a rapid
positive shift in δD values within the onset interval, which does not
seem compatible with the idea of a gradual decrease in pre-CIE n-
alkane input.
The unconformity at 1734.25 mbs, between the marine mudstone
unit and the overlying sandstone-dominated lithology, precludes the
determination of accurate sedimentation rates. However, the most
recent age model established by Röhl et al. (2007), indicates that peak
negative values are reached ca. 60 kyr (3 precession cycles) after the
onset of the CIE. Thus, the recovered portion of the PETM could span
up to ca. 60 kyr. If this is the case, then the sedimentation rate during
the recovered CIE can be estimated at ~ 4.85/60 = ~ 8.08 × 10− 2 m/kyr.
 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200 193

Fig. 8. Partial m/z 191 mass chromatograms of the saturated hydrocarbon fractions, highlighting hopanes and oleanane, for representative sediments from below and within the
Kumara PETM CIE. (A) sample Kum-4, 1747.1 mbs depth, and (B) sample Kum-13, 1737.0 mbs depth: Ts, trinorneohopane; Tm, trisnorhopane. For the αβ configurations, when two
isomers are shown in the chromatogram the first corresponds to the 22R(H) isomer and the second to the 22S(H) isomer. Numbers indicate the number of carbon atoms.

5.2. Depositional environment at Kumara-2 core

5.2.1. Changes in depositional environment and sea level rise

Lithological, palynological and organic biomarker analyses all
indicate marine depositional conditions between 1739.1 and
1734.25 mbs. Dinocysts are recorded in all samples from this interval,
but are absent above and below it; the one exception occurs at
1733.4 mbs, in the lower part of the sandstone-dominated lithology,
where dinocysts comprise 2% of total palynomorphs, reflecting either a
minor marine influence in the base of the sandstone unit or reworking of
older CIE material. The first occurrence of dinocysts coincides with the
presence of a dark non-calcareous mudstone (Fig. 2). Moreover, coal
layers and lenses indicative of a terrestrial depositional environment are
interspersed throughout the rest of the core, but are absent from the
mudstone unit.
Many of the aforementioned biomarker proxies can also reflect the
change in depositional environment. In particular, the shift in TAR
(Fig. 5), marking an increase in the relative concentration of low
molecular weight n-alkanes, possibly derived from algal precursors (e.g.
Gelpi et al., 1970; Naraoka and Ishiwatari, 1999; Duan and Wang, 2002), Fig. 9. Timing of higher plant community change recorded at the Kumara-2 core in New
Zealand. Oleanane concentration is expressed in μg per g of total organic carbon (TOC).
likely reflects the shift to marine conditions. Similarly, the shift to lower The shaded area highlights the PETM CIE and the horizontal dashed lines indicate the
CPI and OEP values (Fig. 5) is probably a consequence of the change in first occurrences of thermophilic angiosperm pollen and the most abundant occurrence
depositional environment, reflecting a decrease in the sedimentary of the dinoflagellate genus Apectodinium, respectively.
194 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200
concentration of terrestrial leaf waxes and a possible dilution by other n-
alkane sources (Rieley et al., 1991; Collister et al., 1994a; Collister et al.,
1994b). We note that the higher molecular weight n-alkanes likely still
have a higher plant origin in the marine interval, but that the leaf waxes
could have been more degraded during transport and diagenetic
reactions could introduce n-alkanes via the degradation of n-alkyl
moieties derived from a range of biological precursors, resulting in lower
CPI/OEP values.
The above results indicate a transient rise in sea level during the
PETM. The Late Paleocene is generally believed to have been an ice-
free Earth, although recent studies support the presence of transient
ice sheets in the Early Paleogene (DeConto and Pollard, 2003; Miller et
al., 2005). However, in the absence of evidence for extensive ice sheets
directly preceding the PETM, the most probable explanation for this
change is a sea level rise caused by the thermal expansion of sea water
(see Sluijs et al., 2008a for a review). Warming of ocean waters during
the PETM was remarkably uniform for both surface and deep waters,
with an average temperature increase of ca. 5 °C (Kennett and Stott,
1991; Bralower et al., 1995; Thomas et al., 1999; Zachos et al., 2003;
Tripati and Elderfield, 2005), which, given the temperature–density
relationship of seawater, should cause a 3–5 m rise in global sea level.
The results from Kumara-2 agree with other evidence for sea level rise
in PETM sections from other geographical locations, including the
North Sea (e.g. Bujak and Brinkhuis, 1998), Arctic Ocean (Sluijs et al.,
2006), Egyptian Tethys (Speijer and Morsi, 2002), New Jersey margin
(Sluijs et al., 2008a) and the Tawanui section in the North Island of
New Zealand (Crouch and Brinkhuis, 2005).
Throughout the CIE at Kumara-2, despite the marine depositional
environment, there is a significant terrestrial contribution to buried
organic matter and palynomorph assemblages: the n-alkane TAR
ranges from 1.3 to 4.2 and terrestrial palynomorphs comprise ≥69% of
the total palynomorph assemblage (Figs. 2 and 5). The upper part of
the recovered CIE is also characterised by an increase in the terrestrial
component of sedimentary organic matter relative to marine OM
(increase in the n-alkane TAR from 1.3 to 4.2) and increased terrestrial
palynomorphs relative to marine palynomorphs compared to the
onset of the CIE. This could reflect marine regression, but n-alkane
δ13C values suggest the CIE is truncated and this interval appears to
precede the recovery stage of the isotope excursion, thus preceding
the termination of the warming period and associated drop in sea
level. We speculate that a possible explanation is an increase in the
amount of terrestrial organic matter delivered to the sediment.
Indeed, previous studies show evidence for increased sedimentation
rates at other New Zealand sites during the PETM (Crouch et al., 2003;
Hollis et al., 2005; Nicolo et al., 2007). Moreover, there is evidence
from many other geographical locations for an increase in weathering
and terrestrial runoff during the PETM, in the form of elevated
sedimentation rates or increased kaolinite and terrestrial organic
matter input (e.g. Schmitz and Pujalte, 2003; Kelly et al., 2005;
Schmitz and Pujalte, 2007).
5.2.2. Further biomarker insight into the depositional environment
The distribution of hydrocarbon biomarkers can reflect thermal
maturity, depositional environment and lithology (Peters et al., 2005).
In the Kumara-2 core, thermal maturity does govern the absolute values
of the hopane ratios, but, because thermal maturity is constant
throughout the studied interval, it cannot explain the observed
variations. Instead, these variations must reflect changes in the
depositional environment. Homohopane indices increase markedly
during the CIE, whereas Pr/Ph ratios and Tm/(Tm + Ts) ratios both
decrease (Fig. 7). All of these trends appear to be consistent with a shift
from oxidising to relatively anoxic depositional conditions (Powell and
McKirdy, 1973; Didyk et al., 1978; Moldowan et al., 1986; Peters and
Moldowan, 1991). However, they cannot be interpreted so simplistically
in this setting. Each of the aforementioned ratios reflects a combination
of source inputs and subsequent diagenetic and catagenetic reactions
that are at least partially dependant on the organic matter source and
host rock lithology (e.g. Rullkötter et al., 1984; Sinninghe Damsté et al.,
1988; Sinninghe Damsté and de Leeuw, 1990). Thus, the trends also
reflect the transition from a fluvial to marine depositional environment.
While we cannot interpret trends in biomarker ratios, we can
consider the absolute values from the marine mudstone interval,
between 1739.1 and 1734.25 mbs. The very high homohopane indices
and low Pr/Ph ratios suggest that the marine depositional environment
was suboxic to anoxic. For example, Peters et al. (1995) interpreted a
homohopane index of 12% as representing anoxic source-rock deposi-
tional conditions, whereas in the Kumara-2 marine interval C35
homohopanes comprise up to 28% of total homohopanes. The high
abundance of Apectodinium dinocysts, a presumed heterotrophic taxon,
suggests nutrient-rich surface waters during the CIE could have been
associated with eutrophication, consistent with other studies in New
Zealand and elsewhere (Crouch et al., 2003; Sluijs et al., 2005; Sluijs et al.,
2008a). Eutrophic conditions and a more anoxic water column have been
reported for the PETM from the New Jersey Shelf, where it is thought to
be a result of enhanced terrestrial runoff and nutrient delivery (Lippert
and Zachos, 2007). These conditions could promote the lowering of the
redox potential of sedimentary pore water (Lippert and Zachos, 2007)
and are consistent with what is observed at Kumara-2.
5.3. Changes in terrestrial plant community
Palynomorph assemblages show that the proportions of fern spores,
gymnosperm and angiosperm taxa change at the onset of the PETM.
Through the lower part of the observed CIE, the gymnosperm relative
abundance declines, fern spore abundance increases and the percentage
of angiosperm taxa drops slightly (Fig. 3). Within the angiosperm
assemblage, there is a noticeable change in the composition with
increases in several taxa, including Spinizonocolpites prominatus (Nypa
mangrove) and Malvacipollis. Both angiosperm and gymnosperm relative
abundance increases in the upper part of the CIE interval. Above the
unconformity at 1734.25 mbs, the Early Eocene sequence is character-
ised by a higher relative abundance of angiosperm palynomorphs than in
the Late Paleocene, with a similar component of gymnosperms and fewer
fern spores. Notably, the most significant change in the plant microfossil
record, an increase in Casuarina (Myricipites harrisii) pollen, occurs in the
Early Eocene sequence.
The dramatic increase in oleanane concentration at the onset of the
CIE provides further evidence for changes in the higher plant community
structure (Fig. 9). β-amyrin, taraxerol, germanicol and oleanoic acid all
have an oleanane-type hydrocarbon skeleton, making this one of the
most widespread fossil triterpenoids, a group of compounds largely
restricted to angiosperm plants (Ten Haven and Rullkötter, 1988;
Rullkötter et al., 1994). Consequently, oleananes have long been used as
angiosperm biomarkers in ancient sediment and petroleum studies (e.g.
Killops and Frewin, 1994; Moldowan et al., 1994). Oleanane concentra-
tion increases rapidly in the lower part of the CIE but then decreases
equally abruptly, before the termination of the CIE, suggesting a
transient shift in the plant community, perhaps due to transitional
climatic conditions. An expansion of angiosperms, in particular the
transient migration of tropical and sub-tropical species to higher
latitudes, has been recognised from locations such as the Bighorn
Basin (Wing et al., 2005) and Arctic (Sluijs et al., 2006), during the PETM.
At Kumara, however, there is no palynological evidence for an overall
angiosperm expansion. Indeed, angiosperm pollen relative abundance
slightly decreases in the lower part of the CIE (Fig. 3). The increased
oleanane concentrations could therefore arise from a reorganisation
rather than an expansion of the angiosperm assemblage: oleanoid-type
compounds are produced in high concentrations by mangrove plants
(e.g. Ghosh et al., 1985; Koch et al., 2003a), and the beginning of the
increase in oleanane concentration coincides with the appearance of
Spinizonocolpites prominatus pollen (Fig. 3), which is considered to have
been produced by Nypa mangrove plants (e.g. Collinson, 1993). This
 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200
increase in concentration could also be due to enhanced preservation
resulting from the transition from an oxic terrestrial to marine
depositional environment. However, the increase in oleanane concen-
tration is not synchronous with this transition and in the latter part of the
recovered CIE concentrations decrease whilst the depositional environ-
ment remains unchanged. Whether the dramatic change in oleanane
concentrations is strictly a consequence of the rise in sea level and
change in depositional environment, or instead reflects more wide-
spread ecosystem changes in New Zealand remains to be seen.
Nonetheless, there is evidence for the development of a transitional
mangrove swamp at Kumara during the PETM.
5.4. Changes in the hydrological cycle
5.4.1. n-alkane δD values
Hydrogen isotope (δD) values of terrestrial higher plant leaf waxes
record: 1) the δD values of meteoric water (Sauer et al., 2001;
Chikaraishi and Naraoka, 2003; Sachse et al., 2004; Rao et al., 2009);
2) the extent of D-enrichment during soil evaporation and leaf
evapotranspiration, which is dependent on humidity (Smith and
Freeman, 2006); and 3) the biological fractionation that occurs during
leaf wax synthesis. Thus, they can be powerful tools in the reconstruc-
tion of past environmental conditions, although an important caveat is
the effect of vegetation change as both evapotranspiration and
biosynthetic effects can vary amongst different taxa. In the Kumara-2
core, δD values of the C27 and C29 n-alkanes range from −137 to −168‰
and values for both are very similar throughout the study interval
(Fig. 6). These values are comparable in magnitude to those observed in
Tanzania during the early stages of the CIE (Handley et al., 2008) and are
more D-enriched than those reported from northern mid latitudes in the
Bighorn Basin (−195 to −185‰; Smith et al., 2007) and the Arctic
(−230 to −260‰; Pagani et al., 2006a, 2006b) across the Paleocene/
Eocene boundary.
Changes in higher plant community can influence the isotopic
composition of leaf waxes (e.g. Chikaraishi and Naraoka, 2003; Liu and
Huang, 2008; Pedentchouk et al., 2008). However, previous studies have
estimated average hydrogen isotopic enrichment factors between C29 n-
alkane and meteoric source water (εC29-GW) during leaf wax lipid
biosynthesis. εC29-GW was determined to be ca. −130‰ to −120‰ for
surface sediment n-alkanes across a transect of 13 European lakes, with
lower values at higher latitudes (Sachse et al., 2004), and −140‰ to
−130‰ for surface soil n-alkanes across 28 sampling sites in Eastern
China, again with lower values at higher latitudes (Rao et al., 2009).
These values are consistent with other reported hydrogen isotopic
composition relationships between surface soil n-alkanes and meteoric
water from a variety of different geographical locations with varying
vegetation types (e.g. Chikaraishi and Naraoka, 2003; Bi et al., 2005;
Sachse et al., 2006; Smith and Freeman, 2006). Assuming an average
εC29-GW of ca. −130‰, Early Paleogene precipitation at Kumara
(paleolatitude 55°S; paleolongitude 170°W) would have had a mean
δD value of ca. −40 to −10‰. Currently, average annual precipitation
δD values for New Zealand range from ca. −55‰ to −27‰, with values
of ca. −40‰ for the Kumara region (Bowen and Revenaugh, 2003;
Bowen, 2009). However, global δDsw values (hydrogen isotopic
composition of seawater) were likely ca. 12‰ lower during the
Paleogene, ca. 8× larger than the putative δ18Osw difference for an ice-
free world (1.5‰; e.g. Shackleton and Kennett, 1975; Shackleton, 1977;
Lear et al., 2000; Schrag et al., 2002; Zachos et al., 2006). If this is the case,
precipitation δD values should be more negative than present day
estimates but the opposite is observed in the Kumara-2 core.
There are several reasons for this potential discrepancy. First, the
εC29-GW could have been lower than −130‰; that could arise from
either a more arid climate state or from the specific vegetation regime.
Alternatively, meteoric water could have been more D-enriched during
the Cenozoic, which could be indicative of: 1) less precipitation locally
or during water vapour transport from the source area (e.g. Pagani et al.,
195
2006a, 2006b); or 2) a lower isotope effect during evaporation and
source water vapour formation, arising from much warmer ocean
surface temperatures around New Zealand. Given that there is little
precipitation induced fractionation of New Zealand meteoric water in
the present day, it seems unlikely that this value was even lower during
the Paleogene. Instead, we interpret the higher values as a consequence
of warmer oceans, a hypothesis which should be tested by adding
hydrogen isotopic components to general circulation models.
5.4.2. Stratigraphic changes in n-alkane δD values
There are several variations in the n-alkane δD record, with shifts
in the upper and lower parts of the core being comparable to those
occurring at the PETM (Fig. 6). We consider each of these discreetly
and for each discuss the potential influence of vegetation change or a
marine contribution to the HMW n-alkane pool.
5.4.2.1. Prior to the PETM. From 1744.42 to 1737.02 mbs, preceding and
spanning the onset of the CIE, n-alkane δD values decrease from −145 to
−165‰ (Fig. 6). This decrease in δD values starts prior to the inferred
changes in plant community structure and the change in depositional
environment at 1739.1 mbs. Crucially, either an increased angiosperm
(Pedentchouk et al., 2007, 2008) or marine contribution would be
expected to result in more D-enriched rather than depleted values; this
is not observed, suggesting that organic matter source changes are not
the primary control on changes in n-alkane δD values. As such, our data
suggest that prior to and during the onset of the PETM meteoric water
was becoming D-depleted due to more precipitation and/or that
evaporative enrichment was decreasing perhaps due to a more humid
climate. The former could arise not only from increased precipitation in
the New Zealand region but also a shift to a more distant source, such
that water vapour has been fractionated to a greater degree during
transport. Distinguishing local and regional changes will require greater
geographical coverage; nonetheless, these data suggest changes in the
hydrological cycle prior to the PETM.
5.4.2.2. During the PETM. As discussed above, n-alkanes in the two
lowermost samples (1737.97 and 1737.02 mbs) within the CIE have
relatively low δD values. Above this, the n-alkane δD record becomes
more complex, with large positive and negative shifts (Fig. 6). These
shifts occur after the beginning of the marine mudstone unit and
change in plant microfossil composition, suggesting that changes in n-
alkane source are not the sole controlling factors. Nonetheless, δD
values in the PETM interval should be interpreted cautiously. While
detailed age models are lacking from all four sites, the Kumara δD record
is broadly similar to those from Tanzania (Handley et al., 2008), the
Arctic (Pagani et al., 2006b) and the Bighorn Basin (44°N) in North
America (Smith et al., 2007): all of these sites exhibit a dramatic positive
excursion during the early part of the CIE, and at the Arctic, Bighorn
Basin and Kumara sites the positive shift is shortly followed by a return
to lower δD values; unfortunately, the Tanzanian record is truncated and
it is not possible to comment on whether a similar return may also occur
there. Interestingly, in both the Kumara and Tanzanian records, the
positive δD excursion does not occur at the base of the CIE and instead
lags it, in apparent contrast to the Arctic and Bighorn Basin records.
From the Arctic record, Pagani et al. (2006b) interpreted the positive
shift in C27 and C29 n-alkane δD values during the early part of the CIE as
an increase in the δD of meteoric water, caused by decreased
precipitation, and isotopic distillation, at lower latitudes, an interpretation
consistent with an observed decrease in Arctic Ocean salinity (Sluijs et al.,
2006; Sluijs et al., 2008b). Arctic air masses are particularly susceptible to
distillation processes due to the long pathway of vapour transport and
extensive precipitation that occurs along it; however, isotopic distillation
may also have affected the Kumara site. If so, the positive excursion
reflects either a shift to more local, as opposed to tropical, water sources
or less precipitation during transport (Pagani et al., 2006b). Alternatively,
the positive shift could record an increase in the temperature of the
196 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200
source waters (e.g. Gat, 1996) and less fractionation during water vapour
formation. A further explanation is that the shift records more arid
conditions, bringing about enrichment of soil or leaf water via increased
evaporation (Sachse et al., 2004); indeed, this explanation was invoked to
explain the positive excursion observed in the Bighorn Basin (Smith et al.,
2007) and is consistent with other climate indicators from that region
(Wing et al., 2005; Smith and Freeman, 2006; Kraus and Riggins, 2007).
Globally and locally, the PETM is characterised by evidence for a
more active hydrological cycle, including increased sedimentary
kaolinite contents (e.g. Robert and Chamley, 1991; Gibson et al., 1993;
Kaiho et al., 1996; Schmitz and Pujalte, 2003; Zachos et al., 2006),
suggesting either more humid conditions (Robert and Kennett, 1994;
Gibson et al., 2000; Bolle and Adatte, 2001) or increased soil erosion
(Thiry and Dupuis, 2000; Schmitz and Pujalte, 2003), and increased
sedimentation rates (e.g. Crouch et al., 2003; Lippert and Zachos, 2007;
Sluijs et al., 2008b). Notably, studies have shown that sedimentation rates
increased at several New Zealand marine PETM sections (Hollis et al.,
2005; Nicolo et al., 2007), while in the Kumara sequence there is an
increase in the proportion of terrigenous biomarkers within the marine
mudstone unit. Thus, the simplest explanation for our δD record is
increased export of D-enriched water to New Zealand, analogous to that
inferred by Pagani et al. (2006b) for the Arctic. However, the Tanzanian
PETM section is also characterised by a positive δD excursion and
increased sedimentation rate. It is difficult to envisage how water vapour
isotopic distillation, which is already minimal, could have decreased at
this tropical site. Instead, it is argued that Tanzania experienced a more
arid (higher δD values) but more seasonal climate (increased sedimen-
tation rate); such a model could also apply to New Zealand and should be
explicitly tested in future climate simulations.
Regardless of mechanism, the Kumara climatic perturbation reflected
by the positive δD excursion was transient and the associated
hydrological regime quickly returned to conditions similar to those
directly preceding the onset of the PETM within the CIE. This appears to be
a global characteristic of PETM δD records, with only the truncated record
from Tanzania being an exception (Pagani et al., 2006b; Smith et al., 2007;
Handley et al., 2008). Thus, it appears that any perturbation in the
hydrological regime, at least with respect to isotopic partitioning, was a
transient response to PETM warming.
5.4.2.3. Post PETM. In the upper part of the core (1721.54 to 1710 mbs),
n-alkane δD values increase from ca. −160 to −135‰ (Fig. 6) and are
also apparently unrelated to changes in the depositional environment or
vegetation groups. This increase, particularly in the upper 10 m of the
core, could record either increasing aridity or decreasing water vapour
isotopic distillation as discussed above. Intriguingly, it is at the top of this
interval that the most dramatic vegetation change in the Kumara-2 core
is recorded: a shift to abundant Casuarina (Myricipites harrisii) pollen,
which is recorded in sequences throughout New Zealand. In modern
settings, Casuarina species are well adapted to dry habitats or prolonged
dry seasons (Heywood, 1978; Osundina, 1997), and locally drier
conditions during the Early Eocene may therefore have played a role
in this notable vegetation change.
5.5. The carbon isotope excursion
5.5.1. Magnitude of the CIE
Assuming peak negative carbon isotope values are recovered, the
magnitude of the CIE in the Kumara-2 core, as recorded by the δ13C
values of higher plant leaf wax n-alkanes, is ca. 4.5‰. There is much
debate concerning the fidelity with which different sedimentary
archives record the actual shift in atmospheric CO2 δ13C values during
the PETM. The magnitude of the isotope excursion in terrestrial records
is often larger than that found in marine settings: terrestrial paleosols
typically record a CIE of −4 to −5‰ (e.g. Koch et al., 1992; Koch et al.,
2003b; Schmitz and Pujalte, 2003), compared to a −2.5 to −3‰
excursion in deep sea foraminifera δ13C values (e.g. Kennett and Stott,
1991; Thomas et al., 2002). Few leaf wax lipid compound-specific δ13C
records exist for the PETM (Kaiho et al., 1996; Hasegawa et al., 2006;
Pagani et al., 2006b; Smith et al., 2007; Handley et al., 2008), yet these
are crucial for the interpretation of the magnitude of the CIE as recorded
in the terrestrial carbon pool. Various attempts have been made to
reconcile these records or argue which more closely represents the
atmospheric CIE (Bowen et al., 2004; Smith et al., 2007).
In addition to the isotopic composition of atmospheric CO2, factors
which affect carbon isotopic fractionation during photosynthesis will
also influence the δ13C values of terrestrial higher plant n-alkanes (e.g.
Diefendorf et al., 2010). These include changes in humidity (e.g.
Farquhar et al., 1989) and shifts in the composition of the higher plant
community, especially changes in the proportion of gymnosperms to
angiosperms (Chikaraishi and Naraoka, 2003; Smith et al., 2007). A
further concern in the Kumara-2 core is the potential change in the
source of n-alkanes, as marine organic matter can be 13C-enriched
relative to terrestrial organic matter (Popp et al., 1989). However, the
difference between the δ13C values of terrestrial and aquatic organic
matter is generally smaller in a high pCO2 greenhouse world such as the
Paleogene. Also, as discussed above, n-alkane hydrogen isotopes show
no consistent D-enrichment through the marine interval as would be
expected if they derived from marine organic matter (Fig. 6).
Increases in humidity result in increased carbon isotopic fractiona-
tion during photosynthesis (e.g. Farquhar et al., 1989; Diefendorf et al.,
2010). Thus, a potential increase in humidity during the PETM could
result in the amplification of a negative CIE. While it is probable that
several factors influence n-alkane δD values in the Kumara record, the
most negative n-alkane δ13C values coincide with some of the most
positive δD values (Fig. 6), which is inconsistent with elevated humidity
enhancing carbon isotope fractionation by plants and amplifying the
CIE. These relationships are similar to observations in Tanzania
(Handley et al., 2008) and the Bighorn Basin (Smith et al., 2007).
Several studies have shown that n-alkanes derived from gymnos-
perms are typically more 13C-enriched compared to those found in
angiosperms grown under the same climatic conditions (Leavitt and
Newberry, 1992; Flanagan et al., 1997; Chikaraishi and Naraoka, 2003;
Diefendorf et al., 2010). Results from the Arctic also show that during the
PETM the magnitude of the negative CIE recorded in angiosperm-
specific biomarkers is greater than that in gymnosperm-specific
compounds from the same sediments (Schouten et al., 2007), likely
due to changes in water use efficiency. Therefore, it is important to be
able to assess potential changes in the plant community when
interpreting terrestrial carbon isotope excursions. As described in
Section 5.3, there is evidence at Kumara-2 for an increase in the relative
abundance of angiosperms compared to gymnosperms at the onset of
the CIE and an increase in fern spores in the lower part of the CIE, and
these could have affected the magnitude of the CIE. However, terrestrial
higher plant community structure, as recorded by palynomorph relative
abundances, remains relatively unchanged during the CIE even across
the interval where δ13C values decrease to a minimum at 1735.92 mbs.
Also, the increase in oleanane concentration occurs in the early stages of
the PETM (Fig. 9). At 1734.5 mbs, δ13C values remain depleted by ca.
4.5‰ relative to pre-excursion values, whilst oleanane concentrations
have decreased to values found in the lower part of the core. Therefore,
while the initial change in terrestrial plant composition may influence
the initial CIE values, it seems that changes in plant community do not
significantly affect the most negative n-alkane δ13C values, which
suggests that the −4.5‰ shift does reflect primarily a change in the
carbon isotopic composition of atmospheric CO2. This value is very
similar to that of −4.6‰, obtained from plant leaf wax n-alkanes from
the Bighorn Basin (Smith et al., 2007) when attempting to account for
changes in mean annual precipitation and changes in plant community
structure (Diefendorf et al., 2010).
A CIE of −4.5‰ has important implications for estimating the quantity
of carbon added to the ocean–atmosphere system and its isotopic
composition. Such an isotopic shift would require the addition of 3600 PgC
 L. Handley et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 305 (2011) 185–200
derived from methane hydrates (assuming a δ13C value of −60‰),
which is inconsistent with estimates of the Paleocene hydrate reservoir
(Buffett and Archer, 2004). Model simulations by Zeebe et al. (2009),
based on the magnitude of marine CaCO3 dissolution associated with the
PETM carbon pulse, estimate an input of ca. 3000 PgC with a carbon
isotopic composition lighter than −50‰, assuming a CIE of −3‰. In
contrast, simulations by Panchuk et al. (2008) require a carbon pulse of
at least 6800 PgC with an average δ13C value of −22‰, based on a −4‰
excursion, a scenario which is more compatible with a CIE of −4.5‰.
Furthermore, Zeebe et al. (2009) argued that the addition of 3000 PgC to
the ocean–atmosphere system was not sufficient to drive reported
global sea surface temperature increases of 5–8 °C (e.g. Kennett and
Stott, 1991; Sluijs et al., 2006; Zachos et al., 2006) and that other
unrecognised forcing mechanisms must play a significant role. In
contrast, a larger carbon input similar in size to that invoked by Panchuk
et al. (2008), can yield an increase in pCO2 consistent with PETM
warming and with the observed − 4.5‰ CIE. This supports the
hypothesis that carbon sources that were less 13C-depleted than
methane hydrates also contributed to the PETM CIE (e.g. Kurtz et al.,
2003; Svensen et al., 2004; Storey et al., 2007).
5.5.2. Timing of the CIE and sea level rise
The onset of the CIE is gradual in all 3 n-alkane records, with 3
intermediate δ13C values spanning over 3 m of sediment before maximum
negative values are attained (Fig. 2). This gradual onset is not a common
feature of PETM records and could provide direct evidence that the release
of carbon into the atmosphere was not ‘instantaneous’. This interpretation
does require caution, however, as an alternative mechanism could be
mixing of pre-excursion n-alkanes into the excursion interval. The
transport of n-alkanes into the sedimentary record, particularly into
marine sediments, can occur with significant lags (N1000 yr) as shown by
radiocarbon analyses of recent sediments (Eglinton et al., 1997;
Smittenberg et al., 2006).
The timing of the CIE relative to the PETM temperature increase is
currently a topic of much interest. In northeastern North America,
increases in sea surface temperature (SST) may have occurred prior to
the onset of the CIE and maximum warming predates the most 13C-
depleted values in the marine realm (Sluijs et al., 2007). Likewise, sea
level rise at these sites, believed to be caused at least partially by the
thermal expansion of ocean waters, may have been initiated 20 to
200 kyr prior to the CIE (Sluijs et al., 2008a). Such offsets suggest that the
massive carbon input invoked as the cause of the warming during the
PETM may not have been geologically instantaneous. The Kumara record
allows these hypotheses to be explored further. If the sea level rise at
Kumara-2 is due to thermal expansion of ocean waters, then the sudden
transition to marine depositional conditions would be the result of
increased ocean water temperatures. Geochemical and palynological
samples at 1737.97 m and 1737.02 mbs are the first combined analyses
to record marine sedimentation. While both samples have lower δ13C
values than underlying sediments, they do not reflect the most negative
part of the CIE. The lack of a well-constrained age model and
sedimentation rates makes detailed interpretation of the timing of the
changes associated with the PETM difficult. However, the evidence
suggests the sea level rise, and inferred increase in temperature,
occurred prior to the maximum negative carbon isotopic shift. The rise
in sea level required to flood the study site and whether such a rise was
rapid or gradual is unclear from the Kumara-2 core. These changes
therefore either coincided with the first input of 13C-depleted carbon
into the atmosphere or slightly preceded it. Apectodinium dinocysts
occur in the very first marine sediments, and the increase in their relative
abundance also precedes the occurrence of the lowest n-alkane δ13C
values. Similarly, initiation of noticeable changes in the plant commu-
nity, as recorded by palynomorphs and oleanane concentrations, seem
to occur prior to the most negative n-alkane δ13C values, further
suggesting an offset between climatic perturbations and the peak of the
197
CIE. The record from Kumara-2 provides further evidence for sea level
rise, and possibly warming, prior to the peak of the CIE during the PETM.
6. Conclusions
We have identified a new PETM section in New Zealand that occurs
over a 4.85 m interval and is characterised by a negative CIE of 4.5‰,
recorded in higher plant leaf wax n-alkanes. In the Kumara-2 core, South
Island, dramatic changes in depositional environment during the PETM
are interpreted as evidence for a sea level rise, with a transition from a
terrestrial to a near-shore marine setting observed in lithological,
palynological and organic biomarker records. Evidence for sea level rise
coincides with the initiation of the negative CIE but predates the most
13
C-depleted values in the terrestrial higher plant n-alkane record. Other
proxies suggest that this marine depositional environment was anoxic
or suboxic, possibly with nutrient-rich surface waters during part of the
PETM. Higher plant δD values are harder to interpret due to complex
source changes but suggest that the PETM was characterised by notable
hydrological variations that are similar to those observed in North
America, the Arctic and Eastern Africa. A negative shift in δD values
across the transition into the PETM apparently reflects an initial
decrease in precipitation-induced isotopic distillation during water
vapour transport to New Zealand. Intriguingly, dramatic changes in
higher plant δD values occur in horizons preceding and following the
PETM. Climatic and/or depositional environment changes caused
variations in terrestrial plant assemblages, with the appearance of
pollen associated with thermophilic conditions and the development of
Nypa mangrove swamps. The onset of the CIE also saw an increase in
fern spores and an initial decrease in gymnosperms. The above
observations, combined with the gradual onset of the CIE, suggest that
the injection of 13C-depleted carbon into the ocean–atmosphere system
was not geologically instantaneous and that carbon continued to be
released after an initial sea level rise (and inferred temperature
increase), inconsistent with the hypothesis of a single catastrophic
release of carbon as the sole driver of warming during the PETM.
Acknowledgements
Palynological processing was completed by Roger Tremain, GNS
Science. We thank Dr. Robert Berstan and Dr. Ian Bull of the Bristol Node
of the Natural Environment Research Council (NERC) Life Sciences Mass
Spectrometry Facility for technical assistance. Discussions and com-
ments from Chris Hollis and Ian Raine greatly improved the manuscript.
EMC acknowledges research support by the Royal Society of New
Zealand Marsden Fast-Start Fund (contract 03-GNS-001) and the GNS
Science Global Change Through Time Programme (Foundation for
Research, Science and Technology contract C05X0701). We also thank
the NERC for funding LH's PhD. We also thank Professor Thierry Corrège,
Professor Scott Wing and two anonymous referees for their thorough
critical evaluations and comments that helped improve this manuscript.
Appendix A. Supplementary data
Supplementary data to this article can be found online at doi:10.1016/
j.palaeo.2011.03.001.
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