GDGT THERMOMETRY:

LIPID TOOLS FOR RECONSTRUCTING PALEOTEMPERATURES

JESSICA E. TIERNEY

Woods Hole Oceanographic Institution, Woods Hole, MA USA 02543

tierney@whoi.edu

ABSTRACT.—Microbial communities adjust the chemical structure of their cell membranes in response to
environmental temperature. This enables the development of lipid-based paleothermometers such as the
glycerol dialkyl glycerol tetraether (GDGT) proxies described here. Surface-sediment calibrations estab-
lish a strong empirical relationship between the relative distribution of GDGTs and temperature. GDGT
proxies can be used in marine, lacustrine, and paleosol sequences as long as the organic material is not
thermally mature. Thus far, GDGT proxies have been applied to sediments dating back to the middle Ju-
rassic. Many of the key uncertainties of these proxies are related to our emerging understanding of ar-
chaeal (and for the branched GDGTs, bacterial) ecology.

INTRODUCTION paleo sea-surface temperature (SST) proxy (UK

37) can be applied widely in marine environments
′

THE LAST twenty-five years have witnessed the
growth and expansion of a new technique for es-
timating paleotemperatures based on the use of
biomarkers: organism-specific, fossil lipids (fats)
found in sedimentary organic matter. Biomarkers
enhance our ability to reconstruct paleoenviron-
ments in geologic history, in part because they are
subject to a different set of diagenetic alterations
than hard parts of fossils. They may be well pre-
served in sedimentary environments where tradi-
tional skeletal temperature proxies (e.g., calcare-
ous foraminifera) typically are not, thereby en-
hancing the range of depositional conditions from
which paleotemperature information can be ex-
tracted.
Biomarker-based paleothermometers are built
upon the biochemical principle that microorgan-
isms adjust the rigidity of their cell membrane
structures by altering the number of double bonds,
rings or branches in response to environmental
temperature (e.g., Ray et al., 1971; Kita et al.,
1973; Nozawa et al., 1974). The first biomarker-
based paleotemperature proxy was based on the
relative distribution of unique long-chain (C37) tri-
and di-unsaturated ketones (alkenones) produced
by marine haptophyte algae, such as the ubiqui-
tous coccolithophorid Emiliania huxleyi (Volkman
et al., 1980; Marlowe et al., 1984). The alkenone
that are mid-Paleogene in age or younger, and has
been a mainstay of paleoclimate reconstruction
since its development in the late 1980s (Herbert,
2003). There are, however, some limitations to the
alkenone proxy. Extant haptophyte species that
the modern calibrations of the alkenone proxy are
based on evolved relatively recently (e.g., 0.28
Ma for Emiliania huxleyi, Thierstein et al., 1977),
so alkenones found in older sedimentary se-
quences can only be presumed to be produced by
ancient relatives with a similar temperature sensi-
tivity. Also, the alkenone calibrations to SST are
limited to ~28°C, such that the proxy cannot be
used in some areas of the tropical oceans, nor in
ancient hothouse climates.
In the last decade, a new biomarker paleo-
temperature approach based on the relative abun-
dances of glycerol dialkyl glycerol tetraethers
(GDGTs) has been developed that complements
and extends the capabilities of the alkenone proxy.
GDGTs are relatively large (up to 86 carbon at-
oms) membrane lipids produced by Archaea and
some Bacteria. They are common, typically abun-
dant, easy-to-analyze lipids found in a variety of
environments (lakes, soils, oceans). Such attrib-
utes make GDGTs a promising universal tool for
estimating temperatures in the geologic past, es-
pecially in deep geologic time.

In Reconstructing Earth’s Deep-Time Climate—The State of the Art in 2012, Paleontological Society Short Course,
November 3, 2012. The Paleontological Society Papers, Volume 18, Linda C. Ivany and Brian T. Huber (eds.),
pp. 115–131. Copyright © 2012 The Paleontological Society.
 THE PALEONTOLOGICAL SOCIETY PAPERS, VOL. 18

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FIGURE 1.—A) Core structures of the isoprenoidal glycerol dialkyl glycerol tetraethers (isoGDGTs), with mass-to-
charge ratios (m/z) on the right associated with analysis via HPLC/positive ion APCI. B) Common polar head-
groups of intact isoGDGTs, which would replace one or both of the terminal hydroxyl groups indicated in (A). C)
Core structures of branched glycerol dialkyl glycerol tetraethers (brGDGTs).

WHAT ARE GDGTs? GDGT structures remain in ancient sediments.

There are two main types of GDGTs: the iso-
prenoidal GDGTs (isoGDGTs) and the non-
isoprenoidal, branched GDGTs (brGDGTs). The
isoGDGTs consist of two head-to-head C40 iso-
prenoid (i.e., made of isoprene units) chains with
a varying number of cyclopentane (five-sided)
and cyclohexane (six-sided) rings, connected by
ether bonds to two terminal glycerol groups (Fig-
ure 1). The brGDGTs are structurally similar, but
have branched C30 alkyl chains containing 4–6
methyl groups instead of the C40 isoprenoidal
chains (Figure 1). Additional polar headgroups,
including hexose and phosphate moieties, are at-
tached to the core GDGT structure when the
membrane lipid is intact (Sturt et al., 2004;
Schouten et al., 2008a; Pitcher et al., 2010; and
see Fig. 1). Similar polar headgroups accompany
the brGDGTs (Liu et al., 2010; Peterse et al.,
2011). These polar headgroups are typically
quickly lost during diagenesis; only the “core”
IsoGDGTs are characteristic lipids of Ar-
chaea, and are produced by a number of methano-
genic, hyperthermophilic, and mesophilic species,
although not all species produce each kind of
isoGDGT shown in Figure 1. The isoGDGT pa-
leothermometer rests on the assumption that the
dominant producers of isoGDGTs are members of
the recently renamed phylum Thaumarchaeota
(formerly a division of the Crenarchaeota;
Brochier-Armanet et al., 2008; Spang et al.,
2010). In many environments, this is a reasonable
assumption because other Archaea that produce
GDGTs (e.g., thermophile Archaea) are restricted
to distinct environmental niches. In contrast,
Thaumarchaeota are a ubiquitous mesophilic
group in the global oceans, possibly representing
up to 20% of the ocean’s picoplankton (Karner et
al., 2001). Known species of Thaumarchaeota are
nitrifiers: they convert ammonium to nitrate and
fix bicarbonate autotrophically to form their bio-
mass (Könneke et al., 2005). Nitrifying Thaumar-

116
 TIERNEY: RECONSTRUCTING PALEOTEMPERATURES USING GDGT THERMOMETRY
chaeota and their GDGTs are also found in soils
and lakes (Ochsenreiter et al., 2003; Leininger et
al., 2006; Llirós et al., 2010; Schouten et al.,
2012). Concentrations of isoGDGTs in soils are
low relative to marine levels (Weijers et al.,
2006b), but concentrations in lakes are often quite
high (Tierney et al., 2010b) and have enabled the
application of the isoGDGT paleothermometer to
certain lake environments (see below).
Thaumarchaeota are the only Archaea known
to make the distinctive GDGT crenarchaeol,
which has a cyclohexyl ring in addition to the cy-
clopentyl rings (Figure 1), and is a diagnostic
biomarker for these species in both moderate- and
high-temperature environments (Sinninghe Dam-
sté et al., 2002b; Pearson et al., 2004; de la Torre
et al., 2008). Thaumarchaeota also produce
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smaller amounts of a crenarchaeol regioisomer
(Figure 1; oft-abbreviated as cren’) that plays a
role in the temperature predictability of the
isoGDGT paleothermometer: relatively more of
the regioisomer is observed at higher tempera-
tures.
BrGDGTs share many structural characteris-
tics with the isoGDGTs, including the ether bonds
to terminal glycerol groups, a feature in mem-
brane lipids typically seen only in Archaea (with
some exceptions, e.g., see Weijers et al., 2006a,
and references therein). Yet both the chain archi-
tecture (branched vs. isoprenoidal) and the stereo-
chemistry of the glycerol groups on the brGDGTs
are diagnostic of Bacteria (Weijers et al., 2006a).
BrGDGTs are commonly found in soils, peats,
lakes, and marginal/deltaic environments, and are
not present in pelagic marine environments
(Hopmans et al., 2004), suggesting that they are
associated with terrestrial organisms. However, in
spite of their ubiquity, efforts to identify the or-
ganism(s) responsible for these compounds have
not been highly successful (e.g., Weijers et al.,
2009). Recently, Sinninghe Damsté et al. (2011)
demonstrated that a strain of Acidobacteria pro-
duces one type of brGDGT (brGDGT-I in Figure
1), confirming suspicions that this phylum of Bac-
teria, which is diverse, commonly found in peats
in soils, but not well characterized, may be a
source of brGDGTs (Weijers et al., 2006a, 2009).
However, the other eight brGDGTs utilized in
brGDGT-based temperature proxies are, at pre-
sent, “orphan” compounds.
GDGTs—or chemical remnants of them—
have been observed in both modern and ancient
sedimentary deposits and oils for some time (e.g.,
Chappe et al., 1980; Brassell et al., 1981; Hoefs et
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FIGURE 2.—A) HPLC trace of isoGDGTs from a
tropical marine sediment. TEX86 value is calibrated to
SST using the Kim, et al. (2010) TEXH86 calibration.
(B) HPLC trace of brGDGTs from a freshwater lake.
MBT and CBT values are calibrated to MAAT using
the Tierney et al. (2010b) lakes calibration. All num-
bers correspond to the structures in Figure 1.
al., 1997), but were difficult to analyze because
intact GDGTs are too large for gas chromatogra-
phy. It was not until the relatively recent devel-
opment of a high-performance liquid-
chromatography mass-spectrometry method
(Hopmans et al., 2000) that GDGTs became a fo-
cus of both organic geochemical and paleoclima-
tological research. Figure 2 illustrates some typi-
cal chromatograms of both iso- and br-GDGTs
using high-performance liquid chromatography-
atmospheric pressure chemical ionization-mass
spectrometry (HPLC-APCI-MS), which separates
compounds by mass and polarity. The run time for
a single LC/MS analysis is 60–70 minutes, and
preparative procedures are relatively minimal (ex-
traction followed by column chromatography for
 THE PALEONTOLOGICAL SOCIETY PAPERS, VOL. 18
purification), making GDGT analysis sufficiently
rapid for use in paleoclimate studies. Details of
the GDGT LC/MS methodology may be found in
Schouten et al. (2007b).
HOW DO GDGTS RECORD
PALEOTEMPERATURES?
isoGDGTs: the TEX86 paleothermometer
In response to temperature variations, the mi-
crobial producers of GDGTs produce compounds
with different numbers of rings in their isoprenoid
chains: a GDGT with more rings has a higher
melting point and is more stable at warm tempera-
tures (Gliozzi et al., 1983). Although mesophilic
Thaumarchaeota have not yet been cultured in
different temperature environments, thermophile
relatives of Thaumarchaeota that are more readily
manipulated in culture produce more cyclic
isoGDGTs at higher temperatures (de Rosa et al.,
1980; Uda et al., 2001). Similarly, mesocosm
studies (experiments in which natural seawater is
manipulated in the laboratory) show that more of
the cyclic isoGDGTs are present in seawater at
higher temperatures (Wuchter et al., 2004;
Schouten et al., 2007a). Schouten et al. (2002)
developed an index to mathematically represent
this degree of cyclization called TEX86 (the Tet-
raEther indeX of 86 carbons; numbers correspond
to compounds labeled in Figure 1; cren′ stands for
the crenarchaeol regioisomer):
Schouten et al. (2002) empirically calibrated
TEX86 to SST using a set of 43 modern surface
sediments, yielding a strong linear relationship:
TEX86 = 0.015 × SST + 0.27 (r2 = 0.92, n = 43)
The paucity of pure Thaumarchaeotal cultures,
along with the surprising observations that Thau-
marchaeota seem to produce less of the crenar-
chaeol isomer in mesocosms than in the open
ocean (Wuchter et al., 2004; Schouten et al.,
2007a) and that the isomer may have a different
source (Shah et al., 2008), have thwarted attempts
to calibrate TEX86 to SST experimentally. This
leaves the TEX86 proxy reliant on empirical core-
top calibration, a practice that is commonly
adopted for other paleo-SST proxies (e.g., alke-
none UK′37 and foraminiferal Mg/Ca). Since
Schouten et al. (2002) developed the linear equa-
118
tion given above, efforts have been made to ex-
pand the collection of modern core-top sediments
available to constrain the TEX86 proxy and better
understand its predictive ability (Kim et al., 2008;
Liu et al., 2009; Kim et al., 2010). The current
calibration dataset includes 350+ core tops from
around the global ocean, though the distribution
of those core tops is not uniform (Figure 3). The
relationship between TEX86 and SST remains
largely linear (Figure 4), although non-linear rela-
tionships to SST have been proposed (Liu et al.,
2009; Kim et al., 2010) based on observations that
TEX86 is more sensitive to SST changes at the
high end of the temperature range and less sensi-
tive at the lower end of the calibration range (e.g.,
Schouten et al., 2003). Both linear and non-linear
regressions through the modern core-top dataset
perform comparably (Figure 4).
The core-top studies also indicate that there
are certain areas in the marine realm where TEX86
is unreliable, or necessitates a different calibra-
tion. These areas include the polar oceans, where
the relationship between TEX86 and SST is poor
(Kim et al., 2008, 2010). This could reflect a re-
duced sensitivity of TEX86 in cold waters, or con-
versely, inaccurate mean annual SST estimates at
high latitudes. Kim et al. (2010) proposed an al-
ternate functional form of TEX86, called “TEXL86”
(L for low-temperature) that has better predict-
ability at low temperatures, but is less precise
given the entire global SST range (Table 1). Inter-
estingly, TEXL86 excludes the regioisomer:
IsoGDGT distributions are also quite different in
the semi-enclosed Red Sea, necessitating a differ-
ent calibration (Trommer et al., 2009, Table 1)
and perhaps indicating the contribution of unique
archaeal species (Eder et al., 2002; Ionescu et al.,
2009) to the sedimentary isoGDGT pool.
TEX86 may be used in some (typically large)
lakes to infer lake-surface temperature (LST)
(Powers et al., 2004, 2005; Tierney et al., 2008;
Blaga et al., 2009; Powers et al., 2010; Tierney et
al., 2010a); core tops used to constrain the lake
calibrations are shown in Figure 3. Unfortunately,
TEX86 does not appear to be universally applica-
ble in lakes. Reasons for this are not well under-
stood, but it may be that smaller lakes do not have
the chemistry or limnology that supports large
populations of lacustrine Thaumarchaeota. In an-
oxic lakes or in anoxic sediment columns, Ar-
 TIERNEY: RECONSTRUCTING PALEOTEMPERATURES USING GDGT THERMOMETRY

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FIGURE 3.—A) Locations of sediment core-top calibration points for TEX86, including data from Kim et al. (2010),
Ho et al. (2011), Trommer et al. (2009), Chazen (2011), Leider et al. (2010), Seki et al. (2009), Castañeda et al.
(2010), Shintani et al. (2010), Powers et al. (2010), Blaga et al. (2009) and Tierney et al. (2010a) and excluding
duplicates. (B) Locations of sediment core-top calibration points for MBT/CBT, including data from Tierney et al.
(2010b), Blaga et al. (2010), Zink et al. (2010), Sun et al. (2011), and Pearson et al. (2011).

chaea performing methanogenesis or anaerobic
oxidation of methane (AOM) may produce
isoGDGTs (see below), compromising the Thau-
marchaeotal TEX86 signature (Blaga et al., 2009;
Powers et al., 2010). In small lakes receiving
large amounts of soil organic matter, some of the
isoGDGTs may derive from soil Thaumarchaeota,
again complicating the sedimentary signal (Blaga
et al., 2009). As with the marine TEX86 calibra-
tion, the relationship between TEX86 and LST is
generally linear, although a non-linear form is
also possible. Tierney et al. (2010a) proposed a
“warm lakes” calibration with a shallower linear
slope (see Table 1) to account for the apparent
increased sensitivity of lacustrine TEX86 at higher
LSTs, indicating that a nonlinear model could be
appropriate (Figure 4).
Presently, there are a number of calibrations
for TEX86, reflecting ongoing attempts to refine
the relationship between TEX86 and temperature
(Table 1). The most common calibrations used to
date are the Kim et al. (2010) “TEXH86” calibra-
tion (where TEXH86 is simply the base-10 loga-
rithimic transform of TEX86) for marine SST, and
the Powers et al. (2010) calibration for lake LST.
brGDGTs: the MBT/CBT paleothermometer
Because the producers of most of the
brGDGTs have not been identified, and no species
that produce any of these lipids other than
brGDGT-I have been identified in culture, the
physiological relationship between brGDGT cyc-
lization and/or methylation to temperature is not
understood. We might expect that such a relation-
ship exists, but to date, it relies solely on empiri-
cal evidence in the form of core-top/topsoil stud-
ies. Weijers et al. (2007c) studied a global collec-
tion of topsoils and identified two major environ-
mental parameters that had a statistical relation-
ship to brGDGT distributions: soil temperature
(approximated by mean annual air temperature;
MAAT) and soil pH. The degree of cyclization of
the brGDGTs seemed to be related only to soil pH
in a non-linear fashion, implying a power law re-
lationship. Thus, Weijers et al. (2007c) devised an
index representing the cyclization of the

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 THE PALEONTOLOGICAL SOCIETY PAPERS, VOL. 18

TABLE 1.—Sediment core top TEX86 calibrations. *= calibration applies just to the Red Sea, where TEX86 distribu-
tions are different from the open ocean, ‡=TEXL86 is an alternate functional form of TEX86 arguably better for pre-
diction at low SSTs, see main text and Kim et al. (2010) for more details, †=lake calibrations.

Range Equation n r2 RMSE Reference

0–30 T E X86 = 0.015 × T + 0.27 43 0.92 N/A Schouten et al. (2002)

22–30 T E X86 = 0.027 × T + 0.016 24 0.78 N/A Schouten et al. (2003)

5–30 T = −10.78 + 56.2 × T E X86 223 0.94 1.7 Kim et al. (2008)

25–28* T E X86 = 0.035 × T − 0.09 11 0.90 N/A Trommer et al. (2009)

-3–30 T = 50.475 − 16.332 × (1/T E X86) 287 0.82 3.7 Liu et al. (2009)

-3–30‡ T = 49.9 + 67.5 × T E X L86 396 0.86 4.0 Kim et al. (2010)

5–30 T = 38.6 + 68.4 × log(T E X86) 255 0.86 2.5 Kim et al. (2010)

4–30† T = −14.0 + 55.2 × T E X86 12 0.86 3.6 Powers et al. (2010)

10–30† T = 3.50 + 38.9 × T E X86 13 0.92 2.1 Tierney et al. (2010a)

brGDGTs called the CBT (Cyclization of and CBT (as a surrogate for the pH influence) to
Branched Tetraethers) index: predict MBT, which could be inverted to solve for
MAAT:

MBT = 0.122 + 0.187 × CBT + 0.020 × MAAT

that could be linearly related to pH:
CBT = 3.33 − 0.38 × pH
The degree of methylation of soil brGDGTs was
found to relate to both temperature and pH.
Weijers et al. (2007c) devised the MBT (Methyla-
tion of Branched Tetraethers) index to represent
the degree of methylation (numbers refer to struc-
tures in Figure 1; denominator indicates the sum
of all nine brGDGT compounds):
MBT is reasonably correlated with MAAT alone
(r2 =0.62), but is better constrained when both pH
and MAAT are used as predictors (r2 = 0.82),
therefore, Weijers et al. (2007c) used both MAAT
This relation has a slightly higher r2 of 0.77.
However, when the regression is recalibrated with
MAAT as the dependent variable (necessary for
prediction of MAAT), the r2 statistic drops to 0.62
(Figure 5).
The fact that brGDGTs are abundant in a wide
variety of lake basins (Tierney and Russell, 2009;
Sinninghe Damsté et al., 2009; Blaga et al., 2010;
Bechtel et al., 2010; Tierney et al., 2010b; Tyler et
al., 2010; Zink et al., 2010; Sun et al., 2011) of-
fers the tantalizing possibility that these com-
pounds could be used to develop a universal la-
custrine temperature proxy. Early applications of
the Weijers et al. (2007c) equation to lacustrine
brGDGTs (driven by the assumption that all
brGDGTs are soil-derived) revealed that the re-
sulting temperatures were 10°C or greater differ-
ent from observed MAAT (Tierney and Russell,

120
 TIERNEY: RECONSTRUCTING PALEOTEMPERATURES USING GDGT THERMOMETRY

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FIGURE 4.—TEX86 regressions to SST and LST respectively, with best-fit linear and non-linear models. The marine
TEX86 data shown exclude data from the Red Sea (Trommer et al., 2009) and the polar oceans (SST<2, Kim et al.,
2010) where the relationship between TEX86 and SST is different and/or poor. RMSE = root mean square error.

2009; Zink et al., 2010; Tyler et al., 2010); thus, EXAMPLE APPLICATIONS OF GDGT
the soil calibration was not applicable. This may PROXIES
suggest that lacustrine brGDGTs are produced in
situ with a different sensitivity to lake tempera- GDGTs have been used to reconstruct both air
ture—a hypothesis also supported by the presence and water temperatures on a variety of geologic
of intact polar brGDGT in lakes (Tierney et al., timescales, but have been especially useful for
2012). However, recent attempts to develop lake- estimating temperatures in the Mesozoic and early
specific brGDGT distributions are promising and Cenozoic, where there are few applicable methods
demonstrate that lake sediments perform similar for estimating paleotemperature. In one of the
to or better than soils in predicting MAAT (Figure earliest applications of the TEX86 proxy, Schouten
5). et al. (2003) reconstructed low-latitude SSTs dur-
For both soils and lakes, the MBT/CBT tem- ing select intervals in the middle Cretaceous (Al-
perature proxy is considerably less accurate in bian–Cenomanian–Turonian), a hothouse period
predicting temperature than TEX86, with a root in Earth history where temperatures are relatively
mean square error near 5°C. Alternate functional poorly constrained. They estimated low-latitude
forms representing the distribution of brGDGTs SSTs of 32–36°C, in general agreement with
may improve predictive performance and are be- δ18O-based estimates from well-preserved Ceno-
ginning to be explored. Tierney et al. (2010b) manian foraminifera (Schouten et al., 2003).
proposed a calibration based on the fractional GDGTs also have been used to provide both
abundance (relative to the sum of all nine low- and high-latitude constraints on temperature
GDGTs) of the three major non-cyclic brGDGTs excursions during the Paleocene–Eocene Thermal
that provides more precise prediction of MAAT in Maximum (PETM), a brief interval when massive
tropical East African lakes (Figure 5, Table 2). amounts of greenhouse gases were injected into
Similarly, Pearson et al. (2011) proposed a cali- the atmosphere ~55 million years ago, causing
bration based on the fractional abundances of rapid and extreme warming. Zachos et al. (2006)
brGDGT-III, brGDGT-II, and brGDGT-Ib for a applied TEX86 to a section from Wilson Lake,
more globally distributed set of lakes (Table 2). A New Jersey (paleolatitude of 36°N), and found
list of brGDGT-based calibrations is provided in that SSTs were ~25–30°C prior to and after the
Table 2. PETM, but reached a maximum of ~35°C during
the event (Figure 6). Sluijs et al. (2006) and
Weijers et al. (2007b) applied TEX86 and the

121
 THE PALEONTOLOGICAL SOCIETY PAPERS, VOL. 18

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-123412&5,/6742/6&2/-5/,829,/ -123412&5,/6742/6&2/-5/,829,/ -123412&5,/6742/6&2/-5/,829,/

FIGURE 5.—brGDGT regressions to MAAT for (A) soils (data from Weijers et al., 2007c), (B) lakes (data from
Tierney et al., 2010b; Blaga et al., 2010; Zink et al., 2010; Sun et al., 2011), and (C) East African lakes, using an
alternative functional form (Tierney et al., 2010b, see Table 2 for the equation).

MBT/CBT proxy, respectively, to the PETM sec- anthropogenic climate change has had a strong
tion of a drill core taken from the Lomonosov impact on the thermal structure of Lake Tangany-
Ridge (paleolatitude of 85°N), and reconstructed ika.
surprisingly warm temperatures for the high Arc- BrGDGTs have not been used as widely as
tic (Figure 6). Taken at face value, these PETM TEX86 for paleoclimate reconstruction because
GDGT data suggest an extremely warm world their dependence on temperature was only de-
with a surprisingly minimal latitudinal gradient in scribed in 2007 and, to date, is not well con-
temperature (~10°C) compared to present-day strained. In addition to the PETM study, Weijers
gradients (20°C). However, it should be noted that et al. (2007a) used MBT/CBT to reconstruct
because the TEX86 values at Wilson Lake exceed MAAT in the Congo Basin, using deltaic sedi-
those observed in the modern ocean, the inferred ments from the Congo Fan. Their data indicate a
temperatures rely on an extrapolation of the cali- LGM–present change of ~3.5–4°C, a reasonable
bration regression lines; thus, the absolute values finding for the deep tropics, and in agreement
are highly uncertain. Nevertheless, such data pro- with independent proxy data from Africa. Fawcett
vide a hypothesis of how Earth systems responded et al. (2011) used MBT/CBT to reconstruct tem-
to what were likely very high levels of atmos- perature within a Pleistocene lacustrine deposit
pheric carbon dioxide during the PETM. from the Valles Caldera, and estimated glacial/
GDGT proxies also have utility on more re- interglacial thermal variability on the order of
cent timescales, either as a complement to other ~8°C, which is in general agreement with pollen-
paleotemperature proxies or (as is sometimes the based estimates. Neither brGDGTs nor isoGDGTs
case with deep-time studies) because it is the only have been used, as of yet, to reconstruct tempera-
proxy method available in a given region or depo- tures in ancient lake basins.
sitional setting. For example, Tierney et al.
(2010a) used TEX86 in Lake Tanganyika to recon- LIMITATIONS ON THE USE OF GDGT
struct temperatures for the past 1500 years in East PALEOTHERMOMETERS
Africa, a region where there are few options for
recent temperature reconstruction (there are no Preservation
developed tree-ring chronologies, and stable iso- GDGTs are relatively refractory compounds,
topes generally reflect hydroclimatic variability). but they do degrade over time, with isoGDGTs
TEX86 shows evidence for warm conditions dur- apparently degrading faster than brGDGTs (Hu-
ing the Medieval Warm Period, followed by cool/ guet et al., 2008). However, diagenetic degrada-
variable temperatures during the Little Ice Age tion does not affect the TEX86 index within ana-
(Figure 7). In the last 150 years, TEX86 indicates a lytical error (Sinninghe Damsté et al., 2002a;
warming of ~2°C, an event unprecedented in the Schouten et al., 2004; Kim et al., 2009; Huguet et
last 1500 years (Figure 7). These data suggest that al., 2009). When sedimentary sequences undergo

122
 TIERNEY: RECONSTRUCTING PALEOTEMPERATURES USING GDGT THERMOMETRY

TABLE 2.—Topsoil (Weijers et al., 2007c) or lacustrine (all others) core top brGDGT calibrations. *=pH calibration
from CBT, †=uses African lakes data only, ‡=uses New Zealand lakes only, §=This calibration predicts mean sum-
mer temperature (MST) not MAAT.

Range Equation n r2 RMSE Reference

-5–30 MBT = 0.122 + 0.187 × CBT + 0.020 × MAAT 90 0.77 N/A Weijers et al. (2007c)

3–8* CBT = 3.33 − 0.38 × pH 90 0.70 N/A Weijers et al. (2007c)

0–26† MAAT = 11.84 + 32.54 × MBT − 9.32 × CBT 39 0.89 3.0 Tierney et al. (2010b)

0–26† MAAT = 50.47 − 74.18 × fbrGDGT III − 39 0.94 2.2 Tierney et al. (2010b)
31.60 × f brGDGT II − 34.69 × f brGDGT I
6–15‡ MAAT = 55.01 × MBT − 6.055 10 0.74 N/P Zink et al. (2010)

-5–30 MAAT = 3.949 − 5.593 × CBT + 38.213 × MBT 100 0.73 4.3 Sun et al. (2011)

5–30§ MST = 20.9 − 20.5 × f brGDGT III − 12 × 85 0.88 2.0 Pearson et al. (2011)
fbrGDGT II + 98.1 × f brGDGT Ib

catagenesis, GDGTs break down more rapidly and
do so preferentially: hydrous pyrolysis experi-
ments suggest that they degrade between 240–
300°C, and that TEX86 values decline, indicating
preferential destruction of the more cyclic com-
pounds (Schouten et al., 2004). This experimental
evidence suggests that TEX86 is generally not ap-
plicable in more mature sediments (i.e., those
with high amounts of 22S hopanes; 17α,21β (H)-
hopane 22S/(22S+22R) ratios > 0.1). Thus, while
isoGDGT likely have an ancient biosynthetic ori-
gin (Thaumarchaeota have been extant for billions
of years, Spang et al., 2010, although this may or
may not apply to the lipids), and theoretically
TEX86 could be used throughout much of geo-
logic history, the application of the proxy is lim-
ited to rock and sediment sequences that have
been minimally thermally altered.
Diagenetic/catagenic effects on the brGDGT
distributions (MBT/CBT) are not as well con-
strained due to the novelty of the proxy. In a study
of brGDGTs in a suburban lake that became sea-
sonally anoxic and eutrophic as a result of human
disturbance, Tierney et al. (2012) found that there
were more “Type III” (see Figure 1) brGDGTs in
lake sediments that were recently deposited in the
anoxic environment, and less in deeper sediments
that were deposited in the pre-anthropogenic oxy-
genated environment. Similarly, Bechtel et al.
(2010) observed that anoxic lakes yield a “colder”
MBT/CBT signature than oxic lakes, indicating
more methylated brGDGTs in the sediments.
These observations may suggest preferential dia-
genetic loss of Type III brGDGTs upon exposure
to oxygen, but alternatively, could reflect a sensi-
tivity of the microbial producers to anoxia
(Tierney et al., 2012). Further research is needed
to assess the relative diagenetic stability of the
nine brGDGTs.
Ecological constraints
As mentioned previously, the TEX86 proxy is
predicated on members of the phylum Thaumar-
chaeota acting as the primary producers of
isoGDGTs. This is a reasonable assumption in the
global ocean where Thaumarchaeota dominate,
although the contribution of isoGDGTs from
mesophilic Euryarchaeota, also abundant in ma-
rine environments, remains a matter of some un-
certainty and debate (Turich et al., 2007; Schouten
et al., 2008b). Even if the source of isoGDGTs in
the modern ocean can be reasonably constrained
to Thaumarchaeota, it is unlikely that isoGDGTs
are predominantly produced by a single species
(unlike alkenones that select marine species pro-
duce). The lack of regioisomer in cultures of a
dominant marine archaeon, Nitrosopumilus mari-
timus (Schouten et al., 2008a), and the observa-

123
 THE PALEONTOLOGICAL SOCIETY PAPERS, VOL. 18

Paleocene-Eocene such cases, TEX86 cannot be used reliably. Meth-

Thermal Maximum anogenic Archaea and Archaea performing an-
aerobic oxidation of methane (AOM) produce
30 TEX86 isoGDGTs 0–3 (especially GDGT-2, Blumenberg
et al., 2004; Zhang et al., 2011), and are common
in organic-rich, anoxic environments, such as
25 stratified freshwater lakes or marine environments
(e.g., the Black Sea, Wakeham et al., 2003). Diag-
nostic signs of GDGTs originating from
20 methanogenic/AOM archaeal species include high
concentrations of isoGDGTs 0–3 relative to
crenarchaeol and its regioisomer, as well as char-
15 IODP 302 acteristically depleted stable carbon isotope signa-
Lomonosov Ridge tures for biphytanes originating from GDGTs 0–3
MBT/CBT Paleolatitude: 85˚N (Wakeham et al., 2003).
10 The nitrifying metabolism of Thaumarchaeota
380 382 384 386 388 390 also introduces some ambiguity regarding the in-
Core Depth (m) terpretation of TEX86-based SSTs. Because they
40 do not require sunlight and may be outcompeted
TEX86 by faster-growing photosynthetic algae and bacte-
ria, marine Thaumarchaeota tend to reside in the
mesopelagic zone (Massana et al., 1997; Karner et
35 al., 2001; Herndl et al., 2005; Wuchter et al.,
2005; Turich et al., 2007). It follows that Thau-
marchaeota are more likely to be most active and
30 to synthesize most of their biomass in the subsur-
face. Several lines of evidence suggest that this is
the case, including the transcription of genes in-
Wilson Lake, NJ volved in ammonia oxidation (Church et al.,
25 2010) and the natural radiocarbon (14C) content of
Paleolatitude: 36˚N isoGDGTs in both the water column and sedi-
95 100 105 110 ments (Pearson et al., 2001; Ingalls et al., 2006;
Shah et al., 2008), which is more similar to ther-
Core Depth (m) mocline dissolved inorganic carbon (DIC; 14C-
depleted) than surface water DIC (14C-enriched,
FIGURE 6.—TEX86 and MBT/CBT-inferred tempera- due to the presence of “bomb” 14C).
tures during the Paleocene-Eocene Thermal Maximum However, despite these physiological obser-
(PETM) from the high arctic (Lomonosov Ridge, at vations, TEX86 clearly has a robust correlation
top, Sluijs et al., 2006;Weijers et al., 2007b) and the with SST. Several explanations have been pro-
mid-low latitudes (Wilson Lake, Zachos et al., 2006). posed to account for this apparent discrepancy.
TEX86 data are re-calibrated with the Kim et al. (2010) One theory argues that GDGTs from the surface
TEXH86 calibration. Error bars represent the calibra-
ocean are more effectively grazed and exported to
tion root mean square error.
the deep ocean via fecal pellets, thus sedimentary
TEX86 inordinately represents SST (Wakeham et
tion that the genetic sequences of active Archaea al., 2003; Wuchter et al., 2006). This argument is
change as seawater temperatures are manipulated inconsistent with the existing (quite limited)
in mesocosm experiments (Schouten et al., sedimentary 14C data (Pearson et al., 2001), al-
2007b) suggest that the empirical relationship be- though grazing almost certainly plays an impor-
tween TEX86 and temperature represents a com- tant role in the export of GDGTs because archaeal
munity effect rather than a single-species adapta- cells are small and do not sink quickly on their
tion. own (Wakeham et al., 2003). An alternative ex-
In some environments, non-Thaumarchaeotal planation is correlation: if TEX86 actually is re-
archaeal species may contribute a sizable, if not cording subsurface ocean temperatures, this may
dominant amount of sedimentary isoGDGTs. In be difficult to statistically distinguish from SST;

124
 TIERNEY: RECONSTRUCTING PALEOTEMPERATURES USING GDGT THERMOMETRY
26
25.5
!-#"*4(
LAKE SURFACE TEMPERATURE
)&*+$43
25
!"#$"%&'(
)&*+(,"*$-#
24.5
.$//'"(01"(23"
24
23.5
23
22.5
22
500 1000 1500 2000
YEAR AD
FIGURE 7.—TEX86-inferred Lake Tanganyika lake
surface temperatures for the past 1500 years (Tierney
et al., 2010a). Error bars represent the 95% confi-
dence intervals based on a leave-one-out estimation of
the error in the calibration slope.
temperatures at 100–200 m are highly correlated
with SSTs spatially across the global ocean (Hu-
ber, 2010). Everywhere the correlation is robust,
TEX86 will predict SST accurately.
In certain oceanographic environments, such
as near-shore and upwelling areas, TEX86 seems
to be overtly biased towards subsurface tempera-
tures (Huguet et al., 2007; Lee et al., 2008; Lopes
Dos Santos et al., 2010; Chazen, 2011). For ex-
ample, Lopes Dos Santos et al. (2010) found that
the time evolution of TEX86-SST was substan-
tially different from that of alkenone-SST along
the Guinea Margin in the Late Quaternary, and
argued that TEX86 reflected subsurface variability.
Uncertainties surrounding where and why TEX86
reflects subsurface temperatures certainly have
relevance for temperature estimates in deep geo-
logical time, where the paleoceanography often is
not well constrained.
Seasonal changes in Thaumarchaeotal abun-
dance and/or production of isoGDGTs may also
influence sedimentary TEX86. Water-column stud-
ies indicate that Thaumarchaeota and their
isoGDGTs exhibit pronounced seasonal varia-
tions, although the timing of peak abundance var-
ies substantially by environment and geographic
location (Massana et al., 1997; Wuchter et al.,
2006; Galand et al., 2010; Hollibaugh et al., 2010;
Pitcher et al., 2011). Based on limited studies it is
not yet clear how or whether these seasonal cycles
125
are reflected in the GDGT export to, and preser-
vation in, the sedimentary column. For example,
Wuchter et al. (2006) found that the seasonal cy-
cle in TEX86 observed in the Arabian Sea ho-
mogenizes in a deep sediment trap, and Rueda et
al. (2009) found that in spite of a highly seasonal
GDGT production in the water column (Pitcher et
al., 2011), sedimentary TEX86 in the North Sea
best reflects mean annual SST. Some paleocli-
matic studies have argued in favor of a seasonality
bias to explain unreasonable TEX86 temperatures,
such as the very warm temperatures derived for
high latitudes during the Early Eocene (e.g., Fig.
6 and Sluijs et al., 2006, 2011). However, this is
largely a post-hoc interpretation. It may be that
such warm temperatures reflect the inherent diffi-
culties in calibrating TEX86 at high latitudes dur-
ing a hothouse interval, for which we have no
modern analog (Pancost et al., 2011). Further-
more, as TEX86 is explicitly calibrated to mean
annual SST, invocations of a seasonal bias need to
be accompanied by an appropriate seasonal cali-
bration (e.g., Shevenell et al., 2011). Further stud-
ies aimed at constraining possible seasonal biases
in GDGT export and sedimentary TEX86 expres-
sion will be critical towards resolving this issue.
The lack of an identifiable producer funda-
mentally limits the application of brGDGT prox-
ies. Until the producer(s) is/are better character-
ized, it is difficult to identify ecological con-
straints that may interfere with the fidelity of
brGDGTs as temperature recorders (e.g., nutri-
ents, oxygen, community effects). Currently, we
are limited to empirical observations from core-
top studies. Weijers et al. (2007c) detected a sig-
nificant relationship between the MBT index and
precipitation amount in soils, but because precipi-
tation co-varied with temperature in their dataset,
they were not able to determine whether this rela-
tionship was meaningful. In lakes, although tem-
perature is the dominant environmental variable
affecting brGDGT distributions there is some in-
fluence of pH, lake depth (Tierney et al., 2010b;
Pearson et al., 2011), and possibly degree of
bottom-water anoxia (see discussion above;
Tierney et al., 2012). Interestingly, brGDGTs
seem to be absent or have unusual distributions in
soda lakes with a high pH (Tierney et al., 2010b;
Sun et al., 2011), and brGDGT concentrations are
low in high-pH soils (Weijers et al., 2007c). This
is circumstantial evidence that the producers pre-
fer neutral and lower pH environments, and is
supportive of the proposed association with Aci-
dobacteria.
 THE PALEONTOLOGICAL SOCIETY PAPERS, VOL. 18
A potentially severe complicating factor for
application of brGDGT paleothermometers in
lakes is the likelihood that brGDGTs are associ-
ated with both allochthonous soil OM and in-situ
production, each of which appear to have a differ-
ent relationship to temperature (Tierney and Rus-
sell, 2009). However, brGDGT concentrations
(per gram of organic matter) tend to be much
higher in lakes than in soils—sometimes by as
much as an order of magnitude (Tierney and Rus-
sell, 2009; Tierney et al., 2010b)—and the newest
lake calibrations based on alternate functional
forms (i.e., those that are not based on the MBT
or CBT indices) have remarkably good predict-
ability (Tierney et al., 2010b; Pearson et al., 2011,
and see Table 2). Detailed down-core studies will
help address these issues.
A note on calibration uncertainty
Both TEX86 and brGDGT paleothermometers
rely on surface-sediment calibrations to convert
relative abundances to temperature. Global sur-
face calibrations have an advantage in that they
cover a wide diversity of natural environments
and thus incorporate a large range of sources of
variability leading to error. However, the implicit
assumption of this approach is that the Earth sys-
tem is ergodic, having the same type of variability
in modern geographical space as it does in geo-
logical time. Depending on the paleoenvironment,
this assumption may or may not always be valid.
For example, the TEX86 temperatures estimated
for the Cretaceous and for the mid to low latitudes
during the PETM (discussed above) rely on an
extrapolation of the modern calibration equations
to temperatures higher than observed in the mod-
ern oceans. They are also contingent on assuming
that Thaumarchaeota living in (e.g.) the Creta-
ceous oceans experienced a similar sensitivity to
temperature and non-temperature effects as in the
modern oceans. As the latter is very hard to con-
strain with confidence, the error associated with
the absolute temperature estimates in ancient hot-
house environments is almost certainly quite a bit
larger than the root mean square error (RMSE) of
the modern core-top calibrations. Conversely, a
Late Quaternary TEX86 application in a single
tropical locale is unlikely to incorporate sources
of error associated with the polar oceans (and vice
versa), in which case the global core-top calibra-
tion error may be an overestimate. In this situa-
tion, local calibrations can be devised to better
constrain sources of error relevant to the region of
interest (e.g., Shevenell et al., 2011) or, if con-
126
straining absolute temperature error is less impor-
tant than relative changes, error can be estimated
on the calibration slope (e.g., Tierney et al.,
2010a). In sum, the RMSE values shown in Ta-
bles 1 and 2 should not be viewed as immutable
estimates of the error of GDGT-based temperature
inferences. As with any proxy, error needs to be
rigorously assessed within the geological context
at hand, and in light of the climatological hy-
potheses being investigated.
CONCLUSIONS
Although new to the paleotemperature proxy
scene, GDGTs significantly expand the toolkit
available to geologists for reconstructing past
temperatures. Since GDGTs are exceptionally
ubiquitous compounds found in marine sedi-
ments, ancient sedimentary sequences, lakes,
soils, hot springs and even speleothems (Yang et
al., 2011), they offer opportunities to reconstruct
temperatures in geographic places and geological
time intervals where other proxies may not be
available. Many uncertainties, especially ecologi-
cal uncertainties, need to be better constrained so
that GDGT proxies can be applied with more con-
fidence. Nevertheless, as the data in Figure 6 il-
lustrate, GDGTs have already fundamentally in-
fluenced our thinking about climate sensitivity
during ancient hothouse worlds, highlighting their
utility as paleothermometers.
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