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mosphere and oceans from the thermal decomposition of ������������� �n�������
carbonates and organic matter at depth. Weathering fluxes are ����
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modified over time as changes occur in global temperature, �������n������
�����������
continental size, position and relief, and land plant coloniza-
tion. This includes incorporating solar radiation, due to the
����
slow stellar evolution of the sun, and the CO2 greenhouse ef-
fect in general circulation model (GCM) calculations of global
mean surface temperature and river runoff. Volcanic degassing
is guided by the abundance of volcanics, seafloor spreading ����
rates, and the carbonate content of subducting oceanic crust.
The paleo-CO2 results of Rothman (2002) and U. Berner
and Streif (2001), presented by Shaviv and Veizer (2003) as �
additional models, are in fact not based on carbon cycle B
���������������������
modeling, but constitute an extension of the δ13C plankton
CO2 proxy (see below). These authors apply Δ13C, the differ- ����
ence between the δ13C of bulk organic matter and carbonates
(Hayes et al., 1999), to directly calculate paleo-CO2. However,
bulk organic matter can include non-photosynthetic com- ����
pounds as well as terrestrial material derived from rivers, and
the original method was based strictly on marine photosyn-
thetic compounds (Freeman and Hayes, 1992; cf. Royer et al., ����
2001a). In addition, changes in Δ13C over time can be due to
changes in seawater temperature (Rau et al., 1989) or O2 con-
centrations (Beerling et al., 2002), and not only atmospheric �
CO2.
������������������
�� C
Four proxies for pre-Quaternary CO2 levels have been de-
veloped over the past 15 years (consult Royer et al. [2001a] for
further details).
1. The δ13C of pedogenic minerals (calcium carbonate ��
[Cerling, 1991] or goethite [Yapp and Poths, 1992]). The car-
bonate in certain pedogenic minerals is formed from biologi-
cally and atmospherically derived soil CO2. Because these
two components differ in their carbon isotopic compositions, �
the concentration of atmospheric CO2 (p CO2) can be esti- ��� ��� ��� ��� ��� ��� �
mated assuming some knowledge of the biologically derived ���������
p CO2 in the soil, and the δ13C of the atmospheric and biologic
Figure 1. Details of CO2 proxy data set used in this study. A:
constituents. Reliable pedogenic minerals are available back Five-point running averages of individual proxies (see footnote
to the Devonian, and the range of errors are comparably 1). Range in error of GEOCARB III model also shown for
small at high CO2. Some disadvantages of this proxy include comparison. B: Combined atmospheric CO2 concentration record
comparably high errors at low CO2, and the difficulty of as determined from multiple proxies in (A). Black curve represents
extracting organic carbon from the paleosols that contain average values in 10 m.y. time-steps. Gray boxes are ��������
standard
these minerals. ������������
deviations (± 1σ) for each time-step. C: Frequency distribution
2. The δ13C of phytoplankton (Freeman and Hayes, 1992; of CO2 data set, expressed in 10 m.y. time-steps. All data are
Pagani et al., 1999). Most phytoplankton exert little or no ac- calibrated to the timescale of Harland et al. (1990).
tive control on the CO2 entering their cells. Because of this,
the Δ13C between seawater CO2 and phytoplankton photosyn- tracted using fossil plants. High resolution, high precision
thate is affected by seawater p CO2 and can thus be used as a CO2 records are possible, but because the stomatal response
CO2 proxy. High resolution CO2 records are obtainable from to CO2 is species-specific, care must be exercised in pre-
appropriate marine sediment cores, but factors such as cell Cretaceous material.
geometry and growth rate, which also influence the δ13C of 4. The δ11B of planktonic foraminifera (Pearson and Palmer,
phytoplankton, must be carefully considered. 2000). The relative proportions of the two dominant species
3. The stomatal distribution in the leaves of C3 plants (Van of boron in seawater are partially pH-dependent. Because
der Burgh et al., 1993; McElwain and Chaloner, 1995). Unlike these two species differ in their isotopic compositions, p CO2
phytoplankton, most higher land plants have pores that en- information can be retrieved from carbonate tests containing
able them to control the flux of CO2 entering their leaves. trace amounts of boron. As with the phytoplankton proxy,
Because the proportion of these stomatal pores to all the cells high resolution CO2 records are possible, but only after vital
on the leaf epidermis inversely relates to p CO2, information effects and the influence of the total alkalinity and δ11B of the
on the ancient CO2 content of the atmosphere can be ex- ocean are removed.
�����������
������� set. Because the various methods produce similar estimates of
���� CO2 over multimillion-year timescales (Fig. 1A), method-de-
pendent biases are not significant. The binning of the proxy
data into 10 m.y. time-steps reduces their ability to discern
���� short-term events, but makes for the fairest comparison to the
GEOCARB output. The resulting proxy-based curve is highly
correlated with the “best-guess” predictions of GEOCARB III
���� (Fig. 2A; r = 0.71; P = 0.0002)2, indicating that the multimillion-
year scale patterns are a reasonable approximation of the
overall trend of Phanerozoic CO2.
�
B COMPARISON OF CO2 RECORDS TO PHANEROZOIC
�� CLIMATE
C
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����������������
�
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1991; Huber et al., 2000) is incompatible with the long-lived
ice caps that characterize true glacial periods. Indirect evi-
dence for seasonal or alpine ice exists, but these intervals
were likely brief “cold snaps” within an otherwise warm ��
Mesozoic (e.g., Price, 1999). Moreover, indirect evidence
such as ice-rafted debris should be treated cautiously, as such
deposits are found in every Phanerozoic period except the ��
Triassic (Frakes et al., 1992).
The best indirect evidence for Mesozoic ice combines
sea-level considerations with oxygen isotope and strontium ���
������������������
content records (Stoll and Schrag, 1996, 2000; Dromart et al., B
2003; Lécuyer et al., 2003; Miller et al., 2003). These studies ���
corroborate the notion of brief icy intervals (<2 m.y.; see light
blue bands in Fig. 2B) within a globally warm Mesozoic. The
possible presence of brief cold snaps should therefore not ���
be used as a sole criterion for a cool mode: It is increasingly
being recognized that globally warm climates previously con-
sidered stable are in fact quite dynamic (e.g., mid-Cretaceous:
�
Wilson and Norris [2001]; Eocene: Wade and Kroon [2002];
��� ��� ��� ��� ��� ��� �
Holocene: Indermühle et al. [1999]). For example, although
the Turonian (~90 Ma) is one of the best-documented inter- ���������
vals of extreme global warmth in Earth’s history (Wilson et al., Figure 3. Details of δ18O
data set used in this study. A: Low-
2002; Bice et al., 2003), it is straddled by two of the proposed latitude, shallow-marine δ18O carbonate record of Veizer et al.
icy intervals (Fig. 2B). This entire “cool-warm-cool” sequence (1999). The statistical parameters represented by the black curve
lies within the late Cretaceous to early Tertiary “warm mode” and gray boxes are as in Fig. 1B. Dashed line represents linear
of Frakes et al. (1992). regression of data points composing black curve. B: Frequency
�������� All
distribution of δ18O data set, expressed in 10 m.y. time-steps.
Regardless of semantics, the important issue is determin-
ing the forcings responsible for global climate change. To this data are calibrated to the timescale of Harland et al.������������
(1990).
end, Dromart et al. (2003) reported evidence for a temporary
drawdown in atmospheric CO2 across the 160 Ma icy event. to 0.29 (median = 0.10). For comparison, in the CO2 proxy
If correct, a CO2-driven reverse greenhouse effect appears data set, proportions range from 0.01 to 0.36 (median = 0.11;
responsible for this brief cool period. The proxy record of total range = 5354 ppm; data point at 190 Ma excluded). The
CO2 not only records a local CO2 minimum during this event, oxygen isotope and CO2 curves are therefore comparable in
providing independent support for the findings of Dromart et terms of their signal:noise ratios.
al. (2003), but also during the other five proposed icy events After detrending the secular 8‰ shift in δ18O across the
(Fig. 2, A and B). These brief perturbations in the carbon Phanerozoic (Veizer et al., 2000; Fig. 3A), however, the result-
cycle are likely not resolvable with GEOCARB because of ing paleotemperature curve fails two first-order tests with the
the model’s coarse time resolution. As with the bulk of the more robust glacial deposit record: the Ordovician-Silurian
Phanerozoic, a coupling between CO2 and temperature ap- and Mesozoic intervals are too cold for too long. The oxygen
pears strong for the Mesozoic Era. isotope record suggests a 50 m.y. cool interval of equiva-
lent severity to the Permo-Carboniferous and late Cenozoic
THE EFFECT OF SEAWATER pH ON THE δ18O OF between 450 and 400 Ma, but other climate indicators only
MARINE CARBONATE support a 15 m.y. long intermittent cool phase at this time
The rock record of glacial deposits can only be qualita- (Crowell, 1999; Pope and Steffen, 2003), with widespread
tively compared to other records of climate, such as CO2. It glaciation likely lasting <1 m.y. (Brenchley et al., 1994, 2003;
is within this context that the low-latitude paleotemperature Sutcliffe et al., 2000). During the Mesozoic, oxygen isotopes
data of Veizer et al. (2000) and Shaviv and Veizer (2003), suggest another 100 m.y. cool interval of similar severity (220–
based on the shallow-marine δ18O carbonate record of Veizer 120 Ma), but, as discussed above, independent evidence for a
et al. (1999; Fig. 3A), is so appealing. These data are compiled long-lived glaciation at this time is completely lacking. Other
from a range of taxa, including belemnites, brachiopods, factors must therefore influence the δ18O of marine calcite
conodonts, and foraminfera. The most well-represented in- such as alteration during diagenesis (Schrag et al., 1995). Here
tervals are the middle Paleozoic (445–285 Ma), late Jurassic we explore an additional possible bias of δ18O-derived tem-
(165–145 Ma) and Cenozoic (Fig. 3B). The signal:noise ratio peratures due to the carbonate ion effect on oxygen isotope
in this data set can be assessed by comparing the proportion incorporation in carbonates controlled by temporal changes
of the plotted standard deviations (1σ; Fig. 3A) to the total in the pH of seawater (Zeebe, 1999).
range in values (11.2‰). These proportions range from 0.02
�
taking common logarithms:
�
2 log [H+] – log p CO2 – log [Ca++] = log (KoK1K2/Ksp) (4).
�
For a past time (t) and the present (0), using the definition
of pH = –log [H+] and assuming that the equilibrium constants ��
do not change appreciably with time due to minor tempera-
ture changes:
���������
B
���
2 pH(0) – 2 pH(t) – log [p CO2 (t)/p CO2 (0)] – log [(Ca)(t)/
(Ca)(0)] = 0 (5) ���
of the additional term for changes in CaCO3 saturation state. Bice, K.L., Huber, B.T., and Norris, R.D., 2003, Extreme polar warmth during the Cretaceous
greenhouse? Paradox of the late Turonian δ18O record at Deep Sea Drilling Project Site 511:
(Calculated ΔpH values for the Eocene of 0.3–0.4 are in the Paleoceanography, v. 18(2), 1031, p. 1–11.
middle of the range 0.1–0.7 calculated via the boron isotope Brenchley, P.J., Marshall, J.D., Carden, G.A.F., Robertson, D.B.R., Long, D.G.F., Meidla, T.,
paleo-pH method by Pearson and Palmer [2000].) Hints, L., and Anderson, T.F, 1994, Bathymetric and isotopic evidence for a short-lived Late
Ordovician glaciation in a greenhouse period: Geology, v. 22, p. 295–298.
The corrected curves record, on average, higher past tem-
Brenchley, P.J., Carden, G.A., Hints, L., Kaljo, D., Marshall, J.D., Martma, T., Meidla, T., and
peratures than that at present, which is in accord with pa- Nõlvak, J., 2003, High-resolution stable isotope stratigraphy of Upper Ordovician sequences:
leoclimatological observations, especially for the Mesozoic Constraints on the timing of bioevents and environmental changes associated with mass ex-
tinction and glaciation: Geological Society of America Bulletin, v. 115, p. 89–104.
(Vakhrameev, 1991; Huber et al., 2000, 2002). The original Cerling, T.E., 1991, Carbon dioxide in the atmosphere: evidence from Cenozoic and
uncorrected Veizer curve and the cosmic ray flux curve record Mesozoic paleosols: American Journal of Science, v. 291, p. 377–400.
too cold a Phanerozoic past (Fig. 4). Also, the large coolings Crowell, J.C, 1999, Pre-Mesozoic Ice Ages: Their Bearing on Understanding the Climate
System: Boulder, Colorado, Geological Society of America Memoir 192, p. 1–106.
of the uncorrected curve for the Ordovician-Silurian (480–400
Crowley, T.J., 1998, Significance of tectonic boundary conditions for paleoclimate simu-
Ma) and the Triassic-Cretaceous (220–100 Ma) that corre- lations, in Crowley, T.J., and Burke, K., eds., Tectonic Boundary Conditions for Climate
late with intense cosmic ray fluxes, are, with corrections for Reconstructions: New York, Oxford University Press, p. 3–17.
pH, only lesser coolings superimposed on generally warm Crowley, T.J., 2000, Causes of climate change over the past 1000 years: Science, v. 289,
p. 270–277.
periods (Fig. 4). The cosmic ray fluxes and the uncorrected
Crowley, T.J., and Berner, R.A., 2001, CO2 and climate change: Science, v. 292, p. 870–872.
ΔT curve predict long-lived and extensive glaciations during
Demicco, R.V., Lowenstein, T.K., and Hardie, L.A., 2003, Atmospheric pCO2 since 60 Ma
these time periods but there were none, except for a very from records of seawater pH, calcium and primary carbonate mineralogy: Geology, v. 31,
short glaciation lasting at most a few million years at the end p. 793–796.
of the Ordovician (Fig. 4C). By contrast, the corrected Veizer Dromart, G., Garcia, J.-P., Picard, S., Atrops, F., Lécuyer, C., and Sheppard, S.M.F., 2003,
Ice age at the Middle-Late Jurassic transition?: Earth and Planetary Science Letters, v. 213,
curves predict the two major glaciations correctly. These are p. 205–220.
during the two times when low latitude temperature was Ekart, D.D., Cerling, T.E., Montañez, I.P., and Tabor, N.J., 1999, A 400 million year carbon
about the same as, or less than, that at present: the Permo- isotope record of pedogenic carbonate: implications for paleoatmospheric carbon dioxide:
American Journal of Science, v. 299, p. 805–827.
Carboniferious glaciation (centered around 300 Ma) and the
Frakes, L.A., Francis, J.E., and Syktus, J.I., 1992, Climate Modes of the Phanerozoic:
late Cenozoic glaciation (past 30 m.y.). Cambridge, Cambridge University Press, 274 p.
Freeman, K.H., and Hayes, J.M., 1992, Fractionation of carbon isotopes by phytoplankton
CONCLUSIONS and estimates of ancient CO2 levels: Global Biogeochemical Cycles, v. 6, p. 185–198.
We conclude from these considerations that: Harland, W.B., Armstrong, R.L., Cox, A.V., Craig, L.E., Smith, A.G., and Smith, D.G., 1990, A
Geologic Time Scale 1989: Cambridge, Cambridge University Press, 263 p.
1. Proxy estimates of paleo-CO2 agree, within modeling er-
Hayes, J.M., Strauss, H., and Kaufman, A.J., 1999, The abundance of 13C in marine organic
rors, with GEOCARB model results. matter and isotopic fractionation in the global biogeochemical cycle of carbon during the
2. There is a good correlation between low levels of atmo- past 800 Ma: Chemical Geology, v. 161, p. 103–125.
spheric CO2 and the presence of well-documented, long-lived, Horita, J., Zimmermann, H., and Holland, H.D., 2002, Chemical evolution of seawater
during the Phanerozoic: Implications from the record of marine evaporates: Geochimica et
and aerially extensive continental glaciations. Cosmochimica Acta, v. 66, p. 3733–3756.
3. The uncorrected Veizer temperature curve predicts long Huber, B.T., MacLeod, K.G., and Wing, S.L., editors, 2000, Warm Climates in Earth History:
periods of intense global cooling that do not agree with inde- Cambridge, Cambridge University Press, 462 p.
pendent observations of paleoclimate, especially during the Huber, B.T., Norris, R.D., and MacLeod, K.G., 2002, Deep-sea paleotemperature record of
extreme warmth during the Cretaceous: Geology, v. 30, p. 123–126.
Mesozoic. When corrected for pH effects, however, the tem-
Indermühle, A., Stocker, T.F., Joos, F., Fischer, H., Smith, H.J., Wahlen, M., Deck, B.,
perature curve matches the glacial record much better. Mastroianni, D., Tschumi, J., Blunier, T., Meyer, R., and Stauffer, B., 1999, Holocene car-