An approach to estimate Lower Jurassic seawater oxygen-
isotope composition using d
18
O and Mg/Ca ratios of belemnite
calcites (Early Pliensbachian, northern Spain)
Maider Armend ariz,
1
Idoia Rosales,
1
Beatriz B adenas,
2
Laura Pi~ nuela,
3,4
Marc Aurell
2
and
Jos e Carlos Garc ıa-Ramos
3
1
Instituto Geol ogico y Minero de Espa~ na, R ıos Rosas 23, Madrid 28003, Spain;
2
Departamento Ciencias de la Tierra, Universidad de
Zaragoza, Zaragoza 50009, Spain;
3
Museo del Jur asico de Asturias (MUJA), 33328 Colunga, Asturias, Spain;
4
Departamento de
Geolog ıa, Universidad de Oviedo, Oviedo 33005, Spain
ABSTRACT
Palaeotemperature estimates from the oxygen-isotope compo-
sitions of belemnites have been hampered by not knowing
ancient seawater isotope compositions well enough. We have
tackled this problem using Mg/Ca as a proxy for temperature
and here, we present a ~2 Ma record of paired Mg/Ca and
d
18
O measurements of Jurassic (Early Pliensbachian) belem-
nites from the Asturian basin as a palaeo-proxy of seawater
oxygen-isotope composition. From the combined use of the
two approaches, we suggest a d
18
O
w
composition of about
À0.1& for the Jamesoni–Ibex zones. This value may have
been increased by about 0.6& during the Davoei Zone due to
the effect of waters with a different d
18
O
w
composition.
These findings illustrate the inaccuracy of using a globally
homogeneous ice-free value of d
18
O
w
= À1& for d
18
O
carb
-
based palaeotemperature reconstructions. Our data suggest
that previous palaeotemperatures calculated in the region
from d
18
O values of belemnites may have been underesti-
mated as the seawater oxygen isotopic composition could
have been higher.
Terra Nova, 25, 439–445, 2013
Introduction
The use of oxygen-isotope ratios of
belemnites for palaeotemperature cal-
culations has been widely used in the
last six decades. However, these
palaeotemperature calculations have
been used with some uncertainties
due to the poor knowledge of the
ancient seawater oxygen isotopic
composition (d
18
O
w
), and the
unknown species-specific biological
fractionation effects and belemnite
life habitat and habits (e.g. Sælen
et al., 1996; Bailey et al., 2003;
Rosales et al., 2004a; Dutton et al.,
2007; McArthur et al., 2007a; Mut-
terlose et al., 2010). In more recent
years, the Mg/Ca palaeotemperature
proxy has been used in belemnites as
an alternative palaeothermometer
due to the existence of reasonably
good correlation between Mg/Ca and
d
18
O
bel
(e.g. Bailey et al., 2003; Ro-
sales et al., 2004b; Nunn and Price,
2010; Price et al., 2011; Armend ariz
et al., 2012). Moreover, the combina-
tion of these two palaeo-proxies has
the potential to be used to estimate
changes in sea-water oxygen isotopic
composition and polar ice volume,
although its efficacy has been ques-
tioned by some authors due to signif-
icant differences in the Mg/Ca
concentration and a lack of Mg/Ca
and d
18
O correlation between some
belemnite species of the Toarcian
(McArthur et al., 2007a; Li et al.,
2012).
To shed light on this issue, we
examine the potential and consis-
tency of d
18
O and Mg/Ca values of
well-preserved Jurassic belemnites of
the Early Pliensbachian Boreal Realm
of the Asturian basin (Figs 1 and 2) as
palaeoclimatic and palaeoenviron-
mental proxies. To obtain more con-
sistent data avoiding, as much as
possible, the noise introduced by inter-
specimen variability, we used chemo-
stratigraphic records based on curves
obtained from running average values,
which are commonly used in time ser-
ies data to filter short-term fluctua-
tions and highlight the long-term
trends. The use of these curves has pro-
vided a long-term record (~2 Ma
according to Gradstein et al., 2012) of
Mg/Ca ratios of the investigated be-
lemnites that parallel the d
18
O
carb
val-
ues. Assuming a temperature
dependence of Mg/Ca in belemnites
within the range observed in most
modern biogenic calcites, the signifi-
cance of combining the two palaeo-
proxies is that it provides an opportu-
nity to calibrate the local oxygen isoto-
pic composition of seawater for the
Lower Jurassic.
Geological setting, materials and
methods
The Pliensbachian succession of the
Asturian basin (northern Spain)
belongs to the Santa Mera Member
of the Rodiles Formation and corre-
sponds to a rhythmic alternation of
limestone and marl deposited in an
epeiric platform (Su arez Vega, 1974;
Valenzuela et al., 1986). The samples
for this study were collected from
two well-exposed sections of the
Asturian sea cliffs: Punta La Llastra
and Playa de Vega (Fig. 2A). In
these sections, the Pliensbachian suc-
cession comprises ~80 m of marl/cal-
careous mudstones interbedded with
bioclastic tempestites and organic
facies (black shales) at certain strati-
graphic horizons (Fig. 2B; Valenzuela
et al., 1986; Aurell et al., 2003;
B adenas et al., 2009, 2012; Garc ıa-
Ramos and Pi~ nuela, 2010). The suc-
cession contains relatively abundant
para-autochthonous and autochtho-
nous fossils (ammonites, belemnites,
Correspondence: Maider Armend ariz, C/
Calera 1, Tres Cantos, Madrid 28760,
Spain. Tel.: +34-91-7287273; fax: +34-91-
7287202; e-mail: m.armendariz@igme.es
© 2013 John Wiley & Sons Ltd 439
doi: 10.1111/ter.12054