CHEMICAL

GEOLOGY
INCLUDING
ISOTOPE GEOSCIENCE
ELSEVIER Chemical Geology 141 (1997) 211-223

A stable isotope study of fossil mammal remains from the

Paglicci cave, southern Italy, 13 to 33 ka BP:
palaeoclimatological considerations
Antonio Delgado Huertas a,b, Paola Iacumin b,c, Antonio Longinelli b,*
a Estaci6n Experimental del Zaidln, CSIC, Prof. Albareda, 1, 18008 Granada, Spain
b Universit~ di Trieste, Dipartimento di Scienze della Terra, Via E. Weiss, 6, 34127 Trieste, Italy
c UniversitJ Pierre et Marie Curie, Paris 6, Laboratoire de BiogJochimie Isotopique, 4 place Jussieu, 75252 Paris, France

Received 10 September 1996; accepted 18 April 1997

Abstract

A set of 102 samples of fossil skeletal remains of mammals from a sediment sequence from the Paglicci cave in southern
Italy, was studied for the oxygen isotopic composition of bone and tooth phosphate. The samples belong to Cervus elaphus,
Bos primigenius and Equus caballus and come from various levels of a succession spanning about 33 to 13 ka BP
(calibrated 14C ages). On the basis of X-ray diffraction studies on every sample, most of them show no evidence of
recrystallisation and may thus be considered reliable for isotopic study. 8mOp values range from 16.8%o to 20.5%0
(V-SMOW). Cervus and Bos samples show trends in their isotopic values that are similar to each other. The 6 r o t w
calculated from their ~ t8Op values, using previously established equations, form sections of a climatic curve that agree quite
well with the palaeoclimatological curve obtained from the GRIP ice core, despite minor differences in the timing and
intensity of some climatic events. Despite the relatively low latitude of the area and its central position in the Mediterranean
basin, we may conclude that major climatic changes left their signature on the isotopic composition of the samples studied.
© 1997 Elsevier Science B.V.

Keywords: stable isotopes; phosphate; biogenic apatite; palaeoclimatology

1. Introduction high-elevation tropical ice caps (Guilderson et al.,

Recent climatic and environmental variations can
be evaluated by means of high-resolution proxy cli-
mate records. Isotopic, chemical and physical analy-
ses of ice cores from polar areas (Dansgaard et al.,
1993; Kapsner et al., 1995) and, recently, from
* Corresponding author. E-maih labgeois@univ.trieste.it
1994) provided insights into climate changes mainly
at high latitudes. However, quantitative data on con-
tinental areas with temperate or warm climates (low
and middle latitudes) are relatively scarce. Longinelli
and Peretti Padalino (1980) and Longinelli (1984)
suggested the possibility of carrying out quantitative
palaeoclimatological investigations on land by study-
ing the oxygen isotopic composition of phosphate
from fossil mammal bones and teeth and relating
these values to the ~ t S o of environmental water.

0009-2541/97/$17.00 ~ 1997 Elsevier Science B.V. All rights reserved.

PII S 0 0 0 9 - 2 5 4 1 ( 9 7 ) 0 0 0 6 6 - 1
212 A. Delgado Huertas et al. / Chemical Geology 141 (1997) 211-223

According to the results obtained by several authors

(e.g. Koch et al., 1989; Ayliffe et al., 1992; Bryant et
al., 1994; Sanchez Chillon et al., 1994; Iacumin et
al., 1996) the use of isotope analyses on fossil bones
and teeth for quantitative interpretations of palaeocli-
matological and palaeohydrological conditions in
continental areas may be used extensively, at least in
the case of well preserved skeletal remains which did
not undergo taphonomic and diagenetic changes. This
study is a further contribution in this direction, its l
aim being the achievement of quantitative palaeocli- a5o30 ' 16°00 '

matological information on the last glacial and post- 42o(](] '-

glacial time at mid-latitude in a continental area. The

study was carried out on a set of fossils (102 mam-
mal bone and tooth samples) ranging in age between
about 33 ka and 13 ka BP (calibrated ~4C ages) and
coming from the excavations carried out by archae-
ologists in the Paglicci cave.

2. Geography and geomorphology of the area

studied

In the southeasternmost section of Italy (41°39'N,

15°37'E) at the southwestern edge of the Gargano
promontory (Fig. 1) the Paglicci cave is located at
about 100 m.a.s.l. The maximum elevation of the
promontory, running in a west-east direction for
some 60 km, is close to 1000 m.a.s.l. The fossil
record from the cave and a nearby shelter shows that
they were almost continuously occupied by hominids
from about 200 ka to 13 ka (Mezzena and Palma di
Cesnola, 1967; Borgognini et al., 1980; Palma di
Cesnola, 1992). The fossil skeletal material (food
refuse) left by humans provides a long though in-
complete record of palaeoclimatological data through
phosphate isotope (618Op) values.
The elevation of the promontory may complicate
things, introducing a further variable in the recon-
struction of palaeoenvironmental conditions. The
same consideration applies to the presence of two
streams flowing down not far from the cave (Fig. 1)
from an elevation of about 500 m and joining a third
larger stream which flows from NW to SE along the
edge of the S. Severo-Foggia plain. This plain is
part of a warm-temperate area (mean annual temper-
ature about 15 _+ I°C with precipitations lower than
500 m m / y e a r with a mean oxygen isotopic composi-
Fig. 1. Geographic position of the cave studied.
tion close to -6%0 (V-SMOW; unpublished data).
The environmental conditions change rapidly with
elevation so that, on the most elevated section of the
Gargano promontory, the mean annual temperatures
are about 4°C lower (11 _ I°C) and precipitation is
considerably greater (1000 to 1250 mm/year).
3. Materials and methods
The cave is about 60 m long and the sedimentary
deposit reaches its maximum thickness (over 8 m) in
the first section of the cave, where the archaeological
excavations were carded out on an area of about 140
by 160 cm. The 8 m of sediments were divided into
26 different levels, each one being in turn subdivided
into various sub-levels. 29 Iac determinations were
carded out on levels containing a measurable char-
coal residue a n d / o r combusted bones.
Colleagues of the University of Florence supplied
us with a first set of bone and tooth fragments
 A. Delgado Huertas et al. / Chemical Geology 141 (1997) 211-223 213

157 C. elaphus
Most of the measured bones show no evidence of
recrystallization, their crystallinity index ranging be-
tween zero and 0.15. However, in a few cases
changes of the X-ray curve suggest a beginning of a
recrystallization process (Fig. 2) which, however,
3; 3; 3'1 2r9 2'7 2J5
according to the isotopic results, probably affected
Dif~aefionangle(20)
the bone isotopic composition at a very low level.
A portion of each sample, after mechanical clean-
ing, was finely ground in an agate mortar, the amount
154C. elaphus of material varying from a few hundred milligrams
CI = 0.38
in the case of enamel or dentine to 2 or 3 g for bone.
In the case of enamel the powder portion is represen-
tative of the whole tooth. For the measurement of the

Table 1
Age of the stratigraphic levels
b
3'5 3; ;~ 2'9 2'7 2; Stratig. level Conv. J4C age (BP) a Cal. 14Cage (BP) ~
Ditfr~fionangle(20) 2b 11,440 ± 180 13,355
Fig. 2. Examples of X-ray diffraction patterns obtained from 4 11,950 ± 190 13,955
bones of C. elaphus from the same stratigraphic level; despite the 5 13,590 ± 200 16,290
beginning of recrystallizadon shown by sample No. 154 and the 6 14,270 ± 230 17,105
relatively large difference between the CI values the isotopic 7 14,820 ± 210 17,730
results are quite close to one another: No. 157 C I = O ; 5J8Op 9 15,270 ~ 220 18,200
+ 19.0; sample No. 154 CI = 0.38; 81SOp + 18.5. 10 15,320 5:250 18,245
14b 16,310 ± 350 19,205
15b 16,400 ± 200 19,302
belonging to the Cervus elaphus, Bos primigenius 16a 16,450 5:190 19,365
and Equus caballus :species. The samples seem to be 16b7 17,100 5:300 20,255
fairly well preserved, showing no evidence of disso- 16c2 17,200 5:300 20,405
lution or recrystallization under an optical micro- 17a 17,900 5:300 21,360
scope. X-ray diffraction was carried out on all the 17e 19,600 5:300 23,190
18bl 20,160:1:160 23,836
samples studied to check for the possibility of recrys- 18b2 20,200 ± 350 23,884
tallization processes. The measure of the crystallinity 19a 20,730 _+290 24,480
index (CI) can be a way to estimate the diagenetic 20b 21,260 ± 340 25,095
changes in archaeological and palaeontological bone 20c 22,200 ± 200 26,107
phosphate. It is defined as follows by Person et al. 20e-d 22,630 ± 390 26,650
21a 23,040 ± 380 27,130
(1995): 21b 23,470 5:370 27,600
CI = E{ H[202], H[300], H [ 1 1 2 ] } / H [ 2 1 1 ] 21c 24,2105:300 28,415
21 d 24,720 ± 420 28,965
The height ( H ) is the difference between the 22b 26,800 ± 300 31,243
mean value at the top of each peak and the mean 22f4 28,300 ± 400 32,844
value of the ' valley' separating it from the preceding 23a 28,100 ± 400 32,633
24al 29,300 5:600 33,898
peak (Fig. 2b). The height of the highest peak [211]
24b2 34,000 ± 800 38,690
is measured from the baseline taken between 20 ° and
38 ° 2 0. Samples with a larger crystal size or with a Values from: Azzi et al. (1973, 1974, 1977); Evin et al. (1979);
more ordered crystal structure, have peaks with Palma di Cesnola (1992)).
higher intensities and more sharply defined. Crystal- b The calibrated 14C ages were calculated according to Bard et al.
(1993) and Stuiver and Reimer (1993). The following equation
lographic changes could indicate variations of the was used in the case of conv. 14C ages of 19,000 to 35,000 (BP):
pristine ~18Op values, as suggested by Shemesh Cal. age = - 5 . 8 5 x 10 -6 (14C age) 2 + 1.39(14C age)-- 1807
(1990), Ayliffe et al. (1994) and Bryant (1995). (Stuiver and Reimer (1993), according to E. Bard (pers. commun.).
214 A. Delgado Huertas et al. / Chemical Geology 141 (1997) 211-223

oxygen isotopic composition of apatite-phosphate,
after a preliminary treatment by means of 30% H202,
100-120 mg of the powdered sample was dissolved
in 10 M nitric acid and afterwards treated according
to the chemical procedure described by Tudge (1960)
and slightly modified by Longinelli (1965) and by
Kolodny et al. (1983). The final product of the
chemical treatment (BiPO 4) was dried overnight at
about 90°C and then heated in vacuo at 450°C
(Karhu and Epstein, 1986) to obtain the BiPO4-/3
form (Mooney-Slater, 1962) without structural water,
thereby avoiding subsequent rehydration of the sam-
pies. The samples were reacted with BrF s at 300°C
for 3 h in nickel reaction vessels. After conversion of
02 to CO 2, the isotopic measurements were carried
out by means of a Finnigan Delta S mass spectrome-
ter, the overall standard deviation of the measure-
ments being, on average, about ___0.2 to ___0.25%0
(1 o'). All the samples were run at least twice and the
reported data are the mean values of consistent re-
suits.
4. Radiocarbon ages
The 29 radiocarbon ages available for eighteen of
the stratigraphic levels of the Paglicci cave sedi-
ments are reported in Table 1. However, in order
better to compare our results to previous data we
also report the 'corrected' ~4C ages (reported in the

Table 2
Cervus elaphus
Sample No. Stratig. level Conv. 14C age Skeletal component ~ 1 8 0 ( p o 3 - ) vs. V-SMOW * ~lSO(mw)
enamel dentine bone
1 2 metatarsus + 18.6 -6.2
5 3a 11,440 metatarsus + 18.9 - 5.9
10 4b 11,950 tibia + 19.2 - 5.6
15 4c tooth ( M / 3 ) + 17.8 + 18.2 -6.5
20 5a metatarsus + 19.4 - 5.4
25 5b 13,950 tooth (upp. molar) + 18.6 + 18.1 -6.2
29 5c metacarpus + 18.5 - 6.2
33 6a 14,270 tooth (upp. molar) + 17.8 + 16.8 - 6.8
46 6d radius + 18.6 - 6.2
49 7a tooth (upp. molar) + 18.1 + 17.0 -6.6
53 7b 14,820 tooth ( M / 3 ) + 18.5 + 17.5 -6.2
60 7c tooth (upp. premolar) + 18.4 -6.3
63 8a metatarsus + 19.4 - 5.4
67 8b metatarsus + 19.1 - 5.7
75 8d II phalanx + 18.4 -6.3
89 10b metatarsus + 18.9 - 5.9
94 10d 15,320 metatarsus + 18.5 - 6.2
104 10e metacarpus + 18.3 -6.4
118 12f tooth ( P / 3 ) + 17.5 + 18.0 -6.7
126 14b 16,310 metatarsus + 18.6 -6.2
142 18b 20,200 metatarsus + 18.9 - 5.9
147 19a 20,730 metacarpus + 19.5 - 5.4
148 19b tooth ( M / 3 ) + 17.7 + 17.3 - 6.9
154 20a ? + 18.5 -6.2
157 20b 21,260 I phalanx + 19.0 -5.8
160 20c 22,200 tooth ( P / 2 ) and mandib. + 16.8 + 17.6 + 17.8 - 7.7
164 20d 22,630 metatarsus + 20.3 - 4.6
168 20e tibia + 20.5 - 4.5
174 21a 23,040 radius + 19.5 -5.4
177 21b 23,470 tibia + 19.0 -5.8
182 22f 28,300 tooth (upp. molar) + 19.5 + 19.2 -5.4

* The ~180 of meteoric water (~lSOmw) is given only for enamel and bone samples according to the equation reported by D'Angela and
Longinelli (1990).
 A. Delgado Huertas et al./ Chemical Geology 141 (1997) 211-223 215

current literature as 'calibrated' a n d / o r 'calendar'
ages) along with the conventional 14C data. The
corrected ages back to 22 ka were calculated accord-
ing to the method suggested by Bard et al. (1993)
and by Stuiver and Reimer (1993). In the case of
ages from 19 ka to about 35 ka the equation reported
in Keigwin and Jones (1994) elaborated by E. Bard,
was used. The equation is as follows:
Cal. age = - 5 . 8 5 . 1 0 - 6 (14 C age) 2
+ 1.39(14Cage) -- 1807
where ~4C age refers to the conventional age. Even

Table 3
Bos primigenius
Sample No. Stratig level Conv. 14C age Skeletal component ~ l S o ( p o 3 - ) vs. V-SMOW * ~180~mw)
enamel dentine bone
2 2 11,440 tooth ( P / 3 ) + 19.2 + 18.3 - 5.6
6 3a tooth ( M / 2 ) + 18.8 + 18.4 -6.0
11 4b 11,950 tooth ( P / 3 ) + 19.8 +20.1 -5.0
16 4c tooth ( M / l ) + 19.7 +20.3 - 5.1
21 5a metatarsus + 18.9 - 5.9
26 5b 13,590 tooth ( M / 1 ) + 19.0 + 19.4 -5.8
30 5c tooth ( M / l ) + 17.4 + 18.6 -7.4
34 6a 14,270 tooth (incisor) + 17.9 + 18.3 -6.9
39 6b tooth ( P / 4 ) + 18.1 + 17.9 - 6.7
50 7a 14,820 metatarsus + 18.9 - 5.9
54 7b metatarsus + 19.0 - 5.8
58 7c tooth ( P / 2 ) + 18.6 + 18.0 - 6.2
68 8b metacarpus + 19.3 - 5.4
73 8c metacarpus + 18.3 - 6.5
76 8d tooth ( M / 3 ) + 18.7 + 18.8 -6.1
86 lOa 15,320 I phalanx + 18.6 - 6.2
95 lOd tooth ( P / 4 ) + 19.3 + 18.7 - 5.5
98 lOeI tibia + 18.5 -6.3
99 lOeII ? + 18.9 -5.9
101 lOeIII metatarsus + 18.4 - 6.4
108 lOeIV tibia + 18.0 - 6.8
110 lla metatarsus +18.1 -6.7
111 11c mandible +18.6 -6.2
116 12e metatarsus + 18.6 - 6.2
119 12f radius + 18.9 - 5.9
121 12g metatarsus + 17.6 - 7.2
123 12, 13, 14 metatarsus + 18.1 -6.7
127 14b 16,310 metatarsus + 18.4 - 6.4
132 15b 16,400 metatarsus + 18.4 -6.4
134 16a 16,450 metacarpus + 18.1 -6.7
137 17b 17,900 metacarpus + 18.7 -6.1
143 18b 20,200 metacarpus + 19.2 -5.6
149 19b 20,730 tooth ( M / l ) and mandib. + 17.6 + 17.8 + 17.6 -7.26
155 20a metacarpus + 18.3 - 6.5
161 20c 22,200 metatarsus + 17.6 - 7.2
165 20d 22,630 metatarsus + 18.6 - 6.2
180 22a metapode + 18.4 -6.4
181 22d ? + 18.1 -6.7
183 22f metacarpus + 17.9 - 6.9
185 23a 28,100 metapode + 18.5 -6.3

* The 8180 of meteoric water (~lSOmw) is given only for enamel and bone samples according to the equation reported by D'Angela and
Longinelli (1990).
216 A. Delgado Huertas et al. / Chemical Geology 141 (1997) 211-223

though this equation is considered tentative by Bard,
the calculated calendar ages are consistent with other
information according to Keigwin and Jones (1994)
and, at present, they seem to be a reliable means of
calendar chronology.
5. Results and discussion
5.1. Differences between bone, dentine and enamel
isotopic results
The 6180 of bone and tooth phosphate from deer
(C. elaphus), cattle (B. primigenius) and horse (E.
caballus) samples are reported in Tables 2-4, re-
spectively, versus the V-SMOW isotopic standard.
Tooth enamel is widely accepted as the most
reliable material for 6 lSOp analyses. The high chem-
ical stability of enamel, stemming from its miner-
alogical purity, low solubility and porosity and rela-
tively large crystal size probably contribute to its
capability to retain a pristine stable-isotope composi-
tion throughout long periods (at least 4.0 Ma and
even more according to Ayliffe et al., 1994, Bryant
et al., 1994, Bryant, 1995). However, unlike bone
phosphate, tooth phosphate does not renew during
the lifetime of an individual. T h e t$18Op value of
teeth and bones can then differ in the same specimen
as a result of individual migration and the timing of
tooth enamel formation relative to that of bone phos-
phate (Levinson et al., 1987). This is particularly

Table 4
Equus caballus
Sample No. Stratig. level Cony. 14C age Skeletal component ~lSo(PO43-) vs. V-SMOW * ~180(mw)
enamel dentine bone
13 4b 11,950 tooth (P/2) +20.4 +20.2 -3.1
18 4c metapode +19.0 -5.1
28 5b 13,590 tooth (M/3) +19.5 +19.0 -4.4
41 6b 14,270 tooth (M/2) +17.8 +17.7 -6.7
44 6c tibia +18.3 -6.1
47 6d tooth (P/2) +18.8 +18.6 -5.4
56 7b 14,820 metacarpus +18.8 -5.4
61 7c tooth (incisor) +19.2 +19.1 -4.8
70 8b tooth (M/1) +18.9 +19.1 -5.2
74 8c tooth (upp. molar) +18.3 +19.1 -6.1
82 9a 15,270 metapode +19.4 -4.5
84 9d tooth (P/3) +19.2 +18.7 -4.8
87 10a metapode +20.0 -3.7
92 10c tooth (P/2; milk) +19.2 +19.6 -4.8
96 10d 15,320 metapode +19.4 -4.5
103 10elII tooth (P/2) +19.0 +19.2 -5.0
109 10elV tibia +18.9 -5.2
112 llc metacarpus +19.2 -4.8
114 12b metapode +19.6 -4.2
120 12f tooth (M/1) +19.4 +19.9 -4.5
124 12,13, 14 metacarpus +18.8 -5.3
129 14b 16,310 metapode +19.2 -4.8
133 15b 16,400 radius +19.9 -3.8
135 16a 16,450 radius +19.0 -5.0
144 18b 20,200 metacarpus +18.6 -5.6
151 19b 20,730 metapode +18.3 -6.1
158 20b 21,260 metapode +18.3 -6.1
166 20d metapode +17.8 -6.8
170 20e 22,630 I phalanx +18.5 -5.8

* The illSo of meteoric water (~18 OmW) is given only for enamel and bone samples according to the equation reported by Delgado Huertas
et al., 1995.
 A. Delgado Huertas et al. / Chemical Geology 141 (1997) 211-223
true for the teeth that mineralise during the weaning
period which records some nursing effects. Recent
studies showed that the isotopic composition of
phosphate oxygen varies not only between different
teeth from the same jaw of modem and fossil ani-
mals but even within a single tooth in some mam-
malian species, thereby yielding seasonal informa-
tion (Bryant et al., 1996; Fricke and O'Neil, 1996).
These differences may lead to erroneous palaeocti-
matological interpretations. Bones, when isotopically
well preserved, are therefore to be preferred to teeth
for palaeoenvironmental reconstruction also because
of the long residence time, with respect to seasonal
variation, of phosphate molecules in bone which
warrants a better statistical meaning of bone samples
from the climatological point of view.
In the case of horse and wild ox samples there are
no statistically meaningful differences between bone
and tooth 6180. wflues (Tables 3 and 4). On the
contrary, the S lgop values of deer teeth are system-
atically ~so-depleted compared to bone values (Ta-
ble 2). The only sample for which both tooth and jaw
bone were measured agrees with the general be-
haviour. Since diagenetic processes normally affect
preferentially bones leading to an ~80 depletion, this
effect cannot refer to post-depositional processes.
The meaning of the observed difference is not clear
and may perhaps be: referred to a residence time of
fawns at a higher elevation.
12
11-
10-
9-
t, 8-
~'7-
.~5-
E
3-
2-
1-
0-
-2 -1.5 -1 -0.5 0 0.5 1 1.5
A1~:Op(~18Oenamel.818Odentine)
Fig. 3. Histogram repor6ng the frequency distribution of tooth
samples showing isotopic differences between enamel and dentine
(A~80 values) subdivided into classes of 0.5 units per mil.
217
Dentine is also considered to be less resistant than
tooth enamel to diagenesis; almost all the measured
isotopic differences between these two compounds
are within the estimated reproducibility ( + 2 o - =
+ 0.4 to +0.5 per mil) (Fig. 3) In fact, om of 32
teeth measured for both enamel and dentine only 5
(about 15%) show A180 values exceeding +0.8 per
mil. Taking into account the different behaviour of
these two substances as regards their response to
taphonomic and diagenetic processes, these data seem
to support the overall reliability of the isotopic re-
suits obtained. This is probably due either to the
relatively young age of the samples or to the 'pro-
tected' environment inside the cave, a relatively fast
burial of skeletal remains and a fairly constant tem-
perature.
5.2. Relationship between 6180p and 61SOw
A comparison among the isotopic results obtained
from the three species in terms of palaeoclimatologi-
cal conditions is possible after conversion of these
data to 8 ~80 values of environmental water.
The oxygen isotopic composition of local envi-
ronmental water ( 618 Ow) calculated from the 618 Op
values is reported in Tables 2-4. This can be done
according to the isotopic equations suggested by
D'Angela and Longinelli (1990) for Cervus and Bos
and by Delgado Huertas et al. (1995) for Equus.
These equations take into account the different
metabolic processes characteristic of each species
and the overall isotopic fractionation of the oxygen
taken in. These values may be accepted assuming
that: (1) modem deer, cattle and horses take in water
from grass and leaves and free water as did their
fossil analogues; (2) in the hypothesis of domestica-
tion of the animals studied (cattle and horses) no
changes in 818Op was caused by human influence.
The same results are reported graphically in Fig. 4
versus the stratigraphic position o f the relevant sam-
ples.
One of the problems related to the interpretation
2
of the isotope data from this group of samples is the
different mobility of the various species. In the area
studied, Cervus may have moved rapidly to areas
with different elevation, Equus may have moved
over relatively long distances in fiat areas, while Bos
218 A. Delgado Huertas et al. / Chemical Geology 141 (1997) 211-223

was obviously rather slow in its displacements,
spending most of the time in a relatively small area.
One could therefore expect a rather wide range of
isotopic values from deer and a considerably narrow
one from cattle and horses assuming that the dis-
placements of horse herds probably took place pref-
erentially across the plain.
5.3. Horse temporal pattern
Despite the previous considerations, it is apparent
(Fig. 4) that horse results are very close to deer and
cattle data for ages older than about 24 ka (strati-
graphic level 17c) and younger than 18 ka (levels 6
and 8b) while they are almost systematically ~80-en-
riched in the case of all other samples. This different
behaviour is rather difficult to explain: in fact, since
diagenetic effects tend to deplete samples in ~80, it
is unlikely that such an effect may have affected deer
and cattle samples on discrete levels with only minor
effects on horse remains. Moreover, the minor
changes suggested by X-ray diffraction patterns on
the samples studied make it improbable to ascribe
these differences to post-depositional phosphate-
water oxygen isotope exchange. The interpretation
that we can suggest at present is that different causes
may have contributed to these isotopic differences
but they seem to be mainly related to a different

" Deer (C. elaphus)

...o .... Wild ox (B. primigenius)

Horse (E. caballus)

-2-

-3-

-4-

-5-

.~,. ., .... ~...~" ~

' / ::
-7.

-8 III II lit I I I I I I l l l l l l l l II II IIIIIIIII I I I I I I I l l l i l l l l l l II I I I

Strafigraphic level
Fig. 4. Oxygen isotopic composition of environmental water calculated from the glgOp values according to the equations proposed by
D'Angela and Longinelli (1990) for C. elaphus and B. taurus and by Delgado Huertas et al. (t995) for E. caballus. These values are
reported according to the stratigraphic position of the relevant samples. Some calibrated 14C ages are also reported for a better chronological
framing of the curve.
 A. Delgado Huertas et al. / Chemical Geology 141 (1997) 211-223 219

behaviour of the tl~ee species as a response to stratigraphic sequence (Fig. 4), apart from a few
periods with different mean values of environmental cases (e.g. samples from levels 4c, 6b, and 12f),
humidity. In fact, while normally horses also feed on despite the observed differences between deer tooth
dry grass (heavily enriched in 180), cattle and deer and bone isotopic values (Table 2). The observed
avoid as much as possible dry environments. Arid similarity could suggest that deer generally remained
conditions may also have affected in different ways in areas at relatively low elevation and that there was
the isotopic composiition of the streams crossing the a good similarity between the mean values of water
plain or directly flowing from the promontory. ingested by the specimens of the two species, despite
Owing to the good agreement between the iso- their different behaviour (deer is a browser and wild
topic values of cattle and deer, we will consider only ox a grazer).
B. primigenius and C. elaphus for the following The mean t~8Ow values obtained from these two
discussion. species are reported in Fig. 5 versus the stratigraphic
levels of the relevant samples and the calibrated 14C
5.4. Wild ox and deer temporal patterns ages. The two main features of the reported curve are
the large oscillations between 26,650 and 24,480
The values of/~ 180w calculated from B. primige- years BP and the overall evolution towards ~80-en-
nius and C. elaphus are rather similar along the riched values which is apparent between about 19,300

-3-

-4.

-5. 1
IJ
-6.
Ill

-7

I =i~O"

-8 I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I [ t I I I I I I I I I I I I I I I I

Stratigraphic level
Fig. 5. Mean ~ 180 values of environmental water calculated from deer and cattle samples reported according to the stratigraphic position of
the samples. Some calibrated 14C ages are also reported for a better chronological framing of the curve. The mean standard deviation of the
phosphate isotope measurements is about + 0.2 per rail (1 o" ). The slopes of the deer and cattle isotope equations (D'Angela and Longinelli,
1990) are close to unity and, consequently, the mean standard deviation of glsO(H20) values is practically identical to that of phosphate.
220 A. Delgado Huertas et aL / Chemical Geology 141 (1997) 211-223

years BP and the top of the sequence. Obviously
some of the oscillations of the 6 ~80w values may not
be meaningful also because of the relatively small
number of samples measured. In addition, the analyt-
ical error and the intraspecific variations should be
considered. Longinelli (1984) and D'Angela and
Longinelli (1990), studying groups of specimens of
the same species from the same location, quoted
mean standard deviations of the intraspecific values
of about 0.2 to 0.3%~ (1 tr). Therefore, only isotopic
variations equal to or greater than 1 ~ unit could be
considered representative of climatic changes with
reasonable confidence.
5.5. Palaeoclimatological considerations
For palaeoclimatological purposes only the great-
est t5180, variations and the overall temporal pattern
are taken into account.According to the data ob-
tained, major cooling events took place at about 26
ka and 24.8 ka; similar events are recorded at about
19 ka and 16.5 ka, minor oscillation of the curve
taking place repeatedly at different levels. Several
episodes of 180 enrichment are also recorded, the
largest one being shown by deer samples at about
26,650 years BP. As previously pointed out the
overall evolution towards 180-enriched values from

331 I iiiiil
-32

-34_35 iiiiiiili!i!ii!
i i l i!

-0
0 -37-
~ -38- .-1

-39-
--2
-40-
-41- iil i !
'-3 ~"13
-42- •

!
-43 --4 _~.

El "-6

I I I I
i i i ¸¸i! iilii!
I l I I

t'q

Age BP
Fig. 6. Oxygenisotopiccompositionof local meteoricwatercalculatedfromthe ~JSOpvaluescomparedto the isotopiccurveobtainedfrom
the GRIPGreenlandice core
 A. Delgado Huertas et al. / Chemical Geology 141 (1997) 211-223
level 12g to the top of the sequence seems to be
particularly meaningful, suggesting an overall cli-
matic improvement (well documented by means of
many other measurements in a number of papers)
taking place through time despite the repeated oscil-
lations of the environmental conditions.
This pattern is more evident in Fig. 6 where the
t~180w values are reported versus the 14C age, the
chronological position of each sample being interpo-
lated from the available 14C ages. Despite the possi-
ble errors (uncertainty in the 14C ages and in the
exact stratigraphical position of the samples) the
curve described by the 618Ow values between about
19 ka and 13 ka corresponds fairly well to the known
sequence of climatic: events as recorded by the iso-
topic curve obtained from the GRIP ice core
(Dansgaard et al., 1993) despite the large latitudinal
difference. This is quite encouraging from the point
of view of the palaeoclimatological interpretation of
bone and tooth isotopic data. In fact, despite the
incompleteness of our curve, the difficulties arising
from timing correlations and the differential response
of the various techniques of study to climatic events,
some apparent correlations may be settled. One of
the most important i,; between 19,500 ka and 16,000
ka where the climatic improvement is apparent, fol-
lowed by a rapid deterioration at 16,500 ka referred
to the Oldest Dryas.
Chronological correlations among marine, conti-
nental and polar environments and climatic events
are always very difficult.
Moreover, oxygen isotope records of foraminiferal
sequences in the M~:diterranean basin are, unfortu-
nately, either not well detailed in the time period
considered or chronologically not sufficiently de-
fined to allow comparisons with our isotopic curve.
If we take into account the modem mean isotopic
composition of local meteoric water in the Paglicci
area (close to -6%° or slightly heavier) the ~ 180 w
values referred to the coldest episodes are lighter by
about 1.2 to 1.5%o. These values seem acceptable
even though they should be partially corrected for
the isotopic change of Mediterranean sea water
through time, a change that cannot be easily assessed
during the studied period.
The empirical relationship between the annual
mean 6180 of local precipitations and the mean
annual air temperature obtained from modem values
221
in the Mediterranean basin has a slope of 0.39%0 per
°C (Eriksson, 1965, 1966; Hauser et al., 1980). Us-
ing this gradient in the studied area the calculated
difference of the isotopic composition of precipita-
tions between the maximum (at about 26,500 BP)
and the minimum (at about 19,000 BP) (2.8%0 in
180) would correspond to a decrease in the yearly
mean air temperature of about 7°C. This temperature
change seems to be quite a large one. On the basis of
the worldwide gradient (0.7%0 per °C, Dansgaard,
1964) the change would amount to about 4°C. How-
ever, because of the uncertainty in the reliability of
the calculated slope in the case of Pleistocene envi-
ronmental conditions we are unable to discuss this
point further.
6. Conclusions
The following conclusions can be drawn from the
isotopic study carried out on the skeletal remains
from the Paglicci cave.
1. Despite the relative weakness of bones in with-
standing diagenetic processes, it seems that the
samples studied preserved their isotopic composi-
tion fairly well, so that the results obtained and
the palaeoclimatological considerations based on
these values may be considered meaningful.
2. Two of the studied species (Bos and Cervus)
yield similar trends of climatic evolution. From
the top of the section to level 6 and from level 8b
to level 16 (Fig. 4) horses yield heavier isotopic
values. A possible interpretation of this discrep-
ancy may refer to a different behaviour of the
three species as a response to periods with differ-
ent mean values of environmental humidity.
3. The sections of climatic curve that may be drawn
according to the reported data agree quite well
with other previously published palaeoclimatolog-
ical curves based on completely different mea-
surements and criteria. Minor differences in the
timing or intensity of some climatic events may
be noticed, even though these differences do not
alter the substantial agreement between the differ-
ent studies.
4. The overall change which can be calculated for
the isotopic composition of local meteoric water
during the studied period is of about 2.8 per mil.
222 A. Delgado Huertas et a l . / Chemical Geology 141 (1997) 211-223
This value roughly corresponds to an overall
change of about 4°C of the mean annual tempera-
ture, on the basis of present worldwide gradients.
This change would be as high as 7°C taking into
account the modem 6/t gradient observed for the
Mediterranean basin by Eriksson (1965, 1966)
and by Hauser et al. (1980). The latter tempera-
ture gradient seems rather improbable also be-
cause of the latitude of this area.
5. Despite the geographic position practically in the
centre of the Mediterranean basin at a latitude of
about 41 °N, different climatic episodes left ap-
parent isotopic signatures on the samples studied
suggesting that changes of the isotopic composi-
tion of mammal skeletal remains related to the
worldwide climatic evolution during Pleistocene
may probably be traced down to tropical or sub-
tropical latitudes. These results are of importance
to help defining the latitudinal gradient for each
climatic episode if we plan to reconstruct in some
detail the impact of each climatic event along
N - S geographic sections.
Acknowledgements
The authors are deeply indebted to Prof. D. Torre
and to Dr. L. Abbazi of the University of Florence
and to Prof. A. Palma di Cesnola of the University of
Siena (Italy) for kindly supplying fossil material
from the Paglicci cave, and to Dr. J.M. McArthur
and Dr. J.R. O'Neil for their critical review of an
early version of this paper. This study was carried
out within the framework of an EC training project
(A.D.H., Contract ERB-EV5V-CT93-5209) which is
here gratefully acknowledged. This research was car-
ried out with the financial support of the Ministry of
University and Scientific and Technological Re-
search of Italy.
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