a r t i c l e
i n f o
Article history:
Received 3 December 2015
Received in revised form 11 July 2016
Accepted 18 July 2016
Available online xxxx
Keywords:
Uranium series
Alpha spectrometry
Fossil mammals
Bone and tooth
Numeric age
Southern Mexico
a b s t r a c t
Numeric age of Late Pleistocene mammals remains recovered from La Mixteca Alta Oaxaquea have been determined by using uranium series dating (238U-234U-230Th method). Prior to radiometric dating, fossil bone samples
were characterized using different techniques including X-Ray Diffraction, Scanning Electron Microscopy, Spectroscopy Infrared and Neutron Activation Analysis (NAA) in order to verify their composition and diagenetic processes. Uranium and thorium isotopes were measured by alpha spectrometry of electroplated thin sources after
radiochemical separation by liquid-liquid chromatography column packed with Di-(2-Etil-Hexil)-phosphoric
acid (D2EPHA). Fossil bone samples dates were estimated from 234U/238U and 230Th/234U activity ratios considering a closed system in which the sample initially contains some uranium but is free of thorium. The ages obtained (between 88.3 ka and 12.4 ka BP) are all consistent with a Late Pleistocene age. However, some samples
belonging to Bison antiquus yielded ages older than the expected age (around 60 ka as maximum age), which
could be associated with diagenetic alteration suffered these samples during burial. This study gives the rst
numeric ages of some mammal species that inhabited southern Mexico during the Late Pleistocene.
2016 Elsevier Ltd. All rights reserved.
1. Introduction
Records of Late Pleistocene (126 ka11 ka BP) mammals in the Mexican territory are abundant (ArroyoCabrales et al., 2002, 2006). Much
of the Late Pleistocene age was dominated by glaciations, which produced important environmental changes. During this period, the Mexican territory was subject to less extreme weather conditions that the
north and south of America (Ceballos et al., 2010). Many species from
the areas strongly affected by glaciations migrated toward diverse
areas across the country. Fossil remains belonging to these and other
species, particularly mammals, have been found in some areas of Baja
California Sur, Sonora, Nuevo Len, Aguascalientes, Jalisco, Hidalgo,
Tlaxcala, Puebla, San Luis Potos, Mexico, Chiapas and Oaxaca. Most of
the fossil remains have been attributed to species like tortoises,
glyptodonts, camels, bison, mammoths, mastodons and ancient horses
(Arroyo-Cabrales et al., 2005).
Although Late Pleistocene mammal localities are abundant in Mexico
(around 776), formally reported dating of these fossil localities are very
scarce (around 29 localities have numeric ages) and almost all of them
are in central Mexico (ArroyoCabrales et al., 2002; Tovar et al., 2013).
Fossil species provide useful information for paleoclimatic and
paleoenviromental reconstructions. Studies of past changes in the environment and biodiversity often reect on the current situation, and
Corresponding author.
E-mail address: guadalupe.almazan@inin.gob.mx (M.G. Almazn-Torres).
http://dx.doi.org/10.1016/j.jasrep.2016.07.021
2352-409X/ 2016 Elsevier Ltd. All rights reserved.
specically the impact of climate on mass extinctions and biotic evolution (Sahney and Benton, 2008). In order to understand environmental
and climate changes in the past, accurate dating is of fundamental importance. Fossils bones can be accurately and precisely dated by using
uranium-series disequilibrium methods (Bischoff et al., 1995; Garca
et al., 2004), which include a range of techniques involving many different nuclides. 238U234U230Th method that is based on accumulation of
decay products, allows dating materials in the age range of up to 350
500 ka, which makes it particularly suitable for dating Quaternary fossil
bones (Ku, 1976, 2000; Bischoff et al., 1995). In this method, the parent
nuclide may be deposited free of its daughters or a daughter deciency
of known extent may be established, so that at some subsequent time,
the age of the deposit can be determined from the degree of growth of
the daughters toward secular equilibrium with its parent (Ivanovich,
1994). Uranium is assimilated into bone soon after burial in an early uptake, and then would remain as a closed system (i.e. decay products did
not migrate either in or out sample) thereafter (Bischoff et al., 1995).
This has already been demonstrated for younger samples, those within
the range of radiocarbon control for which concordance has been found
between uranium-thorium and radiocarbon dates (Szabo, 1980;
Bischoff and Rosenbauer, 1981; Rae et al., 1987).
In this study, 238U234U230Th method was used to date Late Pleistocene mammals bone remains from La Mixteca Alta Oaxaquea, Northwestern Oaxaca, southern Mexico (Jimnez et al., 2011, 2013). The
Mixteca region is an important Pleistocene fossiliferous area of Oaxaca
state, but unfortunately at present there is only one reported
161
Sample
number
UMPE 0077
Equidae 1
UMPE 0445
UMPE 0021
UMPE 0473
Bovidae 1
Glyptodon
Equidae 2
UMPE 0074
UMPE 0645
Bovidae 2
Mammoth
UMPE 0004
UMPE 0572
UMPE 0464
Bovidae 3
Bovidae 4
Bovidae 5
Species
Locality
Equus
conversidens
Bison antiquus
Glyptotherium sp.
Equus sp.
Bison antiquus
Mammuthus
columbi
Bison antiquus
Bison antiquus
Bison antiquus
Oax-3 La Pedrera
Oax-4 Ro Salado (Bottom)
Oax-4 Ro Salado (Tecolote
site)
Oax-3 La Pedrera
Oax-7 Ro Tejupam
Oax-2 El Pedernal
Oax-7 Ro Tejupam
Oax-6 Caada del Misterio
Fig. 1. Index map of Mexico showing the location of the study area in Oaxaca and the
Pleistocene fossil localities. Stars indicate fossil localities; full names of localities are
given in Table 1.
162
Fig. 2. Fossil specimens sampled for dating (analyzed samples are also shown). 1. UMPE 0077, Equus conversidens skull (Equidae 1). 2. UMPE 0445, Bison antiquus pelvis (Bovidae 1). 3.
UMPE 0021, Glyptotherium sp. caudal tube (Glyptodon). 4. UMPE 0473, Equus sp. tooth fragment (Equidae 2). 5. UMPE 0074, Male Bison antiquus skull (Bovidae 2). 6. UMPE 0645,
Mammuthus columbi skull fragment (Mammoth). 7. UMPE 0004 Bison antiquus radio-ulna (Bovidae 3). 8. Female Bison antiquus skull (Bovidae 4). 9. UMPE 0464 Bison antiquus pelvis
(Bovidae 5).
1986). The respective eluates were then evaporated until incipient dryness. The thin sources for alpha spectrometry were prepared by electrodeposition of alpha emitters on 304 mirror polished stainless steel discs
for 24 h at 15 mA. Finally, the discs were removed and rinsed with deionized water and allowed to dry air. The yield of the extraction process
for alpha emitters was 85 5%. At least two replicates of each sample
were made, but in some cases three or four replicates were necessary
to conrm the results.
4. Results and discussion
4.1. Physical and chemical analysis
A total of nine fossil bone and tooth samples have been analyzed
(Fig. 2). Bone samples studied were identied as: Equidae 1 (Equus
conversidens), Glyptodont (Glyptotherium), Mammoth (Mammuthus
columbi), Bovidae 1, Bovidae 2, Bovidae 3, Bovidae 4 and Bovidae 5
(Bison antiquus). The only sample of tooth was identied as Equidae 2
(Equus sp.).
Mammal bone and tooth is a composite constituted by organic and
inorganic compounds. The organic part consists mainly of collagen
and proteins, while the main inorganic mineral component is hydroxyapatite (Goffer, 1980; Child, 1995). There is a small percentage of other
elements (such as calcium, magnesium and sodium carbonate) incorporated into the bone structure. Natural alteration of bone begins immediately after death and continues after burial. In this context, the
characteristics of the soil environment play an important role in the
163
Fig. 3. Stratigraphic columns of Pleistocene fossil localities in northwestern Oaxaca where sampled specimens where collected.
Fig. 4. Diffraction patterns of fossil bone samples from la Mixteca Alta Oaxaquea, Mexico.
164
Equidae 1
Glyptodont
Mammoth
Bovidae 1
Bovidae 3
Bovidae 5
Bovidae 2
Bovidae 4
Fig. 5. Scanning Electron Microscopy images of fossil bone samples from La Mixteca Alta Oaxaquea, Mexico.
The IR spectrum of bones is characterized by adsorption bands produced by the major molecular species: phosphate group (from the mineral hydroxyapatite), carbonate group (from carbonate substitution for
Equidae 2
Fig. 6. Scanning Electron Microscopy images of fossil tooth sample from La Mixteca Alta Oaxaquea, Mexico.
165
Table 2
The chemical composition of fossil bone and tooth samples examined.
Element (% at.)
Sample
Species
Al
Si
Equidae 1
Bovidae 1
Glyptodont
Equidae 2
Bovidae 2
Mammoth
Bovidae 3
Bovidae 4
Bovidae 5
E. conversidens
B. antiquus
Glyptotherium
Equus sp.
B. antiquus
M. columbi
B. antiquus
B. antiquus
B. antiquus
78.9
20.6
26.9
28.8
27.3
21.1
23.2
23.6
22.5
17.3
47.2
44.3
47.1
42.6
48.0
41.0
51.2
43.0
0.74
0.26
0.66
0.85
0.72
0.45
1.71
0.72
2.03
0.66
main absorbance peak is recorded at 1033 cm1, and the doublet representative of the triply degenerate antisymmetric bending vibration of
the PO34 is recorded at 609 and 563 cm 1. The set of absorption
1
(stretching modes) and
bands of CO2
3 group occur at 1457 cm
872 cm1 (deformational modes). Absorption bands likely related to
the presence of organic matter occur around 2924 cm 1, while the
adsorbed water bands are recorded at 3429, 2350 and 1650 cm1. The
absorption bands associated with secondary mineral phases were
below the detection limit of the IR.
The concentration of uranium and thorium were determined by
Neutron Activation Analysis in order to verify their presence in the fossil
bone samples. The concentrations of uranium ranged from 30 to
115 mg/Kg and thorium from below the detection limit (LD = 0.23) to
3 mg/Kg (Table 3). For most bone samples, uranium and thorium concentrations are signicant and they allow getting reliable uranium series age.
4.2. Uranium series dating
It was assumed that the fossil bone samples analyzed in this study,
after burial have remained as a closed system with respect to uranium
through the time of aging, which means they have not exchanged
230
Th and 234U with the environment. Samples age (t) using
238
U234U230Th method is given by:
Th=234 U
U=234 U 1 exp0 t
i
1 238 U=234 U 0 =0 4 1 exp4 0 t
238
Equidae 1
C-H
O-H
O-H
C-OP=O
C-O
H-O-H
Glyptodont
Transmission (a.u.)
230
C-O
P-O
O-P-O
P-O
Equidae 2
Mg
Na
Fe
Ca
Ca/P
0.29
0.16
1.52
3.35
18.47
21.70
20.59
6.97
9.11
3.04
17.6
0.66
1.33
8.38
10.3
8.25
3.21
3.56
1.41
7.88
2.3
2.5
2.2
2.1
2.5
2.2
2.5
2.1
2.2
0.19
0.45
0.34
0.19
0.29
0.21
0.35
0.28
0.11
2.61
0.53
0.14
0.10
0.20
0.48
0.42
Bovidae 2
Concentration, mg/Kg
Mammoth
Bovidae 3
4000
3500
3000
2500
2000
1500
1000
500
-1
wavenumber (cm )
Fig. 7. IR spectra of fossil bone samples from La Mixteca Alta Oaxaquea, Mexico.
Sample
Species
Uranium
Thorium
Equidae 1
Bovidae 1
Glyptodont
Equidae 2
Bovidae 2
Mammoth
Bovidae 3
Bovidae 4
Bovidae 5
E. conversidens
B. antiquus
Glyptotherium
Equus sp.
B. antiquus
M. columbi
B. antiquus
B. antiquus
B. antiquus
115 18
65.5 13
51 6.5
30 5.0
41 5.0
46 8.0
50 8.0
44 8.0
41 7.0
1.0 0.1
LD = 0.23
1.6 0.3
0.5 0. 1
2.0 0.2
1.0 0.2
3.0 0.3
1.5 0.2
1.6 0.2
LD = limit of detection.
166
Glyptodont
Equidae 1
Mammoth
Bovidae 5
Bovidae 4
Equidae 2
Bovidae 3
Bovidae 2
Fig. 8. Variation of 234U/238U and 230Th/234U ratios with the time in a closed system free of initial 230Th.
respectively) are much older than the expected age (around 60 ka,
which correspond to the rst record of Bison antiquus in North America).
The unreliable ages for these samples could be associated with the physical-chemical alteration due to inclusion of mineral particles from buried soil.
The obtained results allow us to conclude that to achieve a good degree of accuracy with uranium dating method, the preservation of fossil
bone samples is fundamental.
This study gives the rst numeric ages of some mammal species that
inhabited southern Mexico during the Late Pleistocene.
5. Conclusions
Acknowledgment
Table 4
Isotopic activity ratios of fossil bone samples.
Activity ratio
Sample
Species
234
Equidae 1
Bovidae 1
Glyptodont
Equidae 2
Bovidae 2
Mammoth
Bovidae 3
Bovidae 4
Bovidae 5
E. conversidens
B. antiquus
Glyptotherium
Equus sp.
B. antiquus
M. columbi
B. antiquus
B. antiquus
B. antiquus
2.6
0.95
2.73
1.99
0.96
2.26
1.62
1.93
2.01
U/238U
230
Th/234U
0.22
0.58
0.11
0.55
0.45
0.29
0.52
0.24
Estimated age, ka
26 1305
n.d.
84 7100
12 620
88 4415
60 3000
36 1825
73 3687
27 1391
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