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ago. At this time, the marine reptiles, thfe of invertebrates. Russell (2) concludes
Luis Alvarez is professor emeritus of physics at
flying reptiles, and both orders of dino- that about half of the genera living at that Lawrence Berkeley Laboratory, University of Cali-
saurs died out (1), and extinctions oc- time perished during the extinction fornia, Berkeley 94720. Walter Alvarez is an associ-
ate professor in the Department of Geology and
curred at various taxonomic levels event. Geophysics, University of California, Berkeley.
among the marine invertebrates. Dra- Many hypotheses have been proposed Frank Asaro is a senior scientist and Helen Michel is
a staff scientist in the Energy and Environment Divi-
matic extinctions occurred among the to explain the Cretaceous-Tertiary (C-T) sion of Lawrence Berkeley Laboratory.
SCIENCE, VOL. 208, 6 JUNE 1980 0036-8075/80/0606-1095$02.00/0 Copyright © 1980 AAAS 1095
Identification of Extraterrestrial and summarized other previous work. sa, has a matrix of coccoliths and cocco-
Platinum Metals in Deep-Sea Sediments Considerations of this type (23) lith fragments (calcite platelets, on the
prompted us to measure the iridium con- order of 1 micrometer in size, secreted
This study began with the realization centration in the 1-centimeter-thick clay by algae living in the surface waters) and
that the platinum group elements (plati- layer that marks the C-T boundary in a rich assemblage of foraminiferal tests
num, iridium, osmium, and rhodium) some sections in the Umbrian Apen- (calcite shells, generally in the size range
are much less abundant in the earth's nines, in the hope of determining the 0.1 to 2.0 millimeters, produced by
crust and upper mantle than they are in length of time represented by that layer. single-celled animals that float in the sur-
chondritic meteorites and average solar Iridium can easily be determined at low face waters).
system material. Depletion of the plati- levels by neutron activation analysis In some Umbrian sections there is a
num group elements in the earth's crust (NAA) (24) because of its large capture hiatus in the sedimentary record across
and upper mantle is probably the result cross section for slow neutrons, and be- the C-T boundary, sometimes with signs
of concentration of these elements in the cause some of the gamma rays given off of soft-sediment slumping. Where the se-
earth's core. during de-excitation of the decay prod- quence is apparently complete, forami-
Pettersson and Rotschi (17) and Gold- uct are not masked by other gamma rays. nifera typical of the Upper Cretaceous
schmidt (18) suggested that the low con- The other platinum group elements are (notably the genus Globotruncana) dis-
centrations of platinum group elements more difficult to determine by NAA. appear abruptly and are replaced by the
in sedimentary rocks might come largely basal Tertiary foraminifer Globigerina
from meteoritic dust formed by ablation eugubina (16, 26). This change is easy to
when meteorites passed through the at- Italian Stratigraphic Sections recognize because G. eugubina, unlike
mosphere. Barker and Anders (19) the globotruncanids, is too small to see
showed that there was a correlation be- Many aspects of earth history are best with the naked eye or the hand lens (Fig.
tween sedimentation rate and iridium recorded in pelagic sedimentary rocks, 1). The coccoliths also show an abrupt
concentration, confirming the earlier which gradually accumulate in the rela- change, with disappearance of Cre-
Contessa boundary clays, and this value Meter levels. (b) Systems. c
was assumed for all the other samples. (c) Stages. (d) Magnetic a
0L.
polarity zones (black is E0
Twenty-seven of the 28 elements show normal, white is reversed o (33)
very similar patterns of abundance varia- polarity, letters give Gub- a)
_o C_0'
0.
tion, but iridium shows a grossly dif- bio polarity zonation, num- 01) A-
ferent behavior; it increases by a factor bers are equivalent marine 200- 0u _Oc
of about 30 in coincidence with the C-T magnetic anomalies). (e)
Lithology. (f) Samples a (34) 0
C-)
boundary, whereas none of the other ele- used in first NAA study 0C U)
ments as much as doubles with respect (samples I, J, and L are 0
to an "average behavior" shown in the from equivalent positions Cf
lower right panel of Fig. 3. Figure 4 in the Contessa section, 2
km to the northwest). (g) a
O
z
-Bonarelli level
kilometers north of Gubbio), and four 0
100- H a
large samples of the boundary clay from c
0
0
0
the two sections near Gubbio and two 0 0
sections about 30 km to the north (31). 0)
o. _B
0
other samples. a)
C
0
FTert.1 L-
T/C K-
boundary 1 Clay j
region [ rt._
Elemental abundances I
in 12 samples from
two sections at Gubbio Lower port
of Upper
Cretaceous
Fig. 3. Abundance variations of 28 elements in 12 samples from two Gubbio sections. Flags on "average rare earth" diagram are + 30 percent
and include all rare earth aata.
1098 SCIENCE, VOL. 208
zonation indicates that the C-T bounda- the atomic number position of iridium. The Boundary Layers
ries at Gubbio and Stevns Klint are at Iridium has been detected (45) in a warm
least approximately contemporaneous, spring on Mount Hood in northern Cali- The whole-rock composition of the
and they may well be exactly synchro- fornia at a level of 7 x 10-12 g per gram Contessa boundary layer (a mixture of
nous. However, no paleomagnetic re- of water, and in two cold-water sources red and gray clay) is shown in Table 3.
sults are available from Stevns Klint, so at levels of 3 x 10-13 to 4 x 10-13 g per There are two recognizable sublayers,
synchroneity cannot be tested by revers- gram of water. Many other cold-water each about 0.5 cm thick, the upper being
al stratigraphy. sources in this area had Ir levels less red in color and the lower gray. The ele-
than 1 x l0-13 g/g. mental iron content, which may explain
Results from the Danish Section
128,000 134 Cs 1056-0
Seven samples were taken from near
the C-T boundary (Fig. 6). Fractions of | 181Hf 980 mi.
z 260o0 [ A | |
each sample were treated with dilute ni- 126000a19aI-r 39.8-day decay
tric acid, and the residues were filtered,
washed, and heated to 800°C. The yield
of acid-insoluble residue was 44.5 per- 124,000
cent for the boundary fish clay and var-
ied from 0.62 to 3.3 percent for the pelag- u122,o0
12,000 0 131 Ba
ic limestones (Table 1). to
Neutron activation analysis (24) and x- E
E
ray fluorescence (XRF) (42, 43) measure- 0 120,000
E 1 03
acid-insoluble resi- -360
As shown in Table 1, the Ir in the dues from Italian Z
boundary layer residue rises by about a limestones near the 102
factor of 160 over the background level Tertiary - Cretaceous 20 -347.8
(- 0.26 ppb). A 1-cm thickness of this boundary. Error bars : -i
a b c d
3
+3
- 2.7 MA
2
*- +1.2 _ _
E-
- +0.7
C)
T/C
a 0L K
0 D
- -05
_ )
E
IV
w
0.3
- -2.2
0.2 _
--3
0,1 _
0.0 LL_
Mg Ti Na
I I Fig. 6 (left). Stratigraphic section at H0jerup Church, Stevns Klint, Denmark. (a) Lithology (C,
__r~~~0 --5.4 Cerithium limestone; F, fish clay). (b) Stages. (c) Samples analyzed in this study. (d) Meter
levels. Analytical results are given in Tables I to 3. Fig. 7 (right). Major element abundances
L L Li in acid-insoluble fractions from Danish rocks near the Tertiary-Cretaceous boundary. The
crosshatched areas for the Cretaceous and Tertiary values each represent root-mean-square
deviations for three samples. (Only two measurements of magnesium and silicon were included in the Cretaceous values.) For the boundary layer
sample the crosshatched areas are the standard deviations associated with counting errors. Measurements of silicon and magnesium were done
by XRF (42), all others were by NAA.
1100 qr(Fwr'P_
at1n1m,i vnT. )n
v v -. 4vo
billion or higher are more likely to have
produced the Ir anomaly. Figure 10 60 0.06 c
Table 2. Abundance of trace elements in the Danish boundary layer (parts per million).
(1) (1)
Ele- Abundance in (2) El Abundance in (2)
ment whole rock/ Abundance mee-t wholerock/ Abundance
abundance of in residue* abundance of in residue
residue* residue
Enhanced elementst Depleted elements
V 391 ±27 330 ± 31 Mn 102.0 ± 1.3 21.3 ±0.5
Cr 371 ±13 358 ± 9 Rb 27 ± 7 35 ±4
Co 141.6 ±1.8 57.2 ±0.7 Yt 79 ± 6 6.3 ±1.8
Ni 1137 ±31 479 ±14 Zrt 144 ±11 125 ±6
Cut 167 ±14 93 ± 6 Nbt 8 ± 4 6.1 ±1.8
Znt 1027 + 49 378 ± 18 Cs 1.87 ± 0.19 1.51 ± 0.14
As 96 ±8 68 ±4 La 61.1 ±1.6 6.8 ± 0.4
Se§ 46.5 ± 0.6 12.1 ± 0.3 Ce 57.0 ± 1.2 9.7 ± 0.6
Mo 29.0 ± 2.5 20.3 ± 1.4 Nd 63.4 ± 2.7 5.4 ± 0.6
Ag§ 2.6 ± 0.9 3.5 ± 0.7 Sm 11.93 ± 0.08 0.781 ± 0.008
In 0.245 ± 0.022 0.086 ± 0.019 Eu 2.76 ± 0.11 0.121 ± 0.010
Sb 8.0 ± 0.4 6.7 ± 0.4 Th 1.84 ± 0.04 0.148 ± 0.014
Ba 1175 ± 16 747 ± 11 Dy 11.24 ± 0.12 0.908 ± 0.033
Ir 0.0643 ± 0.0029 0.0416 ± 0.0018 Yb 5.02 + 0.09 0.56 ± 0.05
Pb* 64 + 14 28 ± 7 Lu 0.553 ± 0.031 0.083 0.004
Hf 4.34 ± 0.16 3.88 + 0.07
Other elementst Ta 0.508 ± 0.011 0.500 + 0.005
Sc 20.74 + 0.16 14.30 ± 0.14 Th 7.1 ± 0.4 1.28 ± 0.06
Gat 30 ± 6 19.8 ± 3.0 U 8.63 ± 0.09 0.918 + 0.024
SE 1465 ±72 48.1 + 2.4
Au < 0.12 0.027 ± 0.007
*Column I minus column 2 is the amount of an element that dissolved in the acid or was lost in the firing; abundance of residue = 44.5 percent. tElements V, Ag,
and In are at least 20 percent and all other "enhanced elements" are at least a factor of 3 more abundant in the boundary residue than in the other residues. All
"depleted elements" are at least 20 percent less abundant in the boundary residue than in the other residues. "Other elements" do not show a consistent pattern of
boundary residue abundances relative to the others. tMeasured by hard XRF (43). §Flux monitors were used in the NAA measurements of these elements.
The indicated errors are applicable for comparing the two entries for a given element, but calibration uncertainties of possibly 10 to 20 percent must be considered
when the values are used for other purposes.
6 JUNE 1980 1101
extraterrestrial material at the time of the to concentration of normal background must have affected both the Italian and
extinctions, or whether it was formed by iridium at the boundary. These appear to Danish areas at exactly the time of the
the normal, slow accumulation of mete- be much less likely than the sudden-in- C-T extinctions, but at none of the other
oritic material (19), followed by concen- flux model, but we cannot definitely rule times represented by our samples. We
tration in the boundary rocks by some out either one at present. feel that this scenario is too contrived, a
identifiable mechanism. The first scenario requires a physical conclusion that is justified in more detail
There is prima facie evidence for an or chemical change in the ocean waters elsewhere (23).
abnormal influx in the observations that at the time of the extinctions, leading to In summary, we conclude that the
the excess iridium occurs exactly at the extraction of iridium resident in the sea- anomalous iridium concentration at the
time of one of the extinctions; that the water. This would require iridium con- C-T boundary is best interpreted as in-
extinctions were extraordinary events, centrations in seawater that are higher dicating an abnormal influx of extra-
which may well indicate an extraordi- than those presently observed. In addi- terrestrial material.
nary cause; that the extinctions were tion, it suggests that the positive iridium
clearly worldwide; and that the iridium anomaly should be accompanied by a
anomaly is now known from two dif- compensating negative anomaly immedi- Negative Results of Tests for the
ferent areas in western Europe and in ately above, but this is not seen. Supernova Hypothesis
New Zealand. Furthermore, we will show The second scenario postulates a re-
in a later section that impact of a 10-km duction in the deposition rate of all com- Considerable attention has been given
earth-crossing asteroid, an event that ponents of the pelagic sediment except to the hypothesis that the C-T ex-
probably occurs with about the same fre- for the meteoritic dust that carries the tinctions were the result of a nearby su-
quency as major extinctions, may have concentrated iridium. This scenario re- pernova (I1). A rough calculation of the
produced the observed physical and bio- quires removal of clay but not of iridium- distance from the assumed supernova to
logical effects. Nevertheless, one can in- bearing particles, perhaps by currents of the solar system, using the measured
50
C 3
0
30
E 0
E
cn be
0
+1
2 0
to
20
or
-C
10
.2~~~~~~~~~~~~~~
Observedi
0 0
z_ ._ Z -
z<CnI. >U
a
U c.a nU-toaccmo
O- o D
-
R EE REE
Fig. 10 (left). Comparison of observed elemental abundance patterns in the Gubbio section samples with average patterns expected for crustal
material (46). Fig. 11 (right). Comparison of observed elemental abundance patterns in the Gubbio section samples with patterns expected for
carbonaceous chondrites (46).
1102 SCIENCE, VOL. 208
boundary layer and the amount of iridi- samples were obtained-no carriers sample spiked with about 20 picograms
um expected to be blown off in the super- were added. Chemical separations were of 2"Pu; it indicates both the sensitivity
nova explosion, gives about 0.1 Ilight- also performed on the plutonium fraction of NAA for the detection of 244Pu and the
year. The probability is about 10-9 (49) after the neutron irradiation. No signifi- freedom of the purified sample from oth-
that, during the last 100 million years, a cant gamma radiation was observed, oth- er elements that might interfere with the
supernova occurred within this distance er than that associated with the pluto- detection of 244Pu. The plutonium isotop-
from the sun. Any mechanism with such nium isotopes. In order to measure our ic ratios in this sample and in the tracer
a low a priori probability is obviously a chemical yields, Gubbio acid-soluble and were also measured with a single-direc-
one-time-only theory. Nevertheless, be- acid-insoluble residues were spiked with tion-focusing mass spectrometer 5 feet in
cause the theory could be subjected to small amounts of 238Pu tracer. This pluto- radius.
direct experimental tests, it was treated nium isotope is easily detectable through No 244PU was detected in the Gubbio
as a real possibility until we obtained two its alpha decay, as its half-life is only samples (Fig. 12b), with a detection limit
other independent pieces of evidence 87.7 years. In addition, one of the sam- of less than 10 percent of the amount that
that forced us to reject it. ples was spiked with 244P. Figure 12a would be expected to accompany the
Elements heavier than nickel can be shows the gamma-ray spectrum of the measured iridium if a supernova were re-
produced in stars only by neutron cap-
ture followed by beta decay. The most
intense source of neutrons so far postu- Th SC Ti
lated is that produced by the gravitation- Fig. 9. Some of the ppmI ppm
al collapse of the core of a star that leads element abundances 12 30 1.2 - i, >1
measured in acid-in- o OIVa.
immediately to a supernova explosion. soluble residues of m
=
0
In this environment the rapid capture of Cretaceous, boundary 8 20 0.8
neutrons ("r process") leads to the for- layer, and Tertiary
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