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Science, New Series, Vol. 208, No. 4448. (Jun. 6, 1980), pp. 1095-1108.
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Fri Aug 17 10:16:29 2007
6 June 1980, Volume 208, Number 4448
ago. At this time, the marine reptiles, thk of invertebrates. Russell (2) concludes
Luis Alvarez is professor emeritus of physics a t
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 (I), 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 0036-8075/80i0606-1095$02200i0 Copyright O 1980 AAAS 1095
Identification of Extraterrestrial and summarized other previous work. sa, has a matrix of coccoliths and cocco-
Considerations of this type (23) lith fragments (calcite platelets, on the
Platinum Metals in Deep-Sea Sediments
prompted us to measure the iridium con- order of 1 micrometer in size, secreted
This study began with the realization centration in the l-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 difficultto 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 StratigraphicSections 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-
suggestions. Subsequently, the method tively quiet waters of the deep sea as in- taceous forms, at exactly the same level
was used by Ganapathy, Brownlee, and dividual grains settle to the bottom. In as the foraminiferal change, although
Hodge (20) to demonstrate an extra- the Umbrian Apennines of northern pe- this was not recognized until more re-
terrestrial origin for silicate spherules in ninsular Italy there are exposures of pe- cently (27).
deep-sea sediments. Sarna-Wojcicki et lagic sedimentary rocks representing the In well-exposed, complete sections
al. (21) suggested that meteoritic dust ac- time from Early Jurassic to Oligocene, there is a bed of clay about 1 cm thick
cumulation in soil layers might enhance around 185 to 30 million years ago (25). between the highest Cretaceous and the
the abundance of iridium sufficiently to The C-T boundary occurs within a por- lowest Tertiary limestone beds (28). This
permit its use as a dating tool. Recently, tion of the sequence formed by pink bed is free of primary CaC03, so there is
Crocket and Kuo (22) reported iridi- limestone containing a variable amount no record of the biological changes dur-
um abundances in deep-sea sediments of clay. This limestone, the Scaglia ros- ing the time interval represented by the
clay. The boundary is further marked by
a zone in the uppermost Cretaceous in
which the normally pink limestone is
white in color. This zone is 0.3 to 1.O me-
ter thick, varying from section to sec-
tion. Its lower boundary is a gradational
color change; its upper boundary is
abrupt and coincides with the faunal and
floral extinctions. In one section (Con-
tessa) we can see that the lower 5 mm of
the boundary clay is gray and the upper 5
mm is red, thus placing the upper bound-
ary of the zone in the middle of the clay
layer.
The best known of the Umbrian sec-
tions is in the Bottaccione Gorge near
Gubbio. Here some of the first work on
the identification of foraminifera in thin
section was carried out (29); the oldest
known Tertiary foraminifer, G . eu-
gubina, was recognized, named, and
used to define the basal Tertiary biozone
(16, 26); the geomagnetic reversal
stratigraphy of the Upper Cretaceous
and Paleocene was established, corre-
lated to the marine magnetic anomaly se-
quence, and dated with foraminifera
00); and the extinction of most of the
nannoplankton was shown to be syn-
chronous with the disappearance of the
genus Globotruncana (27).
SCIENCE, VOL. 208
Results from the Italian Sections but changes to logarithmic to show re- gives a clear picture of the general trend
sults from 350 m below to 50 m above the of iridium concentrations as a function of
Our first experiments involved NAA boundary. It is also important to note stratigraphic level.
of nine samples from the Bottaccione that analyses from five stratigraphic sec- The pattern, based especially on the
section (two limestone samples from im- tions are plotted on the same diagram on samples from the Bottaccione Gorge and
mediately above and below the boundary the basis of their stratigraphic position Gorgo a Cerbara, shows a steady back-
plus seven limestone samples spaced above or below the boundary. Because ground level of - 0.3 ppb throughout the
over 325 m of the Cretaceous). This was slight differences in sedimentation rate Upper Cretaceous, continuing into the
supplemented by three samples from the probably exist from one section to the uppermost bed of the Cretaceous. The
nearby Contessa section (two from the next, the chronologic sequence of sam- background level in the acid-insoluble
boundary clay and one from the basal ples from different sections may not be residues is roughly comparable to the
Tertiary bed). Stratigraphic positions of exactly correct. Nevertheless, Fig. 5 iridium abundance measured by other
these samples are shown in Fig. 2.
Twenty-eight elements were selected
for study because of their favorable nu- a b c d e f g
clear properties, especially neutron cap-
ture cross sections, half-lives, and gam-
ma-ray energies. The results of these
analyses are presented in Fig. 3 on a log-
arithmic plot to facilitate comparison of
the relative changes in elements over a
wide range of concentrations. The only
preparation given to these samples was
removal of the CaCO, fraction by dis-
solution in dilute nitric acid. Figure 3
shows elemental abundances as gram of
element per gram of insoluble clay resi-
due. The limestones generally contain
about 5 percent clay. The boundary clay
layer contains about 50 percent CaCO,,
but this is coarse-grained calcite that
probably crystallized during deformation
long after deposition. Chemical yields of
Fig. 2. Stratigraphic sec-
iridium in the acid-insoluble fraction av- tion at the Bottaccione
eraged 44 percent for the red and gray Gorge, Gubbio (30). (a)
Contessa boundary clays, and this value Meter levels. (b) Systems.
was assumed for all the other samples. (c) Stages. (d) Magnetic
polarity zones (black is
Twenty-seven of the 28 elements show normal, white is reversed
very similar patterns of abundance varia- polarity, letters give Gub-
tion, but iridium shows a grossly dif- bio polarity zonation, num-
ferent behavior; it increases by a factor bers are equivalent marine
of about 30 in coincidence with the C-T magnetic anomalies). (e)
Lithology. (0 Samples
boundary, whereas none of the other ele- used in first NAA study
ments as much as doubles with respect (samples I, .I, and L are
to an "average behavior" shown in the from equivalent positions
lower right panel of Fig. 3. Figure 4 in the Contessa section, 2
km to the northwest). (g)
shows a typical gamma-ray spectrum Formation names.
used to measure the Ir abundance, 5.5
parts per billion (ppb).
In follow-up experiments we analyzed
five more samples from the Bottaccione
section, eight from Gorgo a Cerbara (28
kilometers north of Gubbio), and four
large samples of the boundary clay from
the two sections near Gubbio and two
sections about 30 km to the north (31).
The chemical yield of iridium in the acid-
insoluble fraction was 95 -+ 5 percent for
the Contessa boundary clay, and a 100
percent yield was assumed for all the
other samples.
Figure 5 shows the results of 29 Ir
analyses completed on Italian samples.
Note that the section is enlarged and that
the scale is linear in the vicinity of the C-
T boundary, where details are important,
6 JUNE 1980
workers (lY, 22, 32) in deep-sea clay The Danish Section at Hojerup Church was studied in detail
sediments. This level increases abruptly, by Christensen cr a l . (14), who sub-
by a factor of more than 30, to 9.1 ppb, To test whether the iridium anomaly is divided it into four thin layers; we ana-
the Ir abundance in the red clay from the a local Italian feature, it was desirable to lyzed a sample mixing the two internal
Contessa section. Iridium levels are high analyze sediments of similar age from layers (units I11 and IV of Christensen et
in clay residues from the first few beds of another region. The sea cliff of Stevns a1 .). These layers are black or dark gray,
Tertiary limestone, but fall off to back- Klint, about 50 km south of Copenhagen, and the lower one contains pyrite con-
ground levels by 1 m above the bound- is a classical area for the C-T boundary cretions; the layers below and above (11
ary. For comparison, the upper dashed and for the Danian or basal stage of the and V) are light gray in color. Undis-
line in Fig. 5 shows an exponential decay Tertiary. A collection of up-to-date pa- turbed lamination in bed IV suggests that
from the boundary clay Ir level with a pers on this and nearby areas has re- no bottom fauna was present during its
half-height of 4.6 cm. cently been published, which includes deposition (14). Above the fish clay, the
To test the possibility that iridium a full bibliography of earlier works Cerithium limestone is present to a thick-
might somehow be concentrated in clay (6, vol. I). ness of about 50 cm in the small basins,
layers, we subsequently analyzed two Our samples were taken at Hojerup disappearing over the banks. It is hard,
red clay samples from a short distance Church (33). At this locality the Maast- yellowish in color, and cut by abundant
below the C-T boundary in the Bot- richtian, or uppermost Cretaceous, is burrows. Above this is a thick bryozoan
taccione section. One is from a distinc- represented by white chalk containing limestone.
tive clay layer 5 to 6 mm thick, 1.73 m black chert nodules in undulating layers The presence of a thin clay layer at the
below the boundary; the other is from a with amplitudes of a few meters and C-T boundary in both the Italian and
I- to 2-mm bedding-plane clay seam 0.85 wavelengths of 10 to 50 m (14). These un- Danish sections is quite striking. How-
m below the boundary. The whole-rock dulations are considered to represent ever, there are notable differences as
analyses of these clays showed no de- bryozoan banks (34). The C-T boundary well. The Danish sequence was clearly
tectable Ir with limits of 0.5 and 0.24 is marked by the fiskrler, or fish clay, deposited in shallower water (-79, and
ppb, respectively. Thus neither clay lay- which is up to 35 cm thick in the deepest the Danish limestones preserve an exten-
ers from below the C-T boundary nor parts of the basins between bryozoan sive bottom-dwelling fauna of bivalves
clay components in the limestone show banks (14) but commonly only a few cen- (36), echinoderms (37), bryozoans, (38),
evidence of Ir above the background lev- timeters thick, thinning or disappearing, and corals (39).
el. over the tops of the banks. The fish clay Foraminifera1 (40) and coccolith (41)
Elemental abundances
in 12 samples from
two sections at Gubb~o
Pig. 3. Abundance variations of 28 elements in 12 sarnples from two Cubbio sections. Flags on "average rare earth" d~agramare 1 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 (4.5) 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 1012g 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 1 0 ' " to 4 X 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 lO-l"/g. mental iron content, which may explain
I 1 I , - 104
-400
- 102
boundary layer residue rises by about a l~mestones near the
factor of 160 over the background level Tert~ary- Cretaceous - 20
-347 8
(- 0.26 ppb). A 1-cm thickness of this boundary Error bars
k-
O'?
{
-; ray clay Red clay -
-
-
polnts) w ~ t h a half-
almost a factor of 20 lower than the ob- filled clrcle and error
served value. So there was probably not bar are the mean and Y)
:
Y)
131 0 Bottaccnone
o Petrlcclo - 104
error that places the value for indium in lrldlum abundance (ppb)
6 JUNE 1980
the color, is significantly higher in the Table 1. Abundance of iridium in acid-in- exception. Its enhancement may be due
residue of the red layer (7.7 versus 4.5 soluble residues in the Danish section. to replacement of iron in the clay lattices
percent) than in the gray, and so is the in the sulfide environment or to a dif-
*
Ir (9.1 0.6 versus 4.0 -t- 0.6 ppb).
Abun-
Abun-
dancet
ferent, more mafic source for the bound-
Boundary samples were analyzed from dance of acid- ary layer clay than for the Tertiary and
the Bottaccione Gorge nearby and two Sample* of insol- Cretaceous clays.
other areas about 30 km to the north. iridium uble Recent unpublished work by D. A.
resi-
In samples taken near the Italian (PPb) Russell of the National Museums of Can-
dues
boundary layer, the chemical composi- ada and by the present authors has
-
tions of all clay fractions were roughly S K , +2.7 m shown that the boundary layer whole-
the same except for the element Ir. How- S K , +1.2m rock concentration of Ir in a section near
ever, there are discernible differences, as SK, +0.7 m Woodside Creek, New Zealand, is ap-
shown in Fig. 9, which suggest that at Boundary proximately 20 times the average con-
least part of the boundary layer clay had SK, 0 . 5 m
centration in the adjacent Cretaceous
SK, 2 . 2 m
a different origin than the Cretaceous SK, -5.4 m and Tertiary limestones.
and Tertiary clays.
The Danish C-T boundary clay is *Numerical values are the distances above (+) or
below (-) the boundary layer; SK, Stevns
somewhat thicker than 1 cm and is di- Klint. tThe boundary layer has a much higher A Sudden Influx of Extraterrestrial
vided into four layers, as mentioned ear- proportion of clay than the pelagic limestones above
and below. SSome iridium dissolved in the nitric Material
lier. Only a single mixed sample from the acid. The whole-rock abundance was 28.6 ? 1.3
two middle layers was measured, so no PP~. To test whether the anomalous iridium
information is available on the chemical at the C-T boundary in the Gubbio sec-
variations within the boundary. The av- tions is of extraterrestrial origin, we con-
erage Ir abundance is 29 ppb in the whole calcite expected from the calcium mea- sidered the increases in 27 of the 28 ele-
rock or 65 ppb based on the weight of surement. The boundary clay fraction is ments measured by NAA that would be
acid-insoluble residue. far different chemically from the lime- expected if the iridium in excess of the
The whole-rock abundances and min- stone clay fractions above and below, background level came from a source
eral composition of the Danish boundary which are similar to each other. Pyrite is with the average composition of the
clay are shown in Table 3, and the abun- present in the boundary clay, and ele- earth's crust. The crustal Ir abundance,
dances of pertinent trace elements are ments that form water-insoluble sulfides less than 0.1 ppb (19, 22), is too small to
shown in Table 2. The major silicate min- are greatly enhanced in this layer. The be a worldwide source for material with
erals that must be present were not de- trace elements that are depleted are an Ir abundance of 6.3 ppb, as found
tected, so the other mineral abundances those that often appear as clay com- near Gubbio. Extraterrestrial sources
were normalized to give the amount of ponents. The element magnesium is an with Ir levels of hundreds of parts per
t -5.4
t -6
Fig. 6 (left). Stratigraphic section at H0je1up Church, Stevns Klint, Denmark. (a) Lithology ( C ,
Cerithium limestone; F, fish clay). (b) Stages. (c) Samples analyzed in this study. (d) Meter
levels. Analytical results are given in Tables 1to 3. Fig. 7 (right). Major element abundances
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.
1 100 SCIENCE. VOL. 208
billion or higher are more likely to have
produced the Ir anomaly. Figure 10
slhQwsthat if the source had an average
earth's crust composition (46), increases
sipificantly above those observed
would be expected in all 27 elements.
Hswever, for a source with average car-
bnitceous chondrite composition (46),
~ n l nyickel should show an elemental in-
crease greater than that observed. As
sbawn in Fig. 11, such an increase in
nickel was not observed, but the predict-
ed effect is small and, given appropriate
csnditions, nickel oxide would dissolve
in seawater (47). We conclude that the
pattern of elemental abundances in the
Gubbio sections is compatible with an
extraterrestrial source for the anomalous
iridium and incompatible with a crustal
sgurce.
The Danish boundary layer, which has
much more Ir than the Italian C-T clay, Fig. 8. Selected trace element abundances of Danish acid-insoluble residues. First bar is the
is even less likely to have had a crustal mean value [root-mean-square deviation (RMSD) is shown by the crosshatched areas] for the
rigi in. Rocks from the upper mantle given element in the three Cretaceous residues. Second bar is the abundance (counting error is
(which has more Ir than the crust) have shown by solid areas) for the given element in the boundary layer residue. Third bar is the mean
value and RMSD for the given element in the three Tertiary residues. Measurements were by
less than 20 ppb (48) and are therefore an NAA, except for zinc, which was measured by XRF (43). Significant amounts of nickel, zinc,
unlikely worldwide source. There are, cobalt, iridium, and thorium in all samples dissolved in the 2N HNO,. Very little cesium, tan-
bswever, localized terrestrial sources talum, or hafnium in any of the samples dissolved in the acid.
with much higher Ir abundances; for ex-
ample, nickel sulfide and chromite ores
(48) have Ir levels of hundreds and thou- ppm) to explain its Ir in this fashion, un- these effects occurring worldwide seems
sands of parts per billion, respectively. less the marine chemistry concentrated less likely than an extraterrestrial origin
The Danish boundary layer, however, Ir preferentially (even in the sulfide envi- for the Ir.
d w s not have enough nickel [506 parts ronrnent) and disposed of the other ele- We next consider whether the Ir
per million (ppm)] or chromium (165 ments elsewhere. The probability of anomaly is due to an abnormal influx of
Table 2. Abundance of trace elements in the Danish boundary layer (parts per million).
(1) (1)
Abundance in (2) Abundance in (2)
Ele- Ele-
whole rock/ Abundance whole rock/ Abundance
ment ment
abundanceof in residue* abundanceof 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
Observed Increases
-
z z ; ; > 5 : : % 5 ~ ~ 2 $ ~ ~ ; 5 : ~ ~ 3 ; : ~ : z~z : : ; > ; Y " : ; f i E I O = : g 2 : j : 3 ~ ~ 3 ; : 3 = 3
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 '44Pu; it indicates both the sensitivity
nova explosion, gives about 0.1 light- also performed on the plutonium fraction of NAA for the detection of 2 4 4 Pand
~ the
year. The probability is about 10-"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 2 4 4 P 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 '"Pu tracer. This pluto- radius.
direct experimental tests, it was treated nium isotope is easily detectable through No 244Puwas 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 ' 4 4 P ~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-
lated is that produced by the gravitation- Fig. 9. Some of the
al collapse of the core of a star that leads element abundances
measured in acid-in-
immediately to a supernova explosion. soluble residues of
In this environment the rapid capture of Cretaceous, boundary
neutrons ("r process") leads to the for- layer, and Tertiary
mation of the heaviest known isotopes. rocks near Gub-
bio. Data include all
The slower capture of neutrons by heavy samples from that
isotopes in highly evolved stars ("s pro- area measured within
cess") leads to a different mix of iso- 19 m of the boundary.
topes (50). There were four sam-
One heavy isotope in particular of- ples from each of the
three layers; the
fered the possibility of testing the super- crosshatched areas
nova hypothesis; this is '44Pu, with a are the standard de-
half-life of 80.5 X 10'jyears. The ex- viations. The abun-
plosion of a supernova should send out dance patterns for
samples from - 27
an expanding shell of newly created km north of Gubbio
heavy elements, with a ratio of Ir atoms are similar to those
to '"Pu atoms equal to about 10" This shown.
value is inferred from the existence of an
anomaly in the meteoritic abundance of
heavy xenon isotopes that is interpreted
as being due to the fission of '"Pu (51). Table 3. Whole-rock composition of the Gubbio and Danish boundary layers (percent).
Any '"Pu incorporated in the earth at the Abundance in boundary layer?
- --
time of the creation of the solar system, Element* or
-- - -
ically separated from 25- and 50-g batch- *Abundance values are for element expressed as form shown. tElements Si, Ca, Mg, S, P, and Gubbio Ti
were measured by soft XRF (42). Some S may be lost in this sample preparation procedure. The Denmark Ti
es of boundary clay and from a 50-g was measured by hard XRF (43). All other measurements were by NAA. Mineral analyses were done by M.
batch of bedding clay from below the Ghiorso and I. S. E. Carrnichael by x-ray diffraction. $Total Fe expressed as FeO. $The CO, abun-
dance was calculated from the Ca abundance by assuming all Ca was present as the carbonate. \/The
C-T boundary, and nearly "mass-free" difference is mainly water and organic material.
6 JUNE 1980
sponsible for the latter. The ocean, how- test whether a supernova was respon- rial because of mixing the protosolar gas
ever, can produce chemical and physical sible for the iridium anomaly involved a cloud. However, different supernovas
changes in depositing materials as well measurement of the isotopic ratio of irid- should produce iridium with different
as diagenetic alterations in the deposited ium in the boundary material. Iridium isotopic ratios because of differences in
sediments, so the absence of measurable has two stable isotopes, 191 and 193, the contributions of the r and s processes
'"Pu is not an absolutely conclusive ar- which would be expected to occur in occasioned by variations in neutron
gument. about the same relative abundances, 37.3 fluxes, reaction times, and so on, from
The second method that was used to to 62.7 percent, in all solar system mate- one supernova to the next. According to
this generally accepted picture, solar
system iridium is a mixture of that ele-
ment produced by all the supernovas
Fig. 12. Gamma-ray that ejected material into the gaseous
spectra of h frac- nebula that eventually condensed to
tions from acid-in-
soluble residues of ir- form the sun and its planets. A particular
radiated boundary supernova would produce Ir with an iso-
layer clay samples topic ratio that might differ from that of
from Gubbio. (a) solar system material by as much as a
Sample had been
spiked with '"h and
factor of 2 (52).
' 3 H P ~containing rela- We therefore compared the isotopic
tively small amounts ratio of Ir from the C-T boundary clay
of 2:%!lpU 240h, and
with that of ordinary Ir, using NAA. This
242F'u. Dashed lines is a new technique (23), which we devel-
show expected ener-
gies and abundances oped because of the extreme difficulty of
Expected Expected of "Tu and equil- determining Ir isotope ratios by mass
posltlon o f ibrated daughter rad- spectrometry. In our earlier analytical
Am K a l iations normalized to work we used only the 74-day 1!'21r,made
Z the 327.2-keV gam-
ma ray of '"F'u (not
from ""Ir by neutron capture. But in this
50
shown). (b) Sample new work we also measured the 18-hour
had been spiked with IY41rmade from the heavier Ir isotope,
'3HFu containing rela- and extensive chemical separations be-
tively small amounts fore and after the neutron irradiations
of ""Yu, and
" 2 h . NO 2 " " P ~was were necessary. Figure 13 contrasts a
detected. typical gamma-ray spectrum of the kind
G a m m a - r a y e n e r g y (keV) used in the isotopic ratio measurement
with one used in an Ir abundance deter-
mination. This comparison demonstrates
the need for chemical purification of the
a G a m m a - r a y spectrum iridium fraction as well as the lack of ma-
5 ' r~ of i r r a d i a t e d jor interfering radiations.
a c i d - i n s o l u b l e fraction
from T / C b o u n d a r y region The final result is that the isotopic ra-
If9 Z a : dec?I
980 m l n c o u nPt a \
limestone tio of the boundary Ir difers by only
0.03 +- 0.65 percent (mean + 1 standard
deviation) from that of the standard.
From this, we conclude that the l!'llr/"'"Ir
Fig. 13. (a) Gamma-
ray spectrum of irra- ratio in the boundary layer and the stan-
diated acid-insoluble dard do not differ significantly by more
residue from bound- than 1.5 percent. Therefore the anoma-
ary layer clay at Gub- lous Ir is very likely of solar system ori-
bio without chemistry
gin, and did not come from a supernova
before or after irradia-
tion. (b) Same as or other source outside the solar system
- - 1-
above with chemistry (53)-for example, during passage of the
7
I
- -7
1-
-, - -
before and after irra- earth through the galactic arms. [In a
m
E G a m m a r a y spectrum of diation used in isotop- very recent paper, Napier and Clube
5
CI
I s OoO - chemically p u r l f l e d ic ratio determina-
suggest that catastrophic events could
~ r r a d ~ a t e Idr f r a c t ~ o n tions. Counting peri-
f r o m T / C b o u n d a r y reglon clay ]=ad decay ods, decay periods, arise from the latter (54).]
p 3 mln count and chemical yields
10 0110 are different for the
two spectra.
The Asteroid Impact Hypothesis
and then in the ocean, which would alter Only three craters 100 km or more in di- Marchand, E. Helley, private communication.
the composition. The enhancements of ameter are known (62). Two of these J. H. Crocket and H. Y. Kuo, Geochim. Cosmo-
metals having water-insoluble sulfides in (Sudbury and Vredefort) are of Pre- These are briefly discussed in L. W. Alvarez,
the Danish C-T boundary compared to cambrian age. For the other, Popigay W. Alvarez, F. Asaro, H. V. Michel, Univ. Cal-
i f . Lawrence Berkeley Lab. Rep. LBL-%(It3
the Italian might be related to an anaero- Crater in Siberia, a stratigraphic age of (1979).
A description of the NAA techniques is given in
bic environment during deposition of the Late Cretaceous to Qua1ernary and a po- Alvarez et a!. (231, appendix 11; I. Perlman and
former and an aerobic one for the latter. tassium-argon date of 28.8 million years F. Asaro, in Science and Archaeology, R. H.
Brill, Ed. (MIT Press, Cambridge, Mass., 1971).
Hydrogen sulfide can be produced by (no further details given) have been re- r. 1x3
n
&--.
bacteria in oxygen-deficient waters, and ported (72, 73). 'Thus, Popigay Crater is 25. These limestones belong to the Umbrian se-
quence, of Jurassic to Miocene age, which has
this would precipitate those metals if probably too young, and at 100-km-di- been described in V. Bortolotti, P. Passerini. M.
they were available. This would not, ameter probably also too small, to be the Sagri. G. Sestini, Sediment. Geol. 4, 341 (1970);
A. Jacobacci, E. Centamore, M. Chiocchini, N.
however, explain the striking depletion C-T impact site. There is about a 213 Malferrari, G. Martelli, A. Micarelli, Note Es-
of some trace elements in the Danish probability that the object fell in the plicativr Carta Geologica d'ltalia (1:50,000).
Foglio 190: "Cagli" (Rome, 1974).
boundary or its very high Ir abundance. ocean. Since the probable diameter of 26. H. P. Luterbacher and I. Premoli Silva, Riv.
Ital. Paleontol. Stratigr. 68, 253 (1%2); I. Pre-
If chondritic Ir with an abundance of the object, 10 km, is twice the typical moli Silva, L. Paggi, S. Monechi, Mem. Soc.
- 500 ppb were diluted 60-fold with oceanic depth, a crater would be pro- Geol. Ital. 15, 21 (1976).
27. S. Monechi, in (6), vol. 2, p. 164.
crustal material, the Ir abundance should duced on the ocean bottom and pulver- 28. D. V. Kent, Geology 5, 769 (1977); M. A. Ar-
be - 8 ppb rather than the 65 ppb ob- ized rock could be ejected. However, in thur, thesis, Princeton University (1979).
29. 0. Renz, Eclogue Geol. Helv. 29, 1 (1936); Serv.
served. Possible solutions to these diffi- this event we are unlikely to find the cra- Ceol. Ital. Mem. Descr. Carta Ceol. Ital. 29, 1
culties may arise when better estimates ter, since bathymetric information is not (1936).
30. M. A. Arthur and A. G. Fischer, Geol. Soc. Am.
of the extent of mixing of asteroidal and sufficiently detailed and since a sub- Brtll. 88, 367 (1977); 1. Premoli Silva, ihid., p.
terrestrial mater~alin the atmosphere are stantial portion of the pre-Tertiary ocean 371; W. Lowrie and W. Alvarez, ibid., p. 374;
W. M. Roggenthen and G. Napoleone, ibid., p.
made, and when the boundary layer has been subducted. 378; W. Alvarez, M. A. Arthur, A. G. Fischer,
W. Lowrie, G. Napoleone, I. Premoli Silva, W.
chemistry is studied at additional loca- M. Roggenthen,ibid., p. 383: W. Lowrie and W.
References and Notes
tions and a better understanding of the Alvarez, Ceophys. J. R . Astron. Soc. 51, 561
1. D. A. Russell, Geol. Assoc. Can. Spec. Rep. I3 (1977); W. Alvarez and W. Lowrie, ibid. 55, 1
marine chemistry is achieved. (19751, p. 119. (1978).
2. --, in (3,p. 1I. 31. Locations of the sections studied are: (i) Bot-
3. M. B. Cita and I. Premoli Silva, Riv. Ital. Pa- taccione Gorge at Gubbio: 43"21.9'N, 12"35.0'E
Ieontol. Stratigr. Mem. 14 (1974), p. 193. (0°7.9' east of Rome); (ii) Contessa Valley, 3 km
Implications 4. D. A. Russell. Annu. Rev. Earth Planet. Sci. 7 . northwest of Gubbio: 43"22.6'N, 12"33.7'E
163 (1979). (O"6.6' east of Rome); (iii) Petriccio suspension
5. K-TEC group (P. Beland et a l . ) , Cretaceous- bridge, 2.3 km west-southwest of Acqualagna:
Among the many implications of the Tertiary E.xtinctions and Possible Terrestrial 43"36.7'N, 1Z038.7'E (O"11.6' east of Rome); (iv)
and Extratrrrr.strial Cau.srs (Proceedings of Acqualagna, road cut 0.8 km southeast of town:
asteroid impact hypothesis, if it is cor- Workshop, National Museum of Natural Sci- 43"36.7'N, 12"40.8'E (0°13.7' east of Rome); and
ences, Ottawa, 16 and 17 Nov. 1976). (v) Gorgo a Cerbara: 43"36.I1N, 12"33.6'E
rect, two stand out prominently. First, if 6. T. Birkelund and R. G. Bromley, Eds., C re- (0'6.5' east of Rome). We thank E. Sannipoli.
the C-T extinctions were caused by an taceorts-Tertiary Boundary Events, vol. 1, The W. S. Leith, and S. Marshak for help in sam-
Maastrichtian and Danian of Denmark (Sym- pling these sections.
impact event, the same could be true of posium, University of Copenhagen, Copenha- 32. J. H. Crocket, J. D. McDougall, R. C. Harriss,
the earlier major extinctions as well. gen. 1979); W. K. Christiansen and T. Birke- Grorhim. Cosmochim. Actcr 37, 2547 (1973).
lund, Eds., ihid., vol. 2, Pri>cc:edings. 33. Location: 5So16.7'N, 12"26.5'E. We thank I.
There have been five such extinctions 7. H. Tappan, Palaeogeogr. Palaeorlimcrtol. Bank and S. Gregersen for taking W.A. to this
since the end of the Precambrian, 570 Palaeoecol. 4, 187 (1968); T. R. Worsley, Na- locality.
ture (London) 230, 318 (1971); W. T. Holser, 34. A. Rosenkrantz and H. W. Rasmussen. Guide to
million years ago, which matches well ibid. 267, 403 (1977); D. M. McLean, Science excursion.^ A42 and C37 (21st International
6 JUNE 1980
Geological Congress, Copenhagen, 1960). part ing in November 1979 [W. Alvarez, L. W. Alva- 70. W. Alvarez and D. W. Vann. Geolucv 7. 66
1, pp. 1-17. rez, F. Asaro, H. V. Michel, Eos 60,734 (1979); (1979); J . E. Fassett, ihid., p. 69; S. C: ~ u c a s
35. F. Surlyk, in (6). vol. 1, p. 164. Geol. Soc. Am. Abstr. Programs 11,350 (197911. and J . K . Rigby, Jr., ihid., p. 323.
36. C. Heinberg, in (6), vol. 1, p. 58. 54. r S. V. M. Clube. NatureILon-
W. M. N a ~ i e and 71. D. A. Russell. Enisodes 1979 No. 4 (1979). D. 21.
37. H. W. Rasmussen, in (6), vol. 1, p. 65; P. Grave- don) 282, '455 (1979). 72. V . L. ~ a s a ~ t i s ,V. .~Mikhaylov,
. T. V. Skliva-
sen, in (6), vol. l , p. 72; U. Asgaard, in ( 6 ) . vol. 55. H. C. Urey, ihid. 242, 32 (1973). novskaya, Sov. Geol. N o . 6 (1971), pp. 143-147:
1, p. 74. 56. E. J. h i k . Ir. Astron. .I. 5 (No. 1). 34 (1958). translated in Geol. Rev. 14, 327 (1972).
38. E. Hakansson and E. Thomsen, in (6). vol. I , p. 57. E. M. Shoemaker, J . G. Williams, E. F. Helin, 73. V . L . Masaytis, Sov. Geol. No. 11 (1975), pp.
,".
7Q R. F. Wolfe, in Asteroids, T. Gehrels, Ed. 52-64; translated in Int. Geol. Rev. 18, 1249
39. S. Floris, in (6), vol. 1, p. 92. (Univ. of Arizona Press, Tucson, 1979), pp. 253- (1976).
40. 1. Bang, in (6), vol. 1, p. 108. 282. 74. It will be obvious to anyone reading this article
41. K. Perch-Nielsen, in (6), vol. 1, p. 115. 58. E.- J. iipik, Adv. Astron. Astrophys. 2, 220 that we have benefited enormously from conver-
42. Soft x-ray fluorescence measurements for major (1%3); ibid. 4, 302 (1964); ihid. 8, 108 (1971). sations and correspondence with many friends
element determinations were made by S. Flex- These review articles give references to Opik's and colleagues throughout the scientific commu-
ser and M. Sturz of Lawrence Berkeley Labora- extensive bibliography on meteorites, Apollo nity. We would particularly like to acknowledge
tory. objects, and asteroids. the help we have received from E. Anders, J. R.
43. Hard x-ray fluorescence measurements for trace 59. C. R. Chapman, J. G. Williams, W. K . Hart- Arnold, M. A. Arthur, A. Buttington, I. S . E.
element determinations were made by R. D. mann, Annu. Rev. Astron. Astrophys. 16, 33 Carmichael, G. Curtis, P. Eberhard, S. Gartner,
Giauque of Lawrence Berkeley Laboratory. (1978). R. L. Garwin, R. A. F. Grieve, E. K. Hyde, W.
44. F. G. Walton Smith, Ed. CRCHandhook ($Ma- 60. G. W. Wetherill, Sci. Am. 240 (No. 3), 54 (1979). Lowrie, C. McKee. M. C. Michel (who was re-
rine Science (CRC Press. Cleveland, 1974), vol. 61. E. M. Shoemaker, personal communication. sponsible for the mass spectrometric measure-
1, p. 11. 62. K. A. F. Grieve and P. B. Robertson. Irartts 38. ments), J. Neil, B. M. Oliver, C. Orth, B. Par-
45. H. A. Wollenberg et a l . , Univ. Colif. L,awrence 212 (1979). doe, I. Perlman, D. A. Russell, A. M. Sessler,
Berkeley Lab. Rep. LRL-7092. revised 1980. 63. R. A. F. G ~ i e v e personal
, communication. and E. Shoemaker. One of us (W.A.) thanks the
46. Enryclopaedia Britannica (Benton, Chicago, 64. G. J. Svmons. Ed.. The Eruption o f Krcrkotocr National Science Foundation for support, the
ed. 15, 1974), vol. 6, p. 702. ond subsequent Phenomena i ~ e ~ oofr the t Kra- other three authors thank the Department of En-
47. K. K. Turekian, Oreons (Prentice-Hall, Engle- katoa Committee of the Royal Society, Harri- ergy for support, and one of us (L.W.A.) thanks
wood Cliffs, N.J., 1976), p. 122. son, London, 1888). the National Aeronautics and Space Administra-
48. J. H. Crocket, Can. Mineral. 17, 391 (1979); J. 65. I. U. Olson and I. Karlen, Am. J. Sci. Radio- tion for support. The x-ray fluorescence mea-
R. Ross and R. Keays, ibid., p. 417. carbon Sunnl. 7 (1965). w. 331: T . A. Rafter and surements of trace elements Fe and Ti by R. D.
> , .
49. 1. S. Shklovskv. Stcnernovoe (Wilev.
, * . New York. B. J. o ' B & ~ , £';or. 8 t h I n f . Conf. Rcrdiocarhon Giauque and of major elements by S. Flexser
1968), p. 377. Dating 1, 241 (1972). and M. Sturz were most appreciated. We appre-
50. D. D. Clayton, Principles of Stellerr Evoltction 66. U. Krihenbiihl, Geochim. Cosmuchim. Acto ciate the assistance of D . Jackson and C.
and Nucleosvnrhesis (McGraw-Hill. New York, 37, 1353 (1973). Nguyen in the sample preparation procedures.
1%8), pp. 546-606. 67. B. Mason, Space Sci. Rev. 1. 621 (1962-1963). We are grateful to T. Lim and the staff of the
51. D. N. Schramm.Anntc. Rev. Asfron. Astruohvs.
12, 389 (1974).
. - 68. R. F. Butler, E. H. Lindsay, L. L . Jacobs, N.
M. Johnson, Noture (London) 267, 318 (1977);
Berkeley Research Reactor for many neutron
irradiations used in this work. We also ap-
52. C. F. McKee, personal communication. E . H. Lindsay, L. L. Jacobs, R. F. Butler, Geol- preciate the efforts of G. Pefley and the staff.
53. These observations were reported at the Ameri- ogy 6,425 (1978). of the Livermore Pool Type Reactor for the
can Geophysical Union meeting in May 1979 69. E. H. Lindsay, R. F. Butler, N. M. Johnson, in irradiations used for the Ir isotopic ratio
and at the Geological Society of America meet- preparation. measurements.