Determination of sulfite and manganese in sediments from the K/T boundary

The solid-state-physics technique of electron spin resonance (ESR) has been employed in an exploratory study of marine limestones and impact-related deposits from Cretaceous-Tertiary (KT) boundary sites including Spain (Sopelana and Caravaca), New Jersey (Bass River), the U.S. Atlantic continental margin (Blake Nose, ODP Leg 171B/1049/A), and several locations in Belize and southern Mexico within -600 km of the Chicxulub crater. The ESR spectra of SO3(1-) (a radiation-induced point defect involving a sulfite ion substitutional for CO3(2-) which has trapped a positive charge) and Mn(2+) in calcite were singled out for analysis because they are unambiguously interpretable and relatively easy to record. ESR signal strengths of calcite-related SO3(1-) and Mn(2+) have been studied as functions of stratigraphic position in whole-rock samples across the KT boundary at Sopelana, Caravaca, and Blake Nose. At all three of these sites, anomalies in SO3(1-) and/or Mn(2+) intensities are noted at the KT boundary relative to the corresponding background levels in the rocks above and below. At Caravaca, the SO3(1-) background itself is found to be lower by a factor of 2.7 in the first 30,000 years of the Tertiary relative to its steady-state value in the last 15,000 years of the Cretaceous, indicating either an abrupt and quasi-permanent change in ocean chemistry (or temperature) or extinction of the marine biota primarily responsible for fixing sulfite in the late Cretaceous limestones. An exponential decrease in the Mn(2+) concentration per unit mass calcite, [Mn(2+)], as the KT boundary at Caravaca is approached from below (1/e characteristic length =1.4 cm) is interpreted as a result of post-impact leaching of the seafloor. Absolute ESR quantitative analyses of proximal impact deposits from Belize and southern Mexico group naturally into three distinct fields in a twodimensional [SO3(1-)]-versus-[Mn(2+)] scatter plot. These fields contain (I) limestone ejecta clasts, (II) accretionary lapilli, and (III) a variety of SO3(1-) -depleted/Mn(2+) enriched impact deposits. Data for the investigated non-impact-related Cretaceous and Tertiary marine limestones (Spain and Blake Nose) fall outside of these three fields. With reference to thes enon-impact deposits, fields I, II, and III can be respectively characterized as Mn(2+) -depleted, SO3(1-) -enhanced, and SO3(1-) -depleted. It is proposed that (1) field I represents calcites from the Yucatin Platform, and that the Mn(2+) -depleted signature can be used as an indicator of primary Chicxulub ejecta in deep marine environments and (2) field II represents calcites that include a component formed in the vapor plume, either from condensation in the presence of CO2/SO3(1-) -rich vapors, or reactions between CaO and CO2/SO3 rich vapors, and that this SO3(1-) -enhanced signature can be used as an indicator of impact vapor plume deposits. Given these two propositions, the ESR data for the Blake Nose deposits are ascribed to the presence of basal coarse calcitic Chicxulub ejecta clasts, while the finer components that are increasingly represented toward the top are interpreted to contain high- SO3(1-) calcite from the vapor plume. The apparently-undisturbed Bass River deposit may contain even higher concentrations of vapor-plume calcite. None of the three components included in field III appear to be represented at distal, deep marine KT-boundary sites; this field may include several types of impact-related deposits of diverse origins and diagenetic histories.

Iridium contents and microprobe analyses of DSDP Leg 77 samples

Restudy of Deep Sea Drilling Project Sites 536 and 540 in the southeast Gulf of Mexico gives evidence for a giant wave at Cretaceous-Tertiary boundary time. Five units are recognized: (1) Cenomanian limestone underlies a hiatus in which the five highest Cretaceous stages are missing, possibly because of catastrophic K-T erosion. (2) Pebbly mudstone, 45 m thick, represents a submarine landslide possibly of K-T age. (3) Current-bedded sandstone, more than 2.5 m thick, contains anomalous iridium, tektite glass, and shocked quartz; it is interpreted as ejecta from a nearby impact crater, reworked on the deep-sea floor by the resulting tsunami. (4) A 50-cm interval of calcareous mudstone containing small Cretaceous planktic foraminifera and the Ir peak is interpreted as the silt-size fraction of the Cretaceous material suspended by the impact-generated wave. (5) Calcareous mudstone with basal Tertiary forams and the uppermost tail of the Ir anomaly overlies the disturbed interval, dating the impact and wave event as K-T boundary age. Like Beloc in Haiti and Mimbral in Mexico, Sites 536 and 540 are consistent with a large K-T age impact at the nearby Chicxulub crater.

Geochemistry of DSDP Hole 86-577B samples

THE chemical, mineralogical and isotopic characteristics of deposits at the Cretaceous/Tertiary (K/T) boundary are suggestive of a large impact event, the prime candidate (Sharpton et al., 1992, doi:10.1038/359819a0) being the Chicxulub crater in Yucatan, Mexico. Spinel-bearing spherules, which may be associated with such impacts, have been reported (Smit and Romein, 1985, doi:10.1016/0012-821X(85)90019-6) at several K/T boundary sites worldwide, but their origin is still uncertain. We have examined the spinel-bearing material recovered from K/T boundary deposits at site 577 in the Pacific Ocean (Heath et al., 1985, doi:10.2973/dsdp.proc.86.104.1985) and find two distinct populations of particles: spherules with dendritic spinel textures dispersed throughout the grains and irregularly shaped fragments with spinels essentially confined to the rim. The morphology and composition of the particles are characteristic of melted and partially melted meteoritic ablation debris, but their location is difficult to reconcile with an impact on the Yucatan peninsula, some 10,000 km away. We suggest instead that the spinel-bearing particles at site 577 are derived from the impact of a 2-km asteroid in the Pacific Ocean, and that several accretionary events of this type are required to explain the global distribution of spinel-bearing spherules at the K/T boundary.

Analyses of shocked quartz from the K-P boundary

The precise cause and timing of the Cretaceous-Paleocene (K-P) mass extinction 65 Ma ago remains a matter of debate. Many advocate that the extinction was caused by a meteorite impact at Chicxulub, Mexico, and a number of potential kill-mechanisms have been proposed for this. Although we now have good constraints on the size of this impact and chemistry of the target rocks, estimates of its environmental consequences are hindered by a lack of knowledge about the obliquity of this impact. An oblique impact is likely to have been far more catastrophic than a sub-vertical one, because greater volumes of volatiles would have been released into the atmosphere. The principal purpose of this study was to characterize shocked quartz within distal K-P ejecta, to investigate whether the quartz distribution carried a signature of the direction and angle of impact. Our analyses show that the total number, maximum and average size of shocked quartz grains all decrease gradually with paleodistance from Chicxulub. We do not find particularly high abundances in Pacific sites relative to Atlantic and European sites, as has been previously reported, and the size-distribution around Chicxulub is relatively symmetric. Ejecta samples at any one site display features that are indicative of a wide range of shock pressures, but the mean degree of shock increases with paleodistance. These shock- and size-distributions are both consistent with the K-P layer having been formed by a single impact at Chicxulub. One site in the South Atlantic contains quartz indicating an anomalously high average shock degree, that may be indicative of an oblique impact with an uprange direction to the southeast +/- 45°. The apparent continuous coverage of proximal ejecta in this quadrant of the crater, however, suggests a relatively high impact angle of >45°. We conclude that some of the more extreme predictions of the environmental consequences of a low-angle impact at Chicxulub are probably not applicable.