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.

(Table 2) Concentrations of dissolved aluminum in interstitial water from sediments of the Indian Ocean

Results are presented of application of laser stepwise photoionization of atoms in combination with thermal atomization of matter in vacuum for direct determination of aluminum dissolved in sea and interstitial waters. Dry residue from evaporation of 40 ?l sea water was atomized in a crucible at 1800°C, and aluminum atoms in the beam thus formed were energized into Rydberg state in two steps by two tunable dye laser beams; the atoms were then ionized by an electric pulse and resulting ions were recorded by secondary emission electron multiplier (ion detector). Ionic signal dependence on sample vaporization time was studied. The procedure is suggested for separating out a selective signal in a single measurement. Dissolved aluminum concentrations in interstitial waters of the Indian Ocean and in waters of the river-sea zone were determined using preliminarily plotted calibration characteristics for aluminum solutions in deionized and sea waters. The minimum detectable Al concentration in seawater was 1 ?g/l that corresponds to 40 pg of Al in a sample.

Age determination of sediment cores close to the Strait of Gibralta

A suit of sediment cores close to and south of the Strait of Gibraltar (12°-36°N, 500-2800 m water depth) were analyzed for stable isotopes in epibenthic foraminifers Cibicidoides wuellerstorfi and Planulina ariminensis. During peak glacial times, the data exhibit higher delta13C values of up to 1.6 per mil at intermediate depths near the Strait of Gibraltar (36°N). The values decrease to the south as evidenced by our data, but also to the north as revealed by data of intermediate depth cores north of 38°N (in Duplessy et al. (1987)). Thus, the distribution pattern of delta13C provides crucial evidence for an increased influence of nutrient depleted Mediterranean Outflow Water (MOW) on the glacial northeast Atlantic hydrography. During oxygen isotope Terminations I and II, the meridional carbon isotope gradient indicates a significantly decreased but still active MOW. As deduced from the delta18O fluctuations, the temperatures of the MOW in the Atlantic were lower during glacial times by as much as 5°C. During glacial times and during Termination I the maximum delta13C values of the MOW correlate with minimum values of the North Atlantic Deep Water (NADW) and vice versa. This inverse response to climatic change of the carbon isotope signals of both water masses indicates, that the supply of saline MOW to the north Atlantic may be less important for the formation of NADW than previously assumed.

Determination of ages and fossil Coleoptera fauna from eight sites in the London region

These data sets report the fossil beetle assemblages identified from the Mesolithic to Late Bronze Age at eight sites in the London region. All but one of the study sites are within 2 km of the modern course of the Thames. The sites produced 128 faunal assemblages that yielded 218 identified species in 41 families of Coleoptera (beetles).  Beetle faunas of Mesolithic age indicate extensive wetlands near the Thames, bordered by rich deciduous woodlands. The proportion of woodland species declined in the Neolithic, apparently because of the expansion of wetlands, rather than because of human activities. The Early Bronze Age faunas contained a greater proportion of coniferous woodland and aquatic (standing water) species. An increase in the dung beetle fauna indicates the presence of sheep, cattle and horses, and various beetles associated with crop lands demonstrate the local rise of agriculture, albeit several centuries after the beginnings of farming in other regions of Britain. Late Bronze Age faunas show the continued development of agriculture and animal husbandry along the lower Thames. About 33% of the total identified beetle fauna from the London area sites have limited modern distributions or are extinct in the U.K. Some of these species are associated with the dead wood found in primeval forests; others are wetland species whose habitat has been severely reduced in recent centuries. The third group is stream-dwelling beetles that require clean, clear waters and river bottoms.

Stable isotope record and age determination of ODP Site 121-758 in the northeastern Indian Ocean

Numerous studies have shown that delta18O records from benthic and planktonic foraminifera, primarily a proxy of global ice volume variations, reflect Milankovitch periodicities. To study climatic response to orbital forcing at Ocean Drilling Program site 758, we have generated continuous delta18O and delta13C records from a single benthic foraminiferal species Cibicides wuellerstorfi for the last 3.6 m.y. and extended the planktonic foraminiferal isotope records of Farrell and Janecek (1991, doi:10.2973/odp.proc.sr.121.124.1991) (0-2.5 Ma, based on Globigerinoides sacculifer) to 3.6 Ma (Chen, 1994). We then constructed an age model by matching, correlating and tuning the benthic delta18O record to a model simulation of ice volume (Imbrie and Imbrie, 1980, doi:10.1126/science.207.4434.943). The filtered 41- and 23-kyr signals based on the resultant astronomically tuned age model are highly correlated to obliquity (r=0.83) and precession (r=0.75), respectively. Although derived with methodology different from Shackleton et al. (1990) and Hilgen (1991, doi:10.1016/0012-821X(91)90206-W, 1991, doi:10.1016/0012-821X(91)90082-S), our results generally agree with their published astronomical timescales for the time interval from 0 to 3.0 Ma, providing additional support for the newly emerging chronology based on orbital tuning. Slight discrepancies exist in the time interval from 3.0 to 3.6 Ma, suggesting several possibilities, including differences in the approaches of orbital tuning and the relatively low amplitude of delta18O variations in our record. However, even if the discrepancies are due to the relatively low amplitude of the isotope signals in our record at 3.0-3.6 Ma, our resultant timescale as a whole does not adversely affect our evaluation of the paleoclimatology and paleoceanography of the Indian Ocean, such as the evolution of the 100-, 41- and 23-kyr cycles, and variation of global ice volume and deepwater temperature during the past 3.6 m.y.

Determination of millennial-scale climate variability based on alkenones in the western Atlantic Ocean

High-resolution records of alkenone-derived sea surface temperatures and elemental Ti/Ca ratios from a sediment core retrieved off northeastern Brazil (4° S) reveal short-term climate variability throughout the past 63,000 a. Large pulses of terrigenous sediment discharge, caused by increased precipitation in the Brazilian hinterland, coincide with Heinrich events and the Younger Dryas period. Terrigenous input maxima related to Heinrich events H6-H2 are characterized by rapid cooling of surface water ranging between 0.5 and 2° C. This signature is consistent with a climate model experiment where a reduction of the Atlantic meridional overturning circulation (AMOC) and related North Atlantic cooling causes intensification of NE trade winds and a southward movement of the Intertropical Convergence Zone, resulting in enhanced precipitation off northeastern Brazil. During deglaciation the surface temperature evolution at the core site predominantly followed the Antarctic warming trend, including a cooling, prior to the Younger Dryas period. An abrupt temperature rise preceding the onset of the Bølling/Allerød transition agrees with model experiments suggesting a Southern Hemisphere origin for the abrupt resumption of the AMOC during deglaciation caused by Southern Ocean warming and associated with northward flow anomalies of the South Atlantic western boundary current.

Equivalent dose, dose rate and age determination of cobble surfaces in the Antarctic

Most current methods of reconstructing past sea levels within Antarctica rely on radiocarbon dating. However, radiocarbon dating is limited by the availability of material for dating and problems inherent with radiocarbon reservoirs in Antarctic marine systems. Here we report on the success of a new approach to dating raised beach deposits in Antarctica for the purpose of reconstructing past sea levels. This new approach is the use of optically stimulated luminescence (OSL) on quartz-grains obtained from the underside of cobbles within raised beaches and boulder pavements. We obtained eight OSL dates from three sites along the shores of Maxwell Bay in the South Shetland Islands of the Antarctic Peninsula. These dates are internally consistent and fit well with previously published radiocarbon ages obtained from the same deposits. In addition, when the technique was applied to a modern beach, it resulted in an age of zero. Our results suggest that this method will provide a valuable tool in the reconstruction of past sea levels in Antarctica and other coarse-grained beach deposits across the globe.

Determination of hydrocarbon gases in mud volcanoes in the Sorokin Trough

Hydrocarbon gases were determined in sediments from three mud volcanoes in the Sorokin Trough. In comparison to a reference station outside the mud volcano area, the deposits are characterized by an enrichment of high-molecular hydrocarbons (C2-C4), an absence of unsaturated homologues, a predominance of iso-butane in comparison with n-butane, and the presence of gas hydrate. The molecular composition of the hydrocarbon gases suggests their deep sources and thermogenic origin. In the pelagic sediments at the reference station, the methane concentration is relatively low (up to 49 ml/l); maximum concentrations are reached in deposits of the Dvurechenskii mud volcano (up to 400 ml/l). It was the first time that gas hydrate was sampled at the Dvurechenskii mud volcano. The gas extracted by dissociation of hydrate samples was dominated by methane (99.5%) with low amounts of ethane and propane (less than 0.5%). The isotopic composition of the methane varies between -62 and -66 per mill PDB in d13C, and between -185 and -209 per mill SMOW in dD, indicating a mainly biogenic origin with an admixture of thermogenic gas.

Age determination of Pacific Ocean sediments

Benthic and planktonic 14C ages are presented for the last glacial termination from marine sediment core VM21-30 from 617 m in the eastern equatorial Pacific. The benthic-planktonic 14C age differences in the core increased to more than 6000 years between Heinrich 1 time and the end of the Younger Dryas period. Several replicated 14C ages on different benthic and planktonic species from the same samples within the deglacial section of the core indicate a minimal amount of bioturbation. Scanning electron microscopy reveals no evidence of calcite alteration or contamination. The oxygen isotope stratigraphy of planktonic and benthic foraminifera does not indicate anomalously old (glacial age) values, and there is no evidence of a large negative stable carbon isotope excursion in benthic foraminifera that would indicate input of old carbon from dissociated methane. It appears, therefore, that the benthic 14C excursion in this core is not an artifact of diagenesis, bioturbation, or a pulse of methane. A benthic D14C stratigraphy reconstructed from the 14C ages from the deglacial section of VM21-30 appears to match that of Baja margin core MV99-MC19/GC31/PC08 (705 m), but the magnitude of the low-14C excursion is much larger in the VM21-30 record. This would seem to imply that the VM21-30 core was closer to the source of 14C-depleted waters during the deglaciation, but the source of this CO2 remains elusive.

(Table 2) Age determination of Aegean Sea sediments

The modern Aegean Sea is an important source of deep water for the eastern Mediterranean. Its contribution to deep water ventilation is known to fluctuate in response to climatic variation on a decadal timescale. This study uses marine micropalaeontological and stable isotope data to investigate longer-term variability during the late glacial and Holocene, in particular that associated with the deposition of the early Holocene dysoxic/anoxic sapropel S1. Concentrating on the onset of sapropel-forming conditions, we identify the start of 'seasonal' stratification and highlight a lag in d18O response of the planktonic foraminifer N. pachyderma to termination T1b as identified in the d18O record of G. ruber. By use of a simple model we determine that this offset cannot be a function of bioturbation effects. The lag is of the order of 1 kyr and suggests that isolation of intermediate/deep water preceded the start of sapropel formation by up to 1.5 kyr. Using this discovery, we propose an explanation for the major unresolved problem in sapropel studies, namely, the source of nutrient supply required for export productivity to reach levels needed for sustained sapropel deposition. We suggest that nutrients had been accumulating in a stagnant basin for 1-1.5 kyr and that these accumulated resources were utilized during the deposition of S1. In addition, we provide a first quantitative estimate of the diffusive (1/e) mixing timescale for the eastern Mediterranean in its "stratified" sapropel mode, which is of the order of 450 years.