Kadesh-Barnea : its importance and probable site, with the story of a hunt for it, including studies of the route of the exodus and the southern boundary of the Holy Land

by H. Clay Trumbull

Chamber evaluation of a personal organic vapor dosimeter at ppb concentrations of VOCs, varying temperatures and humidities with 24 -hour exposures

An exposure system was constructed to evaluate the performance of a personal organic vapor dosimeter (3520 OVM) at ppb concentrations of nine selected target volatile organic compounds (VOCs). These concentration levels are generally encountered in community air environments, both indoor and outdoor. It was demonstrated that the chamber system could provide closely-controlled conditions of VOC concentrations, temperature and relative humidity (RH) required for the experiments. The target experimental conditions included combinations of three VOC concentrations (10, 20 and 200 $\rm\mu g/m\sp3),$ three temperatures (10, 25 and 40$\sp\circ$C) and three RHs (12, 50 and 90% RH), leading to a total of 27 exposure conditions. No backgrounds of target VOCs were found in the exposure chamber system. In the exposure chamber, the variation of the temperature was controlled within $\pm$1$\sp\circ$C, and the variation of RH was controlled within $\pm$1.5% at 12% RH, $\pm$2% at 50% RH and $\pm$3% at 90% RH. High-emission permeation tubes were utilized to generate the target VOCs. Various patterns of the permeation rates were observed over time. The lifetimes and permeation rates of the tubes differed by compound, length of the tube and manufacturer. By carefully selecting the source and length of the tubes, and closely monitoring tube weight loss over time, the permeation tubes can be used for delivering low and stable concentrations of VOCs during multiple days.^ The results of this study indicate that the performance of the 3520 OVM is compound-specific and depends on concentration, temperature and humidity. With the exception of 1,3-butadiene under most conditions, and styrene and methylene chloride at very high relative humidities, recoveries were generally within $\pm$25% of theory, indicating that the 3520 OVM can be effectively used over the range of concentrations and environmental conditions tested with a 24-hour sampling period. Increasing humidities resulted in increasing negative bias from full recovery. Reverse diffusion conducted at 200 $\rm\mu g/m\sp3$ and five temperature/humidity combinations indicated severe diffusion losses only for 1,3-butadiene, methylene chloride and styrene under increased humidity. Overall, the results of this study do not support the need to employ diffusion samplers with backup sections for the exposure conditions tested. ^

The Cenomanian/Turronian Boundary Event at ODP Hole 103-641A

Drilling at ODP Site 641 (on the western margin of Galicia Bank, off northwestern Spain) revealed a thin, but pronounced, interval of black shale and gray-green claystone. Our high-resolution study combines the sedimentology, micropaleontology (palynomorphs and others), organic and inorganic geochemistry, and isotopic values of this layer to demonstrate the distinct nature of the sediment and prove that the sequence represents the local sedimentary expression of the global Cenomanian/Turonian Oceanic Anoxic Event (OAE) of Schlanger and Jenkyns (1976), Arthur and Schlanger (1979), and Jenkyns (1980), also called the Cenomanian/Turonian Boundary Event (CTBE). The most striking evidence is that the strong positive d13C excursion characterizing the CTBE sequences in shallow areas can be traced into a pronounced deep-sea expression, thus providing a good stratigraphic marker for the CTBE in various paleosettings. The isotopic excursion at Site 641 coincides with an extremely enriched trace metal content, with values that were previously unknown for the Cretaceous Atlantic. Similar to other CTBE occurrences, the organic carbon content is high (up to 11%) and the organic matter is of dominantly marine origin (kerogen type II). The bulk mineralogy of the CTBE sediments does not differ significantly from the general trend of Cretaceous North Atlantic sediments (dominance of smectite and zeolite with minor amounts of illite and scattered palygorskite, kaolinite, and chlorite); thus, no evidence for either increased volcanic activity nor a drastic climatic change in the borderlands was found. Results from Site 641 are compared with the CTBE section found at Site 398, DSDP Leg 47B (Vigo Seamount at the southern end of the Galicia Bank).

Chemobiostratigraphy of the Cretaceous/Paleocene boundary at ODP Hole 120-750A

An integrated biostratigraphic and stable isotope investigation was conducted on a high-latitude sequence across the Cretaceous/Paleogene (K/P) boundary recovered in Hole 750A in the southern Indian Ocean. The sequence consists of nannofossil chalk and is discontinuous across the boundary; missing is an estimated 0.3-m.y. late Maestrichtian and early Danian interval. Nonetheless, because calcareous nannofossil Zones NP1 and NP2 are well-developed, micropaleontological studies of the sequence have yielded a detailed record of Danian high-latitude microplankton evolution. In addition, stable carbon isotope analyses of planktonic and benthic foraminifer and bulk samples provide a record of late Maestrichtian and early Danian surface- and deep-water carbon isotope variations. Together, the carbon isotope and carbonate accumulation records serve as an index of regional marine net productivity across the boundary. Earliest Danian nannoplankton assemblages consisted mainly of persistent genera that were generally rare or absent in the Upper Cretaceous at Hole 750A. However, by 0.5-0.6 m.y. after the boundary, newly evolving Danian taxa became dominant. The turnover in nannofossil assemblages was accompanied by significant changes in rates of net productivity as gauged by carbon isotope distributions and carbonate accumulation rates. During the period dominated by persistent taxa, net productivity was extremely low, as reflected by the absence of vertical delta13C gradients and reduced carbonate accumulation rates. Later in the Danian, as new species evolved and flourished, vertical delta13C gradients reappeared and carbonate accumulation rates increased, signaling partial recovery of net productivity in this region. The absolute timing and magnitude of late Maestrichtian and early Danian biotic and geochemical changes in the southern Indian Ocean were similar to those recorded in other pelagic K/P boundary sequences from low- and mid-latitude Atlantic and Pacific sites, indicating that these events were ubiquitous.

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.

Magnetic properties, grain sizes, XRF Scanner Data of sediment core GeoB9307-3

Geochemical and mineralogical proxies for paleoenvironmental conditions have the underlying assumption that climate variations have an impact on terrestrial weathering conditions. Varying properties of terrigenous sediments deposited at sea are therefore often interpreted in terms of paleoenvironmental change. Also in gravity core GeoB9307-3 (18° 33.99' S, 37° 22.89' E), located off the Zambezi River, environmental changes during Heinrich Stadial 1 (HS 1) and the Younger Dryas (YD) are accompanied by changing properties of the terrigenous sediment fraction. Our study focuses on the relationship of variability in the hydrological system and changes in the magnetic properties, major element geochemistry and granulometry of the sediments. We propose that changes in bulk sedimentary properties concur with environmental change, although not as a direct response of climate driven pedogenic processes. Spatial varying rainfall intensities on a sub-basin scale modify sediment export from different parts of the Zambezi River basin. During humid phases, such as HS 1 and the YD, sediment was mainly exported from the coastal areas, while during more arid phases sediments mirror the hinterland soil and lithological properties and are likely derived from the northern Shire sub-basin. We propose that a de-coupling of sedimentological and organic signals with variable discharge and erosional activity can occur.

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.

Distribution of benthos in late Quaternary turbidite layers of sediment cores from the North-West African continental margin

The CaCO3-contents and the fractions > 40 µm have been analysed from 5 kastenloten, one piston core and two kastengreifer taken between Senegal and Cape Verde Islands. Numerous benthonic and planktonic organisms and different terrigenous components have been distinguished. The four cores off Senegal reach middle Wuerm sediments; cores GIK12329-6 and TAG72-1 reach the V-zone and core GIK12331-4 the X-zone (Eem); the two kastengreifer contain sediments of Holocene age. Correlation of the cores has been made. Holocene sedimentation rates decrease from the shallow cores (6-11 cm/1000 years) to the deep-sea (1-2 cm/1000 years). The following climatic variations could be deduced from the sediments off the Senegal: during Holocene climate was in general as today, the Senegal river transporting fine grained material to the sea. The upper Wuerm was arid with no river influence but with red dune sand transported to the continental slope. During middle Wuerm the climate was humid again. The deep-sea cores have been influenced by eolian material from arid regions during glacial and interglacial periods, indicated by relatively high "Wuestenquarz-numbers". However, during Wuerm "Wuestenquarz-numbers" are higher than during Holocene and Eem, indicating that more intensely red coloured sediment was exposed to wind activity on the continent during this period. Varying amounts of terrigenous material and CaCO3-contents indicate varying wind strengths (lower in Holocene and Eem than during Wuerm). The boundary between humid and arid Wuerm climate was at approximately 20 °N. Influence of upwelling is difficult to establish in the sediments off Senegal, because river influence, while increasing fertility also dilutes the diatoms which are typical for upwelling. High amounts of organic carbon, low plankton/benthos ratios of foraminifers and low plankton foraminifer/radiolarian ratios in Holocene sections might be interpreted as influenced by upwelling. Turbidites occur in cores 72 and 31 and at the Holocene/Pleistocene boundary of core GIK12329-6. Their composition indicates provenance from the continental shelf of the Cape Verde Islands for core 31 and the continental shelf and slope off Senegal for core TAG72-1. Volcanic material, rare in the normal pelagic sediment of core GIK12331-4 is more frequent in the turbidites.

Mineralogy and geochemistry of sediments of the Cretaceous/Tertiary boundary at DSDP Holes 62-465 and 62-465A

The complete Paleocene section begins with the basal Tertiary Globigerina eugubina Zone. This zone occurs at 465A-3-3, 4 cm to 465A-3-3, 144 cm and belongs to Lithologic Unit I (Site 465 report, this volume), a homogeneous, white, moderately to highly disturbed nannofossil ooze.