Decomposition studies of group 6 hexacarbonyl complexes. Part 1: Production and decomposition of Mo(CO)6 and W(CO)6

Chemical studies of superheavy elements require fast and efficient techniques, due to short half-lives and low production rates of the investigated nuclides. Here, we advocate for using a tubular flow reactor for assessing the thermal stability of the Sg carbonyl complex – Sg(CO)6. The experimental setup was tested with Mo and W carbonyl complexes, as their properties are established and supported by theoretical predictions. The suggested approach proved to be effective in discriminating between the thermal stabilities of Mo(CO)6 and W(CO)6. Therefore, an experimental verification of the predicted Sg–CO bond dissociation energy seems to be feasible by applying this technique. By investigating the effect of 104,105Mo beta-decay on the formation of 104,105Tc carbonyl complex, we estimated the lower reaction time limit for the metal carbonyl synthesis in the gas phase to be more than 100 ms. We examined further the influence of the wall material of the recoil chamber, the carrier gas composition, the gas flow rate, and the pressure on the production yield of 104Mo(CO)6, so that the future stability tests with Sg(CO)6 can be optimized accordingly.

Murine coronavirus ubiquitin-like domain is important for papain-like protease stability and viral pathogenesis

Ubiquitin-like domains (Ubls) now are recognized as common elements adjacent to viral and cellular proteases; however, their function is unclear. Structural studies of the papain-like protease (PLP) domains of coronaviruses (CoVs) revealed an adjacent Ubl domain in severe acute respiratory syndrome CoV, Middle East respiratory syndrome CoV, and the murine CoV, mouse hepatitis virus (MHV). Here, we tested the effect of altering the Ubl adjacent to PLP2 of MHV on enzyme activity, viral replication, and pathogenesis. Using deletion and substitution approaches, we identified sites within the Ubl domain, residues 785 to 787 of nonstructural protein 3, which negatively affect protease activity, and valine residues 785 and 787, which negatively affect deubiquitinating activity. Using reverse genetics, we engineered Ubl mutant viruses and found that AM2 (V787S) and AM3 (V785S) viruses replicate efficiently at 37°C but generate smaller plaques than wild-type (WT) virus, and AM2 is defective for replication at higher temperatures. To evaluate the effect of the mutation on protease activity, we purified WT and Ubl mutant PLP2 and found that the proteases exhibit similar specific activities at 25°C. However, the thermal stability of the Ubl mutant PLP2 was significantly reduced at 30°C, thereby reducing the total enzymatic activity. To determine if the destabilizing mutation affects viral pathogenesis, we infected C57BL/6 mice with WT or AM2 virus and found that the mutant virus is highly attenuated, yet it replicates sufficiently to elicit protective immunity. These studies revealed that modulating the Ubl domain adjacent to the PLP reduces protease stability and viral pathogenesis, revealing a novel approach to coronavirus attenuation. IMPORTANCE Introducing mutations into a protein or virus can have either direct or indirect effects on function. We asked if changes in the Ubl domain, a conserved domain adjacent to the coronavirus papain-like protease, altered the viral protease activity or affected viral replication or pathogenesis. Our studies using purified wild-type and Ubl mutant proteases revealed that mutations in the viral Ubl domain destabilize and inactivate the adjacent viral protease. Furthermore, we show that a CoV encoding the mutant Ubl domain is unable to replicate at high temperature or cause lethal disease in mice. Our results identify the coronavirus Ubl domain as a novel modulator of viral protease stability and reveal manipulating the Ubl domain as a new approach for attenuating coronavirus replication and pathogenesis.

Influence of Abutment Design on Stiffness, Strength, and Failure of Implant-Supported Monolithic Resin Nano Ceramic (RNC) Crowns

BACKGROUND Recent technical development allows the digital manufacturing of monolithic reconstructions with high-performance materials. For implant-supported crowns, the fixation requires an abutment design onto which the reconstruction can be bonded. PURPOSE The aim of this laboratory investigation was to analyze stiffness, strength, and failure modes of implant-supported, computer-assisted design and computer-aided manufacturing (CAD/CAM)-generated resin nano ceramic (RNC) crowns bonded to three different titanium abutments. MATERIALS AND METHODS Eighteen monolithic RNC crowns were produced and loaded in a universal testing machine under quasi-static condition according to DIN ISO 14801. With regard to the type of titanium abutment, three groups were defined: (1) prefabricated cementable standard; (2) CAD/CAM-constructed individualized; and (3) novel prefabricated bonding base. Stiffness and strength were measured and analyzed statistically with Wilcoxon rank sum test. Sections of the specimens were examined microscopically. RESULTS Stiffness demonstrated high stability for all specimens loaded in the physiological loading range with means and standard deviations of 1,579 ± 120 N/mm (group A), 1,733 ± 89 N/mm (group B), and 1,704 ± 162 N/mm (group C). Mean strength of the novel prefabricated bonding base (group C) was 17% lower than of the two other groups. Plastic deformations were detectable for all implant-abutment crown connections. CONCLUSIONS Monolithic implant crowns made of RNC seem to represent a feasible and stable prosthetic construction under laboratory testing conditions with strength higher than the average occlusal force, independent of the different abutment designs used in this investigation.

Ultrastructure and Pathoanatomy of the Rotator Cuff

The rotator cuff is a complex musculotendinous unit, which plays a major role in glenohumeral joint stability and mobilization. Tears of the rotator cuff tendon and its subsequent changes of the rotator cuff muscle are common, and the incidence increases with age. Several structures such as the muscle, tendon, and bone may contribute to the development of a tear as well as on the outcome following a rotator cuff repair. Knowledge of these structures may help to improve rotator cuff healing after rotator cuff tear. The goal of this chapter is to discuss the evidence which exists with regard to the pathophysiological changes in the muscle, tendon, and bone that lead to a rotator cuff rupture as well as the changes that occur in these structures after a tear has occurred.

IGHD II: A Novel GH-1 Gene Mutation (GH-L76P) Severely Affects GH Folding, Stability, and Secretion

CONTEXT The autosomal dominant form of GH deficiency (IGHD II) is characterized by markedly reduced GH secretion combined with low concentrations of IGF-1 leading to short stature. OBJECTIVE Structure-function analysis of a missense mutation in the GH-1 gene converting codon 76 from leucine (L) to proline (P) yielding a mutant GH-L76P peptide. DESIGN, SETTINGS, AND PATIENTS Heterozygosity for GH-L76P/wt-GH was identified in a nonconsanguineous Spanish family. The index patients, two siblings, a boy and a girl, were referred for assessment of their short stature (-3.2 and -3.8 SD). Their grandmother, father, and aunt were also carrying the same mutation and showed severe short stature; therefore, IGHD II was diagnosed. INTERVENTIONS AND RESULTS AtT-20 cells coexpressing both wt-GH and GH-L76P showed a reduced GH secretion (P < .001) after forskolin stimulation when compared with the cells expressing only wt-GH. In silico mutagenesis and molecular dynamics simulations presented alterations of correct folding and mutant stability compared with wt-GH. Therefore, further structural analysis of the GH-L76P mutant was performed using expressed and purified proteins in Escherichia coli by thermofluor assay and fast degradation proteolysis assay. Both assays revealed that the GH-L76P mutant is unstable and misfolded compared to wt-GH confirming the bioinformatic model prediction. CONCLUSIONS This is the first report of a family suffering from short stature caused by IGHD II, which severely affects intracellular GH folding and stability as well as secretion, highlighting the necessity of functional analysis of any GH variant for defining new mechanisms as a cause for IGHD II.

Dithiothreitol triggers photooxidative stress and fragmentation of the large subunit of ribulose-1,5-bisphosphate carboxylase/oxygenase in intact pea chloroplasts

In intact chloroplasts isolated from mature pea leaves (Pisum sativum L.), the large subunit (LSU) of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco, EC 4.1.1.39) was rapidly fragmented into several products upon illumination in the presence of 1 mM dithiothreitol (DTT). Very similar effects on LSU stability could be observed when illuminated chloroplasts were poisoned with cyanide which, like DTT, inhibits important plastid antioxidant enzymes, or when a light-dependent hydroxyl radical-producing system was added to the incubation medium. Moreover, DTT-stimulated light degradation of LSU was markedly delayed in the presence of scavengers of active oxygen species (AOS). It is therefore suggested that light degradation of LSU in the presence of DTT is mainly due to inhibition of the chloroplast antioxidant defense system and the subsequent accumulation of AOS in intact organelles. When chloroplasts were isolated from nonsenescent or senescent leaves, LSU remained very stable upon incubation without DTT, indicating that the antioxidant system was still functional in the isolated chloroplasts during leaf ageing. Our data support the notion that AOS might be important for the degradation of Rubisco in vivo under oxidative stress.

RNA binding characteristics and overall topology of the vaccinia virus polyadenylation complex

mRNA 3′ polyadenylation is central to mRNA biogenesis in prokaryotes and eukaryotes, and is implicated in numerous aspects of mRNA metabolism, including efficiency of mRNA export from the nucleus, message stability, and initiation of translation. However, due to the great complexity of the eukaryotic polyadenylation apparatus, the mechanisms of RNA 3 ′ end processing have remained elusive. Although the RNA processing reactions leading to polyadenylated messenger RNA have been studied in many systems, and much progress has been made, a complete understanding of the biochemistry of the poly(A) polymerase enzyme is still lacking. My research uses Vaccinia virus as a model system to gain a better understanding of this complicated polyadenylation process, which consist of RNA binding, catalysis and polymerase translocation. ^ Vaccinia virus replicates in the cytoplasm of its host cell, so it must employ its own poly(A) polymerase (PAP), a heterodimer of two virus encoded proteins, VP55 and VP39. VP55 is the catalytic subunit, adding 30 adenylates to a non-polyadenylated RNA in a rapid processive manner before abruptly changing to a slow, non-processive mode of adenylate addition and dissociating from the RNA. VP39 is the stimulatory subunit. It has no polyadenylation catalytic activity by itself, but when associated with VP55 it facilitates the semi-processive synthesis of tails several hundred adenylates in length. ^ Oligonucleotide selection and competition studies have shown that the heterodimer binds a minimal motif of (rU)2 (N)25 U, the “heterodimer binding motif”, within an oligonucleotide, and its primer selection for polyadenylation is base-type specific. ^ Crosslinking studies using photosensitive uridylate analogs show that within a VP55-VP39-primer ternary complex, VP55 comes into contact with all three required uridylates, while VP39 only contacts the downstream uridylate. Further studies, using a backbone-anchored photosensitive crosslinker show that both PAP subunits are in close proximity to the downstream −10 to −21 region of 50mer model primers containing the heterodimer binding motif. This equal crosslinking to both subunits suggests that the dimerization of VP55 and VP39 creates either a cleft or a channel between the two subunits through which this region of RNA passes. ^ Peptide mapping studies of VP39 covalently crosslinked to the oligonucleotide have identified residue R107 as the amino acid in close proximity to the −10 uridylate. This helps us project a conceptual model onto the known physical surface of this subunit. In the absence of any tertiary structural data for VP55, we have used a series of oligonucleotide selection assays, as well as crosslinking, nucleotide transfer assays, and gel shift assays to gain insight into the requirements for binding, polyadenylation and translocation. Collectively, these data allow us to put together a comprehensive model of the structure and function of the polyadenylation ternary complex consisting of VP39, VP55 and RNA. ^

Identification and characterization of Xenopus Kazrin, a nucleocytoplasmic shuttling protein that interacts with ARVCF catenin

In common with other members of the p120-catenin subclass of catenins, ARVCF-catenin appears to have multiple cellular and developmental functions. In Xenopus, our lab recently demonstrated that xARVCF- and Xp120-catenins are each essential for early vertebrate embryogenesis, being functionally linked to Rho-family GTPases (RhoA, Rac) and cadherin metabolic stability. For the project described here, the yeast two-hybrid system was employed to screen a Xenopus laevis neurula library for proteins that interact with xARVCF, resulting in the identification of the Xenopus homolog of Kazrin (xKazrin). Kazrin is a variably-spliced protein of unknown function that has been shown to interact with periplakin and envoplakin, components of desmosomal junctions. Kazrin's primary sequence is highly conserved across vertebrate species and is composed of an amino-terminal nuclear export sequence (NES), a carboxy-terminal nuclear localization sequence (NLS) and a central predicted coiled-coil domain. In vitro and in vivo authenticity tests demonstrated that xARVCF-catenin interacts directly with xKazrin via xARVCF's Armadillo and carboxy-terminal regions and xKazrin's coiled-coil domain. The interaction of xARVCF-catenin with xKazrin is specific and does not extend to the related Xp120-catenin. xKazrin co-localized with E-cadherin at sites of cell-cell contact and could be co-immunoprecipitated with components of the cadherin complex. xKazrin was also present in the cytoplasm and nucleus. Suggestive of a nuclear role, mutation of xKazrin's predicted NLS resulted in nuclear exclusion, while deletion of the predicted NES resulted in loss of sensitivity to nuclear export inhibitors. Within Xenopus embryos, xKazrin was expressed across all developmental stages and appeared at varying levels in adult tissues. Morpholino depletion of xKazrin from Xenopus embryos resulted in axial elongation abnormalities and loss of tissue integrity after neurulation. Over-expression of xKazrin had no effect, while over-expression of a NLS mutant resulted in a mild phenotype similar to that seen in xKazrin depleted embryos. Interestingly, the axial phenotype resulting from reduced xKazrin levels was largely rescuable by xARVCF over-expression. In conjunction with xARVCF-catenin, xKazrin has properties consistent with its function at cell-cell contact sites and in the nucleus. ^

Identification and analysis of novel mitotic inhibitors of the Caenorhabditis elegans Aurora B kinase

Proper execution of mitosis requires the accurate segregation of replicated DNA into each daughter cell. The highly conserved mitotic kinase AIR-2/Aurora B is a dynamic protein that interacts with subsets of cofactors and substrates to coordinate chromosome segregation and cytokinesis in Caenorhabdiris elegans. To identify components of the AIR-2 regulatory pathway, a genome-wide RNAi-based screen for suppressors of air-2 temperature-sensitive mutant lethality was conducted. Here, I present evidence that two classes of suppressors identified in this screen are bona fide regulators of the AIR-2 kinase. The strongest suppressor cdc-48.3, encodes an Afg2/Spaf-related Cdc48-like AAA+ ATPase that regulates AIR-2 kinase activity and stability during C. elegans embryogenesis. Loss of CDC-48.3 suppresses the lethality of air-2 mutant embryos, marked by the restoration of the dynamic behavior of AIR-2 and rescue of chromosome segregation and cytokinesis defects. Loss of CDC-48.3 leads to mitotic delays and abnormal accumulation of AIR-2 during late telophase/mitotic exit. In addition, AIR-2 kinase activity is significantly upregulated from metaphase through mitotic exit in CDC-48.3 depleted embryos. Inhibition of the AIR-2 kinase is dependent on (1) a direct physical interaction between CDC-48.3 and AIR-2, and (2) CDC-48.3 ATPase activity. Importantly, the increase in AIR-2 kinase activity does not correlate with the stabilization of AIR-2 in late mitosis. Hence, CDC-48.3 is a bi-functional inhibitor of AIR-2 that is likely to act via distinct mechanisms. The second class of suppressors consists of psy-2/smk-1 and pph-4.1, which encode two components of the conserved PP4 phosphatase complex that is essential for spindle assembly, chromosome segregation, and overall mitotic progression. AIR-2 and its substrates are likely to be targets of this complex since mitotic AIR-2 kinase activity is significantly increased during mitosis when either PSY-2/SMK-1 or PPH-4.l is depleted. Altogether, this study demonstrates that during the C. elegans embryonic cell cycle, regulators including the CDC-48.3 ATPase and PP4 phosphatase complex interact with and control the kinase activity, targeting behavior and protein stability of the Aurora B kinase to ensure accurate and timely progression of mitosis. ^

IDENTIFICATION AND ANALYSIS OF A NOVEL ROLE FOR THE TOUSLED-LIKE KINASE IN REGULATING MITOTIC SPINDLE DYNAMICS

Deregulation of kinase activity is one example of how cells become cancerous by evading evolutionary constraints. The Tousled kinase (Tsl) was initially identified in Arabidopsis thaliana as a developmentally important kinase. There are two mammalian orthologues of Tsl and one orthologue in C. elegans, TLK-1, which is essential for embryonic viability and germ cell development. Depletion of TLK-1 leads to embryonic arrest large, distended nuclei, and ultimately embryonic lethality. Prior to terminal arrest, TLK-1-depleted embryos undergo aberrant mitoses characterized by poor metaphase chromosome alignment, delayed mitotic progression, lagging chromosomes, and supernumerary centrosomes. I discovered an unanticipated requirement for TLK-1 in mitotic spindle assembly and positioning. Normally, in the newly-fertilized zygote (P0) the maternal pronucleus migrates toward the paternal pronucleus at the posterior end of the embryo. After pronuclear meeting, the pronuclear-centrosome complex rotates 90° during centration to align on the anteroposterior axis followed by nuclear envelope breakdown (NEBD). However, in TLK-1-depleted P0 embryos, the centrosome-pronuclear complex rotation is significantly delayed with respect to NEBD and chromosome congression, Additionally, centrosome positions over time in tlk-1(RNAi) early embryos revealed a defect in posterior centrosome positioning during spindle-pronuclear centration, and 4D analysis of centrosome positions and movement in newly fertilized embryos showed aberrant centrosome dynamics in TLK-1-depleted embryos. Several mechanisms contribute to spindle rotation, one of which is the anchoring of astral microtubules to the cell cortex. Attachment of these microtubules to the cortices is thought to confer the necessary stability and forces in order to rotate the centrosome-pronuclear complex in a timely fashion. Analysis of a microtubule end-binding protein revealed that TLK-1-depleted embryos exhibit a more stochastic distribution of microtubule growth toward the cell cortices, and the types of microtubule attachments appear to differ from wild-type embryos. Additionally, fewer astral microtubules are in the vicinity of the cell cortex, thus suggesting that the delayed spindle rotation could be in part due to a lack of appropriate microtubule attachments to the cell cortex. Together with recently published biochemical data revealing the Tousled-like kinases associate with components of the dynein microtubule motor complex in humans, these data suggest that Tousled-like kinases play an important role in mitotic spindle assembly and positioning.

Design, Synthesis and Development of Transporter Targeting Agents for Image-guided Therapy and Drug Delivery

The purpose of this study was to design, synthesize and develop novel transporter targeting agents for image-guided therapy and drug delivery. Two novel agents, N4-guanine (N4amG) and glycopeptide (GP) were synthesized for tumor cell proliferation assessment and cancer theranostic platform, respectively. N4amG and GP were synthesized and radiolabeled with 99mTc and 68Ga. The chemical and radiochemical purities as well as radiochemical stabilities of radiolabeled N4amG and GP were tested. In vitro stability assessment showed both 99mTc-N4amG and 99mTc-GP were stable up to 6 hours, whereas 68Ga-GP was stable up to 2 hours. Cell culture studies confirmed radiolabeled N4amG and GP could penetrate the cell membrane through nucleoside transporters and amino acid transporters, respectively. Up to 40% of intracellular 99mTc-N4amG and 99mTc-GP was found within cell nucleus following 2 hours of incubation. Flow cytometry analysis revealed 99mTc-N4amG was a cell cycle S phase-specific agent. There was a significant difference of the uptake of 99mTc-GP between pre- and post- paclitaxel-treated cells, which suggests that 99mTc-GP may be useful in chemotherapy treatment monitoring. Moreover, radiolabeled N4amG and GP were tested in vivo using tumor-bearing animal models. 99mTc-N4amG showed an increase in tumor-to-muscle count density ratios up to 5 at 4 hour imaging. Both 99mTc-labeled agents showed decreased tumor uptake after paclitaxel treatment. Immunohistochemistry analysis demonstrated that the uptake of 99mTc-N4amG was correlated with Ki-67 expression. Both 99mTc-N4amG and 99mTc-GP could differentiate between tumor and inflammation in animal studies. Furthermore, 68Ga-GP was compared to 18F-FDG in rabbit PET imaging studies. 68Ga-GP had lower tumor standardized uptake values (SUV), but similar uptake dynamics, and different biodistribution compared with 18F-FDG. Finally, to demonstrate that GP can be a potential drug carrier for cancer theranostics, several drugs, including doxorubicin, were selected to be conjugated to GP. Imaging studies demonstrated that tumor uptake of GP-drug conjugates was increased as a function of time. GP-doxorubicin (GP-DOX) showed a slow-release pattern in in vitro cytotoxicity assay and exhibited anti-cancer efficacy with reduced toxicity in in vivo tumor growth delay study. In conclusion, both N4amG and GP are transporter-based targeting agents. Radiolabeled N4amG can be used for tumor cell proliferation assessment. GP is a potential agent for image-guided therapy and drug delivery.

Yield prediction and inbreeding of maize synthetics generated with lines and single crosses : classic probability

reduce costs and labor associated with predicting the genotypic mean (GM) of a synthetic variety (SV) of maize (Zea mays L.), breeders can develop SVs from L lines and s single crosses (SynL,SC) instead of L+2s lines (SynL). The objective of this work was to derive and study formulae for the inbreeding coefficient (IC) and GM of SynL,SC, SynL, and the SV derived from (L+2s)/2 single crosses (SynSC). All SVs were derived from the same L+2s unrelated lines whose IC is FL, and each parent of a SV was represented by m plants. An a priori probability equation for the IC was used. Important results were: 1) the largest and smallest GMs correspond to SynL and SynL,SC, respectively; 2) the GM predictors with the largest and intermediate precision are those for SynL and SynL,SC, respectively; 3) only when FL=1, or m is large, SynL and SynSC are the same population, but only with SynSC prediction costs and labor undergo the maximum decrease, although its prediction precision is the lowest. To determine the SV to be developed, breeders should also consider the availability of lines, single crosses, manpower and land area; besides budget, target farmers, target environments, etc.

Chemistry of orthopyroxenes, clinopyroxenes, and spinels of ODP Hole 103-637A peridotites

Mineral compositions of the plagioclase-bearing ultramafic tectonites dredged and cored seaward of the continental slope of the Galicia margin (Leg 103, Site 637) were compared to mineral compositions from onshore low-pressure ultramafic bodies (southeastern Ronda, western Pyrenees, and Lizard Point), on the basis of standardized (30-s counting time) probe analyses. The comparison was extended to some plagioclase-free harzburgites related to ophiolites (Santa Elena in Costa Rica, north Oman, and the Humboldt body in New Caledonia) on the basis of new analytical data and data from the literature. The behavior of Cr, Na, Al, Mg, Fe, Ni, and Ti in olivine, pyroxenes, and spinel was examined in order to distinguish between the effects of partial melting and mineral facies change, from the spinel to plagioclase stability fields. The peridotite from the Galicia margin appears slightly depleted in major incompatible elements and experienced a minor partial melting. However, it experienced large scale but heterogeneous recrystallization in the plagioclase field. These features are very similar to those observed in Ronda, whereas in the western Pyrenees the minerals exemplify a very minor partial-melting event (or none at all) and have retained compositions corresponding to those of the relatively high-pressure Seiland sub facies. The minerals from the Lizard Point peridotite have characteristics (low Mg/(Mg + Fe) ratio; high Cr/(Cr + Al) ratio in spinel) more related to cumulate from a differentiated tholeiitic melt than related to ophiolitic tectonite. Diffusion profiles of Al and Cr across pyroxenes and spinel show that recrystallization features occurred at different speeds or temperatures in the different bodies. The pyroxenes from Ronda would have experienced recrystallization about 14 times faster than the peridotite from the Galicia margin. The western Pyrenean lherzolites also experienced rapid recrystallization; nevertheless, because they are of a different mineral facies, the data are not directly comparable to that from Ronda and Galicia. The harzburgite at Santa Elena as well as a xenolith from alkali basalt exemplify rapid cooling characterized by very weak re-equilibration. Recrystallization speed is related to emplacement speed in the present geological environment. The slow-rising Galicia margin peridotite was emplaced by thinning of the lithospheric subcontinental mantle near an incipient mid-oceanic ridge. The fast-rising peridotites from Ronda and the western Pyrenees were hot diapirs emplaced from the asthenosphere along transcurrent faults, possibly related to the opening of the Atlantic Ocean.

Preliminary results and documentation of sediment cores CRP2 and CRP-2A from the Ross Sea off Cape Roberts, Antarctica

The site for CRP-2, 14 km east of Cape Roberts (77.006°S; 163.719°E), was selected to overlap the early Miocene strata cored in nearby CRP-1, and to sample deeper into the east-dipping strata near the western margin ofe he Victoria Land Basin to investigate Palaeogene climatic and tectonic history. CRP-2 was cored from 5 to 57 mbsf (metres below the sea floor) (core recovery 91 %), with a deviation resulting in CRP-2A being cored at the same site. CRP-2A reached down to 624mbsf (recovery 95%), and to strata with an age of c. 33-35 Ma. Drilling took place from 16 October to 25 November 1998, on 2.0-2.2 m of sea ice and through 178 m of water. Core fractures and other physical properties, such as sonic velocity, density and magnetic susceptibility, were measured throughout the core. Down-hole logs for these and other properties were run from 63 to 167 mbsf and subsequently from 200 to 623 mbsf, although density and velocity data could be obtained only to 440 mbsf because of hole collapse. Sonic velocity averages c. 2.0 km S-1 for the upper part of the hole, but there is an sharp increase to c. 3.0 km s-1 and also a slight angular unconformity, at 306 mbsf, corresponding most likely to the early/late Oligocene boundary (c. 28-30 Ma). Velocity then increases irregularly to around 3.6 km s-1 at the bottom of the hole, which is estimated to lie 120 m above the V4/V5 boundary. The higher velocities below 306 mbsf probably reflect more extensive carbonate and common pyrite cementation, in patches, nodules, bedding-parallel masses and as vein infills. Dip of the strata also increases down-hole from 3° in the upper 300 in to over 10° at the bottom. Temperature gradient is 21° k-1. Over 2 000 fractures were logged through the hole. Borehole televiewer imagery was obtained for the interval from 200 to 440 mbsf to orient the fractures for stress field analysis. Lithostratigraphical descriptions on a scale of 1:20 are presented for the full length of the core, along with core box images, as a 200 page supplement to this issue. The hole initially passed through a layer of muddy gravel to 5.5 mbsf (Lithological Sub-Unit or LSU 1.1), and then into a Quaternary diatom-bearing clast-rich diamicton to 21 mbsf (LSU 2. l), with an interval of alternating compact diamicton and loose sand, and containing a rich Pliocene foraminiferal fauna, to 27 mbsf (LSU 2.2). The unit beneath this (LSU 3.1) has similar physical properties (sonic velocity, porosity, magnetic susceptibility) and includes diamictites of similar character to those of LSU 2.1 and 2.2, but an early Miocene (c. 19 Ma) diatom assemblage at 28 mbsf (top of LSU 3.1) shows that this sub-unit is part of the older section. The strata beneath 27 mbsf, primary target for the project, extend from early Miocene to perhaps latest Eocene age, and are largely cyclic glacimarine nearshore to offshore sediments. They are described as 41 lithological sub-units and interpreted in terms of 12 recurrent lithofacies. These are 1) mudstone, 2) inter-stratified mudstone and sandstone, 3) muddy very fine to coarse sandstone, 4) well-sorted stratified fine sandstone, 5) moderately to well-sorted, medium-grained sandstone, 6) stratified diamictite, 7) massive diamictite, 8) rhythmically inter-stratified sandstone and mudstone, 9) clast-supported conglomerate, 10) matrix-supported conglomerate, 11) mudstone breccia and 12) volcaniclastic sediment. Sequence stratigraphical analysis has identified 22 unconformity-bounded depositional sequences in pre- Pliocene strata. They typically comprise a four-part architecture involving, in ascending order, 1) a sharp-based coarse-grained unit (Facies 6,7,9 or 10), 2) a fining-upward succession of sandstones (Facies 3 and 4), 3) a mudstone interval (Facies l), in some cases coarsening upward to muddy sandstones (Facies 3), and 4) a sharp-based sandstone dominated succession (mainly Facies 4). The cyclicity recorded by the strata is interpreted in terms of a glacier ice margin retreating and advancing from land to the west, and of rises and falls in sea level. Analysis of sequence periodicity awaits afirmer chronology. However, apreliminary spectral analysis of magnetic susceptibility for a deepwater mudstone within one of the sequences (from 339 to 347 mbsf) reveals ratios between hierarchical levels that are similar to those of the three Milankovitch orbital forcing periodicities. The strata contain a wide range of fossils, the most abundant being marine diatoms. These commonly form up to 5% of the sediment, though in places the core is barren (notably between 300 and 412 mbsf). Fifty samples out of 250 reviewed were studied in detail. The assemblages define ten biostratigraphical zones, some of them based on local or as yet undescribed forms. The assemblages are neritic, and largely planktonic, suggesting that the sea floor was mostly below the photic zone throughout deposition of the corcd sequence. Calcareous nannofossils, representing incursions of ocean surface waters, are much less common (72 out of 183 samples examined) and restricted to mudstone intervals a few tens of metres thick, but are important for dating. Foraminifera are also sparse (73 out of 135 samples) and represented only by calcareous benthic species. Changing assemblages indicate a shift from inshore environments in the early Oligocenc to outer shelf in the late Oligocenc, returning to inshore in the early Miocene. Marine palynomorplis yielded large numbers of well-preserved forms from most of the 116 samples examined. The new in situ assemblagc found last year in CRP-1 is extended down into the late Oligocene and a further new assemblage is found in the early Oligoccnc. Many taxa are new, and cannot us yet contribute to an improved understanding of chronology or ecology. Marine invertebrate macrofossils, mostly molluscs and serpulid tubes, are scattered throughout the core. Preservation is good in mudstones but poor in other lithologies. Climate on land is reflected in the content of terrestrial palynomorphs, which are extremely scarce down to c. 300 mbsf. Some forms are reworked, and others represent a low growing sparse tundra with at least one species of Nothofagus. Beneath this level, a significantly greater diversity and abundance suggests a milder climate and a low diversity woody vegetation in the early Oligocene, but still far short of the richness found in known Eocene strata of the region. Sedimentary facies in the oldest strata also suggest a milder climate in the oldest strata cored, with indications of substantial glacial melt-water discharges, but are typical of a coldcr climate in late Oligocene and early Miocene times. Clast analyses from diamictites reveal weak to random fabrics, suggesting either lack of ice-contact deposition or post-depositional modification, but periods when ice grounded at the drill site are inferred from thin zones of in-situ brecciated rock and soft-sediment folding. These are more common above c. 300 mbsf, perhaps reflecting more extensive glacial advances during deposition of those strata. Erosion of the adjacent Transantarctic Mountains through Jurassic basalt and dolerite-intruded Beacon strata into basement rocks beneath is recorded by petrographical studies of clast and sand grain assemblages. Core below 310 mbsf contains a dominance of fine-grained Jurassic dolerite and basalt fragments along with Beacon-derived coal debris and rounded quartz grains, whereas the strata above this level have a much higher proportion of basement derived granitoids, implying that the large areas of the adjacent mountains had been eroded to basement by the end of the early Oligocene. There is little indication of rift-related volcanism below 310 mbsf. Above this, however, basaltic and trachytic tephras are common, especially from 280 to 200 mbsf, from 150 to 46 mbsf, and in Pliocene LSU 2.2 from 21 to 27 mbsf. The largest volcanic eruptions generated layers of coarse (up to 1 cm) trachytic pumice lapilli between 97 and 114 mbsf. The thickest of these (1.2 m at 112 mbsf) may have produced an eruptive column extending tens of km into the stratosphere. A source within a few tens of km of the drill site is considered most likely. Present age estimates for the pre-Pliocene sequence are based mainly on biostratigraphy (using mainly marine diatoms and to a lesser extent calcareous nannofossils), with the age of the tephra from 112 to 114 mbsf (21.44k0.05 Ma from 84 crystals by Ar-Ar) as a key reference point. Although there are varied and well-preserved microfossil assemblages through most of the sequence (notably of diatoms and marine palynomorphs), they comprise largely taxa either known only locally or as yet undescribed. In addition, sequence stratigraphical analysis and features in the core itself indicate numerous disconformities. The present estimate from diatom assemblages is that the interval from 27 to 130 mbsf is early Miocene in age (c. 19 to 23.5 Ma), consistent with the Ar-Ar age from 112 to 114 mbsf. Diatom assemblages also indicate that the late Oligocene epoch extends from c. 130 to 307 mbsf, which is supported by late Oligocene nannofossils from 130 to 185 mbsf. Strata from 307 to 412 mbsf have no age-diagnostic assemblages, but below this early Oligocene diatoms and nannofossils have been recovered. A nannoflora at the bottom of the hole is consistent with an earliest Oligocene or latest Eocene age. Magnetostratigraphical studies based on about 1000 samples, 700 of which have so far undergone demagnetisation treatment, have provided a polarity stratigraphy of 12 pre-Pliocene magnetozones. Samples above 270 mbsf are of consistently high quality. Below this, magnetic behaviour is more variable. A preliminary age-depth plot using the Magnetic Polarity Time Scale (MPTS) and constrained by biostratigraphical data suggests that episodes of relatively rapid sedimentation took place at CRP-2 during Oligocene times (c. 100 m/My), but that more than half of the record was lost in a few major and many minor disconformities. Age estimates from Sr isotopes in shell debris and further tephra dating are expected to lead to a better comparison with the MPTS. CRP-2/2A has recorded a history of subsidence of the Victoria Land Basin margin that is similar to that found in CIROS-170 km to the south, reflecting stability in both basin and the adjacent mountains in late Cenozoic times, but with slow net accumulation in the middle Cenozoic. The climatic indicators from both drill holes show a similar correspondence, indicating polar conditions for the Quaternary but with sub-polar conditions in the early Miocene-late Oligocene and indications of warmer conditions still in the early Oligocene. Correlation between the CRP-2A core and seismic records shows that seismic units V3 and V4, both widespread in the Victoria Land Basin, represent a period of fluctuating ice margins and glacimarine sedimentation. The next drill hole, CRP-3, is expected to core deep into V5 and extend this record of climate and tectonics still further back in time.

Mineralogy and diagenesis of slope sediments at DSDP Leg 84 holes

The distribution and composition of minerals in the silt and clay fraction of the fine-grained slope sediments were examined. Special interest was focused on diagenesis. The results are listed as follows. (1) Smectite, andesitic Plagioclase, quartz, and low-Mg calcite are the main mineral components of the sediment. Authigenic dolomite was observed in the weathering zones of serpentinites, together with aragonite, as well as in clayey silt. (2) The mineralogy and geochemistry of the sediments is analogous to that of the andesitic rocks of Costa Rica and Guatemala. (3) Unstable components like volcanic glass, amphiboles, and pyroxenes show increasing etching with depth. (4) The diagenetic alteration of opal-A skeletons from etching pits and replacement by opal-CT to replacement by chalcedony as a final stage corresponds to the typical opal diagenesis. (5) Clinoptilolite is the stable zeolite mineral according to mineral stability fields; its neoformation is well documented. (6) The early diagenesis of smectites is shown by an increase of crystallinity with depth. Only the smectites in the oldest sediments (Oligocene and early Eocene) contain nonexpanding illite layers.