The regulation of protein kinase C by thiol oxidation

The Ser/Thr protein kinase C (PKC) isozyme family plays an important role in cell growth and differentiation and also contributes to key events in the development and progression of cancer. PKC isozymes are activated by phospholipid-dependent mechanisms, and they are also subject to oxidative activation and inactivation. Oxidative regulatory mechanisms are important in the governance of PKC isozyme action. While oxidative PKC activation involves phospho-tyrosine (P-Y) stabilization, the molecular mechanism(s) for oxidative PKC inactivation have not been defined. We previously reported that Thr → Cys peptide-substrate analogs inactivate several PKC isozymes including PKC-α via S-thiolation, i.e., by forming disulfides with PKC thiols. This inactivation mechanism is chemically analogous to protein S-glutathiolation, a post-translational modification that has been shown to oxidatively regulate several enzymes. To determine if PKC-α could be inactivated by S-glutathiolation, we employed the thiol-specific oxidant diamide (0.01–10mM) and 100μM glutathione (GSH). Diamide alone (0.1–5.0 mM) weakly inactivated PKC-α (<20%), and GSH alone had no effect on the isozyme activity. Marked potentiation of diamide-induced PKC-α inactivation (>90%) was achieved by 100μM GSH, resulting in full inactivation of the isozyme. Inactivation was reversed by DTT, consistent with a mechanism involving PKC-α S-glutathiolation. S-glutathiolation was demonstrated as DTT-reversible incorporation of [35S] GSH into PKC-α isozyme structure. These results indicate that a mild oxidative stimulus can inactivate purified PKC-α via S-glutathiolation. In addition, diamide treatment of metabolically labeled NIH3T3 cells induced potent PKC-α inactivation via isozyme [35S] S-thiolation. These results indicate that cellular PKC-α can be regulated via S-glutathiolation. ^

Geochemistry of Cretaceous sills and lava flows of ODP Holes 129-800A and 129-802A

On the basis of their respective eruptive environments and chemical characteristics, alkalic dolerite sills from the northern Pigafetta Basin (Site 800) and tholeiitic pillow lavas from the Mariana Basin (Site 802) sampled during Ocean Drilling Program Leg 129 are considered to represent examples of the widespread mid-Cretaceous volcanic event in the western Pacific. Both groups of basic rocks feature mild, low-grade, anoxic smectite-celadonite-carbonate-pyrite alteration; late-stage oxidation is very limited in extent, with the exception of the uppermost sill unit at Site 800. The aphyric and nonvesicular Site 800 alkalic dolerite sills are all well-evolved mineralogically and chemically, being mainly of hawaiite composition, and are similar to ocean island basalts. They are characterized by high contents of incompatible elements (for example, 300-400 ppm Zr), well-fractionated rare earth element patterns ([La/Yb]N 18-21) and HIMU isotopic characters. They probably represent deep-sea, lateral, intrusive off-shoots from nearby seamounts of similar age. The olivine-plagioclase +/- clinopyroxene phyric tholeiitic pillow lavas and thin flows of Site 802 are nonvesicular and quench-textured throughout. Relative to normal-type mid-ocean ridge basalt, they are enriched in large-ion-lithophile elements, exhibit flat (unfractionated) rare earth element patterns and have distinctive (lower) Zr/Nb, Zr/Ta, La/Ta, and Hf/Th ratios. Overall they are compositionally and isotopically similar to the mid-Cretaceous tholeiites of the Nauru basin and the Ontong-Java and Manihiki plateaus. The Site 802 tholeiites differ from the thickened crustal segments of the oceanic plateaus, however, in apparently representing only a thin veneer over the local basement in an off-axis environment.

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Hole 69-504B and 70-504B

About 150 basalt samples from Hole 504B, near the Costa Rica Rift were analyzed for sulfur content and sulfur-isotope composition. The basement in Hole 504B can be divided into an upper part, which has oxidative alteration (274.5-550 m below sea floor), and a lower part, which has nonoxidative alteration (550-835 m below sea floor) (the interval from 540 to 585 meters actually is transitional). This division is reflected in both the sulfur content and the sulfurisotope composition. Oxidative alteration of basalts by sea water at low temperatures has resulted in a depletion in sulfur in the upper part of the hole (mostly less than 600 ppm S) as compared to fresh sulfur-saturated oceanic tholeiites (900-1200 ppm S). High amounts of sulfur in the lower part of the hole are a result of precipitation of secondary pyrite under non-oxidative or weakly oxidative conditions from solutions which dissolved igneous sulfides. The average sulfur-isotope composition of the primary igneous sulfides is d34S = -0.01 per mil, which is close to the assumed mantle sulfur composition (d34S = 0 per mil. Pyrite and sulfate sulfur extracted together in a separate preparation step (as "pyrite-sulfate" sulfur) indicate addition of sea-water sulfate to the upper part of the basalts. The d34S of secondary pyrite isolated by hand-picking varies between -8.0 and +5.8 per mil; the "pyrite-sulfate" sulfur (d34S = -4.8 to +10.5 per mil), as well as that of the isolated pyrite, may have originated in the precipitation of pyrite from solutions containing sulfur from the dissolution of igneous sulfides, but addition of sulfur transported by hydrothermal solutions cannot be excluded.

Petrology and geochemistry of oceanic intraplate sheet-flow basalts at DSDP Hole 89-462A

Reentry of Hole 462A during Leg 89 resulted in the penetration of a further 140 m of basalt sheet-flows similar to those found during Leg 61 at the same site. Twelve volcanic units (45 to 56) were recognized, comprising a series of rapidly extruded, interlayered aphyric and poorly clinopyroxene-plagioclase-olivine phyric, nonvesicular basalts. All exhibit variable, mild hydration and oxidation, relative to fresh oceanic basalts, produced under reducing, low-CO2-activity conditions within the zeolite facies. Secondary assemblages are dominated by smectites, zeolites, and pyrite, produced by low-temperature reaction with poorly oxygenated seawater. No systematic mineralogical or chemical changes are observed with depth, although thin quenched units and more massive hypocrystalline units exhibit slightly different alteration parageneses. Chemically, the basalts are olivine- and quartz-normative tholeiites, characterized by low incompatible-element abundances, similar to mildly enriched MORB (approaching T-type), with moderate, chrondite-normalized, large-ionlithophile- element depletion patterns and generally lower or near-chrondritic ratios for many low-distribution-coefficient (KD) element pairs. In general, relative to cyclic MORB chemical variation, they are uniform throughout, although 3 chemical megagroups and 22 subgroups are recognized. It is considered that the megagroups represent separate low-pressure-fractionated systems (olivine + Plagioclase ± clinopyroxene), whereas minor variations within them (subgroups) indicate magma mixing and generation of near-steady-state conditions. Overall, relatively minor fractionation coupled with magma mixing produced a series of compositionally uniform lavas. Parental melts were produced by similar degrees of partial melting, although the source may have varied slightly in LIL-element content.

Major, trace and rare earth elements and minerals at DSDP Legs 69-70 Holes

We obtained major and trace element data on 113 samples from basalts drilled during DSDP Legs 69 and 70 in the Costa Rica Rift area. The majority have major and trace element characteristics typical of ocean-ridge tholeiities. Most of the basalts are relatively MgO rich (MgO > 8 wt.%) and have Mg values (MgO/MgO + 0.85FeO x 100) of about 53, characteristics that clearly indicate that the various magmas underwent only a small amount of crystal fractionation before being erupted onto the seafloor. According to their normative mineralogies, the rocks are olivine tholeiites. A few samples plot close to the diopside-hypersthene join of the projected basalt tetrahedron. Except for basalts from two thin intervals in Hole 504B, which differ significantly from all the other basalts of the hole, practically no chemical downhole variation could be established. In the two exceptional intervals, both TiO2 and P2O5 contents are markedly enriched among the major oxides. The trace elements in these intervals are distinguished by relatively high contents of magmatophile elements and have flat to enriched chondrite-normalized distribution patterns of light rare earth elements (LREE). Most of the rocks outside these intervals are strongly depleted in large-ionlithophile (LIL) elements and LREE. We offer no satisfactory hypothesis for the origin of these basalts at this time. They might have originated within pockets of mantle materials that were more primitive than the LIL-element-depleted magmas that were the source of the other basalts. A significant change with depth in the type of alteration occurs in the 561 meters of basalt cored in Hole 504B. According to the behavior of such alteration-sensitive species as K2O, H2O-, CO2, S, Tl, and the iron oxidation ratio, the alteration is oxidative in the upper part and nonoxidative or even reducing in the lower part. The oxidative alteration may have resulted from low temperature basalt/seawater interaction, whereas hydrothermal solutions may be responsible for the nonoxidative alteration.

Geochemistry and radionuclide content of sediment and water samples obtained from the Ob and Irtysh river, Russia

This paper reports the results of the investigations of 2006-2007 on the distribution and migration forms of artificial radionuclides and chemical elements in the Ob-Irtysh water system. Three regions were studied. One of them is a local segment of the Ob River upstream from the confluence with the Irtysh River; its investigation allowed us to estimate the general radioecological state of the aquatic environment affected by the activity of the Tomsk 7 plant. The second region is a local segment of the Irtysh River upstream from its confluence with the Ob River, where the influence of emissions from the NPO Mayak could be estimated. The third region is the water area of the Ob River after its confluence with the Irtysh River. It characterizes the real level of radioactive and chemical contamination of the middle reaches of the Ob River. In order to explain horizontal variations in the distribution of radionuclides in the upper layer of bottom sediments collected at various sites, the results of sorption-kinetic experiments with radioactive tracers in the precipitate-solution system were used. The investigation of the migration forms of trace elements and radionuclides occurring in river water was based on the method of tangential-flow membrane filtration. Chemical element contents were determined in 400-ml water samples. A set of Millipore polysulfone membranes with pore sizes of 8, 1.2, 0.45, 0.1, and 0.025 µm was employed. Taking into account the ultralow specific concentrations of radionuclides in the water, they were analyzed in 300-500 litre samples using Millipore polysulfone membranes with pore sizes of 0.45 µm and 15 kDa. This allowed us to estimate the percentages of cesium-137 and plutonium-239, 240 in the suspended particulate fraction, colloids, and dissolved species.

Geochemistry of lavas from the Lau-Tonga arc and back-arc system

Detailed comparison of mineralogy, and major and trace geochemistry are presented for the modern Lau Basin spreading centers, the Sites 834-839 lavas, the modern Tonga-Kermadec arc volcanics, the northern Tongan boninites, and the Lau Ridge volcanics. The data clearly confirm the variations from near normal mid-ocean-ridge basalt (N-MORB) chemistries (e.g., Site 834, Central Lau Spreading Center) to strongly arc-like (e.g., Site 839, Valu Fa), the latter closely comparable to the modern arc volcanoes. Sites 835 and 836 and the East Lau Spreading Center represent transitional chemistries. Bulk compositions range from andesitic to basaltic, but lavas from Sites 834 and 836 and the Central Lau Spreading Center extend toward more silica-undersaturated compositions. The Valu Fa and modern Tonga-Kermadec arc lavas, in contrast, are dominated by basaltic andesites. The phenocryst and groundmass mineralogies show the strong arc-like affinities of the Site 839 lavas, which are also characterized by the existence of very magnesian olivines (up to Fo90-92) and Cr-rich spinels in Units 3 and 6, and highly anorthitic plagioclases in Units 2 and 9. The regional patterns of mineralogical and geochemical variations are interpreted in terms of two competing processes affecting the inferred magma sources: (1) mantle depletion processes, caused by previous melt extractions linked to backarc magmatism, and (2) enrichment in large-ion-lithophile elements, caused by a subduction contribution. A general trend of increasing depletion is inferred both eastward across the Lau Basin toward the modern arc, and northward along the Tongan (and Kermadec) Arc. Numerical modeling suggests that multistage magma extraction can explain the low abundances (relative to N-MORB) of elements such as Nb, Ta, and Ti, known to be characteristic of island arc magmas. It is further suggested that a subduction jump following prolonged slab rollback could account for the initiation of the Lau Basin opening, plausibly allowing a later influx of new mantle, as required by the recognition of a two-stage opening of the Lau Basin.

Major oxides, trace elements and rare earth elements of selected basalt samples at DSDP Hole 83-504B

DSDP Hole 504B is the deepest section drilled into oceanic basement, penetrating through a 571.5-m lava pile and a 209-m transition zone of lavas and dikes into 295 m of a sheeted dike complex. To define the basement composition 194 samples of least altered basalts, representing all lithologic units, were analyzed for their major and 26 trace elements. As is evident from the alteration-sensitive indicators H2O+, CO2, S, K, Mn, Zn, Cu, and the iron oxidation ratio, all rocks recovered are chemically altered to some extent. Downhole variation in these parameters enables us to distinguish five depth-related alteration zones that closely correlate with changes in alteration mineralogy. Alteration in the uppermost basement portion is characterized by pronounced K-uptake, sulfur loss, and iron oxidation and clearly demonstrates low-temperature seawater interaction. A very spectacular type of alteration is confined to the depth range from 910 to 1059 m below seafloor (BSF). Rocks from this basement portion exhibit the lowest iron oxidation, the highest H2O+ contents, and a considerable enrichment in Mn, S, Zn, and Cu. At the top of this zone a stockwork-like sulfide mineralization occurs. The chemical data suggest that this basement portion was at one time within a hydrothermal upflow zone. The steep gradient in alteration chemistry above this zone and the ore precipitation are interpreted as the result of mixing of the upflowing hydrothermal fluids with lower-temperature solutions circulating in the lava pile. Despite the chemical alteration the primary composition and variation of the rocks can be reliably established. All data demonstrate that the pillow lavas and the dikes are remarkably uniform and display almost the same range of variation. A general characteristic of the rocks that classify as olivine tholeiites is their high MgO contents (up to 10.5 wt.%) and their low K abundances (-200 ppm). According to their mg-values, which range from 0.60 to 0.74, most basalts appear to have undergone some high-level crystal fractionation. Despite the overall similarity in composition, there are two major basalt groups that have significantly different abundances and ratios of incompatible elements at similar mg-values. The majority of the basalts from the pillow lava and dike sections are chemically closely related, and most probably represent differentiation products of a common parental magma. They are low in Na2O, TiO2, and P2O5, and very low in the more hygromagmaphile elements. Interdigitated with this basalt group is a very rarely occurring basalt that is higher in Na2O, TiO2, P2O5, much less depleted in hygromagmaphile elements, and similar to normal mid-ocean ridge basalt (MORB). The latter is restricted to Lithologic Units 5 and 36 of the pillow lava section and Lithologic Unit 83 of the dike section. The two basalt groups cannot be related by differentiation processes but have to be regarded as products of two different parental magmas. The compositional uniformity of the majority of the basalts suggests that the magma chamber beneath the Costa Rica Rift reached nearly steady-state conditions. However, the presence of lavas and dikes that crystallized from a different parental magma requires the existence of a separate conduit-magma chamber system for these melts. Occasionally mixing between the two magma types appears to have occurred. The chemical characteristics of the two magma types imply some heterogeneity in the mantle source underlying the Costa Rica Rift. The predominant magma type represents an extremely depleted source, whereas the rare magma type presumably originated from regions of less depleted mantle material (relict or affected by metasomatism).