Geochemistry of glass shards in the volcanic ash layers of the Izu-Bonin Arc

To examine the processes and histories of arc volcanism and of volcanism associated with backarc rifting. 130 samples containing igneous glass shards were taken from the Plioccne-Quatemai^ succession on the rift Hank (Site 788) and the Quaternary fill in the basin fill of the Sumisu Rift (Sites 790 and 791). These samples were subsequently analyzed at the University of Illinois at Chicago and Shizuoka University. The oxides determined by electron probe do not account for the total weight of the material; differences between summed oxides and 100% arise from the water contents, probably augmented by minor losses thai result from alkali vaporization during analysis. Weight losses in colorless glasses are up to 9%; those in brown glasses (dacitcs to basalts) arc no more than 4.5%; shards from the rift-flank (possibly caused by prolonged proximity to ihc scafloor) generally have higher values than those from the rift-basin fill How much of the lost water is magmatic, and how much is hydrated is uncertain; however, although the shards absorb potassium, calcium, and magnesium during hydration in the deep sea, they do so only to a minor extent that does not significantly alter their major element compositions. Therefore, the electron-probe results are useful in evaluating the magmatism recorded by the shards. Pre- and syn-rift Izu-Bonin volcanism were overwhelmingly dominated by rhyolile explosions, demonstrating that island arcs may experience significant silicic volcanism in addition to the extensive basaltic and basaltic andestic activity, documented in many arcs since the 1970s, that occurs in conjunction with the andesitic volcanism formerly thought to be dominant. Andesitic eruptions also occurred before rifting, but the andesitic component in our samples is minor. All the pre- and syn-rift rhyolites and andesites belong to the low-alkali island-arc tholeiitic suite, and contrast markedly with the alkali products of Holocene volcanism on the northernmost Mariana Arc that have been attributed to nascent rifting. The Quaternary dacites and andesites atop the rift flank and in the rift-basin fill are more potassic than those of Pliocene age, as a result of assimilation from the upper arc crust, or from variations in degrees of partial melting of the source magmas, or from metasomatic fluids. All the glass layers from the rift-flank samples belong to low-K arc-tholeiitic suites. Half of those in the Pliocene succession are exclusively rhyolitic: the others contain minor admixtures of dacite and andesite, or andesite and either basaltic andesite or basalt. In Contrast, the Quaternary (syn-rift) volcaniclastics atop the rift-flank lack basalt and basaltic andesite shards. These youngest sediments of the rift flank show close compositional affinities with five thick layers of coarse, rhyolitic pumice deposits in the basin fill, the two oldest more silicic than the younger ones. The coarse layers, and most thin ash layers that occur in hemipelagites below and intercalated between them, are low-K rhyolites and therefore probably came from sources in the arc. However, several thin rhyolitic ash beds in the hemipelagites are abnormally enriched in potassium and must have been provided by more distal sources, most likely to the west in Japan. Remarkably, the Pliocene-Pleistocene geochemistry of the volcanic front does not appear to have been influenced by the syn-rift basaltic volcanism only a few kilometers away. Rare, thin layers of basaltic ash near the bases of the rift-basin successions are not derived from the arc. They deviate strongly from trends that the arc-derived glasses display on oxide-oxide plots, and show close affinities to the basalts empted all over the Sumisu Rift during rifting. These basalts, and the basaltic ashes in the basal rift-basin fill, arc compositionally similar to those erupted from mature backarc basins elsewhere.

(Table 1) Summary of sampling points described and main petrographic, morphological and geochemical characteristics

Targeted sampling on the Dolgovskoy Mound (northern Shatsky Ridge) revealed the presence of spectacular laterally extensive and differently shaped authigenic carbonates. The sampling stations were selected based on sidescan sonar and profiler images that show patchy backscatter and irregular and discontinuous reflections in the near subsurface. The interpretation of acoustic data from the top part of the mound supports the seafloor observations and the sampling that revealed the presence of a complex subsurface plumbing system characterized by carbonates and gas. The crusts sampled consist of carbonate cemented layered hemipelagic sedimentary Unit 1 associated with several centimetres thick microbial mats. Three different carbonate morphologies were observed: (a) tabular slabs, (b) subsurface cavernous carbonates consisting of void chambers up to 20 cm**3 in size and (c) chimney and tubular conduits vertically oriented or forming a subhorizontal network in the subsurface. The methanogenic origin of the carbonates is established based on visual observations of fluids seepage structures, 13C depletion of the carbonates (d13C varying between -36.7 per mil and -27.4 per mil), and by thin carbonate layers present within the thick microbial mats. Laboratory experiments with a Hele-Shaw cell were conducted in order to simulate the gas seepage through contrasting grain size media present on the seafloor. Combined petrography, visual observations and sandbox simulations allowed a characterization of the dynamics and the structures of the plumbing system in the near subsurface. Based on sample observations and the experiments, three observed morphologies of authigenic carbonates are interpreted, respectively, as (a) Darcian porous flow through the finely laminated clayey/coccolith-rich layers, (b) gas accumulation chambers at sites where significant fluid escape was impeded by thicker clayey layers forming the laminated Unit1 and (c) focussed vertical fluid venting and subhorizontal migration of overpressured fluids released from (b). The Hele-Shaw cell experiments represent a promising tool for investigating shallow fluid flow pathways in marine systems.

Pollen record and lithology of a profile from Dumfriesshire, Scotland

Four samples, G5, G7, G8, and G10, collected by Dr W. W. Bishop from an exposed section in the bank of the River Annan, at Roberthill Farm, Dumfriesshire (S35, 110794) were submitted for pollen analysis (Table I.). The samples, with the exception of the uppermost, were from thin peat layers that lie in the middle of a series of water- laid sands, silts and clays several feet in thickness and now rather strongly arched. The lowermost sample, G5, was taken from an organic layer about | in. thick overlying fine sand and underlying some 2.5 in. of grey, silty fine sand. A narrow layer of sandy peat immediately above the silty, fine sand yielded sample G7, and G8 was collected from a similar peaty layer separated from G7 by more sandy- silty peat. The uppermost sample, G10, was taken from light grey clay 13 in. above sample G8.

(Table 1) Geochemistry of upper Paleocene and upper Eocene glass particles at DSDP Hole 80-549

Two ash horizons have been identified in Hole 549, one in the upper Paleocene (basal NP9), the other in the upper Eocene (NP18); both are mixed lithic crystal tuffs of rhyolitic composition. These tuffs are absent in Hole 550 owing to unconformities, but the basal Eocene (NP10) of Hole 550 includes a series of over 50 thin bentonite layers. Intermediate plagioclase associated with these bentonites indicates that the original ash was of basaltic to andesitic composition. The bentonites are absent in Hole 549, probably because of an unconformity, but they have been identified in Hole 401 (Leg 48, Bay of Biscay). Two of the pyroclastic phases can be matched with phases previously reported for the North Sea Basin. The bentonites of Site 550 are probably equivalent to the widespread "ash series" of northwestern Europe, which may therefore be regarded as being lower Eocene in terms of Martini's calcareous nannoplankton zonation.

(Table 1) Tree age, post fire stand age, and soil organic matter thickness in the western Quebec black spruce boreal ecosystem

The observed long-term decrease in the regional fire activity of Eastern Canada results in excessive accumulation of organic layer on the forest floor of coniferous forests, which may affect climate-growth relationships in canopy trees. To test this hypothesis, we related tree-ring chronologies of black spruce (Picea mariana (Mill.) B.S.P.) to soil organic layer (SOL) depth at the stand scale in the lowland forests of Quebec's Clay Belt. Late-winter and early-spring temperatures and temperature at the end of the previous year's growing season were the major monthly level environmental controls of spruce growth. The effect of SOL on climate-growth relationships was moderate and reversed the association between tree growth and summer aridity from a negative to a positive relationship: trees growing on thin organic layers were thus negatively affected by drought, whereas it was the opposite for sites with deep (>20-30 cm) organic layers. This indicates the development of wetter conditions on sites with thicker SOL. Deep SOL were also associated with an increased frequency of negative growth anomalies (pointer years) in tree-ring chronologies. Our results emphasize the presence of nonlinear growth responses to SOL accumulation, suggesting 20-30 cm as a provisional threshold with respect to the effects of SOL on the climate-growth relationship. Given the current climatic conditions characterized by generally low-fire activity and a trend toward accumulation of SOL, the importance of SOL effects in the black spruce ecosystem is expected to increase in the future.

Grain size composition and geochemistry of volcaniclastic sediments in the Lau Basin

Early Pliocene to Pleistocene volcaniclastic sediments recovered during Ocean Drilling Program Leg 135 from Sites 834 to 839 in the Lau Basin show a wide range of chemical and mineralogical compositions extending the spectrum previously known from the Lau Basin, Lau Ridge and Tofua Arc. The following major types of volcaniclastics have been distinguished: (1) primary fallout ashes originating from eruptions on land, (2) epiclastic deposits that resulted from subaerial and submarine eruptions, (3) subaqueous fallout and pyroclastic flow deposits resulting from explosive submarine eruptions, and (4) hyaloclastites resulting from mechanical fragmentation and spalling of chilled margins of submarine pillow tubes and sheet-lava flows. Vitric shards are mostly basaltic andesitic to rhyolitic and broadly follow two major trends in terms of K2O enrichment: a low-K series (LKS) with about 1 wt% K2O at 70 wt% SiO2, and a very low-K series (VLKS) with only about 0.5 wt% K2O at 70 wt% SiO2. Sites 834 and 835 on "old" backarc basin crust, >4.2 and 3.4 m.y. old, comprise LKS rhyolites >3.3 m.y. old. Calc-alkaline basaltic turbidites originating from the Lau Ridge flowed in at 3.3 Ma. In the period from 3.3 to 2.4 Ma basaltic andesitic to rhyolitic, fine-grained LKS and VLKS volcaniclastics were deposited by turbidity currents and subaerial fallout. Three thin, discrete fallout layers (2.4-3.2 m.y. old) with high-K calc-alkaline compositions probably erupted in New Zealand. Volcaniclastics from Site 836, all <0.6 m.y. old, make up 24% of the sediments and comprise local basaltic andesitic to andesitic hyaloclastites with low Ba/Zr ratios of 0.9 to 1.4 and polymict andesitic sediments with Ba/Zr ratios of up to 5.5, containing clasts altered to lower greenschist facies. In Sites 837-839, drilled on young crust (1.8-2.1 m.y. old), volcaniclastics make up 45%-64% of the total sediment. Glass compositions are often bimodal with a mafic and a rhyolitic population. Large-volume rhyolitic, silt- to lapilli-sized volcaniclastics are interpreted as pyroclastic flows from explosive eruptions on a seamount 25-50 km away from the sites. Ba/Zr ratios are 2 to 4, partially overlapping with some Lau Basin basement lavas that show an "arc" signature, and they can reach values >5 in thin volcaniclastic layers <0.6 m.y. old.

(Table 2) Methane to ethane ratio, and d13C-methane at DSDP Hole 76-533

Natural gas hydrates are clathrates in which water molecules form a crystalline framework that includes and is stabilized by natural gas (mainly methane) at appropriate conditions of high pressures and low temperatures. The conditions for the formation of gas hydrates are met within continental margin sediments below water depths greater than about 500 m where the supply of methane is sufficient to stabilize the gas hydrate. Observations on DSDP Leg 11 suggested the presence of gas hydrates in sediments of the Blake Outer Ridge. Leg 76 coring and sampling confirms that, indeed, gas hydrates are present there. Geochemical evidence for gas hydrates in sediment of the Blake Outer Ridge includes (1) high concentrations of methane, (2) a sediment sample with thin, matlike layers of white crystals that released a volume of gas twenty times greater than its volume of pore fluid, (3) a molecular distribution of hydrocarbon gases that excluded hydrocarbons larger than isobutane, (4) results from pressure core barrel experiments, and (5) pore-fluid chemistry. The molecular composition of the hydrocarbons in these gas hydrates and the isotopic composition of the methane indicate that the gas is derived mainly from microbiological processes operating on the organic matter within the sediment. Although gas hydrates apparently are widespread on the Blake Outer Ridge, they probably are not of great economic significance as a potential, unconventional, energy resource or as an impermeable cap for trapping upwardly migrating gas at Site 533.

Geological and geochemical characteristics of the Tersang gold deposit, Malaysia: implications for genesis and gold exploration

The Central gold belt of peninsular Malaysia comprises a number of gold deposits located in the east of the N-S striking Bentong-Raub Suture Zone. The Tersang gold deposit is one of the gold deposits in the gold belt and hosted in sandstone, rhyolite and breccia units. The deposit has an inferred resource of 528,000 ounces of gold. The geochronology of the Tersang deposit has been newly constrained by LA ICP-MS U-Pb zircon dating. The maximum depositional age of the host sedimentary rocks ranges from Early Carboniferous to Early Permian (261.5 ± 4.9 Ma to 333.5 ± 2.5 Ma) for the host sandstone and Late Triassic for the rhyolite intrusion (218.8 ± 1.7 Ma). Textural characteristics of pyrite have revealed five types including (1) Euhedral to subhedral pyrite with internal fracturing and porous cores located in the sandstone layers (pyrite 1); (2) Anhedral pyrite overgrowths on pyrite 1 and disseminated in stage 1 vein (pyrite 2); (3) Fracture-filled or vein pyrite located in stages 1 and 2 vein (pyrite 3); (4) Euhedral pyrite with internal fractures also located in stage 2 vein (pyrite 4); and (5) Subhedral clean pyrite located in the rhyolite intrusion (pyrite 5). Based on pyrite mapping and spot analyses, two main stages of gold enrichment are documented from the Tersang gold deposit. Gold in sandstone-hosted pyrite 1 (mean 4.3 ppm) shows best correlation with Bi and Pb (as evidenced on pyrite maps). In addition, gold in pyrite 3 (mean 8 ppm) located in stage 2 vein shows a good correlation with As, Ag, Sb, Cu, Tl, and Pb. In terms of gold exploration, we suggest that elements such as As, Ag, Sb, Cu, Tl, Bi, and Pb associated with Au may serve as vectoring tools in gold exploration. Our new geological, structural, geochemical and isotopic data together with mineral paragenesis, pyrite chemistry and ore fluid characteristics indicate that the Tersang gold deposit is comparable to a sediment-hosted gold deposit. Our new genetic model suggests deposition of the Permo-Carboniferous sediments followed by intrusion of rhyolitic magma in the Late Triassic. At a later stage, gold mineralisation overprinted the rhyolite intrusion and the sandstone.

Diffusion boundary layers ameliorate the negative effects of ocean acidification on the temperate coralline macroalga Arthrocardia corymbosa

Anthropogenically-modulated reductions in pH, termed ocean acidification, could pose a major threat to the physiological performance, stocks, and biodiversity of calcifiers and may devalue their ecosystem services. Recent debate has focussed on the need to develop approaches to arrest the potential negative impacts of ocean acidification on ecosystems dominated by calcareous organisms. In this study, we demonstrate the role of a discrete (i.e. diffusion) boundary layer (DBL), formed at the surface of some calcifying species under slow flows, in buffering them from the corrosive effects of low pH seawater. The coralline macroalga Arthrocardia corymbosa was grown in a multifactorial experiment with two mean pH levels (8.05 'ambient' and 7.65 a worst case 'ocean acidification' scenario projected for 2100), each with two levels of seawater flow (fast and slow, i.e. DBL thin or thick). Coralline algae grown under slow flows with thick DBLs (i.e., unstirred with regular replenishment of seawater to their surface) maintained net growth and calcification at pH 7.65 whereas those in higher flows with thin DBLs had net dissolution. Growth under ambient seawater pH (8.05) was not significantly different in thin and thick DBL treatments. No other measured diagnostic (recruit sizes and numbers, photosynthetic metrics, %C, %N, %MgCO3) responded to the effects of reduced seawater pH. Thus, flow conditions that promote the formation of thick DBLs, may enhance the subsistence of calcifiers by creating localised hydrodynamic conditions where metabolic activity ameliorates the negative impacts of ocean acidification.