Geochemistry of volcaniclastites of the western Pacific Ocean

Samples collected from the coarse basal portions of mid-Cretaceous volcaniclastic turbidites from the Mariana and Pigafetta basins are remarkably similar in terms of the petrographic and chemical features of their igneous clasts and bulk rock composition. Clasts of magmatic origin are dominated by glassy vesicular shards, variably phyric, holocrystalline basalts, and crystal fragments (olivine, clinopyroxene, plagioclase, amphibole, and biotite). The composition of the pyroxenes and amphiboles are typical of those found in differentiated hydrous alkali basalts. The bulk chemical composition of the volcaniclastites (based on stable incompatible elements and their ratios in highly vitric samples) is characteristic of alkali basalts found in within-plate oceanic eruptive environments. Miocene volcaniclastites from Site 802 are broadly similar to the Cretaceous samples in terms of clast type and bulk composition, and have also been derived from an oceanic alkali basalt source. The chemistry of the Miocene volcaniclastites differ, however, in having distinctive Zr/Y and Zr/Nb ratios and a more restricted chemical composition. The magmatic products of nearly emergent seamounts within the western Pacific basins appears to have been dominated by alkali basalt volcanism during the mid-Cretaceous and also the Miocene. The highly vitric nature of the Cretaceous and Miocene volcaniclastites, together with the morphology and vesicularity of their shards, suggests that they are the reworked (via mass flow) products of hyaloclastite accumulations produced in a shallow-water eruptive environment, such as that adjacent to nearly emergent seamounts or ocean islands. The association of ooids, reefal debris, and, in rare cases, woody material with the volcaniclastites supports their shallow-water derivation.

Geochemistry at DSDP Leg 70 Holes

The hydrothermal mounds on the southern flank of the Galapagos Spreading Center are characterized by the following main features: 1) They are located over a young basement (0.5 to 0.85 m.y. of age) in a region known for its high sedimentation rate (about 5 cm/10**3 y.) because it is part of the equatorial high biological productivity zone. 2) They are located in a region with generally high heat flow (8 to 10 HFU). The highest heat-flow measurements (up to 10**3 HFU) correspond to mound peaks (Williams et al., 1979), where temperatures up to 15°C were measured during a dive of the submersible Alvin (Corliss et al., 1978). 3) They are often located on small vertical faults which displace the basement by a few meters (Lonsdale, 1977) and affect the 25- to 50-meter-thick sediment cover. Most of these characteristics have also been observed in the other three known cases of hydrothermal deposits with mineral parageneses similar to that of the Galapagos mounds. However, the case of the hydrothermal mounds south of the Galapagos Spreading Center is unique because of the unusual thickness of the hydrothermal deposits present. The mounds are composed of several, up to 4.5-meter-thick, layers of green clays which, in one case (Hole 509B), are overlain by about 1.4 meters of Mn-oxide crust. We suspect that such a large accumulation of hydrothermal products results from the "funnelling" of the hydrothermal solutions exiting from a highly permeable basement along the faults. This chapter reports a preliminary study of those green clays collected by hydraulic piston coring of the Galapagos mounds during Deep Sea Drilling Project (DSDP) Leg 70 of the D/V Glomar Challenger. Green clays have also been reported from three presently or recently active hydrothermal areas in or close to spreading centers.

Representative and whole rock analyses of rocks from Filchnerfjella, Antarctica

The geological history of Filchnerfjella and surrounding areas (2°E to 8°E) in central Dronning Maud Land, East Antarctica, is constructed from metamorphic and igneous petrology, and structural investigations. The geology of Filchner-fjella consists mainly of metamorphic rocks accompanied by intrusive rocks. Two stages of metamorphism can be recognized in this area. The earlier stage metamorphism is defined as a porphyroblast stage (garnet, hornblende, and sillimanite stable), and the later one is recognized as a symplectic stage (orthopyroxene and cordieritestable). Taking metamorphic textures and geothermobarometries into account, the rocks experienced an early high-P/medium-T followed by a low-P and high-T stage. Partial melting took place during the low-P/high-T stage, because probable melt of leucocratic gneiss contains cordierite. The field relationships and petrography of the syenite at Filchnerfjella are similar to those of post-tectonic plutons from central Dronning Maud Land, and most of the post-tectonic intrusive rocks have within-plate geochemical features. The structural history in Filchnerfjella and surrounding areas can be divided into the Pan-African stage and the Meso to Cenozoic stage that relates to the break-up of Gondwana.

Geochemistry of phosphate and glauconites of ODP Leg 128 samples

Glauconites and phosphates have been detected in almost all investigated samples at Sites 798 (uppermost Miocene or lower Pliocene to Pleistocene) and 799 (early middle Miocene to Pleistocene). Autochthonous occurrences appear in very minor quantities (generally below 0.2%) throughout the drilled sequences, whereas allochthonous accumulations are limited to the lower Pliocene or uppermost Miocene sequence at Site 798 (glauconites) and to the upper and middle Miocene sequence at Site 799 (upper and middle Miocene: glauconites; middle Miocene: phosphates). X-ray fluorescence, microprobe, and bulk chemical analyses indicate high variabilities in cations and anions and generally low oxide totals. This is probably related to the substitution of phosphate and fluoride aniors by hydroxide and carbonate anions in phosphates and to the depletion of iron, aluminum, and potassium cations and the enrichment in hydroxide and crystal water in glauconites. Gradients in pore-water contents of dissolved phosphate and fluoride at Sites 798 and 799 suggest a depth of phosphate precipitation between 30 and 50 mbsf, with fluoride as the limiting element for phosphate precipitation at Site 798. Phosphate and fluoride appear to be balanced at Site 799. Crude extrapolations indicate that the Japan-Sea sediments may have taken up approximately 7.2*10**10 g P total/yr during the Neogene and Pleistocene. This amount corresponds to approximately 0.3% of the estimated present-day global transfer of phosphorus into the sediments and suggests that the Japan Sea constitutes an average sink for this element. The two main carriers of phosphorus into the present Japan Sea are the Tshushima and the Liman currents, importing approximately 6.6*10**10 g P and 5.7*10**10 g P per year, respectively. Bulk chemical analyses suggest that at least 36% of P total in the sediments is organically bound phosphorus. This rather high value, which corresponds to the measured Japan-Sea deep-water P organic/P total ratios, probably reflects rapid transport of organic phosphorus into the depth of the Japan Sea.

Geochemistry of ocean floor and forearc serpentinites

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg/g and 30 µg/g, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg/g level), except Sr in carbonate-bearing serpentinites (thousands of µg/g). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

(Supplement) Groundwater quality in Lahore Pakistan: emphasis on Arsenic and Fluoride levels

The dataset provides detailed information on the study that was conducted in Lahore's 7 major towns. The sample was taken from 472 tubewells and analyzed for major cations and anions using APHA 2012 techniques as explained herein. Besides, E.coli determination was done to check for microbial contamination. The data includes results from PHREEQC modeling of As(III)/ As(V) species and saturation indices as well as Aquachem's computed hydrochemical water facies. The WHO (2011) and EPA standards included in Aquachem identified the parameters that where in violation. Bicarbonates dominated the groundwater types with 50.21% of the samples exceeding the EPA maximum permissible limit of 250 mg/L in drinking water. Similarly, 30.51% of the samples had TDS values greater than 500 mg/L while 85.38 % of the samples exceed 10 µg/L threshold limit value of arsenic. Also, instances of high magnesium hazard values were observed which requires constant assessment if the groundwater is used for irrigation. Higher than 50% MH values are detrimental to crops which may reduce the expected yields. The membrane filtration technique using m-Endo Agar indicated that 3.59% samples had TNC (too numerous to count) values for E.coli while 5.06% showed values higher than 0 cfu/ 100 ml acceptable value in drinking water. Any traces of E-coli in a groundwater sample indicate recent fecal contamination. Such outcomes signify presence of enteric pathogens. If the groundwater is not properly dosed with disinfectants it may cause harm to human health. It is concluded that more studies are needed and proper groundwater management implement to safeguard the lives of communities that depend solely on groundwater in the city.

Geochemical composition and atomic formulas of saponites, celadonites and clays from ODP Leg 168 sites

A drilling transect across the sedimented eastern flank of the Juan de Fuca Ridge, conducted during Leg 168 of the Ocean Drilling Program, resulted in the recovery of samples of volcanic basement rocks (pillow basalts, massive basalts, and volcanic glass breccias) that exhibit the effects of low-temperature hydrothermal alteration. Secondary clays are ubiquitous, with Mg-rich and Fe-rich saponite and celadonitic clays commonly accounting for several percent, and up to 10%-20% by volume. Present-day temperatures of the basement sites vary from 15° to 64°C, with the coolest site being about 0.8 Ma, and the warmest site being about 3.5 Ma. Whereas clays are abundant at sites that have been heated to present temperatures of 23°C and higher, the youngest site at 15°C has only a small trace of secondary clay alteration. Alteration increases as temperatures increase and as the volcanic basement ages. The chemical compositions of secondary clays were determined by electron microprobe, and additional trace element data were determined by both conventional nebulization inductively coupled plasma-mass spectroscopy (ICP-MS) and laser-ablation ICP-MS. Trioctahedral saponite and pyrite are characteristic of the interior of altered rock pieces, forming under conditions of low-oxygen fugacity. Dioctahedral celadonite-like clays along with iron oxyhydroxide and Mg-saponite are characteristic of oxidized haloes surrounding the nonoxidized rock interiors. Chemical compositions of the clays are very similar to those determined from other deep-sea basalts altered at low temperature. The variable Mg:Fe of saponite appears to be a systematic function both of the Mg:Fe of the host rock and the oxidation state during water-rock interaction.

Concentrations and accumulation rates of platinum-group elements and rhenium in Pacific and Atlantic sediments, DSDP and ODP data

The nature of Re-platinum-group element (PGE; Pt, Pd, Ir, Os, Ru) transport in the marine environment was investigated by means of marine sediments at and across the Cretaceous-Tertiary boundary (KTB) at two hemipelagic sites in Europe and two pelagic sites in the North and South Pacific. A traverse across the KTB in the South Pacific pelagic clay core found elevated levels of Re, Pt, Ir, Os, and Ru, each of which is approximately symmetrically distributed over a distance of ~1.8 m across the KTB. The Re-PGE abundance patterns are fractionated from chondritic relative abundances: Ru, Pt, Pd, and Re contents are slightly subchondritic relative to Ir, and Os is depleted by ~95% relative to chondritic Ir proportions. A similar depletion in Os (~90%) was found in a sample of the pelagic KTB in the North Pacific, but it is enriched in Ru, Pt, Pd, and Re relative to Ir. The two hemipelagic KTB clays have near-chondritic abundance patterns. The ~1.8-m-wide Re-PGE peak in the pelagic South Pacific section cannot be reconciled with the fallout of a single impactor, indicating that postdepositional redistribution has occurred. The elemental profiles appear to fit diffusion profiles, although bioturbation could have also played a role. If diffusion had occurred over ~65 Ma, the effective diffusivities are ~10**?13 cm**2/s, much smaller than that of soluble cations in pore waters (~10**?6 cm**2/s). The coupling of Re and the PGEs during redistribution indicates that postdepositional processes did not significantly fractionate their relative abundances. If redistribution was caused by diffusion, then the effective diffusivities are the same. Fractionation of Os from Ir during the KTB interval must therefore have occurred during aqueous transport in the marine environment. Distinctly subchondritic Os/Ir ratios throughout the Cenozoic in the South Pacific core further suggest that fractionation of Os from Ir in the marine environment is a general process throughout geologic time because most of the inputs of Os and Ir into the ocean have Os/Ir ratios >/=1. Mass balance calculations show that Os and Re burial fluxes in pelagic sediments account for only a small fraction of the riverine Os (<10%) and Re (<0.1%) inputs into the oceans. In contrast, burial of Ir in pelagic sediments is similar to the riverine Ir input, indicating that pelagic sediments are a much larger repository for Ir than for Os and Re. If all of the missing Os and Re is assumed to reside in anoxic sediments in oceanic margins, the calculated burial fluxes in anoxic sediments are similar to observed burial fluxes. However, putting all of the missing Os and Re into estuarine sediments would require high concentrations to balance the riverine input and would also fail to explain the depletion of Os at pelagic KTB sites, where at most ~25% of the K-T impactor's Os could have passed through estuaries. If Os is preferentially sequestered in anoxic marine environments, it follows that the Os/Ir ratio of pelagic sediments should be sensitive to changes in the rates of anoxic sediment deposition. There is thus a clear fractionation of Os and Re from Ir in precipitation out of sea water in pelagic sections. Accordingly, it is inferred here that Re and Os are removed from sea water in anoxic marine depositional regimes.

Phosphate d18O pore-water profiles of sediment core GeoB11807-2 and GeoB11804-4

Phosphorus cycling in the ocean is influenced by biological and geochemical processes that are reflected in the oxygen isotope signature of dissolved inorganic phosphate (Pi). Extending the Pi oxygen isotope record from the water column into the seabed is difficult due to low Pi concentrations and small amounts of marine porewaters available for analysis. We obtained porewater profiles of Pi oxygen isotopes using a refined protocol based on the original micro-extraction designed by Colman (2002). This refined and customized method allows the conversion of ultra-low quantities (0.5 - 1 µmol) of porewater Pi to silver phosphate (Ag3PO4) for routine analysis by mass spectrometry. A combination of magnesium hydroxide co-precipitation with ion exchange resin treatment steps is used to remove dissolved organic matter, anions, and cations from the sample before precipitating Ag3PO4. Samples as low as 200 µg were analyzed in a continuous flow isotope ratio mass spectrometer setup. Tests with external and laboratory internal standards validated the preservation of the original phosphate oxygen isotope signature (d18OP) during micro extraction. Porewater data on d18OP has been obtained from two sediment cores of the Moroccan margin. The d18OP values are in a range of +19.49 to +27.30 per mill. We apply a simple isotope mass balance model to disentangle processes contributing to benthic P cycling and find evidence for Pi regeneration outbalancing microbial demand in the upper sediment layers. This highlights the great potential of using d18OP to study microbial processes in the subseafloor and at the sediment water interface.

Mineralogy and geochemistry of a basalt from ODP Hole 119-738C

The Lower Cretaceous tholeiitic basalt cored at Site 738, on the southernmost part of the Kerguelen Plateau, shows anomalous Sr, Nd, and Pb isotopic compositions compared to other lavas from Kerguelen Island and the Kerguelen Plateau. The strongly negative value of eNd (- 8.5) and high 207Pb/204Pb ratio (15.71) reflect a long-term evolution in a source high in Nd/Sm and µ. These geochemical properties, not observed in the Indian Ocean mantle plumes (St. Paul, Kerguelen Islands), have been reported for alkali lavas erupted in East Antarctica, thus suggesting that they originate from the Gondwana subcontinental lithosphere.