Chemical composition of zoobenthos and bottom sediments from the gas-hydrate seep area near the Paramushir Island, Kuril Island arc

Bioaccumulation of metals by zoobenthos was investigated during cruise 11A of R/V Akademik Mstislav Keldysh in the vicinity of a gas-hydrate seep off Paramushir Island in the Sea of Okhotsk. Atomic absorption studies of concentrations of Al, Fe, Mn, Ni, Cu and Zn in zoobenthos (polychaetes, bivalves, ophiurans and echinoderms) collected from depths of 700-800 m indicated that their concentrations in individuals near the seep were not significantly different from those in individuals from other communities. Obtained results indicate that sea urchins and holothurians (non-sorting bottom-feeders) can separate mineral fraction of ingested bottom material.

Sedimentation at Manop Site H in the eastern equatorial Pacific

Gravity cores recovered from Manganese Nodule Project site H (6°33'N, 92°49'W) show marked downcore variations in the abundance of calcium carbonate, organic carbon, opal, manganese, and other components deposited over the past 400,000 years. Variations in the downcore abundance of organic carbon, which ranges from 0.2 to 1.0%, can be used to hindcast redox conditions in the surface sediments over this time. The results indicate that the depth to the manganese redox boundary varied from about 5 to 25 cm below the seafloor during four major cycles. Downcore variations in solid phase Mn, Ni, and Cu can be produced by such changes in redox conditions. A model which predicts that solid phase Mn can be trapped and buried when the Mn redox boundary migrates rapidly upward is consistent with the observed organic carbon and Mn records and supports the reconstructed redox variations. The history of redox variations at site H can be explained by changes with time in surface water productivity. Major productivity variations at the site occur over 100-kyr cycles, with relatively higher productivity occurring during glacial stages. Thus Quaternary climate changes influence surface water productivity, redox conditions in sediments, and the cycling of transition metals.

(Table 1) Zoobenthos from the gas-hydrate seep area near the Paramushir Island and its chemical composition

Distributions of Mn, Fe, Cu, Cd, Cr, Co and Ni in sea water are investigated (42 samples, dissolved and particulate forms) in the vicinity of the underwater gas vent field on the northwestern slope of the Paramushir Island. While regular background distributions of the elements occur in the shore zone, there is a column of elevated concentrations of particulate matter, particulate Mn, and dissolved Mn, Fe, Cu, Cd, Cr, Co and Ni that coincides with location of the gas plume. This column can be traced as high as 780 m above the bottom. High metal concentrations in water of the plume are attributable to physico-chemical concentration at the phase interface; the source of elevated mineral concentrations is obviously flux of dissolved minerals from interstitial waters, which extends to considerable distances in vertical direction.

Geochemistry on water profiles from the Kara Sea

As a part of the Russian-German project "Siberian River-Runoff (SIRRO)" the major element composition of the dissolved load and the major and trace element composition of particulate load and bottom sediment of the Yenisei River and Estuary were analyzed and examined in context of the basin lithology and climate. In addition, the processes controlling the transformation of the river load in the estuarine mixing zone were investigated. The chemical composition of the dissolved and particulate load of the Yenisei fluvial endmember is generally comparable to that of other major world rivers. The dissolved load is chiefly controlled by carbonate weathering and the chemical composition of the river suspended particulate matter (SPM) is similar to that of the North American Shale Composite (NASC), which represents the weathering product of the upper continental crust. The Chemical Index of Alteration (CIA) of the Yenisei SPM amounts to 71, which indicates moderate chemical weathering. With regard to the SPM geochemistry, the Yenisei occupies an intermediate position between the adjacent rivers Khatanga and the Lena. Drastic changes in the composition of the river load are seen in the mixing zone between fresh and salt water. While dissolved Na, Ca, Mg, K, CI, S04, F, Br, Sr and HC03 behave conservatively, dissolved Fe is completely removed from solution at very low salinities. Particulate Mn exhibits a pronounced mid-salinity minimum concomitant with a maximum of dissolved Mn, which is probably related to suboxic conditions in the area of the so-called "marginal filter", where highest turbidities are found. The Mn-minimum in SPM is paralleled by depletions of the elements Ba, Zn, Cd, Ni, Cu and V, which can be associated with manganese particles. The estuarine bottom sediments are composed of mud and sand and the sedimentological parameters of the bottom sediments have to be considered for the interpretation of the bulk geochemical data. The chemical composition of the mud is comparable to the SPM, whereas the sand is relatively enriched in Si/Al, Ba/Al, Zr/Al and Sr/Al ratios and depleted in transition metals.

Chemistry of altered basaltic glass shards and zeolites of volcaniclastic sediments from ODP Hole 157-953C

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.

(Table 2) Chemical composition of surface sediments from stations of Cruise 11A of R/V Akademik Mstislav Keldysh

Distributions of Mn, Fe, Cu, Cd, Cr, Co and Ni in sea water are investigated (42 samples, dissolved and particulate forms) in the vicinity of the underwater gas vent field on the northwestern slope of the Paramushir Island. While regular background distributions of the elements occur in the shore zone, there is a column of elevated concentrations of particulate matter, particulate Mn, and dissolved Mn, Fe, Cu, Cd, Cr, Co and Ni that coincides with location of the gas plume. This column can be traced as high as 780 m above the bottom. High metal concentrations in water of the plume are attributable to physico-chemical concentration at the phase interface; the source of elevated mineral concentrations is obviously flux of dissolved minerals from interstitial waters, which extends to considerable distances in vertical direction.

PM2.5, PM10, and PM10-associated elements in the air in Bamako, Mali (2012-2013)

Saharan dust incursions and particulates emitted from human activities degrade air quality throughout West Africa, especially in the rapidly expanding urban centers in the region. Particulate matter (PM) that can be inhaled is strongly associated with increased incidence of and mortality from cardiovascular and respiratory diseases and cancer. Air samples collected in the capital of a Saharan-Sahelian country (Bamako, Mali) between September 2012 - July 2013 were found to contain inhalable PM concentrations that exceeded World Health Organization (WHO) and US Environmental Protection Agency (USEPA) PM2.5 and PM10 24-h limits 58 - 98% of days and European Union (EU) PM10 24-h limit 98% of days. Mean concentrations were 1.2-to-4.5 fold greater than existing limits. Inhalable PM was enriched in transition metals, known to produce reactive oxygen species and initiate the inflammatory reaction, and other potentially bioactive and biotoxic metals/metalloids. Eroded mineral dust composed the bulk of inhalable PM, whereas most enriched metals/metalloids were likely emitted from oil combustion, biomass burning, refuse incineration, vehicle traffic, and mining activities. Human exposure to inhalable PM and associated metals/metalloids over 24-h was estimated. The findings indicate that inhalable PM in the Sahara-Sahel region may present a threat to human health, especially in urban areas with greater inhalable PM and transition metal exposure.

Inorganic and organic geochemistry and sediment descriptions at DSDP Hole 93-603B

About one hundred samples of sediments and rocks recovered in Hole 603B were analyzed for type, abundance, and isotopic composition of organic matter, using a combination of Rock-Eval pyrolysis, C-H-N-S elemental analysis, and isotope-ratio mass spectrometry. Concentrations of major, minor, and trace inorganic elements were determined with a combination of X-ray fluorescence and induction-coupled plasma spectrometry. The oldest strata recovered in Hole 603B (lithologic Unit V) consist of interbedded light-colored limestones and marlstones, and black calcareous claystones of Neocomian age. The inorganic and organic geochemical results suggest a very terrigenous aspect to the black claystones. The organic geochemical results indicate that the limestones and marlstones contain a mixture of highly degraded marine and terrestrial organic matter. Comparison of the Neocomian carbonates at Site 603 with those on the other side of the North Atlantic, off Northwest Africa at Site 367, shows that the organic matter at Site 367 contains more marine organic matter, as indicated by higher pyrolysis hydrogen indices and lighter values of d13C. Comparison of inorganic geochemical results for the carbonate lithologies at Site 603 with those for carbonate lithologies at Site 367 suggests that the Site 603 carbonates may contain clastic material from both North American and African sources. The black claystones at Site 603, on the other hand, probably were derived almost entirely from North American clastic sources. Lithologic Unit IV overlying the Neocomian carbonates, consists of interbedded red, green, and black claystones. The black claystones at Site 603 contain more than ten times the organic carbon concentration of the interbedded green claystones. The average concentration of organic carbon in the black claystones (2.8%), however, is low relative to most mid-Cretaceous black claystones and shales in the Atlantic, particularly those found off Northwest Africa. The geochemical data all suggest that the organic matter in the black claystones is more abundant but generally more degraded than the organic matter in the green claystones, and that it was derived mainly from terrestrial sources and deposited in oxygenated bottom waters. The increased percentage of black claystone beds in the upper Cenomanian section, and the presence of more hydrogen-rich organic matter in this part of the section, probably resulted from the increased production and accumulation of marine organic matter that is represented worldwide near the Cenomanian/Turonian boundary in deep-sea and land sections. A few upper Cenomanian black claystone samples that have hydrogen indices > 150 also contain particularly high concentrations of V and Zn. Most samples of black claystone, however, are not particularly metal-rich compared with other black claystones and shales. Compared with red claystones from lithologic Unit IV, the green and black claystones are enriched in many trace transition elements, especially V, Zn, Cu, Co, and Pb. The main difference between the "carbonaceous" claystones of lithologic Unit IV and "variegated" or "multicolored" claystones of the overlying Upper Cretaceous to lower Tertiary Unit III is the absence of black claystone beds. As observed at several other sites (105 and 386), the multicolored claystones at Site 603 are somewhat enriched in several trace transition elements-especially Cu, Ni, and Cr-relative to most deep-sea clays. The multicolored claystones are not enriched in Fe and Mn, and therefore are not "metalliferous" sediments in the sense of those found at several locations in the eastern Pacific. The source of the slightly elevated concentrations of transition metals in the multicolored claystones probably is upward advection and diffusion of metals from the black claystones of the underlying Hatteras Formation. The red, orange, and green claystone beds of lithologic Unit II (Eocene), like those of Unit III, really represent a continuation of deposition of multicolored claystone that began after the deposition of the Neocomian carbonates. The color of the few black beds that occur within this unit results from high concentrations of manganese oxide rather than high concentrations of organic matter.

Geochemistry, mineralogy, and 40K-40Ar radiometric dating of DSDP Leg 84 basalts - Guatemala Trench

Geochemical (atomic absorption, neutron activation analyses), mineralogical (microprobe), and radiometric (40K - 40Ar) data are presented for five basalts from the Guatemala Trench area (Deep Sea Drilling Project, Leg 84). Strong geochemical and mineralogical differences distinguish two types among these basalts: (1) One basalt (Sample 567A-19,CC), recovered below Upper Cretaceous limestone has the following characteristics: it is quartz normative and has low TiO2, content, as well as low amounts of Cr, Ni and other transition metals, an LREE depleted pattern, and affinities of clinopyroxene phenocryst plotted into the field of tholeiitic and calc-alkalic pyroxenes. (2) Four alkaline basalts, recovered from the mafic and ultramafic acoustic basement, are nepheline normative and show high TiO2 content, high amounts of Cr, Ni and so on, an LREE enriched pattern and compositions of clinopyroxene phenocryst plotted close to or within the field of alkali basalt pyroxenes. These basalts are comparable to those recognized in the lower part of the Santa Elena complex and are clearly different from the oceanic basalts of the Cocos Plate. The radiometric age of the orogenic basalt seems to be close to 80 Ma. The alkaline basalts are clearly older, even if a discrepancy appears between the results of different analyses because of the secondary effects of alteration.

Annotated record of the detailed examination of Mn deposits from DSDP Site 160, Leg 16 (Cores 16-160-1, 16-160-2 and 16-160-3)

DSDP 160 forms part of a series of sites in the eastern equatorial Pacific on the west flank of the East Pacific Rise. Earlier legs of the Deep Sea Drilling Project, in particular Legs 5 and 9, have reported sediments rich in oxides of iron and perhaps other transition metals just above basement in the eastern Pacific. These occurrences roughly define a broad zone on the west flank of the rise. Site DSDP 160 lies on this trend and were selected by the Pacific Site Selection Panel to test the extent of such deposits.

(Table 1) Downcore age and bulk geochemistry of sediment core GS7202-35

The distribution of redox-sensitive metals in sediments is potentially a proxy for past ocean ventilation and productivity, but deconvolving these two major controls has proved difficult to date. Here we present a 740 kyr long record of trace element concentrations from an archived sediment core collected at ~15°S on the western flank of the East Pacific Rise (EPR) on 1.1 Myr old crust and underlying the largest known hydrothermal plume in the world ocean. The downcore trace element distribution is controlled by a variable diagenetic overprint of the inferred primary hydrothermal plume input. Two main diagenetic processes are operating at this site: redox cycling of transition metals and ferrihydrite to goethite transition during aging. The depth of oxidation in these sediments is controlled by fluctuations in the relative balance of bottom water oxygen and electron donor input (organic matter and hydrothermal sulfides). These fluctuations induce apparent variations in the accumulation of redox-sensitive species with time. Subsurface U and P peaks in glacial age sediments, in this and other published data sets along the southern EPR, indicate that basin-wide changes in deep ocean ventilation, in particular at glacial-interglacial terminations II, III, IV, and V, alter the depth of the oxidation front in the sediments. These basin-wide changes in the deep Pacific have significant implications for carbon partitioning in the ocean-atmosphere system, and the distribution of redox-sensitive metals in ridge crest sediment can be used to reconstruct past ocean conditions at abyssal depths in the absence of alternative proxy records.

Annotated record of the detailed examination of Mn deposits from DSDP Site 159, Leg 16 (Cores 16-159-6 and 16-159-12)

DSDP 159 is one of a series of sites in the eastern equatorial Pacific on the west flank of the East Pacific Rise. It was selected by the Pacific Site Selection Panel on the premise that if hydrothermal processes on the crest of the East Pacific Rise supply the transition metals, a broad zone of such deposits should be present immediately above basement over the entire flank of the Rise.

Precious metals and volatiles in rocks of the Mid-Atlantic Ridge near 15°20'N

Distribution patterns of gold, platinum group metals (PGE), and volatile components are studied in the main rock types of the Mid-Atlantic Ridge lithosphere (ultrabasites, gabbro, and basalts) from the transform fracture zone at 15°20'N. It is ascertained that PGE content depends on the reduction degree of fluids, on rock types, and on their formation conditions. It is noted that concentrations of refractory elements (Os, Ir, Rh) decrease, while those of fusible elements (Pt, Pd, Au) increase with depth. The chondrite type of distribution is only noted in the ultrabasite rocks. Increase in water and CO2 contents and in oxidation degree of fluids occurs with transition from basalts to ultrabasites, as well as from normal magmatic systems to fluid-enriched anomalous systems.