Geochemistry of surface sediment samples from the equatorial Atlantic south of the Azores

In order to recognize the distribution of hydrothermal tracers south of the Azores, a series of cores has been sampled during the GEOFAR cruise. The distribution of the Mn concentrations shows that the hydrothermal influence is maximum within and to the north-west of the Lucky Strike segment. North of the East-Azores Fracture Zone the sediments are enriched in Ba which could be derived from different sources. The chemical composition of the interstitial water shows that water advection is limited. Mn, Cu, Ni fluxes evaluated in one site have increased during isotopic stages 4 and 2 and the deglaciation.

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.

Major, trace and rare earth element concentration of ODP Site 210-1277 basalts, Newfoundland margin

Drilling of the distal Newfoundland margin at Ocean Drilling Program Site 1277 recovered part of the transition between exhumed sub-continental mantle lithosphere and normal mid-ocean-ridge basalt (N-MORB) volcanism perhaps related to the initiation of seafloor spreading, which may have occurred near the Aptian/Albian boundary, coincident with the final separation of subcontinental mantle lithosphere. Subcontinental mantle lithosphere was recovered near the crest of a basement high, the Mauzy Ridge. This ridge lies near magnetic Anomaly M1 and is inferred to be of Barremian age. The recovered section is dominated by serpentinized spinel harzburgite, with subordinate dunite and minor gabbroic intrusives, and it includes inferred high-temperature ductile shear zones. The serpentinite is capped by foliated gabbro cataclasite that is interpreted as the product of a major seafloor extensional detachment. The serpentinized harzburgite beneath is highly depleted subcontinental mantle lithosphere that was exhumed to create new seafloor within the ocean-continent transition zone. After inferred removal of overlying brittle crust, the detachment was eroded, producing multiple mass flows that were dominated by clasts of serpentinite and gabbro in a lithoclastic and calcareous matrix. Basaltic lavas were erupted spasmodically, mainly as sheet flows, with subordinate lava breccia, hyaloclastite, and possible pillow lava. The sedimentary-volcanic succession and the exhumed mantle lithosphere experienced later high-angle extensional fracturing and probably faulting. Extensional fissures opened incrementally and were filled with silt-sized carbonate, basalt-derived clastic sediment, and hyaloclastite, forming neptunian dykes and geopetal structures. Chemical analysis of representative basalts for major elements and trace elements were made using a high-precision, high-accuracy X-ray fluorescence method (utilizing increased count times) and by whole-rock inductively coupled plasma-mass spectrometry that yielded additional evidence for rare earth elements. The analyses indicate N-MORB to slightly enriched compositions. The MORB was produced by relatively high degree melting of a fertile mantle source that differed strongly from the cored serpentinized peridotites. The basalts exhibit a distinct negative Nb anomaly on MORB-normalized plots that can be explained by prior extraction of melt from upper mantle that had previously been affected by subduction, possibly during closure of the Iapetus or Rheic oceans. In the proposed interpretation, mantle lithosphere was exhumed to the seafloor and experienced mass wasting to form serpentinite-rich mass flows. The interbedded MORB records the beginning of a transition to "normal" seafloor spreading. This interpretation takes into account drilling results from the Iberia-Galicia margin and the Jurassic Alps-Apennines.

Element stratigraphy across the Cretaceous-Tertiary boundary in ODP Hole 119-738C

Neutron activation analyses of iridium and other chemical elements were performed across a 1-m-thick, partly nonbioturbated, clay-rich interval at the Cretaceous/Tertiary boundary in ODP Hole 738C. The results show that the boundary interval holds one of the highest Ir enrichments (320 ng Ir/cm2) of all known Cretaceous/Tertiary boundary layers. Iridium concentrations are highest (18 ppb Ir, whole-rock samples) a few centimeters above the base of the clayrich interval and gradually tail off upsection. Compared with background levels the most Ir-rich interval also shows strongly enhanced concentrations of Cr (215 ppm) and slightly elevated Co concentrations (13 ppm). The Ir-rich interval shows low As (< 15 ppm) and Sb (<0.8 ppm) concentrations, a fact that is congruent with absence of abundant authigenic sulfides in the sediment. Irregularly distributed Fe enrichments and a greenish gray color of the Fe-rich intervals may indicate the presence of glauconitic clay minerals and suboxic, slightly reducing conditions during deposition. Rare earth element (REE) abundance patterns change considerably across the Cretaceous/Tertiary boundary interval, reflecting either a change in Cretaceous/Tertiary boundary seawater REE composition or the occurrence of different REE fractionation processes due to changing depositional environment. Element-vs.-element ratios of Hf, Ta, Th, U, Cs, and Sc are similar between the most Ir-rich layers of the boundary section and other levels with lower Ir concentrations. This may imply that the clay fraction of the Ir-rich layers of the Cretaceous/Tertiary boundary interval is made up predominantly of locally derived material. Calculated calcite-free abundances of Hf, Ta, Th, U, Cs, and Sc, on the other hand, are reconcilable with an extraneous origin of the bulk of the clay in the most Ir-rich layers. The Ir in the Cretaceous/Tertiary boundary clay-rich zone in Hole 738C is most likely derived from an earth-impacting asteroid; however, the origin of the clay-rich zone remains enigmatic.

Grain size and chemical compositions of bottom sediments from the Amur Bay

Composition of clay minerals in the <0.001 mm size fraction from the uppermost layer of bottom sediments in the northern Amur Bay was determined by X-ray powder diffraction analysis, and enrichment of 33 elements in the <0.001 mm and <0.01 mm size fractions of surface sediments from a number of sites at the marginal filter of the Razdol'naya River were studied by ICP-MS. Fe, U, and chalcophile elements occur in the highest concentrations in sediments from all sampling sites within the filter. The bottom sediments are not enriched in trace, alkali, and alkaline earth elements. Maximum concentrations of chemical elements were found in deposits from the brackish part of the marginal filter, perhaps, because of formation of Fe and Mn (Al) hydroxides. Bottom sediments at the boundary between the brackish and marine parts of the filter contain the lowest concentrations of the examined elements.

Annual variations in composition of the North Dvina River water

New data on elemental composition of particulate matter from the North Dvina River are presented. In May (period of snowmelt flood) it is similar to the upper layer of the continental crust due to active erosion of crust material in the catchment area. In August (summer low water period) impact of biogenic components increases and elevated concentrations of Cd, Sb, Mn, Zn, Pb, and Cu are observed. At other seasons no significant increase in heavy and rare earth element concentrations is observed.

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.

Heavy metal concentrations in fauna from hydrothermal fields of the Mid-Atlantic Ridge

Distributions of Fe, Mn, Zn, Cu, Ni, Co, Cr, Pb, As, Ag, Cd, Se, Sb, and Hg in 128 samples of tissues of organisms that inhabit hydrothermal vent fields of the Mid-Atlantic Ridge (Menez Gwen, Snake Pit, and Rainbow) depending on the abiotic environmental parameters were studied. The majority of the elements studied showed direct correlations between their concentrations in fluids released and in tissues of hydrothermal organisms. A higher degree of bioaccumulation of metals was revealed in Bathymodiolus mussels and Rimicaris shrimps from the Rainbow hydrothermal vent field as compared to their analogues from the Menez Gwen and Snake Pit fields. This corresponds to maximal concentrations of the majority of the metals studied in the Rainbow high-temperature hydrothermal fluids. The highest degree of bioaccumulation of heavy metals was found in gills of symbiotrophic mussels Bathymodiolus and in maxillipeds of ectosymbiotic shrimps Rimicaris, i.e., in organs that function in dependence on chemosynthetic bacteria. Within the Rainbow vent field, the shrimps, which inhabit in biotopes with more high-temperature conditions and therefore are more strongly subjected to influence of fluids, were found to contain higher metal contents than mollusks. Fe-Mn hydroxide films that cover mussel shells might serve as important reservoirs of other metals related to Fe and Mn.

Geochemistry of ODP Site 123-765 sediments

Drilling at Site 765 in the Argo Abyssal Plain sampled sediments and oceanic crust adjacent to the Australian margin. Some day, this site will be consumed in the Java Trench. An intensive analytical program was conducted to establish this site as a geochemical reference section forcrustal recycling calculations. About 150 sediment samples from Site 765 were analyzed for major and trace elements. Downhole trends in the sediment analyses agree well with trends in sediment mineralogy, as well as in Al and K logs. The primary signal in the geochemical variability is dilution of a detrital component by both biogenic silica and calcium carbonate. Although significant variations in the nonbiogenic component occur through time, its overall character is similar to nearby Canning Basin shales, which are typical of average post-Archean Australian shales (PAAS). The bulk composition of the hole is calculated using core descriptions to weight the analyses appropriately. However, a remarkably accurate estimate of the bulk composition of the hole can be made simply from PAAS and the average calcium carbonate and aluminum contents of the hole. Most elements can be estimated within 30% in this way. This means that estimating the bulk composition of other sections dominated by detrital and biogenic components may require little analytical effort: calcium carbonate contents, average Al contents, and average shale values can be taken from core descriptions, geochemical logs, and the literature, respectively. Some of the geochemical systematics developed at Site 765 can be extrapolated along the entire Sunda Trench. However, results are general, and Site 765 should serve as a useful reference for estimating the compositions of other continental margin sections approaching trenches around the world (e.g., outboard of the Lesser Antilles, Aegean, and Eolian arcs).

(Table 2) Contents of trace elements in plankton from the White Sea

With a view to more complete understanding of the role of phyto- and zooplankton in biogeochemical cycles, spatial distributions of Fe, Mn, Co, Ni, Cr, Cu, Cd, Pb, Zn, As, Hg, and Corg in the White Sea seston (21 samples) collected in August 2004 during Cruise 64 of R/V ''Professor Shtokman'' were studied. It was shown that the elements in study are accumulated in plankton with enrichment factors from 10**2 for Hg to 10**5 for Fe, as compared to seawater. Spatial distribution of trace elements is determined by sources of their supply and correlates with distribution of primary production and biomass of zooplankton. Increased values of trace element contents (excluding As) are characteristic of the Dvina Bay, whereas the highest As concentrations were found in the Kandalaksha Bay.

Concentrations of As and other chemical elements in bottom sediments of the Baltic Sea

As is less toxic than Hg, Cd, Pb, Se, Zn, and Cu. The As clarke for clays and shales is 10 ppm. Our samples of bottom sediments from Kurshskii Bay were determined to contain from 15 to 26 ppm As and up to 34 ppm As in the vicinity of the Neman River mouth. Elevated As concentrations (50-114 ppm) were detected in four columns of subsurface bottom sediments (at depths of 10-65 cm) from the Vistula Lagoon. Elevated As concentrations (50-180 ppm) were also found in a few surface samples of sand from the Gdansk Deep near oil platform D-6. These sediments are either partly contaminated with anthropogenic As or contain Fe sulfides and glauconite, which can concentrate As and contain its elevated concentrations. The As concentration in columns of bottom sediments from the Gulf of Finland were at the natural background level (throughout the columns) typical of the area (9-34 ppm). We repeatedly detected very high As concentrations (up to 227 ppm As) in politic ooze from Bornholm Deep, in the vicinity of the sunken vessel with chemical weapons. The sources of elevated As concentrations in the Baltic Sea are the following: (1) chemical weapon (CW) material buried in the floor of the Baltic Sea; (2) As-bearing pesticides, agricultural mineral fertilizers, and burned coal and other fuels; (3) kerogen-bearing Ordovician rocks exposed on the bottom; and (4) As-rich Fe sulfides brought to the area together with construction sand and gravel. This mixture was used in paper production and for the construction of hydraulic engineering facilities in the Vistula Lagoon in the early 20th century and later caused the so-called lagoon disease.

Composition of standard reference samples of Fe-Mn nodules and bottom sediments

The first series of Soviet standard reference samples of composition of ore materials and ocean pelagic sediments has been created. It includes iron-manganese nodules (SDO-4, SDO-5 and SDO-6), ore crusts (SDO-7) diatomaceous ooze (SDO-8), and deep-sea red clays (SDO-9). The standards are intended to serve as a metrologic basis for physical, physicochemical and chemical analyses of iron-manganese minerals and ocean sediments. The standards are provided with certified analyses of rock-forming components and certain trace elements. Certified characteristics are based on statistical analysis of data obtained from an inter-laboratory experiment involving analysis of the standard reference samples by a variety of methods.

Seafloor hydrothermal activity in sediment core MV0502-15JC

A large diameter piston core containing 8.35 m of metalliferous sediment has been recovered from a small abyssal valley in the remote Southwest Pacific Basin (31°42.194'S, 143°30.331'W; 5082 m water depth), providing unique insight into hydrothermal activity and eolian sedimentation there since the early Oligocene. A combination of fish-teeth Sr-isotope stratigraphy and INAA geochemical data reveals an exponentially decreasing hydrothermal flux 31 Ma to the present. Although hydrothermal sedimentation related to seafloor spreading explains this trend, a complex history of late Eocene/early Oligocene ridge jumps, propagating rifts and plate tectonic reorganization of South Pacific seafloor could have also played a role. A possible hiatus in deposition, as recorded by changes in core composition just below 2 m depth, is beyond the resolution of the fish teeth Sr isotope dating method employed here; however, the timing of this interval may be coincident with extinction of the Pacific-Farallon Ridge at ~20 Ma. A low flux eolian component accumulating at this site shows an increase relative to the hydrothermal component above 2 m depth, consistent with dust-generating continental sources far to the west (Australia/New Zealand). This is the first long-term paleoceanographic record obtained from within the South Pacific "bare zone" (Rea et al., 2006), an anomalous region where Pacific seafloor has largely escaped sediment accumulation since the Late Cretaceous.