Rare earth elements determined in Antarctic ice by inductively coupled plasma

Inductively coupled plasma mass spectrometry (ICP-MS) is a suitable tool for multi-element analysis at low concentration levels. Rare earth element (REE) determinations in standard reference materials and small volumes of molten ice core samples from Antarctica have been performed with an ICP-time of flight-MS (ICP-TOF-MS) system. Recovery rates for REE in e.g. SPS-SW1 amounted to not, vert, similar ~103%, and the relative standard deviations were 3.4% for replicate analysis at REE concentrations in the lower ng/l range. Analyses of REE concentrations in Antarctic ice core samples showed that the ICP-TOF-MS technique meets the demands of restricted sample mass. The data obtained are in good agreement with ICP-Quadrupole-MS (ICP-Q-MS) and ICP-Sector Field-MS (ICP-SF-MS) results. The ICP-TOF-MS system determines accurately and precisely REE concentrations exceeding 5 ng/l while between 0.5 and 5 ng/l accuracy and precision are element dependent.

Pigment data set from the SeaWiFS Bio-optical Archive and Storage System (1961-1996)

The oceans play a critical role in the Earth's climate, but unfortunately, the extent of this role is only partially understood. One major obstacle is the difficulty associated with making high-quality, globally distributed observations, a feat that is nearly impossible using only ships and other ocean-based platforms. The data collected by satellite-borne ocean color instruments, however, provide environmental scientists a synoptic look at the productivity and variability of the Earth's oceans and atmosphere, respectively, on high-resolution temporal and spatial scales. Three such instruments, the Sea-viewing Wide Field-of-view Sensor (SeaWiFS) onboard ORBIMAGE's OrbView-2 satellite, and two Moderate Resolution Imaging Spectroradiometers (MODIS) onboard the National Aeronautic and Space Administration's (NASA) Terra and Aqua satellites, have been in continuous operation since September 1997, February 2000, and June 2002, respectively. To facilitate the assembly of a suitably accurate data set for climate research, members of the NASA Sensor Intercomparison and Merger for Biological and Interdisciplinary Oceanic Studies (SIMBIOS) Project and SeaWiFS Project Offices devote significant attention to the calibration and validation of these and other ocean color instruments. This article briefly presents results from the SIMBIOS and SeaWiFS Project Office's (SSPO) satellite ocean color validation activities and describes the SeaWiFS Bio-optical Archive and Storage System (SeaBASS), a state-of-the-art system for archiving, cataloging, and distributing the in situ data used in these activities.

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).

Sr-Nd isotopic analyses of sand-sized sediment from the San Francisco Bay coastal system

A diverse suite of geochemical tracers, including 87Sr/86Sr and 143Nd/144Nd isotope ratios, the rare earth elements (REEs), and select trace elements were used to determine sand-sized sediment provenance and transport pathways within the San Francisco Bay coastal system. This study complements a large interdisciplinary effort (Barnard et al., 2012) that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine-coastal setting. Sand-sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources (fluvial and rock) throughout the bay, adjacent coast, and beaches. Due to their intrinsic geochemical nature, 143Nd/144Nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the Pacific Ocean. For example, Nd isotopes confirm that the predominant source of sand-sized sediment to Suisun Bay, San Pablo Bay, and Central Bay is the Sierra Nevada Batholith via the Sacramento River, with lesser contributions from the Napa and San Joaquin Rivers. Isotopic ratios also reveal hot-spots of local sediment accumulation, such as the basalt and chert deposits around the Golden Gate Bridge and the high magnetite deposits of Ocean Beach. Sand-sized sediment that exits San Francisco Bay accumulates on the ebb-tidal delta and is in part conveyed southward by long-shore currents. Broadly, the geochemical tracers reveal a complex story of multiple sediment sources, dynamic intra-bay sediment mixing and reworking, and eventual dilution and transport by energetic marine processes. Combined geochemical results provide information on sediment movement into and through San Francisco Bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system (e.g., dike and dam construction) as well as those which directly remove sediments from within the Bay, such as aggregate mining and dredging, can have long-lasting effects.

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Images of a groundwater flow system in Nicaragua

Conceptualization of groundwater flow systems is necessary for water resources planning. Geophysical, hydrochemical and isotopic characterization methods were used to investigate the groundwater flow system of a multi-layer fractured sedimentary aquifer along the coastline in Southwestern Nicaragua. A geologic survey was performed along the 46 km2 catchment. Electrical resistivity tomography (ERT) was applied along a 4.4 km transect parallel to the main river channel to identify fractures and determine aquifer geometry. Additionally, three cross sections in the lower catchment and two in hillslopes of the upper part of the catchment were surveyed using ERT. Stable water isotopes, chloride and silica were analyzed for springs, river, wells and piezometers samples during the dry and wet season of 2012. Indication of moisture recycling was found although the identification of the source areas needs further investigation. The upper-middle catchment area is formed by fractured shale/limestone on top of compact sandstone. The lower catchment area is comprised of an alluvial unit of about 15 m thickness overlaying a fractured shale unit. Two major groundwater flow systems were identified: one deep in the shale unit, recharged in the upper-middle catchment area; and one shallow, flowing in the alluvium unit and recharged locally in the lower catchment area. Recharged precipitation displaces older groundwater along the catchment, in a piston flow mechanism. Geophysical methods in combination with hydrochemical and isotopic tracers provide information over different scales and resolutions, which allow an integrated analysis of groundwater flow systems. This approach provides integrated surface and subsurface information where remoteness, accessibility, and costs prohibit installation of groundwater monitoring networks.

Geochemistry of rare earth elements in basalts from Walvis Ridge

Selected basalts from a suite of dredged and drilled samples (IPOD sites 525, 527, 528 and 530) from the Walvis Ridge have been analysed to determine their rare earth element (REE) contents in order to investigate the origin and evolution of this major structural feature in the South Atlantic Ocean. All of the samples show a high degree of light rare earth element (LREE) enrichment, quite unlike the flat or depleted patterns normally observed for normal mid-ocean ridge basalts (MORBs). Basalts from Sites 527, 528 and 530 show REE patterns characterised by an arcuate shape and relatively low (Ce/Yb)N ratios (1.46-5.22), and the ratios show a positive linear relationship to Nb content. A different trend is exhibited by the dredged basalts and the basalts from Site 525, and their REE patterns have a fairly constant slope, and higher (Ce/Yb)N ratios (4.31-8.50). These differences are further reflected in the ratios of incompatible trace elements, which also indicate considerable variations within the groups. Mixing hyperbolae for these ratios suggest that simple magma mixing between a 'hot spot' type of magma, similar to present-day volcanics of Tristan da Cunha, and a depleted source, possibly similar to that for magmas being erupted at the Mid-Atlantic Ridge, was an important process in the origin of parts of the Walvis Ridge, as exemplified by Sites 527, 528 and 530. Site 525 and dredged basalts cannot be explained by this mixing process, and their incompatible element ratios suggest either a mantle source of a different composition or some complexity to the mixing process. In addition, the occurrence of different types of basalt at the same location suggests there is vertical zonation within the volcanic pile, with the later erupted basalts becoming more alkaline arid more enriched in incompatible elements. The model proposed for the origin and evolution of the Walvis Ridge involves an initial stage of eruption in which the magma was essentially a mixture of enriched and depleted end-member sources, with the N-MORB component being small. The dredged basalts and Site 525, which represent either later-stage eruptives or those close to the hot spot plume, probably result from mixing of the enriched mantle source with variable amounts and variable low degrees of partial melting of the depleted mantle source. As the volcano leaves the hot spot, these late-stage eruptives continue for some time. The change from tholeiitic to alkalic volcanism is probably related either to evolution in the plumbing system and magma chamber of the individual volcano, or to changes in the depth of origin of the enriched mantle source melt, similar to processes in Hawaiian volcanoes.

(Tables 1-3) Pb and Sr isotopic data for sediments and rocks from DSDP holes in the Mariana island-arc system

Analyses of the isotopic composition of Pb in (1) western Pacific Ocean sediments [Jurassic(?) to Pleistocene in age, including clays and biogenic oozes], (2) Pacific Ocean basaltic rocks, (3) Mariana frontal arc volcanic rocks (Eocene to Miocene), and (4) Mariana active arc volcanic rocks [Pliocene (?) to Holocene] indicate that Pacific Ocean sediments could not have been a significant component of the source material for the Mariana arc volcanic rocks. Calculations involving the average concentrations and isotopic compositions of Pb in oceanic sediments, sea-floor basaltic rocks, and the Mariana arc volcanic rocks suggest that the sediment component must have been less than 1 percent of this source material. The Pb isotopic compositions of the Mariana arc volcanic rocks lie, within experimental error, along the trend of available Pacific Ocean basalt analyses in versus 207Pb/204Pb versus 206Pb/204Pb and 208Pb/204Pb versus 206Pb/204Pb diagrams. Isotopic analyses of Pb in Pacific Ocean sediments do not lie along this trend; they have higher 207Pb/204Pb and 208Pb/204Pb values for comparable 206Pb/204Pb ratios. Clayey sediments generally have higher 208Pb/204Pb and 207Pb/204Pb ratios than biogenic oozes regardless of the age of the sediment. Comparison of combined Sr and Pb isotopic analyses for (1) mantle-derived materials erupted through oceanic crust, (2) altered ocean-floor basaltic rocks, and (3) volcanic rocks from oceanic island arcs suggests that the Mariana arc volcanic rocks were derived, at least in part, from altered Pacific lithosphere subducted beneath the Mariana arc. Unaltered basalts from the Mariana inter-arc basin (Mariana Trough) have Pb and Sr isotopic compositions that are very similar to those reported for some Hawaiian volcanic rocks but distinct from Mariana active and frontal arc compositions. These observations, in addition to existing major-and trace-element data, support a mantle origin for the interarc basin volcanic rocks. Dacites dredged from the Mariana remnant arc (South Honshu Ridge) have Pb isotopic compositions that are within experimental error of the active-arc analyses, consistent with a genetic relation.