Comparison of nitrogen isotopic values from different preparation methods

We are writing to comment on the work of Tamburini et al. (2003, doi:10.1029/2000PA000616). During the course of subsequent discussions between the authors and ourselves, it has become clear that the published sedimentary nitrogen isotopic values for Ocean Drilling Program (ODP) Site 724 are in error. Our reanalysis of sediment samples from the same intervals has revealed a significant offset from the original d15N data, requiring a revised assessment of their initial interpretation. The purposes of this comment are to (1) address the origin of these errors; (2) outline a protocol for future validation of nitrogen isotopic analyses; and (3) provide revised interpretations of the sedimentary d15N data in terms of the regional relative contributions of denitrification and nitrogen fixation and mean state of the southwest monsoon. (2) Nitrogen isotopic values measured on late Quaternary sediments at Arabian Sea ODP Site 724 by Tamburini et al. (2003, doi:10.1029/2000PA000616) are inexplicably different from a number of published records of d15N from very nearby on the Oman margin (Altabet et al., 1995, doi:10.1038/373506a0; 1999, doi:10.1029/1999PA900035; 2002, doi:10.1038/415159a; Higginson et al., 2004, doi:10.1016/j.gca.2004.03.015) and elsewhere in the Arabian Sea (Reichart et al., 1998, doi:10.1029/98PA02203). These data were generated using similar instrumentation (elemental analyzer coupled with an isotope ratio mass spectrometer) and analytical methodology to those already published. Concerned by this clear discrepancy, we analyzed aliquots of sediment from the same depth intervals for nitrogen abundance and bulk sedimentary nitrogen isotopes. We have been unable to duplicate the values published by Tamburini et al. (2003, doi:10.1029/2000PA000616 ), even after analysis of multiple replicates and due consideration of natural sediment heterogeneities and postrecovery sample storage.

Color reflectance and XRF drill core scanner data of ANDRILL core AND-2A

The compositional record of the AND-2A drillcore is examined using petrological, sedimentological, volcanological and geochemical analysis of clasts, sediments and pore waters. Preliminary investigations of basement clasts (granitoids and metasediments) indicate both local and distal sources corresponding to variable ice-volume and ice-flow directions. Low abundance of sedimentary clasts (e.g., arkose, litharenite) suggests reduced contributions from sedimentary covers while intraclasts (e.g., diamictite, conglomerate) attest to intrabasinal reworking. Volcanic material includes pyroclasts (e.g., pumice, scoria), sediments and lava. Primary and reworked tephra layers occur within the Early Miocene interval (1093 to 640 metres below sea floor mbsf). The compositions of volcanic clasts reveal a diversity of alkaline types derived from the McMurdo Volcanic Group. Finer-grained sediments (e.g., sandstone, siltstone) show increases in biogenic silica and volcanic glass from 230 to 780 mbsf and higher proportions of terrigenous material c. 350 to 750 mbsf and below 970 mbsf. Basement clast assemblages suggest a dominant provenance from the Skelton Glacier - Darwin Glacier area and from the Ferrar Glacier - Koettlitz Glacier area. Provenance of sand grains is consistent with clast sources. Thirteen Geochemical Units are established based on compositional trends derived from continuous XRF scanning. High values of Fe and Ti indicate terrigenous and volcanic sources, whereas high Ca values signify either biogenic or diagenic sources. Highly alkaline and saline pore waters were produced by chemical exchange with glass at moderately elevated temperatures.

Average chemical composition of lake ores of Finland and North-Eastern Russia extracted in the late nineteen century

According to Solitander C. P., the extraction of lake ore from Eastern Finland lakes considerably rose in the 1870 - 1880 period in relation with the increasing demand from the ironworks being operated in the region. In St. Petersburg, Nicholas Putiloff, a business tycoon and State Minister owned the Haapakosken, Huutokosken and Oravin ironworks which were using 99% of lake ore for their supply. During this period the biggest production came from lake Sysmäjärvi in the Joroinen county with 3676 tonnes at an average concentration of 35.94% Fe, 4.55% Mn, 0.26% P and 0.04% S. The Värtsilä ironworks used the lake ore coming from 49 lakes, the biggest production coming from lake Loitimojärvi with 14535 tonnes of ore with a medium at concentration of 30.8% Fe. Möhkö ironworks took advantage of the 59 lakes, the largest of which was from lake Koitere with 4301 tonnes at 41.3% Fe. The Karttula ironworks were also significant in the consumption of ferromanganese lake ore.

Pore water and solid phase geochemistry of sediment core US5B

Studies of authigenic phosphorus (P) minerals in marine sediments typically focus on authigenic carbonate fluorapatite, which is considered to be the major sink for P in marine sediments and can easily be semi-quantitatively extracted with the SEDEX sequential extraction method. The role of other potentially important authigenic P phases, such as the reduced iron (Fe) phosphate mineral vivianite (Fe(II)3(PO4)*8H2O) has so far largely been ignored in marine systems. This is, in part, likely due to the fact that the SEDEX method does not distinguish between vivianite and P associated with Fe-oxides. Here, we show that vivianite can be quantified in marine sediments by combining the SEDEX method with microscopic and spectroscopic techniques such as micro X-ray fluorescence (µXRF) elemental mapping of resin-embedded sediments, as well as scanning electron microscope-energy dispersive spectroscopy (SEM-EDS) and powder X-ray diffraction (XRD). We further demonstrate that resin embedding of vertically intact sediment sub-cores enables the use of synchrotron-based microanalysis (X-ray absorption near-edge structure (XANES) spectroscopy) to differentiate between different P burial phases in aquatic sediments. Our results reveal that vivianite represents a major burial sink for P below a shallow sulfate/methane transition zone in Bothnian Sea sediments, accounting for 40-50% of total P burial. We further show that anaerobic oxidation of methane (AOM) drives a sink-switching from Fe-oxide bound P to vivianite by driving the release of both phosphate (AOM with sulfate and Fe-oxides) and ferrous Fe (AOM with Fe-oxides) to the pore water allowing supersaturation with respect to vivianite to be reached. The vivianite in the sediment contains significant amounts of manganese (~4-8 wt.%), similar to vivianite obtained from freshwater sediments. Our results indicate that methane dynamics play a key role in providing conditions that allow for vivianite authigenesis in coastal surface sediments. We suggest that vivianite may act as an important burial sink for P in brackish coastal environments worldwide.

Geochemistry, and Nd- and Pb-isotopic composition of basalts from the upper oceanic crust of the Costa Rica Rift

The DSDP/ODP Hole 504B, drilled in the 5.9 Ma southern flank of the Costa Rica Rift, represents the deepest section through modern ocean floor basaltic basement. The hole penetrates a 570 m thick volcanic zone, a 210 m thick transition zone of volcanic rocks and dykes, and 1056 m of dykes. A representative selection of these basalt types has been investigated with respect to Nd and Pb isotopes. The epsilonNd of the basalts varies from 7.62 to 11.16. This range in the Nd-isotope composition represents about 67% of the total range reported for Pacific MORB. The Pb-isotope composition also shows significant variation, with 206Pb/204Pb varying from 17.90 to 18.82. The isotopic data show that a small volume of enriched mantle existed in the source. The large ranges in isotopic composition in a single drill hole demonstrate the importance of small-scale mantle heterogeneities in the petrogenesis of MORB. Fractional melting and extraction of small magma batches by channelled flow, and small, short-lived crustal magma reservoirs, with limited potential for mixing of the mantle derived magmas, are favored by these isotopic data.

(Table T2) Biogenic opal in Palmer Deep sediments at ODP Site 178-1098

High-resolution records of sedimentary proxies provide insights into fine-scale geochemical responses to climatic forcing. Gamma-ray attenuation (GRA) bulk-density data and magnetic stratigraphy records from Palmer Deep, Site 1098, show variability close to the same scale as ice cores, making this site ideal for high-resolution geochemical investigations. In conjunction with shipboard geophysical measurements, silica records allow high-resolution evaluation of the frequencies and amplitudes of biogenic variability. This provides investigators additional data sets to evaluate the global extent of climatic events that are presently defined by regional oceanic data sets (e.g., Younger Dryas in the North Atlantic) and to evaluate the potential mechanisms that link biological productivity and climate in the Southern Ocean. In addition, because of the observed links between diatom blooms and export productivity (Michaels and Silver, 1988, doi:10.1016/0198-0149(88)90126-4), biogenic silica may be an indicator of the efficiency of the biological pump (removal of organic carbon from the euphotic zone and burial within the sediments). Because the net removal of CO2 (on short time scales up to millennial, the balance between upwelled CO2, carbon fixation, and the removal of organic carbon from the surface ocean) can determine the atmospheric concentration; proxies that allow us to quantify export production yield insights into carbon cycle responses. In today's ocean, diatoms are integrally linked with new production (production based on the use of nitrate and molecular nitrogen rather than ammonium, which is generated by the microbial degradation of organic carbon) (Dugdale and Goering, 1967). Thus, as with nutrient utilization proxies, biogenic silica may be a good indicator of export production. The difficulties lie in translating the biogenic opal burial records to export production. Numerous factors control the preservation of sedimentary biogenic silica, including depth of the water column, water temperature, trace element chemistry, grazing pressure, bloom structure, and species composition of the diatom assemblage (Nelson et al., 1995, doi:10.1029/95GB01070). In addition, several recent investigations have noted additional complications. Iron limitation increases the uptake of Si relative to carbon (Hutchins et al., 1998, ; Takeda, 1998, doi:10.1038/31674). In the Southern Ocean, iron limitation could produce more robust, and thus better preserved, diatoms; thus, the burial record may be a record of iron limitation rather than of the export of organic carbon (Boyle, 1998). In addition, laboratory experiments show that bacteria accelerate the dissolution of biogenic silica (Bidle and Azam, 1999, doi:10.1038/17351). Both the species composition and temperature seem to influence the amount of dissolution. Evidence of recycling of silicic acid within the photic zone (Brzezinski et al., 1997) suggests that the silica pump (removal from the euphotic zone of silica relative to nitrogen and phosphorus) may work with variable efficiency. This becomes an issue when trying to reconstruct the removal of organic carbon from sedimentary biogenic silica records. In fact, there is a wide range in the Si:Corganic molar ratio in the Southern Ocean (0.18-0.81) (Nelson et al., 1995; Ragueneau et al., 2000, doi:10.1016/S0921-8181(00)00052-7). Thus, the presence (or absence) of biogenic silica alone may tell us little about the export productivity, complicating the interpretation of age-related trends. One recent assessment has added some hope to links between productivity and opal burial in the Southern Ocean (Pondaven et al., 2000). Quantitative comparison of different productivity proxies will greatly aid in this evaluation.