(Table 4) Chemistry of iron-rich basalts from ODP Hole 106-648B

Analysis numbers 344-370, SAMF 12.5-12.7; 442-369, SAMF 12.7-12.9; 422-77, SAMF 12.9-13.1; 95-156, SAMF 13.1-13.3; 272-82, SAMF 13.3-13.5; 285-33, SAMF 13.5-13.7. Analyses are listed in depth order within each SAMF division.

(Table 1, page 168) Iron, manganese, and phosphorus concentrations in Fe-Mn-concretions from the Gulf of Bothnia, northern Baltic Sea

Fe-Mn-concretions of a spheroidal type were found according to electron probe determinations to consist of alternating iron- and manganese-rich layers. This pattern was ascribed to seasonal variations in the physico-chemical conditions governing the precipitation of the hydrous oxides of iron and manganese. Calculations based on the rhythmic growth of the concretions investigated gave a mean accumulation rate of 0.15-0.20 mm/yr. The rather high phosphorus content (average 3.5 % P2O5) of the concretions was found to be concentrated in the iron-rich layers, probably as a result of the scavenging effect of ferric hydroxide.

(Table 2, Page 106-107) Composition of the HCl-soluble fraction in Barents Sea iron-manganese deposits

Ferromanganese concretions from ten stations in the Barents Sea have been analysed for 24 elements. The deposits occur as discoidal and flat concretions and as coatings, in the latter case on lithified or detrital material or as extensive pavements on the Svalbard shelf. The concretions are compositionally similar to Baltic concretions but differ considerably from deep-ocean nodules, particularly in Cu, Ni and Co contents. Statistical analyses reveal distinct correlations between Mn, Na, Ba, Ni and Cu; the Mn-rich coatings showed enrichment of Mo, Zn and possibly Co in a Mn-phase. The iron phase holds high concretions of P and As. Two iron-rich concretions with high contents of P, Ca, Sr, Y, Yb and La were found east and northeast of Spitsbergen Banken, probably indicating upwelling of nutrient-rich, cold polar water along the Svalbard shelf.

(Table 1, page 126) Concentration of elements in Fe and Mn rich pisoliths (nodules) from Lake Storsjoen, South Norway

A detailed description of the ores of Lake Storsjoen was given by Vogt J. H. L., 1915 who pointed out that the ores may be divided into two principal types; first, iron ore with 2% or less of manganese (ex: Ertemalm), and, second, ores with manganese contents of up to 30% (ex: Korinter). The iron-rich ore sometimes occurs as a conglomerate embedded in manganese-rich ores, clearly demonstrating that two distinctly different precipitates are involved. In the iron-rich ore, a concentric structure is common of which light brown layers of loose, almost dusty material alternate with hard and brittle black layers, the thickness of each being 0.5 mm or less. The analyses presented in this paper seem to demonstrate that the composition of the sedimentary ores of Lake Storsjden could result from fluctuations in the composition of ground waters feeding the lake.

Sediment and pore water geochemistry of sediment cores, Potter Cove, King George Island

Redox-sensitive trace metals (Mn, Fe, U, Mo, Re), nutrients and terminal metabolic products (NO3-, NH4+, PO43-, total alkalinity) were for the first time investigated in pore waters of Antarctic coastal sediments. The results of this study reveal a high spatial variability in redox conditions in surface sediments from Potter Cove, King George Island, western Antarctic Peninsula. Particularly in the shallower areas of the bay the significant correlation between sulphate depletion and total alkalinity, the inorganic product of terminal metabolism, indicates sulphate reduction to be the major pathway of organic matter mineralisation. In contrast, dissimilatory metal oxide reduction seems to be prevailing in the newly ice-free areas and the deeper troughs, where concentrations of dissolved iron of up to 700 µM were found. We suggest that the increased accumulation of fine-grained material with high amounts of reducible metal oxides in combination with the reduced availability of metabolisable organic matter and enhanced physical and biological disturbance by bottom water currents, ice scouring and burrowing organisms favours metal oxide reduction over sulphate reduction in these areas. Based on modelled iron fluxes we calculate the contribution of the Antarctic shelf to the pool of potentially bioavailable iron (Feb) to be 6.9x10**3 to 790x10**3 t/yr. Consequently, these shelf sediments would provide an Feb flux of 0.35-39.5/mg/m**2/yr (median: 3.8 mg/m**2/yr) to the Southern Ocean. This contribution is in the same order of magnitude as the flux provided by icebergs and significantly higher than the input by aeolian dust. For this reason suboxic shelf sediments form a key source of iron for the high nutrient-low chlorophyll (HNLC) areas of the Southern Ocean. This source may become even more important in the future due to rising temperatures at the WAP accompanied by enhanced glacier retreat and the accumulation of melt water derived iron-rich material on the shelf.

Mineralogy of sediment core GeoB3313-1

Geochemical and clay mineral parameters of a high accumulation marine sediment core from the Chilean continental slope (41°S) provide a 7700 yr record of rainfall variability in southern Chile related to the position of the Southern Westerlies. We especially use the iron content, measured with a time-resolution of ca. 10 yr on average, of 14C-accelerator mass spectrometry dated marine sediments as a proxy for the relative input of iron-poor Coastal Range and iron-rich Andean source rocks. Variations in this input are most likely induced by rainfall changes in the continental hinterland of the core position. Based on these interpretations, we find a pronounced rainfall variability on multi-centennial to millennial time-scales, superimposed on generally more arid conditions during the middle Holocene (7700 to 4000 cal yr B.P.) compared to the late Holocene (4000 to present). This variability and thus changes in the position of the Southern Westerlies are first compared to regional terrestrial paleoclimate data-sets from central and southern Chile. In order to derive possible wider implications and forcing mechanisms of the Holocene latitudinal shifts of the Southern Westerlies, we then compare our data to ice-core records from both tropical South America and coastal Antarctica. These records show similar bands of variability centered at ca. 900 and 1500 yr. Comparisons of band pass filters suggest a close connection of shifts of the Southern Westerlies to changes within the tropical climate system. The correlation to climate conditions in coastal Antarctica shows a more complicated picture with a phase shift at the beginning of the late Holocene coinciding with the onset of the modern state of El Niño-Southern Oscillation system. The presented data provide further evidence that the well known millennial-scale climate variability during the last glacial continued throughout the Holocene.

Chemistry of gabbroic rocks of ODP Hole 118-735B

We present results of a microprobe investigation of fresh and least-deformed and metamorphosed gabbroic rocks from Leg 118, Hole 735B, drilled on the east side of the Atlantis II Fracture Zone, Southwest Indian Ridge. This rock collection comprises cumulates ranging from troctolites to olivine-gabbro and olivine-gabbronorite to ilmenite-rich ferrogabbros and ferrogabbronorites. As expected, the mineral chemistry is variable and considerably expands the usual oceanic reference spectrum. Olivine, plagioclase, and clinopyroxene are present in all the studied samples. Orthopyroxene and ilmenite, although not rare, are not ubiquitous. Olivine compositions range from Fo85 to Fo30, while plagioclase compositions vary from An70 to An27. Mg/(Mg + Fe2+) of clinopyroxene (mostly diopside to augite) varies from 0.88 to 0.54. Mg/(Mg + Fe2+) of orthopyroxene varies from 0.84 to 0.50. These minerals are not significantly zoned. All mineralogical data indicate that fractional crystallization is an important factor for the formation of cumulates. However, sharp contacts, interpreted as layering boundaries or intrusion margins, suggest polycyclic fractionation of several magma batches of limited volumes. Calculated compositions of magmas in equilibrium with the most magnesian mineral samples at the bottom of the hole represent fractionated liquids through separation of olivine, plagioclase, and clinopyroxene at moderate to low pressures (less than 9 kb). Crystallization of orthopyroxene and ilmenite occurs in the most differentiated liquids. Mixing of magmas having various compositions before entering the cumulate zone is another mechanism necessary to explain extremely differentiated iron-rich gabbros formed in this slow-spreading ridge environment.

Stable isotope composition of carbonates in the Tyrrhenian Sea

The Messinian evaporitic succession recovered at ODP Sites 652, 653, and 654 in the Tyrrhenian Sea was generated under various environmental conditions which ranged from brackish to hypersaline, as deduced from the sedimentary facies and stable isotope compositions of the carbonate and sulfate deposits. Water in the basins had to be shallow to undergo such rapid and large geochemical variations. The marine influence was omnipresent in the basin at least during the deposition of sulfate evaporites; seawater or marine brines might have been supplied either by direct input into evaporitic lagoons as at Sites 653 and 654, or by subterraneous infiltration in marginal areas as at Site 652. Episodes of severe dilution by continental waters occurred frequently throughout Messinian times in the more basinal areas at Sites 653 and 654, while a fresh water body was standing permanently at Site 652. The high heat flow present at Site 652 was responsible for a major late authigenesis of iron-rich dolomites, which was initiated during the subsidence of the basin and ended before Pliocene.

Phosphorus partition and acumulation rates in sediments of ODP Legs 130 and 138

Understanding phosphorus (P) geochemistry and burial in oceanic sediments is important because of the role of P for modulating oceanic productivity on long timescales. We investigated P geochemistry in seven equatorial Pacific sites over the last 53 Ma, using a sequential extraction technique to elucidate sedimentary P composition and P diagenesis within the sediments. The dominant P-bearing component in these sediments is authigenic P (61-86% of total P), followed in order of relative dominance by iron-bound P (7-17%), organic P (3-12%), adsorbed P (2-9%), and detrital P (0-1%). Clear temporal trends in P component composition exist. Organic P decreases rapidly in younger sediments in the eastern Pacific (the only sites with high sample resolution in the younger intervals), from a mean concentration of 2.3 µmol P/g sediment in the 0-1 Ma interval to 0.4 µmol/g in the 5- 6 Ma interval. Over this same time interval, decreases are also observed for iron-bound P (from 2.1 to 1.1 µmol P/g) and adsorbed P (from 1.5 to 0.7 µmol P/g). These decreases are in contrast to increases in authigenic P (from 6.0-9.6 µmol P/g) and no significant changes in detrital P (0.1 µmol P/g) and total P (12 µmol P/g). These temporal trends in P geochemistry suggest that (1) organic matter, the principal shuttle of P to the seafloor, is regenerated in sediments and releases associated P to interstitial waters, (2) P associated with iron-rich oxyhydroxides is released to interstitial waters upon microbial iron reduction, (3) the decrease in adsorbed P with age and depth probably indicates a similar decrease in interstitial water P concentrations, and (4) carbonate fluorapatite (CFA), or another authigenic P-bearing phase, precipitates due to the release of P from organic matter and iron oxyhydroxides and becomes an increasingly significant P sink with age and depth. The reorganization of P between various sedimentary pools, and its eventual incorporation in CFA, has been recognized in a variety of continental margin environments, but this is the first time these processes have been revealed in deep-sea sediments. Phosphorus accumulation rate data from this study and others indicates that the global pre-anthropogenic input rate of P to the ocean (20x10**10 mol P/yr) is about a factor of four times higher than previously thought, supporting recent suggestions that the residence time of P in the oceans may be as short as 10000-20000 years.

Petrography and mineral compositions of gabbros at DSDP Leg 60 Holes

The compositions, mineralogies, and textures of gabbros recovered in polymict breccias in Hole 453 indicate that they are the cumulus assemblages of calc-alkalic crystal fractional on that occurred beneath the West Mariana Ridge. They are among a class of gabbros known only from other calc-alkalic associations (e.g., the Lesser Antilles and the Peninsular Ranges batholith of Southern California) and differ from gabbros of stratiform complexes, ophiolites, and the ocean crust. Particularly abundant in the Hole 453 breccias are olivine-bearing gabbros with extremely calcic Plagioclase (An94-97) but with fairly iron-rich olivines (Fo76-77). Other gabbros contain biotite and amphibole and occur in breccias with fairly high-grade greenschist facies (amphibole-chlorite-stilpnomelane) metabasalts. One unusual gabbro has experienced almost complete subsolidus recrystallization to an assemblage of aluminous magnesio-hornblende, anorthite, and green hercynitic spinel. This reaction, the extremely calcic Plagioclase, the occurrence of biotite and amphibole, and the association with greenschist facies metamorphic rocks suggest that crystallization of the gabbros occurred at elevated P(H2O). Comparisons with other calc-alkalic gabbro suites suggest pressures in excess of 4 kbar (about 12 km depth). The gabbros were exposed by the early stages of opening of the Mariana Trough and imply that considerable uplift may have attended rifting. They were also subjected to hydrothermal alteration after breccia formation, resulting in formation of chlorite, epidote, actinolite, and prehnite. Temperatures of at least 200°C - and probably 350°C - were reached, and most likely could not have been attained without extrusion or intrusion of magmas nearby, even though no such rocks were cored.