(Table 2, page 725) Solid phase chemistry of ferromanganese precipitates from Nova Scotian lakes

Sediments associated with freshwater ferromanganese concretions in Lake Charlotte, Nova Scotia, contained microscopic precipitates of manganese and iron. These precipitates were dispersed throughout the sediment and were as rich in nickel, cobalt, and copper as deep sea concretions. In addition, the development of the precipitates appeared to be associated with the microbial oxidation of manganese. Results from the deployment of poisoned and unpoisoned dialysis probes or peepers demonstrated that microbial manganese oxidation and nickel binding were closely associated, causing a fivefold enhancement of abiotic processes such as adsorption.

Mineralogical, geochemical, and lipid biomarker study of cabonate precipitates at station GeoB9908-1

Carbonate precipitates recovered from 2,000 m water depth at the Dolgovskoy Mound (Shatsky Ridge, north eastern Black Sea) were studied using mineralogical, geochemical and lipid biomarker analyses. The carbonates differ in shape from simple pavements to cavernous structures with thick microbial mats attached to their lower side and within cavities. Low d13C values measured on carbonates (-41 to -32 per mill V-PDB) and extracted lipid biomarkers indicate that anaerobic oxidation of methane (AOM) played a crucial role in precipitating these carbonates. The internal structure of the carbonates is dominated by finely laminated coccolith ooze and homogeneous clay layers, both cemented by micritic high-magnesium calcite (HMC), and pure, botryoidal, yellowish low-magnesium calcite (LMC) grown in direct contact to microbial mats. d18O measurements suggest that the authigenic HMC precipitated in equilibrium with the Black Sea bottom water while the yellowish LMC rims have been growing in slightly 18O-depleted interstitial water. Although precipitated under significantly different environmental conditions, especially with respect to methane availability, all analysed carbonate samples show lipid patterns that are typical for ANME-1 dominated AOM consortia, in the case of the HMC samples with significant contributions of allochthonous components of marine and terrestrial origin, reflecting the hemipelagic nature of the primary sediment.

Fluid compositions and mineralogy of precipitates from Mid Atlantic Ridge hydrothermal vents at 4°48'S

The effect of volcanic activity on submarine hydrothermal systems has been well documented along fast- and intermediate-spreading centers but not from slow-spreading ridges. Indeed, volcanic eruptions are expected to be rare on slow-spreading axes. Here we report the presence of hydrothermal venting associated with extremely fresh lava flows at an elevated, apparently magmatically robust segment center on the slow-spreading southern Mid-Atlantic Ridge near 5°S. Three high-temperature vent fields have been recognized so far over a strike length of less than 2 km with two fields venting phase-separated, vapor-type fluids. Exit temperatures at one of the fields reach up to 407°C, at conditions of the critical point of seawater, the highest temperatures ever recorded from the seafloor. Fluid and vent field characteristics show a large variability between the vent fields, a variation that is not expected within such a limited area. We conclude from mineralogical investigations of hydrothermal precipitates that vent-fluid compositions have evolved recently from relatively oxidizing to more reducing conditions, a shift that could also be related to renewed magmatic activity in the area. Current high exit temperatures, reducing conditions, low silica contents, and high hydrogen contents in the fluids of two vent sites are consistent with a shallow magmatic source, probably related to a young volcanic eruption event nearby, in which basaltic magma is actively crystallizing. This is the first reported evidence for direct magmatic-hydrothermal interaction on a slow-spreading mid-ocean ridge.

Description and chemical composition of manganese nodules collected in the Pacific Ocean

Chemical and X-ray analyses were performed on the fifteen manganese nodules collected from the Pacific Ocean floor. The results were discussed compared with the previous data on the manganese nodules. Minerals were found to be todorokite, delta-MnO2 and other silicates, montmorillonite, illite, phillipsite and alpha-Si02. Average composition shows that copper is concentrated on the deep sea nodules more than the shallow ones, and that the todorokite rich nodules contain more copper and nickel than the delta-MnO2 rich ones. The analyses of fresh water iron-manganese precipitates by bacterial activity suggest that biological process is one of the important factors on the genesis of the sedimentary iron-manganese deposits, in¬cluding the manganese nodule.

Geo-referenced photo-mosaics of the Menez Gwen Hydrothermal Vent (Mid-Atlantic Ridge)

The Menez Gwen hydrothermal vents, located on the flanks of a small young volcanic structure in the axial valley of the Menez Gwen seamount, are the shallowest known vent systems on the Mid-Atlantic Ridge that host chemosynthetic communities. Although visited several times by research cruises, very few images have been published of the active sites, and their spatial dimensions and morphologies remain difficult to comprehend. We visited the vents on the eastern flank of the small Menez Gwen volcano during cruises with RV Poseidon (POS402, 2010) and RV Meteor (M82/3, 2010), and used new bathymetry and imagery data to provide first detailed information on the extents, surface morphologies, spatial patterns of the hydrothermal discharge and the distribution of dominant megafauna of five active sites. The investigated sites were mostly covered by soft sediments and abundant white precipitates, and bordered by basaltic pillows. The hydrothermally-influenced areas of the sites ranged from 59 to 200 m**2. Geo-referenced photomosaics and video data revealed that the symbiotic mussel Bathymodiolus azoricus was the dominant species and present at all sites. Using literature data on average body sizes and biomasses of Menez Gwen B. azoricus, we estimated that the B. azoricus populations inhabiting the eastern flank sites of the small volcano range between 28,640 and 50,120 individuals with a total biomass of 50 to 380 kg wet weight. Based on modeled rates of chemical consumption by the symbionts, the annual methane and sulfide consumption by B. azoricus could reach 1760 mol CH4 yr**-1 and 11,060 mol H2S yr**-1. We propose that the chemical consumption by B. azoricus over at the Menez Gwen sites is low compared to the natural release of methane and sulfide via venting fluids.

Mass accumulation rates, age, sedimentation rate and bulk density at the East Pacific Rise

The rate at which hydrothermal precipitates accumulate, as measured by the accumulation rate of manganese, can be used to identify periods of anomalous hydrothermal activity in the past. From a preliminary study of Sites 597 and 598, four periods prior to 6 Ma of anomalously high hydrothermal activity have been identified: 8.5 to 10.5 Ma, 12 to 16 Ma, 17 to 18 Ma, and 23-to-27 Ma. The 18-Ma anomaly is the largest and is associated with the jump in spreading from the fossil Mendoza Ridge to the East Pacific Rise, whereas the 23-to-27-Ma anomaly is correlated with the birth of the Galapagos Spreading Center and resultant ridge reorganization. The 12-to-16-Ma and 8.5-to-10.5-Ma anomalies are correlated with periods of anomalously high volcanism around the rim of the Pacific Basin and may be related to other periods of ridge reorganization along the East Pacific Rise. There is no apparent correlation between periods of fast spreading at 19°S and periods of high hydrothermal activity. We thus suggest that periods when hydrothermal activity and crustal alteration at mid-ocean ridges are the most pronounced may be periods of large-scale ridge reorganization.

Geochemistry of Fe-Mn crusts in sediments of the Central Indian Ridge

Layered Fe-Mn crusts from the off-axis region of the first segment of the Central Indian Ridge north of the Rodrigues Triple Junction were studied geochemically and mineralogically. Vernadite (delta-MnO2) is the main mineral oxide phase. 230Thxs and Co concentrations suggest high growth rates of up to 29 mm/Myr and a maximum age of the basal crust layer of 1 Ma. Whereas most of the major and minor elements show concentrations which are typical of hydrogenetic formation, Co, Pb, Ni and Ti concentrations are strikingly lower. Concentrations and distribution of the strictly trivalent rare-earths and yttrium (REY) are typical of hydrogenetic ferromanganese oxide precipitates, but in marked contrast, the crusts are characterized by negative CeSN (shale normalized) anomalies and (Ce/Pr)SN ratios less than unity. Profiles through the crusts reveal only minor variations of the REY distribution and (Ce/Pr)SN ratios range from 0.45 to 0.68 (compared to ratios of up to 2 for typical hydrogenetic crusts from the Central Indian Basin). The apparent bulk partition coefficients between the crusts and seawater suggest that for the strictly trivalent REY the adsorption-desorption equilibrium has been reached. Positive Ce anomalies in the partition coefficient patterns reveal preferential uptake of Ce, but to a lesser extent than in normal hydrogenetic crusts. A new parameter (excess Ce, Cexs) to quantify the degree of decoupling of Ce from REY(III) is established on the basis of partition coefficients. Cexs/Cebulk ratios suggest that the CIR crusts formed by precipitation of Fe-Mn oxides from a hydrothermal plume and that in hydrothermal plumes and normal seawater the enrichment of Ce results from the same oxidative sorption process. The growth rates, calculated with 230Thxs data as well as with the Co formula, are inversely related to Cexs.

Radioisotope stratigraphy, sedimentology and geochemistry of Late Quaternary sediments from the Eastern Arctic Ocean

To reconstruct Recent and past sedimentary environments, marine sediments of Upper Pleistocene and Holocene ages from the eastern Arctic Ocean and especially from the Nansen-Gakkel Ridge (NGR) were investigated by means of radioisotopic, geochemical and sedimentological methods. In combination with mass physical property data and lithological analysis these investigations allow clearly to characterize the depositional environments. Age dating by using the radioisotope 230Th gives evidence that the investigated sediments from the NGR are younger than 250,000 years. Identical lithological sediment sequences within and between sediment cores from the NGR can be related to sedimentary processes which are clearly controlled by palaeoclimate. The sediments consist predominantly of siliciclastic, terrigenous ice-rafted detritus (IRD) deriving from assorted and redeposited sediments from the Siberian shelfs. By their geochemical composition the sediments are similar to mudstone, graywacke and arcose. Sea-ice as well as icebergs play a major roll in marine arctic sedimentation. In the NGR area rapid change in sedimentary conditions can be detected 128,000 years ago. This was due to drastic change in the kind of ice cover, resulting from rapid climatic change within only hundreds of years. So icebergs, deriving mostly from Siberian shelfs, vanished and sea-ice became dominant in the eastern Arctic Ocean. At least three short-period retreats of the shelf ice between 186,000 and 128,000 years are responsible for the change of coarse to fine-grained sediments in the NGR area. These warmer stages lasted between 1,000 and 3,000 years. By monitoring and comparing the distribution patterns of sedimentologic, mass physical and geochemical properties with 230Th ex activity distribution patterns in the sediment cores from the NGR, there is clear evidence that sediment dilution is responsible for high 230Th ex activity variations. Thus sedimentation rate is the controlling factor of 230Th ex activity variations. The 230Th flux density in sediments from the NGR seems to be highly dependent On topographic Position. The distribution patterns of chemical elements in sediment cores are in general governed by lithology. The derivation of a method for dry bulk density determination gave the opportunity to establish a high resolution stratigraphy on sediment cores from the eastern Arctic Ocean, based on 230Thex activity analyses. For the first time sedimentation and accumulation rates were determined for recent sediments in the eastern Arctic Ocean by 230Th ex analyses. Bulk accumulation rates are highly variable in space and time, ranging between 0.2 and 30 g/cm**2/ka. In the sediments from the NGR highly variable accumulation rates are related to the kind of ice cover. There is evidence for hydrothermal input into the sediments of the NGR. Hydrothermal activity probably also influences surficial sediments in the Sofia Basin. High contents of As are typical for surficial sediments from the NGR. In particular SL 370-20 from the bottom of the rift valley has As contents exceeding in parts 300 ppm. Hydrothermal activity can be traced back to at least 130,000 years. Recent to subrecent tectonic activity is documented by the rock debris in KAL 370 from the NGR. In four other sediment cores from the NGR rift valley area tectonically induced movements can be dated to about 130,000 years ago, related most probably to the rapid climate change. Processes of early diagenesis in sediments from the NGR caused the aobilization and redeposition of Fe, Mn and Mo. These diagenetic processes probably took place during the last 130,000 years. In sediment cores from the NGR high amounts of kaolinite are related to coarse grained siliciclastic material, probably indicating reworking and redeposition of siberian sandstones with kaolinitic binding material. In contrast to kaolinite, illite is correlated to total clay and 232Th contents. Aragonite, associated with serpentinites in the rift valley area of the NGR, was precipitated under cold bottom-water conditions. Preliminary data result in a time of formation about 60 - 80 ka ago. Manganese precipitates with high Ni contents, which can be related to the ultrabasic rocks, are of similar age.

Geochemical and isotopic composition of sediments and pore waters from ODP Leg 164 sites

Authigenic carbonates were recovered from several horizons between 0 and 52 mbsf in sediments that overlay the Blake Ridge Diapir on the Carolina Rise (Ocean Drilling Program [ODP] Site 996). Active chemosynthetic communities at this site are apparently fed by fluid conduits extending beneath a bottom-simulating reflector (BSR). Gas hydrates occur at several depth intervals in these near-surface sediments. The carbonate nodules are composed of rounded to subangular intraclasts and carbonate cemented mussel shell fragments. Electron microprobe and X-ray diffraction (XRD) investigations show that aragonite is the dominant authigenic carbonate. Authigenic aragonite occurs both as microcrystalline, interstitial cement, and as cavity-filling radial fibrous crystals. The d13C values of the authigenic aragonite vary between -48.4 per mil and -30.5 per mil (Peedee belemnite [PDB]), indicating that carbon derived from 13C-depleted methane is incorporated into these carbonates. The d13C of pore water sum CO2 values are most negative in the upper 10 mbsf, near the sediment/water interface (-38 per mil ± 5 per mil), but noticeably more positive below 25 mbsf (+5 per mil ± 6 per mil). Because carbonates derive their carbon from HCO3-, dissimilarities between the d13C values of carbonate precipitates recovered from greater than 10 mbsf and d13C values of the associated pore fluids suggests that these carbonates formed near the seafloor. Differences of about 1 per mil in the oxygen isotopic composition of carbonate precipitates from different depths are possibly related to changes in bottom-water conditions during glacial and interglacial time periods. Measurements of the strontium isotopic composition on 13 carbonate samples show 87Sr/86Sr values between 0.709125 and 0.709206 with a mean of 0.709165, consistent with the approximate age of their host sediment. Furthermore, the 87Sr/86Sr values of six pore-water samples from Site 996 vary between 0.709130 and 0.709204. The similarity of these values to seawater (87Sr/86Sr = 0.709175), and to 87Sr/86Sr values of pore water from similar sample depths elsewhere on the Blake Ridge (Sites 994, 995, and 997), indicates a shallow Sr source. The 87Sr/86Sr values of the authigenic carbonates at Site 996 are not consistent with the Sr isotopic values predicted for carbonates precipitated from fluids transported upward along fault conduits extending through the base of the gas hydrate-stability zone. Based on our data, we see no evidence of continuing carbonate diagenesis with depth. Therefore, with the exception of their seafloor expression as carbonate crusts, fossil vent sites will not be preserved. Because these authigenic features apparently form only at the seafloor, their vertical distribution and sediment age imply that seepage has been going on in this area for at least 600,000 yr.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.