Geochemical analysis of two sediment cores from the southern Mendeleev Ridge

We present results of an inorganic geochemical pore water and sediment study conducted on Quaternary sediments from the western Arctic Ocean. The sediment cores were recovered in 2008 from the southern Mendeleev Ridge during RV Polarstern Expedition ARK-XXIII/3. With respect to sediment sources and depositional processes, peaks in Ca/Al, Mg/Al, Sr/Al and Sr/Mg indicate enhanced input of both ice-rafted (mainly dolomite) and biogenic carbonate during deglacial warming phases. Distinct and repetitive brown layers enriched in Mn (oxyhydr)oxides occur mostly in association with these carbonate-rich intervals. For the first time, we show that the brown layers are also consistently enriched in scavenged trace metals Co, Cu, Mo and Ni. The bioturbation patterns of the brown layers, specifically well-defined brown burrows into the underlying sediments, support formation close to the sediment-water interface. The Mn and trace metal enrichments were probably initiated under warmer climate conditions. Both river runoff and melting sea ice delivered trace metals to the Arctic Ocean, but also enhanced seasonal productivity and organic matter export to the sea floor. As Mn (oxyhydr)oxides and scavenged trace metals were deposited at the sea floor, a co-occurring organic matter "pulse" triggered intense diagenetic Mn cycling at the sediment-water interface. These processes resulted in the formation of Mn and trace metal enrichments, but almost complete organic matter degradation. As warmer conditions ceased, reduced riverine runoff and/or a solid sea ice cover terminated the input of riverine trace metal and fresh organic matter, and greyish-yellowish sediments poor in Mn and trace metals were deposited. Oxygen depletion of Arctic bottom waters as potential cause for the lack of Mn enrichments during glacial intervals is highly improbable. While the original composition and texture of the brown layers resulted from specific climatic conditions (including transient Mn redox cycling at the sediment-water interface), pore water data show that early diagenetic Mn redistribution is still affecting the organic-poor sediments in several meters depth. Given persistent steady state diagenetic conditions, purely authigenic Mn-rich brown layers may form, while others may completely vanish. The degree of diagenetic Mn redistribution largely depends on the depositional environment within the Arctic Ocean, the availability of Mn and organic matter, and seems to be recorded by the Co/Mo ratios of single Mn-rich layers. We conclude that brown Arctic sediment layers are not necessarily synchronous features, and correlating them across different parts of the Arctic Ocean without additional age control is not recommended.

(Table 4+5, Page 290) Distribution of Mn, Fe, Cu. Pb, Zn, Ni and Co in single manganese nodules

Chemical analyses of manganese nodules from the Central Pacific Basin show that their chemical composition varies regionally, although that of the associated sediments is markedly uniform throughout the basin. Mn content varies from 16 to 32% in average. Its higher value is generally found in nodules from siliceous clay and a few from deep-sea clay. Fe content tends to enrich in nodules from deep-sea clay area. Most manganese nodules, except those from deep-sea clay, are remarkably depleted in Fe compared with ones from the other Pacific regions. Mostly, Cu and Ni contents exceed 1% in nodules from siliceous clay, and decrease towards the northwest of the basin where deep-sea clay is distributed. The inter-element relationship between manganese nodules and associated sediments suggests that the mechanism of incorporation of major and minor elements in nodules is apparently different from that of the associated sediments. This finding seems to provide a new interpretation on the problem why manganese nodules having low accumulation rate are not buried by the associated sediments with greater sedimentation rate and then occur on sediment-seawater interface.

Geochemical analysis of minerals from sediment core CRP-2 in the Ross Sea, Antarctica

Distribution patterns, petrography, whole-rock and mineral chemistry, and shape and fabric data are described for the most representative basement lithologies occurring as clasts (granule to bolder grain-size class) from the 625 m deep CRP-2/2A drillcore. A major change in the distribution pattern of the clast types occurs at c. 310 mbsf., with granitoid-dominated clasts above and mainly dolerite clasts below; moreover, compositional and modal data suggest a further division into seven main detrital assemblages or petrofacies. In spite of this variability, most granitoid pebbles consist of either pink or grey biotite±hornblende monzogranites. Other less common and ubiquitous lithologies include biotite syenogranite, biotite-hornblende granodiorite, tonalite, monzogranitic porphyries (very common below 310 mbsf), microgranite, and subordinately, monzogabbro, Ca-silicate rocks, biotite-clinozoisite schist and biotite orthogneiss (restricted to the pre-Pliocene strata). The ubiquitous occurrence of biotite±hornblende monzogranite pebbles in both the Quaternary-Pliocene and Miocene-Oligocene sections, apparently reflects the dominance of these lithologies in the onshore basement, and particularly in the Cambro-Ordovician Granite Harbour Igneous Complex which forms the most extensive outcrop in southern Victoria Land. The petrographical features of the other CRP-2/2A pebble lithologies are consistent with a supply dominantly from areas of the Transantarctic Mountains facing the CRP-2/2A site, and they thus provide further evidence of a local provenance for the supply of basement clasts to the CRP-2/2A sedimentary strata.

Porewater concentrations, pH, single cell number, anaerobic oxidation of methane (AOM) rate, sulfate reduction (SR) rate of samples during METEOR cruise M76/3b at the REGAB cold seep site from the West African margin in 2008

The giant pockmark REGAB (West African margin, 3160 m water depth) is an active methane-emitting cold seep ecosystem, where the energy derived from microbially mediated oxidation of methane supports high biomass and diversity of chemosynthetic communities. Bare sediments interspersed with heterogeneous chemosynthetic assemblages of mytilid mussels, vesicomyid clams and siboglinid tubeworms form a complex seep ecosystem. To better understand if benthic bacterial communities reflect the patchy distribution of chemosynthetic fauna, all major chemosynthetic habitats at REGAB were investigated using an interdisciplinary approach combining porewater geochemistry, in situ quantification of fluxes and consumption of methane, as well bacterial community fingerprinting. This study revealed that sediments populated by different fauna assemblages show distinct biogeochemical activities and are associated with distinct sediment bacterial communities. The methane consumption and methane effluxes ranged over one to two orders of magnitude across habitats, and reached highest values at the mussel habitat, which hosted a different bacterial community compared to the other habitats. Clam assemblages had a profound impact on the sediment geochemistry, but less so on the bacterial community structure. Moreover, all clam assemblages at REGAB were restricted to sediments characterized by complete methane consumption in the seafloor, and intermediate biogeochemical activity. Overall, variations in the sediment geochemistry were reflected in the distribution of both fauna and microbial communities; and were mostly determined by methane flux.

Ba, Mn, and Mg record derived from Hoeglundina elegans of sediment core SLA-9

The evolution of productivity, redox conditions, temperature, and ventilation during the deposition of an Aegean sapropel (S1) is independently constrained using bulk sediment composition and high-resolution single specimen benthic foraminiferal trace metal and stable isotope data. The occurrence of benthic foraminifer, Hoeglundina elegans (H. elegans), through a shallow water (260 m) sapropel, permits for the first time a comparison between dissolved and particulate concentrations of Ba and Mn and the construction of a Mg/Ca-based temperature record through sapropel S1. The simultaneous increase in sedimentary Ba and incorporated Ba in foraminiferal test carbonate, (Ba/Ca)H. elegans, points to a close coupling between Ba cycling and export productivity. During sapropel deposition, sedimentary Mn content ((Mn/Al)sed) is reduced, corresponding to enhanced Mn2+ mobilization from sedimentary Mn oxides under suboxic conditions. The consequently elevated dissolved Mn2+ concentrations are reflected in enhanced (Mn/Ca)H. elegans levels. The magnitude and duration of the sapropel interruption and other short-term cooling events are constrained using Mg/Ca thermometry. Based on integrating productivity and ventilation records with the temperature record, we propose a two-mode hysteresis model for sapropel formation.

Annotated record and spectrochemical analyses of Mn nodules from Georgia Strait, British Columbia obtained during CNAV Laymore in 1970

A study of the distribution, dispersal and composition of surficial sediments in the Strait of Georgia, B.C., has resulted in the understanding of basic sedimentologic conditions within this area. The Strait of Georgia is: a long, narrow, semi-enclosed basin with a restricted circulation and a single, main, sediment source. The Fraser. River supplies practically all the sediment now being deposited in the Strait of Georgia, the bulk of it during the spring and summer freshet. This river is building a delta into the Strait from the east side near the south end. Ridges of Pleistocene deposits within the Strait and Pleistocene material around the margins, like bedrock exposures, provide local sources of sediment of only minor importance. Rivers and streams other than the Fraser contribute insignificant quantities of sediment to the Strait. Sandy sediments are concentrated in the vicinity of the delta, and in the area to the south and southeast. Mean grain size decreases from the delta toward the northwest along the axis of the Strait, and basinwards from the margins. Silts and clays are deposited in deep water west and north of the delta front, and in deep basins northwest of the delta. Poorly sorted sediments containing a gravel component are located near tidal passes, on the Vancouver Island shelf area, on ridge tops within the Strait, and with sandy sediments at the southeastern end of the study area. The Pleistocene ridges are areas of non-deposition, having at most a thin veneer of modern mud on their crests and upper flanks. The southeastern end of the study area contains a thick wedge of shandy sediment which appears to be part of an earlier delta of the Fraser River. Evidence suggests that it is now a site of active submarine erosion. Sediments throughout the Strait are compositionally extremely similar, with-Pleistocene deposits of the Fraser River drainage basin providing the principal, heterogeneous source. Gravels and coarse sands are composed primarily of lithic fragments, dominantly of dioritic to granodloritlc composition. Sand fractions exhibit increasing simplicity of mineralogy with decreasing grain-size. Quartz, felspar, amphibole and fine-grained lithic fragments are the dominant constituents of the finer sand grades. Coarse and medium silt fractions have compositions similar to the fine sands. Fine silts show an increase in abundance of phyllosilicate material, a feature even more evident in the clay-size fractions on Montmorillonite, illite, chlorite, quartz and feldspar are the main minerals in the coarse clay fraction, with minor mixed-layer clays and kaolinite. The fine clay fraction is dominated by montmorillonite, with lesser amounts of illite and chlorite. The sediments have high base-exchange capacities, related to a considerable content of montmorillonite. Magnesium is present in exchange positions in greater quantity in Georgia Strait sediments than in sediments from the Fraser River, indicating a preferential uptake of this element in the marine environment. Manganese nodules collected from two localities in the Strait imply slow sediment accumulation rates at these sites. Sedimentation rates on and close to the delta, and in the deep basins to the northwest, are high.

Mn/Ca and Fe/Ca systematics in benthic foraminifera from the Peruvian OMZ

In this study we present an initial dataset of Mn/Ca and Fe/Ca ratios in tests of benthic foraminifera from the Peruvian oxygen minimum zone (OMZ) determined with SIMS. These results are a contribution to a better understanding of the proxy potential of these elemental ratios for ambient redox conditions. Foraminiferal tests are often contaminated by diagenetic coatings, like Mn rich carbonate- or Fe and Mn rich (oxyhydr)oxide coatings. Thus, it is substantial to assure that the cleaning protocols are efficient or that spots chosen for microanalyses are free of contaminants. Prior to the determination of the element/Ca ratios, the distributions of several elements (Ca, Mn, Fe, Mg, Ba, Al, Si, P and S) in tests of the shallow infaunal species Uvigerina peregrina and Bolivina spissa were mapped with an electron microprobe (EMP). To visualize the effects of cleaning protocols uncleaned and cleaned specimens were compared. The cleaning protocol included an oxidative cleaning step. An Fe rich phase was found on the inner test surface of uncleaned U. peregrina specimens. This phase was also enriched in Al, Si, P and S. A similar Fe rich phase was found at the inner test surface of B. spissa. Specimens of both species treated with oxidative cleaning show the absence of this phase. Neither in B. spissa nor in U. peregrina were any hints found for diagenetic (oxyhydr)oxide or carbonate coatings. Mn/Ca and Fe/Ca ratios of single specimens of B. spissa from different locations have been determined by secondary ion mass spectrometry (SIMS). Bulk analyses using solution ICP-MS of several samples were compared to the SIMS data. The difference between SIMS analyses and ICP-MS bulk analyses from the same sampling sites was 14.0-134.8 µmol mol-1 for the Fe/Ca and 1.68(±0.41) µmol mol-1 for the Mn/Ca ratios. This is in the same order of magnitude as the variability inside single specimens determined with SIMS at these sampling sites (1sigma[Mn/Ca] = 0.35-2.07 µmol mol-1; 1sigma[Fe/Ca] = 93.9-188.4 µmol mol-1). The Mn/Ca ratios in the calcite were generally relatively low (2.21-9.93 µmol mol-1) but in the same magnitude and proportional to the surrounding pore waters (1.37-6.67 µmol mol-1). However, the Fe/Ca ratios in B. spissa show a negative correlation to the concentrations in the surrounding pore waters. Lowest foraminiferal Fe/Ca ratios (87.0-101.0 µmol mol-1) were found at 465 m water depth, a location with a strong sharp Fe peak in the pore water next to the sediment surface and respectively, high Fe concentrations in the surrounding pore waters. Previous studies found no living specimens of B. spissa at this location. All these facts hint that the analysed specimens already were dead before the Fe flux started and the sampling site just recently turned anoxic due to fluctuations of the lower boundary of the OMZ near the sampling site (465 m water depth). Summarized Mn/Ca and Fe/Ca ratios are potential proxies for redox conditions, if cleaning protocols are carefully applied. The data presented here may be rated as base for the still pending detailed calibration.

Annotated record of the detailed examination of Mn deposits from DEEPSONDE Expedition stations near the East Pacific Rise

Basalts from the base of a small seamount on ~1.5-m.y.-old crust west of the East Pacific Rise (EPR) at 9°N are intermediate in chemical and isotopic composition between light-rare-earth-element-depleted tholeiite (normal midocean ridge basalt (MORB)) and alkali basalt. Like oceanic alkali basalt, these rocks contain significantly more Ba, K, P, Sr, Ti, U, and Zr than normal MORB. Since the absolute abundances of these elements are still well below alkali basalt levels, the label transitional is adopted for these basalts. A series of fractionated MORB also occurs in this area, northwest of the Siqueiros Fracture Zone - Transform Fault. The normal tholeiites are either olivine-plagioclase or plagioclase-clinopyroxene phyric, while the transitional basalts are spinel-olivine phyric. Fractional crystallization quantitatively accounts for the chemical variability of the tholeiitic series but not for the transitional basalts. The tholeiitic series probably evolved in a crustal magma chamber ~4 km below the crest of the East Pacific Rise. 143Nd/144Nd and other chemical data suggest that the large-ion-lithophile-enriched transitional basalts may represent a hybrid of normal MORB and Siqueiros area alkali basalt. Incompatible element plots of K, P, and U indicate possible derivation of the transitional basalts by magma mixing. Magma mixing of unfractionated normal MORB and Siqueiros alkali basalt has been quantified. Derivation of the transitional basalts from a 1:1 mixture is supported by all available chemical data, including Cr, Cu, Nd, Ni, Sm, Sr, U, and V. This magma mixing apparently occurred at ?<~30 km depth within a few tens of kilometers from the EPR axis. These Siqueiros area EPR transitional basalts are compared with Mid-Atlantic Ridge (MAR) transitional basalts from the Iceland and Azores areas. The Siqueiros area basalts reflect a profound chemical and isotopic heterogeneity in the upper mantle, similar to that found along the MAR. Unlike the MAR, the EPR shows no evidence of plumelike bulges and associated large-scale outpourings of nonnormal MORB resulting from these mantle heterogeneities. Siqueiros alkali basalt and MORB, as well as transitional basalt and MORB, were recovered from single dredge hauls. Such close spatial and temporal proximity of the inferred mantle sources places severe constraints on geometric and physicochemical upper mantle models.

Annotated record and chemical composition of Mn deposits from R/V Mahi Cruise Abyssal Hills 69 stations

A University of Hawaii oceanographic cruise, Abyssal Hills 69, with the R/V Mahi, was carried out to study the association of manganese nodules with an abyssal hill. Manganese nodules from three dredge hauls on an abyssal hill located at 36°W and 157°W exhibited differences in morphology and composition between stations only three miles apart. The morphology of the nodules suggests that nodules from a single site have similar morphologies because they began growth at the same time, probably because of a volcanic event. Differences in morphology between stations indicate a local supply of elements. Atomic absorption analysis for manganese, iron, cobalt, nickel, and copper revealed that nodules nearest to a probable fault line and source of volcanism have a, lower manganese to iron ratio than nodules farther removed. This finding supports the theory that volcanism contributes to the formation of some nodules. Additional evidence showing association with volcanism consists of volcanic nuclei in nodules, crusts formed on layers of volcanic ash, and basalt encrusted to various degrees. The variation in cobalt, nickel, and copper contents Gt the nodules from a single dredge is two-to threefold, but iron content is more uniiorm. Four of the six cores from the area increased in manganese concentration with depth, suggesting that diffusion is concentrating manganese in the upper zone of the sediments or in nodules. The author concludes that volcanism is contributing to the formation of nodules by supplying nuclei and transition elements, but is not necessary for the formation of manganese nodules.