Annotated record of the detailed examination of Mn deposits from the Snellius II - Cruise 4 stations in the vicinity of the island of Misool, Eastern Indonesia

The chemical analyses of ferromanganese encrustations found on the seabed west of Misool, eastern Indonesia, indicate that these deposits formed in a way different from that of world-wide occurring manganese nodules. Ferromanganese coated pebbles and fragments that were found in the deeper parts of the study area probably originate from nearby ridges. The ferromanganese crust on the upper part of a dolomite fragment of ?30 kg is likely to be formed by hydrogenous processes, whereas that from the lower part seems to be formed by diagenetic processes mainly. These assumptions are supported by pore-water data from two box cores taken in the same area. The manganese and iron profiles versus depth in these cores indicate a high flux of these metals to the uppermost sediment layer, and possibly into the overlying bottom water. Factor analysis for the principal components of the microprobe analytical results of the mainly hydrogenous ferromanganese crust demonstrates a strong correlation of manganese with the trace metals, of iron with phosphorus and an antipathetic relationship between iron and manganese. Similar results have also been reported for abyssal manganese nodules in the world oceans. Factor analysis for the principal components of the analytical data obtained for the diagenetic ferromanganese crust results in a clear dolomite (Ca/Mg) dilution factor only.

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.

Description, geochemistry and growth rate of buried nodules from the Central Indian Basin

Buried nodules from siliceous sediments in the central Indian Basin are morphologically variable and mineralogically consist of d-MnO2 and incipient todorokite. Compositionally they are weakly diagenetic. The sediment coarse fractions (>63 µm) at different depths show variable abundances of micronodules, volcanic glass shards and biodebris. Dissolution of biodebris increases and abundance of micronodules decreases with increasing depth. Enrichment in Mn, Fe, Cu, Ni, Co, together with a decrease in organic carbon in the sediment column, may result from diagenetic metal remobilization. Diagenetically remobilized trace metals might have been utilized for the growth of micronodules over the buried nodules.

(Table 2, Page 275) Elemental concentrations in manganese nodules used in seawater contact experiments

The gross changes in concentrations of several trace elements in seawater after contact with ferro-manganese particle suspensions has been determined. Cobalt, Fe, and Zn concentrations in the seawater were greatly increased after contact with the par¬ticles. The concentrations of Rb, U, Cs, Sb, and Ag were altered to a lesser degree by this treatment. Similar results were observed where seawater was con¬tacted with suspensions of pelagic sediments. Of the trace elements measured, cobalt and iron appear to be the best elemental indicators of the presence of manganese mining effluents in the ocean. The addi¬tions of the essential elements Co, Fe and Zn toge¬ther with nutrients from the bottom waters may pro¬duce increased biological productivity. However, the toxic trace metals, such as Hg, Cu and Cd which could enter ocean water from the nodules and sedi¬ment and which may be high in effluent-affected areas should be investigated before conclusions as to the likely impact can be reached. Trace element analysis of seawater samples collected at a Pacific Ocean manganese nodule dredging site showed high t race element concentrations, but these are believed to have resulted from contamination during sample collection or storage rather than from the dredging operations.

(Table 2, page 50) Toolik lake sediment chemistry (0-1 cm interval)

The sediments within Toolik Lake in arctic Alaska are characterized by extremely low rates of organic matter sedimentation and unusually high concentrations of iron and manganese. Pore water and solid phase measurements of iron, manganese, trace metals, carbon, nitrogen, phosphorus, and sulfur are consistent with the hypothesis that the reduction of organic matter by iron and manganese is the most important biogeochemical reaction within the sediment. Very low rates of dissolved oxygen consumption by the sediments result in an oxidizing environment at the sediment-water interface. This results in high retention of upwardly-diffusing iron and manganese and the formation of metal-enriched sediment. Phosphate in sediment pore waters is strongly adsorbed by the metal-enriched phases. Consequently, fluxes of phosphorus from the sediments to overlying waters are very small and contribute to the oligotrophic nature of the Toolik Lake aquatic system. Toolik Lake contains an unusual type of lacustrine sediment, and in many ways the sediments are similar to those found in oligotrophic oceanic environments.

Biogeochemical data from terrestrial and aquatic ecosystems in a periglacial catchment, West Greenland

Global warming is expected to be most pronounced in the Arctic where permafrost thaw and release of old carbon may provide an important feedback mechanism to the climate system. To better understand and predict climate effects and feedbacks on the cycling of elements within and between ecosystems in northern latitude landscapes, a thorough understanding of the processes related to transport and cycling of elements is required. A fundamental requirement to reach a better process understanding is to have access to high-quality empirical data on chemical concentrations and biotic properties for a wide range of ecosystem domains and functional units (abiotic and biotic pools). The aim of this study is therefore to make one of the most extensive field data sets from a periglacial catchment readily available that can be used both to describe present-day periglacial processes and to improve predictions of the future. Here we present the sampling and analytical methods, field and laboratory equipment and the resulting biogeochemical data from a state-of-the-art whole-ecosystem investigation of the terrestrial and aquatic parts of a lake catchment in the Kangerlussuaq region, West Greenland. This data set allows for the calculation of whole-ecosystem mass balance budgets for a long list of elements, including carbon, nutrients and major and trace metals.

(Table 3, Page 417) Table 3. The concentrations of Zn, Cu, Pb, Cd, Ni, Co, Ag, Mn and Fe in a soluble in 1M HCl fraction of ferromanganese nodules of Slupsk Furrow in the southern Baltic sea

The concentration of Zn, Cu, Pb, Cd, Ni, Co, Ag, Mn, Fe, Ca, Mg, K and Na in molluscs Macoma balthica, Mya arenaria, Cardium glaucum, Mytilus edulis and Astarte borealis from the southern Baltic was determined. The surface sediments and ferromanganese concretions associated with the molluscs were also analysed for concentration of these metals. Species- and region-dependent differences in the metal levels of the organisms were observed. The properties of molluscs analysed which have a tendency toward elevated biological tolerance of selected trace metals were specified. The interelement relationship between metal concentrations in the soft tissue and the shell was estimated and was discussed.

Geochemical analysis at ODP Site 207-1261 from the Demerara Rise in the western equatorial Atlantic

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (~15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ~15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ?90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ~15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS**- production.

Geochemical analysis at ODP Site 207-1259 from the Demerara Rise in the western equatorial Atlantic

Organic carbon-rich shales deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 were drilled during ODP Leg 207 at Demerara Rise. We present integrated high-resolution geochemical records of core intervals from ODP Sites 1259 and 1261 both from nannofossil biozone CC14. Our results reveal systematic variations in marine and detrital sediment contribution, depositional processes, and bottom water redox conditions during black shale formation at two locations on Demerara Rise in different paleo-water depths. A combination of redox proxies (Fe/S, P/Al, C/P, redox-sensitive/sulfide-forming trace metals Mn, Cd, Mo, Ni, V, Zn) and other analytical approaches (bulk sediment composition, P speciation, electron microscopy, X-ray diffraction) evidence anoxic to sulfidic bottom water and sediment conditions throughout the deposition of black shale. These extreme redox conditions persisted and were periodically punctuated by short-termed periods with less reducing bottom waters irrespective of paleo-water depth. Sediment supply at both sites was generally dominated by marine material (carbonate, organic matter, opal) although relationships of detrital proxies as well as glauconitic horizons support some influence of turbidites, winnowing bottom currents and/or variable detritus sources, along with less reducing bottom water at the proposed shallower location (ODP Site 1259). At Site 1261, located at greater paleo-depth, redox fluctuations were more regular, and steady hemipelagic sedimentation sustained the development of mostly undisturbed lamination in the sedimentary record. Strong similarities of the studied deposits exist with the stratigraphic older Cenomanian-Turonian OAE2 black shale sections at Demerara Rise, suggesting that the primary mechanisms controlling continental supply and ocean redox state were time-invariant and kept the western equatorial Atlantic margin widely anoxic over millions of years.

Noble metals and associated trace elements in sulfides from the active TAG mound, ODP Site 158-957

Primary sulfides from cores of ODP Holes 158-957M, 158-957C, and 158-957H on the active TAG hydrothermal mound (Mid-Atlantic Ridge, 26°08'N) have been studied for concentrations of several chemical elements. Based on 262 microprobe analyses it has been found that the sulfides have extremely heterogeneous distribution of noble metals (Au, Ag, Pt, and Pd) and several associated elements (Hg, Co, and Se). Noble metals are arranged in the following order in terms of decreasing abundance, i.e. concentration level above detection limits (the number of analyses containing a specific element is given in parentheses): Au (65), Ag (46), Pt (21), and Pd (traces). The associated trace elements have the following series: Co (202), Hg (132), and Se (49). The main carriers of "invisible" portion of the noble metals are represented by pyrite (Au, Hg), marcasite and pyrite (Ag, Co), sphalerite and chalcopyrite (Pt, Pd), and chalcopyrite (Se). Noble metal distribution in sulfides reveals a lateral zonality: maximal concentrations and abundance of Au in chalcopyrite (or Pt and Ag in chalcopyrite and pyrite) increase from the periphery (Hole 957H) to the center (holes 957C and 957M) of the hydrothermal mound, while Au distribution in pyrite displays a reversed pattern. Co concentration increases with depth. Vertical zonality in distribution of the elements mentioned above and their response to evolution of ore genesis are under discussion in the paper.

Geochemistry and trace elements at DSDP Hole 78-543A

The upper part of the basaltic substratum of the Atlantic abyssal plain, approaching subduction beneath the Barbados Ridge and thus presumably beneath the Lesser Antilles island arc, is made of typical LREE-depleted oceanic tholeiites. Mineralogical (microprobe) and geochemical (X-ray fluorescence, neutron activation analyses) data are given for 12 samples from the bottom of Hole 543A, which is 3.5 km seaward of the deformation front of the Barbados Ridge complex. These basalts are overlain by a Quaternary to Maestrichtian-Campanian sedimentary sequence. Most of the basalts are relatively fresh (in spite of the alteration of olivine and development of some celadonite, clays, and chlorite in their groundmass), and their mineralogical and geochemical compositions are similar to those of LREE-depleted recent basalts from the Mid-Atlantic Ridge. The most altered samples occur at the top of the basaltic sequence, and show trends of enrichment in alkali metals typical of altered oceanic tholeiites.