Trace element geochemistry at DSDP Leg 82 Holes

Forty-three samples from DSDP Holes 556-559 and 561-564 were analyzed for rare earth elements (REE), Sc, Cr, Co, Hf, Ta, and Th by instrumental neutron activation analysis. The recovered basalts range from those depleted in light REE (LREE) to those enriched in LREE. The two types of basalts occur together in Holes 558 and 561. The depleted basalts have remarkably constant La/Yb, La/Sm, and La/Ti ratios and apparently derive from a large, homogeneous, mantle source underneath a segment (1200 km long) of the Mid-Atlantic Ridge. The almost twofold variation in the concentrations of incompatible trace elements in the depleted basalts is primarily due to different degrees of batch partial melting. The variation of highly to moderately incompatible elements in the Leg 82 enriched basalts can be successfully explained in terms of source mixing between depleted mantle sources and alkaline or nephelinitic magmas similar to Azores Islands magmas. However, the correlation of LREE enrichment with distance from the Azores Triple Junction is tenuous at best, and the enriched alkaline component is probably not directly related to the Azores volcanism.

Major and trace element concentration of melt inclusions from Zhupanovsky volcano, Kamchatka

The paper presents data on naturally quenched melt inclusions in olivine (Fo 69-84) from Late Pleistocene pyroclastic rocks of Zhupanovsky volcano in the frontal zone of the Eastern Volcanic Belt of Kamchatka. The composition of the melt inclusions provides insight into the latest crystallization stages (~70% crystallization) of the parental melt (~46.4 wt % SiO2, ~2.5 wt % H2O, ~0.3 wt % S), which proceeded at decompression and started at a depth of approximately 10 km from the surface. The crystallization temperature was estimated at 1100 ± 20°C at an oxygen fugacity of deltaFMQ = 0.9-1.7. The melts evolved due to the simultaneous crystallization of olivine, plagioclase, pyroxene, chromite, and magnetite (Ol: Pl: Cpx : (Crt-Mt) ~ 13 : 54 : 24 : 4) along the tholeiite evolutionary trend and became progressively enriched in FeO, SiO2, Na2O, and K2O and depleted in MgO, CaO, and Al2O3. Melt crystallization was associated with the segregation of fluid rich in S-bearing compounds and, to a lesser extent, in H2O and Cl. The primary melt of Zhupanovsky volcano (whose composition was estimated from data on the most primitive melt inclusions) had a composition of low-Si (~45 wt % SiO2) picrobasalt (~14 wt % MgO), as is typical of parental melts in Kamchatka and other island arcs, and was different from MORB. This primary melt could be derived by ~8% melting of mantle peridotite of composition close to the MORB source, under pressures of 1.5 ± 0.2 GPa and temperatures 20-30°C lower than the solidus temperature of 'dry' peridotite (1230-1240°C). Melting was induced by the interaction of the hot peridotite with a hydrous component that was brought to the mantle from the subducted slab and was also responsible for the enrichment of the Zhupanovsky magmas in LREE, LILE, B, Cl, Th, U, and Pb. The hydrous component in the magma source of Zhupanovsky volcano was produced by the partial slab melting under water-saturated conditions at temperatures of 760-810°C and pressures of ~3.5 GPa. As the depth of the subducted slab beneath Kamchatkan volcanoes varies from 100 to 125 km, the composition of the hydrous component drastically changes from relatively low-temperature H2O-rich fluid to higher temperature H2O-bearing melt. The geothermal gradient at the surface of the slab within the depth range of 100-125 km beneath Kamchatka was estimated at 4°C/km.

(Table 1, page 41), Chemical and radiocativity analysis of manganese crusts from the Lika river, Vermland, Sweden and ferromanganese ore from lake Tisjoen, Dalecarlia, Sweden

The trace element content of different bog ores has been measured and it appeared that most of these elements are enriched in the manganiferous bog ores as compared with the ferriferous ones. The manganiferous bog ores have also proved to have a higher radioactivity than the ferriferous ones.

Analysis of manganese deposits from the Pacific Ocean

Sea floor dredging by the H.M.S. Challenger, the U.S.S. Albatross, the U.S.S. EPC(R) 857, and vessels of the Scripps Institution of Oceanography shows that extensive deposits of manganese nodules are on the deep sea floor and that crusts of manganese dioxide cover many seamounts. Sea floor photography reveals that in some places these crusts are quite continuous and the nodules are closely packed. These crusts and nodules are fully oxidized and hydrated mixtures of man¬ganese and iron plus earthy impurities. Also, relatively high concen¬trations of the trace elements nickel, copper, and cobalt are present.

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.

Trace element contents in bottom sediments from the North Indian Ocean

Contents and distributions of Cu, Ni, Co, V, Cr, Zn, Pb, Mo, W, and Zr in near-coast and pelagic sediments of the Northern Indian Ocean are under consideration in the paper. Chemical analyses showed enrichment of pelagic clayey radiolarian oozes by Mn, Cu, Ni, Co, Pb, W, and Mo. According to enrichment factors these elements have the following order: Mo> Mn> Cu> Ni> Co> Pb> W. Enrichment of pelagic sediments from the Indian Ocean is mainly determined by the mechanism of the sedimentation process. Enrichment factors of Cu, Ni, Co, W, Mo, and Mn in pelagic sediments of the North Indian Ocean are intermediate between ones in pelagic sediments of the Pacific and Atlantic Oceans.

(Tables 1-3) Silicon dioxide, Corg and trace element concentrations in sediments of the outer Eckernfoerder Bay, Western Baltic Sea

The main question, posed in the work scheme before laboratory analysis was started, was expressed as follows: Do marked seasonal fluctuations occur in trace element content of the sediment surface, and what are the probable influences of factors such as changing hydrographical parameters, plankton sequence etc. ? Special attention was paid to elements known as pollutants, for example mercury. Within this framework samples have been analysed for their contents of manganese, iron, zinc, lead, and mercury. The amounts of silica and organically-bound carbon serve in most cases as reference values for the trace element content. On sand temporary conditions of increased C org content raise the concentrations of all determined elements. Especially the values reached for mercury in July are worth nothing. It is concluded that Zn, Pb, and Hg tend to enrich with respect to C org as the decomposition of organic matter progresses. On mud-sand flocculation and precipitation of Mn/Fe-hydroxides probably represent an additional concentrating factor for the other elements as the relationship of the results for zinc and manganese shows. Manganese may indicate a seasonally related concentrating cycle at the sediment surface.

(Table S1) Trace element and isotopic compositions of anhydrites sampled in the Manus Basin, Papua New Guinea

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REEN patterns measured in anhydrite from mid-ocean ridge deposits. The REEN patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. 87Sr/86Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate d34S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate d34S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO2 degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.

Seawater carbonate chemistry and trace element accumulation during experiments with common cuttlefish, Sepia officinalis, 2009

Cephalopods play a key role in many marine trophic networks and constitute alternative fisheries resources, especially given the ongoing decline in finfish stocks. Along the European coast, the eggs of the cuttlefish Sepia officinalis are characterized by an increasing permeability of the eggshell during development, which leads to selective accumulation of essential and non-essential elements in the embryo. Temperature and pH are two critical factors that affect the metabolism of marine organisms in the coastal shallow waters. In this study, we investigated the effects of pH and temperature through a crossed (3?2; pH 8.1 (pCO2, 400 ppm), 7.85 (900 ppm) and 7.6 (1400 ppm) at 16 and 19°C, respectively) laboratory experiment. Seawater pH showed a strong effect on the egg weight and non-significant impact on the weight of hatchlings at the end of development implying an egg swelling process and embryo growth disturbances. The lower the seawater pH, the more 110 mAg was accumulated in the tissues of hatchlings. The 109Cd concentration factor (CF) decreased with decreasing pH and 65Zn CF reached maximal values pH 7.85, independently of temperature. Our results suggest that pH and temperature affected both the permeability properties of the eggshell and embryonic metabolism. To the best of our knowledge, this is one of the first studies on the consequences of ocean acidification and ocean warming on metal uptake in marine organisms, and our results indicate the need to further evaluate the likely ecotoxicological impact of the global change on the early-life stages of the cuttlefish.

Seawater carbonate chemistry and conditions of Mytilus edulis extracellular body fluids and shell composition in a pH-treatment experiment: Acid-base status, trace elements and delta11B, 2012

Mytilus edulis were cultured for 3 months under six different seawater pCO2 levels ranging from 380 to 4000 µatm. Specimen were taken from Kiel Fjord (Western Baltic Sea, Germany) which is a habitat with high and variable seawater pCO2 and related shifts in carbonate system speciation (e.g., low pH and low CaCO3 saturation state). Hemolymph (HL) and extrapallial fluid (EPF) samples were analyzed for pH and total dissolved inorganic carbon (CT) to calculate pCO2 and [HCO3]. A second experiment was conducted for 2 months with three different pCO2 levels (380, 1400 and 4000 µatm). Boron isotopes (delta11B) were investigated by LA-MC-ICP-MS (Laser Ablation-Multicollector-Inductively Coupled Plasma-Mass Spectrometry) in shell portions precipitated during experimental treatment time. Additionally, elemental ratios (B/Ca, Mg/Ca and Sr/Ca) in the EPF of specimen from the second experiment were measured via ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometry). Extracellular pH was not significantly different in HL and EPF but systematically lower than ambient water pH. This is due to high extracellular pCO2 values, a prerequisite for metabolic CO2 excretion. No accumulation of extracellular [HCO3] was measured. Elemental ratios (B/Ca, Mg/Ca and Sr/Ca) in the EPF increased slightly with pH which is in accordance with increasing growth and calcification rates at higher seawater pH values. Boron isotope ratios were highly variable between different individuals but also within single shells. This corresponds to a high individual variability in fluid B/Ca ratios and may be due to high boron concentrations in the organic parts of the shell. The mean delta11B value shows no trend with pH but appears to represent internal pH (EPF) rather than ambient water pH.

Major element compositions, minerals and trace elements at DSDP Leg 67 Holes

Mineralogical (microprobe) and geochemical (X-ray fluorescence, neutron activation analyses) data are given for 18 samples of volcanic rocks from the Guatemala Trench area (Deep Sea Drilling Project Leg 67). Typical fresh oceanic tholeiites occur in the trench itself (Hole 500) and in its immediate vicinity on the Cocos Plate (Site 495). Several samples (often reworked) of "spilitic" oceanic tholeiites are also described from the Trench: their mineralogy (greenschist facies association - actinolite + plagioclase + chlorite) and geochemistry (alteration, sometimes linked to manganese and zinc mineralization) are shown to result from high-temperature (300°-475°C) hydrothermal sea water-basalt interactions. The samples studied are depleted in light rare-earth elements (LREE), with the exception of the slightly LREE-enriched basalts from Hole 500. The occurrence of such different oceanic tholeiites in the same area is problematic. Volcanic rocks from the Guatemala continental slope (Hole 494A) are described as greenschist facies metabasites (actinolite + epidote + chlorite + plagioclase + calcite + quartz), mineralogically different from the spilites exposed on the Costa Rica coastal range (Nicoya Peninsula). Their primary magmatic affinity is uncertain: clinopyroxene and plagioclase compositions, together with titanium and other hygromagmaphile element contents, support an "active margin" affinity. The LREE-depleted patterns encountered in the present case, however, are not frequently found in orogenic samples but are typical of many oceanic tholeiites.

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.