Chemistry of altered basalts from ODP Hole 123-765D

Volcanic basement recovered at Hole 765D is characterized by nonpervasive, oxidative alteration, typical of seafloor weathering. Chilled margins and the mesostasis of the lavas are variably altered to assemblages of celadonite, Fe-oxyhydroxides, zeolites, and calcite with trace saponite. Plagioclase is partially altered to Ca-Na zeolites and/or albite. Well-developed alteration halos parallel fracture surfaces and extend several centimeters into the surrounding rock. These clay-rich halos are enriched in K2O and Fe2O3 relative to the adjacent clay-poor rock. The halos and adjacent rock are characterized by d18O values 2 per mil-3 per mil higher than those of fresh MORB. The "freshness" of the samples and the scarcity of saponite suggest that the duration of seawater circulation was short-lived. Albitization of plagioclase indicates that the volcanic rocks were altered initially at low temperatures and were subsequently reheated off-axis in a closed environment. Reheating did not result in significant modification of the bulk composition of the crust.

Diffusion transport of water in basalts

Studying diffusive transport in porous rocks is of fundamental importance in understanding a variety of geochemical processes including: element transfer, primary mineral dissolution kinetics and precipitation of secondary phases. Here we report new findings on the relationship between diffusive transport and textural characteristics of the pore systems on the example of mid-oceanic ridge basalts having different degree of alteration but very similar bulk pore volume. Diffusion processes in porous basalts were studied in situ using H2O -> D2O exchange experiments. The effective diffusion coefficients of water molecules increase systematically from 5.05*10**-11 to 1.19*10**-10 m**2/s for fresh and moderately altered basalts and from 2.40*10**-11 to 6.72*10**-11 m**2/s for completely altered basalt as temperature increases from 5 to 50 °C. The activation energy of the diffusion process increases from 12.29 ± 0.71 kJ/mol for fresh and moderately altered basalts to 14.3 ± 1.33 kJ/mol for completely altered basalt. The results indicate that neither the bulk porosity nor the degree of alteration can be used as proxies for the efficiency of element transport during MORB-water interaction. The formation of secondary phases that replace primary minerals and fill the pore space in the rock leads to the formation of tiny pores and phases with large specific surface area. These factors might have a dominant control on the transport properties of altered basaltic rocks.

Sulphur geochemistry of whole-rock samples from ODP Hole 176-735B

Sulfide petrography plus whole rock contents and isotope ratios of sulfur were measured in a 1.5 km section of oceanic gabbros in order to understand the geochemistry of sulfur cycling during low-temperature seawater alteration of the lower oceanic crust, and to test whether microbial effects may be present. Most samples have low SO4/Sum S values (<= 0.15), have retained igneous globules of pyrrhotite ± chalcopyrite ± pentlandite, and host secondary aggregates of pyrrhotite and pyrite laths in smectite ± iron-oxyhydroxide ± magnetite ± calcite pseudomorphs of olivine and clinopyroxene. Compared to fresh gabbro containing 100-1800 ppm sulfur our data indicate an overall addition of sulfide to the lower crust. Selection of samples altered only at temperatures <= 110 °C constrains microbial sulfate reduction as the only viable mechanism for the observed sulfide addition, which may have been enabled by the production of H2 from oxidation of associated olivine and pyroxene. The wide range in d34Ssulfide values (-1.5 to + 16.3 per mil) and variable additions of sulfide are explained by variable epsilon sulfate-sulfide under open system pathways, with a possible progression into closed system pathways. Some samples underwent oxidation related to seawater penetration along permeable fault horizons and have lost sulfur, have high SO4/Sum S (>= 0.46) and variable d34Ssulfide (0.7 to 16.9 per mil). Negative d34Ssulfate-d34Ssulfide values for the majority of samples indicate kinetic isotope fractionation during oxidation of sulfide minerals. Depth trends in sulfide-sulfur contents and sulfide mineral assemblages indicate a late-stage downward penetration of seawater into the lower 1 km of Hole 735B. Our results show that under appropriate temperature conditions, a subsurface biosphere can persist in the lower oceanic crust and alter its geochemistry.

Radionuclides in ice cores I and II from Vernagferner, Austria

Fission product (90Sr-90Y, 137Cs, total beta) and 21OPb-210Po activities were measured in core samples from the temperate vernagtferner (3150 m altitude, Oetztal Alps, Austria). The results show that the investigated fission products are transported with water resulting from melting processes, and are sorbed on dust or dirt horizons. These products are, therefore, not suited for dating temperate glaciers. 210Pb is also transported with water and displaced from its original deposition. However, despite large fluctuations, the specific activity of 210Pb decreases with depth, and can be used to estimate accumulation rates and the age of the ice. The average annual accumulation rate amounts to about 80 cm water equivalent, and the deepest sample (81 m i.e. ab. 65 m w. e.) was deposited in the beginning of this century. These results agree with data obtained from other observations on this glacier and show that the 210Pb_method is suitable to date temperate glaciers, if the ice cores cover a time interval of about 100 years (i.e. ab. 4 half-lives of 210Pb). The surface activity of 210Pb was found to be 5 ± 1 dpm per kg of ice in agreement with other locations in the Alps and with measurements of fresh snow.

(Table 1) Effects of desiccation on photochemical processes and nitrogenase activity in Nostoc commune s.l. colonies

The effects of desiccation on photochemical processes and nitrogenase activity were evaluated in Nostoc commune s.l. colonies in situ from a wet thufur meadow at Petuniabukta, Billefjorden, Central Svalbard, during the 2009 arctic summer. The colonies were collected in the fully hydrated state, and were subjected to slow desiccation at ambient temperatures (5 - 8°C) and low light (30 - 80 µmol/m**2/s). For each colony the weight, area, photochemical performance, and nitrogenase activity were determined at the beginning, as well as on every day during the first four days of the experiment; thereafter, on every second day until desiccation was complete. The photochemical performance was evaluated from variable chlorophyll fluorescence parameters (FV/FM, Phi(PSII) , qP, and NPQ), and the nitrogenase activity was estimated by an acetylene-ethylene reduction assay. A significant decrease in the photochemically active area was recorded from the third day, when the colony had lost approximately 40% of its original weight indicating some changes in the extracellular matrix, and stopped on the 14th to 18th day. No effects of the desiccation on the main photochemical parameters (FV/FM, Phi(PSII), qP) were observed up to the sixth to eighth days of desiccation. Slightly lower values of FV/FM and Phi(PSII) recorded in fully-hydrated colonies could be caused by impaired diffusion of CO2 into cells. The steep reduction of photochemical activity occurred between the eighth and tenth day of the experiment, when the colony had lost approximately 80% of its fully-hydrated weight. The nitrogenase activity was highest on the first day, probably due to improved diffusion of N2 into cells, then declined, but was detectable until the sixth day of the experiment. Since Nostoc commune s.l. colonies were capable of photosynthesis and nitrogen fixation to the level of ca. 60% of its fully-hydrated weight, even partly-hydrated colonies contribute substantially to carbon and nitrogen cycling in the High Arctic wet meadow tundra ecosystem.

Benthic foraminifera abundance data of sediment core GeoB7926-2

We present a high resolution, multiproxy study of the relationship between pelagic and benthic environments of a coastal upwelling system in the subtropical NE Atlantic Ocean. Marine sediments corresponding to late MIS3 to the Holocene in the radiocarbon dated core GeoB7926, retrieved off Mauritania (21°N) were analysed to reconstruct productivity in surface waters and its linkage to deep waters during the last 35 ka BP. High latitude cold events and changes in atmospheric and oceanographic dynamics influenced upwelling intensity over this time period. Subsequently, this caused changes in primary productivity off this low-latitude coastal upwelling locality. The benthic foraminiferal fauna displays four main community shifts corresponding to fundamental climatic events, first of all during late MIS3 (35-28 ka BP), secondly from 28 to 19 ka BP (including Heinrich event 2 and the LGM), thirdly within Heinrich event 1, the Bølling Allerød and the Younger Dryas (18-11.5 ka BP) and finally during the Holocene (11.5-0 ka BP). In particular, strong pelagic-benthic coupling is apparent in MIS 3, as demonstrated by increased primary productivity, indicated by moderate DAR and the dominance of benthic foraminiferal species which prefer fresh phytodetritus. A decline in upwelling intensity and nutrient availability follows, which resulted in a proportionately larger amount of older, degraded matter, provoking a shift in the benthic foraminifera fauna composition. This rapid response of the benthic environment continues with a progressive increase in upwelling intensity due to sea level and oceanographic changes and according high surface production during the LGM. During Heinrich event 1 and the Younger Dryas, extreme levels of primary production actually hindered benthic environment through the development of low oxygen conditions. After this period, a final change in benthic foraminiferal community composition occurs which indicates a return to more oxygenated conditions during the Holocene.

Geochemistry at DSDP Site 60-456

Basalts in two holes spaced 200 meters apart at DSDP Site 456 in the Mariana Trough both show a downward sequence of nonoxidative and oxidative zones of alteration, each 10 to 15 meters thick, overlying fresh basalts. Basalts in the nonoxidative zone have been extensively chloritized and have vein and vesicle fillings of quartz, opal, chlorite, calcite, and pyrite. Minor sulfides are chalcopyrite and digenite. Basalts in the oxidative zone have abundant smectites and iron hydroxides and are variably enriched in K, Rb, and Ba, unlike the nonoxidative basalts above them. We propose that the oxidative zone was a zone of mixing between high-temperature, reduced hydrothermal fluids moving horizontally beneath impermeable sediments at the top of the pillowed basement lavas and cold, oxygenated seawater in interpillow voids deeper in the basement. Recrystallized vitric tuffs immediately above the basalts containing authigenic quartz and wairakite, as well as occurrence of chlorite, epidote, and chalcopyrite in the basalts, suggest temperatures of alteration in excess of 200°C.

Biomarkers in surface sediments from the Ob and Yenisei estuaries and the southern Kara Sea

Organic-geochemical bulk parameter (Total organic carbon contents, C/N ratios and d13Corg values), biogenic opal and biomarkers (n-alkanes, fatty acids, sterols and amino acids) were determined in surface sediments from the Ob and Yenisei estuaries and the adjacent southern Kara Sea. Maximum TOC contents were determined in both estuaries, reaching up to 3 %. Relatively high C/N ratios around 10, light d13Corg values of -26.5 per mil (Yenisei) and -28 to -28.7 per mil (Ob), and maximum concentrations of long-chain n-alkanes of up to about 10 µg/g Sed clearly show the predominance of terrigenous organic matter in the sediments from the estuaries. Towards the open Kara Sea, all p arameters indicate a decrease in terrigenous organic carbon. Brassicasterol as well as the short-chain n-alkanes parallel this trend, suggesting that these biomarkers are probably also related to a terrigenous (fresh-water phytoplankton) source. Amino acid spectra show characteristic trends from the Yenisei Estuary to the open Kara Sea revealing increasing state of degradation. Sedimentary organic matter in the Yenisei Estuary is relatively less degraded compared to the Ob Estuary and the open Kara Sea.

Biogeochemistry of the Darwin Mounds, NE Atlantic

The Darwin Mounds are a series of small (<=5 m high, 75-100 m diameter) sandy features located in the northern Rockall Trough. They provide a habitat for communities of Lophelia pertusa and associated fauna. Suspended particulate organic matter (sPOM) reaching the deep-sea floor, which could potentially fuel this deep-water coral (DWC) ecosystem, was collected during summer 2000. This was relatively "fresh" (i.e. dominated by labile lipids such as polyunsaturated fatty acids) and was derived largely from phytoplankton remains and faecal pellets, with contributions from bacteria and microzooplankton. Labile sPOM components were enriched in the benthic boundary layer (~10 m above bottom (mab)) relative to 150 mab. The action of certain benthic fauna that are exclusively associated with the DWC ecosystem (e.g. echiuran worms) leads to the subduction of fresh organic material into the sediments. The mound surface sediments are enriched in organic carbon, relative to off-mound sites. There is no evidence for hydrocarbon venting at this location.

Sapropel cycles in the Mediterranean Sea

Water column stratification increased at climatic transitions from cold to warm periods during the late Quaternary and led to anoxic conditions and sapropel formation in the deep eastern Mediterranean basins. High-resolution data sets on sea-surface temperatures (SST) (estimated from UK'37 indices) and d18O of planktonic foraminifer calcite (d18Ofc) across late Pleistocene sapropel intervals show that d18Ofc decreased (between 1 and 4.6 per mil) and SST increased (between 0.7° and 6.7°C). Maximal d18Oseawater depletion of eastern Mediterranean surface waters at the transition is between 0.5 and 3.0 per mil, and in all but one case exceeded the depletion seen in a western Mediterranean core. The depletion in d18Oseawater is most pronounced at sapropel bases, in agreement with an initial sudden input of monsoon-derived freshwater. Most sapropels coincide with warming trends of SST. The density decrease by initial freshwater input and continued warming of the sea surface pooled fresh water in the surface layer and prohibited deep convection down to ageing deep water emplaced during cold and arid glacial conditions. An exception to this pattern is "glacial" sapropel S6; its largest d18Oseawater depletion (3 per mil) is almost matched by the depletion in the western Mediterranean Sea, and it is accompanied by surface water cooling following an initially rapid warming phase. A second period of significant isotopic depletion is in isotope stage 6 at the 150 kyr insolation maximum. While not expressed as a sapropel due to cold SST, it is in accord with a strengthened monsoon in the southern catchment.

Chemical composition of altered volcanic rocks from ODP Sites 193-1188 and 193-1189

The conventional model of leaching volcanic rocks as a source of metals in a seafloor hydrothermal systems has been tested by examining the behavior of Pb and other trace elements during hydrothermal alteration. ODP Leg 193 drill sites 1188 (Snowcap) and 1189 (Roman Ruins) on Pual Ridge in the eastern Manus Basin offshore eastern Papua New Guinea provide a unique three-dimensional window into an active back-arc hydrothermal system. We investigate by means of a LA-ICP-MS microbeam technique the capacity of Pb to be leached from a host volcanic rock exposed to various types and intensities of alteration. Our results are in general agreement with previous studies that utilized bulk analytical techniques but provide a more detailed explanation of the processes. Fresh representative dacitic lavas from the Pual Ridge have an average whole rock Pb content of 5.2 ppm, an average interstitial glass Pb content of 5.6 ppm and an average plagioclase Pb content of 1.0 ppm. Altered matrix samples have highly variable Pb values ranging from 0 to 52.4 ppm. High Pb values in altered samples are associated with a low temperature chlorite and clay mineral assemblage, in some cases overprinted by a high temperature (up to 350°C) silica-rich "bleaching" alteration. Only the most highly altered matrix samples have REE patterns that differ from the fresh Pual Ridge dacite. This may represent either different lava histories or alteration characteristics that have affected normally immobile REEs. Altered samples with the highest Pb values have similar REE patterns to those of the local unaltered lavas. They are compositionally similar to typical Pual Ridge dacites indicating a genetic relationship between the main regional volcanic suite and the subseafloor hydrothermally altered, Pb-enriched material. Relative loss/gain for Pb between the analyzed altered samples and a calculated precursor show a maximum relative gain of 901%. Samples with relative Pb gain from both drill sites are associated with lower temperature alteration mineral assemblages characterized by pervasive chloritization. The related lower temperature (220-250°C) neutral to slightly acidic fluids have been ascribed by others to return circulation of hydrothermal fluids that did not interact with seawater. Because altered samples have a higher Pb content than the fresh precursor, leaching of fresh volcanic rocks cannot be the source of Pb in the hydrothermal systems.

Petrology and geochemistry of basalts at DSDP Hole 86-581

Approximately 5 m of aphyric to sparsely phyric basalt was recovered from Hole 581, the only hole on Leg 86 where basement was cored. The occurrence of samples with altered glassy rinds indicates that at least three cooling units (pillows or thin flows) were sampled. The samples were moderately to intensely altered; groundmass crystals are generally fresh, but all glass is altered. Alteration is greatest in vesicular samples, but most of the samples have fractures filled with iron oxyhydroxide, clay, and/or calcite. All 13 samples analyzed are moderately fractionated aluminous N-type mid-ocean ridge basalts. The samples can be divided into two groups based on TiO2 and FeO contents. The least-evolved group may be derived from a more primitive mid-ocean ridge basalt by the crystallization of 18% plagioclase, 24% clinopyroxene, and 3% olivine. The more evolved group may be derived from the first group by the fractionation of 18% plagioclase, 11% clinopyroxene, and 3% olivine. However, higher Ce/Yb ratios in the more evolved group cannot be produced by fractionation and thus we must invoke a more complex process such as dynamic melting to relate the two groups to a common source.

Primary composition, alteration, and origin of Cretaceous volcaniclastic rocks at DSDP Site 89-585

An upper Aptian to middle Albian series of volcaniclastic rocks more than 300 m thick was drilled at Site 585 in the East Mariana Basin. On the basis of textural and compositional (bulk-rock chemistry, primary and secondary mineral phases) evidence, the volcaniclastic unit is subdivided into a lower (below 830 m sub-bottom) and an upper (about 670-760 m) sequence; the boundary in the interval between is uncertain owing to lack of samples. The rocks are dominantly former vitric basaltic tuffs and minor lapillistones with lesser amounts of crystals and basaltic lithic clasts. They are mixed with shallow-water carbonate debris (ooids, skeletal debris), and were transported by mass flows to their site of deposition. The lower sequence is mostly plagioclase- and olivine-phyric with lesser amounts of Ti-poor clinopyroxene. Mineralogical and bulk-rock chemical data indicate a tholeiitic composition slightly more enriched than N-MORB (normal mid-ocean ridge basalt). Transport was by debris flows from shallow-water sites, as indicated by admixed ooids. Volcanogenic particles are chiefly moderately vesicular to nonvesicular blocky shards (former sideromelane) and less angular tachylite with quench plagioclase and pyroxene, indicating generation of volcanic clasts predominantly by spalling and breakage of submarine pillow and/or sheet-flow lavas. The upper sequence is mainly clinopyroxene- and olivine-phyric with minor plagioclase. The more Ti-rich clinopyroxene and the bulk-rock analyses show that the moderately alkali basaltic composition throughout is more mafic than the basal tholeiitic sequence. Transport was by turbidity currents. Rounded epiclasts of crystalline basalts are more common than in the lower sequence, and, together with the occurrence of oxidized olivine pseudomorphs and vesicular tachylite, are taken as evidence of derivation from eroded subaerially exposed volcanics. Former sideromelane shards are more vesicular than in the lower sequence; vesicularity exceeds 60 vol.% in some clasts. The dominant clastic process is interpreted to be by shallow-water explosive eruptions. All rocks have undergone low-temperature alteration; the dominant secondary phases are "palagonite," chlorite/smectite mixed minerals, analcite, and chabazite. Smectite, chlorite, and natrolite occur in minor amounts. Phillipsite is recognized as an early alteration product, now replaced by other zeolites. During alteration, the rocks have lost up to 50% of their Ca, compared with a fresh shard and fresh glass inclusions in primary minerals, but have gained much less K, Rb, and Ba than expected, indicating rapid deposition prior to significant seafloor weathering.