The geochemistry, mineralogy, and petrology of basalts at DSDP Leg 59 Holes

Legs 59 and 60 of the International Phase of Oceanic Drilling (IPOD) were designed to study the nature and history of volcanism of the active Mariana arc, its currently spreading inter-arc basin (the Mariana Trough), and the series of inactive basins and intervening ridges that lie to the west. The older basins and ridges were drilled during Leg 59 as the first part of a transect of single-bit holes drilled in each major basin and ridge. The eastern part of the transect - the technically active region - was drilled during Leg 60. The evolution of island-arc volcanos and magma genesis associated with lithospheric subduction remain some of the most complex petrologic problems confronting us. Many types of source material (mantle, oceanic crust, continental crust) and an unusually wide range of possible physical conditions at the time of magma genesis must be identified even before the roles of partial melting and subsequent magma fractionation, mixing, and contamination can be assessed.

(Table 1) Comparison of diatom-bound and bulk sedimentary d15N values of ODP Holes 175-1082A and 175-1084A

The Matuyama Diatom Maximum (MDM) is a time of peak opal accumulation from 2.6 to ~2.0 Ma within the Benguela Current upwelling system that was initiated by increased influence of Southern Ocean water on the eastern South Atlantic. We measured opal, total organic carbon (TOC), and CaCO3 fluxes and C and N stable isotopes in sediments deposited from 2.4 to 1.95 Ma at Sites 1082 and 1084 to explore the biogeochemical dynamics within the Benguela region. The infusion of Southern Ocean water delivered dissolved nutrients and Southern Ocean flora and fauna, resulting in local opal accumulation increasing up to 8 g/cm**2/ky and the production of diatom mats. Some d15N measurements of diatom-bound organic matter indicate that the mats grew within the Benguela region. The bulk sediment d15N records are taken to reflect changes in the d15N of nitrate in the incoming water, where lower values at 2.4 Ma reflect less nitrate utilization in the Antarctic. A long-term increase in relative nitrate uptake in the Southern Ocean is evidenced by the gradual increase in d15N toward 1.9 Ma.

(Figure 1 and 2) Phosphorus pools in the investigated sediments quantified by SEDEX sequential extraction and distribution of recovered 33P spike between sedimentary P pools after incubation

Phosphorus is an essential nutrient for life. In the ocean, phosphorus burial regulates marine primary production**1, 2. Phosphorus is removed from the ocean by sedimentation of organic matter, and the subsequent conversion of organic phosphorus to phosphate minerals such as apatite, and ultimately phosphorite deposits**3, 4. Bacteria are thought to mediate these processes**5, but the mechanism of sequestration has remained unclear. Here, we present results from laboratory incubations in which we labelled organic-rich sediments from the Benguela upwelling system, Namibia, with a 33P-radiotracer, and tracked the fate of the phosphorus. We show that under both anoxic and oxic conditions, large sulphide-oxidizing bacteria accumulate 33P in their cells, and catalyse the nearly instantaneous conversion of phosphate to apatite. Apatite formation was greatest under anoxic conditions. Nutrient analyses of Namibian upwelling waters and sediments suggest that the rate of phosphate-to-apatite conversion beneath anoxic bottom waters exceeds the rate of phosphorus release during organic matter mineralization in the upper sediment layers. We suggest that bacterial apatite formation is a significant phosphorus sink under anoxic bottom-water conditions. Expanding oxygen minimum zones are projected in simulations of future climate change**6, potentially increasing sequestration of marine phosphate, and restricting marine productivity.

Composition of sedimentary rocks from the Burun-Tas Formation, Bol'shoi Lyakhov Island (New Siberian Islands)

Graywackes and shales of the Bol'shoi Lyakhov Island originally attributed to Mesozoic were subsequently considered based on microfossils as Late Proterozoic in age. At present, these sediments in the greater part of the island are dated back to Permian based on palynological assemblages. In the examined area of the island, this siliciclastic complex is intensely deformed and tectonically juxtaposed with blocks of oceanic and island-arc rocks exhumed along the South Anyui suture. The complex is largely composed of turbidites with members displaying hummocky cross-stratification. Studied mineral and geochemical charac¬teristics of the rocks defined three provenances of clastic material: volcanic island arc, sedimentary cover and/or basement of an ancient platform, and exotic blocks of oceanic and island-arc rocks such as serpentinites and amphibolites. All rock associations represent elements of an orogenic structure that originated by collision of the New Siberian continental block with the Anyui-Svyatoi Nos island arc. Flyschoid sediments accumu¬lated in a foredeep in front of the latter structure in the course of collision. Late Jurassic volcanics belonging to the Anyui-Svyatoi Nos island arc determine the lower age limit of syncollision siliciclastic rocks. Presence of Late Jurassic zircons in sandstones of the flyschoid sequence in the Bol'shoi Lyakhov Island is confirmed by fission-track dating. The upper age limit is determined by Aptian-Albian postcollision granites and diorites intruding the siliciclastic complex. Consequently, the flyschoid sequence is within stratigraphic range from the terminal Late Jurassic to Neocomian. It appears that Permian age of sediments suggested earlier is based on redeposited organic remains. The same Late Jurassic-Neocomian age and lithology are characteristic of fossiliferous siliciclastic sequences of the Stolbovoi and Malyi Lyakhov islands, the New Siberian Archipelago, and of graywackes in the South Anyui area in the Chukchi Peninsula. All these sediments accumulated in a spacious foredeep that formed in the course the late Cimmerian orogeny along the southern margin of the Arctic conti¬nental block.

Organic geochemical parameters (biomarker) in sedimentary sequences and sediment traps

For the reconstruction of sea-ice variability, a biomarker approach which is based on (1) the determination of sea-ice diatom-specific highly-branched isoprenoid (IP25) and (2) the coupling of phytoplankton biomarkers and IP25 has been used. For the first time, such a data set was obtained from an array of two sediment traps deployed at the southern Lomonosov Ridge in the central Arctic Ocean at water depth of 150 m and 1550 m and recording the seasonal variability of sea ice cover in 1995/1996. These data indicate a predominantly permanent sea ice cover at the trap location between November 1995 and June 1996, an ice-edge situation with increased phytoplankton productivity and sea-ice algae input in July/August 1996, and the start of new-ice formation in late September. The record of modern sea-ice variability is then used to better interpret data from sediment core PS2458-4 recovered at the Laptev Sea continental slope close to the interception with Lomonosov Ridge and recording the post-glacial to Holocene change in sea-ice cover. Based on IP25 and phytoplankton biomarker data from Core PS2458-4, minimum sea-ice cover was reconstructed for the Bølling/Allerød warm interval between about 14.5 and 13 calendar kyr BP, followed by a rapid and distinct increase in sea-ice cover at about 12.8 calendar kyr BP. This sea-ice event was directly preceded by a dramatic freshwater event and a collapse of phytoplankton productivity, having started about 100 years earlier. These data are the first direct evidence that enhanced freshwater flux caused enhanced sea-ice formation in the Arctic at the beginning of the Younger Dryas. In combination with a contemporaneous, abrupt and very prominent freshwater/meltwater pulse in the Yermak Plateau/Fram Strait area these data may furthermore support the hypothesis that strongly enhanced freshwater (and ice) export from the Arctic into the North Atlantic could have played an important trigger role for the onset of the Younger Dryas cold reversal. During the Early Holocene, sea-ice cover steadily increased again (ice-edge situation), reaching modern sea-ice conditions (more or less permanent sea-ice cover) probably at about 7-8 calendar kyr BP.

Sedimentary n-alkanes, their hydrogen isotopes, GDGTs and d15N as well as d13Corg of lake Nam Co, Tibet

The transition from the last Glacial to the current Interglacial, the Holocene, represents an important period with climatic and environmental changes impacting ecosystems. In this study, we examined the interplay between the Indian Ocean Summer Monsoon (IOSM) and the Westerlies at lake Nam Co, southern Tibet to understand the climatic effects on the ecosystem. Different organic geochemical proxies (n-alkanes, glycerol dialkyl glycerol tetraethers, dD, d13Corg, d15N) are applied to reconstruct the environmental and hydrological changes on one of the longest available paleorecords at the Tibetan Plateau. Based on our paleohydrological dD proxies, the aquatic signal lags the terrestrial one due to specific ecological thresholds, which, in addition to climatic changes, can influence aquatic organisms. The aquatic organisms' response strongly depends on temperature and associated lake size, as well as pH and nutrient availability. Because the terrestrial vegetation reacts faster and more sensitively to changes in the monsoonal and climatic system, the dD of n-C29 and the reconstructed inflow water signal represent an appropriate IOSM proxy. In general, the interplay of the different air masses seems to be primarily controlled by solar insolation. In the Holocene, the high insolation generates a large land-ocean pressure gradient associated with strong monsoonal winds and the strongest IOSM. In the last glacial period, however, the weak insolation promoted the Westerlies, thereby increasing their influence at the Tibetan Plateau. Our results help to elucidate the variable IOSM, and they illustrate a remarkable shift in the lake system regarding pH, d13Corg and d15N from the last glacial to the Holocene interglacial period.

Younger Dryas-Holocene sedimentary plant-wax hydrogen isotopes from the southern European Alps

We present a Younger Dryas-Holocene record of the hydrogen isotopic composition of sedimentary plant waxes (dDwax) from the southern European Alps (Lake Ghirla, N-Italy) to investigate its sensitivity to climatic forcing variations in this mid-latitude region (45°N). A modern altitudinal transect of dD values of river water and leaf waxes in the Lake Ghirla catchment is used to test present-day climate sensitivity of dDwax. While we find that altitudinal effects on dDwax are minor at our study site, temperature, precipitation amount, and evapotranspiration all appear to influence dDwax to varying extents. In the lake-sediment record, dDwax values vary between -134 and -180 per mil over the past 13 kyr. The long-term Holocene pattern of dDwax parallels the trend of decreasing temperature and is thus likely forced by the decline of northern hemisphere summer insolation. Shorter-term fluctuations, in contrast, may reflect both temperature and moisture-source changes. During the cool Younger Dryas and Little Ice Age (LIA) periods we observe unexpectedly high dDwax values relative to those before and after. We suggest that a change towards a more D-enriched moisture source is required during these intervals. In fact, a shift from northern N-Atlantic to southern N-Atlantic/western Mediterranean Sea sources would be consistent with a southward migration of the Westerlies with climate cooling. Prominent dDwax fluctuations in the early and middle Holocene are negative and potentially associated with temperature declines. In the late Holocene (<4 kyr BP), excursions are partly positive (as for the LIA) suggesting a stronger influence of moisture-source changes on dDwax variation. In addition to isotopic fractionations of the hydrological cycle, changes in vegetation composition, in the length of the growing season, and in snowfall amount provide additional potential sources of variability, although we cannot yet quantitatively assess these in the paleo-record. We conclude that while our dDwax record from the Alps does contain climatic information, it is a complicated record that would require additional constraints to be robustly interpreted. This also has important implications for other water-isotope-based proxy records of precipitation and hydro-climate from this region, such as cave speleothems.

Lithic grain and mineral composition of sand and sandstones from the North Pacific Ocean and the Bering Sea (Table 3)

Sand and sandstone compositions from different types of basins reflect provenance terranes governed by plate tectonics. One hundred and one thin sections of Upper Miocene to Holocene sand-sized material were examined from DSDP/IPOD Sites in the North Pacific Ocean and the Bering Sea. The Gazzi-Dickinson point-counting method was used to establish compositional characteristics of sands from different tectonic settings. Continental margin forearc sands from the western North America continental margin arc system are clearly different from backarc/marginal-sea sands from the Aleutian intraoceanic arc system. The forearc sands have average QFL percentages of 29-42-29, LmLvLst percentages of 32-34-34, 3 Fmwk%M and 0.82 P/F. Aleutian backarc sands have average QFL percentages of 8-22-69. LmLvLst percentages of 9-85-6, 0.5 Fmwk%M and 0.96 P/F. A trend of increasing QFL%Q and decreasing LmLvLst%Lv westward in the backarc region of the Aleutian Ridge reflects the influence of the Asiatic continental margin. Aleutian backarc sands without continental influence have average QFL percentages of 1-20-79, LmLvLst percentages of 1-98-1, 0 Fmwk%M and 0.99 P/F. Of the continental margin forearc samples, sands on the Astoria Fan (west of the Oregon-Washington trench) contain the highest LmLvLst%Lv and lowest P/F; sands from mixed transform-fault and trench settings (Delgada Fan and Gulf of Alaska samples) have slightly higher Qp/Q (0.03); and sands from the Pacific-Juan de Fuca-North America triple junction have the highest Fmwk%M. Delgada Fan and Gulf of Alaska sands have average QFL percentages of 27-38-35, LmLvLst percentages of 37-26-37, 2 Fmwk%M and 0.86 P/F. Astoria Fan sands have average QFL percentages of 35-41-24, LmLvLst percentages of 30-47-23, 3 Fmwk%M and 0.74 P/F. The triple-junction sands have average QFL percentages of 28-59-13, LmLvLst percentages of 25-26-49, 9 Fmwk%M and 0.87 P/F. The petrologic data from the modern ocean basins examined in this study can provide useful analogs for interpretation of ancient oceanic sequences. Our data suggest some refinements of, but generally substantiate, existing petrologic models relating sandstone composition to tectonic setting.

Potential Shifts in Canadian High Arctic Sedimentary Organic Matter Composition With Permafrost Active Layer Detachments

Increased temperature and precipitation in Arctic regions have led to deeper thawing and structural instability in permafrost soil. The resulting localized disturbances, referred to as active layer detachments (ALDs), may transport organic matter (OM) to more biogeochemically active zones. To examine this further, solid state cross polarization magic angle spinning 13C nuclear magnetic resonance (CPMAS NMR) and biomarker analysis were used to evaluate potential shifts in riverine sediment OM composition due to nearby ALDs within the Cape Bounty Arctic Watershed Observatory, Nunavut, Canada. In sedimentary OM near ALDs, NMR analysis revealed signals indicative of unaltered plant-derived material, likely derived from permafrost. Long chain acyclic aliphatic lipids, steroids, cutin, suberin and lignin occurred in the sediments, consistent with a dominance of plant-derived compounds, some of which may have originated from permafrost-derived OM released by ALDs. OM degradation proxies for sediments near ALDs revealed less alteration in acyclic aliphatic lipids, while constituents such as steroids, cutin, suberin and lignin were found at a relatively advanced stage of degradation. Phospholipid fatty acid analysis indicated that microbial activity was higher near ALDs than downstream but microbial substrate limitation was prevalent within disturbed regions. Our study suggests that, as these systems recover from disturbance, ALDs likely provide permafrost-derived OM to sedimentary environments. This source of OM, which is enriched in labile OM, may alter biogeochemical patterns and enhance microbial respiration within these ecosystems.

Strength of the Iberian intraplate lithosphere: Cenozoic deformations and seismicity

Previous studies about the strength of the lithosphere in the Iberia centre fail to resolve the depth of earthquakes because of the rheological uncertainties. Therefore, new contributions are considered (the crustal structure from a density model) and several parameters (tectonic regime, mantle rheology, strain rate) are checked in this paper to properly examine the role of lithospheric strength in the intraplate seismicity and the Cenozoic evolution. The strength distribution with depth, the integrated strength, the effective elastic thickness and the seismogenic thickness have been calculated by a finite element modelling of the lithosphere across the Central System mountain range and the bordering Duero and Madrid sedimentary basins. Only a dry mantle under strike-slip/extension and a strain rate of 10-15 s-1, or under extension and 10-16 s-1, causes a strong lithosphere. The integrated strength and the elastic thickness are lower in the mountain chain than in the basins. These anisotropies have been maintained since the Cenozoic and determine the mountain uplift and the biharmonic folding of the Iberian lithosphere during the Alpine deformations. The seismogenic thickness bounds the seismic activity in the upper–middle crust, and the decreasing crustal strength from the Duero Basin towards the Madrid Basin is related to a parallel increase in Plio–Quaternary deformations and seismicity. However, elasto–plastic modelling shows that current African–Eurasian convergence is resolved elastically or ductilely, which accounts for the low seismicity recorded in this region.

Interannual and (multi-)decadal variability in the sedimentary BIT index of Lake Challa, East Africa, over the past 2200 years: assessment of the precipitation proxy

The branched vs. isoprenoid tetraether (BIT) index is based on the relative abundance of branched tetraether lipids (brGDGTs) and the isoprenoidal GDGT crenarchaeol. In Lake Challa sediments the BIT index has been applied as a proxy for local monsoon precipitation on the assumption that the primary source of brGDGTs is soil washed in from the lake's catchment. Since then, microbial production within the water column has been identified as the primary source of brGDGTs in Lake Challa sediments, meaning that either an alternative mechanism links BIT index variation with rainfall or that the proxy's application must be reconsidered. We investigated GDGT concentrations and BIT index variation in Lake Challa sediments at a decadal resolution over the past 2200 years, in combination with GDGT time-series data from 45 monthly sediment-trap samples and a chronosequence of profundal surface sediments.

Our 2200-year geochemical record reveals high-frequency variability in GDGT concentrations, and therefore in the BIT index, superimposed on distinct lower-frequency fluctuations at multi-decadal to century timescales. These changes in BIT index are correlated with changes in the concentration of crenarchaeol but not with those of the brGDGTs. A clue for understanding the indirect link between rainfall and crenarchaeol concentration (and thus thaumarchaeotal abundance) was provided by the observation that surface sediments collected in January 2010 show a distinct shift in GDGT composition relative to sediments collected in August 2007. This shift is associated with increased bulk flux of settling mineral particles with high Ti / Al ratios during March–April 2008, reflecting an event of unusually high detrital input to Lake Challa concurrent with intense precipitation at the onset of the principal rain season that year. Although brGDGT distributions in the settling material are initially unaffected, this soil-erosion event is succeeded by a massive dry-season diatom bloom in July–September 2008 and a concurrent increase in the flux of GDGT-0. Complete absence of crenarchaeol in settling particles during the austral summer following this bloom indicates that no Thaumarchaeota bloom developed at that time. We suggest that increased nutrient availability, derived from the eroded soil washed into the lake, caused the massive bloom of diatoms and that the higher concentrations of ammonium (formed from breakdown of this algal matter) resulted in a replacement of nitrifying Thaumarchaeota, which in typical years prosper during the austral summer, by nitrifying bacteria. The decomposing dead diatoms passing through the suboxic zone of the water column probably also formed a substrate for GDGT-0-producing archaea. Hence, through a cascade of events, intensive rainfall affects thaumarchaeotal abundance, resulting in high BIT index values.

Decade-scale BIT index fluctuations in Lake Challa sediments exactly match the timing of three known episodes of prolonged regional drought within the past 250 years. Additionally, the principal trends of inferred rainfall variability over the past two millennia are consistent with the hydroclimatic history of equatorial East Africa, as has been documented from other (but less well dated) regional lake records. We therefore propose that variation in GDGT production originating from the episodic recurrence of strong soil-erosion events, when integrated over (multi-)decadal and longer timescales, generates a stable positive relationship between the sedimentary BIT index and monsoon rainfall at Lake Challa. Application of this paleoprecipitation proxy at other sites requires ascertaining the local processes which affect the productivity of crenarchaeol by Thaumarchaeota and brGDGTs.

The occurrence of PAHs and faecal sterols in Dublin Bay and their influence on sedimentary microbial communities

The source, concentration, and potential impact of sewage discharge and incomplete organic matter (OM) combustion on sedimentary microbial populations were assessed in Dublin Bay, Ireland. Polycyclic aromatic hydrocarbons (PAHs) and faecal steroids were investigated in 30 surface sediment stations in the bay. Phospholipid fatty acid (PLFA) content at each station was used to identify and quantify the broad microbial groups present and the impact of particle size, total organic carbon (%TOC), total hydrogen (%H) and total nitrogen (%N) was also considered. Faecal sterols were found to be highest in areas with historical point sources of sewage discharge. PAH distribution was more strongly associated with areas of deposition containing high %silt and %clay content, suggesting that PAHs are from diffuse sources such as rainwater run-off and atmospheric deposition. The PAHs ranged from 12 to 3072 ng/g, with 10 stations exceeding the suggested effect range low (ERL) for PAHs in marine sediments. PAH isomer pair ratios and sterol ratios were used to determine the source and extent of pollution. PLFAs were not impacted by sediment type or water depth but were strongly correlated to, and influenced by PAH and sewage levels. Certain biomarkers such as 10Me16:0, i17:0 and a17:0 were closely associated with PAH polluted sediments, while 16:1ω9, 16:1ω7c, Cy17:0, 18:1ω6, i16:0 and 15:0 all have strong positive correlations with faecal sterols. Overall, the results show that sedimentary microbial communities are impacted by anthropogenic pollution.

Assessment of heavy metals' bonding with various sedimentary phases in Shefa-Rud river (Guilan Province)

In the present investigation, bulk and chemical partitioning of elements in the Shefa-Rud riverbed sediments are studied. Higher concentrations of elemental concentrations have been observed in estuarine zone when compared with riverine sediments (except for Al, Fe, Pb and Mn). Manganese is mobilized under anoxic conditions prevailing in the Caspian Sea. Lithogenous materials are greatly diluted in the estuarine zone by various pollutants present in the Caspian Sea. Organic metallic bonds are not significantly present in the area of study. Geological units of the area of study have resulted in the lower concentrations of elemental concentrations of riverbed sediments when compared with published values for mean crust and world sediments ones. Though, cluster analysis has clearly shown the importance of alumina-silicates in controlling the distribution of Fe and Mn in riverbed sediments but it could not depict controlling mechanism for other studied elements. Geochemical Index (Igeo) and Enrichment Factor (EF) values are indicative of a clean environment throughout the river course. These values are in a well agreement with results of chemical partitioning data. Quantification of EF values is not logically possible and therefore Igeo values can be used more effectively.