Annotated record of the detailed examination of Mn deposits from the VERMILION SEA Expedition stations

On Vermilion Sea Expedition two research vessels among which the R/V Spencer F. Baird conducted a geological and geophysical exploration of the Gulf of California from February to May, 1959. Support was obtained from the Office of Naval Research and the Bureau of Ships of the U. S. Navy and from a grant of the American Petroleum Institute. Study of the canyons was one feature of the first part of the expedition. Submarine canyon studies were directed by Francis P. Shepard, Professor of Submarine Geology, aboard the research vessel Spencer F. Baird. The expedition found that the narrow channel between Angel de la Guarda Island, toward the head of the Gulf, and the peninsula is scoured almost free of sediments by strong currents. On the other side of Angel de la Guarda Island, between it and the mainland, one of the dredge hauls brought up a manganese nodule. It came from a depth of approximately 1500 feet. This is the shallowest water in which the nodules have been found. Studies have been under way some time on the feasibility of mining such nodules from the sea floor. They contain cobalt, nickel, copper and other valuable metals. (also in, Scripps Institution of Oceanography Vermilion Sea Expedition to the Gulf of California, http://library.ucsd.edu/dc/object/bb34484017)

Sulfate and nitrate firn concentrations on the Greenland ice sheet

Intercomparison of three new chemical ice core records from northern Greenland (covering the time span from approximately 1500 A.D. to present) with previously published records for southern and central Greenland reveals a uniform timing of anthropogenic changes in sulfate and nitrate firn concentrations over the entire ice sheet. The anthropogenic sulfate increase started around 1890, was interrupted by a transient decrease in the 1930s, and has resumed a major increase since 1950. Since the late 1970s though, a significant 30% decline in Greenland sulfate firn levels can be documented. The maximum anthropogenic increase in northern Greenland sulfate firn concentrations (up to 200-230 ppb) is 2-3 times larger than in southern and central Greenland. Nitrate records show an essentially steady increase since 1950 and, documented for the first time, a slight reduction during most recent years. Maximum nitrate firn levels of 100-130 ppb exceed the preindustrial background by 100% all over the Greenland ice sheet. Comparison with anthropogenic SO2 and NO x emission records indicates that the major increase in sulfate firn concentrations since 1950 can be attributed to Eurasian sources, while firn levels during the first half of this century appear to be dominated by North American emissions. A stronger North American source contribution is indicated over the entire 20th century in the case of nitrate. Applying a macroscopic deposition model separate time series for wet and dry deposition were derived which revealed a close correspondence of wet deposited sulfate with the timing of U.S. emissions, while the temporal evolution of Eurasian emissions is mainly reflected in the dry sulfate deposition record. During this century wet sulfate deposition increased by a factor of two while the total dry sulfate deposition flux increased by more than 500%. Wet and dry nitrate deposition both increased by 100% during the same period.

Horizontal profiles of longwave and shortwave radiation components over sea ice near Barrow, Alaska during the 2011 melt

An integrated instrument package for measuring and understanding the surface radiation budget of sea ice is presented, along with results from its first deployment. The setup simultaneously measures broadband fluxes of upwelling and downwelling terrestrial and solar radiation (four components separately), spectral fluxes of incident and reflected solar radiation, and supporting data such as air temperature and humidity, surface temperature, and location (GPS), in addition to photographing the sky and observed surface during each measurement. The instruments are mounted on a small sled, allowing measurements of the radiation budget to be made at many locations in the study area to see the effect of small-scale surface processes on the large-scale radiation budget. Such observations have many applications, from calibration and validation of remote sensing products to improving our understanding of surface processes that affect atmosphere-snow-ice interactions and drive feedbacks, ultimately leading to the potential to improve climate modelling of ice-covered regions of the ocean. The photographs, spectral data, and other observations allow for improved analysis of the broadband data. An example of this is shown by using the observations made during a partly cloudy day, which show erratic variations due to passing clouds, and creating a careful estimate of what the radiation budget along the observed line would have been under uniform sky conditions, clear or overcast. Other data from the setup's first deployment, in June 2011 on fast ice near Point Barrow, Alaska, are also shown; these illustrate the rapid changes of the radiation budget during a cold period that led to refreezing and new snow well into the melt season.

Climate variability in the Aegean Sea (marine record M2, Athos basin) during the past 1500 years

We provide new evidence on sea surface temperature (SST) variations and paleoceanographic/paleoenvironmental changes over the past 1500 years for the north Aegean Sea (NE Mediterranean). The reconstructions are based on multiproxy analyses, obtained from the high resolution (decadal to multi-decadal) marine record M2 retrieved from the Athos basin. Reconstructed SSTs show an increase from ca. 850 to 950 AD and from ca. 1100 to 1300 AD. A cooling phase of almost 1.5 °C is observed from ca. 1600 AD to 1700 AD. This seems to have been the starting point of a continuous SST warming trend until the end of the reconstructed period, interrupted by two prominent cooling events at 1832 ± 15 AD and 1995 ± 1 AD. Application of an adaptive Kernel smoothing suggests that the current warming in the reconstructed SSTs of the north Aegean might be unprecedented in the context of the past 1500 years. Internal variability in atmospheric/oceanic circulations systems as well as external forcing as solar radiation and volcanic activity could have affected temperature variations in the north Aegean Sea over the past 1500 years. The marked temperature drop of approximately ~2 °C at 1832 ± 15 yr AD could be related to the 1809 ?D 'unknown' and the 1815 AD Tambora volcanic eruptions. Paleoenvironmental proxy-indices of the M2 record show enhanced riverine/continental inputs in the northern Aegean after ca. 1450 AD. The paleoclimatic evidence derived from the M2 record is combined with a socio-environmental study of the history of the north Aegean region. We show that the cultivation of temperature-sensitive crops, i.e. walnut, vine and olive, co-occurred with stable and warmer temperatures, while its end coincided with a significant episode of cooler temperatures. Periods of agricultural growth in Macedonia coincide with periods of warmer and more stable SSTs, but further exploration is required in order to identify the causal links behind the observed phenomena. The Black Death likely caused major changes in agricultural activity in the north Aegean region, as reflected in the pollen data from land sites of Macedonia and the M2 proxy-reconstructions. Finally, we conclude that the early modern peaks in mountain vegetation in the Rhodope and Macedonia highlands, visible also in the M2 record, were very likely climate-driven.

Stable carbon isotope composition of benthic foraminifera from sediments of the Skagerrak, North Sea

The sediment cores 225514 and 225510 were recovered from 420 and 285 m water depth, respectively. They were investigated for their benthic foraminiferal delta13C during the last 500 years. Both cores were recovered from the southern flank of the Skagerrak. The delta13C values of Uvigerina mediterranea and other shallow infaunal species in both cores indicate that organic matter rain rates to the seafloor varied around a mean value until approximately AD 1950 after which they increased. This increase might result from changes in the North Atlantic Current System and a co-occurring persistently high North Atlantic Oscillation index state in the 1980s to 1990s, rather than from anthropogenic eutrophication. Using delta13C mean values of multiple species, we reconstruct delta13C gradients of dissolved inorganic carbon (DIC) within pore waters for the time periods AD 1500 to 1950 and AD 1950 to 2000. The calculated delta13CDIC ranges, interpreted as indicating total organic matter remineralization due to respiration, are generally bigger in Core 225514 than in Core 225510. Since mean delta13C values of U. mediterranea suggest that organic matter rain rates were similar at both locations, differences in total organic matter remineralization are attributed to differing oxygen availability. However, oxygen concentrations in the overlying bottom water masses are not likely to have differed significantly. Thus, we suggest that organic matter remineralization was controlled by oxygen availability within the sediments, reflecting strong differences in sedimentation rates at the two investigated core sites. Based on the assumptions that tests of benthic foraminiferal species inhabiting the same microhabitat depth should show equal delta13C values unless they are affected by vital effects and that Globobulimina turgida records pore water delta13CDIC, we estimate microhabitat-corrected vital effects for several species with respect to G. turgida: >0.7 per mil for Cassidulina laevigata, >1.3 per mil for Hyalinea balthica, and >0.7 per mil for Melonis barleeanus. Melonis zaandami seems to closely record pore water delta13CDIC.

Particle concentration and size distribution in the NGRIP ice core

A novel laser microparticle detector used in conjunction with continuous sample melting has provided a more than 1500 m long record of particle concentration and size distribution of the NGRIP ice core, covering continuously the period approximately from 9.5-100 kyr before present; measurements were at 1.65 m depth resolution, corresponding to approximately 35-200 yr. Particle concentration increased by a factor of 100 in the Last Glacial Maximum (LGM) compared to the Preboreal, and sharp variations of concentration occurred synchronously with rapid changes in the delta18O temperature proxy. The lognormal mode µ of the volume distribution shows clear systematic variations with smaller modes during warmer climates and coarser modes during colder periods. We find µ ~ 1.7 µm diameter during LGM and µ ~ 1.3 µm during the Preboreal. On timescales below several 100 years µ and the particle concentration exhibit a certain degree of independence present especially during warm periods, when µ generally is more variable. Using highly simplifying considerations for atmospheric transport and deposition of particles we infer that (1) the observed changes of µ in the ice largely reflect changes in the size of airborne particles above the ice sheet and (2) changes of µ are indicative of changes in long range atmospheric transport time. From the observed size changes we estimate shorter transit times by roughly 25% during LGM compared to the Preboreal. The associated particle concentration increase from more efficient long range transport is estimated to less than one order of magnitude.

Manganese concentrations and flux data of sediments from Broken and Ninetyeast Ridge

Decomposition of organic matter combined with density stratification generate a pronounced intermediate water oxygen minimum zone (OMZ) in the northwest Indian Ocean. This zone currently lies between water depths of 200 and 2000 m and extends approximately 5000 km southeast from the Arabian coast. Based upon benthic foraminiferal assemblage changes, it has been suggested that this OMZ was even more extensive during the late Miocene-early Pliocene (6.5-3.0 Ma), with a maximum volume and/or intensity at approximately 5.0 Ma. While this inference may contribute to an understanding of the history of northwest Indian Ocean upwelling, corroborating geochemical evidence for this interpretation has heretofore been lacking. Ocean Drilling Program (ODP) sites 752, 754, and 757 on Broken and Ninetyeast ridges are located within central Indian Ocean intermediate water depths (1086-1650 m) but outside the present lateral dimensions of the Indian Ocean OMZ. High-resolution chemical analyses of sediment from these sites indicate significant reductions in the flux of Mn and normalized Mn concentrations between 6.5 and 3.0 Ma that are most pronounced at approximately 5.0 Ma. Because late Miocene-Pliocene paleodepths for these sites were essentially the same as at present and because extremely low sedimentation rates (0.3-1.3 cm/ky) most likely precluded sedimentary metal oxide diagenesis, we suggest that the observed Mn depletions reflect diminished deposition of reducible Mn oxyhydroxide phases within O2 deficient intermediate waters and that this effect was most intense at approximately 5.0 Ma. This interpretation implies that waters with less than 2.0 mL/L O2 extended at least 1500 km beyond their present limits and is consistent with changes in benthic foraminifera assemblages. We further suggest this expanded Indian Ocean OMZ is related to regionally and/or globally increased biological productivity.

Chemistry and accumulation rates of Jurassic to early Cretaceous sediments from the central equatorial Pacific

Sedimentation in the central Pacific during the Jurassic and Early Cretaceous was dominated by abundant biogenic silica. A synthesis of the stratigraphy, lithology, petrology, and geochemistry of the radiolarites in Sites 801 and 800 documents the sedimentation processes and trends in the equatorial central Pacific from the Middle Jurassic through the Early Cretaceous. Paleolatitude and paleodepth reconstructions enable comparisons with previous DSDP sites and identification of the general patterns of sedimentation over a wide region of the Pacific. Clayey radiolarites dominated sedimentation on Pacific oceanic crust within tropical paleolatitudes from at least the latest Bathonian through Tithonian. Radiolarian productivity rose to a peak within 5° of the paleoequator, where accumulation rates of biogenic silica exceeded 1000 g/cm**2/m.y. Wavy-bedded radiolarian cherts developed in the upper Tithonian at Site 801 coinciding with the proximity of this site to the paleoequator. Ribbon-bedding of some radiolarian cherts exposed on Pacific margins may have formed from silicification of radiolarite deposited near the equatorial high-productivity zone where radiolarian/clay ratios were high. Silicification processes in sediments extensively mixed by bioturbation or enriched in clay or carbonate generally resulted in discontinuous bands or nodules of porcellanite or chert, e.g., a "knobby" radiolarite. Ribbon-bedded cherts require primary alternations of radiolarian-rich and clay-rich layers as an initial structural template, coupled with abundant biogenic silica in both layers. During diagenesis, migration of silica from clay-rich layers leaves radiolarian "ghosts" or voids, and the precipitation in adjacent radiolarite layers results in silicification of the inter-radiolarian matrix and infilling of radiolarian tests. Alternations of claystone and clay-rich radiolarian grainstone were deposited during the Callovian at Site 801 and during the Berriasian-Valanginian at Site 800, but did not silicify to form bedded chert. Carbonate was not preserved on the Pacific oceanic floor or spreading ridges during the Jurassic, perhaps due to an elevated level of dissolved carbon dioxide. During the Berriasian through Hauterivian, the carbonate compensation depth (CCD) descended to approximately 3500 m, permitting the accumulation of siliceous limestones at near-ridge sites. Carbonate accumulation rates exceeded 1500 g/cm**2/m.y. at sites above the CCD, yet there is no evidence of an equatorial carbonate bulge during the Early Cretaceous. In the Barremian and Aptian, the CCD rose, coincident with the onset of mid-plate volcanic activity. Abundance of Fe and Mn and the associated formation of authigenic Fe-smectite clays was a function of proximity to the spreading ridges, with secondary enrichments occurring during episodes of spreading-center reorganizations. Callovian radiolarite at Site 801 is anomalously depleted in Mn, which resulted either from inhibited precipitation of Mn-oxides by lower pH of interstitial waters induced by high dissolved oceanic CO2 levels or from diagenetic mobilization of Mn. Influx of terrigenous (eolian) clay apparently changed with paleolatitude and geological age. Cyclic variations in productivity of radiolarians and of nannofossils and in the influx of terrigenous clay are attributed to Milankovitch climatic cycles of precession (20,000 yr) and eccentricity (100,000 yr). Diagenetic redistribution of biogenic silica and carbonate enhanced the expression of this cyclic sedimentation. Jurassic and Lower Cretaceous sediments were deposited under oxygenated bottom-water conditions at all depths, accompanied by bioturbation and pervasive oxidation of organic carbon and metals. Despite the more "equable" climate conditions of the Mesozoic, the super-ocean of the Pacific experienced adequate deep-water circulation to prevent stagnation. Efficient nutrient recycling may have been a factor in the abundance of radiolarians in this ocean basin.

Nitrogen isotopic composition in South China Sea sediments

The d15N of surface and down-core sediments spanning the last 20-200 kyr from the entire South China Sea (SCS) ranges only from ~3.0 to ~6.5 per mil, with no correlation with discernible paleoclimatic/oceanographic changes. Detailed profiles of the uppermost sediment column, including fluff samples, indicate a minor diagenetic overprint of 0.3-1.2 per mil at the sediment-water interface. The absence of any correlation with reconstructed (glacial-interglacial) changes in primary production, terrigenous input, and/or sea level related basin configuration is attributed to a complete consumption of nitrate during primary production in this marginal basin during at least the last 140,000 years. This, in turn, implies that the d15N of the nitrate used during primary production remained approximately constant during the last climatic cycle. The proposed scenario infers an unchanged nitrogen isotopic composition of the western Pacific subsurface nitrate between glacial and interglacial stages as well as during terminations and thus constrains proposed changes in the oceanic N inventory.