Strontium and rubidium isotopes in serpentinites from ODP Site 195-1200

Subduction of the Pacific plate beneath the Mariana forearc releases fluids to the overlying mantle wedge that ascend, producing serpentinite "mud" that discharges on the ocean floor. As part of Leg 195 of the Ocean Drilling Program cores were obtained from drill-holes into the mud volcanoes. We report the isotopic composition of Sr in water squeezed from intervals of the cores, in the serpentinite mud, in leaches of the serpentinite mud, and in entrained small harzburgitic clasts. Except in the upper few meters below the seawater-mud interface, where pore water approaches seawater Sr concentration and isotopic ratio, Sr concentration and isotopic composition remain constant at 3-6 µmol/kg and ~0.7054. Because the elemental chemistry of the pore water is unlike seawater, this isotopic composition reflects fluids derived from the subducted slab, probably modified by reaction with mantle material during ascent. Higher Sr isotopic ratios, up to 0.7087, - but not with higher Sr concentrations in pore water - occur superimposed on an advection profile at 13-16 mbsf surrounding a thin layer of foraminiferal sand. Since the upward seepage velocity of slab fluids in the mud volcano vents is a few cm/yr, exchange of Sr between these carbonates and the rising fluids must have occurred within a maximum of a few hundred years, essentially instantaneously given the millions, or tens of millions, of years the mud volcanoes have been in existence. In contrast, the strontium isotopic compositions of leached serpentinite mud, and of small harzburgite clasts entrained in the mud, are always significantly greater than that of the pore water. In small harzburgite clasts the ratio reaches 0.7088, almost as high as the seawater value of 0.7092 and much higher than the value of typical mantle-derived strontium of ~0.704. The serpentinite muds and harzburgite clasts clearly equilibrated with seawater Sr when they were initially deposited at the surface of the seamount, but following burial they have not fully equilibrated with strontium in the pore water now discharging through the vents. These variations in the strontium isotopic composition of solids and pore waters are more consistent with episodic expulsion of fluids in the subduction zone than steady state flow. Whereas strontium in carbonates equilibrates isotopically within a few hundred years, strontium in buried harzburgite clasts does not equilibrate in the same time, assuming steady state rates of upward fluid flow. By inference, the harzburgite clasts and associated serpentinite mud must have been near the seafloor, unburied, for a yet undetermined but much longer period of time to have equilibrated from ~0.704 to 0.709 prior to subsequent burial. It may be possible to characterize at least the periodicity of fluid release in the mud volcano setting by investigating the zonation of strontium isotopic composition of hartzburgite clasts throughout the 60-meter deep composite cores.

Foraminiferal abundances and preservation in ODP Hole 130-805C

Downcore changes in various carbonate dissolution indexes are documented for Hole 805C for the last 1.2 m.y. These indexes include degree of fragmentation of planktonic foraminifers, percent sand, abundance ratio of species of contrasting solution susceptibilities (Globigerinoides sacculifer vs. Pulleniatina, Globorotalia tumida, and Globorotalia menardii), and the difference in d18O between species of contrasting solution susceptibilities (G. sacculifer vs. Pulleniatina). These preservation indexes have been combined into a single composite dissolution index that corresponds closely to the d18O record. The rate of change of the oxygen isotope signal is also important, with glacial-to-interglacial transitions corresponding to maximum preservation events and vice versa. For information on changing productivity (which is important because an increased supply of organic matter may enhance dissolution by lowering pH upon degradation), we present the abundance of coarse-fraction benthic foraminifers per gram and the ratio between two planktonic foraminiferal species, one of which is strongly associated with equatorial upwelling (Globorotalia tumida vs. Pulleniatina). Our results suggest that productivity plays a subordinate role in determining foraminifer preservation. Furthermore, our results confirm previous observations that associate enhanced preservation events with glacial periods and with glacial-to-interglacial transitions. A correlation between preservation and sedimentation rates of these carbonate-rich sediments could not be established. Notable differences are present between the responses of individual dissolution indexes, indicating that processes other than dissolution determine proxy indexes to varying degrees.

Geochemistry of boninite and harzburgite of ODP Leg 125 basement samples

Holes drilled into the volcanic and ultrabasic basement of the Izu-Ogasawara and Mariana forearc terranes during Leg 125 provide data on some of the earliest lithosphere created after the start of Eocene subduction in the Western Pacific. The volcanic basement contains three boninite series and one tholeiite series. (1) Eocene low-Ca boninite and low-Ca bronzite andesite pillow lavas and dikes dominate the lowermost part of the deep crustal section through the outer-arc high at Site 786. (2) Eocene intermediate-Ca boninite and its fractionation products (bronzite andesite, andesite, dacite, and rhyolite) make up the main part of the boninitic edifice at Site 786. (3) Early Oligocene intermediate-Ca to high-Ca boninite sills or dikes intrude the edifice and perhaps feed an uppermost breccia unit at Site 786. (4) Eocene or Early Oligocene tholeiitic andesite, dacite, and rhyolite form the uppermost part of the outer-arc high at Site 782. All four groups can be explained by remelting above a subduction zone of oceanic mantle lithosphere that has been depleted by its previous episode of partial melting at an ocean ridge. We estimate that the average boninite source had lost 10-15 wt% of melt at the ridge before undergoing further melting (5-10%) shortly after subduction started. The composition of the harzburgite (<2% clinopyroxene, Fo content of about 92%) indicates that it underwent a total of about 25% melting with respect to a fertile MORB mantle. The low concentration of Nb in the boninite indicates that the oceanic lithosphere prior to subduction was not enriched by any asthenospheric (OIB) component. The subduction component is characterized by (1) high Zr and Hf contents relative to Sm, Ti, Y, and middle-heavy REE, (2) light REE-enrichment, (3) low contents of Nb and Ta relative to Th, Rb, or La, (4) high contents of Na and Al, and (5) Pb isotopes on the Northern Hemisphere Reference Line. This component is unlike any subduction component from active arc volcanoes in the Izu-Mariana region or elsewhere. Modeling suggests that these characteristics fit a trondhjemitic melt from slab fusion in amphibolite facies. The resulting metasomatized mantle may have contained about 0.15 wt% water. The overall melting regime is constrained by experimental data to shallow depths and high temperatures (1250? C and 1.5 kb for an average boninite) of boninite segregation. We thus envisage that boninites were generated by decompression melting of a diapir of metasomatized residual MORB mantle leaving the harzburgites as the uppermost, most depleted residue from this second stage of melting. Thermal constraints require that both subducted lithosphere and overlying oceanic lithosphere of the mantle wedge be very young at the time of boninite genesis. This conclusion is consistent with models in which an active transform fault offsetting two ridge axes is placed under compression or transpression following the Eocene plate reorganization in the Pacific. Comparison between Leg 125 boninites and boninites and related rocks elsewhere in the Western Pacific highlights large regional differences in petrogenesis in terms of mantle mineralogy, degree of partial melting, composition of subduction components, and the nature of pre-subduction lithosphere. It is likely that, on a regional scale, the initiation of subduction involved subducted crust and lithospheric mantle wedge of a range of ages and compositions, as might be expected in this type of tectonic setting.

Mineralogical assemblage in sediment core GeoB12309-5 and in area samples from the Makran subduction zone

In order to study late Holocene changes in sediment supply into the northern Arabian Sea, a 5.3 m long gravity core was investigated by high-resolution geochemical and mineralogical techniques. The sediment core was recovered at a water depth of 956 m from the continental slope off Pakistan and covers a time span of 5 kyr. During the late Holocene source areas delivering material to the sampling site did, however, not change and were active throughout the year.

Plume-top altitude time-series during 2010 volcanic eruption of Eyjafjallajökull

The eruption of Eyjafjallajökull volcano in 2010 lasted for 39 days, 14 April-23 May. The eruption had two explosive phases separated by a phase with lava formation and reduced explosive activity. The height of the plume was monitored every 5 min with a C-band weather radar located in Keflavík International Airport, 155 km distance from the volcano. Furthermore, several web cameras were mounted with a view of the volcano, and their images saved every five seconds. Time series of the plume-top altitude were constructed from the radar observations and images from a web camera located in the village Hvolsvöllur at 34 km distance from the volcano. This paper presents the independent radar and web camera time series and performs cross validation.

Sea surface temperature reconstruction of sediment profile W8709A-8

Assessment of changes in surface ocean conditions, in particular, sea-surface temperature (SST), is essential to understand long-term changes in climate especially in regions where continental climate is strongly influenced by oceanographic processes. To evaluate changes in SST in the northeast Pacific, we have analyzed long-chain alkenones of prymnesiophyte origin at 38 depths in a piston and associated trigger core collected beneath the contemporary core of the California Current System at 42°N, ~270 km off the coast of Oregon/California. The samples span 30,000 years of deposition at this location. Unsaturation patterns (UK'37) in the alkenone series display a statistically significant difference (p <<0.001) between interglacial (0.44 ± 0.02, n = 11) and glacial (0.29 ± 0.04, n = 20) intervals of the cores. Detailed examination of other compositional features of the C37, C38, C39 alkenone series and a related C36 alkenoate series measured downcore suggests the published UK'37 - temperature calibration (UK'37 = 0.034 * T + 0.039 ) , defined for cultures of a strain of Emiliania huxleyi isolated from the subarctic Pacific, provides best estimates of winter SST at our study site. This inference is purely statistical and does not imply, however, that the phytoplankton source of these biomarkers is most productive in winter or at the ocean surface. The temperature record for UK'37 implies (1) an ~4°C shift occurred in winter SST from ~7.5 ± 1.1°C at the last glacial maximum to ~11.7 ± 0.7°C in the present interglacial period, and (2) this warming trend was confined to the time frame 14-10 Ka within the glacial to interglacial transition period. These conclusions are corroborated entirely by results from an independent SST transformation of radiolarian species assemblage data obtained from the same core materials.

Porphyrin geochemistry of DSDP Hole 71-511

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The "black shale" sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50-75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C26 max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Physical oceanography and hydrochemistry measured on water bottle samples during METEOR cruise M10/1

During a R.V. Meteor JGOFS-NABE cruise to a tropical site in the northeast Atlantic in spring 1989, three different vertical regimes with respect to nitrate distribution and availability within the euphotic zone were observed. Besides dramatic variations in the depth of the nitracline, a previously undescribed nose-like nitrate maximum within the euphotic zone was the most prominent feature during this study. Both the vertical structure of phytoplankton biomass and the degree of absolute and relative new production were related to the depth of the nitracline, which in turn was dependent on the occurrence/non-occurrence of the subsurface subtropical salinity maximum (Smax). The mesoscale variability of the nitracline depth, as indicated from a pre-survey grid, and published data on the frequent occurrence of the Smax in tropical waters suggest higher variability of new production and F-ratio than usually expected for oligotrophic oceans. The importance of salt fingering and double diffusion for nitrate transport into the euphotic zone is discussed.

Seawater carbonate chemistry and carbon allocation, growth and morphology of the coccolithophore Emiliania huxleyi (calcifying strain CCMP 371) during experiments, 2011

Coccolithophores are unicellular phytoplankton that produce calcium carbonate coccoliths as an exoskeleton. Emiliania huxleyi, the most abundant coccolithophore in the world's ocean, plays a major role in the global carbon cycle by regulating the exchange of CO2 across the ocean-atmosphere interface through photosynthesis and calcium carbonate precipitation. As CO2 concentration is rising in the atmosphere, the ocean is acidifying and ammonium (NH4) concentration of future ocean water is expected to rise. The latter is attributed to increasing anthropogenic nitrogen (N) deposition, increasing rates of cyanobacterial N2 fixation due to warmer and more stratified oceans, and decreased rates of nitrification due to ocean acidification. Thus future global climate change will cause oceanic phytoplankton to experience changes in multiple environmental parameters including CO2, pH, temperature and nitrogen source. This study reports on the combined effect of elevated pCO2 and increased NH4 to nitrate (NO3) ratio (NH4/NO3) on E. huxleyi, maintained in continuous cultures for more than 200 generations under two pCO2 levels and two different N sources. Here we show that NH4 assimilation under N-replete conditions depresses calcification at both low and high pCO2, alters coccolith morphology, and increases primary production. We observed that N source and pCO2 synergistically drive growth rates, cell size and the ratio of inorganic to organic carbon. These responses to N source suggest that, compared to increasing CO2 alone, a greater disruption of the organic carbon pump could be expected in response to the combined effect of increased NH4/NO3 ratio and CO2 level in the future acidified ocean. Additional experiments conducted under lower nutrient conditions are needed prior to extrapolating our findings to the global oceans. Nonetheless, our results emphasize the need to assess combined effects of multiple environmental parameters on phytoplankton biology in order to develop accurate predictions of phytoplankton responses to ocean acidification.

Flow conditions, bed form dimensions and shear stress experiments

Large asymmetric bed forms commonly develop in rivers. The turbulence associated with flow separation that develops over their steep lee side is responsible for the form shear stress which can represent a substantial part of total shear stress in rivers. This paper uses the Delft3D modeling system to investigate the effects of bed form geometry and forcing conditions on flow separation length and associated turbulence, and bed form shear stress over angle-of-repose (30 lee side angle) bed forms. The model was validated with lab measurements that showed sufficient agreement to be used for a systematic analysis. The influence of flow velocity, bed roughness, relative height (bed form height/water depth), and aspect ratio (bed form height/length) on the variations of the normalized length of the flow separation zone, the extent of the wake region (where the turbulent kinetic energy (TKE) was more than 70% of the maximum TKE), the average TKE within the wake region and the form shear stress were investigated. Form shear stress was found not to scale with the size of the flow separation zone but to be related to the product of the normalized extent of the wake region (extent of the wake region/extent of water body above the bed form) and the average TKE within the wake region. The results add to understanding of the hydrodynamics of bed forms and may be used for the development of better parameterizations of smallscale processes for application in large-scale studies.

Inorganic and organic geochemistry and sediment descriptions at DSDP Hole 93-603B

About one hundred samples of sediments and rocks recovered in Hole 603B were analyzed for type, abundance, and isotopic composition of organic matter, using a combination of Rock-Eval pyrolysis, C-H-N-S elemental analysis, and isotope-ratio mass spectrometry. Concentrations of major, minor, and trace inorganic elements were determined with a combination of X-ray fluorescence and induction-coupled plasma spectrometry. The oldest strata recovered in Hole 603B (lithologic Unit V) consist of interbedded light-colored limestones and marlstones, and black calcareous claystones of Neocomian age. The inorganic and organic geochemical results suggest a very terrigenous aspect to the black claystones. The organic geochemical results indicate that the limestones and marlstones contain a mixture of highly degraded marine and terrestrial organic matter. Comparison of the Neocomian carbonates at Site 603 with those on the other side of the North Atlantic, off Northwest Africa at Site 367, shows that the organic matter at Site 367 contains more marine organic matter, as indicated by higher pyrolysis hydrogen indices and lighter values of d13C. Comparison of inorganic geochemical results for the carbonate lithologies at Site 603 with those for carbonate lithologies at Site 367 suggests that the Site 603 carbonates may contain clastic material from both North American and African sources. The black claystones at Site 603, on the other hand, probably were derived almost entirely from North American clastic sources. Lithologic Unit IV overlying the Neocomian carbonates, consists of interbedded red, green, and black claystones. The black claystones at Site 603 contain more than ten times the organic carbon concentration of the interbedded green claystones. The average concentration of organic carbon in the black claystones (2.8%), however, is low relative to most mid-Cretaceous black claystones and shales in the Atlantic, particularly those found off Northwest Africa. The geochemical data all suggest that the organic matter in the black claystones is more abundant but generally more degraded than the organic matter in the green claystones, and that it was derived mainly from terrestrial sources and deposited in oxygenated bottom waters. The increased percentage of black claystone beds in the upper Cenomanian section, and the presence of more hydrogen-rich organic matter in this part of the section, probably resulted from the increased production and accumulation of marine organic matter that is represented worldwide near the Cenomanian/Turonian boundary in deep-sea and land sections. A few upper Cenomanian black claystone samples that have hydrogen indices > 150 also contain particularly high concentrations of V and Zn. Most samples of black claystone, however, are not particularly metal-rich compared with other black claystones and shales. Compared with red claystones from lithologic Unit IV, the green and black claystones are enriched in many trace transition elements, especially V, Zn, Cu, Co, and Pb. The main difference between the "carbonaceous" claystones of lithologic Unit IV and "variegated" or "multicolored" claystones of the overlying Upper Cretaceous to lower Tertiary Unit III is the absence of black claystone beds. As observed at several other sites (105 and 386), the multicolored claystones at Site 603 are somewhat enriched in several trace transition elements-especially Cu, Ni, and Cr-relative to most deep-sea clays. The multicolored claystones are not enriched in Fe and Mn, and therefore are not "metalliferous" sediments in the sense of those found at several locations in the eastern Pacific. The source of the slightly elevated concentrations of transition metals in the multicolored claystones probably is upward advection and diffusion of metals from the black claystones of the underlying Hatteras Formation. The red, orange, and green claystone beds of lithologic Unit II (Eocene), like those of Unit III, really represent a continuation of deposition of multicolored claystone that began after the deposition of the Neocomian carbonates. The color of the few black beds that occur within this unit results from high concentrations of manganese oxide rather than high concentrations of organic matter.

Skill sorting, inter-industry skill wage premium, and production chains: evidence from India 1999-2000

This paper proposes a mechanism that links industry’s technological characteristics (i.e. quality of non-labor inputs, which is proxied by the length of industry production chains), industry-specific skill wage premium, and skill sorting across industries. It is hypothesized that high-skilled workers are sorted into industries where they can receive a higher skill wage premium, by working with better quality non-labor input. The quality of non-labor inputs is assumed to be worse in industries with longer production chains due to the increased involvement of low-skilled labor and poor infrastructure over the sequential production. By examining Indian wage and employment data for 1999-2000, empirical evidence to support this mechanism can be obtained: First, the skill wage premium is lower [higher] in industries with longer [shorter] production chains. Second, the skill wage premium is lower [higher] in industries with a higher [lower] proportion of low-skilled workers producing inputs outside their own industry. Third, the proportion of high-skilled workers is larger in industries with shorter production chains and lower ratio of low-skilled labor involved, i.e., a skill sorting trend can be observed.

Forecasting Electricity Prices and their volatilities using Unobserved Components.

The liberalization of electricity markets more than ten years ago in the vast majority of developed countries has introduced the need of modelling and forecasting electricity prices and volatilities, both in the short and long term. Thus, there is a need of providing methodology that is able to deal with the most important features of electricity price series, which are well known for presenting not only structure in conditional mean but also time-varying conditional variances. In this work we propose a new model, which allows to extract conditionally heteroskedastic common factors from the vector of electricity prices. These common factors are jointly estimated as well as their relationship with the original vector of series, and the dynamics affecting both their conditional mean and variance. The estimation of the model is carried out under the state-space formulation. The new model proposed is applied to extract seasonal common dynamic factors as well as common volatility factors for electricity prices and the estimation results are used to forecast electricity prices and their volatilities in the Spanish zone of the Iberian Market. Several simplified/alternative models are also considered as benchmarks to illustrate that the proposed approach is superior to all of them in terms of explanatory and predictive power.

Comparison of vibration and rolling noise emission of resilient and solid monobloc railway wheels in underground lines

Flat or worn wheels rolling on rough or corrugated tracks can provoke airborne noise and ground-borne vibration, which can be a serious concern for nearby neighbours of urban rail transit lines. Among the various treatments used to reduce vibration and noise, resilient wheels play an important role. In conventional resilient wheels, a slightly prestressed V­shaped rubber ring is mounted between the steel wheel centre and tyre. The elastic layer enhances rolling noise and vibration suppression, as well as impact reduction on the track. In this paper the effectiveness of resilient wheels in underground lines, in comparison to monobloc ones, is assessed. The analysed resilient wheel is able to carry greater loads than standard resilient wheels used for light vehicles. It also presents a greater radial resiliency and a higher axial stiffness than conventional V­wheels. The finite element method was used in this study. A quarter car model was defined, in which the wheelset was modelled as an elastic body. Several simulations were performed in order to assess the vibrational behaviour of elastic wheels, including modal, harmonic and random vibration analysis, the latter allowing the introduction of realistic vertical track irregularities, as well as the influence of the running speed. Due to numerical problems some simplifications were needed. Parametric variations were also performed, in which the sensitivity of the whole system to variations of rubber prestress and Poisson’s ratio of the elastic material was assessed.Results are presented in the frequency domain, showing a better performance of the resilient wheels for frequencies over 200 Hz. This result reveals the ability of the analyzed design to mitigate rolling noise, but not structural vibrations, which are primarily found in the lower frequency range.