Geochemical analyses of chert nodules and beds from deep-sea sediments (Table 1)

Concentrations of Fe, Mg, Ca, Sr, Mn, Zn, and other heavy metals were analyzed by atomic absorption spectrometry in 27 chert samples from the Pacific deep sea, 17 chert samples from land, and 4 associated sediments from the Pacific Ocean. Among the elements, Fe and Mg concentrations are highly correlatable as are the relationships between Ca and Sr, or between Ca and CO2. The correlation between Fe and Mg is particularly high for Pacific deep-sea flints and cherts, and for cherts of deep-sea origin from outcrops on land. Enrichments in heavy metals were recognized in some deep-sea cherts; volcanogenic cherts are enriched in Fe, a chert nodule containing basaltic fragments is enriched in Zn and Cr, and biogenically enclosed carbonates in flint nodules are enriched in Mn. The correlation of Fe and Mg and their constant ratio [Mg(%)/Fe(%)] of around 0.33 might be characteristic features in the pelagic clays contained in deep-sea flints and cherts, and the concentrations of heavy metals in them would be controlled by the concentrations of Fe-Mg correlated clays. Although the mineralogical nature of the Fe-Mg clay in deep-sea cherts was not clarified by dissolution experiments on opaline minerals in chert, the high concentrations of Fe-montmorillonite and fine-grained olivine or other ferromagnesian silicate minerals in the clay may result in the high correlations between Fe and Mg.

Calcareous nannofossil during the Paleocene Eocene Thermal Maximum in sediments of Walvish Ridge

Compositions and abundances of calcareous nannofossil taxa have been determined in a ca 170 kyrs long time interval across the Paleocene/Eocene boundary at 1-cm to 10-cm resolution from two ODP Sites (1262, 1263) drilled along the flank of the Walvis Ridge in the South Atlantic. The results are compared to published data from ODP Site 690 in the Weddell Sea. The assemblages underwent rapid evolution over a 74 kyrs period, indicating stressed, unstable and/or extreme photic zone environments during the PETM hyperthermal. This rapid evolution, which created 5 distinct stratigraphic horizons, is consistent with the restricted brief occurrences of malformed and/or weakly calcified morphotypes. The production of these aberrant morphotypes is possibly caused by major global scale changes in carbon cycling in the ocean-atmosphere system, affecting also photic zone environments. No marked paleoecologically induced changes are observed in abundances of the genera Discoaster, Fasciculithus and Sphenolithus at the Walvis Ridge sites. Surprisingly, there is no significant correlation in abundance between these three genera, presumed to have had a similar paleoecological preference for warm and oligotrophic conditions.

Middle Miocene stable carbon and oxygen isotope record of foraminifera of ODP Hole 120-747A

Paleoceanographic variability at southern high latitude Ocean Drilling Program (ODP) Site 747 was investigated in this study through the interval which spans the Middle Miocene Climate Transition (MMCT). Between 15.0 and 12.2 million years ago (Ma), foraminiferal d18O records derived from both benthic (Cibicidoides spp.) and planktonic taxa (Globorotalia praescitula and Globigerina bulloides) reveal a history of changes in water column thermal and salinity structure and a strong imprint of seasonality. Prior to the MMCT, in the interval between 14.35 and 13.9 Ma, G. bulloides displays relatively high d18O values similar to those of G. praescitula, interpreted to indicate weakening of the thermocline and/or increased seasonality with cooler early-spring and/or late-fall temperatures. Following this interval, G. bulloidesd18O values diverge significantly from benthic and G. praescitula values, with G. bulloides values remaining relatively low for at least 600 kyr following the benthic foraminiferal d18O shift during the MMCT at ~13.9 Ma. This divergence in d18O records occurs in direct association with the Mi3 cooling and glaciation event and may suggest: (1) a strengthening of the vertical temperature gradient, with greater cooling of deep waters than surface waters, (2) changes in the depth habitat of G. bulloides, (3) changes in the dominant season of G. bulloides calcification, (4) modification of surface-water d18O values in association with enhanced sea-ice formation, (5) increased surface-water carbonate ion concentration, and/or (6) a significant decrease in surface-water salinity across the MMCT. The first of these possible scenarios is not likely, particularly in light of recent Mg/Ca evidence for significant surface-water cooling in the Southern Ocean associated with the MMCT. Of the remaining possibilities, we favor a change in surface salinity to explain the observed trends in d18O values and hypothesize that surface salinity may have decreased by up to 2 salinity units at ~13.9 Ma. In this scenario, the development of a lower-salinity Antarctic surface layer coincided with regional cooling of both surface and deep waters of the Southern Ocean during the Mi3 glaciation of East Antarctica, and contributed into the dominance of Neogloboquadrina spp. between 13.8 and 13.2 Ma. Additionally, the distinct patterns observed in planktonic foraminiferal d18O records spanning the MMCT correspond with changes in the vertical d13C gradient between planktonic and benthic foraminiferal records and major changes in planktonic foraminiferal assemblages at Site 747, providing further evidence of the environmental significance of this climatic transition.

Chemical and Sr isotopic compositions of pore fluids and marine carbonates from ODP Hole 130-807A

The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment-water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. L_Sr is derived from isotopic data and modeling, and allows us to infer the values of L_Ca and L_Mg. The small value for L_Ca indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment-water interface to 7.1+/-0.1 at 400-800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for L_Mg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.

Sediments in arctic sea ice - entrainment, characterization and quantification

Sediments in Arctic sea ice are important for erosion and redistribution and consequently a factor for the sediment budget of the Arctic Ocean. The processes leading to the incorporation of sediments into the ice are not understood in detail yet. In the present study, experiments on the incorporation of sediments were therefore conducted in ice tanks of The Hamburg Ship Model Basin (HSVA) in winter 1996/1997, These experiments showed that on average 75 % of the artificial sea-ice sediments were located in the brine-channel system. The sediments were scavenged from the water column by frazil ice. Sediments functioning as a nucleus for the formation of frazil ice were less important for the incorporation. Filtration in grease ice during relatively calm hydrodynamic conditions was probably an effective process to enrich sediments in the ice. Wave fields did not play an important role for the incorporation of sediments into the artificial sea ice. During the expedition TRANSDRIFT III (TDIII, October 1995), different types of natural, newly-formed sea ice (grease ice, nilas and young ice) were sampled in the inner Laptev Sea at the time of freeze-up. The incorporation of sediments took place during calm meteorological conditions then. The characteristics of the clay mineral assemblages of these sedirnents served as references for sea-ice sediments which were sampled from first-year drift ice in the outer Laptev Sea and the adjacent Arctic Ocean during the POLARSTERN expedition ARK-XI/1 (July-September 1995). Based on the clay mineral assemblages, probable incorporation areas for the sedirnents in first-year drift ice could be statistically reconstructed in the inner Laptev Sea (eastern, central, and Western Laptev Sea) as well as in adjacent regions. Comparing the amounts of particulate organic carbon (POC) in sea-ice sediments and in surface sediments from the shelves of potential incorporation areas often reveals higher values in sea-ice sediments (TDIII: 3.6 %DM; ARK-XI/1: 2.3 %DM). This enrichment of POC is probably due to the incorporation process into the sea ice, as could be deducted from maceral analysis and Rock-Eval pyrolysis. Both methods were applied in the present study to particulate organic material (POM) from sea-ice sediments for the first time. It was shown that the POM of the sea-ice sediments from the Laptev Sea and the adjacent Arctic Ocean was dominated by reworked, strongly fragmented, allochthonous (terrigenous) material. This terrigenous component accounted for more than 75 % of all counted macerals. The autochthonous (marine) component was also strongly fragmented, and higher in the sediments from newly-formed sea ice (24 % of all counted macerals) as compared to first-year drift ice (17 % of all counted macerals). Average hydroge indices confirmed this pattern and were in the transition zone between kerogen types II and III (TDIII: 275 mg KW/g POC; ARK-XI/1: 200 mg KW/g POC). The sediment loads quantified in natural sea ice (TDIII: 33.6 mg/l, ARK-XI/1: 49.0 mg/l) indicated that sea-ice sediments are an important factor for the sediment budget in the Laptev Sea. In particular during the incorporation phase in autumn and early winter, about 12 % of the sediment load imported annually by rivers into the Laptev Sea can be incorporated into sea ice and redistributed during calm meteorological conditions. Single entrainment events can incorporate about 35 % of the river input into the sea ice (ca. 9 x 10**6 t) and export it via the Transpolar Drift from the Eurasian shelf to the Fram Strait.

Seasonal variations in surface metabolite composition of Fucus vesiculosus and Fucus serratus sampled at outer Kiel Fjord (August 2012 - July 2013)

The chemical composition of surface associated metabolites of two Fucus species (Fucus vesiculosus and Fucus serratus) was analysed by means of gas chromatography-mass spectrometry (GC-MS) to describe temporal patterns in chemical surface composition. Method: The two perennial brown macroalgae F. vesiculosus and F. serratus were sampled monthly at Bülk, outer Kiel Fjord, Germany (54°27'21 N / 10°11'57 E) over an entire year (August 2012 - July 2013). Per month and species six non-fertile Fucus individuals were collected from mixed stands at a depth of 0.5 m under mid water level. For surface extraction approx. 50 g of the upper 5-10 cm apical thalli tips were cut off per species. The surface extraction of Fucus was performed according to the protocol of de Nys and co-workers (1998) with minor modifications (see Rickert et al. 2015). GC/EI-MS measurements were performed with a Waters GCT premier (Waters, Manchester, UK) coupled to an Agilent 6890N GC equipped with a DB-5 ms 30 m column (0.25 mm internal diameter, 0.25 mM film thickness, Agilent, USA). The inlet temperature was maintained at 250°C and samples were injected in split 10 mode. He carrier gas flow was adjusted to 1 ml min-1. Alkanes were used for referencing of retention times. For further details (GC-MS sample preparation and analysis) see the related publication (Rickert et al. submitted to PLOS ONE).

Exploring the potential of clumped isotope thermometry on coccolith-rich sediments as a sea surface temperature proxy

Understanding past changes in sea surface temperatures (SSTs) is crucial; however, existing proxies for reconstructing past SSTs are hindered by unknown ancient seawater composition (foraminiferal Mg/Ca and d18O), or reflect subsurface temperatures (TEX86) or have a limited applicable temperature range (Uk'37). We examine clumped isotope (D47) thermometry to fossil coccolith-rich material as an SST proxy, as clumped isotopes are independent of original seawater composition and applicable to a wide temperature range and coccolithophores are widespread and dissolution resistant. The D47-derived temperatures from <63, <20, <10 and 2-5 µm size fractions of two equatorial Pacific late Miocene-early Pliocene sediment samples (c1; c2) range between ~18-29 {degree sign}C, with c1 temperatures consistently above c2. Removing the >63 µm fraction removes most non-mixed layer components; however, the D47-derived temperatures display an unexpected slight decreasing trend with decreasing size fraction. This unexpected trend could partly arise because larger coccoliths (5-12 µm) are removed during the size fraction separation process. The c1 and <63 µm c2 D47-derived temperatures are comparable to concurrent Uk'37 SSTs. The <20, <10 and 2-5 µm c2 D47-derived temperatures are consistently cooler than expected. The D47-Uk'37 temperature offset is probably caused by abiotic/diagenetic calcite present in the c2 2-5 µm fraction (~53% by area), which potentially precipitated at bottom water temperatures of ~6 {degree sign}C . Our results indicate that clumped isotopes on coccolith-rich sediment fractions have potential as an SST proxy, particularly in tropical regions, providing that careful investigation of the appropriate size fraction for the region and timescale is undertaken.

Late Pliocene and Early Pleistocene dinoflagellate cysts and sea surface temperture reconstruction for several IODP and DSDP sites in the North Atlantic

In an attempt to document the palaeoecological affinities of individual extant and extinct dinoflagellate cysts, Late Pliocene and Early Pleistocene dinoflagellate cyst assemblages have been compared with geochemical data from the same samples. Mg/Ca ratios of Globigerina bulloides were measured to estimate the spring-summer sea-surface temperatures from four North Atlantic IODP/DSDP sites. Currently, our Pliocene-Pleistocene database contains 204 dinoflagellate cyst samples calibrated to geochemical data. This palaeo-database is compared with modern North Atlantic and global datasets. The focus lies in the quantitative relationship between Mg/Ca-based (i.e. spring-summer) sea-surface temperature (SSTMg/Ca) and dinoflagellate cyst distributions. In general, extant species are shown to have comparable spring-summer SST ranges in the past and today, demonstrating that our new approach is valid for inferring spring-summer SST ranges for extinct species. For example, Habibacysta tectata represents SSTMg/Ca values between 10° and 15°C when it exceeds 30% of the assemblage, and Invertocysta lacrymosa exceeds 15% when SSTMg/Ca values are between 18.6° and 23.5°C. However, comparing Pliocene and Pleistocene SSTMg/Ca values with present day summer values for the extant Impagidinium pallidum suggests a greater tolerance of higher temperatures in the past. This species occupies more than 5% of the assemblage at SSTMg/Ca values of 11.6-17.9°C in the Pliocene and Pleistocene, whereas present day summer SSTs are around -1.7 to 6.9°C. This observation questions the value of Impagidinium pallidum as reliable indicator of cold waters in older deposits, and may explain its bipolar distribution.

Rates of egg production, grazing and mortatlity of Calanus finmarchicus measured experimentally in the North Atlantic during the Maria S. Merian cruise MSM26, spring 2013

An incubation experiment at five different temperatures was used to assess the potential for adaptation of Calanus finmarchicus to future warming of the ocean. During a short term (3 h) and long term (6 day) exposure of individual females to a gradient of temperature stress, egg production and fecal pellet production were monitored to indicate secondary production and grazing rates. A longer term (10 day) exposure to elevated temperatures followed by a return to ambient sea temperatures was used to assess the potential recovery of individuals exposed to temperature stress. Females were picked out from WP2 net samples and acclimatised in 2 L bottles of GFF filtered seawater with Thalassiosira weissflogii as prey for >48 h at ambient SST. Experimental bottles were filled with filtered seawater (GFF filtered from non-toxic seawater supply) and acclimated to experimental temperature overnight (0, 5, 10, 15 and 20 °C). Individual females were transferred into bottles using forceps and the bottles were inoculated with T. weissflogii to a final concentration of 5 µg chl L-1. Bottles were then placed into water baths and incubated for 3h or 6 d, and monitored for egg and fecal pellet production rates. A 10 day exposure experiment was used to test the potential for recovery from temperature stress, by returning females incubated at 5, 10, 15 and 20 °C back to 10 °C for 24 h and counting egg and fecal pellet production.

Organic carbon, age, lithology, and CPI-alkenes at DSDP Sites 57-440 and 56-436

"Bound" and "free" solvent-extractable lipids have been examined from Sections 440A-7-6, 440B-3-5, 440B-8-4, 440B-68-2, and 436-11-4. The compound classes studied include aliphatic and aromatic hydrocarbons, ketones, alcohols, and carboxylic acids. Carotenoids and humic acids have also been examined. The quantitative results are considered in terms of input indicators, diagenesis parameters, and structural classes. A difference in input is deduced across the Japan Trench, with a higher proportion of autochthonous components on the western inner trench slope compared with the more easterly, outer trench, wall and greater input in the early Pleistocene than in the Miocene. A variety of diagenetic transformations is observed at Site 440 as sample depth increases. Results are compared with those of samples from Atlantic Cretaceous sediments and from the Walvis Bay high productivity area.

Calcareous nannofossils from the Sumisu Rift and Izu-Bonin Forearc Basin

During Ocean Drilling Program Leg 126, we recovered three expanded Pleistocene sections from the active backarc rift (Sumisu Rift) and three expanded Oligocene-Miocene sections from the forearc basin of the Izu-Bonin volcanic island arc. Quantitative analysis of the Pleistocene nannofossils revealed five major assemblages between 0 and LO Ma: Assemblage 1 (Holocene-0.085 Ma) contains dominant Emiliania huxleyi; Assemblage 2 (ca. 0.085-0.275 Ma) contains dominant small Gephyrocapsa and common E. huxleyi and Gephyrocapsa oceanica; Assemblage 3 (ca. 0.275-0.6 Ma) contains dominant Gephyrocapsa caribbeanica; Assemblage 4 (ca. 0.6-0.9 Ma) contains a peak abundance of small Gephyrocapsa in the middle part, and dominant occurrences of two types of G. caribbeanica in the lower and upper parts; and Assemblage 5 (ca. 0.9-1.0 Ma) contains dominant small Gephyrocapsa and common G. caribbeanica and Reticulofenestra asanoi. These assemblages are largely synchronous with similar assemblages recognized from tropical and subtropical regions, and can be used for finer subdivision of the Pleistocene than that based on standard Pleistocene nannofossil datums. The Oligocene-Miocene sections contain several hiatuses: up to 3 m.y. may be missing from the uppermost Oligocene (Zone CP19) at Sites 792 and 793; all of Zone CN2 is missing at Sites 792 and 793; part of Zone CN3 and all of Zone CN4 are missing at Site 792. Biochronology of several nannofossil datums at Leg 126 sites indicate that Sphenolithus distentus, Sphenolithus ciperoensis, Cyclicargolithus floridanus, and Discoaster kugleri have diachronous occurrences compared with other sites in the western Pacific Ocean and Philippine Sea.

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.

Silicate mineralogy of basalts at DSDP Leg 54 Holes

Basalts drilled from the East Pacific Rise, OCP Ridge, and Siqueiros fracture zone during Leg 54 are texturally diverse. Dolerites are equigranular at Sites 422 and 428 and porphyritic, with phenocrysts of plagioclase (An69.73) and Ca-rich clinopyroxene (Ca42Mg48Fe10) at Site 427. The East Pacific Rise lavas and some of those from the OCP Ridge are fine-grained and porphyritic. The majority of the large crystals are clustered skeletal glomerocrysts of plagioclase An64-77), together with olivine (Fo80-87), Ca-rich clinopyroxene, or both. Euhedral phenocrysts of plagioclase, together with olivine, Carich clinopyroxene, and Cr-Al spinel in some cases, occur in most of the fine-grained lavas. These phenocrysts are small (maximum dimension <1 mm in all but one sample), sparse (combined modal amount <1% in all samples), and distinctive from the megacrysts which characterize many ocean-floor lavas. In two East Pacific Rise lavas, zoned plagioclase (An83 cores) is the sole phenocryst phase. In other porphyritic lavas from all the main East Pacific Rise and OCP Ridge units drilled during Leg 54, the plagioclase phenocrysts contain cores of bytownite (An79-87) surrounded by more-sodic feldspar (An67-77). Core/rim relationships vary from continuous normal zoning, through discontinuous zoning, to extensive resorption of the calcic cores in some samples. The compositions of the plagioclase calcic cores are systematically related to those of the glomerophyric plagioclase and olivine in the lavas containing them. Furthermore, only one compositional population of calcic cores occurs in each rock. The possible causes of these relationships are far from clear. Magma mixing, although superficially applicable, is inconsistent with important aspects of the phenocryst mineralogy of these particular lavas. A more satisfactory model to explain both phenocryst zoning and rapid glomerocryst growth immediately before extrusion may be constructed by postulating influx of water into the upwelling magmas within Layer 3 of the oceanic crust beneath the East Pacific Rise, and subsequent loss of part of this water during effervescence within feeder dykes between Layer 3 and the ocean floor. It is shown that this model is fully consistent with published data on water and carbon dioxide contents and ratios in the pillow-margin glasses, vesicles, and phenocryst inclusions of ocean-floor basalts. The evidence for the precipitation of plagioclase- dominated crystalline assemblages from these magmas in the upper part of Layer 3 is concordant with recent geophysically based modeling of the structure of the East Pacific Rise. Calcium-rich clinopyroxenes in dolerites from the OCP Ridge and Siqueiros fracture zone show radial, oscillatory, and sector-zoning. In Sample 428A-5-2 (Piece 5a), the compositional trends resulting from this zoning closely resemble those of the pyroxenes in some lunar lavas. The controls on crystallization of interstitial pigeonite - epitaxial upon augite - in this rock are discussed. Both sector-zoning of the augite and nucleation of pigeonite within microvolumes of magma with a low Ca(Mg + Fe) ratio appear to be important factors.

Fossil pollen record of composite sediment core TMD from Tso Moriri, analysis of modern surface pollen samples, mean annual precipitation reconstruction, and digitisation and recalibration of different discussed palaeoclimate proxy records

This paper presents a new fossil pollen record from Tso Moriri (32°54'N, 78°19'E, 4512 m a.s.l.) and seeks to reconstruct changes in mean annual precipitation (MAP) during the last 12,000 years. This high-alpine lake occupies an area of 140 km**2 in a glacial-tectonic valley in the northwestern Himalaya. The region has a cold climate, with a MAP <300 mm, and open vegetation. The hydrology is controlled by the Indian Summer Monsoon (ISM), but winter westerly-associated precipitation also affects the regional water balance. Results indicate that precipitation levels varied significantly during the Holocene. After a rapid increase in MAP, a phase of maximum humidity was reached between ca. 11 to 9.6 cal ka BP, followed by a gradual decline in MAP. This trend parallels the reduction in the Northern Hemisphere summer insolation. Comparison of different palaeoclimate proxy records reveal evidence for a stronger Holocene decrease in precipitation in the northern versus the southern parts of the ISM domain. The long-term trend of ISM weakening is overlaid with several short periods of greater dryness, which are broadly synchronous with the North Atlantic cold spells, suggesting reduced amounts of westerly-associated winter precipitation. Compared to the mid and late Holocene, it appears that westerlies had a greater influence on the western parts of the ISM domain during the early Holocene. During this period, the westerly-associated summer precipitation belt was positioned at Mediterranean latitudes and amplified the ISM-derived precipitation. The Tso Moriri pollen record and moisture reconstructions also suggest that changes in climatic conditions affected the ancient Harappan Civilisation, which flourished in the greater Indus Valley from approximately 5.2 to 3 cal ka BP. The prolonged Holocene trend towards aridity, punctuated by an interval of increased dryness (between ca. 4.5 to 4.3 cal ka BP), may have pushed the Mature Harappan urban settlements (between ca. 4.5 to 3.9 cal ka BP) to develop more efficient agricultural practices to deal with the increasingly acute water shortages. The amplified aridity associated with North Atlantic cooling between ca. 4 to 3.6 and around 3.2 cal ka BP further hindered local agriculture, possibly causing the deurbanisation that occurred from ca. 3.9 cal ka BP and eventual collapse of the Harappan Civilisation between ca. 3.5 to 3 cal ka BP.

Seawater carbonate chemistry during experiments with Mytilus edulis, 2008

The effects of medium term (32 d) hypercapnia on the immune response of Mytilus edulis were investigated in mussels exposed to acidified (using CO2) sea water (pH 7.7, 7.5 or 6.7; control: pH 7.8). Levels of phagocytosis increased significantly during the exposure period, suggesting an immune response induced by the experimental set-up. However, this induced stress response was suppressed when mussels were exposed to acidified sea water. Acidified sea water did not have any significant effects on other immuno-surveillance parameters measured (superoxide anion production, total and differential cell counts). These results suggest that ocean acidification may impact the physiological condition and functionality of the haemocytes and could have a significant effect on cellular signalling pathways, particularly those pathways that rely on specific concentrations of calcium, and so may be disrupted by calcium carbonate shell dissolution.