Temperature proxies of sediment cores from the Sea of Marmara

Reconstructing ocean temperature values is a major target in paleoceanography and climate research. However, most temperature proxies are organism-based and thus suffer from an "ecological bias". Multiproxy approaches can potentially overcome this bias but typically require more investment in time and resources, while being susceptible to errors induced by sample preparation steps necessary before analysis. Three lipid-based temperature proxies are widely used: UK'37 (based on long chain alkenones from phytoplanktonic haptophytes), TEX86 [based on glycerol dialkyl glycerol tetraethers (GDGTs) from pelagic archaea] and LDI (based on long chain diols from phytoplanktonic eustigmatophytes). So far, separate analytical methods, including gas chromatography (GC) and liquid chromatography (LC), have been used to determine these proxies. Here we present a sensitive method for determining all three in a single normal phase high performance LC-atmospheric pressure chemical ionization mass spectrometry (NP-HPLC-APCI-MS) analysis. Each of the long chain alkenones and long chain diols was separated and unambiguously identified from the accurate masses and characteristic fragmentation during multiple stage MS analysis (MS2). Comparison of conventional GC and HPLC-MS methods showed similar results for UK'37 and LDI, respectively, using diverse environmental samples and an Emiliania huxleyi culture. Including the three sea surface temperature (SST) proxies; the NP-HPLC-APCI-MS method in fact allows simultaneous determination of nine paleoenvironmental proxies. The extent to which the ecology of the source organisms (ecological bias) influences lipid composition and thereby the reconstructed temperature values was demonstrated by applying the new method to a sediment core from the Sea of Marmara, covering the last 21 kyr BP. Reconstructed SST values differed considerably between the proxies for the Last Glacial Maximum (LGM) and the period of Sapropel S1 formation at ca. 10 kyr BP, whereas the trends during the late Holocene were similar. Changes in the composition of alkenone-producing species at the transition from the LGM to the Bølling/Allerød (B/A) were inferred from unreasonably high UK'37-derived SST values (ca. 20 °C) during the LGM. We ascribe discrepancies between the reconstructed temperature records during S1 deposition to habitat change, e.g. a different depth due to changes in nutrient availability.

Trace-element geochemistry of tholeiitic basalts from DSDP Hole 55-433C

Hole 433C, a multiple re-entry hole drilled in 1862 meters of water on Suiko Seamount in the central Emperor Seamounts, penetrated 387.5 meters of lava flows overlain by 163.0 meters of sediments. The recovered volcanic rocks consist of three flow units (1-3) of alkalic basalt underlain by more than 105 flows or flow lobes (Flow Units 4-67) of tholeiitic basalt. This study reports trace-element, including rare-earth element (REE), data for 25 samples from 24 of the least altered tholeiitic flows. These data are used to evaluate the origin and evolution of tholeiitic basalts from Suiko Seamount and to evaluate changes in the mantle source between the time when Suiko Seamount formed, 64.7 ± 1.1 m.y. ago (see Dalrymple et al., 1980), and the present day. Stearns (1946), Macdonald and Katsura (1964) and Macdonald (1968) have established that chemically distinct lavas erupt during four eruptive stages of development of a Hawaiian volcano. These stages, from initial to final, are shield-building, caldera-filling, post-caldera, and post-erosional. The lavas of the shield-building stage are tholeiitic basalts, which erupt rapidly and in great volume. The shield-building stage is quickly followed by caldera collapse and by the caldera-filling stage, during which the caldera is filled by tholeiitic and alkalic lavas. During the post-caldera stage, a relatively thin veneer of alkalic basalts and associated differentiated lavas are erupted, sometimes accompanied by minor eruptions of tholeiitic lava. After a period of volcanic quiescence and erosion, lavas of the nephelinitic suite, which include both alkalic basalts and strongly SiO2-undersaturated nephelinitic basalts, may erupt from satellite vents during the post-erosional stage. Many Hawaiian volcanoes develop through all four stages; but individual volcanoes have become extinct before the cycle is complete. We interpret the tholeiitic lavas drilled on Suiko Seamount to have erupted during either the shield-building or the caldera-filling stage, and the overlying alkalic flows to have erupted during either the caldera-filling or the post-caldera stage (see Kirkpatrick et al., 1980).

Stable isotope record of the Okhotsk Sea

Stable isotope data on benthic foraminifera from more than 30 cores on the northern Emperor Seamounts and in the Okhotsk Sea are synthesized in paleohydrographic profiles spanning the depth range 1000-4000 m. Holocene (core-top) benthic foraminiferal d18O and d13C data are calibrated to modern hydrographic properties through measurements of d13C of SumCO2 and d18O of seawater. Cibicidoides stable isotope ratios are close to the d13C and equilibrium d18O of seawater, whereas Uvigerina d18O and d13C are variably offset from Cibicidoides. Glacial maximum d13C of Cibicidoides displays a different vertical profile than that of the Holocene. When results are adjusted by +0.32 per mil to account for the secular change in d13C during the last glacial maximum, the data coincide with the modern seawater and foraminiferal curves deeper than ~2 km. However, at shallower depths d13C gradually increases by as much as 1 per mil above the modern value. Furthermore, above 2 km the benthic d18O decreases by ~0.5 per mil. These results are consistent with a benthic front at ~2 km in the North Pacific (see Herguera et al., 1992), but they differ from interpretations based on trace metal data which indicate a source of nutrient-depleted deep water during glaciation. The isotopic data suggest that during glaciation there was a better ventilated watermass at intermediate depths in the far northwestern Pacific, it was relatively fresher than deep waters there, and deep waters were as nutrient-rich as today.

Radiocarbon ages and clay minerals in sediment cores obtained during a 2009 Jan Mayen cruise to the Norwegian Sea

The origin of two acoustic sediment units has been studied based on lithological facies, chronology and benthic stable isotope values as well as on foraminifera and clay mineral assemblages in six marine sediment cores from Kveithola, a small trough west of Spitsbergenbanken on the western Barents Sea margin. We have identified four time slices with characteristic sedimentary environments. Before c. 14.2 cal. ka, rhythmically laminated muds indicate extensive sea ice cover in the area. From c. 13.9 to 14.2 cal. ka, muds rich in ice-rafted debris were deposited during the disintegration of grounded ice on Spitsbergenbanken. From c. 10.3 to 13.1 cal. ka, sediments with heterogeneous lithologies suggest a shifting influence of suspension settling and iceberg rafting, probably derived from a decaying Barents Sea Ice Sheet in the inner-fjord and land areas to the north of Kveithola. Holocene deposition was episodic and characterized by the deposition of calcareous sands and shell debris, indicative of strong bottom currents. We speculate that a marked erosional boundary at c. 8.2 cal. ka may have been caused by the Storegga tsunami. Whilst deposition was sparse during the Holocene, Kveithola acted as a sediment trap during the preceding deglaciation. Investigation of the deglacial sediments provides unprecedented details on the dynamics and timing of glacial retreat from Spitsbergenbanken.

Geochemistry, isotopes, trace elements and fluid inclusion geothermometry at DSDP Hole 83-504B

Stockwork-like metal sulfide mineralizations were found at 910-928 m below seafloor (BSF) in the pillow/dike transition zone of Hole 504B. This is the same interval where most physical properties of the 5.9-m.y.-old crust of the Costa Rica Rift change from those characteristic of Layer 2B to those of Layer 2C. The pillow lavas, breccias, and veins of the stockwork-like zone were studied by transmitted and reflected light microscopy, X-ray diffraction, and electron microprobe analysis. Bulk rock oxygen isotopic analyses as well as isolated mineral oxygen and sulfur isotopic analyses and fluid inclusion measurements were carried out. A complex alteration history was reconstructed that includes three generations of fissures, each followed by precipitation of characteristic hydrothermal mineral parageneses: (1) Minor and local deposition of quartz occurred on fissure walls; adjacent wall rocks were silicified, followed by formation of chlorite and minor pyrite I in the veins, whereas albite, sphene, chlorite and chlorite-expandable clay mixtures, actinolite, and pyrite replaced igneous phases in the host rocks. The hydrothermal fluids responsible for this first stage were probably partially reacted seawater, and their temperatures were at least 200-250° C. (2) Fissures filled during the first stage were reopened and new cracks formed. They were filled with quartz, minor chlorite and chlorite-expandable clay mixtures, traces of epidote, common pyrite, sphalerite, chalcopyrite, and minor galena. During the second stage, hydrothermal fluids were relatively evolved metal- and Si-rich solutions whose temperatures ranged from 230 to 340° C. The fluctuating chemical composition and temperature of the solutions produced a complex depositional sequence of sulfides in the veins: chalcopyrite I, ± Fe-rich sphalerite, chalcopyrite II ("disease"), Fe-poor sphalerite, chalcopyrite III, galena, and pyrite II. (3) During the last stage, zeolites and Mg-poor calcite filled up the remaining spaces and newly formed cracks and replaced the host rock plagioclase. Analcite and stilbite were first to form in veins, possibly at temperatures below 200°C; analcite and earlier quartz were replaced by laumontite at 250°C, whereas calcite formation temperature ranged from 135 to 220°C. The last stage hydrothermal fluids were depleted in Mg and enriched in Ca and 18O compared to seawater and contained a mantle carbon component. This complex alteration history paralleling a complex mineral paragenesis can be interpreted as the result of a relatively long-term evolution of a hydrothermal system with superimposed shorter term fluctuations in solution temperature and composition. Hydrothermal activity probably began close to the axis of the Costa Rica Rift with the overall cooling of the system and multiple fracturing stages due to movement of the crust away from the axis and/or cooling of a magmatic heat source.

40Ar-39Ar geochronological studies on rocks at DSDP Leg 58 Holes

The technique of 40Ar-39Ar step-heating dating was applied to three rock samples from core of DSDP Site 443, one sample from Site 445, and four samples at Site 446. All sites were drilled during DSDP Leg 58. At Site 443 (Shikoku Basin), about 116 meters of basalt basement was drilled. Three samples were chosen for dating from different levels in the basalt; two samples are aphyric basalt, and the other is subophitic dolerite. At Site 445 (Daito Ridge), no basement rock was drilled; however, conglomeratic sandstone was cored in the lower part of the hole. 40Ar-39Ar dating was applied to a basalt pebble in the conglomerate. At Site 446 (Daito Basin), the lower cored sequence is clay stone interlayered with 16 basalt sills. Four samples were chosen from sills at different levels.

Calibration and application of B/Ca, Cd/Ca, and d11B in Neogloboquadrina pachyderma (sinistral)

The North Atlantic and Norwegian Sea are prominent sinks of atmospheric CO2 today, but their roles in the past remain poorly constrained. In this study, we attempt to use B/Ca and d11B ratios in the planktonic foraminifera Neogloboquadrina pachyderma (sinistral variety) to reconstruct subsurface water pH and pCO2 changes in the polar North Atlantic during the last deglaciation. Comparison of core-top results with nearby hydrographic data shows that B/Ca in N. pachyderma (s) is mainly controlled by seawater [B(OH)4]?/[HCO3]? with a roughly constant partition coefficient (KD =([B/Ca]of CaCO3)/([B(OH)4]-/[HCO3]-)of seawater) of 1.48 ± 0.15 * 10**-3 (2sigma), and d11B in this species is offset below d11B of the borate in seawater by 3.38 ± 0.71 per mil (2sigma). These values represent our best estimates with the sparse available hydrographic data close to our core-tops. More culturing and sediment trap work is needed to improve our understanding of boron incorporation into N. pachyderma (s). Application of a constant KD of 1.48 * 10**-3 to high resolution N. pachyderma (s) B/Ca records from two adjacent cores off Iceland shows that subsurface pCO2 at the habitat depth of N. pachyderma (s) (~50 m) generally followed the atmospheric CO2 trend but with negative offsets of ~10-50 ppmv during 19-10 ka. These B/Ca-based reconstructions are supported by independent estimates from low-resolution d11B measurements in the same cores. We also calibrate and apply Cd/Ca in N. pachyderma (s) to reconstruct nutrient levels for the same down cores. Like today's North Atlantic, past subsurface pCO2 variability off Iceland was significantly correlated with nutrient changes that might be linked to surface nutrient utilization and mixing within the upper water column. Because surface pCO2 (at 0 m water depth) is always lower than at deeper depths and if the application of a constant KD is valid, our results suggest that the polar North Atlantic has remained a CO2 sink during the calcification seasons of N. pachyderma (s) over the last deglaciation.

Age datums, and abundance of Discoaster brouweri and Coccolithus pelagicus in ODP Site 180-1115 sediments

The relative abundance of warm-water Discoaster brouweri vs. cool-water Coccolithus pelagicus provides a useful proxy for interpreting Pliocene surface water temperature trends at Ocean Drilling Program Site 1115 (Solomon Sea). Surface waters were mostly warm during the early Pliocene with a slightly cooler interval centered on 4.5 Ma. A more pronounced cool interval occurred at ~3.2 Ma. The early and mid-Pliocene cool periods may reflect Antarctic glacial growth. A mid-Pliocene warm interval occurred from ~3.1 to 2.8 Ma. Temperature began to decline beginning ~2.7 Ma, marking the onset of Northern Hemisphere glaciation. This long-term decline in surface water temperature is interrupted by a brief warming event at ~2.3 Ma.

Age determination of sediment cores from the Weddell Sea

We report here the results of a study aimed at providing radiometric age control on glacial events in the Weddell Sea during the late Quaternary. Sediment cores from the eastern continental shelf, where the East Antarctic ice sheet was grounded, have recovered glacial-marine sediments resting on tills and the latter deposits predate the isotope stage 2 last glacial maximum. Sediment cores from the continental slope and rise sampled a prominent ice-rafted debris layer, and radiocarbon ages indicate that this ice-rafting event took place prior to 26 000 yr B.P. Thus, the combined data indicate that significant deglaciation of the Weddell Sea continental shelf took place prior to the last glacial maximum. Our data also suggest that the ice masses that border the Weddell Sea are more extensive than they were during the previous glacial minimum.

Mercury species concentrations near Casey station, Antarctica and along the SR3 CASO-GEOTRACES transect

We present here the first mercury speciation study in the water column of the Southern Ocean, using a high-resolution south-to-north section (27 stations from 65.50°S to 44.00°S) with up to 15 depths (0-4440 m) between Antarctica and Tasmania (Australia) along the 140°E meridian. In addition, in order to explore the role of sea ice in Hg cycling, a study of mercury speciation in the 'snow-sea ice-seawater' continuum was conducted at a coastal site, near the Australian Casey station (66.40°S; 101.14°E). In the open ocean waters, total Hg (Hg(T)) concentrations varied from 0.63 to 2.76 pmol/L with 'transient-type' vertical profiles and a latitudinal distribution suggesting an atmospheric mercury source south of the Southern Polar Front (SPF) and a surface removal north of the Subantartic Front (SAF). Slightly higher mean Hg(T) concentrations (1.35 ± 0.39 pmol/L) were measured in Antarctic Bottom Water (AABW) compared to Antarctic Intermediate water (AAIW) (1.15 ± 0.22 pmol/L). Labile Hg (Hg(R)) concentrations varied from 0.01 to 2.28 pmol/L, with a distribution showing that the Hg(T) enrichment south of the SPF consisted mainly of Hg(R) (67 ± 23%), whereas, in contrast, the percentage was half that in surface waters north of PFZ (33 ± 23%). Methylated mercury species (MeHg(T)) concentrations ranged from 0.02 to 0.86 pmol/L. All vertical MeHg(T) profiles exhibited roughly the same pattern, with low concentrations observed in the surface layer and increasing concentrations with depth up to an intermediate depth maximum. As for Hg(T), low mean MeHg(T) concentrations were associated with AAIW, and higher ones with AABW. The maximum of MeHg(T) concentration at each station was systematically observed within the oxygen minimum zone, with a statistically significant MeHg(T) vs Apparent Oxygen Utilization (AOU) relationship (p <0.001). The proportion of Hg(T) as methylated species was lower than 5% in the surface waters, around 50% in deep waters below 1000 m, reaching a maximum of 78% south of the SPF. At Casey coastal station Hg(T) and Hg(R) concentrations found in the 'snow-sea ice-seawater' continuum were one order of magnitude higher than those measured in open ocean waters. The distribution of Hg(T) there suggests an atmospheric Hg deposition with snow and a fractionation process during sea ice formation, which excludes Hg from the ice with a parallel Hg enrichment of brine, probably concurring with the Hg enrichment of AABW observed in the open ocean waters. Contrastingly, MeHg(T) concentrations in the sea ice environment were in the same range as in the open ocean waters, remaining below 0.45 pmol/L. The MeHg(T) vertical profile through the continuum suggests different sources, including atmosphere, seawater and methylation in basal ice. Whereas Hg(T) concentrations in the water samples collected between the Antarctic continent and Tasmania are comparable to recent measurements made in the other parts of the World Ocean (e.g., Soerensen et al., 2010; doi:10.1021/es903839n), the Hg species distribution suggests distinct features in the Southern Ocean Hg cycle: (i) a net atmospheric Hg deposition on surface water near the ice edge, (ii) the Hg enrichment in brine during sea ice formation, and (iii) a net methylation of Hg south of the SPF.

Lead 210 and silicate profiles from sediments of the equatorial Pacific and South Atlantic

Particle mixing rates have been determined for 5 South Atlantic/Antarctic and 3 equatorial Pacific deep-sea cores using excess 210Pb and 32Si measurements. Radionuclide profiles from these siliceous, calcareous, and clay-rich sediments have been evaluated using a steady state vertical advection diffusion model. In Antarctic siliceous sediments210Pb mixing coefficients (0.04-0.16 cm**2/y) are in reasonable agreement with the 32Si mixing coefficient (0.2 or 0.4 cm**2/y, depending on 32Si half-life). In an equatorial Pacific sediment core, however, the 210Pb mixing coefficient (0.22 cm**2/y) is 3-7 times greater than the 32Si mixing coefficient (0.03 or 0.07 cm**2/y). The difference in 210Pb and 32Si mixing rates in the Pacific sediments results from: (1) non-steady state mixing and differences in characteristic time and depth scales of the two radionuclides, (2) preferential mixing of fine-grained clay particles containing most of the 210Pb activity relative to coarser particles (large radiolaria) containing the 32Si activity, or (3) the supply of 222Rn from the bottom of manganese nodules which increases the measured excess 210Pb activity (relative to 226Ra) at depth and artificially increases the 210Pb mixing coefficient. Based on 32Si data and pore water silica profiles, dissolution of biogenic silica in the sediment column appears to have a minor effect on the 32Si profile in the mixed layer. Deep-sea particle mixing rates reported in this study and the literature do not correlate with sediment type, sediment accumulation rate, or surface productivity. Based on differences in mixing rate among three Antarctic cores collected within 50 km of each other, local variability in the intensity of deep-sea mixing appears to be as important as regional differences in sediment properties.

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

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

Pedology, geochronology, palynology and macrofossils of soil profiles in the Altdarss area, german Baltic Sea coast

A new site with Lateglacial palaeosols covered by 0.8 - 2.4 m thick aeolian sands is presented. The buried soils were subjected to multidisciplinary analyses (pedology, micromorphology, geochronology, dendrology, palynology, macrofossils). The buried soil cover comprises a catena from relatively dry ('Nano'-Podzol, Arenosol) via moist (Histic Gleysol, Gleysol) to wet conditions (Histosol). Dry soils are similar to the so-called Usselo soil, as described from sites in NW Europe and central Poland. The buried soil surface covers ca. 3.4 km**2. Pollen analyses date this surface into the late Aller0d. Due to a possible contamination by younger carbon, radiocarbon dates are too young. OSL dates indicate that the covering by aeolian sands most probably occurred during the Younger Dryas. Botanical analyses enables the reconstruction of a vegetation pattern typical for the late Allerod. Large wooden remains of pine and birch were recorded.

Isotopic ratios, concentration of noble gases and mineral and bulk composition of extraterrestrial dust particles in Dome Fuji ice core, East Antarctica

Two silicate-rich dust layers were found in the Dome Fuji ice core in East Antarctica, at Marine Isotope Stages 12 and 13. Morphologies, textures, and chemical compositions of constituent particles reveal that they are high-temperature melting products and are of extraterrestrial origin. Because similar layers were found ~2000 km east of Dome Fuji, at EPICA (European Project for Ice Coring in Antarctica)-Dome C, particles must have rained down over a wide area 434 and 481 ka. The strewn fields occurred over an area of at least 3 × 10**6 km**2. Chemical compositions of constituent phases and oxygen isotopic composition of olivines suggest that the upper dust layer was produced by a high-temperature interaction between silicate-rich melt and water vapor due to an impact explosion or an aerial burst of a chondritic meteoroid on the inland East Antarctic ice sheet. An estimated total mass of the impactor, on the basis of particle flux and distribution area, is at least 3 × 10**9 kg. A possible parent material of the lower dust layer is a fragment of friable primitive asteroid or comet. A hypervelocity impact of asteroidal/cometary material on the upper atmosphere and an explosion might have produced aggregates of sub-µm to µm-sized spherules. Total mass of the parent material of the lower layer must exceed 1 × 10**9 kg. The two extraterrestrial horizons, each a few millimeters in thickness, represent regional or global meteoritic events not identified previously in the Southern Hemisphere.

Ash layer characteristics and major element oxide content of glasses from ODP Sites 162-982 and 162-985

The Cenozoic volcanic activity on Iceland has been recorded in North Atlantic sediments drilled during several Ocean Drilling Program (ODP)/Deep Sea Drilling Project legs (Legs 104, 151, 152, 162, and 163). Leg 162 (North Atlantic-Arctic Gateways II) recovered ash layers at Sites 982, 985, and 907 (Jansen, Raymo, Blum, et al., 1996, doi:10.2973/odp.proc.ir.162.1996). The revisited Site 907 was first drilled during Leg 151, and the ash from this site has been described in detail by Lacasse et al. (1996, doi:10.2973/odp.proc.sr.151.122.1996) and Werner et al. (1996, doi:10.2973/odp.proc.sr.151.123.1996). Site 982 is located within the Hatton-Rockall Basin on the Rockall Plateau, which is situated west of the British Isles. Site 985 is located northeast of Iceland at the foot of the eastern slope of the Iceland Plateau, adjacent to the Norwegian Basin. Here we report chemical analyses of Neogene tephra layers from Holes 982A, 983B, 982C, 985A, and 985B. The sedimentary sequence at Site 982 spans the lower Miocene-Holocene; Site 985 recovered sediments spanning the upper Oligocene-Holocene. Twenty-two distinct ash layers and ash-bearing sediments were sampled in Holes 982A-982C (Cores 162-982A-16H through 24H, 162-982B-14H through 56X, and 162-982C-15H through 27H), and 59 ash layers were sampled in Holes 985A and 985B (Cores 162-985A-11H through 59X, and 162-985B-11H through 14H). Almost 50% of the sampled ash is strongly altered (predominantly from Site 985). A cluster of altered thin layers in the lower Pliocene of Site 985 (top of Unit III) is remarkable.