Analyses of shocked quartz from the K-P boundary

The precise cause and timing of the Cretaceous-Paleocene (K-P) mass extinction 65 Ma ago remains a matter of debate. Many advocate that the extinction was caused by a meteorite impact at Chicxulub, Mexico, and a number of potential kill-mechanisms have been proposed for this. Although we now have good constraints on the size of this impact and chemistry of the target rocks, estimates of its environmental consequences are hindered by a lack of knowledge about the obliquity of this impact. An oblique impact is likely to have been far more catastrophic than a sub-vertical one, because greater volumes of volatiles would have been released into the atmosphere. The principal purpose of this study was to characterize shocked quartz within distal K-P ejecta, to investigate whether the quartz distribution carried a signature of the direction and angle of impact. Our analyses show that the total number, maximum and average size of shocked quartz grains all decrease gradually with paleodistance from Chicxulub. We do not find particularly high abundances in Pacific sites relative to Atlantic and European sites, as has been previously reported, and the size-distribution around Chicxulub is relatively symmetric. Ejecta samples at any one site display features that are indicative of a wide range of shock pressures, but the mean degree of shock increases with paleodistance. These shock- and size-distributions are both consistent with the K-P layer having been formed by a single impact at Chicxulub. One site in the South Atlantic contains quartz indicating an anomalously high average shock degree, that may be indicative of an oblique impact with an uprange direction to the southeast +/- 45°. The apparent continuous coverage of proximal ejecta in this quadrant of the crater, however, suggests a relatively high impact angle of >45°. We conclude that some of the more extreme predictions of the environmental consequences of a low-angle impact at Chicxulub are probably not applicable.

(Table 1) Organic geochemistry of ODP Hole 134-832B and Site 134-833

Ocean Drilling Program (ODP) Leg 134 was located in the central part of the New Hebrides Island Arc, in the Southwest Pacific. Here the d'Entrecasteaux Zone of ridges, the North d'Entrecasteaux Ridge and South d'Entrecasteaux Chain, is colliding with the arc. The region has a Neogene history of subduction polarity reversal, ridge-arc collision, and back-arc spreading. The reasons for drilling in this region included the following: (1) to determine the differences in the style and time scale of deformation associated with the two ridge-like features (a fairly continuous ridge and an irregularly topographic seamount chain) that are colliding with the central New Hebrides Island Arc; (2) to document the evolution of the magmatic arc in relation to the collision process and possible Neogene reversal of subduction; and (3) to understand the process of dewatering of a small accretionary wedge associated with ridge collision and subduction. Seven sites were occupied during the leg, five (Sites 827-831) were located in the d'Entrecasteaux Zone where collision is active. Three sites (Sites 827, 828, and 829) were located where the North d'Entrecasteaux Ridge is colliding, whereas two sites (Sites 830 and 831) were located in the South d'Entrecasteaux Chain collision zone. Sites 828 (on North d'Entrecasteaux Ridge) and 831 (on Bougainville Guyot) were located on the Pacific Plate, whereas all other sites were located on a microplate of the North Fiji Basin. Two sites (Sites 832 and 831) were located in the intra-arc North Aoba Basin. Results of Leg 134 drilling showed that forearc deformation associated with the North d'Entrecasteaux Ridge and South d'Entrecasteaux Chain collision is distinct and different. The d'Entrecasteaux Zone is an Eocene subduction/obduction complex with a distinct submerged island arc. Collision and subduction of the North d'Entrecasteaux Ridge results in off scraping of ridge material and plating of the forearc with thrust sheets (flakes) as well as distinct forearc uplift. Some offscraped sedimentary rocks and surficial volcanic basement rocks of the North d'Entrecasteaux Ridge are being underplated to the New Hebrides Island forearc. In contrast, the South d'Entrecasteaux Chain is a serrated feature resulting in intermittent collision and subduction of seamounts. The collision of the Bougainville Guyot has indented the forearc and appears to be causing shortening through thrust faulting. In addition, we found that the Quaternary relative convergence rate between the New Hebrides Island Arc at the latitude of Espiritu Santo Island is as high as 14 to 16 cm/yr. The northward migration rate of the d'Entrecasteaux Zone was found the be ~2 to 4 cm/yr based on the newly determined Quaternary relative convergence rate. Using these rates we established the timing of initial d'Entrecasteaux Zone collision with the arc at ~3 Ma at the latitude of Epi Island and fixed the impact of the North d'Entrecasteaux Ridge upon Espiritu Santo Island at early Pleistocene (between 1.89 and 1.58 Ma). Dewatering is occurring in the North d'Entrecasteaux Ridge accretionary wedge, and the wedge is dryer than other previously studied accretionary wedges, such as Barbados. This could be the result of less sediment being subducted at the New Hebrides compared to the Barbados.

Geochemistry of volcanivlastic sediments of ODP Sites 134-832 and 134-833

Volcaniclastic sediments of North Aoba Basin (Vanuatu) recovered during Ocean Drilling Program (ODP) Leg 134 show a mineralogical and chemical overprint of low grade hydrothermal alteration superimposed on the primary magmatic source compositions. The purpose of this study was to identify authigenic mineral phases incorporated in the volcaniclastic sediments, to distinguish authigenic chemical and mineralogical signals from the original volcaniclastic mineralogical and chemical compositions, and to determine the mechanism of authigenic minerals formation. Mineralogical, micro-chemical and bulk chemical analyses were utilized to identify and characterize authigenic phases and determine the original unaltered ash compositions. 117 volcaniclastic sediment samples from North Aoba Basin Sites 832 and 833 were analyzed. Primary volcaniclastic materials accumulated in North Aoba Basin can be divided into three types. The older basin-filling sequences show three different magmatic trends: high K, calc-alkaline, and low K series. The most recent accumulations are rhyodacitic composition and can be attributed to Santa Maria or Aoba volcanic emissions. Original depositional porosity of volcaniclastic sediments is an important factor in influencing distribution of authigenic phases. Finer-grained units are less altered and retain a bulk mineralogical and chemical composition close to the original pyroclastic rock composition. Coarser grained units (microbreccia and sandstones) are the major hosts of authigenic minerals. At both sites, authigenic minerals (including zeolites, clay minerals, Mg-carbonates, and quartz) exhibit complex zonation with depth that crosses original ash depositional boundaries and stratigraphic limits. The zeolite minerals phillipsite and analcime are ubiquitous throughout the altered intervals. At Site 832, the first zeolite minerals (phillipsite) occur in Pleistocene deposits as shallow as 146 meters below seafloor (mbsf). At Site 833 the first zeolite minerals (analcime) occur in Pleistocene deposits as shallow as 224 mbsf. The assemblage phillipsite + analcime + chabazite appears at 635 mbsf (Site 832) and at 376 mbsf (Site 833). Phillipsite + analcime + chabazite + thomsonite + heulandite are observed between 443 and 732 mbsf at Site 833. Thomsonite is no longer observed below 732 mbsf at Site 833. Heulandite is present to the base of the sections cored. The zeolite assemblages are associated with authigenic clay minerals (nontronite and saponite), calcite, and quartz. Chlorite is noticeable at Site 832 as deep as 851 mbsf. Zeolite zones are present but are less well defined at Site 832. Dolomite and rare magnesite are present below 940 m at Site 832. The coarse-grained authigenic mineral host intervals exhibit geochemical signatures that can be attributed to low grade hydrothermal alteration. The altered intervals show evidence of K2O, CaO, and rare earth elements mobilization. When compared to fine-grained, unaltered units, and to Santa Maria Island volcanics rocks, the altered zones are relatively depleted in rare earth elements, with light rare earth elements-heavy rare earth elements fractionation. Drilling at Site 833 penetrated a sill complex below 840 m. No sill was encountered at Site 832. Complex zonation of zeolite facies, authigenic smectites, carbonates and quartz, and associated geochemical signatures are present at both sites. The mineralogical and chemical alteration overprint is most pronounced in the deeper sections at Site 832. Based on mineralogical and chemical evidence at two locations less than 50 km apart, there is vertical and lateral variation in alteration of the volcaniclastic sediments of North Aoba Basin. The alteration observed may be activated by sill intrusion and associated expulsion of heated fluids into intervals of greater porosity. Such spatial variation in alteration could be attributed to the evolution of the basin axis associated with subduction processes along the New Hebrides Trench.

High resolution color reflectance and hematite and goethite record of ODP Hole 184-1143A in the South China Sea

Precipitation has a larger variability than temperature in tropical monsoon regions, thus it is an important climate variable. However, reconstructions of long-term rainfall histories are scarce because of the lack of reliable proxies. Here we document that iron oxide minerals, specifically the ratio of hematite to goethite (Hm/Gt), is a reasonable precipitation proxy. Using diffuse reflectance spectrophotometry, we measured samples from Ocean Drilling Program (ODP) 1143 drilling site (9°21.72'N, 113°17.11'E, 2777 m water depth) for hematite and goethite, whose formation processes are favored by opposing climate conditions. In order to determine the content of hematite and goethite we produced a set of calibration samples by removing the iron oxides to generate the natural matrix to which hematite and goethite in known percentages were added. From these calibration samples we developed a transfer function for determining hematite and goethite concentration from a sample's spectral reflectance. Applying this method to ODP 1143 sediments (top 34 m of a 510 m core with sampling interval of 10 cm) we were able to reconstruct a continuous precipitation history for SE Asia of the past 600 kyr using the Hm/Gt ratio as a proxy of the precipitation variability of Asian monsoon. The reliability of this Hm/Gt proxy is corroborated by its consistency with the stalagmite delta18O data from South China. Comparing long-term Hm/Gt records with the surface temperature gradient of equatorial Pacific Ocean, we found that monsoon precipitation and El Niño are correlated for the last 600 kyr. The development of El Niño-like conditions decreased SE Asia precipitation, whereas precipitation increases in response to La Niña intensification

High-resolution pollen record of ODP Hole 175-1078C

To address the connection between tropical African vegetation development and high-latitude climate change we present a high-resolution pollen record from ODP Site 1078 (off Angola) covering the period 50-10 ka BP. Although several tropical African vegetation and climate reconstructions indicate an impact of Heinrich Stadials (HSs) in Southern Hemisphere Africa, our vegetation record shows no response. Model simulations conducted with an Earth System Model of Intermediate Complexity including a dynamical vegetation component provide one possible explanation. Because both precipitation and evaporation increased during HSs and their effects nearly cancelled each other, there was a negligible change in moisture supply. Consequently, the resulting climatic response to HSs might have been too weak to noticeably affect the vegetation composition in the study area. Our results also show that the response to HSs in southern tropical Africa neither equals nor mirrors the response to abrupt climate change in northern Africa.

Impact of high pCO2 and warmer temperatures on the process of silica biomineralization in the sponge Mycale grandis

Siliceous sponges have survived pre-historical mass extinction events caused by ocean acidification and recent studies suggest that siliceous sponges will continue to resist predicted increases in ocean acidity. In this study, we monitored silica biomineralization in the Hawaiian sponge Mycale grandis under predicted pCO2 and sea surface temperature scenarios for 2100. Our goal was to determine if spicule biomineralization was enhanced or repressed by ocean acidification and thermal stress by monitoring silica uptake rates during short-term (48 h) experiments and comparing biomineralized tissue ratios before and after a long-term (26 d) experiment. In the short-term experiment, we found that silica uptake rates were not impacted by high pCO2 (1050 µatm), warmer temperatures (27°C), or combined high pCO2 with warmer temperature (1119 µatm; 27°C) treatments. The long-term exposure experiments revealed no effect on survival or growth rates of M. grandis to high pCO2 (1198 µatm), warmer temperatures (25.6°C), or combined high pCO2 with warmer temperature (1225 µatm, 25.7°C) treatments, indicating that M. grandis will continue to prosper under predicted increases in pCO2 and sea surface temperature. However, ash-free dry weight to dry weight ratios, subtylostyle lengths, and silicified weight to dry weight ratios decreased under conditions of high pCO2 and combined pCO2 warmer temperature treatments. Our results show that rising ocean acidity and temperature have marginal negative effects on spicule biomineralization and will not affect sponge survival rates of M. grandis.

High-pressure experiments on a natural olivine gabbro from ODP Hole 176-735B

We have conducted high-pressure experiments on a natural oceanic gabbro composition (Gb108). Our aim was to test recent proposals that Sr-enrichment in rare primitive melt inclusions from Mauna Loa, Hawaii, may have resulted from melting of garnet pyroxenite formed in the magma source regions by reaction of peridotite with siliceous, Sr-enriched partial melts of eclogite of gabbroic composition. Gb108 is a natural, Sr-enriched olivine gabbro, which has a strong positive Sr anomaly superimposed on an overall depleted incompatible trace element pattern, reflecting its origin as a plagioclase-rich cumulate. At high pressures it crystallises as a coesite eclogite assemblage, with the solidus between 1,300 and 1,350°C at 3.5 GPa and 1,450 and 1,500°C at 4.5 GPa. Clinopyroxenes contain 4-9% Ca-eskolaite component, which varies systematically with pressure and temperature. Garnets are almandine and grossular-rich. Low degree partial melts are highly siliceous in composition, resembling dacites. Coesite is eliminated between 50 and 100°C above the solidus. The whole-rock Sr-enrichment is primarily hosted by clinopyroxene. This phase dominates the mode (>75 wt%) at all investigated PT conditions, and is the major contributor to partial melts of this eclogite composition. Hence the partial melts have trace element patterns sub-parallel to those of clinopyroxene with ~10* greater overall abundances and with strong positive Sr anomalies. Recent studies of primitive Hawaiian volcanics have suggested the incorporation into their source regions of eclogite, formerly gabbroic material recycled through the mantle at subduction zones. The models suggest that formerly gabbroic material, present as eclogite in the Hawaiian plume, partially melted earlier than surrounding peridotite (i.e. at higher pressure) because of the lower solidus temperature of eclogite compared with peridotite. This produced highly siliceous melts which reacted with surrounding peridotite producing hybrid pyroxene + garnet lithologies. The Sr-enriched nature of the formerly plagioclase-rich gabbro was present in the siliceous partial melts, as demonstrated by these experiments, and was transferred to the reactive pyroxenite. These in turn partially melted, producing Sr-enriched picritic liquids which mixed with normal picritic partial melts of peridotite before eruption. On rare occasions these mixed, relatively Sr-rich melts were trapped as melt inclusions in primitive olivine phenocrysts.Yaxley-Sobolev