Geochemistry of mafic clasts of ODP Holes 125-778A and 125-779A

Clasts of metamorphosed mafic igneous rock of diverse composition were recovered in two drill sites on a serpentine mud volcano in the outer Mariana forearc during Ocean Drilling Program Leg 125. These clasts are xenolithic fragments that have been entrained in the rising serpentine mud, and make up less that 9% of the total rock recovered at Sites 778 and 779. Most samples are metabasalt or metadiabase, although one clast of possible boninite and one cumulate gabbro were recovered. On the basis of trace element signatures, samples are interpreted to represent both arc-derived and mid-ocean ridge-derived compositions. Rocks with extremely low TiO2 (<0.3 wt%) and Zr (<30 ppm) are similar to boninite series rocks. Samples with low TiO2 (<0.9 wt%) and Zr (<50 ppm) and extreme potassium enrichment (K2O/Na2O >3.9) may represent island arc rocks similar to shoshonites. However, the K2O/Na2O ratios are much higher than those reported for shoshonites from modem or ancient arcs and may be the result of metamorphism. Samples with moderate TiO2 (1.4 to 1.5 wt%) and Zr (72 to 85 ppm) are similar to rocks from mid-ocean ridges. A few samples have TiO2 and Zr intermediate between island arc and mid-ocean ridge basalt-like rocks. Two samples have high iron (Fe2O3* = >12.8 to 18.5 wt%) (Fe2O3* = total iron calculated as Fe2O3) and TiO2 (>2.3 wt%) and resemble FeTi basalt recovered from mid-ocean ridges. Metamorphism in most samples ranges from low-temperature zeolite, typical of ocean floor weathering, to prehnite-pumpellyite facies and perhaps lower greenschist. Blue amphibole and lawsonite minerals are present in several samples. One diabase clast (Sample 9) exhibits Ca enrichment, similar to rodingite metamorphism, typical of mafic blocks in serpentinized masses. The presence of both low-grade (clays and zeolites) and higher grade (lawsonite) metamorphism indicates retrograde processes in these clasts. These clasts are fragments of the forearc crust and possibly of the subducting plate that have been entrained in the rising serpentine and may represent the deepest mafic rocks ever recovered from the Mariana forearc. The variable compositions and degree of metamorphism of these clasts requires at least two tectonic origins. The recovery of clasts with mid-ocean ridge and arc chemical affinities in a single drill hole requires these clasts to have been "mixed" on a small scale either (1) in the forearc crustal sequence, or (2) after inclusion in the rising serpentine mud. The source of the MORB-like samples and an explanation for the presence of both MORB-like and arc-like rocks in close proximity is critical to any model of the evolution of the Mariana forearc. The source of the MORB-like samples likely will be one (or more) of the following: (1) accretion of Pacific plate lithosphere, (2) remnants of original forearc crust (trapped plate), (3) volcanism in the supra-subduction zone (arc or forearc) environment, or (4) derivation from the subducting slab by faulting along the dÈcollement.

Mineralogy of serpentine muds of ODP Leg 125 holes (Table 1)

Large serpentinite seamounts are common in the forearc regions between the trench axis and the active volcanic fronts of the Mariana and Izu-Bonin intraoceanic arcs. The seamounts apparently form both as mud volcanoes, composed of unconsolidated serpentine mud flows that have entrained metamorphosed ultramafic and mafic rocks, and as horst blocks, possibly diapirically emplaced, of serpentinized ultramafics partially draped with unconsolidated serpentine slump deposits and mud flows. The clayand silt-sized serpentine recovered from three sites on Conical Seamount on the Mariana forearc region and from two sites on Torishima Forearc Seamount on the Izu-Bonin forearc region is composed predominantly of chrysotile, brucite, chlorite, and clays. A variety of accessory minerals attest to the presence of unusual pore fluids in some of the samples. Aragonite, unstable at the depths at which the serpentine deposits were drilled, is present in many of the surficial cores from Conical Seamount. Sjogrenite minerals, commonly found as weathering products of serpentine resulting from interaction with groundwater, are found in most of the samples. The presence of aragonite and carbonate-hydroxide hydrate minerals argues for interaction of the serpentine deposits with fluids other than seawater. There are numerous examples of sedimentary serpentinite deposits exposed on land that are very similar to the deposits recovered from the serpentine seamounts drilled on ODP Leg 125. We suggest that Conical Seamount may be a type locality for the study of in situ formation of many of these sedimentary serpentinite bodies. Further, we suggest that both the deposits drilled on Conical Seamount and on Torishima Forearc Seamount demonstrate that serpentinization can continue in situ within the seamounts through interaction of the serpentine deposits with both seawater and subduction-related fluids.

Flows with 'Cu-type' characteristics at ODP Hole 104-642E (Table 1)

Native Cu occurs in amygdules, fractures and groundmass of tholeiites from Ocean Drilling Program Site 642 on the Vøring Plateau. Similar occurrences have been reported in other tholeiites of the early Tertiary North Atlantic Volcanic Province drilled at Deep Sea Drilling Project Sites 342 on the Vøring Plateau and 553 on the Rockall Plateau. The flows containing the native Cu have distinctive alteration patterns characterized by the combination of reddened flow tops, distinctive pastel coloration of the upper parts of the flows, relative abundance of celadonite, and the presence of native Cu. These associations suggest that subaerial weathering and subsequent seawater-basalt interaction are related to the occurrence of native Cu. An additional factor may be the increase in compatibility of Cu in silicates and Fe- Ti oxides that may accompany sub-solidus oxidation of basaltic flows. Native Cu occurrences in Site 642 tholeiites have some striking similarities to the large native Cu deposits in the Precambrian basalts of the Keweenaw Peninsula, Michigan, that are suggestive of similar mineralization processes.

Age determination and grain size distribution of sediment core GeoB3375-1

The palaeoclimatic conditions during the Last Glacial Maximum (LGM) of southern South America and especially latitudinal shifts of the southern westerly wind belt are still discussed controversially. Longer palaeoclimatic records covering the Late Quaternary are rare. A particularly sensitive area to Late Quaternary climatic changes is the Norte Chico, northern Chile, because of its extreme climatic gradients. Small shifts of the present climatic zonation could cause significant variations of the terrestrial sedimentary environment which would be recorded in marine terrigenous sediments. To unveil the history of shifting climatic zones in northern Chile, we present a sedimentological study of a marine sediment core (GeoB 3375-1) from the continental slope off the Norte Chico (27.5°S). Sedimentological investigations include bulk- and silt grain-size determinations by sieving, Atterberg separation, and detailed SediGraph analyses. Additionally, clay mineralogical parameters were obtained by X-ray diffraction methods. The 14C-dated core, covering the time span from approximately 10,000 to 120,000 cal. yr B.P., consists of hemipelagic sediments. Terrigenous sedimentological parameters reveal a strong cyclicity, which is interpreted in terms of variations of sediment provenance, modifications of the terrestrial weathering regimes, and modes of sediment input to the ocean. These interpretations imply cyclic variations between comparatively arid climates and more humid conditions with seasonal precipitation for northern Chile (27.5°S) through the Late Quaternary. The cyclicity of the terrigenous sediment parameters is strongly dominated by precessional cycles. For the palaeoclimatic signal, this means that more humid conditions coincide with maxima of the precession index, as e.g. during the LGM. Higher seasonal precipitation for this part of Chile is most likely derived from frontal winter rain of the Southern Westerlies. Thus, the data presented here favour not only an equatorward shift of this atmospheric circulation system during the LGM, but also precession-controlled latitudinal movements throughout the Late Quaternary. Precessional forcing of latitudinal movements of the westerly atmospheric circulation system may be conceivable through teleconnections to the Northern Hemisphere monsoonal system in the Atlantic Ocean region.

Sedimentology and mineralogy of surface sediments from the Chilean continental margin

The regional patterns of texture and composition of modern continental slope and pelagic sediments off Chile between 25°S and 43°S reflect the latitudinal segmentation of geological, morphological, and climatic features of the continental hinterland. Grain-size characteristics are controlled by the grain-size of source rocks, the weathering regime, and mode of sediment input (eolian off northern Chile vs fluvial further south). Bulk-mineral assemblages reveal a low grade of maturity. Regional variations are governed by the source-rock composition of the different geological terranes and the relative source-rock contribution of the Coastal Range and Andes, as controlled by the continental hydrology. The relative abundance of clay minerals is also predominantly influenced by the source-rock composition and partly by continental smectite neoformation. Latitudinal variations of illite crystallinities along the Chilean continental slope (and west of the Peru-Chile trench) clearly reflect modifications of the weathering regime which correspond to the strong climatic zonation of Chile.

Late Quaternary geochemical record of sediment core GeoB3375-1

Analyses of terrigenous sediments from the Chilean continental slope off the southern border of the Atacama desert (27.5°S), focusing on illite crystallinity and the Fe:Al ratio of the sediments, reveal a high-frequency variability of the position of the Southern Westerlies, which is very similar to the coeval short-term climatic events known from Greenland ice cores and from North Atlantic sediments. Besides showing dominantly precession-driven variability in precipitation over the Andes, these analyses also reveal rapid changes in weathering intensity along the Chilean Coastal Range during the last 80,000 years. These rapid changes occur at much shorter timescales than the 19-100 kyr orbital forcing of the Milankovitch cycles.

Planktonic foraminifera, nannofossils and stable isotope record across tghe Paleocene-Eocene thermal maximum of ODP Hole 113-690B

The carbonate saturation profile of the oceans shoaled markedly during a transient global warming event known as the Paleocene-Eocene thermal maximum (PETM) (circa 55 Ma). The rapid release of large quantities of carbon into the ocean-atmosphere system is believed to have triggered this intense episode of dissolution along with a negative carbon isotope excursion (CIE). The brevity (120-220 kyr) of the PETM reflects the rapid enhancement of negative feedback mechanisms within Earth's exogenic carbon cycle that served the dual function of buffering ocean pH and reducing atmospheric greenhouse gas levels. Detailed study of the PETM stratigraphy from Ocean Drilling Program Site 690 (Weddell Sea) reveals that the CIE recovery period, which postdates the CIE onset by ~80 kyr, is represented by an expanded (~2.5 m thick) interval containing a unique planktic foraminiferal assemblage strongly diluted by coccolithophore carbonate. Collectively, the micropaleontological and sedimentological changes preserved within the CIE recovery interval reflect a transient state when ocean-atmosphere chemistry fostered prolific coccolithophore blooms that suppressed the local lysocline to relatively deeper depths. A prominent peak in the abundance of the clay mineral kaolinite is associated with the CIE recovery interval, indicating that continental weathering/runoff intensified at this time as well (Robert and Kennett, 1994). Such parallel stratigraphic changes are generally consonant with the hypothesis that enhanced continental weathering/runoff and carbonate precipitation helped sequester carbon during the PETM recovery period (e.g., Dickens et al., 1997, doi:10.1130/0091-7613(1997)025<0259:ABOGIT>2.3.CO;2 ; Zachos et al., 2005, doi:10.1126/science.1109004).

Trace element concentrations and Li isotope composition in DSDP and ODP sediments from island arcs

We have studied the sedimentary and basaltic inputs of lithium to subduction zones. Various sediments from DSDP and ODP drill cores in front of the Mariana, South Sandwich, Banda, East Sunda and Lesser Antilles island arcs have been analysed and show highly variable Li contents and d7Li values. The sediment piles in front of the Mariana and South Sandwich arcs largely consist of pelagic sediments (clays and oozes). The pelagic clays have high Li contents (up to 57.3 ppm) and Li isotope compositions ranging from +1.3? to +4.1?. The oozes have lower Li contents (7.3-16 ppm) with d7Li values of the diatom oozes from the South Sandwich lower (+2.8? to +3.2?) than those of the radiolarian oozes from the Mariana arc (+8.1? to +14.5?). Mariana sediment also contains a significant portion of volcanogenic material, which is characterised by a moderate Li content (14 ppm) and a relatively heavy isotope composition (+6.4?). Sediments from the Banda and Lesser Antilles contain considerable amounts of continental detritus, and have high Li contents (up to 74.3 ppm) and low d7Li values (around 0?), caused by weathering of continental bedrock. East Sunda sediments largely consist of calcareous oozes. These carbonate sediments display intermediate to high Li contents (2.4-41.9 ppm) and highly variable d7Li values (-1.6? to +12.8?). Basaltic oceanic crust samples from worldwide DSDP and ODP drill cores are characterised by enrichment of Li compared to fresh MORB (6.6-33.1 vs. 3.6-7.5 ppm, respectively), and show a large range in Li isotope compositions (+1.7? to +11.8?). The elemental and isotopic enrichment of Li in altered basalts is due to the uptake of isotopically heavy seawater Li during weathering. However, old oceanic crust samples from Sites 417/418 exhibit lighter Li isotope compositions compared to young basaltic crust samples from Sites 332B and 504B. This lighter Li isotope signature in old crust is unexpected and further research is needed to explore this issue.

Interstitial-water geochemistry of Kerguelen Plateau sediments

This report synthesizes all of the interstitial-water chemistry studies associated with the Kerguelen Plateau phase of ODP Leg 119. Sediments were cored at six sites (49°24'S to 59°36'S) in water depths ranging from 564 to 4082 m. A total of 77 interstitial-water samples was recovered as part of the routine sampling protocol. In addition, a novel, highresolution pore-water sampling program was tested during Leg 119 that enabled us to pinpoint reaction zones and extend our data base to deeper, drier levels that were heretofore inaccessible. Data collected include interstitial-water sodium, potassium, calcium, magnesium, pH, alkalinity, sulfate, ammonia, phosphate, aqueous silica, salinity, chloride, oxidation-reduction potentials, and sediment chemistry. The northern sector (Sites 736 and 737) is characterized by the highest sedimentation rates (up to 140 m/m.y.) and thermal gradients (70°-98°C/km) encountered on the Kerguelen Plateau during Leg 119. Site 737 represents the most reactive sediment column cored on the Kerguelen Plateau. Major cation fluxes at Site 737 are the strongest measured during Leg 119. High dissolved calcium concentrations (141.5 mM) were encountered near the bottom of Hole 737B. Elevated temperatures promote silica diagenesis and the alteration of volcanic material below 300 mbsf, and a diagenetic front was discovered near 370 mbsf at Site 737. The southern portion of the Kerguelen Plateau (Sites 738 and 744) records the lowest sedimentation rates (less than 5 m/m.y.) and thermal gradients (43°C/km) of the three study areas. Major cation fluxes at the southern sites are the lowest that we measured on the Kerguelen Plateau. High-resolution sampling provided evidence for significant silica release to the pore waters during the weathering of basement basalt. The relatively low thermal gradient does not appear to be sufficient for the formation of the opal-CT and quartz chert beds and nodules that were encountered below 120 mbsf at Site 738. Sediment-accumulation rates on the Eastern Kerguelen Sediment Ridge (Sites 745 and 746) are intermediate to those of the northern and southern sites. Deposition below the regional CCD accounts for the nearly carbonate-free, siliceous sediments. Despite their low organic carbon contents (mean = 0.15%), sediments on the Eastern Kerguelen Sediment Ridge exhibit the highest pore-water alkalinity (6.77 mM), ammonium (0.50 mM), and phosphate (23 µM) concentrations measured on the Kerguelen Plateau. Major cation fluxes are intermediate to those calculated for the northern and southern sites. The Eastern Kerguelen Sediment Ridge interstitial waters are unusual, however, in that the downward flux of magnesium is greater than the upward flux of calcium.

Phosphorus concentrations and accumulation rates of ODP Leg 130 sites

Little is known about the fluxes to and from the ocean during the Cenozoic of phosphorus (P), a limiting nutrient for oceanic primary productivity and organic carbon burial on geologic timescales. Previous studies have concluded that dissolved river fluxes increased worldwide during the Cenozoic and that organic carbon burial decreased relative to calcium carbonate burial and perhaps in absolute terms as well. To examine the apparent contradiction between increased river fluxes of P (assuming P fluxes behave like the others) expected to drive increased organic carbon burial and observations indicating decreased organic carbon burial, we determined P accumulation rates for equatorial Pacific sediments from Ocean Drilling Program leg 138 sites in the eastern equatorial Pacific and leg 130 sites on the Ontong Java Plateau in the western equatorial Pacific. Although there are site specific and depth dependent effects on P accumulation rates, there are important features common to the records at all sites. P accumulation rates declined from 50 to 20 Ma, showed some variability from 20 to 10 Ma, and had a substantial peak from 9 to 3 Ma centered at 5-6 Ma. These changes in P accumulation rates for the equatorial Pacific are equivalent to substantial changes in the P mass balance. However, the pattern resembles neither that of weathering flux indicators (87Sr/86Sr and Ge/Si ratios) nor that of the carbon isotope record reflecting changes in organic carbon burial rates. Although these P accumulation rate patterns need confirmation from other regions with sediment burial significant in global mass balances (e.g., the North Pacific and Southern Ocean), it appears that P weathering inputs to the ocean are decoupled from those of other elements and that further exploration is needed of the relationship between P burial and net organic carbon burial.

Velocities and elastic moduli of basalts from Pacific DSDP sites

Compressional (Vp) and shear (Vs) wave velocities have been measured to 10 kb in 32 cores of basalt from 14 Pacific sites of the Deep Sea Drilling Project. Both Vp and V s show wide ranges (3.70 to 6.38 km/sec for Vp and 1.77 to 3.40 km/sec for V s at 0.5 kb) which are linearly related to density and sea floor age, confirming earlier findings by Christensen and Salisbury of decreasing velocity with progressive submarine weathering based on studies of basalts from five sites in the Atlantic. Combined Pacific and Atlantic data give rates of decreasing velocity of -1.89 and -1.35 km/sec per 100 my for Vp and Vs respectively. New analyses of oceanic seismic refraction data indicate a decrease in layer 2 velocities with age similar to that observed in the laboratory, suggesting that weathering penetrates to several hundred meters in many regions and is largely responsible for the extreme range and variability of layer 2 refraction velocities.

Major and trace elements and minerals at DSDP Hole 79-544A

Fifty m of basement rocks underlying 185 m of Neogene and Mesozoic sediments were drilled seaward of the Mazagan Slope about 100 km west of Casablanca during Leg 79. These rocks are metagranites with mylonitic textures consisting dominantly of quartz, plagioclase, and potassium feldspar. Chemically, they are strongly peraluminous. This along with the absence of hornblende suggest that these rocks are similar to the S-type granites. Petrographic and chemical data suggest the possible existence of a former weathering surface on top of the Mazagan metagranite.

Geochemistry on smectites in sediment cores CRP-1 and CRP-2 from the Ross Sea, Antarctica

TEM (transmission electron microscopy) observations and microanalyses on smectite microparticles in the sediments of the CRP-2A core were carried out to determine their origin (authigenic or detrital) and the source rocks. Smectites are dioctahedral and are Fe-rich members of the nontronite-beidellite series. They generally display both flaky and hairy shapes, but no large compositional difference between the two forms was observed. Flaky smectites are detrital while hairy smectites probably formed in situ through the reorganisation of previous flaky particles. The source rocks for smectites are probably represented by the McMurdo Volcanic Group to the south, but also by the Ferrar Dolerites and Kirkpatrick Basalts in the Transantarctic Mountains. CRP-2A smectites are Fe and Mg richer than those of the coeval or not coeval levels of the CIROS-I, DSDP 270 and 274 cores. The average compositions of smectite in CRP-1 and CRP-2A cores show a downcore trend toward more alluminiferous terms, which might reflect the increase of the chemical weathering processes on the continent.