Composition of matrix glasses and melt inclusions of fallout tephra from ODP Hole 125-782A

We studied the systematics of Cl, F and H2O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ~400-4000 ppm and F ~70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (~6600-8600 ppm) and F (~780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H2O of basalt to andesite melt inclusions in plagioclase is estimated to range from ~2 to ~10 wt% H2O. The Izu magmas should be undersaturated in H2O and the halogens at their preferred levels of crystallization in the middle to lower crust (~3 to ~11 kbar, ~820° to ~1200°C). A substantial portion of the original H2O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H2O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H2O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94+/-0.25 wt%, F = 990+/-270 ppm and H2O = 25+/-7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (~77-129%). Conversely, H2O (~13-22% recycled at arc) and F (~4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H2O, the calculated percentage of Cl and H2O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (~37000 km), the global arc outflux of fluid-recycled Cl and H2O at subduction zones amounts to Cl ~2.9-3.8 mln ton/yr and H2O ~70-100 mln ton/yr, respectively - comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ~0.3-0.4 mln ton/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H2O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H2O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (~9.5), slab melting will still produce components with low Cl/F ratios (~0.9), similar to those characteristic of the upper continental crust (Cl/F ~0.3-0.9).

Geochemistry of pore fluids and bulk solids of ODP Site 195-1200, South Chamorro Seamount

At the South Chamorro Seamount in the Mariana subduction zone, geochemical data of pore fluids recovered from Ocean Drilling Program Leg 195 Site 1200 indicate that these fluids evolved from dehydration of the underthrusting Pacific plate and upwelling of fluids to the surface through serpentinite mud volcanoes as cold springs at their summits. Physical conditions of the fluid source at 27 km were inferred to be at 100°-250°C and 0.8 GPa. The upwelling of fluid is more active near the spring in Holes 1200E and 1200A and becomes less so with increasing distance toward Hole 1200D. These pore fluids are depleted in Cl and Br, enriched in F (except in Hole 1200D) and B (up to 3500 µM), have low 11B (16-21), and have lower than seawater Br/Cl ratios. The mixing ratios between seawater and pore fluids is calculated to be ~2:1 at shallow depth. The F, Cl, and Br concentrations, together with B concentrations and B isotope ratios in the serpentinized igneous rocks and serpentine muds that include ultramafic clasts from Holes 1200A, 1200B, 1200D, 1200E, and 1200F, support the conclusion that the fluids involved in serpentinization originated from great depths; the dehydration of sediments and altered basalt at the top of the subducting Pacific plate released Cl, H2O, and B with enriched 10B. Calculation from B concentrations and upwelling rates indicate that B is efficiently recycled through this nonaccretionary subduction zone, as through others, and may contribute the critical missing B of the oceanic cycle.

Geochemistry of Lesser Antilles lavas

We present new U-series disequilibrium and radiogenic isotope data for 7 mafic lavas from the Lesser Antilles arc. These are combined with published data in an internally consistent model that quantitatively estimates the amount of sediment and fluid added to the source of the Lesser Antilles arc system. Some lavas form an array consistent with bulk sediment addition (0.2-2%) whereas others appear to require addition of 0.4-2% sediment melt, particularly in the south of the arc. Evidence for both bulk sediment and sediment melt addition can be found within both the northern and central sections of the arc suggesting a thermal structure whereby the upper portions of the subducted sediment pile lie close to their solidus beneath much of the arc. Addition of up to 5% fluid derived from altered oceanic crust to these sediment enriched mantle wedge source regions can simulate the majority of the lavas on a plot of 207Pb/204Pb versus Ce/Pb. By taking into account the range in calculated wedge compositions and allowing for some mobility of Th in the fluid, the same model can also account for much of the observed range of U-Th-Ra disequilibria, especially if the eclogitic residue contains trace amounts of rutile. The implication of this more complex model is that the time scales for fluid addition and differentiation could be significantly shorter than those estimated in some previous studies.

Benthic foraminiferal Mg/Ca ratios

Core-top samples from different ocean basins have been analyzed to refine our current understanding of the sensitivity of benthic foraminiferal calcite magnesium/calcium (Mg/Ca) to bottom water temperatures (BWT). Benthic foraminifera collected from Hawaii, Little Bahama Bank, Sea of Okhotsk, Gulf of California, NE Atlantic, Ceara Rise, Sierra Leone Rise, the Ontong Java Plateau, and the Southern Ocean covering a temperature range of 0.8 to 18°C were used to revise the Cibicidoides Mg/Ca-temperature calibration. The Mg/Ca-BWT relationship of three common Cibicidoides species is described by an exponential equation: Mg/Ca = 0.867 ± 0.049 exp (0.109 ± 0.007 * BWT) (stated errors are 95% CI). The temperature sensitivity is very similar to a previously published calibration. However, the revised calibration has a significantly different preexponential constant, resulting in different predicted absolute temperatures. We attribute this difference in the preexponential constant to an analytical issue of accuracy. Some genera, notably Uvigerina, show apparently lower temperature sensitivity than others, suggesting that the use of constant offsets to account for vital effects in Mg/Ca may not be appropriate. Downcore Mg/Ca reproducibility, as determined on replicate foraminiferal samples, is typically better than 0.1 mmol/mol (2 S.E.). Thus, considering the errors associated with the Cibicidoides calibration and the downcore reproducibility, BWT may be estimated to within ±1°C. Application of the revised core-top Mg/Ca-BWT data to Cenozoic foraminiferal Mg/Ca suggests that seawater Mg/Ca was not more than 35% lower than today in the ice-free ocean at 50 Ma.

Geochemistry and Hg isotopic composition of mid-Pleistocene sapropel of ODP Hole 161-974C

The concentrations of mercury (Hg) and other trace metals (Ni, Cu, Zn, Mo, Ba, Re, U) and the Hg isotopic composition were examined across a dramatic redox and productivity transition in a mid-Pleistocene Mediterranean Sea sapropel sequence. Characteristic trace metal enrichment in organic-rich layers was observed, with organic-rich sapropel layers ranging in Hg concentration from 314 to 488 ng/g (avg = 385), with an average enrichment in Hg by a factor of 5.9 compared to organic-poor background sediments, which range from 39 to 94 ng/g Hg (avg = 66). Comparison of seawater concentrations and sapropel accumulations of trace metals suggests that organic matter quantitatively delivers Hg to the seafloor. Near complete scavenging of Hg from the water column renders the sapropel Hg isotopic composition representative of mid-Pleistocene Mediterranean seawater. Sapropels have an average d202Hg value of -0.91 per mil ± 0.15 per mil (n = 5, 1 SD) and D199Hg value of 0.11 per mil ± 0.03 per mil (n = 5, 1 SD). Background sediments have an average d202Hg of -0.76 per mil ± 0.16 per mil (n = 5, 1 SD) and D199Hg of 0.05 per mil ± 0.01 per mil (n = 5, 1 SD), which is indistinguishable from the sapropel values. We suggest that the sapropel isotopic composition is most representative of the mid-Pleistocene Tyrrhenian Sea.

Sand fraction, foraminifer isotopic composition and foraminifer element ratios of ODP Site 198-1209 sediments, Shatsky Rise

Stable oxygen and carbon isotope measurements (d18O and d13C) of planktonic and benthic foraminifers were conducted to assess the temperature history and circulation patterns over Shatsky Rise during the Paleocene and Eocene. A record of Mg/Ca for benthic foraminifers was also constructed in order to better determine the relative influence of temperature, salinity, and/or ice volume upon the benthic d18O record. Isotopic analyses were carried out on several planktonic taxa (Acarinina, Morozovella, Globigerinatheka, Praemurica, and Subbotina) as well as several benthic taxa (Nuttalides, Oridorsalis, Cibicidoides, Gavelinella, and Lenticulina). Elemental analyses were restricted to three benthic taxa: Nuttalides, Oridorsalis, and Gavelinella. All specimens were derived from the composite sediment section recovered from Ocean Drilling Program Site 1209 on the Southern High of Shatsky Rise.

TOC, carbonate, opal composition and trace element concentration from ODP Holes 175-1082A and 175-1084A

Distinctive light-dark color cycles in sediment beneath the Benguela Current Upwelling System indicate repetitive alternations in sediment delivery and deposition. Geochemical proxies for paleoproductivity and for depositional conditions were employed to investigate the paleoceanographic processes involved in creating these cycles in three mid-Pleistocene intervals from ODP Sites 1082 and 1084. Concentrations of total organic carbon (TOC) vary between 3.5 and 17.1%. Concentrations of CaCO3 vary inversely to TOC and Al, which suggests that both carbonate dissolution and terrigenous dilution contribute to the light-dark cycles. Opal concentrations are independent of both TOC and CaCO3, therefore eliminating diatom production and lateral transport of shelf material as causes of the light-dark cycles. d13Corg and d15Ntot values do not vary across light-dark sediment intervals, implying that the extent of relative nutrient utilization did not change. The stable d15Ntot values represent a balanced change in nitrate supply and export production and therefore indicate that productivity was elevated during deposition of the TOC-rich layers. Parallel changes in concentrations of indicator trace elements and TOC imply that changes in organic matter delivery influenced geochemical processes on the seafloor by controlling consumption of pore water oxygen. Cu, Ni, and Zn are enriched in the darker sediment as a consequence of greater organic matter delivery. Redox-sensitive metals vary due to loss (Mn and Ba) or enrichment (Mo) under reducing conditions created by TOC oxidation. Organic matter delivery impacts subsequent geochemical changes such as carbonate dissolution, sulfate reduction and the concentration of metals. Thus, export production is considered ultimately responsible for the generation of the color cycles.

Table A1 LA-ICP-MS zircon U-Pb data of Laoniushan granitoids

The NWW-striking Qinling Orogen formed in the Triassic by collision between the North China and Yangtze Cratons. Triassic granitoid intrusions, mostly middle- to high-K, calc-alkaline in composition, are widespread in this orogen, but contemporaneous intrusions are rare in the southern margin of the North China Craton, an area commonly considered as the hinterland belt of the orogen. In this paper, we report zircon U-Pb ages, elemental geochemistry, and Sr-Nd-Hf isotope data for the Laoniushan granitoid complex that was emplaced in the southern margin of the North China Craton. Zircon U-Pb dating shows that the complex was emplaced in the late Triassic (228±1 to 215±4 Ma), indicating that it is part of the post-collisional magmatism in the Qinling Orogen. The complex consists of, from early to late, biotite monzogranite, quartz diorite, quartz monzonite, and hornblende monzonite, which have a wide compositional range, e.g., SiO2=55.9-70.6 wt%, K2O+Na2O=6.6-10.2 wt%, and Mg# of 24 to 54. Rocks of the biotite monzogranite have high Al2O3(15.5-17.4 wt%), Sr(396-1398 ppm) and Ba(1284-3993 ppm) contents and La/Yb(mostly 14-30) and Sr/Y(mostly 40-97) ratios, but low Yb(mostly 1.3-1.6 ppm) and Y(mostly14-19 ppm) contents, features typical of adakite. The quartz monzonite, hornblende monzonite and quartz diorite have a shoshonitic affinity, with K2O up to 5.58 wt% and K2O/Na2O ratios averaging 1.4. The rocks are characterized by strong LREE/HREE fractionation in chondrite-normalized REE pattern, without obvious Eu anomalies, and show enrichment in large ion lithophile elements but depletion in high field strength elements (Nb, Ta, Ti). The biotite monzogranite (228 Ma) has initial 87Sr/86Sr ratios of 0.7061 to 0.7067, eNd(t) values of -9.2 to -12.6, and ?Hf(t) values of -9.0 to -15.1; whereas the shoshonitic granitoids (mainly 217-215 Ma) have similar initial 87Sr/86Sr ratios (0.7065 to 0.7075) but more radiogenic eNd(t) (-12.4 to -17.0) and eHf(t) (-14.1 to -17.0). The Sr-Nd-Hf isotope data indicate that the rocks were likely generated by partial melting of an ancient lower continental crust with heterogeneous compositions, as partly confirmed by the widespread presence of the early Paleoproterozoic inherited zircons. Mafic microgranular enclaves (MMEs), characterized by fine-grained igneous textures and an abundance of acicular apatites, are common in the Laoniushan complex. Compared with the host rocks, they have lower SiO2 (48.6-53.7 wt.%) and higher Mg# (51-56), Cr (122-393 ppm), and Ni (24-79 ppm), but equivalent Sr-Nd isotope compositions, indicating that the MMEs likely originated from an ancient enriched lithospheric mantle. The abundance of MMEs in the granitoid intrusions suggests that magma mixing plays an important role in the generation of the Laoniushan complex. Collectively, it is suggested that the Laoniushan complex was a product of post-collisional magmatism related to lithospheric extension following slab break-off. Formation of the adakitic and shoshonitic intrusions in the Laoniushan complex indicates that the Qinling Orogen had evolved into a post-collisional setting by about 230-210 Ma.

Geochemistry of ODP Site 202-1233 and river sediments

Bulk sediment chemistry from three Chilean continental margin Ocean Drilling Program sites constrains regional continental erosion over the past 30,000 years. Sediments from thirteen rivers that drain the (mostly igneous) Andes and the (mostly metamorphic) Coast Range, along with existing rock chemistry datasets, define terrestrial provenance for the continental margin sediments. Andean river sediments have high Mg/Al relative to Coast-Range river sediments. Near 36°S, marine sediments have high-Mg/Al (i.e. more Andean) sources during the last glacial period, and lower-Mg/Al (less Andean) sources during the Holocene. Near 41°S a Ti-rich source, likely from coast-range igneous intrusions, is prevalent during Holocene time, whereas high-Mg/Al Andean sources are more prevalent during the last glacial period. We infer that there is a dominant ice-sheet control of sediment sources. At 36°S, Andean-sourced sediment decreased as Andean mountain glaciers retreated after ~17.6 ka, coincident with local oceanic warming and southward retreat of the Patagonian Forest and, by inference, westerly winds. At 41°S Andean sediment dominance peaks and then rapidly declines at ~19 ka, coincident with local oceanic warming and the earliest deglacial sea-level rise. We hypothesize that this decreased flux of Andean material in the south is related to rapid retreat of the marine-based portion of the Patagonian Ice Sheet in response to global sea-level rise, as the resulting flooding of the southern portion of the Central Valley created a sink for Andean sediments in this region. Reversal of the decreasing deglacial Mg/Al trend at 41°S from 14.5 to 13.0 ka is consistent with a brief re-advance of the Patagonian ice sheet coincident with the Antarctic Cold Reversal.

Geochemistry of sediments in the central equatorial Pacific Ocean

In order to quantify changes in export production and carbonate dissolution over the past 1 Myr in the central equatorial Pacific Ocean we analyzed Ba, P, Al Ti, and Ca in 1106 samples from five piston cores gathered from 5°S to 4°N at 140°W. We focused on Ba/Ti, Al/Ti, and P/Ti ratios as export proxies and employed areally integrated time slice as well as time series strategies. Carbonate maxima from 0-560 kyr are characterized by 15-30% greater export than carbonate minima. The increases in export fall on glacial delta18O transitions rather than glacial maxima. From 560-800 kyr, overlapping with the mid-Pleistocene transition, there is a very large increase in total export yet no glacial-interglacial variability. The highest latitudes (5°S and 4°N) record minimal absolute export change from glacials to interglacials and yet record the most extreme minima in percent CaCO3, indicating that carbonate records there are dominated by dissolution, whereas near the equator they are more influenced by changes in export.

Stable isotope and Mg/Ca ratios of Paleogene benthic foraminifera in the western North Atlantic

Global cooling and the development of continental-scale Antarctic glaciation occurred in the late middle Eocene to early Oligocene (~38 to 28 million years ago), accompanied by deep-ocean reorganization attributed to gradual Antarctic Circumpolar Current (ACC) development. Our benthic foraminiferal stable isotope comparisons show that a large d13C offset developed between mid-depth (~600 meters) and deep (>1000 meters) western North Atlantic waters in the early Oligocene, indicating the development of intermediate-depth d13C and O2 minima closely linked in the modern ocean to northward incursion of Antarctic Intermediate Water. At the same time, the ocean's coldest waters became restricted to south of the ACC, probably forming a bottom-ocean layer, as in the modern ocean. We show that the modern four-layer ocean structure (surface, intermediate, deep, and bottom waters) developed during the early Oligocene as a consequence of the ACC.

Geochemistry of sands and sandstones in ODP Leg 126 sites

During Ocean Drilling Program Leg 126, six sites were cored in a young backarc rift basin and its flanks (rift onset 1.1-3.56 Ma) and in the forearc basin of the Izu-Bonin Arc. In the backarc area, strata are younger than about 4.5 Ma, whereas in the forearc, ages are about 0-31 Ma in sections punctuated by important Miocene unconformities. Bulk chemical analyses of volcaniclastic turbidite sands and sandstones, derived directly from the arc, were obtained from 271 atomic absorption analyses (major elements), 253 XRF analyses (trace elements) and 16 ICP-MS analyses (trace and rare-earth elements). Of the 271 samples, 78 come from the backarc area and the remainder from the forearc. The sands and sandstones reflect the igneous compositions of their sources. Most are formed of materials derived from subalkaline, low-K andesites, and dacites, although compositions range from basalt to rhyolite. Basic and acid andesites are predominant in Oligocene rocks; in contrast, Pliocene-Pleistocene sediments were derived from acid andesitic to rhyolitic sources. The oldest sandstones, estimated to have an age of about 31 Ma, were derived from an arc tholeiitic, not boninitic, source. The 26-31 Ma sandstones furthest to the north, at Sites 787 and 792, have higher relative concentrations of Ti, Zr, and Y than do those at southern Site 793. Data from younger samples indicate that, for more than 30 m.y., the average composition of volcaniclastic sediments and volcanism near Aoga Shima was more basic than to the south, near Sumisu Jima. Using the sandstones as igneous proxies, we conclude that magmas erupted along the arc have become more depleted in light-rare-earth elements (LREE) with time. There was a major change in rare-earth-element (REE) concentrations in the late Oligocene, from essentially flat patterns (normalized La/Yb about 1-1.5) to LREE-depleted patterns (normalized La/Yb about 0.5). At the same time, Zr/Y ratios decreased from about 2-4 to about 1.5-2.5. These changes may reflect a shift in provenance, or changes in the composition of the mantle wedge beneath the arc. In the backarc area, lithic clasts and glass shards of rift-facies basalt are present in sediments as old as 2.35-3.15 Ma. Two samples of mafic sand from the backarc basin have flat REE patterns (normalized La/Yb about 1.0), like some of the <1-Ma rift lavas and unlike pre-rift sand and sandstone samples. These possibly represent the local effects of sedimentary mixing of detritus from arc and backarc eruptions because no evidence from the arc itself exists to suggest a recent change in the REE content of magmas.

Geochemistry of oceanic flood basalts from the Caribbean plate

The thick oceanic crust of the Caribbean plate appears to be the tectonized remnant of an eastern Pacific oceanic plateau that has been inserted between North and South America. The emplacement of the plateau into its present position has resulted in the obduction and exposure of its margins, providing an opportunity to study the age relations, internal structure and compositional features of the plateau. We present the results of 40Ar-39Ar radiometric dating, major-, trace-element, and isotopic compositions of basalts from some of the exposed sections as well as drill core basalt samples from Leg 15 of the Deep Sea Drilling Project. Five widely spaced, margin sections yielded ages ranging from 91 to 88 Ma. Less well-constrained radiometric ages from the drill cores, combined with the biostratigraphic age of surrounding sediments indicate a minimum crystallization age of ~90 Ma in the Venezuelan Basin. The synchroneity of ages across the region is consistent with a flood basalt origin for the bulk of the Caribbean plateau i.e., large volume, rapidly erupted, regionally extensive volcanism.. The ages and compositions are also consistent with plate reconstructions that place the Caribbean plateau in the vicinity of the Galápagos hotspot at its inception. The trace-element and isotopic compositions of the ~90 Ma rocks indicate a depleted mantle and an enriched, plume-like mantle were involved in melting to varying degrees across the plateau. Within the same region, a volumetrically secondary, but widespread magmatic event occurred at 76 Ma, as is evident in Curacao, western Colombia, Haiti, and at DSDP Site 152/ODP Site 1001 near the Hess Escarpment. Limited trace-element data indicate that this phase of magmatism was generally more depleted than the first. We speculate that magmatism may have resulted from upwelling of mantle, still hot from the 90 Ma event, during lithospheric extension attending gravitational collapse of the plateau, andror tectonic emplacement of the plateau between North and South America. Still younger volcanics are found in the Dominican Republic (69 Ma) and the Quepos Peninsula of Costa Rica (63 Ma). The latter occurrence conceivably formed over the Galápagos hotspot and subsequently accreted to the western edge of the plateau during subduction of the Farallon plate.