Isotopic composition and major and trace element concentrations of mafic rocks obtained from western Dronning Maud Land

On the basis of new bulk major and trace element (including REE) as well as Sm-Nd and Rb-Sr isotope data, used in conjunction with available geochronological data, a post-tectonic mafic igneous province and four groups of pre- to syntectonic amphibolite are distinguished in the polymetamorphic Maud Belt of western Dronning Maud Land, East Antarctica. Protoliths of the Group 1 amphibolites are interpreted as volcanic arc mafic intrusions with Archaean to Palaeoproterozoic Nd model ages and depletion in Nb and Ta. Isotopic and lithogeochemical characteristics of this earliest group of amphibolite indicate that the Maud Belt was once an active continental volcanic arc. The most likely position of this arc, for which a late Mesoproterozoic age (c. 1140 Ma) is indicated by available U-Pb single-zircon age data, was on the southeastern margin of the Kaapvaal-Grunehogna Craton. The protoliths of Group 2 amphibolites are attributed to the 1110 Ma Borgmassivet-Umkondo thermal event on the basis of comparable Nd model ages and trace element distributions. Group 3 amphibolite protoliths are characterized by mid-ocean ridge basalt-type REE patterns and low Th/Yb ratios, and they are related to Neoproterozoic extension. Group 4 amphibolite protoliths are distinguished by high Dy/Yb ratios and are attributed to a phase of syntectonic Pan-African magmatism as indicated by Rb-Sr isotope data.

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.

Nd isotope composition of fossil fish teeth of ODP Hole 119-738B

We report an optimized method for extracting neodymium (Nd) from fossil fish teeth with a single-stage column (125 µl stem volume; LN Resin, Eichrom Industries, Darien Illinois) for isotopic analysis by multi-collector inductively coupled mass spectrometry (MC-ICMPS). Three reference materials (basalt: BCR-2, BHVO-2; phosphate: fossil bone composite) and splits of fossil fish teeth samples previously processed with existing two-stage column methods were processed using the single-stage column method. 143Nd/144Nd values of reference materials agree within error with published values, and the values for fish teeth correspond with sample splits processed with two-stage columns. Precision to ± ~0.23 epsilon-Nd was achieved for 30 ng Nd samples of reference materials, and Nd isotope measurements of fossil fish tooth sample replicates as small as 7 ng Nd were reproducible within long term instrumental uncertainty. We demonstrate the utility of the new method with the first high resolution Nd isotope record spanning the ~40.0 Ma middle Eocene Climatic Optimum, which shows an excursion of 0.65 epsilon-Nd during the peak warming at the study site (Ocean Drilling Program Leg 119, Site 738; 30 kyr sample spacing from 40.3 to 39.6 Ma). LN Resin is already used in standard methods for separating Nd, and Nd isotopes are routinely measured by MC-ICPMS with high efficiency inlet systems. Our innovation is a single, small volume LN Resin column for Nd separation. The streamlined approach results in a 10X increase in sample throughput.