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 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.

Seawater carbonate chemistry and zooxanthellate coral Cladocora caespitosa boron isotopic and elemental systematics during experiments, 2011

Boron isotopic and elemental systematics are used to define the vital effects for the temperate shallow water Mediterranean coral Cladocora caespitosa. The corals are from a range of seawater pH conditions (pHT ~ 7.6 to ~ 8.1) and environmental settings: (1) naturally living colonies harvested from normal pH waters offshore Levanto, (2) colonies transplanted nearby a subsea volcanic vent system, and (3) corals cultured in aquaria exposed to high (700 µatm) and near present day (400 µatm) pCO2 levels. B/Ca compositions measured using laser ablation inductively coupled mass spectrometry (LA-ICPMS) show that boron uptake by C. caespitosa cultured at different pCO2 levels is independent of ambient seawater pH being mainly controlled by temperature-dependent calcification. In contrast, the boron isotope compositions (delta11Bcarb) of the full suite of corals determined by positive thermal ionisation mass spectrometry (PTIMS) shows a clear trend of decreasing delta11Bcarb (from 26.7 to 22.2 %o) with decreasing seawater pH, reflecting the strong pH dependence of the boron isotope system. The delta11Bcarb compositions together with measurements of ambient seawater parameters enable calibration of the boron pH proxy for C. caespitosa, by using a new approach that defines the relationship between ambient seawater pH (pHsw) and the internally controlled pH at the site of calcification (pHbiol). C. caespitosa exhibits a linear relationship between pHsw and the shift in pH due to physiological processes (deltapH = pHbiol - pHsw) giving the regression deltapHClad = 4.80 - 0.52* pHsw for this species. We further apply this method ("deltapH-pHsw") to calibrate tropical species of Porites, Acropora, and Stylophora reported in the literature. The temperate and tropical species calibrations are all linearly correlated (r2 > 0.9) and the biological fractionation component (deltapH) between species varies within ~ 0.2 pH units. Our "deltapH-pHsw" approach provides a robust and accurate tool to reconstruct palaeoseawater pHsw for both temperate and tropical corals, further validating the boron fractionation factor (alphaB3-B4 = 1.0272) determined experimentally by Klochko et al. (2006) and the boron isotope pH proxy, both of which have been the foci of considerable debate.

Nd and Sr isotope compositions, REE concentrations and Al/Ca ratios of different phases of surface sediments in the South Pacific

The radiogenic isotope composition of neodymium (Nd) and strontium (Sr) are useful tools to investigate present and past oceanic circulation or input of terrigenous material. We present Nd and Sr isotope compositions extracted from different sedimentary phases, including early diagenetic Fe-Mn coatings, "unclean" foraminiferal shells, fossil fish teeth, and detritus of marine surface sediments (core-tops) covering the entire midlatitude South Pacific. Comparison of detrital Nd isotope compositions to deep water values from the same locations suggests that "boundary exchange" has little influence on the Nd isotope composition of western South Pacific seawater. Concentrations of Rare Earth Elements (REE) and Al/Ca ratios of "unclean" planktonic foraminifera suggest that this phase is a reliable recorder of seawater Nd isotope composition. The signatures obtained from fish teeth and "nondecarbonated" leachates of bulk sediment Fe-Mn oxyhydroxide coatings also agree with "unclean" foraminifera. Direct comparison of Nd isotope compositions extracted using these methods with seawater Nd isotope compositions is complicated by the low accumulation rates yielding radiocarbon ages of up to 24 kyr, thus mixing the signal of different ocean circulation modes. This suggests that different past seawater Nd isotope compositions have been integrated in authigenic sediments from regions with low sedimentation rates. Combined detrital Nd and Sr isotope signatures indicate a dominant role of the Westerly winds transporting lithogenic material from South New Zealand and Southeastern Australia to the open South Pacific. The proportion of this material decreases toward the east, where supply from the Andes increases and contributions from Antarctica cannot be ruled out.

Lead and strontium isotope composition, mass accumulation rates and rare earth elements of selected samples from DSDP Sites 92-597 to 92-601

Most of the Pb isotope data for the Leg 92 metalliferous sediments (carbonate-free fraction) form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts (MORB) toward the field for Mn nodules. These arrays are directed closely to the average values of Mn nodules, the composition of which reflects the Pb isotope composition of seawater (Reynolds and Dasch, 1971). Since the Leg 92 samples are almost devoid of continentally derived detritus, it can be inferred that the more radiogenic end-member is seawater. The less radiogenic end-member lies in the very middle of the MORB field, and hence can be considered to reflect the Pb isotope composition of typical ocean-ridge basalt. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb from the two different end-member sources. According to this model, eight samples from Sites 599 to 601 contain 50 to 100% basaltic Pb. Five of these samples have compositions that are identical within the uncertainty of the analyses. We use the average of these five values to define our unradiogenic end-member in the linear mixing model. The ratios used for this average are 206Pb/204Pb = 18.425 ± 0.010; 207Pb/204Pb = 15.495 ± 0.018; 208Pb/204Pb = 37.879 ± 0.068. These values should approximate the average Pb isotope composition of discharging hydrothermal solutions, and therefore also that of the basaltic crust, over the period of time represented by these samples ( 4 m.y., from 4 to 8 Ma). Sr isotope ratios show a significant range of values, from 0.7082 to 0.7091. The lower ratios are well outside the value of 0.70910 ± 6 for modern-day seawater (Burke et al., 1982). However, most values correspond very closely to the curve of 87Sr/86Sr versus age for seawater, with older samples having progressively lower 87Sr/86Sr ratios. The simplest explanation for this progressive reduction is that recrystallization of the abundant biogenic carbonate in the sediments released older seawater Sr which was incorporated into ferromanganiferous phases during diagenesis. Leg 92 metalliferous sediments have total rare earth element (REE) contents that range on a carbonate-free basis from 131 to 301 ppm, with a clustering between 167 and 222 ppm. The patterns have strong negative Ce anomalies. Samples from Sites 599 to 601 display a slight but distinct enrichment in the heavy REE relative to the light REE, whereas those from Sites 597 to 598 show almost no heavy REE enrichment. The former patterns (those for Sites 599 to 601) are interpreted as indicating moderate diagenetic alteration of metalliferous sediments originating at the EPR axis; the latter reflect more complete diagenetic modification.

Nd isotopic composition of fossil fish teeth and debris from ODP Legs 138, 165, and 202

Changes in circulation associated with the shoaling of the Isthmus of Panama and the Caribbean carbonate crash in the Miocene were investigated using Nd isotopes from fossil fish teeth and debris from two sites in the Caribbean Basin (Ocean Drilling Program Sites 998 and 999) and two sites in the eastern equatorial Pacific (Sites 846 and 1241). The total range for e-Nd values measured from 18 to 4.5 Ma in the Caribbean is -7.3 to 0. These values are higher than Atlantic water masses (~-11) and range up to values equivalent to contemporaneous Pacific water masses, confirming that flow into the Caribbean Basin was composed of a mixture of Pacific and Atlantic waters, with an upper limit of almost pure Pacific-sourced waters. Throughout the Caribbean record, particularly during the carbonate crash (10-12 Ma), low carbonate mass accumulation rates (MARs) correlate with more radiogenic e-Nd values, indicating increased flow of corrosive Pacific intermediate water into the Caribbean Basin during intervals of dissolution. This flow pattern agrees with results from general ocean circulation models designed to study the effect of the shoaling of the Central American Seaway. Low carbonate MARs and high e-Nd values also correlate with intervals of increased Northern Component Water production and, therefore, enhanced conveyor circulation, suggesting that the conveyor may respond to changes in circulation associated with shoaling of the Central American Seaway. Reduced Pacific throughflow related to shoaling of the seaway led to a gradual increase in carbonate preservation and more Atlantic-like e-Nd values following the carbonate crash.

Geochemistry of ODP Hole 183-1137A basalts

The Kerguelen Plateau and Broken Ridge in the southern Indian Ocean together represent one of the most voluminous large igneous provinces (LIPs) ever emplaced on Earth. A scientific objective of Ocean Drilling Program (ODP) Leg 183 was to constrain the post-melting magma evolution of Kerguelen Plateau magmas. In an effort to better understand this evolution, isotopic and trace element analysis of individual plagioclase crystals hosted within two Kerguelen Plateau basalts recovered from Elan Bank were undertaken. Previous whole-rock studies established that the two host basalts investigated in this study are samples of crustally contaminated (lower group) and relatively uncontaminated (upper group) basalt. Plagioclase phenocrysts from the uncontaminated basalt are dominantly normal zoned and exhibit a 87Sr/86SrI range of 0.704845-0.704985, which overlaps uncontaminated group whole-rock values previously reported. Plagioclase crystals from the contaminated basalt are dominantly reverse zoned and exhibit a 87Sr/86SrI range of 0.705510-0.705735, which all lie within contaminated group whole-rock values previously reported. There are no systematic within crystal core to rim variations in 87Sr/86SrI from either group, with the exception that contaminated group crystal rims have overall less radiogenic 87Sr/86SrI than other zones. These observations indicate that crustal assimilation occurred before the formation of Unit 10 plagioclase phenocrysts, which is supported by parent magma trace element abundance data inverted using carefully calculated partition coefficients. Trace element diffusion modeling indicates that the upper group basalt (Unit 4) experienced a more vigorous eruptive flux than the lower group basalt (Unit 10). We suggest that plagioclase phenocrysts in both the upper and lower group basalts originated from the shallowest section of what was likely a complex magma chamber system. We contend that the magmatic system contained regions of extensive plagioclase-dominated crystal mush. Crustal assimilation was not a significant ongoing process in this portion of the Elan Bank magmatic system. Both basalts exhibit compelling evidence for remobilization and partial resorption of crystalline debris (e.g., reverse zoned crystals, glomerocrysts). We suggest Unit 4 and 10 magmas ascended different sections of the Elan Bank magma system, where the Unit 10 magmas ascended a section of the magma system that penetrated a stranded fragment of continental crust.

Utility of thallium and geochemical analysis of Mariana arc sediments from ODP Hole 129-801A and 129-801B

We provide the first exploration of thallium (Tl) abundances and stable isotope compositions as potential tracers during arc lava genesis. We present a case study of lavas from the Central Island Province (CIP) of the Mariana arc, supplemented by representative sedimentary and altered oceanic crust (AOC) inputs from ODP Leg 129 Hole 801 outboard of the Mariana trench. Given the large Tl concentration contrast between the mantle and subduction inputs coupled with previously published distinctive Tl isotope signatures of sediment and AOC, the Tl isotope system has great potential to distinguish different inputs to arc lavas. Furthermore, CIP lavas have well-established inter island variability, providing excellent context for the examination of Tl as a new stable isotope tracer. In contrast to previous work (Nielsen et al., 2006b), we do not observe Tl enrichment or light epsilon 205Tl (where epsilon 205Tl is the deviation in parts per 10,000 of a sample 205Tl/203Tl ratio compared to NIST SRM 997 Tl standard) in the Jurassic-aged altered mafic ocean crust subducting outboard of the Marianas (epsilon 205Tl = - 4.4 to 0). The lack of a distinctive epsilon 205Tl signature may be related to secular changes in ocean chemistry. Sediments representative of the major lithologies from ODP Hole Leg 129 801 have 1-2 orders of magnitude of Tl enrichment compared to the CIP lavas, but do not record heavy signatures (epsilon 205Tl = - 3.0 to + 0.4), as previously found in similar sediment types (epsilon 205Tl > + 2.5; Rehkämper et al., 2004). We find a restricted range of epsilon 205Tl = - 1.8 to - 0.4 in CIP lavas, which overlaps with MORB. One lava from Guguan falls outside this range with epsilon 205Tl = + 1.2. Coupled Cs, Tl and Pb systematics of Guguan lavas suggests that this heavy Tl isotope composition may be due to preferential degassing of isotopically light Tl. In general, the low Tl concentrations and limited isotopic range in the CIP lavas is likely due to the unexpectedly narrow range of epsilon 205Tl found in Mariana subduction inputs, coupled with volcaniclastic, rather than pelagic sediment as the dominant source of Tl. Much work remains to better understand the controls on Tl processing through a subduction zone. For example, Tl could be retained in residual phengite, offering the potential exploration of Cs/Tl ratios as a slab thermometer. However, data for Tl partitioning in phengite (and other micas) is required before developing this application further. Establishing a database of Tl concentrations and stable isotopes in subduction zone lavas with different thermal parameters and sedimentary inputs is required for the future use of Tl as a subduction zone tracer.

Description, geochemistry, mineralogy and isotopes of sulfides from ODP Site 193-1189, PACMANUS field

Chemical and isotopic data for rare massive and semimassive sulfide samples cored at Site 1189 (Roman Ruins, PACMANUS) suggest their genetic relationship with sulfide chimneys at the seafloor. Sand collected from the hammer drill after commencement of Hole 1189B indicates that at least the lower section of the cased interval was occupied by material similar to the stockwork zone cored from 31 to ~100 meters below seafloor (mbsf) in this hole, but with increased content of barite, sphalerite, and lead-bearing minerals. Fractional crystallization of ascending hydrothermal fluid involving early precipitation of pyrite may explain vertical mineralogical and chemical zoning within the stockwork conduit and the high base and precious metal contents of Roman Ruins chimneys. A mineralized volcaniclastic unit cored deep in Hole 1189A possibly represents the lateral fringe of the conduit system. Lead isotope ratios in the sulfides differ slightly but significantly from those of fresh lavas from Pual Ridge, implying that at least some of the Pb within the Roman Ruins hydrothermal system derived from a deeper, more radiogenic source than the enclosing altered volcanic rocks.

Platinum-group, major, and trace element abundances in ODP Leg 183 basalts

Seventeen basalts from Ocean Drilling Program (ODP) Leg 183 to the Kerguelen Plateau (KP) were analyzed for the platinum-group elements (PGEs: Ir, Ru, Rh, Pt, and Pd), and 15 were analyzed for trace elements. Relative concentrations of the PGEs ranged from ~0.1 (Ir, Ru) to ~5 (Pt) times primitive mantle. These relatively high PGE abundances and fractionated patterns are not accounted for by the presence of sulfide minerals; there are only trace sulfides present in thin-section. Sulfur saturation models applied to the KP basalts suggest that the parental magmas may have never reached sulfide saturation, despite large degrees of partial melting (~30%) and fractional crystallization (~45%). First order approximations of the fractionation required to produce the KP basalts from an ~30% partial melt of a spinel peridotite were determined using the PELE program. The model was adapted to better fit the physical and chemical observations from the KP basalts, and requires an initial crystal fractionation stage of at least 30% olivine plus Cr-spinel (49:1), followed by magma replenishment and fractional crystallization (RFC) that included clinopyroxene, plagioclase, and titanomagnetite (15:9:1). The low Pd values ([Pd/Pt]_pm < 1.7) for these samples are not predicted by currently available Kd values. These Pd values are lowest in samples with relatively higher degrees of alteration as indicated by petrographic observations. Positive anomalies are a function of the behavior of the PGEs; they can be reproduced by Cr-spinel, and titanomagnetite crystallization, followed by titanomagnetite resorption during the final stages of crystallization. Our modeling shows that it is difficult to reproduce the PGE abundances by either depleted upper or even primitive mantle sources. Crustal contamination, while indicated at certain sites by the isotopic compositions of the basalts, appears to have had a minimal affect on the PGEs. The PGE abundances measured in the Kerguelen Plateau basalts are best modeled by melting a primitive mantle source to which was added up to 1% of outer core material, followed by fractional crystallization of the melt produced. This reproduces both the abundances and patterns of the PGEs in the Kerguelen Plateau basalts. An alternative model for outer core PGE abundances requires only 0.3% of outer core material to be mixed into the primitive mantle source. While our results are clearly model dependent, they indicate that an outer core component may be present in the Kerguelen plume source.