Evidence for mantle metasomatism: an oxygen and strontium isotope study of the Vulsinian District, Central Italy

This paper presents new O and Sr isotope data for lavas from the northern part of the Roman perpotassic province. The samples comprise the tephritic leucititic to leucite phonolitic lavas and the saturated lavas from the Vulsinian District, the olivine leucite melilitite of San Venanzo, and the kalsilite diopside melilitite of Cupaello. Previous oxygen isotope work on the lavas of the Vulsinian District suggested crustal contamination of “normal” mantle-derived magmas. The new data cover the ranges previously found. O and Sr isotope ratios of evolved lavas of the undersaturated suite indicate assimilation in variable amounts of up to ca. 10% of continental crustal material. The saturated lavas probably assimilated large amounts (up to ca. 50%) of crust. Lavas chemically identified as corresponding to little modified mantle-derived liquids are high in both⁸⁷Sr/⁸⁶Sr andδ¹⁸O: 0.7103−0.7107, +7.8 to +9.4 (Vulsini), 0.7104, +12.3 (San Venanzo) and 0.7112, +14.4 (Cupaello). These high values are interpreted to have been inherited from a metasomatized parental mantle. Hydrous fluids enriched in large-ion lithophile elements and high inδ¹⁸O and⁸⁷Sr/⁸⁶Sr are thought to have mixed with mantle of “normal”δ¹⁸O and⁸⁷Sr/⁸⁶Sr. The fluids probably origi dehydration of continent-derived sediments, which were subducted beneath a mantle wedge in the continent-continent collision of the Corsica-Sardinia block and the Adriatic (Italian) plate. This hypothesis is supported by Pb and Nd isotopic evidence and is probably valid for the entire Roman Province.     

Oxygen isotope evidence for submarine hydrothermal alteration of the Del Puerto ophiolite, California

The oxygen isotope compositions and metamorphic mineral assemblages of hydrothermally altered rocks from the Del Puerto ophiolite and overlying volcaniclastic sedimentary rocks at the base of the Great Valley sequence indicate that their alteration occurred in a submarine hydrothermal system. Whole rock δ¹⁸O compositions decrease progressively down section (with increasing metamorphic grade): +22.4‰ (SMOW) to +13.8 for zeolite-bearing volcaniclastic sedimentary rocks overlying the ophiolite; +19.6 to +11.6 for pumpellyite-bearing metavolcanic rocks in the upper part of the ophiolite's volcanic member; +12.3 to +8.1 for epidote-bearing metavolcanic rocks in the lower part of the volcanic member; +8.5 to +5.7 for greenschist facies rocks from the ophiolite's plutonic member; +7.6 to +5.8 for amphibolite facies or unmetamorphosed rocks from the plutonic member.

Modelling of fluid-rock interaction in the Del Puerto ophiolite indicates that the observed pattern of upward enrichment in whole rock δ¹⁸O can be best explained by isotopic exchange with discharging¹⁸O-shifted seawater at fluid/rock mass ratios near 2 and temperatures below 500°C.¹⁸O-depleted plutonic rocks necessarily produced during hydrothermal circulation were later removed as a result of tectonism. Submarine weathering and later burial metamorphism at the base of the Great Valley sequence cannot by itself have produced the zonation of hydrothermal minerals and the corresponding variations in oxygen isotope compositions. The pervasive zeolite and prehnite-pumpellyite facies mineral assemblages found in the Del Puerto ophiolite may reflect its origin near an island arc rather than deep ocean spreading center.     

Oxygen isotope evidence for the origin of enriched mantle beneath the mid-Atlantic ridge

Geochemical variations in mid-ocean ridge basalts have been attributed to differing proportions of compositionally distinct mantle components in their sources, some of which may be recycled crust. Oxygen isotopes are strongly fractionated by near-surface interactions of rocks with the hydrosphere, and thus provide a tracer of near-surface materials that have been recycled into the mantle. We present here oxygen isotope analyses of basaltic glasses from the mid-Atlantic ridge south of and across the Azores platform. Variations in δ¹⁸O in these samples are subtle (range of 0.47‰) and may partly reflect shallow fractional crystallization; we present a method to correct for these effects. Relatively high fractionation-corrected δ¹⁸O in these samples is associated with geochemical indices of enrichment, including high La/Sm, Ce/Pb, and ⁸⁷Sr/⁸⁶Sr and low ¹⁴³Nd/¹⁴⁴Nd. Our results suggest two first-order conclusions about these enriched materials: (1) they are derived (directly or indirectly) from recycled upper oceanic crustal rocks and/or sediments; and (2) these materials are present in the north Atlantic MORB sources in abundances of less than 10% (average 2–5%). Modeling of variations of δ¹⁸O with other geochemical variables further indicates that the enriched component is not derived from incorporation of sediment or bulk altered oceanic crust, from metasomatism of the mantle by hydrous or carbonate-rich fluids, or from partial melting of subducted sediment. Instead, the data appear to require a model in which the enriched component is depleted mantle that has been metasomatized by small-degree partial melts of subducted, dehydrated, altered oceanic crust. The age of this partial melting is broadly constrained to 250 Ma. Reconstructed plate motions suggest that the enriched component in the north Atlantic mantle may have originated by subduction along the western margin of Pangea.     

Open-system degassing of sulfur from Krakatau 1883 magma

We present the first sulfur and oxygen isotopic data for tephra from the catastrophic 1883 eruption of Krakatau. Sulfur isotopic ratios in unaltered Krakatau tephra erupted August 26–27, 1883 are markedly enriched in ³⁴S relative to mantle sulfur. High δ³⁴S values of +6.3 to +16.4‰ can best be explained by open-system or multi-stage degassing of SO₂ from the oxidized rhyodacitic and gray dacitic magmas with ³⁴S enrichment of SO²⁻₄ remaining in the melt. Lower whole-rock δ³⁴S values of +2.6‰ and +4.0‰ in two oxidized gray dacitic samples indicate more primitive subarc mantle sulfur in the 1883 magma chamber. Initial δ³⁴S of the rhyodacitic magma was probably in the +1.5‰ to +4.0‰ range and similar to δ³⁴S values measured in arc volcanic rocks from the Mariana Arc.     

An oxygen isotopic profile through the upper kilometer of the oceanic crust, DSDP Hole 504B

DSDP Hole 504B is the deepest basement hole in the oceanic crust, penetrating through a 571.5 m pillow section, a 209 m lithologic transition zone, and 295 m into a sheeted dike complex. An oxygen isotopic profile through the upper crust at Site 504 is similar to that in many ophiolite complexes, where the extrusive section is enriched in¹⁸O relative to unaltered basalts, and the dike section is variably depleted and enriched. Basalts in the pillow section at Site 504 haveδ¹⁸O values generally ranging from +6.1 to +8.5‰ SMOW(mean= +7.0‰), although minor zeolite-rich samples range up to 12.7‰. Rocks depleted in¹⁸O appear abruptly at 624 m sub-basement in the lithologic transition from 100% pillows to 100% dikes, coinciding with the appearance of greenschist facies minerals in the rocks. Whole-rock values range to as low as +3.6‰, but the mean values for the lithologic transition zone and dike section are +5.8 and +5.4‰, respectively.

Oxygen and carbon isotopic data for secondary vein minerals combined with the whole rock data provide evidence for the former presence of two distinct circulation systems separated by a relatively sharp boundary at the top of the lithologic transition zone. The pillow section reacted with seawater at low temperatures (near 0°C up to a maximum of around 150°C) and relatively high water/rock mass ratios (10–100); water/rock ratios were greater and conditions were more oxidizing during submarine weathering of the uppermost 320 m than deeper in the pillow section. The transition zone and dikes were altered at much higher temperatures (up to about 350°C) and generally low water/rock mass ratios ( 1), and hydrothermal fluids probably contained mantle-derived CO₂. Mixing of axial hydrothermal fluids upwelling through the dike section with cooler seawater circulating in the overlying pillow section resulted in a steep temperature gradient ( 2.5°C/m) across a 70 m interval at the top of the lithologic transition zone. Progressive reaction during axial hydrothermal metamorphism and later off-axis alteration led to the formation of albite- and Ca-zeolite-rich alteration halos around fractures. This enhanced the effects of cooling and¹⁸O enrichment of fluids, resulting in local increases inδ¹⁸O of rocks which had been previously depleted in¹⁸O during prior axial metamorphism.     

Correlated chemical and isotopic zoning in carbonates in the martian meteorite ALH84001

The meteorite ALH84001, a sample of the ancient martian crust, contains small quantities (1%) of strongly chemically zoned carbonate. High spatial resolution (10 μm) ion microprobe analyses show that the chemical zoning is strongly correlated with variations in oxygen isotope ratios. Early formed Ca,Fe-rich cores have δ¹⁸O 7‰ increasing to 22‰ SMOW in the more Mg-rich outer cores and magnesite rims. Isolated areas of ankerite appear to be isotopically lighter with δ¹⁸O 1‰. The large range in δ¹⁸O requires a significant range in either fluid isotopic composition, or temperature, or both, in the course of the deposition sequence. Our data are inconsistent with formation of the zoned carbonates by closed system Rayleigh fractionation. There is no unique interpretation of the oxygen data, but the recent observation of existence of Δ¹⁷O excesses in the carbonate appears to rule out models which involve high temperature isotopic exchange with silicate. Comparison with terrestrial analogues suggests that ALH84001 carbonates formed in a hydrothermal system with T<400°C, and which, at least in the early stages of formation, may have involved water with δ¹⁸O < 0‰ SMOW. The later stages of deposition probably occurred at temperatures below 150°C, a conclusion which does not preclude the co-existence of thermophilic bacteria; temperatures during earlier stages of deposition are less likely to have been hospitable to bacteria.     

Isotopic characteristics of precipitation in Slovenia and Croatia: Comparison of continental and maritime stations

The stable isotopic composition of hydrogen and oxygen (δ²H and δ¹⁸O) and tritium activity (³H) were monitored in monthly precipitation at two continental stations (Ljubljana, Zagreb) and six stations along the eastern Adriatic coasts of Slovenia and Croatia in the period 2001–2003. Mean air temperatures and amount of precipitation were also recorded.

Distinct differences in both meteorological and isotopic data between the continental and maritime stations were observed. Seasonal variations in δ¹⁸O are smaller at the maritime stations than at the continental ones due to smaller seasonal temperature variations. A good correlation between δ¹⁸O and δ²H was obtained for each station, and the local meteoric water lines are close to the Global Meteoric Water Line, with a decreasing trend of slope for the south-Adriatic stations. Good correlations between δ¹⁸O in monthly precipitation and mean monthly air temperature were observed at all stations. The slope of δ¹⁸O vs. T varied between 0.37‰ °C⁻¹ and 0.15‰ °C⁻¹. Mean ³H activity and seasonal variation of ³H activity are smaller at maritime stations than at continental ones. Additionally, ³H activity decreases in the NW–SE direction of the Adriatic coast.

The study of spatial variations over this relatively small area rich in geographical and climatic diversities showed the complexity of the isotopic composition of precipitation and the isotopic data obtained for eight stations, most of them in the karstic area along the Adriatic coast, and gave valuable information for regional hydrological investigations and modelling of isotope variability over the Mediterranean basin.     

Lithium isotope fractionation in the southern Cascadia subduction zone

We present lithium (Li) abundances and isotope compositions for a suite of anhydrous olivine tholeiites (HAOTs) and hydrous basalt-andesitic (BA) lavas from the Mt. Shasta and Medicine Lake regions, California. The values of δ⁷Li vary from + 0.9‰ to + 6.4‰ and correlate inversely with distance from the trench. These data are consistent with continuous isotope fractionation of Li during dehydration of the subducted oceanic lithosphere, an interpretation corroborated by uniformly high pre-eruptive H₂O contents in basaltic andesites accompanied by high Li, Rb, Sr, Ba and Pb abundances. The subduction-derived component that was added to these hydrous magmas is shown to be very similar beneath both Mt. Shasta and Medicine Lake volcanoes despite characteristically distinct Li isotope compositions in the magmas themselves. More evolved andesites and dacites from Mt. Shasta have δ⁷Li from + 2.8 to + 6.9‰ which is identical with the range obtained for HAOTs and BA lavas from Mt. Shasta. Therefore, Li isotopes do not provide evidence for any other crustal component admixed to Mt. Shasta andesites or dacites during magmatic differentiation and magma mixing in the crust.     

Preliminary stratigraphic and structural architecture of Bhutan: Implications for the along strike architecture of the Himalayan system

High-precision in-situ ion microprobe (SIMS) oxygen isotope analysis of zircons from two diorite intrusions associated with the late Caledonian Lochnagar pluton in Scotland has revealed large differences in the degree of heterogeneity in zircon δ¹⁸O between the diorites. Zircon crystals from the Cul nan Gad diorite (CnG) show a unimodal distribution of oxygen isotope values (δ¹⁸O = 6.0 ± 0.6‰ (2σ)) and no or only minor grain-scale variation. Those from the Allt Darrarie diorite (AD1) show a large range in δ¹⁸O and an apparent bimodal distribution with modes of 6.6 ± 0.4‰ and 7.3 ± 0.4‰. Variations of up to 1.2‰ occur between and within grains; both an increase and decrease in δ¹⁸O with zircon growth has been observed. The δ¹⁸O composition of growing zircon can only change if open-system processes affect the magma composition, i.e. if material of contrasting δ¹⁸O composition is added to the magma. The variability in AD1 is interpreted to represent a cryptic record of magma mixing. A ‘deep crustal hot zone’ is a likely site for generation of the dioritic magmas which developed by mixing of residual melts and crustal partial melts or by melting of mafic lower crustal rocks. The overall small number of zircons with mantle-like δ¹⁸O values (5.3 ± 0.6‰ (2σ)) in the Lochnagar diorites is largely the product of crustal differentiation rather than crustal growth.

The δ¹⁸O of quartz from the CnG and AD1 diorites shows only minor variation (CnG: 10.9 ± 0.5‰ (2σ), AD1: 11.7 ± 0.6‰ (2σ)) within single populations, with no evidence of mixing. Quartz–zircon isotopic disequilibrium is consistent with later crystallisation of quartz from late magmatic fluids, and in case of the AD1 diorite after the inferred magma mixing from a homogenised, higher δ¹⁸O melt.

High-precision SIMS oxygen isotope analysis of zircon provides a new approach to identifying and resolving previously undetected early-stage magma mixing and constraining the compositions and origins of the component magmas. A combination of zircon, quartz and whole-rock data has proven to be a powerful tool in reconstructing the petrogenetic evolution of diorite from early crystallisation to late alteration.     

Trace element transport rates in subduction zones: evidence from Th, Sr and Pb isotope data for Tonga-Kermadec arc lavas

Trace element and Th, Sr and Pb isotope data for young lavas from the Tonga-Kermadec arc in the southwest Pacific suggest that geochemical variations in the lavas along the arc are linked to differences in the material being subducted beneath the arc. Lavas from the southern (Kermadec) segment of the arc have relatively radiogenic Pb isotope compositions, which reflects a contribution from subducted sediment. In contrast, much of the Pb in Tonga lavas is derived from the altered oceanic crust in the subducting Pacific Plate, and lavas from the northernmost Tonga islands of Tafahi and Niuatoputapu contain Pb and Sr derived from the subducted part of the Louisville Seamount Chain. The origin of the Pb in the lavas from these two islands can thus be traced to a point on the subducting slab, and this observation is used to estimate the rate at which trace elements are transported beneath the arc. Our calculations suggest that fluid-soluble elements such as U, Sr and Pb are transported from the subducted slab, across the mantle wedge and back to the surface in lavas over a period of approximately 2–3 Ma, and that magmas are erupted at the surface less than 350 ka after the melts are generated in the mantle wedge.     

Link between SSZ ophiolite formation, emplacement and arc inception, Northland, New Zealand: U–Pb SHRIMP constraints; Cenozoic SW Pacific tectonic implications

New U–Pb age-data from zircons separated from a Northland ophiolite gabbro yield a mean ²⁰⁶Pb/²³⁸U age of 31.6 ± 0.2 Ma, providing support for a recently determined 28.3 ± 0.2 Ma SHRIMP age of an associated plagiogranite and  29–26 Ma ⁴⁰Ar/³⁹Ar ages (n = 9) of basalts of the ophiolite. Elsewhere, Miocene arc-related calc-alkaline andesite dikes which intrude the ophiolitic rocks contain zircons which yield mean ²⁰⁶Pb/²³⁸U ages of 20.1 ± 0.2 and 19.8 ± 0.2 Ma. The ophiolite gabbro and the andesites both contain rare inherited zircons ranging from 122–104 Ma. The Early Cretaceous zircons in the arc andesites are interpreted as xenocrysts from the Mt. Camel basement terrane through which magmas of the Northland Miocene arc lavas erupted. The inherited zircons in the ophiolite gabbros suggest that a small fraction of this basement was introduced into the suboceanic mantle by subduction and mixed with mantle melts during ophiolite formation.

We postulate that the tholeiitic suite of the ophiolite represents the crustal segment of SSZ lithosphere (SSZL) generated in the southern South Fiji Basin (SFB) at a northeast-dipping subduction zone that was initiated at about 35 Ma. The subduction zone nucleated along a pre-existing transform boundary separating circa 45–20 Ma oceanic lithosphere to the north and west of the Northland Peninsula from nascent back arc basin lithosphere of the SFB. Construction of the SSZL propagated southward along the transform boundary as the SFB continued to unzip to the southeast. After subduction of a large portion of oceanic lithosphere by about 26 Ma and collision of the SSZL with New Zealand, compression between the Australian Plate and the Pacific Plate was taken up along a new southwest-dipping subduction zone behind the SSZL. Renewed volcanism began in the oceanic forearc at 25 Ma producing boninitic-like, SSZ and within-plate alkalic and calc-alkaline rocks. Rocks of these types temporally overlap ophiolite emplacement and subsequent Miocene continental arc construction.     

Geochemistry of late Cenozoic lavas on Kunashir Island, Kurile Arc

Middle Miocene to Quaternary lavas on Kunashir Island in the southern zone of the Kurile Arc were examined for major, trace, and Sr–Nd–Pb isotope compositions. The lavas range from basalt through to rhyolite and the mafic lavas show typical oceanic island arc signatures without significant crustal or sub-continental lithosphere contamination. The lavas exhibit across-arc variation, with increasingly greater fluid-immobile incompatible element contents from the volcanic front to the rear-arc; this pattern, however, does not apply to some other incompatible elements such as B, Sb, and halogens. All Sr–Nd–Pb isotope compositions reflect a depleted source with Indian Ocean mantle domain characteristics. The Nd and Pb isotope ratios are radiogenic in the volcanic front, whereas Sr isotope ratios are less radiogenic. These Nd isotope ratios covary with incompatible element ratios such as Th/Nd and Nb/Zr, indicating involvement of a slab-derived sediment component by addition of melt or supercritical fluid capable of mobilizing these high field-strength elements and rare earth elements from the slab. Fluid mobile elements, such as Ba, are also elevated in all basalt suites, suggesting involvement of slab fluid derived from altered oceanic crust. The Kurile Arc lavas are thus affected both by slab sediment and altered basaltic crust components. This magma plumbing system has been continuously active from the Middle Miocene to the present.     

A comparison of the toluene distillation and vacuum/heat methods for extracting soil water for stable isotopic analysis

Hanford Loam, from Richland, Washington, was used as a test soil to determine the precision, accuracy and nature of two methods to extract soil water for stable isotopic analysis: azeotropic distillation using toluene, and simple heating under vacuum. The soil was oven dried, rehydrated with water of known stable isotopic compositions, and the introduced water was then extracted.

Compared with the introduced water, initial aliquots of evolved water taken during a toluene extraction were as much as 30 ‰ more depleted in D and 2.7 ‰ more depleted in ¹⁸O, whereas final aliquots were as much as 40 ‰ more enriched in D and 14.3 ‰ more enriched in ¹⁸O. Initial aliquots collected during the vacuum/heat extraction were as much as 64 ‰ more depleted in D and 8.4 ‰ more depleted in ¹⁸O than was the introduced water, whereas the final aliquots were as much as 139 ‰ more enriched in D, and 20.8 ‰ more enriched in ¹⁸O. Neither method appears quantitative; however, the difference in stable isotopic composition between the first and last aliquots of water extracted by the toluene method is less than that from the vacuum/heat method. This is attributed to the smaller fractionation factors involved with the higher average temperatures of distillation of the toluene. The average stable isotopic compositions of the extracted water varied from that of the introduced water by up to 1.4 ‰ in δD and 4.2 ‰ in δ¹⁸O with the toluene method, and by 11.0 ‰ in δD and 1.8 ‰ in δ¹⁸O for the vacuum/heat method.

The lack of accuracy of the extraction methods is thought to be due to isotopic fractionation associated with water being weakly bound (not released below 110°C) in the soil. The isotopic effect of this heat-labile water is larger at low water contents (3.6 and 5.2% water by weight) as the water bound in the soil is a commensurately larger fraction of the total. With larger soilwater contents the small volume of water bound with an associated fractionation is not enough to affect the remaining unbound introduced soil water. Pretreatment of the soil to equilibrate the heat-labile water to the test water produced good results for the toluene distillation but not the vacuum/heat extraction method.

Vapors collected over the soils also show stable isotopic variations related to soilwater content. These vapors also appear to be in closer equilibrium with the free water, as extracted by the toluene method, than with the originally introduced water; thus, the soil vapors do not appear to be isotopically affected by the heat-labile water.

The toluene method appears to be better for extracting soil water for stable isotopic analysis because it allows more precise temperature control and excludes the extraction of heat-labile water which is isotopically fractionated. The bound nature of this heat-labile water limits association with the hydrologically active soil water; thus, the exclusion of this water from the soil water attained by toluene distillation may be advantageous. However, the azeotropic nature of toluene distillation affords no benefit and the extraction procedure must continue to completion.     

Magmatic response to early aseismic ridge subduction: the Ecuadorian margin case (South America)

A geochemical and isotopic study of lavas from Pichincha, Antisana and Sumaco volcanoes in the Northern Volcanic Zone (NVZ) in Ecuador shows their magma genesis to be strongly influenced by slab melts. Pichincha lavas (in fore arc position) display all the characteristics of adakites (or slab melts) and were found in association with magnesian andesites. In the main arc, adakite-like lavas from Antisana volcano could be produced by the destabilization of pargasite in a garnet-rich mantle. In the back arc, high-niobium basalts found at Sumaco volcano could be produced in a phlogopite-rich mantle. The strikingly homogeneous isotopic signatures of all the lavas suggest that continental crust assimilation is limited and confirm that magmas from the three volcanic centers are closely related. The following magma genesis model is proposed in the NVZ in Ecuador: in fore arc position beneath Pichincha volcano, oceanic crust is able to melt and produces adakites. En route to the surface, part of these magmas metasomatize the mantle wedge inducing the crystallization of pargasite, phlogopite and garnet. In counterpart, they are enriched in magnesium and are placed at the surface as magnesian andesites. Dragged down by convection, the modified mantle undergoes a first partial melting event by the destabilization of pargasite and produces the adakite-like lavas from Antisana volcano. Lastly, dragged down deeper beneath the Sumaco volcano, the mantle melts a second time by the destabilization of phlogopite and produces high-niobium basalts. The obvious variation in spatial distribution (and geochemical characteristics) of the volcanism in the NVZ between Colombia and Ecuador clearly indicates that the subduction of the Carnegie Ridge beneath the Ecuadorian margin strongly influences the subduction-related volcanism. It is proposed that the flattening of the subducted slab induced by the recent subduction (<5 Ma?) of the Carnegie Ridge has permitted the progressive warming of the oceanic crust and its partial melting since ca. 1.5 Ma. Since then, the production of adakites in fore arc position has deeply transformed the magma genesis in the overall arc changing from ‘typical’ calc-alkaline magmatism induced by hydrous fluid metasomatism, to the space- and time-associated lithology adakite/high-Mg andesite/adakite-like andesite/high-Nb basalts characteristic of slab melt metasomatism.     

Silicic arc volcanism in Central Luzon, the Philippines: Characterization of its space, time and geochemical relationship

Abstract   The silicic volcanic rocks in Central Luzon show a temporal and spatial relationship with its geochemistry. Volcanic centers dated to approximately 5 Ma are silicic in geochemical composition whereas those between <5–1 Ma expose basaltic to andesitic rocks. Volcanic centers dated <1 Ma are characterized by a wide range of geochemistry encompassing basaltic through andesitic to dacitic signatures. Aside from changes in geochemistry through time, the areas (i.e. fore-arc to back-arc region) where the volcanic centers are formed also vary. The shift in the location of the volcanic centers in Central Luzon is attributed to changes in the dip of subduction of the South China Sea crust along the Manila Trench. Flat subduction resulted from the subduction of the Scarborough Seamount Chain, an oceanic bathymetric high along the Manila Trench west of northern Luzon. However, collision of Luzon with Taiwan in the north and Palawan in the south resulted in steepening of the subduction angle. The silicic volcanic centers in the forearc (Ce/Yb = 20–140) and back-arc (Ce/Yb = 20–60) regions are generally characterized by higher Ce/Yb compared to the basaltic-andesitic volcanic rocks in the main volcanic arc (Ce/Yb = 20) and back-arc (Ce/Yb = 20–30) regions. This across-arc geochemical variation highlights the contributions from the slab, mantle and crust coupled with the effects of geochemical processes that include partial melting, fractionation, magma mixing and mantle–melt interaction.     

Large scale isotopic Sr, Nd and O isotopic anatomy of altered oceanic crust: DSDP/ODP sites417/418

Large-scale compositional domains at DSDP/ODP drill sites 417A, 417D and 418A were analyzed for O, Sr and Nd isotope ratios, and REE, U, K, Rb and Sr abundances, to constrain the bulk chemical composition of the oceanic crust that is recycled at subduction zones. The combination of the three sites gives the composition of the upper oceanic crust in this region over a distance of about 8 km. The δ¹⁸O_SMOW and⁸⁷Sr/⁸⁶Sr_meas of compositional domains 10–100 m in size correlate well, with a range of 7.7–19.2 and 0.70364–0.70744, and mean of 9.96 and 0.70475, respectively. The Rb inventory of the upper crust increases by about an order of magnitude, while Sr contents remain constant. U abundances increase moderately under oxidizing alteration conditions and nearly triple in the commonly reducing alteration environments of the upper oceanic crust. REEs are influenced by alteration only to a small extent, and recycled oceanic crust is similar to MORB with respect to¹⁴³Nd/¹⁴⁴Nd. Even though the average composition of the upper oceanic crust is well defined, the large scale composition varies widely. Highly altered compositional domains may not have a large impact on the average composition of the oceanic crust, but they may preferentially contribute to fluids or partial melts derived from the crust by prograde metamorphic reactions.     

Glacial–interglacial changes in Subantarctic sea surface temperature and δO-water using foraminiferal Mg

Laboratory culturing experiments with living Globigerina bulloides indicate that Mg/Ca is primarily a function of seawater temperature and suggest that Mg/Ca of fossil specimens is an effective paleotemperature proxy. Using culturing results and a core-top Neogloboquadrina pachyderma calibration, we have estimated glacial–interglacial changes in sea surface temperature (SST) using planktonic Mg/Ca records from core RC11-120 in the Subantarctic Indian Ocean (43°S, 80°E) and core E11-2 in the Subantarctic Pacific Ocean (56°S, 115°W). Our results suggest that glacial SST was about 4°C cooler in the Subantarctic Indian Ocean and 2.5°C cooler in the Subantarctic Pacific. Comparison of SST and planktonic δ¹⁸O records indicates that changes in SST lead changes in δ¹⁸O by on average 1–3 kyr. The glacial–interglacial temperature change indicated by the Subantarctic Mg/Ca records suggests that temperature accounts for 40–60% of the foraminiferal δ¹⁸O change. We have used the Mg/Ca-based SST estimates and δ¹⁸O determinations to generate site-specific seawater δ¹⁸O records, which suggest that seawater δ¹⁸O was on average 1‰ more positive during glacial episodes compared with interglacial episodes.     

Atmospheric noble gases in volcanic glasses from the southern Lau Basin: origin from the subducting slab?

Noble gas concentrations and isotopic compositions have been determined for four submarine volcanic glasses from the Valu Fa Ridge (VFR) in the southern Lau Basin. The samples are the least differentiated ones from this area, and they display enrichments in fluid-mobile elements similar to the nearby island arc. ³He/⁴He ratios are slightly below average MORB (6.8–7.8 times atmospheric), whereas Ne, Ar, Kr, and Xe have isotopic compositions very similar to air. Together with previously published data from the Valu Fa Ridge and other spreading segments in the Lau Basin, our data show a systematic latitudinal variation of increasing Ne, Ar, Kr, and Xe abundances from north to south as well as Ne and Ar isotopic compositions changing from MORB-like to atmosphere-like in the same direction. Moreover, isotopic compositions and noble gas abundances of the lavas correlate strongly with Ba/Nb ratios and H₂O concentrations. Based on these observations and mass balance arguments, we propose that the atmospheric noble gases come from the subducting oceanic crust and are not due to shallow contamination with air dissolved in seawater or assimilation of old crust. Our data suggest that the noble gases released from the subducting slab are atmospheric and thus contain little or no solar He and Ne. In addition to the fact that ratios of He to heavy noble gases are small in aged ocean crust, He has possibly fractionated from the other noble gases due to its higher diffusivity, and thus He transport from the subducting slab into the mantle wedge is probably insignificant. We propose that the ³He/⁴He ratios lower than MORB observed in the VFR lavas result from radiogenic ingrowth of He in a highly depleted, and hence degassed, mantle wedge after the enrichment of U and Th released from the downgoing slab.     

Hydrochemical and stable isotope evidence for the extent and nature of the effective Chalk aquifer of north Norfolk, UK

In eastern England the Chalk aquifer is covered by extensive Pleistocene deposits which influence the hydraulic conditions and hydrochemical nature of the underlying aquifer. In this study, the results of geophysical borehole logging of groundwater temperature and electrical conductivity and depth sampling for major ion concentrations and stable isotope compositions (δ¹⁸O and δ²H) are interpreted to reveal the extent and nature of the effective Chalk aquifer of north Norfolk. It is found that the Chalk aquifer can be divided into an upper region of fresh groundwater, with a Cl concentration of typically less than 100 mg l⁻¹, and a lower region of increasingly saline water. The transition between the two regions is approximately 50 m below sea-level, and results in an effective aquifer thickness of 50–60 m in the west of the area, but less than 25 m where the Eocene London Clay boundary is met in the east of the area. Hydrochemical variations in the effective aquifer are related to different hydraulic conditions developed in the Chalk. Where the Chalk is confined by low-permeability Chalky Boulder Clay, isotopically depleted groundwater (δ¹⁸O less than −7.5‰) is present, in contrast to those areas of unconfined Chalk where glacial deposits are thin or absent (δ¹⁸O about −7.0‰). The isotopically depleted groundwater is evidence for groundwater recharge during the late Pleistocene under conditions when mean surface air temperatures are estimated to have been 4.5°C cooler than at the present day, and suggests long groundwater residence times in the confined aquifer. Elevated molar Mg:Ca ratios of more than 0.2 resulting from progressive rock-water interaction in the confined aquifer also indicate long residence times. A conceptual hydrochemical model for the present situation proposes that isotopically depleted groundwater, occupying areas where confined groundwater dates from the late Pleistocene, is being slowly modified by both diffusion and downward infiltration of modem meteoric water and diffusive mixing from below with an old saline water body.     

Stable isotope values of Costa Rican surface waters

Stable isotope data of surface waters from the humid tropics in general, and Costa Rica in particular, are scarce. To improve our understanding of the spatial distribution of stable isotopes in surface waters, we measured δ¹⁸O and δD in river and lake (n=63) and precipitation (n=3) samples from Costa Rica. We also present data from the IAEA/WMO isotopes in precipitation network as context for our study. Surface water isotope values do not strongly correlate with elevation, stream head elevation, stream length, distance from Caribbean Sea, or estimated mean annual precipitation for the country as a whole. However, the data show distinct regional trends. The δ¹⁸O and δD values downwind of mountain ranges are inversely related to the altitude of the ranges the air masses traverse. In the lee of the high Talamanca Range, δ¹⁸O values are 6–8‰ lower, while in the lee of the lower Tilarán Range δ¹⁸O values are 2–3‰ lower than upwind sites along the Caribbean Slope. An altitude effect of −1.4‰ δ¹⁸O/km is present on the Pacific slope of southern Costa Rica, equivalent to a temperature effect of −0.3‰/°C. The Nicoya and Osa Peninsulas have higher values than upwind sites, suggesting input of Pacific-sourced moisture, evaporative enrichment, or decreased condensation temperatures. Elevated and increasing d-excess values inland along the Nicaragua Trough suggest a recycled component may be an important contributor to the water budget. These data provide preliminary stable isotope information for Costa Rica, and will benefit paleoclimatic research in the region. More detailed studies would be beneficial to our understanding of the controls on stable isotope composition of tropical waters.