The Oxidation State of Sulfur in Lunar Apatite

Lunar apatites contain hundreds to thousands of parts per million of sulfur. This is puzzling because lunar basalts are thought to form in low oxygen fugacity (f(sub O2)) conditions where sulfur can only exist in its reduced form (S2()), a substitution not previously observed in natural apatite. We present measurements of the oxidation state of S in lunar apatites and associated mesostasis glass that show that lunar apatites and glass contain dominantly S2(), whereas natural apatites from Earth are only known to contain S6+. It is likely that many terrestrial and martian igneous rocks contain apatites with mixed sulfur oxidation states. The S6(+)/S2() ratios of such apatites could be used to quantify the f(sub O2) values at which they crystallized, given information on the portioning of S6(+) and S2() between apatite and melt and on the S6(+)/S2() ratios of melts as functions of f(sub O2) and melt composition. Such a well-calibrated oxybarometer based on this the oxidation state of S in apatite would have wide application

Variations in Fe\u3csup\u3e3+\u3c/sup\u3e/∑Fe of Mariana Arc Basalts and Mantle Wedge \u3cem\u3ef\u3c/em\u3eO\u3csub\u3e2\u3c/sub\u3e

Arc basalts are more oxidized than mid-ocean ridge basalts, but it is unclear whether this difference is due to differentiation processes in the Earth’s crust or to a fundamental difference in the oxygen fugacity of their mantle sources. Distinguishing between these two hypotheses is important for understanding redox-sensitive processes related to arc magmatism, and thus more broadly how Earth materials cycle globally. We present major, volatile, and trace element concentrations in combination with Fe3+/∑Fe ratios determined in olivine-hosted glass inclusions and submarine glasses from five Mariana arc volcanoes and two regions of the Mariana Trough. For single eruptions, Fe3+/∑Fe ratios vary along liquid lines of descent that are either slightly oxidizing (olivine + clinopyroxene + plagioclase fractionation, CO2 ± H2O degassing) or reducing (olivine + clinopyroxene + plagioclase ± magnetite fractionation, CO2 + H2O + S degassing). Mariana samples are consistent with a global relationship between calc-alkaline affinity and both magmatic H2O and magmatic oxygen fugacity, where wetter, higher oxygen fugacity magmas display greater affinity for calc-alkaline differentiation. We find, however, that low-pressure differentiation cannot explain the majority of variations observed in Fe3+/∑Fe ratios for Mariana arc basalts, requiring primary differences in magmatic oxygen fugacity. Calculated oxygen fugacities of primary mantle melts at the pressures and temperatures of melt segregation are significantly oxidized relative to mid-ocean ridge basalts (∼QFM, where QFM is quartz–fayalite–magnetite buffer), ranging from QFM + 1·0 to QFM + 1·6 for Mariana arc basalts, whereas back-arc related samples record primary oxygen fugacities that range from QFM + 0·1 to QFM + 0·5. This Mariana arc sample suite includes a diversity of subduction influences, from lesser influence of a homogeneous H2O-rich component in the back-arc, to sediment melt- and fluid-dominated influences along the arc. Primary melt oxygen fugacity does not correlate significantly with sediment melt contributions (e.g. Th/La), nor can it be attributed to previous melt extraction in the back-arc. Primary melt oxygen fugacity correlates strongly with indices of slab fluids (e.g. Ba/La) from the Mariana Trough through the Mariana arc, increasing by 1·5 orders of magnitude as Ba/La increases by a factor of 10 relative to mid-ocean ridge basalts. These results suggest that contributions from the slab to the mantle wedge may be responsible for the elevated oxygen fugacity recorded by Mariana arc basalts and that slab fluids are potentially very oxidized

Variations in Fe^(3+)/∑Fe of Mariana Arc Basalts and Mantle Wedge ƒO_2

Arc basalts are more oxidized than mid-ocean ridge basalts, but it is unclear whether this difference is due to differentiation processes in the Earth’s crust or to a fundamental difference in the oxygen fugacity of their mantle sources. Distinguishing between these two hypotheses is important for understanding redox-sensitive processes related to arc magmatism, and thus more broadly how Earth materials cycle globally. We present major, volatile, and trace element concentrations in combination with Fe^(3+)/∑Fe ratios determined in olivine-hosted glass inclusions and submarine glasses from five Mariana arc volcanoes and two regions of the Mariana Trough. For single eruptions, Fe^(3+)/∑Fe ratios vary along liquid lines of descent that are either slightly oxidizing (olivine + clinopyroxene + plagioclase fractionation, CO_2 ± H_2O degassing) or reducing (olivine + clinopyroxene + plagioclase ± magnetite fractionation, CO_2 + H_2O + S degassing). Mariana samples are consistent with a global relationship between calc-alkaline affinity and both magmatic H_2O and magmatic oxygen fugacity, where wetter, higher oxygen fugacity magmas display greater affinity for calc-alkaline differentiation. We find, however, that low-pressure differentiation cannot explain the majority of variations observed in Fe^(3+)/∑Fe ratios for Mariana arc basalts, requiring primary differences in magmatic oxygen fugacity. Calculated oxygen fugacities of primary mantle melts at the pressures and temperatures of melt segregation are significantly oxidized relative to mid-ocean ridge basalts (∼QFM, where QFM is quartz–fayalite–magnetite buffer), ranging from QFM + 1·0 to QFM + 1·6 for Mariana arc basalts, whereas back-arc related samples record primary oxygen fugacities that range from QFM + 0·1 to QFM + 0·5. This Mariana arc sample suite includes a diversity of subduction influences, from lesser influence of a homogeneous H_2O-rich component in the back-arc, to sediment melt- and fluid-dominated influences along the arc. Primary melt oxygen fugacity does not correlate significantly with sediment melt contributions (e.g. Th/La), nor can it be attributed to previous melt extraction in the back-arc. Primary melt oxygen fugacity correlates strongly with indices of slab fluids (e.g. Ba/La) from the Mariana Trough through the Mariana arc, increasing by 1·5 orders of magnitude as Ba/La increases by a factor of 10 relative to mid-ocean ridge basalts. These results suggest that contributions from the slab to the mantle wedge may be responsible for the elevated oxygen fugacity recorded by Mariana arc basalts and that slab fluids are potentially very oxidized

Age of Izu-Bonin-Mariana arc basement

Documenting the early tectonic and magmatic evolution of the Izu–Bonin–Mariana (IBM) arc system in the Western Pacific is critical for understanding the process and cause of subduction initiation along the current convergent margin between the Pacific and Philippine Sea plates. Forearc igneous sections provide firm evidence for seafloor spreading at the time of subduction initiation (52 Ma) and production of “forearc basalt”. Ocean floor drilling (International Ocean Discovery Program Expedition 351) recovered basement-forming, low-Ti tholeiitic basalt crust formed shortly after subduction initiation but distal from the convergent margin (nominally reararc) of the future IBM arc (Amami Sankaku Basin: ASB). Radiometric dating of this basement gives an age range (49.3–46.8 Ma with a weighted average of 48.7 Ma) that overlaps that of basalt in the present-day IBM forearc, but up to 3.3 m.y. younger than the onset of forearc basalt activity. Similarity in age range and geochemical character between the reararc and forearc basalts implies that the ocean crust newly formed by seafloor spreading during subduction initiation extends from fore- to reararc of the present-day IBM arc. Given the age difference between the oldest forearc basalt and the ASB crust, asymmetric spreading caused by ridge migration might have taken place. This scenario for the formation of the ASB implies that the Mesozoic remnant arc terrane of the Daito Ridges comprised the overriding plate at subduction initiation. The juxtaposition of a relatively buoyant remnant arc terrane adjacent to an oceanic plate was more favourable for subduction initiation than would have been the case if both downgoing and overriding plates had been oceanic

Origin of depleted basalts during subduction initiation and early development of the Izu-Bonin-Mariana island arc: Evidence from IODP expedition 351 site U1438, Amami-Sankaku basin

The Izu-Bonin-Mariana (IBM) island arc formed following initiation of subduction of the Pacific plate beneath the Philippine Sea plate at about 52 Ma. Site U1438 of IODP Expedition 351 was drilled to sample the oceanic basement on which the IBM arc was constructed, to better understand magmatism prior to and during the subduction initiation event. Site U1438 igneous basement Unit 1 (150 m) was drilled beneath 1460 m of primarily volcaniclastic sediments and sedimentary rock. Basement basalts are microcrystalline to fine-grained flows and form several distinct subunits (1a-1f), all relatively mafic (MgO = 6.5–13.8%; Mg# = 52–83), with Cr = 71–506 ppm and Ni = 62–342 ppm. All subunits are depleted in non-fluid mobile incompatible trace elements. Ratios such as Sm/Nd (0.35–0.44), Lu/Hf (0.19–0.37), and Zr/Nb (55–106) reach the highest values found in MORB, while La/Yb (0.31–0.92), La/Sm (0.43–0.91) and Nb/La (0.39–0.59) reach the lowest values. Abundances of fluid-mobile incompatible elements, K, Rb, Cs and U, vary with rock physical properties, indicating control by post-eruptive seawater alteration, but lowest abundances are typical of fresh, highly depleted MORBs. Mantle sources for the different subunits define a trend of progressive incompatible element depletion. Inferred pressures of magma segregation are 0.6–2.1 GPa with temperatures of 1280–1470 °C. New 40Ar/39Ar dates for Site U1438 basalts averaging 48.7 Ma (Ishizuka et al., 2018) are younger that the inferred age of IBM subduction initiation based on the oldest ages (52 Ma) of IBM forearc basalts (FAB) from the eastern margin of the Philippine Sea plate. FAB are hypothesized to be the first magma type erupted as the Pacific plate subsided, followed by boninites, and ultimately typical arc magmas over a period of about 10 Ma. Site U1438 basalts and IBM FABs are similar, but Site U1438 basalts have lower V contents, higher Ti/V and little geochemical evidence for involvement of slab-derived fluids. We hypothesize that the asthenospheric upwelling and extension expected during subduction initiation occurred over a broad expanse of the upper plate, even as hydrous fluids were introduced near the plate edge to produce FABs and boninites. Site U1438 basalts formed by decompression melting during the first 3 Ma of subduction initiation, and were stranded behind the early IBM arc as mantle conditions shifted to flux melting beneath a well-defined volcanic front

Neogene Uplift and Magmatism of Anatolia: Insights from Drainage Analysis and Basaltic Geochemistry

It is generally agreed that mantle dynamics have played a significant role in generating and maintaining the elevated topography of Anatolia during Neogene times. However, there is much debate about the relative importance of subduction zone and asthenospheric processes. Key issues concern onset and cause of regional uplift, thickness of the lithospheric plate, and the presence or absence of temperature and/or compositional anomalies within the convecting mantle. Here, we tackle these interlinked issues by analyzing and modeling two disparate suites of observations. First, a drainage inventory of 1,844 longitudinal river profiles is assembled. This geomorphic database is inverted to calculate the variation of Neogene regional uplift through time and space by minimizing the misfit between observed and calculated river profiles subject to independent calibration. Our results suggest that regional uplift commenced in the east at 20 Ma and propagated westward. Secondly, we have assembled a database of geochemical analyses of basaltic rocks. Two different approaches have been used to quantitatively model this database with a view to determining the depth and degree of asthenospheric melting across Anatolia. Our results suggest that melting occurs at depths as shallow as 60 km in the presence of mantle potential temperatures as high as 1400°C. There is evidence that potential temperatures are higher in the east, consistent with the pattern of sub-plate shear wave velocity anomalies. Our combined results are consistent with isostatic and admittance analyses and suggest that elevated asthenospheric temperatures beneath thinned Anatolian lithosphere have played a first order role in generating and maintaining regional dynamic topography and basaltic magmatism

The Thickness of the Mantle Lithosphere and Collision-Related Volcanism in the Lesser Caucasus

The Lesser Caucasus mountains sit on a transition within the Arabia–Eurasia collision zone between very thin lithosphere (<100 km) to the west, under Eastern Anatolia, and a very thick lithospheric root (up to 200 km) in the east, under western Iran. A transect of volcanic highlands running from NW to SE in the Lesser Caucasus allows us to look at the effects of lithosphere thickness variations on the geochemistry of volcanic rocks in this continental collision zone. Volcanic rocks from across the region show a wide compositional range from basanites to rhyolites, and have arc-like geochemical characteristics, typified by ubiquitous negative Nb–Ta anomalies. Magmatic rocks from the SE, where the lithosphere is thought to be thicker, are more enriched in incompatible trace elements, especially the light rare earth elements, Sr and P. They also have more radiogenic ⁸⁷Sr/⁸⁶Sr, and less radiogenic ¹⁴³Nd/¹⁴⁴Nd. Across the region, there is no correlation between SiO₂ content and Sr–Nd isotope ratios, revealing a lack of crustal contamination. Instead, ‘spiky’ mid-ocean ridge basalt normalized trace element patterns are the result of derivation from a subduction-modified mantle source, which probably inherited its subduction component from subduction of the Tethys Ocean prior to the onset of continent–continent collision in the late Miocene. In addition to the more isotopically enriched mantle source, modelling of non-modal batch melting suggests lower degrees of melting and the involvement of garnet as a residual phase in the SE. Melt thermobarometry calculations based on bulk-rock major elements confirm that melting in the SE must occur at greater depths in the mantle. Temperatures of melting below 1200°C, along with the subduction-modified source, suggest that melting occurred within the lithosphere. It is proposed that in the northern Lesser Caucasus this melting occurs close to the base of the very thin lithosphere (at a depth of ∼45 km) as a result of small-scale delamination. A striking similarity between the conditions of melting in NW Iran and the southern Lesser Caucasus (two regions between which the difference in lithosphere thickness is ∼100 km) suggests a common mechanism of melt generation in the mid-lithosphere (∼75 km). The southern Lesser Caucasus magmas result from mixing between partial melts of deep lithosphere (∼120 km in the south) and mid-lithosphere sources to give a composition intermediate between magmas from the northern Lesser Caucasus and NW Iran. The mid-lithosphere magma source has a distinct composition compared with the base of the lithosphere, which is argued to be the result of the increased retention of metasomatic components in phases such as apatite and amphibole, which are stabilized by lower temperatures prior to magma generation

Olivine-melt relationships and syneruptive redox variations in the 1959 eruption of Kīlauea Volcano as revealed by XANES

The 1959 summit eruption of Kīlauea Volcano exhibited high lava fountains of gas-rich, primitive magma, containing olivine + chromian spinel in highly vesicular brown glass. Microprobe analysis of these samples shows that euhedral rims on olivine phenocrysts, in direct contact with glass, vary significantly in forsterite (Fo) content, at constant major-element melt composition, as do unzoned groundmass olivine crystals. Ferric/total iron (Fe^(+3)/Fe^T)ratios for matrix and interstitial glasses, plus olivine-hosted glass inclusions in eight 1959 scoria samples have been determined by micro X-ray absorption near-edge structure spectroscopy (μ-XANES). These data show that much of the variation in Fo content reflects variation in oxidation state of iron in the melt, which varies with sulfur concentration in the glass and (locally) with proximity to scoria edges in contact with air. Data for 24 olivine-melt pairs in the better-equilibrated samples from later in the eruption show K_D averaging 0.280 ± 0.03 for the exchange of Fe and Mg between olivine and melt, somewhat displaced from the value of 0.30 ± 0.03 given by Roeder and Emslie (1970). This may reflect the low SiO_2 content of the 1959 magmas, which is lower than that in most Kīlauea tholeiites. More broadly, we show the potential of μ-XANES and electron microprobe to revisit and refine the value of K_D in natural systems. The observed variations of Fe^(+3)/Fe^T ratios in the glasses reflect two distinct processes. The main process, sulfur degassing, produces steady decrease of the Fe^(+3)/Fe^T ratio. Melt inclusions in olivine are high in sulfur (1060–1500 ppm S), with Fe^(+3)/Fe^T = 0.160–0.175. Matrix glasses are degassed (mostly S < 200 ppm) with generally lower Fe^(+3)/Fe^T (0.114–0.135). Interstitial glasses within clumps of olivine crystals locally show intermediate levels of sulfur and Fe^(+3)/Fe^T ratio. The correlation suggests that (1) the 1959 magma was significantly reduced by sulfur degassing during the eruption and (2) the melts originally had Fe^(+3)/Fe^T ≥ 0.175, consistent with oxygen fugacity (fO_2) at least 0.4 log units above the fayalite-magnetite-quartz (FMQ) buffer at 1 atm and magmatic temperature of 1200 °C. The second process is interaction between the melts and atmospheric oxygen, which results in higher Fe^(+3)/Fe^T ratios. Detailed μ-XANES traverses show gradients in Fe^(+3)/Fe^T of 0.145 to 0.628 over distances of 100–150 μm in thin, visibly reddened matrix glass bordering some scoriae, presumably caused by contact with air. This process was extremely rapid, giving insight into how fast the Fe^(+3)/Fe_T ratio can change in response to changes in external conditions

Interplay of crystal fractionation, sulfide saturation and oxygen fugacity on the iron isotope composition of arc lavas: An example from the Marianas

Subduction zone systems are central to a multitude of processes from the evolution of the continental crust to the concentration of metals into economically viable deposits. The interplay between oxygen fugacity, sulfur saturation, fluid exsolution and fractionating mineral assemblages that gives rise to typical arc magma chemical signatures is, however, still poorly understood and novel geochemical approaches are required to make further progress. Here we examine a well-characterized suite of arc lavas from the Marianas (W. Pacific) for their stable Fe isotope composition. In agreement with previous work and mass balance considerations, contributions from sediments and/or fluids are shown to have negligible effect on Fe isotopes. Instead, we focus on disentangling processes occurring during basalt through dacite differentiation using a sample suite from the island of Anatahan. Anatahan whole rock Fe isotope compositions (δ57Fe) range from −0.05 ± 0.05 to 0.17 ± 0.03 (2 S.D.)‰. A fractionation model is constructed, where three distinct stages of differentiation are required to satisfy the combined major and trace element and isotopic observations. In particular, the sequestration of isotopically heavy Fe into magnetite and isotopically light Fe into sulfide melts yields important constraints. The data require that lavas are first undersaturated with respect to crystalline or molten sulfide, followed by the crystallisation of magnetite, which then triggers late sulfide saturation. The model demonstrates that the final stage of removal of liquid or crystalline sulfide can effectively sequester Cu (and presumably other chalcophiles) and that late stage exsolution of magmatic fluids or brines may not be required to do this, although these processes are not mutually exclusive. Finally, the new Fe isotope data are combined with previous Tl-Mo-V stable isotope determinations on the same samples. Importantly, the multi-valent transition metal stable isotope systems of Fe and V are decoupled by sulfide saturation, thus providing a potential tool to constrain its somewhat intractable timing. The observed decoupling of notionally redox-sensitive tracers underlines the caution required in the application of transition metal isotopes as direct redox proxies

Sulfur from the subducted slab dominates the sulfur budget of the mantle wedge under volcanic arcs

Sulfur is of a crucial importance in the Earth system influencing biological, climate, ore-forming, and redox processes. Subduction zones play a key role in the global sulfur cycle. Arc magmas have higher sulfur contents and are more oxidised than mid-ocean ridge basalts (MORBs) due to either an oxidised mantle source or magma differentiation. Melt oxidation state and sulfur content may interrelate, as sulfur is a potential oxidising agent during slab-mantle interaction. Here, we use melt inclusions (MIs) to determine the sulfur isotopic composition (δ34S) of primary arc magmas from three volcanic centres along the Central American Volcanic Arc (CAVA): Fuego (Guatemala), Cerro Negro (Nicaragua), and Turrialba (Costa Rica). These three locations sample much of the global arc magma trace element variability: Ba/La ratios range from 22 (Turrialba) to 118 (Cerro Negro). Melt δ34S values are between -0.5‰ and +4.9‰. Sulfur contents and δ34S values of homogenised and naturally quenched MIs overlap, indicating post-entrapment processes do not affect sulfur contents and sulfur isotope ratios in the studied MIs. Degassing causes limited sulfur isotope fractionation; calculated gas-melt isotope fractionation factors are between 0.998-1.001. Our model calculations predict that most volcanic gases along the CAVA have δ34S between -1‰ and +6‰, becoming enriched in 34S as degassing progresses. We estimate initial melt δ34S values for Fuego, Cerro Negro, and Turrialba to be +0.7±1.4‰, +2.2±1.0‰, and +1.6±0.8‰ (two standard errors), respectively. All these values are elevated compared to MORBs (-0.9‰). Addition of oxidised slab material enriched in 34S to the mantle wedge can explain elevated arc primary melt δ34S and the oxidising conditions observed in arc magmas globally. Based on mass balance, a slab component with δ34S between +2‰ to +5‰ is present in the mantle wedge under the CAVA, elevating local arc mantle S contents to 360±30 ppm at Fuego, 462±11 ppm at Cerro Negro. Modelling suggests that 40-70% of sulfur in the mantle wedge originates from a slab-derived component. Slab subduction is expected to have major control on the evolution of Earth's sulfur cycle and mantle oxidation state over its geological history