Redox heterogeneity in MORB as a function of mantle source

The oxidation state of Earth’s upper mantle both influences and records mantle evolution, but systematic fine-scale variations in upper mantle oxidation state have not previously been recognized in mantle-derived lavas from mid-ocean ridges. Through a global survey of mid-ocean ridge basalt glasses, we show that mantle oxidation state varies systematically as a function of mantle source composition. Negative correlations between Fe3+/ΣFe ratios and indices of mantle enrichment such as 87Sr/86Sr, 208Pb/204Pb, Ba/La, and Nb/Zr ratios reveal that enriched mantle is more reduced than depleted mantle. Because upper mantle carbon may act to simultaneously reduce iron and generate melts that share geochemical traits with our reduced samples, we propose that carbon creates magmas at ridges that are reduced and enriched

Mantle melting as a function of water content beneath back-arc basins

Subduction zone magmas are characterized by high concentrations of H_(2)O, presumably derived from the subducted plate and ultimately responsible for melting at this tectonic setting. Previous studies of the role of water during mantle melting beneath back-arc basins found positive correlations between the H_(2)O concentration of the mantle (H_(2)O_o ) and the extent of melting (F), in contrast to the negative correlations observed at mid-ocean ridges. Here we examine data compiled from six back-arc basins and three mid-ocean ridge regions. We use TiO_2 as a proxy for F, then use F to calculate H_(2)O_o from measured H_(2)O concentrations of submarine basalts. Back-arc basins record up to 0.5 wt % H_(2)O or more in their mantle sources and define positive, approximately linear correlations between H_(2)O_o and F that vary regionally in slope and intercept. Ridge-like mantle potential temperatures at back-arc basins, constrained from Na-Fe systematics (1350°–1500°C), correlate with variations in axial depth and wet melt productivity (∼30–80% F/wt % H_(2)O_o ). Water concentrations in back-arc mantle sources increase toward the trench, and back-arc spreading segments with the highest mean H_(2)O_o are at anomalously shallow water depths, consistent with increases in crustal thickness and total melt production resulting from high H_(2)O. These results contrast with those from ridges, which record low H_(2)O_o (<0.05 wt %) and broadly negative correlations between H_(2)O_o and F that result from purely passive melting and efficient melt focusing, where water and melt distribution are governed by the solid flow field. Back-arc basin spreading combines ridge-like adiabatic melting with nonadiabatic mantle melting paths that may be independent of the solid flow field and derive from the H_(2)O supply from the subducting plate. These factors combine significant quantitative and qualitative differences in the integrated influence of water on melting phenomena in back-arc basin and mid-ocean ridge settings

Heterogeneities from the first 100 million years recorded in deep mantle noble gases from the Northern Lau Back-arc Basin

Heavy noble gases (Ne, Ar, Xe) can record long-lasting heterogeneities in the mantle because of the production of isotopes from extant (238U, 40K) and extinct (129I and 244Pu)13 radionuclides. However, the presence of ubiquitous atmospheric contamination, particularly for ocean island basalts (OIBs) that sample the Earth’s deep mantle, have largely hampered precise characterization of the mantle source compositions. Here we present new high-precision noble gas data from gas-rich basalts erupted along the Rochambeau Rift in the northwestern corner of the Lau Basin. The strong influence of a deep mantle plume in the Rochambeau source is apparent from low 4He/3He ratios down to 25,600 (3He/4He of 28.1 RA). We find that the Rochambeau source is characterized by low ratios of radiogenic to non-radiogenic nuclides of Ne, Ar, and Xe (i.e., low 21Ne/22Ne, 40Ar/36Ar, and 129Xe/130Xe) compared to the mantle source of mid-ocean ridge basalts (MORBs). Additionally, we observe differences in elemental abundance patterns between the Rochambeau source and the mantle source of MORBs as characterized by the gas-rich popping rock from the Mid-Atlantic Ridge. However, the 3He/22Ne ratio of the Rochambeau plume source is significantly higher than the Iceland and Galapagos plume sources, while the 3He/36Ar and 3He/130Xe ratios appear to be similar. The difference in 3He/22Ne between Rochambeau and the Galapagos and Iceland plume sources could reflect long lasting accretional heterogeneities in the deep mantle or some characteristic of the back-arc mantle source. High-precision xenon isotopic measurements indicate that the lower 129Xe/130Xe ratios in the Rochambeau source cannot be explained solely by mixing atmospheric xenon with MORB31 type xenon; nor can fission-produced Xe be added to MORB Xe to produce the compositions seen in the Rochambeau basalts. Deconvolution of fissiogenic xenon isotopes demonstrate a higher proportion of Pu-derived fission Xe in the Rochambeau 33 source compared to the MORB source. Therefore, both I/Xe and Pu/Xe ratios are different between OIB and MORB mantle sources. Our observations require heterogeneous volatile accretion and a lower degree of processing for the mantle plume source compared to the MORB source. Since differences in 129Xe/130Xe ratios have to be produced while 129I is still alive, OIB and MORB sources were degassed at different rates for the first 100 Ma of Solar System history, and subsequent to this period, the two reservoirs have not been homogenized. In combination with recent results from the Iceland plume, our observations require the preservation of less-degassed, early-formed heterogeneities in the Earth’s deep mantle throughout Earth’s history

Classroom enrichment through children's specialties.

Thesis (Ed.M.)--Boston Universit

The influence of magmatic differentiation on the oxidation state of Fe in a basaltic arc magma

Subduction zone basalts are more oxidized than basalts from other tectonic settings (e.g., higher Fe 3 + /∑Fe), and this contrast may play a central role in the unique geochemical processes that generate arc and continental crust. The processes generating oxidized arc magmas, however, are poorly constrained, although they appear inherently linked to subduction. Near-surface differentiation processes unique to arc settings might drive oxidation of magmas that originate in equilibrium with a relatively reduced mantle source. Alternatively, arc magmas could record the oxidation conditions of a relatively oxidized mantle source. Here, we present new measurements of olivine-hosted melt inclusions from a single eruption of Agrigan volcano, Marianas, in order to test the influence of differentiation processes vs. source conditions on the Fe 3 + /∑Fe ratio, a proxy for system oxygen fugacity (fO 2 ). We determined Fe 3 + /∑Fe ratios in glass inclusions using μ-XANES and couple these data with major elements, dissolved volatiles, and trace elements. After correcting for post-entrapment crystallization, Fe 3+ /∑Fe ratios in the Agrigan melt inclusions (0.219 to 0.282), and their modeled fO 2 s (ΔQFM +1.0 to +1.8), are uniformly more oxidized than MORB, and preserve a portion of the evolution of this magma from 5.7 to 3.2 wt.% MgO. Fractionation of olivine ±clinopyroxene ±plagioclase should increase Fe 3+ /∑Fe as MgO decreases in the melt, but the data show Fe 3+ /∑Fe ratios decreasing as MgO decreases below 5 wt.% MgO. The major element trajectories, taken in combination with this strong reduction trend, are inconsistent with crystallization of common ferromagnesian phases found in the bulk Agrigan sample, including magnetite. Rather, decreasing Fe 3+ /∑Fe ratios correlate with decreasing S concentrations, suggesting that electronic exchanges associated with SO 2 degassing may dominate Fe 3+ /∑Fe variations in the melt during differentiation. In the case of this magma, the dominant effect of differentiation on magmatic fO 2 is reduction rather than oxidation. Tracing back Agrigan melts with MgO&gt;5 wt.% (i.e., minimally degassed for S) along a modeled olivine fractionation trend to primary melts in equilibrium with Fo 90 olivine reveals melts in equilibrium with the mantle beneath Agrigan at fO 2 s of ΔQFM +1 to +1.6, significantly more oxidized than current constraints for the mantle beneath midocean ridges

The oxidation state of Fe in MORB glasses and the oxygen fugacity of the upper mantle.

Micro-analytical determination of Fe3+/ΣFe ratios in mid-ocean ridge basalt (MORB) glasses using micro X-ray absorption near edge structure (μ-XANES) spectroscopy reveals a substantially more oxidized upper mantle than determined by previous studies. Here, we show that global MORBs yield average Fe3+/ΣFe ratios of 0.16±0.01 (n=103), which trace back to primary MORB melts equilibrated at the conditions of the quartz-fayalite-magnetite (QFM) buffer. Our results necessitate an upward revision of the Fe3+/ΣFe ratios of MORBs, mantle oxygen fugacity, and the ferric iron content of the mantle relative to previous wet chemical determinations. We show that only 0.01 (absolute, or \u3c10%) of the difference between Fe3+/ΣFe ratios determined by micro-colorimety and XANES can be attributed to the Mössbauer-based XANES calibration. The difference must instead derive from a bias between micro-colorimetry performed on experimental vs. natural basalts. Co-variations of Fe3+/ΣFe ratios in global MORB with indices of low-pressure fractional crystallization are consistent with Fe3+ behaving incompatibly in shallow MORB magma chambers. MORB Fe3+/ΣFe ratios do not, however, vary with indices of the extent of mantle melting (e.g., Na2O(8)) or water concentration. We offer two hypotheses to explain these observations: The bulk partition coefficient of Fe3+ may be higher during peridotite melting than previously thought, and may vary with temperature, or redox exchange between sulfide and sulfate species could buffer mantle melting at ~QFM. Both explanations, in combination with the measured MORB Fe3+/ΣFe ratios, point to a fertile MORB source with greater than 0.3wt.% Fe2O3. © 2011

Determination of Fe\u3csup\u3e3+\u3c/sup\u3e/ΣFe of XANES basaltic glass standards by Mössbauer spectroscopy and its application to the oxidation state of iron in MORB

To improve the accuracy of X-ray absorption near-edge structure (XANES) calibrations for the Fe3 +/ΣFe ratio in basaltic glasses, we reevaluated the Fe3 +/ΣFe ratios of glasses used as standards by Cottrell et al. (2009), and available to the community (NMNH catalog #117393). Here we take into account the effect of recoilless fraction on the apparent Fe3 +/ΣFe ratio measured from room temperature Mössbauer spectra in that original study. Recoilless fractions were determined from Mössbauer spectra collected from 40 to 320 K for one basaltic glass, AII_25, and from spectra acquired at 10 K for the 13 basaltic glass standards from the study of Cottrell et al. (2009). The recoilless fractions, f, of Fe2 + and Fe3 + in glass AII_25 were calculated from variable-temperature Mössbauer spectra by a relative method (RM), based on the temperature dependence of the absorption area ratios of Fe3 + and Fe2 + paramagnetic doublets. The resulting correction factor applicable to room temperature determinations (C293, the ratio of recoilless fractions for Fe3 + and Fe2 +) is 1.125 ± 0.068 (2σ). Comparison of the spectra at 10 K for the 13 basaltic glasses with those from 293 K suggests C293 equal to 1.105 ± 0.015 (2σ). Although the 10 K estimate is more precise, the relative method determination is believed to be more accurate, as it does not depend on the assumption that recoilless fractions are equal at 10 K. Applying the effects of recoilless fraction to the relationship between Mössbauer-determined Fe3 +/ΣFe ratios and revised average XANES pre-edge centroids for the 13 standard glasses allows regression of a new calibration of the relationship between the Fe XANES pre-edge centroid energy and the Fe3 +/ΣFe ratio of silicate glass. We also update the calibration of Zhang et al. (2016) for andesites and present a more general calibration for mafic glasses including both basaltic and andesitic compositions. Recalculation of Fe3 +/ΣFe ratios for the mid-ocean ridge basalt (MORB) glasses analyzed previously by XANES by Cottrell and Kelley (2011) results in an average Fe3 +/ΣFe ratio for MORB of 0.143 ± 0.008 (1σ), taking into account only analytical precision, and 0.14 ± 0.01(1σ), taking into account uncertainty on the value of C293. This revised average is lower than the average of 0.16 ± 0.01 given by Cottrell and Kelley (2011). The revised average oxygen fugacity for MORB based on the database of Cottrell and Kelley (2011) is − 0.18 ± 0.16 log units less than the quartz-fayalite-magnetite buffer of Frost (1991) at 100 kPa (∆ QFM = − 0.18 ± 0.16)

Forearc Peridotites from Tonga Record Heterogeneous Oxidation of the Mantle following Subduction Initiation

The elevated oxygen fugacity recorded by subduction-related lavas and peridotites, relative to their mid-ocean ridge counterparts, fundamentally influences the petrogenesis of arc magmas. However, the timing, process, and spatial extent of oxidizing mass transfer at subduction zones remain unknown. Forearc peridotites, which are sometimes exposed on the trench wall of the overriding plate, record chemical fingerprints of the melting and melt–rock interaction processes that occur during and following subduction initiation, and thus provide insight into the spatial and temporal evolution of this oxidized signature. In this study, we present new major element, trace element, and oxygen fugacity data for a suite of forearc peridotites recovered from the Tonga Trench, in addition to a new assessment of literature data for previously studied forearc peridotites. For Tonga samples and literature data for forearc, ridge, and subduction-zone peridotites, we calculate oxygen fugacity (fO2) using an updated method. In contrast to previous studies, we find that spinel Cr#, a proxy for extent of melt extraction, does not correlate with oxygen fugacity, such that many forearc peridotites with high spinel Cr# do not record oxygen fugacity higher than the mid-ocean ridge peridotite array. Combining these observations with trace element modeling, we conclude that forearc peridotites are less pervasively influenced by oxidation owing to subduction processes than previously reported. The oxygen fugacity recorded by Tonga forearc peridotites is heterogeneous between dredges and homogeneous within dredges. To explore these variations, we grouped the dredges into two categories. Group I peridotites have high spinel Cr#, extremely depleted trace element compositions and oxygen fugacity values consistent with the mid-ocean ridge peridotite array. We interpret these to be the residues of large degrees of fractional melting, with little influence from arc-like melts or fluids, formed during the first stages of subduction initiation. Group II peridotites have lower spinel Cr#, enriched light rare earth elements, and oxygen fugacity elevated by ≥1 log unit above the mid-ocean peridotite array. We interpret these peridotites to be the residues of flux melting, initiated once corner flow is established in the young subduction zone. We conclude that the forearc mantle is not pervasively oxidized relative to mid-ocean ridge mantle, and that the asthenospheric mantle in the proto-subduction zone region is not oxidized prior to subduction initiation. As the oxidized signature in Group II peridotites accompanies geochemical evidence of interaction with subduction-related fluids and melts, this suggests that the sub-arc mantle is oxidized concurrently with addition of subduction fluids to the mantle wedge

The Viability of Using Rapid Judgments as a Method of Deception Detection

Rapid Judgments (RJs) are quick assessments based on indirect verbal and nonverbal cues that are known to be associated with deception. RJs are advantageous because they eliminate the need for expensive detection equipment and only require minimal training for coders with relatively accurate judgments. Results of testing on two different datasets showed that trained coders were reliably making RJs after watching both long and short interaction segments but their judgments were not more accurate than the expert interviewers. The RJs did not discriminate between truth and deception as hypothesized. This raises more questions about the conditions under which making RJs from verbal and nonverbal cues achieves accurate detection of veracity.18 month embargo; published online: 25 January 2017This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]