The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from −0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ⁵⁶Fe values (relative to IRMM-14) ranging from −0.18(±0.02) to −2.290(±0.006) ‰, and corresponding δ⁵⁷Fe values of −0.247(±0.014) and −3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus’s theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.     

Gold partitioning in melt-vapor-brine systems

We used laser-ablation inductively coupled plasma mass spectrometry to measure the solubility of gold in synthetic sulfur-free vapor and brine fluid inclusions in a vapor + brine + haplogranite + magnetite + gold metal assemblage. Experiments were conducted at 800°C, oxygen fugacity buffered at Ni-NiO (NNO), and pressures ranging from 110 to 145 MPa. The wt% NaCl eq. of vapor increases from 2.3 to 19 and that of brine decreases from 57 to 35 with increasing pressure. The composition of the vapors and brines are dominated by NaCl + KCl + FeCl₂ + H₂O. Gold concentrations in vapor and brine decrease from 36 to 5 and 50 to 28 μg/g, respectively, and the calculated vapor:brine partition coefficients for gold decrease from 0.72 to 0.17 as pressure decreases from 145 to 110 MPa. These data are consistent with the thermodynamic boundary condition that the concentration of gold in the vapor and brine must approach a common value as the critical pressure is approached along the 800°C isotherm in the NaCl-KCl-FeCl₂-HCl-H₂O system.We use the equilibrium constant for gold dissolution as AuOH⁰, extrapolated from lower temperature and overlapping pressure range, to calculate expected concentrations of AuOH⁰ in our experimental vapors. These calculations suggest that a significant quantity of gold in our experimental vapors is present as a non-hydroxide species. Possible chloridogold(I) species are hypothesized based on the positively correlated gold and chloride concentrations in our experimental vapors. The absolute concentration of gold in our synthetic vapor, brine, and melt and calculated mass partition coefficients for gold between these physicochemically distinct magmatic phases suggests that gold solubility in aqueous fluids is a function of aqueous phase salinity, specifically total chloride concentration, at magmatic conditions. However, though we highlight here the effect of salinity, the combination of our data with data sets from lower temperatures evinces a significant decrease in gold solubility as temperature drops from 800°C to 600°C. This decrease in solubility has implications for gold deposition from ascending magmatic fluids.     

Rapid magmatic processes accompany arc–continent collision: the Western Bismarck arc, Papua New Guinea

New U–Th–Ra, major and trace element, and Sr–Nd–Pb isotope data are presented for young lavas from the New Britain and Western Bismarck arcs in Papua New Guinea. New Britain is an oceanic arc, whereas the latter is the site of an arc–continent collision. Building on a recent study of the Manus Basin, contrasts between the two arcs are used to evaluate the processes and timescales of magma generation accompanying arc–continent collision and possible slab detachment. All three suites share many attributes characteristic of arc lavas that can be ascribed to the addition of a regionally uniform subduction component derived from the subducting altered oceanic crust and sediment followed by dynamic melting of the modified mantle. However, the Western Bismarck arc lavas diverge from the Pb isotope mixing array formed by the New Britain and the Manus Basin lavas toward elevated ²⁰⁸Pb/²⁰⁴Pb. We interpret this to reflect a second and subsequent addition of sediment melt at crustal depth during collision. ²³⁸U and ²²⁶Ra excesses are preserved in all of the lavas and are greatest in the Western Bismarck arc. High-Mg andesites with high Sr/Y ratios in the westernmost arc are attributed to recent shallow mantle flux melting at the slab edge. Data for two historical rhyolites are also presented. Although these rhyolites formed in quite different tectonic settings and display different geochemical and isotopic compositions, both formed from mafic parents within millennia.     

Mo isotope fractionation during adsorption to Fe (oxyhydr)oxides

Molybdenum (Mo) isotopes have great potential as a paleoredox indicator, but this potential is currently restricted by an incomplete understanding of isotope fractionations occurring during key (bio)geochemical processes. To address one such uncertainty we have investigated the isotopic fractionation of Mo during adsorption to a range of Fe (oxyhydr)oxides, under variable Mo/Fe-mineral ratios and pH. Our data confirm that Fe (oxyhydr)oxides can readily adsorb Mo, highlighting the potential importance of this removal pathway for the global Mo cycle. Furthermore, adsorption of Mo to Fe (oxyhydr)oxides is associated with preferential uptake of the lighter Mo isotopes. Fractionations between the solid and dissolved phase (Δ⁹⁸Mo) increase at higher pH, and also vary with mineralogy, increasing in the order magnetite (Δ⁹⁸Mo = 0.83 ± 0.60‰) < ferrihydrite (Δ⁹⁸Mo = 1.11 ± 0.15‰) < goethite (Δ⁹⁸Mo = 1.40 ± 0.48‰) < hematite (Δ⁹⁸Mo = 2.19 ± 0.54‰). Small differences in isotopic fractionation are also seen at varying Mo/Fe-mineral ratios for individual minerals. The observed isotopic behaviour is consistent with both fractionation during adsorption to the mineral surface (a function of vibrational energy) and adsorption of different Mo species/structures from solution. The different fractionation factors determined for different Fe (oxyhydr)oxides suggests that these minerals likely exert a major control on observed natural Mo isotope compositions during sediment deposition beneath suboxic through to anoxic (but non-sulfidic) bottom waters. Our results confirm that Mo isotopes can provide important information on the spatial extent of different paleoredox conditions, providing they are used in combination with other techniques for evaluating the local redox environment and the mineralogy of the depositing sediments.     

Highly fractionated I-type granites in NE China (II): isotopic geochemistry and implications for crustal growth in the Phanerozoic

NE China is the easternmost part of the Central Asian Orogenic Belt (CAOB). The area is distinguished by widespread occurrence of Phanerozoic granitic rocks. In the companion paper (Part I), we established the Jurassic ages (184–137 Ma) for three granitic plutons: Xinhuatun, Lamashan and Yiershi. We also used geochemical data to argue that these rocks are highly fractionated I-type granites. In this paper, we present Sr–Nd–O isotope data of the three plutons and 32 additional samples to delineate the nature of their source, to determine the proportion of mantle to crustal components in the generation of the voluminous granitoids and to discuss crustal growth in the Phanerozoic.

Despite their difference in emplacement age, Sr–Nd isotopic analyses reveal that these Jurassic granites have common isotopic characteristics. They all have low initial ⁸⁷Sr/⁸⁶Sr ratios (0.7045±0.0015), positive _Nd(T) values (+1.3 to +2.8), and young Sm–Nd model ages (720–840 Ma). These characteristics are indicative of juvenile nature for these granites. Other Late Paleozoic to Mesozoic granites in this region also show the same features. Sr–Nd and oxygen isotopic data suggest that the magmatic evolution of the granites can be explained in terms of two-stage processes: (1) formation of parental magmas by melting of a relatively juvenile crust, which is probably a mixed lithology formed by pre-existing lower crust intruded or underplated by mantle-derived basaltic magma, and (2) extensive magmatic differentiation of the parental magmas in a slow cooling environment.

The widespread distribution of juvenile granitoids in NE China indicates a massive transfer of mantle material to the crust in a post-orogenic tectonic setting. Several recent studies have documented that juvenile granitoids of Paleozoic to Mesozoic ages are ubiquitous in the Central Asian Orogenic Belt, hence suggesting a significant growth of the continental crust in the Phanerozoic.     

Geochemistry, Geochronology and Isotopic Evolution of the Chewore-Rufunsa Terrane, Southern Irumide Belt: a Mesoproterozoic Continental Margin Arc

The southern Irumide Belt (SIB) is an ENE–WSW-trending,late Mesoproterozoic orogenic belt located between the Congo–Tanzania–Bangweulu(CTB) and Kalahari cratons in central southern Africa. It isseparated from the late Mesoproterozoic Irumide Belt (IB) tothe north by Permo-Triassic graben, raising the possibilitythat the younger rifts reactivated a suture between the twobelts that has been rendered cryptic as a result of youngerKaroo cover. Both belts are dominated by calc-alkaline gneisses,but in addition the SIB contains abundant metavolcanic and metasedimentaryrocks. In this study we present detailed geochemical, isotopicand geochronological data for volcanic and plutonic lithologiesfrom the southernmost part of the SIB, the Chewore–RufunsaTerrane. This terrane comprises a wide variety of supracrustalto mid-crustal rocks that have major- and trace-element compositionssimilar to magmas formed in present-day subduction zones. Chondrite-normalizedrare earth element (REE) profiles and whole-rock Sm–Ndisotope compositions indicate that the parental supra-subductionmelts interacted with, and were contaminated by sialic continentalcrust, implying a continental-margin-arc setting. Secondaryionization mass spectrometry dating of magmatic zircon has yieldedcrystallization ages between c. 1095 and 1040 Ma, similar toelsewhere in the SIB. U–Pb dating and in situ Lu–Hfisotopic analyses of abundant xenocrystic zircon extracted fromthe late Mesoproterozoic granitoids indicate that the contaminantcontinental basement was principally Palaeoproterozoic in ageand had a juvenile isotopic signature at the time of its formation.These data are in contrast to those for the IB, which is characterizedby younger, c. 1020 Ma, calc-alkaline gneisses that formed bythe direct recycling of Archaean crust without significant additionof any juvenile material. We suggest that the SIB developedby the subduction of oceanic crust under the margin of an unnamedcontinental mass until ocean closure at c. 1040 Ma. Subsequentcollision between the SIB and the CTB margin led to the cessationof magmatism in the SIB and the initiation of compression andcrustal melting in the IB. KEY WORDS: geochemistry; Mesoproterozoic; SHRIMP zircon U–Pb dating; Sm–Nd isotopes; Southern Irumide Belt     

黑龙江杂岩的碎屑锆石年代学及其大地构造意义

黑龙江杂岩带位于佳木斯地体西缘,为佳木斯地体向西与松嫩地体之间俯冲、拼贴、碰撞而形成的高压变质带.黑龙江杂岩沿牡丹江断裂分布,其构造-岩石组合、变质变形特征等显示其为佳木斯地体向松嫩地体俯冲拼帖的过程中形成的增生杂岩,目前保存下来的杂岩带应为大规模增生楔仰冲到佳木斯地体之上的残余部分.88颗碎屑锆石的全部样品SHRIMPU-Ph年代学测试结果显示三个主要年龄区间:170～220Ma,峰值年龄为183Ma;240～338Ma,峰值年龄为256Ma;450～520Ma,峰值年龄为470Ma.而28个碎屑锆石谐和年龄的年龄谱为两组:240～338Ma,峰值年龄为256Ma;450～500Ma,峰值年龄为470Ma.碎屑锆石年龄数据分析得到,240～338Ma峰期年龄为256Ma的年龄应代表黑龙江杂岩主体岩石的沉积年龄上限;而450～500Ma的年龄谱对应于佳木斯地体的基底变质岩年龄,显示佳木斯地体的基底变质岩曾为黑龙江杂岩的物源区;而170～210Ma,峰期年龄为183Ma的不谐和年龄应为受印支期-早侏罗世构造热事件的扰动年龄,与该区变质单矿物的Ar-Ar年龄相一致,应代表了该区陆-陆碰撞的时代.上述年龄为黑龙江杂岩的形成与演化提供了重要的地质年代学制约,即黑龙江杂岩的原岩成岩时代上限为早三叠世,佳木斯地体向西的俯冲时代主体为印支期,而陆-陆拼贴及碰撞过程主要为晚印支期并可能持续到早侏罗世.这些结果将为揭示我国东北地区构造演化的年代学格架以及三叠纪古亚洲构造域向环太平洋构造域叠加和转换的动力学背景研究提供新的基本地质事实依据.     

Micro- and nano-textural evidence of Ti(–Ca–Fe) mobility during fluid–rock interactions in carbonaceous lawsonite-bearing rocks from New Zealand

Understanding the mobility of chemical elements during fluid–rock interactions is critical to assess the geochemical evolution of a rock undergoing burial and metamorphism and, more generally, to constrain the geochemical budget of the subduction factory. In particular, determining the behavior and mobility of Ti in aqueous fluids constitutes a great challenge that is still under scrutiny. Here, we study plant fossils preserved in blueschist metasedimentary rocks from the Marybank Formation (New Zealand). Using scanning and transmission electron microscopies (SEM and TEM), we show that the carbonaceous material (CM) composing the fossils contains abundant nano-inclusions of Ti- and Fe-oxides. These nanocrystals are mainly anatase, rutile, and Fe–Ti oxides. The mineral composition observed within the fossils is significantly different from that detected in the surrounding rock matrix. We propose that Ti and Fe might have been mobilized by the alteration of a detrital Ti–Fe-rich protolith during an early diagenetic event under acidic and reducing conditions. Aqueous fluids rich in organic ligands released by the degradation of organic matter may have been involved. Moreover, using mass balance and petrological observations, we show that the contrasted mineralogy between the rock matrix and the fossil CM might be the consequence of the chemical isolation of fossil CM during the prograde path of the rock. Such an isolation results from the early formation of quartz and Fe-rich phyllosilicate layers enclosing the fossil as characterized by SEM and TEM investigations. Overall, this study shows that investigating minerals associated with CM down to the nanometer scale in metamorphic rocks can provide a precious record of early prograde geochemical conditions.     

<Superscript>10</Superscript>Be, <Superscript>18</Superscript>O and radiogenic isotopic constraints on the origin of adakitic signatures: a case study from Solander and Little Solander Islands,New Zealand

Subduction-related Quaternary volcanic rocks from Solander and Little Solander Islands, south of mainland New Zealand, are porphyritic trachyandesites and andesites (58.20–62.19 wt% SiO₂) with phenocrysts of amphibole, plagioclase and biotite. The Solander and Little Solander rocks are incompatible element enriched (e.g. Sr ~931–2,270 ppm, Ba ~619–798 ppm, Th ~8.7–21.4 ppm and La ~24.3–97.2 ppm) with MORB-like Sr and Nd isotopic signatures. Isotopically similar quench-textured enclaves reflect mixing with intermediate (basaltic-andesite) magmas. The Solander rocks have geochemical affinities with adakites (e.g. high Sr/Y and low Y), whose origin is often attributed to partial melting of subducted oceanic crust. Solander sits on isotopically distinct continental crust, thus excluding partial melting of the lower crust in the genesis of the magmas. Furthermore, the incompatible element enrichments of the Solander rocks are inconsistent with partial melting of newly underplated mafic lower crust; reproduction of their major element compositions would require unrealistically high degrees of partial melting. A similar argument precludes partial melting of the subducting oceanic crust and the inability to match the observed trace element patterns in the presence of residual garnet or plagioclase. Alternatively, an enriched end member of depleted MORB mantle source is inferred from Sr, Nd and Pb isotopic compositions, trace element enrichments and εHf ? 0 CHUR in detrital zircons, sourced from the volcanics. ¹⁰Be and Sr, Nd and Pb isotopic systematics are inconsistent with significant sediment involvement in the source region. The trace element enrichments and MORB-like Sr and Nd isotopic characteristics of the Solander rocks require a strong fractionation mechanism to impart the high incompatible element concentrations and subduction-related (e.g. high LILE/HFSE) geochemical signatures of the Solander magmas. Trace element modelling shows that this can be achieved by very low degrees of melting of a peridotitic source enriched by the addition of a slab-derived melt. Subsequent open-system fractionation, involving a key role for mafic magma recharge, resulted in the evolved andesitic adakites.     

A review of the geodynamic setting of large-scale Late Mesozoic gold mineralization in the North China Craton: an association with lithospheric thinning

Abundant gold deposits are distributed along the margins of the North China Craton (NCC). Occurring throughout the Precambrian basement and located in or proximal to Mesozoic granitoids, these deposits show a consistent spatial–temporal association with Late Jurassic–Early Cretaceous magmatism and are characterized by quartz lode or disseminated styles of mineralization with extensive alteration of wall rock. Their ages are mainly Early Cretaceous (130–110 Ma) and constrain a very short period of metallogenesis. Sr–Nd–Pb isotopic tracers of ores, minerals and associated rocks indicate that gold and associated metals mainly were derived from multi-sources, i.e., the wall rocks (Precambrian basement and Mesozoic granites) and associated mafic rocks.Previous studies, including high surface heat flow, uplift and later basin development, slow seismic wave speeds in the upper mantle, and a change in the character of mantle xenoliths sampled by Paleozoic to Cenozoic magmas, have been used to suggest that ancient, cratonic mantle lithosphere was removed from the base of the NCC some time after the Ordovician, and replaced by younger, less refractory lithospheric mantle. The geochemistry and isotopic compositions of the mafic rocks associated with gold mineralization (130–110 Ma) indicate that they were derived from an ancient enriched lithospheric mantle source; whereas, the mafic dikes and volcanic rocks younger than 110 Ma were derived from a relatively depleted mantle source, i.e., asthenospheric mantle. According to their age and sources, relation to magmatism and geodynamic framework, the gold deposits were formed during lithospheric thinning. The removal of lithospheric mantle and the upwelling of new asthenospheric mantle induced partial melting and dehydration of the lithospheric mantle and lower crust due to an increase of temperature. The fluids derived from the lower crust were mixed with magmatic and meteoric waters, and resulted in the deposition of gold and associated metals.