δ66Zn Values Research Articles

Zinc and cadmium isotopic constraints on metal sources of the Xitieshan Pb-Zn deposit, NW China

Over the past two decades, Zn-Cd isotopes in sphalerite have been employed to study ore formation processes, identify ore metal sources, and investigate post-ore metamorphism and deformation in metallic ore deposits. In this study, we examine the Zn-Cd isotope compositions of the Xitieshan intrusion-related carbonate-replacement Pb-Zn deposit situated in Qinghai Province, at the northern edge of the Tibet Plateau in Northwestern China. This deposit primarily contains two types of ore bodies, one embedded in marble and the other in schist. The ore body within the marble remains unaltered, while the sulfides in the schist exhibit distinct signs of metamorphism and deformation. Zn-Cd isotopes were analyzed in both the undeformed and the deformed sphalerite. The δ66Zn values (relative to JMC Lyon) ranged from 0.15 ‰ to 0.39 ‰ for the undeformed sphalerite and from 0.03 ‰ to 0.19 ‰ for the altered sphalerite. Likewise, the δ114/110Cd values (relative to NIST 3108) ranged from −0.10 ‰ to + 0.02 ‰ and −0.06 ‰ to −0.01 ‰, respectively. The undeformed sphalerite (Sp1) displayed a significant positive correlation between δ66Zn values and altitude, suggesting Rayleigh fractionation as a dominant factor. Conversely, the deformed sphalerite (Sp2) exhibited a pronounced negative correlation, possibly attributed to the involvement of sulfide melts during syntectonic remobilization. Additionally, we observed a decoupling of Cd isotopes from Zn isotopes, indicating a potential divergence in their sources. While the Zn in the deposit primarily originated from magmatic hydrothermal fluids, a minor fraction of the Cd might be derived from the surrounding carbonate rocks. For ore deposits that have undergone metamorphism and deformation, Cd isotopes might experience minimal or negligible fractionation during these processes, potentially preserving valuable information about the source characteristics. In contrast, Zn isotopes are more likely to undergo fractionation during metamorphism and deformation, which should be used with caution for tracing the metal sources.

Carbonated eclogitic component beneath eastern China revealed by olivine phenocrysts in nephelinites

Carbonates subducted into the mantle alongside mafic material play a critical role in the deep cycling of carbon. This recycled oxidized carbon strongly affects the physical properties of the mantle, changes the local mantle oxidation state, and enhances its ability to melt. Olivine phenocrysts, which are the first to crystallize from mantle-derived magma, record the lithology of the mantle source and provide a new perspective on CO2-rich mantle domains. Here we present data for olivine phenocrysts from Cenozoic nephelinites from eastern China, which have extremely high Ca (1108–6575 ppm) and Mn (1595–5065 ppm) and low Fo (71–85) contents and differ from olivine crystallized from CO2-poor mantle-derived melts (e.g., peridotitic or pyroxenitic mantle-derived melts; Ca < 3000 ppm, Mn < 2500 ppm). This can be explained if the olivine phenocrysts are in equilibrium with melts derived from a carbonated eclogite source, because melts produced experimentally from carbonated eclogite have high Ca and Mn and low MgO contents. The nephelinites have lower δ26Mg (−0.46‰ to −0.37‰) and higher δ66Zn (0.40‰ to 0.56‰) values compared with normal (MORB-source) mantle, lending further support to the influence of carbonated components during the formation of the nephelinites. Decreases in the Ca and Mn contents of the olivine phenocrysts with increasing Fo contents are due to mixing between the initial melt and a reacted melt produced by melt–peridotite interaction during ascent. Our findings demonstrate that the signature of carbonated eclogite in the mantle can be recorded by olivine compositions. This highlights the importance of olivine phenocrysts for tracing CO2-rich lithologies in the mantle and that high Ca and Mn contents of olivine phenocrysts suggest a carbonated eclogite source.

Cadmium and zinc isotope compositions indicate metal sources and retention mechanisms in different soil particle size fractions

Soil particle size may significantly affect metal distribution and stable isotopic behavior. Here, two soils were separated into four particle size fractions, namely fine sand, silt, fine silt, and colloidal particles and used to determine cadmium (Cd) and zinc (Zn) concentrations and isotope compositions. Concentrations of Cd and Zn were generally enriched in the finer particles and positively correlated with the iron (Fe) and manganese (Mn) oxide contents. However, Cd concentration in the fine sand was higher than in the silt fraction due to the higher soil organic matter contents in the former particle fraction. The maximum δ114/110Cd value was found in the colloidal particles (−0.02 and 0.01‰) of both soils while the minimum was in the silt particles (−0.12 and 0.06‰). Incorporation into the mineral lattice of Fe and Mn oxides is suggested to explain the slight enrichment of heavy Cd isotopes in the colloidal fraction. The similar δ66Zn values of the four particle fractions (0.20–0.29‰ with a mean of 0.25‰) indicate similar Zn sources in different particle sizes. Metal isotopic fingerprint of different soil particle size fractions provides further insight into the underlying metal retention mechanisms within soil micro-zones and helps in tracing metal sources and biogeochemical processes.

Tracing acid mine drainage and estuarine Zn attenuation using Cd and Zn isotopes

It has been estimated that the acid mine drainage (AMD) impacted Odiel river basin in southern Spain supplies 0.37% and 15% of the global riverine fluxes of Cd and Zn to the oceans, respectively (Sarmiento et al., 2009). However, the behaviour of Cd and Zn in the Ria of Huelva estuary, which connects the Odiel and Tinto watersheds with the Gulf of Cadiz, has yet to be fully investigated. Furthermore, very few studies have investigated Cd and Zn isotope behaviour in estuaries worldwide. This study presents Cd and Zn concentrations and isotopic compositions for the Ria of Huelva estuary and surrounding watersheds, sampled in 2017 and 2019. Sulfide-rich rock samples extracted from three mines yield Cd and Zn isotope compositions that range from –0.14‰ to +0.07‰ (n = 4) for δ114Cd and –0.01‰ to +0.29‰ (n = 4) for δ66Zn. However, a uniform riverine signal of about +0.02‰ for Cd and +0.17‰ for Zn indicates that tracing of individual mining regions using Cd and Zn isotopes is challenging. Limited variability was observed in dissolved δ114Cd values throughout the watershed, including AMD, the estuary, and the Gulf of Cadiz, with a mean value of ±0.00 ± 0.13‰ (n = 25, 2 SD; excludes one AMD outlier, at +0.48‰), including both 2017 and 2019 data. By contrast, δ66Zn values ranged from –0.12‰ to +0.35‰ (n = 28) for the same geographical and temporal scope. In May 2017, a large spill from an abandoned mine, La Zarza, resulted in a drastic increase in the concentrations of trace metals reaching the estuary compared to 2019, but no impact of this mine spill on Cd or Zn isotope compositions is observed. In 2019, an increase in δ66Zn values in the estuary coincided with high pH values (up to pH = 8.8) and chloride concentrations (2.73%), which may reflect an alkaline anthropogenic input from the active neighbouring industrial complex. Overall, Cd concentrations and isotope compositions in the estuary are largely consistent with conservative mixing behaviour. By contrast, Zn behaviour is non-conservative, with removal of 49–97% of dissolved riverine Zn in the estuary during the period 2017–2019, associated with a relatively small isotopic shift to lighter Zn isotope compositions. Removal of Zn to the particulate phase in the Ria of Huelva estuary therefore largely attenuates high riverine Zn fluxes from AMD, indicating that previously estimated Odiel river basin Zn fluxes were overestimated. Nevertheless, the variable but generally light AMD Cd and Zn isotope compositions, coupled with high dissolved metal concentrations, suggest that Cd and Zn isotopes may be useful tracers of regionally averaged AMD inputs to the Gulf of Cadiz and beyond.

Tightly coupled Ca-Zn-Sr isotope co-variations in basalts caused by recycled calcium carbonate in the mantle source

The deep carbon cycle requires tracers to understand carbon sequestration and mobility in the deep Earth. Recently, the use of metal stable isotopes has emerged as a promising and innovative approach to address element cycles, such as the use of magnesium and zinc isotopes to trace the magnesium carbonate cycle. However, despite the prevalence of calcium carbonate as the dominant sedimentary carbonate during the Phanerozoic era, its tracking through the use of metal stable isotopes has proven challenging. Here we show that deep subduction of Phanerozoic calcium carbonates can significantly decrease the δ44/40Ca value, while simultaneously increasing the δ66Zn value and 87Sr/86Sr ratio of the mantle. The Neogene Dalihu basalts in Inner Mongolia have high 87Sr/86Sr ratios, ranging from 0.7058 to 0.7063, which are positively correlated with Sr/Nd ratio, indicating the presence of sedimentary carbonate within their mantle source. The Dalihu basalts exhibit significantly lower δ44/40Ca values (0.51 to 0.70‰) but higher δ66Zn values (0.35 to 0.45 ‰) than the mantle. These low δ44/40Ca values cannot be attributed to partial melting, even when considering the jadeite effect. Our calculations indicate that adding 5–10% recycled calcium carbonate into the mantle source explains the high 87Sr/86Sr ratio and δ66Zn values but low δ44/40Ca values of the Dalihu basalt. Therefore, recycled calcium carbonate directly influences correlated Ca-Zn-Sr isotope variation, thereby providing compelling evidence for its role in the deep carbon cycle. Our findings suggest that combining metal stable isotopes with radiogenic Sr isotope is a powerful tracer of the deep carbon cycle.

High-precision zinc isotope measurement of chemically different geostandards by multicollector inductively coupled plasma mass spectrometry.

Zinc isotopes are becoming increasingly applicable in high-temperature geochemistry, for example in crust-mantle interaction and volatilization-related processes. The published zinc isotope data for some commonly used reference materials, however, show large interlaboratory offsets. In addition, there is still limited data for zinc isotope compositions of many widely used geological reference materials. For precise and accurate zinc isotopic ratio analysis of chemically diverse geostandards, including ultramafic to felsic igneous rocks, carbonatites, sediments and soils, an improved procedure for chemical purification of zinc was introduced in this study. The factors potentially affecting zinc isotopic ratio measurement were assessed. The accuracy and long-term reproducibility were obtained by measurements on both synthetic solutions and well-characterized geostandards. Purification of geologic samples with different zinc concentrations and matrix compositions yields consistent elution curves with nearly 100% recovery. Acidity and concentration mismatches and the presence of some matrix elements (e.g., Mg, Ti and Cr) have significant impacts on the precision and accuracy of zinc isotopic ratio measurement. The zinc isotope compositions of a suite of reference materials were measured using this method. The present study describes methods for the chemical purification of zinc and high-precision and accurate zinc isotopic ratio measurements using multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS). The long-term external reproducibility for δ66 Zn values is ±0.04‰ (2SD). High-quality zinc isotope data of chemically different geostandards were reported to stimulate future interlaboratory calibrations.

Influence of subducted carbonate on the composition of basalts in the Paleo-Asian Ocean domain

The fate of subducted carbonate of the Paleo-Asian Ocean and its control on the compositional variability of Cenozoic basalts to the west of the Daxing'anling–Taihang Gravity Lineament remain uncertain. Here we report major- and trace-element contents and Zn–Sr–Nd isotopic data for Cenozoic basalts from eastern Mongolia. The studied basalt samples from eastern Mongolia are classified as nephelinite, basanite, alkaline basalt, and tholeiite. They have different Zn–Sr–Nd isotopic compositions (δ66Zn = 0.38‰ ± 0.02‰ to 0.50‰ ± 0.04‰, 87Sr/86Sr = 0.704239–0.705175, εNd = 4.72–5.67) but display trace-element signatures of sedimentary marine carbonate, reflecting mantle heterogeneity and marine carbonate imprint. Compared with the high-Si tholeiites, which were erupted over thinner lithosphere, the nephelinites–basanites–alkaline basalts erupted over thicker lithosphere have higher δ66Zn values, La/Yb, Sm/Yb, and Nb/Y ratios, and Nb contents, indicating that these low-Si basalts were the product of lower-degree melting of carbonated mantle under higher pressure. By combining our data with available data for Cenozoic basalts from central Inner Mongolia, we suggest that the compositions of the nephelinite–basanite–alkaline-basalt–tholeiite suite show systematic spatial variation with respect to the northward subduction zone of the Paleo-Asian Ocean. The tholeiites, which have lower δ66Zn values, SiO2 contents, and Sm/Yb ratios, are dominant near the subduction zone, whereas the basanites and alkaline basalts, which have higher δ66Zn values, Sm/Yb ratios, and SiO2 contents, are dominant in the region far from the subduction zone. On the basis of a mixing model for Sr–Nd–Zn isotopic compositions, we suggest that the mantle source of the basanites and alkaline basalts incorporated a higher proportion of marine carbonate, whereas the tholeiite mantle source incorporated a higher proportion of siliceous sediments. We deduce that with increasing depth of slab subduction, more sedimentary carbonates and lesser siliceous sediments were released from the subducted slab.

The role of recycled oceanic crust in the alkaline basalts: Evidence from Zn isotopic compositions of alkaline basalts from the Madeira hotspot (eastern North Atlantic)

Plate tectonic processes introduce oceanic crust (as eclogite) into the sources of oceanic island basalts (OIB). The fate of this recycled material in the deep mantle is still poorly understood. Here we present a systematic study of Zn isotopes on well-characterized alkaline basalts (<5 Ma) from the Madeira Islands in the eastern North Atlantic. Our analyses show that the δ66Zn values of alkaline basalts range from 0.25‰ to 0.34‰, with an average of 0.30 ± 0.05‰ (2SD, N = 15), which is similar to the average of mid-ocean ridge basalts (MORB) (0.28 ± 0.03‰, 2SD), and ∼ 0.14‰ higher than that of the asthenospheric mantle (0.16 ± 0.06‰, 2SD). However, these alkaline basalts have higher Zn/Fe ratios (up to 14.20) than MORB (generally less than 12). Model calculations show that the partial melting of mantle peridotite cannot simultaneously produce the observed MORB-like δ66Zn values and trace element ratios. After excluding the effects of post-eruption alteration, crystal fractionation, and the assimilation of crustal materials during magma upwelling on Zn isotopic compositions of the studied samples, we suggest that the MORB-like δ66Zn values reflect the mixing of peridotite melt and eclogite/pyroxenite-derived melt in the magma source of the Madeira hotspot. This is supported by trace element ratios and radiogenic isotopes, such as high Zn/Fe and Dy/Yb ratios and 206Pb/204Pb values. Our new data provide independent evidence in support of the important role of recycled oceanic crust in the source and generation of alkaline OIBs, and also highlight that such sources are not ubiquitously carbonated.

Carbonate-silicate interaction in subducting slabs recorded by Zn isotopes in western Alps metasediments

Carbonate-silicate interaction within subduction channels influences the chemical and physical properties of subducting carbon and is crucial to understanding the fate of carbonates in subduction zones. However, geochemical evidence for such interaction is still limited. Here we investigate zinc isotopes (expressed as δ66ZnJMC-Lyon) to decipher potential carbonate-silicate interaction in subducting slabs given the remarkable Zn isotopic difference between silicate and carbonate components. A suite of high- to ultrahigh-pressure metasediments containing variable amounts of carbonates from the Schistes Lustrés nappe (western Alps) record subduction processes to various depths (∼15–90 km) in a cool geothermal condition (∼8°C/km). Despite a broad range of metamorphic grades (0.8–2.9 GPa and 300–630°C) and carbonate contents (0–49 wt%), the bulk metasediments have nearly constant δ66Zn values (av. 0.21±0.05‰, 2sd, n=12), which are indistinguishable from their putative protoliths (0.25±0.07‰, 2sd, n=5). The lack of systematic variation of bulk sediment δ66Zn with metamorphic grades implies a limited transfer of Zn during prograde metamorphism. Therefore, sediments will preserve their original Zn isotopic compositions after subduction into the mantle. By contrast, the carbonate components in sediments obtained by leaching exhibit a progressive decline in δ66Zn from 0.82±0.01‰ to 0.20±0.04‰ and a modest increase in Zn concentration with pressure. These variations are best interpreted as a result of prolonged closed-system Zn isotopic exchange between isotopically heavy carbonates and light silicate components in the subducting slab. Our results demonstrate that a considerable amount of carbonates in subducting sediments can be retained at least down to the depths of the sub-arc mantle (>90 km). The strong pressure-dependent Zn isotopic fractionation (R2=0.87) during carbonate-silicate interaction makes Zn isotopes a novel proxy for the storage depth of subducting carbonates.

The formation and aqueous alteration of CM2 chondrites and their relationship to CO3 chondrites: A fresh isotopic (O, Cd, Cr, Si, Te, Ti, and Zn) perspective from the Winchcombe CM2 fall

AbstractAs part of an integrated consortium study, we have undertaken O, Cd, Cr, Si, Te, Ti, and Zn whole rock isotopic measurements of the Winchcombe CM2 meteorite. δ66Zn values determined for two Winchcombe aliquots are +0.29 ± 0.05‰ (2SD) and +0.45 ± 0.05‰ (2SD). The difference between these analyses likely reflects sample heterogeneity. Zn isotope compositions for Winchcombe show excellent agreement with published CM2 data. δ114Cd for a single Winchcombe aliquot is +0.29 ± 0.04‰ (2SD), which is close to a previous result for Murchison. δ130Te values for three aliquots gave indistinguishable results, with a mean value of +0.62 ± 0.01‰ (2SD) and are essentially identical to published values for CM2s. ε53Cr and ε54Cr for Winchcombe are 0.319 ± 0.029 (2SE) and 0.775 ± 0.067 (2SE), respectively. Based on its Cr isotopic composition, Winchcombe plots close to other CM2 chondrites. ε50Ti and ε46Ti values for Winchcombe are 3.21 ± 0.09 (2SE) and 0.46 ± 0.08 (2SE), respectively, and are in line with recently published data for CM2s. The δ30Si composition of Winchcombe is −0.50 ± 0.06‰ (2SD, n = 11) and is essentially indistinguishable from measurements obtained on other CM2 chondrites. In conformity with petrographic observations, oxygen isotope analyses of both bulk and micromilled fractions from Winchcombe clearly demonstrate that its parent body experienced extensive aqueous alteration. The style of alteration exhibited by Winchcombe is consistent with relatively closed system processes. Analysis of different fractions within Winchcombe broadly support the view that, while different lithologies within an individual CM2 meteorite can be highly variable, each meteorite is characterized by a predominant alteration type. Mixing of different lithologies within a regolith environment to form cataclastic matrix is supported by oxygen isotope analysis of micromilled fractions from Winchcombe. Previously unpublished bulk oxygen isotope data for 12 CM2 chondrites, when combined with published data, define a well‐constrained regression line with a slope of 0.77. Winchcombe analyses define a more limited linear trend at the isotopically heavy, more aqueously altered, end of the slope 0.77 CM2 array. The CM2 slope 0.77 array intersects the oxygen isotope field of CO3 falls, indicating that the unaltered precursor material to the CMs was essentially identical in oxygen isotope composition to the CO3 falls. Our data are consistent with earlier suggestions that the main differences between the CO3s and CM2s reflect differing amounts of water ice that co‐accreted into their respective parent bodies, being high in the case of CM2s and low in the case of CO3s. The small difference in Si isotope compositions between the CM and CO meteorites can be explained by different proportions of matrix versus refractory silicates. CMs and COs may also be indistinguishable with respect to Ti and Cr isotopes; however, further analysis is required to test this possibility. The close relationship between CO3 and CM2 chondrites revealed by our data supports the emerging view that the snow line within protoplanetary disks marks an important zone of planetesimal accretion.

Late Pleistocene zinc isotopic indices of paleoproductivity variations in the tropical West Pacific

The tropical western Pacific (TWP) plays a significant role in modulating the global climate, with solar radiation, sea surface temperature, and monsoon circulation. Marine prime productivity fluctuations in the TWP can change the global carbon cycle. However, isotopic geochemical evidence reconstructing the changes of productivity in the western Pacific warm pool (WPWP) is currently lacking. The forcing mechanism that changes productivity in the WPWP remains uncertain. Here, we used the Zinc isotope (δ66Zn) composition in sediment carbonate with Ba/Ti ratios and differences in foraminiferal carbon isotopes between the surface, and thermocline obtained from the Ocean Drilling Program (ODP) Site 807A to reconstruct paleoproductivity and nutricline depth over the last 550 ka period. The Zn isotopic composition signal exhibited a generally fluctuating increase, which is similar in a trend found in the Ba/Ti records. In a periodogram of marine productivity tracing, δ66Zn and Ba/Ti showed periodicities of 33 and 31 ka, respectively, suggesting the influence of long-term El Niño Southern Oscillation (ENSO)-like forcing. Good coherence between the paleoproductivity records and the nutricline suggests that nutricline changes could be the primary controlling factor in changes in paleoproductivity. During El Niño-like conditions, the shallow nutricline in the WPWP can result in high prime productivity accompanied by high δ66Zn values. In addition, the higher productivity and shallower nutricline coeval with the occurrence of low CO2 concentrations in the Antarctic ice core might indicate that biological export production at low latitudes could act as a significant sink in the global carbon cycle and modify atmospheric CO2 concentrations. Our new datasets of sedimentary carbonates in the tropical ocean can provide better insight and constrain on marine Zn biogeochemical cycle and a strong potential tracer in paleoproductivity.

Spatial and temporal trends in δ66Zn and 206Pb/207Pb isotope ratios along a rural transect downwind from the Upper Silesian industrial area: Role of legacy vs. present-day pollution

Transect sampling is an under-exploited tool in isotope studies of atmospheric pollution. Few studies have combined Zn and Pb isotope ratios to investigate whether atmospheric pollution at a receptor site is dominated by a different anthropogenic source of each of these toxic elements. It has been also unclear whether pollution abatement strategies in Central Europe have already resulted in regionally well-mixed background isotope signature of atmospheric Zn and Pb. Zinc and lead isotope ratios were determined in snow collected along a rural transect downwind from the Upper Silesian industrial area (southern Poland). Spatial and temporal gradients in δ66Zn and 206Pb/207Pb ratios at four sites were compared with those of ore and coal collected in eight Czech and Polish mining districts situated at distances of up to 500 km. Snow pollution was extremely high 8 km from Olkusz in 2011 (1670 μg Zn L−1; 240 μg Pb L−1), sharply decreased between 2011 and 2018, and remained low in 2019–2021. Snow pollution was lower at sites situated 28–68 km from Olkusz. Across study sites, mean δ66Zn and 206Pb/207Pb ratios of snow were −0.13‰ and 1.155, respectively. With an increasing distance from Olkusz, the δ66Zn values first increased and then decreased, while the 206Pb/207Pb ratios first decreased and then increased. The δ66Zn values in snow plotted closer to those of Upper Silesian ores (−0.20‰) than to the δ66Zn values of Upper Silesian stone coal (0.52‰), showing predominance of smelter-derived over power-plant derived Zn pollution. The 206Pb/207Pb ratios of Upper Silesian coal (1.171) and Upper Silesian ores (1.180) were higher compared to those of snow. A206Pb/207Pb vs.208Pb/207Pb plot identified legacy pollution from leaded gasoline as the low-radiogenic mixing end-member. Across the transect sites, only the last sampling campaign exhibited a high degree of isotope homogenization for both Zn and Pb.

Acid mine drainage and smelter-derived sources affecting water geochemistry in the upper Nakdong River, South Korea

Both the smelter and acid mine drainage (AMD) in uppermost streams impact water geochemistry and deteriorate water quality. Efficient water quality management requires identifying the contribution of each source to stream water geochemistry. In this study, we aimed to determine the natural and anthropogenic sources (AMD and smelting) affecting water geochemistry by considering seasonality. Water samples were collected, from May 2020 to April 2021, in a main channel (Nakdong River) and tributaries in a small watershed including mines and smelters. The watershed is characterized by a carbonate-rich area in the upper-middle reaches and silicate-rich area in the middle-lower reaches. On the plots of Ca/Na vs. Mg/Na and 2(Ca + Mg) vs. HCO3 + 2SO4, the water geochemistry was predominantly explained by the carbonate and silicate weathering associated with sulfuric and carbonic acids. According to typical δ15N values for sources, nitrate contribution from soil-N mainly impacted water geochemistry, regardless of seasonality; the contribution from agricultural activity and sewage was negligible. Water geochemistry in the main channel samples was discriminated before and after passing through the smelter. The effects of the smelter were evident in elevated SO4, Zn, and Tl concentrations and in δ66Zn values; this was further supported by the relationships between Cl/HCO3 and SO4/HCO3 and between δ66Zn and Zn. These results were pronounced during winter, when the flush-out effect was absent. Our results suggest that multi-isotopes and chemical composition analyses can trace multiple sources influencing the water geochemistry in watersheds containing AMD and smelters.

Tracing Sediment Melt Activity in the Sub‐Continental Lithosphere: Insights From Zn‐Fe Stable Isotopes

AbstractRecycling of upper crustal sediments through slab subduction contributes to sub‐continental lithospheric refertilization and heterogeneity. However, the nature of recycled upper crustal components is unclear and direct evidence for sediment melt activity in the sub‐continental lithosphere is lacking. Here, we integrate major and trace elements, zircon U‐Pb dating, Sr‐Nd‐Zn‐Fe isotopic compositions of clinopyroxenites (crust‐mantle boundary) and a “glassy” xenolith from the North China Craton to relate their petrogenesis to the potential recycling of upper continental crust and provide direct insight into the sediment melt‐rock interaction. The clinopyroxenites have relatively uniform δ56Fe values (the permil deviation of the 56Fe/54Fe ratio from the IRMM014; −0.05‰–0.07‰, except for one outlier) and are not affected by melt metasomatism. The clinopyroxenites have highly variable whole‐rock δ66Zn values (the permil deviation of the 66Zn/64Zn ratio from the JMC‐Lyon standard) between 0.04‰ and 0.46‰, that closely correlate with Rb/La, K/U, Ba/Th, and Th/Nb ratios, and generate arrays that trend toward a composition similar to the “glassy” xenolith. The “glassy” xenolith has a high δ66Zn value (0.43‰ ± 0.05‰, 2SD) and a significantly low 143Nd/144Nd ratio (0.510991). This evidence implies that the “glassy” xenolith may represent a quenched sediment melt formed by the melting of carbonate‐bearing terrigenous sediments that may also be responsible for the metasomatism of clinopyroxenite xenoliths. The geochemical evidence from the “glassy” and clinopyroxenite xenoliths provides a direct evidence for the activity of sediment melt with upper continental crust components in the sub‐continental lithosphere.

Zinc isotope fractionation during mid-ocean ridge basalt differentiation: Evidence from lavas on the East Pacific Rise at 10°30′N

Zinc (Zn) isotope data for mid-ocean ridge basalts (MORB) are scarce. The possible effects of MORB differentiation and mantle compositional heterogeneity on MORB Zn isotope compositions are poorly understood. In this paper, we report Zn isotope data of MORB lavas from the East Pacific Rise (EPR) at 10°30′N, which are understood to have been derived by a similar extent of melting from a compositionally uniform mantle source but manifest significantly varying extents of magma differentiation (MgO = 7.38–1.76 wt%) to demonstrate unequivocal Zn isotope fractionation during MORB differentiation. These lavas have a small δ66Zn (relative to the JMC-Lyon standard) range of 0.21–0.32‰, with an average of 0.26 ± 0.07‰ (2SD, N = 24), overlapping with literature data. However, δ66Zn values show significant correlations with indices of magma differentiation (e.g., MgO and CaO), with the more differentiated samples having isotopically heavier Zn. We can thus conclude that MORB differentiation can lead to ∼0.1‰ δ66Zn elevation, which is similar to that observed in Hawaiian Kilauea Iki lava lake samples. Fractional crystallization of olivine and clinopyroxene at MgO > ∼3.5 wt% and clinopyroxene and Fe–Ti oxides dominated by ilmenite at MgO < ∼3.5 wt% results in the observed Zn isotope fractionation. The δ66Zn values for primitive N-MORB and MORB source mantle are estimated to be ∼0.22‰ and ∼0.17‰, respectively. Furthermore, we observe a positive correlation between δ66Zn and [La/Sm]N in primitive (MgO = 7.58–9.01 wt%) literature MORB, indicating the existence of possible Zn isotope heterogeneity in the oceanic upper mantle. We thus predict heavy Zn isotope enrichment in mantle sources for E-MORB samples with high [La/Sm]N, which requires future testing.

Kinetic zinc isotope fractionation in olivine phenocrysts records magma evolution history of intra-plate basalts

In the past few years, zinc isotope systematics of basaltic magmas have been widely used as novel proxies for terrestrial mantle heterogeneity induced by recycled crustal materials and for planet formation and evolution. The influence of crystal-melt isotope disequilibrium during magma differentiation on the zinc isotopic composition of basaltic melts, nonetheless, has received little attention. In addition, no quantitative constraint has yet been given for the diffusion-driven Zn isotope fractionation between olivine crystals and melts. Here we present high-precision zinc isotope data (δ66ZnJMC-Lyon) for a series of olivine phenocrysts separated from intra-plate alkali basalts from the Jiaodong Peninsula in Eastern China, together with in-situ chemical analysis. Olivine phenocrysts have Zn isotopic compositions which are too light in comparison with the host basaltic melts (Δ66Znol-melt = −0.41‰ to −0.10‰; n = 16) to be explained by equilibrium isotope fractionation at magmatic temperatures. Instead, the decrease of δ66Zn values with decreasing Mg# (i.e., Mg/[Mg + Fe2+] × 100) and increasing Zn + Fe2+ contents in olivine phenocrysts suggests diffusion-driven kinetic fractionation during olivine crystallization. The data is well-fitted with a diffusion model in which Zn together with Fe2+ diffuse from surrounding melt into olivine crystals and approximately equal flux of Mg diffuses into melt due to the large chemical gradient, yielding a kinetic Zn isotope fractionation factor βZn of 0.07. By utilizing the fractional crystallization model under equilibrium or disequilibrium conditions, it is suggested that diffusion-induced isotope disequilibrium during olivine crystallization may drive Zn isotopic composition of the residual melt toward heavier values. When using zinc isotope systematics of any basaltic magma to probe the source heterogeneity, this impact must be taken into account if the Zn isotope disequilibrium widely exists in olivine phenocrysts. Based on the time-related quantitative diffusion model, our results show that the magma residence time for strongly alkali basaltic lavas (∼20 days) is 10–60 times shorter than that for weakly alkali basaltic lavas (6 months to 4 years). This supports the generation of weakly alkali basalts via interaction between silica-undersaturated melts and the surrounding lithospheric mantle, implying a probable common mechanism in intra-plate basalts that could be comparable globally. Thus, Zn isotope disequilibrium between olivine crystals and melts could provide valuable information on the evolution history of intra-plate basaltic magmas.

A Mantle Plume Connection for Alkaline Lamprophyres (Sannaites) from the Permian Tarim Large Igneous Province: Petrological, Geochemical and Isotopic Constraints

AbstractThe origin of lamprophyres associated with large igneous provinces (LIPs) remains controversial, particularly whether they are derived by direct melting of mantle plumes, or from previously metasomatized domains in thermally perturbed subcontinental lithosphere. Here, we report the petrological and geochemical characteristics of a recently identified suite of alkaline lamprophyres (sannaites) that represent the final pulse of magmatism in the Permian Tarim LIP in NW China. The sannaites display porphyritic texture with phenocrysts of olivine, clinopyroxene, hornblende, phlogopite, and titanomagnetite in a groundmass of plagioclase, clinopyroxene, nepheline, hornblende, biotite, and titanomagnetite with minor pyrite and apatite. Carbonate ocelli and almost pure albite in the groundmass are interpreted to have crystallized from immiscible carbonate and hydrous fluids, respectively, produced by late-stage magmatic segregation. The rocks show low to moderate SiO2 (37.7–49.3 wt.%) and MgO (2.74–9.91 wt.%), together with high Fe2O3T (up to 22.7 wt.%) and alkali contents (up to 9.02 wt.% Na2O + K2O). They are characterized by high incompatible element abundances, especially a marked enrichment in large-ion lithophile elements (Rb and Ba) and light rare-earth elements (e.g. La and Ce) relative to P and high-field-strength elements (e.g. Ti). They show a relatively restricted range of δ66Zn values between 0.22‰ and 0.46‰ with an average of 0.37 ± 0.04‰ (2SE, n = 10), which is marginally heavier than that of MORBs (0.27 ± 0.05‰). Their (87Sr/86Sr)t values range from 0.7035 to 0.7061, εNd(t) from −0.97 to +5.62, and δ26Mg from −0.36‰ to −0.17‰ (n = 8), the latter being consistent with those of global MORBs. Based on the correlation between Zn isotopes and TiO2–FeO concentrations, we infer that the heavy Zn isotopes in some of the sannaites resulted from fractional crystallization of Fe–Ti oxide minerals. The whole rock geochemical features of these rocks (negative K anomalies and enrichment in large-ion lithophile elements) and rhyolite–MELTS simulations suggest that the primary magmas of the sannaites were derived from an amphibole-bearing enriched lithospheric mantle source. Metasomatism and related formation of amphibole-bearing metasomatized mantle may be linked to sublithospheric melts/fluids derived from the Tarim plume in the earlier stages of plume activity, rather than slab-derived fluids or carbonate melts as suggested in previous studies for other alkaline mantle-derived magmas. Partial melting may have been triggered by the thermal input from the Tarim plume during a later stage. This study suggests that exotic, alkali-rich magmas can be produced during the multi-stage evolution of large mantle plumes, involving complex cycles of lithospheric mantle metasomatism and later melting of previously enriched domains.

The geochemistry of zinc and copper stable isotopes in marine hydrothermal brine pools: Perspectives from metalliferous sediments of the Atlantis II Deep, Red Sea

This study provides a zinc and copper stable isotope characterization (δ66Zn, δ68Zn, and δ65Cu) of metalliferous seafloor sediments from the Atlantis II Deep, a hydrothermally influenced brine basin in the Red Sea. Samples collected from box cores that capture the entire stratigraphy in the Deep have δ66Zn and δ65Cu values of −0.31 to 0.34 ‰ (0.02 ‰ median) and − 1.81 to 1.02 ‰ (−0.34 ‰ median) relative to the JMC-Lyon and NIST SRM 976 standards, respectively. These results suggest enrichments of light stable isotopes in sediments compared to the hydrothermal inputs to the basin, which likely overlap the mantle-like isotopic signatures of basalts beneath the Deep. Such shifts to lower δ66Zn and δ65Cu values are consistent with widespread metal sulfide deposition from the brines because sulfide anions preferentially consume the light stable isotopes of zinc and copper. However, this interpretation contrasts with observations in the open ocean, where the fractionation of zinc and copper stable isotopes is strongly influenced by biological utilization and organic matter. Previous studies proposed that metal deposition in the Atlantis II Deep is also driven by adsorption onto iron oxides/hydroxides and their weakly crystalline (Si-)Fe-OOH precursor phases within the brines. However, because this process should accumulate heavy zinc and copper stable isotopes, its influence on isotopic fractionation is likely limited. Controls by metal sulfide precipitation are also indicated by spatial covariations between δ66Zn and concentrations of zinc and copper, that is, δ66Zn values increase whereas metal contents decrease with distance away from hydrothermal venting. Comparable trends are lacking for copper isotopes, perhaps because of additional influence by redox processes or, compared to zinc, a much stronger influence by adsorption onto (Si-)Fe-OOH phases, particularly in areas distal to hydrothermal venting where reduced sulfur could be scarce. Collectively, our results from the Atlantis II Deep indicate that zinc and copper stable isotopes could provide information about base and precious metals deposits from similar paleoenvironments. Firstly, zinc and copper stable isotopes shed light on metal sourcing and accumulation processes. Secondly, mineral precipitation in hydrothermally influenced brine pools produces zinc stable isotope patterns that, at least theoretically, could be of interest in mineral exploration at sub-basin and deposit scales.

High-precision zinc isotopic characterization of twenty soil reference materials from China determined by MC-ICP-MS.

Zinc isotopic ratios serve as powerful tools for tracing biochemical cycling of metals at Earth's surface, including the distribution, transportation, and enrichment of zinc (Zn) in soil. To conduct such studies and enable inter-laboratory comparisons, high-precision Zn isotopic measurements require the use of soil reference materials (RMs). However, there have been limited reports on the high-precision Zn isotope ratios of soil RMs thus far. In this study, we have developed a two-step Zn chemical separation protocol utilizing Bio-Rad AG MP-1M resin columns. This method has demonstrated excellent reproducibility for measuring the external δ66Zn values (relative to JMC-Lyon) of standard soil reference materials over an extended time period, with a better than 0.06‰ (2SD) precision. Remarkably, this study is the first to report the Zn isotopic compositions of 20 soil reference materials from various soil types in China. With the exception of one sample obtained from a mining area, the Zn isotopic compositions of all the analyzed soil reference materials exhibit remarkable similarity, with an average δ66Zn value of 0.31 ± 0.12‰, which aligns closely with the values observed in igneous rocks. The exceptional sample, with a higher δ66Zn value of 0.61 ± 0.02‰, indicates potential contamination during mining activities.

Speciation and isotopic analysis of zinc in size-fractionated aerosol samples related to its source and chemical processes

Zinc (Zn) in aerosols plays important roles for biological activity and attracts public attention from the perspective of environmental measures. Because of its high volatility and water solubility, Zn is readily released into the atmosphere by human activities and supplied to natural water. To explore the origin and formation process of Zn in atmospheric aerosols, it is important to investigate isotopic (= δ66Zn) and speciation information of Zn in size-fractioned aerosols. We measured light δ66Zn (e.g., δ66ZnIRMM = −1.32‰ as the lowest value; IRMM-3702 is used for the normalization in this study) mainly for the particles ranging from 0.65 to 4.7 μm for the samples collected at Tsukuba, Chiba, and a motorway tunnel (Yasumiyama Tunnel in Hiroshima) in particular for the samples collected in 2002, but δ66ZnIRMM in the particle sizes increased above −0.8‰ for the samples collected in 2011 and 2016. Zn species in aerosols were estimated based on X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy, suggesting that (i) Zn oxalate and sulfate and (ii) Zn oxide, sulfide, and carbonate are main Zn species in fine and coarse particles, respectively. In particular, Zn chloride was found mainly in the middle particle size range (2.1–4.7 μm), which corresponds to the range with light δ66Zn, suggesting that the light δ66Zn was caused by emission of Zn chloride during artificial combustion processes in accordance with other studies. The origins of Zn in aerosols are assumed to have three endmembers; (A) tire and brake wears and road dust, (B) industrial emissions, and (C) vehicular exhaust. Their formation mechanisms are related to vaporization and mixing processes based on the results of combined analysis of atmospheric concentration, speciation, and isotopic composition of Zn with different particle sizes. These trends could be successfully interpreted by species-specific δ66Zn values: component (A) consisting mainly of Zn oxide and sulfide with relatively heavier δ66Zn, component (B) Zn chloride and sulfate secondarily formed in the droplet mode having lightest δ66Zn among all the species, and (C) Zn oxalate with δ66Zn closer to 0‰ due to its emission by the complete combustion in vehicle engines. Species-specific Zn isotope data obtained by the simultaneous application of speciation and isotopic analyses of Zn in size-fractionated aerosols complementary provide novel information on the initial generation and secondary processes for the formation of Zn species in the aerosols.