Radiogenic Research Articles

Magnesium isotopes and zircon geochemistry verify the entrainment of garnet increasing the maficity of S-type granites

It is controversial how S-type granites get higher maficity (MgO + FeOt) than initial melts derived from metasedimentary rocks. Different models, including source-controlled processes (residual/peritectic mineral assemblage entrainment), mixing of magmas derived from different source rocks, and fractional crystallization, have been proposed. However, whole-rock major-trace element and radiogenic isotope data generally provide ambiguous constraints to these models, and the entrained minerals can be later modified by host magmas to have re-equilibrated compositions or replaced by new mineral phases. We address this issue by means of whole-rock Mg isotope and zircon trace element and O isotope analyses on the ∼250 Ma Jiuzhou S-type granite pluton from South China. δ26Mg values of the granites exhibit a negative relationship with increasing maficity, varying from −0.14‰ at 3.00 wt% to −0.43‰ at 8.72 wt%. Zircon yields high and variable δ18O values of 10.0–15.2‰, suggesting that the dominant source rocks are metasedimentary rocks with heterogeneous compositions. No relationship between zircon δ18O value versus whole-rock δ26Mg value or maficity is observed, indicating that magma mixing has played a negligible role in the origin of the granites. Meanwhile, neither Hf nor Ti concentration in zircon shows correlation with whole-rock maficity, precluding fractional crystallization as the dominant mechanism for the compositional variation of the granites. Instead, zircon from granite samples with different maficities seems to have grown from magmas with different compositions but rather similar initial magma temperatures of ca. 810–850 °C as suggested by the upper limit values of the Ti-in-zircon thermometer. Consequently, the negative relationship between δ26Mg value and maficity is best explained as melt entraining a solid assemblage from the melting source, with garnet as the main ferromagnesian phase because this phase is enriched in lighter Mg isotopes than other ferromagnesian phases. This conclusion is supported by the negative relationship between δ26Mg and (Yb/Dy)N values, since garnet is also enriched in heavy rare earth elements (HREE). Furthermore, phase equilibrium modeling using the sample with the lowest δ26Mg value and highest maficity indicates that garnet is always the dominant ferromagnesian phase (exceeding 50% to nearly 100% among the ferromagnesian phases) in the solid assemblage, which equilibrates with melt across a variety of P–T–H2O initial magma conditions (6–8 kbar/800–900 °C/1–5 wt% H2O) at the melting sources. Simple mixing calculations also confirm that the mixing between melt and a solid assemblage consisting mainly of garnet can account for the compositional variation of Mg isotopes with maficity. This study highlights the advantage of integrated geochemical analyses, particularly Mg isotopes, in placing important constraints on the petrogenetic processes that produce high-maficity S-type granites.

Formation of calcium chloride brines in volcaniclastic-rich sediments

The Amami-Sankaku Basin, located in the Philippine Sea, records approximately 50 million years of sediment accumulation and diagenesis of volcanic ash derived from the Kyushu-Palau and Kyushu-Ryukyu arcs. Analyses of porewater and sediment samples from the 1461-m core recovered at IODP Expedition 351, Site U1438, included major and trace elements, strontium radiogenic isotope ratio (87Sr/86Sr), and taxonomic identification of archaeal classes and bacterial orders. Sediment X-ray diffraction and thin section analyses show that smectite, zeolites and chlorite are the main authigenic minerals. A multicomponent solute diffusion and reaction numerical model was developed to simulate the long-term diagenesis that took place in this sedimentary sequence and to account for the transition to a calcium chloride brine at about 670 mbsf. Numerical results indicate that 45% of the initial amount of volcanic ash has been dissolved at 750 mbsf. At this depth, 13% of the initial water (H2O) in the pore space is estimated to have been transferred to the solid phase by the formation of zeolites, which accounts for an increase in porewater chloride concentration. In contrast, dissolution of anorthite and volcanic ash combined with sodium uptake by zeolites accounts for the predominance of calcium in the brine. In the upper 160 m of the sedimentary column, the electrochemical migration of solutes causes chloride to move in the opposite direction of the concentration gradient, i.e., uphill diffusion, sustaining downward diffusion of seawater chloride into the sediments.

Lead isotopic fingerprinting as a tracer to identify the sources of heavy metals in sediments from the Four Rivers’ inlets to Dongting Lake, China

In this study, Pb isotopic composition of bulk sediments and 1 M HCl leachates/residues of samples from the Four Rivers’ inlets to Dongting Lake (China) was determined to identify and differentiate the source of Pb inputs. Results highlighted that Xiangjiang river (XY-QS) sediments were highly enriched in Pb with less radiogenic Pb isotopes (e.g., 206Pb/207Pb ratios of 1.1830 ± 0.003), indicating the predominance of anthropogenic Pb inputs. In contrast, sediments of the Zijiang, Yuanjiang and Lishui rivers (ZD-LH) were moderately enriched in Pb and exhibited more radiogenic Pb (e.g., 206Pb/207Pb ratios of 1.1880 ± 0.008). Results from 1 M HCl extraction of XY-QS sediments illustrated that anthropogenic Pb was removed, which resulted in differentiation of 206Pb/207Pb isotope ratios between leachates (1.1740 ± 0.005) and residues (1.1846 ± 0.008), however, this difference was not observed in ZD-LH sediments (leachates: 1.1887 ± 0.009; residues: 1.1887 ± 0.008). Residual Pb isotope ratios suggested that Pb isotopic composition of lithologically inherited Pb in inlet sediments was similar, which was attributed to mixing, hydrological sorting, and averaging of different Pb sources from diverse geological settings. Pb isotopic tracing showed that Pb in XY-QS sediments resulted from the mixing of two end member sources, an anthropogenic source (less radiogenic Pb) from downstream ore smelting and upstream ore mining activities (53%) and a lithological source (37%) from granite through weathering. In contrast, Pb in ZD-LH sediments resulted from the mixing of multiple sources including Pb from upstream mining activities (20%), coal combustion (20%), and lithologically inherited Pb (60%) while surface sediments from the Yuanjiang river contained Pb from diesel oil usage (50%). Results from this study highlight the utility of a Pb isotope approach for identifying and differentiating Pb source inputs in diverse sediments from the Four River inlets to Dongting Lake (China).

Correlations among large igneous provinces related to the West Gondwana breakup: A geochemical database reappraisal of Early Cretaceous plumbing systems

The opening and spreading of the Atlantic Ocean between Africa and South America evolved during the Early Cretaceous and were preceded by dramatic tholeiitic (mafic) magmatism and minor silicic and alkaline volcanism. These features are presently recognized from the equatorial regions of Brazil and Africa to the Falklands and South Africa. In southeastern South America, continental flood basalts and related plumbing systems constitute the Paraná Magmatic Province (PMP), whose African counterpart is the Etendeka Magmatic Province (EMP). In northeastern Brazil, dike swarms and sill complexes compose the Equatorial Atlantic Magmatic Province (EQUAMP). As a common feature, these provinces are chemically represented by two prevalent magma types: (1) tholeiitic basalts and basaltic andesites with low Ti (TiO2 < ∼2 wt.%), also including transitional Ti tholeiites with TiO2 ∼ 2.7–1.7 wt.%, and low incompatible element contents. This type is predominantly found in the southern PMP and EMP, with minor occurrences in the EQUAMP. (2) Tholeiitic basalts and basaltic andesites with high Ti (TiO2 > ∼2 wt.%) and incompatible element contents. High Ti tholeiites are relevant in the northern PMP and EMP, and dominant in EQUAMP. Evolved rocks (SiO2 = 57–65 wt.%) interpreted as byproducts of assimilation and/or fractional crystallization (AFC) processes from high Ti tholeiitic magmas, are scarce (but present) in all three provinces. An accurate analysis of multivariable databases collected from the literature for dikes and sills, including major and trace element and radiogenic isotope data, reveals close similarities in their geochemical signatures. In a paleogeographic reconstruction of West Gondwana, the intrusive remnants of the PMP, EMP and EQUAMP are spread over an area of nearly 10 × 106 km2, forming perhaps the most extensive set of plumbing systems on Earth, with a relatively consistent chronology based on a vast collection of K–Ar and 40Ar/39Ar data available in the literature. This work provides the first comprehensive data comparison to support the existence of what may have been a single intercontinental-scale magmatic province of West Gondwana.

Dust sources in Westernmost Asia have a different geochemical fingerprint to those in the Sahara

Dust is an important component of Earth's climate system, directly affecting the global radiation budget and hydrological cycle. The interaction of aerosols with clouds and its impact on regional and global energy budgets remains one of the largest sources of uncertainty in climate model predictions. Records of terrigenous dust accumulation in geological archives also provide a potentially powerful way to assess past changes in hydroclimate. Western Asia, including the Arabian Peninsula, is second only to the Saharan Desert in contributing dust to the global atmosphere. Yet, while satellite-derived maps of dust source activation frequency (DSAF) provide an increasingly granular understanding of the different dust sources within these regions today, our ability to fingerprint their windblown contributions to geological archives is rudimentary, severely limiting the use of dust-based records to reconstruct past changes in continental hydroclimate. A main limitation is a poor understanding of the mineralogical and geochemical composition of the bedrock geology and, more importantly, of the readily deflated unconsolidated sediments in these regions. Here we use published data to produce a DSAF map, centred on the Arabian Peninsula and extending from North Africa to Western Asia (∼40-10 °N; ∼25–65 °E), and we present new radiogenic isotope (Sr and Nd) data from unconsolidated surface sediment samples at active dust-producing sites. We combine our new Sr and Nd data with sparse data on sediments from the literature and the DSAF data to define three new preferential dust source areas (PSAs) in Westernmost Asia: (i) the central belt of the Arabian Peninsula, (ii) the Southern Levant and (iii) Mesopotamia. All three of these PSAs are geochemically distinct from Saharan dust sources. Long-range sediment transport by the Blue Nile and its tributaries, and the Tigris-Euphrates river systems exerts a strong influence on the geochemical fingerprints of dust sources in the Eastern Sahara and Mesopotamia, respectively. The isotopic signature of active dust sources in the central belt of the Arabian Peninsula shows only modest correspondence to underlying bedrock geology suggesting wide scale mixing by aeolian transport internally and/or a weak imprint of palaeo humidity (e.g. localized river reactivation) on dust source composition in comparison to the Eastern Sahara. Our results provide surer foundations for fingerprinting the sources of continental dust accumulating in marine, lacustrine, speleothem and ice archives, an important step in improving our understanding of Quaternary rainfall climate in arguably the most water-stressed region on Earth.

Reactive-transport modeling of neodymium and its radiogenic isotope in deep-sea sediments: The roles of authigenesis, marine silicate weathering and reverse weathering

Dissolved Rare Earth Elements (REE) and radiogenic neodymium (Nd) isotope composition (εNd) of seawater are widely used geochemical tools in studying marine processes, but their modern ocean budgets are poorly understood. Recent discoveries of large benthic fluxes of REE with unique εNd signatures from marine sediments, particularly in the deep-sea, have led to a “bottom-up” hypothesis, which suggests that early diagenesis below the sediment-water interface (SWI) controls the ocean's REE and εNd budgets. To investigate such sedimentary processes, we created a reactive-transport model for the biogeochemical cycling of Nd and εNd in marine sediments. Here, we attempt to quantify the roles of authigenesis, marine silicate weathering and reverse weathering in the diagenetic cycling of Nd and εNd at a deep-sea (3000 m) site on the Oregon margin.Our model predicts that, at this site, Nd carried by Fe/Mn oxides into sediments eventually transforms to authigenic Nd-phosphate, during which ∼9% of the incoming solid Nd flux is released as a dissolved benthic flux back to the overlying bottom water. We also find that the classic reversible scavenging formulation applied to Nd co-cycling with Fe/Mn oxides is inconsistent with the data. Rather, a co-precipitation formulation, assuming Nd is structurally incorporated into Fe/Mn oxides, successfully simulates the data. The model also shows that authigenesis alone cannot explain the pore water and authigenic εNd, which are both more radiogenic than bottom water at this site. However, the weathering of volcanic silicates sourced from the local subduction zone can successfully explain εNd. We suggest that, because reverse weathering by authigenic clay formation maintains the under-saturation of primary silicates in pore water, marine silicate weathering can proceed. The processes we model likely affect the sedimentary cycling of many other trace elements and isotopes, with much broader implications for the understanding of ocean biogeochemistry.

Characterization of Saharan and Sahelian dust sources based on geochemical and radiogenic isotope signatures

Mineral dust can significantly impact climate and biogeochemical cycles on Earth. To understand dust provenance, an accurate characterization of dust sources and emission regions is required. In this study, we combine rare-earth element patterns, elemental ratios, and radiogenic Sr-Nd-Pb isotopes to discriminate dust sources from key regions in North Africa responsible for ∼55% of the total dust load emitted annually on Earth. This new dataset, based on fifty-nine analyses of deflatable fine soil material, improves our current knowledge about North African dust sources, especially those underrepresented in Saharan-Sahelian regions. Six potential source areas (PSA) – Libya-Algeria-Mali (PSALAM), Libya-Egypt (PSALE), Bodélé Depression (PSABD), Mali Center (PSAMC), West African Coast (PSAWAC) and Mauritania (PSAMa) – are defined based on several lithogenic tracers as well as on the geological subdivision of North African geological provinces, providing a unique chemical and isotope fingerprint for each PSA. For example, the PSABD – the main dust activation area in North Africa – is clearly distinguished from western African sources using Pb isotopes. Major elements show a large variability within each PSA and are not alone diagnostically useful. Comparison of the newly defined PSA with aerosols collected in remote locations over the North Atlantic shows that their sources are predominantly from western African regions (PSALAM and PSAWAC). Bodélé-derived dust has a limited impact on the bulk dust transported over the tropical North Atlantic, regardless of the season and altitude of dust transport. The low impact of the Bodélé Depression can be explained by a high deposition rate (wet and dry) of aerosols along its southwestward trajectory. A detailed analysis of dust collected over South America during winter will be essential to confirm this observation at a global scale. The present dataset can be efficiently used to track modern dust emissions as well as their changes at the scale of glacial/interglacial cycles or during the development of African Humid Periods as stored in sedimentary archives.

Mafic to felsic dyke swarms in coastal Guangdong, China: geochemical and geochronological constraints on the latest Mesozoic geodynamics on the southern margin of the South China Block

AbstractThe coastal region of Guangdong Province, China, is characterized by well-developed dyke swarms. The dykes with widths of decimetres to metres and lengths of tens of metres occur along straight and planar fractures cutting granites or volcanic rocks with Jurassic to Early Cretaceous ages. They show steep attitudes with strikes varying from NNW to NNE and from NE to SE, consistent with a stress regime transition from E–W to N–S extension. Major-element analysis on representative dyke samples reveals a composition range from basaltic to andesitic with a few dacitic outliers. Trace elements of most samples show notable Nb–Ta negative anomalies and Pb positive anomalies on the primitive mantle normalized spidergrams, characteristic of arc-related rocks. Among these, several dacite samples show notable fractionated medium rare earth elements and heavy rare earth elements and high Sr/Y (47–74) and La/Yb (15–21) ratios indicative of adakitic affinity. A few samples lack anomalies in Nb and Ta and have primitive trace-element ratios (e.g. Nb/La and Sr/Nd) or initial ϵNd values resembling ocean island basalt-like rocks. Rare earth element distribution patterns of all samples are right inclined and generally absent of Eu anomalies, which together with other trace-element indexes indicate an origin from heterogeneous mantle sources with depths below the stability field of plagioclase. Radiogenic isotopes, especially those of Nd and Sr (or Nd–Pb), define an array extended from the depleted to enriched mantle (EMII) provenance. LA-ICP-MS dating of zircon obtains ages between 110 and 70 Ma indicating emplacement of these dykes in latest Early to Late Cretaceous time, a time just before initiation of the South China Sea basin. In the context of regional geodynamics, it is proposed that these dykes were formed in a tectonic setting transiting from a Pacific-related back-arc to a passive continental margin pertaining to the development of the South China Sea basin.

Evolution of Hawaiian Volcano Magmatic Plumbing System and Implications for Melt/Edifice and Melt/Lithosphere Interaction: Constraints from Hualālai Xenoliths

Abstract The evolution of Hawaiian magmatic storage and transport systems in response to variations in magma supply over the course of volcano lifespan can have a significant influence on the type and amount of wallrock material that is assimilated by ponded melts prior to eruption. Understanding this plumbing evolution is therefore critical for evaluating the extent to which such melt/wallrock interaction affects the geochemical signals of Hawaiian basalts. We have examined mineral major and trace element and Sr-Nd-Pb-Hf-Os-O isotope variations in a suite of cumulate and lower Pacific crust xenoliths from the Ka‘ūpūlehu flow, Hualālai Volcano, Hawai‘i in order to constrain the depths of magma storage during Hualālai shield- and post-shield-stage volcanism and the effects of edifice and Pacific crust assimilation. Xenoliths range from 1- and 2-pyroxene gabbros to dunites. Pressures of equilibration for gabbroic and pyroxenitic xenoliths, calculated using two-pyroxene and clinopyroxene-only thermobarometry, suggest that most xenoliths, including both shield- and post-shield-stage cumulates, formed within the Pacific lower crust, at pressures &amp;gt;0.24 GPa. However, two gabbros record lower equilibration pressures (&amp;lt;0.2 GPa) and may have formed within the volcanic edifice. Dunite xenoliths also appear to have formed at shallower depths than most gabbro and pyroxenite xenoliths, inconsistent with a single liquid line of descent. These results indicate that, although shallow (intra-edifice) magma chambers are active during Hawaiian shield-stage volcanism, some magmas also pond and fractionate within or near the base of the Pacific crust during the shield stage. Mass and energy constrained geochemical modeling suggests that ponded melts are likely to assimilate significant quantities of wallrock material, with the mass ratio of assimilated material to crystals fractionated approaching one, regardless of depth of ponding. Elevated 187Os/188Os in some evolved post-shield-derived xenoliths are consistent with assimilation of lower Pacific crust, and low δ18O in xenoliths recording shallow equilibration pressures are consistent with edifice assimilation. However, the effects of assimilation on other radiogenic isotopes appear to be limited in most xenoliths and, by inference, in erupted basalts. Melt–wallrock reaction also appears to have modified the composition of the local Pacific crust. Although plagioclase from the lower oceanic crust record unradiogenic Sr-isotopes similar to mid-ocean ridge basalt (MORB), pyroxene Sr-Nd-Hf and whole-rock Os-isotopes have been variably affected by interaction with Hawaiian melts, resulting in a hybrid isotopic composition intermediate between MORB and Hawaiian shield-stage basalts. These hybrid isotopic compositions are qualitatively similar to Hawaiian rejuvenation-stage basalts. Similar hybridization is likely to have altered the isotopic composition of the Pacific lithospheric mantle. Therefore, Pb-isotope differences between MORB and rejuvenation-stage Hawaiian melts do not preclude melt generation within the Pacific lithosphere or asthenosphere. The isotopic signatures of rejuvenation-stage basalts may represent a unique depleted component within the Hawaiian plume, as suggested by previous studies, but requires additional investigation in light of these results.

Mixing Loops, Mixing Envelopes, and Scattered Correlations among Trace Elements and Isotope Ratios Produced by Mixing of Melts Derived from a Spatially and Lithologically Heterogenous Mantle

Abstract Mixing has been widely used in the interpretation of radiogenic isotope ratios and highly incompatible trace element variations in basalts produced by melting of a heterogeneous mantle. The binary mixing model is constructed by considering mass balance of endmember components, which is independent of physical state and spatial distribution of the endmembers in the mantle source. Variations of radiogenic isotope ratios and highly incompatible trace elements in basalts also depend on the size and spatial distribution of chemical and lithological heterogeneities in the mantle source. Here we present a new mixing model and a mixing scheme that take into account of the size, spatial location, and melting history of enriched mantle (EM) and depleted mantle (DM) parcels in the melting column. We show how Sr, Nd, and Hf concentrations and isotope ratios in the aggregated or pooled melt collected at the top of the melting column vary as a function of location of the EM parcel in the melting column. With changing location of the EM parcel in the upwelling melting column, compositions of the pooled melt do not follow a single mixing curve expected by the binary mixing model. Instead, they define a mixing loop that has an enriched branch and a depleted branch joined by two extreme points in composition space. The origin of the mixing loop can be traced back to four types of EM distribution or configuration in the melting column. The shape of the mixing loop depends on the relative melting rate of the EM to that of the DM and the number and spacing of EM parcels in the melting column. Probabilities of sampling the enriched and depleted branches in the pooled melt are proportional to volume fractions of the enriched and depleted materials in the mantle source. Mixing of pooled melts from a bundle of melting columns results in mixing envelopes in the isotope ratio correlation diagrams. The mixing envelope is a useful tool for studying chemical variations in mantle-derived melts. As an application, we consider scattered correlations in 87Sr/86Sr vs. 143Nd/144Nd and 143Nd/144Nd vs. 176Hf/177Hf in mid-ocean ridge basalts. We show that such correlations arise naturally from melting of a spatially heterogeneous mantle.

The Mesoproterozoic Nampula Subdomain in southern Malawi: Completing the story from Mozambique

New field mapping, lithostratigraphic, whole-rock geochemical, U–Pb zircon and radiogenic isotope data on the Nampula Subdomain of southernmost Malawi show good correlation with those published from adjacent NE and NW Mozambique. The oldest rocks, dated between ∼1180 and 1070 Ma form a complexly interlayered sequence of supracrustal layered paragneisses and migmatites (Nampula Group), intimately interlayered with intermediate-basic (Mocuba Suite) and felsic (Mamala Suite) gneisses, likely meta-volcanic and meta-plutonic in origin. The Mocuba Suite has typical calc-alkaline, I-Type granitoid, TTG compositions, with generally positive ϵNd values, NdTdm ages around 1.2 Ga and low initial 87Sr/86Sr ratios. These characteristics indicate generation in a juvenile volcanic arc setting at this time. Minor exceptions include a few samples which show limited input of Palaeoproterozoic crust. The Nampula arc is viewed as one of a number that developed in a closing oceanic basin which lay between the Archaean-Palaeoproterozoic Congo-Bangweulu-Ubendian-Tanzania cratonic blocks in the north and the Zimbabwe Craton to the SW, and which can be traced “southwards” in Gondwana to continue in the NE part of the ∼1 Ga Maud belt in East Antarctica. The Nampula arc-complex was intruded at ∼1040 by syn-to late tectonic sheets of megacrystic granite/augen gneisses of the Culicui Suite and, at ∼1000 Ma, by a number of bodies of late-to post-tectonic, massif-type anorthosite (Tengani Suite), which are unique to the Malawian segment of the Nampula Subdomain. The anorthosites are considered to have intruded at a post-tectonic stage under a late Mesoproterozoic extensional regime. The rocks underwent deformation and high grade metamorphism in both the Mesoproterozoic (Irumide) and Neoproterozoic-Cambrian (Pan-African) orogenies. P-T data suggest the latter attained peak granulite facies conditions of ∼800 °C at a maximum of 13–18 kbar, comparable with Neoproterozoic granulites in adjacent areas. The data presented here do not rule out either Irumide (∼1 Ga) juxtaposition of the Congo and Kalahari cratons (in Rodinia), or Pan-African (∼0.5 Ga) collision (Gondwana). Instead of this “either-or” situation, a recent hypothesis suggests accretion/collision occurred during both orogenies, separated by a period of drift apart, by the “strange attractor” phenomenon. Our data do not rule exclude that contention; rather, they tend to support it.

Barium isotopes in ocean island basalts as tracers of mantle processes

The compositions of ocean island basalts (OIB) can record signatures of ancient subducted crust that has been recycled through the mantle. Based on their radiogenic isotope, major and trace element compositions, several geochemically-extreme mantle compositions are suggested to host components of recycled crust. Barium (Ba) stable isotopes can serve as a tracer of crustal recycling into the mantle sources of OIB because 1) Ba isotopes are fractionated in surface crustal reservoirs and 2) Ba is highly enriched in crust relative to the mantle. Therefore, the Ba isotopic compositions of the subducted crust could be detected in OIB. Here, we characterized Ba isotopic compositions of fresh OIB from hotspots sampling a range of mantle compositions. We first explore δ138/134Ba (permil deviation of the 138Ba/134Ba ratio from the standard SRM3104a) in a suite of Hekla samples and demonstrate that magmatic differentiation does not impact the δ138/134Ba values of OIB over MgO concentrations from 2.3 to 8.0 wt%, and higher MgO lavas are unlikely to experience δ138/134Ba fractionation. After excluding OIB samples that experienced low-temperature alteration—which may shift the δ138/134Ba values of samples away from their mantle sources—the δ138/134Ba values of Samoan (including EM2 and high 3He/4He) lavas range from -0.07 to 0.07‰, while for Cook-Austral (HIMU) lavas the δ138/134Ba values range from 0.00 to 0.11‰, and for St. Helena (HIMU) samples the δ138/134Ba values range from 0.02 to 0.05‰. High 3He/4He (> 20 Ra, ratio to atmosphere) lavas from Vestfirðir of Iceland (-0.09 to 0.14‰) and Samoa (-0.02 to 0.01‰) also exhibit Ba isotopic variability. An extreme EM2 lava examined here (143Nd/144Nd = 0.512582) has lighter Ba isotopic composition (-0.07 ± 0.02‰, 2SE) than the depleted mantle sampled by MORB (0.05 ± 0.05‰, 2SD). The Samoan lavas show a possible positive trend between δ138/134Ba values and 143Nd/144Nd ratios, and can be modeled as a binary mixing between the high 3He/4He (FOZO) mantle and recycled heterogeneous continental crust. In contrast, the extreme HIMU composition (206Pb/204Pb > 21.7) shows heavier Ba isotope signatures (0.11 ± 0.02‰, 2SE); δ138/134Ba values positively correlate strongly with 206Pb/204Pb ratios in HIMU lavas, consistent with a contribution from recycled oceanic crust.

The multi-isotope biogeochemistry (S, C, N and Pb) of Hypogymnia physodes lichens: air quality approach in the Świętokrzyski National Park, Poland

ABSTRACT The isotope biogeochemistry of bioindicators has widely demonstrated its added value in environmental issues by allowing to precisely identify sources of contamination. Most of the studies are based on studying one or two isotope systematics. Here, we are presenting an innovative multi-proxy approach that combines chemistry with both stable (C, S, N) and radiogenic (Pb) isotope systematics. Using Hypogymnia physodes bioindicators, we evaluated air quality in the complex environment of the Świętokrzyski National Park (ŚNP, Poland) with the ultimate objective of isotopically identifying the sources responsible for the observed contamination. Combining the isotope systematics showed that home heating is a major source of contamination in winter, whereas the contribution of road traffic increases during the summer. Pb isotope ratios identified industrial activities as the major source of this metal in the atmosphere.

Petrological and Geochemical Study of Sundoro Volcano, Central Java, Indonesia: Temporal Variations in Differentiation and Source Processes During the Growth of an Individual Volcano

Abstract Volcanic rocks of the Java sector of Sunda arc have a wide range of isotopic compositions that indicate significant addition of subjected sediment. What processes control these geochemical characteristics is a topic of long-standing debate. Here we report Sr–Nd–Pb radiogenic isotope ratios and geochemical data from stratigraphically well-constrained rocks of Sundoro volcano in central Java that represent the volcano’s activity since 34 ka. The rocks range from basalt (51 wt % SiO2) to andesite (63 wt % SiO2) and are dominated by basaltic andesite. We divide them into magma types A, B and C, having low, medium and high 87Sr/86Sr and Pb isotopic ratios, respectively. According to various differentiation indices, the three magma types have separate, parallel 87Sr/86Sr, Ba/Zr and La/Yb trends and disparate Pb isotopic trends. The dominant process of intracrustal differentiation appears to be magma mixing, in which each of the three magma types represents the mixing of a distinct mafic end-member and a distinct felsic end-member. The distinct geochemical profiles of these magma types indicate that the three mafic end-members are genetically unrelated and that their differences may represent characteristics of their magma sources. On the basis of trace element ratios (Ba/Yb and La/Yb) and Sr–Nd–Pb isotopic compositions, we estimate that magma types A, B and C represent mantle wedge materials fluxed by ~1%, ~1.5% and ~2% slab-derived materials containing 50%, 55% and 65% sediment component, respectively, reflecting increasing proportions of sediments and increasing slab flux. Geochemical data from Merapi volcano, interpreted using the same approach, reveal a similar increase in the slab-derived flux to the magma source, raising the possibility that such short-lived variations in magma genesis, perhaps related to the subduction of bathymetric relief features, characterize the unusual magmatism beneath the volcanic front of the central Java sector of the Sunda arc.

Petrogenesis of Havre Volcano in the Kermadec Arc: 2012 Eruption of a Chemically Homogeneous Rhyolite

The 2012 Havre submarine eruption produced a 1.5 km3 bulk rock volume or 0.52 km3 dense rock equivalent volume of rhyolite emplaced as minor lava flows, a field of sunken seafloor pumice, and a volumetrically dominant pumice raft. This moderately large volume of medium-K (1.4–1.6 wt% K2O) rhyolite pumice is relatively chemically homogeneous (71.5–73.0 wt% SiO2), and no trace element variation or cryptic zoning has been detected despite the textural diversity of pumice material. Radiogenic isotope ratios (87Sr/86Sr 0.703693–0.703744; 206Pb/204Pb 18.7648–18.7781; 208Pb/204Pb 38.587–38.605; 143Nd/144Nd 0.513001–0.513020) demonstrate the Havre rhyolite is sourced from mantle similar to regional eruptive products of the Kermadec arc volcanic front. Providing some further insight into the Havre magmatic system is an abundance of diverse volcanic rock fragments primarily embedded in the banded raft pumice. Embedded rock fragments represent a variety of fresh to hydrothermally altered lavas ranging in composition from basaltic to rhyolitic (50.6–72.3 wt% SiO2) and are likely sourced from varying depths within the volcanic conduit during explosive fragmentation. The diverse embedded volcanic rock fragments, therefore, represent earlier erupted lavas that constructed Havre volcano and are snapshots of the petrogenetic history of Havre. Magnesian augite in basaltic to basaltic andesite embedded rock fragments has a similar compositional range (En55Fs12Wo33 to En39Fs26Wo35) to the previously documented antecrystic clinopyroxene observed in the 2012 rhyolite pumice raft. Herein, we explain how this large volume of chemically homogeneous crystal-poor rhyolite can be generated in an oceanic arc setting based on major and trace element petrogenetic models. Rhyolite-MELTS crystal fractionation models indicate the antecrystic mineral compositions within the Havre pumice of plagioclase (An55–78), and magnesian augites (En53Fs10Wo37 to En40Fs26Wo34) are the primary phases that would crystallize in basaltic to andesitic melt compositions. Modeling indicates that the forerunner basaltic magma must be a relatively dry (∼1 wt% H20) low-K tholeiitic basalt in composition and would require ∼78% crystallization at different pressures to ultimately generate the Havre 2012 rhyolite.

Fault zone fluid pathways in the carbonate Irecê basin, NE Brazil

AbstractWe applied field structural data and isotope geochemical (δ13C, δ18O and 87Sr/86Sr) analyses to understand the relationship among calcite veins, fault damage zones and carbonate host rocks in a thrust fault damage zone in the Achado quarry, Irecê Basin in the São Francisco Craton, NE Brazil. Our results reveal three hydrological packages with different rheological behaviours in a stratified carbonate succession. The upper package includes the Achado fault damage zone that is characterised by interlayered dolomitised grainstones and mudstones. These rocks display high positive δ13C values (10‰–13‰), negative δ18O values (mean −6.34‰) and radiogenic (87Sr/86Sr) isotope values (0.70885–0.71519). A second package is marked by a cataclastic brittle shear zone lateral parallel to dolograinstones bedding. These rocks show low to positive δ13C values (−3.41‰ to +8.85‰), more positive δ18O values (mean −3.73‰) and radiogenic (87Sr/86Sr) isotope values (0.71039–0.71373). The lower package is characterised by well‐preserved pristine limestone succession that shows δ13C values ranging between −0.46‰ and +3.17‰, mean δ18O = −5.41‰ and less radiogenic 87Sr/86Sr values (0.70762–0.70818). In contrast to the upper and intermediate packages, rocks from the lower one exhibit very low permeability and behaved as a seal for fluid migration. Fluid flow occurred several times during basin evolution, for example along syn‐rift fault damage zones, bedding‐parallel carbonate breccia, thrust faults, cataclastic shear zones, synorogenic conjugate shear fractures or joints and opening mode I fracture‐fill calcite veins. These fractures allowed pervasive fluid flow in the porous intermediate cataclastic shear zone where fluids flowed and formed veins, as diffuse fluid flow in randomly oriented fracture swarms, or channelised fluid flow in aligned fracture corridors. They record significant centimetre‐scale to km‐scale hydrological behaviour within carbonate layers. Most carbonates that are associated with veins, fault damage zones and hydraulic breccia were formed by fluids of the same origin with low δ13C (−6.0 to −2.0‰) and δ18O (−6.0 to −8.5‰) values, and more radiogenic 87Sr/86Sr values compared to the carbonate host rocks.

Intensification of Asian dust storms during the Mid-Pliocene Warm Period (3.25–2.96 Ma) documented in a sediment core from the South China Sea

Dust storms are an important component of the global climate system. At the same time, they also bear a risk for human health by causing pulmonary diseases. Today, East Asian dust storms account for as much as half of the global dust emissions and temporarily affect highly populated areas. Therefore, understanding their mechanisms and predicting their evolution under warmer near-future climate conditions is of major interest. The mid-Pliocene Warm Period (mPWP; 3.264–3.025 Ma) is considered one of the best analogues from the past for anthropogenic climate change. Consequently, understanding the climate dynamics and associated environmental change during the mPWP can help with predicting the environmental effects of warmer-than-present climates. In order to reconstruct Asian dust storm evolution during the mPWP we have analyzed a sediment core from the northern South China Sea (SCS) for its elemental composition, grain-size variations and radiogenic isotope signature for the interval spanning from 3.69 to 2.96 Ma. We show that shortly after the first strong northern hemisphere glaciation (Marine Isotope Stage [MIS] M2; 3.25 Ma) atmospherically transported dust appeared in the northern SCS and this dust deposition prevailed throughout the mPWP. Atmospheric dust input further intensified with the onset of the MIS KM2 glaciation at 3.15 Ma, with distinct and strong dust storms occurring periodically from that time onwards. The increase in atmospherically transported dust can be attributed to the cooling and drying of interior Asia over the course of the mPWP along with an intensification of the East Asian Winter Monsoon and a potential southward shift of the westerlies.

Secular evolution of the subcontinental lithospheric mantle beneath Indian cratons: Insights from geochemistry and geochronology of the Precambrian mafic dykes

The Indian Shield is comprised of the Dharwar, Bastar, Singhbhum, Bundelkhand, and Aravalli Cratons, intruded by distinct mafic dyke swarms of different generations (ca. 2.8–0.8 Ga). Most of these dykes are tholeiitic basalt to basaltic-andesite, including boninite. Some other subordinate dyke rocks are of komatiitic, picritic, and andesitic compositions. The vast areal extent of these dykes indicates that they are remnants of Precambrian Large Igneous Provinces (LIPs). The present study reviews the existing geochronological and geochemical data of various Precambrian mafic dyke swarms intruding in all Indian cratons, to track temporal changes in composition of the underlying subcontinental lithospheric mantle (SCLM). Most of these dykes have crust-like abundances of incompatible trace-element. Even the primitive dykes (Mg# = 82–64) exhibit crust-like incompatible element patterns. However, some also have depleted mantle-like abundances of incompatible elements. Most of the dykes also have high concentrations of compatible trace elements (e.g., Cr and Ni). The age-corrected radiogenic Nd isotope compositions (ɛ Nd(i) ) of these dykes vary between the upper continental crust and depleted mantle ɛ Nd growth arrays. The elemental composition and ɛ Nd(i) of these dykes suggest their derivation from a heterogeneous SCLM comprising enriched (metasomatized) and depleted mantle components. The negative as well as positive ɛ Nd(i) values exhibited by the ca. 2.8 Ga (oldest) dykes suggest the presence of enriched mantle materials distributed within a depleted-SCLM already by ca. 2.8 Ga. The enrichment must have occurred before ca. 2.8 Ga due to subduction-released fluids. Later, the SCLM beneath Indian cratons evolved with a composition consisting of an enriched/metasomatized mantle component and a depleted mantle component. • Geochemistry of 2.8–0.8 Ga mafic dyke swarms of Indian cratons have been reviewed. • They originated from heterogeneous SCLM containing enriched & depleted components. • Subduction-driven metasomatism of global SCLM occurred during the Archean.

Radiogenic isotope record of magma genesis and lithospheric geodynamics of the Rukwa Rift Basin, Tanzania, from mid Mesozoic to present

The Western Branch of the East African Rift System has experienced multiple episodes of basin development and intraplate alkaline volcanism since the Jurassic, however the geodynamic processes and lithospheric evolution involved in this protracted geological history remains poorly defined. Here, we present Sm-Nd, Lu-Hf, and Rb-Sr isotopic data of igneous minerals for three magmatic episodes that coincide with basin reactivation in the Rukwa Rift of southwestern Tanzania, respectively represented by: (1) the Jurassic to Cretaceous Panda Hill carbonatite; (2) the late Oligocene phonolitic‑carbonatitic Nsungwe Formation tuffs; and (3) the Miocene–recent bi-modal volcanism of the Rungwe Volcanic Province. Of these, the Nsungwe Formation tuffs offer a discrete record of the early phases of lithospheric disturbance associated with modern rifting of the Western Branch.Alkaline magmas erupted prior to the Miocene are isotopically distinct (ɛNd +0.5 to +1.5 and 87Sr/86Sr 0.7041) from modern Rungwe lavas and likely originate from a lithospheric mantle that experienced enrichment during the Pan-African Orogeny (~550–700 Ma). Consistent with previous studies, our results indicate that Rungwe Volcanic Province magmas were generated from a mixed, isotopically-enriched component of the lithospheric mantle that may have developed during the ca. 1.0 Ga Irumide Orogeny. The observed change in the source region of rift lavas though time is consistent with progressing melting of a compositionally layered lithosphere. Combined with existing geophysical and sedimentological data, we hypothesise that the lithosphere beneath the Rukwa-Malawi-Usangu junction of the Western Branch experienced an episode of destabilisation and foundering (lithospheric drip), during the early stages of East African Rift development.

Identifying Tethys oceanic fingerprint in post-collisional potassium-rich lavas in Tibet using thallium isotopes

Following the Indian-Asian continental collision, the Tibetan Plateau experienced continuous magmatism from south to north, most of which is characterized by high potassium (K) content and negative niobium‑tantalum‑titanium (Nb-Ta-Ti) anomalies. We performed the first exploration using thallium (Tl) isotopes as potential tracers of the source of post-collisional K-rich magmatism. A case study on Tl isotope systematics of K-rich lavas in Ashikule volcanic basin (AVB) in northwestern Tibet is provided, which represents the youngest volcanism in Tibet. Thallium abundances of the AVB lavas are significantly enriched compared to other magmatic settings, with concentrations from 148 to 8259 ng/g. Thallium isotope ratios (reported as ε205Tl) extend to some of the heaviest yet measured in igneous materials, with a range of ε205Tl between −2.7 and + 6.4 ε-units. We evaluate if secondary processes can account for the range in Tl isotope ratios, systematically examining the influences of alteration, degassing, fractional crystallization, and assimilation. Only two samples appear to be influenced by secondary processes, interpreted as kinetic fractionation during degassing, and one sample may be contaminated by sulfides with coupled elevated Tl and Pb contents. The remainder of the Tl isotope ratio range (−2.0 to +5.1 ε-units) we interpret to reflect the source region(s) from which the magmas are derived. The AVB lavas have restricted strontium and neodymium isotopes, suggestive of a homogeneous source, and therefore an apparent decoupling of radiogenic and stable isotope systems is apparent in these lavas. The variation in Tl isotope ratios is interpreted to reflect the contribution of oceanic sediments, which may be associated with ancient Paleo- and Neo-Tethys subductions.