Radiogenic Values Research Articles

Evaporite sequences as archives for Mg isotope compositions of seawater - Evidence from a Tethys marginal shelf basin in the Anisian

Evaporites have recently been suggested as a potential archive for recording the Mg isotope compositions (δ26Mg) of coeval seawater. However, episodic dolomitization during the deposition of massive evaporites could cause considerable Mg removal and isotopic fractionation. To constrain the hydrological changes and influence of dolomitization on ambient brine δ26Mg, we present petrographic and mineralogical features, as well as Mg-C-O-Sr isotope data extracted from carbonate phases of a middle Triassic (ca. 247 Myr) marine anhydrite-dolostone sequence from a drill core in eastern China. The drilled lithologies are characterized by massive dolostone layers in the lower part, followed by an upward decline in dolomite contents accompanied by a rise in anhydrite. Multiple lines of evidence consistently point to a syn-depositional origin for the dolostones in a marginal basin of the Tethys Ocean and a lack of diagenetic alteration since deposition. We reconstructed the dynamic changes of δ26Mg values of basin waters based on Mg isotope compositions in dolomite leachates. According to our findings, the δ26Mg values of the basin waters were remarkably high (about 0.38 ± 0.05‰) at the onset of evaporation, indicating a significant Mg sink of the massive dolomitization. The δ26Mg of brine in the basin then changed towards the value of coeval seawater (about −0.32 ± 0.05‰) starting with the deposition of evaporites. Concurrently, 87Sr/86Sr ratios of dolomites shift from radiogenic values towards contemporaneous seawater composition. Our results demonstrate that the evaporite basin was not strictly restricted, and water exchange with the open ocean never ceased. Modeling calculation reveals that, even when the seawater exchange rate is far below the average ocean circulation, δ26Mg of brine in the basin will reach the value of open ocean within 1 Myr, completely removing the influence of early dolomitization. We suggested that massive marine evaporite sequences have the potential to record the long-term evolution of seawater Mg isotopes.

Significance of highly siderophile element and Re–Os isotope systematics in global carbonatites

The systematics of highly siderophile elements (HSE) in carbonatites have rarely been investigated although carbonatite melts are among key metasomatic agents in the Earth's mantle. Thus, establishing the Os isotope systematics of carbonatites is of prime importance because carbonatite metasomatism might play a determining role in driving 187Os/188Os signature of the Earth's mantle as a consequence of extreme mobility of carbonatite liquids. In this study, a suite of carbonatites from continental settings was analyzed for HSE abundances and Re–Os isotope systematics, combined with detailed petrography of sulfide phases, to provide constraints on the HSE behavior during the formation of carbonatite melts, the role of sulfides in distribution of HSE and the reliability of Re–Os isotope compositions. All investigated carbonatites display low ΣHSE <1 ppb whereby calciocarbonatites exhibit supra-chondritic OsN/IrN ratios from ∼1.4 to 15, in contrast to magnesiocarbonatites and Mg/Fe-rich carbonatites showing exclusively sub-chondritic OsN/IrN. We posit that preferential removal of Os over Ir during the segregation of calcite-normative melts from the co-existing S-rich silicate melts is the main driver of Os/Ir elemental fractionation. The present-day 187Os/188Os ratios in carbonatites range from mildly unradiogenic (∼0.124) to extremely radiogenic values (∼115–152), with 187Os/188Os(i) ratios spanning from negative to highly radiogenic (∼17) values, paralleled by highly variable 187Re/188Os ratios between 0.096 and ∼ 26,000, and without any clear relationship to the carbonatite type or emplacement age. The Re–Os systematics of carbonatites appear to be significantly modified by hydrothermal processes resulting in either removal of both Re and Os, or Re addition and, consequently, commonly negative calculated γOs values, which may indicate a rather limited potential of the Re–Os systematics to evaluate the nature of carbonatite melts. Conversely, limited Re–Os data for the samples that were likely not affected by late-stage perturbation indicate a largely radiogenic 187Os/188Os nature of carbonatite melts. Nevertheless, carbonatite melts may, in part, be responsible for the radiogenic γOs values commonly observed in mantle-derived silicate melts influenced by carbonatite-like metasomatism.

Re-Os Systematics in the Layered Rocks and Cu-Ni-PGE Sulfide Ores from the Dovyren Intrusive Complex in Southern Siberia, Russia: Implications for the Original Mantle Source and the Effects of Two-Stage Crustal Contamination

The Dovyren Intrusive Complex (Northern Baikal region, 728 ± 3 Ma) includes the dunite–troctolite–gabbronorite Yoko–Dovyren massif (YDM) associated with a sequence of underlying mafic-to-ultramafic sills, locally demonstrating interbedding relations with the most primitive rocks of the pluton. These sills and apophyses contain sulfide mineralization ranging from globular to net-textured and massive ores. Major types of the YDM cumulates and sulfide mineralization were examined for their PGE contents and Re-Os isotopic systematics. The ten analyzed samples included chilled and basal rocks, poorly mineralized troctolite, PGE-rich anorthosite, as well as three samples from a thick ore-bearing apophysis DV10 connected with the YDM. These samples yielded a Re-Os isochron with an age of 759 ± 36 Ma and an initial 187Os/188Os of 0.1309 ± 0.0026 (MSWD = 110), which is in consistent with the previously reported U–Pb zircon age. It is shown that being recalculated to γOs(t) at t = 728 Ma, these isotopic compositions demonstrate three clusters regarding the relationship between γOs(t) and 187Re/188Os: (i) the chilled gabbronorite (YDM) and subcontact olivine gabbronorite (DV10) yielded the most radiogenic values of γOs(t) 10.5 and 10.0 among basal ultramafics, (ii) plagiodunite, troctolite, and sulfide ores showed lower radiogenic compositions, with γOs(t) ranging from 7.3 to 8.7, (iii) olivine gabbronorite, plagioperidotite, and one sample of PGE-rich anorthosite yield very primitive γOs(t) in the range 4.5 to 5.6 (on average 5.2 ± 0.6). The lowest values of γOs(t) for the least fractionated rocks of the YDM suggest a primitive mantle source, formed from a partly contaminated Neoarchean protolith, which is considered to be anomalous in Upper Riphean due to very low εNd(t) of −16 for the most primitive Dovyren magma (Fo88-parent). The highest values of γOs(t) and relative enrichment in the 34S isotope in the chilled gabbronorite (YDM) and subcontact olivine gabbronorite (DV10) evidence that their primitive to evolved magmatic precursors could be affected by a metamorphic fluid enriched in radiogenic 187Os, originating in the exocontact halo due to the thermal decomposition of pyrite from the dehydrated country rocks. This is consistent with the second-stage contamination of the Dovyren magma by the hosting crustal rocks (probably of 10 wt% shists), generating more evolved Fo86-parent magma with higher εNd(t) of −14.

Viscous Relaxation of Oort and Edgeworth Craters on Pluto: Possible Indicators of an Epoch of Early High Heat Flow

AbstractImpact craters, with their well‐defined initial shapes, have proven useful as heat flow probes of a number of icy bodies, provided characteristics of viscous relaxation can be identified. For Pluto's numerous craters, such identifications are hampered/complicated by infilling and erosion by mobile volatile ices, but not in every case. Large craters offer relatively deep probes of rheological structure, and on Pluto two large old craters in a major dark (volatile‐ice free) region are probably the best examples for possible viscous relaxation: Oort (115‐km diameter) and Edgeworth (140‐km diameter). They are similar in size, location, and apparent age (morphological preservation), but may or may not be coeval. Edgeworth is particularly shallow and its floor appears bowed up above the original ground plane, a classic hallmark of viscous relaxation in which viscosity decreases sharply with depth. Oort is less relaxed, but may be somewhat younger and less affected by an early epoch of high heat flow. Finite element calculations show that this heat flow would have to have been substantial to explain Edgeworth's upbowed floor by viscous relaxation, several times steady‐state radiogenic values for present‐day surface temperatures. We expect Pluto's brittle ice lithosphere to be fractured and porous, however, markedly reducing thermal conductivity and increasing temperatures at depth and relaxation for a given heat flow. We find that most relaxation occurs well within 100 Myr after impact for Edgeworth and Oort, and focus attention on a temporal (and/or regional) epoch of elevated heat flow, possibly tied to the serpentinization of Pluto's rocky core.

Hafnium isotope systematics of zircon in high-grade metamorphic rocks of the Anabar shield, Siberia: Radiogenic Hf without mantle input?

The timing for the onset of plate tectonics, along with the secular changes in the tectonic settings of continental crust formation, continue to be debated. Recent interpretations based on the increase in zircon 176Hf/177Hf ratios at the time of crystallisation (expressed as εHf(t) with respect to chondritic evolution) have been used to ascertain changes in geodynamic settings in the early Earth, specifically in the 3.8–3.6 Ga interval. This increase is widely interpreted as a change in magma generation, from source(s) dominated by ancient crust to source(s) dominated by juvenile inputs from the mantle. At issue, Hf isotope variations remain limited in the early Earth due to the long decay of the LuHf system. This feature, along with the scarcity of rocks and minerals of Eo/Mesoarchaean and Hadean ages, generate large uncertainties over the nature and the timing of the interactions between mantle and crustal reservoirs. The distinction between mantle and crustal sources becomes much clearer in the Palaeoproterozoic, and the study of ancient terranes with several billion years of protracted crustal evolution may hold the key to unlock complex mantle–crust interactions. Here we investigate high-grade metamorphic rocks from the Anabar shield, which contain zircons that crystallised between the Eoarchaean (oldest core at 3814 ± 16 Ma) and the Palaeoproterozoic (youngest core at 2251 ± 15 Ma and youngest rim at 1910 ± 21 Ma). The combination of in situ UPb and Hf isotope analyses in zircon indicates the formation of the continental crust in the Siberian Craton in the Eoarchaean, and a conspicuous metamorphic event at 2.0–1.9 Ga. We demonstrate that 2.0–1.9 Ga zircon ages reflect recrystallisation processes under subsolidus conditions, involving the breakdown of high-Lu/Hf minerals (i.e. garnet and pyroxene). The εHf(t) shift at 2.0–1.9 Ga towards more radiogenic values may not be related to a change in magmatic style and sources, but rather to resetting of the LuHf system in response to heating and metamorphic reactions on a mineral scale. Our findings challenge the widely-evoked mechanism of changes in tectonic style and magma sources to account for vertical arrays in the εHf(t) versus crystallisation age space. This calls for considering alternative options, including those based on petrographic data, when interpreting Hf isotope variations in the Hadean/Archaean detrital zircon record.

Eolian versus fluvial supply to the northern Arabian Sea during the Holocene based on Nd isotope and geochemical records

The north-eastern Arabian Sea (NE-AS) comes under a strong influence of land–ocean–climate interactions and regulates biogeochemical processes through the supply of huge amounts of dissolved and particulate materials and nutrients via eolian and fluvial supply. These processes underwent dramatic changes in the coastal regions due to sea-level rise and climate change during the Holocene; however, their relative roles remain elusive. The NE-AS receives large amounts of dissolved and particulate fluxes, and therefore, reconstruction of the past surface water Nd isotope composition (εNd) and tracing the provenance of sediment using detrital εNd and geochemical records would enable us to assess the role of various processes controlling these fluxes to the northern Arabian Sea. In this study, we have generated authigenic and detrital εNd records and geochemical records in a sediment core from the coastal region of the NE-AS, offshore Saurashtra. We found that the authigenic εNd profile closely followed the Holocene sea-level records; early Holocene less radiogenic values (∼ −8) were sharply shifted to more radiogenic values (∼ −5.5) during the mid-Holocene (6–7 ka) and thereafter remained stable, close to the modern surface water εNd value. The detrital εNd record broadly followed the authigenic εNd record, however, they differ in magnitude. The geochemical records based on major and trace elemental abundances show a similar trend to the authigenic εNd record and concomitant changes with the Holocene sea-level. Our investigation reveals that lower sea-level stand combined with a stronger monsoon during the early Holocene resulted in enhanced fluvial weathering fluxes from the west-flowing rivers and contributed to less radiogenic Nd. This situation changed dramatically during the mid-Holocene due to the weakening of the south-west monsoon and rapid sea level rise, which caused enhanced influence of open ocean water characterised by more radiogenic εNd (∼6) derived from the dissolution of dust from Arabia and African desserts. This dramatic shift in εNd profile indicates the enhanced influence of eolian over the fluvial supply of chemical weathering and erosion fluxes during the mid-Holocene. This observation is also consistent with the higher sedimentation rates with more radiogenic detrital supply. The finding of enhanced influence of eolian over fluvial mode of weathering and erosional inputs to the northern Arabian Sea has important implications for past nutrient supply (fluxes and compositions) and its impact on biogeochemical processes in the Arabian Sea.

A high-resolution Os-Nd-Pb isotopic record of a hydrogenous Fe[sbnd]Mn crust from the Northwestern Pacific and its response to plate motion

Ferromanganese crusts are ideal archives of the isotopic composition of ambient deep waters. The cause of the long-term variations of Nd and Pb in the North Pacific deep water has not been well constrained because of a lack of reliable dating method. In this study, we documented the long-term Sr-Os-Nd-Pb isotopic evolution and major elements chemistry of a ferromanganese crust that grew in Northwestern Pacific deep water. The crust was dated using Os isotopic stratigraphy and has a maximum age of 86 Ma. In the early Cenozoic, εNd values increased from −5.3 to −4.0, and the Pb isotope ratios decreased, which can be explained by an input from the margin of South America that contributed both Nd and Pb to the Pacific deep water. The synchronous variations of Nd and Pb isotopic compositions were relate to the reduction of the source. Since Miocene, εNd value trended to more radiogenic values of −4.8 to −3.3 with oscillation owe to the decreased and pulsed input of the southern component water into the Pacific caused by the closure of the Indonesian seaway. The Pb isotope ratios increased after 35 Ma but remained lower than those of central North Pacific crusts. The Pb isotopic compositions did not respond to the one order of magnitude increase in dust flux and increase of Al content along with Pb isotope ratios since 10 Ma, which support that the arc-derived Pb dominated the Pb isotopic signature as the crust moved from the southern to northern Pacific, although Asian dust may have contributed to the Pb budget.

Authigenic and Detrital Carbonate Nd Isotope Records Reflect Pulses of Detrital Material Input to the Labrador Sea During the Heinrich Stadials

AbstractLimited constraints on the variability of the deep‐water production in the Labrador Sea complicate reconstructions of the strength of the Atlantic Meridional Overturning Circulation (AMOC) during the Late Quaternary. Large volumes of detrital carbonates were repeatedly deposited in the Labrador Sea during the last 32 kyr, potentially affecting radiogenic Nd isotope signatures. To investigate this the Nd isotope compositions of deep and intermediate waters were extracted from the authigenic Fe‐Mn oxyhydroxide fraction, foraminiferal coatings, the residual silicates and leachates of dolostone grains. We provide a first order estimation of Nd release via dissolution of detrital carbonates and its contribution to the authigenic ԑNd signatures in the Labrador Sea. During the Last Glacial Maximum the Nd isotope signatures in the Labrador Sea would allow active water mass mixing with more radiogenic ɛNd values (−12.6 and −14) prevailing in its eastern part whereas less radiogenic values (ɛNd ∼ −18.4) were found on the western Labrador slope. The deposition of detrital carbonates during Heinrich stadials (2,1) was accompanied by negative detrital and authigenic Nd isotope excursions (ɛNd ∼ −31) that were likely controlled by dissolution of dolostone or dolostone associated mineral inclusions. This highly unradiogenic signal dominated the authigenic phases and individual water masses in the Labrador Sea, serving as potential source of highly unradiogenic Nd to the North Atlantic region, while exported southward. The Holocene authigenic ɛNd signatures of the coatings and leachates significantly differed from those of the detrital silicates, approaching modern bottom water mass signatures during the Late Holocene.

National-scale distribution of strontium isotope ratios in environmental samples from South Korea and its implications for provenance studies

Successful application and accurate interpretation of strontium (Sr) isotope ratios (87Sr/86Sr) requires underlying information about the large-scale variabilities in their signatures from a variety of environmental samples, which can be correlated with the Sr isotopic signatures of underlying local geology. In this national-scale study, we analyzed 87Sr/86Sr in soil, plants, stream water, and Chinese mystery snail (Cipangopaludina chinensis) shells collected from South Korea to evaluate large-scale spatial variabilities, interpret relationships among isotopic signatures of various sample types, and generate spatial distribution isoscapes reflecting the heterogeneity of isotopic signatures across South Korea. Non-parametric comparisons among environmental samples showed non-significant differences in their isotopic ratios. The 87Sr/86Sr of plant and soil samples were strongly correlated (R2adj = 0.93), suggesting that both reflect national-scale lithological properties. Similarly, the 87Sr/86Sr of shells showed strong correlations with the 87Sr/86Sr of both plant and soil samples (R2adj = 0.90). The 87Sr/86Sr signatures of environmental samples in this study aligned with expected Sr isotopic values and generally reflected local geology. Spatial distribution maps of samples showed similar 87Sr/86Sr spatial patterns, with high radiogenic values from granitic and granitic gneiss rocks systems and low radiogenic values from volcanic and sedimentary rock systems. Stream water samples showed significant correlations with soil and plant isotopic ratios, but with a low coefficient of determination (R2adj = 0.68). The deviations were much larger for samples with 87Sr/86Sr > 0.720. Further study is needed to improve the accuracy of baseline determination and interpretation of stream water isotopic variations.

Evaluation of Re–Os geochronology and Os isotope fingerprinting of Late Cretaceous terrestrial oils in Taranaki Basin, New Zealand

The rhenium-osmium (Re–Os) isotope system has been applied to several marine and lacustrine petroleum systems worldwide, showing good potential for dating crude oils and correlating them to their source rocks. Here we explore the applicability of the Re–Os geochronometer and Os isotope fingerprinting to terrestrial oils by comparing the Re and Os systematics of Late Cretaceous terrestrial oils from Taranaki Basin, New Zealand, and their correlated coaly source rocks. Comparison is also made with selected Late Cretaceous–Paleocene marine oils and source rocks with varying levels of terrestrial organic matter input.The asphaltene fractions of nine genetically related terrestrial oils from the Maui, Maari-Manaia and Tui Area fields in offshore Taranaki Basin contain low concentrations of Re (0.18–0.45 ppb) and 192Os (1.3–12.7 ppt) comparable to their correlated Late Cretaceous coaly source rocks (Rakopi and North Cape formations; Re 0.19–0.37 ppb, 192Os 5.3–9.6 ppt). The Re and 192Os concentrations in these terrestrial oils are generally one to two orders of magnitude lower than those in marine-sourced oils from the Kora Field in offshore Taranaki Basin and surface seeps in East Coast Basin.The 187Re/188Os and 187Os/188Os ratios of the terrestrial oils failed to yield a precise Re–Os isochron age. We attribute this to: (1) insufficient homogenisation of oils with widely variable initial 187Os/188Os (Osi) values inherited from thick, coaly source rock intervals (up to about 2700 m) within the Maui sub-basin and northern Kahurangi Trough kitchens; (2) insufficient spread of 187Re/188Os values (only 275 units); (3) insufficient time since oil expulsion (modelled to be from approximately 10 Ma to the present day) for the evolution of an isochron; and (4) possible effects of water washing of the oil columns. Although all of the studied oils are water-washed to varying degrees, there is no definitive evidence that water washing has disturbed the Re–Os systematics.The Osi values for the studied terrestrial oils inherited at the modelled time of oil expulsion (approximately 10 Ma) display a wide range (0.47–1.14) and do not provide a unique fingerprint of their Late Cretaceous coaly source rock formations. Osmium isotope compositions therefore appear to have limited potential for broad oil-source rock correlation within the predominantly coal-sourced petroleum systems of Taranaki Basin. The Osi values may, however, provide useful distinction of the terrestrial oils emanating from the Kahurangi Trough (Tui Area oils) from those of the Maui sub-basin (Maui and Maari-Manaia oils) based on the significantly more radiogenic values of the Tui Area oils (0.84–1.14 compared with 0.47–0.65 from Maui and Maari-Manaia oils). Overall, this study has provided useful insights into the potential application of the Re–Os isotope system to terrestrial, coal-sourced petroleum systems.

Processes Associated with Multiphase Dolomitization and Other Related Diagenetic Events in the Jurassic Samana Suk Formation, Himalayan Foreland Basin, NW Pakistan

Foreland fold and thrust belts always represent a complex diagenetic history of carbonate succession, particularly multiphase dolomitization, due to the multi-sourcing nature of fluids affecting syn-to post-depositional successions. The present work documents a comprehensive study on the diagenetic changes, particularly dolomitization patterns in the Jurassic carbonates (Samana Suk Fm) in the Lesser Himalayan fold and thrust belt, NW Pakistan. To better understand the processes involved, integrated field/petrographic, geochemical, isotopic, and micro-thermometric studies were carried out. Field observations indicate that dolostones appear as light grey to brown stratabound and patchy units within the formation. Petrographic analysis reveals that fabric destructive matrix dolomite (RD-I) and fabric preserving replacive dolomite (RD-II) phases are present as distinct units. In addition, saddle dolomite cement (SD) and fracture-filling calcite (CC) are also observed in association with replacive dolomite cement. Geochemical analysis (EPMA) showed that Fe, Mn, and Ba concentrations in matrix dolomite are relatively less than those of replacive/saddle dolomite and fracture-filling calcite, suggesting a hydrothermal source of replacive/saddle dolomite in reducing conditions. Furthermore, stable isotope studies of RD-I showed non-depleted δ18O values, which represent coeval seawater signatures of Jurassic carbonates. RD shows depleted δ18O values and non-depleted δ13C, respectively, indicating burial or elevated temperature of dolomitization. Fracture-filled calcite represents lighter δ18O values and δ13C, indicative of relatively high temperatures. 87Sr/86Sr ratios of all diagenetic phases range from 0.707718 to 0.710747, showing more radiogenic values indicates interaction fluids with more radiogenic sources. Fluid inclusion micro-thermometry data of saddle dolomite shows TH ranging from 102.8 to 186 °C, and salinity ranging from 11.7 to 19.4 eq. wt.% NaCl, suggesting hot saline brines are responsible for the dolomitization. Fracture-filling calcite shows TH ranging from 68.0 to 98.4 °C and salinity ranging from 6.9 to 13.1 eq. wt.%. NaCl suggests moderately hot and saline solutions are responsible for their formation. In conclusion, the above-mentioned studies indicate two distinct processes of dolomitization are involved in the formation of matrix and replacive/saddle-type dolomites. RD-I has formed in the evaporative setting, whereas RD has formed due to the interaction of hydrothermal fluids during burial. Fracture-filling calcite is produced from hot subsurface solutions during uplift related to the Himalayan orogeny.

A multi-proxy, bioavailable strontium isotope baseline for southern Almería, Spain: Using modern environmental samples to constrain the isotopic range of bioavailable strontium

The Spanish region of Almería is well known for its rich geological records and its richness in archaeological remains. Sr isotopes have been applied in archaeology as a powerful tracing tool for individual human and animal mobility, but their application requires extensive regional baselines as reference against which the target materials can be compared. This study presents Sr concentrations and 87Sr/86Sr values of modern environmental proxies (plants, soils and surface waters) from southern Almería to establish such a bioavailable Sr isotope baseline for this region. Additionally, this study evaluates differences in bioavailable 87Sr/86Sr signatures of the plants, soil leachates and surface waters and tests three soil leaching agents, ultrapure water (mq), 1M NH4NO3 and 0.1M HNO3, to better understand variations of Sr isotope signatures captured by the different proxies and to evaluate their suitability for baseline constructions. Our results define a wide range of 87Sr/86Sr values ranging from 0.70836 to 0.71630. Our data reveals a strong influence of the local surface lithology on bioavailable 87Sr/86Sr compositions. While the plants and soil leachates generally returned similar 87Sr/86Sr values, surface waters from the same sites sometimes returned significantly less radiogenic values likely due to transported, carbonate-derived Sr from their catchment areas. The different soil leaching procedures returned leachable fractions with similar 87Sr/86Sr values, but a slight bias was observed for soils with a carbonate component signifying the overall strong control of bioavailable Sr by carbonates. We propose to define bioavailable Sr isotope baselines as the average bioavailable 87Sr/86Sr ratio ± double standard deviation (x̅± 2σ) of 1) plants and soil leachates and 2) surface waters for each surface lithology. The soil and plant-based baselines define the narrowest range in 87Sr/86Sr for areas dominated by Cenozoic volcanic rocks while the widest range is seen in areas dominated by high grade Paleozoic metamorphic rocks. Due to the scarcity of surface water run-off in the arid region of southern Almería, surface water based 87Sr/86Sr baselines could only be defined for sites dominated by Cenozoic sediments and high grade Paleozoic metamorphic rocks.

Depth Profiles of Re-Os Geochemistry in Drill Cores from Hole U1530A in Brothers Volcano Hydrothermal Field, Kermadec Arc: Mobilization and Extreme Enrichment of Os by Volcanic Gas

AbstractBetter understanding metallogenesis in oceanic crust depends on costly sea-floor drilling projects in areas where metal-bearing deposits, such as sea-floor massive sulfide deposits, are currently forming. In 2018, International Ocean Discovery Program (IODP) Expedition 376 recovered drill cores from an active hydrothermal field at Brothers volcano, in the Kermadec arc. These provide insight into the formation of mineral deposits along arcs, the structure and permeability of hydrothermal sites, and the relationship between the discharge of magmatic fluids and the deep biosphere. We report whole-rock major and trace element compositions and the Re-Os isotope geochemistry of hydrothermally altered volcanic rocks in a core from Hole U1530A, extending 453 m beneath the sea floor, and unaltered volcanic rocks in cores from four other drilling sites and interpret these data to better understand subseafloor mixing of hydrothermal fluids and ambient seawater. The core exhibits more radiogenic 187Os/188Os values than typical basal values in four intervals. We propose two causal mechanisms of these radiogenic values: (1) mixing between seawater and hydrothermal fluid, associated with abundant deposition of sulfide or sulfate minerals; and (2) ingress of seawater with radiogenic 187Os/188Os values, associated with abundant chlorite and high porosity. Extreme Os enrichments up to 61.5 ppb are interpreted as the result of mobilization of Os as OsO4 or OsF6 and transport by volcanic gas, which also affected the Re-Os geochemistry of the rocks from the other Expedition 376 holes. Mobilization and transport of Os by volcanic gas may be an appreciable factor in the influx of unradiogenic Os into the ocean.

Boundary processes and neodymium cycling along the Pacific margin of West Antarctica

Neodymium (Nd) isotopes have been utilized as a tracer of water mass source in the modern ocean and in palaeoceanographic studies, though the oceanic cycling of Nd is not yet fully constrained. Recent studies have highlighted the importance of processes that occur near the seawater – sediment interface in altering the Nd isotopic composition of bottom waters. The two major observed processes “boundary exchange” and “benthic flux” have been suggested as playing an important role in setting water mass compositions, however, more studies are needed to constrain their chemical mechanism and the extent to which these processes set the composition of deep waters. The Antarctic continental margin is an important place to study these processes because Antarctic-sourced waters dominate the Southern Ocean and ventilate the global deep ocean. This study is the first to measure and compare seawater, porewater and sediment data from along the margin of Antarctica to examine the nature of potential boundary processes. We show that a process similar to boundary exchange seems to be occurring within porewaters, modifying porewater chemistry by shifting its Nd isotopic ratios to more radiogenic values without significantly increasing the concentration of dissolved Nd. We hypothesize that this shift results from partial dissolution of radiogenic detrital particles, such as smectite, amphibole and/or volcanic glass, while re-scavenging maintains low Nd concentrations. We infer the existence of benthic flux of porewaters to deep waters by examining chemical gradients in porewaters and show that it is much lower on the Antarctic margin compared to other studies. Benthic flux appears to be slightly higher along the Antarctic Peninsula than in the Bellingshausen Sea due to partial degradation of organic matter and associated dissolution of Fe-Mn oxyhydroxides. Taken together, boundary processes do not significantly change the Nd isotopic composition of Antarctic margin seawater because while the porewaters have an altered Nd isotopic composition the Nd concentration of these porewaters is low compared to other settings.

New insights into the mantle source of a large igneous province from highly siderophile element and Sr-Nd-Os isotope compositions of carbonate-rich ultramafic lamprophyres

Despite being volumetrically minor components, carbonate-rich ultramafic magmas like aillikites represent good candidates to investigate the compositional variations in plume and/or lithospheric mantle sources because they represent low-degree melts which preferentially sample highly fusible components including recycled crustal material. To gain new insights into the composition of the plume-related magmas and, more broadly, the petrogenesis of ultramafic lamprophyres, we have undertaken the first comprehensive study of bulk rock and mineral (olivine and Ti-magnetite) highly siderophile element (HSE) abundances and Re-Os isotopes combined with in situ major-, trace-element and Sr-Nd isotope analyses of apatite and perovskite from the Permian Wajilitag aillikites of the Tarim large igneous province, China. The Wajilitag aillikites have high PPGE (Pt and Pd) contents relative to IPGE (Os, Ir and Ru), which can be ascribed to low-degree partial melting and/or fractionation of olivine and laurite. Measured 187Os/188Os ratios are moderately to highly radiogenic (0.186–0.313) with age-corrected γOs values up to +113. In situ Sr and Nd isotope analyses of apatite phenocrysts (87Sr/86Sr(i) = 0.70349–0.70384; εNd(i) = +1.3 to +4.9) and fresh perovskite grains (87Sr/86Sr(i) = 0.70340–0.70390; εNd(i) = +1.3 to +3.8) exhibit limited variability both within and across samples from different aillikite dykes and the only volcanic pipe in the area. These Nd isotopic values resemble those from bulk-rock samples (εNd(i) = +1.9 to +5.2), whereas Sr in apatite and perovskite extends to marginally less radiogenic values than the bulk-rock compositions (87Sr/86Sr(i) = 0.70362–0.70432). The moderately depleted Sr-Nd isotope compositions of magmatic apatite and perovskite, and the previously reported mantle-like C isotope values of these samples suggest that the aillikites and their carbon probably derived from a sub-lithospheric (plume) source with minimal contribution of deeply subducted material. Conversely, the radiogenic Os isotope compositions of the Tarim aillikites and separated minerals require some contribution from recycled crustal material in the plume source. Mass balance calculations suggest that the radiogenic Os isotopes and moderately depleted Sr-Nd isotopes can be reproduced by less than one third of eclogite component addition to a moderately depleted mantle source. We conclude that the combination of complementary isotopic systems can enlighten contributions from different components to mantle-derived magmas and, in this case, clarifies the occurrence of carbon-free subducted oceanic crust in the Tarim plume.

INVESTIGATION OF GEOTHERMAL ENERGY RESOURCE POTENTIAL USING AERO-MAGNETIC AND AERO-RADIOMETRIC DATA OF KANO, NIGERIA

This study focused on investigating the geothermal resource potential in Kano using high resolution aeromagnetic and radiometric data. A total of sixteen (16) sheets of aeromagnetic data with a block dimension of 55 km x 55 km were processed. Thus, the spectral centroid method which result from low wave number part of the wave number-scaled (depth to the centroid) and high-wave-number portion of the power spectrum (depth to the top) were estimated. Thus, the Curie point depth (CPD), geothermal gradient and heat flow were determined using appropriate parameters. The results showed that the CPD values range from 4.27 km to 19.59 km with an average of 11.83 km, and geothermal gradient ranges from 29.6 oC/km to 135.7 oC/m with an average of 82.7 oC/km while the heat flow ranges from 74 mW/m2 to 339.2 mW/m2 with the average of 206.6 mW/m2. Areas with high heat flow and shallow CPD could be prospective areas for geothermal energy. The values of the radiogenic heat obtained in the study area range from 0.15 to 2.77 μW/m3. It was observed that the highest radiogenic heat generation in the area is greater than the average radiogenic heat values in the continental crust. The information obtained from temperature to depth model reveals that, the Curie temperature could be reached at the depths of 6 km within the regions.

Absence of a strong, deep-reaching Antarctic Circumpolar Current zonal flow across the Tasmanian gateway during the Oligocene to early Miocene

The vigorous eastward flow of the Antarctic Circumpolar Current (ACC) connects all major ocean basins and plays a prominent role in the transport of heat, carbon and nutrients around the globe. However, the establishment of a deep circumpolar flow, similar to the present-day ACC, remains controversial thereby obscuring our understanding of its climatic impact. Deciphering the chemical composition of Circumpolar Deep Water (CDW) within the ACC can provide critical insights about its development and evolution. Here we present new fossil fish teeth/bone debris neodymium isotope (εNd) records from Deep Sea Drilling Project (DSDP) Sites 278 and 274 in the southwest Pacific Ocean, with the aim to trace changes in deep water masses across the Tasmanian Gateway between the early Oligocene and early Miocene (~ 33–22 Ma). Site 274 provides the first Nd isotope record proximal to the Ross Sea during the Oligocene (33.5–23.4 Ma). Its Nd isotope composition shows excursions to very radiogenic values, εNd(t) = −3.1 and εNd(t)= − 3.7, at 33.5 Ma and 23.8 Ma, respectively, in response to major steps in Antarctic ice sheet expansion. A shift to lower, more unradiogenic εNd(t) values between 29.7 and 29.1 Ma is linked to an increased influence of proto-CDW upwelling at the site. In contrast, the Nd isotope record from Site 278 in the southern Emerald Basin shows little variability (εNd(t) = −6.0 to −6.7) throughout the Oligocene and early Miocene (30.9–21.8 Ma). Comparison with published data north of the ACC path, demonstrates the presence of two deep water masses in the South Pacific prior to the inferred onset of the ACC (33–30 Ma), one occupying depths between ~2500 and 3000 m (εNd(t)= ~ −3 to −5) and a deep/bottom water mass (> 3000 m) with a more unradiogenic Nd isotope composition (εNd(t)= ~ −6). Site 278 located close to the proto-polar front (proto-PF) indicates that following the inferred onset of the ACC, deep waters bathing the southern Emerald Basin remained more radiogenic in the Southwest Pacific compared to sites along the proto-PF in the South Atlantic and Indian Ocean (εNd(t)= ~ −8.1). This indicates a provinciality in Nd isotope compositions of deep waters along the proto-PF across the Tasmanian Gateway. Our data are incompatible with the existence of a modern-like homogenous (lateral and vertical) Nd isotope composition of CDW along the main flow path of the ACC in all oceanic basins in the Oligocene to early Miocene. We attribute distinct Nd isotope compositions of deep waters across the Tasmanian Gateway to reflect a less deep reaching and weaker ACC (proto-ACC) than today. Our findings suggest that the modern strong and deep-reaching ACC flow must have been developed at a later point in the Neogene.

Apatites for destruction: Reference apatites from Morocco and Brazil for U-Pb petrochronology and Nd and Sr isotope geochemistry

In situ apatite U-Pb petrochronology and Sr-Nd isotope geochemistry requires well-characterized and matrix-matched references materials (RMs), yet only a few suitable apatite RMs are currently available. To ameliorate this issue, we determined the U-Pb, Sm-Nd, and Sr isotopic and elemental compositions of a suite of prospective apatite RMs using isotope dilution (ID) TIMS and laser ablation (LA) ICP-MS. The two RMs, from Morocco (MRC-1) and Brazil (BRZ-1), are cm-sized and available in significant quantities. The U-Pb ID-TIMS data yield an isochron age of 153.3 ± 0.2 Ma for MRC-1. This age is consistent with laser ablation split stream ICP-MS (LASS) analyses that produce an isochron age of 152.7 ± 0.6 Ma. The weighted mean of ID-TIMS analyses for 143Nd/144Nd analyses is 0.512677 ± 3, for 147Sm/144Nd is 0.10923 ± 9, and for 87Sr/86Sr is 0.707691 ± 2. The range and mean of TIMS Sm-Nd isotopic data are reproducible by LA-ICP-MS, but laser ablation Sr data are consistently offset towards more radiogenic values. For BRZ-1 apatite, ID-TIMS U-Pb analyses are dispersed, but a subset of the data yields a coherent age intercept of 2078 ± 13 Ma. The vast majority of LASS spot transects across the apatite produce an isochron that define a younger age of 2038 ± 14 Ma. We interpret this as incorporation of cryptic, younger altered domains within BRZ-1. Discordant U-Pb spot analyses are associated with chemically distinct cracks, likely a result of fluid infiltration. The weighted means of ID-TIMS analyses of BRZ-1 yield 143Nd/144Nd = 0.510989 ± 5, 147Sm/144Nd = 0.10152 ± 8, and 87Sr/86Sr = 0.709188 ± 3. The distribution of Nd isotopic compositions of this RM measured by LA-MC-ICP-MS analyses are comparable to TIMS analyses. By contrast, 87Sr/86Sr measurements by LA-ICP-MS are inaccurate and exhibit large uncertainties, but this RM can be useful for empirically correcting in situ 87Sr/86Sr measurements. The data indicate that MRC-1 apatite may serve well as a U-Pb, Sm-Nd, and Sr RM, whereas BRZ-1 apatite has the most potential as a Sm-Nd RM. These potential RMs provide new benchmarks for in situ apatite chemical analyses and inter-laboratory calibrations.

A strontium isoscape of Italy for provenance studies

We present a novel database of biological and geological 87Sr/86Sr values (n = 1920) from Italy, using literature data and newly analysed samples, for provenance purposes. We collected both bioavailable and non-bioavailable (i.e. rocks and bulk soils) data to attain a broader view of the Sr isotope variability of the Italian territory. These data were used to build isotope variability maps, namely isoscapes, through Kriging interpolations. We employed two different Kriging models, namely Ordinary Kriging and Universal Kriging, with a geolithological map of Italy categorized in isotope classes as external predictor. Model performances were evaluated through a 10-fold cross validation, yielding accurate 87Sr/86Sr predictions with root mean squared errors (RMSE) ranging between 0.0020 and 0.0024, dependent on the Kriging model and the sample class. Overall, the produced maps highlight a heterogeneous distribution of the 87Sr/86Sr across Italy, with the highest radiogenic values (>0.71) mainly localized in three areas, namely the Alps (Northern Italy), the Tuscany/Latium (Central Italy) and Calabria/Sicily (Southern Italy) magmatic/metamorphic terrains. The rest of the peninsula is characterized by values ranging between 0.707 and 0.710, mostly linked to sedimentary geological units of mixed nature. Finally, we took advantage of the case study of Fratta Polesine, to underscore the importance of choosing appropriate samples when building the local isoscape and of exploring different end-members when interpreting the local Sr isotope variability in mobility and provenance studies. Our user-friendly maps and database are freely accessible through the Geonode platform and will be updated over time to offer a state-of-the-art reference in mobility and provenance studies across the Italian landscape.

The chemostratigraphy and environmental significance of the Marlstone and Junction Bed (Beacon Limestone, Toarcian, Lower Jurassic, Dorset, UK)

AbstractTwo fallen blocks of the Marlstone and stratigraphically overlying Junction Bed sampled on the beach below Doghouse Cliff in Dorset, UK (Wessex Basin) have been examined for carbon and oxygen isotopes of bulk carbonate as well as for strontium, carbon and oxygen isotopes and Mg:Ca ratios in the contained belemnites. The sequence, which contains most of the Toarcian zones and subzones within a metre or less of grey to yellow to pink, red and brown fossil-rich nodular limestone, is extremely condensed and lithologically similar to pelagic red limestones of the Tethyan Jurassic that are locally mineralized with Fe-Mn oxyhydroxides (e.g., Rosso Ammonitico). Strontium-isotope ratios of the contained belemnites are compatible with existing reference curves and both blocks show a rise to more radiogenic values post-dating the Pliensbachian–Toarcian boundary. The high degree of correlation between the relatively negative carbon and oxygen isotopes of the bulk carbonate is compatible with significant diagenetic overprint, and contrasts with higher carbon-isotope values in coeval condensed coccolith-rich limestones elsewhere. Evidence for the characteristic signature of the Toarcian Oceanic Anoxic Event, as represented by organic-rich sediment, is absent, possibly owing to a stratigraphic gap. Both blocks exhibit abrupt carbon-isotope shifts to lower values, one of which could represent the limbs of an incompletely recorded negative excursion associated with the Toarcian Oceanic Anoxic Event. That the Toarcian Oceanic Anoxic Event was also a significant hyperthermal is illustrated in both blocks by a drop in oxygen-isotope values and rise in Mg:Ca ratios of belemnites close to the base of the Junction Bed in the lowest part of theserpentinumzone.