Sr Isotope Ratios Research Articles

The oxygen fugacity of intermediate shergottite NWA 11043: implications for Martian mantle evolution

Shergottite meteorites, classified as depleted, intermediate, or enriched based on incompatible trace elements and specific radiogenic isotope compositions (Sr, Nd, and Hf isotope ratios), point to multiple Martian mantle source regions. The oxygen fugacity (fO2) of these mantle regions, determined from early crystallizing minerals using the olivine-pyroxene-spinel oxybarometer, appears to correlate with incompatible trace element enrichment and isotope compositions. However, values derived from the vanadium-in-olivine oxybarometer challenge this correlation, hinting at potential biases in oxybarometry or complexities in the redox conditions of the Martian mantle. By analyzing the intermediate shergottite Northwest Africa (NWA) 11043 with various oxybarometers, this study deduced its origin from a reduced mantle source, with an average fO2 value of −0.77 ± 0.35 relative to the iron-wüstite (IW) buffer. Notably, these values coincide with those of depleted shergottites, which represent the depleted Martian mantle region. This redox similarity between intermediate and depleted shergottites contrasts with earlier notions that postulated intermediate shergottites as a mix of depleted and enriched mantle derivatives. Moreover, intermediate shergottites such as NWA 11043, Elephant Moraine (EETA) 79001A, and Allan Hills (ALH) 77005 display 176Hf/177Hf values akin to those of depleted shergottites, suggesting that intermediate mantle components can be separated from the depleted mantle source at approximately 2.2 Ga based on model age calculations. Therefore, there presents a consistent redox state between mantle magma sources of both intermediate and depleted shergottites since the Hesperian period, while enriched shergottites lean toward more oxidized conditions past source formation.This study prompts a reassessment of conventional theories, emphasizing the nuanced redox evolution of the Martian mantle across distinct mantle source regions and underscoring the complexity of the redox evolution of the Martian mantle. The emergence of chemically diverse mantle reservoirs might predominantly arise from early magma ocean differentiation processes, albeit with inherent oxidation nuances. The differences in fO2 observed between intermediate and depleted shergottites underscore the need for more in-depth studies to decipher Martian mantle differentiation and evolution.

Sampling Earth’s mantle at intra-transform spreading ridges

The Doldrums transform system, located in the Equatorial Atlantic at 7–8°N, is a 110 km-wide multi-fault shear zone, with five active transform faults separated by four short intra-transform ridge segments (ITRs). The two central ITRs, ITR-2 and ITR-3, are significantly deeper than the peripheral ridge segments, suggesting differences in the thermal conditions of the sub-ridge mantle. New chemical and radiogenic isotope data from on-axis lavas erupted across the transform domain reveal that the basalts from ITR-3 are enriched in alkalis (Na2O + K2O = 4.3 wt%; Na8 up to 3.7) and light rare earth elements (La/Sm)N = 0.86–0.97). However, these basalts have lower Sr and Pb isotope ratios than MORB from the Equatorial Atlantic (i.e., 87Sr/86Sr ∼ 0.70237 and 206Pb/204Pb ∼ 18), and relatively high Nd and Hf isotope ratios (143Nd/144Nd = 0.51315–0.51325; 176Hf/177Hf = 0.2832–0.28325). Hence, the mantle underlying ITR-3 is, on average, depleted in highly incompatible elements. Thermal models of the sub-ridge mantle show that it is also the coldest mantle region under the Doldrums system with the lowest crust production. Considering its location in the central transform domain, it is likely that the local mantle underwent melting beneath adjacent segments of the Mid-Atlantic Ridge (MAR) before remelting below ITR-3. We propose that the initial melting event beneath the MAR selectively removed the most fusible, geochemically enriched mantle components, leaving behind a predominantly peridotitic source, characterized by comparatively low Sr and Pb isotope ratios. Therefore, MORB from intra-transform ridge segments, such as those within the Doldrums transform system, provide a rare opportunity to constrain the isotopic composition of highly incompatible element depleted peridotitic mantle, which is a ubiquitous, but otherwise often camouflaged component of Earth’s mantle.

Uranium-series and strontium isotope systematics in soil carbonates from dryland Critical Zones: Implications for soil inorganic carbon storage and transformation

Soil carbonates are dominantly present in dryland Critical Zone (CZ) and their formation could lead to important long-term carbon sequestration in arid to semiarid soils if the Ca ions were derived from silicate weathering or other non-carbonate sources. In managed CZ systems such as agricultural areas converted from natural drylands, irrigation has profound effects on the dryland CZ inorganic carbon storage, especially by modifying dissolution and precipitation dynamics of soil carbonates via controls of irrigation intensity and water chemistry, soil properties, and hydrological flow paths. These processes could lead to transformation of inorganic carbon in soils and groundwater aquifers underneath drylands. One key knowledge gap in studying soil carbonates from managed dryland CZ systems is to detect the formation of soil carbonates under irrigated conditions and distinguish them effectively from soil carbonates formed under natural conditions.Here, we explore the potential of using U-series and strontium isotopes to investigate the formation timescales and conditions of soil carbonates in both natural and managed dryland CZ in Chihuahua Desert of American Southwest. We obtained new U-series and Sr isotope ratios from mature stage V natural soil carbonates in the Jornada Basin of southern New Mexico and compared to previously published U-series and Sr isotope results for younger Jornada soil carbonates as well as irrigation impacted soil carbonates from the Rio Grande floodplains in west Texas. Specifically, we applied the U-series dating method (238U-234U-230Th) to estimate the timescales of soil carbonate formation under both natural climatic conditions and impacts of modern agriculture irrigation. In addition, we showed that the initial (234U/238U) activity ratios recorded in these soil carbonates reflect the systematic changes of soil infiltration rates in both natural and managed dryland CZ. We also utilized Sr isotope ratios (87Sr/86Sr) in soil carbonates, dust, and irrigation water to trace the Ca sources in soil carbonates from natural and managed dryland CZ. Soil carbonates from both settings were characterized by slightly radiogenic 87Sr/86Sr ratios, consistent with their potential of long-term carbon storage in drylands.U-series and Sr isotope systematics characterize important differences in soil carbonates from natural and managed dryland CZ with respect to their Ca sources, timescales of carbonate formation and transformation, and availability of soil moisture. Soil carbonates formed, accumulated, and transformed in natural drylands with long time scales but under irrigated arid agricultural areas its formation is significantly modified by irrigation and other agriculture practices, with implications for long- and short-term inorganic carbon sequestration in both systems of drylands.

Petrology and Geochemistry of an Unusual Granulite Facies Xenolith of the Late Oligocene Post-Obduction Koum Granodiorite (New Caledonia, Southwest Pacific): Geodynamic Inferences

Pressure–temperature estimates of a xenolith found within a post-obduction granodiorite in southern New Caledonia provide evidence for subcrustal, granulite facies, peak crystallisation conditions (ca. 850 °C—8.5 ± 1.0 kbar), followed by isobaric cooling to 700 °C, and final decompression with partial rehydration at ca. 650 °C—3.5 kbar. The xenolith, dated at 24.7 Ma (U-Pb zircon), i.e., the same age as the granodiorite host rock, has low SiO2 (35.5 wt%) and high Al2O3 (33.2 wt%) contents, suggesting that it is the restite of a previous melting episode, while the elevated Ca (Ba and Sr) contents suggest mantle metasomatism. Although the concentrations of Rb, K, Ca, Ba, and Sr have been strongly modified, some geochemical (REE patterns and some “immobile” trace element ratios) and isotopic (Sr and Nd isotopic ratios, U-Pb zircon age) characteristics of the granulite facies xenolith are similar to those of the xenoliths found in other Late Oligocene intrusions in southern New Caledonia; therefore, this rock is interpreted to be related to an early magmatic episode. The rock protolith was emplaced and equilibrated at the base of the crust where it underwent ductile deformation. Younger ascending magma picked it up and they eventually crystallised together at a shallow crustal level, near the tectonic sole of the ophiolite. The recrystallisation and ductile deformation at ~8.5 kbar suggest that a rheological discontinuity existed at about 25–28 km, probably representing the Moho. It is concluded that a continental crust of normal thickness must have existed beneath New Caledonia at about 24 Ma, i.e., 10 Ma after obduction.

Hydrous veined mantle lithosphere and implications for the source of Zealandia intraplate magmas

Although amphibole has long been predicted to be a major component in the mantle source of intraplate volcanic rocks in New Zealand, the physical evidence for this phase, despite inspection of hundreds of peridotite mantle xenoliths from across the country, is limited to a handful of samples in which it is mostly a sparse component. Here, we present a suite of ultra-refractory peridotite xenoliths in an ultramafic lamprophyre from the intraplate Alpine Dike Swarm, New Zealand, that contain abundant MARID-like veins of mica (phlogopite), amphibole (pargasite) and clinopyroxene, with minor to trace rutile, ilmenite, carbonate and apatite. A key feature of inspecting these formerly refractory peridotites (olivine Mg# commonly >92) is that the chemistry of the precipitated metasomatic agent is less diluted than in cases where an invading melt reacts with fertile lithosphere. The bulk compositions of the precipitated veins vary between sub-alkaline basalt and alkaline basanite, with the peridotite wallrock hosting the basanite veins commonly enriched in Fe ± K, Ti and Al. Amphibole in all veins has high Nb, and the 24 Ma age-corrected 87Sr/86Sr values for diopside and amphibole (0.7027 to 0.7031) are indicative of derivation from a depleted mantle free of crustal material, and thus not related to subduction and arc magmatism. The Sr isotope ratios also overlap with the composition of many primitive intraplate magmas across Zealandia. Melt modelling indicates that partial melting of the veins could generate magmas with geochemical aspects of the known intraplate rocks. These rare veined peridotite occurrences therefore confirm that the Zealandia mantle lithosphere contains fusible zones that, if melted, could have played an important role in the source of intraplate basaltic magma.

Deciphering mantle source heterogeneity in space and time in the back-arc of a contemporary subduction system: A regional study of the Sredinny Range, Kamchatka

We present here the first regional set of Sr-Nd-Pb isotopic compositions, major and trace element compositions and KAr ages for a representative suite of back-arc samples of the Sredinny Range (SR) of Kamchatka. Together with previously published analyses, this unique dataset allowed us to trace the source heterogeneity and invoke new mechanisms to explain the variably enriched geochemical signatures. Our results indicate that the Sr isotopic ratios and the LILE content of the studied rocks were mainly influenced by the subduction fluid. Neodymium isotopes, as well as the HFSE and REE distributions in the rocks, require a more complex explanation, depending on the geographical location of the studied samples and the age of their eruption. Melts representing Miocene rocks of the northern part of the SR and most of the rocks from the eastern and central flanks of the SR (from Miocene until present) were produced from a depleted MORB-like metasomatized mantle, and were then exposed to varying degrees of crustal assimilation and fractional crystallization. Higher HFSE contents and lower 143Nd/144Nd ratios in the western flank lavas, as well as high HFSE contents in the Quaternary lavas of the northern part of the SR and some of the lavas from the eastern flank of the southern part of the SR, require an alternative source for their enrichment. Delamination of the lithosphere explains the unusual, enriched signature of these rocks, whereas their variably enriched neodymium isotope ratios identify the various ages of the separation of the lithosphere from the mantle. The Nd isotopic composition of the rocks together with their HFSE content, therefore, serves as an unusual tracer for the enriched mantle domain, showing the presence of the older lithospheric blocks and indicating the timeframes for this source involvement in magma generation.

Neoproterozoic sedimentary rocks in the Liantuo Formation in South China and their implication based on geochronological and Sr–Nd–Hf–Pb isotope insights

Deposition of the Liantuo Formation is closely associated with the evolutionary history of the Rodinia supercontinent, as indicated by the breakup of the Yangtze Craton in South China. In this paper, we also carried out a detailed UPb zircon examination of the Liantuo Formation. Radiometric dating of sandstone within the Liantuo Formation suggested that it was deposited ca. 790 Ma, which coordinated with the age-paleopole contradictions in the Liantuo Formation for exploring the evolutionary history of the Yangtze Block during the breakup of the Rodinia supercontinent. All the Liantuo sandstones and shales have variable Sr isotopic compositions, with initial Sr isotope ratios ranging from 0.6920 to 0.7217, which support significant fluvial contributions during the deposition of the Liantuo Formation. Samples of the Liantuo Formation show distinct variations in NdHf isotopic compositions, suggesting that the Nantuo Formation received relatively juvenile materials (e.g., the newly formed Neoproterozoic rocks from the northern margin of the Yangtze Block), whereas the Liantuo Formation received relatively mature inputs (e.g., the Huangling granitoids and/or Kongling complex). The samples from the Liantuo Formation also contain various Pb isotopes (206Pb/204Pb = 17.56–17.76, 207Pb/204Pb = 15.05–15.43 and 208Pb/204Pb = 35.51–36.79). These values are also close to the Pb isotopic compositions of the Kongling complex, which suggest that the sedimentary rocks were enriched (the Kongling complex) and are consistent with the NdHf isotope data. That is, the major provenance of the Liantuo Formation is from the South China Block basement, which is the local Kongling complex. In contrast, the Luoquan diamictite can represent the well-mixed composition of the upper continental crust (UCC) in the North China Block during the Neoproterozoic.

Petrogenesis and Tectonic Significance of Shenxianshui Alkaline Granite in Gejiu, Yunnan Province, China

AbstractThe Shenxianshui granites in the western Gejiu area were formed in the Late Cretaceous. Laser ablation inductively coupled plasma mass spectrometry indicates zircon U‐Pb ages ranging from 90.67 ± 0.7 to 85.97 ± 0.6 Ma. The intrusive rocks are peraluminous (A/CNK = 1.03 to 1.33) and calc‐alkaline, showing an affinity towards I‐type granite. Large ion lithophilic elements are enriched in K and Rb, while high field strength elements are depleted. Moreover, light rare earth elements are significantly enriched, showing a slight negative Eu anomaly (Eu/Eu* = 0.39 to 0.58). Shenxianshui granite has a relatively high initial Sr isotope ratio (87Sr/86Sr)i (0.7098–0.7105), negative εNd(t) values (−7.99 to −7.44) and negative εHf(t) values (−8.37 to −2.58). Combined with previous studies, these characteristics suggest that the Shenxianshui alkaline granites were formed in a post‐collision extensional environment. The alkaline granitic magma possibly originated from the partial melting of the lower crust during the Mesoproterozoic era and may have contained mantle source materials. Shenxianshui alkaline granite was formed from mixed magma with a high degree of crystal differentiation. The abundance of ore‐forming elements indicates that Shenxianshui granite has the potential to mineralize key metals and rare earth elements.

Evaporation-free tandem-column separation for Sr from geological samples with high Rb/Sr ratios

A novel tandem column method was devised for effective purification of Sr from geological samples characterized by relatively high Rb/Sr ratios, employing a strategic sequence of columns of AG50-X12 cation resin, Chelex-100 chelating resin and AG50-X8 cation resin. The process initiates with the AG50-X12 column to remove most of the matrix elements, followed by the Chelex-100 column to remove the residual Rb under alkaline conditions despite its inability to adsorb alkali metals such as Na, K, and Rb. The Sr fraction was eluted directly into the Chelex-100 column from the AG50-X12 column by a NH3-NH4Cl solution. The final purification through the AG50-X8 column to eliminate residual NH4Cl ensures the effective removal of matrix elements (such as K, Na, Li, Ti, Al, Fe, Mg, Mn and Ca) and Rb. The Chelex-100 resin acts comparatively to a similar Sr-specific resin for Rb and Sr. This method proved its efficacy and precision by aligning the Sr isotopic ratios from a range of reference materials, (JR-1, JR-2, JB-2, BCR-2, BHVO-2, W-2, GSP-2, CRPG Mica-Mg, CRPG Mica-Fe and NIST SRM 987) with their published values, demonstrating its reliability for Sr isotope analysis in complex geological matrices.

Signature of Sr isotope ratios and the contents of elements as a tool to distinguish wine regions in China

This study investigated 120 Chinese wines from seven regions and had two objectives: to clarify the Sr isotope ratios and elemental characteristics of each region and to develop a strategy to distinguish the geographic origin of wine without authentic samples to predict its origin. The analyzed 87Sr/86Sr values ranged from 0.708256 to 0.715148, which correlated with the geological characteristics of the regions where they were grown. The Hexi Corridor exhibited the highest ratios of Sr isotopes, while Xinjiang had the lowest. The 87Sr/86Sr values were applied to establish a prediction map which was evaluated through cross-validation. The prediction error was found to be less than 0.00074. The Sr isotope ratio could remain stable for an extended period in a specific location. This map shows the feasibility of identifying wine origin and could be applied to other food products. Adding Sr isotope ratios could improve the accuracy in tracing wine origin.

Chemical and 87Sr/86Sr signatures of rainwaters at two active central volcanoes in São Miguel (Azores) – first survey

Rainwater samples were collected during final of February and early March of 2022, at Furnas and Fogo volcanoes, São Miguel (Azores), both of which display secondary manifestations of volcanism. The major-ion composition reveals that marine aerosols contribute significantly to the chemistry of these rainwaters, showed by the proximity of some samples to the Na/Cl ratio of the seawater. The 87Sr/86Sr ratios (0.70849–0.71027) presented by the rainwater samples are similar to the seawater, indicating that marine sprays are possibly the major source of dissolved Sr, with values within the range of values presented by rainwater on the Portuguese mainland. However, other sources, such as volcanic emissions and mineral dust components showed to have also an impact. The 87Sr/86Sr ratios depicted by one sample (CC) deviates from the above mentioned values, exhibiting a lower strontium isotopic ratio (0.70701), which suggests the influence of the fumarolic fluids. Some trace elements (Al, Fe, Mn, Ni, Cu, Zn, Rb, Sr, Ba and REE) content also confirms the influence of the fumarolic emissions, at least in samples collected near Furnas Village fumarolic field (Furnas volcano), and the influence of mineral dust from the surrounding continents (positive anomalies in Eu). Overall, the proximity to an active fumarolic field had a significant impact on the chemistry of meteoric waters, as seen not only in the major-ions, but also in trace elements and in the Sr isotopic ratios.

Petrogenesis of Mesozoic pegmatites in the Dahongliutan Li-mineralized belt (Western Kunlun, NW China)

The genesis of pegmatite and the associated Li-mineralization mechanism remain debated. The intimate temporal-spatial relationship between the pegmatites in the Dahongliutan Li-mineralized belt (incl. #509 Daoban and Akshay Li-poor pegmatites, and Akshay Li-rich pegmatite) and the Dahongliutan granite pluton allows us to discuss the origin of pegmatite and the Li-mineralization mechanism by conducting detailed geochemical and geochronological investigations on the two rock units in the Western Kunlun orogen (NW China). The Li-poor pegmatites in the Dahongliutan Li-mineralized belt exhibit similar or much lower Li, Rb, and Cs compared to the adjacent granite, and their εNd(t) values (-8.7–-10.0) are significantly lower than those of the granite (-7.5–-8.1) as well. However, the Akshay Li-rich pegmatite shows extremely high Li, Rb, Nb, Ta, and initial Sr isotopic ratios (0.7223–0.7227, obtained from apatite), in contrast to the Dahongliutan granite (ISr = 0.7108–0.7157). The whole-rock δ7Li values of the Dahongliutan granite, pegmatites, and the wall-rock Bayanharshan Group metapelite are + 0.76–+5.67 ‰, +0.8–+14.4 ‰, and −4.2–+2.8 ‰, respectively. Zircon and cassiterite U-Pb dating yielded 206Pb/238U ages of 216 ± 2 Ma and 195 ± 2 Ma for the #509 Daoban Li-poor pegmatite and Akshay Li-rich pegmatite, respectively. Modeling of trace elements and Li isotopes suggests that the pegmatites in the Dahongliutan Li-mineralized belt did not originate from fractional crystallization of granitic magma. Instead, they may have formed through direct anatexis under amphibolite-facies conditions. Abundant Li-rich claystone, occasionally accompanied by evaporite, may exist in the magma source of the Li-rich pegmatite, which is the key factor controlling pegmatitic Li mineralization.

Contribution of carbonatite and recycled oceanic crust to petit-spot lavas on the western Pacific Plate

Abstract. Petit-spot volcanoes, occurring due to plate flexure, have been reported globally. As the petit-spot melts ascend from the asthenosphere, they provide crucial information of the lithosphere–asthenosphere boundary. Herein, we examined the lava outcrops of six monogenetic volcanoes formed by petit-spot volcanism in the western Pacific. We then analyzed the 40Ar/39Ar ages, major and trace element compositions, and Sr, Nd, and Pb isotopic ratios of the petit-spot basalts. The 40Ar/39Ar ages of two monogenetic volcanoes were ca. 2.6 Ma (million years ago) and ca. 0 Ma. The isotopic compositions of the western Pacific petit-spot basalts suggest geochemically similar melting sources. They were likely derived from a mixture of high-μ (HIMU) mantle-like and enriched mantle (EM)-1-like components related to carbonatitic/carbonated materials and recycled crustal components. The characteristic trace element composition (i.e., Zr, Hf, and Ti depletions) of the western Pacific petit-spot magmas could be explained by the partial melting of ∼ 5 % crust bearing garnet lherzolite, with 10 % carbonatite flux to a given mass of the source, as implied by a mass-balance-based melting model. This result confirms the involvement of carbonatite melt and recycled crust in the source of petit-spot melts. It provides insights into the genesis of tectonic-induced volcanoes, including the Hawaiian North Arch and Samoan petit-spot-like rejuvenated volcanoes that have a similar trace element composition to petit-spot basalts.

Multi-tracer approach to constrain groundwater flow and geochemical baseline assessments for CO2 sequestration in deep sedimentary basins

Geological storage of gases will be necessary in the push to net zero and the energy transition to reduce carbon emissions to atmosphere. These include CO2 geological storage in suitable sandstone reservoirs. Understanding groundwater flow, connectivity and hydrogeochemical processes in aquifer and storage systems is vital to prevent risk and protect important water resources, such as the Great Artesian Basin. Here, we provide a ‘tool-box’ of geochemical assessment methods to provide information on flow patterns through the basin's aquifers (changes in chemistry along flow path), stagnant versus flowing conditions (cosmogenic isotopes and noble gases), inter-aquifer connectivity and seal properties (major ions, Sr and stable isotopes), water quality (major ions and metals) and general assessments on residence times of groundwater (cosmogenic isotopes and noble gases). This information can be used with reservoir and groundwater models to inform on possible changes in the above-mentioned processes and serve as input parameters for CO2 injection impact modelling. We demonstrate the use and interpretation on an example of a potential CO2 storage geological sequestration site in the Surat Basin, part of the Great Artesian Basin, and the aquifers that overly the reservoir. The stable water isotopes are depleted compared to average rainfall and most likely indicate greater contributions from monsoonal rain events from the northern monsoonal troughs, where amount and rainout effects lead to the depletion rather than colder recharge climates. This is supported by the modern recharge temperatures from noble gases. Inter-aquifer mixing between the Precipice Sandstone reservoir and the Hutton Sandstone aquifer seems unlikely as the Sr isotope ratios are distinctly different suggesting that the Evergreen Formation is a seal in the locations sampled. Mixing, however, occurs on the edges of the basin, especially in the south-east and east where the Surat Basin transitions into the Clarence-Moreton Basin. Groundwater flow appears to be to the south in the Precipice Sandstone, with a component of flow east to the Clarence-Morton Basin. The cosmogenic isotopes and noble gases strongly indicate very long residence times of groundwater in the central south Precipice Sandstone around a proposed storage site. 14C values below analytical uncertainty, R36Cl ratios at secular equilibrium as well as high He concentrations and high 40Ar/36Ar ratios support the argument that groundwater flow in this area is extremely slow or groundwater is stagnant. The results of this study reflect the geological and hydrogeological complexities of sedimentary basins and that baseline studies, such as this one, are paramount for management strategies.

The Early Cenozoic Volcanism of the Northern Okhotsk Region System of Grabens and Faults

Abstract —We studied geochemical compositions of the early Paleocene basaltic and andesite dikes associated to linear zones of the Lankovo–Omolon shearing system (Northern Okhotsk region) and basalts of the Evdyreveem volcanic field associated to the Okhotsk–Penzhinsk fault system, and compared them to other synchronous manifestations of basic volcanism: andesibasalts and andesites of the studied earlier Garmanda field, as well as with the Late Cretaceous basalts of the Mygdykit Formation of the Northern Okhotsk region, roofing the Okhotsk–Chukotka volcanic belt. The isotopic composition of Sr and Nd in dikes, the distribution of major and trace elements with the ratios of noncoherent elements indicate the formation of volcanic bodies in the environment of continental margin rifting, which is confirmed by the combination of depleted, intraplate and above subduction geochemical features of their composition. Such behavior of the elements indicates multi-stage processes of the earlier Mesozoic supra-subduction fluid metasomatosis. Melting of an ancient buried Cretaceous slab may explain the appearance of such “above subduction” marks as the Nb–Ta negative anomalies in the studied basaltoids. Andesite dikes are characterized by higher isotope ratios of Nd and lower Sr, with lower absolute concentrations of trace elements and more pronounced anomalies on spider plots.

Compositional variations in shield-stage volcanism in Fogo, Cape Verde islands

The intraplate oceanic island of Fogo (Cape Verde islands) is in the shield-stage of its evolution. It experienced a major lateral collapse ca. 70 ka ago, after which a sequence of lavas about 2 km thick infilled the collapse scar, with eruptions continuing to the present day. Nearly 100 lavas from before and after the collapse have been sampled and analysed for bulk rock compositions. These lavas have been divided into five Formations (2 pre-collapse and 3 post-collapse), using stratigraphic principles. There is little difference in the major and trace element compositions of pre- and post-collapse lavas, and the main process that gives rise to their diversity is fractional crystallization of observed mineral phases. Pre-collapse lavas show a narrower range of bulk compositions than the post-collapse lavas, but this may be because the sampling strategy avoided these more altered and poorly exposed lavas. A group of high-P2O5 lavas, erupted both before and after the collapse, may have been extensively contaminated by local seamount-stage intrusive carbonatites. A subset of 30 samples was analysed for Sr, Nd and Pb isotope ratios. They show a plume component which has interacted with two contaminants: (1) an increase in 87Sr/86Sr and decrease in 143Nd/144Nd with decreasing MgO, which indicates varying amounts of assimilation of an enriched lithospheric component coupled to fractionation (AFC), and (2) contamination of the more fractionated magmas, without further fractionation, involving the suspected carbonatite contaminant which originates from a more isotopically depleted source. Overall trends of increasing 87Sr/86Sr, and slight decreases in 143Nd/144Nd and all radiogenic Pb isotope ratios, with decreasing age of eruption, indicate a general increase in the assimilated lithospheric component throughout shield-stage activity. However, there is no clear evidence of any change in isotope compositions across the period of the collapse. All Formations show similar wide and overlapping ranges of isotope compositions, regardless of the timescales represented by each Formation. This implies that much short-term variation in the magma sources was superimposed on the overall trend of increasing lithospheric assimilation.

Capabilities and limitations of Pb, Sr and Fe isotopic analysis of iron-rich slags: a case study on the medieval port at Hoeke (Belgium).

In this work, an analytical approach was developed for Pb, Sr, and Fe isotopic analysis of archaeological samples recovered from an iron work site by using multi-collector inductively coupled plasma - mass spectrometry (MC-ICP-MS). The sample types include slag, coal, clay and hammer scales, all obtained from an archaeological site at Hoeke (Belgium). Despite the wide concentration range of the target elements present in the samples and some sample manipulations necessarily performed outside of a clean laboratory facility, the analytical procedure yielded accurate and precise results for QA/QC standards while blank levels were negligible. Preliminary results concerning Pb, Sr and Fe isotope ratio variations in archaeological materials associated with iron working processes are provided. The samples revealed high variability in metal isotopic compositions, with the 208Pb/207Pb ratio ranging from 2.4261 to 2.4824, the 87Sr/86Sr ratio from 0.7100 to 0.7220, and δ 56Fe values from -0.34 to +0.08‰, which was tentatively attributed to the mixing of materials during the iron production process or variability within the source material. Also, contamination introduced by coal and furnace/hearth lining material could have contributed to the wide range of isotopic compositions observed. Because of the absence of information and data for primary ore samples to compare with, the provenance of the materials could not be established. The present study highlights the challenges in interpreting archaeological data, particularly in terms of the isotopic variability observed. It underscores the necessity of integrating analysis data with historical and archaeological knowledge. Further research, involving detailed analysis of these source materials combined with robust historical evidence, is essential to validate hypotheses concerning the origin of iron.

The relative contribution of mantle and continental crustal sources to primitive arc magmas: Insights from the early Palaeozoic Famatinian - Puna arc

Subduction zone magmatism plays a crucial role in driving the exchange of chemical elements between Earth's interior and surface. This survey focuses on the compositional analysis of primitive mafic rocks within an ancient Early Palaeozoic subduction-related magmatic belt. The primary objective is to assess the petrological processes involved in the cycling of chemical elements from the Earth's surface, through the slab and mantle reservoirs, to the crustal arc magmatic systems. By examining the composition of primitive mafic rocks and utilizing inverse modelling techniques, we estimate the composition of the ambient mantle source, which appears to have undergone depletion due to melt extraction before being metasomatized by slab agents. The inverse approach reveals that fluid-mobile elements (Th, U, La, Ce, and Sr) were primarily derived from the slab contribution and suggests that subduction had influenced the abundances of Nb and Ta in the modified mantle source. Conversely, Zr, Hf, and Ti were sourced from the ambient mantle. However, the available mineral/melt partition coefficients used in inverse modelling may overestimate the contribution of Sr and Nb from the slab. Instead, forward modelling is limited by the incomplete preservation of ancient volcanic arc geology. The forward mixing models that consider the interaction between slab-released sedimentary-derived melts and the ambient depleted mantle can explain the observed variations in Nd and Sr isotopic ratios in primitive mafic rocks. Two-component mixing shows that a small mass fraction (≤1.5 wt%) of average Cambrian continental sediments subducted beneath the Early Ordovician arc into a MORB-depleted mantle source account for the abundance of sedimentary-supplied elements such as Th, La, and Ba, as well as radiogenic isotope ratios of 143Nd/144N and 87Sr/86Sr in the primitive mafic magmas. The chemical and isotopic composition of deep-seated primitive mafic rocks reveals a decoupling between incompatible trace elements, which display minimal variation, and radiogenic isotopic ratios, which exhibit a wide range and reflect contributions from continental crustal reservoirs. To explain the observed variations in trace elements and isotopes, we propose a simple model involving simultaneous bulk assimilation (A) and imperfect fractional crystallization (IFC) in an open igneous system, where crystal accumulation and assimilation occur concurrently. Especially, deep crustal physicochemical interaction of primitive arc magmas with supracrustal host rocks may mask the expected clear signature of subarc mantle petrological processes. Our assessment of the Famatinian-Puna arc, an ancient subduction zone, concurs with estimates from active volcanic arcs, underscoring the general applicability of this study case to subduction zone magmatism.

A proof-of-concept study: Determining the geographical origin of Brazilwood, (Paubrasilia echinata) with the use of strontium isotopic fingerprinting

The illicit exploitation of Brazilwood (Paubrasilia echinata) presents a significant challenge in Brazil, given its substantial value in the global production of bows for musical instruments. To address timber provenance, the use of strontium (Sr) isotope ratios as indicators of bedrock signatures has emerged as a robust tool in forensic investigations. In this study, we critically evaluate the efficacy of this approach using Sr isotope data derived from bulk soils and trees collected at two distinct sites in Brazil. Despite the statistically indistinguishable 87Sr/86Sr ratios observed in the investigated tree species, the compiled 87Sr/86Sr isotope ratios of Brazilwood from Brazilwood National Park (PNPB) and the ES Group provide valuable insights into the potential application of this method for tracing forensic timber seizures. This pilot study also addresses crucial sampling considerations.While the regional signatures exhibit clear distinctions, the limited sample sizes underscore the necessity for supplementary methods to confidently attribute timber to a specific source forest. In isolation, this method proves most effective in refuting presumed timber provenances rather than definitively confirming them. The discussion delves into the nuances of the Sr isotope data, emphasizing the importance of increasing the number of samples and exploring complementary techniques for a more comprehensive and reliable assessment of timber origin.

The role of post-mortem alteration in tooth enamel revisited: A combined strontium isotope and geochemical evaluation

Assessing post-mortem alteration of tooth enamel in archaeological burial sites of interest is critical and required in order to accurately interpret the isotope composition of bioavailable Sr for use in determining migration patterns of populations in ancient civilizations. Several statistical approaches have been established to evaluate the degree of post-mortem alteration within tooth enamel, and these are based on the incorporation of trace elements (Mn, V, Fe, REEs, Th, U) typically present within the burial environment. In this study, both new and previously reported chemical data and radiogenic Sr isotope ratios for both modern-day and archaeological tooth enamel samples are presented, which range from pristine to altered in nature. Significant correlations between elevated abundances of mobile elements (V, Fe, Nd, U) and their corresponding Sr isotope signatures are limited and are most prevalent when the latter are compared to their Fe contents. Tooth enamel samples affected by diagenesis based on their outlier chemical composition do not necessarily record perturbed Sr isotope signatures, and therefore should not be precluded precipitously from provenance studies.