Radiogenic Isotope Ratios Research Articles

The origin of solutes in groundwater in a hyper-arid environment: A chemical and multi-isotope approach in the Atacama Desert, Chile

The major ion and the multi-isotopic composition (87Sr/86Sr, δ11B, δ34S(SO4) and δ18O(SO4)) of groundwater from the Central Depression in northern Chile is investigated to identify the origin of groundwater solutes in the hyper-arid core of the Atacama Desert. The study area is between the Cordillera de Domeyko and the Central Depression, at latitudes 24–25°S, and is characterized by near-zero air moisture conditions, rare precipitation and very limited runoff. Groundwater composition varies from Ca-HCO3 to Ca, Na-SO4 type below elevations of 3400 m a.s.l. The rCl/rBr ratio of meteoric waters and groundwater overlap, but significantly increase in the aquifer as salinity goes up due to evapoconcentration far from the Domeyko Cordillera. The wind-displaced dust originating in the Central Depression (87Sr/86Sr: 0.706558–0.710645; δ34S(SO4): 0 to +4‰) affects the precipitation composition in the highest parts of the Domeyko Cordillera (87Sr/86Sr: 0.706746–0.709511; δ34S(SO4): +1 to +6‰), whose δ34S(SO4) and δ11B values are greatly different from marine aerosols, discarding its contribution to dust at this distance inland. Sr and S isotopic values in groundwater indicate a strong relation with three main geological units: i) Paleozoic rocks contribute high radiogenic strontium isotope ratios to groundwater (0.707011–0.714862), while sulphate isotopic composition is probably acquired from atmospheric dust (>− 1.4‰), ii) Jurassic marine limestones contribute low-radiogenic strontium isotopic ratios to groundwater (<0.70784), while sulphate can be related to oxidized sulphides that change the isotopic signatures of sulphur (<−1.2‰), and iii) mixed salts in the Atacama Gravels contribute lower radiogenic strontium isotopic ratios and sulphate to groundwater (87Sr/86Sr: <0.707324; δ34S(SO4): +0.1 to +7.7).These three processes reflect water-rock interactions. The δ11B of groundwater generally up to +13‰, does not increase along the regional groundwater flow path, discarding fractionation by interaction with clays. These results improve the understanding of the groundwater evolution in hyper-arid systems through a new conceptual model.

Revision of the crocodilians from the Oligocene of Monteviale, Italy, and the diversity of European eusuchians across the Eocene-Oligocene boundary

ABSTRACTCrocodilian remains from the Oligocene fossil locality of Monteviale, northeastern Italy, have historically been referred to different genera, but all material was recently assigned to Diplocynodon cf. D. ratelii Pomel, 1847. The purpose of the present work is to clarify the systematics of the known crocodilian remains from Monteviale. The largest collection is housed in Padua, Italy, but museums in La Rochelle, France; Basel, Switzerland; and London, United Kingdom reposit crocodilian remains of uncertain provenance but which are clearly from either Monte Bolca or Monteviale. Radiogenic strontium isotope ratios were measured on the embedding lignite of those specimens to investigate their provenance. The material belongs to the genus Diplocynodon, but it clearly differs from D. ratelii because the nasal elements are excluded from the external nares. Diplocynodon from Monteviale shares the same general suture pattern of the skull with the two species D. tormis and D. muelleri. Diplocynodon muelleri and specimens from Monteviale are also congruent in terms of shape and proportion of the supratemporal fenestrae. However, a revision of D. muelleri is currently needed; thus, the Monteviale species is identified as Diplocynodon cf. D. muelleri. In order to examine the relationships of Diplocynodon from Monteviale, a phylogenetic analysis was carried out and points to a particularly close relationship among D. muelleri, D. tormis, and the Diplocynodon from Monteviale. The occurrence of Asiatosuchus in Monteviale is rejected, supporting the hypothesis of a reduction in crocodilian diversity around the Eocene-Oligocene boundary in Europe.

Second-stage Caribbean Large Igneous Province volcanism: The depleted Icing on the enriched Cake

A long-standing question has been whether the Lower Nicaraguan Rise in the western Caribbean Sea represents thinned continental crust or is part of the Caribbean Large Igneous Province (CLIP). During the R/V Meteor cruise M81/2, the northeastern part of the Lower Nicaraguan Rise including the Hess Escarpment was extensively sampled. Only volcanic and carbonate rocks were recovered and no metamorphic rocks or rocks with continental crustal affinities, indicating that at least the uppermost basement is volcanic and belongs to a volcanic province, probably the CLIP. We provide a comprehensive geochemical dataset, including major and trace elements and Sr-Nd-Hf-Pb double spike isotope ratios, for the volcanic rocks. The basalts are geochemically subdivided into two groups: 1) depleted and 2) enriched. The majority belong to the depleted group with 6–9 wt% MgO and highly depleted incompatible element (e.g. (La/Yb)N = 0.15–0.76, (La/Sm)N = 0.21–0.65) compositions and depleted radiogenic isotope (e.g. εNdi = 8.9–11.0, εHfi = 13.6–16.5, 206Pb/204Pbi = 18.28–18.98) ratios. The subordinate enriched group basalts have 5–8 wt% MgO and were solely recovered from the lower part of the central Hess Escarpment. These rocks possess enriched incompatible element ((La/Sm)N = 1.15–1.60, (La/Yb)N = 1.40–2.57) and isotopic (εNdi = 7.52–8.34, εHfi = 12.6–12.9, 206Pb/204Pbi = 18.87–19.07) ratios resembling E-MORB. The depleted group is distinct from Pacific and Atlantic MORB based on combined 206Pb/204Pb, 143Nd/144Nd and 176Hf/177Hf data. It is similar, but not identical to the highly depleted Gorgona komatiites, thought to be generated during the CLIP event, and depleted Galápagos hotspot track lavas accreted to the Pacific margin of Central America. Ages of ~81 Ma from rocks drilled on the Hess Escarpment postdate the main CLIP phase (95-83 Ma), and indicate that at least the northeastern part of the Nicaraguan Rise formed during a later volcanic event. Lithospheric thinning after the main CLIP phase is suggested to have triggered upwelling of still anomalously hot, partially-melted or unmelted CLIP mantle material to form the younger depleted group of lavas. Our investigations imply that second-stage melting to generate depleted compositions during formation of oceanic large igneous provinces, as has been recently proposed for the Manihiki Plateau, is a more common process than originally thought.

Investigating ocean island mantle source heterogeneity with boron isotopes in melt inclusions

Recycling of the lithosphere via subduction drives the trace element and isotopic heterogeneity of the mantle, yet, the inventory of volatile elements in the diverse array of mantle reservoirs sampled at ocean islands remains uncertain. Boron is an ideal tracer of volatile recycling because it behaves similarly to volatiles during high-temperature geochemical reactions and carries a distinctive isotope signature into the mantle, but is subsequently little-influenced by degassing on return to the surface. Furthermore, B-rich recycled lithologies will have a strong influence on typical upper mantle compositions characterized by low B concentrations (<0.2 μg/g and δ11B −7.1 ± 0.9‰). Here, we present and compare the B abundances and isotope compositions, together with the volatile element contents (H2O, CO2, and Cl) of basaltic glasses and olivine-hosted melt inclusions from two different ocean island localities (La Palma, Canary Islands, and Piton de Caille, La Réunion Island). Our results suggest that olivine hosted melt inclusions are protected from contamination during ascent and provide more robust estimates of primary mantle source δ11B than previous bulk rock studies. We find that the δ11B of the La Réunion samples (−7.9 ± 0.5‰ (2σ)) overlaps with the recently defined MORB datum, indicating that the depleted upper-mantle and ‘primitive mantle’ reservoirs are indistinguishable with respect to δ11B, or that B concentrations are sufficiently low that they are diluted by partial melting in the uppermost mantle. In contrast, the La Palma samples, notable for their radiogenic Pb isotope ratios, are characterized by δ11B values that are distinctly isotopically lighter (−10.5 ± 0.7‰ (2σ)) than La Réunion or MORB. We suggest these isotopically light values are derived from significantly dehydrated recycled materials preserved in the La Palma mantle source region, in keeping with their lower B/Zr and H2O/Ce. This work therefore provides strong new support for subduction zone processing as a mechanism for generating radiogenic Pb isotopic signatures and volatiles heterogeneities in the mantle.

Hanzhong bronzes and highly radiogenic lead in Shang period China

For decades, the origin of the bronzes with distinct highly radiogenic lead isotopic ratios in Shang period China has been a puzzle. This paper presents new lead isotope data for bronze objects from the Hanzhong region, one of the key regional bronze cultures during Shang period China. On the basis of a synthetical investigation of the typological, chemical and lead isotopic features of Hanzhong bronzes and their relations to other regional bronze cultures, we propose the Qinling area as a potential region of origin for the metals containing highly radiogenic lead used by several contemporaneous but culturally/politically distinct entities across a vast territory. Taking into account both archaeological and geological evidence, this working hypothesis draws attention not merely to the geological provenance of metal resources, but also to the mechanisms of metal production and circulation as well as broader social-economic dynamics.

Submarine Deep‐Water Lava Flows at the Base of the Western Galápagos Platform

AbstractTo investigate the initial phases of magmatism at the leading edge of the upwelling mantle plume, we mapped, photographed, and collected samples from two long, deep‐water lava flows located at the western base of the Galápagos Platform using the remotely operated vehicle Hercules. Lavas were recovered from four areas on the seafloor west of Fernandina volcano, including the western flow fronts of two deep‐water flows, heavily sedimented terrain between the two flows, and the eastern, shallower end of one flow. The sediment cover and morphologies are distinct between the western flow fronts and the eastern region based on seafloor imagery, suggesting that the long lava flows are not a single eruptive unit. Major and trace element concentrations reveal both tholeiitic and alkalic compositions and support the interpretation that multiple eruptive units comprise the deep‐water flows. Alkalic lavas have higher [La/Sm]N ratios (2.05–2.12) and total alkali contents (5.18–5.40) compared to tholeiitic lavas, which have [La/Sm]N ratios ranging from 1.64 to 1.68 and total alkali contents ranging from 3.07 to 4.08 wt%. Radiogenic isotope ratios are relatively homogeneous, suggesting a similar mantle source. We use petrologic models to assess three alternative mechanisms for the formation of the alkalic magmas: (1) high‐pressure crystallization of clinopyroxene, (2) mixing of high silica and mafic magmas, and (3) variable extents of melting of the same mantle source. Our modeling indicates that the alkalic samples form from lower extents of melting compared to the tholeiitic lavas and suggests that the deep‐water alkalic lavas are analogous to the initial, preshield building phase observed south of Hawaii and at the base of Loihi Seamount.

Nutrient cycling in a tropical montane rainforest under a supply-limited weathering regime traced by elemental mass balances and Mg stable isotopes

Forest ecosystem nutrition and rock weathering are intimately linked through the supply of mineral nutrients and recycling (re-utilisation of nutrients released from plant litter during mineralisation). Here, we report on novel applications of Mg stable isotopes in combination with mass balance calculations to quantify nutrient supply (from bedrock, atmospheric wet and dry deposition) and recycling in a tropical ecosystem, characterised by a supply-limited weathering regime in the Central Highlands of Sri Lanka. We measured Mg stable isotopes, radiogenic Sr isotope ratios, and element concentrations in the different compartments of the Earth's Critical Zone (bedrock, saprolite, soil, soil pore water, stream water and vegetation) as tracers for element mass fluxes and pathways. We find that in the clay-rich saprolite Mg isotopes are fractionated towards isotopically heavy Mg during secondary mineral formation. Soil pore water and stream water are the complementary isotopically light reservoirs. The Mg isotope composition of above-ground vegetation is on average identical to soil pore water. Based on these observations we suggest that a tight near-surface mineral nutrient loop between plants and soil sustains the tropical forest ecosystem. This loop is disconnected from the rock weathering nutrient source in the saprolite beneath soil. External atmospheric wet and dry inputs (mainly Mg and Ca) strongly contribute to the plant-available nutrient budget that the nutrient depleted regolith does not supply. These findings, based on Mg stable isotopes, agree with independently-obtained information on bio-element (P, K, Ca, Mg, Si) recycling. This nutrient supply setting contrasts with that reported for the Southern Sierra Nevada (USA), where a kinetically limited weathering regime prevails. Our study illustrates the application of new flux estimators based on elemental and metal stable isotope measurements across a range of climate and weathering regimes.

In situ Pb-Pb isotopic dating of sulfides from hydrothermal deposits: a case study of the Lala Fe-Cu deposit, SW China

Precisely dating different generations of mineralization is important for understanding the origin and tectonic environment of ore formation. In this study, we have dated two generations of sulfides from the Lala Fe-Cu deposit, SW China, using in situ Pb-Pb isotopic data obtained by the LA-MC-ICPMS technique. The Lala deposit is composed of Fe-Cu ore bodies hosted in sedimentary-volcanic rocks of the Paleoproterozoic Hekou Group. It has a paragenetic sequence of pre-ore banded pyrite (Stage I) and Na alteration (Stage II), followed by early Fe (Stage III) and late Cu (Stage IV) mineralization. The sulfides in the deposit have dominantly formed in two stages, including pyrite from stratiform pyrite bands in the host rocks (i.e., Stage I) and epigenetic pyrite-chalcopyrite in Fe-Cu ore (i.e., Stage IV). The sulfides of both stages have highly radiogenic Pb isotopic ratios which form linear trends in the 207Pb/204Pb versus 206Pb/204Pb diagram. The regression trend for Stage I pyrite grains defines an errorchron age of 1669 ± 110 Ma (MSWD = 32), undistinguishable from zircon LA-ICPMS U-Pb ages of volcanic rocks in the Hekou Group (i.e., ~ 1700 Ma). The regressions for Stage IV pyrite and chalcopyrite yield younger errorchron ages of 1088 ± 88 Ma (MSWD = 93) and 1053 ± 220 Ma (MSWD = 15), respectively. Taking pyrite and chalcopyrite together, an errorchron age of 1053 ± 75 Ma (MSWD = 108) is obtained. These errorchron ages agree well with the molybdenite Re-Os age of the Fe-Cu ore (1086 ± 8 Ma). Despite the large error and MSWD values that are interpreted to be related to the small variation of initial ratios, or post-ore open system behavior, the good agreement with the precise zircon U-Pb and molybdenite Re-Os ages indicates that the Pb-Pb errorchron ages for Stage I and IV sulfides are geologically meaningful. Therefore, this study shows that the in situ Pb isotopic analyses can yield geologically meaningful Pb-Pb ages for radiogenic Pb-rich sulfide minerals. We also propose that in situ Pb-Pb isotopic dating may be more promising for Precambrian deposits containing sulfides with ingrown Pb, particularly for those involving multiple mineralization/hydrothermal events but without relevant minerals for precise Re-Os or U-Pb dating.

Controls on the solute geochemistry of subglacial discharge from the Russell Glacier, Greenland Ice Sheet determined by radiogenic and stable Sr isotope ratios

We used radiogenic and stable Sr isotope ratios (87Sr/86Sr and δ88/86Sr) to examine controls on solute acquisition in subglacial discharge from the Russell Glacier, a land-terminating lobe of the Greenland Ice Sheet (GrIS) located in western Greenland. The study focused on two melt seasons in 2014 and 2015. Subglacial discharge 87Sr/86Sr ratios are 13,000 ppm higher than those measured for bedload and suspended sediment digests, and are more similar to those of bedload sediment leachates. These results point to the preferential dissolution of minerals with high 87Sr/86Sr ratios. Analyses of mineral separates from bulk rocks demonstrate that biotite, chlorite, hornblende, and K-feldspar have relatively high 87Sr/86Sr ratios. Subglacial discharge δ88/86Sr values are ∼0.10‰ higher than those for bedload and suspended sediment digests. Isotope fractionation during secondary mineral formation and/or adsorption cannot account for the difference between subglacial discharge and bedrock δ88/86Sr values, as suspended and bedload sediment leachates and digests produced similar δ88/86Sr values and are within the range for bulk silicate Earth. Consistent with the interpretation of 87Sr/86Sr ratios, we attribute the difference to the preferential dissolution of minerals with high δ88/86Sr values. Mineral separates display a wide range of δ88/86Sr values (∼0.40‰). Those having high δ88/86Sr values include hornblende and K-feldspar, as well as apatite and titanite. Taken together, the preferential weathering of predominately silicate minerals explains the Sr isotope geochemistry of subglacial discharge.Subglacial discharge from the Russell Glacier feeds the proglacial Akuliarusiarsuup Kuua River (AKR). Along a 32 km transect of the AKR from the GrIS margin toward the coast, riverine 87Sr/86Sr ratios increase from ∼0.722 to ∼0.747 in an approximately step-wise pattern that corresponds to point-source inputs of additional subglacial discharge. Major cation concentrations and 87Sr/86Sr ratios minimally vary along lengths of the transect with no hydrological inputs. This suggests that proglacial chemical weathering is negligible and likely does not contribute significantly to GrIS solute fluxes.In general, this study supports the recent contention that silicate mineral weathering dominates the solute geochemistry of GrIS subglacial discharge in contrast to valley glaciers, which typically show substantial contributions from carbonate and sulfide weathering regardless of primary bedrock composition. Ice sheet subglacial chemical weathering may therefore have a greater impact on long-term atmospheric CO2 drawdown than previously realized.

The contrasting geochemical message from the New Caledonia gabbronorites: insights on depletion and contamination processes of the sub-arc mantle in a nascent arc setting

The New Caledonia ophiolite hosts one of the rare examples of crust-mantle sections built in a nascent arc environment, providing the unique opportunity to investigate the first stages of arc magmatism in a subduction setting. The sequence consists of refractory harzburgites, overlain by ultramafic (dunites and wehrlites) and mafic lithologies (gabbronorites). The gabbronorites occur in the upper part of the sequence as decimetre to metre-size sills. They are mainly formed (≃ 55 to 70 vol%) of Ca-rich plagioclase (An up to 96 mol%) and high Mg# (88–92), Al2O3-poor (1.5–2.4 wt%) clinopyroxene (8–20 vol%), often rimmed by interstitial or poikilitic orthopyroxene (6–27 vol%). Mg-rich olivine (3–15 vol%, Fo = 87–89 mol%) occurs as anhedral, resorbed crystals. Whole rock (WR) compositions exhibit high Mg# (86–92) and strikingly low trace element contents. They own LREE-depleted patterns, with nearly flat (0.82 ≤ DyN/YbN ≤ 1.00) and low HREE (YbN = 0.2–0.9) and positive Eu anomalies. Clinopyroxene trace element chemistry mirrors the extreme depletion of the WR. By contrast, FME enrichments are observed for WR and clinopyroxene. Geochemical models show that the gabbronorites crystallized from primitive, ultra-depleted melts bearing evidence of fluid contamination processes, but with significantly different geochemical signatures compared to boninitic rocks worldwide, i.e. lower LREE-MREE, and absence of Nb depletion and Zr–Hf enrichments. Nd isotopes (+ 8.2 ≤ eNdi ≤ + 13.1), together with radiogenic Pb isotopic ratios, support an origin from a DMM source variably modified by slab fluids. We propose that the geochemical signature of the New Caledonia gabbronorites reflect emplacement of primitive, non-aggregated, magma batches in the lower fore-arc crust, during the first phases of arc formation.

Lead isotope and metal source of Shang bronzes: a response to Sun et al.’s comments

In this brief response to Sun et al.’s () comments on our paper, we re‐emphasize that archaeological, chemical and isotopic evidence are all relevant to the discussion about the metal source of the Shang period with highly radiogenic lead isotope ratios. The southern African bronzes have much lower lead contents and quite different lead isotopic signatures than the Shang bronzes. More importantly, there was no metallurgy of any kind in southern Africa before c.200 ce, so southern Africa cannot possibly be the source of Shang bronze, which date to about 1500 to 1000 bce.

Generation of syntectonic calc-alkaline, magnesian granites through remelting of pre-tectonic igneous sources – U-Pb zircon ages and Sr, Nd and Pb isotope data from the Donkerhoek granite (southern Damara orogen, Namibia)

The 541 ± 4 Ma-old magnesian, weakly peraluminous, calc-alkalic Donkerhoek Onanis granite is part of the ca. 6000 km2 large Donkerhoek batholith in the Southern Zone of the Damara orogen of Namibia. Linear major and trace element variations and decreasing MgO, FeO, Al2O3, CaO, K2O, Na2O, Ba and Sr concentrations with increasing SiO2 indicate that this part of the batholith represent a coherent mass and underwent fractional crystallization processes. The Donkerhoek Onanis granites are isotopically evolved (initial εNd: −4.7 to −12.3, initial 87Sr/86Sr: 0.7099–0.7157) with moderately radiogenic Pb isotope ratios (206Pb/204Pb: 17.26–18.22; 207Pb/204Pb: 15.59–15.67; 208Pb/204Pb: 37.60–38.06). Beside heterogeneities imparted by the sources, an evaluation of LREE fractionation and Nd isotope data suggests that AFC processes also modified some samples. Based on the chemical and isotope data, the Donkerhoek Onanis granites cannot be derived by partial melting of Al- and Fe-rich metasedimentary rocks of the Kuiseb formation in which they intruded. Instead, melting of meta-igneous crustal sources with Proterozoic crustal residence ages is more likely. Three igneous to meta-igneous rock suites from the area (Matchless amphibolites, Proterozoic mafic to felsic gneisses from the southern Kalahari craton basement, syn-tectonic Salem granodiorites to granites) are potential sources. An evaluation of chemical and isotope data suggests that remelting of early syn-orogenic Salem-type granites is the most likely process which would also explain the existence of ca. 563 ± 4 Ma-old zircon in the Donkerhoek Onanis granites. Comparison of the Donkerhoek Onanis granites with experimentally derived melt compositions from an intermediate igneous parent indicates temperatures between 800 and 850 °C. It is suggested that the Pan-African igneous activity in this part of the Damara Belt was a moderate-temperature intra-crustal event. Although there are some compositional similarities with juvenile granites generated in subduction zones, unradiogenic Pb isotope ratios and moderately radiogenic Sr and unradiogenic Nd isotopes suggest that reprocessed crustal rocks are more likely sources. Previously obtained high δ18O values of the Donkerhoek Onanis granites ranging from 11.8 to 13.6‰, covering the range of δ18O values obtained on Salem-type granites from the area (12.5–13.3‰) confirm this view. In contrast to igneous processes along active continental margins that produce juvenile batholiths with calc-alkaline affinities, this igneous event was not a major crust-forming episode and the Donkerhoek Onanis granites represent reprocessed crustal material.

Unexpected HIMU-type late-stage volcanism on the Walvis Ridge

Volcanic activity at many oceanic volcanoes, ridges and plateaus often reawakens after hiatuses of up to several million years. Compared to the earlier magmatic phases, this late-stage (rejuvenated/post-erosional) volcanism is commonly characterized by a distinct geochemical composition. Late-stage volcanism raises two hitherto unanswered questions: Why does volcanism restart after an extended hiatus and what is the origin of this volcanism? Here we present the first 40Ar/39Ar age and comprehensive trace element and Sr–Nd–Pb–Hf isotopic data from seamounts located on and adjacent to the Walvis Ridge in the South Atlantic ocean basin. The Walvis Ridge is the oldest submarine part of the Tristan-Gough hotspot track and is famous as the original type locality for the enriched mantle one (EM I) end member. Consistent with the bathymetric data, the age data indicates that most of these seamounts are 20–40 Myr younger than the underlying or nearby Walvis Ridge basement. The trace element and isotope data reveal a distinct compositional range from the EM I-type basement. The composition of the seamounts extend from the St. Helena HIMU (high time-integrated 238U/204Pb mantle with radiogenic Pb isotope ratios) end member to an enriched (E) Mid-Ocean-Ridge Basalt (MORB) type composition, reflecting a two-component mixing trend on all isotope diagrams. The EMORB end member could have been generated through mixing of Walvis Ridge EM I with normal (N) MORB source mantle, reflecting interaction of Tristan-Gough (EM I-type) plume melts with the upper mantle. The long volcanic quiescence and the HIMU-like geochemical signature of the seamounts are unusual for classical hotspot related late-stage volcanism, indicating that these seamounts are not related to the Tristan-Gough hotspot volcanism. Two volcanic arrays in southwestern Africa (Gibeon-Dicker Willem and Western Cape province) display similar ages to the late-stage Walvis seamounts and also have HIMU-like compositions, suggesting a larger-scale event at ∼77–49 Ma. We propose that the EM I-like mantle plumes rise from the edges of the African Large Low Shear Velocity Province (LLSVP; Tristan-Gough, Discovery and Shona hotspot), whereas the HIMU-dominated intraplate lavas (St. Helena, Gibeon-Dicker Willem and Western Cape province) and the late-stage Walvis seamounts tap material from internal portions of the African LLSVP, suggesting possible lateral and/or vertical chemical zonation of the African LLSVP.

Isotopic constraints on contamination processes in the Tonian Goiás Stratiform Complex

The Tonian Goiás Stratiform Complex (TGSC, Goiás, central Brazil), is one of the largest mafic-ultramafic layered complexes in the world, emplaced during the geotectonic events that led to the Gondwana accretion. In this study, we present trace elements and in-situ U/Pb-Lu-Hf analyses of zircons and 87Sr/86Sr ratios of plagioclases from anorthosites and gabbros of the TGSC.Although formed by three isolated bodies (Cana Brava, Niquelândia and Barro Alto), and characterized by a Lower and Upper Sequence (LS and US), our new U/Pb zircon data confirm recent geochemical, geochronological, and structural evidences that the TGSC has originated from a single intrusive body in the Neoproterozoic.New Hf and Sr isotope ratios construe a complex contamination history for the TGSC, with different geochemical signatures in the two sequences. The low Hf and high Sr isotope ratios of the Lower Sequence (εHf(t) from −4.2 down to −27.5; 87Sr/86Sr = 0.706605–0.729226), suggest the presence of a crustal component and are consistent with contamination from meta-pelitic and calc-silicate rocks found as xenoliths within the Sequence. The more radiogenic Hf isotope ratios and low Sr isotope composition of the Upper Sequence (εHf(t) from 11.3 down to −8.4; 87Sr/86Sr = 0.702368–0.702452), suggest a contamination from mantle-derived metabasalts in agreement with the occurrences of amphibolite xenoliths in the US stratigraphy. The differential contamination of the two sequences is explained by the intrusion of the TGSC in a stratified crust dominated by metasedimentary rocks in its deeper part and metavolcanics at shallower levels. Moreover, the differential thermal gradient in the two crystallizing sequences might have contributed to the preservation and recrystallization of inherited zircon grains in the US and total dissolution or magmatic overgrowth of the LS zircons via melt/rock reaction processes.

Evidence for melting of subducting carbonate-rich sediments in the western Aegean Arc

Subduction of sediments affects the composition of the Earth's mantle and the formation of melts in subduction zones. The sediment thickness of ~8 km along the Hellenic Trench is the largest observed globally and significant volumes of these sediments are subducted. Magmas erupting in the Aegean Arc reflect sediment subduction but they also assimilated sediments during ascent, making distinction of the two processes difficult. In this study, we present geochemical data from olivines in lavas and enclaves from the peninsula of Methana in the western Aegean Arc. The olivines have high forsterite (Fo) contents of 90–92% and contain Cr-spinel with Cr# >60 originating from a primitive melt in equilibrium with a highly depleted mantle wedge. The high δ18OVSMOW of ~6.5‰ of the olivines imply input of up to 6.5% sediment component into the mantle wedge. Incompatible element and radiogenic isotope ratios suggest that the sediment component is added as a carbonate-rich melt. Low Ni contents and small rounded sulphide inclusions in the Fo-rich olivines indicate the formation of an immiscible sulphide liquid during olivine crystallization. The input of carbonate-rich sediment reduced the mantle and the co-existing primitive melts, and possibly added S leading to sulphide saturation. This study shows that olivine crystals and their inclusions provide important insights into the mantle wedge, sediment subduction and its effects on the primary magma composition and can indeed be used to distinguish between a mantle and crustal origin of the sediment signature.

Trace element and stable (C, O) and radiogenic (Sr) isotope geochemistry of stromatolitic carbonate rocks of the Mesoarchaean Pongola Supergroup: Implications for seawater composition

The Mesoarchaean Pongola Supergroup hosts one of the oldest well-preserved stromatolitic carbonate successions. Major- and trace-element geochemistry along with C, O, and Sr isotopic analyses of three stratigraphic sections of stromatolitic carbonate rocks were undertaken in order to infer the depositional environment, and to unravel the chemical characteristics of contemporaneous seawater. The carbonate rocks consist mainly of dolomite and, to a lesser extent, ankerite. Their variable Sr concentrations of ~95 to 450mg/kg are interpreted as resulting from early to late dolomitization of metastable carbonates (aragonite and/or high-Mg calcite), facies control and calcitization during meteoric diagenesis. δ18O values range from −19.6 to −12.0‰ VPDB and reflect recrystallization of carbonates caused by high water-rock interactions during diagenesis and metamorphism. A δ13C value of 2.5‰ VPDB was measured in carbonate samples least affected by alteration, and we suggest that it approximates the composition of dissolved inorganic carbon in coeval seawater. The samples display variable 87Sr/86Sr isotopic ratios, from as low as 0.708 to 0.777. These ratios are considerably higher than those expected in Archaean open-ocean water masses buffered by hydrothermal interaction with the mantle. We interpret the highly radiogenic Sr isotopic ratios in some carbonate samples to reflect isotopic exchange with radiogenic Sr from siliciclastic/volcaniclastic components in the samples and fluids from clay-rich layers intercalated with the carbonates. The least radiogenic Sr isotopic ratio may approximate the mixed isotopic composition of seawater in the epicontinental basin and of riverine freshwater draining the Kaapvaal Craton. The dolomitic carbonate samples show shale-normalized rare earth element and yttrium distribution patterns that resemble those of modern ocean water with positive LaSN, GdSN and YSN anomalies, superchondritic Y/Ho ratios, a small negative CeSN anomaly and depleted light rare earth elements relative to the heavy rare earth elements. These anomalies are not as pronounced as expected for an open marine setting, which together with the Sr isotopic results support a more restricted setting with riverine input and fluctuations in marine ingressions. A convex-upward shale-normalized rare earth element and yttrium pattern is probably a result of several factors, including organic matter complexation, and element fractionation during estuarine mixing. The small negative CeSN anomaly may suggest small amounts of free oxygen in shallow waters due to local oxygenic microbial activity.

The prevalence of kilometer-scale heterogeneity in the source region of MORB upper mantle.

The source regions of mid-ocean ridge basalts (MORB) are heterogeneous, consisting of chemically and lithologically distinct domains of variable size. Partial melting of such heterogeneous mantle sources gives rise to diverse isotopic compositions of MORB and abyssal peridotites. Variations in radiogenic isotope ratios in MORB are attributed to mixing of melts derived from enriched and depleted mantle components. However, melt mixing alone cannot fully account for the difference between the average 143Nd/144Nd in abyssal peridotites and their spatially associated MORB. We show that the more depleted Nd isotope composition in abyssal peridotites is a natural consequence of melt migration-induced mixing or smearing in the melting column. Sub-kilometer scale enriched mantle components or heterogeneities are significantly damped or homogenized in both the residue and erupted melt during their transit through the melting region. Heterogeneities with larger size and higher incompatible trace element abundance are more resistive to the mixing processes. The size-sensitive mixing depends on a parameter called the enrichment strength, which is the product of the heterogeneity size and the ratio between incompatible trace element abundance in the enriched and depleted mantle sources. Observed Nd-Hf isotope variations in MORB and abyssal peridotites can be reproduced if the enrichment strength is 20 to 60 km. These heterogeneities could be on the kilometer scale and have similar isotope ratios to but less incompatible trace element abundances than recycled oceanic crust.

Geochemistry and Origin of the Neoproterozoic Natkusiak Flood Basalts and Related Franklin Sills, Victoria Island, Arctic Canada

The Natkusiak continental flood basalts and Franklin sills of Victoria Island preserve an exceptional record of the ca. 716–723 Ma Franklin large igneous province and are synchronous with major climatic variations and breakup of the supercontinent Rodinia. The Natkusiak Formation basalts record an early phase of discontinuous rubbly flows (<100 m, low-Ti Type 1 magmas) overlain by a thicker series of extensive tholeiitic sheet flows (~1100 m, high-Ti Type 2 magmas). Coeval intrusions hosted by underlying Shaler Supergroup sedimentary rocks are differentiated low-Ti Type 1 Franklin sills and doleritic high-Ti Type 2 sills, both of which show correlations in isotope plots with the northernmost basalts on Victoria Island. Whole-rock Pb-Sr-Nd-Hf isotopic compositions from 66 samples indicate that the earliest magmas (Type 1) had similar primary melt compositions (Fo90 olivine) to oceanic island basalts and incorporated up to 10% granitoid basement (initial eNd = –0.8 to –7, Nb/La = 0.42 to 0.67), a relatively weak continental signature compared to many other continental flood basalt provinces. Type 2 doleritic sills and the northern sheet flow basalts incorporated up to 5% granitoid (initial eNd = +0.9 to +5.5), consistent with a waning continental influence during maturation of the magmatic system. Radiogenic isotope ratios are not correlated with indices of fractional crystallisation, which indicates that the continental material was either dispersed within the melt source, or that magmas were heterogeneously contaminated prior to differentiation. In the southwestern part of Victoria Island, Type 1 basalts show negligible continental influence (Nb/La = 0.81 to 0.94) and have unusually high initial eNd ratios (+4.4 to +11.8) that are decoupled from initial eHf (+0.8 to +11.1). These radiogenic eNd compositions persist throughout the southern volcanic stratigraphy and indicate involvement of a component with high time-integrated Sm/Nd that lacked correspondingly high Lu/Hf. We suggest that the source region for the southwestern Natkusiak basalts and related sills included isotopically matured oceanic crust, which was recycled through the asthenospheric mantle into a laterally heterogeneous plume. The distinct trace element signatures of the southern and northern sources became attenuated with the onset of voluminous melting (corresponding to emplacement of the Type 2 doleritic sills and sheet flow basalts) and may reflect contributions from hydrous eclogitic material emplaced into the lithospheric mantle during the ca. 1.9 Ga Wopmay Orogeny. As both the northern and southern volcanic rocks exhibit contrasting isotopic signatures throughout the preserved stratigraphy, the magma plumbing system must have limited lateral mixing and homogenisation, which allowed for the expression of distinct mantle source signatures in the high-level sills and basaltic lavas.

Tracing ancient hydrogeological fracture network age and compartmentalisation using noble gases

We show that fluid volumes residing within the Precambrian crystalline basement account for ca 30% of the total groundwater inventory of the Earth (> 30 million km3). The residence times and scientific importance of this groundwater are only now receiving attention with ancient fracture fluids identified in Canada and South Africa showing: (1) microbial life which has existed in isolation for millions of years; (2) significant hydrogen and hydrocarbon production via water–rock reactions; and (3) preserving noble gas components from the early atmosphere. Noble gas (He, Ne, Ar, Kr, Xe) abundance and isotopic compositions provide the primary evidence for fluid mean residence time (MRT). Here we extend the noble gas data from the Kidd Creek Mine in Timmins Ontario Canada, a volcanogenic massive sulfide (VMS) deposit formed at 2.7 Ga, in which fracture fluids with MRTs of 1.1–1.7 Ga were identified at 2.4 km depth (Holland et al., 2013); to fracture fluids at 2.9 km depth. We compare here the Kidd Creek Mine study with noble gas compositions determined in fracture fluids taken from two mines (Mine 1 & Mine 2) at 1.7 and 1.4 km depth below surface in the Sudbury Basin formed by a meteorite impact at 1.849 Ga.The 2.9 km samples at Kidd Creek Mine show the highest radiogenic isotopic ratios observed to date in free fluids (e.g. 21Ne/22Ne = 0.6 and 40Ar/36Ar = 102,000) and have MRTs of 1.0–2.2 Ga. In contrast, resampled 2.4 km fluids indicated a less ancient MRT (0.2–0.6 Ga) compared with the previous study (1.1–1.7 Ga). This is consistent with a change in the age distribution of fluids feeding the fractures as they drain, with a decreasing proportion of the most ancient end-member fluids. 129Xe/136Xe ratios for these fluids confirm that boreholes at 2.4 km versus 2.9 km are sourced from hydrogeologically distinct systems. In contrast, results for the Sudbury mines have MRTs of 0.2–0.6 and 0.2–0.9 Ga for Mines 1 and 2 respectively. While still old compared to almost all groundwaters reported in the literature to date, these younger residence times compared to Kidd Creek Mine are consistent with significant fracturing created by the impact event, facilitating more hydrogeologic connection and mixing of fluids in the basin. In all samples from both Kidd Creek Mine and Sudbury, a 124-128Xe excess is identified over modern air values. This is attributed to an early atmospheric xenon component, previously identified at Kidd Creek Mine but which has to date not been observed in fluids with a residence time as recent as 0.2–0.6 Ga. The temporal and spatial sampling at Kidd Creek Mine is also used to verify our proposed conceptual model which provides key constraints regarding distribution, volumes and residence times of fracture fluids on the smaller, regional, scale.

Canyon Creek revisited: New investigations of a late prehispanic turquoise mine, Arizona, USA

Turquoise has been used in the American Southwest since “time immemorial,” and remains an important material for contemporary indigenous groups of the region. Detailed studies of ancient turquoise mines are few, however, and inferences of turquoise procurement and provenance have been limited. Our intensive investigation of one mine, the Canyon Creek locale in Arizona, integrates archaeology and geochemistry to enhance understanding of the mine and its output. A detailed description of the mine's morphology and geologic setting lays foundations for interpreting an isotopic analysis of specimens from the mine's four localities. The analysis reveals extremely radiogenic Pb isotope ratios, which distinguish Canyon Creek turquoise from that of other known sources in the American Southwest. Its distinctive isotopic signature makes Canyon Creek turquoise readily identifiable in archaeological assemblages. The presence of turquoise from Canyon Creek at late prehispanic settlements in east-central Arizona helps clarify the mine's chronology of use and regional distribution. Our observations suggest the mine was larger than previously supposed, and that it provided an important source of turquoise for inhabitants of the region during the thirteenth and fourteenth centuries AD.