Isotope Perspective Research Articles

Copper Isotopic Perspectives on Supergene Processes: Implications for the Global Cu Cycle

Research Article| October 01, 2015 Copper Isotopic Perspectives on Supergene Processes: Implications for the Global Cu Cycle Ryan Mathur; Ryan Mathur 1Department of Geology, Juniata CollegeHuntingdon, PA 16652, USAE-mail: mathurr@juniata.edu Search for other works by this author on: GSW Google Scholar Matthew S. Fantle Matthew S. Fantle 2Department of Geosciences, Penn State UniversityUniversity Park, PA 16802, USAE-mail: mfantle@psu.edu Search for other works by this author on: GSW Google Scholar Author and Article Information Ryan Mathur 1Department of Geology, Juniata CollegeHuntingdon, PA 16652, USAE-mail: mathurr@juniata.edu Matthew S. Fantle 2Department of Geosciences, Penn State UniversityUniversity Park, PA 16802, USAE-mail: mfantle@psu.edu Publisher: Mineralogical Society of America First Online: 09 Mar 2017 Online Issn: 1811-5217 Print Issn: 1811-5209 © 2015 by the Mineralogical Society of America Elements (2015) 11 (5): 323–329. https://doi.org/10.2113/gselements.11.5.323 Article history First Online: 09 Mar 2017 Cite View This Citation Add to Citation Manager Share Icon Share Facebook Twitter LinkedIn MailTo Tools Icon Tools Get Permissions Search Site Citation Ryan Mathur, Matthew S. Fantle; Copper Isotopic Perspectives on Supergene Processes: Implications for the Global Cu Cycle. Elements 2015;; 11 (5): 323–329. doi: https://doi.org/10.2113/gselements.11.5.323 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentBy SocietyElements Search Advanced Search Abstract A compilation of copper isotopic compositions (δ65Cu) from supergene systems suggests distinct differences in the mean δ65Cu of Cu in leach cap (δ65Cu = −1.2 ± 3.5‰), enrichment zone (mean δ65Cu = +1.2 ± 4.2‰), and fluids (mean δ65Cu = +0.9 ± 1.3‰) relative to the high-temperature sulfides that comprise the primary ore (δ65Cu = +0.1 ± 0.6‰). These isotopic differences can be explained by the oxidative dissolution of primary ore minerals, such as chalcopyrite, and the subsequent precipitation of oxides in the near-surface system and of sulfides at depth. A dynamic mass balance model predicts the observed Cu isotopic compositions of the Cu reservoirs in nature and constrains the temporal isotopic evolution of supergene systems. From the model, these systems isotopically evolve to substantial extents over 500 ka to 5 Ma time scales. In relatively closed systems, percent-level loss of Cu from the solid (with δ65Cu values >>0‰) is possible, suggesting that supergene systems are important components of the global Cu cycle. You do not have access to this content, please speak to your institutional administrator if you feel you should have access.

Roman and late-Roman glass from north-eastern Italy: The isotopic perspective to provenance its raw materials

In this study, the strontium, neodymium and oxygen isotopic composition of Roman (1st–3rd century AD) and late-Roman glass (4th–6th century AD) from Adria and Aquileia, two of the most important archaeological sites of north-eastern Italy, is discussed.The majority of glass analysed, independent from age, shows values of strontium isotope ratios close to that of modern seawater, indicating that the source of lime in the glass was marine shell, and likely coastal sands were used in its production. The Nd signature of all late-Roman glasses from Aquileia and of the majority of the Roman ones from Adria, independent from their chemical composition, is homogeneous and higher than −6 εNd, supporting the hypothesis of an eastern Mediterranean origin, probably located on Syro-Palestinian coast. However, the composition of late-Roman samples with HIMT signature, with lower 87Sr/86Sr values correlated to higher contents in Fe2O3, TiO2, MgO and lower contents in CaO, suggests an area of origin for this glass on the Egyptian coast. In addition, the different Nd signatures of two Adria Roman glasses (εNd < −7) suggest their primary production in western Mediterranean. Oxygen isotopes proved to be a further diagnostic method to discriminate natron and soda plant ash glass, and different silica sources, in the case of the soda plant ash glass. The combination of isotopic and chemical data supports the hypothesis of an eastern Mediterranean origin for late-Roman glass, which may be produced in few primary workshops on the Syro-Palestinian and Egyptian coast, although not necessarily in the same ateliers as have been identified so far. In the case of the Roman glass investigated, although the majority of data suggests an eastern Mediterranean origin, on the basis of Nd isotopes and chemical compositions, the existence of other primary glass producers located in the western Mediterranean can be suggested.

Insights into the coupling of upper ocean-benthic carbon dynamics in the western Arctic Ocean from an isotopic (13C, 234Th) perspective

The coupling of upper ocean-benthic carbon dynamics in the ice-free western Arctic Ocean (the Chukchi Sea and the Canada Basin) was evaluated during the late July-early September 2003 using natural stable (13C) and radioactive (238U-234Th) isotope tracers. POC export flux estimated from 234Th/238U disequilibria and dissolved CO2 concentration ([CO2(aq)]) pointed out that the strengthened biological pump in the Chukchi Shelf have significantly lowered [CO2(aq)] and altered the magnitude of isotopic (12C/13C) fractionation during carbon fixation in the surface ocean. Further, δ13C signatures of surface sediments (δ13Csed) are positively correlated to those of weighted δ13CPOC in upper ocean (δ13Csed =13.64+1.56×δ13CPOC, r2=0.73, p<0.01), suggesting that the POC isotopic signals from upper ocean have been recorded in the sediments, partly due to the rapid export of particles as evidenced by low residence times of the highly particle-reactive 234Th from the upper water column. It is suggested that there probably exists an upper ocean-benthic coupling of carbon dynamics, which likely assures the sedimentary δ13C record an indicator of paleo-CO2 in the western Arctic Ocean.

Runoff to boreal lakes linked to land cover, watershed morphology and permafrost thaw: a 9‐year isotope mass balance assessment

AbstractStable isotopes of oxygen and hydrogen were measured in water samples collected annually from a representative suite of 50 lakes in northeastern Alberta over a 9‐year period and are interpreted using a steady‐state isotope mass balance model to determine water yield and runoff ratios for the lake watersheds and residence time of the lakes. This isotopic perspective on hydrology of the region provides new insight into the role of land cover, watershed morphometry, climatic drivers and permafrost thaw on lakes. Bog cover, permafrost and presence of thaw features in bogs are found to be the dominant hydrologic drivers, although morphometric properties such as elevation, lake area and drainage basin area are also influential. In addition to quantifying the hydrologic fluxes, the analysis establishes contrasting conditions in more southerly lakes, located in the Stony Mountains and west of Fort McMurray, as compared with more northerly sites in the Birch Mountains, Caribou Mountains and northeast of Fort McMurray, mainly because of contributions from thawing permafrost at the northerly sites. Distinct hydrologic conditions are also noted for Shield systems north of Lake Athabasca where bogs and permafrost are absent. While permafrost thaw is not directly labelled by oxygen and hydrogen isotope composition, isotope mass balance calculations suggest that contributions of up to several hundred millimetres per year are occurring in 14 of the 50 lake watersheds under study. Several of these lakes have water yields in excess of precipitation in some years, and regional groups of lakes display significant correlations between water yield and percentage of bogs that have collapsed. Copyright © 2015 John Wiley &amp; Sons, Ltd.

Oxidative release of chromium from Archean ultramafic rocks, its transport and environmental impact – A Cr isotope perspective on the Sukinda valley ore district (Orissa, India)

This study investigates Cr isotope fractionation during soil formation from Archean (3.1–3.3Ga) ultramafic rocks in a chromite mining area in the southern Singhbhum Craton (Orissa, India). The Cr-isotope signatures of two studied weathering profiles, range from non-fractionated mantle values to negatively fractionated values as low as δ53Cr=−1.29±0.04‰. Local surface waters are isotopically heavy relative to the soils. This supports the hypothesis that during oxidative weathering isotopically heavy Cr(VI) is leached from the soils to runoff.The impact of mining pollution is observed downstream from the mine where surface water Cr concentrations are significantly increased, accompanied by a shift to less positive δ53Cr values relative to upstream unpolluted surface water. A microbial mat sample indicates that microbes have the potential to reduce and immobilize Cr(VI), which could be a factor in controlling the hazardous impact of Cr(VI) on health and environment.The positive Cr isotope signatures of the Brahmani estuary and coastal seawater collected from the Bay of Bengal further indicate that the positively fractionated Cr isotope signal from the catchment area is preserved during its transport to the sea. Isotopically lighter Cr(VI) downstream from the mine is probably back-reduced to Cr(III) during riverine transport leading to similar Cr-isotope values in the estuary as observed upstream from the mine.

Ore-forming timing of polymetallic-fluorite low temperature veins from Central Pyrenees: A Pb, Nd and Sr isotope perspective

Vein fluorite deposits (Tebarray, Lanuza, Bielsa-Parzán, Bizielle and Yenefrito) as well as one MVT-style fluorite mineralization (Portalet) in the Central Pyrenees are the focus in this contribution. These deposits are made up of fluorite, barite, base metal sulphides, calcite, and quartz and are hosted in sedimentary rocks and granites of Palaeozoic age. Generally, these mineral occurrences, typically associated with Late Palaeozoic steeply dipping faults are similar with respect to geologic setting, mineralogy and geochemical trends to other fluorite and base metal veins located in the Central Pyrenees. Veins occurring along such faults most likely represent channelways used by mineralizing solutions that were expelled from the basement. Previous work argued for genetic processes involving circulation of mineralising fluids during the Triassic–Lower Cretaceous period, which is often considered to represent a period of heat, fluid, and mass transfers related to rifting events in the western European basins, which is related to the opening of the Atlantic.A major goal of this study was to decipher the timing of fluid flow and ore formation on the basis of Nd–Sm dating of fluorite sampled from a number of deposits sharing a similar geological framework. No precise age(s) could be obtained due to a scatter in data, but results from the Portalet MVT-style deposit point to a mid-Triassic age (around 220Ma) for this mineralization. The model that best explains the diagenetic stratabound mineralization at Portalet is gravity-driven fluid flow involving basinal brines during a rifting stage. Indeed, the formation of horst and graben structures during Early Alpine extensional tectonics favoured the infiltration of meteoric water into uplifted blocks, followed by fluid migration through the deeper parts of the basins whereby heat and dissolved components were acquired. This model also explains diagenetic changes recorded in the host limestone at Portalet. Also, overall Pb, Sr and Nd isotopic ratios measured in galena and fluorite suggest that differences in host rock and in the lithology of the basement seem to have exerted control on the chemistry of mineralizing fluids providing each deposit with distinctive characteristics.

The reduction and oxidation of ceria: A natural abundance triple oxygen isotope perspective

Ceria (CeO2) is a heavily studied material in catalytic chemistry for use as an oxygen storage medium, oxygen partial pressure regulator, fuel additive, and for the production of syngas, among other applications. Ceria powders are readily reduced and lose structural oxygen when subjected to low pO2 and/or high temperature conditions. Such dis-stoichiometric ceria can then re-oxidize under higher pO2 and/or lower temperature by incorporating new oxygen into the previously formed oxygen site vacancies. Despite extensive studies on ceria, the mechanisms for oxygen adsorption–desorption, dissociation–association, and diffusion of oxygen species on ceria surface and within the crystal structure are not well known. We predict that a large kinetic oxygen isotope effect should accompany the release and incorporation of ceria oxygen. As the first attempt to determine the existence and the degree of the isotope effect, this study focuses on a set of simple room-temperature re-oxidation experiments that are also relevant to a laboratory procedure using ceria to measure the triple oxygen isotope composition of CO2.Triple-oxygen-isotope labeled ceria powders are heated at 700°C and cooled under vacuum prior to exposure to air. By combining results from independent experimental sets with different initial oxygen isotope labels and using a combined mass-balance and triangulation approach, we have determined the isotope fractionation factors for both high temperature reduction in vacuum (⩽10−4mbar) and room temperature re-oxidation in air. Results indicate that there is a 1.5‰±0.8‰ increase in the δ18O value of ceria after being heated in vacuum at 700°C for 1h. When the vacuum is broken at room temperature, the previously heated ceria incorporates 3–19% of its final structural oxygen from air, with a δ18O value of 2.1-4.1+7.7‰ for the incorporated oxygen. The substantial incorporation of oxygen from air supports that oxygen mobility is high in vacancy-rich ceria during re-oxidation at room temperature. The quantified oxygen isotope fractionation factors are consistent with the direct involvement of O2 in the rate limiting step for ceria reoxidation in air at room temperature. While additional parameters may reduce some of the uncertainties in our approach, this study demonstrates that isotope effects can be an encouraging tool for studying oxygen transport kinetics in ceria and other oxides. In addition, our finding warns of the special cares and limits in using ceria as an exchange medium for laboratory triple oxygen isotope analysis of CO2 or other oxygen-bearing gases.

A combined Y/Ho, high field strength element (HFSE) and Nd isotope perspective on basalt weathering, Deccan Traps, India

High-precision high field strength element (HFSE: Zr, Hf, Nb, Ta, Th, U, W, Mo), Y/Ho, and Nd isotope chemostratigraphy of two contrasting Deccan Traps weathering profiles – an ancient, deeply weathered laterite, and a younger (Quaternary), more moderately weathered saprolite – are used to reconstruct different aspects of basalt weathering. Precision of the HFSE analyses is demonstrated through a report of the long-term concentrations and ratios determined in United States Geological Survey (USGS) and Geological Survey of Japan (GSJ) basalt rock standards (BHVO-1, BHVO-2, BIR-1, BCR-2, JB-2).The oxyanion-forming members (U, Mo, W) are the most mobile of the considered HFSE group. Extreme loss of W, far exceeding those of U and Mo during certain stages of basalt alteration, is first reported here. The ability to strongly fractionate Mo and W during weathering may contribute to solving the unresolved mass imbalance between the crustal and marine inventories of W. By contrast, Zr, Hf, Nb, and Ta preserve the ratios of the parent basalt in the profiles due to their limited mobility; these are therefore of great potential value in reconstructing basalt flow stratigraphy and correlating lava flows in weathered flood basalt provinces. Of the HFSE, Th is not a good choice as a conservative element because it is strongly susceptible to addition of aeolian dust; this is evidenced by strong excursions in Th/Nb that are correlatable with alkali element enrichment and less radiogenic 143Nd/144Nd ratios.The chemical fingerprints of dust were identified in a paleo-flow top of the saprolite profile, suggesting that dust accumulation occurred during periods of quiescence between basaltic eruptions. During protracted exposure and laterite development, the magnitude to which dust overprints the basalt chemistry increases substantially as evident from much less radiogenic Nd isotope ratios and higher Th/Nb ratios in the Bidar profile relative to the protolith basalt. Attempts at quantifying the magnitude of dust accumulation in the laterite based on Th enrichment indicate a mass fraction of greater than 0.5 when the dust is assumed to have the chemistry of average upper continental crust. Although mixing models between the basalt and assumed dust composition cannot unambiguously constrain the dust source, the Nd isotope mixture preserved in the laterite points to a relatively young crustal dust source (e.g., similar to loess in composition) rather than the Precambrian shield rocks in the vicinity of the Deccan Traps. The contrasting topologies of dust-derived Nd and dust-derived Th in the laterite appears to record both physical transport of dust (Th) through permeable laterite horizons as well as transport by chemical dissolution and precipitation (Nd) at an inferred paleo-water table and in deep saprolite zones.Yttrium and Ho fractionate substantially during all observed stages of weathering, with Y/Ho ratios ranging from 26.5 to 21.9 in the moderately weathered saprolite profile and from 30.2 to 14.7 in the laterite profile. The single strongly superchondritic Y/Ho ratio of 30.2 in the laterite is restricted to a sample at depth, and appears to fingerprint the deposition of REE derived from dissolution higher in the profile. Decrease in the Y/Ho ratio relative to the protolith basalt (24.4–24.7) in both profiles inversely correlates with chemical weathering indices, and suggests that Y/Ho ratios have significant potential as a silicate weathering proxy. Consequently, suspended vs. dissolved river loads may record the differing behaviour of these elements during weathering.

Involvement of fluids in the metamorphic processes within different zones of the Southern Marginal Zone of the Limpopo complex, South Africa: An oxygen isotope perspective

We present oxygen isotope data obtained by laser fluorination for three outcrops from the South Marginal Zone (SMZ) of the Limpopo granulite complex, South Africa. These outcrops are located within the granulite zone (Bandelierkop quarry), on the retrograde (anthophyllite-in) isograd (Manamead locality), and within the zone of rehydrated granulite south of the retrograde isograd (Klipbank locality). Studied samples also include felsic (granitoid) rocks that occur as intrusive bodies, veins and veinlets in the host tonalite gneisses or the metapelite. The tonalite gneiss (TG) and the K-feldspar-rich segregations (Kfs-G) at Klipbank have marginally different δ18О (whole rock, WR) values (7.9 and 7.3% correspondingly). The Kfs-G may have formed by partial melting of the TG in the presence of external saline H2O–CO2 fluid. Metapelites at Manamead locality have δ18O values (9.5–10.3‰) lower than those at Bandelierkop quarry (10.0–11.4‰). The two-mineral oxygen isotope temperature estimates for metapelite minerals from Manamead cluster around two values: 620±30 and 730±40°C. Oxygen isotope temperature estimates for the metapelites from Bandelierkop quarry define a narrow temperature range of 700–740°С. The oxygen isotope temperatures are in reasonable agreement with the results of “classical” geothermobarometry. The δ18О values of the whole rocks and individual constituent minerals of metapelites strongly negatively correlate with the rocks’ volatile content (LOI values). This suggests that a fluid phase was involved in the hydration of metapelites in the vicinity of the regional anthophylite-in isograd of the Southern Marginal Zone. The fluid may have been released during crystallization of leucogranite melt. Oxygen isotope and geochemical features of the leucogranite indicate genetic relation to the tonalitic Baviaanskloof gneisses, but do not support the formation of leucogranite via in situ partial melting of metapelites.

Dynamic intermediate ocean circulation in the North Atlantic during Heinrich Stadial 1: A radiocarbon and neodymium isotope perspective

AbstractThe last deglaciation was characterized by a series of millennial‐scale climate events that have been linked to deep ocean variability. While often implied in interpretations, few direct constraints exist on circulation changes at mid‐depths. Here we provide new constraints on the variability of deglacial mid‐depth circulation using combined radiocarbon and neodymium isotopes in 24 North Atlantic deep‐sea corals. Their aragonite skeletons have been dated by uranium‐series, providing absolute ages and the resolution to record centennial‐scale changes, while transects spanning the lifetime of a single coral allow subcentennial tracer reconstruction. Our results reveal that rapid fluctuations of water mass sourcing and radiocarbon affected the mid‐depth water column (1.7–2.5 km) on timescales of less than 100 years during the latter half of Heinrich Stadial 1. The neodymium isotopic variability (−14.5 to −11.0) ranges from the composition of the modern northern‐sourced waters towards more radiogenic compositions, suggesting the presence of a greater southern‐sourced component at some times. However, in detail, simple two‐component mixing between well‐ventilated northern‐sourced and radiocarbon‐depleted southern‐sourced water masses cannot explain all our data. Instead, corals from ~15.0 ka and ~15.8 ka may record variability between southern‐sourced intermediate waters and radiocarbon‐depleted northern‐sourced waters, unless there was a major shift in the neodymium isotopic composition of the northern end‐member. In order to explain the rapid shift towards the most depleted radiocarbon values at ~15.4 ka, we suggest a different mixing scenario involving either radiocarbon‐depleted deep water from the Greenland‐Iceland‐Norwegian Seas or a southern‐sourced deep water mass. Since these mid‐depth changes preceded the Bolling‐Allerod warming and were apparently unaccompanied by changes in the deep Atlantic, they may indicate an important role for the intermediate ocean in the early deglacial climate evolution.

Water balance along a chain of tundra lakes: A 20-year isotopic perspective

Summary Stable isotope measurements and isotope mass balance (IMB) calculations are presented in support of an unprecedented 20-year water balance assessment for a tailings pond and a chain of downstream lakes at the Salmita–Tundra mine site, situated near Courageous Lake, Northwest Territories, Canada (65°03′N; 111°11′W). The method is shown to provide a comprehensive annual and interannual perspective of water balance fluxes along a chain of lakes during the period 1991–2010, without the need for continuous streamflow gauging, and reveals important lake-order-dependent patterns of land-surface runoff, discharge accumulation, and several key diagnostic ratios, i.e., evaporation/inflow, evaporation/evapotranspiration, land-surface-runoff/precipitation and discharge/ precipitation. Lake evaporation is found to be a significant component of the water balance, accounting for between 26% and 32% of inflow to natural lakes and between 72% and 100% of inflow to mine-tailings ponds. Evaporation/evapotranspiration averages between 7% and 22% and is found to be higher in low-precipitation years, and in watersheds with a higher proportion of lakes. Runoff ratios for land-surface drainages and runoff ratios for watersheds (including lakes) ranged between 14–47% and 20–47%, respectively, and were higher in low precipitation years, in watersheds with a higher proportion of lakes, and in watersheds less affected by mining development. We propose that in general these two runoff ratios will likely converge as lake order increases and as land cover conditions become regionally representative. Notably, the study demonstrates application of IMB, validated with streamflow measurements, to constrain local water balance in a remote low-arctic region. For IMB chain-of-lakes applications, it underlines the importance of accounting for evaporatively-enriched upstream sources to avoid overestimation of evaporation losses.

Iron sources and dissolved‐particulate interactions in the seawater of the Western Equatorial Pacific, iron isotope perspectives

AbstractThis work presents iron isotope data in the western equatorial Pacific. Marine aerosols and top core margin sediments display a slightly heavy Fe isotopic composition (δ56Fe) of 0.33 ± 0.11‰ (2SD) and 0.14 ± 0.07‰, respectively. Samples reflecting the influence of Papua New Guinea runoff (Sepik River and Rabaul volcano water) are characterized by crustal values. In seawater, Fe is mainly supplied in the particulate form and is found with a δ56Fe between −0.49 and 0.34 ± 0.07‰. The particulate Fe seems to be brought mainly by runoff and transported across continental shelves and slopes. Aerosols are suspected to enrich the surface Vitiaz Strait waters, while hydrothermal activity likely enriched New Ireland waters. Dissolved Fe isotopic ratios are found between −0.03 and 0.53 ± 0.07‰. They are almost systematically heavier than the corresponding particulate Fe, and the difference between the signature of both phases is similar for most samples with Δ56FeDFe – PFe = +0.27 ± 0.25‰ (2SD). This is interpreted as an equilibrium isotopic fractionation revealing exchange fluxes between both phases. The dissolved phase being heavier than the particles suggests that the exchanges result in a net nonreductive release of dissolved Fe. This process seems to be locally significantly more intense than Fe reductive dissolution documented along reducing margins. It may therefore constitute a very significant iron source to the ocean, thereby influencing the actual estimation of the iron residence time and sinks. The underlying processes could also apply to other elements.

Changes in atmospheric nitrate deposition in Germany – An isotopic perspective

We investigated the isotopic composition of atmospheric NO3− deposition at a moderately polluted site in Western Europe over an annual cycle from December 2011 to November 2012. On average, we measured load-weighted δ15N values of +0.1 and +3.0‰ in wet and dry deposition, respectively. A comparison to source-specific N emission trends and to isotope data from the 1980s reveals distinct changes in δ15N–NO3− values: In contrast to the increasing relative importance of isotopically depleted natural NOx sources, we find an increase of isotope values in comparison to historical data. We explore the role of land-based N sources, because backward trajectories reveal a correlation of higher δ15N to air mass origin from industrialized areas. Nowadays isotopically enriched NOx of coal-fired power plants using selective catalytic converters and land-based vehicle emissions, which use same technology, are apparently the main driver of rising δ15N values in nitrate deposition.

Weathering on land and transport of chromium to the ocean in a subtropical region (Misiones, NW Argentina): A chromium stable isotope perspective

We have investigated the pathway of chromium from its mobilization on land and along its riverine transport in a subtropical region of South America (Misiones Province, Argentina), in an attempt to link Cr stable isotope compositions recently measured in seawater with signals prevailing in rivers and, ultimately, with Cr isotope effects observed during oxidative surface weathering in subtropical red soils. Cr concentrations and stable Cr isotopic compositions (expressed as δ53Cr ‰ values) in two typical and representative surface profiles of weathered basalt show significant depletion of Cr in the soils of up to 50%, together with pronounced negatively fractionated δ53Cr values which are indicative of oxidative mobilization of heavy Cr(VI) into the run-off. The behavior of Cr in the studied weathering profiles is not correlated with that of other redox sensitive elements, such as Ce and U; this is essentially due to the affinity of REE and U, but not Cr with secondary phosphates which form during weathering processes.Smaller tributaries in NW Argentina to the Paraná River (second largest river in South America) carry dissolved Cr in the order of 0.7–1.4ppb (13–27nM) with δ53Cr values of +0.2 to +0.4‰, balancing the negatively fractionated weathering products. The isotope composition and concentration of dissolved Cr in the ca. 1200km long Paraná River from Misiones to its estuary and discharge area into the South Atlantic Ocean remains relatively constant with an average Cr concentration around 2.4ppb (46nM) and an average δ53Cr value of +0.32‰. The Cr concentration in the estuary itself drops by ca. 50% but with only minor change in its Cr isotope composition. Results from the Paraná estuary are identical with recently analyzed surface seawater from the Argentine Basin with Cr contents of ~0.3ppb (~6nM) and δ53Cr values ~+0.4‰ (Bonnand et al., 2013), and indicate that there is only a minimal Cr isotopic variability during riverine transport, even during long transport distances as shown in our example of the Paraná River. Simple Cr input flux calculations reveal that the Paraná River accounts for ~5% of the total yearly Cr flux to the world's oceans today and that its isotopic signature seems to be, at least locally, imparted to the surface seawater of the Argentine Basin. Whether or not this Cr isotope signature is generally exhibited by the world's oceans needs further investigations, particularly the characterization of seawater around the globe.

Ocean redox structure across the Late Neoproterozoic Oxygenation Event: A nitrogen isotope perspective

The end of the Neoproterozoic Era (1000 to 541 Ma) is widely believed to have seen the transition from a dominantly anoxic to an oxygenated deep ocean. This purported redox transition appears to be closely linked temporally with metazoan radiation and extraordinary perturbations to the global carbon cycle. However, the geochemical record of this transition is not straightforward, and individual data sets have been variably interpreted to indicate full oxygenation by the early Ediacaran Period (635 to 541 Ma) and deep ocean anoxia persevering as late as the early Cambrian. Because any change in marine redox structure would have profoundly impacted nitrogen nutrient cycling in the global ocean, the N isotope signature of sedimentary rocks (δ15Nsed) should reflect the Neoproterozoic deep-ocean redox transition. We present new N isotope data from Amazonia, northwest Canada, northeast Svalbard, and South China that span the Cryogenian glaciations (∼750 to 580 Ma). These and previously published data reveal a N-isotope distribution that closely resembles modern marine sediments, with a mode in δ15N close to +4‰ and range from −4 to +11‰. No apparent change is seen between the Cryogenian and Ediacarian. Data from earlier Proterozoic samples show a similar distribution, but shifted slightly towards more negative δ15N values and with a wider range. The most parsimonious explanation for the similarity of these N-isotope distribution is that as in the modern ocean, nitrate (and hence O2) was stable in most of the middle–late Neoproterozoic ocean, and possibly much of Proterozoic Eon. However, nitrate would likely have been depleted in partially restricted basins and oxygen minimum zones (OMZs), which may have been more widespread than in the modern ocean.

Lithium systematics in howardite–eucrite–diogenite meteorites: Implications for crust–mantle evolution of planetary embryos

We present lithium (Li) abundances and isotope compositions in a suite of howardites, eucrites and diogenites (HEDs). These meteorites most likely originated from asteroid Vesta and were delivered to Earth by a series of independent impact events. The Li concentrations show striking differences between Li-poor diogenites plus cumulate eucrites and Li-enriched eucrites whilst howardites have Li abundances intermediate between eucrites and diogenites. Contrary to Li elemental inter-group differences, Li isotope compositions are irresolvable among these individual groups of HED meteorites despite their wildly distinct petrography, attesting to insignificant Li isotope fractionation during formation of a thick basaltic crust by melting of the Vestan mantle. The mean Li isotope composition of Bulk Silicate Vesta is estimated at 3.7±0.6‰ (1σ), intermediate to that of the Earth versus Mars and Moon but identical with these terrestrial bodies within uncertainty. This further validates largely homogeneous inner Solar System solids from the Li isotope perspective and supports the lack of loss of moderately volatile elements from planetary embryos during their magmatic histories because Li does not follow depletion trends inferred from more volatile elements. Pasamonte eucrite has the same Li isotope composition as other eucrites although it may not be directly linked to Vesta. These observations are also important for generating Li elemental and isotope signatures in juvenile basaltic crusts of large terrestrial planets and numerous planetary embryos in the early Solar System. A combination of CV+L chondrites may be less suitable for building Vesta from Li perspective but this may face sampling bias of available data and only further analyses may resolve this issue. Alternatively, significant shift of ∼1‰ towards heavier Li isotope compositions must have occurred during thermal processing of CV+L (2.2–2.8‰) mixture in order to account for the observed Li isotope systematics in HED meteorites. No correlation is observed between Li versus Zn, Fe or Si isotopes, respectively, implying unrelated processes of forming stable isotope variations observed in HED meteorites.

Midwater zooplankton and suspended particle dynamics in the North Pacific Subtropical Gyre: A stable isotope perspective

We used amino acid (AA) compound‐specific isotope analysis (δ15NAA and δ13CAA values) of midwater zooplankton and suspended particles to examine their dynamics in the mesopelagic zone. Suspended particle δ15NAA values increased by up to 14‰ with depth, whereas particle trophic status (measured as trophic position, TP) remained constant at 1.6 ± 0.07. Applying a Rayleigh distillation model to these results gave an observed kinetic isotope fractionation of 5.7 ± 0.4‰, similar to that previously measured for protein hydrolysis. AA‐based degradation index values also decreased with depth on the particles, whereas a measure of heterotrophic resynthesis (ΣV) remained constant at 1.2 ± 0.3. The main mechanism driving 15N enrichment of suspended particles appears to be isotope fractionation associated with heterotrophic degradation, rather than a change in trophic status or N source with depth. In zooplankton the “source” AA phenylalanine (Phe) became 15N enriched by up to 3.5‰ with depth, whereas zooplankton TP increased by up to 0.65 between the surface ocean and midwaters. Both changes in the δ15N values of food resources at the base of the zooplankton food web and changes in zooplankton TP drive observed zooplankton 15N enrichment with depth. Midwater zooplankton δ15NPhe values were lower by 5–8‰ compared with suspended particles, indicating this organic matter pool is not a significant zooplankton food resource at depth. Instead, 62–88% of the N sustaining midwater zooplankton is surface derived, obtained through consumption of sinking particles, carnivory of vertical migrants, or direct feeding in surface waters at night.

An isotopic perspective on the correlation of surface ocean carbon dynamics and sea ice melting in Prydz Bay (Antarctica) during austral summer

The stable carbon isotope composition of particulate organic carbon (δ13CPOC) and naturally occurring long-lived radionuclide 226Ra (T1/2=1600a) were applied to study the variations of upper ocean (<100m) carbon dynamics in response to sea ice melting in Prydz Bay, East Antarctica during austral summer 2006. Surface δ13CPOC values ranged from −27.4‰ to −19.0‰ and generally decreased from inner bay (south of 67°S) toward the Antarctic Divergence. Surface water 226Ra activity concentration ranged from 0.92 to 2.09Bq/m3 (average 1.65±0.32Bq/m3, n=20) and increased toward the Antarctic Divergence, probably reflecting the influence of 226Ra-depleted meltwater and upwelled 226Ra-replete deep water. The fraction of meltwater, fi, was estimated from 226Ra activity concentration and salinity using a three-component (along with Antarctic Summer Surface Water, and Prydz Bay Deep Water) mixing model. Although the fraction of meltwater is relatively minor (1.6–11.9%, average 4.1±2.7%, n=20) for the surface waters (sampled at ~6m), a positive correlation between surface δ13CPOC and fi (δ13CPOC=0.94×fi−28.44, n=20, r2=0.66, p<0.0001) was found, implying that sea ice melting may have contributed to elevated δ13CPOC values in the inner Prydz Bay compared to the open oceanic waters. This is the first time for a relationship between δ13CPOC and meltwater fraction to be reported in polar oceans to our knowledge. We propose that sea ice melting may have affected surface ocean δ13CPOC by enhancing water column stability and providing a more favorable light environment for phytoplankton photosynthesis, resulting in drawdown of seawater CO2 availability, likely reducing the magnitude of isotope fractionation during biological carbon fixation. Our results highlight the linkage of ice melting and δ13CPOC, providing insights into understanding the carbon cycling in the highly productive Antarctic waters.

A stable isotope (δ13C and δ15N) perspective on human diet on rapa nui (Easter Island) ca. AD 1400–1900

Ecological and environmental evidence suggests that Rapa Nui was among the most marginally habitable islands in Eastern Polynesia, with only a fraction of the biotic diversity found on archipelagos to the west, and capable of sustaining many fewer cultigens traditionally transported by Polynesian colonizers. However, archaeological evidence for human dietary adaptations under such restrictions is limited. Little is known about the particulars of the subsistence base and dietary changes on Rapa Nui that may be associated with a hypothesized late prehistoric decline in the quality and diversity of food sources. To better understand prehistoric Rapa Nui diet we examined stable carbon and nitrogen isotope compositions of human teeth along with archaeological faunal material thought to comprise the Rapa Nui food web. Our results indicate that contrary to previous zooarchaeological studies diet was predominantly terrestrial throughout the entire sequence of occupation, with reliance on rats, chickens and C3 plants. While a few individuals may have had access to higher trophic level marine resources, this is evident only later in time (generally post-AD 1600). A decline in (15)N through time was observed, and may be attributed to declines in available terrestrial proteins; however, presently we cannot rule out the effect of changing soil and plant baseline δ(15)N. Our results also suggest differential access to higher trophic level marine resources among contemporaneous populations, but more research is required to clarify this observation.

Sulfur, Carbon, Hydrogen, and Oxygen Isotope Geochemistry of the Idaho Cobalt Belt

Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ 34 S values are nearly uniform throughout the Blackbird district, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ ( n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore formation as H 2 S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form volcanogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit types that form in deeper environments and could be related to metamorphic processes or magmatic processes, although the isotopic evidence for magmatic components is relatively weak.