A geochemical study of the winonaites: Evidence for limited partial melting and constraints on the precursor composition

The winonaites are primitive achondrites which are associated with the IAB iron meteorites. Textural evidence implies heating to at least the Fe, Ni–FeS cotectic, but previous geochemical studies are ambiguous about the extent of silicate melting in these samples. Oxygen isotope evidence indicates that the precursor material may be related to the carbonaceous chondrites. Here we analysed a suite of winonaites for modal mineralogy and bulk major- and trace-element chemistry in order to assess the extent of thermal processing as well as constrain the precursor composition of the winonaite-IAB parent asteroid. Modal mineralogy and geochemical data are presented for eight winonaites. Textural analysis reveals that, for our sub-set of samples, all except the most primitive winonaite (Northwest Africa 1463) reached the Fe, Ni–FeS cotectic. However, only one (Tierra Blanca) shows geochemical evidence for silicate melting processes. Tierra Blanca is interpreted as a residue of small-degree silicate melting. Our sample of Winona shows geochemical evidence for extensive terrestrial weathering. All other winonaites studied here (Fortuna, Queen Alexander Range 94535, Hammadah al Hamra 193, Pontlyfni and NWA 1463) have chondritic major-element ratios and flat CI-normalised bulk rare-earth element patterns, suggesting that most of the winonaites did not reach the silicate melting temperature. The majority of winonaites were therefore heated to a narrow temperature range of between ∼1220 (the Fe, Ni–FeS cotectic temperature) and ∼1370 K (the basaltic partial melting temperature). Silicate inclusions in the IAB irons demonstrate partial melting did occur in some parts of the parent body (Ruzicka and Hutson, 2010), thereby implying heterogeneous heat distribution within this asteroid. Together, this indicates that melting was the result of internal heating by short-lived radionuclides. The brecciated nature of the winonaites suggests that the parent body was later disrupted by a catastrophic impact, which allowed the preservation of the largely unmelted winonaites. Despite major-element similarities to both ordinary and enstatite chondrites, trace-element analysis suggests the winonaite parent body had a carbonaceous chondrite-like precursor composition. The parent body of the winonaites was volatile-depleted relative to CI, but enriched compared to the other carbonaceous classes. The closest match are the CM chondrites; however, the specific precursor is not sampled in current meteorite collections

Tracing acid mine drainage and estuarine Zn attenuation using Cd and Zn isotopes

It has been estimated that the acid mine drainage (AMD) impacted Odiel river basin in southern Spain supplies 0.37% and 15% of the global riverine fluxes of Cd and Zn to the oceans, respectively (Sarmiento et al., 2009). However, the behaviour of Cd and Zn in the Ria of Huelva estuary, which connects the Odiel and Tinto watersheds with the Gulf of Cadiz, has yet to be fully investigated. Furthermore, very few studies have investigated Cd and Zn isotope behaviour in estuaries worldwide. This study presents Cd and Zn concentrations and isotopic compositions for the Ria of Huelva estuary and surrounding watersheds, sampled in 2017 and 2019. Sulfide-rich rock samples extracted from three mines yield Cd and Zn isotope compositions that range from –0.14‰ to +0.07‰ (n = 4) for δ114Cd and –0.01‰ to +0.29‰ (n = 4) for δ66Zn. However, a uniform riverine signal of about +0.02‰ for Cd and +0.17‰ for Zn indicates that tracing of individual mining regions using Cd and Zn isotopes is challenging. Limited variability was observed in dissolved δ114Cd values throughout the watershed, including AMD, the estuary, and the Gulf of Cadiz, with a mean value of ±0.00 ± 0.13‰ (n = 25, 2 SD; excludes one AMD outlier, at +0.48‰), including both 2017 and 2019 data. By contrast, δ66Zn values ranged from –0.12‰ to +0.35‰ (n = 28) for the same geographical and temporal scope. In May 2017, a large spill from an abandoned mine, La Zarza, resulted in a drastic increase in the concentrations of trace metals reaching the estuary compared to 2019, but no impact of this mine spill on Cd or Zn isotope compositions is observed. In 2019, an increase in δ66Zn values in the estuary coincided with high pH values (up to pH = 8.8) and chloride concentrations (2.73%), which may reflect an alkaline anthropogenic input from the active neighbouring industrial complex. Overall, Cd concentrations and isotope compositions in the estuary are largely consistent with conservative mixing behaviour. By contrast, Zn behaviour is non-conservative, with removal of 49 to 97% of dissolved riverine Zn in the estuary during the period 2017 to 2019, associated with a relatively small isotopic shift to lighter Zn isotope compositions. Removal of Zn to the particulate phase in the Ria of Huelva estuary therefore largely attenuates high riverine Zn fluxes from AMD, indicating that previously estimated Odiel river basin Zn fluxes were overestimated. Nevertheless, the variable but generally light AMD Cd and Zn isotope compositions, coupled with high dissolved metal concentrations, suggest that Cd and Zn isotopes may be useful tracers of regionally averaged AMD inputs to the Gulf of Cadiz and beyond

Neodymium isotope analyses after combined extraction of actinide and lanthanide elements from seawater and deep-sea coral aragonite

Author Posting. © American Geophysical Union, 2016. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 17 (2016): 232–240, doi:10.1002/2015GC006130.Isotopes of the actinide elements protactinium (Pa), thorium (Th), and uranium (U), and the lanthanide element neodymium (Nd) are often used as complementary tracers of modern and past oceanic processes. The extraction of such elements from low abundance matrices, such as seawater and carbonate, is however labor-intensive and requires significant amounts of sample material. We here present a combined method for the extraction of Pa, Th, and Nd from 5 to 10 L seawater samples, and of U, Th, and Nd from <1 g carbonate samples. Neodymium is collected in the respective wash fractions of Pa-Th and U-Th anion exchange chromatographies. Regardless of the original sample matrix, Nd is extracted during a two-stage ion chromatography, followed by thermal ionization mass spectrometry (TIMS) analysis as NdO+. Using this combined procedure, we obtained results for Nd isotopic compositions on two GEOTRACES consensus samples from Bermuda Atlantic Time Series (BATS), which are within error identical to results for separately sampled and processed dedicated Nd samples (εNd = −9.20 ± 0.21 and −13.11 ± 0.21 for 15 and 2000 m water depths, respectively; intercalibration results from 14 laboratories: εNd = −9.19 ± 0.57 and −13.14 ± 0.57). Furthermore, Nd isotope results for an in-house coral reference material are identical within analytical uncertainty for dedicated Nd chemistry and after collection of Nd from U-Th anion exchange chromatography. Our procedure does not require major adaptations to independently used ion exchange chromatographies for U-Pa-Th and Nd, and can hence be readily implemented for a wide range of applications.Funding that supported this work was received from the National Science Foundation (NSF 0752402), the Leverhulme Trust (RPG-398), the Natural Environmental Research Council (NE/J021636/1 and NE/N003861/1), the European Research Council (278705), and the Grantham Institute for Climate Change.2016-07-0

The evolution of the Antarctic Circumpolar Current in the SouthwestPacific sector of the Southern Ocean throughout the Cenozoic era

EGU General Assembly in Viena, Austria, 7–12 April 2019The establishment and evolution of the Antarctic Circumpolar Current (ACC) throughout the Cenozoic remainspoorly known, mainly because of the lack of continuous long-term records at strategic locations. Here we presentnew records from marine sediments collected by the Deep Sea Drilling Project (DSDP) Site 278, located in theSouthwestern Pacific sector of the Southern Ocean (Southern Emerald Basin), spanning from the mid-Oligoceneto the Pleistocene (ie. the∼28-2 Ma). Our site is ideally situated to reconstruct changes in the ACC sincethe mid-Oligocene as it remained along the polar frontal zone as shown by paleolatitude reconstructions andmicrofossil assemblage data. To track its evolution, we combined (i) mean grain size of sortable silt (SS) datawith (ii) primary productivity proxies including biogenic silica (BSi), calcium carbonate (CaCO3) and organicmatter, and (iii) neodymium isotope ratios (εNd) generated from fossil fish teeth and debris. Our results documenta significant increase in SS, enhanced marine productivity and a decrease inεNd values towards present-dayCircumpolar deep waterεNd values, suggesting a progressive strengthening of the proto-ACC flow over the last28 Ma. However, we find that the development of a modern-like, homogenous and deep-reaching current wasfully established solely during the Pliocene-Pleistocene transition, concomitantly with the onset of the NorthernHemisphere glaciation

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

The vigorous eastward flow of the Antarctic Circumpolar Current (ACC) connects all major ocean basins and plays a prominent role in the transport of heat, carbon and nutrients around the globe. However, the establishment of a deep circumpolar flow, similar to the present-day ACC, remains controversial thereby obscuring our understanding of its climatic impact. Deciphering the chemical composition of Circumpolar Deep Water (CDW) within the ACC can provide critical insights about its development and evolution. Here we present new fossil fish teeth/bone debris neodymium isotope (ε) records from Deep Sea Drilling Project (DSDP) Sites 278 and 274 in the southwest Pacific Ocean, with the aim to trace changes in deep water masses across the Tasmanian Gateway between the early Oligocene and early Miocene (~ 33–22 Ma). Site 274 provides the first Nd isotope record proximal to the Ross Sea during the Oligocene (33.5–23.4 Ma). Its Nd isotope composition shows excursions to very radiogenic values, ε = −3.1 and ε − 3.7, at 33.5 Ma and 23.8 Ma, respectively, in response to major steps in Antarctic ice sheet expansion. A shift to lower, more unradiogenic ε values between 29.7 and 29.1 Ma is linked to an increased influence of proto-CDW upwelling at the site. In contrast, the Nd isotope record from Site 278 in the southern Emerald Basin shows little variability (ε = −6.0 to −6.7) throughout the Oligocene and early Miocene (30.9–21.8 Ma). Comparison with published data north of the ACC path, demonstrates the presence of two deep water masses in the South Pacific prior to the inferred onset of the ACC (33–30 Ma), one occupying depths between ~2500 and 3000 m (ε ~ −3 to −5) and a deep/bottom water mass (> 3000 m) with a more unradiogenic Nd isotope composition (ε ~ −6). Site 278 located close to the proto-polar front (proto-PF) indicates that following the inferred onset of the ACC, deep waters bathing the southern Emerald Basin remained more radiogenic in the Southwest Pacific compared to sites along the proto-PF in the South Atlantic and Indian Ocean (ε ~ −8.1). This indicates a provinciality in Nd isotope compositions of deep waters along the proto-PF across the Tasmanian Gateway. Our data are incompatible with the existence of a modern-like homogenous (lateral and vertical) Nd isotope composition of CDW along the main flow path of the ACC in all oceanic basins in the Oligocene to early Miocene. We attribute distinct Nd isotope compositions of deep waters across the Tasmanian Gateway to reflect a less deep reaching and weaker ACC (proto-ACC) than today. Our findings suggest that the modern strong and deep-reaching ACC flow must have been developed at a later point in the Neogene.Funding to this research is provided by the Alexander S. Onassis Public Benefit Foundation Ph.D. research grant: F ZL 016-1/2015-2016; the Spanish Ministry of Economy, Industry and Competitivity (grants CTM2017-89711-C2-1/2-P), co-funded by the European Union through FEDER funds; and an ECORD Research grant awarded to DE. PKB and FH acknowledge funding through the European Research Council starting grant #802835 OceaNice and NWO polar programme grant ALWPP2016.001. This paper is a contribution to the SCAR PAIS Programme