Hf isotope compositions and HREE variations in off-craton garnet and spinel peridotite xenoliths from central Asia

Garnet-facies continental mantle is poorly understood because the vast majority of mantle xenoliths in continental basalts are spinel peridotite. Peridotite xenoliths from Vitim (southern Siberia) and Mongolia provide some of the best samples of garnet and garnet-spinel facies off-craton lithospheric mantle. Garnets in those fertile to moderately depleted lherzolites show a surprisingly broad range of HREE abundances, which poorly correlate with modal and major oxide compositions. Some garnets are zoned and have Lu-rich cores. We argue that these features indicate HREE redistribution after the partial melting, possibly related to spinel-garnet phase transition on isobaric cooling. Most peridotites from Vitim have depleted to ultra-depleted Hf isotope compositions (calculated from mineral analyses: ε_Hf(0) = +17 to +45). HREE-rich garnets have the most radiogenic ε_Hf values and plot above the mantle Hf-Nd isotope array while xenoliths with normal HREE abundances usually fall within or near the depleted end of the MORB field. Model Hf isotope ages for the normal peridotites indicate an origin by ancient partial melt extraction from primitive mantle, most likely in the Proterozoic. By contrast, an HREE-rich peridotite yields a Phanerozoic model age, possibly reflecting overprinting of the ancient partial melting record with that related to a recent enrichment in Lu. Clinopyroxene-garnet Lu-Hf isochron ages (31-84 Ma) are higher than the likely eruption age of the host volcanic rocks (∼16 Ma). Garnet-controlled HREE migration during spinel-garnet and garnet-spinel phase transitions may be one explanation for extremely radiogenic ¹⁷⁶Hf/¹⁷⁷Hf reported for some mantle peridotites; it may also contribute to Hf isotope variations in sub-lithospheric source regions of mantle-derived magmas.     

The age of SNC meteorites and the antiquity of the Martian surface

We report new Sm-Nd, Lu-Hf, and Pb-Pb mineral and whole-rock isotope data for the basaltic shergottite Zagami, as well as Pb-Pb whole-rock isotope data for the basaltic shergottite Los Angeles, the lherzolitic shergottite Dar-al-Gani 476 (DaG 476), and the clinopyroxenite Nakhla. In agreement with previous findings, our new Sm-Nd and Lu-Hf mineral ages on the Martian meteorite Zagami are young (155 and 185 Ma, respectively). The ²⁰⁷Pb/²⁰⁶Pb-²⁰⁴Pb/²⁰⁶Pb compositions of the insoluble fractions of shergottites (Zagami, Los Angeles, and literature data for Shergotty and EETA79001) form an excellent alignment indicative of a 4.0 Ga crystallization age. The range of Pb isotope compositions observed in the leachates of these samples attests to negligible contamination of the shergottites by terrestrial Pb and argues against mixing relationships. The age of 4.048 ± 0.017 Ga (MSWD = 1.5) provided by the Pb isotope compositions of the Zagami whole-rock and residues is therefore taken to date the crystallization of this rock, which, so far, was believed to be only ∼ 180 Ma old. Based on this result, we argue that the lithosphere of Mars is extremely old and that most mineral ages were reset recently by acidic aqueous solutions percolating through the Martian surface. This interpretation is consistent with photographic interpretations of erosional features on Mars. It also relieves the constraint imposed by the presence of anomalies of ¹⁴²Nd and ¹⁸²W (both products of extinct radioactive nuclides) that the Martian mantle should have preserved primordial isotopic heterogeneities, thus allowing for the planet interior to be actively convecting.     

Comparative stable isotope geochemistry of Ni, Cu, Zn, and Fe in chondrites and iron meteorites

High-precision Ni isotopic variations are reported for the metal phase of equilibrated and unequilibrated ordinary chondrites, carbonaceous chondrites, iron meteorites, mesosiderites, and pallasites. We also report new Zn and Cu isotopic data for some of these samples and combine them with literature Fe, Cu, and Zn isotope data to constrain the fractionation history of metals during nebular (vapor/solid) and planetary (metal/sulfide/silicate) phase changes.The observed variations of the ⁶²Ni/⁵⁸Ni, ⁶¹Ni/⁵⁸Ni, and ⁶⁰Ni/⁵⁸Ni ratios vary linearly with mass difference and define isotope fractionation lines in common with terrestrial samples. This implies that Ni was derived from a single homogeneous reservoir. While no ⁶⁰Ni anomaly is detected within the analytical uncertainties, Ni isotopic fractionation up to 0.45‰ per mass-difference unit is observed. The isotope compositions of Ni and Zn in chondrites are positively correlated. We suggest that, in ordinary chondrites, exchange between solid phases, in particular metal and silicates, and vapor followed by mineral sorting during accretion are the main processes controlling these isotopic variations. The positive correlation between Ni and Zn isotope compositions contrasts with a negative correlation between Ni (and Zn) and Cu isotope compositions, which, when taken together, do not favor a simple kinetic interpretation. The observed transition element similarities between different groups of chondrites and iron meteorites are consistent with the genetic relationships inferred from oxygen isotopes (IIIA/pallasites and IVA/L chondrites). Copper is an exception, which we suggest may be related to separate processing of sulfides either in the vapor or during core formation.     

Measuring ignitability for in situ burning of oil spills weathered under Arctic conditions: from laboratory studies to large-scale field experiments

This paper compares the ignitability of Troll B crude oil weathered under simulated Arctic conditions (0%, 50% and 90% ice cover). The experiments were performed in different scales at SINTEF’s laboratories in Trondheim, field research station on Svalbard and in broken ice (70-90% ice cover) in the Barents Sea. Samples from the weathering experiments were tested for ignitability using the same laboratory burning cell. The measured ignitability from the experiments in these different scales showed a good agreement for samples with similar weathering. The ice conditions clearly affected the weathering process, and 70% ice or more reduces the weathering and allows a longer time window for in situ burning. The results from the Barents Sea revealed that weathering and ignitability can vary within an oil slick. This field use of the burning cell demonstrated that it can be used as an operational tool to monitor the ignitability of oil spills.     

Retrieval of boreal forest LAI using a forest reflectance model and empirical regressions

Spectral invariants provide a novel approach for characterizing canopy structure in forest reflectance models and for mapping biophysical variables using satellite images. We applied a photon recollision probability (p) based forest reflectance model (PARAS) to retrieve leaf area index (LAI) from fine resolution SPOT HRVIR and Landsat ETM+ satellite data. First, PARAS was parameterized using an extensive database of LAI-2000 measurements from five conifer-dominated boreal forest sites in Finland, and mixtures of field-measured forest understory spectra. The selected vegetation indices (e.g. reduced simple ratio, RSR), neural networks and kNN method were used to retrieve effective LAI (L_e) based on reflectance model simulations. For comparison, we established empirical vegetation index-LAI regression models for our study sites. The empirical RSR–L_e regression performed best when applied to an independent test site in southern Finland [RMSE 0.57 (24.2%)]. However, the difference to the best reflectance model based retrievals produced by neural networks was only marginal [RMSE 0.59 (25.1%)]. According to this study, the PARAS model provides a simple and flexible modelling tool for calibrating algorithms for LAI retrieval in conifer-dominated boreal forests. The advantage of PARAS is that it directly uses field measurements to parameterize canopy structure (LAI-2000, hemispherical photographs) and optical properties of foliage and understory.     

147Sm‐143Nd and 176Lu‐176Hf systematics of eucrite and angrite meteorites

Comparative planetary geochemistry provides insight into the origin and evolutionary paths of planetary bodies in the inner solar system. The eucrite and angrite achondrite groups are particularly interesting because they show evidence of early planetary differentiation. We present ¹⁴⁷Sm‐¹⁴³Nd and ¹⁷⁶Lu‐¹⁷⁶Hf analyses of eight noncumulate (basaltic) eucrites, two cumulate eucrites, and three angrites, which together place new constraints on the evolution and differentiation histories of the crusts of the eucrite and angrite parent bodies and their mantle mineralogies. The chemical compositions of both eucrites and angrites indicate similar evolutionary paths and petrogenetic models with formation and isolation of differentiated crustal reservoirs associated with segregation of ilmenite. We report a ¹⁴⁷Sm‐¹⁴³Nd mineral isochron age for the Moama cumulate eucrite of 4519 ± 34 Ma (MSWD = 1.3). This age indicates protracted magmatism within deep crustal layers of the eucrite parent body lasting up to about 50 Ma after the formation of the solar system. We further demonstrate that the isotopic compositions of constituent minerals are compromised by secondary processes hindering precise determination of mineral isochron ages of basaltic eucrites and angrites. We interpret the changes in geochemistry and, consequently, the erroneous ¹⁴⁷Sm‐¹⁴³Nd and ¹⁷⁶Lu‐¹⁷⁶Hf internal mineral isochron ages of basaltic eucrites and angrites as the result of metamorphic events such as impacts (effects from pressure, temperature, and peak shock duration) on the surfaces of the eucrite and angrite parent bodies.     

Carbon Budget and Molecular Structure of Natural Organic Matter in Bank Infiltrated Groundwater

Managed aquifer recharge (MAR) provides means to remove natural organic matter (NOM) from surface waters. Recent studies have explored the degree of NOM removal in groundwater. In this study, we further elaborate the NOM removal at a lakeside natural bank infiltration site that functions as a surrogate for MAR. Our objective was to quantify the carbon budget in the aquifer based on concentration measurements of dissolved (in)organic carbon, and the molecular changes in NOM using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). According to the carbon budget, only 25% of the dissolved carbon entering the aquifer was organic, and it predominantly originated from lake water. Of the inorganic majority, on average 40% was produced in the vadose zone above the groundwater table, 31% in the lake bank, 22% in the aquifer as a result of degrading organic matter of lake water, and 7% in the lake. Seasonal concentration variations suggested that the lake bank was the main carbon source in the summer, increasing the carbon concentration of infiltrating lake water, that is, 3.0 mg/L to 7.9 mg/L. FT-ICR MS results showed 4960 to 5330 individual compounds in lake and groundwater. NOM removal in the aquifer was selective: the relative abundance of oxygen-containing species decreased from 75 to 31%, while the relative abundance of sulfur-containing species increased from 15 to 57%. The average molecular weights of both species remained unchanged. The study highlighted the role of lake bank processes and sulfur-containing species in groundwater quality.     

Intraseasonal variability in subtropical South America as depicted by precipitation data

Daily precipitation data from three stations in subtropical Argentina are used to describe intraseasonal variability (20–90 days) during the austral summer. This variability is compared locally and regionally with that present in outgoing longwave radiation (OLR) data, in order to evaluate the performance of this variable as a proxy for convection in the region. The influence of the intraseasonal activity of the South American Seesaw (SASS) leading convection pattern on precipitation is also explored. Results show that intraseasonal variability explains a significant portion of summer precipitation variance, with a clear maximum in the vicinity of the SASS subtropical center. Correlation analysis reveals that OLR can explain only a small portion of daily precipitation variability, implying that it does not constitute a proper proxy for precipitation on daily timescales. On intraseasonal timescales, though, OLR is able to reproduce the main features of precipitation variability. The dynamical conditions that promote the development of intraseasonal variability in the region are further analyzed for selected summers. Seasons associated with a strong intraseasonal signal in precipitation variability show distinctive wet/dry intraseasonal periods in daily raw data, and are associated with a well defined SASS-like spatial pattern of convection. During these summers, strong large-scale forcing (such as warm El Niño/Southern Oscillation (ENSO) events and/or tropical intraseasonal convective activity), and Rossby-wave-like circulation anomalies extending across the Pacific Ocean, are also observed.     

Constraints on source-forming processes of West Greenland kimberlites inferred from Hf-Nd isotope systematics

Kimberlites from West Greenland have Hf-Nd isotope as well as major and trace element compositions that are similar to other Group I kimberlites, but that are distinctive in the spectrum of magmas sampled at Earth’s surface. The West Greenland kimberlites have ε_Ndi that ranges from +1.6 to +3.1 and ε_Hfi that ranges from −4.3 to +4.9. The samples exhibit ubiquitous negative Δε_Hfi (deviation from the ocean island basalt ε_Hf-ε_Nd reference line), ranging from −1.8 to −11.2. The kimberlites are characterized by steep heavy rare earth element patterns, positive Ta-Nb anomalies and negative Hf-Zr anomalies. These chemical signals are consistent with the presence of ancient, subducted oceanic crust in the kimberlite source region. In the model we present, dewatering and possibly partial melting of rutile-bearing oceanic crust during subduction results in characteristic trace element patterns in the residual crust. During aging, the Hf-Nd isotopic composition of this dewatered/partially melted EMORB-type crust evolves to negative Δε_Hfi values. Metasomatic fluids derived from this ancient subducted oceanic crust infiltrate and impart their trace element and isotopic signal on proximal peridotitic mantle. Melting of this metasomatized mantle peridotite results in kimberlite magmas.