On the Lu-Hf Isotope Geochemistry of Silicate Rocks

This paper reviews the history (TIMS, hot‐SIMS, MC‐ICP‐MS), significance, geochemical behaviour and current uncertainties (λ¹⁷⁶ Lu, Hf‐Nd Bulk Silicate Earth) surrounding the Lu‐Hf isotope system, and thus marks two decades of its application to geochemical problems. An appendix further presents (a) improvements to the original chemistry protocol of Blichert‐Toft et al. (1997) for application to Mg‐rich samples and (b) a compilation of previously published and new Hf isotope determinations by MC‐ICP‐MS for a set of international rock reference materials. Prior to the advent of multiple‐collector plasma source mass spectrometry (MC‐ICP‐MS), routine analysis of the Lu‐Hf isotope system developed only slowly because of the extreme difficulty of measuring Hf isotope compositions with thermal ionisation mass spectrometry, caused by the very high first ionisation potential of Hf. However, Hf isotope compositions can be measured relatively easily using MC‐ICP‐MS and this new technique now provides reproducible measurements at high precision regardless of the matrix from which Hf is separated. Of the commonly used long‐lived radiogenic isotope systems, only the Sm‐Nd and Lu‐Hf isotope systems are unaffected by parent/daughter fractionations related to volatile nebular processes and core formation. While other systems (Rb‐Sr, U‐Th‐Pb, Re‐Os) may also be used to investigate the chemical evolution of the Earth, Moon, Mars and parent bodies of differentiated meteorites, the larger uncertainties in their bulk chemical and isotopic values limit their application to determine geochemical budgets and assess planetary mantle‐crust evolution. In the study of garnet‐bearing rocks, both for dating purposes and as an isotopic tracer for source provenance and mantle processes, the Lu‐Hf isotope system likewise is of major interest because of the high partition coefficient of Lu compared to Hf for garnet with respect to other minerals. Furthermore, the larger Lu/Hf fractionation compared to Sm/Nd during melting beneath ridges produces proportionally higher Lu/Hf in the residue and faster in‐growth of a radiogenic Hf isotopic signature (compared to Nd), which may help shed light on the dynamics of mantle melting. While the chemistry protocol and mass spectrometric technique for high‐precision Lu‐Hf isotope analysis have been resolved in satisfactory ways over the past five years, more accurate determination of the decay constant for ¹⁷⁶ Lu, at present known with a precision of only about 4%, still needs to be completed and a consensus reached on which value to use for future Lu‐Hf isotope studies. Although the current combined Lu‐Hf and Sm‐Nd Bulk Silicate Earth parameters are plagued by possible incompatibilities in chondrite selection and potential interlaboratory biases, a more accurate set of values may not be readily established owing to heterogeneities in the isotopic composition of chondrites that far exceed present analytical accuracy.     

Petrology and geochemistry of the unbrecciated achondrite Northwest Africa 1240 (NWA 1240): an HED parent body impact melt

NWA 1240 is an unusual eucrite recently recovered in Morocco as a single stone of 98 g. It is an unbrecciated greenish-brown rock nearly devoid of fusion crust. It displays porphyritic texture consisting of skeletal hollow low-Ca pyroxene phenocrysts set in a variolitic (fan-spherulitic) mesostasis of fine elongate pyroxene and plagioclase crystals. Minor phases are skeletal chromite, iron, silica, troilite, ilmenite and minute amounts of phosphate and fayalite. Pyroxenes are unequilibrated and show one of the widest ranges of composition so far described for a eucrite, from En_76.0Wo_1.9Fs_22.1 to compositions nearly devoid of Mg (unusual ferrosilite and Fe-augite symplectites and possibly pyroxferroite). Plagioclase crystals contain significant amounts of Fe and Mg, which are possibly controlled by the Ca(Mg,Fe²⁺)Si₃O₈ plagioclase component.To discuss the potential effects of hot-desert weathering on NWA 1240, we have analyzed a series of Saharan eucrites (Agoult, Aoufous, Igdi, Smara, NWA 047 and NWA 049) and large aliquots (0.39 to 2.8 g) of eucrite falls (Bereba, Bouvante, Jonzac, Juvinas and Serra de Magé). These results indicate that among the elements we have determined, Pb, Ba and Sr are the most sensitive indicators of Saharan weathering.The bulk composition of NWA 1240 has been determined for 45 elements by ICP-AES and ICP-MS. The data show that the meteorite is not significantly weathered: its Pb concentration is very low; Ba and Sr concentrations are not anomalously high; the Th/U and Hf/Sm ratios are chondritic (Th/U = 3.65, Hf/Sm = 0.74). NWA 1240 is rich in MgO (10.4 wt%) and Cr₂O₃ (0.71 wt%), and displays striking similarities with cumulate eucrites, such as having similar incompatible trace element patterns and a significant positive Eu anomaly (Eu/Eu* = 1.37). The combination of fast cooling and cumulate eucrite-dominated composition suggests that NWA 1240 is not an igneous rock but rather an impact melt.     

考虑目标光谱差异的机载离散激光雷达叶面积指数反演

利用间隙率模型反演LAI（Leaf Area Index），需要同时获取冠层间隙率和消光系数，后者与冠层叶倾角分布有关。基于点云数量构建激光雷达穿透指数LPI （LiDAR Penetration Index），用以代替冠层间隙率GF （Gap Fraction），并利用间隙率模型反演冠层LAI是利用LiDAR PCD（LiDAR Point Cloud Data）数据反演冠层LAI主要思路。冠层和背景的光谱差异是影响PCD数据中冠层和背景点云数量的重要因素，因此从LPI到GF的校正需要获取背景和冠层的后向散射系数比（μ=ρg/ρv）。本文基于PCD数据中点云强度进行μ值获取，用以实现LPI到GF的校正；在假设区域内叶倾角满足椭球形叶倾角分布的基础上，利用样地尺度下的多角度GF，采用有约束的非线性最优化方法获取椭球形叶倾角分布参数χ，实现冠层消光系数的获取；最后利用间隙率模型实现基于PCD数据的LAI反演。本文探讨了基于PCD数据进行冠层LAI反演时，样地尺度Rxy_Tile、样方尺度Rxy_Plot以及进行背景和冠层分割的高度阈值Ht对模型的影响。结果显示，由于区域内地衣植被广泛覆盖，基于点云强度的μ 值接近1，符合区域特点；经过μ值校正后的GF对冠层间隙率具有较好的反映能力（R2=0.78,RMSE=0.09）；对于优势种明显的区域，基于样地尺度内多角度GF的χ值反演受样地内冠间大间隙的影响，选择合适的样地尺度能够减小LAI反演过程中的系统性误差；结合地面参考数据，确定的最优Rxy_Tile、Rxy_Plot和Ht分别为950 m、10 m和2.6 m，在此基础上反演的LAI与地面测量数据具有高度的一致性（R2=0.84,RMSE=0.51）；与Rxy_Plot相比，基于间隙率模型的LAI反演对Ht的选择更为敏感。     

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.     

Separation of Hf and Lu for high-precision isotope analysis of rock samples by magnetic sector-multiple collector ICP-MS

Potential applications of the Lu-Hf isotope system have long been impeded by the analytical difficulties of obtaining data on a wide variety of geological materials. Many of these limitations will now be eliminated because Hf isotopes can be readily measured with high precision and accuracy on small and/or Hf-poor samples using the newly developed magnetic sector-multiple collector ICP-MS, also known as MC-ICP-MS or the `Plasma 54'. We present here a new method to separate and determine isotopic compositions of both Hf and Lu from various types of geological materials using MC-ICP-MS. The chemical separation of Hf and Lu has been designed to take advantage of the characteristics of this unique instrument. The separation of Hf can be achieved with a straightforward two-step ion-exchange column chemistry, which has a high efficiency (better than 85% recovery) and low blanks (typical total blanks less than 150 pg for the largest samples of 1 g bulk rock). The isolation of Lu is achieved with a single-stage ion-exchange column procedure with near 100% yields and blanks below 20 pg. Hf isotopic compositions can be routinely measured on 50 ng Hf with an internal precision better than 20 ppm in less than 15 min and with an external precision better than 40 ppm. Our value for the ¹⁷⁶Hf/¹⁷⁷Hf ratio of the JMC 475 Hf standard currently is 0.282163 ± 9 (2s). The Lu isotopic ratio is measured rapidly and precisely without isolating Lu from the bulk of Yb, and a mass fractionation correction increases the accuracy of the results compared with TIMS data. Our current reproducibility of the Lu/Hf ratio is ≈1%. Selected Lu-Hf isotope analyses of some modern and ancient geological samples validate the technique we have described here and illustrate the new opportunities for Lu-Hf isotope geochemistry that have opened up with the advent of magnetic-sector ICP mass spectrometry. Received: 12 September 1996 / Accepted: 13 January 1997     

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.