Solubility of manganotantalite, zircon and hafnon in highly fluxed peralkaline to peraluminous pegmatitic melts

The behavior of tantalum and zirconium in pegmatitic systems has been investigated through the determination of Ta and Zr solubilities at manganotantalite and zircon saturation from dissolution and crystallization experiments in hydrous, Li-, F-, P- and B-bearing pegmatitic melts. The pegmatitic melts are synthetic and enriched in flux elements: 0.7–1.3 wt% Li₂O, 2–5.5 wt% F, 2.8–4 wt% P₂O₅ and 0–2.8 wt% B₂O₃, and their aluminum saturation index ranges from peralkaline to peraluminous (ASI_Li = Al/[Na + K + Li] = 0.8 to 1.3) with various K/Na ratios. Dissolution and crystallization experiments were conducted at temperatures varying between 700 and 1,150°C, at 200 MPa and nearly water-saturated conditions. For dissolution experiments, pure synthetic, end member manganotantalite and zircon were used in order to avoid problems with slow solid-state kinetics, but additional experiments using natural manganotantalite and zircon of relatively pure composition (i.e., close to end member composition) displayed similar solubility results. Zircon and manganotantalite solubilities considerably increase from peraluminous to peralkaline compositions, and are more sensitive to changes in temperature or ASI of the melt than to flux content. A model relating the enthalpy of dissolution of manganotantalite to the ASI_Li of the melt is proposed: ∆H _diss (kJ/mol) = 304 × ASI_Li − 176 in the peralkaline field, and ∆H _diss (kJ/mol) = −111 × ASI_Li + 245 in the peraluminous field. The solubility data reveal a small but detectable competitivity between Zr and Ta in the melt, i.e., lower amounts of Zr are incorporated in a Ta-bearing melt compared to a Ta-free melt under the same conditions. A similar behavior is observed for Hf and Ta. The competitivity between Zr (or Hf) and Ta increases from peraluminous to peralkaline compositions, and suggests that Ta is preferentially bonded to non-bridging oxygens (NBOs) with Al as first-neighbors, whereas Zr is preferentially bonded to NBOs formed by excess alkalies. As a consequence Zr/Ta ratios, when buffered by zircon and manganotantalite simultaneously, are higher in peralkaline melts than in peraluminous melts.     

Growth of bultfonteinite and hydrogarnet in metasomatized basalt xenoliths in the B/K9 kimberlite, Damtshaa, Botswana: insights into hydrothermal metamorphism in kimberlite pipes

Metamorphic assemblages within Karoo basalt xenoliths, found within volcaniclastic kimberlite of the B/K9 pipe, Damtshaa, Botswana, constrain conditions of kimberlite alteration. Bultfonteinite and chlorite partially replace the original augite-plagioclase assemblage, driven by the serpentinisation of the kimberlite creating strong chemical potential gradients for Si and Mg. Hydrogarnet and serpentine replace these earlier metamorphic assemblages as the deposits cool. The bultfonteinite (ideally Ca₂SiO₂[OH,F]₄) and hydrogarnet assemblages require a water-rich fluid containing F⁻, and imply hydrothermal alteration dominated by external fluids rather than autometamorphism from deuteric fluids. Bultfonteinite and hydrogarnet are estimated to form at temperatures of ca. 350–250°C, which are similar to those for serpentinisation. Alteration within the B/K9 kimberlite predominantly occurs between 250 and 400°C. We attribute these conditions to increased efficiency of mass transfer and chemical reactions below the critical point of water and a consequence of volume-increasing serpentinisation and metasomatic reactions that take place over this temperature range. A comparison of the B/K9 kimberlite with kimberlites from Venetia, South Africa suggests that the composition and mineralogy of included xenoliths affects the alteration assemblages within kimberlite deposits.     

Melt extraction and melt refertilization in mantle peridotite of the Coast Range ophiolite: an LA–ICP–MS study

The middle Jurassic Coast Range Ophiolite (CRO) is one of the most important tectonic elements in western California, cropping out as tectonically dismembered elements that extend 700 km from south to north. The volcanic and plutonic sections are commonly interpreted to represent a supra-subduction zone (SSZ) ophiolite, but models specifying a mid-ocean ridge origin have also been proposed. These contrasting interpretations have distinctly different implications for the tectonic evolution of the western Cordillera in the Jurassic. If an SSZ origin is confirmed, we can use the underlying mantle peridotites to elucidate melt processes in the mantle wedge above the subduction zone. This study uses laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) to study pyroxenes in peridotites from four mantle sections in the CRO. Trace element signatures of these pyroxenes record magmatic processes characteristic of both mid-ocean ridge and supra-subduction zone settings. Group A clinopyroxene display enriched REE concentrations [e.g., Gd (0.938–1.663 ppm), Dy (1.79–3.24 ppm), Yb (1.216–2.047 ppm), and Lu (0.168–0.290 ppm)], compared to Group B and C clinopyroxenes [e.g., Gd (0.048–0.055 ppm), Dy (0.114–0.225 ppm), Yb (0.128–0.340 ppm), and Lu (0.022–0.05 ppm)]. These patterns are also evident in orthopyroxene. The differences between these geochemical signatures could be a result of a heterogeneous upper mantle or different degrees of partial melting of the upper mantle. It will be shown that CRO peridotites were generated through fractional melting. The shapes of REE patterns are consistent with variable degrees of melting initiated within the garnet stability field. Models call for 3% dry partial melting of MORB-source asthenosphere in the garnet lherzolite field for abyssal peridotites and 15–20% further partial melting in the spinel lherzolite field, possibly by hydrous melting for SSZ peridotites. These geochemical variations and occurrence of both styles of melting regimes within close spatial and temporal association suggest that certain segments of the CRO may represent oceanic lithosphere, attached to a large-offset transform fault and that east-dipping, proto-Franciscan subduction may have been initiated along this transform.     

The pattern of Ni and Co abundances in lunar olivines

Near liquidus experiments on peridotite and other olivine normative compositions from 1.7 to 6 GPa confirm the applicability of exchange-based empirical models of Ni and Co partitioning between olivine and silicate liquids with compositions close to the liquidus of peridotite. Given that most estimates of lunar bulk composition are peridotitic, the partitioning models thus lend themselves to calculation of olivine compositions produced during the early stages of magma ocean crystallization. Calculation of olivine compositions produced by fractional crystallization of a model lunar magma ocean, initially 700 km deep, reveals a prominent maximum in Ni concentration versus fraction crystallized or Mg’ (molar MgO/(MgO + FeO)), but a pattern of monotonically increasing Co concentration. These patterns qualitatively match the puzzling patterns of Ni and Co concentrations observed in lunar rocks in which forsteritic olivines in magnesian suite cumulates have lower Ni and Co abundances than do less magnesian olivines from low-Ti mare basalts, and olivines from the ferroan anorthosite suite (FAS) have lower Ni, but similar Co to mare basalt olivines.The Ni and Co abundances in olivines from the magnesian suite cumulates can be reconciled in terms of fractional crystallization of a deep magma ocean which initially produces a basal dunite comprised of the hottest and most magnesian olivine overlain by an olivine-orthopyroxene (harzburgite) layer that is in turn overlain by an upper zone of plagioclase-bearing cumulates. The ultramafic portion of the cumulate pile overturns sending the denser harzburgite layer, which later becomes a portion of the green glass source region, to the bottom of the cumulate pile with Ni- and Co-rich olivine. Meanwhile, the less dense, but hottest, most magnesian olivines with much lower Ni and Co abundances are transported upward to the base of the plagioclase-bearing cumulates where subsequent heat transfer leads to melting of mixtures of primary dunite, norite, and gabbronorite with KREEP (a K-REE-P enriched component widely believed to be derived from the very latest stage magma ocean liquid). These hybrid melts have Al₂O₃, Ni, and Co abundances and Mg’ appropriate for parent magmas of the magnesian suite. Ni and Co abundances in the FAS are consistent with either direct crystallization from the magma ocean or crystallization of melts of primary dunite-norite mixtures without KREEP.     

Effect of temperature and mass transport on transition metal isotope fractionation during electroplating

Transition metal stable isotope signatures can be useful for tracing both natural and anthropogenic signals in the environment, but only if the mechanisms responsible for fractionation are understood. To investigate isotope fractionations due to electrochemistry (or redox processes), we examine the stable isotope behavior of iron and zinc during the reduction reaction  + 2e⁻ = M_metal as a function of electrochemical driving force, temperature, and time. In all cases light isotopes are preferentially electroplated, following a mass-dependent law. Generally, the extent of fractionation is larger for higher temperatures and lower driving forces, and is roughly insensitive to amount of charge delivered. The maximum fractionations are δ^56/54Fe = −4.0‰ and δ^66/64Zn = −5.5‰, larger than observed fractionations in the natural environment and larger than those predicted due to changes in speciation. All the observed fractionation trends are interpreted in terms of three distinct processes that occur during an electrochemical reaction: mass transport to the electrode, chemical speciation changes adjacent to the electrode, and electron transfer at the electrode. We show that a large isotope effect adjacent the electrode surface arises from the charge-transfer kinetics, but this effect is attenuated in cases where diffusion of ions to the electrode surface becomes the rate-limiting step. Thus while a general increase in fractionation is observed with increasing temperature, this appears to be a result of thermally enhanced mass transport to the reacting interface rather than an isotope effect associated with the charge-transfer kinetics. This study demonstrates that laboratory experiments can successfully distinguish isotopic signatures arising from mass transport, chemical speciation, and electron transfer. Understanding how these processes fractionate metal isotopes under laboratory conditions is the first step towards discovering what role these processes play in fractionating metal isotopes in natural systems.     

The consumption of space: Land, capital and place in the New Zealand wine industry

Geographers have developed a keen interest in the social production of space - in the way meanings and values are ascribed to places as a result of changing social, cultural and political processes. There is a need to explore this approach further, seeing how social and economic values of places are inter-related and how these values are constructed in often deliberate and concerted ways. There is also a need to explore how such values are consumed: how the values in place are traded, appropriated and redistributed, both through the products of places and in land markets. This paper examines the New Zealand wine industry where certain wine regions have been identified and developed in ways which attempt to emphasise their distinctiveness in terms of wine quality and thus enhance the value of the wine produced. Different strategies have been employed in this process of place construction and this reflects the differential role of capital, striving on the one hand to increase the price and marketability of the products of distinctive places but, on the other, careful not to over-inflate land values and thus restrict further expansion. The paper suggests that the issue of consumption of space, involving a complex relationship amongst land, capital and place, is worthy of further exploration.     

翼龙重建：方法论的一个研究例子

Reconstructions of fossil animals are widespread and often very high profile, yet many of these reconstructions exhibit low standards of scientific accuracy.     

Trinitite—the atomic rock

On 16 July 1945, the first atomic bomb was detonated at the Alamogordo Bombing range in New Mexico, USA. Swept up into the nuclear cloud was the surrounding desert sand, which melted to form a green glassy material called ‘trinitite’. Contained within the glass are melted bits of the first atomic bomb and the support structures and various radionuclides formed during the detonation. The glass itself is marvelously complex at the tens to hundreds of micrometre scale, and besides glasses of varying composition also contains unmelted quartz grains. Air transport of the melted material led to the formation of spheres and dumbbell shaped glass particles. Similar glasses are formed during all ground level nuclear detonations and contain forensic information that can be used to identify the atomic device.     

The construction and development of SHRIMP I: An historical outline

In 1973 Bill Compston advocated the building of an ion microprobe at the Research School of Earth Sciences (RSES) at the Australian National University (ANU). The commercial ion probes available at this time were too small to have sufficient sensitivity for trace element analysis and too low in mass resolution to avoid molecular interferences. The project commenced in 1974 with the appointment of a former ANU PhD student Steve Clement who had expertise in beam transport theory. To achieve high sensitivity and high mass resolution, beam transport theory indicated that a much larger magnet than in any commercially available mass spectrometer would be required. Clement chose an ion optical design, by Professor Matsuda of Osaka University in 1974, which had the required combination of high mass resolution and high transmission. Clement's job was to produce the detailed scientific designs and machine drawings for the new instrument as well as testing the completed instrument. Clement coined the term SHRIMP-Sensitive High Resolution Ion MicroProbe. By the end of 1977 nearly all the components had been manufactured and the big electromagnet had been successfully tested. In the following year the secondary mass analyzer was assembled and tested using a thermal ionization source and showed great promise with flat-topped peaks at 5000 resolution and 50% transmission with 50 V energy spread. At this stage the machine had far exceeded the specifications for the available commercial ion probes. Continued development during 1981 to the point where the original design specifications were fully realized was time consuming since learning how to use the entirely novel instrument was no simple task; no one else had an instrument like SHRIMP. The application of the instrument to zircon U–Pb geochronology established the necessary operating conditions for measuring Pb isotopic compositions and the elemental ratios Pb/U and U/Zr from 20 μm diameter spots on single zircon grains. Application of this in the early 1980s started a revolution in Precambrian geology by the ability to produce rapidly accurate and precise age determinations on structurally complex zircon samples.     

Got green? addressing environmental justice in park provision

We present a pragmatic approach to assist planners in addressing racial inequities in park access. Utilizing the Los Angeles metropolitan region as an example, we used Thiessen polygons to delineate a service area for each park, and described potential park congestion or ‘pressure’ in each park service area. Results show that Latinos, African-Americans, and low-income groups in general were likely to live close to parks with higher potential park congestion. On the other hand, predominantly White, high-income areas were typically located close to parks with lower potential park congestion levels. The park service area analysis presented here facilitates the identification of areas with greater park need and provides a pragmatic way to redress existing disparities in park access. Built into a set of web-based decision support tools, the approach fosters greater community participation and empowers local stakeholders in the process of park provision.