Experimental and computational study of trace element distribution between orthopyroxene and anhydrous silicate melt: substitution mechanisms and the effect of iron

Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 to $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 , D values for highly charged elements vary from $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 through $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 and $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 to $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 , and are all virtually independent of temperature. Cr and Co are the only compatible trace elements at the studied conditions. To elucidate charge-balancing mechanisms for incorporation of REE into Opx and to assess the possible influence of Fe on Opx-melt partitioning, we compare our experimental results with computer simulations. In these simulations, we examine major and minor trace element incorporation into the end-members enstatite (Mg₂Si₂O₆) and ferrosilite (Fe₂Si₂O₆). Calculated solution energies show that R²⁺ cations are more soluble in Opx than R³⁺ cations of similar size, consistent with experimental partitioning data. In addition, simulations show charge balancing of R³⁺ cations by coupled substitution with Li⁺ on the M1 site that is energetically favoured over coupled substitution involving Al–Si exchange on the tetrahedrally coordinated site. We derived best-fit values for ideal ionic radii r ₀, maximum partition coefficients D ₀, and apparent Young’s moduli E for substitutions onto the Opx M1 and M2 sites. Experimental r ₀ values for R³⁺ substitutions are 0.66–0.67 ? for M1 and 0.82–0.87 ? for M2. Simulations for enstatite result in r ₀ = 0.71–0.73 ? for M1 and ~0.79–0.87 ? for M2. Ferrosilite r ₀ values are systematically larger by ~0.05 ? for both M1 and M2. The latter is opposite to experimental literature data, which appear to show a slight decrease in $ r_{0}^{{{\text{M}}2}} $ r_{0}^{{{\text{M}}2}} in the presence of Fe. Additional systematic studies in Fe-bearing systems are required to resolve this inconsistency and to develop predictive Opx-melt partitioning models for use in terrestrial and lunar magmatic differentiation models.     

Discriminant analysis for estimation of groundwater age from hydrochemistry and well construction: application to New Zealand aquifers

Concentrations of tritium, chlorofluorocarbons and sulfur hexafluoride have been measured at over 100 groundwater monitoring sites across New Zealand, followed by interpretation of groundwater age distribution using the exponential-piston flow model. Interpreted mean residence times ranged from less than 1 year to more than 100 years, with the 25th, 50th (median) and 75th percentiles being approximately 10, 40 and 100 years, respectively. Classification functions derived from discriminant analysis and based on nine input variables (well depth, electrical conductivity and the concentrations of the ions Na, K, Ca, Mg, HCO₃, Cl and SO₄) allowed assignment of 71% of the sites to the correct of four age categories (mean residence time 10 years or less, 11–40 years, 41–100 years, or more than 100 years). The discriminant analysis classification functions were more effective than regression methods for estimating groundwater age from hydrochemistry and well depth, and can thus be used to predict the groundwater age category for any monitoring site in New Zealand.     

HYTEC results of the MoMas reactive transport benchmark

A specific benchmark has been developed by the French research group MoMas in order to improve numerical solution methods applied by reactive transport models, i.e., codes that couple hydrodynamic flow and mass transport in porous media with geochemical reactions. The HYTEC model has been applied to this benchmark exercise, and this paper summarizes some of the principal results. HYTEC is a general-purpose code, applied by industrials and research groups to a wide variety of domains, including soil pollution, nuclear waste storage, cement degradation, water purification systems, storage of CO₂, and valorization of stabilized wastes. The code has been applied to the benchmark test-cases without any specific modification. Apart from the benchmark imposed output, additional information is provided to highlight the behavior of HYTEC specifically and the simulation results in particular.     

From Tethys to Eastern Paratethys: Oligocene depositional environments, paleoecology and paleobiogeography of the Thrace Basin (NW Turkey)

The Oligocene depositional history of the Thrace Basin documents a unique paleogeographic position at a junction between the Western Tethys and the Eastern Paratethys. As part of the Tethys, shallow marine carbonate platforms prevailed during the Eocene. Subsequently, a three-staged process of isolation started with the Oligocene. During the Early Rupelian, the Thrace Basin was still part of the Western Tethys, indicated by typical Western Tethyan marine assemblages. The isolation from the Tethys during the Early Oligocene is reflected by oolite formation and endemic Eastern Paratethyan faunas of the Solenovian stage. The third phase reflects an increasing continentalisation of the Thrace Basin with widespread coastal swamps during the Late Solenovian. The mollusc assemblages are predominated by mangrove dwelling taxa and the mangrove plant Avicennia is recorded in the pollen spectra. The final continentalisation is indicated by the replacement of the coastal swamps by pure freshwater swamps and fluvial plains during the Late Oligocene (mammal zone MP 26). This paleogeographic affiliation of the Thrace Basin with the Eastern Paratethys after ~32 Ma contrasts all currently used reconstructions which treat the basin as embayment of the Eastern Mediterranean basin.     

Uncertainty and risk in climate projections for the 21st century: comparing mitigation to non-intervention scenarios

Probabilistic climate projections based on two SRES scenarios, an IMAGE reference scenario and five IMAGE mitigation scenarios (all of them multi-gas scenarios) using the Bern2.5D climate model are calculated. Probability distributions of climate model parameters that are constrained by observations are employed as input for the climate model. The sensitivity of the resulting distributions with respect to prior assumptions on climate sensitivity is then assessed. Due to system inertia, prior assumptions on climate sensitivity play a minor role in the case of temperature projections for the first half of the 21st century, but these assumptions have a considerable influence on the distributions of the projected temperature increase in the year 2100. Upper and lower probabilities for exceeding 2°C by the year 2100 are calculated for the different scenarios. Only the most stringent mitigation measures lead to low probabilities for exceeding the 2°C threshold. This finding is robust with respect to our prior assumptions on climate sensitivity. Further, probability distributions of total present-value damages over the period 2000–2100 for the different scenarios are calculated assuming a wide range of damage cost functions, and the sensitivity of these distributions with respect to the assumed discount rate is investigated. Absolute values of damage costs depend heavily on the chosen damage cost function and discount rate. Nevertheless, some robust conclusions are possible.     

Navigating the dilemmas of climate policy in Europe: evidence from policy evaluation studies

Climate change is widely recognised as a ‘wicked’ policy problem. Agreeing and implementing governance responses is proving extremely difficult. Policy makers in many jurisdictions now emphasise their ambition to govern using the best available evidence. One obvious source of such evidence is the evaluations of the performance of existing policies. But to what extent do these evaluations provide insights into the difficult dilemmas that governors typically encounter? We address this question by reviewing the content of 262 evaluation studies of European climate policies in the light of six kinds of dilemma found in the governance literature. We are interested in what these studies say about the performance of European climate policies and in their capacity to inform evidence-based policy-making. We find that the evaluations do arrive at common findings: that climate change is framed as a problem of market and/or state failure; that voluntary measures tend to be ineffective; that market-based instruments tend to be regressive; that EU-level policies have driven climate policies in the latecomer EU Member States; and that lack of monitoring and weak enforcement are major obstacles to effective policy implementation. However, we also conclude that the evidence base these studies represent is surprisingly weak for such a high profile area. There is too little systematic climate policy evaluation work in the EU to support systematic evidence-based policy making. This reduces the scope for sound policy making in the short run and is a constraint to policy learning in the longer term.     

What do near-term observations tell us about long-term developments in greenhouse gas emissions?

Long-term scenarios developed by integrated assessment models are used in climate research to provide an indication of plausible long-term emissions of greenhouse gases and other radiatively active substances based on developments in the global energy system, land-use and the emissions associated with these systems. The phenomena that determine these long-term developments (several decades or even centuries) are very different than those that operate on a shorter time-scales (a few years). Nevertheless, in the literature, we still often find direct comparisons between short-term observations and long-term developments that do not take into account the differing dynamics over these time scales. In this letter, we discuss some of the differences between the factors that operate in the short term and those that operate in the long term. We use long-term historical emissions trends to show that short-term observations are very poor indicators of long-term future emissions developments. Based on this, we conclude that the performance of long-term scenarios should be evaluated against the appropriate, corresponding long-term variables and trends. The research community may facilitate this by developing appropriate data sets and protocols that can be used to test the performance of long-term scenarios and the models that produce them.     

Discussion: Oil seepage or fossil podzol? An Early Oligocene oil seepage at the southern rim of the North Sea Basin,near Leuven (Belgium). Reply by the Authors

Geologie en Mijnbouw -     

Bitching about a billboard: Advertising, gender and canine (re)presentations

There is an increasing presence of animal representations in advertising and these are frequently visible in the urban landscape via billboards. We contend that billboards constitute a banal, yet influential, component of the built environment in which subtle, yet powerful, interplays of gender and local culture can literally take place. We consider a controversial billboard campaign that displayed the image of a cross-dressed dog in Auckland in 1999. An analysis of the image and objections lodged against it allows us to conclude that in conveying a public service message, this campaign mounted by the Royal Society for the Prevention of Cruelty to Animals, unintentionally performed another service: engaging the public in (re)interpreting the gendered nature of animal representation     

Biogeography and climatic change as a context to human dispersal out of Africa and within Eurasia

The dispersal of the genus Homo occurred against a background of continuous environmental change. Here, dispersals of large mammals through the Levantine Corridor and into Western Europe and Java are studied and compared to existing records of climatic change and dispersals of early humans and lithic industry.The first human dispersal (with Oldowan lithic industry) out of Africa, around or shortly before 1.8 Ma may have been triggered by biological evolution and increased social organisation, rather than environmental change. After that event, increasing aridity led to decreased faunal exchange between Africa and Eurasia and may have isolated the human populations of Africa and Africa. Southern (Java) and Eastern Asia (China) also seem to have been isolated. Human dispersal into Western Europe may have been limited by closed environments in Central Europe until about 1.2 Ma ago, when faunal dispersal into Europe suggests the cyclic spread of open environments to the west. Acheulean technology originated in Africa, some 1.6–1.5 Ma ago, but its dispersal into Eurasia may have been obstructed by an arid Southwest Asia, until broadly about 0.9 Ma ago, when faunal exchange suggests that the area became temporarily less dry. By 0.6–0.5 Ma ago it reached Europe.