A New LA‐ICP‐MS Method for Ti in Quartz: Implications and Application to High Pressure Rutile‐Quartz Veins from the Czech Erzgebirge

Experimental determination of the pressure and temperature controls on Ti solubility in quartz provides a calibration of the Ti‐in‐quartz (TitaniQ) geothermometer applicable to geological conditions up to ~ 20 kbar. We present a new method for determining ⁴⁸Ti mass fractions in quartz by LA‐ICP‐MS at the 1 μg g^?1 level, relevant to quartz in HP‐LT terranes. We suggest that natural quartz such as the low‐CL rims of the Bishop Tuff quartz (determined by EPMA; 41 ± 2 μg g^?1 Ti, 2s) is more suitable than NIST reference glasses as a reference material for low Ti mass fractions because matrix effects are limited, Ca isobaric interferences are avoided, and polyatomic interferences at mass 48 are insignificant, thus allowing for the use of ⁴⁸Ti as a normalising mass. Average titanium mass fraction from thirty‐three analyses of low temperature quartz from the Czech Erzgebirge is 0.9 ± 0.2 μg g^?1 (2s) using ⁴⁸Ti as a normalising mass and Bishop Tuff quartz rims as a reference material. The 2s average analytical uncertainty for individual analyses of ⁴⁸Ti is 8% for 50 μm spots and 7% for 100 μm spots, which offers much greater accuracy than the 21–41% uncertainty (2s) incurred from using ⁴⁹Ti as an analyte.     

The Budget of Turbulent Kinetic Energy in the Urban Roughness Sublayer

Full-scale observations from two urban sites in Basel, Switzerland were analysed to identify the magnitude of different processes that create, relocate, and dissipate turbulent kinetic energy (TKE) in the urban atmosphere. Two towers equipped with a profile of six ultrasonic anemometers each sampled the flow in the urban roughness sublayer, i.e. from street canyon base up to roughly 2.5 times the mean building height. This observational study suggests a conceptual division of the urban roughness sublayer into three layers: (1) the layer above the highest roofs, where local buoyancy production and local shear production of TKE are counterbalanced by local viscous dissipation rate and scaled turbulence statistics are close to to surface-layer values; (2) the layer around mean building height with a distinct inflexional mean wind profile, a strong shear and wake production of TKE, a more efficient turbulent exchange of momentum, and a notable export of TKE by transport processes; (3) the lower street canyon with imported TKE by transport processes and negligible local production. Averaged integral velocity variances vary significantly with height in the urban roughness sublayer and reflect the driving processes that create or relocate TKE at a particular height. The observed profiles of the terms of the TKE budget and the velocity variances show many similarities to observations within and above vegetation canopies.     

Improved regional scale processes reflected in projected hydrological changes over large European catchments

For the fourth assessment report of the Intergovernmental Panel on Climate Change (IPCC), the recent version of the coupled atmosphere/ocean general circulation model (GCM) of the Max Planck Institute for Meteorology has been used to conduct an ensemble of transient climate simulations These simulations comprise three control simulations for the past century covering the period 1860–2000, and nine simulations for the future climate (2001–2100) using greenhouse gas (GHG) and aerosol concentrations according to the three IPCC scenarios B1, A1B and A2. For each scenario three simulations were performed. The global simulations were dynamically downscaled over Europe using the regional climate model (RCM) REMO at 0.44° horizontal resolution (about 50 km), whereas the physics packages of the GCM and RCM largely agree. The regional simulations comprise the three control simulations (1950–2000), the three A1B simulations and one simulation for B1 as well as for A2 (2001–2100). In our study we concentrate on the climate change signals in the hydrological cycle and the 2 m temperature by comparing the mean projected climate at the end of the twenty-first century (2071–2100) to a control period representing current climate (1961–1990). The robustness of the climate change signal projected by the GCM and RCM is analysed focussing on the large European catchments of Baltic Sea (land only), Danube and Rhine. In this respect, a robust climate change signal designates a projected change that sticks out of the noise of natural climate variability. Catchments and seasons are identified where the climate change signal in the components of the hydrological cycle is robust, and where this signal has a larger uncertainty. Notable differences in the robustness of the climate change signals between the GCM and RCM simulations are related to a stronger warming projected by the GCM in the winter over the Baltic Sea catchment and in the summer over the Danube and Rhine catchments. Our results indicate that the main explanation for these differences is that the finer resolution of the RCM leads to a better representation of local scale processes at the surface that feed back to the atmosphere, i.e. an improved representation of the land sea contrast and related moisture transport processes over the Baltic Sea catchment, and an improved representation of soil moisture feedbacks to the atmosphere over the Danube and Rhine catchments.     

Parameterization of snow-free land surface albedo as a function of vegetation phenology based on MODIS data and applied in climate modelling

The aim of this study was to develop an advanced parameterization of the snow-free land surface albedo for climate modelling describing the temporal variation of surface albedo as a function of vegetation phenology on a monthly time scale. To estimate the effect of vegetation phenology on snow-free land surface albedo, remotely sensed data products from the Moderate-Resolution Imaging Spectroradiometer (MODIS) on board the NASA Terra platform measured during 2001 to 2004 are used. The snow-free surface albedo variability is determined by the optical contrast between the vegetation canopy and the underlying soil surface. The MODIS products of the white-sky albedo for total shortwave broad bands and the fraction of absorbed photosynthetically active radiation (FPAR) are analysed to separate the vegetation canopy albedo from the underlying soil albedo. Global maps of pure soil albedo and pure vegetation albedo are derived on a 0.5° regular latitude/longitude grid, re-sampling the high-resolution information from remote sensing-measured pixel level to the model grid scale and filling up gaps from the satellite data. These global maps show that in the northern and mid-latitudes soils are mostly darker than vegetation, whereas in the lower latitudes, especially in semi-deserts, soil albedo is mostly higher than vegetation albedo. The separated soil and vegetation albedo can be applied to compute the annual surface albedo cycle from monthly varying leaf area index. This parameterization is especially designed for the land surface scheme of the regional climate model REMO and the global climate model ECHAM5, but can easily be integrated into the land surface schemes of other regional and global climate models.     

A study of garnets from eclogite and peridotite xenoliths found in kimberlite

The chemical compositions of garnets from 58 eclogite, 72 peridotite and 4 pyroxenite xenoliths in kimberlites have been estimated from their unit cell edge length and refractive indices. The samples studied were obtained from 17 kimberlite occurrences and include all those of known source which remain in the famous Williams (1932) collection which is stored at the University of Cape Town. Every suitable sample available to the authors has been examined.A gap in the range of garnet volume percentages occurs in the samples studied between approximately 15 and 30%. Garnet peridotites characteristically have <15% garnet and eclogites >30% garnet. Very rare exceptions occur. Our collection contains no eclogites with olivine and only one with orthopyroxene. All but two of the peridotite-pyroxenite group contain orthopyroxene. The garnets from the peridotites and pyroxenites plot on a pyrope-almandine-uvarovite triangle in a narrow band with a remarkably constant almandine/uvarovite ratio. Garnets from the eclogites are plotted on a pyrope-almandine-grossularite triangle and have a wide spread of compositions. These fall into 4 groups viz. eclogite I, eclogite II, kyanite eclogite and corundum eclogite.The reasons for the differences in garnet chemistry are considered and a tentative evolutionary scheme suggested by partial melting of the garnet peridotite which is assumed to occur in the upper mantle. Recent models of upper mantle composition and the genesis of garnet-bearing xenoliths in kimberlite are briefly and critically examined.S.A. UMP Publication No. 9.     

A case for hornblende dominated fractionation of arc magmas: the Chelan Complex (Washington Cascades)

Amphibole fractionation in the deep roots of subduction-related magmatic arcs is a fundamental process for the generation of the continental crust. Field relations and geochemical data of exposed lower crustal igneous rocks can be used to better constrain these processes. The Chelan Complex in the western U.S. forms the lowest level of a 40-km thick exposed crustal section of the North Cascades and is composed of olivine websterite, pyroxenite, hornblendite, and dominantly by hornblende gabbro and tonalite. Magmatic breccias, comb layers and intrusive contacts suggest that the Chelan Complex was build by igneous processes. Phase equilibria, textural observations and mineral chemistry yield emplacement pressures of ∼1.0 GPa followed by isobaric cooling to 700°C. The widespread occurrence of idiomorphic hornblende and interstitial plagioclase together with the lack of Eu anomalies in bulk rock compositions indicate that the differentiation is largely dominated by amphibole. Major and trace element modeling constrained by field observations and bulk chemistry demonstrate that peraluminous tonalite could be derived by removing successively 3% of olivine websterite, 12% of pyroxene hornblendite, 33% of pyroxene hornblendite, 19% of gabbros, 15% of diorite and 2% tonalite. Peraluminous tonalite with high Sr/Y that are worldwide associated with active margin settings can be derived from a parental basaltic melt by crystal fractionation at high pressure provided that amphibole dominates the fractionation process. Crustal assimilation during fractionation is thus not required to generate peraluminous tonalite.     

The partitioning of seawater cations during the transformation of gypsum to anhydrite

The coprecipitation of Sr, Mg, Na and K with anhydrite during the dehydration of gypsum was studied in laboratory experiments. The partition coefficients of Mg and Sr between anhydrite and solution decrease with increasing temperature. The partition coefficients of the alkali-ions do not depend upon temperature, but are affected by the brine composition.The mechanism of the phase transformation gypsum → anhydrite occurs via dissolution and precipitation, when the coprecipitated-ions are repartitioned between the new phase and the solution. The partition coefficients established in this study are applicable also for primary anhydrite.During the dehydration of gypsum at elevated temperatures metastable bassanite may form as an intermediate stage. The amount of cations coprecipitated with bassanite is much larger than the amount coprecipitated with anhydrite or gypsum. This phenomenon may have an influence on the partitioning of cations during the dehydration of gypsum, particularly on Sr.The partition coefficients of seawater cations between anhydrite and the brine are similar to those between gypsum and the brine. For this reason the coprecipitated-ions are not expected to be good indicators to distinguish between primary and secondary calcium sulfate minerals.The temperature effect on the coprecipitation of Mg and Sr with anhydrite makes these ions possible indicators for the temperature at which the phase transformation occurred. This temperature corresponds to the depth of burial of the gypsum at the stage of dehydration.The coprecipitation of seawater cations with anhydrite in the natural environment was studied in two systems: A small Pleistocene evaporite lens from the Sinai Peninsula and the Triassic anhydrite of the Mohilla Formation, Israel. The coprecipitated-ion composition of these samples was used to derive the conditions under which the anhydrite was formed.     

Constraining input and output fluxes of the southern-central Chile subduction zone: water,chlorine and sulfur

In this paper, we constrain the input and output fluxes of H₂O, Cl and S into the southern-central Chilean subduction zone (31°S–46°S). We determine the input flux by calculating the amounts of water, chlorine and sulfur that are carried into the subduction zone in subducted sediments, igneous crust and hydrated lithospheric mantle. The applied models take into account that latitudinal variations in the subducting Nazca plate impact the crustal porosity and the degree of upper mantle serpentinization and thus water storage in the crust and mantle. In another step, we constrain the output fluxes of the subduction zone both to the subcontinental lithospheric mantle and to the atmosphere–geosphere–ocean by the combined use of gas flux determinations at the volcanic arc, volume calculations of volcanic rocks and the combination of mineralogical and geothermal models of the subduction zone. The calculations indicate that about 68 Tg/m/Ma of water enters the subduction zone, as averaged over its total length of 1,480 km. The volcanic output on the other hand accounts for 2 Tg/m/Ma or 3 % of that input. We presume that a large fraction of the volatiles that are captured within the subducting sediments (which accounts for roughly one-third of the input) are cycled back into the ocean through the forearc. This assumption is however questioned by the present lack of evidence for major venting systems of the submarine forearc. The largest part of the water that is carried into the subduction zone in the crust and hydrated mantle (accounting for two-thirds of the input) appears to be transported beyond the volcanic arc.     

Dissolution of cinnabar (HgS) in the presence of natural organic matter

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 × 10⁻¹³ to 7.16 × 10⁻¹² mol Hg (mg C)⁻¹ m⁻²s⁻¹. Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R² = 0.88), aromaticity (R² = 0.80), and molecular weight (R² = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface.     

New Reference Materials,Analytical Procedures and Data Reduction Strategies for Sr Isotope Measurements in Geological Materials by LA-MC-ICP-MS

Laser ablation multi-collector mass spectrometry (LA-MC-ICP-MS) has emerged as the technique of choice for in situ measurements of Sr isotopes in geological minerals. However, the method poses analytical challenges and there is no widely adopted standardised approach to collecting these data or correcting the numerous potential isobaric inferences. Here, we outline practical analytical procedures and data reduction strategies to help establish a consistent framework for collecting and correcting Sr isotope measurements in geological materials by LA-MC-ICP-MS. We characterise a new set of plagioclase reference materials, which are available for distribution to the community, and present a new data reduction scheme for the Iolite software package to correct isobaric interferences for different materials and analytical conditions. Our tests show that a combination of Kr-baseline subtraction, Rb-peak-stripping using βRb derived from a bracketing glass reference material, and a CaCa or CaAr correction for plagioclase and CaCa or CaAr + REE²⁺ correction for rock glasses, yields the most accurate and precise ⁸⁷Sr/⁸⁶Sr measurements for these materials. Using the analytical and correction procedures outlined herein, spot analyses using a beam diameter of 100 μm or rastering with a 50–65 μm diameter beam can readily achieve < 100 ppm 2SE repeatability ("internal") precision for ⁸⁷Sr/⁸⁶Sr measurements for materials with < 1000 μg g^-1 Sr.