‘Box‐Profile’ Ion Implants as Geochemical Reference Materials for Electron Probe Microanalysis and Secondary Ion Mass Spectrometry

Although electron probe microanalysis and secondary ion mass spectrometry are widely used analytical techniques for geochemical and mineralogical applications, metrologically rigorous quantification remains a major challenge for these methods. Secondary ion mass spectrometry (SIMS) in particular is a matrix‐sensitive method, and the use of matrix‐matched reference materials (RMs) is essential to avoid significant analytical bias. A major problem is that the number of available RMs for SIMS is extremely small compared with the needs of analysts. One approach for the production of matrix‐specific RMs is the use of high‐energy ion implantation that introduces a known amount of a selected isotope into a material. We chose the more elaborate way of implanting a so‐called ‘box‐profile’ to generate a quasi‐homogeneous concentration of the implanted isotope in three dimensions, which allows RMs not only to be used for ion beam analysis but also makes them suitable for EPMA. For proof of concept, we used the thoroughly studied mineralogically and chemically ‘simple’ SiO₂ system. We implanted either ⁴⁷Ti or ⁴⁸Ti into synthetic, ultra‐high‐purity silica glass. Several ‘box‐profiles’ with mass fractions between 10 and 1000 μg g^?1 Ti and maximum depths of homogeneous Ti distribution between 200 nm and 3 μm were produced at the Institute of Ion Beam Physics and Materials Research of Helmholtz‐Zentrum Dresden‐Rossendorf. Multiple implantation steps using varying ion energies and ion doses were simulated with Stopping and Range of Ions in Matter (SRIM) software, optimising for the target concentrations, implantation depths and technical limits of the implanter. We characterised several implant test samples having different concentrations and maximum implantation depths by means of SIMS and other analytical techniques. The results show that the implant samples are suitable for use as reference materials for SIMS measurements. The multi‐energy ion implantation technique also appears to be a promising procedure for the production of EPMA‐suitable reference materials.     

Submarine hydrothermal activity and gold-rich mineralization at Brothers Volcano, Kermadec Arc, New Zealand

Brothers volcano, of the Kermadec intraoceanic arc, is host to a hydrothermal system unique among seafloor hydrothermal systems known anywhere in the world. It has two distinct vent fields, known as the NW Caldera and Cone sites, whose geology, permeability, vent fluid compositions, mineralogy, and ore-forming conditions are in stark contrast to each other. The NW Caldera site strikes for ??600?m in a SW?CNE direction with chimneys occurring over a ??145-m depth interval, between ??1,690 and 1,545?m. At least 100 dead and active sulfide chimney spires occur in this field and are typically 2?C3?m in height, with some reaching 6?C7?m. Their ages (at time of sampling) fall broadly into three groups: <4, 23, and 35?years old. The chimneys typically occur near the base of individual fault-controlled benches on the caldera wall, striking in lines orthogonal to the slopes. Rarer are massive sulfide crusts 2?C3?m thick. Two main types of chimney predominate: Cu-rich (up to 28.5?wt.% Cu) and, more commonly, Zn-rich (up to 43.8?wt.% Zn). Geochemical results show that Mo, Bi, Co, Se, Sn, and Au (up to 91?ppm) are correlated with the Cu mineralization, whereas Cd, Hg, Sb, Ag, and As are associated with the dominant Zn-rich mineralization. The Cone site comprises the Upper Cone site atop the summit of the recent (main) dacite cone and the Lower Cone site that straddles the summit of an older, smaller, more degraded dacite cone on the NE flank of the main cone. Huge volumes of diffuse venting are seen at the Lower Cone site, in contrast to venting at both the Upper Cone and NW Caldera sites. Individual vents are marked by low-relief (??0.5?m) mounds comprising predominately native sulfur with bacterial mats. Vent fluids of the NW Caldera field are focused, hot (??300°C), acidic (pH????2.8), metal-rich, and gas-poor. Calculated end-member fluids from NW Caldera vents indicate that phase separation has occurred, with Cl values ranging from 93% to 137% of seawater values. By contrast, vent fluids at the Cone site are diffuse, noticeably cooler (??122°C), more acidic (pH?1.9), metal-poor, and gas-rich. Higher-than-seawater values of SO₄ and Mg in the Cone vent fluids show that these ions are being added to the hydrothermal fluid and are not being depleted via normal water/rock interactions. Iron oxide crusts 3?years in age cover the main cone summit and appear to have formed from Fe-rich brines. Evidence for magmatic contributions to the hydrothermal system at Brothers includes: high concentrations of dissolved CO₂ (e.g., 206?mM/kg at the Cone site); high CO₂/³He; negative ??D and ??¹⁸O_H2O for vent fluids; negative ??³⁴S for sulfides (to ?4.6??), sulfur (to ?10.2??), and ??¹⁵N₂ (to ?3.5??); vent fluid pH values to 1.9; and mineral assemblages common to high-sulfidation systems. Changing physicochemical conditions at the Brothers hydrothermal system, and especially the Cone site, occur over periods of months to hundreds of years, as shown by interlayered Cu?+?Au- and Zn-rich zones in chimneys, variable fluid and isotopic compositions, similar shifts in ³He/⁴He values for both Cone and NW Caldera sites, and overprinting of ??magmatic?? mineral assemblages by water/rock-dominated assemblages. Metals, especially Cu and possibly Au, may be entering the hydrothermal system via the dissolution of metal-rich glasses. They are then transported rapidly up into the system via magmatic volatiles utilizing vertical (??2.5?km long), narrow (??300-m diameter) ??pipes,?? consistent with evidence of vent fluids forming at relatively shallow depths. The NW Caldera and Cone sites are considered to represent stages along a continuum between water/rock- and magmatic/hydrothermal-dominated end-members.     

Tracing nitrogen in volcanic and geothermal volatiles from the Nicaraguan volcanic front

We report new chemical and isotopic data from 26 volcanic and geothermal gases, vapor condensates, and thermal water samples, collected along the Nicaraguan volcanic front. The samples were analyzed for chemical abundances and stable isotope compositions, with a focus on nitrogen abundances and isotope ratios. These data are used to evaluate samples for volatile contributions from magma, air, air-saturated water, and the crust. Samples devoid of crustal contamination (based upon He isotope composition) but slightly contaminated by air or air-saturated water are corrected using N₂/Ar ratios in order to obtain primary magmatic values, composed of contributions from upper mantle and subducted hemipelagic sediment on the down-going plate. Using a mantle endmember with δ¹⁵N = −5‰ and N₂/He = 100 and a subducted sediment component with δ¹⁵N = +7‰ and N₂/He = 10,500, the average sediment contribution to Nicaraguan volcanic and geothermal gases was determined to be 71%. Most of the gases were dominated by sediment-derived nitrogen, but gas from Volcán Mombacho, the southernmost sampling location, had a mantle signature (46% from subducted sediment, or 54% from the mantle) and an affinity with mantle-dominated gases discharging from Costa Rica localities to the south. High CO₂/N_{2 exc.} ratios (N_{2 exc.} is the N₂ abundance corrected for contributions from air) in the south are similar to those in Costa Rica, and reflect the predominant mantle wedge input, whereas low ratios in the north indicate contribution by altered oceanic crust and/or preferential release of nitrogen over carbon from the subducting slab. Sediment-derived nitrogen fluxes at the Nicaraguan volcanic front, estimated by three methods, are 7.8 × 10⁸ mol N/a from ³He flux, 6.9 × 10⁸ mol/a from SO₂ flux, and 2.1 × 10⁸ and 1.3 × 10⁹ mol/a from CO₂ fluxes calculated from ³He and SO₂, respectively. These flux results are higher than previous estimates for Central America, reflecting the high sediment-derived volatile contribution and the high nitrogen content of geothermal and volcanic gases in Nicaragua. The fluxes are also similar to but higher than estimated hemipelagic nitrogen inputs at the trench, suggesting addition of N from altered oceanic basement is needed to satisfy these flux estimates. The similarity of the calculated input of N via the trench to our calculated outputs suggests that little or none of the subducted nitrogen is being recycled into the deeper mantle, and that it is, instead, returned to the surface via arc volcanism.     

Geochronology of eruptions and parental magma sources of Elbrus volcano,the Greater Caucasus: K-Ar and Sr-Nd-Pb isotope data

Complex geochronological and isotope-geochemical studies showed that the Late Quaternary Elbrus volcano (Greater Caucasus) experienced long (approximately 200 ka) discrete evolution, with protracted periods of igneous quiescence (approximately 50 ka) between large-scale eruptions. The volcanic activity of Elbrus is subdivided into three phases: MiddleNeopleistocene (225–170 ka), Late Neopleistocene (110–70 ka), and Late Neopleistocene-Holocene (less than 35 ka). Petrogeochemical and isotope (Sr-Nd-Pb) signatures of Elbrus lavas point to their mantle-crustal origin. It was shown that hybrid parental magmas of the volcano were formed due to mixing and/or contamination of deep-seated mantle melts by Paleozoic upper crustal material of the Greater Caucasus. Mantle reservoir that participated in the genesis of Elbrus lavas as well as most other Neogene-Quaternary magmatic rocks of Caucasus was represented by the lower mantle “Caucasus” source. Primary melts generated by this source in composition corresponded to K-Na subalkali basalts with the following isotopic characteristics: ⁸⁷Sr/⁸⁶Sr = 0.7041 ± 0.0001, ƒ_Nd = +4.1 ± 0.2, ¹⁴⁷Sm/¹⁴⁴Nd = 0.105–0.114, ²⁰⁶Pb/²⁰⁴Pb = 18.72, ²⁰⁷Pb/²⁰⁴Pb = 15.62, and ²⁰⁸Pb/²⁰⁴Pb = 38.78. The temporal evolution of isotope characteristics for lavas of Elbrus volcano is well described by a Sr-Nd mixing hyperbole between “Caucasus” source and estimated average composition of the Paleozoic upper crust of the Greater Caucasus. It was shown that, with time, the proportions of mantle material in the parental magmas of Elbrus gently increased: from ∼60% at the Middle-Neopleistocene phase of activity to ∼80% at the Late Neopleistocene-Holocene phase, which indicates an increase of the activity of deep-seated source at decreasing input of crustal melts or contamination with time. Unraveled evolution of the volcano with discrete eruption events, lacking signs of cessation of the Late Neopleistocene-Holocene phase, increasing contribution of deep-seated mantle source in the genesis of Elbrus lavas with time as deduced from isotope-geochemical data, as well as numerous geophysical and geological evidence indicate that Elbrus is a potentially active volcano and its eruptions may be resumed. Possible scenarios were proposed for evolution of the volcano, if its eruptive activity were to continue.     

High‐resolution stratigraphic architecture and lithological heterogeneity within marginal aeolian reservoir analogues

Marginal aeolian successions contain different lithological units with variable geometries, dimensions and spatial distributions. Such variations may result in considerable heterogeneity within hydrocarbon reservoirs developed in successions of this type, which poses a high risk to their efficient development. Here, such heterogeneity is described and characterized at inter‐well (<1 km) scales using two well‐exposed outcrop analogues of ‘end member’ marginal aeolian deposits from the Permian Cedar Mesa Sandstone and Jurassic Page Sandstone of south‐central Utah, USA. The sedimentology and stratigraphic architecture of the Cedar Mesa Sandstone was studied in a 1·2 km² area in the Indian Creek region of southern Utah, where the interval consists of interbedded fluvial and aeolian deposits representative of a fluvial‐dominated erg margin. The Page Sandstone was studied in a 4·3 km² area near Escalante, close to the Utah‐Arizona border, where it consists of interbedded sabkha and aeolian deposits representative of a transitional‐marine erg margin. The three‐dimensional stratigraphic architectures of both reservoir analogues have been characterized, in order to establish the dimensions, geometries and connectivity of high‐permeability aeolian sandstones. Facies architecture of the aeolian‐sabkha deposits is characterized by laterally continuous aeolian sandstone layers of relatively uniform thickness that alternate with layers of heterolithic sabkha deposits. Aeolian sandstones are thus likely to form vertically unconnected but laterally widespread flow units in analogous reservoirs. Facies architecture in the aeolian‐fluvial deposits is more complex, because it contains alternating intervals of aeolian sandstone and fluvial heterolithic strata, both of which may be laterally discontinuous at the studied length‐scales. Aeolian sandstones encased by fluvial heterolithic strata may form small, isolated flow units in analogous reservoirs, although the limited continuity of fluvial heterolithic strata results in vertical connectivity between successive aeolian sandstones in other locations. These architectural templates may be used to condition zonation schemes in models of marginal aeolian reservoirs.     

Rapid quantification of humic and fulvic acids by HPLC in natural waters

A simple method based on high-performance size-exclusion chromatography (HPSEC) has been developed for rapid quantification of humic and fulvic acids (HA and FA) in stream waters. A Tsk-gel column was used to separate natural dissolved organic matter (DOM) into two components: peak A and B. In terms of HPSEC chromatograms and fluorescence patterns, peak A and B were similar to the corresponding XAD-extracted HA and FA, respectively. It is suggested that peak A fraction mainly consisted of HA, and peak B fraction FA. The similar separation of HA and FA using HPSEC and a conventional XAD method suggests the consistency of molecular size distribution and physical–chemical properties of DOM. HPSEC offers a simple and rapid method for the quantification of HA and FA instead of tedious extractions of humic substances. Analyses of natural water samples show that the calculation of HA/FA based on UV absorbance was under- or over-estimated, the calibration using the extracted HS allows a more accurate quantification. The fast screening of HA and FA provides useful quantitative and qualitative information that can be used in environmental or monitoring studies.     

Precipitation,temperature and wind in Norway: dynamical downscaling of ERA40

A novel downscaling approach of the ERA40 (ECMWF 40-years reanalysis) data set has been taken and results for comparison with observations in Norway are shown. The method applies a nudging technique in a stretched global model, focused in the Norwegian Sea (67°N, 5°W). The effective resolution is three times the one of the ERA40, equivalent to about 30 km grid spacing in the area of focus. Longer waves (<T42) in the downscaled solution are nudged towards the ERA40 solution, and thus the large-scale circulation is similar in the two data sets. The shorter waves are free to evolve, and produce high intensities of winds and precipitation. The comparison to observations incorporate numerous station data points of (1) precipitation (#357), (2) temperature (#98) and (3) wind (#10), and for the period 1961–1990, the downscaled data set shows large improvements over ERA40. The daily precipitation shows considerable reduction in bias (from 50 to 11%), and twofold reduction at the 99.9 percentile (from −59 to −29%). The daily temperature showed a bias reduction of about a degree in most areas, and relative large RMSE reduction (from 7.5 to 5.0°C except winter). The wind comparison showed a slight improvement in bias, and significant improvements in RMSE.     

Impact of increased vertical resolution on simulation of tropical climate

Summary The aim of this study is to describe the behaviour of tropical dynamics in the ECHAM4 model when increased vertical resolution around the tropopause and in the planetary boundary layer is used. In this work we perform experiments with the ECHAM4 model using T30 horizontal resolution and 19 and 42 vertical levels. The impact of the increased vertical resolution on the simulation of tropical clouds and precipitation has been investigated. Therefore, the dynamic fields related to tropical convection have been analyzed. The results suggest a beneficial effect of the increased number of vertical levels on the convective scheme performance and on the related dynamic fields over the Tropics. The improvement of the rainfall climatologies in the 42-level model has been explained via the impact of vertical resolution on the cloud structure. In the cloud spectrum of the L42 simulation, a third peak appears around 600 hPa, revealing that when using higher vertical resolution the convective parametrization starts to represent cumulus congestus clouds.     

Spatio‐temporal distribution of near‐surface and root zone soil moisture at the catchment scale

Soil moisture is highly variable both spatially and temporally. It is widely recognized that improving the knowledge and understanding of soil moisture and the processes underpinning its spatial and temporal distribution is critical. This paper addresses the relationship between near‐surface and root zone soil moisture, the way in which they vary spatially and temporally, and the effect of sampling design for determining catchment scale soil moisture dynamics. In this study, catchment scale near‐surface (0–50 mm) and root zone (0–300 mm) soil moisture were monitored over a four‐week period. Measurements of near‐surface soil moisture were recorded at various resolutions, and near‐surface and root zone soil moisture data were also monitored continuously within a network of recording sensors. Catchment average near‐surface soil moisture derived from detailed spatial measurements and continuous observations at fixed points were found to be significantly correlated (r² = 0·96; P = 0·0063; n = 4). Root zone soil moisture was also found to be highly correlated with catchment average near‐surface, continuously monitored (r² = 0·81; P < 0·0001; n = 26) and with detailed spatial measurements of near‐surface soil moisture (r² = 0·84). The weaker relationship observed between near‐surface and root zone soil moisture is considered to be caused by the different responses to rainfall and the different factors controlling soil moisture for the soil depths of 0–50 mm and 0–300 mm. Aspect is considered to be the main factor influencing the spatial and temporal distribution of near‐surface soil moisture, while topography and soil type are considered important for root zone soil moisture. The ability of a limited number of monitoring stations to provide accurate estimates of catchment scale average soil moisture for both near‐surface and root zone is thus demonstrated, as opposed to high resolution spatial measurements. Similarly, the use of near‐surface soil moisture measurements to obtain a reliable estimate of deeper soil moisture levels at the small catchment scale was demonstrated. Copyright © 2007 John Wiley & Sons, Ltd.     

Ground freezing monitoring techniques

Ground-freezing is used in mining and civil engineering to make water-bearing strata temporarily impermeable and to increase their compressive and shear strength by transforming joint water and interstitial water into ice. Freezing of rock or soil layers is achieved by means of an array of cased boreholes, through which a cold liquid is circulated in order to remove heat energy, comparable to cooling coils.

Frost expansion from the boreholes into the ground is monitored, for a better and more economic control of the freezing process. For this purpose, instruments for the determination of borehole deviation, for measurement of the temperature field and for an assessment of the degree of freezing with ultrasonic waves, have proved useful. These three techniques are described based on results obtained from field measurements.