Test of statistical means for the extrapolation of soil depth point information using overlays of spatial environmental data and bootstrapping techniques

Hydrological modelling depends highly on the accuracy and uncertainty of model input parameters such as soil properties. Since most of these data are field surveyed, geostatistical techniques such as kriging, classification and regression trees or more sophisticated soil‐landscape models need to be applied to interpolate point information to the area. Most of the existing interpolation techniques require a random or regular distribution of points within the study area but are not adequate to satisfactorily interpolate soil catena or transect data. The soil landscape model presented in this study is predicting soil information from transect or catena point data using a statistical mean (arithmetic, geometric and harmonic mean) to calculate the soil information based on class means of merged spatial explanatory variables. A data set of 226 soil depth measurements covering a range of 0–6·5 m was used to test the model. The point data were sampled along four transects in the Stubbetorp catchment, SE‐Sweden. We overlaid a geomorphology map (8 classes) with digital elevation model‐derived topographic index maps (2–9 classes) to estimate the range of error the model produces with changing sample size and input maps. The accuracy of the soil depth predictions was estimated with the root mean square error (RMSE) based on a testing and training data set. RMSE ranged generally between 0·73 and 0·83 m ± 0·013 m depending on the amount of classes the merged layers had, but were smallest for a map combination with a low number of classes predicted with the harmonic mean (RMSE = 0·46 m). The results show that the prediction accuracy of this method depends on the number of point values in the sample, the value range of the measured attribute and the initial correlations between point values and explanatory variables, but suggests that the model approach is in general scale invariant. Copyright © 2009 John Wiley & Sons, Ltd.     

Topotactic formation of ferrisicklerite from natural triphylite under hydrothermal conditions

The topotactic oxidation and delithiation reaction from triphylite, Li(Fe,Mn)PO₄, leading to ferrisicklerite, Li_<1(Fe³⁺,Mn²⁺)PO₄, was investigated under hydrothermal conditions. A cuboid cut from a triphylite single-crystal (Palermo Mine, New Hampshire, USA) with the composition Li_0.93(3)(Fe²⁺ _0.733(6),Fe³⁺ _0.015(1),Mn²⁺ _0.210(4),Mg_0.063(2))_1.021(8)P_1.00(2)O₄ in addition with ground bulk material were treated with KMnO₄ and 30 % H₂O₂(aq) as oxidizing agent in a 0.1 N hydrochloric acid solution in the temperature range between 60 and 200 °C. At 120 °C a rim of 0.1 mm thickness of ferrisicklerite had formed around the core of unreacted triphylite. The sharp reaction boundary was clearly visible, due to the reddish brown absorption colors of ferrisicklerite, compared to colorless triphylite. Using single-crystal X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS), electron probe micro-analysis (EPMA) and ⁵⁷Fe-Mössbauer spectroscopy the product ferrisicklerite was characterized and its composition determined as Li_0.30(7)(Fe²⁺ _0.049(1)Fe³⁺ _0.65(2)Mn²⁺ _0.218(5)Mg_0.062(2))_0.98(1)P_1.01(3)O₄, with unit cell parameters a?=?4.795(1), b?=?9.992(4), and c?=?5.886(2) Å. EPMA investigations across the reaction boundary showed no changes in the concentrations of Fe, Mn, Mg, and P. In contrast, SIMS measurements clearly proved the delithiated state of the ferrisicklerite product. Polarization microscopy revealed that the orientation of the ferrisicklerite rim was the same as that of the original triphylite single-crystal, confirming the strictly topotactic character of the reaction.     

Mixed-phase clouds cause climate model biases in Arctic wintertime temperature inversions

Temperature inversions are a common feature of the Arctic wintertime boundary layer. They have important impacts on both radiative and turbulent heat fluxes and partly determine local climate-change feedbacks. Understanding the spread in inversion strength modelled by current global climate models is therefore an important step in better understanding Arctic climate and its present and future changes. Here, we show how the formation of Arctic air masses leads to the emergence of a cloudy and a clear state of the Arctic winter boundary layer. In the cloudy state, cloud liquid water is present, little to no surface radiative cooling occurs and inversions are elevated and relatively weak, whereas surface radiative cooling leads to strong surface-based temperature inversions in the clear state. Comparing model output to observations, we find that most climate models lack a realistic representation of the cloudy state. An idealised single-column model experiment of the formation of Arctic air reveals that this bias is linked to inadequate mixed-phase cloud microphysics, whereas turbulent and conductive heat fluxes control the strength of inversions within the clear state.     

Time constraints for low-angle shear zones in the Central Rhodopes (Bulgaria) and their significance for the exhumation of high-pressure rocks

In the Central Rhodopes of southern Bulgaria, an eclogite-bearing rock sheet belonging to the Middle Allochthon (Starcevo Unit) is over- and underlain by eclogite-free, amphibolite-facies rock units along low-angle shear zones, the Borovica Shear Zone at the top and the Starcevo-Ardino Shear Zone at the base. The age of these shear zones is determined by U–Pb zircon dating of pre-, syn- and posttectonic magmatic rocks, mostly pegmatite veins, using LA–SF–ICP–MS. Zircons from pre- to syntectonic pegmatites within the Borovica Shear Zone yielded ages of ca. 45–43?Ma, indicating that the shear zone was active at that time, and zircons from a pretectonic pegmatite and a posttectonic granitoid body within the Starcevo-Ardino Shear Zone yielded ages of ca. 45 and ca. 36?Ma, respectively, giving a time frame for the activity of that shear zone which probably rather postdated the activity of the Borovica Shear Zone. By combining the ages with the kinematics of the shear zones and the metamorphic history of the rock units, the following scenario is sketched: Soon after the Starcevo Unit reached peak pressure (eclogite facies), it was exhumed to a mid-crustal level by top-to-the-north-west, extensional unroofing along the Borovica Shear Zone, in a kinematic framework of orogen-parallel extension. Beginning at ca. 40?Ma, the partly exhumed Starcevo Unit was underthrust from the south-west by continental crust of the foreland (Apulia), forming the Lower Allochthon of the Rhodopes, along the Starcevo-Ardino Shear Zone. These results underline the significance of orogen-parallel extension for the exhumation of high-pressure rocks. With respect to regional geology of the Hellenides and the Aegean, it is found that the tectonic architecture of the Rhodopes is essentially of Tertiary age. Cretaceous syn-metamorphic shear zones do exist but are largely restricted to higher levels of the nappe stack (Upper Allochthon). The Rhodopes do not represent an older essentially Mesozoic core of the Hellenides but are formed by the internal, higher-metamorphic portions of the same major nappe systems as occur in the Hellenides.     

Lithium isotopes as indicators of meteorite parent body alteration

Hydrothermal processing on planetesimals in the early solar system produced new mineral phases, including those generated by the transformation of anhydrous silicates into their hydrated counterparts. Carbonaceous chondrites represent tangible remnants of such alteration products. Lithium isotopes are known to be responsive to aqueous alteration, yet previously recognized variability within whole rock samples from the same meteorite appears to complicate the use of these isotopes as indicators of processing by water. We demonstrate a new way to use lithium isotopes that reflects aqueous alteration in carbonaceous chondrites. Temperature appears to exert a control on the production of acetic acid‐soluble phases, such as carbonates and poorly crystalline Fe‐oxyhydroxides. Temperature and degree of water‐rock interaction determines the amount of lithium isotope fractionation expressed as the difference between whole rock and acetic acid‐leachable fractions. Using these features, the type 1 chondrite Orgueil (δ⁷Li_{(whole rock)} = 4.3‰; Δ⁷Li_{(acetic‐whole)} = 1.2‰) can be distinguished from the type 2 chondrites Murchison (δ⁷Li_{(whole rock)} = 3.8; Δ⁷Li_{(acetic‐whole)} = 8.8‰) and carbonate‐poor Tagish Lake (δ⁷Li_{(whole rock)} = 4.3; Δ⁷Li_{(acetic‐whole)} = 9.4‰). This initial study suggests that lithium isotopes have the potential to reveal the role of liquid water in the early solar system.     

Structure and physical property relations of Mn ilvaite

Structural and compositional data as well as ⁵⁷Fe Mössbauer parameters were determined on a natural Mn-rich monoclinic ilvaite crystal (ideal composition CaFe ₂ ²⁺ Fe³⁺Si₂O₈(OH)) which was used for electrical conductivity and thermopower measurements (part 2 of this paper). A zonar structure was found by electron microprobe analysis with a strong decrease in Mn concentration from the rim to the centre of the crystal in a plane perpendicular to the [001] direction. X-ray powder diffraction analysis of the most Mn-rich composition was performed. Mn²⁺ cations populate preferentially M2 sites of the ilvaite unit cell (space group P21/a), to a lower extent they reside on M1 and a reduced part is on Ca sites. The monoclinic angle was determined to β=90.178(4)°. The structural results are compared to literature data for other natural Mn-rich as well as low-impurity ilvaites; this concerns in particular the lattice b parameter and the undecided issue of the varying β angle. In the literature, the order parameter σ, which describes the varying degree of ordering of Fe²⁺–Fe³⁺ pairs on M11 and M12 sites in chains running parallel to the [001] direction, and structural defects are thought to be related to β. The interrelationship between β and σ with respect to a possible twin domain structure is discussed. Various ⁵⁷Fe Mössbauer spectra were recorded between 151 K and 327 K. Mössbauer parameters and Fe²⁺/Fe³⁺ concentration ratios were determined from the fits to the spectra. Fitting of subspectra was accomplished with the idea to find assignments of Fe²⁺ and Fe³⁺ doublets in agreement with X-ray results. The fraction of Mn²⁺ substituting Fe²⁺ on M1 sites could be estimated.     

Biodegradation of forest floor organic matter bound to minerals via different binding mechanisms

Mineral-associated organic matter (OM) represents a large reservoir of organic carbon (OC) in natural environments. The factors controlling the extent of the mineral-mediated OC stabilization, however, are poorly understood. The protection of OM against biodegradation upon sorption to mineral phases is assumed to result from the formation of strong bonds that limit desorption. To test this, we studied the biodegradation of OM bound to goethite (α-FeOOH), pyrophyllite, and vermiculite via specific mechanisms as estimated from OC uptake in different background electrolytes and operationally defined as ‘ligand exchange’, ‘Ca²⁺ bridging’, and ‘van der Waals forces’. Organic matter extracted from an Oa forest floor horizon under Norway spruce (Picea abies (L.) Karst) was reacted with minerals at dissolved OC concentrations of ∼5-130 mg/L at pH 4. Goethite retained up to 30.1 mg OC/g predominantly by ‘ligand exchange’; pyrophyllite sorbed maximally 12.5 mg OC/g, largely via ‘van der Waals forces’ and ‘Ca²⁺ bridging’, while sorption of OM to vermiculite was 7.3 mg OC/g, mainly due to the formation of ‘Ca²⁺ bridges’. Aromatic OM components were selectively sorbed by all minerals (goethite ? phyllosilicates). The sorption of OM was strongly hysteretic with the desorption into 0.01 M NaCl being larger for OM held by ‘Ca²⁺ bridges’ and ‘van der Waals forces’ than by ‘ligand exchange’. Incubation experiments under aerobic conditions (initial pH 4; 90 days) revealed that OM mainly bound to minerals by ‘ligand exchange’ was more resistant against mineralization than OM held by non-columbic interactions (‘van der Waals forces’). Calcium bridges enhanced the stability of sorbed OM, especially for vermiculite, but less than the binding via ‘ligand exchange’. Combined evidence suggests that the extent and rate of mineralization of mineral-associated OM are governed by desorption. The intrinsic stability of sorbed OM as related to the presence of resistant, lignin-derived aromatic components appears less decisive for the sorptive stabilization of OM than the involved binding mechanisms. In a given environment, the type of minerals present and the solution chemistry determine the operating binding mechanisms, thereby the extent of OM sorption and desorption, and thus ultimately the bioavailability of mineral-associated OM.     

Early core formation in asteroids and late accretion of chondrite parent bodies: Evidence from Hf-W in CAIs, metal-rich chondrites, and iron meteorites

The ¹⁸²Hf-¹⁸²W isotopic systematics of Ca-Al-rich inclusions (CAIs), metal-rich chondrites, and iron meteorites were investigated to constrain the relative timing of accretion of their parent asteroids. A regression of the Hf-W data for two bulk CAIs, various fragments of a single CAI, and carbonaceous chondrites constrains the ¹⁸²Hf/¹⁸⁰Hf and ε_W at the time of CAI formation to (1.07 ± 0.10) × 10⁻⁴ and −3.47 ± 0.20, respectively. All magmatic iron meteorites examined here have initial ε_W values that are similar to or slightly lower than the initial value of CAIs. These low ε_W values may in part reflect ¹⁸²W-burnout caused by the prolonged cosmic ray exposure of iron meteorites, but this effect is estimated to be less than ∼0.3 ε units for an exposure age of 600 Ma. The W isotope data, after correction for cosmic ray induced effects, indicate that core formation in the parent asteroids of the magmatic iron meteorites occurred less than ∼1.5 Myr after formation of CAIs. The nonmagmatic IAB-IIICD irons and the metal-rich CB chondrites have more radiogenic W isotope compositions, indicating formation several Myr after the oldest metal cores had segregated in some asteroids.Chondrule formation ∼2-5 Myr after CAIs, as constrained by published Pb-Pb and Al-Mg ages, postdates core formation in planetesimals, and indicates that chondrites do not represent the precursor material from which asteroids accreted and then differentiated. Chondrites instead derive from asteroids that accreted late, either farther from the Sun than the parent bodies of magmatic iron meteorites or by reaccretion of debris produced during collisional disruption of older asteroids. Alternatively, chondrites may represent material from the outermost layers of differentiated asteroids. The early thermal and chemical evolution of asteroids appears to be controlled by the decay of ²⁶Al, which was sufficiently abundant (initial ²⁶Al/²⁷Al >1.4 × 10⁻⁵) to rapidly melt early-formed planetesimals but could not raise the temperatures in the late-formed chondrite parent asteroids high enough to cause differentiation. The preservation of the primitive appearance of chondrites thus at least partially reflects their late formation rather than their early and primitive origin.