Evaluating the use of 3'-(p-Aminophenyl) fluorescein for determining the formation of highly reactive oxygen species in particle suspensions

Background  

Given the importance of highly reactive oxygen species (hROS) as reactants in a wide range of biological, photochemical, and environmental systems there is an interest in detection and quantification of these species. The extreme reactivity of the hROS, which includes hydroxyl radicals, presents an analytical challenge. 3'-(p-Aminophenyl) fluorescein (APF) is a relatively new probe used for measuring hROS. Here, we further evaluate the use of APF as a method for the detection of hydroxyl radicals in particle suspensions.     

3-D assessment of peak-metamorphic conditions by Raman spectroscopy of carbonaceous material: an example from the margin of the Lepontine dome (Swiss Central Alps)

This study monitors regional changes in the crystallinity of carbonaceous matter (CM) by applying Micro-Raman spectroscopy to a total of 214 metasediment samples (largely so-called Bündnerschiefer) dominantly metamorphosed under blueschist- to amphibolite-facies conditions. They were collected within the northeastern margin of the Lepontine dome and easterly adjacent areas of the Swiss Central Alps. Three-dimensional mapping of isotemperature contours in map and profile views shows that the isotemperature contours associated with the Miocene Barrow-type Lepontine metamorphic event cut across refolded nappe contacts, both along and across strike within the northeastern margin of the Lepontine dome and adjacent areas. Further to the northeast, the isotemperature contours reflect temperatures reached during the Late Eocene subduction-related blueschist-facies event and/or during subsequent near-isothermal decompression; these contours appear folded by younger, large-scale post-nappe-stacking folds. A substantial jump in the recorded maximum temperatures across the tectonic contact between the frontal Adula nappe complex and surrounding metasediments indicates that this contact accommodated differential tectonic movement of the Adula nappe with respect to the enveloping Bündnerschiefer after maximum temperatures were reached within the northern Adula nappe, i.e. after Late Eocene time.     

An Alternative Protocol for Single Zircon Dissolution with Application to (U‐Th‐Sm)/He Thermochronometry

Zircon (U‐Th‐Sm)/He (ZHe) thermochronometry is a powerful tool that has been widely used in geology to constrain the exhumation histories of orogens. In this study, we present an alternative protocol for dissolving zircon grains for determination of parent nuclides. This new alkali fusion procedure developed at the SARM (Service d'Analyse des Roches et des Minéraux) in Nancy, France, is fast (requiring only 2 d, including cleaning steps) and offers several advantages over conventional methods by avoiding: (i) use of HF pressure dissolution and (ii) complete removing of grains from the metal microvials. After dissolution, U, Th and Sm were measured using an ICP‐MS. We tested the new procedure on two different ZHe reference materials, the Fish Canyon Tuff and Buluk Tuff; these provided precision values for ZHe‐age estimations of 9 and 6% (1s), respectively. In addition, using this method, zircons from the Buluk Tuff are shown to be chemically more homogenous and more suitable for assessing the uncertainty of the entire integrated procedure.     

Element budgets of pine stands on lignite and pyrite containing mine soils

To analyze the development of pine ecosystems on lignite and pyrite containing mine soils, four pine stands with ages of 3–35 years were investigated in a chronosequence approach. Bulk precipitation, throughfall and soil solution in depths of 20, 40, 70 and 100 cm were studied over a three-year period to determine element fluxes in these forest ecosystems on extreme acidic and saline soils.Element budgets are controlled by the processes induced by pyrite oxidation such as intensive weathering of primary minerals, precipitation and leaching of secondary phases.Despite low water fluxes, element outputs can reach extraordinary high values due to very high concentrations in the soil solution. Although element outputs decrease drastically with stand age, respectively, site age, they exceed those of comparable pine stands on non-mine sites. Nitrogen release from the lignite fraction represents a special characteristic of the examined substrates. Nitrogen losses beneath the rooted zone can be 34 kg N ha⁻¹ yr⁻¹ in 100 cm depth. Element input and output in the examined ecosystems are far from balance. Closed cycling of nutrients seems to be recognizable in the case of potassium.     

Hydrostatic-system palsas at Toolik lake,Alaska: Field observations and simulation

Stratigraphic and chemical data from the ice core of an ‘anthropogenic palsa’ at Toolik Lake, Alaska, indicate that the mound formed as a consequence of hydrostatic pressure developed in an isolated hydrologic system within the active layer. Survey data for five palsas over a three-year period suggest that growth was essentially complete at the time of the initial survey; a net decrease of summit elevation is apparent in all five mounds, but complete degradation of the palsas would require several decades at observed rates. Because accurate field measurements of thermal and hydrologic evolution in such features are extremely difficult, simulation of the environmental conditions and events involved in palsa growth is an important supplement to field observation. Both analytic and finite-element models yield results that are in substantial agreement with inferences drawn from observational data.     

A statistical model of the geomagnetic field

Summary A statistical model of the geomagnetic field is derived, based on the assumption of an axial geocentric dipole field of strengthH _e at the equator perturbed by randomly directed components of constant magnitudeh. The model fits the dispersions found from an analysis of the 1945 field, and the ratioh/H _e obtained for this field and from the palaeomagnetic data both average to about 0.4. The model predicts that during reversal of the dipole field, the field intensity falls to between 0.2 and 0.4 of the steady field intensity, and this agrees with estimates made from the palaeomagnetic observations.     

Superdense CO2 inclusions in Cretaceous quartz–stibnite veins hosted in low-grade Variscan basement of the Western Carpathians, Slovakia

CO₂ inclusions with density up to 1,197 kg m⁻³ occur in quartz–stibnite veins hosted in the low-grade Palaeozoic basement of the Gemericum tectonic unit in the Western Carpathians. Raman microanalysis corroborated CO₂ as dominant gas species accompanied by small amounts of nitrogen (<7.3 mol%) and methane (<2.5 mol%). The superdense CO₂ phase exsolved from an aqueous bulk fluid at temperatures of 183–237°C and pressures between 1.6 and 3.5 kbar, possibly up to 4.5 kbar. Low thermal gradients (∼12–13°C km⁻¹) and the CO₂–CH₄–N₂ fluid composition rule out a genetic link with the subjacent Permian granites and indicate an external, either metamorphogenic (oxidation of siderite, dedolomitization) or lower crustal/mantle, source of the ore-forming fluids.According to microprobe U–Pb–Th dating of monazite, the stibnite-bearing veins formed during early Cretaceous thrusting of the Gemeric basement over the adjacent Veporic unit. The 15- to 18-km depth of burial estimated from the fluid inclusion trapping PT parameters indicates a 8- to 11-km-thick Upper Palaeozoic–Jurassic accretionary complex overlying the Gemeric basement and its Permo-Triassic autochthonous cover.     

Evaluation of Methods for Determining Crack Initiation in Compression Tests on Low-Porosity Rocks

Laboratory testing of rocks is traditionally carried out to determine the peak strength using the ISRM Suggested Methods or other suitable standards. However, it is well known that in low-porosity crystalline rocks there are at least three distinct stages of compressive loading that can be readily identified if the stress–strain response is monitored during the loading process: (1) crack initiation, (2) unstable crack growth, i.e., crack coalescence and (3) peak strength. Crack initiation is noted as the first stage of stress-induced damage in low-porosity rocks, yet the suggested guidelines of the ISRM for compression tests make no mention of crack initiation. In addition, recent research suggests that crack initiation can be used as an estimate for the in situ spalling strength, commonly observed around underground excavations in massive to moderately jointed brittle rocks. Various methods have been proposed for identifying crack initiation in laboratory tests. These methods are evaluated using ten samples of ?sp? Diorite and the results are compared with a simplified method, lateral strain response. Statistically, all methods give acceptable crack-initiation values. It is proposed that the ISRM Suggested Methods be revised to include procedures suitable for establishing the crack-initiation stress.     

Melting of clinopyroxene + magnesite in iron-bearing planetary mantles and implications for the Earth and Mars

The assemblage clinopyroxene + magnesite was observed in Earth’s high-pressure metamorphic samples, and its stability in subducting slabs was confirmed by experiments. Recent studies also suggested that the fO₂ variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO₂ equilibria in the Martian mantle. Although there is no direct evidence for the stability of the cpx + mc assemblage in Mars mantle, its high-pressure–high-temperature decomposition to cpx + fo + CO₂ makes it a good analogue for the source of carbon metasomatism, in particular, to study nakhlites formation. Iron, which is present in the Earth’s and Martian mantles, may, however, influence the speciation of carbon. We performed experiments on a clinopyroxene + magnesite assemblage at 1.8 and 3.0 GPa and temperatures corresponding to the Earth’s and Martian mantles. The role of iron and of fO₂ was investigated by (1) replacing all or part of the magnesite by siderite FeCO₃, (2) adding Fe⁰ and (3) using graphite C capsules. A carbonate-silicate melt forms at both Earth and Mars conditions. Clinopyroxene and olivine are the main solid phases in the iron-free experiments. Fe²⁺ and Fe⁰ decrease their melting temperatures and increase the silicate fraction in the melt. The produced carbonate-silicate melts may be involved in the formation of some carbon-rich lavas on Earth (e.g., carbonatites, ultramafic lamprophyres, or kamafugites). Our results may also be used to interpret ophiolite samples or inclusions. In particular, we show that wüstite may form in equilibrium with carbonate-silicate melt in opx-(and silica-) poor regions of the mantle below 3 GPa. Our results also confirm the hypothesis of carbon metasomatism in the Martian nakhlites source. Immiscibility or reduction could explain the absence or rarity of C in Martian lavas.