Mineralogical impact on organic nitrogen across a long-term soil chronosequence (0.3-4100 kyr)

Large portions of organic N (ON) in soil exist tightly associated with minerals. Mineral effects on the type of interactions, chemical composition, and stability of ON, however, are poorly understood. We investigated mineral-associated ON along a Hawaiian soil chronosequence (0.3-4100 kyr) formed in basaltic tephra under comparable climatic, topographic, and vegetation conditions. Mineral-organic associations were separated according to density (ρ > 1.6 g/cm³), characterized by X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge fine structure (NEXAFS) and analyzed for amino acid enantiomers and amino sugars. The ¹⁴C activity of mineral-bound OC was estimated by accelerator mass spectrometry. The close OC-ON relationship (r = 0.96) and XPS results suggest that ON exists incorporated in bulk mineral-bound OM and likely becomes associated with minerals as part of sorbing OM. The youngest site (0.3 kyr), with soils mainly composed of primary minerals (olivine, pyroxene, feldspar) and with little ON, contained the largest proportion of hydrolyzable amino sugars and amino acids but with a small share of acidic amino acids (aspartic acid, glutamic acid). In soils of the intermediate weathering stage (20-400 kyr), where poorly crystalline minerals and metal(hydroxide)-organic precipitates prevail, more mineral-associated ON was present, containing a smaller proportion of hydrolyzable amino sugars and amino acids due to the preferential accumulation of other OM components such as lignin-derived phenols. Acidic amino acids were more abundant, reflecting the strong association of acidic organic components with metal(hydroxide)-organic precipitates and variable-charge minerals. In the final weathering stage (1400-4100 kyr) with well-crystalline secondary Fe and Al (hydr)oxides and kaolin minerals, mineral-organic associations held less ON and were, relative to lignin phenols, depleted in hydrolyzable amino sugars and amino acids, particularly in acidic amino acids. XPS and NEXAFS analyses showed that the majority (59-78%) of the mineral-associated ON is peptide N while 18-34% was aromatic N. Amino sugar ratios and d-alanine suggest that mineral-associated ON comprises a significant portion of bacterial residues, particularly in the subsoil. With increasing ¹⁴C age, a larger portion of peptide N was non-hydrolyzable, suggesting the accumulation of refractory compounds with time. The constant d/l ratios of lysine in topsoils indicate fresh proteinous material, likely due to continuous sorption of or exchange with fresh N-containing compounds. The ¹⁴C and the d/l signature revealed a longer turnover of proteinous components strongly bound to minerals (not NaOH-NaF-extractable). This study provides evidence that interactions with minerals are important in the transformation and stabilization of soil ON. Mineral-associated ON in topsoils seems actively involved in the N cycling of the study ecosystems, accentuating N limitation at the 0.3-kyr site but increasing N availability at older sites.     

Reaction-induced fluid flow in synthetic quartz-bearing marbles

The reaction kinetics and fluid expulsion during the decarbonation reaction of calcite+quartz=wollastonite+CO₂ in water-absent conditions were experimentally investigated using a Paterson-type gas apparatus. Starting materials consisted of synthetic calcite/quartz rock powders with variable fractions of quartz (10, 20, and 30 wt%) and grain sizes of 10 µm (calcite) and 10 and 30 µm (quartz). Prior to reaction, samples were HIPed at 700 °C and 300 MPa confining pressure and varying pore pressures. Initial porosity was low at 2.7–6.3%, depending on pore pressure during HIP and the amount and grain size of quartz particles. Samples were annealed at reaction temperatures of 900 and 950 °C at 150 and 300 MPa confining pressures, well within the wollastonite stability field. Run durations were between 10 min and 20 h. SEM micrographs of quenched samples show growth of wollastonite rims on quartz grains and CO₂-filled pores between rims and calcite grains and along calcite grain boundaries. Measured widths of wollastonite rims vs. time indicate a parabolic growth law. The reaction is diffusion-controlled and reaction progress and CO₂ production are continuous. Porosity increases rapidly at initial stages of the reaction and attains about 10–12% after a few hours. Permeability at high reaction temperatures is below the detection limit of 10^–21 m² and not affected by increased porosity. This makes persistent pore connectivity improbable, in agreement with observed fluid inclusion trails in form of unconnected pores in SEM micrographs. Release of CO₂ from the sample was measured in a downstream reservoir. The most striking observation is that fluid release is not continuous but occurs episodic and in pulses. Ongoing continuous reaction produces increase in pore pressure, which is, once having attained a critical value (P_crit), spontaneously released. Connectivity of the pore space is short-lived and transient. The resulting cycle includes pore pressure build-up, formation of a local crack network, pore pressure release and crack closure. Using existing models for plastic stretching and decrepitation of pores along with critical stress intensity factors for the calcite matrix and measured pore widths, it results that P_crit is about 20 MPa. Patterns of fluid flow based on mineralogical and stable isotope evidence are commonly predicted using the simplifying assumption of a continuous and constant porosity and permeability during decarbonation of the rock. However, simple flow models, which assume constant pore pressure, constant fluid filled porosity, and constant permeability may not commonly apply. Properties are often transient and it is most likely that fluid flow in a specific reacting rock volume is a short-lived episodic process.Editorial responsibility: J. Hoefs     

Ground ice and slope sediments archiving late Quaternary paleoenvironment and paleoclimate signals at the margins of El'gygytgyn Impact Crater, NE Siberia

An accumulation terrace close to the El'gygytgyn Impact Crater in northeastern Siberia contains stratigraphic and periglacial evidence of the paleoenvironmental and paleoclimatic history and permafrost dynamics during late Quaternary time. A succession of paleo active-layer deposits that mirror environmental changes records periods favorable for the establishment and growth of ice-wedge polygonal networks and sediment variations. These two elements of the periglacial landscape serve as complementary paleoenvironmental archives that can be traced back to ∼ 14,000 cal yr BP. The slope sediments and the ground ice contained therein have prominent relative maxima and minima in properties (grain size, total organic content, oxygen isotopes). They document a regional early Holocene thermal maximum at about 9000 cal yr BP, followed by a transition to slightly cooler conditions, and a subsequent transition to slightly warmer conditions after about 4000 cal yr BP. Results from sedimentary analysis resemble morphological and geochemical (oxygen and hydrogen isotopes) results from ice wedge studies, in which successive generations of ice-wedge polygonal networks record warmer winters in late Holocene time. Moreover, peaks of light soluble cation contents and quartz-grain surface textures reveal distinct traces of cryogenic weathering. We propose a conclusive sedimentation model illustrating terrace formation in a permafrost terrain.     

The earthquake of Carnuntum in the fourth century a.d. – archaeological results, seismologic scenario and seismotectonic implications for the Vienna Basin fault, Austria

Excavations in the former Roman provincial capital of Pannonia Superior, Carnuntum, 40 km east of Vienna revealed damaged masonry structures from many parts of the ancient settlements. A compilation of structurally damaged buildings has formerly been given by Kandler (Acta Archaeol Acad Sci Hung, 41:313–336, 1989), who related damage to an earthquake in the middle of the fourth century a.d. This paper reviews and supplements these data, and discusses the significance of the style of damage. It is concluded that seismic damage is the only likely interpretation for the damaging mechanism. Although archaeological age dating for the individual collapsed buildings only constrains the timing of their destruction to a few decades around 350 a.d., we assume a single damaging event. In spite of the restrictions on damage assessment by the nature of the archaeological data, it is possible to give a reasonable appraisal of macroseismic intensity. The tentative seismological interpretation of damage leads to an intensity estimate of about nine of the European macroseismic scale (EMS-1998). Comparison with macroseismic data of modern earthquakes in the region, which show a rapid decrease of intensity with distance form the epicentre, indicate a near-by seismic source unless exceptionally high epicentral intensities are assumed for the fourth century event. The most likely source is an active sinistral strike-slip fault (Lassee Fault) passing about 8 km NW of the archaeological site. The fault belongs to Vienna Basin fault system with about 2 mm sinistral movement per year. The system is characterized by fault segmentation and distinct seismicity along the different segments. Moderate seismicity during the last centuries at the southern segments (e.g., Schwadorf 1927, I ₀=8) strongly contrasts from the Lassee fault segment with Carnuntum as the only known severe earthquake. The earthquake of Carnuntum provides evidence for the overall seismic style of deformation along this segment, which previously has not been regarded seismically active. Also, the fourth century earthquake is the strongest event known from the Vienna Basin fault so far.     

Ultrasonic Velocities, Acoustic Emission Characteristics and Crack Damage of Basalt and Granite

Acoustic emissions (AE), compressional (P), shear (S) wave velocities, and volumetric strain of Etna basalt and Aue granite were measured simultaneously during triaxial compression tests. Deformation-induced AE activity and velocity changes were monitored using twelve P-wave sensors and eight orthogonally polarized S-wave piezoelectric sensors; volumetric strain was measured using two pairs of orthogonal strain gages glued directly to the rock surface. P-wave velocity in basalt is about 3 km/s at atmospheric pressure, but increases by > 50% when the hydrostatic pressure is increased to 120 MPa. In granite samples initial P-wave velocity is 5 km/s and increases with pressure by < 20%. The pressure-induced changes of elastic wave speed indicate dominantly compliant low-aspect ratio pores in both materials, in addition Etna basalt also contains high-aspect ratio voids. In triaxial loading, stress-induced anisotropy of P-wave velocities was significantly higher for basalt than for granite, with vertical velocity components being faster than horizontal velocities. However, with increasing axial load, horizontal velocities show a small increase for basalt but a significant decrease for granite. Using first motion polarity we determined AE source types generated during triaxial loading of the samples. With increasing differential stress AE activity in granite and basalt increased with a significant contribution of tensile events. Close to failure the relative contribution of tensile events and horizontal wave velocities decreased significantly. A concomitant increase of double-couple events indicating shear, suggests shear cracks linking previously formed tensile cracks.     

Natronamphibol- (Osannit-) Aegirinschiefer in den Tarntaler Bergen

Ohne ZusammenfassungMit 14 Textabbildungen.Aus Raumgründen kann hier nur ein enger Ausschnitt aus der einschlägigen Literatur gebracht werden.     

A zircon study from the Rhodope metamorphic complex, N-Greece: Time record of a multistage evolution

Zircons from an eclogite and a diamond-bearing metapelite near the Kimi village (north-eastern Rhodope Metamorphic Complex, Greece) have been investigated by Micro Raman Spectroscopy, SEM, SHRIMP and LA-ICPMS to define their inclusion mineralogy, ages and trace element contents. In addition, the host rocks metamorphic evolution was reconstructed and linked to the zircon growth domains.

The eclogite contains relicts of a high pressure stage (ca. 700 °C and > 17.5 kbar) characterised by matrix omphacite with Jd_40–35. This assemblage was overprinted by a lower pressure, higher temperature metamorphic event (ca. 820 °C and 15.5–17.5 kbar), as indicated by the presence of clinopyroxene (Jd_35–20) and plagioclase. Biotite and pargasitic amphibole represent a later stage, probably related to an influx of fluids. Zircons separated from the eclogite contain magmatic relicts indicating Permian crystallization of a quartz-bearing gabbroic protolith. Inclusions diagnostic of the high temperature, post-eclogitic overprint are found in metamorphic zircon domain Z2 which ages spread over a long period (160 – 95 Ma). Based on zircon textures, zoning and chemistry, we suggest that the high-temperature peak occurred at or before ca. 160 Ma and the zircons were disturbed by a later event possibly at around 115 Ma. Small metamorphic zircon overgrowths with a different composition yield an age of 79 ± 3 Ma, which is related to a distinct amphibolite-facies metamorphic event.

The metapelitic host rock consists of a mesosome with garnet, mica and kyanite, and a quartz- and plagioclase-bearing leucosome, which formed at granulite-facies conditions. Based on previously reported micro-diamond inclusions in garnet, the mesosome is assumed to have experienced UHP conditions. Nevertheless, (U)HP mineral inclusions were not found in the zircons separated from the diamond-bearing metapelite. Inclusions of melt, kyanite and high-Ti biotite in a first metamorphic zircon domain suggest that zircon formation occurred during pervasive granulite-facies metamorphism. An age of 171 ± 1 Ma measured on this zircon domain constrains the high-temperature metamorphic event. A second, inclusion-free metamorphic domain yielded an age of 160 ± 1 Ma that is related to decompression and melt crystallization.

The similar age data obtained from the samples indicate that both rock types recorded a high-T metamorphic overprint at granulite-facies conditions at ca. 170 – 160 Ma. This age implies that any high pressure or even ultra-high pressure metamorphism in the Kimi Complex occurred before that time. Our findings define new constraints for the geodynamic evolution for the Alpine orogenic cycle within the northernmost Greek part of the Rhodope Metamorphic Complex. It is proposed that the rocks of the Kimi Complex belong to a suture zone squeezed between two continental blocks and result from a Paleo-ocean basin, which should be located further north of the Jurassic Vardar Ocean.     

The spectral hardening associated with the westward travelling surge

Photometer recordings of auroral emissions from N⁺₂ and OI have demonstrated that the ratios between the emissions show a characteristic plateau just prior to the passage of a westward travelling surge. The plateau may be interpreted as a temporary (approx. 1 min) cessation in the spectral hardening of the precipitating particles associated with the surge. The characteristic energy of the plateau is about one keV above the level prior to the beginning of the surge. The results have been interpreted in terms of an instability that is switched on during the time of the plateau and then turned off when the electron density is increased above a certain limit.