X-ray absorption spectroscopy study on the effect of hydroxybenzoic acids on the formation and structure of ferrihydrite

Organic ligands are known to interfere with the polymerization of Fe(III), but the extent of interference has not been systematically studied as a function of structural ligand properties. This study examines how the number and position of phenol groups in hydroxybenzoic acids affect both ferrihydrite formation and its local (<5 Å) Fe coordination. To this end, acid Fe(III) nitrate solutions were neutralized up to pH 6.0 in the presence of 4-hydroxybenzoic acid (4HB), 2,4-dihydroxybenzoic acid (2,4DHB), and the hydroquinone 3,4-dihydroxybenzoic acid (3,4DHB). The initial molar ligand/Fe ratios ranged from 0 to 0.6. The precipitates were dialyzed, lyophilized, and subsequently studied by X-ray absorption spectroscopy and synchrotron X-ray diffraction. The solids contained up to 32 wt.% organic C (4HB ∼ 2,4DHB < 3,4DHB). Only precipitates formed in 3,4DHB solutions comprised considerable amounts of Fe(II) (Fe(II)/Fe_tot ≤ 6 mol%), implying the abiotic mineralization of the catechol-group bearing ligand during Fe(III) hydrolysis under oxic conditions. Hydroxybenzoic acids decreased ferrihydrite formation in the order 4HB ∼ 2,4DHB ? 3,4DHB, which documents that phenol group position rather than the number of phenol groups controls the ligand’s interaction with Fe(III). The coordination numbers of edge- and double corner-sharing Fe in the precipitates decreased by up to 100%. Linear combination fitting (LCF) of Fe K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra revealed that this decrease was due to increasing amounts of organic Fe(III) complexes in the precipitates. Although EXAFS derived coordination numbers of Fe in ferrihydrite remained constant within error, all organic ligands decreased the coherently scattering domain (CSD) size of ferrihydrite as indicated by synchrotron X-ray diffraction analysis (4HB < 2,4DHB ? 3,4DHB). With decreasing particle size of ferrihydrite its Fe(O,OH)₆ octahedra became progressively distorted as evidenced by an increasing loss of centrosymmetry of the Fe sites. Pre-edge peak analysis of the Fe K-edge XANES spectra in conjunction with LCF results implied that ferrihydrite contains on an average 13 ± 3% tetrahedral Fe(III), which is in very good agreement with the revised single-phase structural model of ferrihydrite (Michel, F. M., Barron, V., Torrent, J., Morales, M. P. et al. (2010) Ordered ferrimagnetic form of ferrihydrite reveals links among structure, composition, and magnetism. Proc. Natl. Acad. Sci. USA107, 2787-2792). The results suggest that hydroxybenzoic acid moieties of natural organic matter (NOM) effectively suppress ferrihydrite precipitation as they kinetically control the availability of inorganic Fe(III) species for nucleation and/or polymerization reactions. As a consequence, NOM can trigger the formation of small ferrihydrite nanoparticles with increased structural strain. These factors may eventually enhance the biogeochemical reactivity of ferrihydrite formed in NOM-rich environments. This study highlights the role of hydroquinone structures of NOM for Fe complexation, polymerization, and redox speciation.     

Wind-induced drift of objects at sea: The leeway field method

A method for conducting leeway field experiments to establish the drift properties of small objects (0.1-25 m) is described. The objective is to define a standardized and unambiguous procedure for condensing the drift properties down to a set of coefficients that may be incorporated into existing stochastic trajectory forecast models for drifting objects of concern to search and rescue operations and other activities involving vessels lost at sea such as containers with hazardous material.An operational definition of the slip or wind and wave-induced motion of a drifting object relative to the ambient current is proposed. This definition taken together with a strict adherence to a 10 m wind speed allows us to refer unambiguously to the leeway of a drifting object. We recommend that all objects if possible be studied using what we term the direct method, where the object’s leeway is studied directly using an attached current meter.We establish a minimum set of parameters that should be estimated for a drifting object for it to be included in the operational forecast models used for prediction of search areas for drifting objects.We divide drifting objects into four categories, depending on their size. For the smaller objects (less than 0.5 m), an indirect method of measuring the object’s motion relative to the ambient current must be used. For larger objects, direct measurement of the motion through the near-surface water masses is strongly recommended. Larger objects are categorized according to the ability to attach current meters and wind monitoring systems to them.The leeway field method proposed here is illustrated with results from field work where three objects were studied in their distress configuration; a 1:3.3 sized model of a 40-foot Shipping container, a World War II mine and a 220 l (55-gallon) oil drum.     

Preface: Proceedings of the 5th International Symposium on Lithographic Limestone and Plattenkalk

Magmatic rocks from the pre-Mesozoic basements of the Sambuco and Maggia nappes have been dated by U–Pb zircon ages with the LA-ICPMS technique. Several magmatic events have been identified in the Sambuco nappe. The mafic banded calc-alkaline suite of Scheggia is dated at 540 Ma, an age comparable to that of mafic rocks in the Austroalpine Silvretta nappe. The Sasso Nero peraluminous augengneiss has an age of 480–470 Ma, like many other “older orthogneisses” in Alpine basement units. It hosts a large proportion of inherited zircons, which were dated around 630 Ma, a Panafrican age indicating the Gondwanan affiliation of the Sambuco basement. The calc-alkaline Matorello pluton yielded ages around 300 Ma, similar to numerous Late Carboniferous intrusions in other basement units of the Lower Penninic (Monte Leone, Antigorio, Verampio) and Helvetic domains (Gotthard and other External Crystalline Massifs). Associated lamprophyric dykes are slightly younger (300–290 Ma), like similar dykes sampled in gneiss blocks included in the sedimentary cover of the underlying Antigorio nappe (290–285 Ma). The Cocco granodiorite and Rüscada leucogranite, both intruding the basement of the neighbouring Maggia nappe, yielded ages of ca. 300–310 Ma, identical within errors to the age of the Matorello pluton. They are significantly older than former age determinations. This age coincidence, coupled with remarkable petrologic similarities between the Cocco and Matorello granodiorites, strongly suggests paleogeographic proximity of the Sambuco and Maggia nappes in Late Carboniferous times. In recent publications these two nappes have been interpreted as belonging to distinct Mesozoic paleogeographic domains: “European” for Sambuco and “Briançonnais” for Maggia, separated by the “Valais” oceanic basin. In this case, the similarity of the Matorello and Cocco intrusions would demonstrate the absence of any significant transcurrent movement between these two continental domains. Alternatively, according to a more traditional view, Sambuco and Maggia might belong to a single large Alpine tectonic unit.     

摄影测量与遥感之发展趋势和展望

0引言摄影测量与遥感的原理可定义为:确定物体表面反射或发射某特定波长的电磁辐射特性(如:能量、相位、极化、传播时间等),并由这些测量值中提取物体及其表面的几何特征(如位     

Integrating radar stratigraphy with high resolution visible stratigraphy of the north polar layered deposits,Mars

Shallow Radar (SHARAD) on board NASA’s Mars Reconnaissance Orbiter has successfully detected tens of reflectors in the subsurface of the north polar layered deposits (NPLD) of Mars. Radar reflections are hypothesized to originate from the same material interfaces that result in visible layering. As a first step towards verifying this assumption, this study uses signal analyses and geometric comparisons to quantitatively examine the relationship between reflectors and visible layers exposed in an NPLD outcrop. To understand subsurface structures and reflector geometry, reflector surfaces have been gridded in three dimensions, taking into account the influence of surface slopes to obtain accurate subsurface geometries. These geometries reveal reflector dips that are consistent with optical layer slopes. Distance–elevation profiling of subsurface reflectors and visible layer boundaries reveals that reflectors and layers demonstrate similar topography, verifying that reflectors represent paleosurfaces of the deposit. Statistical and frequency-domain analyses of the separation distances between successive layers and successive reflectors confirms the agreement of radar reflector spacing with characteristic spacing of certain visible layers. Direct elevation comparisons between individual reflectors and discrete optical layers, while necessary for a one-to-one correlation, are complicated by variations in subsurface structure that exist between the outcrop and the SHARAD observations, as inferred from subsurface mapping. Although these complications have prevented a unique correlation, a genetic link between radar reflectors and visible layers has been confirmed, validating the assumption that radar reflectors can be used as geometric proxies for visible stratigraphy. Furthermore, the techniques for conducting a stratigraphic integration have been generalized and improved so that the integration can be undertaken at additional locations.     

Geochemical studies of the SUBO 18 (Enkingen) drill core and other impact breccias from the Ries crater,Germany

Suevite and melt breccia compositions in the boreholes Enkingen and Polsingen are compared with compositions of suevites from other Ries boreholes and surface locations and discussed in terms of implications for impact breccia genesis. No significant differences in average chemical compositions for the various drill cores or surface samples are noted. Compositions of suevite and melt breccia from southern and northeastern sectors of the Ries crater do not significantly differ. This is in stark contrast to the published variations between within‐crater and out‐of‐crater suevites from northern and southern sectors of the Bosumtwi impact structure, Ghana. Locally occurring alteration overprint on drill cores—especially strong on the carbonate‐impregnated suevite specimens of the Enkingen borehole—does affect the average compositions. Overall, the composition of the analyzed impact breccias from Ries are characterized by very little macroscopically or microscopically recognized sediment‐clast component; the clast populations of suevite and impact melt breccia are dominated consistently by granitic and intermediate granitoid components. The Polsingen breccia is significantly enriched in a dioritic clast component. Overall, chemical compositions are of intermediate composition as well, with dioritic‐granodioritic silica contents, and relatively small contributions from mafic target components. Selected suevite samples from the Enkingen core have elevated Ni, Co, Cr, and Ir contents compared with previously analyzed suevites from the Ries crater, which suggest a small meteoritic component. Platinum‐group element (PGE) concentrations for some of the enriched samples indicate somewhat elevated concentrations and near‐chondritic ratios of the most immobile PGE, consistent with an extraterrestrial contribution of 0.1–0.2% chondrite‐equivalent.     

Multiple ways of producing intermediate and silicic rocks within Thingmúli and other Icelandic volcanoes

Major and trace element compositions of rocks and coexisting phenocrysts of the Thingmúli volcano suggest a revision of the existing models for the formation of intermediate and silicic melts in Iceland. The new data define two compositional tholeiitic trends with a significant gap between them. A high-iron trend (HFe) contains 6–14 wt% total FeO in silicic rocks with c. 1 wt% MgO, as well as sodic plagioclase and hedenbergite phenocrysts. A low-iron trend (LFe) contains 3–5 wt% FeO at c. 1 wt% MgO, which is typical of Iceland but higher than MORB compositions. The most evolved phenocrysts of the LFe trend do not reach iron-rich end members. The HFe trend is interpreted as a result of fractional crystallization; numerical modelling using the MELTS algorithm suggests that crystallization took place under redox conditions constrained to one-log unit below the fayalite-magnetite-quartz oxygen buffer (FMQ-1). The LFe trend is explained by a combination of mixing between rhyolite and ferrobasalt, assimilation of hydrated crust and fractional crystallization under higher redox conditions (FMQ). The two trends and the gap are best defined in a plot of Mg# versus SiO₂ that is useful to unravel petrogenetic processes. For example, intermediate and silicic rocks of the Holocene volcanic systems of spreading rifts (e.g. Krafla), propagating rifts (e.g. Hekla) and off-rifts (Öræfajökull) also fall into high- and low-iron fields and outline a gap similar to Thingmúli. The identification of two compositional trends in erupted intermediate and silicic volcanic products shows that processes in the deep roots of single volcanic systems are highly diverse and likely controlled by local variations in the thermal gradients and the extend of hydrothermal alteration. Generalizations about the relationship between the compositions of intermediate and silicic rocks and plate tectonic setting, therefore, should be avoided.     

Protoliths and phase petrology of whiteschists

Whiteschists appear in numerous high- and ultrahigh-pressure rock suites and are characterized by the mineral assemblage kyanite + talc (+-quartz or coesite). We demonstrate that whiteschist mineral assemblages are well stable up to pressures of more than 4 GPa but may already form at pressures of 0.5 GPa. The formation of whiteschists largely depends on the composition of the protolith, which requires elevated contents of Al and Mg as well as low Fe, Ca, and Na contents, as otherwise chloritoid, amphibole, feldspar, or omphacite are formed instead of kyanite or talc. Furthermore, the stability field of the whiteschist mineral assemblage strongly depends on XCO₂ and fO₂: already at low values of XCO₂, CO₂ binds Mg to carbonates strongly reducing the whiteschist stability field, whereas high fO₂ enlarges the stability field and stabilizes yoderite. Thus, the scarcity of whiteschist is not necessarily due to unusual P–T conditions, but to the restricted range of suitable protolith compositions and the spatial distribution of these protoliths: (1) continental sedimentary rocks and (2) hydrothermally and metasomatically altered felsic to mafic rocks. The continental sedimentary rocks that may produce whiteschist mineral assemblages typically have been deposited under arid climatic conditions in closed evaporitic basins and may be restricted to relatively low latitudes. These rocks often contain large amounts of the clay minerals palygorskite and sepiolite. Marine sediments generally do not yield whiteschist mineral assemblages as marine shales commonly have too high iron contents. Sabkha deposits may have too high CO₂ contents. Protoliths of appropriate geochemical composition occur in and on continental crust. Therefore, whiteschist assemblages typically are only found in settings of continental collision or where continental fragments were involved in subduction. Our calculations demonstrate that whiteschists can form by closed-system metamorphism, which implies that the chemical and isotopic composition of these rocks provide constraints on the development of the protoliths.     

Europeanizing Timisoara: neoliberal reforms, continuity with the past, and unexpected side effects

This paper analyzes how processes of Europeanization opened up opportunities and generated ideals, which in turn changed the articulation between political and economic powers in the city and county of Timisoara, Western Romania. It builds on case studies of local government agencies and foreign investors from Italy. In doing so, it discusses the circular relationship between the European and the local levels of governance: European governance affected the interactions between firms and institutions in the city, while at the same time city authorities used different understandings of ‘Europe’ to pursue their own agenda. It also shows some of the unexpected side-effects of Europeanization, due to the political activism of Italian investors. Beck and Grande’s concept of ‘reflexive modernization’ and the literature on regional economies frame the discussion.