Structural features of humic acids from a sedimentary sequence in the Guadiana estuary (Portugal–Spain border)

The structural characteristics of humic acids (HAs) from two different depths of a sedimentary sequence representing the last 13 kyr in the valley of Guadiana river estuary (SW Portugal/Spain border) have been approached using a combination of spectroscopic techniques, wet chemical degradation methods (sequential oxidation with sodium persulfate followed by KMnO₄, and oxidation with RuO₄) and analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in the presence and absence of tetramethylammonium hydroxyde (TMAH). The aim was to obtain complementary information on the sources and alteration of the organic matter (OM) provided by a previous study on the vertical distribution of terrestrial and phytoplankton biogeochemical markers in the sequence. Both the FT-IR (Fourier transformed infrared) and ¹³C NMR (nuclear magnetic resonance) spectra showed a close similarity with the structural characteristics of the HA samples. NMR signals in the alkyl region (0–45 ppm) as well as FT-IR band patterns typical for methoxyl-substituted aromatic rings pointed to the presence of an important aliphatic domain, as well as to lignin-derived compounds. This finding was confirmed using analytical pyrolysis. In addition, the main TMAH thermochemolysis products were typical lignin-derived methoxyphenols with both guaicyl and syringyl nuclei. The detection of methoxyphenol units with three to six carbon atom (C₃–C₆) side chains suggests that lignin and possibly suberin were only partially degraded. Compounds arising from proteins and polysaccharides were also detected, although in lesser and varying amount. The major products from persulfate oxidation were series of n-alkanes (C₁₆–C₃₃ with clear odd/even predominance) and n-fatty acids, both saturated (C₁₀–C₂₆ with strong even/odd predominance) and unsaturated, which may arise from the above aliphatic biomacromolecules. The major products from permanganate oxidation of the persulfate residue were α,ω-diacids (C₆–C₁₁) originating from oxidation of the ether bonds linking the building blocks constituting the core of the HA structure. Aromatic compounds (phenols, methoxy-dimethoxybenzene carboxylic acid and benzene di-, tri-, tetra- and pentacarboxylic acids), most probably derived from the aromatic backbone of the HAs, that may also include lignin moieties as well as other polyphenols (flavonoids and tannins) were also detected. The RuO₄ oxidation also released series of n-alkanes (C₁₆–C₃₃), linear saturated fatty acids (C₁₀–C₂₈) and α,ω-diacids (C₇–C₂₅), as well as traces of benzene polycarboxylic acids. Regarding the usefulness of the various techniques used, they provide complementary information. Indeed, spectroscopic techniques and analytical pyrolysis provide information on the backbone of the HAs, and on their origin, whereas the oxidative degradations provide different information on the structural features of the HA, particularly the nature of the linking between the building blocks. In general, the data support the idea that the HAs still contain information about the signature of aliphatic and aromatic biomacromolecules contributing to the OM deposited. The presence of lignin-derived residues suggests a large input from terrestrial carbon throughout the core.     

Regional stratigraphy and distribution of epigenetic stratabound celestine, fluorite, barite and Pb–Zn deposits in the MVT province of northeastern Mexico

Northeastern Mexico hosts numerous epigenetic stratabound carbonate-hosted low-temperature hydrothermal deposits of celestine, fluorite, barite and zinc-lead, which formed by replacement of Mesozoic evaporites or carbonate rocks. Such deposits can be permissively catalogued as Mississippi Valley-type (MVT) deposits. The deposits studied in the state of Coahuila are associated with granitic and metasedimentary basement highs (horsts) marginal or central to the Mesozoic Sabinas Basin. These horsts controlled the stratigraphy of the Mesozoic basins and subsequently influenced the Laramide structural pattern. The Sabinas Basin consists of ~6,000-m-thick Jurassic to Cretaceous siliciclastic, carbonate and evaporitic series. The MVT deposits are mostly in Barremian and in Aptian-Albian to Cenomanian formations and likely formed from basinal brines that were mobilized during the Laramide orogeny, although earlier diagenetic replacement of evaporite layers (barite and celestine deposits) and lining of paleokarstic cavities in reef carbonates (Zn–Pb deposits) is observed. Fluid inclusion microthermometry and isotopic studies suggest ore formation due to mixing of basinal brines and meteoric water. Homogenization temperatures of fluid inclusions range from 45°C to 210°C; salinities range from 0 to 26 wt.% NaCl equiv., and some inclusions contain hydrocarbons or bitumen. Sulfur isotope data suggest that most of the sulfur in barite and celestine is derived from Barremian to Cenomanian evaporites. Regional geology and a compilation of metallogenic features define the new MVT province of northeastern Mexico, which comprises most of the state of Coahuila and portions of the neighboring states of Nuevo León, Durango and, perhaps extends into Zacatecas and southern Texas. This province exhibits a regional metal zonation, with celestine deposits to the south, fluorite deposits to the north and barite and Zn–Pb deposits mostly in the central part.     

The El Teniente porphyry Cu–Mo deposit from a hydrothermal rutile perspective

Mineralogical, textural, and chemical analyses (EPMA and PIXE) of hydrothermal rutile in the El Teniente porphyry Cu–Mo deposit help to better constrain ore formation processes. Rutile formed from igneous Ti-rich phases (sphene, biotite, Ti-magnetite, and ilmenite) by re-equilibration and/or breakdown under hydrothermal conditions at temperatures ranging between 400°C and 700°C. Most rutile nucleate and grow at the original textural position of its Ti-rich igneous parent mineral phase. The distribution of Mo content in rutile indicates that low-temperature (∼400–550°C), Mo-poor rutile (5.4 ± 1.1 ppm) is dominantly in the Mo-rich mafic wallrocks (high-grade ore), while high-temperature (∼550-700°C), Mo-rich rutile (186 ± 20 ppm) is found in the Mo-poor felsic porphyries (low-grade ore). Rutile from late dacite ring dikes is a notable exception to this distribution pattern. The Sb content in rutile from the high-temperature potassic core of the deposit to its low-temperature propylitic fringe remains relatively constant (35 ± 3 ppm). Temperature and Mo content of the hydrothermal fluids in addition to Mo/Ti ratio, modal abundance and stability of Ti-rich parental phases are key factors constraining Mo content and provenance in high-temperature (≥550°C) rutile. The initial Mo content of parent mineral phases is controlled by melt composition and oxygen fugacity as well as timing and efficiency of fluid–melt separation. Enhanced reduction of SO₂-rich fluids and sulfide deposition in the Fe-rich mafic wallrocks influences the low-temperature (≤550°C) rutile chemistry. The data are consistent with a model of fluid circulation of hot (>550°C), oxidized (ƒO₂ ≥ NNO + 1.3), SO₂-rich and Mo-bearing fluids, likely exsolved from deeper crystallizing parts of the porphyry system and fluxed through the upper dacite porphyries and related structures, with metal deposition dominantly in the Fe-rich mafic wallrocks.     

Influence of high-pressure processing on the structure and memory effect of synthetic layered double hydroxides

We investigate the structural evolution of synthetic layered double hydroxides (LDH) samples, processed at room temperature and high-pressure (up to 7.7 GPa) in a toroidal chamber with two pressure-transmitting media, lead and graphite, using X-ray diffraction, thermogravimetry and N₂-adsorption isotherms techniques. The X-ray patterns of compacted samples show a decrease in the peak intensities. For both pressure-transmitting media, our samples revealed a reduction of the basal d-spacing for the (003) plane when processed at 7.7 GPa. The expected high-pressure-induced amorphization was not observed. Surprisingly, we find high-pressure processing to have a strong influence on the memory effect of the LDH, due essentially to the reduction of the surface area and pore closing. Even when immersed in water, our samples did not recover the LDH structure, when either calcined at 450°C and compacted at 7.7 GPa, or calcined at 700°C and immediately compacted at 2.5 and 7.7 GPa.     

An array of lens-coupled antennas for cosmic microwave background measurements in the 30 Ghz band

An array of bow-tie slot antennas coupled through an extended hemispherical lens is proposed to operate in the 30?GHz frequency band. The design includes a combination of three microstrip Wilkinson power dividers (WPD) and transitions to coplanar wave guides (CPW) to form the feeding antenna network. This configuration is suitable for the integration with heterodyne imaging detectors commonly used in radioastronomy. Measurements and simulation results exhibit a frequency range of operation from 20 to 40?GHz with a bandwidth of 24% achieved for ?10?dB return loss at the central frequency. The measured radiation patterns show a maximum peak gain of around 13?dB with HPBW of 10° for the E-plane, and whose first side lobes are lower than 13?dB below the main lobe in both angular shift sides. The presented results will be considered as preliminary feasibility studies in the 30?GHz QUIJOTE-CMB Instrument, which is designed to study the anisotropies of the Cosmic Microwave Background (CMB).     

Search for New Parent Bodies of Meteoroid Streams Among Comets. I. Showers of Comets 126P/1996 P1 and 161P/2004 V2 with Radiants on Southern Sky

We deal with theoretical meteoroid streams the parent bodies of which are two Halley-type comets in orbits situated at a relatively large distance from the orbit of Earth: 126P/1996 P1 and 161P/2004 V2. For two perihelion passages of each comet in the far past, we model the theoretical stream and follow its dynamical evolution until the present. We predict the characteristics of potential meteor showers according to the dynamical properties of theoretical particles currently approaching the orbit of the Earth. Our dynamical study reveals that the comet 161P/2004 V2 could have an associated Earth-observable meteor shower, although no significant number of theoretical particles are identified with real, photographic, video, or radar meteors. However, the mean radiant of the shower is predicted on the southern sky (its declination is about −23°) where a relatively low number of real meteors has been detected and, therefore, recorded in the databases used. The shower of 161P has a compact radiant area and a relatively large geocentric velocity of ∼53 km s⁻¹. A significant fraction of particles assumed to be released from comet 126P also cross the Earth’s orbit and, eventually, could be observed as meteors. However, their radiant area is largely dispersed (declination of radiants spans from about +60° to the south pole) and, therefore, mixed with the sporadic meteor background. An identification with real meteors is practically impossible.     

Radio-continuum study of the Nearby sculptor group galaxies. Part 1: NGC 300 at λ=20 cm

A series of new radio-continuum (λ=20 cm) mosaic images focused on the NGC?300 galactic system were produced using archived observational data from the VLA and/or ATCA. These new images are both very sensitive (rms?=60 μJy) and feature high angular resolution (<10?″). The most prominent new feature is the galaxy’s extended radio-continuum emission, which does not match its optical appearance. Using these newly created images a number of previously unidentified discrete sources have been discovered. Furthermore, we demonstrate that a joint deconvolution approach to imaging this complete data-set is inferior when compared to an immerge approach.     

Anion chemistry on Titan: A possible route to large N-bearing hydrocarbons

The reaction of CN^? with cyanoacetylene (HC₃N), has been studied as a function of the HC₃N pressure in a quadrupole tandem mass spectrometer. The mass spectra revealed the fast depletion of the CN^? parent ion and formation of larger anions of rapidly growing size. Most of the ions observed were found to belong to two series of products: (HC₃N)_x·C_2p+1N^? and (HC₃N)_x·C_2pN^? resulting from the sequential additions of HC₃N molecules and loss of HCN or HCCN molecules. The mechanism and energetics of the first two reaction steps are briefly discussed. The laboratory data are compared with those from the Cassini CAPS-ELS spectrometer. It is believed that the reactions observed could account for the growth of anions in Titan’s ionosphere.     

Intercomparison of the LASCO-C2, SECCHI-COR1, SECCHI-COR2, and Mk4 Coronagraphs

In order to assess the reliability and consistency of white-light coronagraph measurements, we report on quantitative comparisons between polarized brightness [pB] and total brightness [B] images taken by the following white-light coronagraphs: LASCO-C2 on SOHO, SECCHI-COR1 and -COR2 on STEREO, and the ground-based MLSO-Mk4. The data for this comparison were taken on 16?April 2007, when both STEREO spacecraft were within 3.1^° of Earth??s heliographic longitude, affording essentially the same view of the Sun for all of the instruments. Due to the difficulties of estimating stray-light backgrounds in COR1 and COR2, only Mk4 and C2 produce reliable coronal-hole values (but not at overlapping heights), and these cannot be validated without rocket flights or ground-based eclipse measurements. Generally, the agreement between all of the instruments?? pB values is within the uncertainties in bright streamer structures, implying that measurements of bright CMEs also should be trustworthy. Dominant sources of uncertainty and stray light are discussed, as is the design of future coronagraphs from the perspective of the experiences with these instruments.