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).     

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.     

The active layer in gravel-bed rivers: An empirical appraisal

The vertical position of the streambed–water boundary fluctuates during the course of sediment transport episodes, due to particle entrainment/deposition and bedform migration, amongst other hydraulic and bedload mechanisms. These vertical oscillations define a topmost stratum of the streambed (i.e. the ‘active layer or active depth’), which usually represents the main source of particles entrained during long and high-magnitude bedload transport episodes. The vertical extent of this layer is hence a capital parameter for the quantification of bedload volumes and a major driver of stream ecology in gravel-bed rivers. However, knowledge on how the active depth scales to flow strength and the nature of the different controls on the relation between the flow strength and the active depth is still scarce. In this paper we present a meta-analysis over active depth data coming from ~130 transport episodes extracted from a series of published field studies. We also incorporate our own field data for the rivers Ebro and Muga (unpublished), both in the Iberian Peninsula. We explore the database searching for the influence of flow strength, grain size, streambed mobility and channel morphology on the vertical extent of the active layer. A multivariate statistical analysis (stepwise multiple regression) confirms that the set of selected variables explains a significant amount of variance in the compiled variables. The analysis shows a positive scaling between active depth and flow strength. We have also identified some links between the active depth and particle travel distances. However, these relations are also largely modulated by other fluvial drivers, such as the grain size of the bed surface and the dominant channel macro-bedforms, with remarkable differences between plane-bed, step-pool and riffle-pool channels. © 2020 John Wiley & Sons, Ltd.     

Comparing single-phase,non-Newtonian approaches with experimental results: Validating flume-scale mud and debris flow in HEC-RAS

Post-fire debris flows and tailing impoundment failures destroy lives and property. These geologic hazards – and other similar processes – fall on a continuum between classic Newtonian flood analyses and geotechnical stability analyses. The US Army Corps of Engineers (USACE) is developing a non-Newtonian library (DebrisLib) that includes a suite of rheological and clastic approaches to hyper-concentrated, mudflow and debris flow dynamics. The Hydrologic Engineering Center (HEC) has implemented these non-Newtonian methods into the widely used, public-domain open-channel hydraulics and morphodynamic software, HEC-RAS (river analysis system). This work presents part of the verification and validation of these non-Newtonian approaches, applying several rheological equations to published laboratory results high-concentration flume experiments. This study tested the linear Bingham model as well as the turbulent and Bagnold quadratic terms of the O'Brien equation. HEC-RAS also includes the non-linear Herschel–Bulkley (HB) approach, which quantifies shear-thickening or shear-thinning processes. The study used these non-Newtonian models in HEC-RAS to simulate 10 of Parsons et al.’s (2001) flume experiments, which measured the snout and plug velocity of fluids with high solid concentrations (C_v = 68–74%) and a broad range of material gradations (d₅₀ = 0.05–1 mm, d₁₅ = 0.006–0.1 mm). The experiments also measured and back-calculated Bingham and HB parameters of the materials, finding HB powers between 0.45 and 1.25 (i.e. fluids that are dilatant, pseudo-plastic and visco-plastic). The rheological models incorporated into DebrisLib and implemented in HEC-RAS reproduce experimental data well for most experiments. The Bingham model generated a plug velocity root-mean-square error (RMSE) of 0.21 m/s using standard flow parameters and Parsons et al.’s calibrated parameters, a substantial improvement over the unmodified shallow water flow equations (RMSE 0.77 m/s). Experiments with strong snout effects tended to generate higher residuals, especially in the snout velocity. The RMSE associated with the O'Brien equation was larger with the Parsons et al. fit parameters, but similar (0.23 m/s) with measured parameters. The turbulent parameter was the largest (often the dominant) parameter in most O'Brien simulations, with the dispersive stress only proving significant for the coarsest material. DebrisLib had to use a modified version of the dispersive term to simulate these concentrations. Both the 2D depth-averaged shallow water equation (SWE) and diffusion wave equation were used to simulate the experiments. The best results were obtained with the SWE with horizontal mixing.