Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases

The stoichiometry and stability of arsenic gaseous complexes were determined in the system As-H₂O ± NaCl ± HCl ± H₂S at temperatures up to 500°C and pressures up to 600 bar, from both measurements of As^(III) and As^(V) vapor-liquid and vapor-solid partitioning, and X-ray absorption fine structure (XAFS) spectroscopic study of As^(III)-bearing aqueous fluids. Vapor-aqueous solution partitioning for As^(III) was measured from 250 to 450°C at the saturated vapor pressure of the system (P_sat) with a special titanium reactor that allows in situ sampling of the vapor phase. The values of partition coefficients for arsenious acid (H₃AsO₃) between an aqueous solution (pure H₂O) and its saturated vapor (K = mAs_vapor /mAs_liquid) were found to be independent of As^(III) solution concentrations (up to ∼1 to 2 mol As/kg) and equal to 0.012 ± 0.003, 0.063 ± 0.023, and 0.145 ± 0.020 at 250, 300, and 350°C, respectively. These results are interpreted by the formation, in the vapor phase, of As(OH)₃(gas), similar to the aqueous As hydroxide complex dominant in the liquid phase. Arsenic chloride or sulfide gaseous complexes were found to be negligible in the presence of HCl or H₂S (up to ∼0.5 mol/kg of vapor). XAFS spectroscopic measurements carried out on As^(III)-H₂O (±NaCl) solutions up to 500°C demonstrate that the As(OH)₃ complex dominates As speciation both in dense H₂O-NaCl fluids and low-density supercritical vapor. Vapor-liquid partition coefficients for As^(III) measured in the H₂O-NaCl system up to 450°C are consistent with the As speciation derived from these spectroscopic measurements and can be described by a simple relationship as a function of the vapor-to-liquid density ratio and temperature. Arsenic^(III) partitioning between vapor and As-concentrated solutions (>2 mol As/kg) or As₂O₃ solid is consistent with the formation, in the vapor phase, of both As₄O₆ and As(OH)₃. Arsenic^(V) (arsenic acid, H₃AsO₄) vapor-liquid partitioning at 350°C for dilute aqueous solution was interpreted by the formation of AsO(OH)₃ in the vapor phase.The results obtained were combined with the corresponding properties for the aqueous As(III) hydroxide species to generate As(OH)₃(gas) thermodynamic parameters. Equilibrium calculations carried out by using these data indicate that As(OH)₃(gas) is by far the most dominant As complex in both volcanic gases and boiling hydrothermal systems. This species is likely to be responsible for the preferential partition of arsenic into the vapor phase as observed in fluid inclusions from high-temperature (400 to 700°C) Au-Cu (-Sn, -W) magmatic-hydrothermal ore deposits. The results of this study imply that hydrolysis and hydration could be also important for other metals and metalloids in the H₂O-vapor phase. These processes should be taken into account to accurately model element fractionation and chemical equilibria during magma degassing and fluid boiling.     

Carbon dioxide on planetary bodies: Theoretical and experimental studies of molecular complexes

An absorption band at ∼4.26 μm wavelength attributed to the asymmetric stretching mode of CO in CO₂ has been found on two satellites of Jupiter and several satellites of Saturn. The wavelength of pure CO₂ ice determined in the laboratory is 4.2675 μm, indicating that the CO₂ on the satellites occurs either trapped in a host material, or in a chemical or physical complex with other materials, resulting in a blue shift of the wavelength of the band. In frequency units, the shifts in the satellite spectra range from 3.7 to 11.3 cm⁻¹. We have performed ab initio quantum chemical calculations of CO₂ molecules chemically complexed with one, two, and more H₂O molecules and molecules of CH₃OH to explore the possibility that the blue shift of the band is caused by chemical complexing of CO₂ with other volatile materials. Our computations of the harmonic and anharmonic vibrational frequencies using high levels of theory show a frequency shift to the blue by 5 cm⁻¹ from pure CO₂ to CO-H₂O, and an additional 5 cm⁻¹ from CO₂-H₂O to CO₂-2H₂O. Complexing with more than two H₂O molecules does not increase the blue shift. Complexes of CO₂ with one molecule of CH₃OH and with one CH₃OH plus one H₂O molecule produce smaller shifts than the CO₂-2H₂O complex. Laboratory studies of CO₂:H₂O in a solid N₂ matrix also show a blue shift of the asymmetric stretching mode.     

Diatom record from Lake Hovsgol, Mongolia, during the last 1 Ma: The results from the HDP-04 drill core

Quantitative diatom abundance and species composition was studied in the longest 81-m Lake Hovsgol drill core, HDP-04. Lake Hovsgol diatom biostratigraphy of the past 1 Ma includes 14 local diatom assemblage zones (LDAZ). Planktonic diatom flora of Lake Hovsgol is dominated by members of Stephanodiscus and Cyclotella. A large-scale shift from Stephanodiscus-dominated to Cyclotella-dominated flora occurred in the mid-Brunhes chron. Significant morphological variability of Cyclotella ocellata complex and Cyclotella cf. minuta, as well as the presence of new extinct endemic taxa of genus Stephanodiscus, suggest long speciation and/or adaptation history of diatom flora. The recognition of taxa morphologically similar to the extinct endemic species of Lake Baikal suggests potential correlation ties between Lake Hovsgol and Lake Baikal diatom biostratigraphies around the MIS 17, MIS 25, and, possibly, MIS 15 interglacial intervals. Narrow peaks of diatom abundance in the Lake Hovsgol sedimentary record are episodic and short-lived. These peaks may represent humid optima of past interglacials and/or interstadials, characterized by elevated surface runoff in the Hovsgol basin and relative highstands of the lake.     

Cenozoic history of the Bering Sea and its northwestern margin

Tectonic reconstructions based on the geodynamic analysis of geologic, paleomagnetic, structural and kinematic data of Cenozoic age from the western Bering Sea region are proposed in the present paper. The most active tectonic and magmatic processes took place in the Komandorsky segment of the Bering Sea, exemplified by the Late Cretaceous–Early Eocene Olutorsky Arc and Eocene–Oligocene Govena–Karaginsky Arc, which was built on the structures of the Olutorsky Arc. A model of the complex collision of these two arcs with the paleocontinental margin, which considers rotations of the geological blocks from the various structural zones of the western margin of the Bering Sea in the horizontal plane (paleomagnetic data), was proposed by the authors. According to this model the collision of the flanks of the Olutorsky and Govena–Karaginsky arcs took place in the Eocene, before the collision of the central parts in the Miocene.     

Correlations between fatty acid composition of seston and zooplankton and effects of environmental parameters in a eutrophic Siberian reservoir

During two sampling seasons we analyzed on weekly basis fatty acid (FA) composition of seston fraction <130 μm and zooplankton fraction >130 μm, and compared them using a multivariate canonical correlation analysis (CCA). Besides, we evaluated a possible impact of water temperature and inorganic nutrients on FA composition of the seston and the zooplankton.In spite of significant differences in percentages of several individual FAs, we found very strong canonical correlation (cross-correlation, 1-week lag) between FA composition of the seston and the zooplankton. The most important factor, providing the overall canonical cross-correlation between FA profiles of the seston and the zooplankton fractions was eicosapentaenoic acid (20:5ω3, EPA). FA composition of the zooplankton fraction had comparatively poor correlations with taxonomic composition of the zooplankton. Thus, seasonal variations of FA composition of the zooplankton were determined primarily by seasonal changes in FA composition of the seston, rather than by taxonomic differences of FA profiles between rotifers, cyclopoids and cladocerans. FA composition of the seston was strongly affected by its taxonomic composition, namely by that of phytoplankton. According to CCA, the highest factor loadings pertained to diatoms interacting with their marker acids, including EPA, and cyanobacteria and greens, interacting with their marker acids. Ciliates and small rotifers composed considerable and sometimes major part of the seston biomass, but according to CCA their contributions to seasonal variations of the total FA profile of the seston were insignificant. This finding indirectly support the conclusion of the other authors, that the main source of FAs presented in ciliates and rotifers must be sought in algae and that they do not modify FA composition of food consumed, apart from repackaging it.Water temperature was the principal environmental parameter which drove the overall variations of FA composition. Factor loadings for the inorganic nutrients were comparatively negligible. The main contribution in the seasonal variation of FA composition of the seston was given by negative interaction between water temperature and percentage of EPA in the seston.     

Improving BeiDou real-time precise point positioning with numerical weather models

Precise positioning with the current Chinese BeiDou Navigation Satellite System is proven to be of comparable accuracy to the Global Positioning System, which is at centimeter level for the horizontal components and sub-decimeter level for the vertical component. But the BeiDou precise point positioning (PPP) shows its limitation in requiring a relatively long convergence time. In this study, we develop a numerical weather model (NWM) augmented PPP processing algorithm to improve BeiDou precise positioning. Tropospheric delay parameters, i.e., zenith delays, mapping functions, and horizontal delay gradients, derived from short-range forecasts from the Global Forecast System of the National Centers for Environmental Prediction (NCEP) are applied into BeiDou real-time PPP. Observational data from stations that are capable of tracking the BeiDou constellation from the International GNSS Service (IGS) Multi-GNSS Experiments network are processed, with the introduced NWM-augmented PPP and the standard PPP processing. The accuracy of tropospheric delays derived from NCEP is assessed against with the IGS final tropospheric delay products. The positioning results show that an improvement in convergence time up to 60.0 and 66.7% for the east and vertical components, respectively, can be achieved with the NWM-augmented PPP solution compared to the standard PPP solutions, while only slight improvement in the solution convergence can be found for the north component. A positioning accuracy of 5.7 and 5.9 cm for the east component is achieved with the standard PPP that estimates gradients and the one that estimates no gradients, respectively, in comparison to 3.5 cm of the NWM-augmented PPP, showing an improvement of 38.6 and 40.1%. Compared to the accuracy of 3.7 and 4.1 cm for the north component derived from the two standard PPP solutions, the one of the NWM-augmented PPP solution is improved to 2.0 cm, by about 45.9 and 51.2%. The positioning accuracy for the up component improves from 11.4 and 13.2 cm with the two standard PPP solutions to 8.0 cm with the NWM-augmented PPP solution, an improvement of 29.8 and 39.4%, respectively.     

Ab initio calculations of 6‐ and 7‐carbon meteoritic amino acids and their diastereomers

Abstract– To better explain the unusual distribution and relative abundances of several 6‐ and 7‐carbon amino acids found in meteorites, their thermodynamic properties were studied using accurate ab initio techniques. In addition to optimized structures and relative energies, vibrational frequency and thermochemical analysis of different diastereomers were performed at temperatures relevant to conditions of synthesis of these amino acids in meteorites. The results of calculations were compared with the measured content of the amino acids in the Murchison meteorite. The distribution of several longer chain amino acids in meteorites seems to point to at least some thermodynamic control in their formation. For diastereomeric compounds, on the other hand, the comparison suggests that their synthetic conditions, or those of their precursors, were far from thermodynamic equilibrium.     

The radioastronomical “time machine” effect can help the solution of the gamma ray bursts mystery

The possible low-frequency radio emission from the progenitors of gamma ray bursts can experience a delay from tens of seconds to hours on the way to the observer due to the dispersion in galactic and extragalactic plasma, and thus reach the observer as a radio afterglow of the burst. This opens a unique possibility (peculiar “time machine”) of seeing what happened at that place before the catastrophe.