Uptake of nitrogen dioxide (NO<Subscript>2</Subscript>) on acidic aqueous humic acid (HA) solutions as a missing daytime nitrous acid (HONO) surface source

A comprehensive kinetic study of a potential daytime nitrous acid (HONO) source reaction, the photoenhanced reduction reaction of the nitrogen dioxide (NO₂) on acidic humic acid (HA), was completed using a wetted-wall flow tube (WWFT) (Fickert et al.: J. Phys. Chem. A. 102, 10689, 1998) photoreactor integrated with a high sensitivity HONO analyser (Wall et al.: J. Atmos. Chem. 55, 31–54, 2006; Huang et al.: Atmos. Environ. 36, 2225–2235, 2002). The nature of this reaction, is of great interest since recently observed, unpredictably high HONO daytime concentrations demand its ordinarily proposed heterogeneous source to proceed 60 times more rapidly at noon than during the night (Kleffmann et al.: ChemPhysChem 8, 1137–1144, 2007). This study investigated the nature of the reduction reaction with simulated colloidal HA aqueous solutions characteristic of anaerobic environmental conditions, varying in acidity, concentration and composition. Typical urban NO₂ levels were investigated. Increasing photoenhanced HONO production with weakening solution acidity was detected due to increased deprotonation of the carboxyl groups within the humic acid. It was deduced that the acidic HA substrate contains numerous feasible chromophoric sensitizer units capable of photochemically reducing NO₂ to HONO, owing to its ‘biofilm’ (Donlan, 2002) function under UV exposure. The mechanism was found to be more effective for HA standards with higher levels of ‘bioactivity’ (refractivity). Using a complex mathematical model developed, incorporating both chemistry and diffusion, reaction probability datasets were produced from the experimental data, providing evidence that this is, indeed, an environmentally important daytime HONO surface source reaction. The parameters required to scale up the data of the photoreactor to that of a regional rural/urban scale were assessed.     

Implementation of novel polygon-based obfuscation methods to improve privacy of agricultural data

Geoprivacy protection is a significant concern when sharing data. To support sustainable land management by leveraging existing agricultural data, research is needed to identify how the polygon nature of static field parcels can be obfuscated to allow data sharing among individuals and organizations. In this study, five adaptive polygon-based obfuscation methods including PN*Rand, PDonut-k, PDensity-k, PAHilb, and PDonut_AHilb methods were developed and applied on the Irish Nutrient Management Planning Online (NMP Online) agricultural dataset. The polygon-based obfuscation methods introduced in this study were designed with the consideration of properties of spatial polygon objects including the spatial coordinates, shape and size of the polygon, topology, and spatial relationship between adjacent polygons that can be used to identify real-world objects. These methods were developed to guarantee that there is no false-identification and non-unique obfuscation which is important for static polygon objects in terms of accuracy and privacy protection. Qualitative approaches were developed to identify the optimal values of inner and outer radii of donut shape based on k-anonymity satisfaction and subsequently obtain the optimal value of k-anonymity. Several evaluation methods were implemented to compare the methods performance. Density-based methods particularly PDonut-AHilb provide the best trade-off between field parcel confidentiality and spatial pattern preservation and should be considered for researchers and practitioners obfuscating polygon data.     

Application of new thermodynamic data to grossular phase relations

Recent low temperature, adiabatic calorimetric heat capacity measurements for grossular have been combined with DSC measurements to give entropies up to 1000 K. In conjunction with enthalpy of solution values for grossular, these data have yielded H _f ^o (298.15K) and G _f ^o (298.15K) values of –1583.2 ± 3.5 and –1496.74 ± 3.7 kcal mol^–1 respectively. For 15 reactions in the CaO-Al₂O₃-SiO₂-H₂O system, thermodynamically calculated P-T curves have been compared with experimental reversals and have shown good agreement in most cases. Calculations indicate that gehlenite is probably totally disordered. Estimates of zoisite and lawsonite entropies are consistent with the phase equilibrium and grossular data, but estimates of the entropies of pyrope and andradite show large discrepancies when compared with experimental reversals.Contribution no. 600 from the Mineralogical Laboratory, The Department of Geology and Mineralogy, The University of Michigan, Ann Arbor, Michigan 48109, USA     

Coalification history of the Stephanian Ciñera-Matallana pull-apart basin,NW Spain: Combining anisotropy of vitrinite reflectance and thermal modelling

The Stephanian Ciñera-Matallana Basin of NW Spain comprises 1,500 m of alluvial to lacustrine coal-bearing sediments, which were deposited in a late Variscan transtensional/transpressional pull-apart setting. The relationship between coalification pattern and rock deformation was evaluated by measurements of the anisotropy of vitrinite reflectance (AVR). The AVR ellipsoids reveal both pre-tectonic elements related to the bedding fabric and syn-tectonic elements related to folding, producing biaxial ellipsoid shapes with the maximum reflectance parallel to fold axes. The mean coalification gradient for the Stephanian succession is about 0.62 %Rr/km. Calculations of the mean palaeo-geothermal gradient are presented on the basis of three different empirical equations. A palaeo-geothermal gradient of 85 °C/km is considered the most realistic, with an overburden of about 1,000 m. 1-D numerical modelling of the burial history results in two possible scenarios, the most preferable involving a palaeo-heat flow of 150 mW/m² and an overburden of ca. 1,050 m. These results indicate that maximum coalification was related to a localised but high palaeo-heat flow/-geothermal gradient. The anisotropy of vitrinite reflectance highlights the interactive and transitional nature of sedimentary compaction and rock deformation on the maturation of organic material within strike-slip fault zones.     

How to Earn the Status of Honest Broker? Scientists’ Roles Facilitating the Political Water Supply Decision-Making Process

“Honest broker” refers to scientists facilitating complex political decisions from a neutral position, aiming to expand the scope of choice available instead of advocating a certain policy. This article reflects on the experiences of three scientists acting as honest brokers while carrying out a multicriteria evaluation to help politicians choose the water supply option for the city of Oulu, Finland. The process was considered successful and many politicians said that they have never before been that well informed when making a decision. The case primarily shows that besides the common knowledge brokerage roles targeting knowledge exchange, the honest brokerage approach relates more to managing social relationships and balancing political games and rapidly evolving discussions. Trustful relationships increased the perceived credibility of the brokers and ensured two-way communication. On the other hand, the brokers faced ethical dilemmas and difficulties of staying impartial while finding out confidential information related to political strategies.     

1–5 μm imaging of 3CRR galaxies: the K–z relation and the geometry of the torus

It has been claimed by Taylor et al. that the low-redshift end of the K – z relation for radio galaxies is too bright by about half a magnitude owing to contributions from the obscured quasar nuclei. Such a result has major implications for the use of the K -band Hubble diagram in understanding the cosmological evolution of radio galaxies. In this paper we present 1–5-μm imaging data of a nearly complete sample of low-redshift radio galaxies; this approach allows us to determine accurately the strengths of any unresolved nuclear components in the galaxies. We detect nuclear sources in five targets, whose broad-band colours are consistent with reddened quasar spectra. In all the five cases the ratio of the inferred intrinsic near-infrared luminosity to the narrow-line luminosity is typical of quasars. We find a correlation between the inferred nuclear extinction and core-to-lobe ratio, which places constraints on the geometry of the torus. We find evidence for a shift of the K – z relation to fainter magnitudes, but by a much smaller amount (∼0.1 mag) than determined by Taylor et al. Under the assumption that the nuclear sources in radio galaxies have the same intrinsic near-infrared spectra as quasars, our multiwavelength images allow us to limit any possible shift to less than 0.3 mag.     

Regime of carbon compounds in carbonatites in Uzbekistan: Evidence from carbon isotopic composition and thermodynamic simulations

Thermodynamic analysis of equilibria between minerals (with regard for their compositions) in carbonatites of the Chagatai complex, Uzbekistan, provides us with the possibility of estimating the oxygen fugacity at which carbonates could occur in equilibrium with elementary carbon. Isotopic studies and thermodynamic simulations show that graphite started to crystallize at 775°C and an oxygen fugacity value approximately one logarithmic unit below the QFM buffer and continued to crystallize with further cooling, simultaneously with a decrease in the Ti concentration in the equilibrium magnetite. Graphite crystallized from carbonatite melt at higher temperatures and likely precipitated from hydrothermal fluid at lower temperatures. The composition of gas in equilibrium with graphite in the C-H-O system was calculated for oxygen fugacity values evaluated for the Chagatai carbonatites. Inasmuch as the values of oxygen potential are almost identical in graphite- and diamond-bearing carbonatites, the presence of graphite in carbonatite dikes and diatremes can be regarded as a prospecting guide in exploration for diamondiferous carbonatites.     

Shock experiments in range of 10–45 GPa with small multidomain magnetite in porous targets

Abstract– Physical properties of multidomain magnetite‐bearing porous pellets shocked up to 45 GPa were measured. The results show general magnetic softening as a result of shock. However, a relative magnetic hardening trend and slight magnetic susceptibility decrease is observed with increasing pressure among shocked samples. Initially, the shock also seems to cause a slight decrease in porosity, but at higher shock pressures macroscopic porosity increases progressively in our pellets. The microscopic porosity remains almost unchanged. Since our samples have distinctly higher initial porosity compared with samples used in previous studies, our results may be representative for impacts into highly porous magnetite‐bearing sedimentary or volcanic rocks and are relevant to impacts into such target rocks on Earth and Mars.     

Terrestrial impact craters: Their spatial and temporal distribution and impacting bodies

The terrestrial impact record contains currently ~145 structures and includes the morphological crater types observed on the other terrestrial planets. It has, however, been severely modified by terrestrial geologic processes and is biased towards young (≤ 200 Ma) and large (≥ 20 km) impact structures on relatively well-studied cratonic areas. Nevertheless, the ground-truth data available from terrestrial impact structures have provided important constraints for the current understanding of cratering processes. If the known sample of impact structures is restricted to a subsample in which it is believed that all structures ≥ 20 km in diameter (D) have been discovered, the estimated terrestrial cratering rate is 5.5±2.7 × 10^?15km^?2a^?1 for D ≥ 20 km. This rate estimate is equivalent to that based on astronomical observations of Earth-crossing bodies. These rates are a factor of two higher, however, than the estimated post-mare cratering rate on the moon but the large uncertainties preclude definitive conclusions as to the significance of this observation. Statements regarding a periodicity in the terrestrial cratering record based on time-series analyses of crater ages are considered unjustified, based on statistical arguments and the large uncertainties attached to many crater age estimates. Trace element and isotopic analyses of generally siderophile group elements in impact lithologies, particularly impact melt rocks, have provided the basis for the identification of impacting body compositions at a number of structures. These range from meteoritic class, e.g., C-1 chondrite, to tentative identifications, e.g., stone?, depending on the quality and quantity of analytical data. The majority of the identifications indicate chondritic impacting bodies, particularly with respect to the larger impact structures. This may indicate an increasing role for cometary impacts at larger diameters; although, the data base is limited and some identifications are equivocal. To realize the full potential of the terrestrial impact record to constrain the character of the impact flux, it will be necessary to undertake additional and systematic isotopic and trace element analyses of impact lithologies at well-characterized terrestrial impact structures.