Atmospheric chemistry of hydrogen fluoride

Although a large volume of monitoring and computer simulation data exist for global coverage of HF, study of HF in the troposphere is still limited to industry whose primary interest is the safety and risk assessment of HF release because it is a toxic gas. There is very limited information on atmospheric chemistry, emission sources, and the behavior of HF in the environment. We provide a comprehensive review on the atmospheric chemistry of HF, modeling the reactions and transport of HF in the atmosphere, the removal processes in the vertical layer immediately adjacent to the surface (up to approximately 500 m) and recommend research needed to improve our understanding of atmospheric chemistry of HF in the troposphere. The atmospheric chemistry, emissions, and surface boundary layer transport of hydrogen fluoride (HF) are summarized. Although HF is known to be chemically reactive and highly soluble, both factors affect transport and removal in the atmosphere, the chemistry can be ignored when the HF concentration is at a sufficiently low level (e.g., 10 ppmv). At a low concentration, the capability for HF to react in the atmosphere is diminished and therefore the species can be mathematically treated as inert during the transport. At a sufficiently high concentration of HF (e.g., kg/s release rate and thousands of ppm), however, HF can go through a series of rigorous chemical reactions including polymerization, depolymerization, and reaction with water to form molecular complex. As such, the HF species cannot be considered as inert because the reactions could intimately influence the plume’s thermodynamic properties affecting the changes in plume temperature and density. The atmospheric residence time of HF was found to be less than four (4) days, and deposition (i.e., atmosphere to surface transport) is the dominant mechanism that controls the removal of HF and its oligomers from the atmosphere. The literature data on HF dry deposition velocity was relatively high compared to many commonly found atmospheric species such as ozone, sulfur dioxide, nitrogen oxides, etc. The global average of wet deposition velocity of HF was found to be zero based on one literature source. Uptake of HF by rain drops is limited by the acidity of the rain drops, and atmospheric particulate matter contributes negligibly to HF uptake. Finally, given that the reactivity of HF at a high release rate and elevated mole concentration cannot be ignored, it is important to incorporate the reaction chemistry in the near-field dispersion close to the proximity of the release source, and to incorporate the deposition mechanism in the far-field dispersion away from the release source. In other words, a hybrid computational scheme may be needed to address transport and atmospheric chemistry of HF in a range of applications. The model uncertainty will be limited by the precision of boundary layer parameterization and ability to accurately model the atmospheric turbulence.     

Multi-Source Emission Determination Using an Inverse-Dispersion Technique

Inverse-dispersion calculations can be used to infer atmospheric emission rates through a combination of downwind gas concentrations and dispersion model predictions. With multiple concentration sensors downwind of a compound source (whose component positions are known) it is possible to calculate the component emissions. With this in mind, a field experiment was conducted to examine the feasibility of such multi-source inferences, using four synthetic area sources and eight concentration sensors arranged in different configurations. Multi-source problems tend to be mathematically ill-conditioned, as expressed by the condition number κ. In our most successful configuration (average κ = 4.2) the total emissions from all sources were deduced to within 10% on average, while component emissions were deduced to within 50%. In our least successful configuration (average κ = 91) the total emissions were calculated to within only 50%, and component calculations were highly inaccurate. Our study indicates that the most accurate multi-source inferences will occur if each sensor is influenced by only a single source. A “progressive” layout is the next best: one sensor is positioned to “see” only one source, the next sensor is placed to see the first source and another, a third sensor is placed to see the previous two plus a third, and so on. When it is not possible to isolate any sources κ is large and the accuracy of a multi-source inference is doubtful.     

Statistical estimation of high-resolution surface air temperature from MODIS over the Yangtze River Delta,China

High-resolution surface air temperature data are critical to regional climate modeling in terms of energy balance, urban climate change, and so on. This study demonstrates the feasibility of using Moderate Resolution Imaging Spectroradiometer (MODIS) land surface temperature (LST) to estimate air temperature at a high resolution over the Yangtze River Delta region, China. It is found that daytime LST is highly correlated with maximum air temperature, and the linear regression coefficients vary with the type of land surface. The air temperature at a resolution of 1 km is estimated from the MODIS LST with linear regression models. The estimated air temperature shows a clear spatial structure of urban heat islands. Spatial patterns of LST and air temperature differences are detected, indicating maximum differences over urban and forest regions during summer. Validations are performed with independent data samples, demonstrating that the mean absolute error of the estimated air temperature is approximately 2.5°C, and the uncertainty is about 3.1°C, if using all valid LST data. The error is reduced by 0.4°C (15%) if using best-quality LST with errors of less than 1 K. The estimated high-resolution air temperature data have great potential to be used in validating high-resolution climate models and other regional applications.     

Glauconites from the Late Palaeocene — Early Eocene Naredi Formation,western Kutch and their genetic implications

Glauconitic minerals are considered as one of the valuable input parameters in sequence stratigraphic analysis of a basin. In the present study glauconitic minerals are reported from subtidal green shale facies in the lower part of the Late Paleocene-Early Eocene Naredi Formation of western Kutch. On the basis of the foraminiferal assemblage the glauconite bearing beds are interpreted to have formed in a mid shelf depositional settings of an unstable marine conditions. XRD studies confirm the glauconite mineralogy of the green pellets and provide an estimation of glauconite maturity. Textural attributes of the glauconites confirm their derivation by different degrees of alteration of precursor feldspar grains. Because of the authigenic origin and autochthonous nature, these glauconites hold promise for understanding sequence stratigraphy of the Palaeogene succession of the western Kutch.     

Formation of the adakite-like granitoid complex and porphyry copper-gold deposit in Shaxi from southern Tancheng-Lujiang fault belt： A clue to the West Pacific plate subduction

On the basis of the geological and geochemical studies, including chemical analysis of bulk rocks, rare-earth and trace element studies, fluid inclusion, and S and O isotopic analyses, the authors described the geo-logical background of the deposit in detail and presented significant proofs for the conditions of formation of the Shaxi porphyry copper-gold deposit. Compared with other large and supper-large porphyry copper deposits in China and the adjacent Cu-Au mineralized areas, the ore-forming processes and conditions were analyzed; and the possibil-ity of forming large porphyry copper deposits in the Shaxi area was discussed. The present study indicated that the ore-forming fluid and material were mainly of magmatic origin, while meteoric water played a certain role in the ore-forming processes. Interactions between subducting and overriding plates provided a major driving force for the formation of igneous rocks and the deposition of metal elements in East China since Jurassic. Based on the geo-chemical data of the Shaxi intrusive, it is found that the copper (gold) mineralization is closely related to the genesis of adakite-like intrusive in the Shaxi area. This adakite-like intrusive was formed in the subduction environment as a result of the subduction of the West Pacific plate toward the East China continent, where there is a great potential-ity to form a large porphyry copper deposit.     

Raman spectroscopic study of K-lingunite at various pressures and temperatures

K-lingunite is a high-pressure modification of K-feldspar that possesses the tetragonal hollandite structure. Variations of the Raman spectra of K-lingunite were studied up to ~31.5 GPa at room temperature, and in the range 79–823 K at atmospheric pressure. The Raman frequencies of all bands were observed to increase with increasing pressure, and decrease with increasing temperature for K-lingunite. This behavior is in line with those observed for most of other materials. New sharp Raman bands appear at pressures greater than 13–15 GPa, suggesting a phase transition in K-lingunite with increasing pressure. The transition is reversible when pressure was released. The appearance of these new Raman bands may correspond to the phase transition revealed earlier at around 20 GPa by X-ray diffraction studies. Instead of transforming back to its stable minerals, such as orthoclase, microcline or sanidine, K-lingunite became amorphous in the temperature range 803–823 K at atmospheric pressure.     

Fragmentation during Rock Falls: Two Italian Case Studies of Hard and Soft Rocks

In recent years, rock fall phenomena in Italy have received considerable attention for risk mitigation through in situ observations and experimental data. This paper reports the study conducted at Camaldoli Hill, in the urban area of Naples, and at Monte Pellegrino, Palermo, Italy. The rocks involved are volcanic Neapolitan yellow tuff (NYT) in the former area and dolomitic limestone in the latter. Both rocks, even though with different strength characteristics, have shown a significant tendency towards rock fragmentation during run out. This behavior was first investigated by comparing the volumes of removable blocks on the cliff faces (V ₀) and fallen blocks on the slopes (V _f). It was assumed that the ratio V _f/V ₀ decreases with the distance (x _f) from the detachment area by an empirical law, which depends on a coefficient α, correlated with the geotechnical properties of the materials involved in the rock fall. Finally, this law was validated by observation of well-documented natural rock falls (Palermo) and by in situ full-scale tests (Naples). From the engineering perspective, consideration of fragmentation processes in rock fall modeling provides a means for designing low-cost mitigation measures.     

Climatic change and Chinese population growth dynamics over the last millennium

The climate–population relationship has long been conceived. Although the topic has been repeatedly investigated, most of the related works are Eurocentric or qualitative. Consequently, the relationship between climate and population remains ambiguous. In this study, fine-grained temperature reconstructions and historical population data sets have been employed to statistically test a hypothesized relationship between temperature change and population growth (i.e., cooling associated with below average population growth) in China over the past millennium. The important results were: (1) Long-term temperature change significantly determined the population growth dynamics of China. However, spatial variation existed, whilst population growth in Central China was shown to be responsive to both long- and short-term temperature changes; in marginal areas, population growth was only sensitive to short-term temperature fluctuations. (2) Temporally, the temperature–population relationship was obscured in some periods, which was attributable to the factors of drought and social buffers. In summary, a temperature–population relationship was mediated by geographic factors, the aridity threshold, and social factors. Given the upcoming threat posed by climate change to human societies, this study seeks to improve our knowledge and understanding of the climate–society relationship.     

A Parameterization of Dry Thermals and Shallow Cumuli for Mesoscale Numerical Weather Prediction

For numerical weather prediction models and models resolving deep convection, shallow convective ascents are subgrid processes that are not parameterized by classical local turbulent schemes. The mass flux formulation of convective mixing is now largely accepted as an efficient approach for parameterizing the contribution of larger plumes in convective dry and cloudy boundary layers. We propose a new formulation of the EDMF scheme (for Eddy Diffusivity\Mass Flux) based on a single updraft that improves the representation of dry thermals and shallow convective clouds and conserves a correct representation of stratocumulus in mesoscale models. The definition of entrainment and detrainment in the dry part of the updraft is original, and is specified as proportional to the ratio of buoyancy to vertical velocity. In the cloudy part of the updraft, the classical buoyancy sorting approach is chosen. The main closure of the scheme is based on the mass flux near the surface, which is proportional to the sub-cloud layer convective velocity scale w _*. The link with the prognostic grid-scale cloud content and cloud cover and the projection on the non- conservative variables is processed by the cloud scheme. The validation of this new formulation using large-eddy simulations focused on showing the robustness of the scheme to represent three different boundary layer regimes. For dry convective cases, this parameterization enables a correct representation of the countergradient zone where the mass flux part represents the top entrainment (IHOP case). It can also handle the diurnal cycle of boundary-layer cumulus clouds (EUROCS\ARM) and conserve a realistic evolution of stratocumulus (EUROCS\FIRE).     

Experimental Investigation of Turbulent Momentum Transfer in a Neutral Boundary Layer over a Rough Surface

The turbulent characteristics of the neutral boundary layer developing over rough surfaces are not well predicted with operational weather-forecasting models. The problem is attributed to inadequate mixing-length models, to the anisotropy of the flow and to a lack of controlled experimental data against which to validate numerical studies. Therefore, in order to address directly the modelling difficulties for the development of a neutral boundary layer over rough surfaces, and to investigate the turbulent momentum transfer of such a layer, a set of hydraulic flume experiments were carried out. In the experiments, the mean and turbulent quantities were measured by a particle image velocimetry (PIV) technique. The measured velocity variances and fluxes \({(\overline{{u_{i}^{\prime}}{u_{j}^{\prime}}})}\) in longitudinal vertical planes allowed the vertical and longitudinal gradients (?/?z and ?/?x) of the mean and turbulent quantities (fluxes, variances and third-order moments) to be evaluated and the terms of the evolution equations for ?e/?t, \({\partial \overline{u^{\prime 2}}/\partial t}\), \({\partial \overline{w^{\prime 2}}/\partial t}\) and \({\partial \overline{{u^{\prime}}{w^{\prime}}}/\partial t}\) to be quantified, where e is the turbulent kinetic energy. The results show that the pressure-correlation terms allow the turbulent energy to be transferred equitably from \({\overline{{u^{\prime}}^{2}}}\) to \({\overline{{w^{\prime}}^{2}}}\). It appears that the repartition between the constitutive terms of the budget of e, \({\overline{{u^{\prime}}^{2}}}\), \({\overline{{w^{\prime}}^{2}}}\) and \({\overline{{u^{\prime}}{w^{\prime}}}}\) is not significantly affected by the development of the rough neutral boundary layer. For the whole evolution, the transfers of energy are governed by the same terms that are also very similar to the smooth-wall case. The PIV measurements also allowed the spatial integral scales to be computed directly and to be compared with the dissipative and mixing length scales, which were also computed from the data.