Gas-Phase OH Oxidation of Monoterpenes: Gaseous and Particulate Products

Smog chamber experiments have beenconducted in which cyclic monoterpenes were oxidisedin the gas phase by OH. The evolved secondary organicaerosol (SOA) was analysed by LC-MSⁿ and thegas-phase products were analysed by FT-IR. Theconcentrations of the identified compoundscorresponded to carbon mass balances in the range of40%–90%. The identified compounds in the particularphase corresponded to 0.5%–4.2% of the reactedcarbon. The most abundant compounds in SOA fromterpenes with an endocyclic C=C double bond wereC₁₀-keto-aldehydes, C₁₀-keto-carboxylicacids, C₁₀-hydroxy-keto-carboxylic acids, andC₁₀-hydroxy-keto-aldehydes (pinonaldehyde,pinonic acid, hydroxy-pinonic acid isomers, andhydroxy-pinonaldehyde isomers from -pinene;3-caronaldehyde, 3-caronic acid, hydroxy-3-caronicacid isomers, and hydroxy-3-caronaldehyde isomers from3-carene). The most abundant compounds in SOA fromterpenes with an exocyclic C=C double bond wereC₉-ketones, C₉-dicarboxylic acids, andC₁₀-hydroxy-keto-carboxylic acids (nopinone,pinic acid, and hydroxy-pinonic acid isomers from-pinene; sabinaketone, sabinic acid andhydroxy-sabinonic acid isomers from sabinene).Decarboxylated analogues of most of the compounds werepresent in SOA in minor concentrations, such asC₉-keto-carboxylic acids (norpinonic acid,nor-3-caronic acid) and C₈-dicarboxylic acids(norpinic acid, nor-3-caric acid, norsabinic acid). InSOA from limonene, which contains an endocyclic aswell as an exocyclic C=C double bond, the mostabundant compounds were a C₁₀-keto-aldehyde andits oxo-derivative (limononaldehyde and keto-limononaldehyde) together with hydroxy-derivatives of aC₁₀-keto-carboxylic acid (isomers ofhydroxy-limononic acid). Also aC₁₀-keto-carboxylic acid (limononic acid) waspresent together with minor concentrations of aC₉-dicarboxylic acids (limonic acid), itsoxo-derivative (keto-limonic acid), and itsdecarboxylated analogue (norlimonic acid). Mechanisticpathways for the formation of these products, some ofwhich are identified here for the first time, areproposed.     

Mineralogical and chemical composition and cosmic‐ray exposure history of two mesosiderites and two iron meteorites

Abstract— We performed a comprehensive study of the noble gas isotopic abundances, radionuclide activities, and mineralogical and chemical composition of two mesosiderites and two iron meteorites. For the mesosiderites Dong Ujimqin Qi and Weiyuan, the silicate and the metal phases were studied. The anomalous ataxite Rafrüti is not chemically related to any other meteorite class, whereas Ningbo is a type IVA octahedrite. The mineralogy and major and trace element abundances of the silicate phases of Dong Ujimqin Qi and Weiyuan are similar to those of other mesosiderites and distinct from those of the howardites. The cosmic‐ray exposure history was studied based on the concentrations of the cosmogenic noble gas nuclei and radionuclide activities. For the iron meteorites, cosmic‐ray exposure ages were calculated from the pairs ¹⁰Be‐²¹Ne, ²⁶Al‐²¹Ne, and ³⁶Cl‐³⁶Ar. Rafrüti yields the youngest exposure age of all ataxites (6.8 ± 1.7 Ma), whereas that of Ningbo with 107 ± 15 Ma falls within the range observed for the other octahedrites. The parent body break‐up times of the mesosiderites Dong Ujimqin Qi and Weiyuan are 252 ± 50 and 25.9 ± 5.0 Ma, respectively. We find no evidence for a common break‐up event for the mesosiderites and the howardites.     

Ensemble-Based Seismic and Production Data Assimilation Using Selection Kalman Model

Data assimilation in reservoir modeling often involves model variables that are multimodal, such as porosity and permeability. Well established data assimilation methods such as ensemble Kalman filter and ensemble smoother approaches, are based on Gaussian assumptions that are not applicable to multimodal random variables. The selection ensemble smoother is introduced as an alternative to traditional ensemble methods. In the proposed method, the prior distribution of the model variables, for example the porosity field, is a selection-Gaussian distribution, which allows modeling of the multimodal behavior of the posterior ensemble. The proposed approach is applied for validation on a two-dimensional synthetic channelized reservoir. In the application, an unknown reservoir model of porosity and permeability is estimated from the measured data. Seismic and production data are assumed to be repeatedly measured in time and the reservoir model is updated every time new data are assimilated. The example shows that the selection ensemble Kalman model improves the characterisation of the bimodality of the model parameters compared to the results of the ensemble smoother.

     

Approximate dynamic model of embedded foundation in time domain

A discrete model to represent the unbounded soil (halfspace) in a soil–structure interaction analysis in the time domain is developed. For each dynamic degree of freedom of the foundation node, the discrete model consists of a mass M₀ which is attached to a rigid support with a spring K and with a damper C₀. In addition, a free node with the mass M₁ is introduced, which is connected to the foundation node with a damper C₁. All coefficients are frequency-independent. The discrete model is semi-empirical. It is based on a semi-infinite truncated cone, whereby, after enforcing the static stiffness, the remaining parameters are modified to achieve an optimal fit of the dynamic-stiffness coefficient in the frequency domain. The spring K is equal to the static stiffness. The coefficients appearing in the equations for the dampers C₀, C₁ and the masses M₀, M₁ are specified (assuming a homogeneous halfspace) for the disc, the embedded cylinder, the rectangle (also embedded) and the strip. A square on a layer whose stiffness increases with depth resting on a homogeneous halfspace is also treated. For an embedded foundation, eccentricities arise. Material damping increases the damper C₀ and the mass M₀.     

Anatomy of a late Pleistocene clinoformal sedimentary body (Le Castella,Calabria, southern Italy): A case of prograding spit system?

The Le Castella marine terrace is the smallest and youngest terrace of the Crotone area (southern Italy), and formed after a rapid marine ingression due to a glacio-eustatic rise outpacing the regional uplift of the area. The most prominent feature of the terrace deposits is a seaward-accreting clinoform about 10 m thick, inferred to be formed during forced regressive conditions. This prograding body is mostly composed of bioclastic material, and shows an internal complexity consisting of alternating oblique and sigmoid elementary units inferred to be produced mainly by changes of accommodation development. Foreset avalancing was due to sediment accumulation by gravity-flow processes, while topsets were characterized by the migration of medium- to large-scale dunes showing a unimodal palaeocurrent pattern, oblique with respect to the dip direction of the large-scale clinoform foresets. The Le Castella clinoform starts to develop from a topographic step on the basement due to tectonics, which also controlled the palaeoshoreline trend.The recognized stratigraphic and facies architectures, the palaeocurrent pattern, and the inferred palaeogeographic setting during deposition, all suggest that the Le Castella clinoform is an example of spit system attached to the mainland and accreted due to longshore transport. The present example contributes to establish criteria allowing the recognition of ancient spit systems, which still are poorly known and rarely documented in the pre-Quaternary geological record.     

Novel mechanism of stream formation in coastal wetlands by crab–fish–groundwater interaction

A novel mechanism of stream development in coastal wetlands was observed in the form of interaction between the burrowing crab (Chasmagnathus granulata) and groundwater seepage. This process may eventually be further promoted by the predatory action of the white croaker fish (Micropogon opercularis). These so-called crab streams occur on the banks of major tidal channels in a salt marsh of the Bahía Blanca Estuary (Argentina). As the tide recedes, water is retained in the crab burrows on the marsh surface. The presence of lateral burrows produced by crab recruits promotes subterranean piping flow driven by the hydraulic head in the vertical burrow. Groundwater generally seeps along the tidal channel banks but is particularly prominent and concentrated where crab burrows perforate the banks. Where predatory attacks by the croaker fish enlarge the burrow mouths, the drainage rills become wider and deeper because more seeping water is collected in the shallow crater from where it is funnelled into the developing streams. The crab stream is then produced by water draining from the crab burrow mouth, acting initially by cut-back erosion and followed by forward erosion of the relatively unconsolidated muddy sediments.     

Multi‐scale modelling approach for the pushover analysis of existing RC shear walls—Part II: Experimental verification

In a companion paper two different modelling approaches have been described, operating at the meso‐scale of the fibre elements and at the micro‐scale of the finite element (FE) method. The aim of this paper is to explore the efficiency of these models in the pushover analysis for the seismic assessment of existing reinforced concrete (RC) structures. To this purpose a prototype reference structure, one of the RC shear walls designed according to the multi‐fuse concept and tested on shaking table for the CAMUS Project, is modelled at different levels of refinement. At the micro‐scale the reinforcement and anchorage details are described with increasing accuracy in separate models, whereas at the meso‐scale one single model is used, where each element represents a large part of the structure. Static incremental non‐linear analyses are performed with both models to derive a capacity curve enveloping the experimental results and to reproduce the damage pattern at the displacement level where failure is reached. The comparison between experimental and numerical results points out the strong and weak points of the different models inside the procedure adopted, and the utility of an integration of results from both approaches. This study confirms, even for the rather difficult case at study, the capability of the pushover in reproducing the non‐linear dynamic response, both at a global and a local level, and opens the way to the use of the models within a displacement‐based design and assessment procedure. Copyright © 2007 John Wiley & Sons, Ltd.     

Surface velocity fields of active rock glaciers and ice-debris complexes in the Central Andes of Argentina

Rock glaciers and transitional ice-debris complexes predominate the Central Andean landform assemblage, yet regional studies on their state of activity and their kinematics remain sparse. Here we utilize the national glacier inventory of Argentina to quantify surface velocity fields of 244 rock glaciers and 51 ice-debris complexes, located in the Cordón del Plata range, Argentina. Applying a feature-tracking approach to repeated RapidEye satellite imagery acquired between 2010 and 2017/18, we find mean displacement rates between 0.37 and 2.61 m year⁻¹ for 149 landforms, while for the remaining 146 features, surface movement remains below our level of detection. We compare our satellite-derived velocity fields with ground-truth data from two local field sites and find closely matching results in magnitude and spatial distribution. With average displacement of one-third of the active rock glaciers and ice-debris complexes exceeding 1 m year⁻¹, the region hosts an exceptional number of fast-flowing periglacial landforms, compared to other mountain belts. Using a random forest model, we test the predictive power of 25 morphometric and topoclimatic candidate predictors for modelling the state of activity of rock glaciers and ice-debris complexes on two different scales. For entire landforms and individual landform segments, constructed along displacement centrelines, we can predict the state of activity with overall accuracies of 70.08% (mean AUROC = 0.785) and 74.86% (mean AUROC = 0.753), respectively. While topoclimatic parameters such as solar radiation and elevation are most important for entire landforms, geometric parameters become more important at the scale of landform segments. Despite tentative correlations between local slope and surface kinematics, our results point to factors integrating slope and distance to the source to govern local deformation. We conclude that feature tracking in optical imagery is feasible for regional studies in remote regions and provides valuable insight into the current state of the Andean cryosphere. © 2020 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd     

Corrections of Systematic Errors and Data Homogenisation in the Daily Temperature Padova Series (1725–1998)

The correction, validation and homogenisation of the long temperature series of Padova (1725–1998) are discussed. After a careful historical investigation made in order to discover the metadata concerning the series, i.e., instrument features, calibrating methodologies, operational procedures (i.e., exposure, timing and number of daily observations), instrument maintenance, relocations and instrument replacements, the series has been corrected for all the systematic errors derived from any change in the instruments or the operative methodology. Above all, correction focused on instrumental drift, scale expansion, building influence, relationship between indoor-outdoor measurements, minima and maxima evaluation from observations performed at different times, homogenisation for difference of level and change of site. Statistical tests applied to the data and the comparison with other known series has clarified some uncertainties about exposure and operational procedures that the historical analysis of metadata was unable to solve. Moreover, gaps have been filled after the comparison of the series with others of neighbouring sites. The critical work of debugging, correcting, validating and homogenising the series is essential for a correct interpretation of data, as in some cases the errors that have been corrected have been found to be greater than the climate signal. Especially in the early period, the algebraic sum of the corrections of the mean daily temperature exceeds 8 ° C, where monthly corrections can reach 6 ° C. After correction, validation and homogenisation, the linear trend of the Padova series is positive, +0.31 ° C/100 yr over the period1774–today. Looking at post-industrial warming, the temperature rise is+0.44 ° C in the last 130 years, which means +0.34 ° C/100 yr, not farfrom the above bulk average.