An insight into the formation of severe ozone episodes: modeling the 21/03/01 event in the ESCOMPTE region

High ozone concentrations are observed more and more frequently in the lower troposphere. The development of such polluted episodes is linked to a complex set of chemical, physical and dynamical parameters that interact with each other. To improve air quality, it is necessary to understand and quantify the role of all these processes on the intensity of ozone formation. The ESCOMPTE program, especially dedicated to the numerical simulation of photochemical episodes, offers an ideal frame to investigate details of the roles of many of these processes through 3D modeling. This paper presents the analysis, with a 3D eulerian model, of a severe and local episode of ozone pollution that occurred on the 21st of March 2001 in the ESCOMPTE region. This episode is particularly interesting due to the intensity of the observed ozone peaks (450 μg/m³ during 15 mn) but also because it did not occur in summer but at the beginning of spring. As part of the premodeling work of the ESCOMPTE program, this study focuses on the sensitivity of the simulated ozone peaks to various chemical and physical phenomena (long-range transport, industrial emissions, local dynamic phenomena…) to determine their influence on the rise of high local photooxidant concentrations and to better picture the photochemistry of the ESCOMPTE region. Through sensitivity tests to dynamical calculation resolution and emissions, this paper shows how the combination of sea and pond breezes with emissions of reactive VOCs can generate local intense ozone peaks.     

Si stable isotopes in the Earth's surface: A review

Silicon (Si) is the second most abundant element on Earth after oxygen. Only few studies have attempted to use stable isotopes of Si as proxies for understanding the Si cycle and its variations in the past. By using three different methods (IRMS, MC–ICP–MS and SIMS), the overall measurements show that the isotopic composition (δ³⁰Si) of terrestrial samples ranges from − 5.7‰ to + 3.4‰. Dissolved Si in rivers and seawater is ³⁰Si-enriched (− 0.8‰ < δ³⁰Si < + 3.4‰) compared to Si in endogeneous rocks (− 1.1‰ < δ³⁰Si < + 0.7‰). This global enrichment is counterbalanced by the Si-bearing phases (biogenic silica, clays, quartz) where Si is, in average, ³⁰Si-depleted (− 5.7‰ < δ³⁰Si < + 2.6‰). These values are the result of fractionation which have been measured or estimated from − 0.3‰ to − 3.8‰. The fractionation is modeled by two types of approaches: the Rayleigh distillation model (closed system) and the steady-state model (open system). These models have been used in the most recent studies to explain the observed δ³⁰Si variations in continental environments and in the sub-Antarctic Ocean.     

A parallel ensemble-based framework for reservoir history matching and uncertainty characterization

We present a parallel framework for history matching and uncertainty characterization based on the Kalman filter update equation for the application of reservoir simulation. The main advantages of ensemble-based data assimilation methods are that they can handle large-scale numerical models with a high degree of nonlinearity and large amount of data, making them perfectly suited for coupling with a reservoir simulator. However, the sequential implementation is computationally expensive as the methods require relatively high number of reservoir simulation runs. Therefore, the main focus of this work is to develop a parallel data assimilation framework with minimum changes into the reservoir simulator source code. In this framework, multiple concurrent realizations are computed on several partitions of a parallel machine. These realizations are further subdivided among different processors, and communication is performed at data assimilation times. Although this parallel framework is general and can be used for different ensemble techniques, we discuss the methodology and compare results of two algorithms, the ensemble Kalman filter (EnKF) and the ensemble smoother (ES). Computational results show that the absolute runtime is greatly reduced using a parallel implementation versus a serial one. In particular, a parallel efficiency of about 35 % is obtained for the EnKF, and an efficiency of more than 50 % is obtained for the ES.     

A posteriori error estimates, stopping criteria, and adaptivity for two-phase flows

This paper develops a general abstract framework for a posteriori estimates for immiscible incompressible two-phase flows in porous media. We measure the error by the dual norm of the residual and, for mathematical correctness, employ the concept of global and complementary pressures in the analysis. Our estimators allow to estimate separately the different error components, namely, the spatial discretization error, the temporal discretization error, the linearization error, the iterative coupling error, and the algebraic solver error. We propose an adaptive algorithm wherein the different iterative procedures (iterative linearization, iterative coupling, iterative solution of linear systems) are stopped when the corresponding errors do not affect significantly the overall error and wherein the spatial and temporal errors are equilibrated. Consequently, important computational savings can be achieved while guaranteeing a user-given precision. The developed framework covers fully implicit, implicit pressure–explicit saturation, or iterative coupling formulations; conforming spatial discretization schemes such as the vertex-centered finite volume method or the finite element method and nonconforming spatial discretization schemes such as the cell-centered finite volume method, the mixed finite element method, or the discontinuous Galerkin method; linearizations such as the Newton or the fixed-point one; and general linear solvers. Numerical experiments for a model problem are presented to illustrate the theoretical results. Only by stopping timely the linear and nonlinear solvers, speedups by a factor between 10 and 20 in terms of the number of total linear solver iterations are achieved.     

Detecting communities with the multi-scale Louvain method: robustness test on the metropolitan area of Brussels

Detecting communities in large networks has become a common practice in socio-spatial analyses and has led to the development of numerous dedicated mathematical algorithms. Nowadays, however, researchers face a deluge of data and algorithms, and great care must be taken regarding methodological questions such as the values of the parameters and the geographical characteristics of the data. We aim here at testing the sensitivity of multi-scale modularity optimized by the Louvain method to the value of the resolution parameter (introduced by Reichardt and Bornholdt (Phys Rev Lett 93(21):218701, 2004.  https://doi.org/10.1103/PhysRevLett.93.218701) and controlling the size of the communities) and to a number of spatial issues such as the inclusion of internal loops and the delineation of the study area. We compare the community structures with those found by another well-known community detection algorithm (Infomap), and we further interpret the final results in terms of urban geography. Sensitivity analyses are conducted for commuting movements in and around Brussels. Results reveal slight effects of spatial issues (inclusion of the internal loops, definition of the study area) on the partition into job basins, while the resolution parameter plays a major role in the final results and their interpretation in terms of urban geography. Community detection methods seem to reveal a surprisingly strong spatial effect of commuting patterns: Similar partitions are obtained with different methods. This paper highlights the advantages and sensitivities of the multi-scale Louvain method and more particularly of defining communities of places. Despite these sensitivities, the method proves to be a valuable tool for geographers and planners.     

Reliable Determination of Ge in Solid Environmental Samples Using a Chemical Preparation Procedure Developed for Si Isotopes and ICP‐MS Analysis

Germanium (Ge) exists at trace levels in the Earth's crust and is a powerful geochemical tracer of the silicon (Si) cycle. This study proposes a simple and reliable method for determining Ge contents in environmental samples using ICP‐MS. As Si and Ge have very similar chemical properties, we investigated the applicability of the chemical preparation procedure developed for Si isotopes for the determination of Ge in environmental samples. Advantages of this procedure are as follows: (a) efficient removal of the matrix and main interferences affecting Ge determinations by ICP‐MS, (b) a low limit of detection (6 ng l^?1), (c) relative repeatability of approximately 3% obtained on ⁷⁴Ge and (d) robustness and accuracy based on agreement within errors with the published Ge values for rock reference materials (BHVO‐2, AGV‐2 and BCR‐2). This procedure allowed revision of the Ge values of three soil reference materials (1.67 ± 0.09 μg g^?1, 2.41 ± 0.18 μg g^?1, 1.89 ± 0.10 μg g^?1 for GBW 07401, GBW 07404 and GBW 07407, respectively) and proposal of a value for the plant reference material ERM‐CD281 (70 ± 3 μg g^?1). This method provides a convenient procedure for determining Ge mass fractions in environmental samples and opens the possibility of coupling two tracers of the Si biogeochemical cycle with a single measurement procedure.     

Acoustic monitoring of gas emissions from the seafloor. Part I: quantifying the volumetric flow of bubbles

Three decades of continuous ocean exploration have led us to identify subsurface fluid related processes as a key phenomenon in marine earth science research. The number of seep areas located on the seafloor has been constantly increasing with the use of multi-scale imagery techniques. Due to recent advances in transducer technology and computer processing, multibeam echosounders are now commonly used to detect submarine gas seeps escaping from the seafloor into the water column. A growing number of en-route surveys shows that sites of gas emissions escaping from the seafloor are much more numerous than previously thought. Estimating the temporal variability of the gas flow rate and volumes escaping from the seafloor has thus become a challenge of relevant interest which could be addressed by sea-floor continuous acoustic monitoring. Here, we investigate the feasibility of estimating the volumetric flow rates of gas emissions from horizontal backscattered acoustic signals. Different models based on the acoustic backscattering theory of bubbles are presented. The forward volume backscattering strength and the inversion volumetric flow rate solutions were validated with acoustic measurements from artificial gas flow rates generated in controlled sea-water tank experiments. A sensitivity analysis was carried out to investigate the behavior of the 120-kHz forward solution with respect to model input parameters (horizontal distance between transducer and bubble stream, bubble size distribution and ascent rate). The most sensitive parameter was found to be the distance of the bubble stream which can affect the volume backscattering strength by 20 dB within the horizontal range of 0–200 m. Results were used to derive the detection probability of a bubble stream for a given volume backscattering strength threshold according to different bubble flow rates and horizontal distance.     

Acoustic monitoring of gas emissions from the seafloor. Part II: a case study from the Sea of Marmara

A rotating, acoustic gas bubble detector, BOB (Bubble OBservatory) module was deployed during two surveys, conducted in 2009 and 2011 respectively, to study the temporal variations of gas emissions from the Marmara seafloor, along the North Anatolian Fault zone. The echosounder mounted on the instrument insonifies an angular sector of 7° during a given duration (of about 1 h). Then it rotates to the next, near-by angular sector and so forth. When the full angular domain is insonified, the “pan and tilt system” rotates back to its initial position, in order to start a new cycle (of about 1 day). The acoustic data reveal that gas emission is not a steady process, with observed temporal variations ranging between a few minutes and 24 h (from one cycle to the other). Echo-integration and inversion performed on the acoustic data as described in the companion paper of Leblond et al. (Mar Geophys Res, 2014), also indicate important variations in, respectively, the target strength and the volumetric flow rates of individual sources. However, the observed temporal variations may not be related to the properties of the gas source only, but reflect possible variations in sea-bottom currents, which could deviate the bubble train towards the neighboring sector. During the 2011 survey, a 4-component ocean bottom seismometer (OBS) was co-located at the seafloor, 59 m away from the BOB module. The acoustic data from our rotating, monitoring system support, but do not provide undisputable evidence to confirm, the hypothesis formulated by Tary et al. (2012), that the short-duration, non-seismic micro-events recorded by the OBS are likely produced by gas-related processes within the near seabed sediments. Hence, the use of a multibeam echosounder, or of several split beam echosounders should be preferred to rotating systems, for future experiments.     

A 520 year record of summer sunshine for the eastern European Alps based on stable carbon isotopes in larch tree rings

A 520-year stable carbon isotope chronology from tree ring cellulose in high altitude larch trees (Larix decidua Mill.), from the eastern European Alps, correlates more strongly with summer temperature than with summer sunshine hours. However, when instrumental records of temperature and sunshine diverge after AD1980, the tree ring time series does not follow warming summer temperatures but more closely tracks summer sunshine trends. When the tree ring stable carbon isotope record is used to reconstruct summer temperature the reconstruction is not robust. Reconstructed temperatures prior to the twentieth century are higher than regional instrumental records, and the evolution of temperature conflicts with other regional temperature reconstructions. It is concluded that sunshine is the dominant control on carbon isotope fractionation in these trees, via the influence of photosynthetic rate on the internal partial pressure of CO₂, and that high summer (July–August) sunshine hours is a suitable target for climate reconstruction. We thus present the first reconstruction of summer sunshine for the eastern Alps and compare it with the regional temperature evolution.