Current model capabilities for simulating black carbon and sulfate concentrations in the Arctic atmosphere: a multi-model evaluation using a comprehensive measurement data set

The concentrations of sulfate, black carbon (BC) and other aerosols in the Arctic are characterized by high values in late winter and spring (so-called Arctic Haze) and low values in summer. Models have long been struggling to capture this seasonality and especially the high concentrations associated with Arctic Haze. In this study, we evaluate sulfate and BC concentrations from eleven different models driven with the same emission inventory against a comprehensive pan-Arctic measurement data set over a time period of 2 years (2008–2009). The set of models consisted of one Lagrangian particle dispersion model, four chemistry transport models (CTMs), one atmospheric chemistry-weather forecast model and five chemistry climate models (CCMs), of which two were nudged to meteorological analyses and three were running freely. The measurement data set consisted of surface measurements of equivalent BC (eBC) from five stations (Alert, Barrow, Pallas, Tiksi and Zeppelin), elemental carbon (EC) from Station Nord and Alert and aircraft measurements of refractory BC (rBC) from six different campaigns. We find that the models generally captured the measured eBC or rBC and sulfate concentrations quite well, compared to previous comparisons. However, the aerosol seasonality at the surface is still too weak in most models. Concentrations of eBC and sulfate averaged over three surface sites are underestimated in winter/spring in all but one model (model means for January–March underestimated by 59 and 37 % for BC and sulfate, respectively), whereas concentrations in summer are overestimated in the model mean (by 88 and 44 % for July–September), but with overestimates as well as underestimates present in individual models. The most pronounced eBC underestimates, not included in the above multi-site average, are found for the station Tiksi in Siberia where the measured annual mean eBC concentration is 3 times higher than the average annual mean for all other stations. This suggests an underestimate of BC sources in Russia in the emission inventory used. Based on the campaign data, biomass burning was identified as another cause of the modeling problems. For sulfate, very large differences were found in the model ensemble, with an apparent anti-correlation between modeled surface concentrations and total atmospheric columns. There is a strong correlation between observed sulfate and eBC concentrations with consistent sulfate/eBC slopes found for all Arctic stations, indicating that the sources contributing to sulfate and BC are similar throughout the Arctic and that the aerosols are internally mixed and undergo similar removal. However, only three models reproduced this finding, whereas sulfate and BC are weakly correlated in the other models. Overall, no class of models (e.g., CTMs, CCMs) performed better than the others and differences are independent of model resolution.

Using data insertion with the NAME model to simulate the 8 May 2010 Eyjafjallajökull volcanic ash cloud

A data insertion method, where a dispersion model is initialized from ash properties derived from a series of satellite observations, is used to model the 8 May 2010 Eyjafjallajökull volcanic ash cloud which extended from Iceland to northern Spain. We also briefly discuss the application of this method to the April 2010 phase of the Eyjafjallajökull eruption and the May 2011 Grímsvötn eruption. An advantage of this method is that very little knowledge about the eruption itself is required because some of the usual eruption source parameters are not used. The method may therefore be useful for remote volcanoes where good satellite observations of the erupted material are available, but little is known about the properties of the actual eruption. It does, however, have a number of limitations related to the quality and availability of the observations. We demonstrate that, using certain configurations, the data insertion method is able to capture the structure of a thin filament of ash extending over northern Spain that is not fully captured by other modeling methods. It also verifies well against the satellite observations according to the quantitative object-based quality metric, SAL—structure, amplitude, location, and the spatial coverage metric, Figure of Merit in Space.

High-resolution simulation of stack pollutant emissions

[EN]A three-dimensional air pollution model for the short-term simulation of emission, transport and reaction of pollutants is presented. In the finite element simulation of these environmental processes over a complex terrain, a mesh generator capable of adapting itself to the topographic characteristics is essential, A local refinement of tetrahedra is used in order to capture the plume rise. Then a wind field is computed by using a mass-consistent model and perturbing its vertical component to introduce the plume rise effect. Finally, an Eulerian convection-diffusionreaction model is used to simulate the pollutant dispersion…

Modeling surface-atmosphere exchange of trace gases and energy within and above the Amazon rain forest

Die vorliegende Dissertation untersucht die biogeochemischen Vorgänge in der Vegetationsschicht (Bestand) und die Rückkopplungen zwischen physiologischen und physikalischen Umweltprozessen, die das Klima und die Chemie der unteren Atmosphäre beeinflussen. Ein besondere Schwerpunkt ist die Verwendung theoretischer Ansätze zur Quantifizierung des vertikalen Austauschs von Energie und Spurengasen (Vertikalfluss) unter besonderer Berücksichtigung der Wechselwirkungen der beteiligten Prozesse. Es wird ein differenziertes Mehrschicht-Modell der Vegetation hergeleitet, implementiert, für den amazonischen Regenwald parametrisiert und auf einen Standort in Rondonia (Südwest Amazonien) angewendet, welches die gekoppelten Gleichungen zur Energiebilanz der Oberfläche und CO2-Assimilation auf der Blattskala mit einer Lagrange-Beschreibung des Vertikaltransports auf der Bestandesskala kombiniert. Die hergeleiteten Parametrisierungen beinhalten die vertikale Dichteverteilung der Blattfläche, ein normalisiertes Profil der horizontalen Windgeschwindigkeit, die Lichtakklimatisierung der Photosynthesekapazität und den Austausch von CO2 und Wärme an der Bodenoberfläche. Desweiteren werden die Berechnungen zur Photosynthese, stomatären Leitfähigkeit und der Strahlungsabschwächung im Bestand mithilfe von Feldmessungen evaluiert. Das Teilmodell zum Vertikaltransport wird im Detail unter Verwendung von 222-Radon-Messungen evaluiert. Die ``Vorwärtslösung'' und der ``inverse Ansatz'' des Lagrangeschen Dispersionsmodells werden durch den Vergleich von beobachteten und vorhergesagten Konzentrationsprofilen bzw. Bodenflüssen bewertet. Ein neuer Ansatz wird hergeleitet, um die Unsicherheiten des inversen Ansatzes aus denjenigen des Eingabekonzentrationsprofils zu quantifizieren. Für nächtliche Bedingungen wird eine modifizierte Parametrisierung der Turbulenz vorgeschlagen, welche die freie Konvektion während der Nacht im unteren Bestand berücksichtigt und im Vergleich zu früheren Abschätzungen zu deutlich kürzeren Aufenthaltszeiten im Bestand führt. Die vorhergesagte Stratifizierung des Bestandes am Tage und in der Nacht steht im Einklang mit Beobachtungen in dichter Vegetation. Die Tagesgänge der vorhergesagten Flüsse und skalaren Profile von Temperatur, H2O, CO2, Isopren und O3 während der späten Regen- und Trockenzeit am Rondonia-Standort stimmen gut mit Beobachtungen überein. Die Ergebnisse weisen auf saisonale physiologische Änderungen hin, die sich durch höhere stomatäre Leitfähigkeiten bzw. niedrigere Photosyntheseraten während der Regen- und Trockenzeit manifestieren. Die beobachteten Depositionsgeschwindigkeiten für Ozon während der Regenzeit überschreiten diejenigen der Trockenzeit um 150-250%. Dies kann nicht durch realistische physiologische Änderungen erklärt werden, jedoch durch einen zusätzlichen cuticulären Aufnahmemechanismus, möglicherweise an feuchten Oberflächen. Der Vergleich von beobachteten und vorhergesagten Isoprenkonzentrationen im Bestand weist auf eine reduzierte Isoprenemissionskapazität schattenadaptierter Blätter und zusätzlich auf eine Isoprenaufnahme des Bodens hin, wodurch sich die globale Schätzung für den tropischen Regenwald um 30% reduzieren würde. In einer detaillierten Sensitivitätsstudie wird die VOC Emission von amazonischen Baumarten unter Verwendung eines neuronalen Ansatzes in Beziehung zu physiologischen und abiotischen Faktoren gesetzt. Die Güte einzelner Parameterkombinationen bezüglich der Vorhersage der VOC Emission wird mit den Vorhersagen eines Modells verglichen, das quasi als Standardemissionsalgorithmus für Isopren dient und Licht sowie Temperatur als Eingabeparameter verwendet. Der Standardalgorithmus und das neuronale Netz unter Verwendung von Licht und Temperatur als Eingabeparameter schneiden sehr gut bei einzelnen Datensätzen ab, scheitern jedoch bei der Vorhersage beobachteter VOC Emissionen, wenn Datensätze von verschiedenen Perioden (Regen/Trockenzeit), Blattentwicklungsstadien, oder gar unterschiedlichen Spezies zusammengeführt werden. Wenn dem Netzwerk Informationen über die Temperatur-Historie hinzugefügt werden, reduziert sich die nicht erklärte Varianz teilweise. Eine noch bessere Leistung wird jedoch mit physiologischen Parameterkombinationen erzielt. Dies verdeutlicht die starke Kopplung zwischen VOC Emission und Blattphysiologie.

Validation of real time dispersion of Tritium clouds over the Western Mediterranean Basin in different assesments

Real time Tritium concentrations in air coming from an ITER-like reactor as source were coupled the European Centre Medium Range Weather Forecast (ECMWF) numerical model with the lagrangian atmospheric dispersion model FLEXPART. This tool ECMWF/FLEXPART was analyzed in normal operating conditions in the Western Mediterranean Basin during 45 days at summer 2010. From comparison with NORMTRI plumes over Western Mediterranean Basin the real time results have demonstrated an overestimation of the corresponding climatologically sequence Tritium concentrations in air outputs, at several distances from the reactor. For these purpose two clouds development patterns were established. The first one was following a cyclonic circulation over the Mediterranean Sea and the second one was based in the cloud delivered over the Interior of the Iberian Peninsula by another stabilized circulation corresponding to a High. One of the important remaining activities defined then, was the tool qualification. The aim of this paper is to present the ECMWF/FLEXPART products confronted with Tritium concentration in air data. For this purpose a database to develop and validate ECMWF/FLEXPART tritium in both assessments has been selected from a NORMTRI run. Similarities and differences, underestimation and overestimation with NORMTRI will allowfor refinement in some features of ECMWF/FLEXPART

Numerical investigation of seawater intrusion at Gooburrum, Bundaberg, Queensland, Australia

Seawater intrusion in coastal agricultural areas due to groundwater abstraction is a major environmental problem along the northeastern coast of Australia. Management options are being explored using numerical modelling, however, questions remain concerning the appropriate level of sophistication in models, choice of seaward boundary conditions, and how to accommodate heterogeneity and data uncertainty. The choice of seaward boundary condition is important since it affects the amount of salt transported into the aquifers and forms the focus of the present study. The impact of this boundary condition is illustrated for the seawater-intrusion problem in the Gooburrum aquifers, which occur within Tertiary sedimentary strata. A two-dimensional variable-density groundwater and solute-transport model was constructed using the computer code 2DFEMFAT (Cheng et al. 1998). The code was tested against an experiment for a steady-state freshwater-saltwater interface and against the Elder (Elder 1967) free-convection problem. Numerical simulations show that the imposition of the commonly-used equivalent hydrostatic freshwater heads, combined with a constant salt concentration at the seaward boundary, results in overestimated seawater intrusion in the lower Gooburrum aquifer. Since the imposition of this boundary condition allows water flow across the boundary, which subsequently takes salt into the aquifer, a careful check is essential to estimate whether too much mass of salt is introduced.

The close circumstellar environment of Betelgeuse II. Diffraction-limited spectro-imaging from 7.76 to 19.50 mu m with VLT/VISIR

Context. Mass-loss occurring in red supergiants (RSGs) is a major contributor to the enrichment of the interstellar medium in dust and molecules. The physical mechanism of this mass loss is however relatively poorly known. Betelgeuse is the nearest RSG, and as such a prime object for high angular resolution observations of its surface (by interferometry) and close circumstellar environment. Aims. The goal of our program is to understand how the material expelled from Betelgeuse is transported from its surface to the interstellar medium, and how it evolves chemically in this process. Methods. We obtained diffraction-limited images of Betelgeuse and a calibrator (Aldebaran) in six filters in the N band (7.76 to 12.81 mu m) and two filters in the Q band (17.65 and 19.50 mu m), using the VLT/VISIR instrument. Results. Our images show a bright, extended and complex circumstellar envelope at all wavelengths. It is particularly prominent longwards of approximate to 9-10 mu m, pointing at the presence of O-rich dust, such as silicates or alumina. A partial circular shell is observed between 0.5 and 1.0 '' from the star, and could correspond to the inner radius of the dust envelope. Several knots and filamentary structures are identified in the nebula. One of the knots, located at a distance of 0.9 '' west of the star, is particularly bright and compact. Conclusions. The circumstellar envelope around Betelgeuse extends at least up to several tens of stellar radii. Its relatively high degree of clumpiness indicates an inhomogeneous spatial distribution of the material lost by the star. Its extension corresponds to an important intermediate scale, where most of the dust is probably formed, between the hot and compact gaseous envelope observed previously in the near infrared and the interstellar medium.

Mechanistic studies of the 'blue' Cu enzyme, bilirubin oxidase, as a highly efficient electrocatalyst for the oxygen reduction reaction

The 'blue copper' enzyme bilirubin oxidase from Myrothecium verrucaria shows significantly enhanced adsorption on a pyrolytic graphite 'edge' (PGE) electrode that has been covalently modified with naphthyl-2-carboxylate functionalities by diazonium coupling. Modified electrodes coated with bilirubin oxidase show electrocatalytic voltammograms for the direct, four-electron reduction of O(2) by bilirubin oxidase with up to four times the current density of an unmodified PGE electrode. Electrocatalytic voltammograms measured with a rapidly rotating electrode (to remove effects of O(2) diffusion limitation) have a complex shape (an almost linear dependence of current on potential below pH 6) that is similar regardless of how PGE is chemically modified. Importantly, the same waveform is observed if bilirubin oxidase is adsorbed on Au(111) or Pt(111) single-crystal electrodes (at which activity is short-lived). The electrocatalytic behavior of bilirubin oxidase, including its enhanced response on chemically-modified PGE, therefore reflects inherent properties that do not depend on the electrode material. The variation of voltammetric waveshapes and potential-dependent (O(2)) Michaelis constants with pH and analysis in terms of the dispersion model are consistent with a change in rate-determining step over the pH range 5-8: at pH 5, the high activity is limited by the rate of interfacial redox cycling of the Type 1 copper whereas at pH 8 activity is much lower and a sigmoidal shape is approached, showing that interfacial electron transfer is no longer a limiting factor. The electrocatalytic activity of bilirubin oxidase on Pt(111) appears as a prominent pre-wave to electrocatalysis by Pt surface atoms, thus substantiating in a single, direct experiment that the minimum overpotential required for O(2) reduction by the enzyme is substantially smaller than required at Pt. At pH 8, the onset of O(2) reduction lies within 0.14 V of the four-electron O(2)/2H(2)O potential.

Fixed bed reactors with catalyst poisoning - first order kinetics.

The long performance of an isothermal fixed bed reactor undergoing catalyst poisoning is theoretically analyzed using the dispersion model. First order reaction with dth order deactivation is assumed and the model equations are solved by matched asymptotic expansions for large Peclet number. Simple closed-form solutions, uniformly valid in time, are obtained.

The effect of protein binding on the hepatic first pass of O-acyl salicylate derivatives in the rat

In this work the in-situ perfused rat liver has been used to examine the effect of changing the protein content of the perfusate on the hepatic extraction of O-acyl esters of salicylic acid. The hepatic availability (F) of these solutes was studied at a flow-rate of 30 mt min(-1) with perfusate albumin concentrations of 0, 2, and 4% w/v. The hepatic availability of the esters was shown to decrease with increasing carbon-chain length in the O-acyl group; for all the esters the hepatic availability increased with increasing albumin concentration in the perfusate. The dispersion-model-derived efficiency number (R-N) Of the esters was shown to increase with increasing lipophilicity and decrease with increasing albumin concentration in the perfusate. The unbound fraction (f(u),) of the esters decreased with lipophilicity. R-N/f(u), for acetylsalicylic acid remained relatively constant as the albumin concentration was increased. However, R-N/f(u), for n-pentanoyl- and n-hexanoylsalicylic acids increased significantly as albumin concentration increased from 0% to 4%. Thus, for the more lipophilic solutes (n-pentanoyl- and n-hexanoylsalicylic acids) the presence of albumin apparently facilitates the uptake of unbound solute relative to acetylsalicylic acid.

Metabolite mean transit times in the liver as predicted by various models of hepatic elimination

Predicted area under curve (AUC), mean transit time (MTT) and normalized variance (CV2) data have been compared for parent compound and generated metabolite following an impulse input into the liver, Models studied were the well-stirred (tank) model, tube model, a distributed tube model, dispersion model (Danckwerts and mixed boundary conditions) and tanks-in-series model. It is well known that discrimination between models for a parent solute is greatest when the parent solute is highly extracted by the liver. With the metabolite, greatest model differences for MTT and CV2 occur when parent solute is poorly extracted. In all cases the predictions of the distributed tube, dispersion, and tasks-in-series models are between the predictions of the rank and tube models. The dispersion model with mixed boundary conditions yields identical predictions to those for the distributed tube model (assuming an inverse gaussian distribution of tube transit times). The dispersion model with Danckwerts boundary conditions and the tanks-in series models give similar predictions to the dispersion (mixed boundary conditions) and the distributed tube. The normalized variance for parent compound is dependent upon hepatocyte permeability only within a distinct range of permeability values. This range is similar for each model but the order of magnitude predicted for normalized variance is model dependent. Only for a one-compartment system is the MIT for generated metabolite equal to the sum of MTTs for the parent compound and preformed metabolite administered as parent.

Hepatic structure-pharmacokinetic relationships: The hepatic disposition and metabolite kinetics of a homologous series of O-acyl derivatives of salicylic acid

1 The hepatic disposition and metabolite kinetics of a homologous series of O-acyl (acetyl, propionyl, butanoyl, pentanoyl, hexanoyl and octanoyl) esters of salicylic acid (C2SA, C3SA, C4SA, C5SA, C6SA and C8SA, respectively) was determined using a single-pass, in-sills rat liver preparation. 2 The hepatic venous outflow profiles for the parent esters and the generated metabolite, salicylic acid (SA) were analysed by HPLC. Non-parametric moments analysis was used to determine the area under the curve (AUC'), mean transit time (MTT) and normalized variance (CV2) for the parent esters and generated SA. 3 Pregenerated SA ([C-14]-salicylic acid) was injected into each liver with the parent ester to determine its distribution characteristics. 4 The overall recovery of ester plus metabolite was 89% of the ester dose injected and independent of the ester carbon number, suggesting that ester extraction was due to hepatic metabolism to salicylic acid. 5 The metabolite AUC' value increased directly with the lipophilicity of the parent ester (from 0.12 for C2SA to 0.95 for C8SA). By contrast, the parent AUC' decreased with the lipophilicity (from 0.85 for C2SA to zero for C8SA). The metabolite MTT value also showed a trend to increase with the lipophilicity of the parent ester (from 15.72 s for C3SA to 61.97 s for C8SA). However, the parent MTT value shows no significant change across the series. 6 The two-compartment dispersion model was used to derive the kinetic parameters for parent ester, pregenerated SA and generated SA. Consequently, these parameters were used to estimate the values of AUG', MITT and CV2 for the parent ester and metabolite. The moments values obtained using the two-compartment dispersion model show similar trends to the corresponding moments values obtained from the outflow profiles using a non-parametric approach. 7 The more lipophilic aspirin analogues are more confined to the portal circulation after oral administration than aspirin due to their more extensive hepatic elimination avoiding systemic prostacyclin inhibition. Given that aspirin's selectivity as an anti-thrombotic agent has been postulated to be due to selective anti-platelet effects in the portal circulation, the more lipophilic and highly extracted analogues are potentially more selective anti-thrombotic agents than aspirin.

Hepatic disposition and metabolite kinetics of a homologous series of diflunisal esters

The hepatic disposition and metabolite kinetics of a homologous series of diflunisal O-acyl esters (acetyl, butanoyl, pentanoyl, anti hexanoyl) were determined using a single-pass perfused in situ rat liver preparation. The experiments were conducted using 2% BSA Krebs-Henseleit buffer (pH 7.4), and perfusions were performed at 30 mL/min in each liver. O-Acyl esters of diflunisal and pregenerated diflunisal were injected separately into the portal vein. The venous outflow samples containing the esters and metabolite diflunisal were analyzed by high performance liquid chromatography (HPLC). The normalized outflow concentration-time profiles for each parent ester and the formed metabolite, diflunisal, were analyzed using statistical moments analysis and the two-compartment dispersion model. Data (presented as mean +/- standard error for triplicate experiments) was compared using ANOVA repeated measures, significance level P < 0.05. The hepatic availability (AUC'), the fraction of the injected dose recovered in the outflowing perfusate, for O-acetyldiflunisal (C2D = 0.21 +/- 0.03) was significantly lower than the other esters (0.34-0.38). However, R-N/f(u), the removal efficiency number R-N divided by the unbound fraction in perfusate f(u), which represents the removal efficiency of unbound ester by the liver, was significantly higher for the most lipophilic ester (O-hexanoyldiflunisal, C6D = 16.50 +/- 0.22) compared to the other members of the series (9.57 to 11.17). The most lipophilic ester, C6D, had the largest permeability surface area (PS) product (94.52 +/- 38.20 mt min-l g-l liver) and tissue distribution value VT (35.62 +/- 11.33 mL g(-1) liver) in this series. The MTT of these O-acyl esters of diflunisal were not significantly different from one another. However, the metabolite diflunisal MTTs tended to increase with the increase in the parent ester lipophilicity (11.41 +/- 2.19 s for C2D to 38.63 +/- 9.81 s for C6D). The two-compartment dispersion model equations adequately described the outflow profiles for the parent esters and the metabolite diflunisal formed from the O-acyl esters of diflunisal in the liver.

Kinetic analysis of vascular marker distribution in perfused rat livers after regeneration following partial hepatectomy

Background/Aims: Liver clearance models are based on information (or assumptions) on solute distribution kinetics within the microvasculatory system, The aim was to study albumin distribution kinetics in regenerated livers and in livers of normal adult rats, Methods: A novel mathematical model was used to evaluate the distribution space and the transit time dispersion of albumin in livers following regeneration after a two-thirds hepatectomy compared to livers of normal adult rats. Outflow curves of albumin measured after bolus injection in single-pass perfused rat livers were analyzed by correcting for the influence of catheters and fitting a long-tailed function to the data. Results: The curves were well described by the proposed model. The distribution volume and the transit time dispersion of albumin observed in the partial hepatectomy group were not significantly different from livers of normal adult rats. Conclusions: These findings suggest that the distribution space and the transit time dispersion of albumin (CV2) is relatively constant irrespective of the presence of rapid and extensive repair. This invariance of CV2 implies, as a first approximation, a similar degree of intrasinusoidal mixing, The finding that a sum of two (instead of one) inverse Gaussian densities is an appropriate empirical function to describe the outflow curve of vascular indicators has consequences for an improved prediction of hepatic solute extraction.