Dispersion modeling of air pollutants in the atmosphere: a review

Modeling of dispersion of air pollutants in the atmosphere is one of the most important and challenging scientific problems. There are several natural and anthropogenic events where passive or chemically active compounds are emitted into the atmosphere. The effect of these chemical species can have serious impacts on our environment and human health. Modeling the dispersion of air pollutants can predict this effect. Therefore, development of various model strategies is a key element for the governmental and scientific communities. We provide here a brief review on the mathematical modeling of the dispersion of air pollutants in the atmosphere. We discuss the advantages and drawbacks of several model tools and strategies, namely Gaussian, Lagrangian, Eulerian and CFD models. We especially focus on several recent advances in this multidisciplinary research field, like parallel computing using graphical processing units, or adaptive mesh refinement.     

Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation

The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO₂²⁺) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10⁻³ M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)₆] octahedral sites over [Al(O,OH)₆] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO₂. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO₂.     

Growth, annealing and recrystallization of zircon and preservation of monazite in high-grade metamorphism: conventional and in-situ U-Pb isotope, cathodoluminescence and microchemical evidence

Zircon and monazite from granulite- to amphibolite-facies rocks of the Vosges mountains (central Variscan Belt, eastern France) were dated by ion-microprobe and conventional U-Pb techniques. Different granulites of igneous (so-called leptynites) and sedimentary origin (kinzigites) and their leucosomes were dated at 334.9 ± 3.6, 335.4 ± 3.6 and 336.7 ± 3.5 Ma (conventional age 335.4 ± 0.6 Ma). Subsequent growth stages of zircon were distinguished by secondary electron (SEM) and cathodoluminescence (CL) imaging: (1) subsolidus growth producing round anhedral morphologies and sector zoning; (2) appearance of an intergranular fluid or melt phase at incipient dehydration melting that first resulted in resorption of pre-existing zircons, followed by growth of acicular zircons or overgrowths on round zircons consisting of planar growth zoning; (3) advanced melting producing euhedral prismatic zircons with oscillatory zoning overgrowing the sector zones. Two further lithologies, the Kaysersberg granite and the Trois-Epis units, were both formerly considered as migmatites. The intrusion of the Kaysersberg granite was dated at 325.8 ± 4.8 Ma. The Trois-Epis unit was found to be the product of volume recrystallization of a former granulite, which occurred under amphibolite-facies conditions 327.9 ± 4.4 Ma ago. The amphibolite-facies overprint of the Trois-Epis zircons led to the complete rejuvenation of most of the zircon domains by annealing and replacement/recrystallization processes. Annealing is assumed to occur in strained lattice domains, which are possibly disturbed by high trace element contents and/or large differences in decay damage between adjacent growth zones. Investigation of cathodoluminescence structures reveals that the replacement occurs along curved chemical reaction fronts that proceed from the surface towards the interior of the zircon. The monazite U-Pb system still records the age of high-grade metamorphism at around 335 Ma. The chemical reagent responsible for the rejuvenation of zircon obviously left the monazite unaffected. Received: 19 February 1998 / Accepted: 19 October 1998     

Soft X-ray spectroscopic studies of the reaction of fractured pyrite surfaces with Cr(VI)-containing aqueous solutions

We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.     

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ⁶⁶Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ⁶⁶Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ⁶⁶Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe₂O₄)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ⁶⁶Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ⁶⁶Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ⁶⁶Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.     

Trace elements in Holocene sediments of the southern Doñana National Park (SW Spain): historical pollution and applications

The multidisciplinary analysis of core sediments from Doñana National Park, south Spain, permits to delimitate both the paleoenvironmental changes and the geochemical evolution of this area during the Holocene. In a first phase (10–6.5 kyr cal), this area was occupied by freshwater/brackish marshes with periodical alternation of dry periods and humid intervals. In a second phase, these marshes were inundated during the Flandrian transgression (~6.5 kyr cal), with the deposition of bioclastic sands. The third phase (6.5–3.6 kyr cal) is characterized by the transition to an old lagoon, with unpolluted, bottom sediments. The geochemical concentrations of these clayey sediments can be used as a geochemical background for present-day and future environmental evaluations of this area. In the following 600 years approximately, two tsunamis caused the partial infilling of this area with bioclastic, marine sediments. In the interval comprised between these two tsunamis, this lagoon was polluted with heavy metals derived from historical mining activities. This environmental contamination represents one of the oldest evidences of mining pollution in the world (>3 kyr cal BP).     

Geological and archaeological chronology of a late Holocene coastal enclosure: The Sanguinet lake (SW France)

Sanguinet lake is separated from the Atlantic Ocean by a wide Holocene coastal dunes system in SW France. The present day lake level is 21 m above mean sea level (msl). It formed when aeolian sand closed the mouth of the small La Gourgue river which gradually became a lagoon and then a lake. Dated sub‐lacustrine archaeological remains (human settlements, canoes, and wooden architectural structures), as well as paleoenvironmental evidence (drowned tree stumps and lagoonal deposits exposed on the beach) are used to interpret the formation and chronology of lake level rise during the past 4000 years. Around 2000–1650 B.C., the river flowed into a lagoon or an estuary which connected with the ocean west of the present Sanguinet Lake. Its level was affected by the tide, which ranged between 2 m below and 3 m above msl. The accumulation of aeolian sand before 1500–1000 B.C. began to close the connection with the sea. At this time, the elevation of the surface of the lake water was approximately 5 m above msl, but it still remained connected to the ocean. Around 1000 B.C., the lake level rose quickly by 1 to 2 m during a period of renewed mobility of the coastal aeolian sand, and continued to rise slowly until about 100 A.D. when there was a gradual closure of the lake outlet. This rise forced people who were living on the lake shore and along the rivers to move to higher land along the valley. The nearby Gallo‐Roman site of Losa was settled at the end of the 1st century B.C.; then the final blocking of the outlet occurred because of spit growth as a result of north‐south littoral drift accompanied by the deposit of aeolian sand. This led to the lake level rising rapidly. Consequently, Losa was abandoned in the 3rd century A.D. and ruins of its temple (at 17 m above msl) were submerged in the 6th century. Further oscillations of the lake level probably correspond to water table fluctuations before it became stable at around 1000 A.D. The highest lake level (23.35 m) was reached during the 18th century as a consequence of modern dune formation, and thus was artificially reduced to 21 m in 1840 by construction of an overflow channel. © 2008 Wiley Periodicals, Inc.     

An overview of climatic variability and its causal mechanisms

A variance spectrum of climatic variability is presented that spans all time scales of variability from about one hour (10⁻⁴ years) to the age of the Earth (4 × 10⁹ years). An interpretive overview of the spectrum is offered in which a distinction is made between sources of variability that arise through stochastic mechanisms internal to the climatic system (atmosphere-ocean-cryosphere) and those that arise through forcing of the system from the outside. All identifiable mechanisms, both internal and external, are briefly defined and clarified as to their essential nature. It is concluded that most features of the spectrum of climatic variability can be given tentatively reasonable interpretations, whereas some features (in particular the quasi-biennial oscillation and the neoglacial cycle of the Holocene) remain fundamentally unexplained. The overall spectrum suggests the existence of a modest degree of deterministic forms of climatic change, but sufficient nonsystematic variability to place significant constraints both on the extent to which climate can be predicted, and on the extent to which significant events in the paleoclimatic record can ever manage to be assigned specific causes.     

Mineralized and unmineralized calderas in Spain; Part II, evolution of the Rodalquilar caldera complex and associated gold-alunite deposits

The Rodalquilar caldera complex is located in the western part of the Cabo de Gata volcanic field in southeastern Spain and is the first documented example of epithermal gold-alunite mineralization within a caldera in Europe. The Rodalquilar caldera is an oval collapse structure having a maximum diameter of 8 km and formed at 11 Ma from eruption of the Cinto ash-flow tuff. The oval Lomilla caldera, with a diameter of 2 km, is nested within the central resurgent dome of the older Rodalquilar caldera. The Lomilla caldera resulted from the eruption of the Lazaras ash-flow tuff which was ponded within the moat of the Rodalquilar caldera. The last phase of volcanic activity in the caldera complex was the emplacement of hornblende andesite flows and intrusions. This magmatic event resulted in structural doming of the caldera, opening of fractures and faults, and provided the heat source for the large hydrothermal systems which deposited quartz-alunite type gold deposits and base metal vein systems. The gold-alunite deposits are enclosed in areas of intense acid sulfate alteration and localized in ring and radial faults and fractures present in the east wall of the Lomilla caldera. Like other acid-sulfate type deposits, the Rodalquilar gold-alunite deposits are closely related in time and space to porphyritic, intermediate composition magma emplaced along caldera structures but unrelated to the caldera forming magmatic system.