Selected topics in arctic atmosphere and climate

This paper summarizes the main elements of four IPY projects that examine the Arctic Atmosphere. All four projects focus on present conditions with a view to anticipating possible climate change. All four investigate the Arctic atmosphere, ocean, ice, and land interfacial surfaces. One project uses computer models to simulate the dynamics of the Arctic atmosphere, storms, and their interactions with the ocean and ice interface. Another project uses statistical methods to infer transports of pollutants as simulated in large-scale global atmospheric and oceanic models verifying results with available observations. A third project focuses on measurements of pollutants at the ice-ocean?Catmosphere interface, with reference to model estimates. The fourth project is concerned with multiple, high accuracy measurements at Eureka in the Canadian Archipelago. While these projects are distinctly different, led by different teams and interdisciplinary collaborators, with different technical approaches and methodologies, and differing objectives, they all strive to understand the processes of the Arctic atmosphere and climate, and to lay the basis for projections of future changes. Key findings include: ? Decreased sea ice leads to more intense storms, higher winds, reduced surface albedo, increased surface air temperature, and enhanced vertical mixing in the upper ocean. ? Arctic warming may affect toxic chemicals by remobilizing persistent organic pollutants and augmenting mercury deposition/retention in the environment. ? Changes in sea ice can dramatically change processes in and at the ice surface related to ozone, mercury and bromine oxide and related chemical/physical properties. ? Structure and properties of the Arctic atmospheric??troposphere to stratosphere??and tracking of transport of pollution and smoke plumes from mid-latitudes to the poles.     

Selection of permeable reactive barrier materials for treating acidic groundwater in acid sulphate soil terrains based on laboratory column tests

The Shoalhaven region of NSW experiences environmental acidification due to acid sulphate soils (ASS). In order to trial an environmental engineering solution to groundwater remediation involving a permeable reactive barrier (PRB), comprehensive site characterisation and laboratory-based batch and column tests of reactive materials were conducted. The PRB is designed to perform in situ remediation of the acidic groundwater (pH 3) that is generated in ASS. Twenty-five alkaline reactive materials have been tested for suitability for the barrier, with an emphasis on waste materials, including waste concrete, limestone, calcite-bearing zeolitic breccia, blast furnace slag and oyster shells. Following three phases of batch tests, two waste materials (waste concrete and oyster shells) were chosen for column tests that simulate flow conditions through the barrier and using acidic water from the field site (pH 3). Both waste materials successfully treated with the acidic water, for example, after 300 pore volumes, the oyster shells still neutralised the water (pH 7).     

Monitoring and early warning of the 2012 Preonzo catastrophic rockslope failure

In this paper, we describe the investigations and actions taken to reduce risk and prevent casualties from a catastrophic 210,000 m³ rockslope failure, which occurred near the village of Preonzo in the Swiss Alps on May 15, 2012. We describe the geological predisposition and displacement history before and during the accelerated creep stage as well as the development and operation of an efficient early warning system. The failure of May 15, 2012, occurred from a large and retrogressive instability in gneisses and amphibolites with a total volume of about 350,000 m³, which formed an alpine meadow 1250 m above the valley floor. About 140,000 m³ of unstable rock mass remained in place and might collapse partially or completely in the future. The instability showed clearly visible signs of movements along a tension crack since 1989 and accelerated creep with significant hydromechanical forcing since about 2006. Because the active rockslide at Preonzo threatened a large industrial facility and important transport routes located directly at the toe of the slope, an early warning system was installed in 2010. The thresholds for prealarm, general public alarm, and evacuation were derived from crack meter and total station monitoring data covering a period of about 10 years, supplemented with information from past failure events with similar predisposition. These thresholds were successfully applied to evacuate the industrial facility and to close important roads a few days before the catastrophic slope failure of May 15, 2012. The rock slope failure occurred in two events, exposing a compound rupture plane dipping 42° and generating deposits in the midslope portion with a travel angle of 39°. Three hours after the second rockslide, the fresh deposits became reactivated in a devastating debris avalanche that reached the foot of the slope but did not destroy any infrastructure. The final run-out distance of this combined rock collapse–debris avalanche corresponded to the predictions made in the year 2004.     

Surface studies of water isotopes in Antarctica for quantitative interpretation of deep ice core data

Polar ice cores are unique climate archives. Indeed, most of them have a continuous stratigraphy and present high temporal resolution of many climate variables in a single archive. While water isotopic records (δD or δ¹⁸O) in ice cores are often taken as references for past atmospheric temperature variations, their relationship to temperature is associated with a large uncertainty. Several reasons are invoked to explain the limitation of such an approach; in particular, post-deposition effects are important in East Antarctica because of the low accumulation rates. The strong influence of post-deposition processes highlights the need for surface polar research programs in addition to deep drilling programs. We present here new results on water isotopes from several recent surface programs, mostly over East Antarctica. Together with previously published data, the new data presented in this study have several implications for the climatic reconstructions based on ice core isotopic data: (1) The spatial relationship between surface mean temperature and mean snow isotopic composition over the first meters in depth can be explained quite straightforwardly using simple isotopic models tuned to d-excess vs. δ¹⁸O evolution in transects on the East Antarctic sector. The observed spatial slopes are significantly higher (～ 0.7–0.8‰·°C^?1 for δ¹⁸O vs. temperature) than seasonal slopes inferred from precipitation data at Vostok and Dome C (0.35 to 0.46‰·°C^?1). We explain these differences by changes in condensation versus surface temperature between summer and winter in the central East Antarctic plateau, where the inversion layer vanishes in summer. (2) Post-deposition effects linked to exchanges between the snow surface and the atmospheric water vapor lead to an evolution of δ¹⁸O in the surface snow, even in the absence of any precipitation event. This evolution preserves the positive correlation between the δ¹⁸O of snow and surface temperature, but is associated with a much slower δ¹⁸O-vs-temperature slope than the slope observed in the seasonal precipitation. (3) Post-deposition effects clearly limit the archiving of high-resolution (seasonal) climatic variability in the polar snow, but we suggest that sites with an accumulation rate of the order of 40 kg.m^?2.yr^?1 may record a seasonal cycle at shallow depths.     

Extreme aridity prior to lake expansion deciphered from facies evolution in the Miocene Ili Basin,south‐east Kazakhstan

Central Asia witnessed progressive aridification during the Miocene, commonly related to mountain uplift, the Paratethys retreat and global climate cooling. However, the formation of Miocene lakes in Central Asia seems to oppose drier conditions, suggesting that the precise timing, extent and forcing of the aridification is still not well constrained. This study presents a facies model for the alluvial–lacustrine part of the Middle to Late Miocene of the Ili Basin, obtained from two successions. The model enables the semi‐quantitative assessment of regional water level and salinity, and characterizes the control of water level on evaporite formation and diagenesis. Both the proximal Kendyrlisai and the distal Aktau successions show an overall increase in water availability from dry mudflat deposits to lacustrine sedimentation with a transitional playa phase. Increasing evaporation rates outpaced the water supply and caused groundwater salinization. Subsequent lake expansion coincided with a basin‐wide desalinization and required a shift to a positive water budget. A climatic control of the hydrological evolution is inferred due to abrupt salinization and a minor tectonic influence. The long‐term water accumulation is probably related to the hydrological closure of the basin in the early Middle Miocene (15·3 Ma). Starting at 14·3 Ma, the step‐wise salinization occurred simultaneously with the global cooling of the Miocene Climate Transition. The Miocene Climate Transition led to extreme aridity in the Ili Basin, highlighted by the early diagenetic formation of displacive anhydrite in the basin centre. The expansion of the freshwater lake (12·7 to 11·5 Ma) was possibly promoted by lower evaporation rates due to decreasing air temperatures in the Ili Basin after the Miocene Climate Transition. The extreme aridity in the Ili Basin is interpreted as a continental counterpart to the Badenian Salinity Crisis in the Central Paratethys. This emphasizes the role of atmospheric forcing on evaporite sedimentation across Eurasia during the Middle Miocene.     

Energetics of nanoparticle oxides: interplay between surface energy and polymorphism†

Many oxides tend to form different structures (polymorphs) for small particles. High temperature oxide melt solution calorimetry has been used to measure the enthalpy as a function of polymorphism and surface area for oxides of Al, Ti, and Zr. The results confirm crossovers in polymorph stability at the nanoscale. The energies of internal and external surfaces of zeolitic silicas with open framework structures are an order of magnitude smaller than those of oxides of normal density.     

Progress and new directions in high temperature calorimetry

Calorimetry at 600–900° C, using Calvet-type microcalorimeters, has provided data in several areas of interest to geology. The best-developed application is solution calorimetry in molten oxide solvents (lead borate, sodium molybdate) to determine the enthalpies of formation of anhydrous silicates and related minerals, the enthalpies of phase transformations and order-disorder reactions, and the enthalpies of mixing in molten salts, glasses, and solid solutions. An attractive feature of the technique is the ability to use rather small samples; ～ 300 mg total often being sufficient for the study of a phase synthesized at high pressure. Current developments include the improvement of precision by careful control of solvent composition and water content, the development of alkali borate or borosilicate solvents for use under atmospheres of controlled oxygen fugacity, and the study of compounds containing fluorine as well as oxygen. In addition, direct-reaction calorimetry at high temperature has been used to study rapid phase transformations and gas-solid reactions. The latter include the oxidation of metals and the thermodynamics of oxides having wide homogeneity ranges, for example wüstite. A recent development is calorimetry at pressures up to 2 kb, using a cold-seal pressure vessel inserted in the calorimeter. Applications include the study of geothermal fluids and, eventually, the study of equilibria involving hydrous phases and water-containing melts and glasses.     

Spinel disproportionation at high pressure: calorimetric determination of enthalpy of formation of Mg2SnO4 and Co2SnO4 and some implications for silicates

The enthalpies of formation from the oxides of Mg₂SnO₄ and Co₂SnO₄ were found by oxide melt solution calorimetry to be +1.13 ± 0.48 kcal/mol and ?2.31 ± 0.28 kcal/mol, respectively. Using these data, the slopes, ?P/?T, for disproportionation of these spinels to the component oxides at high pressure were calculated to be +30.4 ± 4.2 bar/K for Mg₂SnO₄ and ?10.3 ± 2.4 bar/K for Co₂SnO₄, in general agreement with the data of Jackson et al. (1974a,b). Using thermochemical data for the formation of olivines, for olivine-spinel transitions and for the transformation of quartz to stishovite, we calculate pressures for the disproportionation of silicate spinels to be in the range 150–200 kbar. Calculated slopes ?P/?T for the disproportionation reactions are ?10.7, ?24.9, ?11.2, and +7.6 bar/K for Mg₂SiO₄, Fe₂SiO₄, Co₂SiO₄, and Ni₂SiO₄. The large negative slope calculated for Fe₂SiO₄ results from a surprisingly large positive slope reported for the olivine-spinel transition in that compound (Akimoto et al., 1969). Further consideration of the systematic trends in the thermodynamics of spinel formation from the oxides suggests that the silicate spinels should have entropies of formation close to zero, resulting in values of ?P/?T which are zero or at most only slightly negative. This confirms the conclusion of Jackson, Liebermann, and Ringwood that values of ?P/?T for spinel disproportionation are unlikely to be more negative than ?10 bar/K and may well be slightly positive. Reaction of spinels to form other post-spinel phases, particularly ilmenite and perovskite, are discussed in terms of available thermochemical data.     

A catchment water balance model for estimating groundwater recharge in arid and semiarid regions of south-east Iran

This paper presents a new model of the rainfall-runoff-groundwater flow processes applicable to semiarid and arid catchments in south-east Iran. The main purpose of the model is to assess the groundwater recharge to aquifers in these catchments. The model takes into account main recharge mechanisms in the region, including subsurface flow in the valley alluvium in mountainous areas and recharge from the bed of ephemeral rivers. It deals with the effects of spatial variation in the hydrological processes by dividing the catchment into regions of broad hydrologic similarity named as highland, intermediate and aquifer areas. The model is based on the concept of routing precipitation within and through the catchment. The model has been applied to the Zahedan catchment and the results indicate that the groundwater level estimated by the recharge model generally is in agreement with the behaviour of groundwater levels in observation wells. The sensitivity analysis indicates that when the rainfall in the aquifer area is used to replace the values recorded in the intermediate area and the highland area, the recharge estimates are reduced by 42-87%. This result supports the division of the catchment into different zones of hydrological similarity to account for spatial variability of hydrological processes. Electronic Publication