Electronic structures of sulfide minerals — Theory and experiment

The sulfide minerals exhibit a rich diversity in sturctural chemistry and in electrical, magnetic and other physical properties. Models based on molecular orbital theory and incorporating some elements of band theory can be developed to describe the diverse valence electron behavior in these minerals. Qualitative models can be proposed on the basis of observed properties, and the models can be tested and refined using experimental data from X-ray emission and X-ray photoelectron spectroscopy and quantum mechanical calculations performed on cluster units which form the basic building blocks of the crystals. This approach to chemical bonding in sulfide minerals is illustrated for binary non-transition metal sulfides (ZnS, CdS, HgS, PbS), binary transition metal sulfides (FeS₂, CoS₂, NiS₂, CuS₂ ZnS₂) and more complex sulfides (CuFeS₂, Cu₂S, Ag₂S, CuS, Co₃S₄, CuCo₂S₄, Fe₃S₄). The relationship between qualitative and quantitative theories is reviewed with reference to the pyrite-marcasite-arsenopyrite-loellingite series of minerals. Application of the models to understanding structure-determining principles, relative stabilities, solid solution limits and properties such as color, reflectance and hardness are discussed.     

Autogenic avulsion,channelization and backfilling dynamics of debris‐flow fans

Alluvial fans develop their semi‐conical shape by quasi‐cyclic avulsions of their geomorphologically active sector from a fixed fan apex. On debris‐flow fans, these quasi‐cyclic avulsions are poorly understood, partly because physical scale experiments on the formation of fans have been limited largely to turbidite and fluvial fans and deltas. In this study, debris‐flow fans were experimentally created under constant extrinsic forcing, and autogenic sequences of backfilling, avulsion and channelization were observed. Backfilling, avulsion and channelization were gradual processes that required multiple successive debris‐flow events. Debris flows avulsed along preferential flow paths given by the balance between steepest descent and flow inertia. In the channelization phase, debris flows became progressively longer and narrower because momentum increasingly focused on the flow front as flow narrowed, resulting in longer run‐out and deeper channels. Backfilling commenced when debris flows reached their maximum possible length and channel depth, as defined by channel slope and debris‐flow volume and composition, after which they progressively shortened and widened until the entire channel was filled and avulsion was initiated. The terminus of deposition moved upstream because the frontal lobe deposits of previous debris flows created a low‐gradient zone forcing deposition. Consequently, the next debris flow was shorter which led to more in‐channel sedimentation, causing more overbank flow in the next debris flow and resulting in reduced momentum to the flow front and shorter runout. This topographic feedback is similar to the interaction between flow and mouth bars forcing backfilling and transitions from channelized to sheet flow in turbidite and fluvial fans and deltas. Debris‐flow avulsion cycles are governed by the same large‐scale topographic compensation that drives avulsion cycles on fluvial and turbidite fans, although the detailed processes are unique to debris‐flow fans. This novel result provides a basis for modelling of debris‐flow fans with applications in hazards and stratigraphy.     

Geochemical surveillance of active volcanoes: data on the fumaroles of Vulcano (Aeolian Islands,Italy)

Temperature and chemical composition of condensates of higher temperature fumaroles, located on the rim of the crater of Vulcano, were studied over a period of one year. Maximum temperature changed from 216°C (June 1977) to 291°C (May 1978). HCl is the main constituent of condensates which, in comparison with data from fumaroles of other volcanoes, contain also noteworthy quantities of boron and bromine. Since these chemical characteristics suggested the possible inflow of water of marine origin into the volcanic conduit, experimental data on seawater-rock reactions at high temperatures and pressures were taken into account. A model is drafted for the volcanic system, in which the occurrence of an aquifer interposed between the magma chamber and the surface is considered. The vaporization of this aquifer would feed the fumaroles giving rise, through different mixing processes with surface waters, to the observed differences in temperature and chemical composition. However, data available at present are not sufficient to support the proposed model, which must be mainly considered as a working hypothesis.     

Distribution, source and evolution of nitrate in a glacial till of southern Alberta, Canada

This paper addresses the distribution, origin and controls upon nitrate in a 30-km² area of the Interior Great Plains Region of southern Alberta, Canada. High concentrations of nitrate (> 100 mg l⁻¹ NO⁻₃-N) occurred in several isolated enclaves below the water table in brown weathered till. Nitrate concentrations of over 300 mg l⁻¹-N were encountered in groundwater samples collected from these enclaves. Low nitrate concentrations (< 1.1 mg l⁻¹ NO⁻₃-N) were also encountered in the weathered till upgradient and downgradient of the nitrate enclaves. Groundwater samples collected from the underlying grey nonweathered till and bedrock had NO⁻₃-N concentrations of < 1.1 mg l⁻¹.

Through the application of geochemical (NO⁻₃-N and NH⁺₄-N) studies, environmental isotope studies (tritium), microbial analyses (nitrifiers) and laboratory experiments, it was shown that the high nitrates found in the weathered till are the result of the oxidation of ammonium present within the tills. It is postulated that this oxidation occurred during the Holocene epoch when water tables were much lower than present-day levels (5–18 m, and 2 m below ground, respectively).

Through the use of Eh measurements, the enumeration of denitrifying bacteria and laboratory experiments, the potential for denitrification was shown to exist below the present-day water table in the weathered till as well as in the nonweathered till and bedrock. Isotopic data showed that less denitrification may be occurring within the nitrate enclaves than in adjacent downgradient areas.     

Local site effects in Latur, India: an empirical study based on the aftershocks of the Killari earthquake of September 29, 1993

The site amplification is estimated at five seismic stations of the Latur region using the horizontal to vertical spectral ratios of 33 aftershocks of the main Killari earthquake of September 29, 1993 (UTC). Spectral amplifications, ranging from a factor of 2–6 are found to vary with frequency at different places. Significant amplification is found at four sites within the Latur region, at Basavakalyan, Kasgi, Killari, and Mudgad Eakoji villages. Our results show a positive correlation between the site amplification and the damage pattern in area. The pattern and the nature of the site amplification estimated in the present study corroborates also with the analytical models and the borehole data indicating alternating layers of unconsolidated sediments and basaltic rocks.     

Sporadic and recurrent geomagnetic disturbances in 1859–1860 according to the archived data from the Russian network of stations

Based on an analysis of the available archived data from the Russian network of geomagnetic stations, it has been indicated that the known event of August–September 1859 was the first and the greatest event in the series of the recurrent geomagnetic storms. Similar series were repeatedly observed in the next years. These series are caused by the processes on the Sun and in the heliosphere related to the superposition of the solar wind flows. The sporadic and regular components in joint activity of the complex, including active regions and coronal holes on the rotating Sun, play the role of the Bartels M regions responsible for initiation and development of geomagnetic storms. Neither coronal holes nor active regions can separately explain observations. During interpretation, active regions and coronal holes should be considered as a unified complex.     

Degradation and Detoxification of Chlorophenols in Continuous‐Flow Fixed‐Bed Aerobic Reactors

An indigenous bacterial strain of Delftia sp. capable of degrading 2,4‐dicholorophenol and an indigenous bacterial community that degrades 2,4,6‐trichlorophenol (TCP) were employed to inoculate continuous down‐flow fixed‐bed reactors. Continuous‐reactors were constructed from PVC employing hollow PVC cylinders as support material. Synthetic wastewater was prepared by dissolving the corresponding chlorophenol in non‐sterile groundwater. Biodegradation was evaluated by spectrophotometry, chloride release, GC, and microbial growth. Detoxification was evaluated by using Daphnia magna as test organism. Delftia sp. was able to remove an average of 95.6% of DCP. Efficiency in terms of chemical oxygen demand (COD) was of 88.9%. The indigenous bacterial community that degrades TCP reached an average efficiency of 96.5 and 91.6% in terms of compound and COD removal, respectively. In both cases stoichiometric removal of chloride and detoxification was achieved. When synthetic wastewater feed was cut off for 7 days, both reactors showed a fast recovery after inflow restarting, reaching average outlet concentration values within 36 h. The promising behavior of the microorganisms and the low cost of the reactors tested allow us to suggest their possible application to remediation processes.