Hydrosulfide/sulfide complexes of zinc to 250 °C and the thermodynamic properties of sphalerite

The solubility of synthetic ZnS_(cr) was measured at 25–250 °C and P = 150 bars as a function of pH in aqueous sulfide solutions (~ 0.015–0.15 m of total reduced sulfur). The solubility determinations were performed using a Ti flow-through hydrothermal reactor. The solubility of ZnS_(cr) was found to increase slowly with temperature over the whole pH range from 2 to ~ 10. The values of the Zn–S–HS complex stability constant, β, were determined for Zn(HS)₂⁰_(aq), Zn(HS)₃^?, Zn(HS)₄^2?, and ZnS(HS)^?. Based on the experimental values the Ryzhenko–Bryzgalin electrostatic model parameters for these stability constants were calculated, and the ZnS_(cr) solubility and the speciation of Zn in sulfide-containing hydrothermal solutions were evaluated. The most pronounced solubility increase, about 3 log units at m(S_total) = 0.1 for the temperatures from 25 to 250 °C, was found in acidic solutions (pH ~ 3 to 4) in the Zn(HS)₂⁰_(aq) predominance field. In weakly alkaline solutions, where Zn(HS)₃^? and Zn(HS)₄^2? are the dominant Zn–S–HS complexes, the ZnS_(cr) solubility increases by 1 log unit at the same conditions. It was found that ZnS(HS)^? and especially Zn(HS)₄^2? become less important in high temperature solutions. At 25 °C and m(S_total) = 0.1, these species dominate Zn speciation at pH > 7. At 100 °C and m(S_total) = 0.1, the maximum fraction of Zn(HS)₄^2? is only 20% of the total Zn concentration (i.e. at pH_t ~ 7.5), whereas at 350 °C and 3 <pH_t <10, the fraction of Zn(HS)₄^2? and ZnS(HS)^? is less than 0.05% and 2.5% respectively, of the total Zn concentration and Zn(HS)₂⁰ and Zn(HS)₃^? predominate. The measured equilibrium formation constants were combined with the literature data on the stability of Zn–Cl complexes in order to evaluate the concentration and speciation of Zn in chloride solutions. It was found that at acidic pH, and in more saline fluids having total chloride > 0.05 m, Zn–Cl complexes are responsible for hydrothermal Zn transport with no significant contribution of Zn–S–HS complexes. The hydrosulfide/sulfide complexes will play a more important role in lower salinity (< 0.05 m chloride) hydrothermal solutions which are characteristic of many epithermal ore depositing environments. The value of Δ_fG° (β-ZnS_(cr)) = ? 198.6 ± 0.2 kJ/mol at 25 °C was determined via solubility measurements of natural low-iron Santander (Spain) sphalerite.     

High-resolution climate simulation of the last glacial maximum

The climate of the last glacial maximum (LGM) is simulated with a high-resolution atmospheric general circulation model, the NCAR CCM3 at spectral truncation of T170, corresponding to a grid cell size of roughly 75 km. The purpose of the study is to assess whether there are significant benefits from the higher resolution simulation compared to the lower resolution simulation associated with the role of topography. The LGM simulations were forced with modified CLIMAP sea ice distribution and sea surface temperatures (SST) reduced by 1°C, ice sheet topography, reduced CO₂, and 21,000 BP orbital parameters. The high-resolution model captures modern climate reasonably well, in particular the distribution of heavy precipitation in the tropical Pacific. For the ice age case, surface temperature simulated by the high-resolution model agrees better with those of proxy estimates than does the low-resolution model. Despite the fact that tropical SSTs were only 2.1°C less than the control run, there are many lowland tropical land areas 4–6°C colder than present. Comparison of T170 model results with the best constrained proxy temperature estimates (noble gas concentrations in groundwater) now yield no significant differences between model and observations. There are also significant upland temperature changes in the best resolved tropical mountain belt (the Andes). We provisionally attribute this result in part as resulting from decreased lateral mixing between ocean and land in a model with more model grid cells. A longstanding model-data discrepancy therefore appears to be resolved without invoking any unusual model physics. The response of the Asian summer monsoon can also be more clearly linked to local geography in the high-resolution model than in the low-resolution model; this distinction should enable more confident validation of climate proxy data with the high-resolution model. Elsewhere, an inferred salinity increase in the subtropical North Atlantic may have significant implications for ocean circulation changes during the LGM. A large part of the Amazon and Congo Basins are simulated to be substantially drier in the ice age—consistent with many (but not all) paleo data. These results suggest that there are considerable benefits derived from high-resolution model regarding regional climate responses, and that observationalists can now compare their results with models that resolve geography at a resolution comparable to that which the proxy data represent.     

LA-ICP-MS heavy metal analyses of fish scales from sediments of the Oxbow Lake Certak of the Morava River (Czech Republic)

Heavy metal concentrations were studied in the scales of recent and subrecent (2–25 years old) fish buried in the oxbow lake sediments of the Morava River. The samples were taken from two cores up to 4-m deep and analysed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and an electron microprobe analysis (EMPA). The results were compared with heavy metal concentrations of bulk samples of the embedding sediment. The study has revealed substantial differences in heavy metal contents existing between the recent and subrecent fish scales documenting an extreme rapidity of the diagenesis/fossilization processes. The most apparent features of the early fossilization include the quick loss of the mucous envelope, collagen and magnesium and an enormous increase in the heavy metal concentrations in particular iron, which is connected with a colour change. The variations in heavy metal contents in fish scales within a sample are attributed to variations in heavy metal content in the environment and variable amounts of organic matter in the embedding sediment. In contrast to the contamination of the embedding sediment, no general increase in heavy metal concentrations in fish scales was observed down to the cores. It is inferred that the rapid sorption stabilizes the biologic hydroxyapatite of the fish scales, which thus rapidly attain a thermodynamic equilibrium with the embedding water-saturated sediment. The results show that the processes of sorption, fossilization and stabilization of hydroxyapatite can act very quickly over a time scale of several years and represent thus a great advantage in the preservation of the original signals of the ancient environments.     

Geomorphology of coal seam fires

Coal fires occur in underground natural coal seams, in exposed surface seams, and in coal storage or waste piles. The fires ignite through spontaneous combustion or natural or anthropogenic causes. They are reported from China, India, USA, South Africa, Australia, and Russia, as well as many other countries. Coal fires lead to loss of a valuable resource (coal), the emission of greenhouse-relevant and toxic gases, and vegetation deterioration. A dangerous aspect of the fires is the threat to local mines, industries, and settlements through the volume loss underground. Surface collapse in coal fire areas is common. Thus, coal fires are significantly affecting the evolution of the landscape. Based on more than a decade of experience with in situ mapping of coal fire areas worldwide, a general classification system for coal fires is presented. Furthermore, coal seam fire geomorphology is explained in detail. The major landforms associated with, and induced by, these fires are presented. The landforms include manifestations resulting from bedrock surface fracturing, such as fissures, cracks, funnels, vents, and sponges. Further manifestations resulting from surface bedrock subsidence include sinkholes, trenches, depressions, partial surface subsidence, large surface subsidence, and slides. Additional geomorphologic coal fire manifestations include exposed ash layers, pyrometamorphic rocks, and fumarolic minerals. The origin, evolution, and possible future development of these features are explained, and examples from in situ surveys, as well as from high-resolution satellite data analyses, are presented. The geomorphology of coal fires has not been presented in a systematic manner. Knowledge of coal fire geomorphology enables the detection of underground coal fires based on distinct surface manifestations. Furthermore, it allows judgments about the safety of coal fire-affected terrain. Additionally, geomorphologic features are indicators of the burning stage of fires. Finally, coal fire geomorphology helps to explain landscape features whose occurrence would otherwise not be understood. Although coal fire-induced thermal anomalies and gas release are also indications of coal fire activity, as addressed by many investigators, no assessment is complete without sound geomorphologic mapping of the fire-induced geomorphologic features.     

Spectrophotometry of comet Levy (1990c)

Two spectrophotometric scans of comet Levy (1990c) have been analysed to estimate Haser model column densities and production rates of CN andC ₂ molecules.     

Sensitive observations of radio recombination lines in Orion and W51: the data and detection of systematic recombination line blueshifts proportional to impact broadening

Sensitive spectral observations made in two frequency bands near 6.0 and 17.6 GHz are described for Orion and W51. Using frequency switching we were able to achieve a dynamic range in excess of 10,000 without fitting sinusoidal or polynomial baselines. This enabled us to detect lines as weak as T _A ∼1 mK in these strong continuum sources. Hydrogen recombination lines with Δn as high as 25 have been detected in Orion. In the Orion data, where the lines are stronger, we have also detected a systematic shift in the line center frequencies proportional to linewidth that cannot be explained by normal optical depth effects.     

The Kuwae (Vanuatu) eruption of<Emphasis Type="SmallCaps"> AD</Emphasis> 1452: potential magnitude and volatile release

Sometime during AD 1452, according to new evidence, a large-magnitude, initially phreatomagmatic eruption, destroyed the island of Kuwae (16.83°S, 168.54°E), located in the present-day Republic of Vanuatu. It created a 12×6-km submarine caldera composed of two adjacent basins. Based on estimates of caldera volume, between 30 and 60 km³ DRE of dacite magma was ejected as pyroclastic flow and fall deposits during this event. Annual layers of ice dating from the period AD 1450–1460 contain acidity peaks representing fallout of sulfuric acid onto both the Greenland and Antarctic ice caps. These acidity peaks have been attributed by others to the sedimentation of H₂SO₄ aerosols that originated from sulfur degassing during the Kuwae eruption. Improved dating techniques and new data from nineteen ice cores reveal a single acidity peak attributed to Kuwae lasting from 1453 to 1457. In this study, we present new electron microprobe analyses of the S, Cl, and F contents of matrix glasses and glass inclusions in phenocrysts from tephra ejected during the Kuwae eruption. We establish that the Kuwae event did indeed yield a large release of sulfur gases. From our glass inclusion data and analysis, we calculate that the total atmospheric aerosol loading from the 1452 Kuwae eruption was ≫100 Tg H₂SO₄. Much of the volatile mass released during the eruption was probably contained in a separate, volatile-rich, fluid phase within the pre-eruptive Kuwae magma body. Comparing the volatile release of the Kuwae eruption with other large-magnitude eruptions, places Kuwae as the greatest sulfuric acid aerosol producer in the last seven centuries, larger even than sulfur emissions from the eruption of Tambora (Indonesia) in 1815, and possibly Laki (Iceland) in 1783. The severe and unusual climatic effects reported in the mid- to late-1450s were likely caused by the Kuwae eruption.