Mn(II)-catalysed S(IV) oxidation and its inhibition by acetic acid in acidic aqueous solutions

The kinetics of the S(IV) oxidation by oxygen in the presence of Mn(II) ions and acetic acid has been studied. Experiments were carried out at 25°C, 3.5?≤?pH?≤?5.0, [S(IV)]≈1?×?10^?3 mol/dm³, 1?×?10^?6 mol/dm³?≤?[Mn(II)]?≤?1?×?10^?5 mol/dm³, 1?×?10^?6 mol/dm³?≤?[CH₃COOH]?≤?1?×?10^?4 mol/dm³. Based on the experimental results, rate constants and orders of the reactions were determined. Depending on the reaction conditions, the observed rate constants for the Mn(II)-catalysed S(IV) oxidation ranged between 3.91?×?10^?8 and 8.89?×?10^?7 (mol/dm³) s^?1, and in the presence of acetic acid they ranged between 2.95?×?10^?8 and 7.45?×?10^?7 (mol/dm³) s^?1. The reaction order in S(IV) was zero for both reactions. The effect of Mn(II) ion and acetic acid concentrations as well as an initial pH of the solution on the S(IV) oxidation rate was discussed. It was found that the rate of the S(IV) oxidation depends on the initial pH of the solution but it is independent of the pH change during the reaction. Acetic acid has a weak inhibiting effect on the Mn(II)-catalysed S(IV) oxidation. Under the experimental conditions the S(IV) oxidation rate decreased no more than twice.     

U–Pb dating, Hf-isotope characteristics and trace-REE-patterns of zircons from Medet porphyry copper deposit, Bulgaria: implications for timing, duration and sources of ore-bearing magmatism

Precise U–Pb geochronology, Hf isotope compositions and trace element distributions in zircons are combined in the present study to define the timing and sources of the magmatism forming the Medet porphyry copper deposit, Bulgaria. ID-TIMS U–Pb-zircon dating demonstrates that ore-bearing magmatism extended for less than 1.12 Ma. As inferred from the field relationships, it started with the intrusion of a quartz-monzodiorite at 90.59?±?0.29 Ma followed by granodiorite porphyries at 90.47?±?0.30 and 90.27?±?0.60 Ma and by crosscutting aplite dykes at 90.12?±?0.36 Ma. These units were overprinted by potassic alteration and host economic copper-(Mo–Au) mineralization. The main magmatic–hydrothermal activity ceased after that, and a later quartz-granodiorite porphyry dyke, dated at 89.26?±?0.32 Ma, only contains an uneconomic quartz–pyrite mineralization. Assimilation of Lower Paleozoic rocks with a mantle to mantle–crust signature is characteristic of the fertile magma in the Medet deposit, as defined by positive ?-Hf values of the inherited zircons. The positive Ce-anomalies and the higher Eu/Eu* ratios of the zircons in the mineralized Cretaceous rocks of Medet deposit argue for crystallization from a generally more oxidized magma compared to the later quartz-granodiorite porphyry dyke. A change in paleostress conditions occurred during the intrusion of the Medet pluton and its dykes. The initial stage reveals E–W extension associated with N–S compression, whereas the younger granodiorite dyke was emplaced during subsequent N–S extension. The large-scale switch of the extensional stress regime during the mineralization was favourable for ore deposition by channelling the fluids and increasing the effective permeability.     

Chemical and isotopic variations in the Wiśniówka Mała mine pit water,Holy Cross Mountains (south-central Poland)

In 2005 and 2006, hydrogeochemical study was carried out in the bipartite Wiśniówka Mała pit lake of the Holy Cross Mountains (south-central Poland). This is the largest acidic water body in Poland. This report presents the element concentrations in the water and sediment, stable sulfur and oxygen isotope ratios in the soluble sulfates, and stable oxygen isotope ratio in the water. The scope of the investigation also encompassed mineralogical examinations (scanning electron microscope, X-ray diffraction) of the sediment. The results of this study show that there is a spatial and temporal variability in concentrations of most elements and sulfur isotope ratios in the examined pit lake. The water of the western pond displayed a lower pH with a mean of 3.73 and higher conductivity (390 μS cm⁻¹) as well as higher concentrations of sulfates (156 mg L⁻¹) and most of the cations and anions. The concentrations of Fe²⁺ and Fe³⁺ averaged 0.8 and 0.4 mg·L⁻¹. In contrast, the eastern pond water revealed a higher pH (mean of 4.36), lower conductivity (293 μS cm⁻¹) and lower sulfate (90 mg L⁻¹) and trace metal levels. Similar variations were recorded in the stable sulfur isotope ratios. The δ³⁴S_V-CDT(SO₄ ²⁻) values in the water of the western pit pond were in the range of −6.7 to −4.6‰ (mean of −5.6‰), whereas that in the eastern pit pond ranged from −2.2 to −0.9‰ (−1.6‰). The alkalinity of the entire lake water was below 0.1 mg·L⁻¹ CaCO₃. No distinct difference in the δ¹⁸O_V-SMOW(SO₄ ²⁻) was noted between the western and eastern pit ponds. Compared to the Purple Pond in the Sudetes (Poland) and similar sites throughout the world, the examined pit lake is highlighted by distinctly low concentrations of sulfates, iron and other trace metals. Based on this and other studies performed in the Holy Cross Mountains, a conclusion can be drawn that the SO₄ ²⁻ in the Wiśniówka Mała pit lake water is a mixture of SO₄ ²⁻ derived from the following sources: (1) pyrite oxidation (especially in the western pond water), (2) leaching of soluble sulfates from soils and waste material, as well as (3) subordinate deposition of airborne sulfate precipitation.     

Barium and radium discharged from coal mines in the Upper Silesia, Poland

 Waters discharged from coal mines in the Upper Silesia in Poland cause contamination of rivers and their sediments. Saline waters discharged from coal mines of the southern region contain elevated barium and radium. The discharge of these elements can be reduced by treating these waters with sulphates in mine workings. Sources of sulphate used in treatments include gypsum, anhydrite and industrial wastes such as: fly ash, slags and flotation tailings. Gypsum and anhydrite are used in the coal mine workings as components of the fire protection walls. Industrial wastes from power plants are stored in the mine workings as fire- and methane-protection agents. Sulphates precipitate barium and radium from saline waters inflowing into the mine workings. The waters can be treated by flowing them through old mine workings. In this case, the source of sulphates is the natural oxidation of pyrite. Mining activities and the natural process of desulphurisation of the Carboniferous rocks reduce the amount of barium and radium that is discharged in the southern region of Upper Silesia. The processes for reducing the environmental impact of toxic discharges from the mines should be monitored. Received: 3 July 1997 · Accepted: 27 March 2000     

Influence of Atmospheric Carboxylic Acids on Catalytic Oxidation of Sulfur(IV)

The influence of some low weight mono- and di-carboxylic acids, which were selected on the basis of analysis of the water-soluble fraction of size segregated marine and urban aerosols collected in Slovenia, on the kinetics of S(IV) oxidation catalyzed by Mn(II) under conditions representative of tropospheric liquid water, was investigated. Mono-carboxylic acids inhibit the oxidation, with the strongest influence found for formic acid. Inhibition by glycolic and lactic acid was found to be very similar, while the lowest inhibition was caused by acetic acid. Our results are in agreement with the proposed mechanism, i.e. scavenging of sulfate radicals, since the inhibiting effect of the individual acid increases with higher dissociation constant. An exception is formic acid, where the additional inhibiting steps should be responsible for the induction period and thus for higher inhibition. Malic and malonic acids have practically no influence, while oxalic acid slows down the oxidation, although to a lesser extent than mono-carboxylic acids. An extended version of a previously derived generalized simple kinetic model was also derived and applied for predicting the reaction kinetics in the presence of all examined carboxylic acids at pH 3.5 and 4.5.     

Organic petrology, mineralogy and depositional environment of the Kipra lignite seam, Maritza-West basin, Bulgaria

The aim of the present study is to provide additional information about the properties and depositional environment of the Kipra lignite seam, which was deposited during the regressive stage of development of the Maritza-West basin. Petrographical and mineralogical data, along with ash yields and sulphur contents of 24 samples from a seam profile, have been used to study the vertical variation of the depositional settings during peat accumulation and subsequent coalification.The Kipra lignite is characterized by high ash yields and sulphur contents. It formed in a rheotrophic, low-lying mire with alkaline pH value. Vegetation with low preservation potential dominated within the palaeomire. During peat formation, frequent changes of the water level controlled the depositional environment. During the deposition of units 1 and 2, high water energy caused the transportation of high amounts of inorganic material into the mire, resulting in the formation of weakly gelified mineral-rich lignite. The organic matter from units 3 and 4 is characterized by enhanced gelification, which probably reflects the decreasing energy of the system. Good positive correlation between sulphur contents and the GI values was established in units 4, indicating that the gelification of the tissues was probably mainly controlled by the bacterial activity. In contrast, the gelification of the samples from unit 3 of the Kipra seam was probably governed by the redox conditions. The organic matter deposited under relatively wet conditions, in which the thermal and oxidative destruction of the tissues, was limited.A variety of major, minor and accessory minerals are present in Maritza-West lignite. The mineral composition is dominated mainly by pyrite, gypsum and calcite, and to a lesser extent limonite, quartz, kaolinite, montmorillonite, illite, chlorite and plagioclase. Jarosite, hematite, halloysite, mica, K-feldspar, aragonite, siderite, and dolomite were also determined in very low concentrations. These minerals formed syngenetically and epigenetically. The syngenetic stage is characterized mainly by the formation of pyrite, carbonates, silicates and sulphates, whereas the Fe-oxyhydroxides, partially the carbonates and almost all silicates are of detrital origin. During the epigenetic stage, carbonates, sulphates, clay minerals, pyrite, and Fe-oxyhydroxides were formed. Alteration products like gypsum, jarosite, limonite, chlorite, kaolinite, illite, mica, and calcite were generated due to the transformation of detrital and authigenic minerals.     

Late Cretaceous eclogite in the Eastern Rhodopes (Bulgaria): evidence for subduction under the Sredna Gora magmatic arc

International Journal of Earth Sciences - The Rhodopes in Bulgaria and Greece represent a nappe stack of high-grade units with polymetamorphic history. Constraining the time of metamorphism in...     

Organic carbon and nutrient fluxes to the coastal zone from the Sepik River outflow

The Sepik River is a major contributor of water, sediment and associated organic loads to the coastal waters of northern New Guinea and the Bismarck Sea. We compare dissolved and particulate organic carbon data from September 1997 during an extremely dry El Nino year with those from 1996, 1999 and 2000 during La Nina wet season discharges. Estimated Sepik River flux of DOC is 3.2×10¹⁰ mol yr⁻¹ and POC is 1.1×10¹¹ mol yr⁻¹. The estimates for total river nutrient fluxes to the sea are 1.1×10¹⁰ mol yr⁻¹ for nitrogen and 4.6×10⁸ mol yr⁻¹ for phosphorus. The Sepik DOC flux is about equal to that combined from all four major rivers that enter the Gulf of Papua on the south coast of PNG. The Sepik inorganic PIC flux is low (1.4×10⁸ mol yr⁻¹) as the river does not drain carbonate soils. With a narrow continental shelf, and strong coastal currents, much of this exported material is available for long distance transport into the coastal Bismarck Sea and beyond.