A Simple Kinetic Model for Autoxidation of S(IV) Oxides Catalyzed by Iron and/or Manganese Ions

The reaction kinetics of S(IV) autoxidation catalyzed by single metal ions of Mn(II) and Fe(II) or Fe(III) and by a mixture of Mn(II) and Fe(II) under the conditions representative for acidified atmospheric liquid water was investigated. A simple power law kinetic model based on the stability constants for metal-sulfito complexes formed during the first step of a radical chain mechanism predicts well the kinetics for the reactions catalyzed by single metal ions. The calculated stability constants for iron (5.7×10³ dm³ mol^–1) and manganese (10×10⁴ dm³ mol^–1) sulfito complexes are close to those reported in the literature. The catalytic synergism between Mn(II) and Fe(II) was confirmed. For this system the following power law rate equation was suggested:r_tot = S_Fe · r_Fe + S_Mn · r_Mn ,where r_Fe and r_Mn are the reaction rates in the presence of Fe(II) and Mn(II), respectively. S_Fe and S_Mn are proportional factors, which account for the synergistic effect. The proposed power law rate equation predicts the reaction kinetics very well. The values of S_Fe (1.35) and S_Mn (15) indicate that the influence of Fe(II)/Fe(III) on Mn(II)/Mn(III) cycling is larger than, vice versa, agreeing with the reaction mechanism proposed for the S(IV) autoxidation catalyzed by mixed metal ions.     

Intensive sampling of iodine and nutrient speciation in naturally eutrophicated anchialine pond (Rogoznica Lake) during spring and summer seasons

A study of inorganic iodine speciation in the water column of a naturally eutrophicated anchialine pond (Rogoznica Lake, East Adriatic Coast) was conducted in a period between April and July 2004 to obtain information how close the inorganic iodine system is to that of inorganic nutrients during spring, when phytoplankton activity is at maximum, and how the system changes up to summer, when highly reducible redox-conditions prevail in deep water.     

S(IV) Autoxidation in Atmospheric Liquid Water: The Role of Fe(II) and the Effect of Oxalate

The reactivity of dissolved iron compounds towards different pollutants and photooxidants in atmospheric liquid water depends upon the oxidation state and speciation of iron. Our measurements of the oxidation state of dissolved iron eluted from aerosol particles (Dae: 0.4–1.6 m) collected in the urban atmosphere of Ljubljana showed that a large fraction of the iron content is present as Fe(II). The concentration ratio [Fe(II)]/[Fe(III)] varied between 0.9 and 3.1. The kinetics of S(IV) autoxidation catalyzed by Fe(II) under the conditions representative for acidified atmospheric liquid water and the influence of oxalate on this reaction under dark conditions was investigated. The reaction rate is the same if Fe(II) or Fe(III) is used as a catalyst under the condition that Fe(II) can be oxidized in Fe(III), which is the catalytically active species. Oxalate has a strong inhibiting effect on the S(IV) autoxidation in the presence of Fe(II). The reaction is autocatalytic with an induction period, that increases with higher concentrations of oxalate. The inhibiting effect of oxalate differs according to whether iron is initially in the Fe(II) or Fe(III) state. However, in both cases the inhibition by oxalate is a result of the formation of complexes with the catalyst.     

Late Cretaceous porphyry Cu and epithermal Cu–Au association in the Southern Panagyurishte District,Bulgaria: the paired Vlaykov Vruh and Elshitsa deposits

Vlaykov Vruh–Elshitsa represents the best example of paired porphyry Cu and epithermal Cu–Au deposits within the Late Cretaceous Apuseni–Banat–Timok–Srednogorie magmatic and metallogenic belt of Eastern Europe. The two deposits are part of the NW trending Panagyurishte magmato-tectonic corridor of central Bulgaria. The deposits were formed along the SW flank of the Elshitsa volcano-intrusive complex and are spatially associated with N110-120-trending hypabyssal and subvolcanic bodies of granodioritic composition. At Elshitsa, more than ten lenticular to columnar massive ore bodies are discordant with respect to the host rock and are structurally controlled. A particular feature of the mineralization is the overprinting of an early stage high-sulfidation mineral assemblage (pyrite ± enargite ± covellite ± goldfieldite) by an intermediate-sulfidation paragenesis with a characteristic Cu–Bi–Te–Pb–Zn signature forming the main economic parts of the ore bodies. The two stages of mineralization produced two compositionally different types of ores—massive pyrite and copper–pyrite bodies. Vlaykov Vruh shares features with typical porphyry Cu systems. Their common geological and structural setting, ore-forming processes, and paragenesis, as well as the observed alteration and geochemical lateral and vertical zonation, allow us to interpret the Elshitsa and Vlaykov Vruh deposits as the deep part of a high-sulfidation epithermal system and its spatially and genetically related porphyry Cu counterpart, respectively. The magmatic–hydrothermal system at Vlaykov Vruh–Elshitsa produced much smaller deposits than similar complexes in the northern part of the Panagyurishte district (Chelopech, Elatsite, Assarel). Magma chemistry and isotopic signature are some of the main differences between the northern and southern parts of the district. Major and trace element geochemistry of the Elshitsa magmatic complex are indicative for the medium- to high-K calc-alkaline character of the magmas. ⁸⁷Sr/⁸⁶Sr_(i) ratios of igneous rocks in the range of 0.70464 to 0.70612 and ¹⁴³Nd/¹⁴⁴Nd_(i) ratios in the range of 0.51241 to 0.51255 indicate mixed crustal–mantle components of the magmas dominated by mantellic signatures. The epsilon Hf composition of magmatic zircons (+6.2 to +9.6) also suggests mixed mantellic–crustal sources of the magmas. However, Pb isotopic signatures of whole rocks (²⁰⁶Pb/²⁰⁴Pb = 18.13–18.64, ²⁰⁷Pb/²⁰⁴Pb = 15.58–15.64, and ²⁰⁸Pb/²⁰⁴Pb = 37.69–38.56) along with common inheritance component detected in magmatic zircons also imply assimilation processes of pre-Variscan and Variscan basement at various scales. U–Pb zircon and rutile dating allowed determination of the timing of porphyry ore formation at Vlaykov Vruh (85.6 ± 0.9 Ma), which immediately followed the crystallization of the subvolcanic dacitic bodies at Elshitsa (86.11 ± 0.23 Ma) and the Elshitsa granite (86.62 ± 0.02 Ma). Strontium isotope analyses of hydrothermal sulfates and carbonates (⁸⁷Sr/⁸⁶Sr = 0.70581–0.70729) suggest large-scale interaction between mineralizing fluids and basement lithologies at Elshitsa–Vlaykov Vruh. Lead isotope compositions of hydrothermal sulfides (²⁰⁶Pb/²⁰⁴Pb = 18.432–18.534, ²⁰⁷Pb/²⁰⁴Pb = 15.608–15.647, and ²⁰⁸Pb/²⁰⁴Pb = 37.497–38.630) allow attribution of ore-formation in the porphyry and epithermal deposits in the Southern Panagyurishte district to a single metallogenic event with a common source of metals.     

A forecast of public water scarcity on Leu-Rotunda Plain,Romania, for the end of the 21st century

The article examines the risk of water shortages due to the climate change on Leu-Rotunda Plain, which is part of Oltenia Plain in Romania. The region has been exposed to several extreme climatic phenomena, mostly droughts, which has created several problems related to water quality and quantity. The authors defined climate change scenarios using two regional climate models. Water resources under climate change were estimated by a regional numerical groundwater model covering a deep aquifer. The water demand components were estimated for households, industries, services, and livestock, based on specific socio-economic assumptions. A non-probabilistic risk assessment, using simplified fuzzy sets mathematics, was used to estimate water supply, water demand, and the consequences of water shortages. The results of the study revealed significant vulnerability in the water supply, a limited territorial expansion of sewerage networks, an expected increase in households’ demand, an expected increase in industrial and services water demand, a relatively stable demand for water for livestock farming, and an important water shortage in the study area. The authors conclude by highlighting a set of actions to mitigate the risk of the potential crisis.     

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.     

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.     

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.     

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.