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Aquatic Geochemistry (v.12, #3)

Sulphate Sources in the Sava and Ljubljanica Rivers, Slovenia, Inferred from Sulphur and Oxygen Isotope Compositions by Barbara Vokal-Nemec; Janina Szaran; Andrzej Trembaczowski; Stanislaw Halas; Tadej Dolenec; Sonja Lojen (pp. 199-220).

Measurements were made of sulphur and oxygen isotope ratios of sulphate in some Slovenian rivers, lakes and tap waters. δ³⁴S ranged from −0.2 to + 13.3‰, δ¹⁸O ranged from +4.9 to + 13.6‰, and the sulphate content varied from 0.8 to 41.4 mg/L. Rivers flowing from the Julian Alps contain a very low amount of sulphate that is leached from a thin horizon of soil by rain. As confirmed by their low δ¹⁸O values, these sulphates do not enter the rivers directly in rain, but arise from biochemical cycling in the soil. The low δ³⁴S of this sulphate indicates that it originates from the oxidation of sedimentary sulphides. The evolution of sulphates along the river course was investigated for the Sava and Ljubljanica rivers. The variations observed in sulphate from the waters studied result from variations in the contribution of sulphates of different origin. Downstream the Sava River sulphate is depleted in the heavy isotopes of both sulphur and oxygen, with δ-values gradually tending toward the δ-values of groundwater sulphates in the watershed. In contrast, the δ-values of sulphate in the Ljubljanica River are almost constant and similar to those of sulphate in local groundwater. Introduction of water from Italian and Slovenian mines was recorded in the Soča River, where the lowest δ³⁴S value of sulphate sulphur (−0.2‰) was observed. In addition, the influence of sulphate from the oxidation of sedimentary sulphides was recorded in the Sotla River. No evidence was found for introduction of sulphate from factories.

Keywords: Ljubljanica River; oxygen isotopes; Sava River; sulphates; sulphur isotopes

Barium in Deccan Basalt Rivers: Its Abundance, Relative Mobility and Flux by Anirban Das; S. Krishnaswami (pp. 221-238).

The concentration of dissolved Ba in a number of rivers having their drainage almost entirely in Deccan Trap basalts has been measured. These results along with available data on the abundances of major elements in these waters, and on Ba and major elements in bed sediments of these rivers provide a measure of (i) the relative mobility of Ba during chemical weathering and erosion of basalts, particularly with respect to alkaline earths, Mg, Ca and Sr, and (ii) the flux of Ba out of the Deccan and its global significance. The concentration of dissolved Ba ranges from 8 to 105 nM. The average Ba/Mg*, Ba/Ca* and Ba/Sr (* is concentration corrected for atmospheric contribution) in waters is lower than the corresponding mean ratios in Deccan basalts, though they overlap within errors. Majority of the water samples, however, have ratios less than that in basalts. These findings can be interpreted as a cumulative effect of limited release/mobility of Ba during chemical weathering and erosion of basalts and its reactive behaviour in waters which promote its association with clays and oxy-hydroxides of Fe. These results also indicate that during chemical erosion of Deccan basalts, Ba is the least mobile among the alkaline earth elements. The abundance of Ba in sediments and their Ba/Al ratios relative to basalts are consistent with the above conclusion. Ba/Mg and Ba/Ca ratios in water and in sediments from the same location are strongly correlated; however, the mean ratios in waters are far less than those in sediments. This is a result of limited Ba mobility, effectively 5–6 times lower than that of Mg. The annual flux of dissolved Ba out of the Deccan Traps is ~1 × 10⁷ moles, ~ 0.2% of its global riverine transport to oceans. The contribution of dissolved Ba from Deccan Traps, seem lower than its aerial coverage, ~ 0.5% of the global drainage area; the potential causes for this could be the lower abundance of Ba in basalts relative to “average continental crust”, and its behaviour during chemical weathering and erosion.

Keywords: barium; chemical weathering; Deccan basalts; dissolved flux; rivers

On the Direction and Magnitude of Oxygen Isotope Fractionation Between Calcite and Aragonite at Thermodynamic Equilibrium by Gen-Tao Zhou; Yong-Fei Zheng (pp. 239-268).

Oxygen isotope fractionation factors between calcium carbonates and water have been applied to ancient marine geochemistry principally for the purpose of geothermometry. The problem was encountered, however, with respect to the direction and magnitude of oxygen isotope fractionation between calcite and aragonite at thermodynamic equilibrium. This basically involves sound understanding of both thermodynamics and kinetics of oxygen isotope fractionation between inorganically precipitated carbonate and water at low temperatures. Thus the crucial issues are to acknowledge the processes of chemical reaction and isotopic exchange during precipitation of CaCO₃ minerals in solution, the kinetic mechanism of isotope equilibrium or disequilibrium, the effect of polymorphic transition from metastable aragonite to stable calcite under hydrous or anhydrous conditions, and the presence or absence of isotope salt effect on oxygen isotope exchange between carbonate and water in response to the hydrous or anhydrous conditions at thermodynamic equilibrium. Because good agreements exist in carbonate–water oxygen isotope fractionation factors between theoretical calculations and experimental determinations, it is encouraging to applying the thermodynamic and kinetic data to isotopic paleothermometry and geochemical tracing.

Keywords: calcium carbonate; experimental determination; fractionation factor; kinetic mechanism; oxygen isotope; theoretical calculation; thermodynamic equilibrium

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt by J. Sánchez España; E. López Pamo; E. Santofimia Pastor; J. Reyes Andrés; J. A. Martín Rubí (pp. 269-298).

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.

Keywords: acid mine drainage; Fe(III) hydrolysis; schwertmannite; metal sorption; natural attenuation

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Aquatic Geochemistry (v.12, #3)

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Aquatic Geochemistry (v.12, #3)