Determination of historical emission of heavy metals into the atmosphere: Celje case study

The research shows that in the Celje area (Slovenia), the historical anthropogenical emissions are 1,712 tons of Zn and 9.1 tons of Cd. For Zn, this value represents approximately 0.3% of the total Zn production in that area. Close to the former zinc smelting plant, the “Zn precipitation” has been estimated to be up to 0.036 mm. The 100-year Zn production left behind a heavily contaminated area with maximum concentrations of Zn of up to 5.6% in attic dust and 0.85% in the soil, and 456 mg/kg of Cd in attic dust and 59.1 mg/kg in the soil. The calculation of historical emissions is based on the data of heavy metals concentration in the attic dust at 98 sampling points and on the data from 19 measurement sites of the weight of total monthly air deposit. The main idea behind determining past emissions is that when the weight of the deposited dust on a small area is multiplied by the concentration of the element in that area, the mass of the polluter which has been transported to the place of interest by air can be calculated. If we sum up all the weight over the whole geochemical anomaly, we get the quantity of historical emissions.     

The Mammoth Peak sheeted complex,Tuolumne batholith,Sierra Nevada,California: a record of initial growth or late thermal contraction in a magma chamber?

The Mammoth Peak sheeted intrusive complex formed in the interior of a ~7–10 km deep magma chamber, specifically in the Half Dome granodiorite of the Tuolumne batholith, central Sierra Nevada, CA (USA). The sheets consist of fractionated melts with accumulated hornblende, biotite, magnetite, titanite, apatite, and zircon. The accumulation, especially of titanite, had a profound effect on minor and trace elements (Nb, Ta, Ti, REE, U, Th, P, Zr, Hf, etc.), increasing their contents up to five to six times. Our thermal–mechanical modeling using the finite element method shows that cooling-generated tensile stresses resulted in the inward propagation of two perpendicular sets of dilational cracks in the host granodiorite. We interpret the sheeted complex to have formed by a crack-seal mechanism in a high strength, crystal-rich mush, whereby outward younging pulses of fractionated magma were injected into these syn-magmatic cracks at the margin of an active magma chamber. Thermal–mechanical instabilities developed after the assembly of the sheeted complex, which was then overprinted by late ~NW–SE magmatic foliation. This case example provides a cautionary note regarding the interpretation that sheeted zones in large granitoid plutons imply a diking mechanism of growth because the sheeted/dike complexes in plutons (1) may display inverse growth directions from the growth of the overall intrusive sequence; (2) need not record initial chamber construction and instead may reflect late pulsing of magma within an already constructed magma chamber; (3) have an overprinting magmatic fabric indicating the continued presence of melt after construction of sheeted complexes and thus a prolonged thermal history as compared to dikes; and (4) because the scale of the observed sheeted complexes may be small (<1%) in comparison to large homogenous parts of plutons, in which there is no evidence for sheeting or diking. Thus, where extensive dike complexes in plutons are absent, such as in much of the Tuolumne batholith, the application of an incremental diking model to explain chamber construction is at best speculative.     

Magmatic history and geophysical signature of a post-collisional intrusive center emplaced near a crustal-scale shear zone: the Plechý granite pluton (Moldanubian batholith,Bohemian Massif)

The Plechy pluton, southwestern Bohemian Massif, represents a late-Variscan, complexly zoned intrusive center emplaced near the crustal-scale Pfahl shear zone; the pluton thus provides an opportunity to examine the interplay among successive emplacement of large magma batches, magmatic fabric acquisition, and the late-Variscan stress field associated with strike-slip shearing. The magmatic history of the pluton started with the emplacement of the porphyritic Plechy and Haidmühler granites. Based on gravity and structural data, we interpret that the Plechy and Haidmühler granites were emplaced as a deeply rooted, ∼NE–SW elongated body; its gross shape and internal fabric (steep ∼NE–SW magmatic foliation) may have been controlled by the late-Variscan stress field. The steep magmatic foliation changes into flat-lying foliation (particularly recorded by AMS) presumably as a result of divergent flow. Magnetic lineations correspond to a sub-horizontal ∼NE–SW finite stretch associated with the divergent flow. Subsequently, the Třístoličník granite, characterized by steep margin-parallel magmatic foliation, was emplaced as a crescent-shaped body in the central part of the pluton. The otherwise inward-younging intrusive sequence was completed by the emplacement of the outermost and the most evolved garnet-bearing granite (the Marginal granite) along the southeastern margin of the pluton. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A new approach to modeling perpendicular fabrics in porphyritic plutonic rocks using the finite element method

A growing body of field evidence indicates that hypersolidus fabrics preserved in syntectonic plutons are likely to have formed in highly crystallized ‘rigid sponge’ magma. This paper demonstrates that such magma could be idealized as a rheological solid and that the development of non-coaxial fabrics in plutonic rocks can very conveniently be modeled in the framework of solid mechanics. Using the finite element method (FEM), we modeled two strain regimes of small magnitudes (plane-strain horizontal simple shear with the shear strain γ of up to 0.30 and plane-strain pure shear of up to 15% shortening) superposed onto vertically oriented and variously spaced elastic phenocrysts set in the viscoelastic matrix. In the simple shear regime, the phenocrysts slightly rotate toward the shear plane, while the principal strain directions in the matrix are instantaneously oriented at an angle of about 45° or less to the phenocryst fabric. Simple shear thus can only lead to the formation of oblique phenocryst and matrix fabrics. By contrast, the vertical phenocryst fabric is maintained in the pure shear regime, and a new horizontal fabric can develop almost instantaneously in the matrix even for small amounts of superposed shortening (5% shortening after 10 ky in our model). We conclude that such a mechanism can easily produce perpendicular hypersolidus fabrics in plutonic rocks and that only a very short time span (first thousands of years) is required to develop magmatic fabric in a pluton for ‘normal’ rates (10⁻¹⁵ to 10⁻¹³ s⁻¹) of tectonic deformation.     

Modelling of atmospheric dispersion of heavy metals in the Celje area,Slovenia

The aim of this research was to determine how fast the level of heavy metal concentrations in the air decreases in relation to increasing distance from the source of pollution and what the influence area is of the zinc smelting plant which existed for 100 years in Celje. In that period it produced approximately 580,000 tons of raw Zn from sphalerite ore by the pyrometallurgical process. The production left behind a heavily contaminated area, where the concentrations of Pb and Zn in the soil can be expressed as a percentage. A model has been made on the basis of the data of concentrations of Zn and Cd in the soil and attic dust regarding the distance and direction from the source of the pollution. Because Celje lies in a basin we chose a linear model, which describes the decreasing of the concentrations of Zn and Cd only in one direction. Sampling has been conducted on the four river valleys which stretch from the source of the pollution in all four directions: north, west, south and east, up to 13 km from the source. The power function with a negative exponent was used. With the solution to the calculated functions according to the distance, we can estimate the theoretical distance when the concentrations drop to the natural background level. The range of influence of the zinc smelting plant has been estimated to be between 14 and 52 km for the presence of anthropogenic Zn in attic dust and between 9 and 14 km for the presence of anthropogenic Zn in the soil, depending on the direction from the plant. Correlations between the measured values and the ones from the model are high: from 0.75 up to 0.98.     

Floodplain sediments of the 2002 catastrophic flood at the Vltava (Moldau) River and its tributaries: mineralogy,chemical composition,and post-sedimentary evolution

Fine-grained floodplain sediments of the catastrophic 2002 flood deposited along the lower reaches of the Berounka and Vltava Rivers, Czech Republic, were not highly contaminated with heavy metals and other toxic elements. This is due to the dominantly mineral character of the sediments (C_tot in the range 3.97–5.01%, relatively low content of clay minerals), and due to the very high degree of contamination dilution by eroded pre-industrial non-contaminated floodplain sediments. Despite this high degree of dilution, the influence of the small Litavka River, draining the historical Pb–Zn–Ag Příbram ore region, is well visible. The Litavka River is one of important sources of Pb and Zn contamination in the whole Berounka–Vltava–Labe river system. The 2002 flood sediments deposited in the floodplain of the Berounka and Vltava Rivers show poor vertical chemical zoning, except for some components enriched in the uppermost layer by precipitation from evaporated pore-water contained in the mud, i.e. secondary carbonate. The content of C_carb of the sediments (0.05–0.15%) is partly represented by this secondary carbonate, which is later leached by rainwater, and partly by fragments of river mollusk shells. A majority of the heavy metals contained in sediments can be readily leached by diluted acids, and to a much smaller degree by rainwater.     

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.     

Mercury contents in the vertical profiles through alluvial sediments as a reflection of mining in Idrija (Slovenia)

The influence of geomorphological factors to Hg contamination of the Idrijca River alluvial sediments because of the historical mining and ore roasting activities has been studied. Main source of Hg in alluvial sediments was dumping of ore roasting residues and mining waste into the river channel and its erosion downstream. The position of the material in relation to the geomorphological properties is highly related with its Hg content. Floodplains were found to be the most contaminated geomorphological units (mean Hg content 335 mg/kg), with Hg concentration rapidly dropping in the first terrace (155 mg/kg). The least contaminated material was found in the higher terraces (3.8 mg/kg). Sampling upstream Idrija (average Hg content is 22.1 mg/kg) shows that not only mine and ore roasting plant increased Hg levels in alluvial deposits but also contaminated sites upstream Idrija contribute to Hg contamination. Geochemical background for alluvial sediments for this area is estimated to be 0.75 mg/kg. Downstream Idrija, 9 hotspots were determined where highly contaminated material is actively eroded and carries a high risk of further contamination of the So?a River and northern Adriatic Sea ecosystems.     

Influence of sample size on ecological status assessment using marine benthic invertebrate‐based indices

Routine monitoring of the quality status of water bodies demands the best cost‐benefit relation and sample‐size reduction is therefore welcomed. However, great caution is needed because such reduction affects the accuracy and variation of the results. In the present study we tested the influence of sample size (number of replicate samples) on reference condition values and within‐sample ecological quality ratio (EQR) variability of six commonly used ecological indices (taxa richness, Shannon–Wiener diversity, AMBI, Medocc index, Bentix and M‐AMBI). Analysis of soft‐bottom benthic invertebrate data from Slovenian coastal waters showed that sample size influenced the reference condition values of richness/diversity indices (taxa richness and Shannon–Wiener diversity) but not of the sensitivity/tolerance indices (AMBI, Medocc index, Bentix). Increased sample size decreased the within‐sample EQR variability and, concomitantly, increased the accuracy of site ecological status classification for all indices. The size of EQR variability differed depending on the index used. EQR variability of M‐AMBI, an index composed of metrics with different within‐sample EQR variability, was statistically the same as that of the metric with the lowest within‐sample EQR variability. Whether this is a common principle for multimetric indices remains to be confirmed. Based on these results, the use of at least three replicates is suggested to obtain reliable measures of reference condition and EQR for the assessment of ecological status. This level of replication is particularly necessary in areas with high diversity and environmental patchiness, and when richness/diversity measures and indices that include these measures are used.