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.     

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.     

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.     

The Effect of Atmospheric Organic Compounds on the Fe-Catalyzed S(IV) Autoxidation in Aqueous Solution

Laboratory experiments were conducted with real atmospheric aerosol particles as well as with synthetic solutions under dark conditions, to simulate some of the chemical features of aerosols. In solutions obtained by the leaching of aerosols (size range >D _ae: 0.4–1.6 m) that contained sufficient amounts of transition metal ions (e.g. Fe) and organic species (e.g. oxalate), S(IV) oxidation rates were significantly lower than those expected from the Fe-catalyzed S(IV) autoxidation in Milli-Q water. The results suggest that oxalate is responsible for much of the observed inhibition. Acetate and formate also inhibit the reaction, but to a much lesser extent. Oxalate has a strong inhibiting effect on the Fe-catalyzed S(IV) autoxidation at all investigated pH values (2.8, 3.7 and 4.5). It was established that Fe(III)-oxalato complexes affect the redox cycling of Fe(II)/Fe(III) and that the observed decrease of the reaction rate is caused by the reduced amount of catalytically active Fe(III) due to the complexation with oxalate. For the system Fe-S(IV)-O₂-oxalate at initial pH 3.7 the reaction rate was calculated using exponential simplification to account for oxalate influence on the amount of free Fe(III) by the following equation:–r_S(IV) = k · [S(IV)] · [Fe(III))] · e ^-b·[Ox]     

Household dust and street sediment as an indicator of recent heavy metals in atmospheric emissions: a case study on a previously heavily contaminated area

Determination of the origin of heavy metals in the household dust and street sediment in a previously heavily contaminated area was carried out. The main question addressed was the origin of heavy metals in dry and wet air deposits measured in the environmental monitoring programme of the community of Celje. There are two possible sources: present atmospheric emissions by industries in Celje and dusting of previously heavily contaminated soil. Determination of the present emissions was done on the basis of a method based on enrichment factor calculations. Samples of soil, street sediment and household dust in the contaminated area and in a non-contaminated sampling point were analysed. Expected heavy metal concentrations in household dust and street sediment in the previously heavily polluted area according to the level of measured soil contamination were calculated. Expected and measured values were compared to detect possible present atmospheric emissions. The data show higher enrichment with elements related to ironworking activities (Fe, Co, Cr, Mn, Ni) in household dust and street sediment, according to the concentrations in the soil in the vicinity of ironworks in comparison to the reference point. Similar observations can be made at the sampling point, east of a factory producing TiO₂-based white pigment for Ti, because emissions from it are expected. In contrast, the same trend is not observed for elements related to pollution problems in Celje (Cd, Zn, Pb). This indicated that street sediment and household dust might be a good tracer of present atmospheric emissions, despite the fact that the environment was previously highly contaminated. The method yields good results, which fit very well with expectations.     

Development of a River Macrophyte Index (RMI) for assessing river ecological status

We present the process of developing a macrophyte based index (River Macrophyte Index – RMI) for assessing river ecological status, that would be applicable for rivers with moderate to high water alkalinity, flowing over low slope terrain. A reference value and boundary values were determined for five ecological classes. The relation between the developed index and two existing indices, the Reference Index (RI) and the Trophic Index of Macrophytes (TIM), and selected environmental variables was established. The RMI is based on species composition and abundance from 208 sampling sites being in reference or good hydromorphological conditions and differing in the catchment land use. The percentage of natural areas in the sub-catchment was used for classifying macrophyte taxa into 5 ecological groups. 65 plant taxa, of which 47 were identified as indicator taxa, were included in the analysis. To assess the ecological status of a river site, the presence of at least 3 indicator taxa is necessary, otherwise the assessment is considered inconclusive. RMI is expected to indicate multiple pressures on the river, including trophic level. The developed index and RI and TIM indices differed in relation to slope, distance to source and catchment size.     

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.     

Biological and hydromorphological integrity of the small urban stream

Biological and hydromorphological integrity of five reaches of the small urban stream were assessed. Because macroinvertebrate communities respond to both organic pollution and habitat change, impacts of both measures can be hardly separated. In our study on the urbanized small stream, an impact of organic pollution was excluded as all five sampling sites were assessed as moderately polluted. On the other hand differences in morphological degradation of banks and channel of selected sites enabled us to relate hydromorphological stress and biotic metrics and taxa. Physical habitat quality was assessed using River habitat survey (RHS) methodology. A downstream-upstream gradient of physical habitat degradation was observed and related to the macroinvertebrate community characteristics. Similarity analyses and biotic metrics were calculated and correlated with results of the RHS analyses. Composition of the macroinvertebrate assemblages did not follow the longitudinal pattern of habitat modification observed by the RHS analysis. However, some metrics corresponded well. Percentage of detritivores, percentage of Caenis luctuosa, number of individuals, percentage of EPT individuals were best predictors of changes in the physical habitat quality. However, the metric percentage of EPT individuals was negatively correlated to the habitat degradation, what is in contradiction with results from studies of other authors.