Water-soluble main ions in precipitation over the southeastern Adriatic region: chemical composition and long-range transport

Background, aim and scope  

Precipitation samples collected from 1995 to 2000 at meteorological station in the eastern outskirts of Herceg Novi (Montenegro) were analysed on Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl^–, SO₄ ^2–, NO₃ ^– and NH₄ ⁺. Four-day backward trajectory simulations were conducted during the precipitation period to investigate the regional transport of main ions and their deposition in the region of the southeastern Adriatic Sea. The air mass trajectories were classified into six trajectory categories by the origin and direction of their approach to Herceg Novi.     

Polyacetal Polyols for Polyurethanes

The synthesis of telechelic polyacetals with terminal hydroxyl groups (polyacetal polyols), by the reaction of triethylene glycol divinyl ether with dipropylene glycol in the presence of trimethylolpropane or other triols or diols as starters, in acidic catalysis, has been studied. The synthesized liquid polyacetal triols and polyacetal diols were characterized by hydroxyl number, viscosity, acidity, number average molecular weight (M_n), weight average molecular weight (M_w), molecular weight distribution (M_w/M_n), FT-IR spectra. The obtained polyacetals were transformed in cast elastomers by the reaction with the isocyanate Mondur CD (modified diphenyl methane diisocyanate) with properties very close to the elastic polyurethanes obtained by using conventional polyether triols, copolymers propylene oxide–ethylene oxide. The polyacetal polyols are suitable for the synthesis of elastic polyurethanes (polyurethane elastomers, flexible polyurethane foams). Polyacetals are well known biodegradable polymers. Therefore, the polyurethanes based on polyacetal polyols are expected to be biodegradable.     

Bioaccumulation of Metals in Fish of Salmonidae Family and the Impact on Fish Meat Quality

The study was aimed at determining the levels of metals in water samples and muscles of the fish caught in the Una River basin, located in the northwestern part of Bosnia and Herzegovina. For that purpose, three fish species: Brown Trout (Salmo trutta m. fario), Grayling (Thymallus thymallus) and Californian Trout (Salmo gairdneri), together with stem water samples, were analyzed for metal concentrations (Pb, Hg, Cd, As, Mn, Ni, Cu, Cr, Se, Co, Sn, Zn, Fe, Ca, P) during a 2-year period. The fish was captured using electric fishing, nets or fishing equipment. The capture was undertaken on three sites (the river source, the middle flow and the river mouth) of each of the five biggest rivers belonging to the Una River basin (Unac, Krušnica, Sana, Klokot, and Una). The concentrations of metals in each sample were determined via atomic absorption spectrophotometry. In the tested waters, the presence of Mn in concentrations higher than permitted (0.07 mg/l) had been detected. In the tested meat, the following average concentrations of metals (mg/kg) had been found: Pb (0.67), Cd (0.06), Mn (0.65), Ni (0.15), Cu (0.79), Cr (1.05), Se (0.03), Zn (8.92), Fe (5.40), Ca (14.68), and P (10.85). The correlation between Mn concentrations identified in the tested waters and those identified in the meat of Brown Trout was revealed to be statistically significant, which confirms that, over time, bioaccumulation of metals took place. Even though the results were not indicative of contamination, they strongly suggest that constant monitoring of the ecosystems in reference should be implemented.     

Selective removal of heavy metals from metal-bearing wastewater in a cascade line reactor

Goal, Scope and Background This paper is a part of the research work on ‘Integrated treatment of industrial wastes towards prevention of regional water resources contamination — INTREAT’ the project. It addresses the environmental pollution problems associated with solid and liquid waste/effluents produced by sulfide ore mining and metallurgical activities in the Copper Mining and Smelting Complex Bor (RTB-BOR), Serbia. However, since the minimum solubility for the different metals usually found in the polluted water occurs at different pH values and the hydroxide precipitates are amphoteric in nature, selective removal of mixed metals could be achieved as the multiple stage precipitation. For this reason, acid mine water had to be treated in multiple stages in a continuous precipitation system-cascade line reactor. Materials and Methods All experiments were performed using synthetic metal-bearing effluent with chemical a composition similar to the effluent from open pit, Copper Mining and Smelting Complex Bor (RTB-BOR). That effluent is characterized by low pH (1.78) due to the content of sulfuric acid and heavy metals, such as Cu, Fe, Ni, Mn, Zn with concentrations of 76.680, 26.130, 0.113, 11.490, 1.020 mg/dm³, respectively. The cascade line reactor is equipped with the following components: for feeding of effluents, for injection of the precipitation agent, for pH measurements and control, and for removal of the process gases. The precipitation agent was 1M NaOH. In each of the three reactors, a changing of pH and temperature was observed. In order to verify efficiency of heavy metals removal, chemical analyses of samples taken at different pH was done using AES-ICP. Results Consumption of NaOH in reactors was 370 cm³, 40 cm³ and 80 cm³, respectively. Total time of the experiment was 4 h including feeding of the first reactor. The time necessary to achieve the defined pH value was 25 min for the first reactor and 13 min for both second and third reactors. Taking into account the complete process in the cascade line reactor, the difference between maximum and minimum temperature was as low as 6°C. The quantity of solid residue in reactors respectively was 0.62 g, 2.05 g and 3.91 g. In the case of copper, minimum achieved concentration was 0.62 mg/dm³ at pH = 10.4. At pH = 4.50 content of iron has rapidly decreased to < 0.1 mg/dm³ and maintained constant at all higher pH values. That means that precipitation has already ended at pH=4.5 and maximum efficiency of iron removal was 99.53%. The concentration of manganese was minimum at pH value of 11.0. Minimum obtained concentration of Zn was 2.18 mg/dm³ at a pH value of 11. If pH value is higher than 11, Zn can be re-dissolved. The maximum efficiency of Ni removal reached 76.30% at a pH value of 10.4. Discussion Obtained results show that efficiency of copper, iron and manganese removal is very satisfactory (higher than 90%). The obtained efficiency of Zn and Ni removal is lower (72.30% and 76.31%, respectively). The treated effluent met discharge water standard according to The Council Directive 76/464/EEC on pollution caused by certain dangerous substances into the aquatic environment of the Community. Maximum changing of temperature during the whole process was 6°C. Conclusion This technology, which was based on inducing chemical precipitation of heavy metals is viable for selective removal of heavy metals from metal-bearing effluents in three reactor systems in a cascade line. Recommendations and Perspectives The worldwide increasing concern for the environment and guidelines regarding effluent discharge make their treatment necessary for safe discharge in water receivers. In the case where the effluents contain valuable metals, there is also an additional economic interest to recover these metals and to recycle them as secondary raw materials in different production routes. ESS-Submission Editor: PhD Hailong Wang, hailong.wang@ensisjv.com     

Distribution and fractionation of heavy metals in the Tisa (Tisza) River sediments

Introduction In this work, sediments of the River Tisa (Tisza) are studied to assess their environmental pollution levels for some major heavy metals, as well as to predict the investigated elements’ mobility on the basis of their association type with the substrate. The Tisa River catchments area is a subbasin of the River Danube. Part of this river, 166 km long, belongs to the Serbian province of Vojvodina, before it flows into the Danube. It has been chosen for our investigation, because it has been exposed to intense pollution in the last decades. Materials and Methods The river sediment samples were collected at 32 locations. The proportions of sand, silt and clay fractions were determined. The sequential extraction procedure following a modified Tessier method was applied for speciation of the metal forms in the collected samples. The metal concentrations of Zn, Cd, Pb, Ni, Cu, Cr, Fe and Mn in extracts were determined by atomic absorption spectroscopy. Results and Discussion Granulometric analysis showed that some 50% of the Tisa River sediments were silt and clay, while the rest was sand with quartz, as the main constituent. The average metal content of the surface river sediment samples for every fraction of sequential extraction was presented and discussed in relation to pH, Eh and metal fractionation. The average metal content from the Tisa River sediments, obtained as an average of the metal’s concentration released in all five sequential extraction fractions was compared with: average metal contents of the Tisa River sediments in Hungary, metal content in soils formed on the Tisa River alluvium of Vojvodina, average metal content in soils of Vojvodina, and average metal content in soils of Hungary. An assessment of metal pollution levels in Tisa River sediments was made by comparing mean values for obtained results for the Tisa River sediments with the freshwater sediment’s Quality Guidelines as published by US EPA, Environment Canada and soil standards for Serbia. Conclusion According to US EPA and Canadian Quality Guidelines for freshwater sediments, the concentration of heavy metals in Tisa sediments were: (a) much higher than defined concentrations below which harmful effects on river biota are unlikely to be observed, (b) below defined concentrations above which harmful effects on river biota are likely to be observed. The concentration levels of Pb, Ni, Cu and Cr in Tisa River sediments are safe when compared with Serbian MAQ (Maximum Allowed Quantity) standards for soils, but they are unsafe in the case of Zn and Cd. Recommendations and Outlook The quality of sediments in the Tisa River was on the border line between potentially polluted and polluted. This line could very easily be exceeded since the quality of sediments in the Tisa River in Hungary was already worse than in Serbia. These results indicated the need for further monitoring of heavy metals in that locality.     

Levels of PAHs in the soils of Belgrade and its environs

Polycyclic aromatic hydrocarbons (PAHs) were analysed in 39 soil samples (0–10 cm upper layer) collected in Belgrade, the capital of Serbia. The sampling sites were randomly selected from urban, urban/recreational and rural areas; the samples were collected in April and December 2003 and July and October 2004. The sum of the 16 PAHs corresponding to the recreational zone (298 μg/kg) was close to the urban zone (375 μg/kg). Mean soil ΣPAH concentration from rural areas was 18 μg/kg dry weight. Comparing to values observed in the urbanized locations around the world, the overall levels of PAHs in this study are low. The PAH ratios obtained pointed to a domination of pyrogenically formed PAHs in the examined soils. The dominant PAHs in soil samples in urban zones were fluoranthene, benz[a]anthracene, phenanthrene and pyrene, mostly emitted from noncatalyst vehicles which are still in use in Serbia. The total carcinogenic potency for each sampling site was calculated. Regardless of the used carcinogenic activity factors, carcinogenic potency of 7 sites were 3–9 times higher than the reference ones indicating the increased carcinogenic burden of soils from these sites.     

Distribution of heavy elements in urban and rural surface soils: the Novi Sad city and the surrounding settlements, Serbia

Concentrations of ten heavy elements (Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn), as well as the pH values, organic matter contents, and electrical conductivities were measured in the surface soil samples collected from 21 sites of urban areas in the city of Novi Sad, the second largest city in Serbia, its suburban settlement and the nearby villages. Range of the heavy element concentrations was from 0.16 mg/kg (for Hg) to 18,994 mg/kg (for Fe). Significantly higher Hg and Mn concentrations were observed in subgroups with rural and market garden samples in comparison to the subgroups with urban and grassland samples, respectively, while the contents of Pb found in the grasslands subgroup were significantly higher than in the subgroup with market garden soils. Only one sample of urban soil exceeded the maximum permissible value for Zn set by the relevant Serbian legislation. According to the Dutch soil quality standard, the Cd and Co concentrations in majority of the examined soils were higher than the target values for unpolluted soil. The content of Hg was above the target value in 52% of the samples, most of them belonging to the subgroup of market garden soils. The results for the Novi Sad city area were compared to the relevant data available for other cities in the Western Balkan Countries. Principal component analysis of data revealed seven outlying samples, while the rest of the analyzed samples were grouped together indicating similar heavy element patterns most probably due to mixed emission sources.     

Phytoplankton abundance and pigment biomarkers in the oligotrophic, eastern Adriatic estuary

Phytoplankton distribution and environmental characteristics were determined in a shallow, highly stratified and oligotrophic estuary (Zrmanja, eastern Adriatic). Samples were collected in two contrasting seasons; winter (February 2000), when river discharge was high, and in summer (July 2003), a period of drought. Phytoplankton distribution was closely related to salinity gradients, nutrient levels, and water residence time. Microscopic analysis revealed that phytoplankton was composed mainly of marine diatoms, dinoflagellates, cryptophytes, green flagellates, and coccolithophorids. The dominant biomarker pigments were fucoxanthin, alloxanthin and 19'-hexanoyloxyfucoxanthin, while lower, but indicative contributions of peridinin and chlorophyll b were also noted. Maximum abundance and biomass were found in the middle estuary in winter and in the upper estuary in summer. The estuary is mostly P-limited. Development of chain-forming marine diatoms was evident in winter. Due to the reduced nutrient input in summer, the biomass accumulated in the upper estuary (1,000 ng chlorophyll a l(-1)) was composed mostly of nanoplanktonic unicellular diatoms, nanoplanktonic marine dinoflagellates, cryptophytes, and chlorophytes. The concentrations of about 200 ng l(-1) hex-fuco, suggested that the contribution of prymnesiophytes to total biomass was comparable to that of diatoms and dinoflagellates. In the middle estuary and coastal sea, PO(4) and TIN were 3.5 times lower, resulting in a fivefold decrease in biomass (<100 ng chlorophyll a l(-1)). The oligotrophic Zrmanja and other karstic rivers discharging in the eastern Adriatic Sea, provide insufficient source of nutrients and low productivity of the eastern Adriatic Sea.     

Fractionation and potential mobility of trace metals in Danube alluvial aquifer within an industrialized zone

Thirty-five alluvial sediments of the River Danube and 12 groundwater samples were taken within the Pan?evo Oil Refinery (Serbia). The results for groundwater samples exceed European primary drinking water standards for Fe (obtained results, >200 μg/l) and Mn (obtained results, >50 μg/l), while the levels of the trace metals are below the thresholds for drinking water quality. Sediments were treated by sequential extraction procedure with five different solutions, each having a higher extraction capacity than the previous one. We also wanted to determine the possible relationships among trace metals and between sediment properties and elemental concentrations. These solutions partitioned metals into CH₃COONH₄ extractable (F1); HCl carbonate extractable and NH₂OH·HCl easily reducible (F2); (NH₄)₂C₂O₄/H₂C₂O₄ moderately reducible (F3); H₂O₂–HNO₃ organic/sulfide extractable fractions (F4); and HCl acid-soluble residue (F5). The sum of trace metals Ni, Pb, Cu, and Zn associated with the first two fractions (exchangeable, carbonate, and easily reducible) is significant and extremely important because it represents the proportion of heavy metals that can be easily remobilized by changes in environmental conditions such as pH, redox potential, salinity, etc. Sediments located nearer the groundwater flow are exposed to stronger groundwater fluctuation and had a higher quantity of amorphous and less stable substrates of trace metals. Principal component analysis was used to understand and visualize the associations between the trace metals and certain geological forms within analyzed sediments. The observed association between Cr with total sulfur and Mn from the acid-soluble residue could indicate that Cr is in the form of reduced, less toxic Cr(III), which is from the ecochemical point of view very important.     

Characteristics and origin of the hydrogen sulphide spring water from the Split spa (Southern Croatia)

The objective of this paper is to study the hydrological characteristics and origin of the hydrogen sulphide spring water from the Split spa in Southern Croatia in 1987, 1988 and 2003. This paper presents the results of monitoring the content of chlorides and hydrogen sulphide as well as the temperature of the hydrogen sulphide spring water. Since the hydrogen sulphide content during the dry periods significantly differs from the hydrogen sulphide content during rainy periods, this paper also compares the results obtained for those two periods. Under the influence of great quantities of rainfall during cold periods (winter and the beginning of spring) the ratio between seawater and surface water changes and thus the reduction of chlorides and other minerals occurs. The lowered temperature also reduces hydrogen sulphide which can disappear completely. The concentration of 12‰ chlorides (76–94.4% days/year) and 12 mg/L hydrogen sulphide (66.7–88.9% days/year) has been taken as a limit value between water with a normal typical content and water in cold rainy periods. According to the monitoring results it can be concluded that hydrogen sulphide spring water consists of seawater and hydrogencarbonate surface water with a fairly constant content during dry periods while the hydrogencarbonate content increases during rainy periods.