Wastewater reuse in Mediterranean semi-arid areas: The impact of discharges of tertiary treated sewage on the load of polar micro pollutants in the Llobregat river (NE Spain)

The presence of sewage-borne micro contaminants in environmental waters is directly related to the discharge of treated effluents from wastewater treatment plants (WWTP) and the flow rate of the receiving river waters. Mediterranean rivers, in particular, are characterized by important fluctuations in the flow rates and heavy pollution pressures resulting from extensive urban, industrial and agricultural activities. This translates into contamination levels in these rivers often higher than those in other larger European basins. The present work provides an overview of the occurrence of five groups of organic contaminants (131 compounds) namely pharmaceuticals, illicit drugs, polar pesticides, estrogens, alkylphenols and related ethoxylates in WWTP tertiary treatment effluents. Data gathered during a period of water reuse carried out in the lower stretch of the Llobregat river (NE Spain), in the surroundings of the town of Barcelona as a consequence of the severe drought that took place along the years 2007-2008 are presented as illustrative example. In general, measured concentrations of the target compounds were in the low to mid ng L⁻¹ range. The total concentration of each compound class downstream to the discharge point was similar or slightly higher than that found upstream. Regarding the loads calculated for each compound, the relative contribution from the river upstream and the tertiary effluent were highly compound depending with no apparent trend. However, estimation of the overall bulk loads for each compound class determined in the Llobregat river showed the following rank order: pharmaceuticals > alkylphenols > pesticides > illicit drugs ? estrogens.     

The electronic properties of trimethylnaphthalenes as properties for the prediction of biodegradation rates: ab initio and DFT study

There is little information on trimethylnaphthalenes (TMNs) which are constituents of diesel fuel and bitumen emissions. In this study, a theoretical investigation of the electronic properties of all trimethylnaphthalene (TMN) isomers and their relation to biodegradation are presented. Equilibrium geometries, ionization potentials (IPs), electron affinities (EAs), dipole moments and electronic dipole polarizabilities of TMN isomers calculated by ab initio and Density Functional Theory (DFT) methods are reported. Polarizability and dipole moment computations have been performed in gas and in water solution using the polarizable continuum model (PCM). The results obtained show that the IP value varies little along the series of isomers while averaged static dipole polarizabilities (〈α〉) increase on passing from α,α,α-TMN to β,β,β-TMN isomers. This indicates that the binding affinity between TMNs and active site of bacterial enzymes is mainly determined by dispersive and inductive effects. Therefore, the computed polarizability values of TMNs can be used as predictors of the rates of biodegradation of TMNs.     

High natural radiation exposure in radon spa areas: a detailed field investigation in Niska Banja (Balkan region)

The measurement campaigns have been done in the rural community of Niska Banja, a spa town located in southern Serbia, to evaluate population exposure to natural radioactivity. After a screening survey in 200 houses, annual radon and thoron concentrations were measured in 34 houses, and in 2004 a detailed investigation was carried out at six houses with elevated indoor radon concentrations. The paper presents the results of these detailed measurements. The complementary techniques were applied to determine radon and thoron concentrations in indoor air, in soil gas, radon exhalation from soil, soil permeability, and indoor and outdoor gamma doses. Soil and water samples were collected and analysed in the laboratory. Indoor radon and thoron concentrations were found to be more than 1kBqm(-3) and 200Bqm(-3), respectively. Extremely high concentrations of soil-gas radon (>2000kBqm(-3)) and radon exhalation rates (1.5mBqm(-2)s(-1)) were observed. These results will be utilised to set up the methodology for a more systematic investigation.     

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.     

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     

Uptake and biotransformation of arsenate in the lichen Hypogymnia physodes (L.) Nyl

The uptake and metabolism of arsenate, As(V), as a function of time and concentration were examined in the lichen Hypogymnia physodes (L.) Nyl. Lichen thalli were exposed to As(V) in the form of a solution. Exponential uptake of As(V) from 4 microg mL(-1) As(V) solution was accompanied by constant arsenite, As(III), excretion back into the solution. Arsenate taken up into the lichens from 0, 0.1, 1, 10 microg mL(-1) As(V) solutions was partially transformed into As(III), dimethylarsinic acid (DMA) and (mono)methylarsonic acid (MA). 48 h after exposure, the main arsenic compound in the lichens was DMA in 0.1, As(III) in 1 and As(V) in 10 microg mL(-1) treatment. The proportion of methylated arsenic compounds decreased with increasing arsenate concentration in the exposure solution. These results suggest that at least two types of As(V) detoxification exist in lichens; arsenite excretion and methylation.     

Active moss biomonitoring of trace elements with Sphagnum girgensohnii moss bags in relation to atmospheric bulk deposition in Belgrade, Serbia

Active biomonitoring with wet and dry moss bags was used to examine trace element atmospheric deposition in the urban area of Belgrade. The element accumulation capability of Sphagnum girgensohnii Russow was tested in relation to atmospheric bulk deposition. Moss bags were mounted for five 3-month periods (July 2005-October 2006) at three representative urban sites. For the same period monthly bulk atmospheric deposition samples were collected. The concentrations of Al, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, and Pb were determined by instrumental neutron activation analyses and atomic absorption spectrometry. Significant accumulation of most elements occurred in the exposed moss bags compared with the initial moss content. High correlations between the elements in moss and bulk deposits were found for V, Cu, As, and Ni. The enrichment factors of the elements for both types of monitor followed the same pattern at the corresponding sites.     

Assessment of GC–MS response of selected pesticides in apple matrices related to matrix concentration

A uniform analyte response is required for GC–MS analysis in order to obtain acceptable quantitative results. The response of pesticides in complex matrices is susceptible to variation due to the interactions of co-extractives, both with pesticides or with GC–MS system. This study was conducted to determine the magnitude of the interactions, called matrix effect, and their behavior with the matrix dilution. The response of pyrimethanil (4,6-dimethyl-N-phenylpyrimidin-2-amine), cyprodinil (4-cyclopropyl-6-methyl-N-phenylpyrimidin-2-amine), trifloxystrobin (methyl-(2Z)-2-methoxyimino-2-[2-[[(E)-1-[3(trifluoromethyl)phenyl]ethylidene amino]oxymethyl]phenyl]acetate) and bifenthrin(2-methyl-3-phenylphenyl)methyl-3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate), used in apple crops protection, was evaluated in different concentrations of peel and flesh extracts of Granny Smith, Golden Delicious and Demi Rouge, selected as representatives of different matrix types. The matrix effect ranged from ?0.05 to 146.14%, depending on matrix type and pesticide. The highest response variation was observed in extracts of Granny Smith—an enhancement in flesh and suppression in peel extract. With the dilution, the matrix effect decreased with different magnitudes, but for Granny Smith peel extract an inverted effect was observed. The presence of the matrix effect in GC–MS pesticides analysis was obvious, requiring the application of matrix-matched calibration in quantification procedures for each variety, with calibration standards matched by the matrix concentration.     

Malondialdehyde and heavy metal concentrations in tissues of wild boar (Sus scrofa L.) from central Croatia

The aim of this research was to assess the degree of heavy metal (cadmium, lead and mercury) contamination of wild boars from central Croatia and thereby conduct further tests to connect the contamination to oxidative stress occurrence. The highest cadmium concentration was noticed in the kidneys of older boars, the lead concentration was approximately the same in the liver and kidneys, but it was much higher than the concentration in the muscles, while the highest mercury concentration was measured in the kidneys of all wild boars. The correlation between the malondialdehyde (MDA) and the heavy metal concentrations was higher in tissue samples taken from younger animals (1 to 3 years of age) than in the tissue samples taken from older animals (5 to 6 years of age). In the kidneys of all wild boars there was a statistically significant connection between the MDA and cadmium concentration; in the kidneys of younger wild boars there was a statistically significant connection between the MDA and lead concentration. Further research on this topic should focus on MDA potential to find its use, not only as a contamination biomarker in the area of ecotoxicology, but also in the evaluation of the hygienic acceptability of animal products.     

Enzymatic biomarkers as indicators of dietary cadmium in gypsy moth caterpillars

Heavy metals damage the structure, chemistry, and function of cells, including enzyme systems inside them. Variation in the profile of biochemical biomarkers in prevalent species should be used for assessing environmental contamination. The present study pays attention to the phosphatases present in the midgut of gypsy moth fourth instar caterpillars, which had been exposed to short- and long-term cadmium intake at 10 and 30 μg Cd/g dry food. Chronic cadmium ingestion significantly inhibited the activity of all examined phosphatases, while only the activity of lysosomal phosphatase was acutely decreased. Total acid phosphatase activity recovered from both long-term cadmium treatments within 3 days. The low index of phenotypic plasticity was connected to high variability of plasticity. Dependence of phosphatase isoforms on genotype and duration of cadmium treatment was determined. We concluded that, with further investigations, profiling of total acid phosphatase activity, as well as the lysosomal fraction can be used as a biomarker for acute sublethal metal toxicity.