Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Heavy metals in soils: distribution, relationship with soil characteristics and radionuclides and multivariate assessment of contamination sources

The study is dealing with the distribution and the origin of heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) in soils from a priori non-polluted areas. Positive correlations with organic matter and clay content but not with pH have been observed for most of elements analyzed in this study. Correlations of some metals (Cr, Pb and Zn) and radionuclides (238U and 137Cs) observed for analyzed soils could be explained by their common affinity for clay minerals. Enrichment factor (EF) analysis and cluster analysis (CA) highlighted the lithogenic origin of Cr, Cu, Mn, Ni, Pb and Zn and pointed out the primary input of Cd from anthropogenic sources. It also revealed the need for detailed geochemical surveys in the future in order to decrease the uncertainty of discrimination between lithogenic and anthropogenic origin of metals of interest.     

Application of multi-criteria decision-making on strategic municipal solid waste management in Dalmatia, Croatia

The efficiency of providing a waste management system in the coastal part of Croatia consisting of four Dalmatian counties has been modelled. Two multi-criteria decision-making (MCDM) methods, PROMETHEE and GAIA, were applied to assist with the systematic analysis and evaluation of the alternatives. The analysis covered two levels; first, the potential number of waste management centres resulting from possible inter-county cooperation; and second, the relative merits of siting of waste management centres in the coastal or hinterland zone was evaluated. The problem was analysed according to several criteria; and ecological, economic, social and functional criteria sets were identified as relevant to the decision-making process. The PROMETHEE and GAIA methods were shown to be efficient tools for analysing the problem considered. Such an approach provided new insights to waste management planning at the strategic level, and gave a reason for rethinking some of the existing strategic waste management documents in Croatia.     

Influence of Technological Process on Biodegradation of PVA/Waxy Starch Blends in an Aerobic and Anaerobic Environment

Improving biodegradability of PVA/starch blends is a reality already documented by a number of works. Admittedly, mechanical properties of products (for example, tensile strength) are somewhat worse, but suitable composition optimizing or chemical modifying of starch may eliminate the problem to a large degree. This work is an attempt to find another potential effect influencing biodegradability, that of technological procedure for producing films from these blends on an extruder. The procedure with a so-called pre-extrusion step (two-stage) and dry-blend (single-stage) produced blends of slightest differences in achieved biodegradability (virtually within limits of experimental error) in aerobic (76 vs. 79%) as well as anaerobic breakdown (48 vs. 52%). Conversely, morphological analysis exhibited superior homogeneity of films prepared by the two-stage process; their tensile strength was also higher.     

Edaphic factors affecting the vertical distribution of radionuclides in the different soil types of Belgrade, Serbia

The specific activities of natural radionuclides ((40)K, (226)Ra and (232)Th) and Chernobyl-derived (137)Cs were measured in soil profiles representing typical soil types of Belgrade (Serbia): chernozems, fluvisols, humic gleysols, eutric cambisols, vertisols and gleyic fluvisols. The influence of soil properties and content of stable elements on radionuclide distribution down the soil profiles (at 5 cm intervals up to 50 cm depth) was analysed. Correlation analysis identified associations of (40)K, (226)Ra and (137)Cs with fine-grained soil fractions. Significant positive correlations were found between (137)Cs specific activity and both organic matter content and cation exchange capacity. Saturated hydraulic conductivity and specific electrical conductivity were also positively correlated with the specific activity of (137)Cs. The strong positive correlations between (226)Ra and (232)Th specific activities and Fe and Mn indicate an association with oxides of these elements in soil. The correlations observed between (40)K and Cr, Ni, Pb and Zn and also between (137)Cs and Cd, Cr, Pb and Zn could be attributed to their common affinity for clay minerals. These results provide insight into the main factors that affect radionuclide migration in the soil, which contributes to knowledge about radionuclide behaviour in the environment and factors governing their mobility within terrestrial ecosystems.     

Heavy metal concentration in fish tissues inhabiting waters of “Buško Blato” reservoar (Bosnia and Herzegovina)

Heavy metals concentration (mercury, lead, cadmium, arsenic, copper, zinc and chromium) in tissues (muscles, liver, kidney and gonads) of Dalmatian barbelgudgeon, the nase, the souffie and brown trout, inhabiting waters of Busko Blato reservoir in Bosnia and Herzegovina, has been determined by atomic absorption spectrophotometry. The meat of the tested fish sorts does not contain elevated concentration of most analyzed heavy metals with exception of lead (higher than MAC in Italy, Germany and Denmark) and mercury (in muscles of brown trout higher than MAC in most countries). The lowest level of all heavy metals is always detected in gonads, with higher values in fry compared to milt for copper, zinc, chromium and arsenic. The highest copper concentration is observed in the liver from the souffie which is suggested as a suitable biomonitor for copper intoxication. In muscles of all fish sorts, lead was always present in much higher concentration than cadmium, while in kidneys of most fish sorts, lead and cadmium concentrations were similar. We showed that bioaccumulation of some heavy metals in the fish sorts analyzed is tissue and sex dependent. Also, we concluded that the small water exchange in reversible shallow reservoir does not induce elevated concentration of heavy metals in fish tissues inhabiting Busko Blato.     

Precipitation composition and wet deposition temporal pattern in Central Serbia for the period from 1998 to 2004

Bulk samples collected on a daily basis at three principal meteorological stations in central Serbia were analyzed on chloride (Cl(-)), nitrate [Formula: see text], sulfate [Formula: see text], sodium (Na(+)), ammonium [Formula: see text], potassium (K(+)), calcium (Ca(2+)), and magnesium (Mg(2+)) in addition to precipitation amount, pH and conductivity measurements over the period 1998-2004. The data were subjected to variety of analyses (linear regression, principal component analysis, time series analysis) to characterize precipitation chemistry in the study area. The most abundant ion was [Formula: see text] with annual volume weighted mean concentration of 242 microeq L(-1). Neutralization of precipitation acidity occurs both as a result of the dissolution of alkaline compounds containing Ca(2+), Mg(2+), and K(+) as well as the absorption of ammonia. The ratio of [Formula: see text] was above 5, which indicated that the combustion process of low-grade domestic lignite for electricity generation from coal-fired thermal power plants was the main source of pollution in the investigated area. A considerable mean annual bulk wet deposition of SO(4)-S determined by precipitation amount and concentrations of sulfate in the precipitation was calculated to be 12-35 kg ha(-1).     

Genotoxicity screening of the river Rasina in Serbia using the Allium anaphase–telophase test

Evaluation of the presence of genotoxic substances is especially important in rivers that serve as a source of drinking water. Nine water samples collected along the river Rasina in Serbia were analyzed for potential toxic and genotoxic effects using the Allium anaphase-telophase test. Inhibition of root growth relative to the negative control (synthetic water) was observed in all samples. Analysis of the genotoxic potential, through scoring anaphase and telophase aberrations, showed that in seven of the nine samples the level of aberrations was significantly increased relative to the negative control but was lower than that obtained for the positive control (methyl methanesulfonate). Changes in the relation between spindle and chromosome types of aberrations were found in some samples, indicating differences in the potential genotoxic substances present at the analyzed sites. The data, which were obtained from samples collected at the highest level of river water, warn that during periods of low flow the values could reach genotoxic activity. The Allium anaphase-telophase test can be recommended as an monitoring system, that can serve as the first alert for the presence of genotoxic environmental pollutants.     

Chemical dynamics of the Sava riverine system

Presented here is a study of the geochemical dynamics of the entire River Sava watershed, a major tributary of the River Danube which has not previously been investigated. The sampling was performed at 33 selected locations along the main channel of the stream and at its largest tributaries during three sampling seasons (fall 2005, spring 2006 and fall 2006), going from headwater locations to the mouth near the confluence with the Danube. Almost 80% of the solutes are derived from carbonate mineral weathering and represent over 50% of specific HCO(3)(-) flux normalized to unit basin area at the mouth of the Danube. Statistical analysis indicates that agricultural and industrial sources contribute significantly to increased Na(+), K(+), Cl(-), SO(4)(2-) and NO(3)(-) concentrations in tributary waters. Different processes control the water chemistry along the course of the Sava's drainage-the upper reaches are largely regulated by contributions from carbonate mineral weathering, the middle reaches are influenced by agricultural activity and biological processes related to eutrophication, while the lower reaches tend to have more pronounced parameters related to the industrial processing along with leakages from municipal sanitary systems of these higher population density areas.