Clotrimazole is an azole fungicide used as a human pharmaceutical that is known to inhibit cytochrome P450 (CYP) enzymatic activities, including several steroidogenic CYP. In a previous report, we showed that a 7-day exposure to clotrimazole induced the expression of genes related to steroidogenesis in the testes as a compensatory response, involving the activation of the Fsh/Fshr pathway. In this context, the aim of the present study was to assess the effect of an in vivo 21-day chronic exposure to clotrimazole (30–197 μg/L) on zebrafish testis function, i.e., spermatogenesis and androgen release. The experimental design combined (1) gene transcript levels measurements along the brain–pituitary–gonad axis, (2) 11-ketotestosterone (11-KT) quantification in the blood, and (3) histology of the testes, including morphometric analysis. The chronic exposure led to an induction of steroidogenesis-related genes and fshr in the testes as well as fshβ in the pituitary. Moreover, increases of the gonadosomatic index and of the volume proportion of interstitial Leydig cells were observed in clotrimazole-exposed fish. In accordance with these histological observations, the circulating concentration of 11-KT had increased. Morphometric analysis of the testes did not show an effect of clotrimazole on meiotic (spermatocytes) or postmeiotic (spermatids and spermatozoa) stages, but we observed an increase in the number of type A spermatogonia, in agreement with an increase in mRNA levels of piwil1, a specific molecular marker of type A spermatogonia. Our study demonstrated that clotrimazole is able to affect testicular physiology and raised further concern about the impact of clotrimazole on reproduction.

An environmentally friendly and inexpensive substitute to the widely used poly(vinyl alcohol) (PVA) has been developed from soy proteins for textile warp sizing. Textile processing is the major source of industrial water pollution across the world, and sizing and desizing operations account for nearly 30 % of the water consumed in a textile plant. PVA is one of the most common sizing agents used for synthetic fibers and their blends due to PVA's easy water solubility and ability to provide desired sizing performance. However, PVA does not degrade and is a major contributor to pollution in textile effluent treatment plants. Although considerable efforts have been made to replace PVA with biodegradable sizing materials, the performance properties provided by PVA on synthetic fibers and their blends have been unmatched so far. Soy proteins are inexpensive, biodegradable, and have been widely studied for potential use in food packaging, as resins and adhesives. In this research, the potential of using soy proteins as textile sizing agents to replace PVA was studied. Polyester and polyester/cotton rovings, yarns, and fabrics sized with soy protein showed a considerably better improvement in strength and abrasion resistance compared to commercially available PVA-based size. Soy protein size had a 5-day biochemical oxygen demand /chemical oxygen demand ratio of 0.57 compared to 0.01 for PVA indicating that soy protein sizes were easily biodegradable in activated sludge. The total and ammonia nitrogen released from the proteins also did not adversely impact the biodegradability. Good sizing performance and easy biodegradability demonstrate that soy protein-based sizes have potential to replace PVA-based sizes leading to substantial benefits to the textile industry and the environment.

The concentrations, compositional profiles, and possible sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) in water column and surface sediment samples from the lower reaches of the Yangtze River were investigated, and the potential risks posed by these chemicals were evaluated. Concentrations of the 17 2,3,7,8-substituted PCDD/PCDF in the water and sediment samples ranged from 0.45 to 10.0 pg TEQ/L (mean 2.34 pg TEQ/L) and from 0.31 to 51 pg TEQ/g dw (mean 5.25 pg TEQ/g dw), respectively. Water and sediments from the Nanjing-Nantong sections of the Yangtze River were found to have elevated PCDD/PCDF levels, and the PCDD/PCDF TEQ concentrations in 13 sediment samples exceeded the probable effect levels (PEL), above which adverse biological effects are likely. Multivariate statistical analysis indicated that the principal PCDD/PCDF contamination source for the water and sediment was the production and use of pentachlorophenol (PCP) or sodium pentachlorophenate (PCP-Na). PCDD/PCDF concentrations were stable over time near the Yangtze River Estuary but had increased sharply in recent decades in the Nanjing-Nantong section, which will have been related to the growth in industrial activities and other anthropogenic PCDD/PCDF sources. Total organic carbon (TOC) and PCDD/PCDF concentrations correlated significantly (R = 0.474, P < 0.01), suggesting that TOC plays an important role in the transport and re-distribution of PCDD/PCDF in the Yangtze River basin.

In this paper, particular attention was paid to the presence of aerosol solid particles, which occurred mainly as a result of exploitation and coal combustion in the thermal power plants of the Kolubara basin. Not all of the particles created by this type of anthropogenic pollution have an equal impact on human health, but it largely depends on their size and shape. The mineralogical composition and particle size distribution in the samples of aero sediments were defined. The samples were collected close to the power plant and open pit coal mine, in the winter and summer period during the year 2007. The sampling was performed by using precipitators placed in eight locations within the territory of the Lazarevac municipality. In order to characterize the sedimentary particles, several methods were applied: microscopy, SEM-EDX and X-ray powder diffraction. The concentration of aero sediments was also determined during the test period. Variety in the mineralogical composition and particle size depends on the position of the measuring sites, geology of the locations, the annual period of collecting as well as possible interactions. By applying the mentioned methods, the presence of inhalational and respiratory particles variously distributed in the winter and in the summer period was established. The most common minerals are quartz and feldspar. The presence of gypsum, clay minerals, calcite and dolomite as secondary minerals was determined, as well as the participation of organic and inorganic amorphic matter. The presence of quartz as a toxic mineral has a particular impact on human health.

The objective of the Control of Hazardous Substances in the Baltic Sea (COHIBA) project is to support the implementation of the HELCOM Baltic Sea Action Plan regarding hazardous substances by developing joint actions to achieve the goal of "a Baltic Sea with life undisturbed by hazardous substances". One aim in the project was to identify the most important sources of 11 hazardous substances of special concern in the Baltic Sea. Among them are perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In this study, four perfluorinated alkyl acids (PFAAs) were studied: PFOA, PFOS, perfluorohexanoic acid (PFHxA) and perfluorodecanoic acid (PFDA). The occurrence of PFAAs in municipal and industrial wastewater treatment plant effluents (MWWTP1-3, IWWTP1), target industry effluent, storm water, landfill leachate and sludge was studied. Effluents were analysed six times and storm water, leachate and sludge were analysed twice, once in the warm season and once in the cold, during a 1-year sampling campaign. PFOS prevailed in two municipal effluents (MWWTP1 and 3) and industrial effluent (IWWTP1; 7.8-14, 8.0-640 and 320-1,300 ng/l, respectively). However, in one municipal effluent (MWWTP2) PFOA was, in a majority of sampling occasions, the predominant PFAA (9-15 ng/l) followed by PFOS (3.8-20 ng/l). The highest PFAA loads of the municipal effluents were found in the MWWTP3 receiving the biggest portion of industrial wastewater. In storm water the highest concentration was found for PFHxA (17 ng/l). The highest concentration of PFOS and PFOA were 9.9 and 5.1 ng/l, respectively. PFOS, PFOA and PFHxA were detected in every effluent, storm water and landfill leachate sample, whereas PFDA was detected in most of the samples (77 %). In the target industry, PFOS concentrations varied between 1,400 and 18,000 μg/l. In addition, on one sampling occasion PFOA and PFHxA were found (0.027 and 0.009 μg/l, respectively). For effluents, PFAA mass flows into the Baltic Sea were calculated. For municipal wastewater treatment plants average mass flows per day varied for PFOS between 1,073 and 38,880 mg/day, for PFOA 960 and 2,700 mg/day, for PFHxA 408 and 1,269 mg/day and for PFDA 84 and 270 mg/day. In IWWTP mass flows for PFOS, PFOA, PFHxA and PFDA were 495 mg/d, 28 mg/d, 23 mg/d and 0.6 mg/g, respectively.

The present study aims to evaluate the competitive biosorption of lead, cadmium, copper, and arsenic ions by using native algae. A series of experiments were carried out in a batch reactor to obtain equilibrium data for adsorption of single, binary, ternary, and quaternary metal solutions. The biosorption of these metals is based on ion exchange mechanism accompanied by the release of light metals such as calcium, magnesium, and sodium. Experimental parameters such as pH, initial metal concentrations, and temperature were studied. The optimum pH found for removal were 5 for Cd²⁺ and As³⁺ and 3 and 4 for Pb²⁺ and Cu²⁺, respectively. Fourier transformation infrared spectroscopy analysis was used to find the effects of functional groups of algae in biosorption process. The results showed that Pb²⁺ made a greater change in the functional groups of algal biomass due to high affinity to this metal. An ion exchange model was found suitable for describing the biosorption process. The affinity constants sequence calculated for single system was K Pb > K Cᵤ > K Cd > K Aₛ; these values reduced in binary, ternary, and quaternary systems. In addition, the experimental data showed that the biosorption of the four metals fitted well the pseudo-second-order kinetics model.

Pikeperch (Sander lucioperca), European catfish (Silurus glanis), common carp (Cyprinus carpio), and gobies (Neogobius gymnotrachelus, Neogobius melanostomus) were collected from the Danube River (Belgrade section), and samples of liver, muscle, or whole-body composites (in the case of gobies) were analyzed for As, Cu, Fe, Hg, Mn, and Zn with inductively coupled plasma optical spectrometry to find out if there was a correlation between accumulation of these elements in predatory and prey species, as well as in pairs of species with overlapping diets. Concentrations of all analyzed elements were either higher (Cu, Fe, Mn, Zn) in liver than in muscle, or equal (As, Hg), except for Hg in carp, which was higher in muscle. Mercury concentration in liver and muscle of predators (catfish, pikeperch) was significantly (<10⁻⁴) higher than in prey fishes (carp and gobies). The results indicate that Hg concentration was biomagnified through the food chain. Concentrations of As, Fe, and Hg in carp liver and gobies whole-body composite were similar, but carp had significantly (<10⁻⁴) higher values of Zn and Cu in liver. The regression analysis and trendline equations indicate that the concentrations of all tested elements, except for As in liver, and Mn and Fe in muscle, were similar in predatory fish (pikeperch and catfish), on one hand, and in prey fish (carp and gobies), on the other hand. Distinctly high Zn concentration in carp is very common in this species due to its physiology. Concentrations of Hg and Zn were higher than the maximum acceptable concentration due to the high pollution level in this section of the Danube River, accordingly posing a risk for the human consumption of these fish species.

The aim of this study was to evaluate applicability of ion exchange process for organics removal from Douro River surface water at the intake of Lever water treatment plant using magnetized ion exchange resin MIEX®. Qualitative analysis of the natural organic matter present in the surface water and prediction of its amenability to removal in conventional coagulation process were assessed. Results obtained in MIEX®DOC process kinetic batch experiments allowed determination of ion exchange efficiency in dissolved organic carbon (DOC), UV absorbing organics, and true color removal. The data were compared with the efficiencies of the conventional unit processes for organics removal at Lever WTP. MIEX®DOC process revealed to be more efficient in DOC removal than conventional treatment achieving the efficiencies in the range of 61–91 %, lowering disinfection by-products formation potential of the water. DOC removal efficiency at Lever WTP depends largely on the raw water quality and ranges from 28 % for water of moderated quality to 89 % of significantly deteriorated quality. In this work, MIEX®DOC process was also used as a reference method for the determination of contribution of anionic fraction to dissolved organic matter and selectivity of the unit processes at Lever WTP for its removal.

Lead (II) has been as one of the most toxic heavy metals because it is associated with many health hazards. Therefore, people are increasingly interested in discovering new methods for effectively and economically scavenging lead (II) from the aquatic system. Recent studies demonstrate biosorption is a promising technology for the treatment of pollutant streams. To apply these techniques, suitable adsorbents with high efficiency and low cost are demanded. The waste biomass of Bacillus gibsonii S-2 biosorbent was used as low-cost biosorbent to remove metallic cations lead (II) from aqueous solution. To optimize the maximum removal efficiency, the effect of pH and temperature on the adsorption process was studied. The isotherm models, kinetic models and thermodynamic parameters were analysed to describe the adsorptive behaviour of B. gibsonii S-2 biosorbent. The mechanisms of lead (II) biosorption were also analysed by FTIR and EDX. The results showed that the optimum pH values for the biosorption at three different temperatures, i.e. 20, 30 and 40 °C, were determined as 4. The equilibrium data were well fitted to Langmuir model, with the maximum lead (II) uptake capacities of 333.3 mg g⁻¹. The kinetics for lead (II) biosorption followed the pseudo-second-order kinetic equation. The thermodynamic data showed that the biosorption process were endothermic (∆G < 0), spontaneous (∆H > 0) and irreversible (∆S > 0). The mechanism of lead (II) biosorption by the waste biomass of B. gibsonii S-2 biosorbent could be a combination of ion exchange and complexation with the functional groups present on the biosorbent surface. The application of the waste biomass of B. gibsonii S-2 for lead (II) adsorption, characterized with higher lead (II) sorption capacity and lower cost, may find potential application in industrial wastewater treatment.

Polar organic chemical integrative samplers (POCISs) for the monitoring of polar pesticides in groundwater were tested on two sites in order to evaluate their applicability by comparison with the spot-sampling approach. This preliminary study shows that, as in surface water, POCIS is a useful tool, especially for the screening of substances at low concentration levels that are not detected by laboratory analysis of spot samples. For quantitative results, a rough estimation is obtained. The challenge is now to define the required water-flow conditions for a relevant quantification of pesticides in groundwater and to establish more representative sampling rates for groundwater.