INTRODUCTION: Mediterranean rivers are characterized by a high flow variability, which is strongly influenced by the seasonal rainfall. When water scarcity periods occur, water flow, and dilution capacity of the river is reduced, increasing the potential environmental risk of pollutants. On the other hand, floods contribute to remobilization of pollutants from sediments. Contamination levels in Mediterranean rivers are frequently higher than in other European river basins, including pollution by pharmaceutical residues. Little attention has been paid to the transport behavior of emerging contaminants in surface waters once they are discharged from WWTP into a river. In this context, this work aimed to relate presence and fate of emerging contaminants with hydrological conditions of a typical Mediterranean River (Llobregat, NE Spain). METHODS: River fresh water samples were collected twice a week over a period of 5 weeks at three sampling points. Sixty-six pharmaceutical compounds belonging to different therapeutical classes were analyzed by LC-MS/MS. RESULTS AND DISCUSSION: Positive and negative correlations between the concentrations of the target analytes and hydrological variables like river flow and dissolved organic matter were observed pointing out the relevance of different hydrological phenomena like dilution effects or sediment re-suspension. Sensitivity calculations showed that the majority of compounds were sensitive to flow variations

PURPOSE: The aim of this work was to improve the ability of electro-Fenton technique for the remediation of wastewater contaminated with synthetic dyes using a model azo dye such as Azure B. METHODS: Batch experiments were conducted to study the effects of main parameters, such as dye concentration, electrode surface area, treatment time, and voltage. In this study, central composite face-centered experimental design matrix and response surface methodology were applied to design the experiments and evaluate the interactive effects of the four studied parameters. A total of 30 experimental runs were set, and the kinetic data were analyzed using first- and second-order models. RESULTS: The experimental data fitted to the empirical second-order model of a suitable degree for the maximum decolorization of Azure B by electro-Fenton treatment. ANOVA analysis showed high coefficient of determination value (R 2 = 0.9835) and reasonable second-order regression prediction. Pareto analysis suggests that the variables, time, and voltage produce the largest effect on the decolorization rate. CONCLUSION: Optimum conditions suggested by the second-order polynomial regression model for attaining maximum decolorization were dye concentration 4.83 mg/L, electrode surface area 15 cm2, voltage 14.19 V, and treatment time of 34.58 min.

BACKGROUND, AIM, AND SCOPE: 2,2-bis(chlorophenyl)-1,1,1-trichloroethane (DDT) metabolites, other than those routinely measured [i.e., 2,2-bis(chlorophenyl)-1,1-dichloroethylene (DDE) and 2,2-bis(chlorophenyl)-1,1-dichloroethane (DDD)], have recently been detected in elevated concentrations not only in the surface water of Teltow Canal, Berlin, but also in sediment samples from Elbe tributaries (e.g., Mulde and Havel/Spree). This was paralleled by recent reports that multiple other metabolites could emerge from the degradation of parent DDT by naturally occurring organisms or by interaction with some heavy metals. Nevertheless, only very few data on the biological activities of these metabolites are available to date. The objective of this communication is to evaluate, for the first time, the cytotoxicity, dioxin-like activity, and estrogenicity of the least-studied DDT metabolites. METHODS: Four DDT metabolites, p,p′-2,2-bis(chlorophenyl)-1-chloroethylene (DDMU), p,p′-2,2-bis(chlorophenyl)-1-chloroethane (DDMS), p,p′-2,2-bis(4-ch1oropheny1)acetonitrile (DDCN), and p,p′-2,2-bis(chlorophenyl)acetic acid (DDA), were selected based on their presence in environmental samples in Germany such as in sediments from the Mulde River and Teltow Canal. O,p′-DDT was used as reference in all assays. Cytotoxicity was measured by neutral red retention with the permanent cell line RTG-2 of rainbow trout (Oncorhynchus mykiss). Dioxin-like activity was determined using the 7-ethoxyresorufin-O-deetylase assay. The estrogenic potential was tested in a dot blot/RNAse protection-assay with primary hepatocytes from male rainbow trout (O. mykiss) and in a yeast estrogen screen (YES) assay. RESULTS: All DDT metabolites tested revealed a clear dose–response relationship for cytotoxicity in RTG-2 cells, but no dioxin-like activities with RTL-W1 cells. The dot blot/RNAse protection-assay demonstrated that the highest non-toxic concentrations of these DDT metabolites (50 μM) had vitellogenin-induction potentials comparable to the positive control (1 nM 17β-estradiol). The estrogenic activities could be ranked as o,p′-DDT > p,p′-DDMS > p,p′-DDMU > p,p′-DDCN. In contrast, p,p′-DDA showed a moderate anti-estrogenic effect. In the YES assay, besides the reference o,p′-DDT, p,p′-DDMS and p,p′-DDMU displayed dose-dependent estrogenic potentials, whereas p,p′-DDCN and p,p′-DDA did not show any estrogenic potential. DISCUSSION: The reference toxicant o,p′-DDT displayed a similar spectrum of estrogenic activities similar to 17β-estradiol, however, with a lower potency. Both p,p′-DDMS and p,p′-DDMU were also shown to have dose-dependent estrogenic potentials, which were much lower than the reference o,p′-DDT, in both the vitellogenin and YES bioassays. Interestingly, p,p′-DDA did not show estrogenic activity but rather displayed a tendency towards anti-estrogenic activity by inhibiting the estrogenic effect of 17β-estradiol. The results also showed that the p,p′-metabolites DDMU, DDMS, DDCN, and DDA do not show any dioxin-like activities in RTL-W1 cells, thus resembling the major DDT metabolites DDD and DDE. CONCLUSIONS: All the DDT metabolites tested did not exhibit dioxin-like activities in RTL-W1 cells, but show cytotoxic and estrogenic activities. Based on the results of the in vitro assays used in our study and on the reported concentrations of DDT metabolites in contaminated sediments, such substances could, in the future, pose interference with the normal reproductive and endocrine functions in various organisms exposed to these chemicals. Consequently, there is an urgent need to examine more comprehensively the risk of environmental concentrations of the investigated DDT metabolites using in vivo studies. However, this should be paralleled also by periodic evaluation and monitoring of the current levels of the DDT metabolites in environmental matrices. RECOMMENDATIONS AND PERSPECTIVES: Our results clearly point out the need to integrate the potential ecotoxicological risks associated with the “neglected” p,p′-DDT metabolites. For instance, these DDT metabolites should be integrated into sediment risk assessment initiatives in contaminated areas. One major challenge would be the identification of baseline data for such risk assessment. Further studies are also warranted to determine possible additive, synergistic, or antagonistic effects that may interfere with the fundamental cytotoxicity and endocrine activities of these metabolites. For a more conclusive assessment of the spectrum of DDT metabolites, additional bioassays are needed to identify potential anti-estrogenic, androgenic, and/or anti-androgenic effects.

INTRODUCTION: Dissolved organic matter (DOM) is the most active component in environmental system and its chemical and structural characteristics most likely influence its biodegradation. Four surface soil (0–20 cm) and three core sediment samples (0–10 cm) were collected from Wuliangsuhai Lake. The objectives of this study were to investigate the spectral properties and humification degree of DOM and to determine and discuss comparatively the complexing capacities and stability constants of DOM by Cu (II) in the Hetao region. MATERIALS AND METHODS: In this study, fluorescence spectra and fluorescence quenching methods were used to evaluate the humification degree of DOM and calculate the complexing capacities and the stability constants between DOM and Cu (II). RESULTS AND DISCUSSION: Two defined peaks, at wavelengths of 260∼300 nm (peak I) and 300∼350 nm (peak II), could be identified for soil DOM at a Δλ value of 30 nm. In sediment DOM extracts, a third peak (III) was observed near 364 nm. The results show that there is a significant difference in the structure of DOM because of different sources. The humification degree is significantly higher for soil samples than those of sediment samples. The FT-IR spectra of DOM show that structure in sediment DOM is more functional groups than those in soil DOM. DOM has a stronger Cu binding affinity in soils than in sediment in the Hetao region, which may lead to potentially significant influence on the migration and transformation of Cu (II).

BACKGROUND: The state of the art of passive water sampling of (nonpolar) organic contaminants is presented. Its suitability for regulatory monitoring is discussed, with an emphasis on the information yielded by passive sampling devices (PSDs), their relevance and associated uncertainties. Almost all persistent organic pollutants (POPs) targeted by the Stockholm Convention are nonpolar or weakly polar, hydrophobic substances, making them ideal targets for sampling in water using PSDs. Widely used nonpolar PSDs include semi-permeable membrane devices, low-density polyethylene and silicone rubber. RESULTS AND DISCUSSION: The inter-laboratory variation of equilibrium partition constants between PSD and water is mostly 0.2–0.5 log units, depending on the exact matrix used. The sampling rate of PSDs is best determined by using performance reference compounds during field deployment. The major advantage of PSDs over alternative matrices applicable in trend monitoring (e.g. sediments or biota) is that the various sources of variance including analytical variance and natural environmental variance can be much better controlled, which in turn results in a reduction of the number of analysed samples required to obtain results with comparable statistical power. CONCLUSION: Compliance checking with regulatory limits and analysis of temporal and spatial contaminant trends are two possible fields of application. In contrast to the established use of nonpolar PSDs, polar samplers are insufficiently understood, but research is in progress to develop PSDs for the quantitative assessment of polar waterborne contaminants. In summary, PSD-based monitoring is a mature technique for the measurement of aqueous concentrations of apolar POPs, with a well-defined accuracy and precision.

INTRODUCTION: The removal of azo Reactive Red 31(RR31) from synthetic dye solution using tannery sludge-developed activated carbon (TSC) was investigated. METHODS: TSC was prepared from a combination of physical and chemical activation. The developed TSC was characterized by FT-IR, SEM, TG–DTA, specific surface area and zero point charge of pH (pHzpc). The isotherm models, kinetic models and thermodynamic parameters were also analysed to describe the adsorptive behaviour of TSC. The effect of contact time, initial dye concentration, carbon dosage, agitation speed, initial pH and temperature were carried out for batch adsorption studies. The isotherm plot of the dye RR31 on TSC fitted better with the Langmuir adsorption isotherm than the Freundlich model. RESULTS: The maximum monolayer adsorption capacity of TSC in the removal of RR31 ranged from 23.15 to 39.37 mg/g. The thermodynamic parameters showed the endothermic and physical nature of the Reactive Red 31 adsorption on TSC. The entropy and enthalpy values were 181.515 J/Kmol and 5.285 kJ/mol, respectively. CONCLUSION: The developed cationic tannery sludge carbon was found to be an effective adsorbent in the removal of the anionic azo reactive dye RR31.

PURPOSE: Tannins and dyes pose major threat to the environment by generating huge pollution problem. Biodegradation of wattle extract, chrome tannin and dye compounds using suitable fungal culture namely Aspergillus niger, Penicillium sp. were carried out. In addition to these, ozone treatment was carried out to get higher degradation rate. RESULTS: The results were monitored by carrying out chemical oxygen demand (COD), total organic carbon (TOC), and UV–Vis analysis. The results showed that wattle extract (vegetable tannin) gave better biodegradation rate than dye and chromium compounds. Biodegradation plus ozone showed degradation rates of 92–95%, 94–95%, and 85–87% for the wattle extract, dyes, chromium compounds, respectively. UV–Vis showed that there were no peaks observed for biodegraded samples indicating better degradation rates as compared to the control samples. FT-IR spectra analysis suggested that the formation of flavanoid derivatives, chromic oxide and NH2 compounds during degradation of wattle extract, chromium and dye compounds, respectively, at the peaks of 1,601–1,629 cm−1, 1,647 cm−1, and 1,610–1,680 cm−1. CONCLUSION: The present investigation shows that combination of biodegradation with ozone is the effective method for the removal of dyes and tannins. The biodegradation of the said compounds in combination with ozonation showed better rate of degradation than by chemical methods. The combination of biodegradation with ozone helps to reduce pollution problems in terms of COD, TOC, total dissolved solids and total suspended solids.

BACKGROUND, AIM AND SCOPE: The breast milk has been recommended to carry out as a monitoring tool for effectiveness evaluation of the Stockholm Convention on Persistent Organic Pollutants (POPs). Polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloro-ethane (DDT) and its metabolites (DDX), hexachlorbenzene (HCB) and isomers of hexachlocyklohexane (HCHs) have been monitored in the breast milk of nursing mothers in the Czech Republic since 1994 as a part of The Environmental Health Monitoring System. Knowledge about long-term POPs distribution and accumulation in the human body is crucial to understanding uptake, degradation and subsequent effects as well as to conduct risk assessments. The main aim of this study is to evaluate 15-years long-term trends of selected POPs in human milk in the Czech Republic and to elucidate the questionnaire information about the age, parity and social habits, to the final concentrations. This effectiveness evaluation of POPs restriction is quite precisely after 15-years monitoring campaigns. MATERIALS, METHODS AND RESULTS: The human milk samples (4,753 samples) were analysed for a number of chlorinated organic chemicals including PCBs and selected chlorinated pesticides (OCPs, HCB, HCHs, DDX). The relative change of concentration per year for all chemicals was analysed. The remaining percentages of POPs in breast milk in comparison to 1994 are also expressed. Czech population half-lives of POPs in breast milk, derived from either linear or exponential models were computed. CONCLUSIONS AND PERSPECTIVES: The long-term data indicates a continuation of a decreasing trend of POPs concentrations on breast milk. Our study did not confirm lactation and parity as an important outflux resulting in the decrease in concentrations in mothers, which is in the antagonism with most of the studies. The higher BMI was associated with higher amounts of HCB and lower amounts of higher chlorinated PCBs. The results confirm the effectiveness of restrictions of POPs usage in the Czech Republic. This ongoing long-term study is very useful tool for parametric effectiveness evaluation of Stockholm Convention.

PURPOSE: Two series of activated carbons modified by Fe (II) and Fe (III) (denoted as AC/N-Feᴵᴵ and AC/N-Feᴵᴵᴵ), respectively, were used as adsorbents for the removal of phosphate in aqueous solutions. METHOD: The synthesized adsorbent materials were investigated by different experimental analysis means. The adsorption of phosphate on activated carbons has been studied in kinetic and equilibrium conditions taking into account the adsorbate concentration, temperature, and solution pH as major influential factors. RESULTS: Maximum removals of phosphate are obtained in the pH range of 3.78–6.84 for both adsorbents. Langmuir isotherm adsorption equation well describes the experimental adsorption isotherms. Kinetic studies revealed that the adsorption process followed a pseudo-second order kinetic model. Results suggest that the main phase formed in AC/N-Feᴵᴵ and AC/N-Feᴵᴵᴵ is goethite and akaganeite, respectively; the presence of iron oxides significantly affected the surface area and the pore structure of the activated carbon. CONCLUSIONS: Studies revealed that iron-doped activated carbons were effective in removing phosphate. AC/N-Feᴵᴵ has a higher phosphate removal capacity than AC/N-Feᴵᴵᴵ, which could be attributed to its better intra-particle diffusion and higher binding energy. The activation energy for adsorption was calculated to be 22.23 and 10.89 kJ mol⁻¹ for AC/N-Feᴵᴵ and AC/N-Feᴵᴵᴵ, respectively. The adsorption process was complex; both surface adsorption and intra-particle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism.

PURPOSE: The aim of this paper was to develop a new recreational water quality index (RWQI) as a tool to ensure the health of swimmers and to take practical decisions. METHODS: RWQI was elaborated with epidemiological data, and we carried out an exhaustive study of the different guidelines for recreational waters proposed by different organisations around the world. Different parameters were chosen, considering, as a priority, the swimmer’s contact and the possibility of ingestion of water during the recreational activity. Furthermore, rating curves were established for pH, chemical oxygen demand, nitrate, phosphate, detergents, enterococci, total coliforms, faecal coliforms and Escherichia coli. RESULTS AND CONCLUSIONS: The index was applied to the data set on water quality of the Potrero de los Funes River (San Luis, Argentina), generated during 2 years (2009–2010). Following the RWQI values classification, most of the Potrero de los Funes water samples fell in the good quality range during the study period.