Distribution of antidepressants and their metabolites in brook trout exposed to municipal wastewaters before and after ozone treatment--evidence of biological effects

This study examined the tissues distribution of selected serotonin reuptake inhibitors (SSRIs) in brook trout exposed for 3 months to continuous flow-through primary-treated effluent before and after ozone treatment. A reliable analytical method was developed for the quantification of trace amounts of antidepressants in small tissue homogenate extracts. Levels of six antidepressants and four of their N-desmethyl metabolites were determined using liquid chromatography-tandem mass spectrometry. Significant amounts of the SSRIs were found in fish tissue-in decreasing order: liver>brain>muscle. Sertraline and its metabolite desmethylsertraline were the predominant substances observed in most tissues (0.04-10.3 ng g(-1)). However, less SSRIs (0.08-1.17 ng g(-1)) were bioaccumulated in the ozonated effluent. The early molecular effects of these SSRIs on the Na/K-dependent ATPase pump activity in brain synaptosomes where also investigated in vitro and in fish exposed to the municipal effluents. With respect to their potential biological effects, in vitro exposure to selected SSRIs induced a reduction of the brain Na/K-ATPase activity in synaptosomes in a dose-dependent manner. Results showed that Na/K-ATPase activity was readily inhibited by exposure to municipal effluent before and, to a lesser extent, after ozone treatment. Moreover, the Na/K-ATPase activity was significantly and negatively correlated with brain tissue concentrations of fluoxetine (r=-0.57; p<0.03), desmethylsertraline (r=-0.84; p<0.001), and sertraline (r=-0.82; p<0.001). The present study reveals that SSRIs are readily available in fish, biologically active and corroborates previous findings on the serotonergic properties of municipal effluents to aquatic organisms.     

Nonparametric functional data estimation applied to ozone data: prediction and extreme value analysis

The study of extreme values and prediction of ozone data is an important topic of research when dealing with environmental problems. Classical extreme value theory is usually used in air-pollution studies. It consists in fitting a parametric generalised extreme value (GEV) distribution to a data set of extreme values, and using the estimated distribution to compute return levels and other quantities of interest. Here, we propose to estimate these values using nonparametric functional data methods. Functional data analysis is a relatively new statistical methodology that generally deals with data consisting of curves or multi-dimensional variables. In this paper, we use this technique, jointly with nonparametric curve estimation, to provide alternatives to the usual parametric statistical tools. The nonparametric estimators are applied to real samples of maximum ozone values obtained from several monitoring stations belonging to the Automatic Urban and Rural Network (AURN) in the UK. The results show that nonparametric estimators work satisfactorily, outperforming the behaviour of classical parametric estimators. Functional data analysis is also used to predict stratospheric ozone concentrations. We show an application, using the data set of mean monthly ozone concentrations in Arosa, Switzerland, and the results are compared with those obtained by classical time series (ARIMA) analysis.     

Immunosuppression in the infaunal bivalve Scrobicularia plana environmentally exposed to mercury and association with its accumulation

This study aimed to test the hypothesis whether mercury (Hg) activates or suppresses inappropriately the immunity of the bivalve Scrobicularia plana inhabiting a Hg contaminated area (Laranjo basin, Ria de Aveiro, Portugal). Immunity endpoints, as well as lipid peroxidation (LPO) as a sign of damage, were evaluated in parallel with total Hg burden. Bivalves from both moderately (MO) and highly (HI) contaminated sites displayed higher haemolymph Hg load and reduced plasma agglutination. Increased haemocytes density and decreased phagocytosis were observed at HI, whereas increased oxidative burst activity (OBA) was observed at MO, pointing out that the immunotoxicity is a result of Hg direct contact involving no ROS intervention. OBA observed at MO was concomitantly associated to peroxidative damage as depicted by LPO increase in haemocytes and haemolymph plasma. Thus, S. plana can be suggested as a suitable bioindicator of metal pollution in coastal areas on the basis of Hg bioaccumulation and immunotoxicity responses.     

Comparing the sensitivity of soil invertebrates to pesticides with that of Eisenia fetida

The sole routine testing of the standard earthworm Eisenia fetida for the terrestrial risk assessment of pesticides has been under much debate since other soil invertebrates may be more sensitive than this standard test species. However, the very low availability of laboratory toxicity data for taxa other than E. fetida has greatly hampered sensitivity comparisons. In the present study, the relative tolerance (T_rel) approach was used to enable comparing toxicity thresholds obtained from the US-EPA ECOTOX database, for main terrestrial taxonomic groups and pesticidal types of action (insecticides, fungicides, herbicides, and other) separately. Analyses confirmed previously reported lower and higher sensitivity of collembolans to fungicides and insecticides, respectively. However, various other discrepancies in susceptibility relative to E. fetida were encountered as indicated by species sensitivity distributions and/or calculated 95% confidence intervals of T_rel values. Arachnids and isopods were found to be more sensitive to insecticides, and nematodes to fungicides, as compared to E. fetida. Implications of study findings for the terrestrial risk assessment of pesticides are discussed.     

Percolation and batch leaching tests to assess release of inorganic pollutants from municipal solid waste incinerator residues

In this study, percolation and batch leaching tests were considered in order to characterize the behaviour of air pollution control (APC) residues produced in a municipal solid waste incinerator (MSWI) as a function of the liquid to solid ratio (L/S). This waste is hazardous, and taking into account their physical and chemical properties, leaching of contaminants into the environment is the main concern. In our work the leaching behaviour of toxic heavy metals (Pb, Zn, Cr, Ni and Cu) and inorganics associated with soluble salts (Na, K, Ca and Cl) was addressed. Although pH of the leaching solution is the most important variable, L/S may also play an important role in leaching processes. In our work, results from column and batch tests were compared in terms of concentration (mg/L) and releasing (mg/kg). The APC residues revealed to be hazardous according to both tests, and both Pb and Cl⁻ far exceeded the regulatory thresholds. The material exhibits high solubility, and when the liquid to solid ratio was high, more than 50% can be solubilised. The patterns of release may be in some cases availability or solubility controlled, and the former was easier to identify. When the results from column and batch experiments were compared by representing the cumulative released amounts (in mg/kg) as a function of L/S, both curves match for Zn, Ni, Cu, K, Na, Cl and Ca, but for Cr and Pb a significant difference was observed. In fact, the column experiments revealed that under percolation conditions it should be expected slow releasing of Pb along time. From this study, it can be concluded that the released amounts obtained in batch experiments for a certain L/S should be considered as the worst case for medium term. Some simple models proposed on the literature and based on local equilibrium assumption showed good fitting to experimental data for soluble species (non-reactive solutes).     

Chitosan/albumin/CaCO3 as mimics for membrane bioreactor fouling: genesis of structural mineralized-EPS-building blocks and cake layer compressibility

Membrane bioreactor biofouling is usually described as an extracellular matrix in which biopolymers, inorganic salts and active microbes co-exist. For that reason, biomineralization (BM) models can be useful to describe the spatial organization and environmental constraints within the referred scenario. BM arguments were utilized as background in order to (1) evaluate CaCO₃ influence on flux decline; pore blocking and cake layer properties (resistance, permeability and compressibility) in a wide range of Chitosan/Bovine serum albumin (BSA) mixtures during step-pressure runs and, (2) perform membrane autopsies in order to explore the genesis of mineralized extracellular building blocks (MEBB) during cake layer build up. Using low molecular weight chitosan (LC) and BSA, 2 L of 5 LC/BSA mixtures (0.25-1.85 ratio) were pumped to an external ultra filtration (UF) membrane (23.5 cm², hydrophobic, piezoelectric, 100 kDa as molecular weight cut-off). Eight different pressure steps (40 ± 7 to 540 ± 21 kPa) were applied. Each pressure step was held for 900 s. CaCO₃ was added to LC/BSA mixtures at 0.5, 1.5 and 3 mM in order to create MEBB during the filtration tests. Membrane autopsies were performed after the filtration tests using thermo gravimetric, scanning microscopy and specific membrane mass (mg cm⁻²) analyses. Biopolymer-CaCO₃ step-pressure filtration created compressible cake layers (with inner voids). The formation of an internal skeleton of MEBB may contribute to irreversible fouling consolidation. A hypothesis for MEBB genesis and development was set forth.     

Preparation and Characterization of Clay Nanocomposites of Plasticized Starch and Polypropylene Polymer Blends

Plasticized starch (PLS) is a renewable, degradable, and inexpensive polymer, but it suffers from poor mechanical properties. The mechanical properties can be improved by blending PLS with polyolefins, nonetheless, at high PLS content, the mechanical properties remain poor. Here we show that addition of clay can greatly improve the mechanical properties of PLS/polypropylene blends at high starch content. Unmodified and organically modified montmorillonite clays, MMT and Cloisite 30B respectively, were added to blends of glycerol-plasticized starch and polypropylene, compatibilized using maleated polypropylene. TEM indicates that MMT is well dispersed in the PLS phase of the blends, while Cloisite 30B is located both within the PLS phase as well as at the interface between PLS and PP. At high PLS content, the addition of clay increased the tensile strength and tensile modulus by an order of magnitude, while reducing the ultimate elongation only slightly. Such improvements are attributable to both the addition of clay as a reinforcing component, as well as to the change in the two phase morphology due to addition of clay.     

Adverse effects in wild fish living downstream from pharmaceutical manufacture discharges

A set of biochemical and histological responses was measured in wild gudgeon collected upstream and downstream of urban and pharmaceutical manufacture effluents. These individual end-points were associated to fish assemblage characterisation. Responses of biotransformation enzymes, neurotoxicity and endocrine disruption biomarkers revealed contamination of investigated stream by a mixture of pollutants. Fish from sampled sites downstream of the industrial effluent exhibited also strong signs of endocrine disruption including vitellogenin induction, intersex and male-biased sex-ratio. These individual effects were associated to a decrease of density and a lack of sensitive fish species. This evidence supports the hypothesis that pharmaceutical compounds discharged in stream are involved in recorded endocrine disruption effects and fish population disturbances and threaten disappearance of resident fish species. Overall, this study gives argument for the utilisation of an effect-based monitoring approach to assess impacts of pharmaceutical manufacture discharges on wild fish populations.     

Factors affecting 210Po and 210Pb activity concentrations in mussels and implications for environmental bio-monitoring programmes

The activity of ²¹⁰Po and ²¹⁰Pb was determined in mussels of the same size (3.5-4.0 cm shell length) sampled monthly over a 17-month period at the Atlantic coast of Portugal. Average radionuclide concentration values in mussels were 759 ± 277 Bq kg⁻¹ for ²¹⁰Po (range 460-1470 Bq kg⁻¹ dry weight), and 45 ± 19 Bq kg⁻¹ for ²¹⁰Pb (range 23-96 Bq kg⁻¹ dry weight). Environmental parameters and mussel biometric parameters were monitored during the same period. Although there was no seasonal variation of radionuclide concentrations in sea water during the study period, the concentration of radionuclide activity in mussels varied seasonally displaying peaks of high concentrations in winter and low concentrations in summer. Analysis of radionuclide data in relation to the physiological Condition Index of mussels revealed that ²¹⁰Po and ²¹⁰Pb activities in the mussel (average activity per individual) remained nearly constant during the investigation period, while mussel body weight fluctuated due to fat storage/expenditure in the soft tissues. Similar variation of radionuclide concentrations was observed in mussels transplanted from the sea coast into the Tejo Estuary. However, under estuarine environmental conditions and with higher food availability throughout the year, transplanted mussel Condition Index was higher than in coastal mussels and average radionuclide concentrations were 210 ± 75 Bq kg⁻¹ (dry weight) for ²¹⁰Po and 10 ± 4 Bq kg⁻¹ (dry weight) for ²¹⁰Pb, therefore lower than in coastal mussels with similar shell length. It is concluded that the apparent seasonal fluctuation and inter-site difference of radionuclide concentrations were mostly caused by mussel body weight fluctuation and not by radionuclide body burden fluctuation. This interpretation can be extended to the apparent seasonal fluctuation in concentrations of lipophilic and lipophobic contaminants in mussels, and provides an explanation for occasional high concentrations of ²¹⁰Po and man-made contaminants measured in mussels far from pollution sources.