Passive sampling combined with ecotoxicological and chemical analysis of pharmaceuticals and biocides - evaluation of three Chemcatcher™ configurations

Passive sampling is a tool to monitor the presence and concentrations of micropollutants in the aquatic environment. We investigated the duration of integrative sampling and the effects of flow rate on the performance of three configurations of the Chemcatcher - a sampler for polar organic compounds. Chemcatchers were fitted with Empore™ styrenedivinylbenzene (SDB) XC disks (XC), SDB-RPS disks (RPS) or SDB-RPS disks covered with a polyethersulfone membrane (RPS-PES). Samplers were either exposed to treated sewage effluent for 5 days at various flow rates, or at a single flow rate with overlapping exposures of 3-24 days. Chemical analysis focused on a set of pharmaceuticals and biocides and ecotoxicological analysis measured inhibition of photosystem II in algae. For compounds with log K_OW > 2, both XC and RPS disks respond dynamically to higher flow rates; uptake increased up to five-fold when flow increased from 0.03 to 0.37 m s⁻¹. At a flow rate of 0.13 m s⁻¹ the integrative window of SDB disks approached 6 days for more hydrophobic compounds (log K_OW > 3.5). The RPS-PES configuration was less affected by flow and also showed an extended integrative window (up to 24 days). The membrane causes a lag phase of up to 2.3 days which thwarts a sound interpretation of data from sampling periods of less than 10 days.     

Biomass supply in EU27 from 2010 to 2030

With biomass staying high in the EU political agenda and most of the recent documents acknowledging that it has the potential to make a very significant contribution to reaching the 20% target [7 and 6], the issue of supply in terms of feedstock types, availability constraints and costs in different Member States is set to determine the future technology uptake and market deployment prospects.     

A micromechanical formulation for piezoelectric fiber composites with nonlinear and viscoelastic constituents

This study presents a simplified micromechanical model to predict electromechanical behaviors of piezocomposites, having ferroelectric fibers and polymer matrix. A nonlinear electromechanical constitutive model is formulated for the ferroelectric fibers, i.e. PZT fibers. The nonlinearity is due to polarization switching in the PZT materials under high electric field and compression stress. Phenomenological models are used to represent stress–strain and polarization–electric field hysteresis responses during polarization switching. The nonlinear electromechanical constitutive relation is verified using hysteresis polarization and strain responses of PZT-51. Effective responses of piezocomposites at various fiber volume contents, generated using the simplified micromechanical model, are also compared with available experimental data. The effects of viscoelastic polymer matrix on the overall electromechanical hysteresis and creep behaviors of piezocomposites are also examined.     

Fully coupled heat conduction and deformation analyses of nonlinear viscoelastic composites

This study presents an integrated micromechanical model-finite element framework for analyzing coupled heat conduction and deformations of particle-reinforced composite structures. A simplified micromechanical model consisting of four sub-cells, i.e., one particle and three matrix sub-cells is formulated to obtain the effective thermomechanical properties and micro–macro field variables due to coupled heat conduction and nonlinear thermoviscoelastic deformation of a particulate composite that takes into account the dissipation of energy from the viscoelastic constituents. A time integration algorithm for simultaneously solving the equations that govern heat conduction and thermoviscoelastic deformations of isotropic homogeneous materials is developed. The algorithm is then integrated to the proposed micromechanical model. A significant temperature generation due to the dissipation effect in the viscoelastic matrix was observed when the composite body is subjected to cyclic mechanical loadings. Heat conduction due to the dissipation of the energy cannot be ignored in predicting the factual temperature and deformation fields within the composite structure, subjected to cyclic loading for a long period. A higher creep resistant matrix material or adding elastic particles can lower the temperature generation. Our analyses suggest that using particulate composites and functionally graded materials can reduce the heat generation due to energy dissipation.     

Dispersion of carbon nanotubes and its influence on the mechanical properties of the cement matrix

An appropriate dispersion of carbon nanotubes (CNTs) is a prerequisite for their use in improving the mechanical properties of cement-based composites. In this study two types of carbon nanotubes (CNTs) having different morphologies were investigated. To obtain a uniform distribution of CNTs in the cement matrix, the effect of sonication on the deagglomeration of CNTs in combination with anionic and nonionic surfactants in varying concentrations was quantitatively investigated when preparing aqueous dispersions of CNTs for the subsequent use in cement paste. The relationships between the quality of CNT-dispersion on the one hand and the sonication time and surfactant concentration on the other were determined using UV–vis spectroscopy. After dispersion, nitrogen-doped CNTs were found mostly as individual, broken CNTs. In contrast, after the treatment of the mixture of single-, double-, and multi-walled CNTs, a net-like distribution was observed where destruction of the CNTs due to sonication could not be distinguished. Modification of the cement pastes with dispersions of CNTs led to a pronounced increase, up to 40%, in compressive strength and, in some cases, to a moderate increase in tensile strength under high strain-rate loading. However, no significant improvement in strength was observed for quasi-static loading. Microscopic examination revealed that the bridging of the C–S–H phases differed depending on the type of CNT. This explained, at least partly, the observed effects of CNT-addition on the mechanical properties of hardened cement pastes.     

The evaluation of liposome-water partitioning of 8-hydroxyquinolines and their copper complexes

Bioavailability and toxicity of mixtures are urgent research issues, but usually mixtures of exclusively organic chemicals or exclusively metals are investigated. In our study, we explored the role of combinations of hydrophobic ionogenic organic compounds (HIOCs) with copper (Cu2+)for uptake and bioavailability of metals and hydrophobic metal complexes in an in vitro membrane system. We investigated the influence of the interactions of copper and 8-hydroxyquinolines, both components used in formulations of pesticides, on their partitioning into liposomes, which are model systems for biological membranes and are composed of lipid bilayers made of phosphatidylcholine. The test set of compounds comprised the parent compound 8-hydroxyquinoline and 8-hydroxyquinolines with hydrophobic (e.g., 5-chloro-8-hydroxyquinoline, 5,7-dichloro-8-hydroxyquinoline, 5,7-dibromo-8-hydroxyquinoline) and with hydrophilic (e.g., 8-hydroxyquinoline-5-sulfonic acid) substituents. Hydrophobic 8-hydroxyquinolines facilitate the passive uptake of copper into phospholipid bilayers by complex formation. Not only the neutral species of the ligands and their neutral copper ligand complexes are significantly taken up into the membrane, but also the cationic and anionic species of the ligands and the cationic complexes. The neutral, anionic, and cationic species of 8-hydroxyquinoline and the hydrophobic substituted 8-hydroxyquinolines exhibit linear correlations between their logarithmic liposome-water partitioning coefficients (log Klipw) and the logarithmic octanol-water partitioning coefficients of their neutral species (log Kow, neutral). The neutral species show the strongest partitioning followed by the anionic and cationic species. The associated quantitative structure activity relationships describing the dependency of log Klipw of the various species from log Kow, neutral of the neutral ligand species have slopes between 0.9 and 1. In contrast, the partitioning of the neutral and cationic copper-8-hydroxyquinoline complexes is dependent on several factors including the hydrophobicity of the ligand, the effective molecular size, and the polarization of the complex itself. In consequence, there is no linear relationship between log Klipw of these complexes and log Kow of the neutral species of their ligands. The complexes with very bulky substituents showed a reduced uptake. The Klipw of the nominally neutral complexes, where Cu2+ is coordinated with two ligands, were a factor three to four higher than the Klipw of the positively charged complexes with only one ligand. Although liposome-water partitioning merely describes one element of the uptake process into biological membranes, it is a key process for bioavailability of hydrophobic compounds and, presumably, also plays a crucial role for biological uptake of the described metal organic complexes.     

Comparative ecotoxicological hazard assessment of beta-blockers and their human metabolites using a mode-of-action-based test battery and a QSAR approach

We analyzed nontarget effects of the beta-blockers propranolol, metoprolol, and atenolol with a screening test battery encompassing nonspecific, receptor-mediated, and reactive modes of toxic action. All beta-blockers were baseline toxicants and showed no specific effects on energy transduction nor endocrine activity in the yeast estrogen and androgen screen, and no reactive toxicity toward proteins and DNA. However, in a phytotoxicity assay based on the inhibition of the photosynthesis efficiency in green algae, all beta-blockers were 10 times more toxic than their modeled baseline toxicity. Baseline- and phytotoxicity effects increased with hydrophobicity. The beta-blockers showed concentration addition in mixture experiments, indicating a mutual specific nontarget effect on algae. Using literature data and quantitative structure-activity relationships (QSAR), we modeled the total toxic potential of mixtures of the beta-blockers and their associated human metabolites for the phytotoxicity endpoint with two scenarios. The realistic scenario (I) assumes that the metabolites lose their specific activity and act as baseline toxicants. In the worst-case scenario (II) the metabolites exhibitthe same specific mode of action as their parent drug. For scenario (II), metabolism hardly affected the overall toxicity of atenolol and metoprolol, whereas propranolol's hazard potential decreased significantly. In scenario (I), metabolism reduced the apparent EC50 of the mixture of parent drug and metabolite even further. The proposed method is a simple approach to initial hazard assessment of pharmaceuticals and can guide higher tier testing. It can be applied to other classes of pollutants, e.g., biocides, as well as to environmental transformation products of pollutants.     

Effect of low-dose radiation on microbiological, chemical, and sensory characteristics of chicken meat stored aerobically at 4 degrees C

The effect of gamma-radiation (0.5, 1, and 2 kGy) on the shelf life of fresh skinless chicken breast fillets stored aerobically at 4 degrees C was evaluated. Microbiological, chemical, and sensorial changes occurring in chicken samples were monitored for 21 days. Irradiation reduced populations of bacteria, i.e., total viable bacteria, Brochothrix thermosphacta, lactic acid bacteria (LAB), and the effect was more pronounced at the highest dose (2 kGy). Pseudomonads, yeasts and molds, and Enterobacteriaceae were highly sensitive to gamma-radiation and were completely eliminated at all doses. Of the chemical indicators of spoilage, thiobarbituric values for nonirradiated and irradiated aerobically packaged chicken samples were in general low (<1 mg of malonaldehyde per kg of muscle) during refrigerated storage for 21 days. With regard to volatile amines, both trimethylamine nitrogen (TMA-N) and total volatile basic nitrogen (TVB-N) values for nonirradiated aerobically packaged chicken increased steeply, with final values of ca. 20.3 and 58.5 mg N/100 g of muscle, respectively. Irradiated aerobically packaged chicken samples had significantly lower TMA-N and TVB-N values (P < 0.05) of ca. 2.2 to 3.6 and 30.5 to 37.1 mg N/100 g of muscle, respectively, during refrigerated storage for 21 days. Of the biogenic amines monitored, only putrescine and cadaverine were detected in significant concentrations in both nonirradiated and irradiated chicken samples, whereas histamine formation was noted only in nonirradiated samples throughout storage. On the basis of sensorial evaluation, low-dose irradiation (0.5 and 1.0 kGy) in combination with aerobic packaging extended the shelf life of fresh chicken fillets by ca. 4 to 5 days, whereas irradiation at 2.0 kGy extended the shelf life by more than 15 days compared with that of nonirradiated chicken.     

Selection of pfcrt K76 and pfmdr1 N86 Coding Alleles after Uncomplicated Malaria Treatment by Artemether-Lumefantrine in Mali

Background: Artemether-lumefantrine is a highly effective artemisinin-based combination therapy that was adopted in Mali as first-line treatment for uncomplicated Plasmodium falciparum malaria. This study was designed to measure the efficacy of artemether-lumefantrine and to assess the selection of the P. falciparum chloroquine resistance transporter (pfcrt) and P. falciparum multi-drug resistance 1 (pfmdr1) genotypes that have been associated with drug resistance. Methods: A 28-day follow-up efficacy trial of artemether-lumefantrine was conducted in patients aged 6 months and older suffering from uncomplicated falciparum malaria in four different Malian areas during the 2009 malaria transmission season. The polymorphic genetic markers MSP2, MSP1, and Ca1 were used to distinguish between recrudescence and reinfection. Reinfection and recrudescence were then grouped as recurrent infections and analyzed together by PCR-restriction fragment length polymorphism (RFLP) to identify candidate markers for artemether-lumefantrine tolerance in the P. falciparum chloroquine resistance transporter (pfcrt) gene and the P. falciparum multi-drug resistance 1 (pfmdr1) gene. Results: Clinical outcomes in 326 patients (96.7%) were analyzed and the 28-day uncorrected adequate clinical and parasitological response (ACPR) rate was 73.9%. The total PCR-corrected 28-day ACPR was 97.2%. The pfcrt 76T and pfmdr1 86Y population prevalence decreased from 49.3% and 11.0% at baseline (n = 337) to 38.8% and 0% in patients with recurrent infection (n = 85); p = 0.001), respectively. Conclusion: Parasite populations exposed to artemether-lumefantrine in this study were selected toward chloroquine-sensitivity and showed a promising trend that may warrant future targeted reintroduction of chloroquine or/and amodiaquine.