Andrea Pasteris

Introduction of oxygenated side chain into imidazolium ionic liquids: Evaluation of the effects at different biological organization levels

The biological effects of a class of oxygenated imidazolium ionic liquids were studied in comparison with alkyl imidazolium salts (BMIM BF4 and BMIM N(CN)2).The cellular and subcellular effects were evaluated on rat pheochromocytoma PC12 cell lines, through MTT test, lactate dehydrogenase release and acetylcholinesterase inhibition; the eco-toxicological responses were assessed through the acute toxicity tests towards Daphnia magna and Vibrio fischeri. The introduction of ethoxy moieties in the lateral chain of imidazolium cations reduced the biological effects in all the tests. The acute toxicity towards D. magna was not affected by the number of ethoxy units, but the crustacean seemed to be sensitive to the type of anion; on the contrary, a further addition of ethoxy moieties increased the toxicity towards V. fischeri, M(OE)4MIM N(CN)2 being the most toxic oxygenated ionic liquid. In the cytotoxicity assays the salts with oxygenated cations resulted ineffective compared to BMIMs, independently from the anion and the number of ethoxy units in the lateral chain. In order to estimate the influence on membrane fluidity, an analysis of fluorescence anisotropy was done and it indicated that BMIM BF4, the most toxic ionic liquid among the tested ones, led to a destabilization of the model membranes at any molarity.

Acute toxicity of oxygenated and nonoxygenated imidazolium‐based ionic liquids to Daphnia magna and Vibrio fischeri

Room-temperature ionic liquids (RTILs) recently have generated great interest as a result of their potential commercial applications. In particular, because of their negligible vapor pressure and low inflammability, they have been suggested as green alternatives to traditional organic solvents. The toxicity and potential environmental risk of this heterogeneous class of chemicals, however, are poorly understood. An alkyl-substituted RTIL, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]), is one of the most widely used cations of RTILs, and information regarding its toxicity is relatively extensive. On the other hand, oxygenated chain-substituted ionic liquids, 1-methoxyethyl-3-methylimidazolium salts (moemims), are a new class of RTILs that have been poorly studied. Here, we compared the acute toxicity of [bmim][BF(4)] and moemims to the crustacean Daphnia magna (end point, 48-h immobilization) and the bacterium Vibrio fischeri (end point, 15-min inhibition of bioluminescence). The concentrations of [bmim][BF(4)] resulting in 50% of the maximum adverse effect (EC50s) for D. magna and V. fischeri were 5.18 and 300 mg/L, respectively, and were consistent with previously published values. The EC50s of the two moemims for D. magna are very similar, ranging from 209 to 222 mg/L in different experimental trials, and are higher by two orders of magnitude than the EC50 of [bmim][BF(4)]. The EC50s of 1-methoxyethyl-3-methylimidazolium tetrafluoroborate ([moemim][BF(4)]) and 1-methoxyethyl-3-methylimidazolium dicyanamide ([moemim][dca]) for V. fischeri are 3,196 and 2,406 mg/L, respectively. Results indicate that introduction of an oxygenated side chain in the imidazolium cation can greatly reduce the toxicity of RTILs and that these RTILs are less toxic than commonly used chlorinated solvents, such as tricloromethane, but are more toxic than nonchlorinated solvent, such as methanol and acetone.

Freshwater ecotoxicity characterisation factor for metal oxide nanoparticles: A case study on titanium dioxide nanoparticle

The Life Cycle Assessment (LCA) methodology is widely applied in several industrial sectors to evaluate the environmental performance of processes, products and services. Recently, several reports and studies have emphasized the importance of LCA in the field of engineered nanomaterials. However, to date only a few LCA studies on nanotechnology have been carried out, and fewer still have assessed aspects relating to ecotoxicity. This is mainly due to the lack of knowledge in relation on human and environmental exposure and effect of engineered nanoparticles (ENPs). This bottleneck is continued when performing Life Cycle Impact Assessment, where characterization models and consequently characterization factors (CFs) for ENPs are missing. This paper aims to provide the freshwater ecotoxicity CF for titanium dioxide nanoparticles (nano-TiO₂). The USEtox model has been selected as a characterisation model. An adjusted multimedia fate model has been developed which accounts for nano-specific fate process descriptors (i.e. sedimentation, aggregation with suspended particle matter, etc.) to estimate the fate of nano-TiO₂ in freshwater. A literature survey of toxicity tests performed on freshwater organism representative of multiple trophic levels was conducted, including algae, crustaceans and fish in order to collect relevant EC₅₀ values. Then, the toxic effect of nano-TiO₂ was computed on the basis of the HC₅₀ value. Thus, following the principle of USEtox model and accounting for nano-specific descriptors a CF for the toxic impact of freshwater ecotoxicity of 0.28 PAFdaym(3)kg(-1) is proposed.

Toxicity of copper-spiked sediments to Tubifex tubifex (Oligochaeta, Tubificidae): a comparison of the 28-day reproductive bioassay with a 6-month cohort experiment.

Results from a 28-day adult reproductive bioassay using the aquatic oligochaete Tubifex tubifex (Müller, 1774) are compared with life table statistics obtained from a 6-month experiment on cohorts of the same species. This was done by simultaneously performing the two tests on copper spiked sediments. Five concentrations and a control were tested. The 28-day bioassay was performed 3 times in succession. Several endpoints were considered for each test and LOEC, IC10 and IC50 were calculated. IC50 estimates for the number of young produced in the 28-day bioassay range from 81 to 107 mg/kg; IC50 estimates for different endpoints of the cohort experiment ranged from 88 to 106 mg/kg. The 28-day bioassay showed essentially the same sensitivity as the cohort experiment to copper. This suggests that the 28-day reproductive bioassay does provide information that is relevant in assessing long-term toxic effects at the population level.

Quantitative observations on the population ecology of Branchiura sowerbyi (Oligochaeta, Tubificidae)

Cohorts of Branchiura sowerbyi were reared at different temperatures and initial population densities in order to obtain data suitable for the interpretation of population dynamics in field populations. Percent hatching from cocoons reaches its maximum at 25 °C and decreases towards lower and higher temperatures. Embryonic development time, TE, was measured and the relative threshold temperature, 10 °C, calculated by extrapolation. The degree day requirement for embryo development is 195 °C d. The time of first cocoon laying (Tgm) was observed and the ratio TE/Tgm was seen to fit with that of other tubificid species cultured so far. Embryo mortality is rather high, while worm mortality is low or very low. Fecundity increases from 15 to 20 °C but decreases at 25 °C. A mathematical model for the simulation of population densities with four size-stage compartments is suggested. It could be used for the optimization of worm uptake (simulated as stage specific mortality) in mass cultures reared for the production of Branchiura, to be used as food for fish fingerlings.

Observations on cohorts of Tubifex tubifex cultured at different food levels, using cellulose substrate

In order to clarify the relationship between food availability and population dynamics in aquatic oligochaetes, short term cultures and cohort cultures of Tubifex tubifex were reared using substrates with different food concentrations, obtained by mixing sand with different amounts of cellulose powder.

Production and population dynamics of Tubifex tubifex in the profundal zone of a freshwater reservoir in N. Italy

During a study of a pumped storage system from May 1979–June 1980 the profundal macrobenthos of the upper reservoir (Lago di S. Maria Valvestino) was sampled at a fixed station and the population of the tubificid Tubifex tubifex studied in detail. Eggs, embryos and the individuals living in an extra-cocoon stage were counted and individually weighed from monthly samples, according to the methods described in Bonomi & Di Cola (1980). Numerical recruitment during the study period was estimated as 257 000 ind m−2 yr−1; of which 110 000 died either as eggs or as embryos, i.e. inside the cocoons, and a further 128 000 died before they attained sexual maturation. The data seem to confirm the typical demographic strategy of T. tubifex i.e. high fecundity and high mortality in the early life stages. The total annual production of the species was estimated at 91.7 g (w.w.) m−2. The low P/B ratio (2.0 yr−1) is considered to be mainly due to high population densities.

Assessing the environmental hazard of individual and combined pharmaceuticals: acute and chronic toxicity of fluoxetine and propranolol in the crustacean Daphnia magna

Pharmaceuticals are widespread emerging contaminants and, like all pollutants, are present in combination with others in the ecosystems. The aim of the present work was to evaluate the toxic response of the crustacean Daphnia magna exposed to individual and combined pharmaceuticals. Fluoxetine, a selective serotonin re-uptake inhibitor widely prescribed as antidepressant, and propranolol, a non-selective β-adrenergic receptor-blocking agent used to treat hypertension, were tested. Several experimental trials of an acute immobilization test and a chronic reproduction test were performed. Single chemicals were first tested separately. Toxicity of binary mixtures was then assessed using a fixed ratio experimental design. Five concentrations and 5 percentages of each substance in the mixture (0, 25, 50, 75, and 100%) were tested. The MIXTOX model was applied to analyze the experimental results. This tool is a stepwise statistical procedure that evaluates if and how observed data deviate from a reference model, either concentration addition (CA) or independent action (IA), and provides significance testing for synergism, antagonism, or more complex interactions. Acute EC50 values ranged from 6.4 to 7.8 mg/L for propranolol and from 6.4 to 9.1 mg/L for fluoxetine. Chronic EC50 values ranged from 0.59 to 1.00 mg/L for propranolol and from 0.23 to 0.24 mg/L for fluoxetine. Results showed a significant antagonism between chemicals in both the acute and the chronic mixture tests when CA was adopted as the reference model, while absence of interactive effects when IA was used.

Tigriopus fulvus: The interlaboratory comparison of the acute toxicity test.

The paper reports the results of an interlaboratory comparison involving 11 laboratories, with the objectives of apply and validate a new standardized ecotoxicological method on marine crustacean Tigriopus fulvus. Copper was chosen as reference toxicant as indicated in the official method. The results of two independent tests performed by all the participants, demonstrated that the new method is simple, fast and easy to learn. This is confirmed even by the values of z-score index calculated for each laboratory and the relative coefficient of variation (CV) which are 6.32% after 24h, 6.56 after 48h and 35.3% after 96h, mentioned in the ISO standards for the precision of interlaboratory assays. Therefore its use could be recommended in environmental studies and monitoring.

A comparison among different population models for Limnodrilus hoffmeisteri Claparède (Oligochaeta, Tubificidae)

The lack of any reliable method for assessing the age of individuals collected in the field has often been considered a major obstacle for population studies in aquatic oligochaetes. One possible solution could be the adoption of other variables, such as weight or stage, for the definition of the population structure; this approach would be useful if allowed good predictions about population growth. We measured, under laboratory conditions, the effect of age, size and life stage on survival, growth and fecundity of Limnodrilus hoffmeisteri Claparede. The results are used to establish four matrix population models, based respectively on the classification of the individuals by age, weight and stage and on a mixed classification. Matrix population models make the assumptions that the individuals in a population can be arranged in a number of discrete classes and that time is a discrete variable. In these models, the population is represented by a vector (each element in the vector is the number of individuals in a class) and the demographic coefficients (survival, growth and fecundity) are collected in a square matrix. The estimate of λ, the potential long term population growth rate and its confidence interval were taken from the four models using the jackknife method. The width of the confidence interval is a measure of the effectiveness of the models and thus of the classification of the individuals. The results suggest that weight is inefficient as a criterion for the definition of population structure of L hoffmeisteri in comparison to age and stage.