Quantitative structure-activity relationship (QSAR) prediction of (eco)toxicity of short aliphatic protic ionic liquids.

Ionic liquids (ILs) are considered as a group of very promising compounds due to their excellent properties (practical non-volatility, high thermal stability and very good and diverse solving capacity). The ILs have a good prospect of replacing traditional organic solvents in vast variety of applications. However, the complete information on their environmental impact is still not available. There is also an enormous number of possible combinations of anions and cations which can form ILs, the fact that requires a method allowing the prediction of toxicity of existing and potential ILs. In this study, a group contribution QSAR model has been used in order to predict the (eco)toxicity of protic and aprotic ILs for five tests (Microtox®, Pseudokirchneriella subcapitata and Lemna minor growth inhibition test, and Acetylcholinestherase inhibition and Cell viability assay with IPC-81 cells). The predicted and experimental toxicity are well correlated. A prediction of EC50 for these (eco)toxicity tests has also been made for eight representatives of the new family of short aliphatic protic ILs, whose toxicity has not been determined experimentally to date. The QSAR model applied in this study can allow the selection of potentially less toxic ILs amongst the existing ones (e.g. in the case of aprotic ILs), but it can also be very helpful in directing the synthesis efforts toward developing new "greener" ILs respectful with the environment (e.g. short aliphatic protic ILs).

A comparative study of the terrestrial ecotoxicity of selected protic and aprotic ionic liquids.

Ionic liquids (ILs) are a fairly new and very promising group of compounds with a vast variety of possible structures and uses. They are considered to be potentially "green", but their impact on the environment tends to be neglected or not studied enough, especially when it comes to terrestrial ecotoxicity, where there are very few studies performed to date. This work presents a comparative study of the terrestrial ecotoxicity of selected representatives of two ILs groups: a new family of protic ILs (derived from aliphatic amines and organic acids) and some frequently used aprotic ILs (substituted imidazolium and piridinium chlorides). Toxicity of the ILs towards three terrestrial plant species (Allium cepa, Lolium perenne and Raphanus sativus) and soil microorganisms involved in carbon and nitrogen transformation was analyzed. Protic ILs have shown no toxic effect in most of the tests performed. The EC50 values for aprotic ILs are various orders of magnitude lower than the ones for protic ILs in all of the tests. The most toxic ILs are the most complex ones in both of the analyzed groups. Protic ILs seem to have a potential for biodegradation in soil, while aprotic ILs exhibit inhibitory effects towards the carbon transforming microbiota. These findings indicate that protic ILs can be considered as less toxic and safer for the terrestrial environment than the aprotic ILs.

(Eco)toxicity and biodegradability of selected protic and aprotic ionic liquids.

Ionic liquids (ILs) are a promising group of compounds with a large variety of possible structures and uses. They are considered as a potential "green" replacement for traditional volatile organic solvents, but their impact on the environment is often neglected or not studied enough. In the present study, selected representatives of two ILs groups were analyzed: a new family of protic ILs (derived from aliphatic amines and organic acids) and some frequently used aprotic ILs (substituted imidazolium and piridinium chlorides). The aquatic toxicity (test organisms Vibrio fischeri, Pseudokirchneriella subcapitata and Lemna minor) and biodegradability tests were carried out. The additional tests with enzyme (acetylcholinesterase) and leukemia rat cells (IPC-81) provided more in-depth evaluation of toxicity. In our comparative hazard assessment protic ILs have EC50 values >100 mg L(-1) in all of the tests performed, except in the case of three representatives toward Lemna minor. They also show good biodegradability rates. The EC50 values for aprotic ILs are various orders of magnitude lower than the ones for protic ILs in most of the tests and they show a lower biodegradability potential. These findings indicate that protic ILs can be considered as environmentally safer alternatives for more toxic ILs and organic solvents.

Ecotoxicity of Cr, Cd, and Pb on two Mediterranean soils.

Three potentially toxic elements [chromium (Cr), lead (Pb), and cadmium (Cd)] were tested to assess their effects on two soils of different properties and origin. The soils were a granitic soil (Haplic Arenosol), which meets the requirements of OECD ecotoxicity testing, and a calcareous soil (Calcaric Regosol) with properties often found in the Mediterranean areas. The metal concentrations used ranged from 0.001 to 5,000 mg kg(-1) soil. The effects on soil microbial activity and community composition (respirometry and polymerase chain reaction-denaturing gradient gel electrophoresis analysis), as well as the effects on plant germination and elongation (Lactuca sativa), were assessed. The toxicity of the soil water extracts was also evaluated by the growth inhibition of algal populations (Pseudokirschneriella subcapitata). Cr showed the highest level of toxicity to soil organisms in the assays performed because this element remains in soil as anionic form and is less retained by the soil solid matrix than Cd and Pb. The lowest observed-adverse effect level for Cr ranged from approximately 0.1 mg kg(-1) [substrate induced respiration (SIR) test for the granitic soil] to 10 mg kg(-1) (basal respiration and SIR tests for the calcareous soil). For Pb (SIR) and Cd (SIR and alga tests), these levels were approximately 100 mg kg(-1). Germination and algal tests showed higher sensitivity in Regosol soil than in Arenosol soil for Cr due to differences in the bioavailability between the soils. In the cases or areas where alkaline soils are abundant, these should also be considered in laboratory ecotoxicity testing to avoid underestimation of ecotoxicological risks.

The exposition of a calcareous Mediterranean soil to toxic concentrations of Cr, Cd and Pb produces changes in the microbiota mainly related to differential metal bioavailability.

The involvement of the bacterial community of an agricultural Mediterranean calcareous soil in relation to several heavy metals has been studied in microcosms under controlled laboratory conditions. Soil samples were artificially polluted with Cr(VI), Cd(II) and Pb(II) at concentrations ranging from 0.1 to 5000 mg kg(-1) and incubated along 28 d. The lowest concentrations with significant effects in soil respirometry were 10 mg kg(-1) Cr and 1000 mg kg(-1) Cd and Pb. However, only treatments showing more than 40% inhibition of respirometric activity led to significant changes in bacterial composition, as indicated by PCR-DGGE analyses. Presumable Cr- and Cd-resistant bacteria were detected in polluted microcosms, but development of the microbiota was severely impaired at the highest amendments of both metals. Results also showed that bioavailability is an important factor determining the impact of the heavy metals assayed, and even an inverted potential toxicity ranking could be achieved if their soluble fraction is considered instead of the total concentration. Moreover, multiresistant bacteria were isolated from Cr-polluted soil microcosms, some of them showing the capacity to reduce Cr(VI) concentrations between 26% and 84% of the initial value. Potentially useful strains for bioremediation were related to Arthrobacter crystallopoietes, Stenotrophomonas maltophilia and several species of Bacillus.

Terrestrial ecotoxicity of short aliphatic protic ionic liquids.

A study of the ecotoxicity of different short aliphatic protic ionic liquids (PILs) on terrestrial organisms was conducted. Tests performed within the present study include those assessing the effects of PILs on soil microbial functions (carbon and nitrogen mineralization) and terrestrial plants. The results show that the nominal lowest-observed-adverse-effect concentration (LOAEC) values were 5,000 mg/kg (dry soil) for the plant test in two species (Lolium perenne, Allium cepa), 1,000 mg/kg (dry soil) for the plant test in one species (Raphanus sativus), and 10,000 mg/kg (dry soil) for carbon and nitrogen microbial transformation tests (all concentrations are nominal). Most of the median effective concentration values (EC50) were above 1,000 mg/kg (dry soil). Based on the obtained results, these compounds can be described as nontoxic for soil microbiota and the analyzed plants, and potentially biodegradable in soils, as can be deduced from the respirometric experiment. The toxicity rises with the increase of complexity of the PILs molecule (branch and length of aliphatic chain) among the three PILs analyzed.

Ecotoxicity of chlorophenolic compounds depending on soil characteristics.

Three chlorophenolic compounds (2-chlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol) were tested to assess their effects on two soils with different properties: a granitic soil (Haplic Arenosol) and a calcareous one (Calcaric Regosol). Different concentrations of the pollutants (ranging from 0.001 to 10,000 mg kg(-1) soil, d.w.) were assayed for their effects on soil microbial activity and composition, using manometric respirometry and PCR-DGGE analysis, respectively. Other ecotoxicity tests such as Lactuca sativa seedling growth in the contaminated soils and algal growth inhibition (Pseudokirschneriella subcapitata) in their water extracts were done. The behaviour of the pollutants in the soils with respect to biodegradability and volatilization was also investigated. In the Haplic Arenosol, volatilization is the main process affecting 2-chlorophenol. Degradation and fixation of this compound in the soil matrix are favored in the Calcaric Regosol. This is the least toxic pollutant assayed. For 2,4,6-trichlorophenol, the soil pH is a critical parameter in the toxicity assays due to the neutral pKa of the compound. It is toxic in the soil microbial activity assay, but some recovery of the biotic processes can be observed, particularly in the Calcaric Regosol. This compound is more toxic in the Haplic Arenosol than in the Calcaric Regosol. Pentachlorophenol is ionized in both soils due to its low pKa, increasing its water solubility. It is highly toxic to the soil microbiota, thus inhibiting respiration, biodegradation and other biotic dissipation processes. Plant and alga tests, were more sensitive than soil microbial tests, except for PCP. The microbial populations tend to show changes at lower concentrations than the microbial activity. Some soil types (abundant in the Mediterranean area), with alkaline pH and fine textures could show higher level of ecotoxicity for ionizable organic pollutants than the soil type recommended by the OECD in ecotoxicity testing.

Impact of chlorophenols on microbiota of an unpolluted acidic soil: microbial resistance and biodegradation.

The impact of 2-monochlorophenol (MCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) on the microbial community of an acidic forest soil was studied under controlled laboratory conditions by spiking microcosms with the pollutants at concentrations ranging from 0.1 to 5000 mg kg(-1). A decrease in the cumulative respirometric values and changes in the bacterial and fungal community composition were detected at 1000 mg MCP kg(-1), 100 mg TCP kg(-1) and 100 and 1000 mg PCP kg(-1). However, drastic effects on the microbial community were revealed only at higher concentrations of MCP and TCP, although the toxicity of PCP was expected to be stronger. The acidic condition of the soil presumably reduces bioavailability of PCP, leading to less pronounced effects than the other pollutants. This finding highlights the consideration of pollutant bioavailability in each environment to adequately assess contamination effects. Twenty-two different chlorophenol-resistant and potentially degrading microorganisms were isolated from highly polluted microcosms. The most resistant isolates were related to Burkholderia arboris, Bacillus circulans, Paenibacillus taichungensis, Luteibacter rhizovicina and Janibacter melonis. These isolates also showed the capacity to reduce the concentration of TCP or PCP between 15% and 35% after 5 days of incubation (initial concentration of 50 mg L(-1)). The isolate related to B. circulans is an atypical case of a member of the Firmicutes group for which chlorophenol-degrading capacities have been described.

Ecotoxicological tests assessment of soils polluted by chromium (VI) or pentachlorophenol.

Carbon mineralisation and plant germination and growth (Lactuca sativa seeds) tests have been performed in two soils of different properties, experimentally spiked with pentachlorophenol (PCP) or Cr (VI), in concentrations between 0.001 and 1000 mg kg(-1). The evaluation has been done considering the following parameters of carbon transformation test: soil cumulative basal respiration after 14 days incubation, substrate induced respiration after 12 h of glucose addition, and, in the plant germination and growth test: number of germinated seeds, root elongation and total biomass produced. The most sensitive assay found in our work has been carbon mineralisation test, from which the lowest toxic concentrations were obtained (especially substrate induced respiration test). In the plant germination and growth test, the measurement of root elongation has shown the best sensitiveness, followed by plant biomass and seed germination numbers. Regarding the contaminants, the highest toxicity, considering the minimum concentration with toxic effect, has been found in PCP (0.01 mg kg(-1)) in C mineralisation test in the granitic soil. For Cr, the minimum concentration with toxic effect has been 0.1 mg kg(-1), also in the C mineralisation test and the granitic soil. The granitic soil has shown more vulnerability to the pollutants assayed in the respiration test, whereas the calcareous soil has shown more vulnerability in the plant germination and growth test.

Effects of the agronomic use of olive oil mill wastewater: field experiment.

The aim of this study is to assess the effects of olive oil wastewater application on soils. The work consists of field application of the waste at different rates (30, 180, 360 m(3) ha(-1)). Increasing rates of waste enhance the soil fertility due to P, organic matter and N. However, temporary nitrogen immobilisation, increase in salinity values and in phenolic compounds concentrations, both sorbed and soluble forms, have also been observed. Phenolic compounds have been rapidly biodegraded in soil.