2,4-D versus 2,4-D based ionic liquids: Effect of cation on herbicide biodegradation, tfdA genes abundance and microbiome changes during soil bioaugmentation.

The commercial formulations of herbicides rely on surfactants which increase the efficiency of active substance. Herbicidal ionic liquids (ILs), in which cationic surfactants are combined with herbicidal anions, allow for additives' reduction and ensure very good herbicide performance with lower doses. We aimed to test the impact of synthetic and natural cations on biological degradation of 2,4-dichlorophenoxyacetic acid (2,4-D). Although primary biodegradation was high, the mineralization in agricultural soil indicated incomplete conversion of ILs to CO2. Even the introduction of naturally-derived cations resulted in an increase in the herbicide's half-lives - from 32 days for [Na][2,4-D] to 120 days for [Chol][2,4-D] and 300 days for the synthetic tetramethylammonium derivative [TMA][2,4-D]. Bioaugmentation with 2,4-D-degrading strains improves the herbicides' degradation, which was reflected by higher abundance of tfdA genes. Microbial community analysis confirmed that hydrophobic cationic surfactants, even those based on natural compounds, played a negative role on microbial biodiversity. Our study provides a valuable indication for further research related to the production of a new generation of environmentally friendly compounds. Moreover, the results shed a new light on the ionic liquids as independent mixtures of ions in the environment, as opposed to treating them as new type of environmental pollutants.

Glyphosate versus glyphosate based ionic liquids: Effect of cation on glyphosate biodegradation, soxA and phnJ genes abundance and microbial populations changes during soil bioaugmentation.

The applicability of herbicidal ionic liquids (HILs) as an alternative form of herbicides is currently evaluated. Yet, the available research is lacking information on the behaviour of herbicidal ionic liquids upon addition to the environment, i.e., if cations and anions act as separate moieties or remain an ionic salt. Hence, we tested degradation of five HILs with the glyphosate anion, their bioavailability in soil, toxicity towards microorganisms, impact on the biodiversity and the abundance of phnJ and soxA genes. The cations were proven to be slightly or moderately toxic. The properties of cations determined the properties of the whole formulation, which might suggest that cations and anion act as the independent mixture of ions. The mineralisation efficiencies were in the range of 15-53%; however, in the case of cations (except non-toxic choline), only 13-20% were bioavailable for degradation. The hydrophobic cations were proven to be highly sorbed, while the anion was readily available for microbial degradation regardless of its counterion. The approach to enrich test samples with isolated microorganisms specialised in glyphosate degradation resulted in higher degradation efficiencies, yet not high enough to mitigate the negative impact of cations. In addition, increased activity of enzymes participating in glyphosate degradation was observed. In the view of obtained results, the use of cationic surfactants in HILs structure is not recommended, as sorption was shown to be determining factor in HILs degradation efficiency. Moreover, obtained results indicate that corresponding ions in HILs might act as separate moieties in the environment.

Biodegradation half-lives of biodiesel fuels in aquatic and terrestrial systems: A review.

Information on biodegradation kinetics of biodiesel fuels is a key aspect in risk and impact assessment practice and in selection of appropriate remediation strategies. Unfortunately, this information is scattered, while factors influencing variability in biodegradation rates are still not fully understood. Therefore, we systematically reviewed 32 scientific literature sources providing 142 biodegradation and 56 mineralization half-lives of diesel and biodiesel fuels in various experimental systems. The analysis focused on the variability in half-lives across fuels and experimental conditions, reporting sets of averaged half-life values and their statistical uncertainty. Across all data points, biodegradation half-lives ranged from 9 to 62 days, and were 2-5.5 times shorter than mineralization half-lives. Across all fuels, biodegradation and mineralization half-lives were 2.5-8.5 times longer in terrestrial systems when compared to aquatic systems. The half-lives were generally shorter for blends with increasing biodiesel content, although differences in number of data points from various experiments masked differences in half-lives between different fuels. This in most cases resulted in lack of statistically significant effects of the type of blends and experimental system on biodegradation half-lives. Our data can be used for improved characterization of risks and impacts of biodiesel fuels in aerobic aquatic and terrestrial environments, while more experiments are required to quantify biodegradation kinetics in anaerobic conditions. Relatively high biodegradability of biodiesel may suggest that passive approaches to degrade and dissipate contaminants in situ, like monitored natural attenuation, may be appropriate remediation strategies for biodiesel fuels.

Herbicidal Ionic Liquids: A Promising Future for Old Herbicides? Review on Synthesis, Toxicity, Biodegradation, and Efficacy Studies.

The transformation of agrochemicals into herbicidal ionic liquids (HILs) has been suggested as a solution to problems associated with commercial forms of herbicides. The aim of this review was to summarize the latest progress in the field of HILs, including their synthesis as well as physicochemical and biological properties, and to address the areas that require further research in order to ensure their safe commercialization (e.g., data regarding biodegradability, toxicity, and environmental fate). The first part of the review provides an in-depth summary of the current state of knowledge regarding HILs, particularly the anions and cations used for their synthesis. The second part highlights the employed synthesis methods and elucidates their respective advantages and limitations. The third section is focused on the characterization of HILs with emphasis on the methods and factors that are significant in terms of their practical application. Subsequently, the issues associated with the biodegradation and toxic effects of HILs are discussed based on the relevant literature reports. All sections include comprehensively tabulated data in order to enable rapid comparison of utilized approaches. Finally, all the findings are critically analyzed in terms of crucial disadvantages (especially the lack of standardization), which allowed us to establish future recommendations and basic guidelines that are presented in the last section.

Nootropic drugs: Methylphenidate, modafinil and piracetam - Population use trends, occurrence in the environment, ecotoxicity and removal methods - A review.

Pharmaceuticals which originally were designed to treat people with neurological and psychiatric conditions, e.g. Alzheimer's disease or attention deficit hyperactivity disorder (ADHD), are nowadays often misused by students as a 'brain doping' substances. These substances are known as nootropic drugs, smart drugs or cognitive enhancers, as they increase memory, attention and concentration of healthy individuals. Since they are easily available illicitly, their consumption is observed to be growing. Currently, these pharmaceuticals started gaining researchers' attention, especially since they have been recently detected in wastewater, surface water and even drinking water. This review summarises the current state of knowledge on nootropic drugs in terms of their population use trends and ethics, occurrence in the environment and detection techniques, toxicity and removal methods, in example of methylphenidate, modafinil and piracetam - three most popular nootropics. It points out that the main sources of knowledge on cognitive enhancers illicit use are often inconsistent questionnaires, which are not supported by wastewater analysis to become more veracious. Simultaneously, the studies concerning toxicity and removal methods of nootropic drugs are still limited and in many cases environmentally irrelevant. Although the prescription rules has been subjected to more strict control in developed countries, regulatory frameworks with regard to their ecosystem occurrence are still lacking and should be introduced. Moreover, the use of environmentally relevant concentrations in toxicity studies should be a standard, leading to proper ecotoxicity risk assessment. Based on this review, it is recommended to routinely monitor nootropics and their metabolites in waste- and surface waters.