Cations impact the biodegradation of iodosulfuron-methyl herbicidal ionic liquids by fungi.

In the framework of this study, six fungal isolates which demonstrated a high capability for biodegrading iodosulphuron-methyl sodium as well as herbicidal ionic liquids based on this herbicide were isolated from different soil samples. The isolates were identified based on the ITS region, whereas biodegradation residues were determined based on LC-MS/MS. Depending on the isolate, the half-lives values of the biodegraded herbicide or herbicidal ionic liquid ranged significantly from just 1.25 days to more than 40 days. The research findings unveiled that the structure of cations is a central limiting factor affecting fungal growth and herbicide transformation in case of ionic liquids. The length of the alkyl chain has been identified as the primary driver of herbicide toxicity, emphasizing the importance of structural factors in herbicide design. In cases when dodecyl(2-hydroxyethyl)dimethyl cation was used, its biodegradation ranged from 0 to approx. 20% and the biodegradability of the iodosulfuron-methyl was notably limited for the majority of the studied isolates. This knowledge provides guidance for development and selection of herbicides with reduced environmental impact. This study highlights the ecological importance of soil fungi, their potential role in herbicide biodegradation, the influence of cations on fungal growth and herbicide transformation, and the structural factors governing herbicide toxicity. Further research in these areas may lead to more efficient and environmentally friendly approaches to herbicide management.

Critical evaluation of the performance of rhamnolipids as surfactants for (phyto)extraction of Cd, Cu, Fe, Pb and Zn from copper smelter-affected soil.

Rhamnolipids are biosurfactants produced by bacteria belonging to the Pseudomonas genus. They are discussed to complex heavy metal cations stronger than cations of Fe, Ca, Mg. It is therefore suggested to employ rhamnolipids in phytoextraction where their addition to soil should result in preferential complexation of heavy metals that can be taken up by plants, thus enabling rapid and ecological clean-up of contaminated soil. In order to test this concept, we evaluated the rhamnolipid-mediated phytoextraction of heavy metal from soil collected from the vicinity of a copper smelter. The following aspects were investigated: i) selectivity of rhamnolipids towards Cu, Zn, Pb, Cd and Fe during soil washing; ii) phytoextraction efficiency of each ion with respect to the effective concentration of rhamnolipids; iii) possible phytotoxic effects; iv) effect of micro-sized polystyrene amendment. The experiments evaluated soil washing efficiency, BCR (Community Bureau of Reference) sequential extraction to determine the impact of rhamnolipids on the mobility of metal ions, phytoextraction with maize (Zea mays L.) and phytotoxic effects based on dry matter, chlorophyll fluorescence and content. The obtained results indicated that rhamnolipids lack desired selectivity towards heavy metal ions as Fe was complexed more efficiently by 80 % of the available rhamnolipids compared to priority pollutants like Zn, Cu, Pb, which were complexed by only 20 % of the tested rhamnolipids. With increased concentration of rhamnolipids, the soil washing efficiency increased and shifted in favour of Fe, reaching values of approx. 469 mg for Fe and only 118 mg in total of all tested heavy metals. Phytoextraction also favoured the accumulation of Fe, while Cd was not removed from the soil even at the highest applied rhamnolipid concentrations. Considering the selectivity of rhamnolipids and the costs associated with their production, our results suggest the need to search for other alternative (bio)surfactants with better selectivity and lower price.

Chitosan hydrogel modified with lanthanum as a drug delivery system for epigallocatechin gallate: Investigation of hydrogel - drug interaction by FT-IR and Raman spectroscopy.

In the presented work, chitosan hydrogel modified with lanthanum was obtained for the first time. The hydrogel was used as a carrier in the controlled release of epigallocatechin gallate. The work proved the effectiveness of drug sorption by hydrogel and controlled release in simulated body fluids. The drug was released slowly and in a controlled manner from the carrier. The research techniques used in this work (FT-IR spectroscopy and imaging, Raman spectroscopy, SEM/EDS) allowed to confirm the successful retention of EGCG on the hydrogel surface. On the basis of the EDS mapping, it was possible to confirm the even distribution of the lanthanum ions. Using FT-IR imaging, we verified that the drug was evenly distributed on the entire surface of the prepared material. The antifungal effectiveness of the material has been proven on several types of fungi. The research proved that the prepared material is capable of long-term release of the active substance and has antifungal properties. As a result, the prepared material can be successfully used as an implantable hydrogel or a coating in, e.g. titanium implants.

Basic principles for biosurfactant-assisted (bio)remediation of soils contaminated by heavy metals and petroleum hydrocarbons - A critical evaluation of the performance of rhamnolipids.

Despite the fact that rhamnolipids are among the most studied biosurfactants, there are still several gaps which must be filled. The aim of this review is to emphasize and to indicate which issues should be taken into account in order to achieve efficient rhamnolipids-assisted biodegradation or phytoextraction of soils contaminated by heavy metals and petroleum hydrocarbons without harmful side effects. Four main topics have been elucidated in the review: effective concentration of rhamnolipids in soil, their potential phytotoxicity, susceptibility to biodegradation and interaction with soil microorganisms. The discussed elements are often closely associated and often overlap, thus making the interpretation of research results all the more challenging. Each dedicated section of this review includes a description of potential issues and questions, an explanation of the background and rationale for each problem, analysis of relevant literature reports and a short summary with possible application guidelines. The main conclusion is that there is a necessity to establish regulations regarding effective concentrations for rhamnolipids-assisted remediation of soil. The use of an improper concentration is the direct cause of all the other discussed phenomena.

Physicomechanical and Antimicrobial Characteristics of Cement Composites with Selected Nano-Sized Oxides and Binary Oxide Systems.

In recent years, increasing attention has been paid to the durability of building materials, including those based on cementitious binders. Important aspects of durability include the increase of the strength of the cement matrix and enhancement of material resistance to external factors. The use of nanoadditives may be a way to meet these expectations. In the present study, zinc, titanium and copper oxides, used in single and binary systems (to better the effect of their performance), were applied as additives in cement mortars. In the first part of this work, an extensive physicochemical analysis of oxides was carried out, and in the second, their application ranges in cement mortars were determined. The subsequent analyses were employed in determining the physicochemical properties of pristine oxides: Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray fluorescence (EDXRF), scanning electron microscopy (SEM), measurement of the particle size distribution, as well as zeta potential measurement depending on the pH values. Influence on selected physicomechanical parameters of the cement matrix and resistance to the action of selected Gram-positive and Gram-negative bacteria and fungi were also examined. Our work indicated that all nanoadditives worsened the mechanical parameters of mortars during the first 3 days of hardening, while after 28 days, an improvement was achieved for zinc and titanium(IV) oxides. Binary systems and copper(II) oxide deteriorated in strength parameters throughout the test period. In contrast, copper(II) oxide showed the best antibacterial activity among all the tested oxide systems. Based on the inhibitory effect of the studied compounds, the following order of microbial susceptibility to inhibition of growth on cement mortars was established (from the most susceptible, to the most resistant): E. coli < S. aureus < C. albicans < B. cereus = P. aeruginosa < P. putida.

Novel esterquat-based herbicidal ionic liquids incorporating MCPA and MCPP for simultaneous stimulation of maize growth and fighting cornflower.

Modern agricultural practices are often based on the use of mixtures of specific herbicides to achieve efficient crop protection. The major drawbacks of commercial herbicidal formulations include the necessity to incorporate toxic surfactants and high volatility of active substances. Transformation of herbicides into herbicidal ionic liquids (HILs) seems to be a promising alternative which allows to almost completely reduce volatility due to ionic interactions. In the scope of this research, we transformed (2-methyl-4-chlorophenoxy)acetic acid (MCPA) into a quaternary ester (esterquat) with the use of derivatives of 2-dimethylaminoethanol. The obtained esterquats were later coupled with (±)-2-(4-chloro-2-methylphenoxy)propionic acid (MCPP) in the form of an anion. The combination of MCPA and MCPA is commonly applied in the UK, EU countries and also in the USA to increase the spectrum of targeted weed species. In the framework of this study, novel HILs with an esterquat moiety incorporating a long alkyl chain (C8, C9, C10, C11, C12, C14) were prepared and characterized in terms of basic physicochemical properties (solubility and volatility) as well as biodegradability. Their phytotoxicity was assessed towards cornflower (Centaurea cyanus) as a model weed and maize (Zea mays) as a crop plant. The presence of the esterquat cation contributed to satisfactory solubility in water and other low polar solvents, which eliminates the need to add exogenous adjuvants. Further experiments indicated that the tested HILs stimulated the germination stage of maize and maintained high herbicidal activity towards cornflower. No significant differences in terms of properties were observed in case of HILs which included alkyl substituents with an odd number of carbon atoms. Future studies should be focused on structural modifications in order to improve the biodegradability as well as field studies for evaluation of commercial applications.

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.

Biodegradation of Conventional and Emerging Pollutants.

The concerns associated with the contamination of the environment remain a topic of great importance and growing interest [...].

Microbial Degradation of Hydrocarbons-Basic Principles for Bioremediation: A Review.

Crude oil-derived hydrocarbons constitute the largest group of environmental pollutants worldwide. The number of reports concerning their toxicity and emphasizing the ultimate need to remove them from marine and soil environments confirms the unceasing interest of scientists in this field. Among the various techniques used for clean-up actions, bioremediation seems to be the most acceptable and economically justified. Analysis of recent reports regarding unsuccessful bioremediation attempts indicates that there is a need to highlight the fundamental aspects of hydrocarbon microbiology in a clear and concise manner. Therefore, in this review, we would like to elucidate some crucial, but often overlooked, factors. First, the formation of crude oil and abundance of naturally occurring hydrocarbons is presented and compared with bacterial ability to not only survive but also to utilize such compounds as an attractive energy source. Then, the significance of nutrient limitation on biomass growth is underlined on the example of a specially designed experiment and discussed in context of bioremediation efficiency. Next, the formation of aerobic and anaerobic conditions, as well as the role of surfactants for maintaining appropriate C:N:P ratio during initial stages of biodegradation is explained. Finally, a summary of recent scientific reports focused on the removal of hydrocarbon contaminants using bioaugmentation, biostimulation and introduction of surfactants, as well as biosurfactants, is presented. This review was designed to be a comprehensive source of knowledge regarding the unique aspects of hydrocarbon microbiology that may be useful for planning future biodegradation experiments. In addition, it is a starting point for wider debate regarding the limitations and possible improvements of currently employed bioremediation strategies.

Gas-phase hydration of Mg2+ complexes with deprotonated uracil, thymine, uridine, and thymidine.

The gas-phase hydration of Mg2+ complexes with deprotonated uracil (U), thymine (T), uridine (Ur , uracil riboside), and thymidine (Tdr , thymine deoxyriboside) was studied. The aim of the work was to analyze the hydration of product ions (eg, [2U-H+Mg]+ ) formed as a result of the collision induced dissociation of the respective parent ion (eg, [3Ur -H+Mg]+ ). The efficiency of gas-phase hydration of the ions [2U-H+Mg]+ and [2T-H+Mg]+ was similar. However, the efficiency of gas-phase hydration of the ion [U+Ur -H+Mg]+ was much higher than that of gas-phase hydration of the ion [T+Tdr -H+Mg]+ . On the basis of the mass spectra obtained and the performed molecular modelling, it was concluded that in the ion [T+Tdr -H+Mg]+ , we deal with a steric hindrance due to the presence of a sugar moiety, which affects water attachment. In the ion [U+Ur -H+Mg]+ , the position of the sugar moiety does not affect water attachment.

How to accurately assess surfactant biodegradation-impact of sorption on the validity of results.

Surfactants not only are widely used in biotechnological processes but also constitute significant contaminants of the modern world. Among many reports, there is a shortage of works which summarize the issue of surfactant sorption to biomass in a way that would elucidate the biological factors for analysts and analytical factors for microbiologists. The main factor, which is not as obvious as one would expect, is associated with the susceptibility of analytical approaches to errors resulting from incorrect handling of biomass. In case of several publications reviewed in the framework of this study, it was not possible to establish whether the decrease of the analytical signal observed by the authors actually resulted from biodegradation of the surfactant. This review emphasizes the necessity to consider the possibility of surfactant sorption to microbial cells, which may result in significant detection errors as well as conceptual inconsistency. In addition, a reference study regarding representative surfactants (cationic, anionic and non-ionic) as well as yeast, Gram-negative, Gram-positive bacteria, and activated sludge was provided to highlight the possible errors which may arise from disregarding sorption processes when determining degradation of surfactants. This particularly applies to systems which include ionic surfactants and activated sludge as sorption may account for 90% of the observed depletion of the surfactant. Therefore, a systematic approach was proposed in order to improve the credibility of the obtained results. Finally, the need to employ additional procedures was highlighted which may be required in order to verify that the decrease of surfactant concentration results from biodegradation processes.

Hybrid electrochemical and biological treatment of herbicidal ionic liquids comprising the MCPA anion.

The present study was focused on the application of an electrochemical oxidation process combined with biodegradation for the removal of novel Herbicidal Ionic Liquids (HILs) -promising protection plant products which incorporate herbicidal anions and ammonium cations. The influence of carbon chain length (n = 8, 10, 12, 14, 16, 18) in the dialkyldimethylammonium cations on electrochemical oxidation kinetics, degradation efficiency and biodegradation by activated sludge was investigated. It was established that the applied cation influenced the heterogeneous rate constant and diffusion coefficient of electrochemical oxidation. The oxidation efficiency ranged from 17% in case of HILs with C8 alkyl chain to approx. 60% in case of HILs comprising C14 and C16 alkyl chains after 3 h of electrochemical treatment. Subsequent biodegradation studies revealed that electrochemical oxidation improved the mineralization efficiency of the studied HILs. The mineralization efficiency of electrochemically-treated HILs ranged from 28% in case of HILs comprising the C8 alkyl chain to 57% in case of HILs with C14 and C16 alkyl chains after 28 days. In case of untreated HILs, the corresponding mineralization efficiency ranged from 0 to 8%, respectively. This confirms the feasibility of a hybrid electrochemical-biological approach for treatment of herbicidal ionic liquids based on MCPA.

Comparison of metalworking fluids biodegradation efficiency by autochthonous and environmental communities.

The aim of this study was to evaluate the biodegradation potential of microbiota isolated from different environmental niches towards different types of metalworking fluids (MWF). The first experimental stage was focused on the assessment of biochemical oxygen demand reduction efficiency of autochthonous and environmental microbial communities. Based on the obtained results, the following order describing the biodegradation potential of communities from the studied niches was established: petroleum contaminated soil > waste repository ≥ waste MWF tanks > pesticide-treated field > activated sludge > municipal sewage effluents. For comparative purposes, the most efficient community originating from petroleum contaminated soil (PCS1) was selected for further studies along with the most efficient community originating from a waste MWF tank (WMT1). The studied communities achieved 100% biodegradation efficiency of decanedioic and dodecanedioic acids as well as glycerine and polyethoxylated dodecanol. However, the PCS1 community was more versatile and displayed significantly higher biodegradation efficiency of mineral oil (80% compared to 50% in case of WMT1). Similarly, experiments using pristine and spent MWF solutions confirmed that the PCS1 community outperformed the WMT1 community during the biodegradation of MWF containing oil as the main component (COD reduction of 80, 60 and 30% in case of semi-synthetic MWF, soluble oil and spent MWF, respectively). Results of community dynamics assessment using quantitative real-time PCR after the biodegradation of different types of MWF confirmed that the PCS1 community was characterized by high genetic stability and allowed to indicate the potential 'key players'.

Biodiversity of soil bacteria exposed to sub-lethal concentrations of phosphonium-based ionic liquids: Effects of toxicity and biodegradation.

Little is known about the effect of ionic liquids (ILs) on the structure of soil microbial communities and resulting biodiversity. Therefore, we studied the influence of six trihexyl(tetradecyl)phosphonium ILs (with either bromide or various organic anions) at sublethal concentrations on the structure of microbial community present in an urban park soil in 100-day microcosm experiments. The biodiversity decreased in all samples (Shannon's index decreased from 1.75 down to 0.74 and OTU's number decreased from 1399 down to 965) with the largest decrease observed in the microcosms spiked with ILs where biodegradation extent was higher than 80%. (i.e. [P66614][Br] and [P66614][2,4,4]). Despite this general decrease in biodiversity, which can be explained by ecotoxic effect of the ILs, the microbial community in the microcosms was enriched with Gram-negative hydrocarbon-degrading genera e.g. Sphingomonas. It is hypothesized that, in addition to toxicity, the observed decrease in biodiversity and change in the microbial community structure may be explained by the primary biodegradation of the ILs or their metabolites by the mentioned genera, which outcompeted other microorganisms unable to degrade ILs or their metabolites. Thus, the introduction of phosphonium-based ILs into soils at sub-lethal concentrations may result not only in a decrease in biodiversity due to toxic effects, but also in enrichment with ILs-degrading bacteria.

Isolation of rhamnolipids-producing cultures from faeces: Influence of interspecies communication on the yield of rhamnolipid congeners.

The aim of this study was to evaluate the ability of bacterial cultures isolated from cattle, poultry or pig faeces and manure to produce rhamnolipids, as well as to investigate the influence of interspecies communication on possible quantitative differences in the production of rhamnolipid congeners. Initial screening methods (oil spreading, drop collapse, haemolytic activity and emulsification activity) showed that approximately 36% of the 51 isolated cultures exhibited the ability to produce biosurfactants. Subsequent studies using a selected culturable mixed culture (which included Enterococcus faecalis, Pseudomonas aeruginosa and Escherichia coli) revealed that only P. aeruginosa was able to produce this biosurfactant. HPLC-MS analysis showed that the surface active compounds were rhamnolipids. Further comparative studies confirmed that the total yield of rhamnolipids was notably higher in the bioreactor inoculated with the selected mixed culture (940.58±1.10mg/L) compared to the bioreactor inoculated with the axenic strain of P. aeruginosa (108.47±0.41mg/L). Twelve rhamnolipid congeners were identified during cultivation of the selected mixed culture, whereas six congeners were detected during cultivation of the sole axenic strain of P. aeruginosa. Furthermore, increased production of rhamnolipids was observed when the concentration of autoinducer molecules (AI-2) responsible for interspecies signaling increased, suggesting the influence of quorum-sensing communication on biosynthesis efficiency. This observation may be of importance for large-scale production of this biosurfactant, as it opens new possible solutions based on the use of mixed cultures or external addition of stimulating autoinducers.

Evaluating robustness of a diesel-degrading bacterial consortium isolated from contaminated soil.

It is not known whether diesel-degrading bacterial communities are structurally and functionally robust when exposed to different hydrocarbon types. Here, we exposed a diesel-degrading consortium to model either alkanes, cycloalkanes or aromatic hydrocarbons as carbon sources to study its structural resistance. The structural resistance was low, with changes in relative abundances of up to four orders of magnitude, depending on hydrocarbon type and bacterial taxon. This low resistance is explained by the presence of hydrocarbon-degrading specialists in the consortium and differences in growth kinetics on individual hydrocarbons. However, despite this low resistance, structural and functional resilience were high, as verified by re-exposing the hydrocarbon-perturbed consortium to diesel fuel. The high resilience is either due to the short exposure time, insufficient for permanent changes in consortium structure and function, or the ability of some consortium members to be maintained during exposure on degradation intermediates produced by other members. Thus, the consortium is expected to cope with short-term exposures to narrow carbon feeds, while maintaining its structural and functional integrity, which remains an advantage over biodegradation approaches using single species cultures.

Betaine and Carnitine Derivatives as Herbicidal Ionic Liquids.

This study focused on the synthesis and subsequent characterization of herbicidal ionic liquids based on betaine and carnitine, two derivatives of amino acids, which were used as cations. Four commonly used herbicides (2,4-D, MCPA, MCPP and Dicamba) were used as anions in simple (single anion) and oligomeric (two anions) salts. The obtained salts were subjected to analyzes regarding physicochemical properties (density, viscosity, refractive index, thermal decomposition profiles and solubility) as well as evaluation of their herbicidal activity under greenhouse and field conditions, toxicity towards rats and biodegradability. The obtained results suggest that the synthesized herbicidal ionic liquids displayed low toxicity (classified as category 4 compounds) and showed similar or improved efficacy against weed compared to reference herbicides. The highest increase was observed during field trials for salts containing 2,4-D as the anion, which also exhibited the highest biodegradability (>75 %).

Different antibacterial activity of novel theophylline-based ionic liquids - Growth kinetic and cytotoxicity studies.

The aim of this study was to investigate novel theophylline-based ionic liquids and their cytotoxic effects towards model Gram-positive and Gram-negative bacteria (Bacillus cereus and Escherichia coli, respectively). Growth kinetics, respiratory rates and dehydrogenase activities were studied in the presence of ionic liquids at concentrations ranging from 10 to 1000mg/L. Additionally, the influence of ionic liquids on bacterial cells associated with specific interactions based on the structure of cell wall was evaluated. This effect was assessed by viability tests and scanning electron microscope observations. The obtained results confirmed that ionic liquids exhibit different levels of toxicity in relation to Gram-positive and Gram-negative bacteria. Those effects are associated with the chemical structure of the cationic species of the ionic liquids and their critical micelle concentration value. It was established that the presence of an alkyl or allyl group increased the toxicity, whereas the presence of an aryl group in the cation decreased the toxic effect of ILs. Results presented in this study also revealed unexpected effects of self-aggregation of E. coli cells. Overall, it was established that the studied ILs exhibited higher toxicity towards Gram-positive bacteria due to different interactions between the ILs and the cell membranes. These findings may be of importance for the design of ILs with targeted antimicrobial properties.

Comparative study on the biodegradability of morpholinium herbicidal ionic liquids.

This study focused on evaluating the toxicity as well as primary and ultimate biodegradability of morpholinium herbicidal ionic liquids (HILs), which incorporated MCPA, MCPP, 2,4-D or Dicamba anions. The studied HILs were also subjected to determination of surface active properties in order to assess their influence on toxicity and biodegradability. The study was carried out with microbiota isolated from different environmental niches: sediments from river channel, garden soil, drainage trench collecting agricultural runoff stream, agricultural soil and municipal waste repository. The obtained results revealed that resistance to toxicity and biodegradation efficiency of the microbiota increased in the following order: microbiota from the waste repository > microbiota from agricultural soil ≈ microbiota from an agricultural runoff stream > microbiota from garden soil > microbiota from the river sludge. It was observed that the toxicity of HILs increased with the hydrophobicity of the cation, however the influence of the anion was more notable. The highest toxicity was observed when MCPA was used as the anion (EC50 values ranging from 60 to 190 mg L(-1)). The results of ultimate biodegradation tests indicated that only HILs with 2,4-D as the anion were mineralized to some extent, with slightly higher values for HILs with the 4-decyl-4-ethylmorpholinium cation (10-31 %) compared to HILs with the 4,4-didecylmorpholinium cation (9-20 %). Overall, the cations were more susceptible (41-94 %) to primary biodegradation compared to anions (0-61 %). The obtained results suggested that the surface active properties of the studied HILs may influence their toxicity and biodegradability by bacteria in different environmental niches.