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The human antibiotics cefuroxime (CXM) and azithromycin (AZI) are among the most commonly prescribed. A significant portion of both are excreted and has been detected in sewage treatment plant effluents. The increasing use of such effluents in crops for irrigation and as fertilisers poses a threat to soil microbiota because of the presence of antibiotics. The lack of studies on CXM and AZI in soils hinders our understanding of their potential toxic effects on soil bacterial communities and ecosystem services. This study significantly contributes to the literature by quantifying the toxicity of CXM and AZI at varying concentrations in 12 different crop soils and tracking their evolution over time. The study also examined whether antibiotic pressure led to the development of more tolerant bacterial communities. The results of this study are the values of the logarithm of the antibiotic concentration at which 50 % of bacterial growth is inhibited (Log IC 50 ) and indicate that both antibiotics are toxic to soil bacteria. The direct toxicity of CXM (1 day after contamination) was higher (Log IC 50 : 0.9 = 7.9 mg kg -1 ) than that of AZI (Log IC 50 : 3.4 = 2362 mg kg -1 ). However, bacterial growth was less affected by CXM over time, whereas AZI remained toxic in some soils until day 42 (Log IC 50 : 3.2 = 1533 mg kg -1 and 3.4 = 2291 mg kg -1 , respectively). The overall results indicate that selective pressure exerted by antibiotics generates antibiotic tolerance in soils, even at the lowest antibiotic concentration studied (7.8 mg kg -1 ). The general trend was to increase tolerance to higher antibiotic concentrations up to the highest concentration studied (2000 mg kg -1 ). However, the degree of tolerance developed was highly dependent on soil type. More studies should be conducted to quantitatively assess the toxic and tolerance-developing effects of antibiotics in soils. Such information will be valuable for identifying which antibiotics pose a threat to the soil microbiota and consequently to human health., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Pesticides residues can occur in ground and surface waters, and potentially react with chemicals used for water disinfection treatments, such as chlorine. This can lead to the formation of unknown reaction products, which can be more toxic and/or persistent than the active substances themselves, and therefore become a potential risk for human health and environment. Thus, in the framework of the EU Regulation 1107/2009, the identification of these by-products and their potential risk should be assessed. Within the European Food Risk Assessment (EU-FORA) Fellowship Programme, the fellow studied the behaviour of herbicides belonging to the families of imidazolinones and sulfonylureas in waters treated with chlorine disinfectants. Due to their physicochemical properties, these herbicides are susceptible of reaching natural waters. In fact, some of them have been detected in water monitoring programmes. During the experimental part of the present work programme, reactions between the active substances and the most used chlorine disinfecting reactants (hypochlorite and chloramines) were performed. Degradation kinetic parameters such as half-lives and degradation constants were calculated. Results showed that herbicide degradation was both pH and chlorine/chloramines concentration dependent. In order to identify the degradation by-products, high-resolution mass spectrometry experiments were performed, and a possible route of formation of these compounds was proposed. Finally, their risk assessment was carried out by using tox/ecotoxicological properties determined by QSAR methodology and FOCUS modelling for hazard and exposure assessment, respectively. These results will contribute to the definition of a risk assessment scheme for pesticides by-products potentially occurring in drinking water., (© 2022 Wiley‐VCH Verlag GmbH & Co. KgaA on behalf of the European Food Safety Authority.)

Any active substance with phytosanitary capacity intended to be marketed in Europe must pass exhaustive controls to assess its risk before being marketed and used in European agriculture. Since the implementation of Regulation (EC) No 1107/2009, agrochemical companies have been obliged to study the formation of pesticide transformation products (TPs) during the treatment of drinking water containing pesticide residues. However, there is no consensus on how to address this requirement. In this research work, the open literature collection on alloxydim was used to propose potential chlorination paths from alloxydim isomers. Furthermore, several QSAR/QSPR models have been used to fill the of knowledge gap relative to some key parameters in the physico-chemical, environmental and ecotoxicological areas of potential alloxydim TPs from chlorinated water for which little information exists. In this way, it has been possible to estimate the state of aggregation of these TPs (they exist mainly as liquids) as well as their ease of transit between the different phases, to predict their possible behaviour in the three environmental compartments (e.g., thermophysical properties point to a change in their evolution with respect to the parent alloxydim isomers) and to anticipate their potential risk to human and animal health (e.g., all of them cause developmental toxicity). These and other results highlight that the hazards of several TPs, i.e., both chlorinated and nonchlorinated from parent alloxydim or from those obtained after cleavage of the N - O bond and the subsequent reaction with chlorine, should be seriously considered. The obtained results reopen the debate on the implications of the use of QSAR/QSPR models for pesticide risk assessment in the legislative framework., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

In Europe, agencies and official organizations involved in the pesticide control such as the EFSA, ECHA, JRC and ECETOC or even the OECD are pointing out that the software tools based on quantitative structure relationship models, i.e. QSAR and QSPR, have a huge potential to improve the pesticide risk assessment process. In this sense, these non-animal test methods can promote the competitiveness of agriculture in this region: the consumer safety is increased with them due to the possibility of perform an overall better risk assessment of the degradation products and metabolites from pesticides. However, the use of theses computational-based (in silico) tools must be much more systematised and harmonised, improving their validation and including case studies to test them. To open databases, incorporating critical data in an orderly manner for building the models, becomes also necessary. Moreover, quantum chemistry through the Density Functional Theory should be promoted as tool for calculation of quantum descriptors, especially for the study of similar compounds with the same carbon skeleton but differing substitution patterns, e.g. isomers.

The European market for pesticides is currently legislated through the well-developed Regulation (EC) No. 1107/2009. This regulation promotes the competitiveness of European agriculture, recognizing the necessity of safe pesticides for human and animal health and the environment to protect crops against pests, diseases and weeds. In this sense, nanotechnology can provide a tremendous opportunity to achieve a more rational use of pesticides. However, the lack of information regarding nanopesticides and their fate and behavior in the environment and their effects on human and animal health is inhibiting rapid nanopesticide incorporation into European Union agriculture. This review analyzes the recent state of knowledge on nanopesticide risk assessment, highlighting the challenges that need to be overcame to accelerate the arrival of these new tools for plant protection to European agricultural professionals. Novel nano-Quantitative Structure-Activity/Structure-Property Relationship (nano-QSAR/QSPR) tools for risk assessment are analyzed, including modeling methods and validation procedures towards the potential of these computational instruments to meet the current requirements for authorization of nanoformulations. Future trends on these issues, of pressing importance within the context of the current European pesticide legislative framework, are also discussed. Standard protocols to make high-quality and well-described datasets for the series of related but differently sized nanoparticles/nanopesticides are required., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Assessment of two buffered QuEChERS (quick, easy, cheap, effective, rugged, and safe) versions (i.e., citrate and acetate) modified by including methanol to recover the residues of three cyclohexanedione oxime (CHD) herbicides and three of their byproducts from agricultural soil was performed. In this context, a full second-order face-centered factorial experimental design was developed to quantify the influences of the main five variables (i.e., extraction time, water content, soil weight, and extraction solvent volume and composition) on the target compound recoveries. The fitting equations satisfactorily described the extraction process behavior. The mathematical models also showed the most influencing independent variables (i.e., extraction solvent composition and soil weight). Handling simpler expressions was possible with the acetate QuEChERS but not with the citrate QuEChERS. The recoveries of the CHD residues were close to 100% after performing the extraction under suitable conditions. Furthermore, dispersive solid-phase extraction (dSPE) clean-up steps were assessed to reduce the matrix effect in mass spectrometry. In this sense, the citrate QuEChERS in combination with the PSA + C18 clean-up step was the best option for the extraction of CHD residues.

Once applied, an herbicide first makes contact with leaves and soil. It is known that photolysis can be one of the most important processes of dissipation of herbicides in the field. However, degradation does not guarantee detoxification and can give rise to byproducts that could be more toxic and/or persistent than the active substance. In this work, the photodegradation of alloxydim herbicide in soil and leaf cuticle surrogates was studied and a detailed study on the phytotoxicity of the main byproduct on sugar beet, tomato, and rotational crops was performed. Quantitative structure⁻activity relationship (QSAR) models were used to obtain a first approximation of the possible ecotoxicological and environmental implications of the alloxydim and its degradation product. The results show that alloxydim is rapidly degraded on carnauba and sandy loam soil surfaces, two difficult matrices to analyze and not previously studied with alloxydim. Two transformation products that formed in both matrices were identified: alloxydim Z-isomer and imine derivative (mixture of two tautomers). The phytotoxicity of alloxydim and the major byproduct shows that tomato possesses high sensitivity to the imine byproduct, while wheat crops are inhibited by the parent compound. This paper demonstrates the need to further investigate the behavior of herbicide degradation products on target and nontarget species to determine the adequate use of herbicidal products to maximize productivity in the context of sustainable agriculture.

Density functional theory calculations allowed us to study alloxydim herbicide and to identify the most stable conformers, the factors that governs their stability, and the interconversion mechanisms among the most relevant conformers. The degradation chain involves, as a first step, the cleavage of the N-O bond and the formation of a stable intermediate difficult to characterize experimentally. The study performed also allowed us to identify the properties of this elusive intermediate and to determine that the dominant fragmentation process in the gas phase is the homolytic fragmentation. Stability of alloxydim conformers and homolytic fragments were also assessed in the water phase. Computed IR spectra were consistent with those observed experimentally.

The photochemical fate of the herbicide clethodim in natural waters was investigated under simulated and natural sunlight radiation. This herbicide exhibited a rapid degradation rate in simulated aquatic environment with half-lives ranged from 27.9min to 4.6h. The commercial formulation of clethodim showed a faster degradation with half-lives from 19.3min to 1.4h. It has also been demonstrated that the photolytic behavior of clethodim was affected by the water composition and the radiation intensity. Nine major photoproducts were identified and their distribution was dependent on the experimental conditions. Photodegraded solutions of clethodim were shown to be more toxic to the bacteria Vibrio fischeri than the herbicide itself, reaching the maximum toxicity when the herbicide is completely degraded. QSAR analysis of the fate, ecotoxicological and physicochemical endpoints of the degradation products provided positive alerts for several identified by-products. Environmental fate and transport estimates showed that all photoproducts, unlike the active substance, are potential leachers. Moreover, predicted vapor pressures suggested that dermal contact and ingestion are the most probable exposure routes for workers and general population to both clethodim and its photoproducts. These results highlight the importance of the degradation products in attaining a complete knowledge of the fate and behavior of an herbicide in the environment. To our knowledge, this is the first study to report a detailed QSAR study on clethodim photoproducts under environmental conditions. These results provide a very valuable information that will guide further experimental studies leading to a better pesticide risk assessment., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The scientific community and regulatory bodies worldwide, currently promote the development of non-experimental tests that produce reliable data for pesticide risk assessment. The use of standard quantum chemistry methods could allow the development of tools to perform a first screening of compounds to be considered for the experimental studies, improving the risk assessment. This fact results in a better distribution of resources and in better planning, allowing a more exhaustive study of the pesticides and their metabolic products. The current paper explores the potential of quantum chemistry in modelling toxicity and environmental behaviour of pesticides and their by-products by using electronic descriptors obtained computationally. Quantum chemistry has potential to estimate the physico-chemical properties of pesticides, including certain chemical reaction mechanisms and their degradation pathways, allowing modelling of the environmental behaviour of both pesticides and their by-products. In this sense, theoretical methods can contribute to performing a more focused risk assessment of pesticides used in the market, and may lead to higher quality and safer agricultural products. © 2017 Society of Chemical Industry., (© 2017 Society of Chemical Industry.)

Lipoxygenases (LOXs) are iron- or manganese-containing oxidative enzymes found in plants, animals, bacteria and fungi. LOXs catalyze the oxidation of polyunsaturated fatty acids to the corresponding highly reactive hydroperoxides. Production of hydroperoxides by LOX can be exploited in different applications such as in bleaching of colored components, modification of lipids originating from different raw materials, production of lipid derived chemicals and production of aroma compounds. Most application research has been carried out using soybean LOX, but currently the use of microbial LOXs has also been reported. Development of LOX composition with high activity by heterologous expression in suitable production hosts would enable full exploitation of the potential of LOX derived reactions in different applications. Here, we review the biological role of LOXs, their heterologous production, as well as potential use in different applications. LOXs may fulfill an important role in the design of processes that are far more environmental friendly than currently used chemical reactions. Difficulties in screening for the optimal enzymes and producing LOX enzymes in sufficient amounts prevent large-scale application so far. With this review, we summarize current knowledge of LOX enzymes and the way in which they can be produced and applied.

The chemical composition of the lipophilic extract of ripe pulp of banana fruit from several banana cultivars belonging to the Musa acuminata and Musa balbisiana species (namely 'Chinese Cavendish', 'Giant Cavendish', 'Dwarf Red', 'Grand Nain', 'Eilon', 'Gruesa', 'Silver', 'Ricasa', 'Williams' and 'Zelig') was studied by gas chromatography-mass spectrometry for the first time. The banana cultivars showed similar amounts of lipophilic extractives (ca. 0.4% of dry material weight) as well as qualitative chemical compositions. The major groups of compounds identified in these fractions were fatty acids and sterols making up 68.6-84.3% and 11.1-28.0%, respectively, of the total amount of lipophilic components. Smaller amounts of long chain aliphatic alcohols and α-tocopherol were also identified. These results are a relevant contribution for the valorisation of these banana cultivars as sources of valuable phytochemicals (ω-3 and ω-6 fatty acids, and sterols) with well-established beneficial nutritional and health effects., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Background: The European Pesticide Regulation (EC) No. 1107/2009 encourages the use of less harmful active substances. Two main concerns involve the application of cut-off criteria for pesticides without losing tools for future agriculture (especially for minor uses) and the implementation of zonal evaluations. Biopesticides are considered to have lower risks than synthetic pesticides; consequently, there is strong interest for their use in integrated pest management practices., Results: This paper provides an analysis of the current European situation, starting with the first attempts to regulate the use of plant protection products and focusing on the implications of the new legislative criteria for biopesticides., Conclusion: It is important to be aware that biopesticides are still pesticides and fall under the same regulations as their synthetic counterparts. Although manufacturers are still reluctant to commit to such alternatives due to difficulties with approval and registration, biopesticides could be alternatives for traditional plant protection products, either as a base for the synthesis of new products or integrated with traditional plant protection products. In addition, biopesticides have to be used only as indicated on the label, which provides critical information about how to safely handle and use plant protection products., (© 2013 Society of Chemical Industry.)

This study reports the identification of oligomeric alkenylperoxides by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS(2)), during the oxidation of oleic, linoleic and linolenic acids with Fenton's (Fe(2+)/H(2)O(2)) and Fe(2+)/O(2) systems. The reactions were followed by ferrous oxidation-xylenol orange method together with GC-MS and GC-FID, allowing to observe that both oxidation systems are different in terms of hydroperoxide evolution, probably due to the presence of different intermediate reactive species: perferryl ion and OH(·) radical responsible for the decomposition of lipid hydroperoxides and formation of new compounds. The analysis of ESI-MS in the negative mode, obtained after oxidation of each fatty acid, confirmed the presence of the monomeric oxidation products together with other compounds at high mass region above m/z 550. These new ions were attributed to oligomeric structures, identified by the fragmentation pathways observed in the tandem mass spectra., (Copyright © 2012 John Wiley & Sons, Ltd.)

The behavior of Miscanthus x giganteus bark lipophilic extractives during three acid organosolv pulping processes (Acetosolv, formic acid fractionation, and Milox) was investigated. It was demonstrated that nearly 90% of the lipophilic extractives were removed from pulps by either dissolution in the organosolv liquors (fatty acids and alcohols) or extensive degradation (sterols). The organosolv liquors were found to be rich in vanillin, syringaldehyde, and ferulic, vanillic, and p-coumaric acids. The Acetosolv fractionation process was found to be the most efficient in the removal of lipophilic components from pulps, and it was also the process that generated higher amounts of valuable monomeric phenolic compounds that could be exploited within the biorefinery context.

Miscanthus x giganteus stalks were subjected to delignification with formic acid-hydrogen peroxide-water in two stages. A face-centered experimental design was used to study the effects of different variables (formic acid and hydrogen peroxide concentrations, time and temperature) on yield, lignin content and viscosity of pulps on the first stage. Fitting equations described satisfactorily the system behaviour and showed that hydrogen peroxide concentration and temperature were the most influencing variables. A set of independent variables (90% formic acid, 1.5% hydrogen peroxide, 60 min, and 67 degrees Celsius) produced a pulp with low lignin content (kappa 17.2) and high viscosity (899 cm(3)/g), in the first stage. For the second stage a treatment time of 30 min was the more suitable, producing good quality pulps (kappa number 4.6, viscosity 788 cm(3)/g). Phenolic hydroxyl and carboxyl group contents were higher lignins from the first stage., (Copyright 2009 Elsevier Ltd. All rights reserved.)

Miscanthus x giganteus bark samples subjected to fractionation by the Acetosolv process under optimal conditions were bleached using hydrogen peroxide and acetic acid in aqueous media under alkaline conditions. The influence of the main operational variables in the bleaching of Acetosolv pulps of M. x giganteus (i.e. hydrogen peroxide concentration, 3-7%; temperature, 55-75 degrees C; pH 9-11), obtained after treatments, have been assessed on pulp yield, kappa number, viscosity and brightness of bleached pulps. For this purpose, a rotatable and orthogonal second-order factorial design of experiments was used, in order to identify the optimum operating conditions. The obtained empirical mathematical models demonstrate that, in general, the bleaching was efficient, achieving pulps with kappa numbers below 10. The chemical composition and physicochemical properties of the bleached pulps fulfilled the requirements for forthcoming bleaching stages. Moreover, an alkaline extraction stage to eliminate saponifiable groups of Acetosolv pulps was studied, as well as the necessity of use chelating agents in the stage with hydrogen peroxide.

Milled wood lignin (MWL) and acetic and formic acid lignin (AL and FL) from Miscanthus x giganteus bark were produced, respectively, before and after organosolv fractionations under optimal conditions, in terms of organic and hydrochloric acid concentrations, liquid/wood ratio, and reaction time. In order to study the M. x giganteus native lignin structure and its modifications during the fractionation process, the lignins were studied by two-dimensional heteronuclear single quantum coherence (2D-(HSQC)), (13)C- and (31)P nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR), size-exclusion chromatography (SEC) both before and after thioacidolysis, and elemental analysis. In addition, chemical composition analysis was performed on ash, Klason lignin, and carbohydrate content. The analyses demonstrated that M. x giganteus native lignin (MWL) is highly acylated at the C(gamma) of the lignin side chain (46%), possibly with p-coumarate and/or acetate groups. This is newsworthy since several earlier studies showed that acylation at the gamma-carbon commonly occurs in C(3) and CAM grasses, whereas M. x giganteus is a C(4) grass. Furthermore, M. x giganteus showed a low S/G ratio (0.7) and a predominance of beta-O-4' linkages (up to 93% of all linkages). AL and FL lose part of these linkages during organosolv fractionation (up to 21 and 32%, respectively). The p-coumarate groups resist fractionation processes and are still present in high quantities in AL and FL. During the fractionation process, lignin is acetylated (acetic acid process) and condensed, with the G units condensing more than S units. M. x giganteus MWL contains a high content of carbohydrates (22.8%), suggesting that it is a lignin-carbohydrate complex (LCC). AL and FL showed low carbohydrate contents because of the breaking down of the LCC structures. AL and FL have high molecular weights and low polydispersities, and are high in phenolic content, qualities that make these suitable for different applications. These results suggest that refinement of M. x giganteus via organosolv processes could potentially turn this grass into a valuable source of both fiber and lignin.

The chemical composition of the lipophilic extracts of bark and core, of the Miscanthus x giganteus stalk, was studied by gas chromatography-mass spectrometry (GC-MS). Aromatic compounds, sterols, and fatty acids, followed by long-chain fatty alcohols, were the major families of components present in the M. x giganteus stalk. Aromatic compounds are more abundant in the M. x giganteus bark (521 mg/kg of bark), with vanillic acid, vanillin, and p-hydroxybenzaldehyde as the major compounds of this family. In the M. x giganteus core, sterols represent about 949 mg/kg of dry core with beta-sitosterol, 7-oxo-beta-sitosterol, stigmasterol, and campesterol as the major components. The detection of small amounts of esters in the GC-MS analysis with short columns explains the small increase in the abundance of the identified families after alkaline hydrolysis. The high content of valuable sterols and aromatic compounds in M. x giganteus and, particularly, in the core, which is considered a residue in most applications, can open new perspectives for the integrated upgrading of this grass within the biorefinery perspective.

In this work, depithed cardoon stalk (Cynara cardunculus) has been used with the objective of obtaining bleachable pulps. The material, once properly prepared, was subjected to one-step peroxyformic acid delignification. In order to study the process, a face-centred second order factorial design was developed which allowed the determination of the influences of four variables: concentrations of formic acid and hydrogen peroxide in the cooking liquor and the time and temperature of the treatment. Empirical mathematical models have been obtained which predict the yield, kappa index, residual lignin content, and viscosity of the pulps. These models demonstrate that in general the delignification was extensive, producing pulps with kappa indexes less than 25 in the majority of cases, with good yields in the range of 45-60%. However, the pulps seem to have been degraded in the reaction media, as can be deduced from the low viscosity values found: 260-520 mL/g.