Ecotoxicological evaluation of effluent from bovine slaughterhouses disinfected by peracetic acid (PAA) using the bioindicator Girardia tigrina.

The evaluation of the ecotoxicological effects of the effluent after treatment with peracetic acid is relevant to help establish reference concentrations for the disinfection process and waste recovery. Therefore, the objective of this work was to evaluate the ecotoxicity of effluent from a bovine slaughterhouse treated with peracetic acid on Girardia tigrina. The toxicity bioassays for planaria were the acute test (LC50) and chronic assays: locomotion, regeneration, reproduction and fertility. The results showed that the effluent treated with peracetic acid showed less toxicity than the effluent without application of peracetic acid. The effluent after peracetic acid application showed a chronic toxic effect in the reduction of locomotor speed in all studied disinfectant concentrations (0.8, 1.6, 3.3 and 6.6 µg L-1 of peracetic acid) and a delay in the formation of G. tigrina photoreceptors at the concentration of 6.6 µg L-1 of peracetic acid. Peracetic acid concentrations of 0.8, 1.6 and 3.3 µg L-1 were not toxic for blastema regeneration, photoreceptor and auricle formation, fecundity and fertility. In addition, this study assists in defining doses of peracetic acid to be recommended in order to ensure the wastewater disinfection process without causing harm to aquatic organisms.

Interactions between DNA and the acridine intercalator: A computational study.

Cancer is a global public health problem characterized by deviations in the mechanisms that control cell proliferation, resulting in mutations and variations in the structure of DNA. The mechanisms of action of chemotherapeutic drugs are related to their interactions and binding with DNA; consequently, the development of antineoplastic agents that target DNA has extensively focused on use of acridine, a heterocyclic molecule that binds to deoxyribonucleic acid via intercalation, a process that modifies DNA and makes replication impossible. In this context, this study aimed to computationally investigate how acridine intercalators interact with DNA by evaluating the mechanism of interactions, binding, and interaction energies using quantum mechanics calculations. Molecular electrostatic potential (MEP) analysis revealed that acridine has well- distributed negative charges in the center of the molecule, indicative of a dominant electron-rich region. Acridine exhibits well-defined π orbitals (HOMO and LUMO) on the aromatic rings, suggesting that charge transfer occurs within the molecule and may be responsible for the pharmacological activity of the compound. Structural analysis revealed that acridine interacts with DNA mainly through hydrogen bonds between HAcridine… ODNA with bond lengths ranging from 2.370 Što 3.472 Å. The Binding energy (ΔEBind) showed that acridine interacts with DNA effectively for all complexes and the electronic energy results (E+ZPE) for complexes revealed that the complexes are more stable when the DNA-centered acridine molecule. The Laplacian-analysis topological QTAIM parameter (∇2ρ(r)) and total energy (H(r)) categorized the interactions as being non-covalent in nature. The RGD peak distribution in the NCI analysis reveals the presence of van der Waals interactions, predominantly between the intercalator and DNA. Accordingly, we confirm that acridine/DNA interactions are relevant for understanding how the intercalator acts within nucleic acids.

Theoretical study of the adsorption capacity of potentially toxic Cd2+, Pb2+, and Hg2+ ions in hemicellulose matrices.

Hemicellulose is widely available in nature, is a sustainable resource and has a wide range of applications. Among them, adsorption stands out for the removal of potentially toxic ions. Thus, in the study, the adsorption of Cd2+, Pb2+ and Hg2+ ions in two hemicellulose matrices were elucidated through computational simulations using density functional theory. Molecular electrostatic potential and frontier molecular orbitals demonstrated whether the interactions could happen. Four interaction complexes were highlighted due to the interaction energy criteria, ΔEBind, ΔH and ΔG < 0.00 kcal mol-1, that is: Hm1… Pb (1); Hm2… Pb (3); Hm2…Cd (4) and Hm2…Hg (4) and the results show that they occur through physisorption. In structural parameter studies, interaction distances smaller than 3000 Å were identified, which ranged from 2.253 Å to 2.972 Å. From the analysis of the topological parameters of QTAIM, it was possible to characterize the intensities of the interactions, as well as their nature, which were partially covalent or electrostatic in nature. Finally, based on the theoretical results, it can be affirmed that the hemicellulose can interact with Cd2+, Pb2+ and Hg2+ ions, evidencing that this study can support further experimental essays to remove contaminants from effluents.

The combined effects of microbial insecticides and sodium chloride on the development and emergence of Chironomus xanthus.

BACKGROUND: Freshwater organisms are facing increasing salinity levels, not only due to natural environmental processes, but also human activities, which can cause several physiological adaptations to osmotic stress. Additionally, these organisms might also have to deal with contamination by microbial insecticides. Our main goal was to use Chironomus xanthus to assess the chronic effects of increasing the salinity and commercial formulations of the microbial insecticides based on Bacillus thuringiensis subs. kurstaki (Btk) and Beauveria bassiana (Bb) as active ingredients, respectively. RESULTS: A significant interaction of growth was observed between the biopesticide based on Bb and NaCl on the larvae of C. xanthus. Single exposure to NaCl and each one of the formulations demonstrated deleterious impacts not only on larval development, but also on the emergence success and emergence time of this nontarget insect, with potential consequences for freshwater ecosystems due to cascading effects. CONCLUSION: The chronic effects induced by both bioinsecticides show that these formulations can have environmental impacts on nontarget freshwater insects. © 2023 Society of Chemical Industry.

The sexual reproduction of the nontarget planarian Girardia tigrina is affected by ecologically relevant concentrations of difenoconazole: new sensitive tools in ecotoxicology.

The fungicide difenoconazole, widely used to reduce the negative impacts of fungi diseases on areas with intensive farming, can reach freshwater systems causing deleterious effects on nontarget organisms. The acute and chronic toxicity of a commercial formulation containing 250 g L-1 of difenoconazole (Prisma®) as the active ingredient was assessed in the freshwater planarian Girardia tigrina. The endpoints evaluated were feeding rate, locomotion, regeneration, and sexual reproduction of planarians. The estimated 48 h LC50 of the commercial formulation on planarians expressed as the concentration of the active ingredient difenoconazole was 47.5 mg a.i.L-1. A significant decrease of locomotion (LOEC = 18.56 mg a.i.L-1), delayed regeneration (LOEC = 9.28 mg a.i.L-1), and sexual reproduction impairment, i.e., decreased fecundity and fertility rates (LOEC ≤ 1.16 mg a.i.L-1) were observed on planarians exposed to sublethal concentrations of the formulation. This study demonstrated the importance of using reproductive, physiological, and behavioral parameters as more sensitive and complementary tools to assess the deleterious effects induced by a commercial formulation of difenoconazole on a nontarget freshwater organism. The added value and importance of our research work, namely, the impairment of sexual reproduction of planarians, contributes to the development of useful tools for ecotoxicology and highlights the fact that those tools should be developed as guidelines for testing of chemicals. Our results showed that the use of reproductive parameters of Girardia tigrina would help to complement and achieve a better assessment of the risk posed by triazole fungicides to freshwater ecosystems.

Computational study of the interaction of heavy metal ions, Cd(II), Hg(II), and Pb(II) on lignin matrices.

Contamination by heavy metal ions, particularly in water resources, is a severe environmental problem. In this study, the interaction of metal ions, namely, Cadmium Cd(II), Mercury Hg(II), and Lead Pb(II), on lignin matrices was investigated based on theoretical calculations. Binding energy (ΔEBind) values proved that the Pb(II) interacted better with lignin matrices than Cd(II) or Hg(II), having energy values between -8.4 kcal mol-1 to -20.2 kcal mol-1. The Gibbs energy (ΔG) and enthalpy (ΔH) values for Pb(II) were <0, indicating that the process was spontaneous and released heat. However, the lignin matrices studied in this work did not interact efficiently with Cd(II) and Hg(II) ions because almost all ΔEBind, ΔG, and ΔH values were positive. The bond length of the interaction proved that the Pb ions yielded the smallest values, ratifying the values for the interaction energy. Analyses based on the quantum theory of atoms in molecules showed that the interactions between Pb(II) and the matrices were partially covalent, whereas the interactions of Cd(II) and Hg(II) were predominantly electrostatic, justifying the positive values of ΔEBind, ΔG, and ΔH. The natural bond orbital results showed that the ligand orbitals of the matrix interacted with the lone pair antibonding orbital (LP*) of the metal ions. The theoretical results of the study show the possibility of applying lignin to remove heavy metal ions, especially Pb, and providing information for research related to wastewater treatment.

Interaction of glyphosate in matrices of cellulose and diethylaminoethyl cellulose biopolymers: theoretical viewpoint of the adsorption process.

Glyphosate is an herbicide widely used in agricultural activities causing contamination of soils and bodies of water and damage to the biodiversity of ecosystems. In this context, the present study aimed to theoretically study the adsorption potential of the biopolymer cellulose (CE) and its diethylaminoethyl cellulose derivative (DEAEC) with the herbicide glyphosate (GLY). Theoretical calculations were performed using the density functional theory. Molecular electrostatic potential and frontier molecular orbital analyses were performed, which allowed identifying the possible sites of interaction of biopolymers that were in the functional groups -OH and O- of cellulose and in the groups -O- and -NH+(CH2CH3)2 of the DEAEC. Reactivity indices chemical softness and hardness showed that both adsorbents could interact with adsorbate. Simulated IR indicated that the interactions could be evinced in experimental measurements by changes in the bands of glyphosate (ν(P = O), δ(P-O-H), δ(C-N-H)) or in the bands of CE and DEAEC (ν(C-O), ν(C-H), ν(N-H)). The binding energies showed that the GLY interacts more effectively with CE than DEAEC. The ΔH prove that all processes are exothermic and the CE-GLY1 interaction showed value of ΔG < 0. The topological results showed a greater number of interactions with electrostatic nature. The results found in the study show that the theoretical data provides useful information to support the use of biopolymers as matrices for glyphosate adsorption or other contaminants.

When treatment increases the contaminant's ecotoxicity: A study of the Fenton process in the degradation of methylene blue.

The degradation of dyes can generate harmful by-products, thereby requiring the need to evaluate the toxicity to aquatic organisms. This study aims to evaluate the chronic ecotoxicity of methylene blue dye degraded by the Fenton process using the non-target planarian Girardia tigrina as a sensitive bioindicator of environmental contamination. The bioassays evaluated the lethality of several concentrations of the untreated and degraded dye methylene blue (MB), as well as, their sub-lethal effects on locomotion, feeding, regeneration, and reproduction. In both acute and chronic tests, the degraded dye had a stronger toxic effect when compared to the untreated dye. This negative effect after treatment was mainly associated with the presence of residual hydrogen peroxide and iron (and consequently the hydroxyl radical formed). We conclude that the utilization of the Fenton process using less oxidizing agents should be considered as important alternatives for the protection of aquatic ecosystems, without compromising the efficient removal of MB.

Fenton-type process using peracetic acid: Efficiency, reaction elucidations and ecotoxicity.

Recent studies on Fenton-type processes involving peracetic acid (PAA) stimulated further development of advanced oxidative processes (AOPs). The objective of this work was to provide new information about such processes, elucidate their reaction mechanisms both experimentally and theoretically, and verify their possible uses. The Fenton-type reaction of PAA with Fe3+ exhibited a greater dye degradation efficiency than the Fenton process, while the efficiency of the PAA reaction with Fe2+ was very close of Fenton process. Moreover, the processes photocatalyzed by solar radiation demonstrated comparable efficiencies due to the photoreduction of Fe3+ to Fe2+. By conducting theoretical calculations, it was found that the formation of oxidizing radicals during the reaction of PAA with Fe2+ was not thermodynamically favorable and, therefore, unsuitable for practical use. In contrast, the processes occurred in the PAA/Fe3+ system included thermodynamically spontaneous reactions that generated peroxyl (CH3C(O)OO•), alkoxyl (CH3C(O)•), and hydroperoxyl (HO2•) radicals. The ecotoxicological tests demonstrated that the toxicity of the PAA to the organism Dugesia tigrina can be attributed to the presence of H2O2.

Lethal and sublethal effects of the saline stressor sodium chloride on Chironomus xanthus and Girardia tigrina.

Salinization in freshwaters is gradually increasing as a result of human activities and climatic changes. Higher salt content causes stress for freshwater organisms. Sodium chloride (NaCl) is among the most frequently occurring salts in freshwater ecosystems. The objective of the present study was to investigate the lethal and sublethal effects of NaCl on freshwater ecosystems, using as test organism the dipteran Chironomus xanthus and the planarian Girardia tigrina. Acute tests showed that C. xanthus was more sensitive (48-h LC50 (median lethal concentration) of 2.97 g NaCl L-1) than G. tigrina (48-h LC50 of 7.77 g NaCl L-1). C. xanthus larvae growth rate (larvae length and head capsule width) was significantly reduced under exposure to concentrations as low as 0.19 g L-1 NaCl and higher. A delay in the emergence time (EmT50) was also demonstrated for the same concentration. Sublethal NaCl effects in G. tigrina included feeding inhibition (LOEC (lowest observed effect concentration) of 0.4 g L-1), reduced locomotion (LOEC = 0.2 g L-1), and 24-48-h blastema regeneration (LOEC = 0.2 g L-1 and 0.1 g L-1, respectively). The results demonstrated the toxicity of NaCl to C. xanthus and G. tigrina including sublethal effects that can result in negative consequences for populations in natural freshwaters under salinization.

Effects of lethal and sublethal concentrations of peracetic acid and active chlorine of calcium hypochlorite on Chironomus xanthus.

Freshwater ecosystems are vulnerable to residual concentrations of chemical agents from anthropogenic activities, and the real impacts of such compounds can only be evaluated accurately using ecotoxicological tests. The assessment of ecotoxicological effects of peracetic acid (PAA) and the active chlorine of calcium hypochlorite (Ca(ClO)2) on the insect Chironomus xanthus Meigen (Diptera: Chironomidae) is highly relevant as there are few reports on its effects in fresh water ecosystems. To our best knowledge, this is the first study to assess the chronic toxicity of the compounds to C. xanthus. The toxicity bioassays for C. xanthus included the acute effect (CL50) and the chronic effects based on body length, head width, and cumulative emergence. The results obtained in the acute effect tests indicated that the active chlorine of Ca(ClO)2 is 14 fold more toxic than PAA to C. xanthus. In sublethal evaluations, the active chlorine of Ca(ClO)2 presented higher toxicity than PAA in terms of percentage emergence, body development, and head width. In general, the results showed lower PAA toxicity relative to the active chlorine of Ca(ClO)2, demonstrating that PAA is a promising substitute for chlorinated disinfectants. In addition, the study facilitates the establishment of reference values for the safe release of effluents treated with PAA into water bodies.

Peracetic acid: Structural elucidation for applications in wastewater treatment.

Peracetic acid (PAA) is an oxidizer widely used for the sterilization of equipment in hospitals, pharmaceutical, cosmetic and food industries and also for water and wastewater disinfection. Even with its increasing applications, there have been no previous theoretical studies that explain the experimental results based on its molecular behavior. In this context, this work used calculations based on the density functional theory (DFT) combined with experimental results to elucidate the decomposition mechanisms of PAA for predicting its stability and the possible products generated from its decomposition. The results obtained showed that the protonation of PAA promoted its spontaneous decomposition in acetic acid and molecular oxygen. The hydrolysis mechanism of PAA in acidic medium indicated that the low energy difference involved in the mechanism's stages is responsible for the equilibrium between PAA and H2O2. The structural and electronic comparison of PAA with H2O2 showed that the O-O bond length of PAA is longer than that of H2O2 and is also weaker, therefore may demonstrate greater efficiency in advanced oxidative processes by photocatalysis.

Comparative ecotoxicological evaluation of peracetic acid and the active chlorine of calcium hypochlorite: Use of Dugesia tigrina as a bioindicator of environmental pollution.

Chlorine plays a primary role in the disinfection of drinking water and wastewater due to its effectiveness as a biocide; however, there is evidence of the formation of toxic byproducts from its application, and this has promoted the search for alternatives. Alternative disinfectants can be effective in the inactivation of pathogenic microorganisms and are less damaging to human health and aquatic ecosystems. However, more information is needed on the effect of residual concentrations on the environment. This work compares the ecotoxicological effects of PAA disinfectants and the active chlorine of calcium hypochlorite in relation to the organism Dugesia tigrina (planaria), in terms of the acute effects: LC50, and chronic effects: feeding, locomotion, regeneration, reproduction and fertility. The results indicated that the active chlorine was more toxic than PAA, with LC50 (96 h) of 2.63 mg.L-1 and 3.16 mg.L-1, respectively. Sub-lethal exposure to active chlorine was more toxic when compared to PAA, and there was evidence of significantly reduced feeding and locomotion, causing a greater delay in regeneration and impairment in reproduction and fertility. The results allowed the comparison of the two disinfectants using half-life constants of the compounds and the lowest observed effect level (LOEC) of the oxidants. Chlorine represents a greater risk to the ecosystem for a longer period. The results obtained in this study can help in the establishment of discharge limits for PAA in water bodies.

Post-treatment of anaerobic reactor effluent using coagulation/oxidation followed by double filtration.

This study evaluates the efficacy of a sanitary sewage treatment system, proposing post-treatment of the effluent generated by the upflow anaerobic sludge blanket UASB reactor, through a Fenton coagulation/oxidation ((ferric chloride (FC) or ferrous sulfate (FS) and peracetic acid (PAA)), followed by a double filtration system, composed of a gravel ascending drainage filter and a sand descending filter. Following the assessment of treatability, the system efficiency was evaluated using physicochemical and microbiological parameters. In all treatments performed in the pilot unit, total suspended solids (TSS) were completely removed, leading to a decrease in turbidity greater than 90% and close to 100% removal of total phosphorous. In the FC and PAA combination, the effluent was oxygenated prior to filtration, enabling a more significant removal of biochemical oxygen demand (BOD), which characterizes aerobic degradation even in a quick sand filter. The treatments carried out in the presence of the PAA oxidizing agent showed a more significant bleaching of the effluent. Concerning the microbiological parameters, the simultaneous use of PAA and FC contributed to the partial inactivation of the assessed microorganisms. A 65% recovery of the effluent was obtained with the proposed treatment system, considering the volume employed in filter backwashing.