Post-sorption of Cd, Pb, and Zn onto peat, compost, and biochar: Short-term effects of ecotoxicity and bioaccessibility.

Contamination by potentially toxic metals and metalloids (PTMs) has become a significant health and environmental issue worldwide. Sorption has emerged as one of the most prominent strategies for remediating both soil and water contamination. New sorbents are being developed to provide economically viable and environmentally sound alternatives, in alignment with the principles of the Sustainable Development Goals. This research aimed to assess the potential effects on human health and environmental toxicity following the sorption of cadmium (Cd), lead (Pb), and zinc (Zn) using peat, compost, and biochar as sorbents. The peat was collected in Brazil, a country with a tropical climate, while the compost and biochar were produced from the organic fraction of municipal solid waste (OFMSW). In terms of bioaccessibility, the results showed the following order: compost < biochar < peat for Pb, and compost < peat < biochar for Cd and Zn. There was a significant growth inhibition for Eruca sativa and Zea mays exposed to increasing concentrations of PTMs treated with peat and compost. The presence of contaminants played a decisive role on immobilization of neonates of Ceriodaphnia silvestrii after treatments with compost and, especially, peat. However, the biochar addition rate caused a significant influence on the outcomes of ecotoxicity across all tested species. Although the samples treated with biochar exhibited lower residual concentrations of PTMs than those treated with compost and peat, the inherent toxicity of biochar might be attributed to the material itself. The exposure to residual PTM concentrations post-desorption caused ecotoxic effects on tested species, emphasizing the need to assess PTM desorption potential. Peat, compost, and biochar are promising alternatives for the sorption of PTMs, but the addition rates must be properly adjusted to avoid the occurrence of undesirable ecotoxicological effects. This research offers valuable insights for sustainable environmental management and protection by thoroughly investigating the impacts of different sorbents and contaminants on aquatic and terrestrial ecosystems.

Environmentally Relevant Concentrations of the Insecticide Fipronil Modulated Molecular Response in Chironomus riparius.

Pesticides employed worldwide for crop protection easily reach aquatic systems, which act as the main reservoirs, and become a risk factor for aquatic fauna. Fipronil is a broad-spectrum insecticide acting on the insect nervous system; however, other effects and systems unrelated to this mechanism could be affected in non-target organisms. Thus, the present study aimed to assess the impact of fipronil on the suborganismal response (gene expression and enzymatic activity) of Chironomus riparius larvae as a model organism in ecotoxicology. To this end, short-term toxicity tests were carried out with fourth-instar larvae exposed to 0.001, 0.01, and 0.1 µg L-1 of fipronil for 24 and 96 h. Messenger RNA levels of 42 genes related to diverse metabolic pathways were analyzed by real-time polymerase chain reaction, complemented with catalase (CAT), glutathione S-transferase (GST), and acetylcholinesterase (AChE) activities. Few effects were observed at 24 h; however, after longer exposure (96 h), genes involved in the endocrine, detoxification, stress, and immune response pathways were altered. Moreover, fipronil at 96 h increased CAT and GST activity at 0.01 µg L-1 and AChE at the highest concentrations. The results demonstrate that even low environmentally relevant fipronil concentrations can modulate the molecular response of several cellular pathways in C. riparius after short-term exposure. These results bring new information about the underlying response of fipronil and its mode of action on a key aquatic invertebrate. Despite no effects on mortality, strong modulation at the suborganismal level emphasizes the advantage of biomarkers as early damage responses and the harmful impact of this pesticide on freshwater organisms. Environ Toxicol Chem 2024;43:405-417. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Copper and cadmium, isolated and in the mixture, impact the Neotropical freshwater Calanoida copepod Notodiaptomus iheringi: A short-term approach with environmental concentrations.

Metal discharges in aquatic ecosystems are of concern since they affect different trophic levels, altering the functioning of the aquatic food chain. The metals can interact among them and with other pollutants, resulting in complex mixtures whose effects on biota are unpredictable. The impacts of copper (Cu) and cadmium (Cd), isolated and combined, on the freshwater copepod Notodiaptomus iheringi were assessed in acute and sub-chronic exposures. Species sensitivity distribution (SSD) curves were constructed for both metals. In the acute tests antagonism was observed in mortality, while in sub-chronic, mortality was not affected; however, the eggs produced and percentage of viable eggs were significantly altered. Our data suggest that egg production can be a detoxification route in N. iheringi under Cu and mixture exposure. From the SSD curves, N. iheringi was the most sensitive Brazilian species for Cu and the second most sensitive for Cd.

Sugarcane vinasse provokes acute and chronic responses and bioaccumulation of metals in benthic macroinvertebrates.

Brazil is a major producer of sugarcane bioethanol, which has raised concerns about its environmental impact. The industrial process for obtaining ethanol generates a by-product with a high pollution potential called vinasse. If vinasse reaches watercourses, it may affect the biological communities, such as the aquatic macroinvertebrates, which include species sensitive to environmental contamination. Thus, this study evaluated the ecotoxicological effects of sugarcane vinasse on tropical benthic macroinvertebrates (Allonais inaequalis, Chironomus sancticaroli, Strandesia trispinosa, and Hyalella meinerti). The study was divided into three phases. First, acute toxicity tests were carried out with the four species. The species A. inaequalis (average LC50 = 0.460% confidence interval, CI 0.380-0.540%) was more sensitive to vinasse than C. sancticaroli (LC50 0.721%, CI 0.565-0.878%), H. meinerti (EC50 0.781%, CI 0.637-0.925%), and S. trispinosa (EC50 1.283%, CI 1.045-1.522%). In the second phase, the consequences of chronic exposure to vinasse were assessed in the two more sensitive species. Impairments in reproduction and population growth rates for A. inaequalis and on the development, metamorphosis, and body growth of C. sancticaroli larvae occurred. Finally, the bioaccumulation of metals after chronic exposure was determined in the third phase. Vinasse provoked decreases in the body residue of the essential metals Zn and Mn and the accumulation of Cd, Pb, and Cr with the potential for biomagnification throughout the food webs. Low concentrations of vinasse (below 1%) provoked lethal and sublethal effects on benthic organisms, with several cascade effects on aquatic environments, given the ecological importance of this group in freshwater and terrestrial ecosystems.

Ethylparaben Toxicity on Cladocerans Daphnia Similis and Ceriodaphnia Silvestrii and Species Sensitivity Analysis.

Parabens, a group of preservatives with a wide industrial range, threaten human and aquatic biota health due to their toxicity and endocrine disruption potential. As conventional wastewater treatment may not be enough to keep natural environments safe, toxicity studies are useful tools for supporting ecological risk assessments. Here, we focused on assessing ethylparaben's, one of the most common kinds of paraben, toxicity in the cladocerans Daphnia similis and Ceriodaphnia silvestrii. The EC50 sensitivity for D. similis and C. silvestrii was 24 (21-28) mg L- 1 and 25 (19-33) mg L- 1, respectively. Inhibition of reproduction and late development of females were observed in C. silvestrii exposed to 8 mg L- 1. Furthermore, species sensitivity distribution was used to assess ecological risk, and ethylparaben demonstrated low potential risk for aquatic biota.

The acute effects of fipronil and 2,4-D, individually and in mixture: a threat to the freshwater Calanoida copepod Notodiaptomus iheringi.

The magnitude of copepods' responses to pesticides, individually and in mixture, is little understood. The aims of this study were to evaluate: (i) the effects of the pesticides fipronil and 2,4-D, individually and in mixture, on the freshwater copepod Notodiaptomus iheringi; and (ii) the survival and the feeding rate of copepods after the exposure. Acute toxicity tests using the commercial formulations of fipronil and 2,4-D, individually and in mixture, were performed. The LC10-48h, LC20-48h, and LC50-48h of fipronil to N. iheringi were 2.38 ± 0.48, 3.08 ± 1.14, and 4.97 ± 3.30 µg L-1, respectively. For 2,4-D the LC10-48h, LC20-48h, and LC50-48h were 371.18 ± 29.20, 406.93 ± 53.77, and 478.24 ± 107.77 mg L-1, respectively. Morphological damages on the copepods exposed to pesticides were observed at all concentrations. Fungal filaments covering dead organisms were presented at the treatment highest concentration (R5:7.43 ± 2.78 µg L-1 fipronil). The mixture of the pesticides presented synergistic effects on the mortality of N. iheringi. Post-exposure tests showed no difference between the treatments and the control on the mortality and on the feeding rate for 4 h. However, since delayed toxicity of pesticides can occur, longer post-exposure tests using N. iheringi should be tested. N. iheringi is a key species in the aquatic Brazilian ecosystem and showed sensitivity to fipronil and 2,4-D; thus, more studies with this species assessing other responses are recommended.

Environmental Risk Assessment of Drugs in Tropical Freshwaters Using Ceriodaphnia silvestrii as Test Organism.

In this study we evaluated the acute (immobility/mortality) and chronic (survival and reproduction) effects of the drugs caffeine, diclofenac sodium salt, ketoprofen, paracetamol and salicylic acid on the cladoceran Ceriodaphnia silvestrii. The environmental risks of these substances for tropical freshwaters were estimated from the risk quotient MEC/PNEC. Sensitivity in acute exposures varied up on the drug as follows: salicylic acid (EC50 = 69.15 mg L- 1) < caffeine (EC50 = 45.94 mg L- 1) < paracetamol (EC50 = 34.49 mg L- 1) < ketoprofen (EC50 = 24.84 mg L- 1) < diclofenac sodium salt (EC50 = 14.59 mg L- 1). Chronic toxicity data showed negative effects of the drugs on reproduction. Paracetamol and salicylic acid caused reduction in fecundity in concentrations starting from 10 mg L- 1 and 35 mg L- 1, respectively. Ketoprofen caused total inhibition at 5 mg L- 1. MEC/PNEC values were relatively low for all drugs. The risk was estimated as low or insignificant, except for caffeine, whose MEC/PNEC value was greater than 1 (moderate risk).

Phytotoxicity of 2,4-D and fipronil mixtures to three green manure species.

Sugarcane expansion has been associated with soil contamination by agrochemicals. Pesticides can affect plant growth, and their mixture might have potentiated effects on exposed species. This research aimed to evaluate the influence of fipronil on the phytotoxicity of 2,4-D on three green manure plant species: Canavalia ensiformis, Dolichos lablab, and Lupinus albus. Plants were exposed (for 21 days, at 25 °C) to a control soil and five concentrations of each pesticide and their combinations (36 treatments, considering a full-factorial approach). Effect concentrations of 50% growth inhibition (EC50) were estimated. No phytotoxicity effects were identified when plants were exposed to different fipronil concentrations (up to 0.12 mg kg-1). All species exposed to 2,4-D showed a decrease in shoot and root length and fresh/dry biomass. L. albus and D. lablab roots showed the highest sensitivity when exposed to 2,4-D among the endpoints (EC50 = 0.02 and 0.05 mg kg-1, respectively), while C. ensiformis roots were the most tolerant (EC50 = 0.98 mg kg-1). However, the interference of fipronil on the toxicity of 2,4-D was not detected in different mixture proportions, indicating no interaction between pesticides. Residues of 2,4-D might also impair other crops' growth, compromise productivity, and limit phytotechnologies for soil recovery.

Responses of Chironomus sancticaroli to the simulation of environmental contamination by sugarcane management practices: Water and sediment toxicity.

Sugarcane management practices include the application of pesticides, including the herbicide 2,4-D and the insecticide fipronil. In addition, a by-product from the ethanol industry, called vinasse, is commonly applied to fertilize sugarcane areas. The potential risks of these practices to the edge-of-field aquatic ecosystems were assessed in the present study. This was done by contaminating mesocosms with (single and mixtures of) both pesticides and vinasse and evaluating the effects on the midge Chironomus sancticaroli through in-situ and laboratory bioassays. To this end, outdoor mesocosms were treated with fipronil (F), 2,4-D (D), and vinasse (V) alone and with the mixture of fipronil and 2,4-D (M), as well as with both pesticides and vinasse (MV). C. sancticaroli was deployed in mesocosms before contamination in cages, which were taken out 4- and 8-days-post-contamination. Water and sediment samples were also taken for laboratory bioassays on the first day of contamination, as well as 7-, 14-, 21-, 30-, 45-, and 75-days post-contamination. The responses assessed in subchronic assays (8-day) were survival, growth, head capsule width, development, and mentum deformities. Low survival occurred in the in-situ experiments of all treatments due to the low oxygen levels. In the laboratory tests, effects on survival occurred for F, V, and M over time after exposure to both water and sediment. All organisms died post-exposure to water samples from the MV treatment, even 75-days-post-contamination. Impairments in body length and head capsule width occurred for F, V, and M for water and F, V, M, and MV for sediment samples over time. All treatments increased mentum deformities in exposed larvae for any of the sampling periods. The negative effects observed were more significant in the mixture mesocosms (M and MV), thus indicating increased risks from management practices applying these compounds together or with a short time interval in crops.

Using mesocosms to evaluate the impacts of pasture intensification and pasture-sugarcane conversion on tadpoles in Brazil.

This study evaluated the effects of environmental contamination caused by pasture intensification and pasture-sugarcane conversion on oxidative stress, biotransformation, esterase enzymes, and development of Scinax fuscovarious and Physalaemus nattereri. Tadpoles were exposed in mesocosms allocated in three treatments: (1) untreated extensive pasture (EP); (2) intensive-pasture conversion (IP) (2,4-D herbicide + fertilizers); and (3) pasture-sugarcane conversion (SC) (fipronil + 2,4-D + fertilizers). After 7 days of exposure, IP reduced catalase (CAT) and increased malondialdehyde (MDA) levels in P. nattereri, while this treatment decreased glucose-6-phosphate dehydrogenase (G6PDH) and CAT activities in S. fuscovarious. SC decreased CAT, G6PDH, and glutathione S-transferase (GST) activities in P. nattereri. In S. fuscovarius, SC reduced G6PDH, acetylcholinesterase (AChE), and carboxylesterase (CbE) activities. MDA was raised in both tadpole species exposed to SC, evidencing oxidative stress. Integrated biomarker responses showed higher scores in both species exposed to SC. Our results warn that management practices currently applied to sugarcane cultivation in Brazil can negatively impact the functional responses of amphibians at natural systems.

Environmental analysis of the eutrophication and spread of aquatic macrophytes in a tropical reservoir: a case study in Brazil.

Land use changes threaten the maintenance of water quality and challenge the management of tropical reservoirs. In particular, eutrophication alters several ecosystem functions and services, compromising multiple uses of water. For example, in the Lajeado Reservoir (Araraquara, São Paulo, Brazil), aquatic macrophytes rapidly spread and occupied more than 90% of the system's surface area (from 2016 to 2019). In such a scenario, this research aimed to evaluate the eutrophication causes and impacts to provide technical and scientific support to public agencies and propose remediation alternatives. First, a diagnosis of the study area was performed, using available data on land use, water quality, and climate (between 2010 and 2018). Second, water and sediment samples were collected for physical, chemical, and ecotoxicological analyses. The Ecological Risk Assessment consisted of a triad of Lines of Evidence, including physical-chemical, chemical, and ecotoxicological results. The expansion of agricultural activities (e.g., sugarcane cultivation) and diffuse pollution were highlighted among possible causes, and water quality was affected by increases in the concentration of nutrients (e.g., nitrogen and phosphorus), metals (e.g., iron), and emerging contaminants (e.g., pesticides and caffeine). As a result, the Lajeado Reservoir presented a high ecological risk, and alternatives for macrophyte removal are needed. This research involved several stakeholders (i.e., community, government agencies, and universities) who participated more effectively in environmental monitoring and recovery.

Chronic environmentally relevant levels of pesticides disrupt energy reserves, feeding rates, and life-cycle responses in the amphipod Hyalella meinerti.

When pesticides reach the aquatic environment, they can distribute in water and sediment, increasing the risks to benthic organisms, such as amphipods that play a key role in the aquatic food webs. Thus, the present study assessed the consequences of exposure to the insecticide fipronil and herbicide 2,4-D (alone and in mixture) on biochemical markers, feeding rates and the partial life-cycle of Hyalella meinerti. Three concentrations of fipronil (0.1, 0.3, and 0.7 µg L-1) and 2,4-D (19, 124, and 654 µg L-1), and six mixture combinations were assessed. The first experiment was carried out with males and females separately assessing the feeding rates, total carbohydrate content, and lipid profile. The second (partial life-cycle) lasted 49 days, and the survival, growth, and reproductive endpoints were assessed. Both pesticides and their mixture caused decreases in feeding rates, mainly in females. Females also suffered a change in the total carbohydrate content. In addition, there were changes in the percentage of triacylglycerol and phospholipids in males and females. Furthermore, alterations occurred in the percentual of triacylglycerol and phospholipids to both sexes. In the second experiment, fipronil and the mixtures caused decreases in the survival of H. meinerti over time. Exposure to 2,4-D, fipronil, and their mixture impaired the 28-day growth leading to biomass loss ranging from 17-23%, 54-60%, and 22-49%, respectively. The insecticide and mixture caused increases in time to sexual maturation of up to 10 and 6 days, respectively, and reduced the number of formed couples. Furthermore, fipronil decreased reproduction up to 36 times and no juveniles were produced in some mixture combinations. In addition, the pesticides on isolation decreased the juvenile size. Finally, exposure to both pesticides, alone or in a mixture, decreased the intrinsic rate of population growth. The results were observed in concentrations already quantified in water bodies, with risks for ecosystems functioning due to the importance of amphipods in aquatic ecosystems.

Irrigation with Water Contaminated by Sugarcane Pesticides and Vinasse Can Inhibit Seed Germination and Crops Initial Growth.

Sugarcane crops are dependent on chemicals for maintaining plantations. Therefore, environmental consequences concern adjacent areas that can be affected by contaminants in common use, including pesticides and vinasse (i.e., a by-product from the ethanol industry). This study aimed to evaluate phytotoxicity through two plant bioassays with water from mesocosms contaminated with the herbicide 2,4-D (447.0 µg L-1), the insecticide fipronil (63.5 µg L-1), and sugarcane vinasse (1.3%). First, the germination test (4 d) with Eruca sativa L. assessed water samples collected three times after the contamination (2 h, 14 d, and 30 d), considering germination, shoot, and root growth. The results from this bioassay indicated higher phytotoxicity for 2,4-D as it fully inhibited the shoot and root growth even in low concentrations (0.2 µg L-1). However, no significant effect was reported for fipronil and vinasse. Also, the 2,4-D effects drastically decreased due to an expressive concentration reduction (99.4% after 30 d in mixture with vinasse). Second, the irrigation test with Phaseolus vulgaris L. and Zea mays L. considered shoot and root growth and biomass under 21 days after plants emergence. The herbicide 2,4-D inhibited the initial growth of tested species, especially the roots (up to 45% inhibition). Furthermore, sugarcane vinasse caused harmful effects on plant growth (up to 31% inhibition). Therefore, our data showed that these contaminants could inhibit plant germination and initial growth under our tested conditions. These evaluations can endorse risk assessments and water management in sugarcane crops surrounding areas.

Acute toxicity of disinfection by-products from chlorination of algal organic matter to the cladocerans Ceriodaphnia silvestrii and Daphnia similis: influence of bromide and quenching agent.

Algal organic matter (AOM) in water reservoirs is a worldwide concern for drinking water treatment; once it is one of the main precursors for disinfection by-products formation (DBPs). In this context, this study investigated the ecotoxicity of DBPs from chlorination of AOM to Ceriodaphnia silvestrii and Daphnia similis (Crustacea, Cladocera). The bioassays evaluated three scenarios, including the AOM extracted from Chlorella sorokiniana, the quenching condition used in the tests, and the DBPs formed after the chlorination of the two test waters with AOM (with and without bromide presence). The results showed that AOM has no toxic effects for the tested species under typical environmental concentration (5 mg∙L-1). However, since AOM is a potential precursor of DBPs, the toxicity of two test waters (TW-1 and TW-2) after the chlorination process (25 mg Cl2·L-1, for 7 days, at 20 °C) was tested. The sample with higher toxicity to the tested species was TW-1, in which chloroform and chloral hydrate were quantified (615 and 267 µg∙L-1, respectively). However, TW-2 showed lower concentration of chloroform and chloral hydrate (260 and 157 µg∙L-1, respectively), although bromodichloromethane, dibromochloromethane, and bromoform were also detected (464, 366, and 141 µg∙L-1, respectively). Although free chlorine is highly toxic to the tested species, the quenching conditions also affected the organisms' survival due to the use of ascorbic acid and the presence of reaction intermediates. Nonetheless, both species were more affected by TW-1 and TW-2 than the quenching condition. These results endorse the importance of removing the AOM before the disinfection process to avoid the formation of DBPs. In addition, ecotoxicological analyses could provide a more comprehensive assessment of water quality, especially considering the challenges of quantifying DBPs and other emerging contaminants.

Bioconcentration and toxicological impacts of fipronil and 2,4-D commercial formulations (single and in mixture) in the tropical fish, Danio rerio.

The insecticide fipronil and the herbicide 2,4-D are the most applied pesticides in sugarcane crops leading to aquatic contamination. The whole-body bioconcentration of fipronil and 2,4-D, single and in mixture, was evaluated in Danio rerio after 96-h exposure. The activities of catalase (CAT) and glutathione S-transferase(GST) in whole body and in the gills and the acetylcholinesterase (AChE) in muscle were determined. The gill histopathology and the morphology of the pavement (PVC) and the mitochondria-rich(MRC) cells at gill surface were analyzed. Bioconcentration occurred after exposure to fipronil (2.69 L kg-1) and 2,4-D (1.73 L kg-1) single and in mixture of fipronil (3.10 L kg-1) and 2,4-D (1.27 L kg-1). Whole-body CAT activity was unchanged, and its activity decreased in the gills after exposure to fipronil and increased after exposure to 2,4-D and mixture. GST and AChE increased after single exposure to each pesticide and mixture of both. Fish exposed to mixture increased the MRC fractional area (MRCFA) which suggested possible ionic regulation disturbance and reduced the microridge of the PVC surface. Synergistic interactions occurred in the CAT activity and MRCFA after exposure to mixture of pesticides. The results indicate that the recommended application dose of fipronil and 2,4-D, single or in mixture, for sugarcane crops affects this fish species altering its homeostasis.

The Longitudinal Profile of a Stream Contaminated With 2,4-D and its Effects on Non-Target Species.

Pesticides can cause harmful effects to aquatic communities, even at concentrations below the threshold limit established as guidelines for the water bodies by environmental agencies. In this research, an input of the herbicide 2,4-dichlorophenoxyacetic acid (i.e., 2,4-D) was simulated under controlled conditions in a 500-m-long reach of a first-order tropical stream in Southeastern Brazil. Two water samplings at eight stations investigated the stream longitudinal contamination profile. The ecotoxicological effects were analyzed using Eruca sativa L. seed germination assays and the acute and chronic toxicity tests with the neotropical cladoceran Ceriodaphnia silvestrii. Physicochemical parameters of water quality were evaluated to characterize the study area and quantify 2,4-D concentrations along the stream to assess pesticide retention. The 2,4-D concentration was reduced by approximately 50% downstream in the samplings, indicating that the herbicide was retained along the stream. Moreover, C. silvestrii reproduction in long-term assays decreased approximately 50% in the stations with higher concentrations of 2,4-D than the laboratory control. After contamination, E. sativa L. showed a lower average root growth (1.0 cm), statistically different from the control (2.2 cm). On the other hand, similar growth values were obtained among the background and the most downstream stations. Our study highlighted the relevance of reviewing and updating herbicide guidelines and criteria to prevent possible ecological risks.

Whole-body bioconcentration and biochemical and morphological responses of gills of the neotropical fish Prochilodus lineatus exposed to 2,4-dichlorophenoxyacetic acid or fipronil individually or in a mixture.

The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and the insecticide fipronil have been used widely in agriculture and detected in aquatic ecosystems, where they threaten wildlife. This study evaluated the whole-body bioconcentration and the biochemical and morphological changes in the gills of the neotropical fish Prochilodus lineatus exposed for 96 h to 2,4-D or fipronil as single compounds or as a mixture (2,4-D + fipronil). Fish exposed to either compound alone bioconcentrated 2,4-D (77 ± 23 ng g - 1 fish dry mass) and fipronil (789 ± 178 ng g - 1 fish dry mass). Fish exposed to 2,4-D + fipronil bioconcentrated fipronil (683 ± 73 ng g - 1 fish dry mass) but not 2,4-D. In the gills, catalase (CAT) and glutathione-S-transferase (GST) activities and the lipid peroxidation (LPO) level increased after exposure to 2,4-D. GST activity increased after exposure to fipronil. Conversely, no changes occurred in CAT and GST activities and LPO upon exposure to 2,4-D + fipronil. Histopathological changes such as hyperplasia, cellular hypertrophy, epithelial lifting, and vascular congestion were frequent in the gills of fish exposed to 2,4-D or fipronil individually or 2,4-D + fipronil. The mitochondria-rich cell (MRC) density increased on gill surface in fish exposed to fipronil or 2,4-D + fipronil. Only exposure to 2,4-D alone induced oxidative stress in the gills. Most morphological changes showed defense responses against the pesticides; however, hypertrophy and the change in MRC indicated compensatory responses to maintain the gill osmoregulatory function. The 2,4-D + fipronil mixture showed antagonistic interaction, except for the MRC fractional area at gill surface, which showed synergistic interaction. This is the first report showing antagonistic interaction of 2,4-D and fipronil in the gills after exposing fish to the mixture of both pesticides. The biochemical and morphological changes in gills endanger the gill functions, a phenomenon that implies an energy cost for fish.

A review of pesticides sorption in biochar from maize, rice, and wheat residues: Current status and challenges for soil application.

The use of pesticides has been increasing in recent years for maintaining traditional agricultural practices. However, these chemicals are associated with several environmental impacts, demanding urgent remediation techniques. Biochar is a carbonaceous material produced by pyrolysis that has the potential for pesticide sorption and remediation. In this context, this interdisciplinary review systematically assessed the state of the knowledge of crop residues to produce biochar for pesticide sorption. We focused on maize, rice, and wheat residues since these are the three most-produced grains worldwide. Besides, we evaluated different biochar handling, storage, and soil dispersion techniques to ease its implementation in agriculture. In general, pyrolysis temperature influences biochar characteristics and its potential for pesticide sorption. Furthermore, biochar amended soils had greater pesticide sorption capacity, limiting potential leaching and runoff. Most studies showed that the feedstock and specific surface area influence the biochar sorption properties, among other factors. Also, biochar reduces pesticides' bioavailability, decreasing their toxicity to soil organisms and improving soil fertility and crop yields. Nonetheless, the retrieved papers assessed only 21 pesticides, mainly consisting of lab-scale batch experiments. Therefore, there is still a gap in studies evaluating biochar aging, its potential desorption, pesticide co-contaminations, the associated microbiological processes, and field applications. Determining flow properties for biochars of different sizes and pellets is vital for reliable handling equipment design, and performing techno-economic assessment under different farm contexts is encouraged. Ultimately, coupling biochar production with residue management could address this challenge on sustainable agricultural systems.

Multi-generational exposure to fipronil, 2,4-D, and their mixtures in Chironomus sancticaroli: Biochemical, individual, and population endpoints.

Conventional farming delivers a range of pesticides to aquatic ecosystems leading to implications for the indigenous species. Due to the multiple applications and persistence of molecules, organisms may be exposed for a prolonged period over multiple generations. The present study outlines a full life-cycle design over three generations of Chironomus sancticaroli exposed to the insecticide fipronil, the herbicide 2,4-D, and their mixtures. The experiment started with newly hatched larvae from the parental generation and lasted with the emerged adults from the second generation. Five nominal concentrations of fipronil and 2,4-D were tested, as well as six combinations of both pesticides. As additional responses, the total carbohydrates and the lipid classes were evaluated in the parental generation. The first and second generations were more susceptible to the tested compounds compared with the parental ones. Survival of larvae and pupae was decreased by both pesticides and their mixtures along with the generations. Only fipronil impaired the survival of emerged adults. Both pesticides (isolated and in the mixture) altered the emergence and the fraction of males and females. Moreover, the number of eggs produced, and their hatchability decreased. Only one combination of the pesticides increased the content of carbohydrates. Fipronil, 2,4-D, and its mixture altered the profile of the lipid classes. All mixture treatments and the three highest concentrations of fipronil extinguished the population of C. sancticaroli at the end of the first generation. In the remaining treatments with the insecticide, the population did not survive the second generation. Only three concentrations of 2,4-D and the control persisted until the end of the experiment. The results indicate that a prolonged exposition to these pesticides may disrupt the natural populations of exposed organisms with consequences to ecosystems' functioning, considering the importance of chironomids to aquatic and terrestrial environments.

Toxicity of fipronil and 2,4-D formulations (alone and in a mixture) to the tropical amphipod Hyalella meinerti.

Conventional farming uses a large volume of pesticides that may reach aquatic ecosystems. This is also the case for the insecticide fipronil and the herbicide 2,4-D, which are widely used in many crops. This study aimed at evaluating the individual and mixture toxicity of these pesticides to the tropical amphipod Hyalella meinerti. To this end, acute toxicity tests (96 h) were conducted. Chronic bioassays (10 days) were also carried out, in which the body length and dry biomass were evaluated as endpoints. In addition, a complete factorial mixture chronic toxicity test was carried out. H. meinerti was sensitive to fipronil in the acute toxicity tests, with a LC50-96-h of 0.86 µg L-1 (95% CI 0.26-0.46), and no acute effects were observed after 2,4-D exposure even at the highest test concentration of 100 mg L-1. In the chronic toxicity tests, all tested concentrations of both pesticides decreased the growth of H. meinerti, in which losses on biomass reached 45% and 65% for 2,4-D and fipronil, respectively. The pesticide mixture indicated antagonism although it still significantly decreased the body growth. The results obtained indicate a high sensitivity of H. meinerti exposed to environmentally realistic concentrations, demonstrating that there are risks for the species in real field conditions.