A comprehensive assessment of leachate contamination at a non-operational open dumpsite: mycoflora screening, metal soil pollution indices, and ecotoxicological risks.

The final disposal of municipal solid waste (MSW) in dumpsites is still a reality worldwide, especially in low- and middle-income countries, leading to leachate-contaminated zones. Therefore, the aim of this study was to carry out soil and leachate physicochemical, microbiological, and toxicological characterizations from a non-operational dumpsite. The L-01 pond samples presented the highest physicochemical parameters, especially chloride (Cl; 4101 ± 44.8 mg L-1), electrical conductivity (EC; 10,452 ± 0.1 mS cm-1), and chemical oxygen demand (COD; 760 ± 6.6 mg L-1) indicating the presence of leachate, explained by its close proximity to the landfill cell. Pond L-03 presented higher parameters compared to pond L-02, except for N-ammoniacal and phosphorus levels, explained by the local geological configuration, configured as a slope from the landfill cell towards L-03. Seven filamentous and/or yeast fungi genera were identified, including the opportunistic pathogenic fungi Candida krusei (4 CFU) in an outcrop sample. Regarding soil samples, Br, Se, and I were present at high concentrations leading to high soil contamination (CF ≤ 6). Pond L-02 presented the highest CF for Br (18.14 ± 18.41 mg kg-1) and I (10.63 ± 3.66 mg kg-1), while pond L-03 presented the highest CF for Se (7.60 ± 1.33 mg kg-1). The most severe lethal effect for Artemia salina was observed for L-03 samples (LC50: 79.91%), while only samples from L-01 were toxic to Danio rerio (LC50: 32.99%). The highest lethality for Eisenia andrei was observed for L-02 samples (LC50: 50.30%). The applied risk characterization indicates high risk of all proposed scenarios for both aquatic (RQ 375-909) and terrestrial environments (RQ > 1.4 × 105). These findings indicate that the investigated dumpsite is contaminated by both leachate and metals, high risks to living organisms and adjacent water resources, also potentially affecting human health.

Oxidative stress and metal homeostasis alterations in Danio rerio (zebrafish) under single and combined carbamazepine, acetamiprid and cadmium exposures.

Contaminants of emerging concern (CEC) are routinely detected in aquatic environments, especially pharmaceuticals, such as carbamazepine (CBZ), and neonicotinoid pesticides, like acetamiprid (ACT). CECs can interact with each other and with other legislated contaminants like Cd, resulting in unknown effects. Most studies evaluate only the effects of single contaminant exposures on aquatic biota. Therefore, the aim of the present study was to assess the effects of both single and combined CBZ, ACT and Cd exposures on zebrafish brain and liver oxidative stress parameters and metal homeostasis. The biomarkers catalase (CAT), glutathione-S-transferase (GST), total thiols (TOT), metallothionein (MT) and malondialdehyde (MDA) and the essential elements Ca, Cu, K, Na, Mg, Mn and Zn were evaluated after 96-hour static exposures. CBZ, ACT and Cd single (brain and liver) and combined (liver) treatments resulted in oxidative effects in both fish organs, also leading to metal (Ca, Mg, K, Mn, Zn and Cu) homeostasis alterations. ACT exposure resulted in the greatest adverse effects in the brain, while CBZ was the cause of major element homeostasis and oxidative stress alterations in the liver. Lower LPO levels were observed in the combined treatments compared to single treatments, suggesting interactions and contaminant effect attenuation. This study is the first to evaluate the initial effects of combined CBZ, ACT and Cd exposures in zebrafish, paving the way for further investigations concerning other biomarkers during longer exposure times.

Antioxidant system alterations and biological health status of earthworms following long-term exposure to antibiotic-contaminated poultry litter.

Poultry litter is widely applied as a fertilizer even though it is one of the main antibiotic sources to agricultural soils. Long-term sublethal effects (56 days) on the antioxidant system of Eisenia andrei earthworms following exposure to fluoroquinolone-contaminated poultry litter (enrofloxacin + ciprofloxacin) at 5.0, 10, and 20 g kg-1 were evaluated. The following biomarkers were assessed: superoxide dismutase (SOD), catalase (CAT), glutathione-S-transferase (GST), reduced glutathione (GSH), and a lipid peroxidation (LPO) proxy. Significant CAT and SOD increases, and a moderate positive correlation (ρ = 0.67, p < 0.05) between these enzymes was observed. Glutathione-S-transferase levels increased significantly at 10 g kg-1, while GSH exhibited a dose-dependent response at 5.0 mg kg-1 (4-106%), 10 mg kg-1 (28-330 %), and 20 mg kg-1 (45-472%). LPO levels exhibited a decreasing trend with increasing poultry litter concentrations of 8-170% (5.0 g kg-1), 7-104% (10 mg kg-1), and 3-6% (20 mg kg-1). A principal component analysis (PCA) highlighted increased SOD and CAT activities, possibly due to increased reactive oxygen species (ROS) concentrations. Biological health status assessments based on the biomarker response index indicate major alterations in the first month of exposure and becoming moderate in the second month. These findings indicate an antioxidant system attenuation trend. It is possible, however, that successive poultry litter applications may reduce the long-term recovery capacity of the evaluated biomarkers.

Ecotoxicological evaluation of imazalil transformation products on Eisenia Andrei.

Data concerning the toxicity of the transformation products of some pesticides considered emerging contaminants are still incipient. This study aimed to evaluate acute (filter paper contact and avoidance test) and chronic (assays carried out in Red yellow Ultisoil) effects of the transformation products of the fungicide imazalil (IMZ) by heterogeneous photocatalysis (TiO2/UV) in Eisenia andrei. Some endpoints, i.e. biomass variation, disorder in reproduction and avoidance behavior, cytotoxicity (cell density and feasibility), and coelomic fluid (eleocytes and amoebocytes, immune cell) and antioxidant system (catalase (CAT) and glutathione S-transferase (GST)) changes were assessed. The studied degradation times (6, 18, 35 and 90 min) represented 70; 35; 10 and 0% of the initial IMZ concentration (5 mg L-1). No lethality and no significant difference in biomass variations were noted in the acute contact test. Decreased GST and increased CAT activities, as well as cell typing alterations and decreased cell viability and density detected at the 90-min degradation timepoint (PDT-90) indicate direct cytotoxic IMZ transformation product effects. In the avoidance test, no significant earthworm repulsion or attraction was observed. PDT-90 transformation products were responsible for losses in biomass and a reduction in the number of earthworm cocoons and juveniles present in soil. No cytotoxic effects were observed in the long term, although increased CAT and decreased GST activities were observed. Investigations on the relative toxicity of IMZ transformation products are relevant for future discussions regarding the environmental treatment, control and destination of this compound and its derivatives.

Sub-lethal effects of the pesticide imazalil on the earthworm Eisenia andrei: reproduction, cytotoxicity, and oxidative stress.

Although considered an emerging contaminant and detected in the environment, the systematic and penetration fungicide imazalil ((RS)-1-(ß-allyloxy-2,4-dichlorophenylethyl) imidazole) has received relatively little scientific attention with regard to its possible negative effects in the environment. Only a few toxicological studies have assessed the potential environmental effect of imazalil and its impact on organisms. In this context, the aim of the present study is to evaluate the effects of different concentrations of the pesticide imazalil on the earthworm Eisenia andrei in acute contact and chronic tests in natural soil. Moreover, several endpoints, such as biomass loss or gain, reproduction, behavior, effects on immune system cells, and oxidative stress were also evaluated. Imazalil toxicity to E. andrei was determined by three approaches: a filter paper contact test (0, 0.16, 1.66, 16.6, 166 µg.cm-2), an avoidance (0, 0.1, 1, and 10 mg.kg-1), and a chronic test for 45 days (0, 0.01, 0.1, 1, and 10 mg.kg-1). All organisms exposed to the filter paper contact and chronic tests were submitted to two endpoint analyses: first, coelomic fluid collection by the extrusion method to determine density, viability, and cell type; second, oxidative stress assessments by determining GST and CAT enzymatic activities. This study allows for the conclusion that imazalil does not cause immediate earthworm death after exposure (LC50 > 166 µg.cm-1). However, due to several complementary factors, this compound may compromise earthworm health and lead to death, as E. andrei individuals did not avoid the contaminated soil, thus contributing to longer exposure periods and consequent cumulative damage to their systems. Decreased immunocompetent cellular viability (p < 0.05) and density (p < 0.05) in the chronic test are noteworthy, leading to susceptibility to exogenous factors, as well as irreversible cellular damage provoked by oxidative stress, such as cellular membrane rupture.