Pesticides are used worldwide with potential harmful effects on both fauna and flora. The Kibale National Park in Uganda, a site renowned for its biodiversity is surrounded by tea, banana and eucalyptus plantations as well as maize fields and small farms. We previously showed presence of pesticides with potential endocrine disruptive effects in the vicinity. To further investigate the water pollution linked to agricultural pressure in this protected area, we implemented a complementary monitoring strategy based on: analytical chemistry, effects based methods and the deployment of Polar Organic Chemical Integrative Samplers (POCIS). Chemical analysis of the POCIS extracts revealed the presence of 13 pesticides: carbofuran, DEET, 2.4-D amine, carbaryl, ametryn, isoproturon, metolachlor, terbutryn, dimethoate, imidacloprid, picaridin, thiamethoxam, carbendazim, with the first three being present in the largest quantities. Water samples collected at the POCIS sampling sites exhibited thyroid and estrogen axis disrupting activities in vivo, in addition to developmental and behaviour effects on Xenopus laevis tadpoles model. Based on our observations, for the health of local human and wildlife populations, further monitoring as well as actions to reduce agrochemical use should be considered in the Kibale National Park and in regions exposed to similar conditions.

The Marine Monitoring Program (MMP) was established in 2005 to monitor the inshore health of the Great Barrier Reef (GBR) and evaluate progress towards water quality objectives in Reef Water Quality Improvement Plans. The MMP provides information on the magnitude and spatial extent of pesticide contamination, reports on temporal variability, and provides a risk assessment for the biota in the GBR lagoon. However, long-term trends in pesticide contamination of inshore marine waters over the entire monitoring period (2005–2018) have not been assessed. We used up to 14 years of monitoring data for five PSII herbicides (ametryn, atrazine, diuron, tebuthiuron, and hexazinone) to conduct temporal trend analyses at 11 inshore monitoring sites. The trend analyses suggested increasing significant trends (p < 0.05) for the five PSII herbicides concentrations at several monitoring sites. Power analysis indicated that monitoring sites with over 10 years of monitoring data had convincing results with 80% power.

Sugarcane is one of the world’s most important commodities. In order to control weeds in the plantations and increase productivity, the mixing of different herbicides during spraying operations is commonplace. This practice is unregulated, and the impact on water quality and nontarget tropical species is poorly understood. In the present work, exposure and recovery assays were used to evaluate antioxidant enzyme activity and histopathological alterations in the liver of tilapia (Oreochromis niloticus) following exposure to mixtures of the herbicides widely used in sugarcane crops: ametryn (AMT), tebuthiuron (TBUT), diuron (DIU), and hexazinone (HZN). The greatest biochemical changes were observed for the mixture (DIU+HZN)+AMT+TBUT at the highest concentration tested (1/10 96hLC50). This mixture caused a significant increase (p < 0.01) of approximately 82% in GST activity after 14 days of exposure. For three of the mixtures evaluated, GST and CAT could be considered potential biochemical biomarkers of exposure to the herbicide mixtures due to the frequency, intensity, and statistical significance of alterations in the assimilation phase. Although morphological changes were evident in the hepatic tissue, severe damage was only noted in a few samples, and there were no statistically significant differences, relative to the control. The results of hepatic lesion recovery assays suggested that the most sensitive individuals affected by the xenobiotics were unable to achieve full recovery. It is anticipated that the data obtained may assist in the selection of biomarkers for monitoring purposes, as well as in reinforcing standards of conduct in the use of agrochemical mixtures in agriculture.

In this study, a multi-residue method was used to analyze 13 pesticides and 1 degradation product in surface and groundwater in the region with the largest sugar cane production in the world. The potential effects of individual pesticides and their mixtures, for aquatic life and human consumption, were evaluated. For the surface water, 2-hydroxy atrazine, diuron, carbendazim, tebuthiuron, and hexazinone were the most frequently detected (100, 94, 93, 92, and 91%, respectively). Imidacloprid (2579 ng L⁻¹), carbendazim (1114 ng L⁻¹), ametryn (1101 ng L⁻¹), and tebuthiuron (1080 ng L⁻¹) were found at the highest concentrations. For groundwater, tebuthiuron was the only quantified pesticide (107 ng L⁻¹). Ametryn, atrazine, diuron, hexazinone, carbofuran, imidacloprid, malathion, carbendazim, and their mixtures presented risk for the aquatic life. No risk was observed for the pesticides analyzed in this work, alone or in their mixtures for human consumption.

This paper reports the degradation of 10 mg L⁻¹ Ametryn solution with different advanced oxidation processes and by ultraviolet (UV₂₅₄) irradiation alone with the main objective of reducing acute toxicity and increase biodegradability. The investigated factors included Fe²⁺ and H₂O₂ concentrations. The effectiveness of the UV₂₅₄ and UV₂₅₄/H₂O₂ processes were investigated using a low-pressure mercury UV lamp (254 nm). Photo-Fenton process was explored using a blacklight blue lamp (BLB, λ = 365 nm). The UV₂₅₄ irradiation process achieved complete degradation of Ametryn solution after 60 min. The degradation time of Ametryn was greatly improved by the addition of H₂O₂. It is worth pointing out that a high rate of Ametryn removal was attained even at low concentrations of H₂O₂. The kinetic constant of the reaction between Ametryn and HO● for UV₂₅₄/H₂O₂ was 3.53 × 10⁸ L mol⁻¹ s⁻¹. The complete Ametryn degradation by the Fenton and photo-Fenton processes was observed following 10 min of reaction for various combinations of Fe²⁺ and H₂O₂ under investigation. Working with the highest concentration (150 mg L⁻¹ H₂O₂ and 10 mg L⁻¹ Fe²⁺), around 30 and 70% of TOC removal were reached within 120 min of treatment by Fenton and photo-Fenton processes, respectively. Although it did not obtain complete mineralization, the intermediates formed in the degradation processes were hydroxylated and did not promote acute toxicity of Vibrio fischeri. Furthermore, a substantial improvement of biodegradability was obtained for all studied processes.

Ametryne is an herbicide applied to sugar cane cultures to prevent the emergence of weeds. It is a persistent compound that percolates ground and surface water thus impacting aquatic communities. In this study, we evaluated microbial activity in soil with increased concentrations of ametryne solution and commercial Microgeo biofertilizer. The soil subject to analysis was obtained from a sugar cane cultivation area. The concentration used in the experiment was ametryne 12 μg/L and 1 % of biofertilizer. It was used with the Bartha and Pramer respirometric method to quantify CO₂production and determine microbial activity. Complimentary phytotoxicity tests with Lactuca sativa seeds after respirometry experiments were conducted in the soluble fraction of the soil. According to the results, the addition of biofertilizer promoted microbial activity in the presence of ametryne and reduced ametryne phytotoxicity for Lactuca sativa seeds. Thus, Microgeo biofertilizer can potentially improve biodegradation of ametryne through both bioaugmentation and bioestimulation.

The phytoremediation potential of Brazilian trees species Calophyllum brasiliense, Eremanthus crotonoides, Hymenaea courbaril, Inga striata, and Protium heptaphyllum was investigated for contaminated soils containing ametryn and hexazinone. Visual injury, chlorophyll content, plant height, leaf temperature, leaf number, and water-efficient use were evaluated. Residual herbicides at soil substrates were analyzed by LC/MS. Among the species C. brasiliense and H. courbaril were tolerant to both herbicides. P. Heptaphyllum presented tolerance at ametryn treatment. E. crotonoides, I. striata, and P. heptaphyllum died in hexazinone treatment. A high content of residual ametryn was found for E. crotonoides. In ametryn treatment, residual herbicide has decreased for C. brasiliense and E. crotonoides species. C. brasiliense highlighted among others becoming a good agent for phytoremediation of soils contaminated with traces of ametryn and hexazinone.

Ametryn (AMT) is one of the most widely used herbicides in tropical sugarcane crops, the main culture of São Paulo State, Brazil. It is known as a diffuse pollutant, being found in surface water and sediment of water bodies adjacent to the crop fields. In the present study, the toxicity of AMT to zebrafish (Danio rerio) embryos was evaluated using developmental and biochemical endpoints. At the biochemical level, lactate dehydrogenase responded at the lowest concentration tested (4 μg L⁻¹) indicating a high demand of energy required to cope with the stress condition. Antioxidant enzyme levels were changed at intermediate/high concentrations while oxidative damage (lipid peroxidation) was observed at the last concentration tested (10 mg L⁻¹). This suggests that, like for other herbicides from the triazine group, oxidative stress is a major pathway of toxicity for AMT. Several developmental effects such as oedemas and tail deformities were also observed. The 96 h-EC₅₀ values calculated for different developmental parameters were between 17 and 29 mg L⁻¹. AMT also affected hatching (96 h-EC₅₀ = 22.5 mg L⁻¹) and positioning in the water column (96 h-EC₅₀ = 13.2 mg L⁻¹). In a previous work of the group, lethal toxicity of AMT showed to be much higher to adults than to embryos. However, in the present work, sublethal endpoints assessed suggest that important effects are observed at lower concentrations, improving the sensitivity of the embryo test. Moreover, in this work, sublethal effects were observed for concentrations in the same range as the ones found in the environment, and thus, given that this chemical is widely used in tropical fields, a refined evaluation of risk should be performed based on the monitoring of sublethal and long-term parameters and considering mixture scenarios.

Triazines and their degradation products are transported to the aquatic environment, and once there, the probability to reach the marine environment is very high. In this paper, solid phase extraction (SPE) and extraction by matrix solid phase dispersion (MSPD) to analyse nine triazines (ametryn, atrazine, cyanazine, prometryn, propazine, simazine, simetryn, terbuthylazine and terbutryn) and eight degradation products (desethylatrazine, desethyldesisopropylatrazine, desethyl-2-hydroxyatrazine, desethylterbuthylazine, desisopropylatrazine, desisopropyl-2-hydroxyatrazine, 2-hydroxyatrazine and 2-hidroxyterbuthylazine) in seawater and marine sediments samples were used. The analysis was carried out using liquid chromatography with tandem mass spectrometry (LC-ESI-MS/MS). The methods were optimized and validated to achieve a selective and sensitive determination of the analytes from different sample, regardless of its complexity. Under the optimum conditions, the proposed methods provided adequate limits of quantification (0.05–0.45 μg L⁻¹ and 0.23–4.26 μg kg⁻¹ in seawater and marine sediments, respectively). Intra- and inter-day relative standard deviation were below 1.41% for all compounds. Recoveries were evaluated, and acceptable values that ranged from 87.5–99.4 and 60.9–99.7% for the seawater and sediment samples, respectively, were obtained. The proposed methods were applied to the analysis of the target compounds in seawater samples and marine sediments from a coastal area of Galicia (NW of Spain).

Mixture of metals and herbicides in rivers may pose relevant risks for the health of surrounding communities. Humans may be exposed to river pollution through intake of contaminated water and fish, as well as irrigated agricultural products. The aim of this study was to assess the human health risks of environmental exposure to metals and herbicides through water and fish intake in the Pardo River. Metals (Al, As, Be, Cd, Cr, Cu, Pb, Mn, Hg, Ni, Tl, Sn, V, and Zn) were analyzed in river water and in edible fish. Herbicides (ametryn, atrazine, diuron, hexazinone, simazine, and tebuthiuron) were analyzed in river water. Seasonal variances were also studied. Aluminum, Cd, Cu, Mn, Pb, and Zn levels in river water were higher than the USEPA benchmarks. Non-carcinogenic risks due to pollutants mixture exposure were above the limit, and carcinogenic risks of As exposure were >10⁻⁶ in the sampling points during the rainy season. Metal levels in fish were lower than the Brazilian legislation and do not pose a threat to public health. Herbicides were detected in four sampling points, with atrazine concentrations (range 0.16–0.32 μg/L) below the Brazilian standard (2.0 μg/L), but above the European Union standard (0.1 μg/L). Considering the water supply needs of cities located in the Pardo River Basin and the persistence of metals and herbicides, the present study indicated that there was a seasonal influence on non-carcinogenic and carcinogenic risks to human health, especially in the rainy season. Studies for water treatment plants implantation should consider the risks of exposure to persistent substances, in order to protect the population.