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.

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.

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.

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.

Triazine and urea herbicides are two groups of photosystem II inhibiting herbicides frequently detected in surface, ground and marine waters. Yet, there are few water quality guidelines for herbicides. Ecotoxicity thresholds (ETs) for ametryn, hexazinone and simazine (triazine herbicides) and diuron (a urea herbicide) were calculated using the Australian and New Zealand method for deriving guideline values to protect fresh and marine ecosystems. Four ETs were derived for each chemical and ecosystem that should theoretically protect 99, 95, 90 and 80% of species (i.e. PC99, PC95, PC90 and PC80, respectively). For all four herbicides, the phototrophic species were significantly more sensitive than non-phototrophic species, and therefore, only the former data were used to calculate the ETs. Comparison of the ET values to measured concentrations in 2606 samples from 15 waterways that discharge to the Great Barrier Reef (2011–2015) found three exceedances of the simazine PC99, regular exceedances (up to 30%) of the PC99 in a limited number of rivers for ametryn and hexazinone and frequent (> 40%) exceedances of the PC99 and PC95 ETs in at least four waterways for diuron. There were no exceedances of the marine ETs in inshore reef areas. Further, ecotoxicity data are required for ametryn and hexazinone to fresh and marine phototrophic species, for simazine to marine phototrophic species, for tropical phototrophic species, repeated pulse exposures and long-term (2 to 12 months) exposures to environmentally relevant concentrations.

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.

This study assesses the ecological risks (ERA) of pesticides to aquatic organisms in the River Madre de Dios (RMD), which receives surface runoff water from banana, pineapple, and rice plantations on the Caribbean coast of Costa Rica. Water samples collected over 2 years at five sites in the RMD revealed a total of 26 pesticides. Their toxicity risk to aquatic organisms was assessed using three recent ERA models. (1) The PERPEST model showed a high probability (>50 %) of clear toxic effects of pesticide mixtures on algae, macrophytes, zooplankton, macroinvertebrates, and community metabolism and a low probability (<50 %) of clear effects on fish. (2) Species sensitivity distributions (SSD) showed a moderate to high risk of three herbicides: ametryn, bromacil, diuron and four insecticides: carbaryl, diazinon, ethoprophos, terbufos. (3) The multi-substance potentially affected fraction (msPAF) model showed results consistent with PERPEST: high risk to algae (maximum msPAF: 73 %), aquatic plants (61 %), and arthropods (25 %) and low risk to fish (0.2 %) from pesticide mixtures. The pesticides posing the highest risks according to msPAF and that should be substituted with less toxic substances were the herbicides ametryn, diuron, the insecticides carbaryl, chlorpyrifos, diazinon, ethoprophos, and the fungicide difenoconazole. Ecological risks were highest near the plantations and decreased progressively further downstream. The risk to fish was found to be relatively low in these models, but water samples were not collected during fish kill events and some highly toxic pesticides known to be used were not analyzed for in this study. Further sampling and analysis of water samples is needed to determine toxicity risks to fish during peaks of pesticide mixture concentrations. The msPAF model, which estimates the ecological risks of mixtures based on their toxic modes of action, was found to be the most suitable model to assess toxicity risks to aquatic organisms in the RMD. The PERPEST model was found to be a strong tool for screening risk assessments. The SSD approach is useful in deriving water quality criteria for specific pesticides. This study, through the application of three ERA models, clearly shows that pesticides used in plantations within the RMD watershed are expected to have severe adverse effects on most groups of aquatic organisms and that actions are urgently needed to reduce pesticide pollution in this high biodiversity ecosystem.

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.