The occurrence of organic pollutants in soil is a major environmental concern. These compounds can reach the soil in different ways. Point sources, related to pesticides that are used intentionally, can be applied directly to the soil, or reach the soil indirectly due to application to the aerial parts of crops. On the other hand, non-point sources, which reach soils collaterally during irrigation and/or fertilization, or due to the proximity of plots to industrialized urban centers. Long-range transport of global organic pollutants must also be taken into account. In this study, 218 pesticides, 49 persistent organic pollutants, 37 pharmaceutical active compounds and 6 anticoagulant rodenticides were analyzed in 139 agricultural soil samples collected between 2018 and 2020 in the Macaronesia. This region comprised four inhabited archipelagos (Azores, Canary Islands, Cape Verde, and Madeira) for which agriculture is an important and traditional economic activity. To our knowledge, this is the first study on the levels of organic compound contamination of agricultural soils of the Macaronesia. As expected, the most frequently detected compounds were pesticides, mainly fungicides and insecticides. The Canary Islands presented the highest number of residues, with particularly high concentrations of DDT metabolites (p,p’ DDE: 149.5 ± 473.4 ng g⁻¹; p,p’ DDD: 16.6 ± 35.6 ng g⁻¹) and of the recently used pesticide fenbutatin oxide (302.1 ± 589.7 ng g⁻¹). Cape Verde was the archipelago with the least contaminated soils. Very few pharmaceutical active compounds have been detected in all archipelagos (eprinomectin, fenbendazole, oxfendazole and sulfadiazine). These results highlight the need to promote soil monitoring programs and to establish maximum residue limits in soils, which currently do not exist at either continental or local level.

Benzimidazoles are anthelmintics frequently used in sheep farming due to the high susceptibility of these animals to parasitic diseases. Sheep excreta are often disposed onto soils as a fertilizer, and they may contain benzimidazole residues that can contaminate soil and water. This work aimed to assess the leaching behavior of benzimidazole drugs (albendazole, fenbendazole, and thiabendazole) and their metabolites in two Brazilian soils of different textural classifications (sandy and clay), as well as sheep excreta-amended soils, following the OECD 312 Guidelines. Ewes received a single oral dose of 10 mg kg⁻¹ b.w. of either albendazole or fenbendazole. The feces were collected at 24, 48, 72, 96, and 120 h post-dose, and the parent drugs and their metabolites extracted using the QuEChERS approach and quantified by UHPLC-MS/MS. For the leaching assays, a benzimidazole solution was directly applied onto the soil columns, or an amount of 5 g of the medicated sheep feces was distributed over the top of the soil columns. In soil samples, benzimidazoles were extracted by solid-liquid extraction and quantified by UHPLC-MS/MS. For the leaching studies, atrazine was used as a reference substance to determine the relative mobility factor of the analytes of interest. Benzimidazoles were considered slightly to moderately mobile in both soils tested, with a leaching distance of up to 25 cm in a 30-cm soil column. Approximately 3 to 6% of the benzimidazoles present in ewe feces were able to leach into the soil columns. This finding is of concern since benzimidazoles are persistent in soil and may pose a risk to soil biota and induce the development of resistant strains of parasites.

Benzimidazoles (BZ) are among the most used drugs to treat parasitic diseases in both human and veterinary medicine. In this study, solutions fortified with albendazole (ABZ), fenbendazole (FBZ), and thiabendazole (TBZ) were subjected to photoperoxidation (UV/H₂O₂). The hydroxyl radicals generated by the process removed up to 99% of ABZ, and FBZ, in the highest dosage of H₂O₂ (i.e., 1.125 mmol L⁻¹; 4.8 kJ L⁻¹). In contrast, 20% of initial TBZ concentration remained in the residual solution. In the first 5 min of reaction (i.e., up to 0.750 mmol L⁻¹ of H₂O₂), formation of the primary metabolites of ABZ—ricobendazole (RBZ), albendazole sulfone (ABZ-SO₂), and oxfendazole (OFZ)—was observed. However, these reaction products were converted after the reaction time was doubled. The residual ecotoxicity was investigated using the Raphidocelis subcapitata microalgae and the marine bacteria Vibrio fischeri. The results for both microorganisms evidence that the residual solutions are less harmful to these microorganisms. However, after 30 min of reaction, the treated solution still presents a toxic effect for V. fischeri, meaning that longer reaction times are required to achieve an innocuous effluent.

Febantel is widely used anthelmintic drug active against a range of gastrointestinal parasites in animals. Despite the fact that it has been detected in the aquatic environment, there is no information on its environmental fate. Therefore, abiotic elimination processes of febantel in the aquatic environment have been studied. The results of direct and indirect photodegradation experiments showed that febantel was persistent against solar radiation. Kinetics of hydrolytic elimination was pH and temperature dependent with half-lives in the range from 210 min to 99 days. Febantel metabolites, fenbendazole and fenbendazole sulfone, were found as major degradation products using high-resolution mass spectrometry. The proposed hydrolytic degradation pathway consisted of the base catalyzed hydrolysis followed by consecutive oxidative cyclization to the five-membered ring of the benzo-imidazole derivative. Aquatic toxicity of febantel and its hydrolytic mixture were evaluated toward the luminescence bacteria Vibrio fischeri. Investigation of febantel sorption onto river sediments showed that the best agreement was obtained with the linear model (R² > 0.99), while the rate of sorption is the best described with the kinetic model of pseudo-second order. The organic carbon-normalized sorption coefficient, KOC, ranged from 1490 to 3894 L kg⁻¹ for five sediment samples. The results of this research demonstrate that febantel persist in the natural waters and potentially could travel far from the source.

Flubendazole (FLU) and fenbendazole (FEN) belong to benzimidazoles—pharmaceuticals widely used in veterinary and human medicine for the treatment of intestinal parasites as well as for the treatment of systemic worm infections. In recent years, usage of these drugs increased, which resulted in a larger contamination of the environment and possible negative effects on biota. Hence, in our research, we investigated an aquatic ecotoxicity of these pharmaceuticals towards: marine bacteria (Vibrio fischeri), green algae (Scenedesmus vacuolatus), duckweed (Lemna minor) and crustacean (Daphnia magna). Ecotoxicity tests were combined with chemical analysis in order to investigate the actual exposure concentration of the compounds used in the experiment as well as to stability and adsorption studies. As a result, study evaluating sensitivity of different aquatic organisms to these compounds and new ecotoxicological data is presented. The strongest negative impact of FLU and FEN was observed to D. magna.