Pesticide monitoring and ecotoxicological risk assessment in surface water bodies and sediments of a tropical agro-ecosystem.

A pesticide monitoring study including 80 and 60 active ingredients (in surface waters and sediments, respectively) was carried out in a river basin in Costa Rica during 2007-2012. A special emphasis was given on the exceptional ecological conditions of the tropical agro-ecosystem and the pesticide application strategies in order to establish a reliable monitoring network. A total of 135 water samples and 129 sediment samples were collected and analyzed. Long-term aquatic ecotoxicological risk assessment based on risk quotient in three trophic levels was conducted. Short-term risk assessment was used to calculate the toxic unit and prioritization of sampling sites was conducted by the sum of toxic units in both aquatic and sediment compartments. Dimethoate (61.2 µg/L), propanil (30.6 µg/L), diuron (22.8 µg/L) and terbutryn (4.8 µg/L) were detected at the highest concentrations in water samples. Carbendazim and endosulfan were the most frequently detected pesticides in water and sediment samples, respectively. Triazophos (491 µg/kg), cypermethrin (71.5 µg/kg), permethrin (47.8 µg/kg), terbutryn (38.7 µg/kg), chlorpyrifos (18.2 µg/kg) and diuron (11.75 µg/kg) were detected at the highest concentrations in sediment samples. The pesticides carbendazim, diuron, endosulfan, epoxyconazole, propanil, triazophos and terbutryn showed non-acceptable risk even when a conservative scenario was considered. Sum TUsite higher than 1 was found for one and two sampling sites in water and sediment compartments, respectively, suggesting high acute toxicity for the ecosystem. MAIN FINDING OF THE WORK: Exceptional ecological conditions of the tropical agro-ecosystem affect the fate of pesticides in water and sediment environment differently than the temperate one.

Expanding the application scope of on-farm biopurification systems: Effect and removal of oxytetracycline in a biomixture.

Antibiotic-containing wastewaters produced in agricultural activities may depress the pesticide-degrading capacity of biomixtures contained in biopurification systems. This work aimed to assay the effect of oxytetracycline (OTC) on the removal of carbofuran (CFN) in an optimized biomixture, and to determine the capacity of the system to dissipate OTC. During co-application of CFN+OTC, CFN removal and its accelerated degradation were not negatively affected. Similarly, different doses of OTC (10-500mgkg-1) did not significantly affect CFN mineralization, and the process even exhibited a hormetic-like effect. Moreover, the biomixture was able to remove OTC with a half-life of 34.0 d. DGGE-cluster analyses indicated that fungal and bacterial communities remained relatively stable during OTC application and CFN+OTC co-application, with similarities of over 70% (bacteria) and 80% (fungi). Overall, these findings support the potential use of this matrix to discard OTC-containing wastewater in this system originally intended for CFN removal.

Effects of oxytetracycline on the performance and activity of biomixtures: Removal of herbicides and mineralization of chlorpyrifos.

Biopurification systems (BPS) are design to remove pesticides from agricultural wastewater. This work assays for the first time the potential effect of an antibiotic of agricultural use (oxytetracycline, OTC) on the performance of a biomixture (biologically active core of BPS), considering that antibiotic-containing wastewaters are also produced in agricultural labors. The respiration of the biomixture was stimulated in the presence of increasing doses of OTC (≥100mgkg-1), and only slightly increased with lower doses (≤10mgkg-1). When co-applied during the removal of chlorpyrifos, OTC increased chlorpyrifos mineralization rates at low doses, resembling a hormetic effect. The biomixture was also able to remove three herbicides (atrazine, ametryn and linuron) with half-lives of 24.3 d, 43.9 d and 30.7 d; during co-application of OTC at a biomixture-relevant concentration, only the removal of ametryn was significantly inhibited, increasing its half-life to 92.4 d. Ecotoxicological assays revealed that detoxification takes place in the biomixture during the removal of herbicides in the presence of OTC. Overall results suggest that co-application of OTC in a biomixture does not negatively affect the performance of the matrix in every case; moreover, the co-application of this antibiotic could improve the mineralization of some pesticides.

Removal of carbamates and detoxification potential in a biomixture: Fungal bioaugmentation versus traditional use.

The use of fungal bioaugmentation represents a promising way to improve the performance of biomixtures for the elimination of pesticides. The ligninolyitc fungus Trametes versicolor was employed for the removal of three carbamates (aldicarb, ALD; methomyl, MTM; and methiocarb, MTC) in defined liquid medium; in this matrix ALD and MTM showed similar half-lives (14d), nonetheless MTC exhibited a faster removal, with a half-life of 6.5d. Then the fungus was employed in the bioaugmentation of an optimized biomixture to remove the aforementioned carbamates plus carbofuran (CFN). Bioaugmented and non-bioaugmented systems removed over 99% ALD and MTM after 8d of treatment, nonetheless a slight initial delay in the removal was observed in the bioaugmented biomixtures (removal after 3d: ALD 87%/97%; MTM 86%/99%, in bioaugmented/non-bioaugmented systems). The elimination of the other carbamates was slower, but independent of the presence of the fungus: >98% for MTM after 35d and >99.5% for CFN after 22d. Though the bioaugmentation did not improve the removal capacity of the biomixture, it favored a lower production of transformation products at the first stages of the treatment, and in both cases, a marked decrease in the toxicity of the matrix was swiftly achieved along the process (from 435 to 448 TU to values <1TU in 16d).

Simultaneous removal of structurally different pesticides in a biomixture: Detoxification and effect of oxytetracycline.

The biopurification systems (BPS) used for the treatment of pesticide-containing wastewater must present a versatile degrading ability, in order to remove different active ingredients according to the crop protection programs. This work aimed to assay the simultaneous removal of several pesticides (combinations of herbicides/insecticides/fungicides, or insecticides/fungicides) in a biomixture used in a BPS over a period of 115 d, and in the presence of oxytetracycline (OTC), an antibiotic of agricultural use that could be present in wastewater from agricultural pesticide application practices. The biomixture was able to mostly remove the herbicides during the treatment (removal rates: atrazine ≈ linuron > ametryn), and suffered no inhibition by OTC (only slightly for ametryn). Two fungicides (carbendazim and metalaxyl) were removed, nonetheless, in the systems containing only fungicides and insecticides, a clear increase in their half-lives was obtained in the treatments containing OTC. The neonicotinoid insecticides (imidacloprid and thiamethoxam) and the triazole fungicides (tebuconazole and triadimenol) were not significantly eliminated in the biomixture. Globally, the total removal of active ingredients ranged from 40.9% to 61.2% depending on the system, following the pattern: herbicides > fungicides > insecticides. The ecotoxicological analysis of the process revealed no detoxification towards the microcrustacean Daphnia magna, but a significant decay in the phytotoxicity towards Lactuca sativa in some cases, according to seed germination tests; in this case, OTC proved to be partially responsible for the phytotoxicity. The patterns of pesticide removal and detoxification provide inputs for the improvement of BPS use and their relevance as devices for wastewater treatment according to specific pesticide application programs.

Removal of carbofuran is not affected by co-application of chlorpyrifos in a coconut fiber/compost based biomixture after aging or pre-exposure.

Biomixtures constitute the biologically active part of biopurification systems (BPS), which are used to treat pesticide-containing wastewater. The aim of this work was to determine whether co-application of chlorpyrifos (CLP) affects the removal of carbofuran (CFN) (both insecticide/nematicides) in a coconut fiber-compost-soil biomixture (FCS biomixture), after aging or previous exposure to CFN. Removal of CFN and two of its transformation products (3-hydroxycarbofuran and 3-ketocarbofuran) was enhanced in pre-exposed biomixtures in comparison to aged biomixtures. The co-application of CLP did not affect CFN removal, which suggests that CLP does not inhibit microbial populations in charge of CFN transformation. Contrary to the removal behavior, mineralization of radiolabeled (14)C-pesticides showed higher mineralization rates of CFN in aged biomixtures (with respect to freshly prepared or pre-exposed biomixtures). In the case of CLP, mineralization was favored in freshly prepared biomixtures, which could be ascribed to high sorption during aging and microbial inhibition by CFN in pre-exposure. Regardless of removal and mineralization results, toxicological assays revealed a steep decrease in the acute toxicity of the matrix on the microcrustacean Daphnia magna (over 97%) after 8days of treatment of individual pesticides or the mixture CFN/CLP. Results suggest that FCS biomixtures are suitable to be used in BPS for the treatment of wastewater in fields where both pesticides are employed.

Design of an optimized biomixture for the degradation of carbofuran based on pesticide removal and toxicity reduction of the matrix.

Pesticide biopurification systems contain a biologically active matrix (biomixture) responsible for the accelerated elimination of pesticides in wastewaters derived from pest control in crop fields. Biomixtures have been typically prepared using the volumetric composition 50:25:25 (lignocellulosic substrate/humic component/soil); nonetheless, formal composition optimization has not been performed so far. Carbofuran is an insecticide/nematicide of high toxicity widely employed in developing countries. Therefore, the composition of a highly efficient biomixture (composed of coconut fiber, compost, and soil, FCS) for the removal of carbofuran was optimized by means of a central composite design and response surface methodology. The volumetric content of soil and the ratio coconut fiber/compost were used as the design variables. The performance of the biomixture was assayed by considering the elimination of carbofuran, the mineralization of (14)C-carbofuran, and the residual toxicity of the matrix, as response variables. Based on the models, the optimal volumetric composition of the FCS biomixture consists of 45:13:42 (coconut fiber/compost/soil), which resulted in minimal residual toxicity and ∼99% carbofuran elimination after 3 days. This optimized biomixture considerably differs from the standard 50:25:25 composition, which remarks the importance of assessing the performance of newly developed biomixtures during the design of biopurification systems.

Adaptation of biomixtures for carbofuran degradation in on-farm biopurification systems in tropical regions.

A biomixture constitutes the active core of the on-farm biopurification systems, employed for the detoxification of pesticide-containing wastewaters. As biomixtures should be prepared considering the available local materials, the present work aimed to evaluate the performance of ten different biomixtures elaborated with by-products from local farming, in the degradation of the insecticide/nematicide carbofuran (CFN), in order to identify suitable autochthonous biomixtures to be used in the tropics. Five different lignocellulosic materials mixed with either compost or peat and soil were employed in the preparation of the biomixtures. The comprehensive evaluation of the biomixtures included removal of the parent compound, formation of transformation products, mineralization of radiolabeled CFN, and determination of the residual toxicity of the process. Detoxification capacity of the matrices was high, and compost-based biomixtures showed better performance than peat-based biomixtures. CFN removal over 98.5% was achieved within 16 days (eight out of ten biomixtures), with half-lives below 5 days in most of the cases. 3-Hydroxycarbofuran and 3-ketocarbofuran were found as transformation products at very low concentrations suggesting their further degradation. Mineralization of CFN was also achieved after 64 days (2.9 to 15.1%); several biomixtures presented higher mineralization than the soil itself. Acute toxicity determinations with Daphnia magna revealed a marked detoxification in the matrices at the end of the process; low residual toxicity was observed only in two of the peat-based biomixtures. Overall best efficiency was achieved with the biomixture composed of coconut fiber-compost-soil; however, results suggest that in the case of unavailability of coconut fiber, other biomixtures may be employed with similar performance.

Accelerated biodegradation of selected nematicides in tropical crop soils from Costa Rica.

Degradation and mineralization behavior of selected nematicides was studied in soil samples from fields cultivated with banana, potato, and coffee. Degradation assays in most of the studied soils revealed shorter half-lives for carbofuran (CBF) and ethoprophos (ETP) in samples with a history of treatment with these compounds, which may have been caused by enhanced biodegradation. A short half-life value for CBF degradation was also observed in a banana field with no previous exposure to this pesticide, but with a recent application of the carbamate insecticide oxamyl, which supports the hypothesis that preexposure to oxamyl may cause microbial adaptation towards degradation of CBF, an observation of a phenomenon not yet tested according to the literature reviewed. Mineralization assays for CBF and terbufos (TBF) revealed that history of treatment with these nematicides did not cause higher mineralization rates in preexposed soils when compared to unexposed ones, except in the case of soils from coffee fields. Mineralization half-lives for soils unexposed to these pesticides were significantly shorter than most reports in the literature in the same conditions. Mineralization rates for soils with a previous exposure to these pesticides were also obtained, adding to the very few reports found. This paper contributes valuable data to the low number of reports dealing with pesticide fate in soils from tropical origin.

On-farm biopurification systems: role of white rot fungi in depuration of pesticide-containing wastewaters.

Environmental contamination with pesticides is an undesired consequence of agricultural activities. Biopurification systems (BPS) comprise a novel strategy to degrade pesticides from contaminated wastewaters, consisting of a highly active biological mixture confined in a container or excavation. The design of BPS promotes microbial activity, in particular by white rot fungi (WRF). Due to their physiological features, specifically the production of highly unspecific ligninolytic enzymes and some intracellular enzymatic complexes, WRF show the ability to transform a wide range of organic pollutants. This minireview summarizes the potential participation of WRF in BPS. The first part presents the potential use of WRF in biodegradation of pollutants, particularly pesticides, and includes a brief description of the enzymatic systems involved in their oxidation. The second part presents an outline of BPS, focusing on the elements that influence the participation of WRF in their operation, and includes a summary of the studies regarding the fungal-mediated degradation of pesticides in BPS biomixtures and other solid-phase systems that mimic BPS.