Earthworm injury test for in-situ biomonitoring of pesticides in biobeds.

Biobeds are presented as an alternative for good pesticide wastewater management on farms. This work proposes a new test for in-situ biomonitoring of pesticide detoxification in biobeds. It is based on the assessment of visually appreciable injuries to Eisenia fetida. The severity of the injury to each exposed individual is assessed from the morphological changes observed in comparison with the patterns established in seven categories and, an injury index is calculated. A linear relationship between the proposed injury index and the pesticide concentration was determined for each pesticide sprayed individually in the biomixture. The five pesticides used were atrazine, prometryn, clethodim, haloxyfop-P-methyl and dicamba. In addition, a multiple linear regression model (i.e., a multivariate response surface) was fitted, which showed a good generalization capacity. The sensitivity range of the injury test was tested from 0.01 to 630 mg kg-1 as the total pesticide concentration. This index is then used to monitor the detoxification of these pesticides in a biomixture (composed of wheat stubble, river waste, and soil, 50:25:25% by volume) over 210 days. The results are compared with standardized tests (Eisenia fetida avoidance test and Lactuca sativa seed germination test) carried out on the same biomixture. The results are also compared with data on the removal of pesticides. The injury test showed a better correlation with the removal of pesticides than the avoidance test and seed germination test. This simple and inexpensive test has proved to be useful for decontamination in-situ monitoring in biobeds.

Earthworms to improve glyphosate degradation in biobeds.

In this work, earthworm effect on the efficiency of biobeds for glyphosate degradation was studied. Three biomixtures with and without the addition of earthworms (Eisenia fetida species) were evaluated. The initial concentration of glyphosate was 1000 mg/kg biomixture. Glyphosate and biological parameters were measured as a function of time. Earthworm survival, biomass, and reproduction were evaluated as well. All biomixtures that contain earthworms reached 90% of glyphosate degradation at 90 days in comparison with the biomixtures without earthworms that reached 80% approximately at the same time. Also, within the biomixtures that contained earthworms, glyphosate degradation rate was significantly higher in the one made up with soil and wheat stubble (Ws-E) showing excellent capacity for aminomethylphosphonic acid (AMPA) degradation, the main metabolite of glyphosate degradation. In addition, a study performed after the vermiremediation process showed that E. fetida can tolerate high glyphosate concentration without modifications in its life traits. It can be concluded that the use of E. fetida within the biobeds is an excellent combination to improve glyphosate and AMPA removal.

Earthworms to assess the innocuousness of spent biomixtures employed for glyphosate degradation.

In this study, the innocuousness of different biomixtures employed for glyphosate degradation was tested through Eisenia fetida earthworms. Eight biomixtures were prepared with local materials: alfalfa straw (AS), wheat stubble (WS), river waste (RW) and two different soils (A and B). Each biomixture was divided into two equal portions: one without glyphosate application (control substrate) and the other was sprayed with a commercial glyphosate formulation of 1,000 mg glyphosate a.i. kg-1 biomixture (applied substrate). The bioassay started when all sprayed biomixtures reached high percentages of glyphosate degradation (spent biomixtures). Three parameters were studied: survival, adults and juveniles biomass and reproduction. The results allowed the identification of three biomixtures (AWS, BWS and BWSRW) for good maintenance and development of E. fetida. In addition, at the end of the bioassay two of the viable biomixtures (AWS and BWS) showed the highest performance of juvenile earthworms compared to a reference soil. The Principal Component Analysis (PCA) indicated that the biomixtures containing high silt and clay percentages and minor density renders higher values of earthworm growth and reproduction. Therefore, these innocuous biomixtures can be used as organic amendments or recycled materials for new treatments on biobeds.

Arsenic sorption onto titanium dioxide, granular ferric hydroxide and activated alumina: batch and dynamic studies.

The aim of this work was to evaluate and compare the efficiencies of three different adsorbents for arsenic (As) removal from water: titanium dioxide (TiO2), granular ferric hydroxide (GFH) and activated alumina (AA). Equilibrium experiments for dissolved arsenite and arsenate were carried out through batch tests. Freundlich and Langmuir isotherm models were adopted and their parameters were estimated by non-linear regressions. In addition, dynamic experiments were performed in mini fixed bed columns and breakthrough curves were obtained for each combination of sorbate/adsorbent. Experimental results obtained by column assays were compared with predictions of well-known breakthrough models (Bohart-Adams and Clark). Results indicate that As(V) is more easily adsorbed than As(III) for AA and GFH, while TiO2 has a similar behavior for both species. The titanium-based material is the most efficient adsorbent to carry out the process, followed by the GFH.

Modeling of degradation kinetic and toxicity evaluation of herbicides mixtures in water using the UV/H2O2 process.

The UV/H2O2 process was applied to the treatment of different mixtures of herbicides in water. Glyphosate, the herbicide most used in the world, was mixed with other hormonal herbicides with residual activity as 2,4-D and dicamba. The main goals of the study were to develop a kinetic model for interpreting the simultaneous oxidation of two mixtures (glyphosate plus 2,4-D and glyphosate plus dicamba). The model is based on a complete reaction mechanism, which comprises hydrogen peroxide photolysis and decomposition of both herbicides in each mixture studied. It takes into account the effect of non-uniform distribution of the local rate of absorbed photons. Good agreement of experimental data and the model is achieved in spite of differences in the reactivity between glyphosate and 2,4-D (or dicamba). Toxicity assays (employing Vibrio fischeri) were also performed, indicating that the toxicity of the mixture of glyphosate and 2,4-D was significantly reduced after the treatment.

Effectiveness evaluation of glyphosate oxidation employing the H(2)O(2)/UVC process: toxicity assays with Vibrio fischeri and Rhinella arenarum tadpoles.

The H(2)O(2)/UVC process was applied to the photodegradation of a commercial formulation of glyphosate in water. Two organisms (Vibrio fischeri bacteria and Rhinella arenarum tadpoles) were used to investigate the toxicity of glyphosate in samples M(1,) M(2), and M(3) following different photodegradation reaction times (120, 240 and 360 min, respectively) that had differing amounts of residual H(2)O(2). Subsamples of M(1), M(2), and M(3) were then used to create samples M(1,E), M(2,E) and M(3,E) in which the H(2)O(2) had been removed. Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities were measured in tadpoles to determine possible sub-lethal effects. In V. fischeri, M(1,E), which was collected early in the photodegradation process, caused 52% inhibition, while M(3,E), which was collected at the end of the photodegradation process, caused only 17% inhibition. Survival of tadpoles was 100% in samples M(2), M(3), and in M(1,E), M(2,E) and M(3,E). The lowest percentages of enzymatic inhibition were observed in samples without removal of H(2)O(2): 13.96% (AChE) and 16% (BChE) for M(2), and 24.12% (AChE) and 13.83% (BChE) for M(3). These results show the efficiency of the H(2)O(2)/UVC process in reducing the toxicity of water or wastewater polluted by commercial formulations of glyphosate. According to the ecotoxicity assays, the conditions corresponding to M(2) (11 ± 1 mg a.e. L(-1) glyphosate and 11 ± 1 mg L(-1) H(2)O(2)) could be used as a final point for glyphosate treatment with the H(2)O(2)/UV process.

Arsenic (III) oxidation of water applying a combination of hydrogen peroxide and UVC radiation.

Arsenic is toxic to both plants and animals and inorganic arsenicals are proven carcinogens in humans. The oxidation of As(III) to As(v) is desirable for enhancing the immobilization of arsenic and is required for most arsenic removal technologies. The main objective of this research is to apply an Advanced Oxidation Process that combines ultraviolet radiation and hydrogen peroxide (UVC/H(2)O(2)) for oxidizing aqueous solutions of As(III). For that purpose, a discontinuous photochemical reactor (laboratory scale) was built with two 40 W tubular germicidal lamps (λ = 253.7 nm) operating inside a recycling system. The study was made beginning with a concentration of 200 µg L(-1) of As(III), changing the H(2)O(2) concentration and the spectral fluence rate on the reactor windows. Based on references in the literature on the photolysis of hydrogen peroxide, arsenic oxidation and our experimental results, a complete reaction scheme, apt for reaction kinetics mathematical modelling, is proposed. In addition, the effectiveness of arsenic oxidation was evaluated using a raw groundwater sample. It is concluded that the photochemical treatment of As(III) using H(2)O(2) and UVC radiation is a simple and feasible technique for the oxidation of As(III) to As(v).

Dichloroacetic acid degradation employing hydrogen peroxide and UV radiation.

The degradation reaction of dichloroacetic acid employing H(2)O(2) and UVC radiation (253.7nm) has been studied in a well mixed reactor operating inside a recycling system. It has been shown that in an aqueous solution no stable reaction intermediates are formed and, at every time during the reaction, two mols of hydrochloric acid are formed for every mol of dichloroacetic acid that is decomposed and, in the same way, there is a paired agreement between the calculated TOC concentration corresponding to the unaltered dichloroacetic acid and the experimental values measured in the solution. On this basis and classical references from the scientific literature for the H(2)O(2) photolysis, a complete reaction scheme, apt for reaction kinetics mathematical modeling and ulterior scale-up is proposed.