Cristina Susana Zalazar

Glyphosate degradation in water employing the H2O2/UVC process

Glyphosate is the organophosphate herbicide most widely used in the world. Any form of spill or discharge, even if unintentional, can be transferred to the water due to its high solubility. The combination of hydrogen peroxide and UV radiation could be a suitable option to decrease glyphosate concentration to acceptable limits. In this work, the effects of initial pH, hydrogen peroxide initial concentration, and incident radiation in glyphosate degradation were studied. The experimental device was a cylinder irradiated with two tubular, germicidal lamps. Conversion of glyphosate increases significantly from pH = 3-7. From this value on, the increase becomes much less noticeable. The reaction rate depends on the initial herbicide concentration and has an optimum plateau of a hydrogen peroxide to glyphosate molar concentration ratio between 7 and 19. The expected non linear dependence on the irradiation rate was observed. The identification of critical reaction intermediaries, and the quantification of the main end products were possible and it led to propose a plausible degradation path. The achieved quantification of the mineralization extent is a positive indicator for the possible application of a rather simple technology for an in situ solution for some of the problems derived from the intensive use of glyphosate.

Scaling up of a photoreactor for formic acid degradation employing hydrogen peroxide and UV radiation

A model for scaling up a homogeneous photoreactor was developed and experimentally verified in a pilot-plant-size apparatus. The procedure is exemplified by the oxidation of dilute aqueous HCOOH solutions with UV radiation (254 nm) and H2O2. First, the kinetic model and the kinetic parameters of the HCOOH degradation were obtained in a well-stirred, small, batch flat-plate photoreactor (volume=70 ml). The method employed in the analysis of the experimental results yielded reaction-rate expressions for HCOOH and H2O2 that were independent of the reactor configuration. These kinetic equations and the corresponding kinetic constants were then used in a mathematical, fully deterministic model of a continuous-flow, 2-m-long, annular reactor (0.0065 m2 of cross section for flow) operating in a laminar-flow regime to predict exit concentrations of HCOOH. Irradiation was provided in both cases by two different types of germicidal lamps. No additional experiments were made to adjust the reactor-model parameters. Theoretical predictions from the representation of the reactor performance obtained were compared with experimental data furnished by experiments in the much-larger-size, cylindrical-flow reactor. Results showed good agreement for the range of variables explored; they corresponded to expected operating conditions in water streams polluted with low concentrations of organic compounds.

Effectiveness evaluation of glyphosate oxidation employing the H2O2/UVC process: Toxicity assays with Vibrio fischeri and Rhinella arenarum tadpoles

The H2O2/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 M1, M2, and M3 following different photodegradation reaction times (120, 240 and 360 min, respectively) that had differing amounts of residual H2O2. Subsamples of M1, M2, and M3 were then used to create samples M1,E, M2,E and M3,E in which the H2O2 had been removed. Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities were measured in tadpoles to determine possible sub-lethal effects. In V. fischeri, M1,E, which was collected early in the photodegradation process, caused 52% inhibition, while M3,E, which was collected at the end of the photodegradation process, caused only 17% inhibition. Survival of tadpoles was 100% in samples M2, M3, and in M1,E, M2,E and M3,E. The lowest percentages of enzymatic inhibition were observed in samples without removal of H2O2: 13.96% (AChE) and 16% (BChE) for M2, and 24.12% (AChE) and 13.83% (BChE) for M3. These results show the efficiency of the H2O2/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 M2 (11 ± 1 mg a.e. L−1 glyphosate and 11 ± 1 mg L−1 H2O2) could be used as a final point for glyphosate treatment with the H2O2/UV process.

Water disinfection with UVC radiation and H2O2. A comparative study

A generalized kinetic model resulting from several modifications of the one originally known as the Series Event Model has been applied to describe three different disinfection processes and compare their efficiencies. The work was performed in a well-defined, versatile batch reactor employing Escherichia coli as a subrogate bacteria. The following systems were studied: (i) UVC radiation alone, (ii) hydrogen peroxide alone and (iii) UVC radiation combined with hydrogen peroxide. The kinetic parameters of the three models were determined. Within the range of studied operating conditions, the use of UVC alone has shown to produce the best results.

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.

Degradation of a mixture of pollutants in water using the UV/H2O2 process.

The degradation reaction of a simple mixture of pollutants (dichloroacetic acid + formic acid) employing H2O2 and UVC radiation (253.7 nm) has been studied in a well-mixed reactor which operates inside a recycling system. The aim of this work is to develop a systematic methodology for treating degradation of mixtures of pollutants, starting from a rather manageable system to more complex aggregates. In this contribution, the effects of different variables such as hydrogen peroxide/pollutant mixture initial concentration ratio, pH and incident radiation at the reactor wall were studied. The results show that the best degrading conditions are: pH = 3.5 and hydrogen peroxide concentrations from 3.9 to 11.8 mM (134-400 mg/L), for initial concentrations of 1.10 and 0.39 mM for formic acid and dichoroacetic acid respectively (50 mg/L for both pollutants). The influence of the incident radiation at the reactor wall on the degradation rates of the mixture is significant. In addition to this, it has been shown that in the employed aqueous solution no stable reaction intermediates are formed. On this basis, a complete reaction scheme for the mixture is proposed that is suitable for a reaction kinetics mathematical modeling of the mixture and further studies of increasing complexity.

Arsenic removal from water employing a combined system: photooxidation and adsorption

A combined system employing photochemical oxidation (UV/H2O2) and adsorption for arsenic removal from water was designed and evaluated. In this work, a bench-scale photochemical annular reactor was developed being connected alternately to a pair of adsorption columns filled with titanium dioxide (TiO2) and granular ferric hydroxide (GFH). The experiences were performed by varying the relation of As concentration (As (III)/As (V) weight ratio) at constant hydrogen peroxide concentration and incident radiation. Experimental oxidation results were compared with theoretical predictions using an intrinsic kinetic model previously obtained. In addition, the effectiveness of the process was evaluated using a groundwater sample. The mathematical model of the entire system was developed. It could be used as an effective tool for the design and prediction of the behaviour of these types of systems. The combined technology is efficient and promising for arsenic removal to small and medium scale.

Advanced oxidation of commercial herbicides mixture: experimental design and phytotoxicity evaluation

In this work, the suitability of the UV/H2O2 process for commercial herbicides mixture degradation was studied. Glyphosate, the herbicide most widely used in the world, was mixed with other herbicides that have residual activity as 2,4-D and atrazine. Modeling of the process response related to specific operating conditions like initial pH and initial H2O2 to total organic carbon molar ratio was assessed by the response surface methodology (RSM). Results have shown that second-order polynomial regression model could well describe and predict the system behavior within the tested experimental region. It also correctly explained the variability in the experimental data. Experimental values were in good agreement with the modeled ones confirming the significance of the model and highlighting the success of RSM for UV/H2O2 process modeling. Phytotoxicity evolution throughout the photolytic degradation process was checked through germination tests indicating that the phytotoxicity of the herbicides mixture was significantly reduced after the treatment. The end point for the treatment at the operating conditions for maximum TOC conversion was also identified.

Microparticles based on ionic and organosolv lignins for the controlled release of atrazine

Lignins are natural polymers of the lignocellulosic biomass. Nowadays, there is a growing interest in developing value-added products based on lignins due to their renewability, low cost and abundance. In this work, lignin microspheres from organosolv and ionic isolation processes were prepared for the controlled release of atrazine. Microspheres were prepared by the solvent extraction/evaporation technique. The controlled release of atrazine from organosolv and ionic lignins microparticles was studied in water. Mobility experiments were performed in an agricultural soil from Argentina. The results showed that microparticles prepared using dichloromethane as the dispersed phase were spherical, while lignins dispersed in ethyl acetate produce irregular microparticles. Organosolv lignin microparticles presented higher encapsulation efficiency for all herbicide loads. About 98% and 95% of atrazine was released in 24 and 48 h approximately from organosolv and ionic lignin microparticles, respectively. The release profiles of atrazine from both lignin microparticles were not affected by the herbicide load. Atrazine mobility experiments in soil showed that about 80% of free atrazine was leached in 37 days, while 65.0% and 59.7% of the herbicide was leached from ionic and organosolv lignin microparticles, respectively. Thus, atrazine-loaded microparticles could reduce leaching compared to a commercial formulation of free atrazine.

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

ABSTRACT 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.