Oxone-promoted wet air oxidation of landfill leachates

Landfill leachates of the city of Badajoz (in the southwest of Spain) have been treated by wet air oxidation at high temperature (180-270 °C) and pressure (40-70 atm). Typical operating variables such as temperature and oxygen partial pressure have been investigated with no effect of any being found and moderate to low chemical oxygen demand conversions (20-30% depending on initial COD concentration). Initial pH shows a positive influence when acidic conditions are used. Addition of hydrogen peroxide (0.01 M) as a hydroxyl radical promoter is able to provide an additional 15% increase in the final COD removal achieved. If a sulfate radical promoter is used (i.e., Oxone) the process is significantly improved, with COD conversions in the range 60-80%, also depending on the initial COD of the leachates. A first attempt to comprehend the chemistry of this oxidizing system suggests an instantaneous decomposition of Oxone that initiates the radical chain also involving hydroxyl and organic radicals

Fenton-like oxidation of landfill leachate

The treatment of stabilized leachates by means of Fenton's like reagent [Fe(III)-H2O2] has been studied. It has been demonstrated that the oxidation state of the catalyst does not influence the efficacy of the process in terms of chemical oxygen demand depletion profiles. The abrupt increase in temperature experienced in oxidation experiments involves a wastage of hydrogen peroxide diminishing the fraction of this reagent addressed at removing COD. If temperature is kept constant, the hydrogen peroxide uptake is 10 mg of H2O2 consumed per mg of COD abated (from 15 to 30°C). Working temperatures above 30°C does not lead to additional COD conversion, contrarily, the percentage of wasted H2O2 is increased. A rough economic analysis of the process indicates that this treatment can be a suitable alternative to deal with this type of effluents

Stabilized leachates: sequential coagulation–flocculation + chemical oxidation process

The combined sedimentation-chemical oxidation treatment of medium-stabilized landfill leachates has been investigated. The sequence of stages implemented was: (a) coagulation–flocculation by pH decrease (pH 2) to acidic conditions (COD removal ≈ 25% related to COD0 ≈ 7500 ppm); (b) coagulation–flocculation by Fe(III) addition (0.01 M) at pH 3.5 (COD removal ≈ 40% related to COD of supernatant after step (a); (c) Fenton (Fe(III) = 0.01 M; H2O2 = 1.0 M) oxidation (COD removal ≈ 80% related to COD of supernatant after step (a); and (d) coagulation–flocculation of Fenton’s effluent at pH 3.5 (COD removal ≈ 90% related to COD of supernatant after step (a). The use of Kynch theory allows for the design of clarifiers based on the amount of solids fed. For a general example of 1000 m3 day−1 of a feeding stream, clarifier area values of 286, 111 and 231 m2 were calculated for compacting indices of 3.7, 2.67 and 2.83 corresponding to the first, second and third consecutive sedimentation processes, respectively, (steps (a), (b) and (d))

Study of different integrated physical-chemical + adsorption processes for landfill leachate remediation

Some integrated processes to deal with landfill leachates have been investigated and their efficiencies expressed in terms of chemical oxygen demand (COD) removal. The systems tested were the result of different combinations of the following single stages: acidic pH shift (elimination of humic substances), ozonation (O3), coagulation-flocculation with Fe(III) salts, Fenton's oxidation (Fe(III) + H2O2), wet air oxidation (with or without radical promoters), and adsorption onto activated carbon (commercial Norit 0.8 powdered activated carbon). COD removals obtained ranged in the interval of 80-96% for initial COD values close to 11000 mg L-1. None of the processes tested reduced the COD levels sufficiently to allow direct discharge; however, the ratio biochemical oxygen demand (BOD/COD was significantly increased (up to 1000% in some cases, i.e., from 0.1 to values above 1.0). Total carbon reduction achieved ranged from 60 to 94%, while complete decolorization (measured as the absorbance at 410 nm) was obtained in practically all the combinations investigate

Stabilized leachates: Ozone-activated carbon treatment and kinetics

Ozone has been used as a pre-oxidation step for the treatment of stabilized leachates. Given the refractory nature of this type of effluents, the conversion of some wastewater quality parameters has been moderate after 1 h of ozonation (i.e. 30% chemical oxygen demand (COD) depletion). Ozone uptake was calculated in the interval 1.3–1:5 g of ozone per gram of COD degraded. An optimum dose of ozone has been experienced in terms of biodegradability of the processed effluent (60 min of treatment, 1 103 mol L1 ozone inlet feeding concentration and 50 L h1 gas flowrate). pH and other typical hydroxyl radical generator systems exerted no influence on the efficiency of the process, suggesting the negligible role played by the indirect route of oxidation (generation of hydroxyl radicals). The ozonated effluent was thereafter treated in a second adsorption stage by using a commercial activated carbon. Removal levels up to 90% of COD in approximately 120 h were experienced for adsorbent dosages of 30 g L1 : Both steps, the single ozonation and the adsorption stage have been modelled by using different pseudoempirical models. r 2003 Elsevier Ltd. All rights reserved

Simulated solar driven photolytic ozonation for the oxidation of aqueous recalcitrant-to-ozone tritosulfuron. Transformation products and toxicity

The authors are grateful to Junta de Extremadura (Project IB16022), co-financed by the European Funds for Regional Development, for economically supporting this work. Moreover, it is also acknowledged the ‘Servicio de Análisis Elemental y Molecular (SAEM)’ of ‘Servicios de Apoyo a la Investigación de la Universidad de Extremadura (SAIUex)’ for the helping with the intermediate products analyses.This work reports the combination of ozone and solar radiation as an advanced oxidation process to remove the herbicide tritosufuron (TSF) in water. Firstly, the recalcitrance of TSF has been assessed, obtaining an ozonation second order rate constant of 5–154 M−1 min−1 in the range of pH from 5 to 8; while the rate constant with HOradical dot was found to be (1.8–3.1)·109 M−1 s−1. Secondly, the simultaneous application of simulated solar radiation in between 300 and 800 nm and ozone resulted positive in the oxidation rate of TSF. Mineralization extent was also higher. Less effective oxidation was achieved after limiting the radiation to the range 360–800 nm or 390–800 nm; also completely inappropriate for mineralization. Thirdly, the detected transformation products (TPs) demonstrated the vulnerability of TSF molecule to be attacked by HOradical dot in the sulfonylurea bridge. The combination of ozone and radiation of 300–800 nm led to the most effective removal of the TPs. Finally, after the photolytic ozonation treatment toxicity was also evaluated in terms of phytotoxicity towards the germination and root elongation of Lactuca Sativa seeds, and toxicity by immobilization tests of Daphnia Magna.Junta de Extremadura (Project IB16022)European Funds for Regional Developmen

Ozonation, photocatalysis and photocatalytic ozonation of diuron. Intermediates identification

Authors thank economic support received from Gobierno de Extremadura and CICYT of Spain through Projects GRU10012 and CTQ2012-35789-C02-01, respectively. Mr. Rafael Rodríguez Solís also thanks Gobierno de Extremadura, Consejería de Empleo, Empresa e Innovación, and FSE Funds for his Ph.D. grant (PD12058).Aqueous 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron) has been oxidized by ozonation, photocatalysis and photocatalytic ozonation. Diuron degradation takes place via radical pathway through hydroxyl radicals in those systems involving ozone. Diuron elimination in photocatalytic ozonation is not enhanced if compared to single ozonation; however, TOC removal was significantly improved. Specifically, 80% TOC removal in 2 h was reached in photocatalytic ozonation while single ozonation just led to 25% TOC reduction. Photocatalysis required 9 h to reach 25% TOC reduction. Ten transformation by-products generated during the application of the three technologies were tentatively identified by liquid chromatography–quadrupole time-of-flight mass spectrometry (LC–QTOF–MS/MS). Single ozonation and photocatalytic ozonation led to the formation and complete elimination of all by-products. Low weight carboxylic acids evolution suggests that high TOC removal in photocatalytic ozonation is linked to its capacity to oxidize small oxygenated compounds and release of inorganic chloride and nitrate. Toxicity evolution to Vibrio fischeri in photocatalytic ozonation displayed an increase in inhibition at the initial stages (>90% of inhibition), followed by a decrease of this parameter as the reaction progressed. The final treated sample shows a lower toxicity than the initial one (55% vs 20%).Gobierno de Extremadura GRU10012CICYT of Spain CTQ2012-35789-C02-01Gobierno de Extremadura, Consejería de Empleo, Empresa e InnovaciónFSE Funds PD1205

Photocatalytic ozonation of pyridine-based herbicides by N-doped titania

The authors thank the economic support received from Gobierno de Extremadura and CICYT of Spain through Projects GRU10012 and CTQ2012-35789-C02-01, respectively. Mr. Rafael Rodríguez Solís thanks Gobierno de Extremadura, Consejería de Empleo, Empresa e Innovación, and FSE Funds for his Ph.D. grant (PD12058).BACKGROUND: A mixture of three pyridine herbicides in water (clopyralid, triclopyr and picloram) has been treated with photocatalytic processes, involving oxygen or ozone. Nitrogen doped and undoped titania were used in the process. Toxicity evolution during photocatalytic ozonation was monitored considering BOD, Daphnia parvula and fitotoxicity trials. RESULTS: N doped titania with an optimized photoactivity was tested in photocatalytic ozonation, leading to nearly 95% mineralization in 180 min. This catalyst was characterized by SEM, TEM, XRD and XPS techniques (13.5 nm crystal size, anatase phase, 1% N, and formation of O-Ti-N linkage). No loss of photocatalytic activity was observed after five consecutive runs. Although no toxicity from the parent compounds was observed, this parameter increased during the early stages of the oxidation process. When parent compounds were totally degraded and dechlorination was completed, toxicity decayed again to negligible values. CONCLUSION: N doping improves bare titania photoactivity through an optimum amount of N. Photocatalysis/ozone showed better behavior than photocatalysis/oxygen in herbicide removal and mineralization, and no significant loss of activity was observed after five runs. Toxicity initially increased due to toxic byproducts formation; however, it decreased after their abatement.Gobierno de Extremadura GRU10012CICYT of Spain CTQ2012-35789-C02-01Gobierno de ExtremaduraFSE Funds (PD12058

Photocatalytic ozonation of 4-chloro-2-methylphenoxyacetic acid and its reaction intermediate 4-chloro-2-methyl phenol

This work has been supported by the CICYT of Spain (Project CTQ2012-39789-C02-01). Mr. Rafael Rodríguez Solís thanks the Gobierno de Extremadura, Consejería de Empleo, Empresa e Innovación and FSE Funds for his Ph.D. grant (PD12058).Aqueous 4-chloro-2-methylphenoxyacetic acid (MCPA) has been treated by the systems UVA/TiO2/N2, O3, TiO2/O3, UVA/O3, UVA/TiO2/O2, and UVA/TiO2/O3. Under the conditions investigated (T = 20 °C, pH = 4.5, Qgas = 30 L/h, V = 1 L, CO3= 5 ppm, CMCPA = 5 ppm, CTiO2= 0.5 g/L), MCPA is removed in less than 30 min. Photocatalytic ozonation is the most efficient process both in terms of MCPA removal rate (100% conversion in less than 15 min) and mineralization extent (60% after 3 h and 25 °C). 4-Chloro-2-methyl phenol (CMP) is detected in those systems combining TiO2 and UVA radiation. The presence of ozone involves the complete depletion of CMP following its generation. The direct rate constant between CMP and ozone corroborates the high reactivity observed (7.2 ± 0.3 × 104 (M s)−1, 4.4 ± 0.2 × 105 (M s)−1, and 2.9 ± 0.7 × 106 (M s)−1 at pHs 4, 7 and 10, respectively). Identified intermediates detected in the UVA/TiO2/O3 applied to MCPA correspond to oxygenated species derived from the parent compound after loss of some substitution groups. No significant toxicity of intermediates is observed in BOD5, Daphnia parvula, and Culex pipiens larvae tests.CICYT of Spain (Project CTQ2012-39789-C02-01)Gobierno de ExtremaduraFSE Funds (PD12058