Alicia M. Polo

Degradation of chlorophenoxy herbicides by coupled Fenton and biological oxidation

A combined treatment for the degradation of the chlorophenoxy herbicides 2,4-D and MCPA in water by means of Fenton and biological oxidation has been studied. The chemical oxidation step was necessary to achieve an efficient removal of these pollutants due to their toxicity and low biodegradability. Aqueous herbicide solutions (180mgL(-1)) were subjected to Fenton oxidation upon different H2O2 doses (from the theoretical stoichiometric amount referred to initial COD to 20% of this value). The toxicity and biodegradability tests of the Fenton effluents suggested that the ones resulting upon treatment with 80% and 60% of stoichiometric H2O2 were the optimal for subsequent biological treatment dealing with 2,4-D and MCPA, respectively. These effluents were treated in a sequencing batch reactor achieving nearly 90% conversion of organic matter measured as COD.

Coupling Fenton and biological oxidation for the removal of nitrochlorinated herbicides from water.

The combination of Fenton and biological oxidation for the removal of the nitrochlorinated herbicides alachlor, atrazine and diuron in aqueous solution has been studied. The H2O2 dose was varied from 20 to 100% of the stoichiometric amount related to the initial chemical oxygen demand (COD). The effluents from Fenton oxidation were analyzed for ecotoxicity, biodegradability, total organic carbon (TOC), COD and intermediate byproducts. The chemical step resulted in a significant improvement of the biodegradability in spite of its negligible or even slightly negative effect on the ecotoxicity. Working at 60% of the stoichiometric H2O2 dose allowed obtaining highly biodegradable effluents in the cases of alachlor and atrazine. That dose was even lower (40% of the stoichiometric) for diuron. The subsequent biological treatment was carried out in a sequencing batch reactor (SBR) and the combined Fenton-biological treatment allowed up to around 80% of COD reduction.

Integrated CWPO and Biological Treatment for the Removal of 4-Chlorophenol From Water

Catalysts based on pillared clays with Al-Fe have been synthesized from a commercial bentonite and tested for catalytic wet peroxide oxidation (CWPO) of 4-chlorophenol (4-CP). Different H2O2 doses have been tested in order to find the lowest amount of that reagent needed for an efficient oxidation treatment since this is a main component of the economy of the process. Using a hydrogen peroxide dose of 150 mg/L, less than one-half the stoichiometric amount, complete conversion of 4-CP and the most toxic species of the oxidation pathway (aromatics, as 4-chlorocatechol and hydroquinone), was achieved. Short-chain carboxylic acids were the remaining products found after 4 h of reaction together with a small amount of unconverted hydrogen peroxide. The resulting effluents were submitted to a biological treatment for further removal of the remaining oxidation byproducts. Aerobic respirometric studies showed that a dose of hydrogen peroxide below one-half the stoichiometric is sufficient for obtaining an easily biodegradable effluent from the CWPO step.

Identification of by-products and toxicity assessment in aqueous-phase hydrodechlorination of diuron with palladium on activated carbon catalysts

The hydrodechlorination (HDC) of diuron in aqueous phase with hydrogen using two different activated carbon-supported Pd catalysts was studied. A commercial activated carbon and one prepared by chemical activation of grape seeds with phosphoric acid (GS) were evaluated as supports, being the catalysts tested in a wide range of temperature (30-100 °C) and space-time (78-311 kgcat h mol(-1)). Diuron conversion was above 70% under all the conditions tested. The Pd catalyst supported on GS showed the highest activity in terms of diuron conversion within the temperature range studied, allowing nearly complete conversion above 50 °C. However, a gradual loss of activity with time was observed for this catalyst. A complete route of hydrogenation of diuron was elucidated. Two reaction routes one leading to fenuron and another to aniline were identified. As the temperature and space-time were increased, the formation of fenuron (via monuron) was found to be favored. The toxicity of the reaction products was evaluated, being the route to fenuron and monuron, the one giving rise to a significant decrease of ecotoxicity.

Assessment of toxicity and biodegradability on activated sludge of priority and emerging pollutants

ABSTRACT Several methods for evaluating the toxicity and biodegradability of hazardous pollutants (chlorinated compounds, chemical additives and pharmaceuticals) have been studied in this work. Different bioassays using representative bacteria of marine and terrestrial ecosystems such as Vibrio fischeri and Pseudomonas putida have been used to assess the ecotoxicity. Activated sludge was used to analyse the effect of those pollutants in a biological reactor of a sewage treatment plant (STP). The results demonstrate that none of the compounds is toxic to activated sludge, except ofloxacin to P. putida. The additives tested can be considered moderately toxic according to the more sensitive V. fischeri assays, whereas the EC50 values of the pharmaceuticals depend on the specific microorganism used in each test. Regarding the biodegradability, respirometric measurements were carried out for fast biodegradability assessment and the Zahn–Wellens test for inherent biodegradability. The evolution of the specific oxygen uptake rate (SOUR) showed that only diethyl phthalate was easily biodegradable and acetylsalicylic acid was partially biodegradable (98% and 65% degradation, respectively). The persistence of dichloromethane, ofloxacin and hidrochlorothiazide was confirmed along the 28 days of the Zahn-Wellens test whereas 1,1,1-trichloroethane showed inherent biodegradability (74% removal). Most of the chlorinated compounds, pharmaceuticals, bisphenol A and ethylenediaminetetraacetic acid were partially degraded in 28 d with total organic carbon (TOC) reduction ranging from 21% to 51%. Sulphamethoxazole showed certain biodegradation (50% removal) with TOC decrease around 31%, which indicates the formation of non-biodegradable by-products.