Continuous flow operation of solar photo-Fenton fused with NaOCl as a novel tertiary treatment.

A novel strategy based on solar photo-Fenton mediated by ferric nitrilotriacetate (Fe3+-NTA) combined with NaOCl in continuous flow mode for wastewater reclamation has been studied. Escherichia coli (E. coli) inactivation attained ≥ 5 log10-units, meeting the most restrictive EU 2020/741 target (10 CFU/100 mL), and 75% of organic microcontaminant total load was removed. As a remarkable finding, trihalomethanes (THMs) concentration was insignificant, complying by far with the Italian legislation limit. To attain these results, first the effect of liquid depth on E. coli inactivation and imidacloprid (IMD) removal from spiked municipal effluents was evaluated in continuous flow pilot-scale raceway pond reactors at 60-min hydraulic residence time with low reagent concentrations (0.10 mM Fe3+-NTA, 0.73 mM H2O2 and 0.13 mM NaOCl). Disinfection was due to the bactericidal effect of chlorine. In contrast, liquid depth notably influenced microcontaminant removal, highlighting that operation at 10-cm liquid depth allows achieving treatment capacities higher than at 5 cm (16.50 vs 28.20 mg IMD/m2∙day). Next, the monitoring of THMs was carried out to evaluate the generation and degradation of disinfection by-products, along with the removal of actual microcontaminants. These promising results draw attention to the treatment potential and open the way for its commercial application.

Simultaneous bacterial inactivation and microcontaminant removal by solar photo-Fenton mediated by Fe3+-NTA in WWTP secondary effluents.

Simultaneous microorganism inactivation and organic microcontaminant removal in municipal wastewater treatment plant (WWTP) secondary effluents by the solar photo-Fenton process mediated by Fe3+-NTA is studied in depth. To achieve this objective, different key aspects were addressed: (i) the effect of initial Fe3+-NTA concentration at 1:1 molar ratio (0.10-0.30 mM) and H2O2 concentration (1.47-5.88 mM), (ii) the effect of initial microorganism load (103 and 106 CFU/mL) and (iii) the impact of the disinfection target on treatment cost. The first stage of this work was carried out in simulated WWTP effluent spiked with 100 µg/L of imidacloprid (IMD) as model microcontaminant and inoculated with Escherichia coli (E. coli) K-12 as reference strain, in a pilot scale raceway pond reactor with 5-cm of liquid-depth. Secondly, the most cost-effective conditions were validated in actual WWTP effluent. The kinetic analysis revealed that increasing Fe3+-NTA concentration over 0.20 mM does not significantly reduce treatment time due to the limited effect caused on the volumetric rate photon absorption. Treatment cost is determined by the disinfection process, since IMD removal was always faster than E. coli inactivation. The most cost-effective strategy to achieve 10 CFU/100 mL of E. coli (Regulation EU 2020/741) was 0.20/4.41 mM Fe3+-NTA/H2O2, with a cost of 0.32 €/m3. A less restrictive disinfection target, 100 CFU/100 mL, allowed reducing reactant concentration and cost, 0.10/1.47 mM Fe3+-NTA/H2O2 and 0.15 €/m3, respectively. In both cases, no regrowth at 24 h and more than 90% of IMD removal were observed.

Kinetic assessment of antibiotic resistant bacteria inactivation by solar photo-Fenton in batch and continuous flow mode for wastewater reuse.

The presence of antibiotic resistant bacteria in municipal wastewater treatment plants represents a real risk to human health. For the first time, this paper shows that the inactivation rate of cefotaxime resistant bacteria is the same as total bacteria when secondary effluents are treated by the solar photo-Fenton process. To obtain this result, an exhaustive and comparative kinetic study on the inactivation of both total and cefotaxime resistant bacteria (Total coliform, Escherichia coli and Enterococcus sp) was carried out, taking into account the effects of the main operation conditions, such as solar irradiance and iron concentration, and operation mode (batch and continuous). In all the operation conditions studied, no significant differences were found between the first order inactivation rate constants, ki, of total and cefotaxime resistant bacteria. Additionally, ki increased with solar irradiance and iron concentration. As for the effect of the operation mode, the main finding of this work is much quicker inactivation in continuous flow mode than in batch mode, pointing out its potential application at large scale. The best continuous operation condition to inactivate the bacteria to the detection limit (1 CFU mL-1), was at 22.4 min of hydraulic residence time with 5 mg Fe2+ L-1 and 30 mg H2O2·L-1. This treatment time is approximately a third of that reported in batch mode. The efficiency, in terms of figure of merits, of the continuous flow operation was 2.7 m2 of solar collector area to reduce one log of E. coli concentration per m3 of treated water and per hour, in comparison with 2137 m2 calculated for batch operation under the same solar UVA irradiance, 30 W m-2. This paper encourages research into continuous solar disinfection processes due to its enhanced efficiency with regard to the commonly used batch wise operation and shows that efficient removal of total bacteria ensures the removal of antibiotic resistant bacteria.

Application of solar photo-Fenton at circumneutral pH to nanofiltration concentrates for removal of pharmaceuticals in MWTP effluents.

In view of the inefficient elimination of micro-pollutants by today's conventional biological treatments and new legislation requiring elimination of at least 80 % of their concentration, the application of an advanced tertiary treatment must be studied. A good option would be advanced oxidation processes (AOPs), which have very often been combined with physicochemical pre-treatSments to increase efficiency or reduce operating costs. This study focused on the combination of membrane nanofiltration and solar photo-Fenton for the main purpose of removing five pharmaceuticals (sulfamethoxazole, ibuprofen, ofloxacin, carbamazepine and flumequine) from real MWTP effluents under realistic conditions (µg L(-1)). This research also included tests performed with modified photo-Fenton using a low iron concentration at circumneutral pH and a low hydrogen peroxide dose, in an attempt to reduce major treatment costs. Over 80 % of dissolved organic carbon, chemical oxygen demand and turbidity were also retained during nanofiltration, making pharmaceutical removal less efficient in terms of concentrate treatment time than direct treatment, i.e. the concentrate illumination time was around 150 min while direct treatment was around 40 min. Nevertheless, it should be highlighted that, although no savings in installation costs was observed for the combined system (nanofiltration/solar photo-Fenton), the reaction rate improved and so, there was a savings in reagent costs (mainly hydrogen peroxide and sulfuric acid).

Removal of pharmaceuticals from MWTP effluent by nanofiltration and solar photo-Fenton using two different iron complexes at neutral pH.

In recent years, membrane technologies (nanofiltration (NF)/reverse osmosis (RO)) have received much attention for micropollutant separation from Municipal Wastewater Treatment Plant (MWTP) effluents. Practically all micropollutants are retained in the concentrate stream, which must be treated. Advanced Oxidation Processes (AOPs) have been demonstrated to be a good option for the removal of microcontaminants from water systems. However, these processes are expensive, and therefore, are usually combined with other techniques (such as membrane systems) in an attempt at cost reduction. One of the main costs in solar photo-Fenton comes from reagent consumption, mainly hydrogen peroxide and chemicals for pH adjustment. Thus, in this study, solar photo-Fenton was used to treat a real MWTP effluent with low initial iron (less than 0.2 mM) and hydrogen peroxide (less than 2 mM) concentrations. In order to work at neutral pH, iron complexing agents (EDDS and citrate) were used in the two cases studied: direct treatment of the MWTP effluent and treatment of the concentrate stream generated by NF. The degradation of five pharmaceuticals (carbamazepine, flumequine, ibuprofen, ofloxacin and sulfamethoxazole) spiked in the effluent at low initial concentrations (µg L(-1)) was monitored as the main variable in the pilot-plant-scale photo-Fenton experiments. In both effluents, pharmaceuticals were efficiently removed (>90%), requiring low accumulated solar energy (2 kJUV L(-1), key parameter in scaling up the CPC photoreactor) and low iron and hydrogen peroxide concentrations (reagent costs, 0.1 and 1.5 mM, respectively). NF provided a clean effluent, and the concentrate was positively treated by solar photo-Fenton with no significant differences between the direct MWTP effluent and NF concentrate treatments.

Confirming Pseudomonas putida as a reliable bioassay for demonstrating biocompatibility enhancement by solar photo-oxidative processes of a biorecalcitrant effluent.

Experiments based on Vibrio fischeri, activated sludge and Pseudomonas putida have been employed to check variation in the biocompatibility of an aqueous solution of a commercial pesticide, along solar photo-oxidative process (TiO(2) and Fenton reagent). Activated sludge-based experiments have demonstrated a complete detoxification of the solution, although important toxicity is still detected according to the more sensitive V. fischeri assays. In parallel, the biodegradability of organic matter is strongly enhanced, with BOD(5)/COD ratio above 0.8. Bioassays run with P. putida have given similar trends, remarking the convenience of using P. putida culture as a reliable and reproducible method for assessing both toxicity and biodegradability, as a substitute to other more time consuming methods.

A kinetics study on the biodegradation of synthetic wastewater simulating effluent from an advanced oxidation process using Pseudomonas putida CECT 324.

Bacterial growth on mixed substrates is employed for wastewater treatment. Biodegradation kinetics of Pseudomonas putida CECT 324 growth on formic acid, vanillin, phenol and oxalic acid mixtures is described. The experiments were carried out in a stirred-tank fermentor in batch mode at different temperatures (25, 30 and 35 degrees C) and pH (5, 6 and 7). The four compounds selected are typical intermediates in pesticide-contaminated water treated by advanced oxidation processes (AOPs). The toxicity of intermediates was investigated for a combined AOP-biological treatment, and the minimum DOC inhibitory concentration of the intermediate mixture was 175 ppm. The resulting biodegradation and growth kinetics were best described by the sum kinetics with interaction parameters (SKIP) model. Phenol and oxalic acid inhibit P. putida growth, and formic acid consumption strongly affects the biodegradation of oxalic acid. At all the temperatures tested and at pH between 5 and 7, P. putida CECT 324 was able to degrade the four substrates after culture times of 30 h at 30 degrees C and pH 7, which were the best conditions, and after 70 h, under the worst, at 35 degrees C.

Effects of the sporulation conditions on the lovastatin production by Aspergillus terreus.

The production of biomass and lovastatin by spore-initiated submerged fermentations of Aspergillus terreus ATCC 20542 was shown to depend on the age of the spores used for inoculation. Cultures started from older spores produced significantly higher titers of lovastatin. For example, the lovastatin titer increased by 52% when the spore age at inoculation rose from 9 to 16 days. The lovastatin titer for a spore age of 16 days was 186.5+/-20.1 mg L(-1). The time to sporulation on surface cultures was sensitive to the light exposure history of the fungus and the spore inoculation concentration levels. A light exposure level of 140 muE m(-2 )s(-1) and a spore concentration of 1,320 spore cm(-2) produced the greatest extent of sporulation within about 50 h of inoculation. Sporulation was slowed in the dark and with diluted inoculants. A rigorous analysis of the data of statistically designed experiments showed the above observations to be highly reproducible.