Removal of microcontaminants by zero-valent iron solar processes at natural pH: Water matrix and oxidant agents effect.

This work deals with microcontaminants (MCs) removal by natural solar zero-valent iron (ZVI) process at natural pH in actual matrices. Commercial ZVI microspheres were selected as ZVI source and hydrogen peroxide and persulfate were used as oxidant agents. The experimental plan comprised the evaluation of sulphates and carbonates/bicarbonates effect on process performance, the possibility of adding an iron chelate (EDDS) to take advantage of leached iron and the treatment of MCs in actual MWWTP secondary effluent. The presence of sulphates and EDDS addition did not lead to significant changes in the process efficiency, while the carbonates naturally present in natural water (458 mg/L) diminished the treatment time need to reach the decontamination goal. Finally, the treatment of a MCs mixture consisting of Atrazine, Carbendazim, Imidacloprid, and Thiamethoxam in the range of µg/L in actual MWWTP secondary effluent by solar/msZVI/H2O2 and solar/msZVI/S2O82- obtained 7 and 22% of total removal after 180 min, respectively, which indicated a moderate competitiveness of these processes with respect to other advanced oxidation processes.

Evaluation of commercial zerovalent iron sources in combination with solar energy to remove microcontaminants from natural water at circumneutral pH.

Solar zerovalent iron (ZVI) was studied at circumneutral pH in combination with hydrogen peroxide and persulfate for removal of imidacloprid as a model contaminant in natural water. Three commercial ZVI sources, steel wool (ZVI-SW) and two iron micro-powders (ZVI-MS and ZVI-S) were independently evaluated. First, different ZVI corrosion conditions were tested in contact with air, exposed to natural solar radiation and with addition of oxidants, such as H2O2 and S2O82-, demonstrating the importance of released iron. Then, the technical feasibilities of solar/H2O2/ZVI and solar/S2O82-/ZVI were assessed for the elimination of 1 mg/L of imidacloprid. In general, H2O2 concentrations and treatment times were high. Only ZVI-MS (1 mM) reached 80% imidacloprid degradation after 157 min and 3 mM (102 mg/L) of H2O2. Solar/S2O82-/ZVI performance was better, reaching >80% imidacloprid degradation in <60 min with 1 mM (192 mg/L) S2O82- for all ZVI sources. Efficiency was highest with ZVI-MS, which was therefore selected for feasibility testing of a microcontaminant (MC) mixture containing 100 µg/L each of atrazine, carbendazim, imidacloprid and thiamethoxam with both solar/oxidizing agents/ZVI. H2O2 took 180 min to achieve 76% degradation of the sum of MCs, while 80% total degradation was reached after 69 min by adding S2O82-, confirming its higher efficiency. Finally, this study showed that ZVI in combination with solar radiation does not enhance significantly the photocatalytic cycle.

EDDS as complexing agent for enhancing solar advanced oxidation processes in natural water: Effect of iron species and different oxidants.

The main purpose of this pilot plant study was to compare degradation of five microcontaminants (MCs) (antipyrine, carbamazepine, caffeine, ciprofloxacin and sulfamethoxazole at 100 µg/L) by solar photo-Fenton mediated by EDDS and solar/Fe:EDDS/S2O82-. The effects of the Fe:EDDS ratio (1:1 and 1:2), initial iron species (Fe(II) or Fe(III) at 0.1 mM) and oxidizing agent (S2O82- or H2O2 at 0.25-1.5 mM) were evaluated. The higher the S2O82- concentration, the faster MC degradation was, with S2O82- consumption always below 0.6 mM and similar degradation rates with Fe(II) and Fe(III). Under the best conditions (Fe 0.1 mM, Fe:EDDS 1:1, S2O82- 1 mM) antipyrine, carbamazepine, caffeine, ciprofloxacin and sulfamethoxazole at 100 µg/L where 90% eliminated applying a solar energy of 2 kJ/L (13 min at 30 W/m2 solar radiation <400 nm). Therefore, S2O82- promotes lower consumption of EDDS as Fe:EDDS 1:1 was better than Fe:EDDS 1:2. In photo-Fenton-like processes at circumneutral pH, EDDS with S2O82- is an alternative to H2O2 as an oxidizing agent.

Pyrimethanil degradation by photo-Fenton process: Influence of iron and irradiance level on treatment cost.

This study evaluates the combined effect of photo-catalyst concentration and irradiance level on photo-Fenton efficiency when this treatment is applied to industrial wastewater decontamination. Three levels of irradiance (18, 32 and 46W/m2) and three iron concentrations (8, 20 and 32mg/L) were selected and their influence over the process studied using a raceway pond reactor placed inside a solar box. For 8mg/L, it was found that there was a lack of catalyst to make use of all the available photons. For 20mg/L, the treatment always improved with irradiance indicating that the process was photo-limited. For 32mg/L, the excess of iron caused an excess of radicals production which proved to be counter-productive for the overall process efficiency. The economic assessment showed that acquisition and maintenance costs represent the lowest relative values. The highest cost was found to be the cost of the reagents consumed. Both sulfuric acid and sodium hydroxide are negligible in terms of costs. Iron cost percentages were also very low and never higher than 10.5% while the highest cost was always that of hydrogen peroxide, representing at least 85% of the reagent costs. Thus, the total costs were between 0.76 and 1.39€/m3.

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.