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.

Application of solar photo-Fenton in raceway pond reactors: A review.

This work critically reviews the present knowledge about the use of Raceway Pond Reactors (RPR) to treat municipal wastewater treatment plant (MWWTP) secondary effluents by solar photo-Fenton process. The possibility of using RPR to treat industrial wastewater, which has been barely explored, is also reviewed. Initially, the general concepts and operation principles of RPR are described as well as their origin for photo-Fenton applications. Then, the main results and advances related to contaminants of emerging concern (CECs) removal, inactivation of microorganisms, industrial wastewater treatment and kinetic modelling are presented. Key aspects such as the impact of liquid depth, the continuous flow operation feasibility, the increase in treatment capacity, and the kinetic modelling are addressed along the review. At the end, main challenges and research gaps are identified, which should be the focuses of future research.

Comparison of different detoxification pilot plants for the treatment of industrial wastewater by solar photo-Fenton: Are raceway pond reactors a feasible option?

This paper represents a first approach in the study of photoreactor selection to treat industrial wastewater using solar photo-Fenton. In this context, simulated textile industry effluent containing a mixture of four dyes at different initial dissolved organic carbon (DOC) concentrations (45, 90, 180 and 270 mg/L) was treated by using three different solar reactor geometries: (i) tubular (5 cm diameter) provided with compound parabolic collector (ii) tubular (5 cm diameter) provided with flat collector and (iii) open channels forming raceway ponds with two liquid depths (5 and 15 cm). For comparison purposes, mineralisation percentages over 75% and chronic toxicity reduction were set as treatment goals. Regardless of the initial DOC concentration, negligible differences in terms of treatment time and hydrogen peroxide consumptions were found between the flat collector and compound parabolic collector photoreactors. Conversely, the treatment in the raceway pond reactors always resulted in higher values. In spite of this, when the photoreactors were compared in terms of treatment capacity (mg of DOC removed/m2 min) the raceway pond reactor at 15 cm of liquid depth presented the best results, with values as much as two or three times higher than those of the tubular reactors, except for the wastewater with 270 mg of DOC/L for which the raceway pond reactor at 5 cm liquid depth became the best option. When the treatment capacity is modified to include the photoreactor investment (mg of DOC removed/€ m2) the differences between the raceway pond reactor at both liquid depths and the photoreactors with solar collectors increased by as much as two orders of magnitude, which demonstrates the potential application of the former for the treatment of industrial wastewater by solar photo-Fenton.

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.

Techno-economic assessment of a multi-effect distillation plant installed for the production of irrigation water in Arica (Chile).

In the context of a regional Chilean project (FIC Taltape project, BIP code 30158422-0), a multi-effect distillation (MED) pilot plant has been built and installed in a small community in the north of Chile (Taltape, Arica) in order to supply treated water for agricultural and domestic purposes. The aim of this paper is to assess the techno-economic feasibility of this system for supplying water with the required quality to the population. The characterization of the feed water and the effluents from the MED pilot plant (distillate and brine), obtained during five months of operation, has been firstly performed. Then, the prediction of the operation of the water treatment system with solar energy has been carried out using a typical meteorological year and the design of a static solar field that cover the thermal energy needs of the water treatment plant. The annual simulations of the MED pilot plant operating with solar energy showed that the water needs can be mostly covered using a static solar thermal field with a total area of 113.2 m2, which would generate roughly 46% of the total heat required by the water treatment plant. The technical analysis has been completed with an exhaustive economic assessment. The specific water costs have been determined for the MED pilot plant and the scale factor when the productivity is increased up to 5000 m3/day has been evaluated. The cost of distillated water produced by the MED plant varied from 15.0 USD$/m3 for the 10 m3/day production capacity to 1.25 USD$/m3 when this variable is increased to 5000 m3/day.

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.

Dynamic modelling for cork boiling wastewater treatment at pilot plant scale.

Solar photo-Fenton process has been extensively reported to be highly efficient in the remediation of complex industrial wastewater containing several families of pollutants such as pharmaceuticals, dyes, pesticides, derivatives of wine, etc. Moreover, solar photo-Fenton mathematical modelling regarded as a powerful tool for scaling-up and process control purposes is hindered by the complexity and variability of its reaction mechanism which depends on the particular wastewater under study. In this work, non-biodegradable cork boiling wastewater has been selected as a case study for solar photo-Fenton dynamic modelling by using MATLAB® software. First of all physic-chemical pretreatment was applied attaining chemical oxygen demand (COD) reductions between 43 and 70 % and total suspended solid (TSS) reductions between 23 % and 59 %. After solar photo-Fenton treatment, COD decreased between 45 and 90 % after consumptions of H2O2 varying around 1.9 and 2.4 g/L. Individual calibration of the semi-empirical model by using experimental results made it possible to perfectly predict hydrogen peroxide variations throughout the treatment. It must be highlighted that slight deviations between predictions and experimental data must be attributed to important changes in wastewater characteristics.

Economic evaluation of the photo-Fenton process. Mineralization level and reaction time: the keys for increasing plant efficiency.

The use of the solar photo-Fenton process is proposed to degrade Paracetamol in water in order to form biodegradable reaction intermediates which can be finally removed with a downstream biological treatment. Firstly, biodegradability enhancement with photo-Fenton treatment time has been evaluated; the minimum mineralization level should be at least 18.6% where Paracetamol has been degraded and biodegradability efficiency is higher than 40%. 20 mg L(-1) of Fe(2+) and 200 mg L(-1) of H(2)O(2) were selected in a lab-scale study looking at Paracetamol's degradation rate and organic carbon mineralization rate. As a result of scaling up the process at a pilot plant, 157.5 mg L(-1) of Paracetamol (∼1 mM) was treated in 25 min of photo-Fenton treatment achieving the desired biodegradability. A further economic evaluation shows how the proposed treatment strategy markedly increases plant efficiency, resulting in an 83.33% reduction in reagent cost and a 79.11% reduction in costs associated with reaction time. Total cost is reduced from 3.4502 €/m(3) to 0.7392 €/m(3).