Impact of resin loading on ion exchange equilibrium for removal of organic matter and inorganic ions.

Ion Exchange (IEX) applications for drinking water can be limited due to high volumes of brine, brine waste and treated water corrosivity. Reusing the resin by operating at reduced regeneration frequency can overcome this. However, assessing changes on the resin loading over reuse cycles is complex because multiple presaturant ions participate in the exchange and existing models only account for the exchange with one presaturant ion. This study developed a theoretical multicomponent model for the determination of IEX equilibria when the resin loading increases due to reuse. The model suggested that both electrostatic interactions and admicelle formation were the separation mechanisms. The model revealed that under reduced regeneration frequencies, brine use and waste generation can be reduced by more than 90%, where the bicarbonate-form resin offered the potential for lower corrosivity. However, changes in resin loading after 5 reuse cycles showed that the risk of corrosion increased. For the tested source water, reusing the bicarbonate-form resin every 5 cycles would achieve the most sustainable option with 41% NOM removal and 79% brine and waste reduction. Under these conditions, almost 100% of exchange capacity is recovered after regeneration.

Sorptive removal of disinfection by-product precursors from UK lowland surface waters: Impact of molecular weight and bromide.

The current study compared the impact of three different unit processes, coagulation, granular activated carbon (GAC), and a novel suspended ion exchange (SIX) technology, on disinfection by-product formation potential (DBPFP) from two UK lowland water sources with medium to high bromide content. Specific attention was given to the influence of the organic molecular weight (MW) fraction on DBPFP as well as the impact of bromide concentration. Whilst few studies have investigated the impact of MW fractions from Liquid Chromatography with Organic Carbon Detection (LC-OCD) analysis on dissolved organic carbon (DOC) removal by different processes, none have studied the influence of DOC MW fractions from this analysis on DBP formation. The impact of higher bromide concentration was to decrease the total trihalomethane (THM) and haloacetic acid (HAA) mass concentration, in contrast to previously reported studies. Results indicated that for a moderate bromide concentration source (135 µg/L), the THM formation potential was reduced by 22% or 64% after coagulation or SIX treatment, respectively. For a high bromide content source (210 µg/L), the THM formation potential removal was 47% or 69% following GAC or SIX treatment, respectively. The trend was the same for HAAs, albeit with greater differences between the two processes/feedwaters with reference to overall removal. A statistical analysis indicated that organic matter of MW > 350 g/mol had a significant impact on DBPFP. A multiple linear regression of the MW fractions against DBPFP showed a strong correlation (R2 between 0.90 and 0.93), indicating that LC-OCD analysis alone could be used to predict DBP formation with reasonable accuracy, and offering the potential for rapid risk assessment of water sources.

Disinfection by-product formation during UV/Chlorine treatment of pesticides in a novel UV-LED reactor at 285 nm and the mitigation impact of GAC treatment.

The UV/Chlorine process has gained attention in recent years due to the high quantum yield and absorbance of the chlorine species. However, there are still many unknowns around its application as a treatment for drinking water. The potential for the formation of disinfection by-products (DBPs) is one of them. There are no studies reporting on the formation of trihalomethanes (THMs) or haloacetic acids (HAAs) in complex matrices, such as real source waters, at UV wavelengths tailored to the UV/Chlorine process, which has been possible thanks to the development of light emitting diodes (LEDs). In addition, consideration of mitigation measures that might be needed after UV/Chlorine treatment for full scale application have not been previously reported. Specifically, the novelty of this work resides in the use of an innovative reactor using UV-LEDs emitting at 285 nm for the removal of three pesticides (metaldehyde, carbetamide and mecoprop), the evaluation of THM, HAA and bromate formation in real water sources by UV/Chlorine treatment and the mitigation effect of subsequent GAC treatment. A new parameter, the applied optical dose (AOD), has been defined for UV reactors, such as the one in the present study, where the irradiated volume is non-uniform. The results showed the feasibility of using the UV/Chlorine process with LEDs, although a compromise is needed between pH and chlorine concentration to remove pesticides while minimising DBP formation. Overall, the UV/Chlorine process did not significantly increase THM or HAA formation at pH 7.9-8.2 at the studied wavelength. At acidic pH, however, THM formation potential increased up to 30% after UV/Chlorine treatment with concentrations up to 60 µg/L. HAA formation potential increased between 100 and 180%, although concentrations never exceeded 35 µg/L. In all cases, GAC treatment mitigated DBP formation, reducing THM formation potential to concentrations between 3 and 16 µg/L, and HAA formation potential between 4 and 30 µg/L.

Degradation and monitoring of acetamiprid, thiabendazole and their transformation products in an agro-food industry effluent during solar photo-Fenton treatment in a raceway pond reactor.

In this study, pesticides acetamiprid and thiabendazole and their transformation products (TPs), seven from each pesticide, were successfully monitored during solar photo-Fenton treatment in a real secondary effluent from an agro-food industry spiked with 100µgL(-1) of each pesticide. To this end, a highly sensitive procedure was developed, based on liquid chromatography (LC) coupled to hybrid quadrupole-linear ion trap mass spectrometry (QqLIT-MS). In addition, finding low-cost and operational technology for the application of AOPs would then facilitate their use on a commercial level. Simple and extensive photoreactors such as raceway pond reactors (RPRs) are therefore proposed as an alternative for the application of solar photo-Fenton. Results showed that high degradation could be achieved in a complex water matrix (>99% TBZ and 91% ACTM in 240min) using a 120-L RPR pilot plant as novel technology. The analyses indicated that after the treatment only three TPs from ACTM were still present in the effluent, while the others had been removed. The study showed that the goal of either just removing the parent compounds, or going one step further and removing all the TPs, can significantly change the treatment time, which would affect process costs.

New approach to solar photo-Fenton operation. Raceway ponds as tertiary treatment technology.

The photo-Fenton process has proven its efficiency in the removal of micropollutants. However, the high costs usually associated with it prevent a spread of this technology. An important factor affecting costs is the kind of photoreactor used, usually tubular with a reflecting surface. Tubular reactors like compound parabolic collectors, CPCs, involve high capital costs. In comparison, the application of less costly reactors such as the extensive raceway ponds (RPRs) would help to spread the use of the photo-Fenton process as tertiary treatment at commercial scale. As far as the authors know, RPRs have never been used in advanced oxidation processes (AOPs) applications. This work is aimed at studying the applicability of RPRs to remove micropollutants with solar photo-Fenton. For this purpose, a pesticide mixture of commercial acetamiprid (ACTM) and thiabendazole (TBZ) (100µg/L each) was used in simulated secondary effluent. Iron concentration (1, 5.5 and 10mg/L) and liquid depth (5, 10 and 15cm) were studied as process variables. TBZ was removed at the beginning of the treatment (less than 5min), although ACTM removal times were longer (20-40min for the highest iron concentrations). High treatment capacity per surface area was obtained (48mg/hm(2) with 5.5mg Fe/L and 15cm liquid depth), proving the feasibility of using RPRs for micropollutant removal.

Identification and monitoring of thiabendazole transformation products in water during Fenton degradation by LC-QTOF-MS.

This work enabled the identification of major transformation products (TPs) of thiabendazole (TBZ) during the Fenton process. TBZ is a benzimidazole fungicide widely used around the world to prevent and/or treat a wide range of fruit and vegetable pathogens. The degradation of the parent molecule and the identification of the main TPs were carried out in demineralized water. The TPs were monitored and identified by liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-QTOF-MS/MS). Up to 12 TPs were tentatively identified. Most of them were eliminated after 15 min of treatment time and originated from numerous hydroxylations undergone by the aromatic ring during the initial stages of the process.

Application of liquid chromatography quadrupole time-of-flight mass spectrometry to the identification of acetamiprid transformation products generated under oxidative processes in different water matrices.

This work allowed the identification of major transformation products (TPs) of acetamiprid (ACTM) during Fenton process. Acetamiprid is a chloronicotinoid insecticide widely used around the world for its characteristics (high insecticidal activity, good systemic properties, suitable field stability, etc.). The degradation of the parent molecule and the identification of the main TPs were evaluated in different water matrices (demineralized water and real agro-food industrial wastewater). TPs of acetamiprid generated by Fenton experiments were monitored and identified by liquid chromatography quadrupole time-of-flight tandem mass spectrometry (LC-QTOF-MS/MS). Up to 14 TPs were characterized based on the accurate mass of the molecular ion and fragment ions obtained in both full-scan and MS/MS modes. Most of them were eliminated after 75 min of treatment time in demineralized water. However, in real agro-food industrial wastewater, most of them were eliminated at 90 min of treatment time, demonstrating the influence of the matrix composition on the studied compound degradation.

Phenomenological study and application of the combined influence of iron concentration and irradiance on the photo-Fenton process to remove micropollutants.

The presence of low concentrations of persistent pollutants in waters (µg/L or ng/L), also called micropollutants, brings as a consequence the need to apply advanced oxidation treatments for their removal. The successful application of solar-driven photo-Fenton to treat highly polluted wastewaters (g/L and mg/L of pollutants) has prompted its application to lowly polluted effluents. However, a decrease in contaminant concentration may involve an alteration in the intrinsic process phenomenon, which until now has only been widely studied at the milligram-per-litre level or higher with this process. The aim of this research was to study the combined influence of the operating variable (iron concentration) and the environmental variable (irradiance) and application on the photo-Fenton process at pH2.8 when removing micropollutants. For this purpose, experimentation was carried out at laboratory and pilot plant scales with a biocide mixture of acetamiprid (ACTM), thiabendazole (TBZ) and imazalil (IMZ) (100 µg/L each) as the model pollutant. Results indicated that above 15 WUV/m(2) and a light path length of 5 cm (the most commonly used path for this type of application) iron concentration limited the process and there was irradiance excess under these conditions. On the other hand, and given the circumstances of irradiance excess, a higher light path length (10 cm) was assessed. Results showed that path lengths wider than 5 cm are recommended since more wastewater volume could be treated with a higher process rate per surface unit.

Economic evaluation of a combined photo-Fenton/MBR process using pesticides as model pollutant. Factors affecting costs.

The aim of this paper is to carry out an economic assessment on a solar photo-Fenton/MBR combined process to treat industrial ecotoxic wastewater. This study focuses on the impact of the contamination present in wastewater, the photochemical oxidation, the use of an MBR as biological process and the plant size on operating and amortization costs. As example of ecotoxic pollutant, a mixture of five commercial pesticides commonly used in the Mediterranean area has been used, ranging from 500 mg/L to 50mg/L, expressed as dissolved organic carbon concentration. The economic evaluation shows that (i) the increase in pollution load does not always involve an increase in photo-Fenton costs because they also depend on organic matter mineralization; (ii) the use of an MBR process permits lower photochemical oxidation requirements than other biological treatments, resulting in approximately 20% photo-Fenton cost reduction for highly polluted wastewater; (iii) when pollution load decreases, the contribution of reactant consumption to the photo-Fenton process costs increase with regard to amortization costs; (iv) 30% total cost reduction can be gained treating higher daily volumes, obtaining competitive costs that vary from 1.1-1.9 €/m(3), depending on the pollution load.