This study focuses on the treatment of a mature landfill leachate by coagulation and photo-Fenton at different conditions. Optimal coagulation is carried out with ferric chloride in acid conditions; and with alum in near-neutral conditions, to minimize the use of sulphuric acid for pH adjustment (1 g/L vs. 7.2 g/L), the generation of sludge and the increase of conductivity in the final effluent. In both cases, a similar chemical oxygen demand (COD) removal is obtained, higher than 65%, which is high enough for a subsequent photo-Fenton treatment. However, the removal of absorbance at 254 nm (UV-254) was significantly higher with ferric chloride (83% vs. 55%), due to the important removal of humic acids at acid pH. The best results for coagulation are 2 g/L ferric chloride at initial pH = 5 and 5 g/L alum at initial pH = 7. After coagulation with ferric chloride, the final pH (2.8) is adequate for a homogeneous photo-Fenton using the remaining dissolved iron (250 mg/L). At these conditions, using a ratio H₂O₂/COD = 2.125 and 30 min contact time, the biodegradability increased from 0.03 to 0.51. On the other hand, the neutral pH after alum coagulation (6.7) allows the use of zero valent iron (ZVI) heterogeneous photo-Fenton. In this case, a final biodegradability of 0.32 was obtained, after 150 min, using the same H₂O₂/COD ratio. Both treatments achieved similar results, with a final COD, UV-254 and color removal greater than 90%. However, the economic assessment shows that the approach of ferric chloride + homogeneous photo-Fenton is much cheaper (6.4 €/m³ vs. 28.4 €/m³). Although the discharge limits are not achieved with the proposed combination of treatments, the significant increase of the pre-treated leachate biodegradability allows achieving the discharge limits after a conventional biological treatment such as sequencing batch reactor, which would slightly increase the total treatment cost.

An integral treatment process for landfill leachate reverse osmosis concentrate (LLROC) is herein designed and assessed aiming to reduce organic matter content and conductivity, as well as to increase its biodegradability. The process consists of three steps. The first one is a coagulation/flocculation treatment, which best results were obtained using a dosage of 5 g L⁻¹ of ferric chloride at an initial pH = 6 (removal of the 76% chemical oxygen demand (COD), 57% specific ultraviolet absorption (SUVA), and 92% color). The second step is a photo-Fenton process, which resulted in an enhanced biodegradability (i.e., the ratio between the biochemical oxygen demand (BOD₅) and the COD increased from 0.06 to 0.4), and an extra 43% of the COD was removed at the best trialed reaction conditions of [H₂O₂]/COD = 1.06, pH = 4 and [H₂O₂]/[Fe]_mol = 45. An ultra violet-A light emitting diode (UVA-LED) lamp was tested and compared to conventional high-pressure mercury vapor lamps, achieving a 16% power consumption reduction. Finally, an optimized 30 g L⁻¹ lime treatment was implemented, which reduced conductivity by a 43%, and the contents of sulfate, total nitrogen, chloride, and metals by 90%. Overall, the integral treatment of LLROC achieved the removal of 99.9% color, 90% COD, 90% sulfate, 90% nitrogen, 86% Al, 77% Zn, 84% Mn, 99% Mg, and 98% Si; and significantly increased biodegradability up to BOD₅/COD = 0.4.

The objective of this trial was to assess the application of UVA-LED technology as an alternative source of irradiation for photo-Fenton processes, aiming to reduce treatment costs and provide a feasible treatment for landfill leachate. An optimized combination of coagulation with ferric chloride followed by photo-Fenton treatment of landfill leachate was optimized. Three different radiation sources were tested, namely, two conventional high-pressure mercury-vapor immersion lamps (100 W and 450 W) and a custom-designed 8 W 365 nm UVA-LED lamp. The proposed treatment combination resulted in very efficient degradation of landfill leachate (COD removal = 90%). The coagulation pre-treatment removed about 70% of the COD and provided the necessary amount of iron for the subsequent photo-Fenton treatment, and it further favored this process by acidifying the solution to an optimum initial pH of 2.8. The 90% removal of color improved the penetration of radiation into the medium and by extension improved treatment efficiency. The faster the Fenton reactions were, as determined by the stoichiometric optimum set-up reaction condition of [H₂O₂]₀/COD₀ = 2.125, the better were the treatment results in terms of COD removal and biodegradability enhancement because the chances to scavenge oxidant agents were limited. The 100 W lamp was the least efficient one in terms of final effluent quality and operational cost figures. UVA-LED technology, assessed as the application of an 8 W 365 nm lamp, provided competitive results in terms of COD removal, biodegradability enhancement, and operational costs (35–55%) when compared to the performance of the 450 W conventional lamp.

This study focused on the reduction of the treatment cost of mature landfill leachate (LL) by enhancing the coagulation pre-treatment before a UVA-LED photo-Fenton process. A more efficient advanced coagulation pretreatment was designed by combining conventional coagulation (CC) and electro-coagulation (EC). Regardless of the order in which the two coagulations were applied, the combination achieved more than 73% color removal, 80% COD removal, and 27% SUVA removal. However, the coagulation order had a great influence on both final pH and total dissolved iron, which were key parameters for the UVA-LED photo-Fenton post-treatment. CC (pH = 5; 2 g L⁻¹ of FeCl₃6H₂O) followed by EC (pH = 5; 10 mA cm⁻²) resulted in a pH of 6.4 and 100 mg L⁻¹ of dissolved iron, whereas EC (pH = 4; 10 mA cm⁻²) followed by CC (pH = 6; 1 g L⁻¹ FeCl₃6H₂O) led to a final pH of 3.4 and 210 mg L⁻¹ dissolved iron. This last combination was therefore considered better for the posterior photo-Fenton treatment. Results at the best cost-efficient [H₂O₂]:COD ratio of 1.063 showed a high treatment efficiency, namely the removal of 99% of the color, 89% of the COD, and 60% of the SUVA. Conductivity was reduced by 17%, and biodegradability increased to BOD₅:COD = 0.40. With this proposed treatment, a final COD of only 453 mg O₂ L⁻¹ was obtained at a treatment cost of EUR 3.42 kg COD⁻¹.

Formaldehyde is a recalcitrant pollutant, which is difficult to remove from wastewater using conventional and advanced treatments. The objective of this research was to remove the organic matter from formaldehyde from an industrial wastewater, achieving its total mineralization and allowing the reuse of the water. The treatment was based on the reaction of formaldehyde with nitric acid, which was first studied and modelled with synthetic waters. Results show that it was possible to almost completely mineralize the formaldehyde (>95% TOC removal) at the best conditions studied (1.72 M of nitric acid and 85 °C of temperature). The addition of NaNO₂ accelerated this reaction; however, after 2 h of reaction time, its effect was negligible at the maximum concentration of HNO₃ studied. The results obtained with industrial wastewater fit well with the model. It is concluded that formaldehyde in actual wastewaters can be successfully removed through direct mineralization with nitric acid, under selected conditions.