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.
Ion flotation was studied for the removal of cadmium, zinc, and strontium ions from aqueous solutions at pH 5–9 in a customized flotation cell, using an aminopolycarboxylic chelating surfactant, 2-dodecyldiethylenetriamine pentaacetic acid (C12-DTPA) in combination with two foaming agents: dodecyltrimethylammonium chloride (DoTAC) and dimethyldodecylamine-N-oxide (DDAO). The results from experiments showed that both Zn2+ and Cd2+ could be removed via ion flotation to 100% at pH 5, and Sr2+ could be removed via ion flotation to 60%–70% at pH 7–9. The removal of metal ions from the flotation cell was seen to vary with pH, but this was not exclusively related to the magnitudes of the formed metal ion-chelating surfactant conditional stability constants. The removal was also dependent on the foam properties of the samples that were found to vary over the investigated pH interval. The outcome of the investigation points to the chelating surfactant C12-DTPA having excellent chelating properties for all of the studied ions above pH 7. In combination with correctly chosen foaming agents, the optimized surfactant system could be expected to provide very efficient remediation of waters polluted with metal ions via ion flotation.
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.
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