Integration of Fenton's reaction based processes and cation exchange processes in textile wastewater treatment as a strategy for water reuse.

The remediation of a real textile wastewater aiming its reuse in the textile industry was carried out by integrating two processes: (i) a chemical or electrochemical advanced oxidation process (AOP or EAOP) based on Fenton's reaction for organics degradation, and (ii) a cation exchange process using marine macroalgae for removal of the iron acting in the Fenton's reaction based processes. Four AOPs/EAOPs at acidic pH 2.8 were tested: Fenton, photo-Fenton with ultraviolet A (UVA) radiation (PF/UVA), electro-Fenton (EF) and photoelectro-Fenton with UVA radiation (PEF/UVA). These processes provided very high color removals. After a running time of 45 min, the color removals were 68-95% for the Fenton process, 76-94% for the EF process, 80-98% for the PF/UVA process and 85-100% for the PEF/UVA process. In contrast, the mineralization was negligible for all the processes, indicating the generation/presence of persistent colorless compounds. The PF process was selected as first treatment stage due to its ability for color removal and related lower costs. A set of six marine macroalgae (Gracilaria caudata, Gracilaria cervicornis, Ascophyllum nodosum, Fucus spiralis, Laminaria hyperborea and Pelvetia canaliculata) were tested for iron uptake. Laminaria hyperborea showed the highest ion exchange capacity and affinity for iron species. Its application allowed the removal of all the iron acting in the PF process (3.4 mg/L). The textile wastewater resulting from the application of PF process followed by cation exchange with Laminaria hyperborea was successfully reused in scouring, bleaching and dyeing processes.

Application of a micro-meso-structured reactor (NETmix) to promote photochemical UVC/H2O2 processes - oxidation of As(iii) to As(v).

A micro-meso-structured reactor (NETmix) was used for the first time to promote photochemical UVC/H2O2 processes. The NETmix photoreactor consists of a network of chambers and channels, where the liquid flows, sealed with a quartz slab with high UVC transparency. Due to the small size of channels and chambers, the NETmix presents a uniform irradiance through the entire reactor depth, short molecular diffusion distances and large specific interfacial areas, maximizing the pollutant/oxidant contact. In this study, the NETmix photoreactor was evaluated for As(iii) oxidation to As(v) using a photochemical UVC/H2O2 system. The effect of the UVC lamp power (4, 6 or 11 W), the number of UVC lamps (2 or 3 lamps) and the UVC lamp layout (parallel or perpendicular to the flow direction) was evaluated, in order to ensure uniform irradiation of the entire reaction mixture. The optimum H2O2 concentration for each light distribution system was also evaluated. At the best configuration, 3 lamps of 11 W positioned parallel to the flow direction, total As(iii) oxidation ([As(iii)]0 = 1.33 × 10-2 mM) was achieved in 15 min with an absorbed photon flux density of 1.9 × 10-1 einstein per m3 per s. Significant differences were highlighted between the photon flux actually received in the photoreactor and the radiant power emitted by the lamp. A kinetic model able to represent the As(iii) oxidation employing UVC radiation and H2O2 in a micro-meso-structured reactor was presented. The photochemical space time yield (PSTY) values obtained for the micro-meso-structured reactor are higher than for conventional batch reactors, showing that the NETmix technology can be a good solution for application in photochemical processes.

Brown marine macroalgae as natural cation exchangers for toxic metal removal from industrial wastewaters: A review.

The discharge of inadequately treated or untreated industrial wastewaters has greatly contributed to the release of contaminants into the environment, including toxic metals. Toxic metals are persistent and bioaccumulative, being their removal from wastewaters prior to release into water bodies of great concern. Literature reports the use of brown marine macroalgae for toxic metals removal from aqueous solutions as an economic and eco-friendly technique, even when applied to diluted solutions. Minor attention has been given to the application of this technique in the treatment of real wastewaters, which present a complex composition that can compromise the biosorption performance. Therefore, the main goal of this comprehensive review is to critically outline studies that: (i) applied brown marine macroalgae as natural cation exchanger for toxic metals removal from real and complex matrices; (ii) optimised the biosorption process in a fixed-bed column, which was further scaled-up to pilot plants. An overview of toxic metals sources, chemistry and toxicity, which are relevant aspects to understand and develop treatment techniques, is initially presented. The problem of water resources pollution by toxic metals and more specifically the participation of metal finishing industries in the environmental contamination are issues also covered. The current and potential decontamination methods are presented including a discussion of their advantages and drawbacks. The literature on biosorption was reviewed in detail, considering especially the ion exchange properties of cell wall constituents, such as alginate and fucoidan, and their role in metal sequestration. Besides that, a detailed description of biosorption process design, especially in continuous mode, and the application of mechanistic models is addressed.

Cow bones char as a green sorbent for fluorides removal from aqueous solutions: batch and fixed-bed studies.

Cow bone char was investigated as sorbent for the defluoridation of aqueous solutions. The cow bone char was characterized in terms of its morphology, chemical composition, and functional groups present on the bone char surface using different analytical techniques: SEM, EDS, N2-BET method, and FTIR. Batch equilibrium studies were performed for the bone chars prepared using different procedures. The highest sorption capacities for fluoride were obtained for the acid washed (q = 6.2 ± 0.5 mg/g) and Al-doped (q = 6.4 ± 0.3 mg/g) bone chars. Langmuir and Freundlich models fitted well the equilibrium sorption data. Fluoride removal rate in batch system is fast in the first 5 h, decreasing after this time until achieving equilibrium due to pore diffusion. The presence of carbonate and bicarbonate ions in the aqueous solution contributes to a decrease of the fluoride sorption capacity of the bone char by 79 and 31 %, respectively. Regeneration of the F-loaded bone char using 0.5 M NaOH solution leads to a sorption capacity for fluoride of 3.1 mg/g in the second loading cycle. Fluoride breakthrough curve obtained in a fixed-bed column presents an asymmetrical S-shaped form, with a slow approach of C/C 0 â†’ 1.0 due to pore diffusion phenomena. Considering the guideline value for drinking water of 1.5 mg F-/L, as recommended by World Health Organization, the service cycle for fluoride removal was of 71.0 h ([F-]feed âˆ¼ 9 mg/L; flow rate = 1 mL/min; m sorbent = 12.6 g). A mass transfer model considering the pore diffusion was able to satisfactorily describe the experimental data obtained in batch and continuous systems.

Design of a fixed-bed ion-exchange process for the treatment of rinse waters generated in the galvanization process using Laminaria hyperborea as natural cation exchanger.

In this study, the removal of zinc from galvanization wastewaters was performed in a fixed bed column packed with brown macro-algae Laminaria hyperborea, acting as a natural cation exchanger (resin). The rinse wastewater presents a zinc concentration between 9 and 22 mg/L, a high concentration of light metals (mainly Na and Ca), a high conductivity (0.5-1.5 mS/cm) and a low organic content (DOC = 7-15 mg C/L). The zinc speciation diagram showed that approximately 80% of zinc is in the form of Zn(2+) and ≅20% as ZnSO4, considering the effluent matrix. From all operational conditions tested for zinc uptake (17 < bed height<27 cm, 4.5 < flow rate<18.2 BV/h, 0.8 < particle equivalent diameter<2.0 mm), the highest useful capacity (7.1 mg Zn/g algae) was obtained for D/dp = 31, L/D = 11, 9.1 BV/h, τ = 6.4 min, corresponding to a service capacity of 124 BV (endpoint of 2 mg Zn/L). Elution was faster and near to 100% effective using 10 BV of HCl (1 M, 3.0%, 363 g HCl/L of resin), for flow rates higher than 4.5 BV/h. Calcium chloride solution (0.1 M) was selected as the best regenerant, allowing the reuse of the natural resin for more than 3 saturation/elution/regeneration cycles. The best operation conditions were scaled-up and tested in a pre-pilot plant. The scale-up design of the cation exchange process was proposed for the treatment of 2.4 m(3)/day of galvanization wastewater, resulting in an estimated reactants cost of 2.44 €/m(3).