Waste-treating-waste: Effective heavy metals removal from electroplating wastewater by ladle slag.

Ladle slag, a by-product of steelmaking, presents a valuable strategy for waste reduction and valorization in wastewater treatment. This work demonstrates the successful simultaneous removal of Al(III), B(III), Ba(II), Cr(III), Mg(II), Sr(II), Pb(II), and Zn(II), from electroplating wastewater by ladle slag. First, Cr(III) and Pb(II) removals were evaluated in single synthetic systems by analyzing the influence of pH, temperature, and ladle slag dosage. Competitive removal was observed in binary batch experiments of Cr(III) - Pb(II), achieving 88% and 96% removal, respectively, with fast kinetics following a pseudo-second-order model. The findings of XRD, SEM, EDX, and FTIR of the slag after removal helped to elucidate the synergic removal mechanism involving ladle slag dissolution, precipitation, ion exchange, and adsorption in a tight relationship with the solution pH. Lastly, ladle slag was tested in real electroplating wastewater with the aforementioned ions at concentrations ranging from <1 to 1700 mg/L. The removal was performed in two steps, the first attained the following efficiencies: 73% for Al(III), 88% for B(III), 98% for Ba(II), 80% for Cr(III), 82% for Mg(II), 99% for Pb(II), 88% for Sr(II), and 88% for Zn(II). Visual MINTEQ simulation was utilized to identify the different species of ions present during the removal process. Furthermore, the leaching tests indicated a minimal environmental risk of secondary pollution in its application. The results promote an effective and sustainable approach to wastewater treatment within the circular economy.

Thiabendazole degradation by photo-NaOCl/Fe and photo-Fenton like processes, using copper slag as an iron catalyst, in spiked synthetic and real secondary wastewater treatment plant effluents.

Thiabendazole degradation (TBZD) in diferent types of water matrices was assessed by applying two Advanced Oxidation Processes, both using simulated solar light (SSL), copper slag (CS) as an iron based catalyst, and separately H2O2 or NaOCl as oxidants. First, optimum conditions for TBZD were evaluated in distilled water, TBZD = 90% at 60 min for CS-H2O2-SSL, and 92% of TBZD in a twelfth of the time by the system CS-NaOCl-SSL; minimum TBZ depletion variations were observed between the first and the fifth reuse test: 88 ± 2% for CS-H2O2-SSL (60 min) and 90 ± 1% for CS-NaOCl-SSL (5 min). Those conditions were tested using a synthetic (SE) and a real secondary effluent (RE) from a wastewater treatment plant. The CS-H2O2-SSL system achieved TBZD of 88 and 77% after 90 min for SE and RE, with kinetic constants of 0.024 and 0.016 min-1, respectively, whereas photo-NaOCl/Fe showed values of 0.365 and 0.385 min-1 for SE and RE, achieving a 94% TBZD removal in both types of water at 10 min. That might be related to the formation of Cl· and HO• during the photo-NaOCl/Fe process, highlighting that the CS-NaOCl-SSL is an attractive option that has great possibilities for scaling up by a better knowledge in real aqueous matrices.

Loop-mediated isothermal amplification-based electrochemical sensor for detecting SARS-CoV-2 in wastewater samples.

The current pandemic COVID-19 caused by the coronavirus SARS-CoV-2, has generated different economic, social and public health problems. Moreover, wastewater-based epidemiology could be a predictor of the virus rate of spread to alert on new outbreaks. To assist in epidemiological surveillance, this work introduces a simple, low-cost and affordable electrochemical sensor to specifically detect N and ORF1ab genes of the SARS-CoV-2 genome. The proposed sensor works based on screen-printed electrodes acting as a disposable test strip, where the reverse transcription loop-mediated isothermal amplification (RT-LAMP) reaction takes place. Electrochemical detection relies upon methylene blue as a redox intercalator probe, to provide a diffusion-controlled current encoding the presence and concentration of RT-LAMP products, namely amplicons or double-stranded DNA. We test the performance of the sensor by testing real wastewater samples using end-point and time course measurements. Results show the ability of the electrochemical test strip to specifically detect and quantify RT-LAMP amplicons below to ~ 2.5 × 10-6 ng/µL exhibiting high reproducibility. In this sense, our RT-LAMP electrochemical sensor is an attractive, efficient and powerful tool for rapid and reliable wastewater-based epidemiology studies.

Enhanced activated persulfate oxidation of ciprofloxacin using a low-grade titanium ore under sunlight: influence of the irradiation source on its transformation products.

In this work, the activated persulfate oxidation of ciprofloxacin (CIP) using a low-grade titanium ore under sunlight or simulated sunlight were conducted to analyze the CIP degradation efficiency and to identify the transformation products (TPs) generated during oxidation under both types of irradiation sources by using liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). All advance oxidation process experiments were performed in a 2700-mL raceway reactor at a pH value of ~ 6.5 and an initial CIP concentration of 1 mg/L, during 90 min of reaction time. The control experiments carried out under simulated sunlight achieved a 97.7 ± 0.6% degradation efficiency, using 385 W/m2 of irradiation with an average temperature increase of 11.7 ± 0.6 °C. While, the experiments under sunlight reached a 91.2 ± 1.3% degradation efficiency, under an average irradiation value of 19.2 ± 0.3 W/m2 in October-November 2019 at hours between 11:00 am and 3:00 pm with an average temperature increase of 1.4 ± 0.8 °C. Mass spectrometry results indicated that 14 of the 108 possible TPs reported in the literature were detected. The calculated exact mass, measured accurate mass, and its characteristic diagnostic fragment ions were listed, and two new TPs were tentative identified. The TP generation analysis showed that some specific compounds were detected in different time intervals with kinetic variations depending on the irradiation used. Consequently, two CIP degradation pathways were proposed, since the type of irradiation determines the CIP degradation mechanism. Graphical abstract.

Degradation of ciprofloxacin using a low-grade titanium ore, persulfate, and artificial sunlight.

In this study, the magnetic fraction (MF) of a low-grade titanium ore (TO) was successfully used as an alternative Fe2+ source in five reuse cycles, in combination with persulfate (PS) and simulated sunlight (SSL) for the degradation of ciprofloxacin (CIP). The best response of the CIP initial concentration, irradiation time, and doses of MF and PS to degrade completely this pollutant were determined based on an experimental design. However, the individual application of MF, PS, or SSL fails to achieve this goal at the optimal experimental condition. Furthermore, the MF-PS-SSL system showed a higher production of sulfate radicals and a concentration of dissolved Fe2+ ions compared with data obtained for the MF-PS system. The best performance attained by the former system is due to the synergy produced between the photo-generated electrons, and the reaction of PS with the Fe2+ ions leached gradually from the MF, which increased sulfate radical production. After five reuse cycles of the MF, the oxidation system showed a CIP degradation of 100% in 100 min, no residual content of PS, a CIP mineralization of 6%, a marginal increase in the biodegradability (BOD5/COD ratio), a MF loss of 7.5%, and a twofold increase in toxicity; however, this parameter was lower than the effective concentration at 50% inhibition (EC50). The substitution of MF with an iron salt decreased the degradation efficiency of the antibiotic by 14%, probably owing to the immediate excess of Fe2+ in the solution, which can be oxidized to Fe3+ ions, and as a consequence of this, the production rate of the sulfate radical was also reduced.

Optimization of the integral valorization process for orange peel waste using a design of experiments approach: Production of high-quality pectin and activated carbon.

The aim of this study was to optimize the integral valorization of orange peel waste by obtaining activated carbon after a process of pectin recovery in recycling of orange peel by transformation to value-added products of pectin extraction and activated carbon preparation. The study was supported by statistical analysis, and the significant factors and optimal conditions were obtained from the statistical analysis. Using a representative sample of orange peel waste, a yield of 29.37% pectin was recovered at the optimal operating conditions (phosphoric acid as the extraction agent, 95 °C as the impregnation temperature and a 2-hour extraction time). Activated carbon (AC) was prepared from the remaining solid residue. The conditions that improve the resulting material quality were H3PO4 [0.6 M] used as the activating agent, an impregnation temperature of 95 °C, a carbonization temperature of 400 °C and 1 h of carbonization time. The obtained AC showed a sorption capacity of 2342.91 mg g-1, a value higher than that reported for commercial activated carbon. Using a model dye chemical, the sorption kinetics and thermodynamics of AC were found to follow a pseudo-second-order rate and the Freundlich models, respectively. Using the process conditions obtained in this study, it was possible to optimize the yield and also obtain good-quality products from valorization of orange peel.

Enhanced photocatalytic degradation of sulfamethoxazole by deposition of Au, Ag and Cu metallic nanoparticles on TiO2.

Mono- (Au, Ag and Cu) and bi-metallic (Au-Ag and Au-Cu) nanoparticles were deposited on TiO2 and tested for the photocatalytic degradation of sulfamethoxazole using either UV-C or simulated sunlight. The optimal loading of metallic nanoparticles was determined as 1.5 wt% for Au and Ag, and 1.0 wt% for Cu. In the case of bi-metallic nanoparticles, only the ratio 1:0.5 wt% for both Au-Ag and Au-Cu was tested. In experiments using UV-C light, the highest degradation performance was found for Ag/TiO2, while bi-metallic nanoparticles supported on TiO2 also showed increased photocatalytic activity compared with unmodified TiO2. In simulated sunlight irradiation tests, Au/TiO2 showed to be the most efficient material. Complete mineralization of sulfamethoxazole was achieved when surface-modified materials were tested in both UV-C and simulated sunlight experiments. Photolysis was efficient to fully degrade sulfamethoxazole, although mineralization was lower than 10% for both luminic sources. The main by-products of sulfamethoxazole were determined in photolysis and photocatalysis tests using UV-C light, and degradation paths were proposed. By-products showed non-toxicity and low antibiotic activity. Reuse of the catalysts upon three reaction cycles did not result in the loss of activity.

Removal of arsenic III and V from laboratory solutions and contaminated groundwater by metallurgical slag through anion-induced precipitation.

Metallurgical slag was used for the simultaneous removal of high concentrations of arsenite and arsenate from laboratory solutions and severely contaminated groundwater. Apart from demonstrating the high efficiency of arsenic removal in presence of competing species, the work aims to explore the physicochemical mechanisms of the process by means of microscopy observation and a detailed statistical analysis of existing kinetic and isotherm equations. Fitting was performed by non-linear least squares using weighted residuals; ANOVA and bootstrap methods were used to compare the models. Literature suggests that the metal oxides in the slag are efficient adsorbents of As(III) and (V). However, the low surface area of the slag precludes adsorption; SEM observation provide evidence of a mechanism of co-precipitation of lixiviated cations with contaminant anions. The reaction kinetics provide essential information on the interaction between the contaminants, particularly on the common ion effect in groundwater. The Fritz-Schlünder isotherm allows modelling the saturation effect at low slag doses. The efficiency of the process is demonstrated by an arsenic removal of 99% in groundwater using 4-g slag/L, resulting in an effluent with 0.01 mg As/L, which is below Mexican and international standards for drinking water.

Optimization of the synthesis process of an iron oxide nanocatalyst supported on activated carbon for the inactivation of Ascaris eggs in water using the heterogeneous Fenton-like reaction.

An experimental design methodology was used to optimize the synthesis of an iron-supported nanocatalyst as well as the inactivation process of Ascaris eggs (Ae) using this material. A factor screening design was used for identifying the significant experimental factors for nanocatalyst support (supported %Fe, (w/w), temperature and time of calcination) and for the inactivation process called the heterogeneous Fenton-like reaction (H2O2 dose, mass ratio Fe/H2O2, pH and reaction time). The optimization of the significant factors was carried out using a face-centered central composite design. The optimal operating conditions for both processes were estimated with a statistical model and implemented experimentally with five replicates. The predicted value of the Ae inactivation rate was close to the laboratory results. At the optimal operating conditions of the nanocatalyst production and Ae inactivation process, the Ascaris ova showed genomic damage to the point that no cell reparation was possible showing that this advanced oxidation process was highly efficient for inactivating this pathogen.

Inactivation of Ascaris eggs in water using hydrogen peroxide and a Fenton type nanocatalyst (FeOx/C) synthesized by a novel hybrid production process.

Inactivation tests of Ascaris eggs (Ae) were performed using hydrogen peroxide and a Fenton type nanocatalyst supported on activated carbon (AC) (FeOx/C). Blank inactivation tests were also carried out using H2O2 and H2O2/AC as oxidation systems. The FeOx/C nanocatalyst was synthesized through a novel hybrid method developed in this work. The method is based on the incipient impregnation technique, using isopropyl alcohol as dissolvent and chelating agent of the iron salt and the ultrasonic method. The supported nanocatalyst contained 2.61% w/w of total iron and the support 0.2% w/w. Transmission electron microscopy (TEM)-energy dispersive spectrometer (EDS) images permitted verification of the presence of finely dispersed FeOx nanoparticles, with sizes ranging from 19 to 63 nm. SEM-EDS analysis and TEM images also showed good dispersion of iron oxide nanoparticles, most probably maghemite; γ-Fe2O3, able to produce hydroperoxyl radical as reported in the literature. The FeOx/C nanocatalyst-H2O2 system showed an average Ae inactivation efficiency of 4.46% Ae/mg H2O2. This value is significantly higher than the result obtained using the support-H2O2 system and H2O2 alone and it is also better than data reported for the classical Fenton process (homogeneous phase) with or without UV light.

Optimization of Fenton's reagent coupled to Dissolved Air Flotation to remove cyanobacterial odorous metabolites and suspended solids from raw surface water.

Ferrous salts are commonly used as coagulants in Water Treatment Plants (WTPs). When these salts are combined with hydrogen peroxide in acidic conditions - besides coagulation - an additional Advanced Oxidation Process (Fenton's reagent) can take place. Using a response surface methodology, this paper presents the optimization of a novel treatment system constituted by Fenton's reagent (FE) and Dissolved Air Flotation (DAF) for removing 2-Methylisoborneol (MIB), geosmin and Total Suspended Solids (TSS) from raw water. FE was proven able to remove completely both micro pollutants found in the influent of a drinking water treatment plant. Moreover, higher clarification rate was achieved by coupling FE-DAF with respect FE-Sedimentation.