The modified tannin by Mannich reaction was investigated for wastewater treatment. The removal of heavy metals, such as copper, chromium and mercury, in industrial wastewater was evaluated through the coagulation–flocculation technique, using modified Acacia tannin (MAT) as a coagulant agent. The successful tannin modification was evaluated by infrared spectopometry (FTIR), nuclear magnetic resonance (NMR); monitoring the removal of heavy metals was performed by atomic absorption (AA) and a direct mercury analyzer (DMA). Additionally, the parameters of water quality, total suspended solids (TSS), turbidity and chemical oxygen demand (COD) were assessed. Different doses of MAT were evaluated (375 ppm, 750 ppm, 1250 ppm and 1625 ppm) and three different levels of pH (4, 7 and 10). The highest percentages of removal obtained were copper 60%, chromium 87%, mercury 50%–80%, COD 88%, TSS 86% and turbidity 94%, which were achieved with the dose of 375 ppm of MAT at pH 10. The coagulation–flocculation process with the modified Acacia tannin is efficient for the removal of conventional parameters and for a significant removal of the metals studied.
The environment protection has been the starting point for the development of new technologies, which allow the control of highly toxic substances present in the effluents of various industries, whose removal is not feasible by conventional methods. In this research, mixed oxide catalysts Mn and Cu in different molar ratios were prepared from the autocombustion method and characterized by XRD, XRF, TPR-H2, and N2 adsorption–desorption isotherms. The solids were evaluated in the catalytic wet peroxide oxidation of crystal violet (CV) with mild conditions of reaction: 25 °C, normal pressure, airflow of 2 mL/min, and H2O2 0.1 M (2 mL/h). The experimental results indicated degradations of 100% of CV, conversion of the total organic carbon (TOC) of 74%, and elimination of chemical oxygen demand (COD) of 71% in 90 min of reaction. Additionally, the selectivity was monitored by CG-MS, finding that there was almost complete mineralization in a short reaction time, generating intermediate products such as carboxylic acids, alcohols, and amines that do not cause a serious risk to the environment. The Mn–Cu catalyst with molar ratios of 1:2 was the most promising catalyst, displaying a cooperative effect between the two metals, and demonstrating the importance of the redox properties for the elimination of CV dye in wastewater.
The catalytic oxidation of aqueous crystal violet (CV) solutions was investigated using Ni and Fe catalysts supported over Mg–Al oxides synthesized by the autocombustion method. The influence of temperature, loading, and selectivity were studied in the catalytic wet air oxidation (CWAO) of CV. The kind of metal had an important contribution in the redox process as significant differences were observed between Fe, Ni, and their mixtures. The catalysts with only Fe as active phase were more efficient for the oxidation of CV under normal conditions (T = 25 °C and atmospheric pressure) compared to those containing Ni, revealing the influence of the transition metal on catalytic properties. It was found that iron-containing materials displayed enhanced textural properties. The synthesis of Fe/MgAl catalysts by the autocombustion method led to solids with excellent catalytic behavior, 100% CV degradation in eight hours of reaction, 68% selectivity to CO2, and significant reduction of chemical oxygen demand (COD).
Antibiotics and pesticides, as well as various emerging contaminants that are present in surface waters, raise significant environmental concerns. Advanced oxidation processes, which are employed to eliminate these substances, have demonstrated remarkable effectiveness. However, during the degradation process, by-products that are not completely mineralized are generated, posing a substantial risk to aquatic ecosystem organisms; therefore, it is crucial to assess effluent ecotoxicity following treatment. This study aimed to assess the toxicity of effluents produced during the removal of amoxicillin and glyphosate with a Fenton-type process using a laminar structure catalyzed with iron (Fe) and copper (Cu). The evaluation included the use of Daphnia magna, Selenastrum capricornutum, and Lactuca sativa, and mutagenicity testing was performed using strains TA98 and TA100 of Salmonella typhimurium. Both treated and untreated effluents exhibited inhibitory effects on root growth in L. sativa, even at low concentrations ranging from 1% to 10% v/v. Similarly, negative impacts on the growth of algal cells of S. capricornutum were observed at concentrations as low as 0.025% v/v, particularly in cases involving amoxicillin–copper (Cu) and glyphosate with copper (Cu) and iron (Fe). Notably, in the case of D. magna, mortality was noticeable even at concentrations of 10% v/v. Additionally, the treatment of amoxicillin with double-layer hydroxides of Fe and Cu resulted in mutagenicity (IM ≥ 2.0), highlighting the necessity to treat the effluent further from the advanced oxidation process to reduce ecological risks.
Endocrine disruptors such as 17α-ethinylestradiol pose significant ecological risks in aquatic environments. This study assessed the catalytic performance of Fe- and Cu-impregnated delaminated clays (DCs) and layered double hydroxides (LDHs) in a Fenton-like process for EE2 removal. The effects of key parameters—including hydrogen peroxide concentration, initial contaminant load, and catalyst dosage—were analyzed using HPLC-QqTOF. Delaminated clays (DCs) demonstrated higher removal efficiencies compared to layered double hydroxides (LDHs), reaching 55% with Fe and 47% with Cu, while LDHs achieved 40% and 33% for Fe and Cu, respectively. Ecotoxicity was evaluated using bioassays (L. sativa, S. capricornutum, D. magna) and the Ames test. Notably, S. capricornutum exhibited 100% inhibition at the highest tested concentration, with IC50 values of 11.2–12.4 for Cu and 31.5–32.7 for Fe. L. sativa was inhibited by Cu- and Fe-impregnated LDH/DC, with IC50 values of 71.0 (DC-Cu), 56.6 (DC-Fe), and 58.6 (LDH-Fe). D. magna exhibited 17–75% mortality when exposed to untreated EE2, while LC50 values confirmed Cu’s greater toxicity. The Ames test indicated no mutagenic effects. Integrating the Fenton-like process with complementary techniques is recommended to enhance efficiency. These findings highlight the need to optimize operational parameters for effective removal of 17α-ethinylestradiol.