Current status of advancement in remediation technologies for the toxic metal mercury in the environment: A critical review.

Currently, pollution due to heavy metals, in particular dissolved mercury, is a major concern for society and the environment. This work aims to evaluate the current scenario regarding the removal/elimination of mercury. Mercury removal through adsorption is mainly done through artificial resins and metallic-organic frameworks. In the case of the zinc organic framework, it was able to adsorb Hg2+, reaching an adsorption capacity of 802 mg g-1. As for the Hg(0) the coconut husk was found to have the lowest equilibrium time, 30 min, and the highest adsorption capacity of 956.2 mg g-1. Experimental reports and molecular simulation indicate that the adsorption of mercury and other chemical forms occurs due to electrostatic interactions, ion exchange, precipitation, complexation, chelation, and covalent bonds, according to the material nature. The reported thermodynamic results show that, in most cases, the mercury adsorption has an endothermic nature with enthalpy levels below 40 kJ mol-1. Thermal and chemical regeneration methods lead to a similar number of 5 cycles for different materials. The presence of other ions, in particular cadmium, lead, and copper, generates an antagonistic effect for mercury adsorption. Regarding the other current technologies, it was found that mercury removal is feasible through precipitation, phytoremediation, and marine microalgae; all these methods require constant chemicals or a slow rate of removal according to the conditions. Advanced oxidative processes have noteworthy removal of Hg(0); however, Fenton processes lead to mineralization, which leads to Fe2+ and Fe3+ in solution; sonochemical processes are impossible to scale up at the current technology level; and electrochemical processes consume more energy and require constant changes of the anode and cathode. Overall, it is possible to conclude that the adsorption process remains a more friendly, economical, and greener process in comparison with other processes.

Enhanced degradation of Direct Red 80 dye via Fenton-like process mediated by cobalt ferrite: generated superoxide radicals and singlet oxygen.

Azo dyes, widely used in the textile industry, contribute to effluents with significant organic content. Therefore, the aim of this work was to synthesize cobalt ferrite (CoFe2O4) using the combustion method and assess its efficacy in degrading the azo dye Direct Red 80 (DR80). TEM showed a spherical structure with an average size of 33 ± 12 nm. Selected area electron diffraction and XRD confirmed the presence of characteristic crystalline planes specific to CoFe2O4. The amount of Co and Fe metals were determined by ICP-OES, indicating an n(Fe)/n(Co) ratio of 2.02. FTIR exhibited distinct bands corresponding to Co-O (455 cm-1) and Fe-O (523 cm-1) bonds. Raman spectroscopy detected peaks associated with octahedral and tetrahedral sites. For the first time, the material was applied to degrade DR80 in an aqueous system, with the addition of persulfate. Consistently, within 60 min, these trials achieved nearly 100% removal of DR80, even after the material had undergone five cycles of reuse. The pseudo-second-order model was found to be the most fitting model for the experimental data (k2 = 0.07007 L mg-1 min-1). The results strongly suggest that degradation primarily occurred via superoxide radicals and singlet oxygen. Furthermore, the presence of UV light considerably accelerated the degradation process (k2 = 1.54093 L mg-1 min-1). The material was applied in a synthetic effluent containing various ions, and its performance consistently approached 100% in the photo-Fenton system. Finally, two degradation byproducts were identified through HPLC-MS/MS analysis.

Hydrodynamic cavitation-assisted acid pretreatment and fed-batch simultaneous saccharification and co-fermentation for ethanol production from sugarcane bagasse using immobilized cells of Scheffersomyces parashehatae.

A new alternative for hydrodynamic cavitation-assisted pretreatment of sugarcane bagasse was proposed, along with a simultaneous saccharification and co-fermentation (SSCF) process performed in interconnected columns. Influential variables in the pretreatment were evaluated using a statistical design, indicating that an ozone flow rate of 10 mg min-1 and a pH of 5.10 resulted in 86 % and 72 % glucan and xylan hydrolysis yields, respectively, in the subsequent enzymatic hydrolysis process. Under these optimized conditions, iron sulfate (15 mg L-1) was added to assess Fenton pretreatment, resulting in glucan and xylan hydrolysis yields of 92 % and 71 %, respectively, in a material pretreated for 10 min. In SSCF, ethanol volumetric productivities of 0.33 g L-1 h-1 and of 0.54 g L-1 h-1 were obtained in batch and fed-batch operation modes, achieving 26 g L-1 of ethanol in 48 h in the latter mode.

Hybrid polymer aerogels containing porphyrins as catalysts for efficient photodegradation of pharmaceuticals in water.

Polymer aerogels of poly(acrylic acid)/poly(vinyl alcohol) (labeled as CPA) were prepared and tested as support materials for different cationic porphyrin organocatalysts (denoted as TMPyP, TMPyPZn, or TMPyPMn). The hybrid aerogels were characterized by various techniques, while their catalytic activity was investigated towards the photodegradation of amoxicillin (AMX), caffeine (CAF), and naproxen (NPX) under artificial visible light. Photodegradation experiments revealed that the CPA-TMPyPMn aerogel shows superior catalytic potential when compared to the others aerogels or the "free" TMPyPMn porphyrin. All pharmaceuticals were quickly degraded (before 60 min) and high COD removal rates (greater than95%) were achieved at pH 7.0 and room temperature. The CG-MS data confirm the complete degradation of all tested pharmaceuticals catalyzed by CPA-TMPyPMn. Recycling experiments revealed that this hybrid aerogel keeps its photocatalytic efficiency for at least 15 reuse runs. In short, this original photocatalytic system is promising to mediate the removal of pharmaceutical contaminants from the aqueous medium.

A review on recent developments in hydrodynamic cavitation and advanced oxidative processes for pretreatment of lignocellulosic materials.

Environmental problems due to utilization of fossil-derived materials for energy and chemical generation has prompted the use of renewable alternative sources, such as lignocellulose biomass (LB). Indeed, the production of biomolecules and biofuels from LB is among the most important current research topics aiming to development a sustainable bioeconomy. Yet, the industrial use of LB is limited by the recalcitrance of biomass, which impairs the hydrolysis of the carbohydrate fractions. Hydrodynamic cavitation (HC) and Advanced Oxidative Processes (AOPs) has been proposed as innovative pretreatment strategies aiming to reduce process time and chemical inputs. Therefore, the underlying mechanisms, procedural strategies, influence on biomass structure, and research gaps were critically discussed in this review. The performed discussion can contribute to future developments, giving a wide overview of the main involved aspects.

Treatment of textile matrices using Fenton processes: influence of operational parameters on degradation kinetics, ecotoxicity evaluation and application in real wastewater.

Since conventional processes for treating textile effluents have limitations, this work aimed to investigate the application of advanced oxidation technology in this type of matrix. Initially, for a textile dyes mixture in solution, the photo-Fenton/sunlight process proved to be the most efficient among other systems tested. During the tests it was found that the degradation kinetics depends of the pH and catalyst and oxidant concentrations. After 60 min under optimized conditions, the color was reduced by 98.19%, with 92.52% organic matter conversion. Ecotoxicity tests with the Lactuca Sativa vegetable indicated that the dyes were not totally oxidized to inert compounds, although the treated solution did not cause a significant toxic effect for this species. In the second stage of the research, the photodegradation in real samples of textile wastewater was evaluated. The efficiency of the photo-Fenton/sunlight process was lower than that obtained for the dyes solution, a fact attributed to the greater complexity of the real matrix. However, the data also indicated that the combination of coagulation/flocculation and advanced oxidation processes is the most suitable methodology to reduce the fraction of biodegradable compounds. In summary, research has revealed that photocatalytic degradation of dyes through advanced oxidation is an efficient treatment.

Effects of water produced by oil segment on aquatic organisms after treatment using advanced oxidative processes.

The water produced (PW) by the petroleum industry is a potential contaminant to aquatic biota, due to its complex mixture that may contain polycyclic aromatic hydrocarbons (PAHs), organic chemical compounds, including benzene, toluene, ethylbenzene and xylene (BTEX), metals and other components that are known to be toxic. The aim of this investigation was to examine the acute toxicity produced by a PW sample in aquatic organisms Vibrio fischeri and Daphnia similis prior to and after 4 treatments using advanced oxidative processes such as photocatalysis, photoelectrocatalysis, ozonation and photoelectrocatalytic ozonation. Data demonstrated that exposure to PW was toxic to both organisms, as evidenced by reduced luminescence in bacterium Vibrio fischeri and induced immobility in Daphnia similis. After treatment of PW with 4 different techniques, the PW remained toxic for both tested organisms. However, photoelectrocatalysis was more efficient in decreasing toxicity attributed to PW sample. Therefore, data demonstrate the importance of treating PW for later disposal in the environment in order to mitigate ecotoxicological impacts. Further photoelectrocatalysis appeared to be a promising tool for treating PW samples prior to disposal and exposure of aquatic ecosystems.

A comparative study of photo-Fenton process assisted by natural sunlight, UV-A, or visible LED light irradiation for degradation of real textile wastewater: factorial designs, kinetics, cost assessment, and phytotoxicity studies.

The present work aims to evaluate the treatment of the effluent from the textile industry via advanced oxidative processes of photo-Fenton assisted by different sources (natural sunlight, UV-A or visible LED lamps). To identify the best operating conditions, a factorial design was carried out for each process. It was observed that after the optimization of the processes, chemical oxygen demand (COD) removals greater than 88% were achieved. In addition, it was observed that the use of the LED lamp required lower reagent concentrations compared to solar and UV-A sources. A kinetic study was carried out under the best conditions obtained and it was observed that the sources showed rapid evolution, reaching a COD removal equilibrium with 30 min of reaction. Reagent monitoring was also carried out, and it was observed that they were not limiting to the reaction. Phytotoxicity analysis was also satisfactory since the treated effluents allowed a higher relative growth and germination index of the cucumber roots compared to the raw effluent. Finally, the cost analysis indicated that the use of LED lamps resulted in a reduction in electrical consumption compared to the UV-A lamp, as well as a reduction in the cost of reagents due to the lower concentration of reagents required compared to processes assisted by natural sunlight and UV-A.

Adsorptive and photocatalytic activity of Fe3O4-functionalized multilayer graphene oxide in the treatment of industrial textile wastewater.

Multilayer graphene oxide (mGO) was synthesized and functionalized via co-precipitation method to produce magnetic Fe3O4-functionalized multilayer graphene oxide nanocomposite (MmGO). Photocatalytic properties of MmGO were investigated in the photodegradation of raw textile wastewater samples. Fourier-transformed infrared spectroscopy revealed Fe-O vibrations, characterized by the band shift from 636.27 to 587.25 cm-1 on MmGO. X-ray diffraction confirmed the successful oxidation of graphite by the (002) peak at 10° and indicated the presence of Fe3O4 on MmGO surface by the peaks at 2θ 35.8° (311), 42.71° (400), 54.09° (511), and 62.8° (440). There was no detection of coercivity field and remnant magnetization, evidencing a material with superparamagnetic properties. Then, the textile effluent was treated by heterogeneous photo-Fenton (HPF) reaction. A 22 factorial design was conducted to evaluate the effects of MmGO dosage and H2O2 concentration on HPF, with color and turbidity removal as response variables. The kinetic behavior of the adsorption and HPF processes was investigated separately, in which, the equilibrium was reached within 60 and 120 min, for adsorption and HPF, respectively. Pseudo-second-order model exhibited the best fit, with COD uptake capacity at equilibrium of 4094.94 mg g-1, for chemical oxygen demand. The modeling of kinetics data showed that the Chan and Chu model was the most representative for HPF, with initial removal rate of 95.52 min-1. The removal of organic matter was 76.36% greater than that reached by conventional treatment at textile mills. The presence of Fe3O4 nanoparticles attached to MmGO surface was responsible for the increase of electron mobility and the enhancement of its photocatalytic properties. Finally, MmGO presented low phytotoxic to Cucumis sativus L. with a RGI of 0.53. These results bring satisfactory perspectives regarding further employment, on large scale, of MmGO as nanocatalyst of textile pollutants.

Optimization of the photocatalytic degradation process of aromatic organic compounds applied to mangrove sediment.

Polycyclic aromatic hydrocarbons (PAHs) are part of a class of organic compounds resistant to natural degradation. In this way, heterogeneous photocatalysis becomes useful to degrade persistent organic pollutants, however it can be influenced by environmental variables (i.e.: organic matter) and experimental factors such as: mass of the photocatalyst and irradiation time. The objective of this research was to use a factorial design 2k as a function of the multiple response (MR) to evaluate simultaneously experimental conditions for the photodegradation of polycyclic aromatic hydrocarbons in contaminated mangrove sediment and its application in oil from Potiguar Basin in Brazil. The sediment samples collected in Belmonte city (Southern Bahia state) were contaminated with 0.25 mg kg-1 of Acenaphthene, Anthracene, Benzo[a]Anthracene, Indene[1,2,3cd]pyrene, Dibenzo[ah]anthracene, Benzo[ghi]pyrene. Factors such as mass of the photocatalyst and irradiation time were evaluated in factorial design 22, with triplicate from the central point, to 1g of the PAH contaminated sediment. After performing the experiments, it was found that the best experimental condition for the degradation of all PAHs indicated by MR was the central point (0.5 g of photocatalyst and 12h of irradiation). For such conditions, the half-life of PAHs varied from 3.51 to 9.37 h and the degradation speed constant between 0.0740 to 0.1973 h-1. The comparison of the optimized methodology between photolysis tests and heterogeneous photocatalysis was performed using the Kruskal-Wallis test, which indicated a difference for the reference solution, where heterogeneous photocatalysis was more efficient in the degradation of PAHs. The optimized methodology was apply in samples contaminated with crude oil from Potiguar Basin, no significant difference was observed in the aromatic fraction, using for the Kruskal-Wallis test. Heterogeneous photocatalysis has shown to be a promising remediation technique to remedy aromatic organic compounds in mangrove sediments.

Factorial design application in photocatalytic wastewater degradation from TNT industry-red water.

In trinitrotoluene (TNT) purification process, realized in industries, there are two washes carried out at the end of the procedure. The first is performed with vaporized water, from which the first effluent, called yellow water, is originated. Then, a second wash is performed using sodium sulfite, generating the red water effluent. The objective of this work was to get the best conditions for photocatalytic degradation of the second effluent, red water, in order to reduce toxicity and adjust legal parameters according to regulatory agencies for dumping these effluents into waterways. It has used a statistical evaluation for factor interaction (pH, concentration) that affects heterogeneous photocatalysis with titanium dioxide (TiO2). Thus, the treatment applied in the factorial experimental design consisted of using a volume equal to 500 mL of the effluent to 0.1 % by batch treatment, which has changed TiO2 pH and concentration, according to the design, with 20 min time for evaluation, where it was used as response to the reduction of UV-Vis absorption. According to the design responses, it has obtained optimum values for the parameters evaluated: pH = 6.5 and concentration of 100 mg/L of TiO2 were shown to be efficient when applied to red water effluent, obtaining approximately 91 % of discoloration.

Textile wastewater reuse after additional treatment by Fenton's reagent.

This study verifies textile wastewater reuse treated by the conventional activated sludge process and subjected to further treatment by advanced oxidation processes. Three alternative processes are discussed: Fenton, photo-Fenton, and UV/H2O2. Evaluation of treatments effects was based on factorial experiment design in which the response variables were the maximum removal of COD and the minimum concentration of residual H2O2 in treated wastewater. Results indicated Fenton's reagent, COD/[H2O2]/[Fe2+] mass ratio of 1:2:2, as the best alternative. The selected technique was applied to real wastewater collected from a conventional treatment plant of a textile mill. The quality of the wastewater before and after the additional treatment was monitored in terms of 16 physicochemical parameters defined as suitable for the characterization of waters subjected to industrial textile use. The degradation of the wastewater was also evaluated by determining the distribution of its molecular weight along with the organic matter fractionation by ultrafiltration, measured in terms of COD. Finally, a sample of the wastewater after additional treatment was tested for reuse at pilot scale in order to evaluate the impact on the quality of dyed fabrics. Results show partial compliance of treated wastewater with the physicochemical quality guidelines for reuse. Removal and conversion of high and medium molecular weight substances into low molecular weight substances was observed, as well as the degradation of most of the organic matter originally present in the wastewater. Reuse tests indicated positive results, confirming the applicability of wastewater reuse after the suggested additional treatment. Graphical abstract Textile wastewater samples after additional treatment by Fenton's reagent, photo-Fenton and H2O2/UV tested in different conditions.