Eco-friendly nanoparticles: mechanisms and capacities for efficient removal of heavy metals and phosphate from water using definitive screening design approach.

Can nano-zero-valent iron, synthesized using oak leaf extract, be the key solution for water preservation, efficiently removing heavy metal ions and phosphate anions simultaneously? This research unveils how this technology not only promises high efficiency in the remediation of water resources, but also sets new standards for environmentally friendly processes. The high antioxidant capacity and high phenol content indicate suggest the possibility of oak-nZVI synthesis using oak leaf extract as a stable material with minimal agglomeration. The simultaneous removal of Cd and phosphates, as well as and Ni and phosphates was optimized by a statistically designed experiment with a definitive screening design approach. By defining the key factors with the most significant impact, a more efficient and faster method is achieved, improving the economic sustainability of the research by minimizing the number of experiments while maximizing precision. In terms of significance, four input parameters affecting process productivity were monitored: initial metal concentration (1-9 mg L-1), initial ion concentration (1-9 mg L-1), pH value (2-10), and oak-nZVI dosage (2-16 mL). The process optimization resulted in the highest simultaneous removal efficiency of 98.99 and 87.30% for cadmium and phosphate ions, respectively. The highest efficiency for the simultaneous removal of nickel and phosphate ions was 93.44 and 96.75%, respectively. The optimization process fits within the confidence intervals, which confirms the assumption that the selected regression model well describes the process. In the context of e of the challenges and problems of environmental protection, this work has shown considerable potential and successful application for the simultaneous removal of Cd(II) and Ni(II) in the presence of phosphates from water.

Electrocoagulation in treatment of municipal wastewater- life cycle impact assessment.

The purpose of this study is investigation of electrocoagulation (EC) as a treatment of municipal wastewater, integrating life cycle impact assessment (LCIA) for assessing its environmental performance of investigated treatment. The study evaluated the effectiveness of EC in removing physico-chemical and microbial parameters using aluminum (Al) and iron (Fe) electrodes in monopolar and bipolar modes. Bipolar arrangement of Al(-)/Al/Al/Al(+) electrodes achieved the highest removals: 70% COD, 72% BOD5 followed by complete elimination of total phosphorous, turbidity and microbial parameters. This treatment was subject to investigation of the influence of reaction time (t = 10-60 min) on removals at higher current density (CD = 3.33 mA/cm2). In order to reduce energy consumption, the same reaction time range was used with a reduced CD = 2.33 mA/cm2. Following removal efficiencies obtained: 47-72% COD (higher CD) and 53-78% (lower CD); 69-75% BOD5 (higher CD) and 55-74% CD (lower CD); 12-21% NH4- (higher CD) and 7-22% NH4- (lower CD). Total P, NO3- and NO2- compounds showed the same removals regardless the CD. Decrease in current density did not influence removals of total suspended matter, turbidity, salinity as well as microbial parameters. The bipolar arrangement of Al(-)/Al/Al/Al(+) electrodes, assuming a lower CD = 2.33 mA/cm2 and t = 30 min, was assessed with the Recipe 2016Midpoint (H) and USEtox v.2 LCIA methods to explore the environmental justification of using EC for wastewater treatment. The LCIA results revealed that the EC process significantly reduces water eutrophication and toxicity for freshwater and marine ecosystems, but has higher impacts in global warming, fossil fuel consumption, human toxicity, acidification, and terrestrial ecotoxicity due to high energy consumption. This can be mainly explained by the assumption in the study that the EC precipitate is dispersed to agricultural soil without any pre-treatment and material recovery, along with relatively high energy consumption during the process.

"Green" nZVI-Biochar as Fenton Catalyst: Perspective of Closing-the-Loop in Wastewater Treatment.

In the framework of wastewater treatment plants, sewage sludge can be directed to biochar production, which when coupled with an external iron source has the potential to be used as a carbon-iron composite material for treating various organic pollutants in advanced oxidation processes. In this research, "green" synthesized nano zero-valent iron (nZVI) supported on sewage sludge-based biochar (BC)-nZVI-BC was used in the Fenton process for the degradation of the recalcitrant organic molecule. In this way, the circular economy principles were supported within wastewater treatment with immediate loop closing; unlike previous papers, where only the water treatment was assessed, the authors proposed a new approach to wastewater treatment, combining solutions for both water and sludge. The following phases were implemented: synthesis and characterization of nano zero-valent iron supported on sewage sludge-based biochar (nZVI-BC); optimization of organic pollutant removal (Reactive Blue 4 as the model pollutant) by nZVI-BC in the Fenton process, using a Definitive Screening Design (DSD) model; reuse of the obtained Fenton sludge, as an additional catalytic material, under previously optimized conditions; and assessment of the exhausted Fenton sludge's ability to be used as a source of nutrients. nZVI-BC was used in the Fenton treatment for the degradation of Reactive Blue 4-a model substance containing a complex and stable anthraquinone structure. The DSD model proposes a high dye-removal efficiency of 95.02% under the following optimal conditions: [RB4] = 50 mg/L, [nZVI] = 200 mg/L, [H2O2] = 10 mM. pH correction was not performed (pH = 3.2). Afterwards, the remaining Fenton sludge, which was thermally treated (named FStreated), was applied as a heterogeneous catalyst under the same optimal conditions with a near-complete organic molecule degradation (99.56% ± 0.15). It could be clearly noticed that the cumulative amount of released nutrients significantly increased with the number of leaching experiments. The highest cumulative amounts of released K, Ca, Mg, Na, and P were therefore observed at the fifth leaching cycle (6.40, 1.66, 1.12, 0.62, 0.48 and 58.2 mg/g, respectively). According to the nutrient release and toxic metal content, FStreated proved to be viable for agricultural applications; these findings illustrated that the "green" synthesis of nZVI-BC not only provides innovative and efficient Fenton catalysts, but also constitutes a novel approach for the utilization of sewage sludge, supporting overall process sustainability.

Synergistic effect of Fenton oxidation and adsorption process in treatment of azo printing dye: DSD optimization and reaction mechanism interpretation.

The main challenges to overcome within the Fenton process are the acidic pH as an optimal reaction condition, sludge formation in neutral pH medium and high toxicity of treated printing wastewater due to the generation of contaminating by-products. This research discusses the catalytic activity of homogeneous (FeSO4/H2O2) and heterogeneous (Fe2(MoO4)3/H2O2) Fenton processes in treatment of Yellow azo printing dye in synthetic aqueous solution and real printing effluent, with an integration of adsorption on functionalized biochar synthesized from wild plum kernels. The definitive screening design (DSD), was used to design the experiment. Independent variables were initial dye concentration (20-180 mg L-1), iron concentration (0.75-60 mg L-1), pH (2-10) and hydrogen peroxide concentration (1-11 mM). Higher decolourization efficiency of 79% was obtained within homogeneous Fenton treatment of printing wastewater, in comparison to heterogeneous Fenton treatment (54%), after a reaction time of 60 min. Same trend of mineralization degree was established: COD removal was 59% and 33% for homogeneous and heterogeneous Fenton process, respectively. The application of adsorption treatment has achieved significant advantages in terms of toxicity reduction (95%) and decolourization efficiency (90% of TOC removal and 22% of dye removal) of treated samples, even at neutral pH medium. Degradation mechanisms within Fenton and adsorption processes were proposed based on the qualitative gas chromatography/mass spectrometry analysis, physico-chemical properties of dye degradation products and functionalized biochar. Overall, the homogeneous Fenton/adsorption combined process can be potentially used as a treatment to remove azo dyes from contaminated water.

Metal Nanoparticles in Dye Wastewater Treatment - Smart Solution for Clear Water.

BACKGROUND: In past years, nanomaterials have been actively studied and developed and successfully used in many fields. Due to water scarcity, the application of nanomaterials in water and wastewater treatment has drawn significant attention. Due to their superior features, they represent functional materials with great potential for pollution removal and environmental applications. OBJECTIVE: This literature review aims to summarize and present the metal nanoparticles used for dye wastewater treatment. The discussion subject is metallic nanoparticles for mentioned use, with a special focus on iron-based, bimetallic, and photocatalytic nanomaterials. METHODS: Reference search of "metal nanoparticles in dye wastewater treatment" was conducted in detail through the Serbian Library Consortium for Coordinated Acquisition (KoBSON). Published papers search was mainly based on Web of Science and ScienceDirect database focusing on the latest research on this topic. The corresponding literature was carefully read, analyzed, and evaluated. RESULTS: Two hundred and twenty-four scientific and review articles, thesis, and book chapters, patents were evaluated in order to summarise current trends in metal nanoparticle use in wastewater treatment. An increasing trend in scientific research regarding metal nanoparticles can be observed for the removal of different inorganic and organic pollutants. Among the most extensively tested are dye molecules, representing challenging species in terms of degradation and consequent removal. Modification, layering, combination, and green synthesis of metal nanoparticles result in materials capable of efficient and environmentally sustainable wastewater treatment. CONCLUSION: In this paper, an extensive review of metal nanoparticles in dye wastewater treatment is presented. With rapid water demand, the development of sustainable materials and technology is necessary. The use of these materials represents eco-friendly, energy-efficient, and sustainable water purification solutions. However, the matter of usage commercialization is still to be addressed.

A cost effective method for immobilization of Cu and Ni polluted river sediment with nZVI synthesized from leaf extract.

This study investigates the performance of oak (OL) and mulberry (ML) leaves for synthesized of nanoscale zero-valent iron (nZVI), in immobilizing Cu and Ni in contaminated sediment. Characterization of synthesized Fe nanoparticles from oak and mulberry leaf extracts demonstrated that they are nontoxic and stabile nanomaterials for application in the sediment remediation. Effectiveness of stabilization process was performed by microwave-assisted sequential extraction procedure (MWSE) and single-step leaching tests which have been applied to evaluate the metal extraction potential. This research showed that OL-nZVI and ML-nZVI were effective in transforming available Cu and Ni to stable fraction. The maximum residual percentage of Cu increased by 76% and 73%, and for Ni 81% and 80%, respectively, with addition of 5% OL-nZVI and 5% ML-nZVI. Used single-step leaching tests (Toxicity Characteristic Leaching Procedure-TCLP and German standard test- DIN) indicated that all stabilized samples can be considered as non-hazardous waste, as all leached metal concentrations met the appropriate set criteria. Cost analysis showed that the operating cost for contaminated sediment treatment with green synthesized nZVI are 50.37 €/m3/per year. This work provides a new insight into the immobilization mechanism and environmental impact of Cu and Ni in contaminated sediment and potential way of treatment with OL-nZVI and ML-nZVI. Generally, nZVI can be an effective and versatile tool for stabilization of sediment polluted with toxic metals.

The Application of Solar Cells in the Electrokinetic Remediation of Metal Contaminated Sediments.

In this study, solar cells were used to generate an electric field for the electrokinetic remediation of metal contaminated sediment (Nickel, Cadmium, Zinc). For determination of metals mobility, bioavailability and potential toxicity, sequential extraction procedure, simultaneously extracted metals (SEM) and acid-volatile sulphide ratios (AVS) were performed before, during and after treatment.After 21 days of treatment, 63% Ni, 82% Cd and 58% Zn was removed from the anode region. The application of the electric field changed the chemical composition of the sediments. The risk assessment analysis based on pseudo total metals content, the risk assessment code and the relationship between SEM and AVS, indicates that a simple singular approach for risk assessment analysis and evaluation of the quality of sediments is not enough.

Organic and inorganic priority substances in sediments of Ludas Lake, a cross-border natural resource on the Ramsar list.

For the first time, long-term monitoring (from 2002 to 2014) was carried out of surface sediments in Ludas Lake, a Ramsar site in northern Serbia. Organic (16 EPA PAHs, mineral oils, selected pesticides and polychlorinated biphenyls (PCBs)) and inorganic substances (eight heavy metals: Ni, Zn, Cd, Cr, Cu, Pb, As and Hg) were continually investigated. Dibenzo[a,h]anthracene (DahA) and fluorene (Flo) were found at levels indicative of causing adverse effects to biota. Diagnostic ratios of specific PAHs were dominated by high molecular weight components, particularly DahA, which contributed 81.78 % of the total high carcinogens, benzo[b]fluoranthene (BbF) and Flo. Potential ecological risk factors (ERi) and the high relative standard deviations (RSD) obtained (up to 245 %) for the parameters monitored confirm the high periodical anthropogenic impact from industry, municipal wastewater and agriculture. The highest concentration of inorganic pollution found was for Cd (440-831 mg/kg) at all sites, Cu (439 mg/kg) in the eastern part of the lake and Cu (388 mg/kg) and Hg (771 mg/kg) in the northern part of the lake. Based on factor analysis of principal component analysis (PCA/FA), As and phenanthrene (Phe) had significant loadings (0.808 and 0.907, respectively). This association of As with organic anthropogenic sources was also confirmed with the sum of PAHs, pyrene (Pyr) and mineral oil by 3D factor plot, corroborating the theory of As mobilization from metal-reducing microbes as organic (methylated) forms, accelerated by phenanthrene. According to EU national and regional data results, this research suggests that Cu, As, dibenzo[a,h]anthracene and Flo should be added to the list of priority pollutants within the context of applying the European Water Framework Directive (WFD).

Degradation of anthraquinone dye reactive blue 4 in pyrite ash catalyzed Fenton reaction.

Pyrite ash (PA) is created by burning pyrite in the chemical production of sulphuric acid. The high concentration of iron oxide, mostly hematite, present in pyrite ash, gives the basis for its application as a source of catalytic iron in a modified Fenton process for anthraquinone dye reactive blue 4 (RB4) degradation. The effect of various operating variables such as catalyst and oxidant concentration, initial pH and RB4 concentration on the abatement of total organic carbon, and dye has been assessed in this study. Here we show that degradation of RB4 in the modified Fenton reaction was efficient under the following conditions: pH=2.5; [PA]0=0.2 g L(-1); [H2O2]0=5 mM and initial RB4 concentration up to 100 mg L(-1). The pyrite ash Fenton reaction can overcome limitations observed from the classic Fenton reaction, such as the early termination of the Fenton reaction. Metal (Pb, Zn, and Cu) content of the solution after the process suggests that an additional treatment step is necessary to remove the remaining metals from the water. These results provide basic knowledge to better understand the modified, heterogeneous Fenton process and apply the PA Fenton reaction for the treatment of wastewaters which contains anthraquinone dyes.

Use of fly ash for remediation of metals polluted sediment--green remediation.

The aim of this study was to determine the possibility of using fly ash and combination of kaolinite and fly ash for the solidification/stabilization (S/S) of Ni and Zn contaminated sediment from the Krivaja river basin (Serbia), which represents an extraordinary risk to the environment and belongs to the last quality class in the Serbian sediment classification. Fly ash was used as a stabilising agent because it occurs as a secondary industrial product, so in this way two types of waste are immobilized. Microwave assisted BCR sequential extraction procedure was employed to assess potential of Ni and Zn mobility and risk to the aquatic environment. In order to determine the long-term behavior of the S/S mixture, the semi-dynamic ANS 16.1 leaching test was performed. The existing leaching method was modified and acetic acid and humic acid were also used as leachants instead of deionised water, in order to simulate possible "worst case" leaching conditions for S/S waste being disposed of in a landfill environment (acid rain, floods, etc.). S/S effectiveness was evaluated by measuring the cumulative fractions of metals leached, effective diffusion coefficients - De and leachability indices - LX. X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray analyzer (EDS) along with leaching tests were implemented to elucidate the mechanisms responsible for immobilization of the Ni and Zn. The controlling leaching mechanism was found to be diffusion, in all treated samples. Overall, the test results indicated that S/S treatment was effective for immobilization of these two types of waste, and can be considered acceptable for "controlled utilization".