Elimination of hazardous Se(IV) through adsorption-coupled reduction by iron nanoparticles embedded on mesopores of chitin obtained from waste shrimp shells.

Selenium is an essential nutrient for biological function. However, there is a detrimental effect on the aquatic environment associated with higher concentrations of > 40 µg/L. The utilization of waste shrimp shells for the removal of high-concentrated selenium from wastewater is a commendable strategy in both the pollution control and waste management sectors. In the present study, a chitin-iron polymer complex hybrid material (Fe@SHC) was prepared from shrimp shell-derived hydrochar (SHC), and the synthesized composite was successfully employed to uptake selenium from wastewater. The highest removal performance of 79.18 mg/g was attained by Fe@SHC, whereas the capacity of SHC was 15.30 mg/g. It was found that the calcium content of Fe@SHC (1.98%) was lower than that of SHC (25.20%) and pHzpc of Fe@SHC was extended to 7.78 compared with that of SHC (2.00). The abundance of protonated hydroxyl (-OH2+) and amine (-NH3+) functional groups that developed through the iron co-precipitations resulted in the improved adsorption performance of Fe@SHC. XPS analysis demonstrated that the captured Se(IV) species were converted into less hazardous Se(0), which is accompanied by the electron transfer with both N-C = O (acetyl amine) and -NH2 (amine) functional groups. Adsorption kinetics disclosed that the adsorption process was governed by chemical sorption, and the Sips isotherm model provided the most accurate description of the isotherm equilibrium. This study proposed an inexpensive and environmentally friendly method for effective decontamination of Se from wastewater.

Nitrogen-rich carbon composite fabricated from waste shrimp shells for highly efficient oxo-vanadate adsorption-coupled reduction.

Protein, calcium carbonate, and chitin are abundant in shrimp shells. In this study, chemical treatment followed by hydrothermal carbonization was used to synthesize the nitrogen-rich hydrochar (HSHC) from shrimp shells. The untreated hydrochar exhibited a higher amount of calcium (25.37%) and less amount of nitrogen (2.68%) with alkaline pH (9.1). Interestingly chemical pre-treatment on shrimp shells boosted the nitrogen content to 6.81% and eliminated the calcium while controlling the pH to 6.4, which was beneficial for oxo-vanadate removal. The HSHC achieved vanadium(V) adsorption capacity of 21.20 mg/g at an optimal solution pH of 3.0, whereas the pristine hydrochar performed poorly (0.66 mg/g). The abundance of oxygen and nitrogen-based functional groups that developed through the chemical treatment resulted in improved adsorption coupled reduction performance of HSHC. This study proposed an inexpensive and environmentally friendly method for converting waste shrimp shells into value-added adsorbent.

Study on the coordination conduct and kinetic insights within the oxo-vanadate and organic reductive nitrogen and sulfur functionalities during the reduction coupled adsorption processes: Implications in practical applications.

Vanadium(V) is arising wastewater contaminant recently. Although bio-reduction of vanadium(V) is effective, the knowledge of electron transfer pathways and coordination nature by cellular organic functionalities is seriously lacking. Herein, the coordination conduct and kinetic modes for the reduction of V(V) by organic nitrogen and sulfur functionalities in working pHs are comprehensively investigated for the first time. The kinetics follow 3 steps; (1) diffusion of V(V) species, (2) reduction of V(V) to V(IV), and (3) adsorption of existing V species. The diffusion of V(V) is controlled by the protonated =NH2+, -SH2+, -CSH+ functional groups and oxo-vanadate speciation. The reduction of V(V) to V(IV) was efficient by -SH than =NH, -NH- , because of the higher oxidation potential of sulfur and which acted as the sole electron donor in the process. The coordination of V(V)/V(IV) species interacted with oxygen, nitrogen and sulfur atoms via parallel orientation and leads to multi-docking or single-ionic interactions, revealing the previously unrecognized track. Hence, the system tested in four types of wastewaters with different pHs and resulted the comprehensive practical applicability of the system. This study proposes a novel tactic to design an efficient V(V) wastewater treatment system by considering its water parameters.

Lanthanum hydroxide engineered sewage sludge biochar for efficient phosphate elimination: Mechanism interpretation using physical modelling.

In the present study, lanthanum hydroxide (La OH)-engineered sewage sludge biochar (La-SSBC) was utilized for efficient phosphate elimination from an aqueous medium. A high adsorption capacity of 312.55 mg P/g was achieved using La-SSBC at 20 °C, which was an excellent adsorbent performance in comparison to other biochar-based adsorbents. Additionally, the performance of La-SSBC was stable even at wider range of pH level, the existence of abundant active anions, and recycling experiments. Statistical physics modeling with the fitting method based on the Levenberg-Marquardt iterating algorithm, as well as various chemical characterizations, suggested the unique double-layered mechanism of phosphate capturing: one functional group of La-SSBC adsorbent describing a prone direction of the PO4 ions on the stabilize surface in a multi-ionic process, forming the first layer adsorption. Additionally, SSBC played an important role by releasing positively charged cations in solution, overcoming the electronic repulsion to form a second layer, and achieving excellent adsorption capacity. The calculation of multiple physicochemical parameters including adsorption energy further evidenced the process. This two-layered mechanism sheds light on the complex interaction between phosphate and biochar. Moreover, the management of sewage sludge associated with the requirement of cost-effectively and environmentally acceptable mode. Therefore, the present investigation demonstrated an efficient approach of the simultaneous sewage sludge utilization and phosphate removal.

Regulating the redox centers of Fe through the enrichment of Mo moiety for persulfate activation: A new strategy to achieve maximum persulfate utilization efficiency.

Persulfate Fe-based catalytic oxidation is considered as one of the most attractive strategy for the growing concerns of water pollution. However, the undesirable FeIII/FeII redox cycle restrict them from attending the sustainable activity during practical applications. This study was intended to develop a new strategy to regulate the redox cycles of FeIII/FeII by introducing the second redox center of MoS42- in the interlayers of Fe-based layered double hydroxide (FeMgAl-MoS4 LDH). Based on the first-order kinetic model, the fabricated FeMgAl-MoS4 catalyst was 10-100 fold more reactive than the bench marked peroxymonosulfate (PMS) activators including FeMgAl LDHs and other widely reported nano-catalysts such as Co3O4, Fe3O4, α-MnO2, CuO-Fe3O4 and Fe3O4. The enhanced catalytic activity of FeMgAl-MoS4 LDH was related to the continuous regeneration of active sites (FeII/MoIV), excellent PMS utilization efficiency and generation of abundant free radicals. Moreover, the FeMgAl-MoS4/PMS system shows an effective pH range from 3.0 to 7.0 and the degradation kinetics of parahydroxy benzoic acid (PHB) were not effected in the presence of huge amount of background electrolytes and natural organic matters. Based on the in-situ electron paramagnetic resonance spectroscopy (EPR), chemical scavengers, XPS analysis and gas chromatography couple with mass spectrometer (GC-MS), a degradation pathway based on dominant free radicals (•SO4- and •OH), passing through the redox cycles of FeIII/FeII and MoVI/MoIV was proposed for PMS activation. We believe that this strategy of regulating the redox center through MoS42- not only provides a base to prepare new materials with stable catalytic activity but also broaden the scope of Fe-based material for real application of contaminated water.

Adsorptive purification of heavy metal contaminated wastewater with sewage sludge derived carbon-supported Mg(II) composite.

A rod-like SDBC-Mg(II) composite was synthesized and optimized in the conditions of 25% Mg(II) loading and 500 °C calcination temperature. As-prepared SDBC-25%Mg(II)-500 adsorbent attained equilibrium in 30 min, with an extraordinary capacity of 2931.76 mg g-1 (Pb(II)) and 861.11 mg g-1 (Cd(II)), revealing a promising adsorbent for the removal of such metals so far. The adsorption kinetics was well described by the pseudo-second-order model while the adsorption isotherm could be fitted by Redlich-Peterson model. Furthermore, SDBC-25%Mg(II)-500 has a high anti-interference and selectivity in the presence of competing ions/other environmental factors and, also effectively eliminates >99% of Pb2+, Cd2+, Ag+ and Cu2+ ions from pond water, lake water and tap water. The adsorption process demonstrated a synergetic adsorption mechanism comprised of ion exchange with Mg(II), coordination with surface and inner carboxylic or carbonyl functional groups and co-precipitations as metal silicates, which is responsible for its superb adsorption performance. Besides, surface carvings of Mg(II) and tunnels on the rods resulting from the sludge carbonization provided a high surface area (91.57 m2 g-1), extra sorption sites and room for easy pollutant diffusion which contributed to surface physical adsorption. Furthermore, this technique demonstrate an alternative pathway that will relieve the burdens of sewage sludge treatment process and turn this solid waste into highly efficient adsorbent for eliminating heavy metal ions from wastewater. This can be considered as a feasible waste resource utilization to meet with the requirement from both ecology and economy for auspicious applications in industries.