Enhanced adsorptive removal of hexavalent chromium in aqueous media using chitosan-modified biochar: Synthesis, sorption mechanism, and reusability.

Hexavalent chromium (Cr(VI)) is deemed a priority contaminant owing to its carcinogenicity, teratogenicity, and mutagenicity towards flora and fauna. A novel Chitosan-modified Mimosa pigra biochar (CMPBC) was fabricated and the efficiency of Cr(VI) oxyanion removal in aqueous systems was compared with the pristine biochar. The instrumental characterization of X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FT-IR) confirmed the amino modification of MPBC when treated with chitosan. Characteristic features of the Cr(VI) sorptive process by CMPBC and MPBC were examined by performing batch sorption studies. Experimental data suggested that sorption is heavily dependent on pH and the highest adsorption occurred at pH 3.0. The maximum adsorption capacity of CMPBC was 14.6 ± 1.07 mg g-1. It was further noted that the removal efficiency of CMPBC (92%) was considerably greater than that of MPBC (75%) when the solution pH, biochar dose, and initial concentration of Cr(VI) are 3.0, 1.0 g L-1 and 5.0 mg L-1 respectively. The kinetic data were best interpreted by the power function model (R2 = 0.97) suggesting a homogenous chemisorption process. The isotherm data for the removal of Cr(VI) by CMPBC was inferred well by Redlich Peterson (R2 = 0.96) and Temkin (R2 = 0.96) isotherms. Results of sorption-desorption regeneration cycles indicated that the Cr(VI) uptake by CMPBC is not fully reversible. The coexistence of Cr(VI) and Cr(III) on CMPBC was confirmed through the XPS analysis. The electrostatic attractions between cationic surface functionalities and Cr(VI) oxyanions, the partial reductive transformation of Cr(VI) species to Cr(III), as well as complexation of Cr(III) onto CMPBC were identified as the possible mechanisms of mitigation of Cr(VI) by CMPBC. The results and outcomes of this research suggest the possibility of utilizing the CMPBC as an easily available, environmentally sustainable, and inexpensive sorbent to decontaminate Cr(VI) from aqueous media.

Heavy metal dissolution mechanisms from electrical industrial sludge.

In this paper, we investigate the release of heavy metals from sludge produced from an electrical industry using both organic and inorganic acids. Single and sequential extractions were conducted to assess heavy metals in different phases of the sludge. Metal release from sludge was investigated in the presence of three inorganic acids (nitric, sulfuric, and phosphoric) and three organic acids (acetic, malic, and citric) at concentrations ranging from 0.1 to 2.0 mol L-1. Sequential extraction indicated the presence of Cu primarily in the carbonate fraction, Pb in the residual fraction, and Ni in the FeMn oxide fraction. The cumulative release rates of heavy metals (i.e., Pb, Cu, and Ni) by 1.0 mol L-1 of acid increased with the use of the following acids in the order of: malic < sulfuric < acetic < phosphoric < citric < nitric. Acetic acid exhibited the highest release of Cu, at a rate of 72.62 × 10-11 mol m-2 s-1 at pH 1, and malic acid drove the release of Pb at a maximum rate of 3.90 × 10-11 mol m-2 s-1. Meanwhile, nitric acid provided the maximum rate of Ni release (0.23 × 10-11 mol m-2 s-1) at pH 1. The high rate of metal release by organic acids is explained through ligand-promoted mechanisms that enhance the release of metal ions from the sludge. The results from our study emphasize that an understanding of the metal release mechanism is key to selecting the optimal acid for the maximum recovery of heavy metals.

Halide and substituent dependent structural variation in copper(i) halide complexes of 1,5,9-triphosphacyclododecanes.

The reactions of 1,5,9-triethyl-1,5,9-triphosphacyclododecane, [12]-ane-P3Et3, and 1,5,9-tri(2-propyl)-1,5,9-triphosphacyclododecane, [12]-ane-P3iPr3 with copper(i)halides produce either bimetallic species of the type [([12]-ane-P3R3)Cu(CuX2)] (X = halide) or monomeric [([12]-ane-P3R3)CuX] depending on the nature of the halide and, to a lesser extent, the macrocycle. With CuCl only bimetallic complexes are formed with one copper centre bound to the macrocycle and a second attached through a Cu-Cu bond with a mono bridging chloride. CuBr affords monomeric [([12]-ane-P3R3)CuBr] complexes when performed in a 1 : 1 M : L ratio whereas the bimetallic compound [([12]-ane-P3Et3)(CuBr)2], resulted when a 2 : 1 ratio of M : L was employed. With CuI in all ratios only monomeric complexes were obtained. The synthesised complexes have been fully characterised by spectroscopic and analytical techniques and by determination of the molecular structures by single-crystal X-ray diffractometry.