Simultaneous chelated heavy metals removal and sludge recovery through titanium coagulation: From waste to resource.

Green methods for chelated heavy metals treatment and recovery are essential for coordinated development of resources and environment. Herein, a simple and competent method, titanium salt (TiCl4) coagulation was developed to remove and recycle chelated heavy metals. Our results revealed that this method proved to be effective for metals-citrate [Cu(II), Ni(II), Zn(II) and Cr(VI)], achieving removal efficiencies of 95 %, 92 %, 99 %, and 99 % within 30 min, surpassing direct alkaline precipitation and well-used Fe(III) coagulation. Whereafter, the copper-containing sludge was successfully transformed into copper-doped titanium dioxide (TiO2) photocatalysts by facile calcination. Through comprehensively investigating physicochemical properties by a suite of characterization techniques, we confirmed that doping of Cu induced bandgap narrowing, high specific surface area as well as the formation of oxygen vacancy. Accordingly, the recycling photocatalysts showed remarkable enhanced photocatalytic performance than the pristine TiO2, achieving improvement in the degradation efficiency of 82 %, 61 % and 67 % for carbamazepine(CBZ), bisphenol A (BPA) and methyl orange (MO). In addition, both radical (OH and O2-) and non-radical (1O2 and h+) pathways synergistically contributed to the removal of organic pollutants during photocatalysis. Ultimately, based on economic feasibility assessment and life cycle assessment (LCA), the copper-containing titanium coagulation sludge reuse for photocatalyst could bring lower carbon emissions, reduced environmental risks and higher economic benefits. The elucidation of this study provides new insights into the removal and recycle of chelated heavy metals from wastewater by using an environment-friendly and cost-effective method.

Mechanistic insight into pH-dependent adsorption and coprecipitation of chelated heavy metals by in-situ formed iron (oxy)hydroxides.

Fe(III) coagulation-precipitation process has been widely used to remove heavy metals from industrial effluents; however, the influences of organic ligands on the sequestration of different heavy metals in the Fe(III)/metal-EDTA ternary system are not well understood. In this study, the pH-dependent mechanisms of CuII-EDTA and NiII-EDTA removed by in-situ formed iron (oxy)hydroxides were studied using surface complex modeling and a suite of characterization techniques. Results of surface complex model indicated that there should be minimal difference between removal of CuII-EDTA and NiII-EDTA by iron (oxy)hydroxides if adsorption was the dominant mechanism. However, through the speciation analysis and characterization of the precipitates generated after coagulation and precipitation, we have demonstrated that at neutral pH the complexation of Fe(III) and EDTA influenced the surface properties of iron (oxy)hydroxides formed, with the higher removal of Cu2+ (compared to Ni2+) contributed by its coprecipitation with Fe(III). Moreover, at basic pH, decomplexation of CuII-EDTA occurred on the iron (oxy)hydroxides surface with the released copper ions involved in the formation of (oxy)hydroxides. The low removal of nickel (from NiII-EDTA) was ascribed to the higher conditional stability constant of NiII-EDTA. Results of this study have advanced our understanding of the complicated interactions among Fe(III), organic ligands and heavy metals in the industrial effluents, and provide insight to optimization of the process efficiency.

Sulfidation of ferric (hydr)oxides and its implication on contaminants transformation: a review.

Rapid industrialization and urbanization have resulted in elevated concentrations of contaminants in the groundwaters and subsurface soils, posing a growing hazard to humans and ecosystems. The transformation of most contaminants is closely linked to the mineralogy of ferric (hydr)oxides. Sulfidation of ferric (hydr)oxides is one of the most significant biogeochemical reactions in the anoxic environments, causing reductive dissolution and recrystallization of ferric (hydr)oxides and further affecting the transformation of iron-associated contaminants. This paper provides a comprehensive review on the sulfidation process of ferric (hydr)oxides and the transformation of relevant contaminants. This review presents detailed reaction mechanisms between ferric (hydr)oxides and dissolved sulfide, and elucidates the factors (e.g. crystallinity of ferric (hydr)oxides, the ratio of sulfide concentration to the surface area concentration of ferric (hydr)oxides) that control the formation of surface associated Fe(II), iron sulfide minerals, as well as transformation of secondary minerals. Then, we summarized the transformation mechanisms of a variety of typical environmentally relevant contaminants existing in groundwater and subsurface soils, including heavy metals, metal(loid) oxyanions (arsenic, antimony, chromium), radionuclides (uranium, technetium), organic contaminants and phosphate/nitrate species. The general mechanisms of contaminant transformation involve a combination of release, reduction and re-adsorption/incorporation processes, the specific pathway of which is highly dependent on the properties of the contaminant itself and the extent of sulfidation. Moreover, the challenge of extending our knowledge towards in situ remediation, as well as further research needs are identified.