A review on the transformation of birnessite in the environment:Implication for the stabilization of heavy metals

Birnessite is ubiquitous in the natural environment where heavy metals are retained and easily transformed.The surface properties and structure of birnessite change with the changes in external environmental conditions,which also affects the fate of heavy metals.Clarifying the effect and mechanism of the birnessite phase transition process on heavy metals is the key to taking effective measures to prevent and control heavy metal pollution.Therefore,the four transformation pathways of birnessite are summarized first in this review.Second,the relationship between transformation pathways and environmental conditions is proposed.These relevant environmental conditions include abiotic(e.g.,co-existing ions,pH,oxygen pressure,temperature,electric field,light,aging,pressure)and biotic factors(e.g.,microorganisms,biomolecules).The phase transformation is achieved by the key intermediate of Mn(Ⅲ)through interlayer-condensation,folding,neutralizationdisproportionation,and dissolution-recrystallization mechanisms.The AOS(average oxidation state)of Mn and interlayer spacing are closely correlated with the phase transformation of birnessite.Last but not least,the mechanisms of heavy metals immobilization in the transformation process of birnessite are summed up.They involve isomorphous substitution,redox,complexation,hydration/dehydration,etc.The transformation of birnessite and its implication on heavy metals will be helpful for understanding and predicting the behavior of heavy metals and the crucial phase of manganese oxides/hydroxides in natural and engineered environments.

The determinants of effective defluorination by the LiAl-LDHs

Millions of people in poor areas are still under the threat of fluoride contamination.How to effectively separate fluorine in water is an important step to reduce the ecological risk.In this paper,we performed a systematic DFT calculation focused on the defluorination behavior between the LiAl-and MgAl-LDHs.The results indicated that the LiAl-LDHs exhibited high chemical activity before the defluorination,because of the better electronic structure.After the defluorination,the LiAl-LDHs with adsorbed-F–were also more stable than the MgAl-LDHs.In addition,the existence of coordination covalent bond for the adsorbed-F–attached to the LiAl-LDHs was confirmed.This is an important reason for the high defluorination efficiency by the LiAl-LDHs.In addition,a series of weak interaction,including hydrogen bond and van der Waals interaction were also observed.Finally,a LiAl-LDHs with excellent fluoride removal properties were synthesized well by simple hydrothermal method.The results showed that our synthesized LiAl-LDHs with the capacity of 156.09 mg/g,could be effectively defluorinated in water.Notably,it surpasses most materials and has potential applications.

Progress of gaseous arsenic removal from flue gas by adsorption:Experimental and theoretical calculations

Because of its high mobility and difficult capture,gaseous arsenic pollution control has become the focus of arsenic pollution control.It mainly exists in the form of highly toxic As_(2)O_(3)in the flue gas.Therefore,removing gaseous As_(2)O_(3)from flue gas is of great practical significance for arsenic pollution control.Stabilizing gaseous As_(2)O_(3)on the surface of adsorbents by physical or chemical adsorption is an effective way to reduce the content of arsenic in the flue gas and alleviate arsenic pollution.Over the past few decades,various adsorbents have been developed to capture gaseous As_(2)O_(3)in the flue gas,and their adsorption mechanisms have been studied in detail.Thus,it is necessary to review the strategies of arsenic removal from flue gas by adsorption,which can inspire further research.Based on summarizing the morphological distribution of gaseous As_(2)O_(3)in the flue gas,this review further summarizes the removal of gaseous As_(2)O_(3)by several adsorbents and the effect of temperature and the main components of the flue gas on arsenic adsorption.In addition,the mechanism of arsenic removal based on adsorption in the flue gas is discussed in depth through theoretical calculations,which is the particular focus of this review.Finally,prospects based on the present research state of arsenic removal by adsorption are proposed to provide ideas for developing effective and stable adsorbents for arsenic removal from flue gas.

Nanosize-effect on the distribution of heavy metals in copper smelting dust:Based on sophisticated dust sorting approach

Dust particles emitted from smelters can be hazardous to ecosystems and humans,as they are often enriched in metallic compounds.Here,we combined multi-method mineralogical analysis with a sophisticated size sorting approach for copper smelting dust to study the nanosize-effect on heavy metal distribution,which has hitherto been underestimated.Three types of dust were collected from a copper flash smelter and then size-sorted using a Dekati low-pressure impactor.Results showed that all three samples could easily sort out nanoscale dust particles(<1μm,grades 10–2)and even those smaller than 100 nm(grades 5–2).Especially for electrostatic precipitators dust,the mass fraction of nanoscale dust(<1μm)could reach 10.71%.The presence of heavy metals(Pb,Zn,Cu,and As)and their mineral species in dust was examined at various particle sizes.It was discovered that different heavy metals are enriched on nanoparticles in specific sizes.In micron-sized particles,heavy metals are generally found in discrete phases(e.g.,CuSO_(4),PbSO_(4),and As_(2)O_(3)).In nanoscale particles,the dominant phase is Fe_(3)O_(4),while heavy metals are mostly found in lattice substitution(e.g.,CuFe_(2)O_(4)and ZnFe_(2)O_(4)).Two distinct nano-dust morphologies were found:One with irregular mesh or chain structures consisting of particles of a few nanometers,and the other with polygonal crystals in larger sizes of hundreds of nanometers.The enrichment of heavy metals in the latter morphology is more pronounced,possibly because lattice substitution of heavy metals is more likely to occur when polycrystalline particles are formed.

Systematic control technologies for gaseous pollutants from non-ferrous metallurgy

Air pollutant emissions represent a critical challenge in the green development of the non-ferrous metallurgy industry.This work studied the emission characteristics,formation mechanisms,phase transformation and separation of typical air pollutants,such as heavy metal particles,mercury,sulfur oxides and fluoride,during non-ferrous smelting.A series of purification technologies,including optimization of the furnace throat and hightemperature discharge,were developed to collaboratively control and recover fine particles from the flue gas of heavy metal smelting processes,including copper,lead and zinc.Significant improvements have been realized in wet scrubbing technology for removing mercury,fluoride and SO_(2)from flue gas.Gas-liquid sulfidation technology by applying H_(2)S was invented to recycle the acid scrubbing wastewater more efficiently and in an eco-friendly manner.Based on digital technology,a source reduction method was designed for sulfur and fluoride control during the whole aluminum electrolysis process.New desulfurization technologies were developed for catalytic reduction of the sulfur content in petroleum coke at low temperature and catalytic reduction of SO_(2)to elemental sulfur.This work has established the technology for coupling multi-pollutant control and resource recovery from the flue gas from non-ferrous metallurgy,which provides the scientific theoretical basis and application technology for the treatment of air pollutants in the non-ferrous metallurgy industry.

The role of doped-Mn on enhancing arsenic removal by MgAl-LDHs

To meet the challenges posed by global arsenic water contamination, the Mg Al Mn-LDHs with extraordinary efficiency of arsenate removal was developed. In order to clarify the enhancement effect of the doped-Mn on the arsenate removal performance of the LDHs, the cluster models of the Mg Al Mn-LDHs and Mg Al-LDHs were established and calculated by using density functional theory(DFT). The results shown that the doped-Mn can significantly change the electronic structure of the LDHs and improve its chemical activity. Compared with the Mg Al-LDHs that without the doped-Mn, the HOMO-LUMO gap was smaller after doping. In addition, the-OH and Al on the laminates were also activated to improve the adsorption property of the LDHs. Besides, the doped-Mn existed as a novel active site. On the other hand, the Mg Al Mn-LDHs with the doped-Mn, the increased of the binding energy, as well as the decreased of the ion exchange energy of interlayer Cl^(-), making the ability to arsenate removal had been considerably elevated than the Mg Al-LDHs. Furthermore, there is an obvious coordination covalent bond between arsenate and the laminates of the Mg Al MnLDHs that with the doped-Mn.