New insight into the changes in metal-phosphonate complexes from the addition of CaCO3 to enhance ferric flocculation for efficient phosphonate removal.

Due to the stable chelating effect of organic phosphonates in wastewater, phosphonates with increasing emission are difficult to be removed effectively by traditional ferric salt flocculation, which has posed tough challenges for reducing total phosphorus pollution in recent years. In this work, calcium carbonate (CaCO3) was introduced to work together with the widely investigated flocculant of ferric chloride (FeCl3) to realize an efficient removal of nitrilotrismethylenephosphonic acid (NTMP) at much lower dosage of FeCl3. With an aid of synergy effect from together use of CaCO3 and FeCl3, the remaining concentration as low as 0.16 mg-P/L, far below the sewage discharge limit (0.5 mg-P/L), was simply obtained with a significantly reduced Fe/P molar ratio at only 4, resulting from calcium source donor to form more stable Fe-Ca-P tridentate bridging complexes, high affinity towards ferric ions on CaCO3 surface and slow-release alkaline from CaCO3. A comparison among sodium hydroxide (NaOH), calcium hydroxide (Ca(OH)2) and CaCO3 as additives, was carried out to highlight the advantages of using CaCO3 and clarify the mechanism for the greatly improved performance by a set of characterizations including XRD, FTIR, Zeta potential, XPS, SEM-EDS and TG analyses. The addition of CaCO3 in ferric flocculation resulted in further obvious advantages such as 75% shortened settling time and only one-third of sludge volume of the precipitant, beneficial to the sample handling in engineering application. The proposed new approach has been further confirmed to work efficiently on real phosphonate-containing wastewater. Discussion on the interaction between CaCO3 and ferric salts in phosphonate solutions shed new insights into the working mechanism of using CaCO3 for the treatment of phosphonates-containing wastewater.

In-situ production of iron flocculation and reactive oxygen species by electrochemically decomposing siderite: An innovative Fe-EC route to remove trivalent arsenic.

The removal of trivalent arsenic (As (III)) from water has received extensive attention from researchers. Iron electrocoagulation (Fe-EC) is an efficient technology for arsenic removal. However, electrode passivation hinders the development and application of Fe-EC. In this work, an innovative Fe-EC route was developed to remove As (III) through an electrochemical-siderite packed column (ESC). Ferrous ions were produced from siderite near the anode, and hydroxide was generated near the cathode during the electrochemical decomposition of siderite. As a result, an effect of Fe-EC-like was obtained. The results showed that an excellent removal performance of As (III) (>99%) was obtained by adjusting the parameters (As (III) concentration at 10 mg/L, pH at 7, Na2SO4 at 10 mM and the hydraulic retention time at 30 min) and the oxidation rate of As (III) reached 84.12%. The mechanism analysis indicated that As (III) was oxidized to As (Ⅴ) by the produced active oxide species and electrode, and then was removed by capturing on the iron oxide precipitates. As (III) was likely to be oxidized in two ways, one by the reactive oxygen species (possibly •OH, Fe(IV) and •O2- species), and another directly by the anode. The long-term effectiveness of arsenic removal demonstrated that ESC process based on the electrochemical-siderite packed column was an appropriate candidate for treating As (III) pollution.

Enhanced selective copper precipitation by mechanochemically activated benzene tricarboxylic acid.

Toward the treatment of waste solution containing heavy metals, direct precipitation of the metal ions from an acidic solution without alkaline neutralisation is still the greatest challenge. Based on the ligand properties of benzene tricarboxylic acid (BTC) to copper ions, a simple ball milling with 90 min at 400 rpm was used to activate BTC to enhance its capacity for copper removal from the pH of the original solution around 3-4. A set of analytical methods were used to characterise the activated BTC sample and BTC-Cu precipitate before and after copper precipitation. Compared with the raw BTC, the activated BTC could efficiently remove copper ions over 90% from an initial copper concentration of 100 mg/L in a shorter time from an acidic media with lower pH of around 2.60 and the maximum adsorption capacity can be stable at about 111.70 mg/g, resulting from probably the enhanced deprotonation effect for copper incorporation. Furthermore, at controlled dosage, the activated BTC demonstrated much high selectivity on precipitating copper ions from other heavy metals of Ni, Mn, Zn and Cd and provided a new approach for easy copper recycling from waste solution as secondary sources. This process may serve the purpose of recycling both metal and acidic solutions after the purification.

Phosphate removal from aqueous solution by electrochemical coupling siderite packed column.

The use of iron species to remove PO43- is widely used, and the fresh Fe3+ produced in situ demonstrate better effect on the removal of PO43- in many researches. Therefore, in order to develop a simpler and more efficient method for PO43- removal, we designed an easy operation by electrochemically dissolving siderite to produce fresh Fe3+ in situ for PO43- removal from wastewater. Results showed that current intensity at 20 mA, initial pH at 6, initial PO43- concentration at 1 mM and influent flow rate at 2.5 mL min-1 were the best parameters for removing PO43-, ensuring that the PO43- concentration of effluent can be kept below 1 mg L-1 through the electrochemical system. Different from other studies, a large amount of Fe2+ can be dissolved from natural minerals without adding H+ to the system and Fe3+ species are generated in situ from the oxidation of the Fe2+ without using a specific oxidizer. This electrochemical treatment method with siderite as a packed column can be used as a new method of high efficiency, simple operation and low-cost for treating eutrophic water bodies.

Activating CaCO3 to enhance lead removal from lead-zinc solution to serve as green technology for the purification of mine tailings.

Efficient lead removal from metal-containing wastewater, such as acid mine drainage (AMD), is an important step in environmental purification and secondary resources recovery. In this paper, a novel approach by mechanochemically activating CaCO3 through simply wet ball milling in metal-containing solution was developed, where selective Pb2+ precipitation in the form of PbCO3 was achieved based on its reaction with the CO32- from the activated CaCO3. By such milling operation, the removal efficiency of Pb2+ from aqueous solution could reach over 99%, while more than 99% Zn2+ (as well as Mn, Ni and Cd) was remaining in the solutions, demonstrating the feasibility and high effectiveness of precipitating Pb2+ and serving the purpose of recovering other metals without Pb impurity. The solubility differences between Pb carbonate and other carbonates of Zn, Mn, Ni or Cd were understood to be the main pathway and using CaCO3 would offer an easy operation and environmental friendly process to purify the metals-containing wastewater by precipitating Pb, compared with the difficulties when using alkaline neutralization to treat them. In addition, basic zinc carbonate (a zinc-containing ore waste) as an alternative precipitant to CaCO3 in the separation process was also confirmed to increase the zinc recovery in the solution while maintaining high Pb2+ removal efficiency.