Zeolite/ZnAl-layer double hydroxides with different Zn/Al ratios and intercalated anions as the substrate of constructed wetlands: synthesis, characterization and purification effect of Hexavalent chromium.

The study aimed to synthesize novel zeolite substrates modified with four types of ZnAl-LDHs including Cl-LDHs(1:1), Cl-LDHs(3:1), CO3-LDHs(1:1), and CO3-LDHs(3:1); investigate Cr(VI) removal efficiencies in lab-scale constructed wetlands (CWs); and explore the effect of different Zn/Al ratios and intercalated anions on the removal efficiencies of Cr(VI) by modified zeolite. Different ZnAl-LDHs were prepared by co-precipitation method and coated onto the surface of original zeolite. Field emission scanning electron microscope and energy dispersive spectrometer were used to analyze physicochemical properties of zeolite/ZnAl-LDHs. Obtained results confirmed the successful LDHs-coating modification. The results of both X-ray diffraction and Fourier transform infrared suggested that the typical diffraction peak and functional groups of ZnAl-LDHs were detected in modified zeolites, and the peak of CO32- in CO3-LDHs at 1362 cm-1 was stronger and sharper than Cl-LDHs. It could be demonstrated by above results that the synthesis crystallinity and coating effect of CO3-LDHs was better than Cl-LDHs. Furthermore, it could be found that under the condition of same intercalated anion, LDHs with metal molar ratio of 1:1 had better crystallinity than LDHs with metal molar ratio of 3: 1. Subsequent determination of the removal performance of Cr(VI) by purification experiments revealed that zeolite/Cl-LDHs(3:1) showed the best Cr(VI) removal performance, and the removal rate of Cr(VI) was improved by 32.81% compared with the original zeolite, which suggested that could be an efficient substrate of CWs for Cr(VI) removal. The high crystallinity indicated that the structure of LDHs was stable and it was difficult to remove Cr(VI) by ion exchange. The above explained why the Cr(VI) removal efficiency by zeolite/Cl-LDHs is superior to that by zeolite/CO3-LDHs under the condition of same metal molar ratio. With the increase of metal molar ratio, the charge density of LDHs layers and intercalated anion increased, thus enhancing the electrostatic attraction of LDHs layers to Cr(VI) and the interlayer anion exchange capacity. However, the effect of charge density on Cr(VI) removal efficiency may be greater than crystallinity on removal efficiency, which could be responsible for the fact that zeolite/ZnAl-LDHs(3:1) had better Cr(VI) removal efficiency than zeolite/ZnAl-LDHs(1:1) under the condition of same intercalated anion.

Efficiency and mechanisms of cadmium removal via core-shell zeolite/Zn-layer double hydroxides.

To investigate the removal mechanisms of cadmium (Cd) by Zn-layer double hydroxides-modified zeolites substrates in constructed rapid infiltration systems (CRIS), the ZnAl-LDHs and ZnFe-LDHs were synthesized and in-situ coated on the original zeolites through co-precipitation method. The prepared Zn-LDHs-modified and original zeolites were characterized by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) methods, whose results provided the evidences that the Zn-LDHs were successfully coated on the original zeolites. From the results of purification experiments, the average Cd removal rates of ZnAl-LDHs-modified, ZnFe-LDHs-modified and original zeolites were 88.40, 86.00 and 32.52%, respectively; demonstrating that the removal rates of zeolites could significantly improve. Additionally, the modification of Zn-LDHS could enhance the theoretical adsorption ability. According to the results of isothermal adsorption and desorption tests, the desorption rates of Zn-LDHs-modified zeolites were higher than that of original zeolites. Cd adsorption capacity of ZnFe-LDHs-modified zeolites was 1428.57 mg kg-1 and original zeolites was 434.783 mg kg-1. In the adsorption kinetic studies, the pseudo-second-order models were used to well describe the experimental results of Zn-LDHs-modified zeolites, indicating that their adsorption types were attributed to be more stable chemisorption. Besides, the relevant microbial tests also confirmed that microbial enzymatic activity and extracellular polymeric substances (EPS) were significantly promoted on surface of Zn-LDHs-modified zeolites. The contents of EPS on the surface of zeolites were as following: ZnAl-LDHs-modified zeolites (78.58128 µg/g) > ZnFe-LDHs-modified zeolites (71.85445 µg/g) > original zeolites (68.69904 µg/g). Meanwhile, the results of high-throughput sequencing showed that modification by Zn-LDHs improved microbial diversity and relative abundance. The Proteobacteria was the dominant phylum and the Acidobacteria was conducive to Cd removal. Overall, it could be concluded that ZnAl-LDHs-modified zeolites might be applied as an efficient substrate for Cd removal in CRIS.

Removal of Cd(II) by modified maifanite coated with Mg-layered double hydroxides in constructed rapid infiltration systems.

To improve the adsorption performance of Cd(II) by maifanite in constructed rapid infiltration systems (CRIS), Mg-layered double hydroxides (MgAl-LDHs, MgFe-LDHs) are prepared by a co-precipitation method and in-situ coated on the surface of original maifanite. Characterization of the successful LDHs-coating modification is realized by the following: scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), Fourier transform infrared (FTIR) and Brunauer Emmett Teller (BET). In the purification experiments, the average removal rates of Cd(II) were 97.66% for maifanite/MgAl-LDHs and 97.54% for maifanite/MgFe-LDHs, approximately 11% greater than for the original maifanite. Isothermal adsorption experiments and adsorption kinetic experiments were conducted to explore the Cd(II) adsorption mechanism. The modified maifanite demonstrated a higher Langmuir adsorption capacity and stronger surface bond energies compared to the original maifanite. The adsorption type of Cd(II) by maifanite/Mg-LDHs and original maifanite was monolayer adsorption based mainly on chemical adsorption. Furthermore, the extracellular polymeric substances and dehydrogenase activities of the microorganisms were measured and analyzed to study the effect of microorganisms on the removal of Cd(II) in the test columns. High-throughput sequencing technology was also applied to analyze the composition and diversity of bacterial communities. Based on a simple estimation, the synthesis cost of maifanite/MgAl-LDHs was only ¥ 0.33/Kg. In brief, maifanite/Mg-LDHs is an efficient and economical substrate for a CRIS for Cd(II) removal.