Frederick L. Theiss

A review of the removal of anions and oxyanions of the halogen elements from aqueous solution by layered double hydroxides

The application of layered double hydroxides (LDHs) and thermally activated LDHs for the removal of various fluorine (F(-),BF4(-)), chlorine (Cl(-),ClO4(-)), bromine (Br(-),BrO3(-)) and iodine (I(-),IO3(-)) species from aqueous solutions has been reviewed in this article. LDHs and thermally activated LDHs were able to significantly reduce the concentration of selected anions in laboratory scale experiments. The M(2+):M(3+) cation ratio of the LDH adsorbent was an important factor which influenced anion uptake. Though LDHs were able to remove some target anion species through anion exchange and surface adsorption thermal activation and reformation generally produced better results. The presence of competing anions including carbonate, phosphate and sulphate had a significant impact on uptake of the target anion as LDHs typically exhibit lower affinity towards monovalent anions compared to anions with multiple charges. The removal of fluoride and perchlorate from aqueous solution by a continuous flow system utilising fixed bed columns packed with LDH adsorbents has also been investigated. The adsorption capacity of the columns at breakpoint was heavily dependent on the flow rate and lower than result reported for the corresponding batch methods. There is still considerable scope for future research on numerous topics summarised in this article.

Removal of boron species by layered double hydroxides: a review.

Boron, which is an essential element for plants, is toxic to humans and animals at high concentrations. Layered double hydroxides (LDHs) and thermally activated LDHs have shown good uptake of a range of boron species in laboratory scale experiments when compared to current available methods, which are for the most part ineffective or prohibitively expensive. LDHs were able to remove anions from water by anion exchange, the reformation (or memory) effect and direct precipitation. The main mechanism of boron uptake appeared to be anion exchange, which was confirmed by powder X-ray diffraction (XRD) measurements. Solution pH appeared to have little effect on boron sorption while thermal activation did not always significantly improve boron uptake. In addition, perpetration of numerous LDHs with varying boron anions in the interlayer region by direct co-precipitation and anion exchange have been reported by a number of groups. The composition and orientation of the interlayer boron ions could be identified with reasonable certainty by applying a number of characterisation techniques including: powder XRD, nuclear magnetic resonance spectroscopy (NMR), X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy. There is still considerable scope for future research on the application of LDHs for the removal of boron contaminants.

A vibrational spectroscopic study of the silicate mineral analcime - Na2(Al4SiO4O12)·2H2O - a natural zeolite.

We have studied the mineral analcime using a combination of scanning electron microscopy with energy dispersive spectroscopy and vibrational spectroscopy. The mineral analcime Na2(Al4SiO4O12)·2H2O is a crystalline sodium silicate. Chemical analysis shows the mineral contains a range of elements including Na, Al, Fe(2+) and Si. The mineral is characterized by intense Raman bands observed at 1052, 1096 and 1125cm(-1). The infrared bands are broad; nevertheless bands may be resolved at 1006 and 1119cm(-1). These bands are assigned to SiO stretching vibrational modes. Intense Raman band at 484cm(-1) is attributed to OSiO bending modes. Raman bands observed at 2501, 3542, 3558 and 3600cm(-1) are assigned to the stretching vibrations of water. Low intensity infrared bands are noted at 3373, 3529 and 3608cm(-1). The observation of multiple water bands indicate that water is involved in the structure of analcime with differing hydrogen bond strengths. This concept is supported by the number of bands in the water bending region. Vibrational spectroscopy assists with the characterization of the mineral analcime.

Leaching of iodide (I(-)) and iodate (IO3(-)) anions from synthetic layered double hydroxide materials.

Several studies have previously demonstrated that layered double hydroxides (LDHs) show considerable potential for the adsorption of radioiodine from aqueous solution; however, few studies have demonstrated that these materials are able to store radioactive (131)I for an acceptable period. The leaching of iodide (I(-)) and iodate (IO3(-)) form Mg/Al LDHs has been carried out. Contact time appeared to be a more significant variable for the leaching of iodate (IO3(-)) compared to that of iodide (I(-)). Experimental results are fitted to the pseudo second order model, suggesting that diffusion is likely to be the rate-limiting step. The presence of carbonate in the leaching solution appeared to significantly increase the leaching of iodide (I(-)) as did the presence of chloride to a lesser extent. The maximum amount of iodate (IO3(-)) leached using ultrapure water as the leaching solution was 21% of the iodate (IO3(-)) originally present. The corresponding result for iodide (I(-)) was even lower at 3%.

Vibrational spectroscopic study of the natural layered double hydroxide manasseite now defined as hydrotalcite-2H – Mg6Al2(OH)16[CO3]⋅4H2O

Raman and thermo-Raman spectroscopy have been applied to study the mineral formerly known as manasseite now simply renamed as hydrotalcite-2H Mg6Al2(OH)16[CO3]⋅4H2O. The mineral is a member of the homonymous hydrotalcite supergroup. Hydrogen bond distances calculated using a Libowitzky-type empirical function varied between 2.61 and 3.00Å. Stronger hydrogen bonds were formed by water units as compared to the hydroxyl units. Raman spectroscopy enabled the identification of bands attributed to the hydroxyl units. Two Raman bands at 1059 and 1064 cm(-1) are assigned to symmetric stretching modes of the carbonate anion. Thermal treatment shifts these bands to higher wavenumbers indicating a change in the strength of the carbonate bonding.

Sorption of iodide (I−) from aqueous solution using Mg/Al layered double hydroxides

In this article, the authors report the adsorption of iodide by Mg/Al LDHs and thermally activated LDH materials in laboratory scale batch experiments. The optimal Mg/Al cation ratio was 3:1while the percentage iodide uptake increased with increasing adsorbent dose up to 1g/20mL of solution. The effect of initial iodide concentration was investigated using the Langmuir and Freundlich adsorption isotherm models, while the pseudo second order kinetic model appeared to provide the best fit for the experimental data. High iodide uptake of over 80% could be achieved without completely eliminating dissolved or atmospheric carbonate and leaching of 131I from LDHs did not appear to be a significant problem over the period of 28days investigated. These results demonstrate that LDHs, which are already commercially available in large quantities, are a technology that shows considerable promise for the removal of radioiodine from aqueous solution.

A vibrational spectroscopic study of the silicate mineral pectolite – NaCa2Si3O8(OH)

The mineral pectolite NaCa₂Si₃O₈(OH) is a crystalline sodium calcium silicate which has the potential to be used in plaster boards and in other industrial applications. Raman bands at 974 and 1026 cm(-1) are assigned to the SiO stretching vibrations of linked units of Si₃O₈ units. Raman bands at 974 and 998 cm(-1) serve to identify Si₃O₈ units. The broad Raman band at around 936 cm(-1) is attributed to hydroxyl deformation modes. Intense Raman band at 653 cm(-1) is assigned to OSiO bending vibration. Intense Raman bands in the 2700-3000 cm(-1) spectral range are assigned to OH stretching vibrations of the OH units in pectolite. Infrared spectra are in harmony with the Raman spectra. Raman spectroscopy with complimentary infrared spectroscopy enables the characterisation of the silicate mineral pectolite.

A vibrational spectroscopic study of the phosphate mineral vantasselite Al4(PO4)3(OH)3·9H2O.

We have studied the phosphate mineral vantasselite Al₄(PO₄)₃(OH)₃·9H₂O using a combination of SEM with EDX and Raman and infrared spectroscopy. Qualitative chemical analysis shows Al, Fe and P. Raman bands at 1013 and 1027 cm(-1) are assigned to the PO₄(3-)ν₁ symmetric stretching mode. The observation of two bands suggests the non-equivalence of the phosphate units in the vantasselite structure. Raman bands at 1051, 1076 and 1090 cm(-1) are attributed to the PO₄(3-)ν₃ antisymmetric stretching vibration. A comparison is made with the spectroscopy of wardite. Strong infrared bands at 1044, 1078, 1092, 1112, 1133, 1180 and 1210 cm(-1) are attributed to the PO₄(3-)ν₃ antisymmetric stretching mode. Some of these bands may be due to δAl₂OH deformation modes. Vibrational spectroscopy offers a mechanism for the study of the molecular structure of vantasselite.

A vibrational spectroscopic study of the silicate mineral normandite – NaCa(Mn2+,Fe2+)(Ti,Nb,Zr)Si2O7(O,F)2

We have studied the mineral normandite using a combination of scanning electron microscopy with energy dispersive spectroscopy and vibrational spectroscopy. The mineral normandite NaCa(Mn(2+),Fe(2+))(Ti,Nb,Zr)Si2O7(O,F)2 is a crystalline sodium calcium silicate which contains rare earth elements. Chemical analysis shows the mineral contains a range of elements including Na, Mn(2+), Ca, Fe(2+) and the rare earth element niobium. No Raman bands are observed above 1100 cm(-1). The mineral is characterised by Raman bands observed at 724, 748, 782 and 813 cm(-1). Infrared bands are broad; nevertheless bands may be resolved at 723, 860, 910, 958, 933, 1057 and 1073 cm(-1). Intense Raman bands at 454, 477 and 513 cm(-1) are attributed to OSiO bending modes. No Raman bands are observed in the hydroxyl stretching region, but low intensity infrared bands are observed at 3191 and 3450 cm(-1). This observation brings into question the true formula of the mineral.

Spectroscopic characterisation of the LDH mineral quintinite Mg4Al2(OH)12CO3·3H2O

Raman and infrared spectroscopy coupled with scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) have been applied to study the natural hydrotalcite quintinite Mg4Al2(OH)12[CO3]·3H2O. SEM shows the mineral to be a homogenous phase. Quintinite is composed of Mg and Al as the major elements with minor amounts of Fe. Two Raman bands at 1046 and 1062 cm are assigned to the ν1 symmetric stretching modes of the carbonate anion. Thermal treatment shifts these bands to higher wavenumbers indicating a change in the carbonate bonding. Hydrogen bond distances are calculated using a Libowitzky-type empirical function and varied between 2.61 and 3.00 Å. Stronger hydrogen bonds were formed by water units as compared to the hydroxyl units.