Removal of toxic arsenic and antimony from groundwater Spiro Tunnel Bulkhead in Park City Utah using colloidal iron hydroxide : comparison with reverse ssmosis

Verification testing of two model technologies in pilot scale to remove arsenic and antimony based on reverse osmosis and chemical coagulation/filtration systems was conducted in Spiro Tunnel Water Filtration Plant located in Park City, Utah, US. The source water was groundwater in abandoned silver mine, naturally contaminated by 60-80 ppb of arsenic and antimony below 10 ppb. This water represents one of the sources of drinking water for Park City and constitutes about 44% of the water supply. The failure to remove antimony efficiently by coagulation/filtration (only 4.4% removal rate) under design conditions is discussed in terms of the chemistry differences between Sb (III, V) and As (III, V). Removal of Sb(V) at pH > 7, using coagulation/filtration technology, requires much higher (50 to 80 times) concentration of iron (III) than As. The stronger adsorption of arsenate over a wider pH range can be explained by the fact that arsenic acid is tri-protic, whereas antimonic acid is monoprotic. This difference in properties of As(V) and Sb(V) makes antimony (V) more difficult to be efficiently removed in low concentrations of iron hydroxide and alkaline pH waters, especially in concentration of Sb < 10 ppb.

Synthesis and characterisation of metal oxyhydroxide and oxide nanomaterials

In this work, a range of nanomaterials have been synthesised based on metal oxyhydroxides MO(OH), where M=Al, Co, Cr, etc. Through a self-assembly hydrothermal route, metal oxyhydroxide nanomaterials with various morphologies were successfully synthesised: one dimensional boehmite (AlO(OH)) nanofibres, zero dimensional indium hydroxide (In(OH)3) nanocubes and chromium oxyhydroxide (CrO(OH)) nanoparticles, as well as two dimensional cobalt hydroxide and oxyhydroxide (Co(OH)2 & CoO(OH)) nanodiscs. In order to control the synthetic nanomaterial morphology and growth, several factors were investigated including cation concentration, temperature, hydrothermal treatment time, and pH. Metal ion doping is a promising technique to modify and control the properties of materials by intentionally introducing impurities or defects into the material. Chromium was successfully applied as a dopant for fabricating doped boehmite nanofibres. The thermal stability of the boehmite nanofibres was enhanced by chromium doping, and the photoluminescence property was introduced to the chromium doped alumina nanofibres. Doping proved to be an efficient method to modify and functionalize nanomaterials. The synthesised nanomaterials were fully characterised by X-ray diffraction (XRD), transmission electron microscopy (TEM) combined with selected area electron diffraction (SAED), scanning electron microscopy (SEM), BET specific surface area analysis, X-ray photoelectron spectroscopy (XPS) and thermo gravimetric analysis (TGA). Hot-stage Raman and infrared emission spectroscopy were applied to study the chemical reactions during dehydration and dehydroxylation. The advantage of these techniques is that the changes in molecular structure can be followed in situ and at the elevated temperatures.

Red mud from Brazil : thermal behavior and physical properties

The main constituents of red mud produced in Aluminio city (S.P. – Brazil) are iron, aluminium and silicon oxides. It has been determined that the average particle diameter for this red mud is between 0.05 and 0.002mm. It is observed that a decrease in the percentage of smaller particles occurs at temperatures greater than 400°C. This observation corresponds with the thermal analysis and X-ray diffraction (XRD) data, which illustrate the phase transition of goethite to hematite. A 10% mass loss is observed in the thermal analysis patterns due to the hydroxide – oxide phase transitions of iron (primary phase transition) and aluminium (to a lesser extent). The disappearance and appearance of the different phases of iron and aluminium confirms the decomposition reactions proposed by the thermal analysis data. This Brazilian red mud has been classified as mesoporous at all temperatures except between 400 and 500°C where the classification changes to micro/mesoporous.

Kinetic study of goethite dehydration and the effect of aluminium substitution on the dehydrate

Goethite and Al-substituted goethite were synthesized and were characterized using XRD and XRF. The kinetic study of goethite dehydrate was investigated by TG and DTG at different heating rates (2, 5, 10, 15, 20 ◦C/min) and the effect of Al substitution for Fe on dehydrate was studied. The results showed that two types of absorbed water with the same Ed values of 3.4, 6.2 kJ/mol were confirmed on goethite and Alsubstituted goethite. Three types of hydroxyl units were proved, one being on the surface and the other two being in the structure of goethite. The substitution of Al for Fe in the structure of goethite decreases the desorption rate of hydroxyl, increases the dehydroxylation temperature, broadens the desorption peaks in DTG curves, and improves the Ed values from 19.4, 20.4, 26.1 kJ/mol to 21.6, 30, 33.6 kJ/mol when Al substitution comes to 9.1%.

A density functional theory study of CO2 and N2 adsorption on aluminium nitride single walled nanotubes

Strong binding of isolated carbon dioxide (CO2) on aluminium nitride (AlN) single walled nanotubes is verified using two different functionals. Two optimized configurations corresponding to physisorption and chemisorption are linked by a low energy barrier, such that the chemisorbed state is accessible and thermodynamically favored at low temperatures. In contrast, N2 is found only to form a physisorbed complex with the AlN nanotube, suggesting the potential application of aluminium nitride based materials for CO2 fixation. The effect of nanotube diameter on gas adsorption properties is also discussed. The diameter is found to have an important effect on the chemisorption of CO2, but has little effect on the physisorption of either CO2 or N2.

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 3.00 Å. 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.

Mid- and near-infrared spectroscopic investigation of homogeneous cation distribution in MgxZnyAl(x+y)/2-layered double hydroxide (LDH)

In this report, a detailed FTIR fitting analysis was used to recognize Mg, Zn and Al homogeneous distribution in MgxZnyAl(x+y)/2-Layered double hydroxide (LDH) hydroxyl layer. In detail, OH-Mg2Al:OH-Mg3 ratios decreased from 95.2:4.8 (MIR) and 94.2:5.8 (NIR) to 58.9:41.1 (MIR) and 61.8:38.2 (NIR), when Mg:Al increased from 2.2:1.0 to 4.1:1.0 in MgAl-LDHs. These fitting results were similar with theoretical calculations of 94.3:5.7 and 59.0:41.0. In a further analysis of MgxZnyAl(x+y)/2-LDHs, OH bonded Zn2Mg, Zn2Al, MgZnAl, Mg2Al and Mg2Zn peaks were identified at 3420, 3430, 3445–3450, 3454 and 3545 cm-1, respectively. With the decrease of Mg:Zn from 3:1 to 1:3, metal-hydroxyl bands changed from OH-Mg2Al and MgZnAl (with a ratio of 49.4:50.6) to OH-MgZnAl and Zn2Al (with a ratio of 55.0:45.0). They were also similar with theoretical calculations of 47.6:52.4 and 54.6:45.4. As a result, these results show that there is an ordered cation distribution in MgxZnyAl(x+y)/2-LDH, and FTIR is feasible in recognizing this structure.

Measurement of the first neutron diffraction peak of D2O flowing in a 2 mm diameter aluminium tube as a function of temperature

A pilot experiment was performed using the WOMBAT powder diffraction instrument at ANSTO in which the first neutron diffraction peak (Q0) was measured for D2O flowing in a 2 mm internal diameter aluminium tube. Measurements of Q0 were made at -9, 4.3, 6.9, 12, 18.2 and 21.5 °C. The D2O was circulated using a siphon with water in the lower reservoir returned to the upper reservoir using a small pump. This enabled stable flow to be maintained for several hours. For example, if the pump flow increased slightly, the upper reservoir level rose, increasing the siphon flow until it matched the return flow. A neutron wavelength of 2.4 Å was used and data integrated over 60 minutes for each temperature. A jet of nitrogen from a liquid N2 Dewar was directed over the aluminium tube to vary water temperature. After collection of the data, the d spacing of the aluminium peaks was used to calculate the temperature of the aluminium within the neutron beam and therefore was considered to be an accurate measure of water temperature within the beam. Sigmaplot version 12.3 was used to fit a Weibull five parameter peak fit to the first neutron diffraction peak. The values of Q0 obtained in this experiment showed an increase with temperature consistent with data in the literature [1] but were consistently higher than published values for bulk D20. For example at 21.5 °C we obtained a value of 2.008 Å-1 for Q0 compared to a literature value of 1.988 Å-1 for bulk D2O at 20 °C, a difference of 1%. Further experiments are required to see if this difference is real or artifactual.

Vibrational spectroscopic study of the sulphate mineral glaucocerinite (Zn,Cu)10Al6(SO4)3(OH)32⋅18H2O – a natural layered double hydroxide

We have studied the molecular structure of the mineral glaucocerinite (Zn,Cu)5Al3(SO4)1.5(OH)16�9(H2O) using a combination of Raman and infrared spectroscopy. The mineral is one of the hydrotalcite supergroup of natural layered double hydroxides. The Raman spectrum is characterised by an intense Raman band at 982 cm�1 with a low intensity band at 1083 cm�1. These bands are attributed to the sulphate symmetric and antisymmetric stretching mode. The infrared spectrum is quite broad with a peak at 1020 cm�1. A series of Raman bands at 546, 584, 602, 625 and 651 cm�1 are assigned to the m4 (SO4)2� bending modes. The observation of multiple bands provides evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 762 cm�1 is attributed to a hydroxyl deformation mode associated with AlOH units. Vibrational spectroscopy enables aspects of the molecular structure of glaucocerinite to be determined.

Mechanochemical synthesis of aluminium nanoparticles and their deuterium sorption properties to 2 kbar

A mechanochemical synthesis process has been used to synthesise aluminium nanoparticles. The aluminium is synthesised via a solid state chemical reaction which is initiated inside a ball mill at room temperature between either lithium (Li) or sodium (Na) metal which act as reducing agents with unreduced aluminium chloride (AlCl3). The reaction product formed consists of aluminium nanoparticles embedded within a by-product salt phase (LiCl or NaCl, respectively). The LiCl is washed with a suitable solvent resulting in aluminium (Al) nanoparticles which are not oxidised and are separated from the byproduct phase. Synthesis and washing was confirmed using X-ray diffraction (XRD). Nanoparticles were found to be ∼25–100nm from transmission electron microscopy (TEM) and an average size of 55nm was determined fromsmall angle X-ray scattering (SAXS) measurements. As synthesised Al/NaCl composites, washed Al nanoparticles, and purchased Al nanoparticles were deuterium (D2) absorption tested up to 2 kbar at a variety of temperatures, with no absorption detected within system resolution.

Effect of strong acids on red mud structural and fluoride adsorption properties

The removal of fluoride using red mud has been improved by acidifying red mud with hydrochloric, nitric and sulphuric acid. This investigation shows that the removal of fluoride using red mud is significantly improved if red mud is initially acidified. The acidification of red mud causes sodalite and cancrinite phases to dissociate, confirmed by the release of sodium and aluminium into solution as well as the disappearance of sodalite bands and peaks in infrared and X-ray diffraction data. The dissolution of these mineral phases increases the amount of available iron and aluminium oxide/hydroxide sites that are accessible for the adsorption of fluoride. The removal of fluoride is dependent on the charge of iron and aluminium oxide/hydroxides on the surface of red mud. Acidifying red mud with hydrochloric, nitric and sulphuric acid resulted in surface sites of the form ≡ SOH2+ and ≡ SOH. Optimum removal is obtained when the majority of surface sites are in the form ≡ SOH2+ as the substitution of a fluoride ion doesn’t cause a significant increase in pH. This investigation shows the importance of having a low and consistent pH for the removal of fluoride from aqueous solutions using red mud.

Implication of calcium hydroxide in the seawater neutralisation of bauxite refinery liquors

Tricalcium aluminate, hydrocalumite and residual lime have been identified as reversion contributing compounds after the seawater neutralisation of bauxite refinery residues. The formation of these compounds during the neutralisation process is dependent on the concentration of residual lime, pH and aluminate concentrations in the residue slurry. Therefore, the effect of calcium hydroxide (CaOH2) in bauxite refinery liquors was analysed and the degree of reversion monitored. This investigation found that the dissolution of tricalcium aluminate, hydrocalumite and CaOH2 caused reversion and continued to increase the pH of the neutralised residue until a state of equilibrium was reached at a solution pH of 10.5. The dissolution mechanism for each compound has been described and used to demonstrate the implications that this has on reversion in seawater neutralised Bayer liquor. This investigation describes the limiting factors for the dissolution and formation of these trigger compounds as well as confirming the formation of Bayer hydrotalcite (mixture of Mg6Al2(OH)16(CO32-,SO42-)•xH2O and Mg8Al2(OH)12(CO32-,SO42-)•xH2O) as the primary mechanism for reducing reversion during the neutralisation process. This knowledge then allowed for a simple but effective method (addition of magnesium chloride or increased seawater to Bayer liquor ratio) to be devised to reduce reversion occurring after the neutralisation of Bayer liquors. Both methods utilise the formation of Bayer hydrotalcite to permanently (stable in neutralised residue) remove hydroxyl (OH-) and aluminate (Al(OH)4-) ions from solution.

Vibrational spectroscopy of the sulphate mineral sturmanite from Kuruman manganese deposits, South Africa

The mineral sturmanite is a hydrated calcium iron aluminium manganese sulphate tetrahydroxoborate hydroxide of formula Ca6(Fe, Al, Mn)2(SO4)2(B(OH)4)(OH)12•26H2O. We have studied the mineral sturmanite using a number of techniques, including SEM with EPMA and vibrational spectroscopy. Chemical analysis shows a homogeneous phase, composed by Ca, Fe, Mn, S, Al and Si. B is not determined in this EPMA technique. An intense Raman band at 990 cm−1 is assigned to the SO42− symmetric stretching mode. Raman spectroscopy identifies multiple sulphate symmetric stretching modes in line with the three sulphate crystallographically different sites. Raman spectroscopy also identifies a band at 1069 cm−1 which may be attributed to a carbonate symmetric stretching mode, indicating the presence of thaumasite. Infrared spectra display two bands at 1080 and 1107 cm−1 assigned to the SO42− antisymmetric stretching modes. The observation of multiple bands in this ν4 spectral region offers evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 3622 cm−1 is assigned to the OH unit stretching vibration and the broad feature at around 3479 cm−1 to water stretching bands. Infrared spectroscopy shows a set of broad overlapping bands in the OH stretching region. Vibrational spectroscopy enables an assessment of the molecular structure of sturmanite to be made.

Characterization of the sulphate mineral coquimbite, a secondary iron sulphate from Javier Ortega mine, Lucanas Province, Peru – Using infrared, Raman spectroscopy and thermogravimetry

The mineral coquimbite has been analysed using a range of techniques including SEM with EDX, thermal analytical techniques and Raman and infrared spectroscopy. The mineral originated from the Javier Ortega mine, Lucanas Province, Peru. The chemical formula was determined as ðFe3þ 1:37; Al0:63ÞP2:00ðSO4Þ3 9H2O. Thermal analysis showed a total mass loss of 73.4% on heating to 1000 C. A mass loss of 30.43% at 641.4 C is attributed to the loss of SO3. Observed Raman and infrared bands were assigned to the stretching and bending vibrations of sulphate tetrahedra, aluminium oxide/hydroxide octahedra, water molecules and hydroxyl ions. The Raman spectrum shows well resolved bands at 2994, 3176, 3327, 3422 and 3580 cm 1 attributed to water stretching vibrations. Vibrational spectroscopy combined with thermal analysis provides insight into the structure of coquimbite.