Migration of Alkaline Constituents and Restoration Evaluation in Bauxite Residue Disposal Areas.

Bauxite residue is a highly alkaline waste from alumina refining, and is mainly disposed by stacking with high environmental risks. Here, the migration of alkaline constituents and the restoration evaluation with phosphogypsum were discussed by soil column experiments to investigate the alkaline regulation in bauxite residue disposal areas (BRDAs). The pH, free alkali, exchangeable sodium in the top layer (0-25 cm depth) covered with BR and phosphogypsum mixtures were reduced from 10.89 ± 0.02, 285.45 ± 21.15 mmol/kg, 385.63 ± 30.34 mg/kg to 9.00 ± 0.50, 12.50 ± 1.50 mmol/kg, 97.00 ± 10.50 mg/kg. For the sublayers, including depths of 35, 45, 55 cm, these values dropped to 9.86, 10.06, 10.03; 38.23, 86.12, 148.00 mmol/kg; 152.90, 246.00, 305.00 mg/kg, respectively. These results indicated alkaline indicators for phosphogypsum amended BR declined dramatically, and the parameters for sublayers were also decreased due to the migration of alkaline constituents. The physicochemical properties for amended BR could meet the conditions for plant growth. This research provided a reference for alkalinity regulation in BRDAs by phosphogypsum.

Optimisation of zeolite LTA synthesis from alum sludge and the influence of the sludge source.

Generation of alum sludge (AS) at drinking water treatment plants represents an environmental liability and adds to the cost of water purification. Consequently, this study explored the feasibility of using low and high carbon containing alum sludge from two water treatment plants to synthesize zeolite LTA. The hypothesis was that zeolite LTA synthesis was dependant upon alum sludge source and that a range of strategies may be required to optimize zeolite crystallinity. Zeolite characteristics such as morphology, phase composition, crystallinity, and particle size distribution were recorded. "One pot" hydrothermal synthesis of precursor gel with molar composition 4.2Na2O:Al2O3:1.2SiO2:168H2O at 80°C for 3 hr resulted in 25 and 46 wt.% zeolite LTA from high and low carbonaceous sludge, respectively. Prior to hydrothermal reaction stage it was discovered that ageing of the gel, addition of zeolite LTA seeds, ultrasonic treatment and calcination all promoted zeolite LTA formation. Calcination of the alum sludge at 700°C for 2 hr before hydrothermal synthesis resulted in particle size reduction and the highest amount of crystalline zeolite LTA: 79 wt.% from low carbon sludge and 65 wt.% from high carbon sludge. Notably, the zeolite crystallinity reported in this study was the higher than previous studies on this topic. The outlined approach may allow value adding of alum waste and produce a commodity which could be used locally by the water treatment plant as a water softener.

Effect of struvite and organic acids on immobilization of copper and zinc in contaminated bio-retention filter media.

Few studies have been carried out to connect nutrient recovery as struvite from wastewater and sustainable utilization of the recovered struvite for copper and zinc immobilization in contaminated soil. This study revealed the effect of struvite on Cu and Zn immobilization in contaminated bio-retention soil in the presence of commonly exuded plant organic acids. The research hypothesis was that the presence of both struvite and organic acids may influence the immobilization of Cu and Zn in soil. The outcome of this research confirmed that more than 99% of Cu and Zn was immobilized in bio-retention filter media by struvite application. Water-soluble Cu and Zn concentrations of struvite treated soil were less than 1.83 and 0.86 mg/kg respectively, and these concentrations were significantly lower compared to the total Cu and Zn content of 747.05 mg/kg in the contaminated soil. Application of struvite to Cu- and Zn-contaminated soil resulted in formation of compounds similar to zinc phosphate tetrahydrate (Zn3(PO4)2•4H2O) and amorphous Cu and Zn phases. Struvite was effective in heavy metal remediation in acidic soil regardless of the presence of Ca impurities in struvite and the presence of plant organic acids in soil. Overall, this study revealed that struvite recovered from wastewater treatment plants has potential for use as an amendment for heavy metal remediation in contaminated bio-retention soil.

Using water quality and isotope studies to inform research in chronic kidney disease of unknown aetiology endemic areas in Sri Lanka.

Chronic Kidney Disease of unknown aetiology (CKDu) is a major public health concern in dry climatic, agricultural regions of Sri Lanka. The chemistry of groundwater (the main source of drinking water) in the area has been studied extensively, in relation to the occurrence of CKDu. This paper investigates water quality studies published in CKDu affected areas of Sri Lanka and also presents a new data set of 27 hydrochemical and isotopic samples collected from groundwater wells in selected CKDu endemic areas in Sri Lanka. The study outcomes do not provide evidence of pollutants such as heavy metals in groundwater. However, the study identifies elevated concentrations of silica which requires further investigation. Two groups of groundwater have been identified based on the isotopic results suggesting different sources or origins. The available water quality data, including the data from this study, is not sufficient to answer questions on whether the chemistry of groundwater is related to the CKDu occurrence. However, this study identifies the importance of detailed investigation into degradation products of agrochemicals, the organic matter content and the influence of elevate silica concentration in groundwater. The study also provides research directions in the form of isotopic tracers and the frequency of sampling that is needed to capture potential pollutants in future groundwater quality studies in CKDu endemic areas in Sri Lanka.

Effect of Ca:Mg ratio and high ammoniacal nitrogen on characteristics of struvite precipitated from waste activated sludge digester effluent.

This study revealed the relationship between the presence of calcium impurities and ammoniacal nitrogen concentration upon crystallization of struvite. The research hypothesis was that the presence of both calcium and high concentrations of ammoniacal nitrogen (328-1000 mg/L) in waste activated sludge may influence the struvite quality and acid stability. Hence, we studied the impact of Ca:Mg ratio upon morphology, particle size, purity and dissolution of struvite, in the presence of varying levels of excess ammoniacal nitrogen. X-ray diffraction revealed that up to 31.4% amorphous material was made which was assigned to hydroxyapatite. Increasing the ammoniacal nitrogen concentration and elevation of the Mg:Ca ratio maximized the presence of struvite. Struvite particle size was also increased by ammoniacal nitrogen as was twinning of the crystals. Tests with dilute solutions of organic acid revealed the sensitivity of struvite dissolution to the physical characteristics of the struvite. Smaller particles (21.2 µm) dissolved at higher rates than larger particles (35.86 µm). However, struvite dissolved rapidly as the pH was further reduced irrespective of the physical characteristics. Therefore, addition of struvite to low pH soils was not viewed as beneficial in terms of controlled nutrient release. Overall, this study revealed that waste activated sludge effluent with high ammoniacal nitrogen was prospective for synthesis of high quality struvite material.

Phosphogypsum stabilization of bauxite residue: Conversion of its alkaline characteristics.

Reduction of the high alkalinity of bauxite residue is a key problem to solve to make it suitable for plant growth and comprehensive utilization. In this study, phosphogypsum, a waste product from the phosphate fertilizer industry, was used to drive the alkaline transformation of the bauxite residue. Under optimal water washing conditions (liquid/solid ratio of 2 mL/g, 30°C, 24 hr), the impact of quantity added, reaction time and reaction mechanism during phosphogypsum application were investigated. Phosphogypsum addition effectively lowered pH levels and reduced the soluble alkalinity by 92.2%. It was found that the concentration of soluble Na and Ca ions in the supernatant increased gradually, whilst the exchangeable Na+ and Ca2+ in solid phase changed 112 mg/kg and 259 mg/kg, respectively. Ca2+ became the dominant element in the solid phase (phosphogypsum addition of 2%, liquid/solid ratio of 2 mL/g, 30°C, 12 hr). X-ray diffraction data indicated that cancrinite and hydrogarnet were the primary alkaline minerals. SEM images suggested that phosphogypsum could promote the formation of stable macro-aggregates, whilst the content of Ca2+ increased from 5.6% to 18.2% and Na reduced from 6.8% to 2.4%. Treatment with phosphogypsum could significantly promote the transformation of alkalinity cations by neutralization, precipitation and replacement reactions. This research provided a feasible method to promote soil formation of bauxite residue by phosphogypsum amendment.

Stochastic techno-economic analysis of the production of aviation biofuel from oilseeds.

BACKGROUND: The economic viability of hydrodeoxygenation process using Camelina, Carinata and Jatropha feedstocks for aviation biofuel production was evaluated for two product profiles: (i) maximum diesel production and (ii) maximum jet fuel production (HRJ). RESULTS: Deterministic analysis of Camelina and Carinata diesel facilities returned positive NPVs and IRRs of 25 and 18%, respectively. Stochastic analysis suggested that the probabilities of positive NPVs were 75, 59 and 15%, respectively, for Camelina, Carinata and Jatropha diesel plants. Jet fuel facilities presented probabilities of loss of 98, 99 and 100% for Camelina, Carinata and Jatropha scenarios, respectively. Sensitivity analysis determined that financial performance was majorly influenced by feedstock and fuel prices. Categories of subsidies to enhance the attractiveness of the projects were studied. CONCLUSIONS: Camelina, Carinata and Jatropha plants targeting HRJ required incentives of 0.31, 0.39 and 0.61 US$/L of biofuel produced, respectively, to reduce the probabilities of loss to approximately 30%.

Acid Mine Drainage Treatment Using Bayer Precipitates Obtained from Seawater Neutralization of Bayer Liquor.

Bayer precipitates from the seawater neutralization of Bayer liquor waste from the alumina industry are shown to be a prospective solution for the remediation of acid mine drainage (AMD) water. Precipitates are varied in composition, albeit they are generally comprised of hydrotalcite (Mg6Al2(OH)16CO3∙xH2O), calcite (CaCO3), aragonite (CaCO3), mixed metal hydroxides (Mg2Al(OH)7), and halite (NaCl). Brucite (Mg(OH)2) is detected for lower Bayer liquor concentrations (1-3 g L-1 Al2O3) when the concentrations of aluminum and hydroxyl species are insufficient to promote hydrotalcite formation. The neutralizing capacity of the precipitates also varies with Bayer liquor composition. Treatment of AMD water with Bayer precipitates met discharge pH guidelines. The dissolution of hydrotalcite and brucite (1-3 g L-1 Bayer precipitates only) is responsible for the Bayer precipitate's neutralizing capacity, while calcium carbonate has a buffering affect at around pH 7. Manganese ions are the most challenging species to remove because high pH values are required (pH > 9), which is not possible with all precipitates tested. One caveat is that increasing the degree of manganese removal generates issues with excessive dissolved aluminum which exceeds discharge limits. Future research should address this latter problem and facilitate implementation of this approach to AMD remediation.

Catalytic degradation of Orange II in aqueous solution using diatomite-supported bimetallic Fe/Ni nanoparticles.

A functional diatomite-supported Fe/Ni nanocomposite successfully remediated Orange II contaminant in aqueous solution. The hypothesis was that diatomite-supported Fe/Ni would not only be more effective than Fe/Ni but also require less metallic loading to effect the catalytic reaction. Batch experiments indicate that 99.00% of Orange II was removed using diatomite-supported Fe/Ni, while only 86.64 and 3.59% of Orange II were removed using bimetallic Fe/Ni nanoparticles and diatomite, after 6 h of reaction, respectively. Characterisation by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) indicates that the use of diatomite as a support material reduced the aggregation of bimetallic Fe/Ni nanoparticles, thereby resulting in an enhancement in the reactivity. A synergistic mechanism for the removal of Orange II by diatomite-supported Fe/Ni was proposed which involves adsorption, followed by catalytic reduction. This study has demonstrated that diatomite may be a suitable support material for stabilizing and dispersing bimetallic Fe/Ni nanoparticles and the resulting diatomite-supported Fe/Ni composite could be a promising catalyst for the remediation of dye-contaminated wastewater.

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. 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. However, concentrated acids have a negative effect on adsorption due to the dissolution of these iron and aluminium oxide/hydroxide sites. 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 does not 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.

Vibrational spectroscopic study of the mineral pitticite Fe, AsO4, SO4, H2O.

Some minerals are colloidal and show no X-ray diffraction patterns. Vibrational spectroscopy offers one of the few methods for the determination of the structure of these minerals. Among this group of minerals is pitticite, simply described as (Fe, AsO(4), SO(4), H(2)O). In this work, the analogue of the mineral pitticite has been synthesised. The objective of this research is to determine the molecular structure of the mineral pitticite using vibrational spectroscopy. Raman and infrared bands are attributed to the AsO(4)(3-), SO(4)(2-) and water stretching and bending vibrations. The Raman spectrum of the pitticite analogue shows intense peaks at 845 and 837cm(-1) assigned to the AsO(4)(3-) stretching vibrations. Raman bands at 1096 and 1182cm(-1) are attributed to the SO(4)(2-) antisymmetric stretching bands. Raman spectroscopy offers a useful method for the analysis of such colloidal minerals.

Vibrational spectroscopy of synthetic stercorite H(NH4)Na(PO4)·4H2O--a comparison with the natural cave mineral.

In order to mimic the chemical reactions in cave systems, the analogue of the mineral stercorite H(NH(4))Na(PO(4))·4H(2)O has been synthesised. X-ray diffraction of the stercorite analogue matches the stercorite reference pattern. A comparison is made with the vibrational spectra of synthetic stercorite analogue and the natural Cave mineral. The mineral in nature is formed by the reaction of bat guano chemicals on calcite substrates. A single Raman band at 920 cm(-1) (Cave) and 922 cm(-1) (synthesised) defines the presence of hydrogen phosphate in the mineral. In the synthetic stercorite analogue, additional bands are observed and are attributed to the dihydrogen and phosphate anions. The vibrational spectra of synthetic stercorite only partly match that of the natural stercorite. It is suggested that natural stercorite is more pure than that of synthesised stercorite. Antisymmetric stretching bands are observed in the infrared spectrum at 1052, 1097, 1135 and 1173 cm(-1). Raman spectroscopy shows the stercorite mineral is based upon the hydrogen phosphate anion and not the phosphate anion. Raman and infrared bands are found and assigned to PO(4)(3-), H(2)O, OH and NH stretching vibrations. Raman spectroscopy shows the synthetic analogue is similar to the natural mineral. A mechanism for the formation of stercorite is provided.