Enhanced bio-recovery of aluminum from low-grade bauxite using adapted fungal strains.

Filamentous fungi have been proved to have a pronounced capability to recover metals from mineral ores. However, the metal recovery yield is reduced due to toxic effects triggered by various heavy metals present in the ore. The current study highlights the fungal adaptations to the toxic effects of metals at higher pulp densities for the enhanced bio-recovery of aluminum from low-grade bauxite. In the previous studies, a drastic decrease in the aluminum dissolution was observed when the bauxite pulp density was increased from 1 to 10% (w/v) due to the high metal toxicity and low tolerance of Aspergillus niger and Penicillium simplicissium to heavy metals. These fungi were adapted in order to increase heavy metal tolerance of these fungal strains and also to get maximum Al dissolution. A novel approach was employed for the adaptation of fungal strains using a liquid growth medium containing 5% bauxite pulp density supplemented with molasses as an energy source. The mycelia of adapted strains were harvested and subsequently cultured in a low-cost oat-agar medium. Batch experiments were performed to compare the aluminum leaching efficiencies in the direct one-step and the direct two-step bioleaching processes. FE-SEM analysis revealed the direct destructive and corrosive action by the bauxite-tolerant strains due to the extension and penetration of the vegetative mycelium filaments into the bauxite matrix. XRD analysis of the bioleached bauxite samples showed a considerable decline in oxide minerals such as corundum and gibbsite. Results showed a high amount of total Al (≥ 98%) was successfully bioleached and solubilized from low-grade bauxite by the adapted fungal strains grown in the presence of 5% pulp density and molasses as a low-cost substrate. Graphical abstract.

Enhanced recovery of aluminum from wastewater using a fluidized bed homogeneously dispersed granular reactor.

The recovery of aluminum from wastewater is one of the main environmental issues that need to be addressed in the aluminum finishing industry. A new technique of converting a soft slurry into hard granules using the homogeneous granulation process in the fluidized-bed reactor (FBR) can respond to this problem. It is a better method of remediation than producing a slurry containing 70% water. This study deals with the recovery of aluminum from aqueous solutions using Fluidized-bed homogeneous granulation process (FBHGP) without seeds. The hydraulic operating conditions were optimized using Box-Behnken Design (BBD) to attain the optimum aluminum removal (AR%) and granulation ratio (GR%). Optimum values of AR% = 98.8% and GR% = 96.9% were attained at the following conditions: influent aluminum concentration, 334.1 mg L-1; precipitant pH, 10.4; molar ratio (MR) of precipitant to metal [OH-]in/[Al3+]in, 2.5. The characteristics of the granules were comparable with those of orthorhombic structure of aluminum oxide (Al2.66O4). FBHGP was proven to be effective as dictated by the reaction mechanism in the recovery of aluminum from aluminum-rich aqueous solutions.

Direct Observation of Hydrangea Blue-Complex Composed of 3-O-Glucosyldelphinidin, Al3+ and 5-O-Acylquinic Acid by ESI-Mass Spectrometry.

The blue sepal color of hydrangea is due to a metal complex anthocyanin composed of 3-O-glucosyldelphinidin (1) and an aluminum ion with the co-pigments 5-O-caffeoylquinic acid (2) and/or 5-O-p-coumaroylquinic acid (3). The three components, namely anthocyanin, Al3+ and 5-O-acylquinic acids, are essential for blue color development, but the complex is unstable and only exists in an aqueous solution. Furthermore, the complex did not give analyzable NMR spectra or crystals. Therefore, many trials to determine the detailed chemical structure of the hydrangea-blue complex have not been successful to date. Instead, via experiments mixing 1, Al3+ and 2 or 3 in a buffered solution at pH 4.0, we obtained the same blue solution derived from the sepals. However, the ratio was not stoichiometric but fluctuated. To determine the composition of the complex, we tried direct observation of the molecular ion of the complex using electrospray-ionization mass spectrometry. In a very low-concentration buffer solution (2.0 mM) at pH 4.0, we reproduced the hydrangea-blue color by mixing 1, 2 and Al3+ in ratios of 1:1:1, 1:2:1 and 1:3:1. All solution gave the same molecular ion peak at m/z = 843, indicating that the blue solution has a ratio of 1:1:1 for the complex. By using 3, the observed mass number was m/z = 827 and the ratio of 1, 3 and Al3+ was also 1:1:1. A mixture of 1, 3-O-caffeoylquinic acid (4) and Al3+ did not give any blue color but instead was purple, and the intensity of the molecular ion peak at m/z = 843 was very low. These results strongly indicate that the hydrangea blue-complex is composed of a ratio of 1:1:1 for 1, Al3+ and 2 or 3.

Removal of heavy metals from aluminum anodic oxidation wastewaters by membrane filtration.

Aluminum manufacturing has been reported as one of the largest industries and wastewater produced from the aluminum industry may cause significant environmental problems due to variable pH, high heavy metal concentration, conductivity, and organic load. The management of this wastewater with a high pollution load is of great importance for practitioners in the aluminum sector. There are hardly any studies available on membrane treatment of wastewater originated from anodic oxidation. The aim of this study is to evaluate the best treatment and reuse alternative for aluminum industry wastewater using membrane filtration. Additionally, the performance of chemical precipitation, which is the existing treatment used in the aluminum facility, was also compared with membrane filtration. Wastewater originated from anodic oxidation coating process of an aluminum profile manufacturing facility in Kayseri (Turkey) was used in the experiments. The characterization of raw wastewater was in very low pH (e.g., 3) with high aluminum concentration and conductivity values. Membrane experiments were carried out with ultrafiltration (PTUF), nanofiltration (NF270), and reverse osmosis (SW30) membranes with MWCO 5000, 200-400, and 100 Da, respectively. For the chemical precipitation experiments, FeCl3 and FeSO4 chemicals presented lower removal performances for aluminum and chromium, which were below 35% at ambient wastewater pH ~ 3. The membrane filtration experimental results show that, both NF and RO membranes tested could effectively remove aluminum, total chromium and nickel (>90%) from the aluminum production wastewater. The RO (SW30) membrane showed a slightly higher performance at 20 bar operating pressure in terms of conductivity removal values (90%) than the NF 270 membrane (87%). Although similar removal performances were observed for heavy metals and conductivity by NF270 and SW30, significantly higher fluxes were obtained in NF270 membrane filtration at any pressure that there were more than three times the flux values in SW30 membrane filtration. Due to the lower heavy metal (<65%) and conductivity (<30%) removal performances of UF membrane, it could be evaluated as pretreatment followed by NF filtration to protect and extend NF membrane life. The water treated by both NF and RO could be recycled back into the process to be reused with economic and environmental benefits.

Detoxification of polluted marine sediments using water treatment sludge.

The purpose of this study was development of the optimal conditions for the inertization of the polluted marine sediments using groundwater treatment sludge highly enriched in iron and aluminum. For that purpose fine-grained sediment (>85% clay and silt fraction) highly enriched in copper and zinc was amended with the waste sludge (from 10% to 50%). The sample with the optimum percentage of the waste sludge was further subjected the thermal treatment at 200-800°C. The efficiency of the treatment was determined by the leaching tests and toxicity testing using Hordeum vulgare L. as biosystem. The percentage of the seed germination, the root elongation, and the germination index before and following the treatment were determined. Untreated sediment leachate caused significant arrest in the percentage of the seed germination (6.7 ± 6.7%), the root elongation (1.9 ± 2.2%), and the germination index (0.2 ± 0.3%) with EC50 of 24.9%, suggesting a significant toxic potential of the sediments. After amendment with 30% of the waste sludge the concentrations of the considered micropollutants decreased below regulated values while all three toxicological parameters showed no significant difference compared to the negative control. The toxicity of the sediment was completely removed following the thermal treatment at 400°C.

[Determination of residual aluminium Ion in Huoxiang Zhengqi pellets by GFAAS with EDTA complexation extraction].

To establish an EDTA complexation extraction pretreatment combining with GFAAS method for the determination of residual aluminium ion in Huoxiang zhengqi pellets without digestive treatment, systematical investigation was made on sample preparation, and EDTA was used for the complexation extraction of residual aluminium ion in samples. The pH, concentration and volume of extraction solution, the temperature and time of microwave extraction, and graphite furnace temperature program were investigated. The results were compared with the microwave digestion. It was showed that, 0.1 g of sample weight was added in 20 mL 0.05 mol x L(-1) EDTA solution (pH 3.5), followed by heating at 150 degrees C for 10 min in the microwave extraction device. The determination of GFAAS was performed at optimized detection wavelength (257.4 nm) as well as graphite furnace temperature program, the detection limits and quantification limits were 2.37 µg x L(-1) and 7.89 µg x L(-1), respectively. The precision (RSD) was less than 2.3%. The average recovery was 96.9% -101%. The present method is easy, rapid and accurate for the determination of residual aluminium ion in Huoxiang zhengqi pellets.

Amelioration of an Ultisol profile acidity using crop straws combined with alkaline slag.

The acidity of Ultisols (pH <5) is detrimental to crop production. Technologies should be explored to promote base saturation and liming effect for amelioration of Ultisol pH. Column leaching experiments were conducted to investigate the amelioration effects of canola straw (CS) and peanut straw (PS) in single treatment and in combination whether with alkaline slag (AS) or with lime on Ultisol profile acidity. The treatment without liming materials was set as control, and the AS and lime in single treatment are set for comparison. Results indicated that all the liming materials increase soil profile pH and soil exchangeable base cations at the 0-40-cm depth, except that the lime had amelioration effect just on 0 to 15-cm profile. The amelioration effect of the liming materials on surface soil acidity was mainly dependent on the ash alkalinity in organic materials or acid neutralization capacity of inorganic materials. Specific adsorption of sulfate (SO4(2-)) or organic anions, decarboxylation of organic acids/anions, and the association of H(+) with organic anions induced a "liming effect" of crop residues and AS on subsoil acidity. Moreover, SO4(2-) and chloride (Cl(-)) in PS, CS, and AS primarily induced base cations to move downward to subsoil and exchange with exchangeable aluminum (Al(3+)) and protons (H(+)). These anions also promoted the exchangeable Al to leach out of the soil profile. The CS was more effective than PS in decreasing soil acidity in the subsoil, which mainly resulted from higher sulfur (S) and Cl content in CS compared to PS. The CS combined with AS was the better amendment choice in practical agricultural systems.

Aluminium involvement in neurotoxicity.

The aetiology of neurodegenerative diseases (ND) seems to involve susceptibility genes and environmental factors. Toxic metals are considered major environmental pollutants. Following our study of a case of multiple sclerosis (MS) improvement due to removal of aluminium (Al) and other toxic metals, we have examined the possible relationship between Al intoxication and ND. We used the slow intravenous treatment with the chelating agent EDTA (calcium disodium ethylene diamine tetraacetic acid) (chelation test) to remove Al and detected it in the urine collected from the patients for 12 hours. Patients affected by MS represented 85.6% of total ND. Al was present in 44.8% of cases comprehensive of ND and healthy patients. Al levels were significantly higher in ND patients than in healthy subjects. We here show that treatment of patients affected by Al burden with ten EDTA chelation therapies (EDTA intravenous administration once a week) was able to significantly reduce Al intoxication.

Recovery of phosphorus and aluminium from sewage sludge ash by a new wet chemical elution process (SESAL-Phos-recovery process).

The potential of a new wet chemical process for phosphorus and aluminium recovery from sewage sludge ash by sequential elution with acidic and alkaline solutions has been investigated: SESAL-Phos (sequential elution of sewage sludge ash for aluminium and phosphorus recovery). Its most innovative aspect is an acidic pre-treatment step in which calcium is leached from the sewage sludge ash. Thus the percentage of alkaline soluble aluminium phosphates is increased from 20 to 67%. This aluminium phosphate is then dissolved in alkali. Subsequently, the dissolved phosphorus is precipitated as calcium phosphate with low heavy metal content and recovered from the alkaline solution. Dissolved aluminium is recovered and may be reused as a precipitant in wastewater treatment plants.

Understanding removal of phosphate or arsenate onto water treatment residual solids.

Chemical and physical characterization methods were used to analyze ferric, alum, and lime water treatment residual solids (WTRSs) in order to describe why phosphate or arsenate adsorption occurred on the WTRSs, and why ferric WTRSs were the stronger adsorbent for both phosphate and arsenate. In total, five WTRSs, two ferric, two alum, and one lime, were analyzed. Elemental analysis of the WTRSs showed lime residuals contained the greatest molar amount of the primary element (7.04 mol Ca/kg solid), followed by the ferric residuals (4.86-4.96 mol Fe/kg solid) whereas alum residuals contained the least amount of primary element as compared to the ferric or alum residual solids (3.62-4.67 mol Al/kg solid). Mercury porosimetry identified more small pores (<0.006 µm) in a ferric WTRSs when compared to an alum WTRSs, indicating that a more detailed pore structure allowing for intraparticle phosphate or arsenate diffusion might be present in the ferric solid. Similarly, SEM images at 1000 times magnification showed a porous surface in both ferric WTRSs, whereas the alum WTRSs showed a smooth surface at the same magnification. Several general equations to describe phosphate or arsenate adsorption on WTRSs were provided.

Implementation of an MgO-based metal removal step in the passive treatment system of Shilbottle, UK: column experiments.

Three laboratory column experiments were performed to test the suitability of two different MgO-rich reagents for removal of Mn and Al from the out-flowing waters of Shilbottle passive treatment system (Northumberland, UK). The input water was doped with 100 mg/L Zn in order to extrapolate results to waters in sulphide mining districts. One column was filled with a Dispersed Alkaline Substrate (DAS) containing 12.5% (v/v) caustic magnesia precipitator dust (CMPD) from Spain mixed with wood shavings, two columns were filled with DAS containing wood shavings and 12.5% or 25% (v/v), respectively, of dolomitic lime precipitator dust (DLPD) from Thrislington, UK. The two columns containing 12.5% of CMPD or DLPD completely removed the contaminants from the inflow water during the first 6 weeks of the experiment (mean removal of 88 mg/L Al, 96 mg/L Zn and 37 mg/L Mn), operating at an acidity load of 140 g acidity/m(2)day. At this moment, a substantial increase of the Al and Mn water concentration in the out-flowing waters of Shilbottle occurred (430 g acidity/m(2)day), leading to passivation of the reactive material and to the development of preferential flow paths within less than another 6 weeks, probably mainly due to Al precipitates. Al should be removed prior to MgO treatment.

Applications of methacrylate-based monolithic supports for speciation analysis.

Liquid chromatography combined with element specific detection is commonly applied in speciation analysis. In these analyses, to obtain reliable data chemical species should not be transformed. To preserve chemical species during the separation step, fast chromatographic procedures and mild separation conditions are required. Monolithic supports that enable rapid chromatographic separations have rarely been used in speciation analysis. Methacrylate-based anion- and cation-exchange monolithic supports offer separation of charged chemical species of elements and can be used as a complementary tool to particle-packed liquid chromatographic columns. The present paper presents an overview of successful applications of methacrylate-based monolithic supports in speciation of zinc (Zn), chromium (Cr), and aluminium (Al) in environmental, occupational health, and biological samples. Measures of analytical performance of convective interaction media (CIM) monolithic chromatographic supports, namely selectivity, sensitivity, and time of analysis, are compared to those of particle-packed columns. The potential of CIM monolithic chromatography in speciation analysis is critically discussed. Direct comparison of the experimental data in speciation of elements by ion-exchange monolithic and fast protein liquid chromatography is reported for the first time. Finally, some recommendations are given for further investigations of the potential of monolithic chromatography and its implementations in different fields of element speciation analysis.

Sulfuric acid baking and leaching of spent Co-Mo/Al2O3 catalyst.

Dissolution of metals from a pre-oxidized refinery plant spent Co-Mo/Al(2)O(3) catalyst have been tried through low temperature (200-450 degrees C) sulfuric acid baking followed by mild leaching process. Direct sulfuric acid leaching of the same sample, resulted poor Al and Mo recoveries, whereas leaching after sulfuric acid baking significantly improved the recoveries of above two metals. The pre-oxidized spent catalyst, obtained from a Korean refinery plant found to contain 40% Al, 9.92% Mo, 2.28% Co, 2.5% C and trace amount of other elements such as Fe, Ni, S and P. XRD results indicated the host matrix to be poorly crystalline gamma- Al(2)O(3). The effect of various baking parameters such as catalyst-to-acid ratio, baking temperature and baking time on percentage dissolutions of metals has been studied. It was observed that, metals dissolution increases with increase in the baking temperature up to 300 degrees C, then decreases with further increase in the baking temperature. Under optimum baking condition more than 90% Co and Mo, and 93% Al could be dissolved from the spent catalyst with the following leaching condition: H(2)SO(4)=2% (v/v), temperature=95 degrees C, time=60 min and Pulp density=5%.

Approaches for the treatment of waste streams of the aluminium anodising industry.

The aluminium anodising industry is an important industrial sector that invariably generates great amounts of different waste streams. Classical and especially new-developing technologies dealing with them are reviewed. Innovative methods are mainly based on engineering geochemical processes, looking for the recovery of resource materials and the reduction of emissions to the environment. These represent a promising alternative to the classical method (neutralisation process and anodising mud disposal) which is an end-of-pipe solution. Among the treatments recently proposed, there are the use of anodising mud in the manufacture of refractory bodies, and the synthesis of useful minerals from the wastewaters arising from the etching, anodising and brightening processes. The viability of the application of such methods in the treatment of waste streams of the aluminium anodising industry is discussed, pointing out the main shortcomings and benefits of each of them. For those methods appearing environmentally friendly the process cost and the actual marketability of the final products should be determinant on their near future applicability.

Phosphorus recovery from digested sewage sludge as MAP by the help of metal ion separation.

This study was designed to solve metal ion influence problem on phosphorus recovery from digested sewage sludge as MAP. The experimental steps were proceeded to maximize MAP production and its quality. Used experimental steps were: All digested sewage sludge samples were taken from Stuttgart University sewage treatment plant for research and education (LFKW). Four different forms of LFKW digested sewage sludge were used as feeding sample. These were: original digested sludge, diluted digested sludge, centrifuged digested sludge and incinerated digested sludge. A Donnan membrane unit having a Nafion 117 (DuPont) cation exchange membrane was used to remove metal ions from the samples used. Highest metal ion removal efficiencies, which were 98%, 97%, and 80% for Al, Ca and Fe ions, respectively, were obtained from incinerated digested sludge run. Incinerated digested sludge run was used as preliminary step for MAP production and high quality MAP was produced. Produced MAP fulfils all requirements related with Düngemittelverordnung 2003 and it could be used as a fertilizer in Germany.

Ameliorating caustic properties of aluminum extraction residue to establish a vegetative cover.

High pH, electrical conductivity (E.C.), and extractable Na levels in the residue remaining after aluminum was extracted from bauxite were greater than can support vigorous plant growth. These caustic properties must be ameliorated so that vegetation could be established on the surface of large disposal ponds. Fresh residue was added to 14 field lysimeters of dimensions 3 m long x 3 m wide x 1 m deep. Internal drainage was enhanced in some lysimeters and restricted in others. Gypsum applied at the rate of 7.5% of the weight of the top 15 cm of residue in selected lysimeters. These management issues were studied to determine how their influence would lower chemical properties to support vegetation. Residue samples were removed annually for 5 years after the lysimeters were established to determine changes in pH, E.C., and extractable Na and Al over time. Plant species C. dactylon (bermudagrass), Atriplex nummalari (oldman saltbush), and Atriplex canescens (fourwing saltbush) were planted either as seeds or transplants beginning the third year after lysimeter establishment. Residue pH, E.C. Na, and Al decreased annually, but more gradually in restricted drainage. Species survival in the enhanced drainage treatments was more vigorous with gypsum amendments beginning in the third year after lysimeter establishment. This coincided with a decrease in the mean pH below 9.5 and decrease in mean E.C. below 10 dS/m. Extractable Na and Al did not seem to influence survivability. Survival of seeded and transplanted C. dactylon was greater than the two Atriplex spp. each year. This study proved that the caustic properties of this residue could be lowered enough to support vegetation, but not without appropriate drainage. The addition of gypsum amendments and appropriate amounts of supplemental water would accelerate the timeframe for vegetation establishment probably at a level commensurate with the application rate of both inputs in a well-drained system.

Selective recovery of Mo, Co and Al from spent Co/Mo/gamma-Al2O3 catalyst: effect of calcination temperature.

A combination of pyro and hydrometallurgical process has been proposed to selectively recover molubdenum, cobalt and aluminium from the spent catalyst containing 12.3% Mo; 31.8% Al; 2.38% Co; 9.5% S and 2.9% C. Before a two-stage alkali-acid leaching process to selectively target Mo, Co and Al from the uncrushed sample, the spent catalyst was calcined at different temperatures. Characterization of different calcined samples was carried out by different instrumental analysis like XRD, TG/DTA, IR and SEM in order to understand the structural changes and dissolution behavior of spent catalyst. It was found that calcination at 500 degrees C preferred for spent catalyst roasting since the surface and pore structures obtained by roasting at this temperature facilitated dissolution of calcined spent catalyst in the leachant. Mo was selectively separated and recovered from the leach liquor by carbon adsorption method; whereas, Al and Co were separated by an organo-phosphinic-based extractant, Cyanex 272. In the whole process, 95.9% Mo, 89.6% Co and 39.8% Al was recovered from the spent catalyst. Finally, a complete process flowsheet has been presented.

Processing of spent NiMo and CoMo/Al2O3 catalysts via fusion with KHSO4.

This work describes a route for processing spent commercial hydrorefining (HDR) catalysts (CoMo and NiMo/Al2O3), containing support additives, for recovering active phase and support components. Samples were used as catalysts in diesel hydrotreaters. They had neither been submitted to mechanical stresses nor overheating while under operation. The route is based on fusion of samples with KHSO4. Four experimental parameters were optimized: reaction time, sample/flux mass ratio, temperature, and sample physical characteristics (ground/non-ground). After fusion, the solid was dissolved in water (90-100 degrees C); the insoluble matter presented low crystallization. Several phases were identified: silicates, spinel-like compounds and aluminosilicates. Cobalt, nickel, molybdenum and aluminum were recovered by conventional precipitation techniques or selective solvent-extraction procedures, with at least 85 wt.% yield. Final liquid colorless effluents are obtained as neutral solutions of alkali sulfates or chlorides and a water insoluble solid after fusion, which can be either sent to industrial dumps or co-processed. Fusion with KHSO4 was shown to be applicable to the catalysts of the present study, and the optimized experimental parameters are much less drastic than the conventional pyrometallurgical routes proposed in the literature.

Morin applied in speciation of aluminium in natural waters and biological samples by reversed-phase high-performance liquid chromatography with fluorescence detection.

A reversed-phase high-performance liquid chromatographic method with fluorescence detection for the determination of labile monomeric aluminium has been developed through pre-column complexation using morin as the analytical reagent. The highly fluorescent aluminium-morin complex (excitation wavelength 418 nm, emission wavelength 490 nm) was separated on a Spherisorb ODS 2 column with an eluent consisting of 30% methanol and 70% water (pH 1.0 with perchloric acid). The most remarkable point of this protocol was that only the most toxic aluminium species, that is, free aqua-aluminium ion and its monomeric hydroxo complex ions, selectively respond among various aluminium complexes. This strategy has been successfully applied to direct fractionation of the toxic aluminium in natural waters and biological samples without any pretreatment.