Examining a synchrotron-based approach for in situ analyses of Al speciation in plant roots.

Aluminium (Al) K- and L-edge X-ray absorption near-edge structure (XANES) has been used to examine Al speciation in minerals but it remains unclear whether it is suitable for in situ analyses of Al speciation within plants. The XANES analyses for nine standard compounds and root tissues from soybean (Glycine max), buckwheat (Fagopyrum tataricum), and Arabidopsis (Arabidopsis thaliana) were conducted in situ. It was found that K-edge XANES is suitable for differentiating between tetrahedral coordination (peak of 1566 eV) and octahedral coordination (peak of 1568 to 1571 eV) Al, but not suitable for separating Al binding to some of the common physiologically relevant compounds in plant tissues. The Al L-edge XANES, which is more sensitive to changes in the chemical environment, was then examined. However, the poorer detection limit for analyses prevented differentiation of the Al forms in the plant tissues because of their comparatively low Al concentration. Where forms of Al differ markedly, K-edge analyses are likely to be of value for the examination of Al speciation in plant tissues. However, the apparent inability of Al K-edge XANES to differentiate between some of the physiologically relevant forms of Al may potentially limit its application within plant tissues, as does the poorer sensitivity at the L-edge.

27Al and 31P NMR spectroscopy method development to quantify aluminum phosphate in adjuvanted vaccine formulations.

A novel qNMR method is described for the quantitative determination of total aluminum and phosphate in aluminum phosphate (AlPO4) adjuvanted vaccine samples using solution 27Al and 31P nuclear magnetic resonance (NMR) spectroscopy. External standard calibrations of AlPO4 solutions established excellent linearity in the range of 15-40 × 10-3 M and additional studies determined the level of detection for both nuclei. A commercialized combination vaccine product (Quadracel®), along with several individual adsorbed antigen components used in the vaccine were employed as model systems for method development. The developed method is also capable of quantitating the free phosphate (i.e. the fraction not bound to AlPO4 particles) in adjuvanted vaccines. This study is the first demonstration of a solution NMR method that is suitable for measuring total aluminum, and free and total phosphate concentrations in vaccine formulations consisting of antigen(s) adsorbed to aluminum adjuvant, in a single analytical workflow.

Phenolic alkaloid oleracein E attenuates oxidative stress and neurotoxicity in AlCl3-treated mice.

AIMS: Chelation therapy and antioxidant supplements have been demonstrated to be useful in ameliorating aluminum (Al) induced neurotoxicity. Oleracein E (OE) is a phenolic antioxidant alkaloid which possesses a rare tetrahydroisoquinoline/pyrrolidone tricyclic skeleton and a catechol moiety. The aim of this study was to investigate whether OE can chelate with Al and alleviate AlCl3-induced oxidative stress and neurotoxicity. MAIN METHODS: Kunming mice were administered AlCl3 (40mg/kg/d, i.p., 28days), with co-administration of OE (3mg/kg/d, 15mg/kg/d, i.g.) and the positive control piracetam (PA, 400mg/kg/d, i.g.). The Al contents in the brain and plasma were determined using ICP-MS. Al chelating ability of OE was assayed using UV spectroscopy. MDA, GSH, SOD or CAT, in the brain or plasma were determined. HE staining was used to examine hippocampal morphology alterations. IHC staining was employed to measure the expression of apoptotic-related proteins Bax, Bcl-2 and Caspase-3. KEY FINDINGS: AlCl3 remarkably increased the brain and plasma Al contents, increased lipid peroxidation and induced hippocampal neuronal damage. OE chelated with Al to form a stable complex. An increase in brain Al content by OE (15mg/kg) likely occurred through chelating with Al, which reduced the toxicity of free Al ion in the brain. OE significantly decreased MDA by regulating some antioxidant biomarkers. Furthermore, OE significantly ameliorated the protein expression changes in some apoptotic indices induced by AlCl3. SIGNIFICANCE: The phenolic alkaloid OE, as an antioxidant, Al chelator and apoptosis inhibitor, alleviates oxidative stress and neurotoxicity induced by AlCl3.

Sequential electrodialytic recovery of phosphorus from low-temperature gasification ashes of chemically precipitated sewage sludge.

Phosphorus recycling from secondary materials like sewage sludge ashes offers an alternative to mining of phosphates from primary resources and a mean to counteract the current phosphorous rock depletion concern. A separation of P from the bulk ash is normally required, due to its low plant availability and the presence of heavy metals. Previously, more than 80% of P was recovered from incineration sewage sludge ashes using a two-compartment electrodialytic cell. In contrast, the recovery was below 30% for ashes from low-temperature gasification using the same setup. The low recovery was due to a high presence of Al- and Fe(III)-P bindings. In the present study, an electrodialytic process combining sequentially a pair of two-compartment cells allowed a recovery of up to 70% of phosphorus from these ashes. The use of a second cell, where the ash was suspended in an alkaline solution, allowed the P solubilisation from aluminium and ferric phosphates. In addition, P was separated from most metals as they became insoluble under the prevailing chemical environment. The obtained ratio of Al, Fe, Mg and most heavy metals to P was comparable to wet process phosphoric acid. Therefore, this sequential process was found to be suitable to recycle P and potentially use it in the production of common fertilizers like diammonium phosphate.

Mineral phases and metals in baghouse dust from secondary aluminum production.

Baghouse dust (BHD) is a solid waste generated by air pollution control systems during secondary aluminum processing (SAP). Management and disposal of BHD can be challenging in the U.S. and elsewhere. In this study, the mineral phases, metal content and metal leachability of 78 BHD samples collected from 13 different SAP facilities across the U.S. were investigated. The XRD semi-quantitative analysis of BHD samples suggests the presence of metallic aluminum, aluminum oxide, aluminum nitride and its oxides, spinel, elpasolite as well as diaspora. BHD also contains halite, sylvite and fluorite, which are used as fluxes in SAP activities. Total aluminum (Al) in the BHD samples averaged 18% by weight. Elevated concentrations of trace metals (>100 µg L(-1) As; >1000 µg L(-1) Cu, Mn, Se, Pb, Mn and Zn) were also detected in the leachate. The U.S. toxicity characteristic leaching procedure (TCLP) results showed that some samples leached above the toxicity limit for Cd, Pb and Se. Exceeding the TCLP limits in all sample is independent of facilities generating the BHD. From the metal content perspective only, it appears that BHD has a higher potential to exhibit toxicity characteristics than salt cake (the largest waste stream generated by SAP facilities).

What do results of common sequential fractionation and single-step extractions tell us about P binding with Fe and Al compounds in non-calcareous sediments?

Correct identification of P forms together with their main Fe and Al binding partners in non-calcareous sediments is of crucial importance for evaluation of P cycling in water bodies. In this paper, we assess extraction methods frequently used for this purpose, i.e., a sequential five-step fractionation (water, bicarbonate buffered dithionite solution (BD), NaOH, HCl, nitric-perchloric acid), ascorbate extraction (pH ~7.5), and oxalate extraction (pH ~3), directly on a range of laboratory prepared Fe and Al minerals enriched with adsorbed P. Extraction selectivity and efficiency for particular P, Fe and Al forms were also verified by specific combinations of these extraction methods applied on freshwater sediment samples. In the sequential fractionation, BD was highly effective in dissolving both amorphous and crystalline Fe (hydr)oxides and the associated P, while neither FeS nor Al (hydr)oxides were dissolved. The following NaOH extraction effectively dissolved both amorphous and crystalline Al (hydr)oxides. The high solubilizing power of BD and NaOH to dissolve crystalline Fe and Al oxides that have only a small P-sorption ability prevents the use of resulting Fe/P and Al/P ratios as simple predictors of total P sorption capacity of sediments and soils. Ascorbate non-selectively extracted small proportions of FeS and amorphous Fe and Al (hydr)oxides, but significant amounts of adsorbed P, which hinders its use for the characterization of P forms in non-calcareous sediments. Similar nonselective characteristics were found for oxalate extractions. As oxalate extracts most of the adsorbed phosphate, it is not possible to use it unambiguously to determine specific Fe/P and Al/P ratios of active complexes. However, this method is convenient (and more selective than NaOH step in the sequential fractionation) for the determination of amorphous Al (hydr)oxides.

Total allowable concentrations of monomeric inorganic aluminum and hydrated aluminum silicates in drinking water.

Maximum contaminant levels are used to control potential health hazards posed by chemicals in drinking water, but no primary national or international limits for aluminum (Al) have been adopted. Given the differences in toxicological profiles, the present evaluation derives total allowable concentrations for certain water-soluble inorganic Al compounds (including chloride, hydroxide, oxide, phosphate and sulfate) and for the hydrated Al silicates (including attapulgite, bentonite/montmorillonite, illite, kaolinite) in drinking water. The chemistry, toxicology and clinical experience with Al materials are extensive and depend upon the particular physical and chemical form. In general, the water solubility of the monomeric Al materials depends on pH and their water solubility and gastrointestinal bioavailability are much greater than that of the hydrated Al silicates. Other than Al-containing antacids and buffered aspirin, food is the primary source of Al exposure for most healthy people. Systemic uptake of Al after ingestion of the monomeric salts is somewhat greater from drinking water (0.28%) than from food (0.1%). Once absorbed, Al accumulates in bone, brain, liver and kidney, with bone as the major site for Al deposition in humans. Oral Al hydroxide is used routinely to bind phosphate salts in the gut to control hyperphosphatemia in people with compromised renal function. Signs of chronic Al toxicity in the musculoskeletal system include a vitamin D-resistant osteomalacia (deranged membranous bone formation characterized by accumulation of the osteoid matrix and reduced mineralization, reduced numbers of osteoblasts and osteoclasts, decreased lamellar and osteoid bands with elevated Al concentrations) presenting as bone pain and proximal myopathy. Aluminum-induced bone disease can progress to stress fractures of the ribs, femur, vertebrae, humerus and metatarsals. Serum Al ≥100 µg/L has a 75-88% positive predictive value for Al bone disease. Chronic Al toxicity is also manifest in the hematopoietic system as an erythropoietin-resistant microcytic hypochromic anemia. Signs of Al toxicity in the central nervous system (speech difficulty to total mutism to facial grimacing to multifacial seizures and dyspraxia) are related to Al accumulation in the brain and these symptoms can progress to frank encephalopathy. There are four groups of people at elevated risk of systemic Al intoxication after repeated ingestion of monomeric Al salts: the preterm infant, the infant with congenital uremia and children and adults with kidney disease. There is a dose-dependent increase in serum and urinary Al in people with compromised renal function, and restoration of renal function permits normal handling of systemically absorbed Al and resolution of Al bone disease. Clinical experience with 960 mg/day of Al(OH)(3) (~5 mg Al/kg-day) given by mouth over 3 months to men and women with compromised renal function found subclinical reductions in hemoglobin, hematocrit and serum ferritin. Following adult males and females with reduced kidney function found that ingestion of Al(OH)(3) at 2.85 g/day (~40 mg/kg-day Al) over 7 years increased bone Al, but failed to elicit significant bone toxicity. There was one report of DNA damage in cultured lymphocytes after high AlCl(3) exposure, but there is no evidence that ingestion of common inorganic Al compounds presents an increased carcinogenic risk or increases the risk for adverse reproductive or developmental outcomes. A number of studies of Al exposure in relation to memory in rodents have been published, but the results are inconsistent. At present, there is no evidence to substantiate the hypothesis that the pathogenesis of Alzheimer's Disease is caused by Al found in food and drinking water at the levels consumed by people living in North America and Western Europe. Attapulgite (palygorskite) has been used for decades at oral doses (recommended not to exceed two consecutive days) of 2,100 mg/day in children of 3-6 years, 4,200 mg/day in children of 6-12 years, and 9,000 mg/day in adults. Chronic ingestion of insoluble hydrated Al silicates (in kg) can result in disturbances in iron and potassium status, primarily as a result of clay binding to intestinal contents and enhanced fecal iron and zinc elimination. Sufficiently high doses of ingested Al silicates (≥50 g/day) over prolonged periods of time can elicit a deficiency anemia that can be corrected with oral Fe supplements. There is essentially no systemic Al uptake after ingestion of the hydrated Al silicates. Rats fed up to 20,000 ppm Ca montmorillonite (equivalent to 1,860 ppm total Al as the hydrated Al silicate) for 28 weeks failed to develop any adverse signs. The results of dietary Phase I and II clinical trials conducted in healthy adult volunteers over 14 days and 90 days with montmorillonite found no adverse effects after feeding up to 40 mg/kg-day as Al. Since the Al associated with ingestion of hydrated Al silicates is not absorbed into the systemic circulation, the hydrated Al silicates seldom cause medical problems unless the daily doses consumed are substantially greater than those used clinically or as dietary supplements. A no-observable-adverse-effect-level (NOAEL) of 13 mg/kg-day as total Al can be identified based on histologic osteomalacia seen in adult hemodialysis patients given Al hydroxide for up to 7 years as a phosphate binder. Following U.S. EPA methods for calculation of an oral reference dose (RfD), an intraspecies uncertainty factor of 10x was applied to that value results in a chronic oral reference dose (RfD) of 1.3 mg Al/kg-day; assuming a 70-kg adult consumes 2 L of drinking water per day and adjusting for a default 20% relative source contribution that value corresponds to a drinking water maximum concentration of 9 mg/L measured as total Al. A chronic NOAEL for montmorillonite as representative of the hydrated Al silicates was identified from the highest dietary concentration (20,000 ppm) fed in a 28-week bioassay with male and female Sprague-Dawley rats. Since young rats consume standard laboratory chow at ~23 g/day, this concentration corresponds to 56 mg Al/kg-day. Application of 3x interspecies uncertainty factor and a 3x factor to account for study duration results in a chronic oral RfD of 6 mg Al/kg-day. Of note, this RfD is 5-10 fold less than oral doses of Al silicates consumed by people who practice clay geophagy and it corresponds to a maximum drinking water concentration of 40 mg Al/L. To utilize the values derived here, the risk manager must recognize the particular product (e.g., alum) or source (e.g., groundwater, river water, clay or cement pipe) of the Al found in tap water, apply the appropriate analytical methods (atomic absorption, energy dispersive X-ray diffraction, infrared spectral analysis and/or scanning transmission electron microscopy) and compare the results to the most relevant standard. The drinking water concentrations derived here are greater than the U.S. EPA secondary maximum contaminant level (MCL) for total Al of 0.05-0.2 mg/L [40 CFR 143.3]. As such, domestic use of water with these concentrations is likely self-limiting given that its cloudy appearance will be greater than the maximum permitted (0.5-5.0 nephalometric turbidity units; 40 CFR Parts 141 and 142). Therefore, the organoleptic properties of Al materials in water determine public acceptance of potable water as contrast to any potential health hazard at the concentrations ordinarily present in municipal drinking water.

Characterization and analyses of acid-extractable and leached trace elements in dental cements.

AIMS: Determination of the elemental constitution and investigation of the total and leachable arsenic, chromium and lead in Portland cement, pure tricalcium silicate, Biodentine, Bioaggregate and mineral trioxide aggregate (MTA) Angelus. METHODOLOGY: The chemical composition of Portland cement, MTA Angelus, tricalcium silicate cement, Biodentine and Bioaggregate was determined using X-ray fluorescence (XRF). Measurements of arsenic, lead and chromium were taken with inductively coupled plasma-mass spectrometry (ICP-MS), following acid digestion on the hydrated material and on leachates of cements soaked in Hank's balanced salt solution (HBSS). RESULTS: All the cements investigated had a similar oxide composition with the main oxide being calcium and silicon oxide. Both the Portland cement and MTA Angelus had an additional aluminium oxide. The dental cements included a radiopacifying material. All the materials tested had higher acid-extractable arsenic content than the level set by ISO 9917-1 (2007) and an acceptable level of lead. Regardless these high levels of trace elements present in the materials, the leaching in HBSS was minimal for all the dental material tested in contrast to the high levels displayed by Portland cement. CONCLUSIONS: Dental materials based on tricalcium silicate cement and MTA Angelus release minimal quantities of trace elements when in contact with simulated body fluids. The results of acid extraction could be affected by nonspecific matrix effects by the cement.

Morphological and chemical analysis of different precipitates on mineral trioxide aggregate immersed in different fluids.

The purpose of this study was to analyze the ultrastructures and chemical compositions of precipitates formed on mineral trioxide aggregate (MTA; White ProRoot MTA) immersed in distilled water (DW) or phosphate buffered saline (PBS), based on the attribution that MTA's bioactivity and sealing ability are influenced by its interaction with the external fluid environment. After 1 and 14 days of immersion, precipitates formed on MTA disks were analyzed using wavelength-dispersive X-ray spectroscopy electron probe microanalyzer with image observation function (SEM-EPMA; EPMA1601, Shimadzu, Kyoto, Japan), and Fourier transform-infrared (FT-IR) spectroscopy. On DW specimens, cubic-like crystals containing Ca, O, and C (17, 66, and 17 at% respectively) were produced. State analysis of calcium k(ß)spectrum also revealed calcium hydroxide. On PBS specimens, acicular-spherical and lath-like crystals with Ca/P molar ratios of 1.42 and 1.58 respectively were produced. In conclusion, the precipitates formed on DW specimens were identified as calcium carbonate and calcium hydroxide primarily, whereas the precipitates on PBS specimens were inferred to be amorphous calcium phosphate.

Exposure to chemical agents in aluminium potrooms.

OBJECTIVES: To assess the effects of modernization of aluminium production on reducing the chemical health hazards in the working environment in aluminium potrooms (smelter). Modernization included the introduction ofa technique of point feeding of alumina and aluminium fluoride into the pots, semi-automatic equipment and computerized control. METHODS: Periodical environmental measurements of chemical substances, dusts containing alumina and fluorides, and gases, i.e., carbon monoxide, carbon dioxide, sulphur dioxide, hydrogen fluoride, nitrogen dioxide, and difluorosulphide, were performed at the same workplaces before (1986-1988) and sixteen years later, after modernization (2004). The measured values were compared with the recommended occupational safety and health standards. RESULTS: The concentrations of total dust (alumina and fluorides) and gases, i.e., carbon monoxide, carbon dioxide, sulphur dioxide, hydrogen fluoride and phenol, were above the recommended standards in 76.6% (95/124) of the samples before modernization and in only 23.8% (57/240) of the samples tested after modernization. Before modernization in almost all jobs the workers were simultaneously exposed to higher concentrations of all chemical agents present in the working environment. After modernization high concentrations of hydrogen fluoride were the primary pollutant in this plant (GM = 4.5451 ppm), while the presence of other gases was significantly reduced. Dusts containing alumina and fluorides and hydrogen fluoride gas were still present in considerable concentrations in the working environments of jobs such as changing and covering of anodes. CONCLUSION: The modernization of the aluminium smelter plant reduced the concentrations of the most harmful substances in the working environment and reduced the number of jobs where workers were simultaneously exposed to a variety of health hazards.

Synthesis of nanocrystalline (Co, Ni)Al2O4 spinel powder by mechanical milling of quasicrystalline materials.

In the present study, attempts have been made to synthesize the nano-crystalline (Co, Ni)Al2O4 spinel powders by ball milling and subsequent annealing. An alloy of Al70Co15Ni15, exhibiting the formation of a complex intermetallic compound known as decagonal quasicrystal is selected as the starting material for mechanical milling. It is interesting to note that this alloy is close to the stoichiometry of aluminum and transition metal atoms required to form the aluminate spinel. The milling was carried out in an attritor mill at 400 rpm for 40 hours with ball to powder ratio of 20 : 1 in hexane medium. Subsequent to this annealing was performed in an air ambience for 10, 20, and 40 h at 600 degrees C in side the furnace in order to oxidize the decagonal phase and finally to form the spinel structure. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the formation of nano-sized decagonal phase after milling and then (Co, Ni)Al2O4 spinel type phase after annealing. The XRD studies reveal the lattice parameter to be 8.075 angstroms and the lattice strain as 0.6%. The XRD and TEM explorations of spinel phase indicate the average grain size to be approximately 40 nm.

Interactive effects of soil acidity and fluoride on soil solution aluminium chemistry and barley (Hordeum vulgare L.) root growth.

A greenhouse study was conducted to determine if concentrations of fluoride (F), which would be added to acid soils via P fertilisers, were detrimental to barley root growth. Increasing rates of F additions to soil significantly increased the soil solution concentrations of aluminium (Al) and F irrespective of the initial adjusted soil pH, which ranged from 4.25 to 5.48. High rates of F addition severely restricted root growth; the effect was more pronounced in the strongly acidic soil. Speciation calculations demonstrated that increasing rates of F additions substantially increased the concentrations of Al-F complexes in the soil. Stepwise regression analysis showed that it was the combination of the activities of AlF2(1+) and AlF(2+) complexes that primarily controlled barley root growth. The results suggested that continuous input of F to soils, and increased soil acidification, may become an F risk issue in the future.

Chemical forms of aluminum in xylem sap of tea plants (Camellia sinensis L.).

To identify the chemical forms of aluminum (Al) transported from roots to shoots of tea plants (C. sinensis L.), 27Al-nuclear magnetic resonance and 19F NMR spectroscopy were used to analyze xylem sap. The concentration of Al in collected xylem sap was 0.29 mM, twice as high as that of F. Catechins were not detected in xylem sap. The concentration of malic acid in xylem sap was higher than that of citric acid, whereas the concentration of oxalic acid was negligible. There were two signals in the 27Al NMR spectra of xylem sap, a larger signal at 11 ppm and a smaller one at -1.5 ppm. The former signal was consistent with the peak for an Al-citrate model solution, suggesting that an Al-citrate complex was present in xylem sap. Although the latter signal at -1.5 ppm was thought to indicate the presence of an Al-F complex (at 1.7 ppm) in xylem sap, there was only one signal at -122 ppm in the 19F NMR spectrum of xylem sap, indicating that the main F complex in xylem sap was F-. These results indicate that Al might be translocated as a complex with citrate, while Al-malate, Al-oxalate and Al-F complexes are not major Al complexes in xylem sap of tea plants.

Fatal aluminum phosphide poisoning.

A 39-year-old man committed suicide by ingestion of aluminum phosphide, a potent mole pesticide, which was available at the victim's workplace. The judicial authority ordered an autopsy, which ruled out any other cause of death. The victim was discovered 10 days after the ingestion of the pesticide. When aluminum phosphide comes into contact with humidity, it releases large quantities of hydrogen phosphine (PH3), a very toxic gas. Macroscopic examination during the autopsy revealed a very important asphyxia syndrome with major visceral congestion. Blood, urine, liver, kidney, adrenal, and heart samples were analyzed. Phosphine gas was absent in the blood and urine but present in the brain (94 mL/g), the liver (24 mL/g), and the kidneys (41 mL/g). High levels of phosphorus were found in the blood (76.3 mg/L) and liver (8.22 mg/g). Aluminum concentrations were very high in the blood (1.54 mg/L), brain (36 microg/g), and liver (75 microg/g) compared to the usual published values. Microscopic examination revealed congestion of all the organs studied and obvious asphyxia lesions in the pulmonary parenchyma. All these results confirmed a diagnosis of poisoning by aluminum phosphide. This report points out that this type of poisoning is rare and that hydrogen phosphine is very toxic. The phosphorus and aluminum concentrations observed and their distribution in the different viscera are discussed in relation to data in the literature.