Rapid trace element analysis of microgram soft materials with cryogenic milling and laser ablation spectroscopy.

Trace element analysis of soft materials, to determine the content of low concentration elements, is important in many industries such as food quality control and medical biopsy analysis. Many of these applications would benefit from faster analysis with smaller sample requirements. Further, some natural samples are soft and have high water content, which brings challenges to element analysis. Here, we develop a cryogenic pelletization pretreatment to address those challenges. The soft samples are cryogenically milled, freeze-dried, and pelletized before elemental analysis. Analysis is performed by laser ablation spectroscopy, the combination of laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS), to rapidly analyze light and heavy analytes. For this initial study, aluminum (Al) content in soft samples is determined by LIBS and lead (Pb) content by LA-ICP-MS. The standard addition method is performed to build calibration curves for element quantification. The measurements are compared with a Hong Kong government certified acid digestion and ICP-MS procedure. The experiment is performed on standard reference materials and selected food samples. The relative errors compared with certified measurements are less than 10% for all samples, with Al content ranging from 63-1466 µg/g and Pb content from 0.37-2.35 µg/g (dry mass). Microscopy of pellets shows that laser ablation spectroscopy can be performed with 100 µg of sample (dry mass). Total analysis time from raw sample to final measurement, including preparation, is under 1 h. The results indicate that the laser ablation spectroscopy with cryogenic pelletization is a promising technique for many applications such as screening of small food samples for toxic metals and trace element analysis of millimeter biopsies.

Chemical Speciation of Aluminum in Wine by LC-ICP-MS.

Aluminum is very common in the natural environment and in everyday human life. We are living in the "aluminum age." Its average daily intake should not exceed a few mg/day. Unfortunately, despite the growing number of alarming data about the toxicity of this element, human exposure to aluminum is constantly increasing. The toxicity and bioavailability of aluminum depends mainly on the form in which it occurs. The main variables conditioning the form are the concentration, the type, the molar ratio of aluminum to ligand, the pH value, and the temperature. This research presents a new method for speciation analysis of both inorganic and organic aluminum complexes in model solutions by LC-ICP-MS. Different solutions with variable pH values and different Al/ligand molar ratios (fluorides and several organic ligands, e.g., citrates and oxalates ions) were used. The chromatographic separation process was carried out based on isocratic and gradient elution, using a cation exchange analytical column. All determinations have been confirmed based on chemical equilibrium modeling programs. The new developed method was successfully applied for the first time in speciation analysis of real samples: white and red wine.

Phosphine detection in veterinary samples using headspace gas chromatography/tandem mass spectrometry with multiple reaction monitoring.

RATIONALE: Determination of phosphine exposure from zinc or aluminum phosphide fumigants continues to be a routine analytical requirement in veterinary forensic toxicology. There is a need for a more reliable and specific method than simple gas chromatography/mass spectrometry (GC/MS) analysis of sample solvent extracts, as GC/MS of extracts on capillary columns used for general screens involves significant interference from air peaks. METHODS: GC/MS/MS headspace analysis of acid-generated phosphine gas enabled study of the feasibility of devising multiple reaction monitoring (MRM) approaches to the determination of phosphine with greater specificity. RESULTS: Collision-induced dissociation in GC/MS/MS showed that phosphine generated m/z 34 → 31, 32 and 33 ion transitions by sequential proton release as well as minor transitions m/z 34 → 47, 34 → 63 and 63 → 31.5 by intermolecular collisions and double charging. Study of the formation of these product ions enabled development of MRM settings for a highly useful headspace method for phosphine detection. CONCLUSIONS: The method was validated over a working range of 5-100 ppm of phosphide generating phosphine gas which enabled retention of regular screen capillary columns without necessitating separation from air components. The method should have adequate sensitivity and reliability for veterinary toxicology laboratories confronting specimens from animals poisoned by crop fumigants.

Assessment of membrane bioreactor fouling with the addition of suspended aluminum nitride nanoparticles.

In this study, we assessed fouling in a membrane bioreactor (MBR) with the addition of suspended aluminum nitride (AlN) nanoparticles (NPs). Three parallel laboratory-scale submerged MBRs were operated with 0, 10, and 50 mg AlN NPs/L for over 70 days. The results showed that the addition of suspended AlN NPs did not significantly affect pollutant biodegradation; there was only a slight decrease in NH4+-N removal. Furthermore, the membrane's permeability was increased with effective fouling mitigation by the addition of a high amount of suspended AlN NPs. This was because the suspended AlN NPs decreased the content of polysaccharides in both the extracellular polymeric substances and soluble microbial products, and decreased the sludge floc size. However, the AlN NPs also promoted pore-blocking, particularly standard blocking, which enhanced irreversible fouling. Additionally, owing to the larger ionic radius and higher electronegativity, the AlN NPs inhibited the accumulation of framework components (SiO2). Therefore, suspended AlN NPs resulted in a thinner cake layer.

Total Recoverable Aluminum: Not Totally Relevant for Water Quality Standards.

A large water quality data set, representing more than 100 surface-water locations sampled from 2007 to 2017 in the Los Alamos area of New Mexico, USA's Pajarito Plateau, was assembled to evaluate Al concentrations in unfiltered and filtered samples. Aluminum concentrations often exceeded United States Environmental Protection Agency (USEPA) and New Mexico ambient water quality criteria (AWQC), regardless of filter size and sample location. However, AWQC are based on laboratory toxicity studies using soluble Al salts and do not reflect natural conditions in Pajarito Plateau surface waters. The plateau is predominately covered by glassy and recrystallized volcanic ashes (e.g., Bandelier Tuff) containing colloidal to sand-sized aluminosilicates. Samples from natural background drainages and areas downstream of developed regions exhibited similar Al concentrations, suggesting that AWQC exceedances are caused by naturally elevated Al concentrations. Solubility calculations indicated that most samples were oversaturated with respect to amorphous Al(OH)3 (s). Therefore, AWQC exceedances are likely artifacts of the "total recoverable" sample preparation, which includes acidification and partial digestion, thereby liberating nonbioavailable Al from aluminosilicates. Accordingly, Al concentrations were strongly associated with suspended sediment concentrations (SSCs), implying that aluminosilicates in suspended sediment contributed to AWQC exceedances and Al oversaturation. Solid-phase particle characterization, using X-ray diffraction (XRD) and scanning electron microscopy with electron dispersive spectroscopy (SEM/EDS) did not identify potentially bioavailable amorphous Al(OH)3 (s) in any sample tested. Thus, current sample collection and analysis protocols should not be used to evaluate attainment of Al AWQC on the Pajarito Plateau or locations where aluminosilicates are substantial contributors to total recoverable Al. A sample preparation method (e.g., pH 4 extraction) capable of differentiating nonbioavailable and bioavailable forms of Al is recommended. Otherwise, current New Mexico and USEPA sample preparation approaches will continue to generate artifactual AWQC exceedances in surface waters that contain aluminosilicates. Integr Environ Assess Manag 2019;00:1-14. © 2019 SETAC.

Distribution and phytotoxicity of soil labile aluminum fractions and aluminum species in soil water extracts and their effects on tall fescue.

Soil acidification can alter the biogeochemistry of ecosystems and adversely affect biota; however, there are still many debates about the toxicity of aluminum (Al) fractions and Al species in soil:water extracts to plants. In this study, five crude soils with different pH values (4.92-8.51) were collected, seeded with tall fescue and grown in rhizosphere boxes for 120 days. Then, soil properties, labile Al fractions and Al species in soil:water extracts were determined, and their toxicities to plants were analyzed. Our study showed that a stable exchangeable Al fraction (ExAl) pool exists and is supplied by other labile Al fractions. Dissolution of Al from adsorbed hydroxyl-Al fraction (HyAl) and organic-Al fraction (OrAl) may play important roles in soil Al toxicity, as HyAl and OrAl account for major parts of soil labile Al. Additionally, Al3+ and mononuclear hydroxyl-Al species in soil:water extracts have few effects to plants. Nevertheless, high negative correlations were found between Al-F- complexes and tall fescue biomass, indicating their toxicity in the natural soil environment. Thus, in many cases, Al3+ toxicity should not be emphasized because of its lower activity in soil water extracts. Moreover, toxicities of AlF3(aq) and AlF4- to plants should be emphasized, because they have been confirmed in soil water extracts in this study.

A paper platform for colorimetric determination of aluminum hydrochloride in antiperspirant samples.

A simple, fast, low-cost, portable, and eco-friendly method using a spot test on a paper platform, together with diffuse reflectance spectroscopy, was developed and validated for the quantification of aluminum hydrochloride, a potential neurotoxic agent, in antiperspirant samples. The determination of aluminum hydrochloride was performed at a wavelength of 615 nm, by measuring consumption of the purple colorimetric reagent Alizarin S, due to reaction with aluminum. The linear range was from 10.0 to 125.0 mg L-1 and could be described by the equation: AR = 0.4479 - 0.002543 CAl (R = 0.999). The limits of detection (LOD) and quantification (LOQ) were 3.06 and 10.2 mg L-1, respectively. The method was specific, accurate, and repeatable, with relative standard deviation (RSD) <5.0%. The recovery was between 92.2 and 103.4%. The method was successfully used for the determination of aluminum hydrochloride in commercial antiperspirant samples, revealing concentrations below the maximum permitted by current legislation.

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.

Characterization of drilling waste from shale gas exploration in Central and Eastern Poland.

The purpose of this research was to determine and evaluate the chemical properties of drilling waste from five well sites in Central and Eastern Poland. It was found that spent drilling fluids can contain high values of nickel and mercury (270 and 8.77 mg kg-1, respectively) and can exceed the maximum permissible limits recommended by the EC regulations for safety of soils (75 mg kg-1 for nickel and 1.5 mg kg-1 for mercury). The heavy metal concentrations in the studied drill cuttings did not exceed the maximum permissible limits recommended by the EC regulation. Drilling wastes contain macroelements (e.g., calcium, magnesium, and potassium) as well as trace elements (e.g., copper, iron, zinc, and manganese) that are essential for the plant growth. It was stated that water extracts of drilling fluids and drill cuttings, according to anions presence, had not any specific constituents of concern based on FAO irrigation guidelines, the USEPA WQC, and toxicity values. X-ray diffraction analysis was used to understand the structure and texture of waste drilling fluid solids and drill cuttings. Analysis of the mineralogical character of drilling fluid solids revealed that they contained calcite, quartz, muscovite, sylvite, barite, dolomite, and orthoclase. Drill cuttings contained calcite quartz, muscovite, barite, dolomite, and barium chloride.

Utilization of calcium-based and aluminum-based materials for the treatment of stabilized landfill leachate: a comparative study.

This study explored the efficiencies and mechanisms of refractory organic matters removal in the stabilized landfill leachate by adding different reagents. Calcium-based and aluminum-based materials were added into the leachate as comparing experiments. XRD, FTIR, and EEM were adopted to analyze the solid products and leachate. As a result, the in situ synthesized CaAl-LDHs were more beneficial for refractory organic matters removal, especially for benzodiazepines. When CaAl-LDHs were formed, the removal efficiencies of COD, UV254, and TOC were best and achieved 58.48, 81.22, and 71.30%, respectively. For fluorescent substances, humic acid-like and fulvic acid-like compounds were efficiently removed by CaAl-LDHs. In particular, CaAl-LDHs had selective removal effects on fulvic acid-like compounds, which were characteristic of small molecular weight and major carboxyl groups.

Diagnosis of aluminum phosphide poisoning using a new analytical approach: forensic application to a lethal intoxication.

Aluminum phosphide (AlP) is an effective and cheap pesticide that is commonly used worldwide, but it is also a common cause of human poisoning and carries a high mortality rate. AlP reacts with moisture in air, water, and hydrochloric acid in the stomach to produce phosphine (PH3) gas. Two routes of exposure are ingestion of AlP and inhalation of phosphine generated by the action of moisture on AlP. Absorbed phosphine is rapidly metabolized into phosphite and hypophosphite. A method is described for the analysis of the phosphine metabolites in various biological matrices. The method involves reacting the sample with zinc and aqueous H2SO4 in a volatile organic analysis vial. The metabolites were transformed into phosphine gas and then analyzed by headspace gas chromatography coupled with mass spectrometry (HS-GC-MS). This method is capable of detecting quantities of PH3 as low as 0.2 µg/mL in a sample. After validation, the method was applied to animal experiments and a real case of human AlP intoxication. This approach has the advantage of detecting metabolites of PH3, in case the PH3 was converted, and can be considered a useful additional tool for the diagnosis of AlP poisoning in forensic science.

Impact of aluminum chloride on process performance and microbial community structure of granular sludge in an upflow anaerobic sludge blanket reactor for natural rubber processing wastewater treatment.

In this study, granular sludge formation was carried out using an aluminum chloride supplement in an upflow anaerobic sludge blanket (UASB) reactor treating natural rubber processing wastewater. Results show that during the first 75 days after the start-up of the UASB reactor with an organic loading rate (OLR) of 2.65 kg-COD·m(-3)·day(-1), it performed stably with a removal of 90% of the total chemical oxygen demand (COD) and sludge still remained in small dispersed flocs. However, after aluminum chloride was added at a concentration of 300 mg·L(-1) and the OLR range was increased up to 5.32 kg-COD·m(-3)·day(-1), the total COD removal efficiency rose to 96.5 ± 2.6%, with a methane recovery rate of 84.9 ± 13.4%, and the flocs began to form granules. Massively parallel 16S rRNA gene sequencing of the sludge retained in the UASB reactor showed that total sequence reads of Methanosaeta sp. and Methanosarcina sp., reported to be the key organisms for granulation, increased after 311 days of operation. This indicates that the microbial community structure of the retained sludge in the UASB reactor at the end of the experiment gave a good account of itself in not only COD removal, but also granule formation.

Effects of Aluminum Exposure on the Bone Stimulatory Growth Factors in Rats.

Aluminum (Al) is considered to be a potentially toxic metal and inhibits bone formation. Transforming growth factor ß1 (TGF-ß1) and bone morphogenetic protein 2 (BMP-2) play an important role in regulating the bone formation. Therefore, this study aimed to investigate the effects of Al on the TGF-ß1 and BMP-2 in rats. In this study, Wistar rats were randomly divided into Al-treated group and control group. The Al-treated rats were provided with drinking water containing 100 mg/L AlCl3, and the control rats were given distilled water for 30, 60, and 90 days, respectively. Ten rats were sacrificed in each group every 30 days. The Al-treated rats showed lower body weight and higher serum and bone levels of Al compared with the control rats. The expression levels of TGF-ß1 and BMP-2 were also significantly decreased in the Al-treated rats. Serum levels of bone gamma-carboxyglutamic acid protein (BGP), carboxy-terminal propeptide of type I procollagen (PICP), and bone alkaline phosphatase (B-ALP) were markedly lower in the Al-treated groups than in the control group. These results indicate that Al inhibits the expression of TGF-ß1 and BMP-2 in bone, which inhibits the activity of osteoblasts and reduces the synthesis of BGP, B-ALP, and type I collagen, thereby inhibiting bone formation.

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).

A case of accidental fatal aluminum phosphide poisoning involving humans and dogs.

Aluminum phosphide is one of the commonest poisons encountered in agricultural areas, and manner of death in the victims is often suicidal and rarely homicidal or accidental. This paper presents an unusual case, where two humans (owner and housemaid) and eight dogs were found dead in the morning hours inside a room of a house, used as shelter for stray dogs. There was allegation by the son of the owner that his father had been killed. Crime scene visit by forensic pathologists helped to collect vital evidence. Autopsies of both the human victims and the dogs were conducted. Toxicological analysis of viscera, vomitus, leftover food, and chemical container at the crime scene tested positive for aluminum phosphide. The cause of death in both humans and dogs was aluminum phosphide poisoning. Investigation by police and the forensic approach to the case helped in ascertaining the manner of death, which was accidental.

Reduced aluminum contamination decreases parenteral nutrition associated liver injury.

PURPOSE: Parenteral nutrition-associated cholestasis remains a significant problem, especially for the surgical neonates. Aluminum is a toxic element known to contaminate parenteral nutrition. We hypothesize that parenterally administered aluminum causes liver injury similar to that seen in parenteral nutrition-associated cholestasis. METHODS: Twenty 3- to 6-day-old domestic pigs were divided into 5 equal groups. A control group received daily intravenous 0.9% NaCl. Each subject in experimental groups received intravenous aluminum chloride at 1500 µg kg(-1) d(-1) for 1, 2, 3, or 4 weeks. At the end of the study, blood was sampled for direct bilirubin and total bile acid levels. Liver, bile, and urine were sampled for aluminum content. Liver tissue was imaged by transmission electron microscopy for ultrastructural changes. RESULTS: Transmission electron microscopy revealed marked blunting of bile canaliculi microvilli in all experimental subjects but not the controls. Serum total bile acids correlated with the duration of aluminum exposure. The hepatic aluminum concentration correlated with the duration of aluminum exposure. CONCLUSIONS: Parenterally infused aluminum resulted in liver injury as demonstrated by elevated bile acids and by blunting of the bile canaliculi microvilli. These findings are similar to those reported in early parenteral nutrition-associated liver disease.

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.

An analytical procedure for the determination of aluminum used in antiperspirants on human skin in Franz™ diffusion cell.

A local case report of hyperaluminemia (aluminum concentration: 3.88 µmol/L) in a woman using an aluminum-containing antiperspirant for 4 years raises the question of possible transdermal uptake of aluminum salt as a future public health problem. Prior to studying the transdermal uptake of three commercialized cosmetic formulas, an analytical assay of aluminum (Al) in chlorohydrate form (ACH) by Zeeman Electrothermal Atomic Absorption Spectrophotometer (ZEAAS) in a clean room was optimized and validated. This analysis was performed with different media on human skin using a Franz(™) diffusion cell. The detection and quantification limits were set at ≤ 3 µg/L. Precision analysis as within-run (n = 12) and between-run (n = 15-68 days) yield CV ≤ 6%. The high analytic sensitivity (2-3 µg/L) and low variability should allow an in vitro study of the transdermal uptake of ACH.

Heavy metal analysis of ortho MTA and ProRoot MTA.

INTRODUCTION: Recently, several kinds of mineral trioxide aggregate (MTA)-based products have been introduced in endodontics. Ortho MTA (BioMTA, Seoul, Republic of Korea) is one of those products, which was developed for retrograde filling, perforation repair, orthograde root canal obturation, and direct pulp capping. The inclusion of heavy metals in MTA-based materials is of concern because they come into direct contact with hard and soft tissues. The aim of this study was to investigate and compare the levels of arsenic (As), chromium (Cr), hexavalent chromium (Cr(6+)), and lead (Pb) in Ortho MTA and ProRoot MTA. METHODS: One gram of each MTA was digested using a mixture of hydrochloric and nitric acids and filtered. The As, Cr, and Pb in the resulting filtrates were analyzed by inductively coupled plasma-optical emission spectrometry. The level of Cr(6+) was measured by the methods suggested in the Korean Standard L 5221. The results were statistically analyzed using the Mann-Whitney U test. RESULTS: The concentration of As in ProRoot MTA was 1.16 ppm, but As was not detected in Ortho MTA. Cr(6+) and Pb were not detected in either MTA. Ortho MTA contained significantly less Cr than ProRoot MTA (P < .05). CONCLUSIONS: Ortho MTA and ProRoot MTA meet the ISO specification 9917-1 regarding the safety limits of As and Pb and are safe biomaterials when the purity of As, Cr(6+), and Pb is considered.

Analysis of aluminium content and iron homeostasis in nipple aspirate fluids from healthy women and breast cancer-affected patients.

Aluminium is not a physiological component of the breast but has been measured recently in human breast tissues and breast cyst fluids at levels above those found in blood serum or milk. Since the presence of aluminium can lead to iron dyshomeostasis, levels of aluminium and iron-binding proteins (ferritin, transferrin) were measured in nipple aspirate fluid (NAF), a fluid present in the breast duct tree and mirroring the breast microenvironment. NAFs were collected noninvasively from healthy women (NoCancer; n = 16) and breast cancer-affected women (Cancer; n = 19), and compared with levels in serum (n = 15) and milk (n = 45) from healthy subjects. The mean level of aluminium, measured by ICP-mass spectrometry, was significantly higher in Cancer NAF (268.4 ± 28.1 µg l(-1) ; n = 19) than in NoCancer NAF (131.3 ± 9.6 µg l(-1) ; n = 16; P < 0.0001). The mean level of ferritin, measured through immunoassay, was also found to be higher in Cancer NAF (280.0 ± 32.3 µg l(-1) ) than in NoCancer NAF (55.5 ± 7.2 µg l(-1) ), and furthermore, a positive correlation was found between levels of aluminium and ferritin in the Cancer NAF (correlation coefficient R = 0.94, P < 0.001). These results may suggest a role for raised levels of aluminium and modulation of proteins that regulate iron homeostasis as biomarkers for identification of women at higher risk of developing breast cancer. The reasons for the high levels of aluminium in NAF remain unknown but possibilities include either exposure to aluminium-based antiperspirant salts in the adjacent underarm area and/or preferential accumulation of aluminium by breast tissues.