Al Hydroxide Research Articles

Spectroscopic investigation on the chemical forms of Cu during the synthesis of zeolite X at low temperature

The direct synthesis of zeolites in polluted soils has proved to be a promising process for the stabilization of metals inside these minerals. Nevertheless, more detailed information about this process is still needed in order to better foresee the fate of metals in treated soils. In this work, zeolite X has been synthesized under alkaline conditions in an aqueous solution containing 2500 mg kg −1 of Cu, starting from Na silicate and Al hydroxide at 60 °C. Aluminium, Si and Cu concentrations in the aqueous phase, during zeolite synthesis, were measured over a period of 160 h. The solid products have been characterized over time by XRD, SEM-EDX, ESR, FT-IR, and synchrotron radiation X-ray microbeam absorption near edge structure (μ-XANES) and extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. It appears that the marked reduction of Cu concentration in solution is not only due to a simple precipitation effect, but also to processes connected with the formation of zeolite X which could entrap, inside its porous structure, nano- or micro-occlusions of precipitated Cu hydroxides and/or oxides. In addition, EXAFS observations strengthen the hypothesis of the presence of different Cu phases even at a short-range molecular level and suggest that some of these occlusions could be even bound to the zeolite framework. The results suggest that zeolite formation could be used to reduce the availability of metals in polluted soils.

Clay mineralogy and its relationship to soil solution composition in soils from different weathering environments of humid Asia: Japan, Thailand and Indonesia

We studied the relationship between the clay mineralogy of subsurface soils from 204 sites and their water extracts in upland soils of humid Asia (Japan, Thailand and Indonesia) to understand their formation. The clay minerals were identified by XRD and the kaolin minerals and gibbsite were quantified with DTA. Their thermodynamic stability was related to the ion activity of soil water extracts. In soils on mica-free andesitic or mafic parent material, kaolin minerals and smectite dominated in all regions. Among mica-containing soils derived from felsic or sedimentary rocks, mineralogical and soil solution compositions indicate that, in Thailand, mica was stable at high pH (5.4–6.5), whereas in soils from Japan and Indonesia mica turned into hydroxy-Al interlayered vermiculite (HIV) or vermiculite at lower pH (4.3–5.5). In Japanese soils, HIV and gibbsite form under high activity of Al–OH species. In contrast, the low activity of Al–OH species in Indonesian soils resulted in the dissolution of Al hydroxides between 2:1 layers and gibbsite and the dominance of kaolin minerals and vermiculite. We conclude that three factors play an important role for the clay mineralogy in humid Asia: the nature of parent material (i.e. presence or absence of mica), soil pH (as affected by precipitation and evapotranspiration) and activity of Al–OH species in soil solution (reflecting soil age).

Properties of surface-modified colloidal particles

AbstractThe reactivity of colloidal particles is regulated by their surface properties. These properties affect the wettability, flocculation-dispersion characteristics, ion exchange, sorption capacities and transport of inorganic colloids. Most studies have focused on hydrophilic, charged-particle surfaces, often ignoring the alterations in surface properties produced by the adsorption of natural organic matter, surfactants and other compounds. Adsorption of these substances can potentially render a surface substantially more hydrophobic. Nevertheless, comparatively little is known about changes in surface properties and reactivity of minerals upon sorption of hydrophobic organic compounds. In this study, the properties of four minerals (kaolinite, pyrophyllite, montmorillonite and Min-U-Sil®) and two inorganic materials (X-ray amorphous Al hydroxide and X-ray amorphous Si oxide) were compared before and after treatment with the common silylating agent, trimethylchlorosilane (TMCS). The samples were characterized by measurements of total carbon, cation exchange capacity (CEC), particle size, specific surface area (SSA), electrophoretic mobility, contact angle, particle aggregation, and by X-ray diffraction and diffuse reflectance infrared spectroscopy. For the layer silicates, surface coverage was limited to ∼2% trimethyl silane (TMSi). TMSi covered 7.5% of the Min-U-Sil® surface and 33% of the X-ray amorphous Si oxide. Treatment did not affect the structure of the minerals but reduced the CEC, SSA and electrophoretic mobilities. Water contact angles increased to between 18 and 114° with treatment. While the apolar characteristic of the surfaces decreased minimally with treatment, the Lewis acid/base properties were substantially reduced and interfacial free energy shifted from positive to negative values indicating a more hydrophobic surface character. For all the samples except kaolinite, these changes affected the stability of the colloids in suspension depending upon solution pH. Although the grafting of TMSi altered colloidal mineral surface properties and increased their hydrophobicity, these changes were not sufficient to predict colloid aggregation behavior.

Selenite Adsorption Mechanisms on Pure and Coated Montmorillonite: An EXAFS and XANES Spectroscopic Study

Selenite (SeO32−) is an oxyanion of environmental importance due to its toxicity to animals at higher concentrations, notably waterfowl and grazing animals. Sorption of SeO32− with mineral phases typically controls the movement and bioaccessibility of SeO32− in soils and sediments. Previous studies have successfully utilized synchrotron‐based Extended X‐ray Absorption Fine Structure (EXAFS) and X‐ray Absorption Near Edge Structure (XANES) spectroscopy to determine SeO32− bonding mechanisms on Fe and Mn oxides, but the direct evidence of SeO32− surface complexation mechanisms on important mineral phases such as Al hydroxide and aluminosilicate minerals is still lacking. In this study both EXAFS and XANES spectroscopy was conducted on aqueous SeO32− solutions and on a variety of Al‐bearing sorption samples at pH 4.5. The sorbents chosen were a hydroxyaluminosilicate (HAS) polymer, a hydroxyaluminum (HYA) polymer, montmorillonite, and both HYA and HAS coated montmorillonite. For SeO32− sorption on montmorillonite, only bidentate binuclear inner‐sphere complexation was observed. For the hydroxyaluminum and hydroxyaluminosilicate polymers, a mixture of outer‐sphere and bidentate binuclear inner‐sphere was observed. When montmorillonite was coated with either HYA or HAS polymers then adsorption behavior was intermediate between that of the mineral and the pure polymer. Since temperate soils often contain aluminum‐hydroxy and aluminosilicate coated minerals rather than discrete Al hydroxide minerals and pristine clay surfaces, the adsorption mechanisms observed on these coated surfaces are more realistic of the natural environment than sorption on pure minerals.

Relative Efficacy of a Drinking‐Water Treatment Residual and Alum in Reducing Phosphorus Release from Poultry Litter

Amending poultry litter with alum (aluminum sulfate) effectively reduces soluble phosphorus (P) concentrations, but the practice can be expensive. Aluminum (Al)‐based drinking‐water treatment residuals (WTRs) can be obtained free of charge and are enriched in Al hydr(oxides) that make them efficient P sorbents. Substituting Al‐WTRs for alum would be a cost‐effective practice to reduce soluble P in manures when compared with alum‐only use. The research studied the reductions in soluble P, Al, and total organic carbon (TOC) concentrations in suspensions prepared by mixing variable Al‐WTR and alum rates (0 to 25% by weight) with poultry litter. Suspensions were maintained at pH of 6.5 during the sorption step, and allowed to react up to 50 d, without shaking. On a per‐mole of oxalate‐extractable Al basis, the Al‐WTR was nearly as effective as alum in reducing P release. Increasing mixed alum/WTR mass loads resulted in greater soluble P reduction, simply due to increased molar Al/P ratios. Contact time did not significantly influence soluble P reduction. Two significant advantages of Al‐WTRs compared to alum indicated by this study are cost effectiveness and significantly less release of dissolved Al. Soluble Al and TOC concentrations were least for suspensions with the lowest soluble P levels, suggesting that P was removed from solution as an organo‐Al‐P amorphous phase. The amount of P desorbed from the mixtures decreased to <1% with increasing molar Al/P ratios ≥1. Results suggest that Al‐WTR application with or without alum can reduce soluble P in poultry litter; however, field validation of the amendment effectiveness is needed. This research was supported by the Florida Agricultural Experiment Station and a grant from a USEPA grant CP‐82963801, and approved for publication as Journal Series No. R‐10112.

A simple model to predict the removal of oil suspensions from water using the electrocoagulation technique

A simple model has been developed to predict the removal of hydrocarbon fractions from wastewater using sacrificial Al anodes. The model was successfully applied to the interpretation of experimental data obtained in a laboratory electrochemical cell operated in a batchwise manner. The adsorption equilibrium of organic matter on Al hydroxide was modelled using three equations, with the best results obtained using a Langmuir-type equation. The model was able to describe the effects of current density and pollutant concentration on the efficiency of wastewater treatment. Different values were obtained for the parameters depending on the nature of the hydrocarbon suspension. Aluminium hydroxide showed a far higher affinity for the oil/kerosene suspension but exhibited a higher capacity to remove heavy oil suspensions. The removal rates of pollutants were found to depend on the initial concentration and the current density. When the current density was sufficient to destabilise the emulsion, the zeta potential of the clear fraction measured at pH 7.0 became positive. This change was also characterised by a significant reduction in turbidity. Furthermore, the application of higher current densities did not allow further treatment of the water. However, the efficiency of emulsion destabilisation was found to depend on the concentration and current densities that were too low were ineffective.

Proton Buffering and Metal Leaching in Sandy Soils

Recent developments in acidification research focused on the leaching of metals from contaminated soil. In this paper the buffering of sandy soils upon acidification is studied in relation to the release of major (Al, Ca, Mg) and trace metals (Cu, Cd, Ni, Zn) from the soil reactive surface. The buffering process and the (de)sorption of metals are described with a mechanistic multisurface model, expressing the sorption onto different soil surfaces (organic matter, clay, Fe (hydr)oxides). The pH of sandy soil samples is predicted upon proton addition in combination with the behavior of major and trace metals. Acidification of contaminated sandy soil samples, with different pH levels and metal contents, is performed in a flow-through reactor by flushing the samples with acid solution. Acidification has taken place in successive steps of proton addition and followed by sampling. Prediction of pH upon acidification with a multisurface model gives satisfying results for all samples studied. The pH is modeled reasonably well between pH 6 and 4. Below pH 4 the predicted pH values are slightly too low, probably due to the buffering by Al-containing minerals (e.g., Al hydroxide), which are not included in the model. Desorption of major and trace metals upon pH decrease is, in general, predicted well, within a factor of 1-5 on a linear scale. Overall prediction of proton buffering in combination with desorption of metals in sandy soil samples, over a wide pH range and metal content, is done quite well for the studied metals with the multisurface model.

Arsenic Speciation in As(III)- and As(V)-Treated Soil Using XANES Spectroscopy

Arsenic (As) is a toxic trace element that occurs naturally in groundwater and soils. Understanding the reactions of arsenite (As(III)) and arsenate (As(V)) with soil and mineral surfaces is critical for predicting the fate and transport of As in the environment and developing better ways to remediate As-contaminated areas. This investigation uses X-ray absorption near edge spectroscopy (XANES) to evaluate the solid phase oxidation state and mineral surface binding sites in three agricultural soil samples from California, USA by fitting linear combinations of XANES spectra derived from several synthetic and well characterized As(III)- and As(V)-treated model compounds (Fe and Al metal hydroxides and aluminosilicate illite clay mineral). The results suggest that As(III) is either partially or completely oxidized to As(V) when reacted with soil in an aqueous, batch reaction. The As(III)-treated Aiken soil was composed of 60% As(III) attached to surfaces similar to lepidocrocite (γ-FeOOH)) and 40% As(V) attached to aluminosilicate (illite). The Fallbrook soil completely oxidized As(III) and the product was As(V) adsorbed on Al hydroxide (gibbsite, γ-Al(OH)3) (62%), illite (16%), and lepidocrocite (γ-FeOOH) (22%). The reaction of As(III) with Wyo soil resulted in 42% As(III) adsorbed on surface similar to goethite and 58% As(V) adsorbed on lepidocrocite. Arsenic(V) adsorption on soil resulted in stable As(V) surface complexes that were well described by XANES spectra from As(V) adsorption complexes on gibbsite, illite, and lepidocrocite.

Distribution and mobility of arsenic in the Río Dulce alluvial aquifers in Santiago del Estero Province, Argentina

Factors controlling arsenic (As) mobilization in the aquifers of the Río Dulce alluvial cone were investigated. Groundwater analyses show severe As contamination (average concentration of 743 μg/L) from geogenic sources, but spatial variability of As concentration is considerable. Sequential leaching of sediment samples from unsaturated zone using de-ionised water, bicarbonate, acetate, and oxalate extracted As to different extents. Sediment oxalate extraction showed that Al and Mn oxide and hydroxides are more abundant than Fe oxides and hydroxides, in spite of similar total Fe, Mn, and Al concentrations in the sediment. Speciation calculations performed for saturated zone samples indicated that Fe and Al oxides and hydroxides are stable in groundwater, suggesting that As adsorption processes may be to some extent controlled by the presence of Fe and Al mineral phases. Principal Component Analysis (PCA) showed that As is related to F, V, Mo, B, Si, most likely due to their common origin in volcanic ash. This suggests the volcanic ash as the probable source of groundwater As. Locally, elevated pH values linked to carbonate dissolution, cation exchange, and dissolution of silicates promote release of adsorbed As. Another factor contributing to the release of As locally may be the input of organic matter from excessive irrigation. The conceptual model of As release includes: i) As influx from dissolution of volcanic glass in volcanic ash, ii) adsorption of As on the surface of Fe and Al mineral phases in relatively low pH zones, and iii) high mobility of As in high pH zones. Future work should be focused on the determination of mineralogical forms of As in volcanic ash and on detailed investigation on factors controlling As mobility.

The Chemical Species of Aluminum Influences Its Paracellular Flux across and Uptake into Caco-2 Cells, a Model of Gastrointestinal Absorption

Aluminum (Al) can cause neurotoxicity, a low-turnover osteomalacia, and microcytic anemia. To test the null hypothesis that the chemical form (species) of Al does not influence its mechanism or rate of absorption from the gastrointestinal tract, Al flux across and uptake into Caco-2 cells was investigated. Caco-2 cells were grown on porous membranes mounted in vertical diffusion chambers or in 35-mm-diameter plastic cell culture dishes. When 8 mM 27Al was introduced as the ion, citrate, maltolate, fluoride, or hydroxide, the apical to basolateral apparent permeability (Papp) of Al correlated highly with the Papp of lucifer yellow (LY), a paracellular marker, except when introduced as Al hydroxide. The uptake rate of Al when introduced as the fluoride was > when introduced as the ion > maltolate > citrate > hydroxide. The activation energy of Al introduced as the ion, citrate, maltolate, and fluoride, determined from Arrhenius plots, was 13-22 KJ/mol, suggesting diffusion-mediated uptake. With exposure to 2 microM Al (containing 26Al as a tracer) introduced as the ion, hydroxide, citrate, and fluoride, Al and LY Papp were consistent with results obtained with 8 mM Al, but were not Al species dependent. Approximately 0.015% of the 26Al fluxed across the cell monolayer; 0.75% was associated with cells. Lumogallion staining imaged by confocal laser microscopy showed Al co-localized with DAPI in the nucleus. The results suggest that (1) soluble Al species predominantly diffuse through the paracellular pathway, (2) the ligand-dependent flux rate of Al is due to an effect on the tight junctions, (3) Caco-2 cell uptake of Al is a diffusion process, and (4) the ligand can influence the rate of cellular Al uptake.

Bonding of urethane reactants to aluminum surface

Reaction mechanism of urethane components (phenyl isocyanate and isopropanol) on Al hydroxide surface was studied using molecular modeling, and compared with real systems by measurement of electrochemical potential and optical observation. Charge of the phenyl isocyanate was concentrated on N and O atoms, implying that the reaction of the phenyl isocyanate on substances takes place through these atoms. Due to low energy difference between the lowest unoccupied molecular orbital (LUMO) of the phenyl isocyanate and the highest occupied molecular orbital (HOMO) of Al hydroxide, it was found that the mixture of phenyl isocyanate and alcohol segregates to the Al surface. Heat of formation for the reaction steps of the phenyl isocyanate on the Al hydroxide cluster is negatively larger than that of the isopropanol-Al interaction. Variation of electrochemical potential of Al surface in the urethane reactants was measured. As a result, it was found that the phenyl isocyanate rapidly reacted with the Al surface, and the reaction products were observed after drying. An optical micrograph of the Al sample held in the isopropanol was very similar to that for a bare Al surface. Evolution of bubbles on the Al surface was expected to be H2O formed by the formation of hydrogen bonding between the urethane and the hydroxyl groups bound on the Al surface.

Regulating the mobility of Cd, Cu and Pb in an acid soil with amendments of phosphogypsum, sugar foam, and phosphoric rock

SummaryWhen acid soil has been contaminated by metals as a result of industrial discharges, accidental spills, or acid mine drainage it may be desirable to retain the metals in the soil rather than allow them to leach away. We have investigated the potential of phosphogypsum (PG), sugar foam (SF), and phosphoric rock (PR) to regulate the availability and mobility of Pb, Cd and Cu. We have also identified changes in attenuation during incubation for 1 year and the effect of aging on metal speciation in amended soils. We studied miscible displacement in columns of undisturbed soil previously treated with solutions of the amendments and soluble metals and, subsequently, single and sequential chemical metal extractions. All amendments increased the soil's metal retention capacity. This, in turn, increased the amount of metal extractable by diethylenetriaminepentaacetic acid (DTPA). However, over time the amounts of DTPA‐extractable metal decreased, particularly for Cu and Pb. Both Cu and Cd were held preferentially within the acetic acid‐extractable fraction (operationally defined exchangeable fraction – EX fraction), whereas Pb was associated mainly with the hydroxylammonium‐extractable fraction (operationally defined bound to Fe and Al hydroxides – OX fraction). Both Pb and Cu in the oxide and organic fractions increased in the PG‐ and SF‐treated soils. In general, the distribution of metal did not change in the PR‐treated columns after the incubation. Finally, scanning electron microscopy in back‐scattered electron mode (SEM–BSE) showed the formation of Al‐hydroxy polymers which provides the soils with additional cation sorption capacity. In the PG‐ and PR‐treated columns, P and S were associated with these formations. The three metals were associated with the Al polymers, probably through direct coordination or the formation of ternary complexes with the inorganic ligands phosphate and sulphate.

Long-term phosphorus effects on evolving physicochemical properties of iron and aluminum hydroxides

Iron (Fe) and aluminum (Al) hydroxides are highly reactive components in environmental processes, such as contaminant fate and transport. Phosphorus (P) sorption by these components can decrease environmental problems associated with excess accumulation of P in soils. The long-term stability of P sorbed by Fe/Al hydroxides is of major concern. Synthetic Fe and Al hydroxides coprecipitated with P (1:1 metal:P molar ratio) were incubated at 70 °C for 24 months to simulate natural long-term weathering processes that could influence the stability of sorbed P. Heat incubation (70 °C) of the untreated (no P) Al hydroxides resulted in drastic decreases (within the first month of incubation) in oxalate–Al extractability, specific surface area (SSA), and micropore volume with time. These changes were consistent with the formation of pseudoboehmite. Untreated Fe hydroxides showed no formation of crystalline components following heating (70 °C) for 24 months. Much smaller changes in oxalate-Al, P extractability, and SSA values were observed in the P-treated Al particles when compared with the untreated. Phosphorus treatment of both Fe and Al hydroxides stabilized the particle surfaces and prevented structural arrangements toward a long-range ordered phase. Slight reduction in SSA of the P-treated particles was related to dehydration phenomena during heating at 70 °C. Monitoring of physicochemical properties of the solids after heating at 70 °C for 2 years showed that sorbed P may be stable in the long-term. Understanding long term physicochemical properties may help engineers to optimize the Fe/Al hydroxides performance in several environmental/industrial applications.

Hydrochemistry, mineralogy and sulfur isotope geochemistry of acid mine drainage at the Mt. Morgan mine environment, Queensland, Australia

Mineralogical, hydrochemical and S isotope data were used to constrain hydrogeochemical processes that produce acid mine drainage from sulfidic waste at the historic Mount Morgan Au–Cu mine, and the factors controlling the concentration of SO 4 and environmentally hazardous metals in the nearby Dee River in Queensland, Australia. Some highly contaminated acid waters, with metal contents up to hundreds of orders of magnitude greater than the Australia–New Zealand environmental standards, by-pass the water management system at the site and drain into the adjacent Dee River. Mine drainage precipitates at Mt. Morgan were classified into 4 major groups and were identified as hydrous sulfates and hydroxides of Fe and Al with various contents of other metals. These minerals contain adsorbed or mineralogically bound metals that are released into the water system after rainfall events. Sulfate in open pit water and collection sumps generally has a narrow range of S isotope compositions ( δ 34S = 1.8–3.7‰) that is comparable to the orebody sulfides and makes S isotopes useful for tracing SO 4 back to its source. The higher δ 34S values for No. 2 Mill Diesel sump may be attributed to a difference in the source. Dissolved SO 4 in the river above the mine influence and 20 km downstream show distinctive heavier isotope compositions ( δ 34S = 5.4–6.8‰). The Dee River downstream of the mine is enriched in 34S ( δ 34S = 2.8–5.4‰) compared with mine drainage possibly as a result of bacterial SO 4 reduction in the weir pools, and in the water bodies within the river channel. The SO 4 and metals attenuate downstream by a combination of dilution with the receiving waters, SO 4 reduction, and the precipitation of Fe and Al sulfates and hydroxides. It is suggested here that in subtropical Queensland, with distinct wet and dry seasons, temporary reducing environments in the river play an important role in S isotope systematics.

Review

We compare the performance of three most accepted reagents for organic matter removal: hydrogen peroxide (H2O2), sodium hypochlorite (NaOCl) and disodium peroxodisulfate (Na2S2O8). Removal of organic matter from soil is mostly incomplete with the efficiency of removal depending on reaction conditions and sample properties. Generally, NaOCl and Na2S2O8 are more effective in organic C removal than H2O2 Alkaline conditions and additives favoring dispersion and/or desorption of organic matter, such as sodium pyrophosphate, seem to be crucial for C removal. Pyrophosphate and additives for pH control (bicarbonate) may irreversibly adsorb to mineral surfaces. In soils with a large proportion of organic matter bound to the mineral matrix, for example subsoils, or rich in clay-sized minerals (Fe oxides, poorly crystalline Fe and Al phases, expandable phyllosilicates), C removal can be little irrespective of the reagents used. Residual organic C seems to seems to represent largely refractory organic matter, and comprises mainly pyrogenic materials and aliphatic compounds. If protected by close association with minerals, other organic constituents such as low-molecular weight carboxylic acids, lignin-derived and N-containing compounds may escape chemical destruction. For determination of mineral phase properties, treatment with H2O2 should be avoided since it may promote organic-assisted dissolution of poorly crystalline minerals at low pH, disintegration of expandable clay minerals, and transformation of vermiculite into mica-like products due to NH4+ fixation. Sodium hypochlorite and Na2S2O8 are less harmful for minerals than H2O2 While the NaOCl procedure (pH 9.5) may dissolve Al hydroxides, alkaline conditions favor the precipitation of metals released upon destruction of organic matter. Prolonged heating to >40°C during any treatment may transform poorly crystalline minerals into more crystalline ones. Sodium hypochlorite can be used at 25°C, thus preventing heat-induced mineral alteration.

Surface charge evolution of mineral-organic complexes during pedogenesis in Hawaiian basalt

Changes in surface charge of soil particles that accompany mineral transformations during soil formation were measured for a humid tropical chronosequence in Hawaiian basalt ranging in lava flow age from 0.3 to 4100 kiloyears (ky). Parent mineralogy is dominated by glass, olivine, pyroxene, and feldspar, whereas poorly crystalline (PC) weathering products (allophane, microcrystalline gibbsite, ferrihydrite) accumulate in early to intermediate weathering stages (through 400 ky), and crystalline secondary minerals (kaolinite, gibbsite, goethite) are dominant in the oldest (1400 and 4100 ky) soils. Detailed characterization of the solid phase was accomplished with chemical extractions, X-ray diffraction analysis, and molecular spectroscopy (FTIR and 13C MAS NMR). Simultaneous proton titration and background ion adsorption measurements were made on LiCl saturated soils over a range in pH (2–9) and ionic strength (0.001 and 0.01 M LiCl). Dependence of variable surface charge on solution composition reflects the changing nature of mineral-organic interactions over the course of pedogenesis. Points of zero net proton charge (PZNPC) ranged from 3.4 to 6.2 and 2.0 to 5.8 at 0.001 and 0.01 M ionic strength ( I), respectively. Intermediate-aged soils containing the highest mass concentration of humified soil organic matter (SOM) and its complexes with PC minerals gave rise to the steepest charging curves (largest pH dependence) and highest PZNPC values. Surface charge properties of these soils most closely reflected their weakly acidic Al and Fe hydroxide constituents, which is consistent with metal hydroxide saturation of organic functional groups, rather than organic coating of mineral surfaces. Charging curves were less steep and PZNPC values were lower for the older soils, consistent with SOM coating of more crystalline goethite, kaolinite, and gibbsite surfaces in a soil system less impacted by labile Al and Fe.

The effects of post-persulfate-digestion procedures on total phosphorus analysis in water.

There are differences between the EPA Method 365 and the APHA-AWWA-WEF's Standard Method 4500 with respect to the post-digestion treatment procedures of the persulfate-digested water. The effects on total phosphorus analysis of different post-digestion treatment procedures, such as neutralization and reacidification, and shaking/settling, were investigated in this study using the total phosphorus measurements of water samples from the Everglades Round Robin (ERR) study and comparing the results with the ERR study. The effects of the insoluble particles or phosphorus adsorption/precipitation on/with Al and Fe hydroxides in different post-digestion treatment procedures adequately accounted for the differences between the most probable value and the higher or lower total phosphorus measurements reported in the ERR study. Based on the results of this investigation we recommend that a clearly defined set of digestion and post-digestion treatment procedures be adopted as the standard for total phosphorus analysis using the ascorbic acid method.

The kinetic study of the synthesis of magnesium aluminate spinel from mechanochemically treated mixtures of oxide-hydroxide

The kinetics of solid-state reaction of magnesium aluminate (MA) spinel formation from the mechanically activated mixtures of both Mg and Al oxides and hydroxides was studied in situ by high-temperature X-ray diffraction at elevated temperatures. The degree of conversion α of the MA spinel formation was determined by the Rietveld method. The dependence of the conversion degree of the MA spinel formation on the time of isothermal heating of the particular mixtures was studied. Time dependence α(t) of the crystalline MgAl2O4 formation at the temperature T was analysed by the equation corresponding to the first order kinetics α(t) = P1 · [1 − P2 · exp(−k · t)], where P1, P2, and k are the parameters. The rate constants k and the activation energies of the crystalline MgAl2O4formation for the selected mixtures were calculated by the fitting the kinetic data. Comparison of acquired data shows that the most beneficial results for MA spinel synthesis were obtained from the mechanically activated hydroxide mixture Mg(OH)2 + Al(OH)3.

Mineralogical study of secondary mineral phases from weathered MSWI bottom ash: implications for the modelling and trapping of heavy metals

A mineralogical study of 3 samples of municipal solid waste incineration bottom ash collected from different storage sites and with storage times varying from 3 weeks to 2 years, has enabled identification of the main secondary mineral species formed during weathering. The frequencies of the secondary phases were determined and a diagram is proposed for the relative distribution of the newly formed mineral phases: calcite ≫ Fe oxides quartz ⩾ sulphates and/or ettringite (depending on the amount of reactive Al present in the bottom ash). This approach, involving careful sampling, sample preparation and the combined use of various analytical techniques, also showed the high frequency of Al hydroxides and amorphous phases and helped to identify more than 30 sulphates s.l. (sulphates, chromates, vanadates, etc.). Most of the secondary minerals (carbonates and sulphates s.l.) have broad metal trapping capacities for heavy element uptake (Pb, Zn, Cd, As, V, Cr, etc.) due to their crystal-chemistry characteristics. Ca-oxalates were also identified. Mineralogical data from the study provide new input for thermochemical models. The relative stability of metal uptake and the extent of associated neogenesis occurring during bottom-ash decomposition is discussed. Sulphate minerals (and certain heavy metal oxides (zincite)), which are extremely sensitive to environmental conditions, can trap metals only temporarily, as opposed to Fe oxyhydroxides (As, etc.) and carbonates (Pb, Zn, Cd), which are more stable under atmospheric conditions and constitute more sustainable trapping media with higher liquid/solid (L/S) ratios. Finally, a composite predictive diagram is proposed for the mineralogical evolution of bottom ash that accounts for variations in L/S ratios.

Toxoplasma gondii vs ionizing radiation: intestinal immunity induced in C57BL/6J mice by irradiated tachyzoites

We studied the oral route for the development of a vaccine for toxoplasmosis, using parasites irradiated with 60 Cobalt, as an alternative for vaccine development to this worldwide parasitic infection. We evaluated the development of immunity at serum or mucosal levels, and their efficiency to protect the mice against challenge with oral cysts of the ME-49 strain. C57Bl/6j isogenic mice were immunized by oral route with 10 255 Gy irradiated tachyzoites from RH strain, at several protocols using milk as anti-peptic adjuvant and alum hydroxide as antacid. The preparations of irradiated tachyzoites induced production of serum IgG and IgA in immunized mice, as determined by ELISA, with IgG2a as the dominant subclass, similar to chronic infection. Their use with adjuvant allowed the excretion of significant amounts of IgA in stools also IgG, despite a lesser extent. There are suggestions of tolerance induction at mucosal level, with lower antigen induced proliferation and lower in vitro antibody production by spleen and gut lymphocytes, with the latter doses, specially when milk was used as adjuvant. All oral preparations induced some quantitative protection against challenge, which was similar to the parenteral route only isolated alum hydroxide was used as adjuvant.