Investigation of sodium silicate-derived gels as encapsulants for hazardous materials--the case of scorodite.

High content arsenic waste generated in the metallurgical industry can be converted into a synthetic mineral, scorodite, FeAsO4·2H2O, and deposited into a landfill site. Scorodite is most stable in weakly acidic to neutral pH range under oxic conditions. A novel way to enhance the range of stability for scorodite is to encapsulate it with an inert material. In this work, silicate gel is developed and investigated as a possible encapsulating material for scorodite. The initial method of gel formation in this study produced a silicate gel with high alkalinity (pH 10) that was incompatible with scorodite. A reverse titration method was developed producing a gel with optimum pH profile (5-6.5). This technique proved to have only marginal effect on scorodite stabilization prompting an investigation of different ageing techniques (drying; 22, 44°C and hydrothermal treatment; 110, 160°C) as a means of producing silica-like coatings with better stabilization potential. Interestingly most of these measures proved counterproductive as aged scorogels showed a higher release of As than scorodite alone. Through surface-sensitive depth profile analysis (XPS), and molecular-sensitive analysis (Raman and FTIR mapping), it was discovered that the silicate engaged into an "ion-exchange" type reaction on the surface of scorodite by bonding to iron, hence the observed release of arsenic. Development of a hydrothermally-induced iron silicate layer may lead to an effective encapsulant.

The effect of copper on the precipitation of scorodite (FeAsO4·2H2O) under hydrothermal conditions: evidence for a hydrated copper containing ferric arsenate sulfate-short lived intermediate.

The effect of copper sulfate on scorodite precipitation and its mechanism of formation at 150 °C was investigated. Scorodite was determined to be the dominant phase formed under all conditions explored (0.61 < Fe(III)/As(V) < 1.87, 0.27-0.30 M Fe(SO(4))(1.5), 0-0.3 M CuSO(4), 0-0.3 M MgSO(4), at 2.5 h and 150 °C). The produced scorodite was found to incorporate up to 5% SO(4) and ≤1% Cu or Mg in its structure. The precipitation of scorodite was stoichiometric, i.e. the Fe/As molar ratio in the solids was equal to one independent of the starting Fe/As ratio in the solution. The presence of excess ferric sulfate in the initial solution (Fe/As>1) was found to slow down the ordering of the H-bond structure in scorodite. Precipitation under equimolar concentrations (As = Fe = Cu = 0.3 M), short times and lower temperatures (30-70 min and 90-130 °C) revealed the formation of a Cu-Fe-AsO(4)-SO(4)-H(2)O short lived gelatinous intermediate that closely resembled the basic ferric arsenate sulfate (BFAS) type of phase, before ultimately converting fully to the most stable scorodite phase (96 min and 138 °C). This phase transition has been traced throughout the reaction via elemental (ICP-AES, XPS), structural (PXRD, TEM) and molecular (ATR-IR, Raman) analysis. ATR-IR investigation of an arsenic containing industrial residue produced during pressure leaching of a copper concentrate (1 h and 150 °C) found evidence of the formation of an arsenate mineral form resembling the intermediate basic ferric arsenate sulfate phase.

The elimination of selenium(IV) from aqueous solution by precipitation with sodium sulfide.

In this study, the removal/precipitation of selenium with sodium sulfide from initially weakly acidic sulfate solutions containing 300 mg/L of selenium(IV) at 23 °C was studied. The results showed that, below a pH of approximately 7.0, the precipitation reaction was complete at a sulfide to selenium ratio above 1.8 and less than 11 with less than 0.005 mg/L of soluble selenium remaining in solution. When the pH rose between 7.0 and 9.5 the precipitation of selenium was incomplete. Above pH 9.5 the solution turned dark red but no precipitation was apparent. The precipitation reaction started as soon as the sodium sulfide was added in the selenium-bearing solution and was completed in less than 10 min. The orange "selenium sulfide" precipitates, characterized using X-ray diffraction, scanning electron microscopy and chemical analysis, were crystalline in the form of aggregated dense particles with their sulfur/selenium molar ratio varying from 1.7 to 2.3. The precipitate was deduced to be a Se-S solid solution consisting of ring molecules of the following Se(n)S(8-n) formula, where n = 2.5-3. Long term leachability tests (>2 month equilibration) under ambient conditions at pH 7 showed the produced precipitate to be essentially insoluble (<0.005 mg/L).

Scorodite encapsulation by controlled deposition of aluminum phosphate coatings.

A new stabilization process for scorodite (FeAsO(4).2H(2)O) solids based on the concept of encapsulation by controlled deposition of mineral coatings immune to pH or redox potential variations is described. The stability of the encapsulated scorodite with aluminum phosphates under simulated anoxic and oxic environments is demonstrated. Encapsulation experiments were carried out at 95 degrees C using 50 g/L scorodite in acidic sulphate solution containing 0.16 mol/L of P(V) with Al(III) to P(V) molar ratio of 1 and precipitation pH of 1.7. The encapsulated particles were characterised by XRD, SEM, TOF-SIMS and TOF-LIMS. The coating was crystalline AlPO(4).1.5H(2)O ranging in thickness from 2.5 to 3.5 microm. Encapsulation of scorodite particles with hydrated aluminum phosphate appears to be effective in controlling/suppressing the release of arsenic under both oxic and anoxic conditions by more than one order of magnitude.

Examples of charging effects on the spectral quality of X-ray microanalysis on a glass sample using the variable pressure scanning electron microscope.

The performance of X-ray microanalysis in the variable pressure or environmental scanning electron microscope (VP-SEM or ESEM) is limited by skirting. Under certain conditions, charging effects can occur and change the X-ray emission, which affects the X-ray microanalysis. The conventional way to evaluate charging is to calculate the Duane-Hunt limit by fitting the X-ray intensity region located below the energy cut-off. Nevertheless, this method appears to have serious limitations for instance in the case of strong insulators. A perfect example of this limitation is to study the evolution of composition of an alkali glass with time. This paper reports on the evolution of the sodium X-ray intensity with time depending on accelerating voltage, pressure and presence of a surface coating. For certain conditions, a decrease of sodium X-ray intensity with time was observed but for other conditions the reverse behavior was noticed. The increase of sodium X-ray intensity with time was obtained when the force created by the surface electrons was stronger than the force generated by electrons trapped in the interaction volume, whereas the decrease of sodium X-ray intensity occurred when the force generated by electrons trapped in the interaction volume was the stronger. The variations of sodium X-ray intensity were also compared to the variation of the Duane-Hunt limit, the determination of which is studied in detail in this article.

Skirting: a limitation for the performance of X-ray microanalysis in the variable pressure or environmental scanning electron microscope.

The variable pressure or environmental scanning electron microscope (VP-SEM; ESEM) has become the microscope of choice for many scientists and technologists. Hence, the development of robust methods for X-ray microanalysis, limited by skirting, has become critical. In this paper, two pressure variation correction methods (Doehne and Gauvin) are compared. Both of these methods appear to be effective; the results were found to be well within 10% of the values obtained at 0 Pa. The Doehne method is dependent on an empirical factor (D), therefore the accuracy of the results will depend on the accuracy of this value. Also the Doehne method is compromised by the nonlinearity of the response with pressure. The Gauvin method is more user-friendly and more precise when considering the total range of pressure.

The stability of hydrated aluminium phosphate, AlPO4 x 1.5H2O.

The dissolution mechanism and stability of a synthetic hydrated aluminium phosphate, AlPO4 x 1.5H20 (AlPO4-H3) was investigated at 22 degrees C over the pH range 2.4 to 8.8. AlPO4 x 1.5H2O was found to be more soluble than the better known dihydrate (variscite, AIPO4 x 2H2O) hence proving to be metastable. This material was determined to undergo incongruent dissolution at pH around 3.0 and higher producing initially amorphous Al(OH)3 which gradually (within 30-day dissolution period) converted to the stable gibbsite phase. Upon evaluation of the experimental data with PHREEQC it was possible to calculate the solubility product ( logKsp ) and the standard Gibbs free energy of formation (deltaGf,0) for AlPO4 x 1.5H2O to be respectively-- 20.46+/-0.40 and -1980.5+/-.0 kJ mol(-1) at 22 degrees C.