The many roles of mellitic acid during barium sulfate crystallization.

The various roles of mellitic acid during barium sulfate crystallization from nucleation to mesocrystal formation are explored and elucidated.

Ecological risk assessment for perfluorohexanesulfonic acid (PFHxS) in soil using species sensitivity distribution (SSD) approach.

Perfluorohexanesulfonic acid (PFHxS) is one of the persistent organic pollutants that has been recommended to be listed in Annex A of the Stockholm Convention. It has gained increasing attention in recent years due to its toxic effects. The guideline values of PFHxS are commonly associated with PFOS in various countries and regulatory agencies. In this study, multispecies bioassays were conducted to determine the ecological toxic effects of PFHxS, including plants, soil invertebrates, and soil microorganisms, which indicated the EC10/NOEC values ranged from 2.9 to 250 mg/kg. Where possible, logistic models were used to calculate the EC30 values for various endpoints. The species sensitivity distributions were employed to estimate the ecological investigation levels for PFHxS contamination in soils using toxicity results from literature and this study. The calculation using EC10/NOEC values from both literature and this study indicated a most conservative HC5 as 1.0 mg/kg (hazardous concentration for 5 % of the species being impacted). However, utilisation of EC30 values derived from this study resulted in a much higher HC5 for PFHxS in contaminated soils (13.0 mg/kg) which is at the higher end of the existing guideline values for PFOS for protecting ecological systems. The results obtained in this study can be useful in risk assessment processes to minimize any uncertainty using combined values with PFOS.

The interaction of EDTA with barium sulfate.

Ethylenediaminetetraacetic acid (EDTA) is a known complexing agent that interacts with a host of cations. In this paper, various techniques are used to elucidate the mechanism of interaction between EDTA and barium sulfate surfaces. It is shown that complexation with metal ions is not sufficient to explain the inhibition of barite crystallization but that other processes such as chemisorption must also occur. EDTA is shown to always adsorb as the mono-protonated species - suggesting that the molecule is able to lose a proton when it adsorbs at lower pH. Molecular modelling shows that the interaction of the surface barium ions with the carboxylate group is an important one. Finally, in situ turbidity measurements provide information about the mechanism of nucleation/growth modification. It is found that the EDTA molecule inhibits barium sulfate nucleation and that this could be its primary means of inhibiting precipitation of barium sulfate.

Molecular modeling of phosphonate molecules onto barium sulfate terraced surfaces.

The adsorption of phosphonate molecules onto mineral surfaces is of interest due to their use as scale inhibitors. Molecular modeling is an important tool that can aid the fundamental understanding of how these inhibitors operate. This paper presents an empirical molecular mechanics study of the adsorption of a series of straight chain phosphonate molecules onto barium sulfate. It has been found that inhibition can be predicted for this straight chain series of molecules, which differ by the number of phosphonate groups present as well as by the chain length. Even more importantly, the modeling results can predict which faces will be preferred, and this has been verified by scanning and transmission electron microscopy on the resultant barite particles. It has been found that, in general, lattice matching results in the lowest replacement energy for all of the organic molecules investigated. The agreement between the experiment and the model confirms that the dominant mechanism of interaction for the additives on barium sulfate is via the deprotonated phosphonate groups with the barium ions on the surface.

Synthesis and characterisation of ferrihydrite/silica co-precipitates.

The effect of the presence of soluble silicates on ferrihydrite precipitation and some properties of the products formed in co-precipitation of ferrihydrite and silica have been investigated. The co-precipitates were formed using a continuous crystallisation process in which a combined iron/silicon feed solution was reacted with sodium hydroxide at a constant rate, while maintaining pH at 2.65 and temperature at 85 degrees C. The products of co-precipitation and the supernatant solutions were characterised using a variety of analytical techniques including X-ray diffraction (XRD), transmission electron microscopy (TEM) and surface charge measurements. The addition of silicates was shown to have a significant impact on the crystallinity and surface charge of the precipitates formed. For products collected after five residence times in the continuous crystalliser, co-precipitates formed from ferric sulfate solution were found to contain considerably less silica than those formed from ferric nitrate. We conclude that adsorption of silicate species on ferrihydrite surfaces speeds up the polymerisation process, and that sulfate ion competes with silicate for surface adsorption sites. Thus, the precipitation of silica proceeds much more rapidly in ferric nitrate media, than in ferric sulfate.

Arsenic removal from aqueous solution via ferrihydrite crystallization control.

Removal of arsenate anion from aqueous solution by coprecipitation with ferrihydrite has been studied under conditions in which the Fe/As ratio is maintained at a constant level, while the degree of supersaturation with respect to the iron oxide precipitate is varied. An Fe/As ratio of 12 was chosen, and supersaturation was controlled by varying the iron concentration or the pH. The relationship between supersaturation and arsenic removal was found to follow an exponential curve, with greater arsenic removal occurring at higher supersaturation ratios for each of the pH values tested. Higher supersaturation ratios were required to achieve a given level of arsenic removal at pH 7 than would be required to achieve the same level of removal at pH 3.5. The results provide important guidelines for selection of appropriate concentrations of iron(III) required for arsenic removal under various circumstances. Powder XRD analysis of the arsenate-ferrihydrite precipitates showed an increasing degree of structural order with decreasing levels of supersaturation. TEM images of the precipitates revealed that aggregates with a morphology similar to that of schwertmannite are formed in some samples at low supersaturation levels. The results described in this paper indicate that the overall efficiency of arsenic removal involves a combination of both supersaturation and pH effects, with pH controlling the affinity of arsenate for the ferrihydrite surface, and supersaturation controlling the surface area and physical properties of the ferrihydrite product.