Sulfide induced phosphate release from iron phosphates and its potential for phosphate recovery.

Sulfide is frequently suggested as a tool to release and recover phosphate from iron phosphate rich waste streams, such as sewage sludge, although systematic studies on mechanisms and efficiencies are missing. Batch experiments were conducted with different synthetic iron phosphates (purchased Fe(III)P, Fe(III)P synthesized in the lab and vivianite, Fe(II)3(PO4)2*8H2O), various sewage sludges (with different molar Fe:P ratios) and sewage sludge ash. When sulfide was added to synthetic iron phosphates (molar Fe:S = 1), phosphate release was completed within 1 h with a maximum release of 92% (vivianite), 60% (purchased Fe(III)P) and 76% (synthesized Fe(III)P). In the latter experiment, rebinding of phosphate to Fe(II) decreased net phosphate release to 56%. Prior to the re-precipitation, phosphate release was very efficient (P released/S input) because it was driven by Fe(III) reduction and not by, more sulfide demanding, FeSx formation. This was confirmed in low dose sulfide experiments without significant FeSx formation. Phosphate release from vivianite was very efficient because sulfide reacts directly (1:1) with Fe(II) to form FeSx, without Fe(III) reduction. At the same time vivianite-Fe(II) is as efficient as Fe(III) in binding phosphate. From digested sewage sludge, sulfide dissolved maximally 30% of all phosphate, from the sludge with the highest iron content which was not as high as suggested in earlier studies. Sludge dewaterability (capillary suction test, 0.13 ± 0.015 g2(s2m4)-1) dropped significantly after sulfide addition (0.06 ± 0.004 g2(s2m4)-1). Insignificant net phosphate release (1.5%) was observed from sewage sludge ash. Overall, sulfide can be a useful tool to release and recover phosphate bound to iron from sewage sludge. Drawbacks -deterioration of the dewaterability and a net phosphate release that is lower than expected-need to be investigated.

Vivianite as the main phosphate mineral in digested sewage sludge and its role for phosphate recovery.

Phosphate recovery from sewage sludge is essential in a circular economy. Currently, the main focus in centralized municipal wastewater treatment plants (MWTPs) lies on struvite recovery routes, land application of sludge or on technologies that rely on sludge incineration. These routes have several disadvantages. Our study shows that the mineral vivianite, Fe2(PO4)3 × 8H2O, is present in digested sludge and can be the major form of phosphate in the sludge. Thus, we suggest vivianite can be the nucleus for alternative phosphate recovery options. Excess and digested sewage sludge was sampled from full-scale MWTPs and analysed using x-ray diffraction (XRD), conventional scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), environmental SEM-EDX (eSEM-EDX) and Mössbauer spectroscopy. Vivianite was observed in all plants where iron was used for phosphate removal. In excess sludge before the anaerobic digestion, ferrous iron dominated the iron pool (≥50%) as shown by Mössbauer spectroscopy. XRD and Mössbauer spectroscopy showed no clear correlation between vivianite bound phosphate versus the iron content in excess sludge. In digested sludge, ferrous iron was the dominant iron form (>85%). Phosphate bound in vivianite increased with the iron content of the digested sludge but levelled off at high iron levels. 70-90% of all phosphate was bound in vivianite in the sludge with the highest iron content (molar Fe:P = 2.5). The quantification of vivianite was difficult and bears some uncertainty probably because of the presence of impure vivianite as indicated by SEM-EDX. eSEM-EDX indicates that the vivianite occurs as relatively small (20-100 µm) but free particles. We envisage very efficient phosphate recovery technologies that separate these particles based on their magnetic properties from the complex sludge matrix.

Enhanced biofilm solubilization by urea in reverse osmosis membrane systems.

Chemical cleaning is routinely performed in reverse osmosis (RO) plants for the regeneration of RO membranes that suffer from biofouling problems. The potential of urea as a chaotropic agent to enhance the solubilization of biofilm proteins has been reported briefly in the literature. In this paper the efficiency of urea cleaning for RO membrane systems has been compared to conventionally applied acid/alkali treatment. Preliminary assessment confirmed that urea did not damage the RO polyamide membranes and that the membrane cleaning efficiency increased with increasing concentrations of urea and temperature. Accelerated biofilm formation was carried out in membrane fouling simulators which were subsequently cleaned with (i) 0.01M sodium hydroxide (NaOH) and 0.1M hydrochloric acid (HCl) (typically applied in industry), (ii) urea (CO(NH2)2) and hydrochloric acid, or (iii) urea only (1340 g/Lwater). The pressure drop over the flow channel was used to evaluate the efficiency of the applied chemical cleanings. Biomass removal was evaluated by measuring chemical oxygen demand (COD), adenosine triphosphate (ATP), protein, and carbohydrate content from the membrane and spacer surfaces after cleaning. In addition to protein and carbohydrate quantification of the extracellular polymeric substances (EPS), fluorescence excitation-emission matrix (FEEM) spectroscopy was used to distinguish the difference in organic matter of the remaining biomass to assess biofilm solubilization efficacy of the different cleaning agents. Results indicated that two-stage CO(NH2)2/HCl cleaning was as effective as cleaning with NaOH/HCl in terms of restoring the feed channel pressure drop (>70% pressure drop decrease). One-stage cleaning with urea only was not as effective indicating the importance of the second-stage low pH acid cleaning in weakening the biofilm matrix. All three chemical cleaning protocols were equally effective in reducing the concentration of predominant EPS components protein and carbohydrate (>50% reduction in concentrations). However, urea-based cleaning strategies were more effective in solubilizing protein-like matter and tyrosine-containing proteins. Furthermore, ATP measurements showed that biomass inactivation was up to two-fold greater after treatment with urea-based chemical cleanings compared to the conventional acid/alkali treatment. The applicability of urea as an alternative, economical, eco-friendly and effective chemical cleaning agent for the control of biological fouling was successfully demonstrated.

Vivianite as an important iron phosphate precipitate in sewage treatment plants.

Iron is an important element for modern sewage treatment, inter alia to remove phosphorus from sewage. However, phosphorus recovery from iron phosphorus containing sewage sludge, without incineration, is not yet economical. We believe, increasing the knowledge about iron-phosphorus speciation in sewage sludge can help to identify new routes for phosphorus recovery. Surplus and digested sludge of two sewage treatment plants was investigated. The plants relied either solely on iron based phosphorus removal or on biological phosphorus removal supported by iron dosing. Mössbauer spectroscopy showed that vivianite and pyrite were the dominating iron compounds in the surplus and anaerobically digested sludge solids in both plants. Mössbauer spectroscopy and XRD suggested that vivianite bound phosphorus made up between 10 and 30% (in the plant relying mainly on biological removal) and between 40 and 50% of total phosphorus (in the plant that relies on iron based phosphorus removal). Furthermore, Mössbauer spectroscopy indicated that none of the samples contained a significant amount of Fe(III), even though aerated treatment stages existed and although besides Fe(II) also Fe(III) was dosed. We hypothesize that chemical/microbial Fe(III) reduction in the treatment lines is relatively quick and triggers vivianite formation. Once formed, vivianite may endure oxygenated treatment zones due to slow oxidation kinetics and due to oxygen diffusion limitations into sludge flocs. These results indicate that vivianite is the major iron phosphorus compound in sewage treatment plants with moderate iron dosing. We hypothesize that vivianite is dominating in most plants where iron is dosed for phosphorus removal which could offer new routes for phosphorus recovery.

Geopolymerisation of fly ashes with waste aluminium anodising etching solutions.

Combined management of coal combustion fly ash and waste aluminium anodising etching solutions using geopolymerisation presents economic and environmental benefits. The possibility of using waste aluminium anodising etching solution (AES) as activator to produce fly ash geopolymers in place of the commonly used silicate solutions was explored in this study. Geopolymerisation capacities of five European fly ashes with AES and the leaching of elements from their corresponding geopolymers were studied. Conventional commercial potassium silicate activator-based geopolymers were used as a reference. The geopolymers produced were subjected to physical, mechanical and leaching tests. The leaching of elements was tested on 28 days cured and crushed geopolymers using NEN 12457-4, NEN 7375, SPLP and TCLP leaching tests. After 28 days ambient curing, the geopolymers based on the etching solution activator showed compressive strength values between 51 and 84 MPa, whereas the commercial potassium silicate based geopolymers gave compressive strength values between 89 and 115 MPa. Based on the regulatory limits currently associated with the used leaching tests, all except one of the produced geopolymers (with above threshold leaching of As and Se) passed the recommended limits. The AES-geopolymer geopolymers demonstrated excellent compressive strength, although less than geopolymers made from commercial activator. Additionally, they demonstrated low element leaching potentials and therefore can be suitable for use in construction works.

Immobilisation of lead smelting slag within spent aluminate-fly ash based geopolymers.

This study presents the solidification/stabilisation and immobilisation of lead smelting slag (LSS) by its incorporation in coal fly ash - blast furnace slag based geopolymers. It also explores the use of a spent aluminium etching solution (AES) as geopolymer activator instead of the commonly used silicate solutions. The compressive strength of the geopolymers produced with the AES was lower than when applying a K-silicate solution as activator (100MPa versus 80MPa after 28 days). Compressive strength was not affected when up to 10% of the FA was replaced by LSS. NEN 12457-4, TCLP, SPLP and NEN 7375 leaching tests indicated that mobile Pb from LSS was highly immobilised. The diffusion leaching test NEN 7375 revealed exceeding of the Dutch Soil Quality Regulation threshold limits only for Se and Sb. On the condition that the remaining excess leaching can be reduced by further refinement of the mixture recipes, the proposed process will have the potential of producing waste-based construction materials that may be applied under controlled conditions in specific situations.

Ultrasonic reactivation of phosphonate poisoned calcite during crystal growth.

The effect of ultrasonic irradiation (42,150 Hz, 17 W dm(-3)/7.1 W cm(-2)) on the growth of calcite in the presence of the inhibitor nitrilotris(methylene phosphonic acid) (NTMP) was investigated at constant composition conditions. In seeded growth experiments, it was found that the inhibiting effect of NTMP on crystal growth could be seriously mitigated under influence of ultrasonic irradiation. An approximately twofold increase in volumetric growth rate was achieved during ultrasonic irradiation, and recovery of the growth rate following inhibition was strongly enhanced compared to growth experiments without ultrasonic irradiation. The results could be explained in part by the physical effect of ultrasound that causes breakage and attrition of poisoned crystals, which resulted in an increase in fresh surface area. Mass spectroscopy analysis of sonicated NTMP solutions revealed that there is also a chemical effect of ultrasound that plays an important role. Several breakdown products were identified, which showed that ultrasound caused the progressive loss of phosphonate groups from NTMP, probably by means of physicochemically generated free radicals and/or pyrolysis in the hot bubble-bulk interface.

Visualization of acoustic cavitation effects on suspended calcite crystals.

The acoustic cavitation (42,080 Hz, 7.1 W cm(-2) or 17 W) effects on suspended calcite crystals, sized between 5 and 50 µm, have been visualized for the first time using high speed photography. High speed recordings with a duration of 1 s containing up to 300,000 frames per second, revealed the effect of cluster and streamer cavitation on several calcite crystals. Cavitation clusters, evolved from cavitation inception and collapse, caused attrition, disruption of aggregates and deagglomeration, whereas streamer cavitation was observed to cause deagglomeration only. Cavitation on the surface gave the crystals momentum. However, it is shown that breakage of accelerated crystals by interparticle collisions is unrealistic because of their small sizes and low velocities. Crystals that were accelerated by bubble expansion, subsequently experienced a deceleration much stronger than expected from drag forces, upon bubble collapse. Experiments with pre-dried crystals seemed to support the current theory on bubble nucleation through the presence of pre-existing gas pockets. However, experiments with fully wetted crystals also showed the nucleation of bubbles on the crystal surface. Although microjet impingement on the crystal surface could not be directly visualized with high speed photography, scanning electron microscopy (SEM) analysis of irradiated calcite seeds showed deep circular indentations. It was suggested that these indentations might be caused by shockwave induced jet impingement. Furthermore, the appearance of voluminous fragments with large planes of fracture indicated that acoustic cavitation can also cause the breakage of single crystal structures.

Adsorptive removal of nitrilotris(methylenephosphonic acid) antiscalant from membrane concentrates by iron-coated waste filtration sand.

Iron-coated waste filtration sand was investigated as a low-cost adsorbent for the removal of nitrilotris(methylenephosphonic acid) (NTMP) from membrane concentrates. The adsorption of this phosphonate-based antiscalant on this material was measured and compared with two commercially available anion exchange resins and activated carbon. Comprehensive adsorption experiments were conducted in several synthetic concentrate solutions and in a concentrate collected from a full scale nano-filtration brackish water desalination plant. The effect of pH, ionic strength and the presence of competitive anions on the equilibrium adsorption were investigated. The results showed that, in contrast to the anion exchange resins, the adsorption on coated filtration sand is not suppressed at increasing ionic strength and is much less affected by the competitive anions carbonate and sulphate. The adsorption decreased slightly when the pH was raised from 7.0 to 8.0. The adsorption isotherms in the real nano-filtration concentrate, measured in the concentration interval of 5-50 mg dm(-1) NTMP, showed that the maximum adsorption capacity of coated filtration sand was 4.06 mg g(-1). The adsorption capacity per unit mass of the adsorbents at low NTMP concentration (12.5 mg dm(-3)) followed the decreasing order Amberlite IRA-410>coated filtration sand>Amberlite IRA-900>Norit SAE Super. This demonstrates that the use of iron-coated waste filtration sand offers a promising means for the removal of NTMP from membrane concentrates.

Release of PLGA-encapsulated dexamethasone from microsphere loaded porous surfaces.

The aim of the present study was to investigate the morphology and function of a drug eluting metallic porous surface produced by the immobilization of poly lactide-co-glycolide microspheres bearing dexamethasone onto plasma electrolytically oxidized Ti-6Al-7Nb medical alloy. Spheres of 20 microm diameter were produced by an oil-in-water emulsion/solvent evaporation method and thermally immobilized onto titanium discs. The scanning electron microscopy investigations revealed that the size distribution and morphology of the attached spheres had not changed significantly. The drug release profiles following degradation in phosphate buffered saline for 1000 h showed that, upon immobilisation, the spheres maintained a sustained release, with a triphasic profile similar to the non-attached system. The only significant change was an increased release rate during the first 100 h. This difference was attributed to the effect of thermal attachment of the spheres to the surface.

Size effect of PLGA spheres on drug loading efficiency and release profiles.

Drug delivery systems (DDS) based on poly (lactide-co-glycolide) (PLGA) microspheres and nanospheres have been separately studied in previous works as a means of delivering bioactive compounds over an extended period of time. In the present study, two DDS having different sizes of the PLGA spheres were compared in morphology, drug (dexamethasone) loading efficiency and drug release kinetics in order to investigate their feasibility with regard to production of medical combination devices for orthopedic applications. The loaded PLGA spheres have been produced by the oil-in-water emulsion/solvent evaporation method following two different schemes. Their morphology was assessed by scanning electron microscopy and the drug release was monitored in phosphate buffer saline solution at 37 degrees C for 550 h using high performance liquid chromatography. The synthesis schemes used produced spheres with two different and reproducible size ranges (20 +/- 10 and 1.0 +/- 0.4 microm) having a smooth outer surface and regular shape. The drug loading efficiency of the 1.0 microm spheres was found to be 11% as compared to just 1% for the 20 microm spheres. Over the 550 h release period, the larger spheres (diameter 20 +/- 10 microm) released 90% of the encapsulated dexamethasone in an approximately linear fashion whilst the relatively small spheres (diameter 1.0 +/- 0.4 microm) released only 30% of the initially loaded dexamethasone, from which 20% within the first 25 h. The changes observed were mainly attributed to the difference in surface area between the two types of spheres as the surface texture of both systems was visibly similar. As the surface area per unit volume increases in the synthesis mixture, as is the case for the 1.0 microm spheres formulation, the amount of polymer-water interfaces increases allowing more dexamethasone to be encapsulated by the emerging polymer spheres. Similarly, during the release phase, as the surface area per unit volume increases, the rate of inclusion of water into the polymer increases, permitting faster diffusion of dexamethasone.

A method for lipase co-precipitation in a biodegradable protein matrix.

This article presents a novel method for immobilization of active ingredients. The method is based on CO(2) aided active ingredient co-precipitation with glycinin, a biodegradable protein matrix from edible soybean protein. Glycinin precipitates abundantly under isoelectric conditions and serves as the matrix within which the active substance is trapped during the precipitation process. The enzyme lipase from Candida rugosa was successfully co-precipitated into the protein pellet to prove the principle. It was shown that the lipase within the co-precipitate retained lipase and esterase activity under different pH conditions. In some cases the activity was even higher than the activity of crude lipase, possibly due to the protective role of the matrix protein. Due to the retained lipase activity and food-grade quality of the binary precipitate, it has potential of being used in the food or pharmaceutical industry. Additional quality of the binary precipitate is the potentially significantly reduced downstream processing due to the fact that no organic solvents or precipitants were used in the precipitation process.

Carbon dioxide induced soybean protein precipitation: protein fractionation, particle aggregation, and continuous operation.

A novel protein fractionation technique using a volatile electrolyte has been developed. Carbon dioxide was used to isoelectrically precipitate 80% and 95% pure glycinin and beta-conglycinin fractions from soybean isolate. The protein fractions precipitated as primary particles 0.2-0.3 microm in diameter, which under optimum conditions may be recovered as aggregates up to 500 microm in diameter. The dependency of protein fractionation efficiency on aggregate settling rates has been demonstrated. The isoelectric points of the two main soybean fractions, glycinin and beta-conglycinin, were calculated to be pH 5.2 and 4.95, respectively. Solution pH was accurately controlled by pressure in the isoelectric pH range of the different soybean protein fractions, and a pH "overshoot" was eliminated. Volatile electrolyte technology was also applied to a continuous process in order to eliminate the particle recovery concerns associated with batch precipitation and to demonstrate the potential for scale-up. Glycinin was effectively recovered on-line (94% glycinin recovery) with a purity approaching that of the batch process (95%).

Fractionation of soybean proteins with pressurized carbon dioxide as a volatile electrolyte.

Fractionation of specific proteins from plant material is a complex and involved science, yet pure protein extracts are in high demand by a wide range of food and pharmaceutical industries. In this study carbon dioxide has been used as a volatile electrolyte to isoelectrically precipitate two major protein constituents of soybean. Carbon dioxide was shown to be effective in purifying glycinin and beta-conglycinin in a three-step process as 95% and 80% concentrated fractions with precipitation yields of 28% and 21%, respectively. Recycling of the mixed precipitate of the intermediary step enables complete separation into the concentrated fractions. Fractionation acidity was precisely controlled by a simple modification of pressure. In addition, the occurrence of a pH overshoot was prevented at any point in the fractionation vessel, as the pH minimum was defined by its equilibrium relationship with carbon dioxide operating pressure. The removal of the glycinin precipitate was an important factor in the purification procedure. The yield of the individual concentrated glycinin and beta-conglycinin precipitate fractions was a function of carbon dioxide pressure, extract concentration and, to a much lesser extent, temperature.

Isoelectric precipitation of soybean protein using carbon dioxide as a volatile acid.

A novel process is presented for the isoelectric precipitation of soy protein, using carbon dioxide as a volatile acid. By contacting a soy meal extract with pressurized carbon dioxide, the solution pH was decreased to the isoelectric region of the soy proteins. Complete precipitation of the precipitable soy proteins could be achieved for protein concentrations up to 40 g/l at pressures less than 50 bar. Isoelectric precipitation with a volatile acid enabled accurate control of the solution pH by pressure and eliminated the local pH overshoot, usual in conventional precipitation techniques. The advantage of the improved precipitation control was reflected by the morphology of the precipitate particles. Protein aggregates formed by CO2 were perfectly spherical whereas protein precipitated by sulfuric acid had an irregular morphology. The influence of process variables to control particle size is discussed.