Rheological characterisation of alginate-like exopolymer gels crosslinked with calcium.

Bacterial alginate-like exopolymers (ALE) gels have been used in this work as a model for the extracellular polymeric matrix of biofilms. Aim was to relate the mechanical properties and strength of this matrix that make biofilms as persistent to cleaning as they are, to the complex cohesive molecular interactions involved. Mechanical properties of the gels as a function of CaCO3 concentration were investigated using dynamic and static rheology. Gels with relatively low CaCO3 concentrations, between 100 µmol and 300 µmol per g ALE, were found to exhibit similar viscoelastic behaviour as real biofilms, with elastic moduli between 50 Pa and 100 Pa and dissipation factors between 0.2 and 0.3. Increasing CaCO3 concentrations resulted in an increase of the elastic modulus up to 250 Pa, accompanied by an increase in brittleness. At a CaCO3 concentration of 1250 µmol per g ALE this trend stopped, probably due to disturbance of the continuous ALE network by precipitation of salts. Therefore, overdosing of Ca salts can be an adequate approach for the removal of biofouling. All gels exhibited permanent strain hardening under medium strain, and their mechanical properties showed dependency on their strain history. Even after application of an oscillatory strain with 200% amplitude that caused the gel structure to collapse, the gels recovered 65 to 90% of their original shear modulus, for the major part within the first 20 s. Recovery was slightly less for gels with high CaCO3 concentration. In creep tests fitted with a Burgers model with multiple Kelvin elements at least three different interactions in the ALE gels could be distinguished with characteristic retardation times in the range of 10, 100 and 1000 s. Further identification of the mechanisms underlying the gel mechanics will allow the development of targeted strategies to undermine the mechanical strength of biofouling and aid the cleaning process.

Multicomponent mass transport modeling of water desalination by reverse osmosis including ion pair formation.

Reverse Osmosis (RO) is one of the main membrane technologies currently used for the desalination of seawater and brackish water to produce freshwater. However, the mechanism of transport and separation of ions in RO membranes is not yet fully understood. Besides acid-base reactions (i.e., including the H+-ion), at high concentrations, the salt ions can associate and form ion pairs. In this study, we investigate how to include the formation of these ion pairs in the extended Donnan steric partitioning pore model. We study the desalination of a water source where three ion pairs can be formed (NaCl, MgCl+, and MgCl2) and also include water self-dissociation and the carbonate system. The model assumes infinitely fast reactions, which means that the participating ions are locally at chemical equilibrium with one another. A square stoichiometric reaction matrix composed of active species, moieties, and reactions is formulated. As the final constraint equation, we use the charge balance. The model predicts profiles in concentration, flux, and reaction rates across the membrane for all species and calculates the retention per group of ions. Ion pair formation has an influence on the fluxes of individual ions and therefore influences the retention of ions.

Effect of dissolved oxygen concentration on the bioflocculation process in high loaded MBRs.

High-loaded membrane bioreactors (HL-MBRs), i.e. MBRs which are operated at extremely short sludge and hydraulic retention times, can be applied to flocculate and concentrate sewage organic matter. The concentrated organics can be used for energy recovery, or for the production of more valuable organic chemicals. Little is known about the effect of the dissolved oxygen concentration (DO) on this bioflocculation process. To examine this effect, two HL-MBRs were operated, respectively at a low (1 mg L(-1)) and a higher (4 mg L(-1)) DO. The higher DO resulted in a better flocculation efficiency, i.e. 92% of the colloidal COD in the sewage flocculated compared to 69% at the lower DO. The difference was attributed to a higher microbial production of extracellular polymeric substances at a DO of 4 mg L(-1) and to more multivalent cations (calcium, iron and aluminium) being distributed to the floc matrix. In addition, the HL-MBR that was operated at a DO of 4 mg L(-1) gave a bigger mean floc size, a lower supernatant turbidity, better settleability and better membrane filterability than the HL-MBR that was operated at a DO of 1 mg L(-1).

High loaded MBRs for organic matter recovery from sewage: effect of solids retention time on bioflocculation and on the role of extracellular polymers.

High loaded MBRs (HL-MBR) can concentrate sewage organic matter by aerobic bioflocculation for subsequent anaerobic conversion to methane or volatile fatty acids. In the range of very short solid retention times (SRT), the effect of SRT on bioflocculation and EPS production in HL-MBR was investigated. This short SRT range was selected to find an optimum SRT maximising recovery of organics by aerobic bioflocculation and minimizing losses of organics by aerobic mineralization. Bioflocculation was studied in five HL-MBRs operated at SRTs of 0.125, 0.25, 0.5, 1 and 5 d. The extent of flocculation, defined as the fraction of suspended COD in the concentrate, increased from 59% at an SRT of 0.125 d to 98% at an SRT of 5 d. The loss of sewage organic matter by biological oxidation was 1, 2, 4, 11 and 32% at SRT of 0.125-5 d. An SRT of 0.5-1 d gave best combination of bioflocculation and organic matter recovery. Bound extracellular polymeric substances (EPS) concentrations, in particular EPS-protein concentrations, increased when the SRT was prolonged from 0.125 to 1 d. This suggests that these EPS-proteins govern the bioflocculation process. A redistribution took place from free (supernatant) EPS to bound (floc associated) EPS when the SRT was prolonged from 0.125 to 1 d, further supporting the fact that the EPS play a dominant role in the flocculation process. Membrane fouling was most severe at the shortest SRTs of 0.125 d. No positive correlation was detected between the concentration of free EPS and membrane fouling, but the concentration of submicron (45-450 nm) particles proved to be a good indicator for this fouling.

Fouling control mechanisms of demineralized water backwash: Reduction of charge screening and calcium bridging effects.

This paper investigates the impact of the ionic environment on the charge of colloidal natural organic matter (NOM) and ultrafiltration (UF) membranes (charge screening effect) and the calcium adsorption/bridging on new and fouled membranes (calcium bridging effect) by measuring the zeta potentials of membranes and colloidal NOM. Fouling experiments were conducted with natural water to determine whether the reduction of the charge screening effect and/or calcium bridging effect by backwashing with demineralized water can explain the observed reduction in fouling. Results show that the charge of both membranes and NOM, as measured by the zeta potential, became more negative at a lower pH and a lower concentration of electrolytes, in particular, divalent electrolytes. In addition, calcium also adsorbed onto the membranes, and consequently bridged colloidal NOM and membranes via binding with functional groups. The charge screening effect could be eliminated by flushing NOM and membranes with demineralized water, since a cation-free environment was established. However, only a limited amount of the calcium bridging connection was removed with demineralized water backwashes, so the calcium bridging effect mostly could not be eliminated. As demineralized water backwash was found to be effective in fouling control, it can be concluded that the reduction of the charge screening is the dominant mechanism for this.