Effects of humic acid on physical and hydrodynamic properties of kaolin flocs by particle image velocimetry

The physical and hydrodynamic properties of kaolin flocs including floc size, strength, regrowth, fractal structure and settling velocity were investigated by in situ particle image velocimetry technique at different humic acid concentration. Jar-test experimental results showed that the adsorbed humic acid had a significant influence on the coagulation process for alum and ferric chloride. Kaolin flocs formed with the ferric chloride were larger and stronger than those for alum at same humic acid concentration. Floc strength and regrowth were estimated by strength factor and recovery factor at different humic acid concentration. It was found that the increased humic acid concentration had a slight influence on the strength of kaolin flocs and resulted in much worse floc regrowth. In addition, the floc regrowth after breakage depended on the shear history and coagulants under investigation. The changes in fractal structure recorded continuously by in situ particle image velocimetry technique during the growth-breakage-regrowth processes provided a supporting information that the kaolin flocs exhibited a multilevel structure. It was proved that the increased humic acid concentration resulted in decrease in mass fractal dimension of kaolin flocs and consequently worse sedimentation performance through free-settling and microbalance techniques.     

The impact of pH on floc structure characteristic of polyferric chloride in a low DOC and high alkalinity surface water treatment

The adjustment of pH is an important way to enhance removal efficiency in coagulation units, and in this process, the floc size, strength and structure can be changed, influencing the subsequent solid/liquid separation effect. In this study, an inorganic polymer coagulant, polyferric chloride (PFC) was used in a low dissolved organic carbon (DOC) and high alkalinity surface water treatment. The influence of coagulation pH on removal efficiency, floc growth, strength, re-growth capability and fractal dimension was examined. The optimum dosage was predetermined as 0.150 mmol/L, and excellent particle and organic matter removal appeared in the pH range of 5.50-5.75. The structure characteristics of flocs formed under four pH conditions were investigated through the analysis of floc size, effect of shear and particle scattering properties by a laser scattering instrument. The results indicated that flocs formed at neutral pH condition gave the largest floc size and the highest growth rate. During the coagulation period, the fractal dimension of floc aggregates increased in the first minutes and then decreased and larger flocs generally had smaller fractal dimensions. The floc strength, which was assessed by the relationship of floc diameter and velocity gradient, decreased with the increase of coagulation pH. Flocs formed at pH 4.00 had better recovery capability when exposed to lower shear forces, while flocs formed at neutral and alkaline conditions had better performance under higher shear forces.     

Floc structural characteristics using conventional coagulation for a high doc, low alkalinity surface water source

Removal of natural organic matter (NOM) is well established using metal salt coagulants. In addition, flocculant aids are also commonly used to improve solid removal. The objectives of this paper is to describe the impacts of both NOM and polymer on floc structure. The study offers a comparison of floc physical characteristics for coagulant precipitate flocs, organic-coagulant flocs and organic-coagulant-polymer flocs for optimum coagulant and polymer doses. A ferric sulphate-based coagulant was used as the primary coagulant and the polymer selected was a high molecular weight (MW) cationic polydiallyldimethylammonium chloride (polyDADMAC). Floc size, breakage, re-growth and settling characteristics were measured. Precipitate flocs were larger than organic flocs and had better settling characteristics when compared to NOM-coagulant flocs. When polymer was added, floc size and compaction was seen to further reduce. An explanation was offered in terms of the mode of flocculation involved. Floc breakage behaviour showed that polymer reduced the rate of floc degradation but did not greatly improve floc re-growth potential after breakage, which was generally poor for all of the suspensions.     

Coagulation dynamics of fractal flocs induced by enmeshment and electrostatic patch mechanisms

The size and structure of flocs during floc formation were monitored for various coagulation mechanisms. Two distinctive mechanisms, namely, enmeshment and electrostatic patch, govern the dynamics of kaolin particles coagulation by polyaluminum chloride (PACl). They were investigated by small angle static light scattering (SASLS) and solid-state ²⁷Al NMR. In addition, a novel wet SEM (WSEM) was used in-situ to image the morphology of the aggregate in aqueous solution. Synthetic suspended particles were coagulated by two PACl products, a commercial product (PACl) and one laboratory product (PACl-E). The PACl-E contained more than 60% Al₁₃ while the PACl contained only 7% Al₁₃, with large percentage of colloidal Al. For coagulation by PACl at neutral pH and high dosage where the strong repulsion between particles occurs, the enmeshment ruled by reaction-limited aggregation (RLA) results in larger sweep flocs as well as higher fractal dimensional structure. For coagulation by PACl-E at alkaline pH and low dosage, the flocs were coagulated predominately by electrostatic patch with Al₁₃ aggregates. At such condition, it is likely that diffusion-limited aggregation (DLA) predominately rule PACl-E coagulation. The fractal dimension (D_s) values of PACl and PACl-E flocs formed at enmeshment and electrostatic patch increased with dosage, respectively. When breakage of flocs occurs, the breakage rate of PACl-E flocs is slower than that of sweep flocs. By WSEM imaging, the adsorption of spherical Al precipitates onto the particles was observed to form sweep flocs with a rough and ragged contour, while the PACl-E flocs were formed with a smooth and glossy structure.     

Comparison of coagulation behavior and floc structure characteristic of different polyferric-cationic polymer dual-coagulants in humic acid solution

Three polyferric-cationic polymer dual-coagulants were comparatively evaluated in terms of coagulation behavior and floc structure characteristic in the coagulation of humic acid (HA) solution. The first dual-coagulant, PFC-PDADMAC, was prepared by premixing of polyferric chloride (PFC) and polydiallyldimethylammonium (PDADMAC) before dosing. The other two were achieved by dosing PFC and PDADMAC in different order. For the given neutral condition, all three dual-coagulants gave similar HA removal before reaching optimal dosage. The strongest charge neutralization and narrowest effective coagulation dosage range were obtained when PFC was dosed firstly. While the weakest charge neutralization and the broadest effective coagulation dosage were obtained when PDADMAC was used as the primary coagulant. The HA removal of all three dual-coagulants was slightly pH dependent for optimum coagulant doses. Fe(III) hydrolysis species distributions of the dual-coagulants in coagulation process were measured by ferron method. PFC-PDADMAC gave the highest content of active Fe(III) coagulating species which is responsible for the coagulation performance of ferric coagulant. The evolution of floc size and floc fractal dimension (D_f) in coagulation process was measured under optimum dose and neutral condition by laser diffraction instrument and small-angle laser light scattering (SALLS), respectively. All three dual-coagulants gave similar final floc size but different floc growth rate and floc structure. Both the growth rate and D_f were in the same order: PFC dosed firstly > PDADMAC dosed firstly > PFC-PDADMAC.     

吸附架桥机理主导下APAM的多级絮凝效能

对吸附架桥机理主导下阴离子聚丙烯酰胺(APAM)的絮凝过程进行了研究,通过改变絮凝剂投加工况,对比分析常规絮凝与多级絮凝在污染物去除效果、絮体性能、絮体生长动力学与污泥调理能耗等方面的差异。结果表明,相同投药量下,两级絮凝的出水浊度低于三级絮凝和常规絮凝,两级絮凝在最少的APAM投加量(2 mg/L)下达到最低的出水浊度(19.53 NTU);与常规絮凝相比,两级絮凝的絮体成长速率、平均粒径和沉降速率分别增加12.67%、30μm、36.74%。两级絮凝在投加间隔为240 s、投配比为1∶1条件下絮凝效能最优,出水浊度为15.34 NTU,絮体沉降速率为1.1 NTU/s,絮体密度达到1.123 4 g/cm³。絮体破碎再絮凝过程中,两级絮凝与常规絮凝破碎后均能恢复至破碎前水平,但破碎后均出现不可逆的絮体结构破损,粒径在0~100μm的絮体颗粒增多,粒径>400μm的絮体减少,破碎后两级絮凝的絮体强度因子(68.15%)高于常规絮凝(41.63%),两级絮凝的絮体强度和抗破碎剪切能力更高。在剩余污泥调理方面,两级絮凝产生的污泥只需要投加40mg/L的APAM就可以达到最低的滤饼含水率(75.5%)。因此,两级絮凝可以显著提升除浊效能与絮体性能,是强化絮凝的发展方向。     

Breakage and re-growth of flocs: effect of additional doses of coagulant species

Several polyaluminum chloride (PACl) coagulants were prepared, with different OH/Al ratios (B values), and characterized by Ferron assay. These were used in studies of floc formation, breakage and re-growth with kaolin suspensions under controlled shear conditions, using a continuous optical monitoring method. Particular attention was paid to the effect of small additional coagulant dosages, added during the floc breakage period, on the re-growth of broken flocs. The results showed that the re-growth ability was greatly dependent on the nature of the PACl species added as second coagulant. The re-growth ability of broken flocs was greatest when the second coagulant was PACl₀ (i.e. AlCl₃, with B = 0) and least with PACl₂₅ (B = 2.5). In the latter case there was no effect on floc re-growth, irrespective of the initial coagulant used. PACls with intermediate B values gave some improvement in floc re-growth, but less than that with PACl₀. Additional dosage of PACl₀ gave re-grown flocs about the same size or even larger than those before breakage. The re-growth of broken flocs is significantly correlated with the species Al_a (monomeric) and Al_b (polymeric), as determined by Ferron assay. The amorphous hydroxide precipitate formed from PACl₀, (mainly Al_a) can greatly improve the adhesion between broken flocs and give complete re-growth. However, for PACl₂₅, mostly composed of Al_b, the nature of the precipitate is different and there is no effect on floc re-growth.     

Effect of NOM, turbidity and floc size on the PAC adsorption of MIB during alum coagulation

The effect of natural organic material (NOM) and turbidity on the powdered activated carbon (PAC) adsorption of the odour compound 2-methylisoborneol (MIB) was evaluated during alum coagulation. The character of the flocs, in terms of their size and fractal dimensions (Df), was used to interpret the observed adsorption behaviour of MIB during the coagulation process. As the alum dose was increased, the adsorption of MIB decreased. This was determined to be due to the size of the flocs, with larger flocs incorporating PAC into their structure, reducing the efficiency of mixing, and the bulk diffusion kinetics for the MIB molecule. The presence of turbidity also reduced MIB adsorption due to the formation of larger flocs. The character of NOM was found to have a greater influence on the adsorption of MIB than the floc structure.     

Application of fractal dimensions to study the structure of flocs formed in lime softening process

The use of fractal dimensions to study the internal structure and settling of flocs formed in lime softening process was investigated. Fractal dimensions of flocs were measured directly on floc images and indirectly from their settling velocity. An optical microscope with a motorized stage was used to measure the fractal dimensions of lime softening flocs directly on their images in 2 and 3D space. The directly determined fractal dimensions of the lime softening flocs were 1.11-1.25 for floc boundary, 1.82-1.99 for cross-sectional area and 2.6-2.99 for floc volume. The fractal dimension determined indirectly from the flocs settling rates was 1.87 that was different from the 3D fractal dimension determined directly on floc images. This discrepancy is due to the following incorrect assumptions used for fractal dimensions determined from floc settling rates: linear relationship between square settling velocity and floc size (Stokes’ Law), Euclidean relationship between floc size and volume, constant fractal dimensions and one primary particle size describing entire population of flocs. Floc settling model incorporating variable floc fractal dimensions as well as variable primary particle size was found to describe the settling velocity of large (>50 μm) lime softening flocs better than Stokes’ Law. Settling velocities of smaller flocs (<50 μm) could still be quite well predicted by Stokes’ Law. The variation of fractal dimensions with lime floc size in this study indicated that two mechanisms are involved in the formation of these flocs: cluster-cluster aggregation for small flocs (<50 μm) and diffusion-limited aggregation for large flocs (>50 μm). Therefore, the relationship between the floc fractal dimension and floc size appears to be determined by floc formation mechanisms.     

A review of floc strength and breakage

The main focus of the paper is to review current understanding of floc structure and strength. This has been done by reviewing current theoretical understanding of floc growth and breakage and an analysis of different techniques used for measuring floc strength. An overview has also been made of the general trends seen in floc strength analysis. The rate of floc formation is a balance between breakage and aggregation with flocs eventually reaching a steady-state size for a given shear rate. The steady-state floc size for a particular shear rate can, therefore, be a good indicator of floc strength. This has resulted in the development of a range of techniques to measure floc size at different applied shear levels using a combination of one or more of the following tools: light scattering and transmission; microscopy; photography; video and image analysis software. Floc strength may be simply quantified using the initial floc size for a given shear rate and the floc strength factor. More complex techniques have used theoretical modelling to determine whether flocs break by large-scale fragmentation or smaller-scale surface erosion effects, although this interpretation is open to debate. Impeller-based mixing, ultrasound and vibrating columns have all been used to provide a uniform, accurate and controllable dissipation of energy onto a floc suspension to determine floc strength. Other more recent techniques have used sensitive micromanipulators to measure the force required to break or compress individual flocs, although these techniques have been limited to the measurement of only a few hundred flocs. General trends emerge showing that smaller flocs tend to have greater strength than larger flocs, whilst the use of polymer seems to give increased strength to only some types of floc. Finally, a comparison of the strength of different types of floc (activated sludge flocs, organic matter flocs, sweep flocs and charge neutralised flocs) has been made highlighting differences in relative floc strength.     

Predicting the settling velocity of flocs formed in water treatment using multiple fractal dimensions

Here we introduce a distribution of floc fractal dimensions as opposed to a single fractal dimension value into the floc settling velocity model developed in earlier studies. The distribution of fractal dimensions for a single floc size was assumed to cover a range from 1.9 to 3.0. This range was selected based on the theoretically determined fractal dimensions for diffusion-limited and cluster-cluster aggregation. These two aggregation mechanisms are involved in the formation of the lime softening flocs analyzed in this study. Fractal dimensions were generated under the assumption that a floc can have any value of normally distributed fractal dimensions ranging from 1.9-3.0. A range of settling velocities for a single floc size was calculated based on the distribution of fractal dimensions. The assumption of multiple fractal dimensions for a single floc size resulted in a non-unique relationship between the floc size and the floc settling velocity, i.e., several different settling velocities were calculated for one floc size. The settling velocities calculated according to the model ranged from 0 to 10 mm/s (average 2.22 mm/s) for the majority of flocs in the size range of 1-250 μm (average 125 μm). The experimentally measured settling velocities of flocs ranged from 0.1 to 7.1 mm/s (average 2.37 mm/s) for the flocs with equivalent diameters from 10 μm to 260 μm (average 124 μm). Experimentally determined floc settling velocities were predicted well by the floc settling model incorporating distributions of floc fractal dimensions calculated based on the knowledge of the mechanisms of aggregation, i.e., cluster-cluster aggregation and diffusion-limited aggregation.     

Structure of conditioned sludge flocs

Free settling tests, small-angle light scattering, microtome-slicing techniques, and confocal laser scanning microscopy were performed to examine how the cationic flocculation or freezing and thawing affected the floc structure. The floc size, internal pore size, mass fractal dimensions determined from free-settling test or small angle light scattering test, aeral porosity, boundary fractal dimension and Sierpinski carpet fractal dimension of pore boundary from 2D slices, and the volume porosity, compactness, and the pores' box-counting fractal dimension from 3D reconstructed image, were estimated and compared. Cationic flocculation would produce large flocs with internal pores of shape resembling a long "tube" with rough surface. Freezing and thawing would produce flocs with internal pores with lower aspect ratio and a smoother boundary.     

Floc morphology and cyclic shearing recovery: comparison of alum and polyaluminum chloride coagulants

This study investigated the floc formation and re-aggregation potential for alum, polyaluminum chloride (PACl) and a blend of these coagulants. Bench-scale testing included floc morphology characterization for well-developed floc, post-shear floc, and non-settleable (filter influent) floc. Different applications of coagulants were observed to produce non-settleable floc that was morphologically different. The alum treatment had a decrease in average floc size from coagulated to non-settleable conditions, whereas the PACl and PACl/alum treatments resulted in similar sized floc between these processes. Zeta potential distribution measurements showed that the alum treatment resulted in a negative shift from coagulated to non-settleable conditions whereas the PACl and PACl/alum treatments had no significant shift. A photometric dispersion analyzer (PDA) was employed to compare the differences between coagulant treatments with respect to shear induced aggregate breakup and recovery. The PDA allowed a dynamic monitoring of initial floc aggregation and measured the degree of recovery from cyclic shearing. The degree of recovery from shearing was greatest for the PACl/alum treatment likely as a result of increased collision efficiency due to more effective charge neutralization.     

Interaction between Cryptosporidium oocysts and water treatment coagulants

The electrokinetic properties of gamma-irradiated Cryptosporidium oocysts in the presence of coagulants (ferric chloride and alum) and coagulant aids (DADMAC based cationic polyelectrolytes) have been studied. The zeta potential of the oocysts was unaffected by the addition of ferric chloride at all pH values (3-10) studied. Addition of alum resulted in reversal of the oocysts charge, which suggests that the initial stage in the coagulation process leading to floc formation proceeds via the adsorption of hydrolysed aluminium species. The cationic polyelectrolyte Magnafloc LT35 was adsorbed onto iron flocs at doses of 0.1 mg/L even against an electrostatic barrier. The cationic polyelectrolyte only adsorbed and caused charge reversal at the oocyst surface at around 0.4 mg/L, suggesting a lower affinity for this surface. These results indicate that the oocysts, unlike inorganic colloidal materials such as metal oxides, appear to possess a lower surface density of active or charged sites. The lower density of sites, combined with the rapid precipitation of iron salts, may be responsible for the lack of specific adsorption of either hydroxylated ferric species or primary iron hydroxide particles on the oocysts. Further, this suggests that a process of sweep flocculation, where oocysts are engulfed in flocs during coagulation and floc formation, is the more likely mechanism involved. By comparison, it is likely that the specific interaction of hydrolysed aluminium species with the oocysts surface would result in a stronger link at the oocyst-floc interface and that the flocculation process may initially proceed via charge neutralisation.     

Impacts of structural characteristics on activated sludge floc stability

Activated sludge samples from seven full-scale plants were investigated in order to determine the relationship between floc structure and floc stability. Floc stability was determined by shear sensitivity and floc strength. Floc structure was considered in terms of two size scales, the micro- and macrostructure. The microstructure refers to the organization of the floc components, such as the individual microorganisms. The macrostructure refers to the overall floc. The floc macrostructure was characterized by filament index, sludge volume index, size, and fractal dimension. It had a significant impact on floc stability. Large and open flocs with low fractal dimensions containing large number of filaments were more shear sensitive and had lower floc strength compared to small and dense flocs. Fluorescent in situ hybridization analysis indicated that the organization of the bacterial cells might also have an effect on the floc stability.     

Characteristics of aggregates formed by electroflocculation of a colloidal suspension

Electroflocculation (EF) is becoming recognized as an alternative process to conventional coagulation/flocculation, although both are somewhat different. The electrical current applied in EF to generate the active coagulant species creates a unique chemical/physical environment which affects coagulation mechanisms and subsequent aggregate formation. The chemical and physical characteristics of an electroflocculated kaolin suspension and the morphology/fractal dimension of the resulting aggregates were examined. An EF cell was operated in batch mode and comprised of two concentric electrodes-a stainless steel cathode (outer electrode) and an aluminum anode (inner electrode). The cell was run at constant current between 0.05 and 0.3A, velocity gradients were 0-30s(-1). The results show that the simultaneous hydrolysis occurring has a profound effect on the final pH and consequently on the coagulation mechanisms as indicated by differences in zeta potential measured. Moreover, the electrical field induced by passage of a current has an apparent effect on particle transport. A linear correlation between floc size and current was observed and lower fractal dimensions were obtained for larger floc sizes. The fractal dimensions of the flocs obtained in EF are on average lower than those reported for conventional coagulation.     

基于分形理论的混凝控制研究

依据分形理论,针对混凝过程中原水水质、水量的变化,考察了絮凝体分形维数与混凝剂投量和沉后水浊度间的变化关系。结果证实,分形维数的变化能够很好地反映絮凝程度及混凝处理效果,从而为建立以分形维数作为主控特征参数的混凝投药系统提供了依据,并通过大量的基础试验为分形维数模型控制提供了参考。     

Dewatering of alumino-humic sludge: impacts of hydroxide

The paper draws together information on factors which influence the conditioning and dewatering behaviour of an alum sludge gained from the coagulation of a low-turbidity coloured water. A principal focus is the potential impact of aluminium hydroxide on the sludge character. Background information is provided on the composition of the source floc for the domain pH 6.0-6.5 and Al>2.0mg/l. From this, there were many pointers to the presence of Al(OH)(3)(s) within the floc. A series of comparisons were made between an alum sludge and a hydroxide suspension at a concentration equivalent to the coagulant fraction within the sludge. The parameters studied included floc size, floc density, polymer adsorption and dewatering behaviour at different time-scales. In all cases, there were strong similarities in the behaviour of the two suspensions-indicating the potential impact of the hydroxide. There was also evidence of common features being displayed by both the organic fractions and the hydroxide. It was suggested that some of the behavioural features might emanate from a common fractal structure within the source floc, the fractal dimension (approximately 1) being insensitive to composition.     

Effects of chemical amendments on aquatic floc structure, settling and strength

Using a shear-cell/flow-cell combination integrated with an inverted microscope, the behaviour of Hamilton Harbour sediments was studied mixed with three different amendments: alum, chitosan (both coagulants) and a polyacrylamide (a flocculant). Samples from the shear cell were drawn into the flow cell, where floc structure and size were assessed throughout the floc formation and breakage stages using computer image analysis. Settling velocity, density and porosity were also assessed, with results suggesting that amendment addition may be an effective method for the management of high-turbidity environments, provided there are no toxicological effects. In an assessment of performance, it was found that the polyacrylamide flocculant showed the greatest promise in reducing turbidity levels as it produced the largest flocs with the highest settling velocity. Although more prone to break-up, these flocs still remained larger than those formed with alum or chitosan at the same shear. All flocs, regardless of amendment, broke up due to a fracture mechanism rather than by microscale erosion. By improving our understanding of how these amendments may influence floc properties and behaviours, more effective management tools may be developed for the remediation and control of high-turbidity aquatic environments.     

混凝剂中的铝形态对藻类混凝过程的影响

为了考察混凝剂中的铝形态对藻类混凝过程的影响,使用3种具有不同铝形态分布的混凝剂对含藻水进行了混凝试验。结果表明,硫酸铝由于具有较低含量的Alb,电中和能力较差,故需要较大的投量才能去除藻类,形成絮体;含藻水体系中的有机物主要是腐殖酸及富里酸类物质,微生物代谢产物(SMP)在硫酸铝作混凝剂时得到较好的去除,而腐殖酸及富里酸的去除率较低可能是造成硫酸铝混凝效果较差的原因;Alc(Al(30))在混凝中的作用机理主要是吸附架桥作用,可有效去除水体中的有机物,Al₁₃的主要作用机理是电中和作用,可以有效去除水体中的颗粒物;Al₁₃与Al₃₀由于具有形态的稳定性,其混凝过程受pH值的影响较小。絮体强度因子随着pH值的升高先增大后减小,Al₁₃作混凝剂时絮体恢复因子随pH值的升高先增大后减小,而其他两种混凝剂所形成絮体的恢复因子随pH值的升高而增大。