Enhanced coagulation for high alkalinity and micro-polluted water: the third way through coagulant optimization

Conventional coagulation is not an effective treatment option to remove natural organic matter (NOM) in water with high alkalinity/pH. For this type of water, enhanced coagulation is currently proposed as one of the available treatment options and is implemented by acidifying the raw water and applying increased doses of hydrolyzing coagulants. Both of these methods have some disadvantages such as increasing the corrosive tendency of water and increasing cost of treatment. In this paper, an improved version of enhanced coagulation through coagulant optimization to treat this kind of water is demonstrated. A novel coagulant, a composite polyaluminum chloride (HPAC), was developed with both the advantages of polyaluminum chloride (PACl) and the additive coagulant aids: PACl contains significant amounts of highly charged and stable polynuclear aluminum hydrolysis products, which is less affected by the pH of the raw water than traditional coagulants (alum and ferric salts); the additives can enhance both the charge neutralization and bridging abilities of PACl. HPAC exhibited 30% more efficiency than alum and ferric salts in dissolved organic carbon (DOC) removal and was very effective in turbidity removal. This result was confirmed by pilot-scale testing, where particles and organic matter were removed synergistically with HPAC as coagulant by sequential water treatment steps including pre-ozonation, coagulation, flotation and sand filtration.     

Comparison of coagulation performance and floc properties using a novel zirconium coagulant against traditional ferric and alum coagulants

Coagulation in drinking water treatment has relied upon iron (Fe) and aluminium (Al) salts throughout the last century to provide the bulk removal of contaminants from source waters containing natural organic matter (NOM). However, there is now a need for improved treatment of these waters as their quality deteriorates and water quality standards become more difficult to achieve. Alternative coagulant chemicals offer a simple and inexpensive way of doing this. In this work a novel zirconium (Zr) coagulant was compared against traditional Fe and Al coagulants. The Zr coagulant was able to provide between 46 and 150% lower dissolved organic carbon (DOC) residual in comparison to the best traditional coagulant (Fe). In addition floc properties were significantly improved with larger and stronger flocs forming when the Zr coagulant was used with the median floc sizes being 930 μm for Zr; 710 μm for Fe and 450 μm for Al. In pilot scale experiments, a similar improved NOM and particle removal was observed. The results show that when optimised for combined DOC removal and low residual turbidity, the Zr coagulant out-performed the other coagulants tested at both bench and pilot scale.     

Mechanism of natural organic matter removal by polyaluminum chloride: effect of coagulant particle size and hydrolysis kinetics

The mechanism of natural organic matter (NOM) removal by AlCl(3) and polyaluminum chloride (PACl) was investigated through bench-scale tests. The fraction distributions of NOM and residual Al after coagulation in solution, colloid and sediment were analyzed as changes of coagulant dosage and pH. The influence of NOM, coagulant dose and pH on coagulation kinetics of AlCl(3) was investigated using photometric dispersion analyzer compared with PACl. Monomeric Al species (Al(a)) shows high ability to satisfy some unsaturated coordinate bonds of NOM to facilitate particle and NOM removal, while most of the flocs formed by Al(a) are small and difficult to settle. Medium polymerized Al species (Al(b)) can destabilize particle and NOM efficiently, while some flocs formed by Al(b) are not large and not easy to precipitate as compared to those formed by colloidal or solid Al species (Al(c)). Thus, Al(c) could adsorb and remove NOM efficiently. The removal of contaminant by species of Al(a), Al(b) and Al(c) follows mechanisms of complexation, neutralization and adsorption, respectively. Unlike preformed Al(b) in PACl, in-situ-formed Al(b) can remove NOM and particle more efficiently via the mechanism of further hydrolysis and transfer into Al(c) during coagulation. While the presence of NOM would reduce Al(b) formed in-situ due to the complexation of NOM and Al(a).     

Investigating dissolved air flotation performance with cyanobacterial cells and filaments

Dissolved air flotation (DAF) performance with two different naturally occurring cyanobacterial morphologies was investigated with respect to the biomass removal efficiency, the toxin release to water and the coagulant demand by different water background natural organic matter (NOM). Coagulation (C)/Flocculation (F)/DAF bench-scale experiments (2 min coagulation at 380 s⁻¹ with polyaluminium chloride (0.5-4 mg/L Al₂O₃, the dose depending on the water NOM content); 8 min flocculation at 70 s⁻¹; 8 min DAF with 5 bar relative pressure and 8% pressurised recycle) were performed with single cells of Microcystis aeruginosa and Planktothrix rubescens filaments spiked in synthetic waters with different NOM contents (hydrophobic vs. hydrophilic NOM; moderate (2-3 mgC/L) vs. moderate-high concentration (ca. 6 mgC/L)). For both morphologies, the results show no apparent cyanobacterial damage (since the water quality did not degrade in dissolved microcystins and the removal of intracellular microcystins matched the removal of chlorophyll a) and high biomass removal efficiencies (93-99% for cells and 92-98% for filaments) provided optimal coagulant dose for chlorophyll a removal was ensured. Charge neutralisation by the polyaluminium chloride was the main coagulation mechanism of the M. aeruginosa cells and most likely also of the P. rubescens filaments. The specific coagulant demand was severely affected by NOM hydrophobicity, hydrophobic NOM (with a specific UV_254nm absorbance, SUVA, above 4 L/(m mgC)) requiring ca. the triple of hydrophilic NOM (SUVA below 3 L/(m mgC)), i.e. 0.7 vs. 0.2-0.3 mg Al₂O₃/mg DOC.     

Evaluating fluorescence and ultraviolet photometry to assess dissolved organic matter removal during coagulation–flocculation

Ultraviolet absorption at 254 nm (UV₂₅₄) and peaks (A, C and T) fluorescence intensities were evaluated to assess dissolved organic carbon (DOC) removal during coagulation–flocculation. The consistency of fluorescence data was checked to ensure that no inner filter effect, quenching or enhanced intensities affected the data. The decreases in UV₂₅₄ and peak intensities were calculated in percentage terms between raw and clarified water and compared with measured DOC removal. The results indicate that peak A, peak C, peak T and UV₂₅₄ exhibit strong linear relationships (R²: 0.91, 0.89, 0.92 and 0.99, respectively) with DOC removal, implying that these parameters are useful indicators of DOC removal.     

Enhanced coagulation in a typical North-China water treatment plant

The characteristics of typical source waters in northern China and their enhanced coagulation features were studied in this paper. Through bench scale tests, a composite coagulant (HPAC) was selected for this kind of high alkalinity and pH water. It can be 30% more efficient in organic matter (OM) removal than the traditional coagulants (AlCl(3), FeCl(3)), and polyaluminum chloride (PACl), especially more efficient in removing high SUVA, hydrophobic and high molecular weight dissolved organic matter (DOM). It is found that some DOM with low SUVA has precedence over that with high SUVA to be removed at conventional dosages in some seasons, and that the priority of DOM removal is in the same sequence for all the coagulants. DOM with high SUVA is not always more easily removed. When applying HPAC as coagulant, flotation process can remove hydrophobic OM more efficiently than sedimentation process in pilot scale tests.     

Novel ferromagnetic nanoparticle composited PACls and their coagulation characteristics

Effects of magnetic nanoparticles on inorganic coagulants and their coagulation performances were studied in the present work. The Fe₃O₄-SiO₂ core-shell particle (FSCSP) and superfine iron (SI), were compounded with polyaluminium chloride of basicity 2.0 (PACl2.0), providing magnetic PACl2.0s (MPACl2.0s). The physiochemical properties of ferromagnetic nanoparticles were investigated using transmission electron microscopy (TEM), the BET method and a zeta potentiometric analyzer. The Al species distributions of the MPACl2.0s and PACl2.0 were examined by liquid ²⁷Al NMR. Jar tests were employed to evaluate the coagulation performances. Floc properties were assessed by use of the electromotive microscope (EM) and small angle laser light scattering (SALLS). The results showed that modified layers of nanoparticles mitigated agglomeration. FSCSP had a larger specific area and pore volume than SI. The addition of ferromagnetic nanoparticles obviously increased the content of Al_un. MPACl2.0s performed better than PACl2.0 in turbidity removal and DOC removal when dosed less than 0.06 mmol/L as Al. Generally, PACl2.0 + FSCSP (50 mg/L) performed best. Large, loose and weak flocs were produced by MPACl2.0s, which were preferred for the magnetic powder recycling. A plausible structure, Al species-nanoparticles cluster, contributing to the unique properties of MPACl2.0 flocs, was proposed.     

The origin of Al(OH)3-rich and Al13-aggregate flocs composition in PACl coagulation

The composition of hydrolyzed Al species is essential for the understanding of coagulation with Al-based coagulants. Surface characteristics of flocs formed by coagulation with two distinct polyaluminum chloride (PACl) coagulants were identified. One commercial coagulant (PACl-C) with voluminous monomeric Al and colloidal Al(OH)₃ and a custom-made PACl (PACl-Al₁₃) containing high Al₁₃ content were applied to destabilize kaolin particles. The flocs formed by PACl-C and PACl-Al₁₃ at neutral and alkaline pH ranges, respectively, were observed by FE-SEM and HR-TEM. In addition, the Al composition of these flocs was characterized by XPS and HR-XRD, and the imaging of Al(OH)₃ precipitates and Al₁₃ aggregates were conducted by SEM as well as tapping mode AFM in liquid system. The observations of flocs indicate that the morphology of Al(OH)₃-rich flocs are fluffy and porous around the edge of flocs, while the Al₁₃-aggregate flocs have a glossy contour and irregular structure. Both Al(OH)₃-rich and Al₁₃-aggregate flocs do not possess well-formed crystalline structure except for the Al₁₃-like crystal exists in the Al₁₃-aggregate flocs. Among Al(OH)₃ precipitates, colloidal Al(OH)₃ is micro-scale in size, while amorphous Al(OH)₃ is nano-scale. During the formation of Al₁₃ aggregates, some coiled and clustered Al₁₃ aggregates with smoother surface were observed. The XPS study on floc surface showed that tetrahedral (Al^IV) /octahedral (Al^VI) Al ratio on the surfaces of PACl-C and PACl-Al₁₃ flocs is 1:1.6 and 1:9.9, respectively. Of the in situ formed Al₁₃, almost half of Al-hydroxide precipitates on the surface of Al(OH)₃-rich flocs possess the Al^IV center. It also found that the irregularly aggregated Al₁₃ with a similar Al₁₃ crystalline structure subsists on the surface of Al₁₃-aggregate flocs.     

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.     

Preliminary laboratory investigation of disinfection by-product precursor removal using an advanced oxidation process

Natural organic matter (NOM) is ubiquitous in surface and ground waters throughout the world. During drinking water treatment, the NOM that remains in treated water can react with chlorine to form disinfection by‐products. It has been shown that titanium dioxide photocatalysis can achieve over 96% reduction in ultraviolet (UV)₂₅₄ absorbing species such as hydrophobic NOM and over 81% reduction in dissolved organic carbon (DOC). However, an additional filtration stage is required to recover the suspended catalyst before it is suitable for municipal drinking water application. To overcome this problem, we have used immobilised catalysts prepared using chemical sol–gels, and their performance has been assessed during bench‐scale experiments. An immobilised catalyst enables in situ regeneration using UV light and subsequent reuse of the catalyst. In this research, titanium dioxide sol–gels have been used to coat substrates at a laboratory scale. Results showed that the various coatings prepared had different removal efficiencies for both DOC and UV₂₅₄ absorbance. Maximum removals were 1.336 g/m² and 89%, respectively.     

Absorbance spectroscopy-based examination of effects of coagulation on the reactivity of fractions of natural organic matter with varying apparent molecular weights

Absorbance spectra of fractions of natural organic matter (NOM) with varying apparent molecular weights (AMWs) were examined in this study. Size exclusion chromatography (SEC) was employed to obtain AMW distributions for three Australian water sources which represented low- and high-dissolved organic carbon (DOC) surface waters and a source with highly degraded NOM. These waters were coagulated with alum and other coagulants. Effects of coagulation on AMW distributions were quantified based on an absorbance slope index (ASI) calculated using NOM absorbance measured at 220, 230, 254 and 272 nm. This index can be calculated for any AMW fraction of NOM. Similarly to SUVA₂₅₄, ASI values decrease consistently in coagulated waters and are correlated with trihalomethane yields. Comparison of ASI indexes in different water sources indicates the presence of both common trends and differences indicative of NOM site-specificity.     

不同混凝剂除磷性能的对比研究

以含磷水样为研究对象,考察了不同混凝剂(聚合氯化铝、三氯化铁及三氯化铝)的除磷效果及其影响因素,同时比较了不同碱化度PAC除磷效果的差异,明确了聚合氯化铝、三氯化铁及三氯化铝的最佳投加量和最佳pH值.搅拌条件对除磷效果的影响结果表明,混合强度的增大对除磷效果有一定的提高,混合时间以60 s为宜.     

Comparison of polyaluminum silicate chloride and electrocoagulation process,in natural organic matter removal from surface water in Ghochan,Iran

Removal of natural organic matter (NOM) is one of the most important objectives of water treatment plants but reducing these pollutants either present in water as dissolved or suspended form is not as efficient as is required in conventional treatment plants. The purpose of this study was comparison performance of composite polyaluminum silicate chloride (PASiC) and electrocoagulation (EC) process by aluminum electrodes in NOM removal from raw surface water. In this study, the effects of turbidity, total organic compounds (carbons) (TOC), adsorption at a wavelength of 254 nm (UV254), chemical oxygen demand (COD), alkalinity, residual aluminum in finished water by application of EC process and PASiC were investigated. The results demonstrate that PASiC coagulant at optimum concentration of 1–5 ml/L was capable of removing TOC, COD, U.V., and turbidity from raw water by 93.77, 93.5, 63 and 95 %, respectively. In contrast, EC process, removed TOC, COD, UV and turbidity from raw water by 89, 99.75, 37 and 50%, respectively. The pilot-scale results demonstrated the significant advantage of PASiC compared to EC process in removal of NOM and turbidity form raw water. Residual aluminum in finished water was below the recommended WHO guidelines 0.2 mg/L for both processes. Finally it can be concluded that PASiC and EC process are reliable, efficient and cost-effective methods for removal of NOM from surface water.     

Return sludge employed in enhancement of color removal in the integrally industrial wastewater treatment plant

In this study, the recirculation of chemical sludge and integrated sludge were employed for enhancement of color removal in an integrally industrial wastewater treatment plant. The jar test was conducted for simulating chemical coagulation process with different coagulants, aluminum sulfate and polyaluminum chloride (PACl), after different activated sludge systems (with air or high-purity oxygen). The results showed that with sludge recirculation the process of coagulation for the color removal has up to 35% enhancement in comparison with no sludge recirculation. Meanwhile, the color removal enhancement of coagulant aluminum sulfate was approximately 2 to 3-times the color removal enhancement of coagulant PACl at the optimum ratio of return sludge. In coagulation process with influent color of 1220 true color unit (TCU), the optimum dosage of return sludge was 3010mg/L, when coagulant PACl or aluminum sulfate was employed. In coagulation process with influent color of 536 TCU, the optimum dosages of return sludge were 2340 and 4680mg/L using PACl and aluminum sulfate, respectively.     

Polyaluminum chloride with high Al30 content as removal agent for arsenic-contaminated well water

Polyaluminum chloride (PACl) is a well-established coagulant in water treatment with high removal efficiency for arsenic. A high content of Al₃₀ nanoclusters in PACl improves the removal efficiency over broader dosage and pH range. In this study we tested PACl with 75% Al₃₀ nanoclusters (PACl_Al30) for the treatment of arsenic-contaminated well water by laboratory batch experiments and field application in the geothermal area of Chalkidiki, Greece, and in the Pannonian Basin, Romania. The treatment efficiency was studied as a function of dosage and the nanoclusters’ protonation degree. Acid-base titration revealed increasing deprotonation of PACl_Al30 from pH 4.7 to the point of zero charge at pH 6.7. The most efficient removal of As(III) and As(V) coincided with optimal aggregation of the Al nanoclusters at pH 7-8, a common pH range for groundwater. The application of PACl_Al30 with an Al_tot concentration of 1-5 mM in laboratory batch experiments successfully lowered dissolved As(V) concentrations from 20 to 230 μg/L to less than 5 μg/L. Field tests confirmed laboratory results, and showed that the WHO threshold value of 10 μg/L was only slightly exceeded (10.8 μg/L) at initial concentrations as high as 2300 μg/L As(V). However, As(III) removal was less efficient (<40%), therefore oxidation will be crucial before coagulation with PACl_Al30. The presence of silica in the well water improved As(III) removal by typically 10%. This study revealed that the Al₃₀ nanoclusters are most efficient for the removal of As(V) from water resources at near-neutral pH.     

Seasonal variations in natural organic matter and its impact on coagulation in water treatment

In the past decade, a number of UK and US water utilities have been experiencing operational difficulties connected with the increased dissolved organic carbon (DOC) levels during the autumn and winter periods. This has been observed as an increase in the production of disinfection-by-products (DBP), and a greater coagulant demand. Resin adsorption techniques were used to fractionate raw water and investigate the variation in surface charge and coagulant-humic interactions over a 36-month period. A change in the natural organic matter (NOM) composition throughout the year was observed, with the fulvic acid fraction (FAF) increasing from 36% in September to 61% in November. However, a reduction in treatment performance is not simply due to an increase in DOC concentrations (from 4.3 to 14.5 mg L-1), but also a change in the charge density of the NOM. It was found that hydrophilic NOM fractions possess negligible charge density (<0.06 meq g-1DOC), and it is the hydrophobic NOM fractions, FAF in particular, that exert the greater dominance on coagulation control. The hydrophilic NOM fractions are less amenable to removal through conventional coagulation with metal salts, and are therefore likely to indicate the DOC residual remaining after treatment. Understanding the seasonal changes in NOM composition and character and their reactivity with coagulants should lead to a better optimisation of the coagulation process and a more consistent water quality.     

Effects of pre-ozonation on the removal of THM precursors by coagulation

Pre-ozonation in combination with enhanced coagulation was used to remove NOM from lake water as to control the formation of disinfection by-products, DBPs. The effect of the hydrophobicity/hydrophilicity nature of NOM on the performance of the combined pre-ozonation and coagulation process was studied. The hydrophilicity/hydrophobicity property of NOM was characterized in terms of mass distribution of the phydrophilic and the hydrophobilic fractions of NOM. The optimal condition for the combined pre-ozonation-coagulation was established: pH = ca. 9.0 and ozone dose = 0.45 mg-O₃/mg-DOC. Under the optimal condition, it was able to achieve ∼ 60% of THMFP removal. In terms of THMPF, results also indicated that the distribution between the hydrophilic and the hydrophobic fractions of NOM was 57.3 and 98.7 µg-THMFP/mg-DOC, respectively. Ozonation alters the structures and characteristics of NOM thereby affecting the coagulation effectiveness. Pre-ozonation was effective in removing the hydrophobic NOM, with a decrease of THMFP by ∼ 20% versus ∼ 10% for the hydrophilic fraction. The dosage of coagulant also governed DOC removal. The removal of hydrophobic and hydrophilic NOM were in the range of 27-41 and 2.5-22.7%, respectively at alum dosage of 0.41-1.65 (in Al/DOC) and 0.41-1.65 (in Al/DOC) and ozone dose of 0.58-2.93, mg/mg respectively. The adsorption characteristics of the hydrophilic and the hydrophobic fractions of NOM on aluminum hydroxide (from coagulant alum) were studied. Results indicated that the modified Langmuir isotherm of competitive adsorption was able to describe the adsorption of NOM onto hydrous aluminum hydroxide formed during alum coagulation of the lake waters.     

Preparation, characterisation and application of novel composite coagulants for surface water treatment

The development of the Inorganic Polymeric Flocculants (IPFs) can be regarded as significant progress in the coagulation-flocculation field. However, the IPFs may be less efficient when compared to the organic polymers (polyelectrolytes) regarding their aggregation abilities. In order to increase further their flocculation efficiency, the combination of a cationic IPF (polyaluminium chloride, PACl) and an anionic polyelectrolyte in one unique reagent is proposed in this study. During this investigation, several composite coagulants were prepared, which differ on the preparation method and polyelectrolyte content. Major typical properties of the prepared coagulants were examined, i.e. pH, turbidity, conductivity, Al species distribution. The composition, structure and morphology of the composite coagulants were studied in detail as well, with the application of FT-IR, XRD and SEM techniques. Their coagulation performance was investigated in the treatment of a model water sample (simulating surface water) and compared to the respective coagulation performance of PACl and the polyelectrolyte applied as separated reagents (common procedure). Finally, the kinetics of coagulation was studied with application of the Photometric Dispersion Analyser (PDA). From the results, it was revealed that interactions take place between the Al species and the polyelectrolyte molecules, which probably lead to the formation of new, “composite” species. The properties of the composite coagulants are significantly affected by these interactions, leading to more effective water treatment. The simplification of the overall treatment process and the cost-effectiveness are considered as the major advantages of the composite coagulants.     

Pre-coagulation for microfiltration of an upland surface water

The effect of different coagulants on cake formation and hydraulic resistance in membrane filtration of strongly coloured (SUVA> or =4.8) upland surface water has been studied at bench-scale under constant pressure conditions. Coagulants used were aluminium sulphate, polyaluminium chloride, ferric chloride and ferric sulphate. Optimisation of coagulation parameters was carried by conventional jar testing. The R'c (specific cake resistance in m(-2)) values were determined for all coagulants over a range of coagulant doses and slow mixing flocculation periods. Experiments indicated slight differences in cake formation trends between ferric- and aluminium-based coagulants and chloride and sulphate counterions, but that the range of measured R'c values was small (0.9 and 2.6 x 10(18) m(-2)) over the range of doses studied. Greater than 99% UV(254) removal was achieved with every coagulant, whereas dissolved organic carbon (DOC) removal ranged from 78% to 88%. Optimisation of the pre-coagulation-membrane filtration process suggests ferric chloride to be slightly superior for the feedwater matrix studied on the basis of DOC removal, whereas ferric sulphate gave slightly lower filter cake specific resistance values.     

Evaluations of the TiO2/simulated solar UV degradations of XAD fractions of natural organic matter from a bog lake using size-exclusion chromatography

This work reports on the changes in compositions of humic acids (HAs) and fulvic acids (FAs) during photocatalytic degradation. The HAs and FAs were obtained from the XAD-resin fractionation of natural-organic matter (NOM) from a bog lake (Lake Hohloh, Black Forest, Germany). Degussa P-25 titanium dioxide (TiO₂) in a suspension and a solar UV simulator (batch reactor) were used in the experiments. The photocatalytic degradation of the HAs and FAs were monitored using size-exclusion chromatography (SEC) equipped with dissolved organic carbon (DOC) and ultraviolet (UV₂₅₄) detection (SEC-DOC and SEC-UV₂₅₄) and UV–Vis spectrophotometry. The evolutions of the photocatalytic degradations of the HA and FA fractions were selective. The photocatalytic degradation started with the degradations of high molecular weight compounds with relatively high UV₂₅₄ absorbances in the HA and FA fractions to yield low molecular weight compounds showing less specific UV₂₅₄ absorbances. Observance of the same tendency for the original NOM from Lake Hohloh indicates that these XAD-fractions still having complex compound mixtures. However, the larger molecular weight fractions of the FAs showed higher preferential adsorptions onto TiO₂, which caused their faster degradation rates. Furthermore, FAs showed a greater reduction of the total THM formation potential (TTHMFP) and the organic halogen compounds adsorbable on activated carbon formation potential (AOXFP), in comparison with the HAs.