Groundwater arsenic removal by coagulation using ferric(III) sulfate and polyferric sulfate: A comparative and mechanistic study

Elevated arsenic (As) in groundwater poses a great threat to human health. Coagulation using mono-and poly-Fe salts is becoming one of the most cost-effective processes for groundwater As removal. However, a limitation comes from insufficient understanding of the As removal mechanism from groundwater matrices in the coagulation process, which is critical for groundwater treatment and residual solid disposal. Here, we overcame this hurdle by utilizing microscopic techniques to explore molecular As surface complexes on the freshly formed Fe flocs and compared ferric(III) sulfate (FS) and polyferric sulfate (PFS) performance, and finally provided a practical solution in As-geogenic areas. FS and PFS exhibited a similar As removal efficiency in coagulation and coagulation/filtration in a two-bucket system using 5 mg/L Ca(ClO)₂. By using the two-bucket system combining coagulation and sand filtration, 500 L of As-safe water (<10 μg/L) was achieved during five treatment cycles by washing the sand layer after each cycle. Fe k-edge X-ray absorption near-edge structure (XANES) and As k-edge extended X-ray absorption fine structure (EXAFS) analysis of the solid residue indicated that As formed a bidentate binuclear complex on ferrihydrite, with no observation of scorodite or poorly-crystalline ferric arsenate. Such a stable surface complex is beneficial for As immobilization in the solid residue, as confirmed by the achievement of much lower leachate As (0.9 μg/L-0.487 mg/L) than the US EPA regulatory limit (5 mg/L). Finally, PFS is superior to FS because of its lower dose, much lower solid residue, and lower cost for As-safe drinking water.     

Characterization of Fe5(AsO3)3Cl2(OH)4·5H2O, a new ferric arsenite hydroxychloride precipitated from FeCl3–As2O3–HCl solutions relevant to arsenic immobilization

Tooeleite(Fe6(As03)4 SO4(OH)4·4 H_2 O) is widely precipitated for direct As(III) removal from sulfate-rich industrial effluents.However,whether or not Fe(III)-As(III)-Cl(-I) precipitate is produced in chloridizing leaching media for As immobilization is almost unknown.This work founded the existence of ferric arsenite(hydroxy)chloride as a new mineral for As(III)removal.Its chemical composition and solid characterization were subsequently studied by using scanning electron microscope with an energy dispersive spectrometer(SEM-EDS),X-ray diffraction(XRD),infrared(FT-IR),Raman spectroscopy and thermogravimetric(TG)curve.The results showed the formation of a yellow precipitate after 3-days reaction of Fe(III)/As(III) with molar ratio≈1.7 in chloride solution at pH 2.3 neutralized with NaOH.Compared with tooeleite,chemical analysis and solid characterization indicated that Cl(-I)replaces S04(-II) producing ferric arsenite hydroxychloride with formula Fe5(As03)_3-Cl_2(OH)4·5 H_2 O.This new plate shaped solid showed better crytallinity than tooeleite,although it has similar morphology and characteristic bands to tooeleite.The FT-IR bands at 628,964 cm-1 and the Raman bands at 448,610,961 cm-1 were assigned to Fe-O or As(Ⅲ)-O-Fe or As(Ⅲ)-O bending/stretching vibration,indicating that both arsenite and chloride substituted for the position of sulfate for ferric arsenite hydro xychloride produced due to the lack of the SO_4~(2-) vibrations.Cl-(I) also contributed to increase As removal efficiency in aqueous sulfate media under acidic pH conditions via the probable formation of sulfatechloride ferric arsenite.     

Influence of coagulation mechanisms and floc formation on filterability

Minimizing particles in water is a key goal for improving drinking water quality and safety.The media filtration process,as the last step of the solid–liquid separation process,is largely influenced by the characteristics of flocs,which are formed and controlled within the coagulation process.In a laboratory-based study,the impacts of the physical characteristics of flocs formed using aluminum sulfate on the filtration treatment of two comparative water samples were investigated using a photometric dispersion analyzer and a filterability apparatus.In general,the optimum dosage for maximizing filterability was higher than that for minimizing turbidity under neutral p H conditions.For a monomeric aluminum-based coagulant,the charge neutralization mechanism produced better floc characteristics,including floc growth speed and size,than the sweep flocculation mechanism.In addition,the charge neutralization mechanism showed better performance compared to sweep flocculation in terms of DOC removal and floc filterability improvement for both waters,and showed superiority in turbidity removal only when the raw water had high turbidity.For the different mechanisms,the ways that floc characteristics impacted on floc filterability also differed.The low variation in floc size distribution obtained under the charge neutralization mechanism resulted in the flocs being amenable to removal by filtration processes.For the sweep flocculation mechanism,increasing the floc size improved the settling ability of flocs,resulting in higher filter efficiency.     

Interference of iron as a coagulant on MIB removal by powdered activated carbon adsorption for low turbidity waters

Powered activated carbon (PAC) is widely used in water treatment plants to minimize odors in drinking water. This study investigated the removal of 2-methylisoborneol (MIB) by PAC adsorption, combined with coagulation using iron as a coagulant. The adsorption and coagulation process were studied through different case scenarios of jar tests. The analysis evaluated the effect of PAC dosing in the liquid phase immediately before or after the coagulant addition. Ferric sulphate was used as the coagulant with dosages from 10 to 30 mg/L, and PAC dosages varied from 10 to 40 mg/L. The highest MIB removal efficiency (about 70%) was achieved without the coagulant addition and with the highest PAC dosage (40 mg/L). Lower MIB removal efficiencies were observed in the presence of coagulant, showing a clear interference of the iron precipitate or coagulant in the adsorption process. The degree of interference of the coagulation process in the MIB removal was proportional to the ratio of ferric hydroxide mass to the PAC mass. For both cases of PAC dosing, upstream and downstream of the coagulant injection point, the MIB removal efficiency was similar. However, MIB removal efficiency was 15% lower when compared with experiments without the coagulant application. This interference in the MIB adsorption occurs potentially because the coagulant coats the surface of the carbon and interferes with the MIB coming in contact with the carbon’s surface and pores. This constraint requires an increase of the PAC dosage to provide the same efficiency observed without coagulation.     

Characterization of cake layer structure on the microfiltration membrane permeability by iron pre-coagulation

A cake layer is formed by coagulation aggregates under certain transmembrane pressure in the coagulation-microfiltration (MF) process. The characteristics of humic acid aggregates coagulated by different iron-based coagulants, such as charge, size, fractal dimension and compressibility, have an effect on the cake layer structure. At the optimum iron dose of 0.6 to 0.8 mmol/L for ferric chloride (FC) and polymer ferric sulfate (PFS) pre-coagulation, at the point of charge neutralization for near zero zeta potential, the aggregate particles produced possess the greatest size and highest fractal dimension, which contributes to the cake layer being most loose with high porosity and low compressibility. Thus the membrane filterability is better. At a low or high iron dose of FC and PFS, a high negative or positive zeta potential with high charge repulsion results in so many small aggregate particles and low fractal dimension that the cake layer is compact with low porosity and high compressibility. Therefore the membrane fouling is accelerated and MF permeability becomes worse. The variation of cake layer structure as measured by scanning electric microscopy corresponds with the fact that the smaller the coagulation flocs size and fractal dimension are, the lower the porosity and the tighter the cake layer conformation. This also explains the MF membrane flux variation visually and accurately.     

The simultaneous removal of ammonium and manganese from surface water by MeOx: Side effect of ammonium presence on manganese removal

Manganese and ammonium pollution in surface water sources has become a serious issue.In this study, a pilot-scale filtration system was used to investigate the effect of ammonium on manganese removal during the simultaneous removal of ammonium and manganese from surface water using a manganese co-oxide filter film(MeO_x ). The results showed that the manganese removal efficiency of MeO_x in the absence of ammonium was high and stable, and the removal efficiency could reach 70% even at 5.5 °C. When the influent ammonium concentration was lower than 0.7 mg/L, ammonium and manganese could be removed simultaneously. However, at an ammonium concentration of 1.5 mg/L, the manganese removal efficiency of the filter gradually decreased with time(from 96% to 46.20%). Nevertheless, there was no impact of manganese on ammonium removal. The mechanism by which ammonium negatively affected manganese removal was investigated, demonstrating that ammonium affected manganese removal mainly through two possible mechanisms. On one hand, the decreased p H caused by ammonium oxidation was unfavorable for the oxidation of manganese by MeO_x ; on the other hand, the presence of ammonium slowed the growth of new MeO_x and retarded the increase in the specific surface area of the Me Ox-coated sand, and induced changes in the morphology and crystal structure of Me Ox. Consequently, the manganese removal efficiency of the filter decreased when ammonium was present in the inlet water.     

Algal removal from cyanobacteria-rich waters by preoxidation-assisted coagulation–flotation: Effect of algogenic organic matter release on algal removal and trihalomethane formation

The cyanobacteria-bloom in raw waters frequently causes an unpredictable chemical dosing of preoxidation and coagulation for an effective removal of algal cells in water treatment plants. This study investigated the effects of preoxidation with NaOCl and ClO_2 on the coagulation-flotation effectiveness in the removal of two commonly blooming cyanobacteria species, Microcystis aeruginosa(MA) and Cylindrospermopsis raciborskii(CR), and their corresponding trihalomethane(THM) formation potential. The results showed that dual dosing with NaOCl plus ClO_2 was more effective in enhancing the deformation of cyanobacterial cells compared to single dosing with Na OCl, especially for CR-rich water.Both preoxidation approaches for CR-rich water effectively reduced the CR cell count with less remained dissolved organic carbon(DOC), which benefited subsequent coagulation–flotation. However, preoxidation led to an adverse release of algogenic organic matter(AOM) in the case of MA-rich water. The release of AOM resulted in a poor removal in MA cells and a large amount of THM formation after oxidation-assisted coagulation-flotation process. The reduction in THM formation potential of CR-rich waters is responsible for effective algae and DOC removal by alum coagulation. It is concluded that the species-specific characteristic of cyanobacteria and their AOM released during chlorination significantly influences the performance of coagulation–flotation for AOM removal and corresponding THM formation.     

Fast and efficient aqueous arsenic removal by functionalized MIL-100(Fe)/rGO/δ-MnO2 ternary composites: Adsorption performance and mechanism

Because of its significant toxicological effects on the environment and human health,arsenic(As) is a major global issue.In this study,an Fe-based metal-organic framework(MOF)(Materials of Institut Lavoisier:MIL-100(Fe)) which was impregnated with reduced graphene oxide(rGO) by using a simple hydrothermal method and coated with birnessitetype manganese oxide(δ-MnO_2) using the one-pot reaction process(MIL-100(Fe)/rGO/δ-MnO_2 nanocomposites) was synthesized and applied successfully in As removal.The removal efficiency was rapid,the equilibrium was achieved in 40 min and 120 min for As(Ⅲ) and As(Ⅴ),respectively,at a level of 5 mg/L.The maximum adsorption capacities of As(Ⅲ) and As(Ⅴ) at pH 2 were 192.67 mg/g and 162.07 mg/g,respectively.The adsorbent revealed high stability in pH range 2-9 and saturated adsorbent can be fully regenerated at least five runs.The adsorption process can be described by the pseudo-second-order kinetic model and Langmuir monolayer adsorption.The adsorption mechanisms consisted of electrostatic interaction,oxidation and inner sphere surface complexation.     

The impact of preozonation on the coagulation of cellular organic matter produced by Microcystis aeruginosa and its toxin degradation

Ozonation pretreatment is typically implemented to improve algal cell coagulation. However, knowledge on the effect of ozonation on the characteristics and coagulation of associated algal organic matter, particularly cellular organic matter (COM), which is extensively released during algal bloom decay, is limited. Hence, this study aimed to elucidate the impact of ozonation applied before the coagulation of dissolved COM from the cyanobacteria Microcystis aeruginosa. Additionally, the degradation of microcystins (MCs) naturally present in the COM matrix was investigated. A range of ozone doses (0.1–1.0 mg O₃/mg of dissolved organic carbon – DOC) and ozonation pH values (pH 5, 7 and 9) were tested, while aluminium and ferric sulphate coagulants were used for subsequent coagulation. Despite negligible COM removal, ozonation itself eliminated MCs, and a lower ozone dose was required when performing ozonation at acidic or neutral pH (0.4 mg O₃/mg DOC at pH 5 and 7 compared to 0.8 mg O₃/mg DOC at pH 9). Enhanced MC degradation and a similar pattern of pH dependence were observed after preozonation-coagulation, whereas coagulation alone did not sufficiently remove MCs. In contrast to the benefits of MC depletion, preozonation using ≥ 0.4 mg O₃/mg DOC decreased the coagulation efficiency (from 42%/48% to 28%–38%/41%–44% using Al/Fe-based coagulants), which was more severe with increasing ozone dosage. Coagulation was also influenced by the preozonation pH, where pH 9 caused the lowest reduction in COM removal. The results indicate that ozonation efficiently removes MCs, but its employment before COM coagulation is disputable due to the deterioration of coagulation.     

Antimony smelting process generating solid wastes and dust：Characterization and leaching behaviors

A large amount of solid waste has been produced by the antimony smelting process in the＂World Capital of Antimony＂, Xikuangshan area in China. This study comprehensively investigated the physical and chemical characteristics of the various solid wastes, as well as the leaching behavior of the solid wastes, which included water-quenched slag,arsenic-alkali residue, desulfurized slag and blast furnace dust. These four types of waste were enriched in a variety of heavy metals and metalloids and more specifically with As and Sb levels up to 8.6 × 104 and 3.16 × 105mg/kg, respectively, in arsenic-alkali residue. For desulfurized slag and water-quenched slag, the leaching concentration of Sb significantly exceeded the acceptable limits during the leaching tests using the toxicity characteristic leaching procedure and the synthetic precipitation leaching procedure. In addition, As leaching in arsenic-alkali residue was extraordinarily hazardous, being three orders of magnitude higher than the regulatory level of As. According to the results of the extraction tests, all the tested wastes were classified as hazardous waste.     

Influence of the structure and composition of Fe–Mn binary oxides on rGO on As(Ⅲ) removal from aquifers

Fe–Mn binary oxide(FMBO) possesses high efficiency for As(Ⅲ) abatement based on the good adsorption affinity of iron oxide and the oxidizing capacity of Mn(Ⅳ), and the composition and structure of FMBO play important roles in this process.To compare the removal performance and determine the optimum formula for FMBO, magnetic graphene oxide(MRGO)–FMBO and MRGO–MnO_2 were synthesized with MRGO as a carrier to improve the dispersity of the adsorbents in aquifers and achieve magnetic recycling.Results indicated that MRGO–FMBO had higher As(Ⅲ) removal than that of MRGO–MnO_2,although the ratios of Fe and Mn were similar, because the binary oxide of Fe and Mn facilitated electron transfer from Mn(Ⅳ) to As(Ⅲ), while the separation of Mn and Fe on MRGO–MnO_2 restricted the process.The optimal stoichiometry x for MRGO–FMBO(Mn_xFe_(3-x)O_4) was 0.46, and an extraordinary adsorption capacity of 24.38 mg/g for As(Ⅲ) was achieved.MRGO–FMBO showed stable dispersive properties in aquifers, and exhibited excellent practicability and reusability, with a saturation magnetization of 7.6 emu/g and high conservation of magnetic properties after 5 cycles of regeneration and reuse.In addition, the presence of coexisting ions would not restrict the practical application of MRGO–FMBO in groundwater remediation.The redox reactions of As(Ⅲ) and Mn(Ⅳ) on MRGO–FMBO were also described.The deprotonated aqueous As(Ⅲ) on the surface of MRGO–FMBO transferred electrons to Mn(Ⅳ), and the formed As(Ⅴ) oxyanions were bound to ferric oxide as inner-sphere complexes by coordinating their "–OH" groups with Mn(Ⅳ)oxides at the surface of MRGO–FMBO.This work could provide new insights into highperformance removal of As(Ⅲ) in aquifers.     

A novel colorimetric method for field arsenic speciation analysis

Accurate on-site determination of arsenic (As) concentration as well as its speciation presents a great environmental challenge especially to developing countries. To meet the need of routine field monitoring, we developed a rapid colorimetric method with a wide dynamic detection range and high precision. The novel application of KMnO₄ and CH₄N₂S as effective As(Ⅲ) oxidant and As(V) reductant, respectively, in the formation of molybdenum blue complexes enabled the differentiation of As(Ⅲ) and As(V). The detection limit of the method was 8 μg/L with a linear range (R² = 0.998) of four orders of magnitude in total As concentrations. The As speciation in groundwater samples determined with the colorimetric method in the field were consistent with the results using the high performance liquid chromatography atomic fluorescence spectrometry, as evidenced by a linear correlation in paired analysis with a slope of 0.9990-0.9997 (p < 0.0001, n = 28). The recovery of 96%-116% for total As, 85%-122% for As(Ⅲ), and 88%-127% for As(V) were achieved for groundwater samples with a total As concentration range 100-800 μg/L. The colorimetric result showed that 3.61 g/L As(Ⅲ) existed as the only As species in a real industrial wastewater, which was in good agreement with the HPLC-AFS result of 3.56 g/L As(Ⅲ). No interference with the color development was observed in the presence of sulfate, phosphate, silicate, humic acid, and heavy metals from complex water matrix. This accurate, sensitive, and easy-to-use method is especially suitable for field As determination.     

Influence of COM-peptides/proteins on the properties of flocs formed at different shear rates

Coagulation followed by floc separation is a key process for the removal of algal organic matter(AOM) in water treatment. Besides optimizing coagulation parameters,knowledge of the properties of AOM-flocs is essential to maximizing AOM removal.However, the impact of AOM on the floc properties remains unclear. This study investigated how peptides/proteins derived from the cellular organic matter(COM) of the cyanobacterium Microcystis aeruginosa influenced the size, structure, and shape of flocs formed at different shear rates(G). Flocs formed by kaolinite, COM-peptides/proteins and a mixture of the same were studied, and the effect of intermolecular interactions between floc components on floc properties was assessed. The coagulation experiments were performed in a Taylor–Couette reactor, with aluminum(Al) or ferric sulphate(Fe) utilized as coagulants. Image analysis was performed to gauge floc size and obtain data on fractal dimension. It was found that floc properties were affected by the presence of the COM-peptides/proteins and the coagulant used. COM-peptides/proteins increased floc size and porosity and widened floc size distributions. The Fe coagulant produced larger and less compact flocs than Al coagulant. Moreover, the decrease in floc size that occurred in parallel with increase in shear rate was not smooth in progress. A rapid change for the kaolinite-coagulant suspension and two rapid changes for the suspensions containing COM were observed. These were attributed to various intermolecular interactions between floc components participating in coagulation at different G. Based on the results obtained, shear rates suitable for efficient separation of flocs containing COM were suggested.     

Surface clogging process modeling of suspended solids during urban stormwater aquifer recharge

Aquifer recharge,which uses urban stormwater,is an effective technique to control the negative effects of groundwater overexploitation,while clogging problems in infiltration systems remain the key restricting factor in broadening its practice.Quantitative understanding of the clogging process is still very poor.A laboratory study was conducted to understand surface physical clogging processes,with the primary aim of developing a model for predicting suspended solid clogging processes before aquifer recharge projects start.The experiments investigated the clogging characteristics of different suspended solid sizes in recharge water by using a series of one-dimensional fine quartz sand columns.The results showed that the smaller the suspended particles in recharge water,the farther the distance of movement and the larger the scope of clogging in porous media.Clogging extents in fine sand were 1 cm,for suspended particle size ranging from 0.075 to 0.0385 mm,and 2 cm,for particles less than 0.0385 mm.In addition,clogging development occurred more rapidly for smaller suspended solid particles.It took 48,42,and 36 hr respectively,for large-,medium-,and small-sized particles to reach pre-determined clogging standards.An empirical formula and iteration model for the surface clogging evolution process were derived.The verification results obtained from stormwater recharge into fine sand demonstrated that the model could reflect the real laws of the surface clogging process.     

Enhanced remediation of Cr（Ⅵ）-contaminated groundwater by coupling electrokinetics with ZVI/Fe3O4/AC-based permeable reactive barrier

Although widely used in permeation reaction barrier（PRB） for strengthening the removal of various heavy metals, zero-valent iron（ZVI） is limited by various inherent drawbacks, such as easy passivation and poor electron transfer. As a solution, a synergistic system with PRB and electrokinetics（PRB-EK） was established and applied for the efficient removal of Cr（Ⅵ）-contaminated groundwater. As the filling material of PRB, ZVI/Fe₃O₄/activated carbon（ZVI/Fe₃O₄     

Efficacy of two chemical coagulants and three different filtration media on removal of Aspergillus flavus from surface water

Aquatic fungi are common in various aqueous environments and play potentially crucial roles in nutrient and carbon cycling as well as interacting with other organisms. Species of Aspergillus are the most common fungi that occur in water. The present study was undertaken to elucidate the efficacy of two coagulants, aluminum sulfate and ferric chloride, used at different concentrations to treat drinking water, in removing Aspergillusflavus, as well as testing three different filtration media： sand, activated carbon, and ceramic granules, for their removal of fungi from water. The results revealed that both coagulants were effective in removing fungi and decreasing the turbidity of drinking water, and turbidity decreased with increasing coagulant concentration. Also, at the highest concentration of the coagulants, A. flavus was decreased by 99.6% in the treated water. Among ceramic granules, activated carbon, and sand used as media for water filtration, the sand and activated carbon filters were more effective in removing A.flavus than ceramic granules while simultaneously decreasing the turbidity levels in the test water samples. Post-treatment total organic carbon （TOC） and total nitrogen （TN） concentrations in the experimental water did not decrease; on the contrary, TN concentrations increased with the increasing dosage of coagulants. The filtration process had no effect in reducing TOC and TN in tested water.     

Preparation and evaluation of Zr-β-FeOOH for efficient arsenic removal

A Zr-β-FeOOH adsorbent for both As(V) and As(III) removal was prepared by a chemical co-precipitation method.Compared with β-FeOOH,the addition of Zr enhanced the adsorption capacities for As(V) and As(III),especially As(III).The maximum adsorption capacities for As(III) and As(V) were 120 and 60mg/g respectively at pH 7.0,much higher than for many reported adsorbents.The adsorption data accorded with Freundlich isotherms.At neutral pH,for As(V),adsorption equilibrium was approached after 3 hr,while for As(III),adsorption equilibrium was approached after 5 hr.Kinetic data fitted well to the pseudo second-order reaction model.As(V) elimination was favored at acidic pH,whereas the adsorption of As(III) by Zr-β-FeOOH was found to be effective over a wide pH range of 4-10.Competitive anions hindered the adsorption according to the sequence:phosphate > silicate > bicarbonate > sulfate > nitrate,while Ca2+ and Mg2+ increased the removal of As(III) and As(V) slightly.The high adsorption capability and good performance in other aspects make Zr-β-FeOOH a potentially attractive adsorbent for the removal of both As(III) and As(V) from water.     

Fluoride removal by Al, Ti, and Fe hydroxides and coexisting ion effect

Batch experiments were conducted to evaluate fluoride removal by Al,Fe,and Ti-based coagulants and adsorbents,as well as the effects of coexisting ions and formation of aluminum–fluoride complexes on fluoride removal by co-precipitation with alum(Al_2(SO_4)_3·18H_2O).Aluminum sulfate was more efficient than the other coagulants for fluoride removal in the pH range between 6 and 8.Nano-crystalline TiO_2 was more effective for fluoride removal than Al and Fe hydroxides in a pH range of 3–5.Coexisting anions in water decreased the removal of fluoride in the order:phosphate(2.5 mg/L) arsenate(0.1 mg/L) bicarbonate(200 mg/L) sulfate(100 mg/L) = nitrate(100 mg/L) silicate(10 mg/L) at a pH of 6.0.The effect of silicate became more significant at pH 7.0.Calcium and magnesium improved the removal of fluoride.Zeta-potential measurements determined that the adsorption of fluoride shifted the PZC of Al(OH)_3 precipitates from 8.9 to 8.4,indicating the chemical adsorption of fluoride at the surface.The presence of fluoride in solution significantly increased the soluble aluminum concentration at pH 6.5.A Visual MINTEQ modeling study indicated that the increased aluminum solubility was caused by the formation of AlF~(2+),AlF~(+2),and AlF_3complexes.The AlF_x complexes decreased the removal of fluoride during co-precipitation with aluminum sulfate.     

Effects of pre-ozonation on organic matter removal by coagulation with IPF-PACI

Ozone plays an important role as a disinfectant and oxidant in potable water treatment practice and is increasingly being used as a pre-oxidant before coagulation. The purpose of this study is to obtain insight into the mechanisms that are operative in pre-ozonized coagulation. Effects ofpre-ozonation on organic matter removal during coagulation with IPF-PAC1 were investigated by using PDA （photometric disperse analysis）, apparent molecular weight distribution and chemical fractionation. The dynamic formation of flocs during coagulation process was detected. Changes of aquatic organic matter （AOM） structure resulted from the influence of pre-ozonation were evaluated. Results show that dosage of O3 and characteristics of AOM are two of the major factors influencing the performance of O3 on coagulation. No significant coagulation-aid effect of O3 was observed for all experiments using either A1C13 or PAC1. On the contrary, with the application of pre-ozonation, the coagulation efficiency of A1C13 was significantly deteriorated, reflected by the retardation of floc formation, and the removal decreases of turbidity, DOC, and UV254. However, if PACl was used instead of AlCl3, the adverse effects of pre-ozonation were mitigated obviously, particularly when the O3 dosage was less than 0.69 （mg O3/mg TOC）. The difference between removals of UV254, and DOC indicated that pre-ozonation greatly changed the molecular structure of AOM, but its capability of mineralization was not remarkable. Only 5% or so DOC was removed by pre-ozonation at 0.6--0.8 mg/L alone. Fractionation results showed that the organic products of pre-ozonation exhibited lower molecular weight and more hydrophilicity, which impaired the removal of DOC in the following coagulation process.     

Optimisation of chemical purification conditions for direct application of solid metal salt coagulants: Treatment of peatland-derived diffuse runoff

The drainage of peatland areas for peat extraction,agriculture or bioenergy requires affordable,simple and reliable treatment methods that can purify waters rich in particulates and dissolved organic carbon.This work focused on the optimisation of chemical purification process for the direct dosage of solid metal salt coagulants.It investigated process requirements of solid coagulants and the influence of water quality,temperature and process parameters on their performance.This is the first attempt to provide information on specific process requirements of solid coagulants.Three solid inorganic coagulants were evaluated:aluminium sulphate,ferric sulphate and ferric aluminium sulphate.Pre-dissolved aluminium and ferric sulphate were also tested with the objective of identifying the effects of in-line coagulant dissolution on purification performance.It was determined that the pre-dissolution of the coagulants had a significant effect on coagulant performance and process requirements.Highest purification levels achieved by solid coagulants,even at 30% higher dosages,were generally lower(5%-30%) than those achieved by pre-dissolved coagulants.Furthermore,the mixing requirements of coagulants pre-dissolved prior to addition differed substantially from those of solid coagulants.The pH of the water samples being purified had a major influence on coagulant dosage and purification efficiency.Ferric sulphate(70 mg/L) was found to be the best performing solid coagulant achieving the following load removals:suspended solids(59%-88%),total organic carbon(56%-62%),total phosphorus(87%-90%),phosphate phosphorus(85%-92%) and total nitrogen(33%-44%).The results show that the use of solid coagulants is a viable option for the treatment of peatland-derived runoff water if solid coagulant-specific process requirements,such as mixing and settling time,are considered.