United States Environmental Protection Agency Risk Reduction Engineering Laboratory Cincinnati OH 45268 Research and Development EPA/600/S2-89/032 Feb. 1990 James K. Edzwald and James P, Maliey, Jr. The goal of this research was 'to investigate dissolved air flotation (DAF) as a drinking wafer treatment method. Several different water types were examined; low turbidity waters, waters containing aquatic humio substances, and waters with algae. The study design Included synthetic waters so that raw water quality char- acteristics could be controlled and natural waters collected from three water supplies. Flotation studies were conducted using a bench-seal® sys- tem of four parallel units. The study showed that flotation performance depends on raw water quality, prelreatment, bubble size, and bubble volume concentration and'that DAF is "effective in treating water supplies containing humic sub- stances or natural color arid supplies with algae. To remove particles, the particles must first be destabilized with coagulants. A short flocculatlon period ahead of flotation may be beneficial; however, long flocculalion times are not necessary. That DAF is an efficient process is due, in part, to the small bubble size produced by the process (bubble diameters of 10 to 100 pm). The bubble volume con- centration, a design and operational parameter, is controlled by the sstu- rator pressure and recycle ratio. Typica! values of 70 pslg and 8% recycle produced bubble volume concentrations in this research of 4600 ppm. Residual turbidities were significantly lower for DAF than for conventional treatment for all raw water systems, particularly at colder water temperatures. For water syp- piies containing humic substances, there was no significant difference between DAF and conventional treatment In the removals of U¥ absorbance, true color, DOC, and dissolved organic halkte precursors (THM and TOX). The removal of dissolved organic matter depends on coagulant chemistry (i.e., removing the dissolved material from solution Into floe particles) and not on the solid/liquid separation process. This Project Summary was devel- oped by EPA's Risk Reduction Engi- neering Laboratory, Cincinnati, OH, to announce key findings of the research project that is fully documented in a separate report of the same tills (see Project Report ordering Information at back). Introduction • In Europe, DAF is an alternative' clari- fication process to sedimentation in drinking water treatment. In the United States, DAF is not widely used although a few communities have recently installed DAF plants. This project was needed for several reasons. First, there has been little research on DAF; consequently, the design and operation of DAF plants are based largely on prior experience and pilot plant studies. Second, the 1986 amendments to the Safe Drinking Water Act require EPA to establish criteria for filtration of surface water supplies. EPA has proposed a filtered water turbidity of 0.5 IMTU or less. Pretreatment ahead of the filters is an important step in potable water treatment, and DAF is an alter- native pretreatment solid/liquid separation step to sedimentation. DAF should be ------- more efficient than sedimentation in treating waters with low density particles such as algae, alum Hoc, and floe. produced from treating low turbidity, colored waters. Third, the high hydraulic loadings (5 to 15 m3/m2/hr) and short hydraulic detention times (e.g., 10 min) of DAF tanks compared with, conventional settling tanks can provide considerable capita! cost savings. Finally, the ability of DAF to' remove natural color and trihalomethane (THM) precursors needs, investigation. The goal of the research was to investigate DAF as a method of treating two types of water supplies: low turbidity waters containing natural color and water supplies with seasonal algal problems. Specific objectives of the study were: ® to compare DAF with conventional water treatment of coagulation-fioe- culation followed by gravity settling (CGS)for particulate removal (i.e., tur- bidity as well as particle counts for supplies with algae); • to -compare DAF with conventional water treatment for removals of color, dissolved organic carbon (DOC), tri- halomethane (THM) precursors, and total organic halide (TOX) precursors; • to examine the effects on DAF per- formance of raw water quality, water temperature, chemical variables (pH, coagulant type,' and coagulant dose), flocculation period before DAF, and DAF design and operating variables (flotation time, saturator pressure, and recycle ratio); e to evaluate alum and polyaluminum chloride (PACI) as pretreatment coag- ulants for DAF. • Procedyre Several types of synthetic waters and natural waters (actual drinking water supplies) were used. Synthetic waters were used so that raw water quality characteristics of low turbidity waters and waters with aquatic humic substances could be studied at desired concen- trations. The synthetic water systems were: waters prepared with aquatic fulvic acid at concentrations of 2 to 10 mg/L as DOC (true color values of 20 to 100 Pt- Co color units); water prepared with montmorilfonite clay (clay concentration of 20 mg/L and turbidity of J .3 NTU) without fulvic acid to simulate a low turbidity water without color; and waters containing low turbidity from the mont- morillonite clay and fulvic acid (at con- centrations of 2 and 10 mg/L DOC). These two fulvic, acid/clay waters were used to test, low turbidity .water with low and high concentrations of aquatic humic substances. The fulvic acid was extracted from a stream (Provencial Brook), which -"feeds Bickford Reservoir, a water supply for Fitchburg, MA. Three natural waters were used. Washington Mt. Brook was used as a supply of high natural color. Washington Mt. Brook, which is a future water-supply for the towns of .Lee and Lenox, MA, has low turbidity (1 to 5 NTU), low alkalinity (3 to 20 mg/L as CaC03) high true color (50 to 200 Pt-Co color units), high DOC (5 to 12 mg/L), and high THM and TOX precursors (7-day, TTHMFPs and TOXFPs of 500 to 1,600 pg/L and 880 to 3,600 jig/L, respectively). Upper Root Reservoir was used as a low turbidity supply with little natural' color. It is an existing water supply source for Lenox, MA. The raw water tur- bidity is typically 1 to 2 NTU, whereas the true color is generally less than 20 Pt- Co color units.. it has low concentrations of DOC (1.3 to 2.2 mg/L), TTHMFP (100 to 200 ng/L), and TOXFP (200 to 350 iig/L). Wachusett Reservoir was used as a supply for studying the use of DAF to remove algae. The Wachusett Reservoir water is a supply for Boston and sur- rounding communities. It is a high quality supply (Boston currently does not filter) of low turbidity {0.4 to 1.1 NTU), low DOC (2 to 3 mg/L), and low THM precursors (TTHMFPs of 130 to 160 pg/L). Two different algae, Chlorella vulgaris (green alga) and Cyclotella sp. (diatom), were spiked into Wachusett Reservoir water under controlled growth phase conditions to study the effects on DAF performance of algal growth phase and cell number concentrations. Two coagulants were investigated, alum and pofyaluminum chloride (PACI). The PACI, prepared in our laboratory, contained approximately 10% monomeric aluminum and 90% polymeric aluminum species. The dominant fraction of the polymeric aluminum was probably in a form such as AI13O4 (OH)247*- Jar tests were performed on all test waters before the DAF studies to determine pH and coagulant dosages required for removal of humic substances from solution, and to determine coagulation conditions such that the floe particles were unstable (i.e., coagulant dosages needed for particle destabilization), Flotation studies were carried out usiruj a bench-scale system of four parallel units. The synthetic water studies involving fulvic acid and montmorillonite clay were conducted in two stages. In Stage I, a general statistical factorial ex- perimental design in which two levels of each of the variables were studied simul- taneously: pH, temperature, DOC con- centration, clay concentration, floccu- lation time, DAF detention time, and mode of separation (i.-e., DAF vs. gravity settling in conventional treatment). Stage II studies were designed to investigate in greater detail the effects of coagulant dose, flocculation period, temperature, and bubble volume concentration (con- trolled by saturator pressure and recycle ratio) on DAF performance. The per- formance variables measured included residual turbidity, residual dissolved aluminum, and various measurements of dissolved organic matter including UV absorbance (254 nm), DOC, TTHMFP, and TOXFP. The DAF studies of Upper Root Reservoir and Washington Mt. Brook examined coagulant dose, pH, floccu- lation period, and season, (raw water quality and water temperature). Flotation time, recycle, and saturator pressu were normally set at 10 min, 8%, and ',._. pslg, respectively. The DAF studies involving spiking of algae into Wachusett Reservoir were de- signed to; (1) define coagulation condi- tions for DAF treatment; (2) evaluate DAF performance for removals of particulates (algal cells, turbidity), dissolved organic matter, and THM precursors; and (3) examine the influence of algal growth phase, algal type, algal cell number con- centration, flocculation period, water temperature, and bubble volume concen- tration on DAF performance. Algal cul- tures grown in the laboratory under batch growth conditions were spiked at desired initial cell concentrations and growth phase into water collected from the Wachusett Reservoir. Chlorella was used under both log and stationary growth phase conditions to evaluate the effect of algal growth phase, and Cycfcrfe/fa was used under declining growth phase conditions. Standard cell concentrations of Chlorella and Cyclotella were 10s and 5x104 cells/mL, respectively. A floccula- tion period of 5 min was used in standard experiments, followed by 10 min of flotation using a bubble volume concen- tration . (4>b) of 4,600 ppm (i.e., saturate pressure 70 psig, recycle ratio 8%). ( ------- This study established that coagulation is needed for effective flotation as illustrated by the results in Figure 1. Figure 1 shows DAF performance for treatment of a water containing aquatic fulvic acid at a concentration of 5 mg/L as DOC. The results are presented as a function of the coagulant dose, PACI in this case. The UV and DOC data show poor DAF treatment without the addition of coagulant and for low PACI doses. The optimum PACI dose occurs at approxi- mately 2.5 mg/L, Higher PACI doses cause an increase in -turbidity indicating overdosing. The electrophoretic mobility (EPM) data indicate that the electrical charge on the floe particles is near zero at the optimum dose, which in turn,' indicates particle destabilization. Sepa- rately run jar tests indicated the optimum PACI dose .was 2,5 mg/L, which is identical to the DAF results. For all waters tested, the optimum coagulation dosage for particle destabil- ization based on jar tests was found to be the same dose required for optimum treatment in DAF. This means that jar tests can be used to determine coagulant dosages for DAF, thus minimizing the number of tests in pilot plant studies, and can be used to establish coagulant dosages for full-scale plants. The results also indicate that coagulation removes aquatic humic substances from solution by a phase change, from soluble organic matter to floe particles. The particles are formed by precipitation of aluminum- humates or by precipitation of aluminum hydroxide with loss of humic matter from solution by adsorption on the aluminum hydroxide. The mechanism of particle formation depends on the coagulant and the pH conditions. . The study showed that the flocculation period had little effect on DAF per- c "5 i a s> TOO 80 60 40 20 0 . .1-5 j? 1.0 0,5 0 2.0 ^ 1.0 o « 0 i "~ -1.0 -2.0 —. a—— — ~ —-a I 1.0 2.0 3.0 4.0 " PACi Dose (mg/L as Al) • 5.0 "•gure 1. Effect of PACI dose on DAF for 5 mgIL fulvic acid, as DOC (pH 5.5, 25°C, 20-min j flocculation period). formance. Figure 2 illustrates this for two water temperatures when PACI was used as a coagulant to treat water containing fulvic acid, DAF studies with alum showed similar results; however, residual turbidities were generally higher at 4°C, which indicates water temperature has an effect when aium is used as a coagulant. Further analysis of turbidity data indicated that PACi produced lower turbidities than did alum for either DAF or CQS (conventional treatment with settling) treatment under cold water conditions. This is shown by the data in Table 1 for a variety of synthetic waters and for Washington Mt. Brook. The only exception is the one experiment for Upper Root Reservoir, The effect of bubble volume concen- tration on DAF performance was exam- ined. Bubble volume concentration was varied by holding the saturator pressure constant at 70 psig and varying the recycle ratio at 2%, 5%, 8%, and 12% to yield bubble volume concentrations of approximately 1,200, 2,900, 4,600, and 6,600 pprn, respectively. For all of the waters tested without montmoriilonite clay, a bubble volume concentration of 2,900 ppm or less was adequate for good DAF treatment. For waters containing the clay at 20 mg/L, a bubble volume con- centration of 4,600 ppm was needed for effective flotation which indicates more air bubbles are needed to float these high .density particles. This study found that the removal of soluble organic matter (measured as DOC, TTHMFP. and TOXFP or by a surrogate measure such as UV absorb- ance) is independent of the solid/liquid separation step, i.e., DAF vs, conventional treatment with settling. This is illustrated by DOC data in Figure 3 for Washington Mt. Brook, The figure contains a bivariate plot of the data. The 45-degree line represents the "line of equal value"; data points falling on this line indicate an equal response for each level of the independent variable. Each data point represents the results of paired experiments for identical pretreatment conditions followed by DAF or sedi- mentation. That the data fall on the 45- degree line indicates no difference between DAF and conventional treatment, This is an important practical result. DAF treatment has no advantage over con- ventional treatment in removing non- volatile soluble organic matter because removal from solution is due to coagulation. Therefore, for the same coagulant dose, DAF and conventional treatment give the same removals of ------- 2.0 -- 1.S-- 1.0- 0.5-- -p 0.0' 2.0 ~~ _ b- f.5-- 10-- 0.5-- 0.0- 0.5- O Before DAF Q /Wer DAF »&•• 25 "C -0- ...-£! O Before DAF a After OAF 4 °C -B- ...Q.. I 0.0> -0.5' a 4 °c O 25 °C --•B...., JO 15 Flocculation Time (mm) 20 Flgws 2. Effecf of temperature and flocculation time on DAF for 5 mgtt fulvic acid, as DOC (pH 5.5, PACI dose 0.5 mg Alimg DOC. dissolved organic matter. The two processes do differ, however, in their ability to remove the floe particles pro- duced by coagulation (see Comparison section below. Experiments examining the effect of coagulant dose on DAF performance verified the results described earlier: little or no removal of turbidity and algal cells occurs without coagulant addition, and optimum removals by DAF occurs at the optimum coagulant dose based on particle destabilization. Figure 4 illus- trates this for alum for DAF treatment of Chlorella wulgaris at two growth phase conditions (log growth and stationary growth). The data also show that the optimum alum dosage is lower under stationary growth phase conditions than under tog growth conditions as well as better removal of algal cells. Similar results were obtained when PACI was used as the coagulant. DAF removal of Chlorella cells was studied at two water temperatures, 4° and 21 °C. Flocculation periods were at 0, 5, and 20 min. Alum was the coagulant. At 21 °C, ftocculation period had little effect on DAF performance. At 4°C, a 5- min ftocculation period improved the removal of algal cells and turbidity when compared with no floeculation period. There was little benefit, however, in increasing the flocculation period. The results indicate that good separation of algae by DAF occurs .without aggregation of cells to large floe sizes. The effect of bubble volume concen- tration on DAF treatment for three initial CMorelta cell concentrations is, given ir'" Figure 5. Good results were obtained witK the lowest bubble volume concentration (1,200 ppm) for Chlorella at concentra- tions of 2x10" and 1Q5 ceils/mL At 5x1Q5 cells/mL, a bubble volume concentration of 2,900 ppm was needed. For water treatment applications, algal cell concen- trations would typically be below 10s cells/mL so that a bubble volume con- centration of 2,900 ppm (5% recycle, 70 psig saturator pressure) would be more than adequate assuming similar alum dosages (10 to 15 mg/L). Of DAF With DAF was compared, side-by-side, with CGS under the same experimental con- ditions. Experiments were done for syn- thetic and natural waters. In ail experi- ments, the optimum coagulant dosage was used. Rapid mixing was for 2 min (G of 380 sec-1), and flocculation mixing was for 20 min (G of 10 sec-1). For flotation, a saturator pressure of 70 psig and recycle ratio of 8% (bubble volume concentration of 4,600 ppm) were used. The flotation detention time was 10 min, whereas the CGS settling period was 60 min. The ratio of flotation overflow rate to settling overflow rate was 6 to 1 except in thosi experiments with the algae water systems where the ratio was 10 to 1. These ratios are typical of practice. In Figure 6, the comparison of DAF with CGS is illustrated for waters containing atgae. The data (y-axis, DAF data; x-axis CGS data) are below the "line of equal value"; this indicates better DAF than CGS performance. DAF removals were 99% to 99.9% (2 to 3 log reduction); conventional treatment was 90% to 99%. In general, for all the water types studied, DAF produced significantly lower turbidities than did conventional treat- ment, particularly under cold water condi- tions. .When PACI was used as a coagulant in either DAF or CGS treatment, the treated waters had lower turbidities under cold water conditions than when aium was used as a coagulant (see Table 1). This study showed that flotation performance depends on raw water quality, pretreatment (coagulation and flocculation). especially chemical pre- treatment, bubble size, and bubbi. ------- 1. Comparison of Residual Turbidities for Mum and PACI at Cold Water Temperatures Turbidity (NTU) Sample Synthetic Waters: 2 mgIL DOC FA 10 mgil DOC FA 2mg/LDOCFAI 20.6 mg/L clay lOmg/LDOCFAl 20.6 mg/L clay pH 5.5 7.0 5.5 7.0 5.5 7.0 5.5 7.0 Temp ro 4 4 to 5 4 4 4 4 4 to 5 4 Alum 3.41 0.70 3.24 8.80 1.00 0.58 4.00 8.41 It PACI 0.16 0.19 0.94 0.64 1.30 0.45 i.oa 0.80 VV" Alum 3.82 1.14 3.90 T5.7 1.10 1.19 4.75 8.63 riu* PACI O.S8 0.60 1.20 0.51 1.40 1.24 1.52 0.91 Natural Waters: • Washington Mt. Brook 10/27198 1/14/87 Upper Root Reservoir 2/24/87 5.5 6,0 to 6.3 7.7 7 4 3.20 3.38 1.04 1.60 1.07 1.32 5.50 4.63 1.12 2.20 1.44 1.48 100 00 "o I s o: 60 40 20 |— OAF Line of Equal Value Conventional • I I 20 40 60 % Removed 80 100 ;§ure 3. Comparison of DAF with CGS for percent DOC removed for Washington Mt. Brook volume concentration. DAF is effective in treating water supplies containing humic substances or natural color (DOC con- centrations as high as 12 mg/L with true color values of nearly 200 Pt-Co color units were tested) and supplies with algae {celt concentrations as high as 5x105 cells/ml were tested). To remove particles, the particles must first be destabilized with coagulants. For water supplies containing humic substances, the dissolved organic matter must under- go a phase change (soluble matter to particulates) which is accomplished by coagulation. A short flocculation period ahead of flotation may be beneficial; however, long flocculation times are not necessary. Pin-point size floe of 10 to 50 jim should be introduced into the DAF unit. DAF is an efficient process due, in part, to the small bubble size produced by the process (bubble diameters of 10. to 100 ym). The bubble volume concen- tration is a design and operational parameter controlled by the saturator pressure and recycle ratio. Typical values of 70 psig and 8% recycle produced bubble volume concentrations in this research of 4,600 ppm. This bubble concentration is much higher than the particle volume concentrations for the waters tested, and ensured good collision opportunities between particles and bubbles and sufficient bubbles to lower the density of the particles for flotation. Some specific conclusions of this study are: • The optimum coagulation conditions for particle destabilization and particle- particle attachment (i.e., conventional jar test results) are the same as those required for particle destabilization and particle-bubble attachment (DAF re- sults). A practical result is that jar tests can be used to select optimum coagulant dosages for DAF. ® Experiments at low water temperature (4°C) indicated that floccuiatiori period affected DAF performance when treat- ing precipitated aluminum hydroxide particles (alum added to clean water without other particles or contami- nants) and particles produced by the alum coagulation of fulvlc acid at a concentration of 5 mg/L as DOC. How- ever, low temperature experiments us- ing PACI as a coagulant of the fulvic acid at the same concentration indi- cated that - DAF performance was independent of flocculation time within the temperature range (4° to 25 °C) studied. The differences in DAF per- formance observed with alum and ------- PAGI at 4°C support'the hypothesis that particle stability and particle- bubble attachment are a function of the hydrophilic nature of the particles as well as their surface charge. Experiments examining the effects of bubble volume concentration on DAF performance indicated that raw water quality affects the optimum bubble volume concentration. Experimental results indicated that good DAF per- formance was obtained for a bubble concentration of 4,600 ppm {8% recycle, 70 psig saturator pressure) when treating a supply containing a clay; however, good performance was obtained at lower bubble concen- trations when treating waters contain- ing humic substances or algae and no clay. Comparison of DAF with CGS indi- cated comparable removals of DOC, UV, true color, and dissolved organic halide precursors {TTHMFP, TOXFP). These findings support the premise that removal of dissolved contami- nants is independent of the solid/ liquid separation process used. o log Growth Phase D Stationary Growth Phase » Comparable levels of residual dis-x. solved aluminum (RDAI) were also' found after DAF and COS. © DAF produced significantly lower re- sidual turbidities than did CGS in the treatment of low turbidity waters con- taining humic substances, particularly at colder water temperatures. Also, PACI produced tower turbidities than did alum for cold waters. » Optimum coagulant dosages for alum and PACI were tower for DAF treat- ment of CWoreWa under stationary growth phase conditions than under log growth phase conditions. • DAF achieved excellent removals of algae cells, greater than a two log reduction in algal counts, for both Chlorelta and CycloteHa, by using the optimum coagulant dose without a flocculation period. At 4°C, a 5-min flocculation period ahead of flotation improved the removal of algae and gave lower residual turbidity and lower residual dissolved aluminum.hatide precursors (TTHMFP, TOXFP). These findings support the premise The following recommendations are made for future research. First, studies should be conducted that examine the integration of DAF with deep bed filtra- . tion. These studies should compare DA' with filtration to conventional treatment - with filtration under optimum operating conditions for each. Second, operating and capital cost data should be devel- oped for the purpose of producing cost curves so that design engineers can compare DAF with conventional water treatment in predesign studies of water supplies. Finally, the characteristics of sludge from DAF should be evaluated and compared with sludge characteristics from conventional settling processes. DAF may produce a higher solids content sludge, which would yield cost savings in sludge treatment and disposal when compared with that of conventional treatment. The full report was submitted in ful- fillment of Cooperative Agreement No. CR812639 by the University of Massa- chusetts under the sponsorship of the U.S. Environmental Protection Agency. 50 Alum Dose (mg/Lj Figure 4. Effect of alum dose on DAF treatment of Chlorate vuigaris under tog growth and stationary growth phase conditions (10s ce/te/mL, pH 6.5, ffoccu/afr'on time of 5 mm, and 4>b of 4,600 ppm). ------- 4,0 -i 1000 2000 3000 4000 5000 6000 Bubble Volume Concentration (ppm) 7000 Figure 5. Effect of bubble volume concentration on OAF treatment of CMoreifa vulgaris (initial cell concentrations of 2xl04, 10s, and 5xlOs cells/mL; optimum alum dose at pH 6.5). James K, Edzwald is with the University of Massachusetts, Amherst, MA 01003; and James P. Maltey, Jr., is presently at the University of New Hampshire, Durham, NH 03824, Kim fL Fox is the EPA Project Officer (see below). The complete report, entitled "Removal of Humic Substances and Algae by Dissolved Air Flotation," (Order No. PB 89-214 407IAS; Cost $28.95, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road ' ' . Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Risk Reduction Engineering Laboratory \ U.S. Environmental Protection Agency >>) Cincinnati, OH 45268 ------- 2.0 0.0 0.0 1.0 Turbidity (NTU) 1.5 2.0 Log N/Na (Algal-Size) Figure S. Comparison of DAF with CGS treatment for (a) turbidity remaining and (b) removal of algal cells for Chlorella vulgaris and Cydotella sp, at water temperatures of 4" and 21 °C. United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Official Business Penalty for Private Use $300 EPA/600/S2-89/032 ^•jvj-j^UaQFFICIAL. MAI," 000131433; ps fff '89193-3JI78 ------- |