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Holland Company, Inc.

Treatment of High Total Organic Carbon. High Natural Color Source of Supplv Usins Polvaluminum Hvdroxvchloride (pACL)

The following is a summary of a research report prepared to investigate the treatment of a water supply high in both natural color and TOC. This report identifies the treatment results of various types of PACL, as a replacement for the more traditional Alum coagulant treatment programs. The study used different types of water supply, with a focus on low alkalinity, high color (TOC) and compared the different PACL products for efficiency in TOC reduction. The study also compared conventional sedimentation to Dissolved Air flotation svstems.

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SUMMARY OF FINDINGS
The goal of the research was to investigate various types of polyaluminum chlorides (pACls) with respect to treating a high Toc, high color, low aftalinity water supply. Alum was used as a reference coagulant and PACIs of various basicities were studied. pACls with and without sulfate were examined. Research objectives included: 1) to evaluate alum and various pACls by conventional clarification (i.e., sedimentation) and by dissolved air flotation (DAF),2) to examine the effect of water temperature on the effectiveness of alum and the pAcls, and 3) to develop a testing procedure for the evaluation and selection of pACls for treating a high TOC, high color, low alkalinity supply. The testing procedure for evaluation and selection of pACls is addressed in the previous section. g.re, key findings are summarized for the other objectives.

RAW WATER QUALITY AND CHARACTERIZATION


Ashley Reservoir, a water supply for Pittsfield, MA, was used as the model water. Key raw water quality characteristics of this supply are its low alkalinity (< 30 mg/L CaCO3), slightly acidic pH (6-7), low turbidity (0.65-1.7 NTU), high true color (50-80 pt:co), high roc (6-8 mg/L), high DoC (6-7.4 mglL) and high UV absorbance at 254 nm (0 23-0 3i.- t;. it . nature of the natural organic matter (NOM) is easily determined through calculation of the SUVA (specific UV absorbance), which is the raw water UV expressed in m-r divided by the raw water DOC concentration in mg/L. SUVA values for this model supply were 3.g to 4.g indicating that the NoM is composed mostly of aquatic humic matter. This leads to the following important findings that apply to this and simllar waters.

The high humic content (SUVA > 4) and high ToC means that the coagulant dosages for effective treatment of these type water supplies.

NoM

controls

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stoichiometric relationship exists between the optimum coagulant dosage and raw water TOC or UV. Specific relationships were presented in Table l0 at pH 6.3-6.5, and were generally 0.7-l mg Al per mg Toc or 15-20 mg Ar pe, cm-r of UV. These relationships should yield good estimates of coagulant dosing ranges that can be used for jar tests, pilot studies, and full-scale plant triais.
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COAGULATION AT pH 6 TO
Coagulant Chemistry

The best pH conditions to treat this water type by coagulation are between pH 6 and 7, This pH range takes advantage of the chemical speciation of positively charged Al of alum and the PACIs as well as Al solubility considerations, charge on th. dissolved NOM, and floc charge following coagulation. Water temperature affects speciation and solubility, especially for alum' Alum should be used between pH 6 to 6.5 for warrn water conditions tr"y t 10 "Cj and at pH 6.5 to 7 for cold waters (say < 10 "C). PACI solubility depends on pH,in. typ. of pACl (basicity), and water temperature. Their minimum sotuiitity lies betw;en pH 6 and. l depending on PAC1 type and r.vater temperature (Appendix A). Below pH 6 to 7, they can be quite soluble so charge neutralization (chemical reaction with negatively charged dissolved

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NOM) can be effective. Overdosing, however, can lead to poor treatment of particle separation and residual Al problems.
dosages are needed, and lower removals of

Coagulation at higher pH than 6 to 7 is unfavorable for treating this water type. Higher NoM (Toc, Doc, uv) would be found. Sedimentation

The following important findings came out of the study.

Warm Water Settling

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The high basicity PACIs (HBNS and HBS) gave a broad coagulant dosing range of good treatment for turbidity and NOM removal.
The HBNS PACI gave the best removal of NOM.

Cold Water Settlins


The sulfated PACIs performed well, particularly the HBS pACl.

Unlike warrn water settling conditions, the HBNS PACI did not achieve good turbidify reduction.
Ca-based PACIs removals.

did not lower dosages as Al nor did they improve upon NOM

The MBS and HBS PACIs gave the lowest turbidities for a wide range of settling times or sedimentation tank overflow rates indicating formation of denser, more rapid settling floc.

Dissolved

Air Flotation (DAF)

Key findings of the study are listed next.

s e e *

DAF is much more effective in treating this water type than sedimentation. Lower turbidities, sometimes lorver NOM levels, were achieved by DAF compared to
sedimentation.

PACis were effective over a broad dosing range, and often good treatment
achieved at lower dosages than sedimentation.

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cold temperatures than sedimentation. Good treatment performance was achieved under both warm and cold water conditions.
DAF was much less affected by All of the PACIs worked well, but generally better results were observed for the MBS and high basicitl' PACis. The poorer performance observed for the HBNS in cold
water for settling of turbidity was not found for DAF.
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EPA's Enhanced Coagulation requirement for a low alkalinity supply with TOC of 4 to g mg/L is 50% TOC removal. The EPA requirement applies to finished waters, i.e., following filtration. No granular media filtration was used in these laboratory clarification experiments so a better measurement to examine is DOC (filtered samples) against the EpA requirements. Key findings follow.

All the PACI coagulants met the Enhanced Coagulation requirements, and achieved hish
removals of DOC (50-85%) and UV (65_85%)

The high basicity PACIs were effective over a wide dosing range in removing NOM. The HBNS performed quite well for DAF and sedimentation, alihough floc containing particulate carbon may carryover to the filters for cold water sedimeniation
treatment.

ACKNOWLEDGMENTS
The research described in this report was funded by the Holland Company Inc. (Adams, MA), Kemwater North America Company (Savannah, GA), and Kemira kemi AB (Helsingborg, Sweden). We are grateful for their support and for the assistance and advice of Tom and Dan Holland of the Holland Company, of Britt Muotka of Kemwater NA, and of Lars Gillberg of Kemira Kemi AB. We acknowledge Kristen Berger, Mary Donovan, and Wendy L. parmenter for their assistance with laboratory experiments, data management, and graphics. Kristen was an undergraduate student in the Department of Civil and Environmental Engineering. Mary Donovan worked in our laboratory during the summer of 1999 as a Smith College ,.r.ur.i, intem. Wendy Parmenter is a graduate student in the Environmental Engineering program at UMass.

REFERENCES
Edzwald, J.K.' Becker, W.C. and Wattier, K.L. (1985). Surrogate Parameters for Monitoring organic Matter and THM precursors. J. Amer. l4/at. worl<s Assoc.,77 (4), 122-132. Edzwald, J.K. and Van Benschoten, J.B. (1990). Aluminum Coagulation of Natural Organic Matter. In Chemical Water and Wastewater Treatment, H. Hahn and R. Klute 6Os;, Springer Verlag, NY, pp. 34I-359. Edzwald, J.K. (1993). Coagulation in Drinking Water: Particles, Organics, and Coagulants. llat. Sci. Tech,27 (11), 21-35. Edzwald, J.K., et al., (1994). Dissolved Air Flotation: Pretreatment and Comparisons to Sedimentation. In: Chemical Water and Wastewater TreatmentlII, R. Klute and H. H. Hahn (Eds), Springer Verlag, NY, pp. 3-18.. Edzwald, J.K. and Tobiason, J.E. (1998). Enhanced Versus Optimized Multiple Objective Coagulation.In Chemical Water and Wastewater Treatment y , H. Hahn, E. Hoffmann and H. Odegaard, (Eds), Springer Verlag, Ny, pp. lI3_124.

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