Do Cation Exchange Systems Affect the Chlorination Process? Presented By: Jeffrey W. Freeman, P.E., CFM, LEED AP Engineering Enterprises, Inc.

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1 Do Cation Exchange Systems Affect the Chlorination Process? Presented By: Jeffrey W. Freeman, P.E., CFM, LEED AP Engineering Enterprises, Inc. March 22, 2016

2 Presentation Overview Ebony-Ammonia & Ammonium- Ivory Gimme A Breakpoint Holy # of Test Methods Cation Exchange Treatment Exposed

3 Presentation Overview (Cont.) Evidence More Evidence Take That, Variable Ammonia! Acknowledgements and Q&A

4 Ebony-Ammonia & Ammonium-Ivory

5 Ebony-Ammonia & Ammonium-Ivory Ammonia Dissolution In Water pk a = 9.25 NH 3 + H 2 O NH 4+ + OH - Ammonia Ammonium Total Ammonia NH 3 + NH 4 + Free Ammonia NH 3 Only

6 Ebony-Ammonia & Ammonium-Ivory Ammonia & Ammonium Dissolution ph = 9.25; Temperature = 20 O C 9.25 Source: Manual for Bosanska Krupa Nov. 2009

7 Ebony-Ammonia & Ammonium-Ivory Ammonia & Ammonium Dissolution ph = 9.25; Temperature = 20 O C 7.5 Source: Manual for Bosanska Krupa Nov. 2009

8 Ebony-Ammonia & Ammonium-Ivory Chloramine Chemistry Monochloramine Development NH 3 + HOCl NH 2 Cl + H 2 O Dichloramine Development NH 2 Cl + HOCl NHCl 2 + H 2 O Nitrogen Trichloride Development NH 2 Cl + HOCl NCl 3 + H 2 O

9 Gimme a Breakpoint

10 Gimme a Breakpoint Breakpoint Chlorination Overview Hump Total Chlorine Residual Breakpoint Chlorine Added

11 Gimme a Breakpoint Breakpoint Chlorination Overview (Cont.) Total & Free Ammonia Total Chlorine Residual Monochloramine Development Total Ammonia Total Chlorine Free Ammonia Monochloramine To Dichloramine Total Chlorine Dichloramine To N Trichloride Free Chlorine Nitrogen Trichloride Chlorine Added

12 Gimme a Breakpoint Breakpoint Chlorination Overview (Cont.) Total & Free Ammonia Total Chlorine Residual Cl 2 :NH 3 N<5:1 Cl 2 :NH 3 N>5:1 Cl 2 :NH 3 N>7.6 9:1 Monochloramine Total Ammonia Total Chlorine Free Ammonia Monochloramine To Dichloramine Total Chlorine Dichloramine To N Trichloride Free Chlorine NItrogen Trichloride Cl 2 :NH 3 N = 5:1 Cl 2 :NH 3 N = 7.6 9:1 Chlorine Added

13 Gimme a Breakpoint Five (5) Recommended Parameters To Confirm Breakpoint Has Been Achieved: Free Ammonia Total Ammonia Monochloramine Total Chlorine Free Chlorine

14 Holy # of Test Methods

15 Holy # of Test Methods Typical Ammonia Test Methods Nessler Method: No Longer Standard Method Approved Salicylate Method: Recommend For Total Ammonia Indophenol Method: Recommend For Free Ammonia & Monochloramine Ion Selective Electrode: Ideal Method For Precision, But Higher Capital & O&M Costs

16 Holy # of Test Methods Typical Chlorine Test Methods DPD (N,N Diethyl-1,4 Phenylendediamine Sulfate) Recommended For Total Chlorine and Free Chlorine, If Breakpoint Achievement Has Been Confirmed Used With Many Test Kits/Analyzers Free Chlorine Must Be Read Within a Minute of Sample Preparation Total Chlorine To Be Read Within 3 5 Minutes After Sample Prepared Indophenol Recommended For Free Chlorine Confirmation It Is Not An IEPA Approved Method For Free Chlorine Measurement

17 Holy # of Test Methods DPD Free Chlorine Test Method Additional Comments Chloramines Are Known To Interfere With the Free Chlorine DPD Method The Longer The Sample Sits, the Greater the Amount of Interference Occurs DPD Method Is Accurate When Chloramines Are Not Present Excerpts From Hach DPD Free Chlorine Test Method Instructions

18 Holy # of Test Methods Indophenol Free Chlorine Test Method Additional Comments It Is Not An IEPA Approved Test Method Chloramines Do Not Interfere With Method It Is a Good Check To Confirm Past Breakpoint Excerpts From Hach Indophenol Free Chlorine Test Method Instructions

19 Cation Exchange Treatment Exposed

20 Cation Exchange Treatment Exposed Cation Exchange Treatment Summary General Definition of Ion Exchange Treatment (Source: New Hampshire Department of Environmental Services): Ion exchange (IE) is a water treatment method where one or more undesirable contaminants are removed from water by exchange with another nonobjectionable, or less objectionable substance. Both the contaminant and the exchanged substance must be dissolved and have the same type (+,-) of electrical charge. Cation Exchange (CE) Treatment Targets Cations Ions With + Charge Typical Regenerant is Sodium Chloride (NaCl)

21 Cation Exchange Treatment Exposed +1 Sodium +2 Hardness Cations Typical Target Cations In NE IL Copper 2+ Barium & Radium Iron 2+ Zinc 2+ Lead 2+ Source: notes.org/use periodic table/

22 Cation Exchange Treatment Exposed Affinity (/əˈfinədē/): [Biochemistry] the degree to which a substance tends to combine with another. (Source: Source: Water Quality & Treatment, AWWA

23 Cation Exchange Treatment Exposed Ion Exchange General Exchange Process HARDNESS CATIONS Ra 2+ Ba 2+ Ca 2+ Mg 2+ NH + 4 Radium Barium Calcium Magnesium Ammonium Sodium Ca 2+ Ca 2+ Ca 2+ Mg 2+ Mg 2+ Mg 2+ Schematic Cation Exchange Resin Bead Na+

24 Cation Exchange Treatment Exposed Ion Exchange General Exchange Process RADIUM & BARIUM CATIONS Ra 2+ Ba 2+ Ca 2+ Mg 2+ NH + 4 Radium Barium Calcium Magnesium Ammonium Sodium Ra 2+ Ra 2+ Ba 2+ Ba 2+ Ca 2+ Ca 2+ Ca 2+ Mg 2+ Schematic Cation Exchange Resin Bead Mg 2+ Na+ Mg 2+

25 Cation Exchange Treatment Exposed Ion Exchange General Exchange Process AMMONIUM CATIONS Ra 2+ Ba 2+ Radium Barium NH 4 + NH 4 + Ra 2+ Ca 2+ Mg 2+ Ra 2+ Ba 2+ Ca 2+ Mg 2+ Calcium Magnesium Ca 2+ Schematic Cation Exchange Resin Bead Mg 2+ NH 4 + Ammonium Sodium Na+ Ba 2+

26 Cation Exchange Treatment Exposed Ion Exchange General Exchange Process MORE HARDNESS CATIONS Ra 2+ Ba 2+ Radium Barium Ca 2+ Mg 2+ Ra 2+ Ca 2+ Mg 2+ Ra 2+ Ba 2+ Ca 2+ Mg 2+ Calcium Magnesium Ca 2+ Schematic Cation Exchange Resin Bead Mg 2+ NH 4 + Ammonium Sodium NH 4 + NH 4 + Ba 2+

27 Cation Exchange Treatment Exposed Ion Exchange General Exchange Process REGENERATION Ra 2+ Ba 2+ Ca 2+ Mg 2+ NH + 4 Radium Barium Calcium Magnesium Ra 2+ Ca 2+ NH 4 + Ra 2+ Ca 2+ Mg 2+ Schematic Cation Exchange Resin Bead Ammonium Ca Sodium 2+ Mg 2+ Ba 2+ Mg 2+ Ba 2+

28 Cation Exchange Treatment Exposed Ion Exchange WTP Process Flow Schematic Well No. 1 Bypass Flow Control Valve Fl PO 4 Cl 2 Meter Meter Cation Exchange Units Meter Meter Water Distribution System Well No. 2 Meter NaCl Regeneration System Backwash Surge Tank Sanitary Sewer System

29 Evidence

30 Evidence Theory Confirmation No. 1 Village of Montgomery Wells No. 14 & 15 WTP Background Well No. 14 Ironton Galesville DSS Well Raw Water Hardness = 235 mg/l as CaCO 3 Combined Radium = 6.6 pci/l WTP Contains Five (5) CE Units With Bypass Flouride, Polyphosphate and Chlorine Gas Added After CE Units Treated Water Distributed Directly Into System

31 Evidence Theory Confirmation No. 1 (Cont.) Sampling & Testing Summary Occurred Every 30 Minutes From 8:00 AM 2:00 PM on April 3, 2013 Testing Locations Raw Water Post CE/Pre-Chlorination Composite Finished Tested For Five (5) Test Parameters Free & Total Ammonia, Chloramine, Free & Total Chlorine Note: Chlorine Dose = 1.9 mg/l

32 Wells No. 14 & 15 WTP Sample Locations Evidence Well No. 14 Raw Bypass Flow Control Valve Meter Fl PO 4 Cl 2 Finished Meter Meter Well No. 15 Meter Post CE / Pre Chlor (Composite) Cation Exchange Units

33 Raw Water Ammonia Levels WELL NO. 14 AND WELLS NO. 14 & 15 WTP Evidence

34 Raw & Post CE / Pre-Chlor Ammonia Levels WELL NO. 14 AND WELLS NO. 14 & 15 WTP Evidence

35 Evidence Finished Ammonia & Chloramine Levels WELL NO. 14 AND WELLS NO. 14 & 15 WTP Mono To Di Near BP Mono To Di

36 Evidence Finished Ammonia & Chlorine Levels WELL NO. 14 AND WELLS NO. 14 & 15 WTP Mono To Di Past BP Mono To Di

37 Raw & Finished Ammonia & Chlorine Levels WELL NO. 14 AND WELLS NO. 14 & 15 WTP Evidence

38 Finished Chlorine Residuals WELL NO. 14 AND WELLS NO. 14 & 15 WTP Evidence

39 More Evidence

40 More Evidence Theory Confirmation No. 2 Village of Montgomery Well No. 8 WTP Background Well No. 8 Ironton Galesville DSS Well Raw Water Hardness = 210 mg/l as CaCO 3 Combined Radium = 11.5 pci/l WTP Contains Three (3) CE Units With Bypass Flouride, Polyphosphate and Chlorine Gas Added After CE Units Treated Water Distributed Directly Into System

41 More Evidence Theory Confirmation No. 2 (Cont.) Sampling & Testing Summary Occurred Every 30 Minutes From 8:00 AM 2:00 PM on May 20, 2013 Testing Locations Raw Water Post CE/Pre-Chlorination Finished Tested For Five (5) Test Parameters Free & Total Ammonia, Chloramine, Free & Total Chlorine Note: Chlorine Dose = 1.9 mg/l

42 Well No. 8 WTP Sample Locations More Evidence Well No. 14 Raw Bypass Flow Control Valve Meter Fl PO 4 Cl 2 Finished Meter Meter Post CE / Pre Chlor (Composite) Cation Exchange Units

43 Raw Water Ammonia Levels WELL NO. 8 AND WELL NO. 8 WTP More Evidence

44 More Evidence Raw & Post CE / Pre-Chlor Ammonia Levels WELL NO. 8 AND WELL NO. 8 WTP Total NH 13:30 Softener 1: 0 mg/l Softener 2: 0 mg/l Softener 3: 2.1 mg/l Softener 3 In Regen.

45 More Evidence Finished Ammonia & Chlorine Levels WELL NO. 8 AND WELL NO. 8 WTP BP Achieved Mono To Di Mono Near BP

46 More Evidence Raw & Finished Ammonia & Chlorine Levels WELL NO. 8 AND WELL NO. 8 WTP

47 Finished Chlorine Residuals WELL NO. 8 AND WELL NO. 8 WTP More Evidence

48 Take That, Variable Ammonia!

49 Take That, Variable Ammonia! Wells No. 14 & 15 WTP Sample Locations Well No. 14 Bypass Flow Control Valve Meter Fl PO 4 Meter Meter Cl 2 Well No. 15 Meter PLC Free Chlorine Analyzer Cation Exchange Units Ammonia & Monohloramine Analyzer

50 Acknowledgements and Q&A A Big Thank You To: Village of Montgomery Bob Spon (Spon Water Consulting) Terry Engelhardt (Hach)

51 Jeffrey W. Freeman, P.E., CFM, LEED AP Vice President Engineering Enterprises, Inc. (630) Acknowledgements and Q&A

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