Drinking Water Treatment

Water Treatment Chemistry

Overview

Treatment for Potable Water

I. Surface Water Treatment

Primary objectives are to

Remove suspended material (turbidity) and color Eliminate pathogenic organisms

Treatment technologies largely based on coagulation and flocculation

Surface Water Treatment

Coagulants Addition

Surface water from supply

Sedimentatio n basin

Rapid Sand Filter Disinfection

Rapid Flocculation Mix Basin

Sludge

Storage

To Distribution System
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Surface Water Treatment

Removal of turbidity

rapid mix tank flocculation tanks settling (sedimentation) tanks

Major Processes
1. Coagulation and flocculation

Coagulation involves the reduction of electrostatic repulsion such that colloidal particles of identical materials may aggregate. Why: Colloidal particles are prevented from aggregating by electrostatic repulsion of the electrical double layers. They are small in size and very stable in water. How: By the addition of coagulants followed by flocculation
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Colloids

Small particles (0.001 to 1 m) Usually negatively charged Particles repel so suspension is considered stable

Coagulation and Flocculation

+

Coagulation (process)

Colloidal particles (0.001 - 1 m)

+ + + + + + ++ + + + + + ++ + + ++ + + + + ++ + + + + + + +

+ + +

floc (1 - 100 m)
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Coagulation for the Removal of Fine Solids:

Coagulation involves the reduction of electrostatic repulsion such that colloidal particles of identical materials may aggregate. Why: Colloidal particles are prevented from aggregating by electrostatic repulsion of the electrical double layers. They are small in size and very stable in water. How: By the addition of coagulants followed by flocculation

Coagulation is:
Addition and rapid mixing of a coagulant with the water to:

neutralize surface charges collapse the surface layer around the particles allow the particles to come together and agglomerate allow formation of floc that can readily settle

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Mixing, Flocculation & Sedimentation

Coagulant Raw wastewater Rapid mix tank

Mixer

Flocculator

Sedimentation Clarified tank wastewater

Flocculation tank

Sludge

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Common Coagulants

Alum Hydrated aluminum sulfate [Al2(SO4)318H2O] Alum, when added to water, will be hydrolyzed to form gelatinous hydroxide [Al(OH)3] precipitate. This will carry suspended solids as it settles by gravity. Anhydrous Fe3+ Forms Fe(OH)3(s) in a wide range of pH 4-11 Anhydrous Fe2+ (FeSO47H2O) 3+ first at pH higher than 8.5 Must be oxidized to Fe Coagulant Aids (Polyelectrolytes) Natural: Starch, cellulose derivatives, proteinaceous materials, and gums composed of polysaccharides Synthetic polymers

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Coagulants

Non-toxic and relatively inexpensive Insoluble in neutral pH range - do not want high concentrations of metals left in treated water

Trivalent cations are most effective

Concentration

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How does alum work?

Al2(SO4)314H2O 2Al3++ 3SO42-+ 14H2O 2Al3+ + colloids neutralize surface charge 2Al3+ + 6HCO3- 2Al(OH)3(s) + 6CO2 If insufficient bicarbonate is available:

Al2(SO4)314H2O 2Al(OH)3(s) + 3H2SO4 -+ 14H2O

Optimum pH: 5.5 to 6.5 Operating pH: 5 to 8

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Rapid Mixing

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Flocculation

Physical process by which molecules of coagulant and colloidal particles are brought together Formation of aggregates that settle Can occur during settling May be helped by coagulants

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Flocculation

Paddle units rotate slowly, usually <1 rpm Velocity of water: 0.5 - 1.5 ft/sec Detention time of at least 20 min

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Flocculation

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Flocculation is the process that leads to the formation of large voluminous flocs, which are loosely held aggregates of coagulated particles and solids.
The slow mixing is one of the fundamentals necessary to promote collisions between particles to form flocs.

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Determining Coagulant Dose

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Jar Test Example and Calculations for Mixing & Flocculation

See Text-book (Davis & Cornwell)

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2. Sedimentation:
Flocs settle out and is scraped and vacuumed off the bed of large sedimentation tanks. Clarified water drains out of the top of these tanks in a giant decanting process.

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3. Filtration

Removal of those particles that are too small to be effectively removed during sedimentation Sedimentation effluent: 1 - 10 JTU Desired effluent level: <0.3 JTU Slow sand filters Rapid sand filters

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Either slow or rapid filtration (depends on size of plant / volume of water considerations).

Rapid-sand filters force water through a 0.451 m layer of sand (dp=0.4-1.2mm) and work faster, needing a smaller area. But they need frequent back-washing

Slow-sand filters (dp=0.15-0.35mm) require a much larger area but reduce bacteriological and viral levels to a greater degree. The top 1 inch must be periodically scraped off and the filter occasionally back-washed
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Slow Sand Filtration

Source: Back to Basics Guide to Surface Water Treatment, American Water Works Association, 1P-2.5M-73026-11/92-MG

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Rapid Sand Filtration

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Rapid Sand Filtration

Single media: sand Dual media: anthracite coal and sand Multimedia: anthracite coal, sand and garnet

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Rapid Sand Filtration

As particles are removed - filter becomes clogged - headloss increases, turbidity increases Must backwash (takes about 10-15 min) done about once per day Must design to handle flow with one filter out of service

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4. Disinfection - water completely free of suspended sediment is treated with a powerful oxidizing agent usually chlorine, chlorine then ammonia (chloramine), or ozone.

A residual disinfectant is left in the water to prevent reinfection. Chlorine can form harmful byproducts and has suspected links to stomach cancer and miscarriages. Many agencies now residually disinfect with Chloramine.
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Disinfection:

Disinfection is typically the last step in a water / wastewater treatment system

Residual chlorine is needed in distribution system after water / wastewater treatment In addition to disinfection, chlorine also has the following functions:

taste and odor control as an oxidizing agent oxidation of Fe2+ and Mn2+ in groundwater ammonium removal in domestic waste treatment slime, biofouling control
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Disinfectants

Gaseous Cl2 Most commonly used Advantage: provide residual chlorine for the protection from bacterial growth in distribution system Disadvantage: The formation of disinfection byproducts (trihalomethanes) presents a health risk Chlorine dioxide (ClO2): No disinfection by-products such as trihalomethanes Ca(ClO)2: Safer than Cl2 Ozone: generated on site UV lamps
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Chemistry of Chlorine in Water

Cl2 + H2O H+ + Cl- + HOCl -4 + HOCl is a weak acid with Ka = 4.5x10 (HOCl == H + OCl-) HOCl and OCl- are free available chlorine which are very effective in killing bacteria Small amount of ammonium (NH4+) in water is desired Chloramine: NH2Cl, NHCl2, NCl3 Chloramines (combined available chlorine) are weaker disinfectants than free available chlorine but are desired residual chlorine to be retained in water distribution system Excessive amount of ammonium (NH4+) in water is undesirable because it consume excess demand of Cl2
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Chlorination

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Chlorine Demand or Breakpoint Chlorination

Chlorine removal by reducing compounds Chloroorganic and chloramine destruction Formation of free chlorine

Chlorine residual

Chloroorganic and chloramine formation

Free Residual
Breakpoint

Combined Residual

Chlorine added

II. Groundwater Treatment

Primary objectives are to

1. Remove hardness and other minerals 2. Eliminate pathogenic organisms

Treatment technologies largely based on chemical precipitation

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Major ion concentrations - freshwater

Anions

mg/L

Cations

mg/L

HCO3SO4-2

58.4 11.2

Ca+2 Mg+2

15.0 4.1

ClSiO2 NO3-

7.8
13 ~1.0

Na+
K+ Fe+3

6.3
2.3 ~0.7

Total = ~91.4 anions + ~28.4 cations = ~ 120 mg/L (TDS)

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Groundwater Treatment
Addition of Softening Chemicals

Ground water from wells

Sedimentatio n basin

Recarbonation

Rapid Flocculation Mix Basin Disinfection Storage CO2

Sludge

To Distribution System
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Water Softening
(Removal of Hardness (Ca2+, Mg2+)

Hardness is an important water quality parameter in determining the suitability of water for domestic and industrial uses Hard waters require considerable amounts of soap to produce foam Hard waters produce scale in hot-water pipers, heaters and boilers Ca2+ + 2HCO3- CaCO3 (s) + CO2 (g) + H2O Groundwater is generally harder than surface water Principal cations causing hardness and the major anions associated with them (in decreasing order of abundance in natural waters) Cations: Ca2+, Mg2+, Sr2+, Fe2+, Mn2+ 22 Anions: HCO3 , SO4 , Cl , NO3 , SiO3
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Carbonate and Noncarbonate Hardness

Total hardness = Carbonate hardness + Noncarbonate hardness Carbonate hardness = temporary hardness; eliminated at elevated temperatures in boilers

Ca2+ + 2HCO3- CaCO3 + CO2 + H2O Ca2+ + 2HCO3- + Ca(OH)2 2CaCO3 + 2H2O

Noncarbonate hardness = permanent hardness; can not be removed or precipitated by boiling. Noncarbonate hardness cations are associated with SO42-, Cl- and NO3-.
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Example: Hardness Calculation

Calculate the hardness of a water sample with the following analysis:

Cations Na+ Ca2+ Mg2+ Sr2+ mg/L 20 15 10 2 Anions ClSO42NO3Alkalinity mg/L 40 16 1 50

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Water Softening Methods

Ion exchange Reverse osmosis Chemical precipitation (most commonly used): Ca2+, Mg2+ CaCO3 (s), Mg(OH)2 (s)

lime-only process: when Ca2+ is present primarily as bicarbonate hardness lime-soda [Ca(OH)2-Na2CO3] process: when bicarbonate is not present at substantial level
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Lime-Soda [Ca(OH)2-Na2CO3] Process

Lime to remove Ca2+ in the form of carbonate:

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O

Lime to remove Mg2+ in the form of carbonate: Mg(HCO3)2 + Ca(OH)2 MgCO3 + CaCO3 + 2H2O

Additional lime must be added to remove MgCO3 MgCO3 + Ca(OH)2 CaCO3 + Mg(OH)2
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Lime-Soda [Ca(OH)2-Na2CO3] Process (cond)

Mg2+ hardness in the form of a sulfate requires both lime and soda ash: MgSO4 + Ca(OH)2 CaSO4 + Mg(OH)2 CaSO4 + Na2CO3 CaCO3 + Na2SO4

CO2 in the water will also consume lime:

CO2 + Ca(OH)2 CaCO3 + H2O

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