Rick Mealy Program Chemist WI SNR - Lab Certification (608) 264-6006 richard.mealy@dnr.state.wi.

us

pH

George Bowman Inorganics Manager State Laboratory of Hygiene (608) 224-6279 gtb@mail.slh.wisc.edu

Alkalinity

Hardness

Importance of General Chemistry Relationships in Water Treatment

pH Carbonate Chemistry Alkalinity Hardness Effective Disinfection

Basic chlorine systems Alternative disinfection

Arsenic
Session Discussion Topics
Chemistry Treatment

pH
What is it pH and temperature How is it measured Not as simple as you might think

pH is the term used universally to express the intensity of the acidity of a solution. More precisely, acids are defined as those compounds that release a proton (H+, hydrogen ion) whereas bases are those compounds that accept protons. Thus, pH is the measurement of hydrogen ion (H+) activity. Pure water dissociates to yield equivalent concentrations of hydrogen [H+] and hydroxide [OH-] ions: H2O H+ + OH The equilibrium for pure water is [H+] [OH-] = Kw = 10-14 =10-7 10-7 Therefore at equilibrium, [H+] = [OH-] = 10-7 = pH of 7 The scale ranges from 0 to 14 [H+] = 10 0 to 10-14

What is pH?

http://www.johnkyrk.com/pH.html

pH scale

pH = "potential Hydrogen" ion concentration pH is usually expressed as log 1 / [H+] or log [H+] pH tells us whether a solution is acid, alkaline or neutral and relative acidity. It does not tell us how much acid or alkali is present. pH is a critical measurement. Life depends upon it. For instance, human blood is basic with a pH between 7.3 and 7.5.
If the blood pH drops < 7.3, acidosis occurs (diabetes). If blood pH rises > 7.5, alkalosis occurs (Tums OD). Below 7.0 and above 7,8, death occurs

One unit in pH equals a 10x change in acidity.

Two units means 100 times change, 3 units is 1000 times and so on.

pH

*** [OH-] concentration *** (mol/L) ____(mg/L)____ pH 1 x 10-14 1 x 10-13 1x 10-12 10-10 10-8 10-6 10-5 10-3 10-1 1 x 10-11 1x 1 x 10-9 1x 1 x 10-7 1x 1x 0.0000000001 0.000000001 0.00000001 0.0000001 0.000001 0.00001 0.0001 0.001 0.01 0.1 1.0 10 100 1000 10000 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

*** [H+] concentration *** (mg/L) ___ _(mol/L)_ 10000 1000 100 10 1.0 0.1 0.01 0.001 0.0001 0.00001 0.000001 0.0000001 0.00000001 0.000000001 0.0000000001 1 x 100 1 x 10-1 1 x 10-2 1 x 10-3 1 x 10-4 1 x 10-5 1 x 10-6 1 x 10-7 1 x 10-8 1 x 10-9 1 x 10-10 1 x 10-11 1 x 10-12 1 x 10-13 1 x 10-14

1 x 10-4 1x 1 x 10-2 1x 1 x 100

H+ concentration table another view

pH is a measure of the available hydrogen ions (H+) pH is calculated as the negative log of the H+ concentration - log [H+] pH of n = a H+ concentration of 1 x 10 -n pH describes a waters relative acidity, provides no measure of how the water will tolerate addition of acid or base to the system. pH is measured according to electrometric principles based on the Nernst equation. Temperature is the only variable. pH affects nearly every water and wastewater treatment function (wherever some chemistry is involved)

pH - what you need to know

Carbonate Chemistry

Surface Water system CO2

Photosynthesis & Respiration

CO2 aq.

(CO2 + H20)

H2CO3 Carbonic acid

Alkalinity Mg2+ Na+ K+ Ca2+ Hardness

Bicarbonate HCO3 + H+ Carbonate CO 2- + H+ 3 CaCO3

The Carbonate Cycle - Surface Water

CO2 CO2 Un-Saturated Zone

Decaying vegetation CO2 Limestone= CaCO3 Dolomite= CaMg(CO3)2

Rainwater picks up CO2 from the atmosphere. As the water seeps into the soil, further CO2-produced from decaying plants or respiration--is picked up. The reaction of water and CO2 yields carbonic acid--a weak acid. CO2 + H2O H2CO3 The weak acid dissolves limestone and dolomite allowing the water to pick up calcium, magnesium and carbonate ions.

Saturated Zone

H2O +
Ca+2 Mg+2 CO3= HCO3-

How CO2 enters groundwater

When carbon dioxide enters the water: CO2 (air, decaying OM) CO2 (dissolved) + H2O Some of the dissolved CO2 hydrates (reacts with water) to from carbonic acid (H2CO3 ): CO2 + H2O H2CO3 Carbonic acid will dissociate: H2CO3 HCO3- + H+ Forming bicarbonate and a free hydrogen ion HCO3- CO32- + H+

CO2 reactions

Bicarbonate further dissociates: to carbonate and a free hydrogen ion

CO2 input (respiration) (produces H+, decreases pH, more acidic)

pH
Carbonic Acid Bicarbonate Carbonate

CO2 + H2O

H2CO3

HCO3- + H+

CO32- +2 H+

pH
CO2 removal by photosynthesis (removes H+, increases pH)

Biological processes & pH

Flux of carbon dioxide (CO2) and its influence on pH

CO2

photosynthesis (pH ) CO2

CO2

+ CO2

respiration (pH )

CO2 and pH influence

Carbon dioxide not only dissolves in water, it reacts with it.

These reactions get a bit more complicated:

Also have reactions that result in the formation of the hydroxyl ion:
Bicarbonate Carbonic acid

HCO3- + H2O
Carbonate

H2CO3 + OHBicarbonate

CO32- + H2O Further consideration: OH-

HCO3- + OH-

Which form of carbon will dominate?

...depends on the pH

Carbon form vs. pH

Lakes/reservoirs (many western states) that have a lot of carbonate can resist changes in pH with the addition of acids Ability to resist changes in pH with respect to the addition of acid is called Alkalinity or Acid neutralizing capacity (ANC) The Buffer System

The carbonate system is dynamic The main formula is: CO2 + H2O H2CO3 HCO3- + H+ CO32- +2 H+ Additions or reductions to any one side of the reaction will shift the reaction the opposite direction Respiration & photosynthesis affect this reaction by addition of or removal of CO2 Addition of CO2 reduces the pH of a system Removal of CO2 increases the pH of a system

Carbon Cycle - What you need to Know

ALKALINITY
what is it? how is it measured? same as hardness? alkalinity affects on pH changes (treatment) acidity-alkalinity-pH chart

Alkalinity is a total measure of the substances in water that have "acid-neutralizing" ability. Alkalinity indicates a solution's power to react with acid and "buffer" its pH -that is, the power to keep its pH from changing. So... while pH measures the strength of an acid (base), alkalinity measures the ability to neutralize acid (base).
Mathematically, alkalinity can be determined by: Alkalinity = [HCO3-] + 2[CO32-] + [OH-] [H+] Alkalinity provides a buffering capacity to aqueous system. The higher the alkalinity is, the higher the buffering capacity against pH changes.

What is Alkalinity?

10

Alkalinity essentially becomes a measure of the buffering capacity of the Carbonate/Bicarbonate ions --- and to some extent---the hydroxide ions of water. These 3 ions all react with H+ ions to reduce acidity, increasing alkalinity & pH

HCO3- + H+ CO2 + H2O CO3-2 + H+ HCO3 OH- + H+ H2O Alkalinity - closer look

50 ppm Total alkalinity Neutralization with H2SO4

HUGE pH change occurs... with minimal acid addition

Compare the neutralization of NaOH to that of Na2CO3

If trying to control the pH of a process around pH=7 Virtually impossible to use NaOH as the base SHARP inflection point (drop) of titration curve occurs pH 4.3 to 9

Alkalinity and NaOH neutralization

11

100 90 80 70

% Composition

60 50 40 30 20 10 0 P=0

HCO3- CO3= -------- -----CO3= OH-

HCO3CO3= OH-

P = Phenolphthalein Alkalinity T = Total Alkalinity

P<T/2

P=T/2

P>T/2

P=T

Speciation beyond Phenolphthalein Alkalinity

pH = 8.3

pH = 9.9

pH = 14.

An aqueous solution that resists changes in pH when acid or base is added is known to have sufficient buffering capacity. Atmospheric carbon dioxide produces a natural buffer and is the most important buffer system in water and wastewater treatment.
CO2(g) CO2 (aq) + H2O CO2(aq) + H2O H2CO3 H2CO3 H+ + HCO3HCO3- H+ + CO32(A) CO2 equilibrium (B) carbonic acid (C) bicarbonate (D) carbonate

CO2 in solution [CO2(aq)] is in equilibrium with atmospheric CO2(g). This is critical concept, because the change in any components in eqs. (B), (C), or (D) will disrupt that equilibrium causing CO2 to either be released or to be dissolved into solution.

Buffering and the Carbonate System

12

If acid is added: H+ increases in the system. This drives eq. (D) towards left thereby forming more bicarbonate.
The bicarbonate Further combines with H+ and forms carbonic acid [eq. (C)], which dissociates to CO2 and water. The excess carbon dioxide is then released to atmosphere. CO2(g) CO2 (aq) + H2O (A) dissolved CO2 CO2(aq) + H2O H2CO3 H2CO3 H+ + HCO3HCO3- (B) carbonic acid (C) bicarbonate (D) carbonate

H+ + CO32-

pH
Buffering and Carbonate System
If CO2 is stripped out from the system: The above reactions also shift towards left. CO2 is removed from the solution. The pH will increase

If base is added: H+ is consumed in the system. This drives above

eqs. towards right direction. This therefore converts the gaseous carbon dioxide to carbonate.

CO2(g)

CO2 (aq) + H2O

(A) dissolved CO2

(B) carbonic acid (C) bicarbonate (D) carbonate

CO2(aq) + H2O +

OH-

H2CO3 H+ + HCO3H+ + CO32-

H2CO3 HCO3-

pH
Buffering and Carbonate System
If CO2 is bubbled into the system: The above reactions also shift towards right due to formation of carbonic acids. This is because CO2 will combine with water. The pH will decrease.

13

Chemical Effect on pH Effect on Alkalinity NaOH Increase +1.55 mg/L as CaCO3 per mg/L (caustic soda) Ca(OH2) Increase (Lime) +1.21 mg/L as CaCO3 per mg/L

NaHCO3 small +0.60 mg/L as CaCO3 per mg/L (sodium increase bicarbonate) Na2CO3 moderate +0.90 mg/L as CaCO3 per mg/L (soda ash) increase

Chemical Additions to Increase Alkalinity

Alkalinity is a measure of a waters ability to resist pH changes Alkalinity is based on carbonate chemistry Alkalinity is expressed as mg/L as calcium carbonate (CaCO3)

Alkalinity: What You Need to Know

14

HARDNESS
what is it? how is it measured? scale formation preventing scale formation

Hardness is a chemical parameter of water that represents the total concentration of calcium and magnesium ions. Calcium typically represents 2/3 of total hardness; Mg typically about 1/3. ...is commonly confused with alkalinity. The confusion relates to the term used to report both measures, mg/L CaCO3. If limestone is primary source of both hardness and alkalinity, the concentrations will be similar if not identical. Hardness is sometimes expressed in grains per gallon (water treatment industry), but usually as parts per million (ppm) as calcium carbonate equivalent. The degree of hardness standard as developed by the Water Quality Association (WQA) is: Term Grains/gallon mg/L or ppm Soft Less than 1.0 less than 17.1 Slightly Hard 1.0 to 3.5 17.1 to 60 Moderately Hard 3.5 to 7.0 60 to 120 Hard 7.0 to 10.5 120 to 180 Very Hard 10.5 and above 180 and above

Hardness - What is it?

NOTE: 1 grain/gal = 17.1 ppm or mg/L as CaCO3

15

Hardness is reported in several ways, most typically: As mg/L as calcium carbonate (CaCO3)
Regardless of source, reported as equivalent weight of CaCO3)

As grains per gallon (gpg)

1 grain = 0.06479891 gram (g) = 64.79891 milligrams (mg) 1 gallon = 3.7854 L 64.79891 mg x 1 gallon = 17.1 mg/L as CaCO3 gallon 3.7854 Liters

As German degrees of hardness (dGH)

1dGH (German scale) = 10 mg/liter CaO Atomic Weight Ca = 40, O = 16, CaO = 56 So 10 mg/L CaO contains (40/56) *10 = 7.143 mg/liter of Ca Atomic weight CaCO3 = 100 So 7.143 mg/liter of elemental Ca would be expressed as 100/40 * 7.143 = 17.8575 mg/liter(ppm)CaCO3

Hardness and conversion factors

It is called hardness because if calcium and magnesium are present in your water, making a lather or suds for washing is hard (difficult) to do. Thus, cleaning with hard water is hard.
How do people decide when its time to add salt to their water softener???

Common soap is a sodium salt of a fatty acid, stearic acid: Na+C18H35O2

Soap reacts with Calcium (Magnesium) salts to form soap curd

CaSO4 + 2 NaC18H35O2 Ca(C18H35O2)2 + Na2SO4

(soap curd)

Hard water is naturally likely to also have a high pH, because it is also high in carbonates that buffer the pH toward the alkaline side (due to carbonate hardness)

Why hardness?

16

0- 60 mg/L as CaCO3 61-120 mg/L as CaCO3 121-180 mg/L as CaCO3 181-250 mg/L as CaCO3
mg/L 17.1 = grains/gal

USGS Hardness map for WI

Classification of Water based on Hardness USGS Other Scales Soft 0-60 0-75 Mod. Hard 61-120 75-150 Hard 121-180 150-300 Very Hard >180 >300

1. By Titration

Ca & Mg bound up by EDTA

+ Eriochrome Black T

Ca+2

Mg+2

Mg+2 Ca+2

Ca+2 Mg+2

+ Na - EDTA

Mg+2 Ca+2

Red color indicates free Ca & Mg ions

Calcium and magnesium ions in the sample are sequestered upon the addition of disodium ethylenediamine tetraacetate (Na-EDTA). The end point of the reaction is detected by means of Eriochrome Black T indicator, which has a red color in the presence of calcium and magnesium and a blue color when the cations are sequestered.

Blue color indicates all Ca & Mg have been titrated.

How is Hardness Measured?

17

 lowers toxicity of some metals (Pb, Cd, Cr, Zn) causes precipitation of other metals, thereby reducing their bioavailablity hard water requires more soap and synthetic detergents for laundry and washing causes scaling in boilers and industrial equipment

Hardness - Impact

The white solid "scale" that can appear on plumbing components is calcium carbonate or CaCO3. If a water is supersaturated with calcium carbonate, then hardness scale can precipitate. What problems can scale cause?
Valves can leak if calcium carbonate salt crystals develop inside the valve, preventing it from sealing properly. Solenoid valves can leak when scale forms inside. Scale buildup inside flow switches makes them stick. This can cause actual leaks to go undetected or false alarms when there is no leak. Aesthetically, hard water deposits leave stains and build-up on the outside of valves and connections.

Hardness & Scale formation

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Avoiding Scale Problems

If the Langelier Index calculation yields a positive index scaling problems can be avoided by:
Demineralization, Reverse Osmosis, distillation, or deionization. Removing the dissolved minerals will lower the hardness. Softening. Water softening or cation exchange will reduce the calcium and magnesium concentrations in water. Acidification. Lowering the actual pH of the water to below the saturation pHs will prevent scale deposits. Low Temperature. Avoiding high temperatures where scale formation is more likely will prevent scale deposits.

Hardness - Avoiding scale

Has been used successfully by groundwater systems serving < 3,000 Unlikely to be suitable for treating groundwater in systems serving fewer than 500 people unless those systems have a trained operator able to continually monitor the process. Add either hydrated lime [Ca(OH)2] or quicklime [CaO] Goal: raise the pH of the water to about pH 10 to precipitate calcium carbonate (CaCO3) and, if necessary,magnesium hydroxide [Mg(OH)2] (requires raising pH to about 11). Need to pilot test each system on a small-scale Lime-softened water has high causticity and scale-formation potential; Re-carbonation is employed to reduce pH and mitigate scaling of downstream processes and pipelines. Onsite combustion generation of carbon dioxide (CO2) or liquid CO2 is the most common source of carbon dioxide for recarbonation. Best suited to groundwater sources with very stable water quality.

Lime Softening

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Laundering - Fabrics washed in hard water wear out up to 15% quicker (Purdue, 1991) Colors fade & whites darken more quickly when cleaned with hard water. Laundry washed in hard water became re-soiled with greater ease. Hard Water Scale - Can decrease the life of toilet flushing units by 70% (AWWA). Can decrease the life of water faucets by 40% (AWWA). Shortens life of dishwashers and clothes washers by as much as 30%. Water Heater Efficiency - Can reduce a gas water heater's efficiency by as much as 29%, Can reduce an electric water heater's efficiency by as much as 21%. Water heater's useful life can be reduced by as much as 50 % . (USDI) Cleaning Tasks - Time required for typical cleaning tasks was increased by almost 50%. Can result in streaks, spots and film on glass and dishware. Soap curd film on the body can leave skin dry and hair dull and limp.

Hardness - Facts and figures

Due to natural geology, hardness is generally a problem in Wisconsin Scale formation can cause problems throughout a system Its the same CaCO3 that causes scale that is also the source of most of a waters alkalinity. Hardness can result in precipitation of some toxic metals, lowering their bio-availability (Hardness is considered when establishing WPDES discharge permit limits for metals) Any technique that will remove calcium and magnesium ions will reduce hardness

Hardness: What You Need to Know

20

 Langelier (Saturation) Index (LSI, LI) is most commonly used Aggressive Index is also used. These equations estimate the theoretical tendency [of a water] to precipitate a protective coating of calcium carbonate (CO3-2) on a pipe wall. Under-saturated water is corrosive (Negative LSI/ aggressive) Over-saturated water will deposit CaCO3 (Positive LSI / Not aggressive) A thin layer (of CaCO3) is desirable as it keeps water from contacting the pipe, thereby reducing chance for corrosion.

Corrosivity Indices

1. Determine the pH at which CaCO3 is saturated

pH S=CaCO3 saturation = (9.3+A+B) - (C+D) A = (log TDS) - 1 10 B = [-13.12 x (log oC + 273) ] + 34.55 C = (log [Ca+2] mg/L as CaCO3) ] - 0.4 D = (log [Alkalinity] mg/L as CaCO3)
2. Compare actual pH to pH at which CaCO3 is saturated

LSI = pH - pHs=CaCO3 saturation

Langelier Index Explained

3. Actual pH < saturation pH = increasing corrosivity Actual pH > saturation pH = Tends to deposit CaCO3

21

Factors Affecting LSI

LSI will Increase (reduce corrosivity) in value if: Calcium hardness is increased pH is increased TDS is increased (if increase in TDS is due to Ca/Mg) Alkalinity is increased Temperature is increased A change in pH has greatest impact on LSI Ideal LSI = -0.50 to + 0.50

Langlier Index -Factors Affecting It

From: The NALCO Water Handbook. 1979. Nalco Chemical Co.

Hardness = 240 mg/L Alkalinity = 190 mg/L Temp = 70 oF Actual pH = 6.8

pHsat = 7.3

Estimating Langelier Index by nomograph

LSI = 6.8 - 7.3 = - 0.5

22

(Actual)pH=7.26 Temp=20C 1. Determine TDS=400

the pH of carbonate saturation (pHs) Need actual pH, water temp, alkalinity, hardness convert data into the four variables: A,B,C,D pHsat= A + B - C - D
pHsat= 2.10 + 9.86 2.49 2.11 = 7.36
Hardness (mg/L) Alkalinity (mg/L) 10 20 30 40 50 60 70 80 100 130 150 175 200 250 310 400 500 600 700 800 900 1000

Hardness=310 Alkalinity= 130

Temperature Variable
Water Temp (o C/F) "A" 0 / 32 2.60 4 / 39 2.50 8 / 46 2.40 12 / 53 2.30 16 / 60 2.20 20 / 68 2.10 22 / 72 2.06 25 / 77 2.00 30 / 86 1.90 35 / 95 1.80 40 / 104 1.70 50 / 122 1.55

Hardness/ Alkalinity Variable

"C" "D" 1.00 1.30 1.48 1.60 1.70 1.78 1.84 1.90 2.00 2.11 2.18 2.24 2.30 2.40 2.49 2.60 2.70 2.78 2.84 2.90 2.95 3.00

Langlier Index = pHactual- pHsat

Langlier Index = 7.26 - 7.36 = -0.10
LSI Scale - negative less than zero + positive greater than zero close to zero

TDS Variable
TDS (mg/L) 0 25 50 100 200 400 600 1000 > 1300 "B" 9.70 9.72 9.74 9.77 9.83 9.86 9.89 9.90 9.99

Potential No scale potential. Corrosive. Water will dissolve CaCO3 Scale can form CaCO3 precipitation may occur. Borderline scale potential. Water quality and temperature changes, or evaporation could change the index.

TDS can be estimated as 40% of EC

Langlier Index formula

Aggressive Index - Corrosion index calculated from pH, calcium hardness and total alkalinity.
Hardness/ Alkalinity Variable

pHactual + C + D= Aggressive Index

7.26 + 2.49 + 2.11= 11.86 Characteristic Aggressive Index Non-Aggressive > 12.0 Moderate Aggressive 10.0 to 11.9 Highly Aggressive < 10.0 Since Hardness is typically gonna be ~ 150-250 ppm in WI, the C factor will range from 2.2 to 2.5 Alkalinities in WI typically range from 100-150 ppm, thus the D factor will range from 2.00 to 2.18.

Hardness (mg/L) Alkalinity (mg/L) 10 20 30 40 50 60 70 80 100 130 150 175 200 250 310 400 500 600 700 800 900 1000

"C" "D" 1.00 1.30 1.48 1.60 1.70 1.78 1.84 1.90 2.00 2.11 2.18 2.24 2.30 2.40 2.49 2.60 2.70 2.78 2.84 2.90 2.95 3.00

Aggressive Index

Therefore, C + D ranges from 4.2 to 4.7 This means that waters of pH 7.3 to 7.8 and above --or typical for most WI water sources-- will generally be NON-Aggressive. Instead of corrosion, scale formation is of concern.

23

 There are a number of formulae/equations available to estimate a waters corrosivity Corrosivity indices measure a waters ability to either precipitate out or dissolve CaCO3 (corrosive) Both extremes of the scale cause problems EPA generally uses Langelier Index for drinking water systems Aggressive Index is much easier to calculate (need less data) Corrosivity/Aggressiveness: What You Need to Know

The carbonate cycle is dynamic process. Photosynthesis & respiration can change the pH of a system by adding or removing CO2. pH affects many aspects of water treatment including: disinfection, scale formation and corrosion potential. The interaction among pH, alkalinity and hardness has far reaching effect on water treatment. A basic knowledge of general water chemistry relationships can provide a better understanding of water treatment processes. Dont worry about equations & formulas--thats what books are for. Its far more important to understand the processes behind the equations.

Summary

24

CO2 H2CO3 CO32HCO3Ca(HCO3)2 CaCO3 H+ OHPO43-

Carbon dioxide Carbonic acid Carbonate Bicarbonate Calcium bicarbonate Calcium carbonate Hydrogen ion Hydroxyl ion Phosphate ion

Acronyms

Effective Disinfection

25

E. coli
George & Rick Special Limited Engagement

Iron River November 18, 2004

29

26

kill the bugs

Disinfection (Chlorination)

IMA BUG

Focus Point: Disinfection

How does chlorine kill?

Chlorine kills cells by attacking the cell walls. Hypochlorous acid enters the cell wall with water and breaks down enzymes in the cell wall, leaving the bug open to attack. not unlike a series of photon torpedoes knocking shields down leaving the ship vulnerable

27

Coliform bacteria Fecal Coliforms Escherichia coli (E. coli) E. coli O157:H7

Common soil & intestinal bacteria Is the source warmblooded animals? Clear indication of human sewage or animal waste. Many harmless strains

z Very

harmful strain z 2-7% infected develop hemolytic uremic syndrome (HUS) z 3-5% w/ HUS die

The enemy: Primary target bugs

Chlorine gas rapidly hydrolyzes to hypochlorous acid according to: Cl2 + H2O HOCl + H+ + Cl Aqueous solutions of sodium or calcium hypochlorite hydrolyze to: Ca(OCl)2 + 2H2O Ca2+ + 2HOCl + 2OH NaOCl + H2O Na+ + HOCl + OH The two chemical species formed by chlorine in water, hypochlorous acid (HOCl) and hypochlorite ion (OCl ), are commonly referred to as free or available chlorine. Hypochlorous acid is a weak acid and will disassociate according to: HOCl H+ + OCl In waters with pH between 6.5-8.5, the reaction is incomplete and both species (HOCl and OCl ) will be present. Hypochlorous acid is the more germicidal of the two.

Chlorination

28

Percentage of free chlorine species

100 90 80 70 60 50 40 30 20 10 0

Best disinfection pH 6 - 7 ...BUT... 50:50 equilibrium at pH 7.5

HOCl OCl-

Corrosivity concerns below pH 7.5

pH and Free Chlorine Distribution

Chlorine is reduced to chlorides by easily oxidizable stuff (H2S, Fe2+, etc.)

Cl2 Chloramines consumed by broken down reaction with & converted organic to nitrogen matter. If gas which NH3 is leaves the present, system chloramine (Breakpoint). formation begins.

At this point,THM formation can occur

Chlorination Basics

29

What is it? Free chlorine that has combined with ammonia

(NH3)or other nitrogen-containing organic substances. Typically, chloramines are formed .

Where does Present in some source waters (e.g., surface water). Some systems (about 25% of U.S. water NH3, etc come from? supplies) actually ADD ammonia. Why would Monochloramine retains about 5% of free chlorine's disinfection power, but its not powerful enough to you ADD ammonia? continue producing toxic chlorinated organics. Lasts

a lot longer in the mains than free chlorine, Chloramine disinfection does not form nearly as many (as chlorine alone) disinfection byproducts: Trihalomethanes (THMs) Haloacetic Acids (HAAs) THMs = suspect carcinogens (long term ingestion at high levels)

Combined Chlorine

a) Cl2 (gas) + H2O reacts to form hypochlorus acid, HOCl & HCl hydrochloric acid. b) If pH > 8, the HOCl dissociates to hypochlorite ion OClIf however, the pH << 7, then HOCl will not dissociate. c) If NH3 is present, HOCl will react to form one of 3 types of chloramines depending on the pH, temperature, and reaction time. Monochloramine: NH3 + HOCl -> NH2Cl + H2O pH 4.5 to 8 (more common at 8) Dichloramine: NH2Cl + 2HOCl -> NHCl2 + 2H2O pH 4.5 to 8 Trichloramine (stinks!): NHCl2 + 3HOCl -> NCl3 + 3H2O common when pH < 4.5 Chloramines: effective vs. bacteria but NOT viruses. Thus...add more chlorine to prevent the formation of chloramines and form other stronger forms of disinfectants. d) additional free chlorine + chloramine = H+, H2O , and N2 gas which will come out of solution.

Chloramine Formation

30

zRecent

study on effect of chlorine on E. coli z Tested 6 strains of O157:H7 at 4 Cl2 levels 1 0.25 mg/L 1 0.5 mg/L 0 0.5 1 and 2 mins 1 1.0 mg/L 1 2.0 mg/L contact time

z
z

5/6 isolates + E. coli control strain were highly susceptible to chlorine

>7 log10 reduction of each of these strains by 0.25 mg/L free chlorine within 1 min
Each log10 = 90% reduction; 4 log 10 = 99.99% reduction SDWA requires 4 log reduction

Effect of Cl2 on E.coli

From: Reynolds & Richards, 1996. Unit Processes in Environmental Engineering.

Chlorine Concentration mg/L

2-6 C, 99% reduction

pH controlled
HO Cl

OC l-

Insufficient free Cl2

NH
2C

Minutes, tc Hypochlorous acid >> Hypochlorite >> Chloramines

Effectiveness of chlorine forms vs. E. coli

31

Reprinted from Journal American Water Works Association 54, 1379, Nov.1962,
CT= 2 CT= 5 CT= 1 CT= 10

}CT = 0.3

Chlorine vs. time at 0-5 C

Reprinted from Journal American Water Works Association 54, 1379, Nov.1962,

Chlorine vs. time at 10 C

32

Reprinted from Journal American Water Works Association 54, 1379, Nov.1962,

Chlorine vs. time at 20-29 C

100 80 60

20-29C 10 C 0-5C

pH= 7 pH= 8.5

Time, minutes

40 20 10

0 0.02 0.05 0.1

0.2

0.5

10

20

50 100

Chlorine vs. time at composite view

Free Available Chlorine (FAC), ppm

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PROCEDURE FOR DISINFECTION OF DRINKING WATER IN ONTARIO

June 2003

Virus inactivation by Chlorine

Summary of C.t values (mg/L. min)for 99% inactivation (2 log) at 5C (Clark et al, 1993)

Disinfectant Options and Various bugs

a Values for 99.9% inactivation at pH 6-9. b 99% inactivation at pH 7 and 25C. c 90% inactivation at pH 7 and 25C.

34

From: GLI Application Note

#AN-OZ1

4-logs

Disinfectant Options and Giardia

1. The best disinfection occurs at lower pH 2. If you have high alkalinity and high pH (> 8) consider longer chlorine contact time due to reduced efficiency of the hypochlorite form 3. Chlorine (hypochlorite) is a strong base. Therefore, in a low alkalinity system, be wary of pH changes with chlorination.

pH & disinfection (chlorine):

What you need to know

35

Chloramination Bromination Iodination??? Chlorine Dioxide Ozone UV

Chlorination Alternatives

Addition of ammonia (NH3) and chlorine (Cl2) compounds separately. Compounds typically used: Anhydrous ammonia Hypochlorous acid (HOCl) Ammonia is applied first because it tends to prevent formation of trichloramine (chlorinous odor and taste) Adding ammonia first also prevents the formation of THMs. Target ratio: 3:1 HOCl to NH3 produces the best tasting water Reactions Monochloramine: NH3 + Cl2 = NH2Cl + HCl (at pH >8.5) Dichloramine: NH3 + 2Cl2 = NHCl2 + 2HCl (at a pH 4.4 to 5.0) Trichloramine: NH3 + 3Cl2 = NCl3 + 3HCl (at a pH < 5.0)
pH control is key to successful chloramination in public water supplies

Chloramines as a disinfectant

(Note for breakpoint chlorination): To eliminate NH3 in drinking water using the breakpoint process, (e.g., surface water supply) chlorine is fed at a ratio of 10-12 to 1 to the ammonia level. When chloramines are used, the distribution system must be continually monitored for mono- and dichloramine residuals and DO. Total chlorine is not enough.

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 Potential problems with using chloramination: Addition of NH3 may compromise the water quality at the tap Should the residual chloramine be depleted in the distribution system, serious dead-end problems can result. Nitrification can occur. Residual chloramines can pass through RO membranes on dialysis machines which can cause damage to red blood cells. Chloramines are toxic to aquatic life in aquariums. Requires longer contact time to be effective germicidal agent. The process is complex, requires careful control and continual monitoring. Taste and odor problems can occur without properly control. Taste and odor thresholds concentrations: o Free chlorine (HOCl): 20 mg/L o Monochloramine (NH2Cl): 5.0 mg/L o Dichloramine (NHCl2): 0.8 mg/L o Trichloramine (nitrogen trichloride) (NCl3): 0.02 mg/L

Chloramines as a disinfectant

Those elements in the same column share similar properties, thus we can expect Bromine and Iodine to have some disinfectant capability. As one moves downward through a column, molecular weight increases increasing toxicity potential. [Notice the proximity of Iodine (I)to toxic heavy metals such as antimony (Sb) and lead (Pb)]

Periodic Table - Halogen sequence

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Bromine

Iodine
H2O + I2 H+ I- + HOI

H2O + Br2 H+ +Br - + HOBr

Major difference (vs. Cl2): effectiveness starts dropping at pH 8.5 Does form bromaminesas effective as HOBr Bromine is relatively scarce, making it more expensive choice Bromine is more physiologically active thus its use is limited.

Effectiveness NOT affected by pH Does NOT react with ammonia (no Iodamines) Iodine is very scarce, making it a very expensive choice Iodine is extremely physiologically active (i.e., thyroid gland)thus its use is limited.

Bromine & Iodine Disinfection

Initially used at Niagara Falls water utility (ca. 1944) for taste & odor control. Produced by reacting sodium chlorite with chlorine or an acid.

Advantages
Strong disinfectant Does NOT produce THMs effective vs. Cryptosporidium & Giardia weakens organism allowing chlorine to work

DIS-Advantages

Chlorine Dioxide Disinfection

Relatively expensive to generate; explosive above 10% Unstable--reverts to chlorite & chlorate (other DBPs)

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3 O2 2 O3 (ozone) O3 O2 + O (oxygen radical) Bugs killed immediately upon contact (cell rupture) Oxygen radical apparently is the actual cause strongest disinfectant used in water treatment effectiveness unimpaired by NH3 or pH leaves DO in its wake Must be generated on-site no residual difficult to adjust to differing demand expensive

Ozone Disinfection

ADVANTAGES Strong oxidizing power + short contact time = effective kill of bugs & viruses in seconds; Produces no taste or odor; Provides oxygen to the water after disinfecting; Requires no chemicals; Oxidizes iron and manganese; Destroys and removes algae; Reacts with and removes all organic matter; Decays rapidly in water, avoiding any undesirable residual effects; Removes color, taste, and odor; Aids coagulation.

DIS-ADVANTAGES Toxicity with concentration and exposure time; Cost is > chlorination; Installation can be complicated; Ozone-destroying device is required at the exhaust May produce undesirable aldehydes and ketones by reacting with certain organics; No residual in distribution system, post-chlorination is required; Much less soluble in water than chlorine; thus special mixing devices are necessary; and Oxidizes some refractory organics either too slowly or not at all to be of practical significance.

Ozone - Advantages & Disadvantages

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Kill bugs by oxidizing their enzymes and destroying genetic material Most effective wavelength is 2,650 Angstroms() (anything less than 3,100 is effective) Mercury vapor lamp is economical, produces 2,537 Water needs to be clear/colorless and shallow (3-5 deep) No residual effect Cost is high

UV Disinfection

Chlorine in very low doses and minimal contact time can easily kill even the most heinous of bacteria (E. coli O157:H7) Some of the alternative disnfection techniques CAN provide superior disinfection to chlorine, but there are cost and maintenance issues to consider Many alternative techniques still require postchlorination to meet NR 809 requirements.

Disinfection Techniques Summary

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Arsenic In Drinking Water. And Treatment Options

The Safe Drinking Water Act requires EPA to revise the existing 50 parts per billion (ppb) standard for arsenic in drinking water. On January 22, 2001 EPA adopted a new standard and public water systems must comply with the new 10 ppb standard beginning January 23, 2006

Arsenic and Treatment Options

The valence states of As are: -3, 0, +1, +3, and +5 (Welch et al., 1988). Elemental arsenic (valence 0) is rarely found under natural conditions. The +3 and +5 states are found in a variety of minerals and in natural waters. The valence state affects the toxicity of arsenic compounds. arsine (-3) > organo-arsines > arsenites (+3) > arsenates (+5) > arsonium metals (+1) > elemental arsenic (0). Concentrations of As in the earths crust range 1.5 - 5 mg/kg Arsenic is a major constituent of many mineral species in igneous and sedimentary rocks; Igneous rock types-- the highest arsenic levels in basalts. Sedimentary rocks higher As than igneous; particularly Fe/Mn

Arsenic (As) General Information

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Illustration of well bored through bedrock containing arsenic bearing minerals

Sulfide deposits-source of arsenic

Taken from:

Arsenic Where does it come from?

Kahn, B. July 2001. Arsenic Speciation at Landfill Facilities http://www.ccaresearch.org

Oxidising Condition 0.75 0.50 0.25 Eh (volts) 0 -0.25 -0.50 -0.75 Reducing Condition 0

As(V) +5 As(III) +3 AsS +3

Most surface waters Most ground waters

Predicted Landfills

As(III) -3 AsH3 (aq)

2 4 6 pH 8

As

10

12

14

Measure of system state (O2/no O2) Soluble As increases with decreasing Eh & increasing pH As (V) is expected to be the predominant form.

Arsenic Mobility Eh-pH Diagram

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An Arsenic Advisory Area was established by the Dept. of Natural Resources (DNR) in the early 1990s. This area includes a strip of land about ten miles wide extending, in a northeasterly trend, from a location just southwest of Oshkosh, to a location just west of Green Bay.

PWS with As Detects above 5 ppb

Source: http://www.dnr.state.wi.us/org/water/dwg/arsenic/index.htm

6% 12%

2%

1%

Arsenic Levels in Public wells

Note: an additional 4 wells (0.13%) tested at > 50 ppb arsenic

79%
ND-3 ppb 3-5 ppb 5-10 ppb 10-20 ppb 20-50 ppb

2000 DNR study of 3182 PWS wells

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9 Increased risk of skin cancer 9 Increased risk of internal cancers (bladder, prostate, lung and other sites) 9 Thick, rough skin on hands and feet 9 Unusual skin pigmentation (dappling of dark brown or white splotches) 9 Numbness in the hands and feet 9 9 9 9 Circulatory disorders Tremors Stomach pain, nausea, diarrhea Diabetes (not confirmed)

Effects are irreversible

Arsenic Health Effects

http://www4.nationalacademies.org/news.nsf/fc340309c47a1e43852567460067595e/c2f3467f548f460c85256ac4006d092a?OpenDocument

) Both the US Environmental Protection Agency and the World Health Organization have set the standard at 10 g/l.
Here is the cancer risk:
0.5 ppb 1 ppb 3 ppb 5 ppb 10 ppb 20 ppb 1 in 10,000 1 in 5,000 1 in 1,000 1.5 in 1,000 >1 in 333 1 in 143

from: National Academy of Sciences

What level of Arsenic is safe?

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http://www.epa.gov/ogwdw/ars/asdecisiontree/schema_8.html?pg=34

The EPA has developed an extensive Arsenic treatment decision tree. Step 1= if As is in +3 form, you will have to oxidize it to the +5 form EPAs Decision Tree for Arsenic Treatment

Existing Technology
Coagulation/Filtration
Polymer Alum Fe-based
may require use of Fe; sludge issues requires pH < 7.5, may need to add Fe lower pH to 5-7, increase Alum addition pH to 5.5-8.5, increase Fe addition requires pH 10.5-11; add Mg or Fe best with Fe: As of 20:1

Lime Softening Fe/Mn Filtration

Emerging Technology
Ion Exchange Activated Alumina Filtration/Membranes Electrochemical
TSS and Fe ppts clog, anions compete other ions (Cl-, SO4=) compete for sites best with Fe: As of 20:1 currently used in Europe only

Treatment Options Summary

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www.htnweb.com/downloads/hhremove_ar.pdf

Viraraghvan,T., Subramaniam, K.S., and Swaminathan, T. V., - Drinking water without arsenic: A review of treatment technologies, March 1996, ENSIC, Asian Institute of Technology, Bangkok

As Treatment Technology Effectiveness

EPA: Technical Fact Sheet: Final Rule for Arsenic in Drinking Water (January 2001)

Total Annual Costs ($) per Household for Community Water Systems (CWS System Size Annual Household Costs 25-500 501-3,300 3.3K-10K >10K

$ 327-$162

$ 71-$58

$ 38

$32-$0.86

The estimated average annual costs for CWSs, which exceed the final MCL of 10 g/L (required to treat) are shown below categorized by system size.

Average Annual Costs per CWS (Dollars) CWS System Size 25-500 501-3,300 3,300-10,000 10,000 and above Costs ($ ) $6,494-$12,358 $22,100-$53,086 $111, 646 $531,584-$1,340,716
EPA 815-F-00-016

As Treatment Technology Costs

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www.htnweb.com/downloads/hhremove_ar.pdf

As Treatment technology Costs

Viraraghvan,T., Subramaniam, K.S., and Swaminathan, T. V., - Drinking water without arsenic: A review of treatment technologies, March 1996, ENSIC, Asian Institute of Technology, Bangkok

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