Water Quality 

  1. Chlorination
  2. Alternatives to Chlorination
  3. Swimming Pool Standards

 

 

Chlorination 

Chlorination has been used on an emergency basis from as far back as 1850. Continuous chorination of public water supplies began in 1904 in England, and was followed by the U.S. around 1909. After the facilities for gaseous chlorine were developed in 1912, chlorination grew rapidly. In that time, infectious waterborne diseases have decreased dramatically. Chlorine may have saved more lives than antibiotics.

Nevertheless, chlorine has had its share of controversy. Chlorine use was delayed until 1909 in the U.S. because of a lawsuit arguing it was unsafe. Indeed, concentrated chlorine gas is extremely toxic. As recently as the mid-1990's, the Clinton Administration proposed a ban on chlorine (the "Chlorine Zero Discharge Act"). In many ways it is understandable, because chlorine helps makes up dioxins and PCB's, not to mention the CFC's role in stratospheric ozone depletion. However, the law was not passed when a group of scientists pointed out that chlorine is already found in nature [salt (sodium chloride) comes to mind...]. Moreover, chlorine plays a huge role in the safety of our water supplies.

To better understand the issues, we need to take a closer look at chlorine chemistry. Chlorine can be found in gas, liquid, and solid forms as shown below. The key compunds are shown in red, and are further discussed below.

1. Gas: Cl2

C12

+

H20

<-->

HCL

+

HOCl

<-->

OCL-

+

H+

(Elemental Cl gas)

(Hypochlorous Acid)

(Hypochlorite Ion)

2. Liquid: sodium hypochlorite (bleach)

NaOCl

+

H20

<-->

Na+

+

OCL-

< H+>

HOCl

(Sodium Hypochlorite)

(Hypochlorite Ion)

(Hypochlorous Acid)

3. Solid: calcium hypochlorite (as powder or tablets)

Ca(OC1)2

+

H20

<-->

Ca++

+

2 OCL-

< H+>

HOCl

(Calcium Hypochlorite)

(Hypochlorite Ion)

(Hypochlorous Acid)

HCl (hydrochloric acid) is actually ineffective in killing microbes at the concentrations used in water treatment. HOCL (hypochlorous acid) is the active form that kills the microbes (concentrations of about 0.2-1.2 ppm are needed for drinking water supplies). OCl- (hypochlorite ion) also is an active killing ingredient, and along with HOCl makes up what we refer to as "free available chlorine." HOCL is roughly a eighty times more effective in killing power than OCl-, largely because the uncharged HOCL is more effective in penetrating cell walls.

How much chlorine do we need to add? It depends... on the quality of the water. Not all of the chlorine is converted to free available chlorine (i.e., the HOCl and OCl- that makes up the active killing ingredients). The chlorine can participate in a variety of reactions, yielding one of the strangest curves we see in our field:

For a graph like the one above, we normally expect a straight line (i.e., "what you add is what you get" in the form of a residual). But a number of reactions are acting to reduce the free chlorine residual, and we can analyze them by referring to each of the letters in the graph (a, b, c, and d):

a.

Fe++ --> Fe+++

Mn++ --> Mn+++

NO2- --> NO3-

Because of these three reactions, chlorine is reduced to HCl. The more iron, manganese, and nitrites in the water, the more of these reactions that occur.

b. Combined chlorine

b1. Chloro-organics

In the first part of this curve (labelled b1), chlorine is combining with various organics in the water.

b2.  HOCL + NH3     -->  NH2Cl (monochloramine)
       HOCL + NH2Cl  --> NHC12 (dichloramine)
       HOCL + NHC12 --> NC13 (trichloramine)

In the second half of this curve (labelled b2), chlorine is combining with ammonia in the water, forming what we collectively refer to as combine chlorine, or chloramines.

c. --> --> --> HCl + N2

A variety of reactions occur starting with letter c on the curve, ultimately releasing HCl and nitrogen gas. We sometimes refer to this as "burning off the chloramines."

d. Free available chlorine

Once we have "burned off the chloramines," any additional chlorine is converted directly into free available chlorine. Letter d is also referred to as the "breakpoint", and this type of chlorination is referred to as "breakpoint chlorination."

 

 
 
 
 
 

Alternatives to Chlorination    

 

Objective: The purpose of this section is to analyze the alternatives to chlorination for their advantages and disadvantages (relative to traditional chlorination). A "+" means the alternative has a relative advantage over chlorination, and a "-" has a relative disadvantage relative to chlorination.

A. General considerations:
 
   +:  All the alternatives will reduce microbes and THM's
   -:  All the alternatives tend to cost more than chlorination
 
 
B. The alternatives:
 
   1. Chloramines:                                             
                                                               
      +:  chloramine residual is more stable                          
      -:  chloramines need longer contact times                      
          chloramines may add taste and odor                               
          dialysis patients are susceptible                    
                                                               
   2. Chlorine dioxide (ClO2):                                         
                                                               
      +:  ClO2 more effective in disinfection                       
          ClO2 destroys many taste and odor compounds               
      -:  ClO2 must be generated on site                            
          no reliable test for the residual                    
                                                               
   3. Iodine:                                                  
                                                               
      +:  Iodine more effective in disinfection                       
          Iodine has little reaction with organics                        
          Iodine safe to transport                                    
          Iodine leaves a traceable residual                          
      -:  expensive                                            
          taste and odor                                       
                                                               
   4. Ozone (O3):                                                   
                                                               
      +:  Ozone more effective in disinfection                       
          Ozone destroys many taste and odor compounds               
      -:  Ozone must be generated on site                            
          Ozone has no residual protection                               
                                                               
   5. U.V.:                                                    
                                                               
      +:  no added taste or odor  
      -:  interference by turbidity                             
          viruses are especially resistant                      
          no residual protection                                
                                                               
   6. Heat:                                                    
                                                               
      +:  good for emergencies, no taste or odor added         
      -:  impractical for large scale                          
          no residual protection                              
 
 
 
 
 

 

California Swimming Pools Standards

Objective: The purpose of this assignment is understand some of the minimum legal requirements for public pools in California for:

Disinfection

1. Free chlorine residual: at least 1 ppm is required. This is to be achieved by automatic hypochlorinators (units which provide for continuous chlorination) that are listed by NSF (the National Sanitation Foundation).

2. pH: must be between 7.2 to 8.0. If necessary, soda ash can be added to raise the pH. More typically, the pH naturally rises from the use of hypochlorites.

3. Other disinfectants: others may be used, provided that they are registered with the EPA for disinfectant use, and that they provide a protective residual.

 

Clarification

4. Turbidity: the drain must be visible (this is, of course, the deepest point)

5. Filters: filtration units are similar in concept to units discussed for water treatment (e.g., diatomaceous earth filters)

6. Turnover time: this is the time it takes for a unit to filter the complete volume of a pool. The minimum legal standard in California is once every 6 hours for pools, and once every 1/2 hour for spas.

 

Safety

7. Lifesaving equipment: life rings must be at least 17 inches in diameter, with a line (rope) that is long enough to span the maximum width of the pool. Rescue poles (long poles with body hooks) must be at least 12 feet long.

8. Posted signs: if there is no lifeguard, a sign must be posted stating "Warning -- No Lifeguard On Duty."

9. Access: access to the pool must be limited by fencing (at least 4 ft. high) with gates that must be self closing and self latching.

 

Other

10. Records: there must be daily records of maintainence (including chlorine levels, pH, etc.).

11. Spas, hottubs: high temperatures can be especially risky to the elderly; the powerful suction at the bottom of spas can also, in some cases be, risky. Numerous agents can be a risk in spas, including Pseudomonas aeruginosa (causing rashes). Naegleria fowleri, found in warm unfiltered waters, causes a deadly illness called PAM (primary amoebic meningoencephalitis).

 

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