5.3 Chloramines, Chlorine Dioxide, Ozone & UV
Key Takeaways
- Chloramines are weak disinfectants but persist far longer than free chlorine, making them a secondary residual rather than a primary disinfectant.
- The target chlorine-to-ammonia-nitrogen weight ratio for monochloramine formation is about 4:1 to 5:1.
- Chlorine dioxide does not form trihalomethanes, but its chlorite plus chlorate residuals are regulated, with chlorite carrying an MCL of 1.0 mg/L.
- Disinfectant strength ranks ozone first, then chlorine dioxide, then free chlorine, then chloramines; ozone leaves no residual and forms bromate when bromide is present.
- UV inactivates Cryptosporidium and Giardia at low doses but has no effect on viruses at those doses and leaves no residual.
5.3 Chloramines, Chlorine Dioxide, Ozone & UV
Every disinfectant is a trade. Gain oxidizing power and you usually gain disinfection byproducts; gain persistence and you usually lose inactivation strength. South Carolina's facility grouping makes this concrete: a plant that adds chloramine moves into Group II, while a plant using chlorine dioxide, ozone, or UV lands in Group III, V, or VI depending on source water — so the disinfectant you select literally determines the operator class the plant requires.
1. Relative Strength and Persistence
That inversion is the whole story. The strongest disinfectant persists the least; the most persistent disinfects the least. Most modern plants therefore run a two-stage strategy: a strong primary disinfectant for inactivation at the plant, and a persistent secondary disinfectant to hold a residual through the distribution system.
2. Chloramines
Chloramines form when free chlorine reacts with ammonia. The species depends on the chlorine-to-ammonia-nitrogen weight ratio and the pH:
| Species | Forms at | Character |
|---|---|---|
| Monochloramine (NH₂Cl) | Cl₂:N ratio near 4:1 to 5:1, pH above about 8 | The desired species — stable, low taste and odor |
| Dichloramine (NHCl₂) | Higher ratios, lower pH | Strong unpleasant taste and odor |
| Trichloramine (NCl₃) | Excess chlorine, low pH | Very objectionable odor |
Advantages: long-lasting residual deep into the distribution system; substantially lower trihalomethane and haloacetic acid formation; better control of biofilm regrowth over long detention times.
Disadvantages and operational risks:
- Weak disinfectant — provides very little practical CT credit; must not be relied on as the primary disinfectant.
- Nitrification. Excess free ammonia feeds ammonia-oxidizing bacteria in the distribution system. The signature is falling chloramine residual, rising nitrite and nitrate, falling dissolved oxygen and pH, and rising heterotrophic plate counts — most often in summer, in dead ends, and in oversized storage tanks. Control with tank turnover, flushing, residual maintenance, and periodic free chlorine burnouts.
- Toxic to dialysis patients and to fish, requiring notification of hospitals, dialysis centers, and aquarium owners before conversion.
3. Chlorine Dioxide (ClO₂)
Generated on site from sodium chlorite, because it is explosive under pressure and cannot be shipped as a compressed gas.
- Effective across a wide pH range — unlike free chlorine, its performance does not collapse as pH rises.
- Does not form trihalomethanes or haloacetic acids — a major advantage on high-TOC source water.
- Excellent for taste and odor and for iron and manganese oxidation.
- Regulated byproducts: chlorite carries an MCL of 1.0 mg/L, and the chlorine dioxide MRDL is 0.8 mg/L. Chlorite must be monitored daily at the entry point.
- Can cause odor complaints described as kerosene or cat-urine-like, arising from reactions with new carpet and paint indoors.
4. Ozone (O₃)
Generated on site by passing dry air or oxygen through a high-voltage corona discharge.
- The strongest common disinfectant and highly effective against Cryptosporidium, which resists chlorine almost entirely.
- Excellent for taste and odor, color, iron and manganese.
- Leaves no residual whatsoever — a secondary disinfectant is mandatory.
- Forms bromate when the source water contains bromide. Bromate has an MCL of 0.010 mg/L, and controlling it may require pH depression or ammonia addition.
- Breaks large organics into smaller, more biodegradable fragments (AOC/BDOC), which feed regrowth downstream. Ozone is therefore usually paired with biologically active filtration to consume that material before it reaches the distribution system.
- Ozone is toxic to breathe; ambient ozone monitors and off-gas destruct units are required.
5. Ultraviolet (UV) Light
UV inactivates organisms by damaging their nucleic acid so they cannot reproduce. Dose is expressed in millijoules per square centimeter (mJ/cm²).
| Organism | Approximate UV dose for 4-log inactivation |
|---|---|
| Cryptosporidium | ~22 mJ/cm² |
| Giardia | ~22 mJ/cm² |
| Viruses (e.g., adenovirus) | ~186 mJ/cm² |
The exam point: UV is superb against protozoa at low dose — exactly the organisms chlorine struggles with — but achieving virus credit requires an order-of-magnitude higher dose. Plants therefore commonly use UV for Crypto/Giardia credit and chlorine for virus credit.
Operational considerations:
- No residual — a secondary disinfectant is mandatory.
- UV transmittance (UVT) governs performance; turbidity, iron, and organics absorb UV and shield organisms.
- Sleeve fouling and lamp aging reduce delivered dose; sleeves need mechanical or chemical cleaning, and lamps are replaced on an hours-based schedule.
- No disinfection byproducts are formed, which is a significant advantage on high-TOC water.
6. Selection Summary
| Free Cl₂ | Chloramine | ClO₂ | Ozone | UV | |
|---|---|---|---|---|---|
| Residual | Yes | Yes, longest | Short | None | None |
| THM/HAA5 formation | High | Low | None | None (forms bromate) | None |
| Crypto inactivation | Very poor | Very poor | Moderate | Excellent | Excellent |
| Virus inactivation | Good | Poor | Good | Excellent | Poor at typical dose |
| Regulated byproduct | TTHM 0.080, HAA5 0.060 mg/L | — | Chlorite 1.0 mg/L | Bromate 0.010 mg/L | None |
| SC facility group impact | Group I or II | Group II | Group III / IV | Group VI | Group V |
Which disinfectant provides the longest-lasting residual in a distribution system but the weakest inactivation?
A plant using UV as its primary disinfectant must still feed chlorine. Which statement best explains why?
Which regulated byproduct is specifically associated with ozonation of a source water containing bromide?
A chloraminated system reports falling chloramine residual, rising nitrite, and rising heterotrophic plate counts in a summer dead end. What is occurring?