Public Health Risk

Management Plan
Guide
Treatment Processes
– Chlorine Dioxide Disinfection
Version 1, Ref P7.2

June 2001
 Published in June 2001 by
Ministry of Health
PO Box 5013, Wellington, New Zealand

ISBN: 0-478-26144-6 (Booklet)

ISBN: 0-478-26145-4 (Internet)

This document is available on the Ministry of Health’s Web

site:
http://www.moh.govt.nz
Contents

Introduction 1

Risk Summary 2

Risk Information Table 3

Contingency Plans 9

PHRMP Performance Assessment 12

Ref P7.2 Public Health Risk Management Plan Guide: iii

Version 1, June 2001Treatment Processes – Chlorine Dioxide Disinfection
Introduction
Chlorine dioxide (ClO2) treatment is used to disinfect, or oxidise
contaminants in, drinking-water. This Guide is concerned only with
using chlorine dioxide as a disinfectant.

If an event occurs during chlorine dioxide treatment (ie, the treatment

process doesn’t work properly), the following could happen:
 If there is not enough chlorine dioxide, germs can cause sickness
 If there is too much chlorine dioxide, sickness can come from either
the high chlorine dioxide concentration or from chlorine dioxide by-
products
 High concentrations of by-products from chlorine dioxide treatment
can cause sickness, even when the chlorine dioxide levels are
acceptable.

The on-site generation and use of chlorine dioxide can present risks to
the health of treatment plant staff. These are acknowledged, but are
not discussed further as such risks are the subject of health and safety
in employment legislation.

The chlorine dioxide treatment process and the risks associated with it
cannot be viewed in isolation. This Guide only looks at the introduction
of chlorine dioxide into the water. Chlorine dioxide’s value as a
disinfectant is also affected by elements of the water supply system
dealt with in other Guides.

Several factors influence how effective disinfection is:

 whether the chlorine dioxide dose is large enough for other
substances in the water to react with the chlorine dioxide and still
leave enough chlorine dioxide to disinfect the water effectively
(discussed in this document)
 how long the chlorine dioxide is in contact with the water (see
Guide D1)
 water temperature
 turbidity of the water with the chlorine dioxide is added to it; this
can hinder the access of chlorine dioxide to germs (see the S1, P1,
P5 and P6 series of Guides).

If disinfection with chlorine dioxide is going to work as well as possible,

all these factors have to be taken into consideration.

Treating poor quality water with chlorine dioxide can lead to the
formation of high concentrations of chlorite. For this reason, chlorite is
always a Priority 2 determinand (see the DWSNZ:2000 for a definition of
Priority 2 determinands) when chlorine dioxide treatment is used.

Ref P7.2 Public Health Risk Management Plan Guide: 1

Version 1, June 2001Treatment Processes – Chlorine Dioxide Disinfection
2 Public Health Risk Management Plan Guide: Ref P7.2
Treatment Processes – Chlorine Dioxide Disinfection Version 1,
June 2001
Risk Summary
The event creating the greatest risk involved in the chlorine dioxide
treatment of drinking-water is not having enough chlorine dioxide in the
water to kill the germs (see P7.2.1).

The most important preventive measures are:

 monitor the process to be sure there is enough chlorine dioxide in
the water, even when the quality of the incoming water changes
(see P7.2.1.4)
 put alarms on the supplies of chemicals used for chlorine dioxide
generation to let you know when supplies are running low.
Maintain records so you are aware of when this might happen;
always have spare supplies on hand (see P7.2.1.6).

(References in parentheses are to the Risk Information Table.)

Ref P7.2 Public Health Risk Management Plan Guide: 3

Version 1, June 2001Treatment Processes – Chlorine Dioxide Disinfection
Risk Information Table
Reliable information about water quality is essential for the proper
management of a water supply. Knowledgeable and skilled staff are also
essential for minimising the public health risks associated with water
supplies. Please read the staff training (Guide G1) and the monitoring
guides (Guide G2). While we haven’t pointed out every detail of how
these documents are linked with the present document, the links are
many and are important.

NB: This PHRMP assumes chlorine dioxide generation through the

chlorine-chlorite process.

Abbreviations: DWSNZ – Drinking-Water Standards for New Zealand; MAV – Maximum acceptable
value – see DWSNZ: 2000

Causes Preventive Checking preventive measures Corrective

measures action
What to check Signs that action
is needed

Event: CHLORINE DIOXIDE (ClO2) CONCENTRATION TOO LOW

Possible hazards: Germs not killed chlorite (if generator conversion efficiency of chlorite is low).
Level of risk: High1

P7.2.1.1  Routine controller  ClO2 residual  Low ClO2  Identify

Dosing and dosing pump concentration. residual (see cause of fault
malfunction maintenance. Appendix). and rectify.
 Microbiologic
(see Guide  Replacement of al quality.  E. coli or  Manually
P10). controller if coliforms dose reservoir
 Maintenance
suspect. detected in with chlorine
log.
100 mL sample until repaired.
 Alarm system to
of water leaving
warn if ClO2  Replace
the treatment
residual controller.
plant.
concentration is
incorrect.  Frequent repair
needed.
 Maintenance
log not signed
off.

P7.2.1.2  Regular manual  ClO2 residual  Low ClO2  Recalibrate

Dosing checks on concentration. residual (see controller
controller’s calibration of Appendix). sensor.
 Microbiologic
sensor controller (see
al quality.  E. coli or  Increase ClO2
incorrectly DWSNZ: 2000
coliforms dose rate until
Section 3.3.4.8).  Calibration
calibrated. detected in recalibration
schedule.
100 mL sample undertaken.
of water leaving
the treatment
plant.
 Calibration
schedule not
signed off.

1 The consequences of the event, and therefore the level of risk, will be influenced by the quality of
the source water and the effectiveness of treatment processes prior to chlorine dioxide treatment.

4 Public Health Risk Management Plan Guide: Ref P7.2

Treatment Processes – Chlorine Dioxide Disinfection Version 1,
June 2001
 Causes Preventive Checking preventive measures Corrective
measures action
What to check Signs that action
is needed

Event: CHLORINE DIOXIDE (ClO2) CONCENTRATION TOO LOW cont’d

P7.2.1.3  Periodic manual  ClO2 residual  Low ClO2  Adjust

Dosing checks on ClO2 concentration. residual (see controller set-
controller’s residual Appendix). point.
 Flow rates.
set-point concentration,
 E. coli or
especially during  Dose flow
incorrect or coliforms
periods of water rates.
incorrect dose detected in
quality variability.
calculation.  Dose 100 mL sample
 Independent check calculations. of water leaving
on calculations the treatment  Recalculate
(especially after a plant. dose rates and
system change change
 Frequent
when expected settings.
calculation
dose rates are
errors found.  Train staff in
uncertain).
making dose
 Calculation
 Install visual flow calculations.
checks not
indicators to allow
signed off.
flow to be checked
by eye.  Flow rates
lower than
expected.

P7.2.1.4  Ensure that  ClO2 residual  Low ClO2  Replace dose

High ClO2 monitoring of the concentration. residual (see controller with
demand2 ClO2 residual is Appendix) , or more suitable
 Total organic
coupled with adequate so that E. coli or unit.
carbon (TOC)
poor dose ClO2 dosing can be coliforms
or colour.  Manual
control. adjusted to take detected in
monitoring
account of changes 100 mL sample
and manual
in water quality, or of water leaving
ClO2 control
use a controller the treatment
during poor
that automatically plant, only
water quality
adjusts the ClO2 during periods
episodes.
dose to maintain a of poor water
satisfactory quality.  Optimise
residual. upstream
 TOC or colour
processes to
 Upstream highly variable.
better reduce
processes removing
 Inadequate ClO2 demand.
substances
ClO2 residual
contributing to the  Replace
concentration
ClO2 demand from generator with
even when
the water. one with
generator
sufficient
 Ensure ClO2 running at
capacity.
generator can maximum.
deliver the
maximum required
dose rate.

P7.2.1.5  Stand-by  Electricity  Poor continuity  Refuel

Power failure. generator or supply. of power supply. generator (if
battery bank. appropriate).

2 Chlorine dioxide demand is the difference between the amount of chlorine dioxide added to the
water and the chlorine dioxide residual remaining after the chlorine dioxide has reacted with other
substances in the water. If the chlorine dioxide demand of the water increases without an increase
in the dose, too little disinfectant will remain to disinfect the water properly.

Ref P7.2 Public Health Risk Management Plan Guide: 5

Version 1, June 2001Treatment Processes – Chlorine Dioxide Disinfection
 Causes Preventive Checking preventive measures Corrective
measures action
What to check Signs that action
is needed

Event: CHLORINE DIOXIDE (ClO2) CONCENTRATION TOO LOW cont’d

P7.2.1.6  Place alarm on  ClO2 residual  Low ClO2  Install alarm

ClO2 supply supply of chemicals concentration. residual (see system.
exhausted. for ClO2 generation Appendix).
 ClO2 usage.  Hand-dose
to indicate when a
 E. coli or chlorine until
supply is close to  Levels of
coliforms system can be
running out. generation
detected in brought back
chemicals.
 Maintain records of 100 mL sample on line.
ClO2 use to provide of water leaving
a guide to the the treatment
length of time the plant.
chlorine and
 Level of ClO2
chlorite supplies
generation
are likely to last.
chemicals too
 Ensure spare low to allow
supplies of replacement
chemicals are before they run
always kept on site. out.

P7.2.1.7  Preventive  ClO2 residual  Low ClO2  Identify

maintenance concentration. residual (see cause of fault
ClO2 programme. Appendix). and rectify.
generator  Maintenance
malfunction. log.  E. coli or  Dose with
coliforms is chlorine until
detected in system can be
100 mL sample brought back
of water leaving on line.
the treatment
 Soften the water  Clear scale
plant.
used to make up from lines and
the sodium chlorite  Frequent valves.
solution to avoid repairs needed.
clogging by scale (if
water is hard).

P7.2.1.8 (See Guide P7.1 for preventive measures, checks and corrective actions.)
Chlorine flow
not reaching
generator.

P7.2.1.9  Carry out pilot  ClO2 residual  Low ClO2  Modify

ClO2 tests to determine concentration. residual (see chemical feed
generation optimum chemical Appendix). rates until
 Supplier’s
chemistry not feed rates for ClO2 ClO2
certificate of  E. coli or
optimised production. production
analysis for coliforms
(wrong maximised.
 Check chemical chemicals detected in
chlorine and flows are correctly used. 100 mL sample
chlorite ratio, set; pH set point is of water leaving
concentration correct. the treatment
s, or pH); plant.
 Ensure chemicals  Change
chemicals of
are of adequate  Unsatisfactory chemical
unsatisfactory
quality. Obtain chemical supplier.
quality; or
manufacturer’s quality.
wrong
certification.
chemicals  Require
used.  Ensure chemical chemical
storage containers supplier to
are properly only deliver
labelled and an when the
operator is present operator is
to supervise present.
delivery.

6 Public Health Risk Management Plan Guide: Ref P7.2

Treatment Processes – Chlorine Dioxide Disinfection Version 1,
June 2001
 Causes Preventive Checking preventive measures Corrective
measures action
What to check Signs that action
is needed

Event: CHLORINE DIOXIDE (ClO2) CONCENTRATION TOO LOW cont’d

P7.2.1.10  Routine  ClO2 residual  Low ClO2  Identify and

ClO2 supply maintenance of concentration. residual (see rectify causes
adequate, but pumps dosing ClO2 Appendix). of pump
insufficient solution. failure.
 Injector
ClO2 reaching  Pump capacity too blockages.  Obtain a new
dosing point. low to meet pump.
 Pump failure.
maximum ClO2
demand.  Inadequate
pump
specifications.

P7.2.1.11  Ensure ClO2 dosing  ClO2 residual  Low ClO2  Cover open
Exposure to solution is concentration. residual (see channels or
sunlight protected from Appendix). reticulate in
resulting in sunlight. pipes.
 E. coli or
photodecomp coliforms
osition of ClO2. detected in
100 mL sample
of water leaving
the treatment
plant.

P7.2.1.12  Provide staff  Analysis  Independent  Identify staff

ClO2 training for sample records. checks show training needs
monitoring analysis and record monitoring and provide
samples taken keeping. inaccuracies. training.
incorrectly or  Develop
incorrectly monitoring
recorded (see schedule and
Guide D4). roster.

P7.2.1.13  Provide staff  Analysis  Independent  Identify staff

Method of training for sample records. checks show training needs
ClO2 analysis and record monitoring and provide
measurement keeping. inaccuracies. training.
incorrect,
incorrectly
calibrated, or
reagents used
in analysis
have
deteriorated.

Ref P7.2 Public Health Risk Management Plan Guide: 7

Version 1, June 2001Treatment Processes – Chlorine Dioxide Disinfection
 Causes Preventive Checking preventive measures Corrective
measures action
What to check Signs that action
is needed

Event: CHLORINE DIOXIDE (ClO2) CONCENTRATION TOO HIGH

Possible hazards: Chlorite, chlorate, chlorine dioxide.
Level of risk: Low–moderate

P7.2.2.1  Routine controller  ClO2  ClO2 residual  Identify

Dosing and dosing pumps residual concentration cause of fault
malfunction maintenance. concentratio more than 50% of and rectify.
(see Guide n. its MAV.
 Replacement of  Replace
P10). controller if  Maintenanc  Frequent repair controller with
suspect. e log. needed. new unit.
 Fit an alarm to  Maintenance log
indicated incorrect not signed off.
CIO2 concentration.
P7.2.2.2  Regular manual  ClO2  ClO2 residual  Recalibrate
Dosing checks on residual concentration controller
controller’s calibration of concentratio more than 50% of sensor.
sensor controller (see n. its MAV.
 Manually
incorrectly DWSNZ:2000
 Calibration monitor and
calibrated. Section 3.3.4.8).
schedule not adjust ClO2
signed off. dose rate until
recalibration
undertaken.

Event: CHLORINE DIOXIDE (ClO2) CONCENTRATION TOO HIGH cont’d

P7.2.2.3  Periodic manual  ClO2  ClO2 residual  Adjust

Dosing checks on ClO2 residual concentration controller set-
controller’s concentration, concentratio more than 50% of point.
set-point especially during n. its MAV.
incorrect or periods of water
 Flow rates.  Frequent
incorrect dose quality variability.
calculation errors
 Dose
calculation.  Independent check found by checks.
calculations.
on calculations  Recalculate
 Calculation
(especially after a dose rates and
checks not signed
system change change
off.
when expected settings.
dose rates are  Flow rates below
 Train staff in
uncertain). expected values.
making dose
 Install visual flow calculations.
indicators to allow
flow to be checked
by eye.

P7.2.2.4  Use a control  ClO2.  ClO2 residual  Replace dose

Low ClO2 method that links concentration controller with
demand dose control to ClO2 more than 50% of more suitable
coupled with residual at its MAV. unit.
poor ClO2 dose appropriate
 Manual
control. location.
monitoring
and manual
ClO2 control
when water
quality is
variable.

8 Public Health Risk Management Plan Guide: Ref P7.2

Treatment Processes – Chlorine Dioxide Disinfection Version 1,
June 2001
 Causes Preventive Checking preventive measures Corrective
measures action
What to check Signs that action
is needed

P7.2.2.5  Check that a  ClO2.  ClO2 residual  Determine

ClO2 solution satisfactory ClO2 concentration the cause of
 ClO2 level in
strength from concentration is more than 50% of the high ClO2
the ClO2
generator too produced when its MAV. concentration
solution.
high. new supply of and rectify.
 ClO2
chemicals for
concentration in  Provide
generation is first
dosing solution is training in the
brought into use.
too high. preparation of
solutions
(including
calculations).

Event: EXCESSIVE FORMATION OF BY-PRODUCTS FROM CHLORINE DIOXIDE TREATMENT

Possible hazards: Chlorite, chlorate.
Level of risk: Moderate

P7.2.3.1  Carry out pilot  Chlorite.  Elevated levels  Modify

ClO2 tests to determine of chlorite and chemical feed
 Chlorate.
generation optimum chemical chlorate. rates until
chemistry not feed rates for ClO2 ClO2
optimised production. production
(wrong maximised,
 Checks to ensure
chlorine and and by-
chlorite solution
chlorite ratio, products
concentration is
concentration minimised.
correct.
s, or pH).  Identify staff
 Provide staff
training needs
training in chlorite
and provide
solution
training.
preparation.

Event: EXCESSIVE FORMATION OF BY-PRODUCTS FROM CHLORINE DIOXIDE TREATMENT

cont’d

P7.2.3.2  Provision of  TOC/colour.  Elevated  Optimise

Natural treatment TOC/colour. treatment
organic processes upstream parameters in
 Elevated chlorite
matter to reduce levels of upstream
formation.
present in the organic matter in processes to
water being the water. maximise
chlorinated removal of
(reduction of organic
ClO2 to matter.
chlorite).

Ref P7.2 Public Health Risk Management Plan Guide: 9

Version 1, June 2001Treatment Processes – Chlorine Dioxide Disinfection
Contingency Plans
If an event happens despite preventive and corrective actions you have
taken, you may need to consult with the Medical Officer of Health to
assess how serious a problem is.

Event – ClO2 concentration is lower than minimum effective

level

Indicators:  A detectable ClO2 residual cannot be obtained in

the water leaving the treatment plant.
 In 100 ml samples of water leaving the treatment
plant, E. coli or coliforms are continually
detectable, or E. coli is present at elevated levels
(more than 10 per 100 mL).
 Widespread illness in the community.

Required  Follow the actions given in Figure 3.2 of the

actions: DWSNZ: 2000.
 Identify the reason for the failure and rectify.
 Record cause of system failure and steps taken to
correct.
 Modify your PHRMP if necessary.

Responsibilit Manager designated responsible for the water supply.

y:

10 Public Health Risk Management Plan Guide: Ref P7.2

Treatment Processes – Chlorine Dioxide Disinfection Version 1,
June 2001
Event – ClO2 concentration is higher than maximum acceptable
value

Indicators:  Knowledge of a major overdose of ClO2 into the

water.
 Inability to obtain pink colour from DPD indicator
despite high ClO2 dose rates. (NB: This indicates
ClO2 levels well in excess of the MAV – very high
ClO2 levels bleach the pink colour that normally
develops in the presence of ClO2.)
 Change in the odour or taste of the water.
 Widespread levels of taste and odour complaints,
or illness, in the community.

Required  Close down the plant. Provide another source of

actions: potable water until water of acceptable quality can
again be supplied.
 Inform the MOH of the situation.
 Identify the reason for the ClO2 overdose and
rectify.
 Dump the reservoir water, or add chemicals to
neutralise the ClO2 if more appropriate
(neutralisation may be required as a condition of
the Resource Consent, anyway).
 Flush the distribution system, if excessive levels of
ClO2 are also present in the distribution system,
and monitor water quality until ClO2 concentrations
are again back to normal operating levels.
 Warn consumers to thoroughly flush their taps
before drawing water for use (if they are likely to
have been affected).
 Record cause of system failure and steps taken to
correct.
 Modify your PHRMP if necessary.

Responsibilit Manager designated responsible for the water supply.

y:

Ref P7.2 Public Health Risk Management Plan Guide: 11

Version 1, June 2001Treatment Processes – Chlorine Dioxide Disinfection
Event – Chlorite or chlorate concentrations higher than
maximum acceptable value (MAV)

Indicators:  Chlorite concentration more than 0.3 mg/L.

 Chlorate concentration more than 0.3 mg/L.

Required  Decrease the ClO2 dose, and monitor E. coli and

actions: coliforms to ensure that reduction in the ClO 2 has
not led to inadequate disinfection. The ClO 2 dose
should still meet the C.t requirements for
Cryptosporidium inactivation (see Appendix P7.2).
 Inform the MOH of the situation, and determine
what options for treatment changes could be
considered. Supplementary use of chlorine may
provide satisfactory disinfection.
 Record the steps taken to correct the problem.
 Modify your PHRMP if necessary.

Responsibilit Manager designated responsible for the water supply.

y:

12 Public Health Risk Management Plan Guide: Ref P7.2

Treatment Processes – Chlorine Dioxide Disinfection Version 1,
June 2001
PHRMP Performance
Assessment
To ensure that your supply’s Public Health Risk Management Plan is
working properly, periodic checks are needed. The overview document
outlines what needs to be done. The following table provides the
detailed information for checking this particular supply element.

What to  ClO2 concentration.

measure or
 E. coli (faecal indicator), coliforms.
observe:
 Chlorite and chlorate.
Follow the protocols set out in DWSNZ:2000.
Note that the presence of faecal indicators may be
influenced by factors other than the adequacy of the
chlorine dioxide process (eg, chlorine dioxide is not in
contact with water long enough).

How often:  For the monitoring frequencies for E. coli.

Measurements see DWSNZ:2000 Section 3.3.2.

What to do with  Results need to be recorded to meet legislative

the results: requirements or to allow PHRMP performance
assessment. The WINZ database is good for
this.
 The collected data need to be periodically
reviewed to see whether problems with this
supply element are developing. This should be
done as frequently as the manager responsible
considers necessary to minimise risk to public
health arising from this supply element.
 Should this review show any unusual incidents,
indicate that proper procedures are not being
carried out, highlight poor laboratory results or
indicate that poor water quality is reaching
customers, then review the procedures for
managing chlorine dioxide treatment.
 Evaluate the monitoring results, and any actions
taken as the result of having to implement a
contingency plan, to see if the PHRMP needs
modification – eg, preventive measures are up to
date; the contingency plan steps are still
adequate; and changes to the treatment
processes are recognised in the plan.

Ref P7.2 Public Health Risk Management Plan Guide: 13

Version 1, June 2001Treatment Processes – Chlorine Dioxide Disinfection
Responsibility: Manager designated responsible for the water supply.

14 Public Health Risk Management Plan Guide: Ref P7.2

Treatment Processes – Chlorine Dioxide Disinfection Version 1,
June 2001
Appendix (P7.2)

Table (P7.2): C.t values (mg.min/L) for inactivation of Cryptosporidium by

chlorine dioxide*

Temp (°C) 99% 99.9%

0.5 1530 2170

5 829 1180

10 429 609

15 227 322

20 123 174

25 67.8 96.3

30 38.2 54.2

* From Table 13.1 of the Drinking-water Standards for New Zealand 2000.

Ref P7.2 Public Health Risk Management Plan Guide: 15

Version 1, June 2001Treatment Processes – Chlorine Dioxide Disinfection