METHOD 334.

0: DETERMINATION OF RESIDUAL
CHLORINE IN DRINKING WATER USING AN ON-LINE
CHLORINE ANALYZER

Office of Water (4606 M) EPA 815-B-09-013 September 2009 www.epa.gov/safewater

METHOD 334.0: DETERMINATION OF RESIDUAL CHLORINE
IN DRINKING WATER USING AN ON-LINE
CHLORINE ANALYZER

Version 1.0

September 2009

Steven C. Wendelken, Derek E. Losh, and Patricia S. Fair

Office of Ground Water and Drinking Water

TECHNICAL SUPPORT CENTER

OFFICE OF GROUND WATER AND DRINKING WATER
U. S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
 METHOD 334.0

DETERMINATION OF RESIDUAL CHLORINE IN DRINKING WATER

USING AN ON-LINE CHLORINE ANALYZER

1. SCOPE AND APPLICATION

1.1 This method is for the analysis of residual chlorine (free or total) in drinking
water. It is primarily intended to be used by drinking water utilities for
compliance with daily monitoring requirements. This method allows the use of
any type of on-line chlorine analyzer (e.g., amperometric, DPD, etc.) for
compliance monitoring when used in conjunction with a grab sample reference
method that is approved for drinking water compliance monitoring. This method
is intended to be used when chlorine residuals (free or total) are in the range of
0.2 mg/L to 4 mg/L.

1.2 The grab sample reference method must be listed in the methods table of the
regulation under which the monitoring is being conducted. (A method in
Appendix A may be used if it is listed as approved for the regulation.) Color
wheels or optical comparison scales are not allowed for methods which specify
the use of a spectrophotometer.

2. SUMMARY OF METHOD

2.1 An on-line chlorine analyzer is used to continuously monitor the chlorine

concentration at a drinking water sample point. The instrument is calibrated using
aqueous standards or the results from paired grab samples that are collected at the
same sample point and time. The grab samples are analyzed for chlorine (free or
total) using a method that is approved for drinking water compliance monitoring.
The on-line analyzer accuracy is periodically verified/adjusted based on results
from grab sample analyses.

3. INTERFERENCES

3.1 A general discussion of potential interferences to the grab sample measurements

is included in Standard Method 4500-Cl A.1 More specific information is
included with each reference method and should guide the user when selecting a
method. Amperometric titration methods are less subject to interferences from
common oxidizing agents, turbidity and color. Organic contaminants and high
concentrations of monochloramine may produce false free chlorine readings in
colorimetric methods. Colorimetric methods specify procedures to reduce
interferences from copper, chromate, and reduced manganese. Strong oxidizing
agents (e.g., permanganate, ozone) interfere with free chlorine measurements in
all methods.

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 3.2 Consult the manufacturer’s literature regarding potential interferences to the
measurements by on-line chlorine analyzers. Amperometric analyzers are
sensitive to pH, flow and temperature changes, but compensation for these
variables is usually incorporated into the design of the analyzer. DPD analyzers
are subject to the same interferences as the DPD grab sample methods.

4. SAFETY

4.1 The toxicity or carcinogenicity of each reagent used in this method has not been
precisely identified; each chemical compound should be treated as a potential
health hazard, and exposure to these chemicals should be minimized. The
laboratory/water system is responsible for maintaining documentation of OSHA
regulations regarding the safe handling of the chemicals specified in this method.
A reference file of Material Safety Data Sheets (MSDS) should also be made
available to all personnel involved in the chemical analysis. Additional references
to laboratory safety are available.2-5

5. EQUIPMENT AND SUPPLIES

5.1 ON-LINE CHLORINE ANALYZER – The selection of an analyzer must

consider the water quality characteristics of the drinking water, the treatment
process, and the physical location of the analyzer installation. Some of the water
quality parameters to consider include variability in the water pH, temperature,
ionic strength and the presence of potential interferences such as iron, manganese,
and copper. The treatment process dictates whether the on-line analyzer must
measure free or total chlorine residuals. The concentration of residual chlorine
being measured establishes the required instrument range. The range should be
as small as possible, while still bracketing expected concentrations (e.g., Residual
concentrations in the range of 0.5 to 1.5 mg/L should be monitored using an
analyzer with a linear dynamic range of 0 to 2 mg/L rather than 0 to 10 mg/L.)
The analyzer must be installed according to the manufacturer’s instructions so
that changes in pressure or flow will not influence the analyzer measurements.
Install the analyzer as close to the sampling point as feasible and in a location that
is easily accessible for maintenance. Install a sample tap as close as feasible to
the location where the sample enters the analyzer to allow for collection of
discrete grab samples for calibration and accuracy verification.

5.1.1. The analyzer must have a readout at its installation location and the
readings must be continually recorded (hard copy chart or electronic
data). For remote installations, the analyzer should also have the
capability for transmission of the output to a centralized location.

5.1.2. The on-line monitoring system should have the capability to activate an
alarm when the chlorine concentration is outside the normal operating
range.

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 5.1.3. The analyzer must allow manual adjustment for calibration.

5.2 GRAB SAMPLE REFERENCE METHOD – Amperometric titration or N,N-

Diethyl-p-phenylenediamine (DPD) colorimetric methods are the most commonly
used approved grab sample methods. Additional choices are included in the
methods table of the regulation under which monitoring is being conducted.
Consult the method for a listing of equipment and supplies.

5.3 GLASSWARE – Free of chlorine demand. See ASTM D 1253-03 6 or Standard

Method 4500-Cl D 1, if glassware needs to be treated to remove chlorine demand.

5.3.1. BEAKERS – Varying sizes.

5.3.2. VOLUMETRIC FLASKS – Class A, of varying sizes.

5.3.3. PIPETTES – Class A, varying sizes or a variable volume single channel

pipette with disposable plastic tips. (e.g., Eppendorf Series 2000 pipetter,
No. 022470302; or Hach Tensette® pipette, No 1970001)

6. REAGENTS AND STANDARDS

6.1 REFER TO THE ON-LINE CHLORINE ANALYZER OPERATING MANUAL

FOR A LIST OF REAGENTS SPECIFIC TO THE INSTRUMENT– Reagent
grade or better chemicals should be used. Unless otherwise indicated, all reagents
should conform to the specifications of the Committee on Analytical Reagents of
the American Chemical Society, where such specifications are available. Other
grades may be used, provided it is first determined that the reagent is of
sufficiently high purity to permit its use without lessening the quality of the
determination. Reagents must be stored according to the manufacturer's
recommendations and only used within the manufacturer's designated lifespan
(prior to expiration date).

6.2 REFER TO THE SELECTED GRAB SAMPLE METHOD FOR A LIST OF

REAGENTS SPECIFIC TO THE METHOD – Reagent grade or better chemicals
should be used. Unless otherwise indicated, all reagents should conform to the
specifications of the Committee on Analytical Reagents of the American
Chemical Society, where such specifications are available. Other grades may be
used, provided it is first determined that the reagent is of sufficiently high purity
to permit its use without lessening the quality of the determination. Titrants that
are purchased in their diluted form, ready to use in the grab sample method,
should be NIST traceable or certified in an equivalent manner. Reagents must be
stored according to the manufacturer's recommendations and only used within the
manufacturer's designated lifespan (prior to expiration date).

6.3 REAGENT WATER – Purified water (typically either deionized or distilled) is

usually acceptable. Reagent water can be purchased from a scientific supply
company, if it is not available on site. If a chlorine demand is present, suggested

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 procedures for preparing chlorine demand-free water are included in ASTM D
1253-03 6 and Standard Method 4500-Cl C 1.

6.4 CALIBRATION STANDARD SOLUTIONS – Use the type of aqueous standard

(e.g., chlorine or potassium permanganate) specified in the selected grab sample
method. A concentrated stock standard solution can be purchased from a
commercial source (e.g., Environmental Resource Associates, Catalog # 696;
Hach, Product # 1426820, or equivalent). A purchased stock standard must be
NIST traceable or certified in an equivalent manner. The stock standard must be
stored according to the manufacturer's recommendations and only used within the
manufacturer's designated lifespan (prior to expiration date). The stock solution is
diluted using reagent water to obtain calibration standard solutions in the range of
0.2 mg/L to 4.0 mg/L. Calibration standards should be prepared fresh for each
use unless manufacturer’s instructions specify otherwise.

6.5 ROUTINE GRAB SAMPLE CALIBRATION CHECK STANDARD –

Calibration standards prepared above may also be used as calibration check
standards. Calibration check standards must be freshly prepared.

6.6 SECONDARY STANDARD – Colorimetric standards may be purchased for use

with DPD spectrophotometers/colorimeters. The accuracy of secondary standards
must be verified on each recently-calibrated spectrophotometer/colorimeter for
which they will be used. Secondary standards may not be used to calibrate the
spectrophotometer.

6.7 INDEPENDENT REFERENCE SAMPLE – Purchase a chlorine standard

solution that is NIST traceable or certified in an equivalent manner from a
different source than the source of the calibration standards. Calibration standards
and the independent reference samples that are purchased from the same supplier
must be from different lots. The independent reference sample must be stored
according to the manufacturer's recommendations and only used within the
manufacturer's designated lifespan (prior to expiration date).

7. SAMPLE COLLECTION, PRESERVATION, AND STORAGE

7.1 SAMPLE COLLECTION – The grab sample collection point should be as close
as possible to the location where the sample enters the on-line chlorine analyzer,
so that the grab sample reflects the same water as the on-line analyzer is
measuring. A sample line may be equipped with a valve (e.g., T or Y
configuration) that allows for intermittent grab sampling with minimal disruption
of flow to the analyzer. Follow the sample collection instructions specified in the
grab sample method. Collect the grab sample with minimal agitation. Exposure
to sunlight or strong light will cause loss of chlorine. Begin analysis immediately
after sample collection. Do not store samples.

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8. QUALITY CONTROL

8.1 Quality control (QC) procedures are incorporated into analytical methods in order
to demonstrate that the results are valid and within the accuracy and precision
ranges needed for protection of public health. Grab sample methods for
measuring chlorine residuals are designed to be independent of other chlorine
measurement methods. As a result, some of the normal QC requirements may not
be necessary when the grab sample method is used in conjunction with an on-line
chlorine analyzer. For example, Part 4020 in Standard Methods 1 indicates daily
analysis of method blanks, calibration check standards, fortified blanks, and
duplicates (with each batch of samples). Although these QC samples are useful
and may be included as part of the standard operating procedure (SOP), they are
not necessary when the grab sample measurement is being compared to an
analyzer measurement because the comparison of the two measurements serves as
a QC check. If grab sample analyses are only being performed in conjunction
with on-line chlorine analyzers, the analyst is only required to follow the
minimum requirements set forth in this method. However, this method is not
intended to supersede the QC requirements that are requisite when the data are
used for other purposes.

8.2 The requirements of the QC program for the grab sample method that is used as
the reference for the on-line chlorine analyzer consist of an Initial Demonstration
of Capability (IDC) and periodic analyses of calibration check standards and
independent reference samples. The QC program for the on-line chlorine
analyzer consists of an IDC and periodic comparisons of the instrument reading to
results of a sample analyzed using the grab sample reference method. These QC
procedures and the acceptance criteria are described in Sections 10 and 11 of this
method. It is desirable to maintain consistency with regard to personnel
responsible for instrument QA/QC checks and related field sampling.

8.3 OPTIONAL QC – Laboratories/water systems are encouraged to institute

additional QC practices to meet their specific needs. The remainder of this
section describes various optional QC procedures that may be incorporated into a
QC program for grab sample verification of on-line chlorine analyzer
performance.

8.3.1. GRAB SAMPLE DUPLICATE – Analysis of duplicate grab samples

(two samples collected at the same time) provides an estimate of the
precision of the grab sample analyses that are used to verify/adjust the
accuracy of the on-line chlorine analyzer. Poor grab sample precision
can cause problems in the analyzer adjustment. Analysis of grab sample
duplicates is suggested when there are difficulties in adjusting the
analyzer calibration to agree with the grab sample measurement.
Calculate the relative percent difference (RPD) between the Sample
(FD1) and the Sample Duplicate (FD2) as shown below. The RPD for
samples with concentrations greater than the lowest calibration standard
should not exceed 15%. The RPD at concentrations at or near the lowest
calibration standard should not exceed 50%.

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 FD1 − FD 2
RPD = × 100%
(FD1 + FD 2) 2
If the RPD for the Sample and the Sample Duplicate falls outside the
designated range, perform duplicate analyses of a calibration check
standard to verify that the grab sample method is in control.

8.3.2. INDEPENDENT REFERENCE SAMPLE – Analysis of a sample from

an external source (different from the calibration standards) provides an
independent check of the calibration of the grab sample method. It is
recommended semiannually or any time a new calibration curve is
generated.

8.3.3. PROFICIENCY TESTING (PT) or PERFORMANCE EVALUATION

(PE) SAMPLE – Successful participation in a PT or PE Study is a good
QC tool for demonstrating proficiency with the grab sample method. A
certified solution of chlorine whose concentration is unknown to the
analyst can be purchased by the laboratory/water system. An aliquot of
the certified solution is added to a known volume of reagent water and
analyzed as a grab sample. The analytical results are reported to the
PT/PE Study Provider where they are compared to data from all analyses
of the sample. Acceptance criteria are established for each study.
Generally, a different analyst should participate in each study, so that
over time each analyst has an opportunity to demonstrate proficiency. If
the analyst is a field sampler, the sample can be prepared by laboratory
personnel for the analyst.

9. CALIBRATION

9.1 An acceptable initial calibration for the grab sample method must be established
before the results from the grab sample method can be used to verify the accuracy
of an on-line chlorine analyzer. After initial calibration is successful, a calibration
check standard or independent reference sample is periodically analyzed to verify
that the grab sample method calibration is still valid.

9.2 The calibration of the on-line chlorine analyzer is verified against a grab sample
measurement. (On-line chlorine analyzers that use the same chemistry as an
approved grab sample method may use aqueous standards for initial calibration
verification instead of comparison to grab sample measurements. Routine
calibration checks are made by comparison with grab sample measurements.)

9.3 The calibration procedures and acceptance criteria are described in Sections 10
and 11 of this method.

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10. START-UP PROCEDURES

10.1 GRAB SAMPLE METHOD – Refer to the selected grab sample method for a
complete description of the procedure. (Each drinking water regulation includes a
tabular listing of methods that are approved for analyses of compliance samples.
The regulation also identifies how to obtain a copy of each method.) Section 15 –
Table 1 and Flowchart 1 summarize the start up QC for the grab sample method.

10.1.1. Prepare or verify the initial calibration curve. This must be done for
each meter or titrator according to the procedure described below. The
accuracy of secondary standards must also be verified. These steps can
be performed by laboratory personnel or field samplers. A record of the
calibration results must be maintained for each meter/titrator.

10.1.1.1. Prepare a method blank (reagent water) and a set of at least

three aqueous calibration standards. The lowest concentration
calibration standard must be at or below 0.2 mg/L or the
minimum chlorine residual required by the state. The standards
must span the concentration range that is expected to be
observed in the grab samples. (Note: If the range extends
above the maximum concentration specified for the DPD
reagents and colorimeter, prepare three standards within the
range specified by the manufacturer and a fourth standard at
the highest concentration expected for the grab samples.)

10.1.1.2. Analyze the calibration standards and method blank according

to the grab sample procedure. (Note: If the highest
concentration standard is above the maximum concentration
specified for the DPD reagents and colorimeter, dilute and
analyze it according to manufacturer’s instructions. Use the
data from this analysis to check the accuracy of the dilution
process, not the calibration curve.)

10.1.1.2.1. For methods that do not require the preparation of a

curve or that use an internal, factory set calibration
curve, compare the measured concentration of each
standard to the expected value. Each calibration
point must be within ± 15% of its expected value.
If the internal curve does not meet these criteria, the
internal curve must be updated by following the
manufacturers’ instructions for generating/inputting
a curve. Otherwise, send the meter to the vendor
for repair/updating.

10.1.1.2.2. For methods that require the preparation of a curve,

use the concentration of each standard versus the
instrument response to calculate the best fit curve
according to the procedure described in the grab

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 sample method. Validate the curve by calculating
the concentration of each standard using the curve.
Each calibration point must be within ± 15% of its
expected value.

10.1.1.3. If secondary standards are available for the grab sample

method, they must be verified prior to use by analyzing them
immediately after initial calibration is verified. The secondary
standards must be within ± 10% of their expected
concentrations when compared to the initial calibration curve.
New secondary standards must be purchased if this criterion
cannot be met. The secondary standards must meet the
criterion on every meter for which they will be used.
Secondary standards must be verified each time the initial
calibration procedure is repeated. Secondary standards must
not be used beyond the manufacturer’s expiration date.

10.1.2. Each field sampler must perform an initial demonstration of capability

(IDC) prior to using the grab sample method to verify the accuracy of
on-line chlorine analyzers. If the accuracy and precision criteria
described below are not met, determine the source of the problem, take
corrective action and repeat the IDC. The IDC consists of a
demonstration of accuracy and a demonstration of precision using the
procedure described below.

10.1.2.1. INITIAL DEMONSTRATION OF ACCURACY – Prepare

and analyze a method blank (reagent water) and five
independent reference samples at the same concentration. The
concentration of the samples should be in the mid range of the
calibration curve or near the expected concentration of the
water samples. Calculate the average chlorine concentration
for the five analyses. The average concentration for the five
replicates must be within ± 15% of the expected value. The
method blank concentration must be ≤ ⅓ the concentration of
the lowest standard used to prepare/verify the calibration curve
(Section 10.1.1.1).

10.1.2.2. INITIAL DEMONSTRATION OF PRECISION – Using the

same set of replicate data generated for Section 10.1.2.1,
calculate the standard deviation and relative standard deviation
(RSD) of the replicate values. The RSD is calculated using the
equation
S
RSD = × 100%
X
where
S is the standard deviation for the replicate values,
and X is the average value for the replicates.

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 The RSD of the results of the replicate analyses must be ≤15%.

10.1.3. Each field sampler must successfully complete the IDC procedure
described above (Section 10.1.2) prior to using the grab sample method
in conjunction with an on-line chlorine analyzer. Laboratory personnel
may prepare the independent reference samples for analyses by field
samplers. A record of the IDC results must be maintained for each field
sampler.

10.2 ON-LINE CHLORINE ANALYZER – Install the analyzer according to the

manufacturer’s specifications. Follow all start-up procedures outlined in the
operator’s manual including specific instructions regarding calibration of the
analyzer. The following procedure must be followed for each analyzer. (Section
15 – Table 2 and Flowchart 2 summarize the start-up QC for on-line chlorine
analyzers.)

10.2.1. After the analyzer is providing stable readings, proceed with

verifying/adjusting the initial calibration. If the analyzer uses the same
chemistry as an approved grab sample method, the calibration curve can
be established/verified using aqueous chlorine standards in a manner
similar to the grab sample procedure described above in Section 10.1.1.
Alternately, calibration of the analyzer may be verified/adjusted based on
the results of grab sample measurements as described below. All other
types of analyzers must use the following procedure:

10.2.1.1. Collect and analyze a grab sample collected as close as feasible

to the location where the sample enters the on-line chlorine
analyzer. Compare the results from the grab sample analysis to
the measurement made by the on-line chlorine analyzer.

10.2.1.2. Follow the manufacturer’s instructions to adjust the calibration

of the analyzer so it gives the same value as the grab sample
analysis.

10.2.1.3. Repeat steps 10.2.1.1 and 10.2.1.2 until the on-line chlorine
analyzer measurement agrees with the grab sample
measurement. (Ideally, the two measurements will be the
same, but realistically this won’t always be possible. Note that
during routine operation of the analyzer, the readings must be
within ± 0.1 mg/L or ± 15% of the grab sample measurement.
Use that criterion as a guide for deciding when the analyzer
calibration is properly adjusted during this start-up procedure.)

10.2.2. Conduct the initial demonstration of capability (IDC) after the

calibration of the on-line chlorine analyzer has been verified.
Requirements for the IDC are described in 10.2.2.3. The full IDC must
be conducted prior to using the analyzer for compliance monitoring

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measurements. This will take a minimum of 14 days. The data collected
during the IDC must be recorded and maintained.

10.2.2.1. The IDC for the on-line chlorine analyzer is not required if
historical operating data for the on-line chlorine analyzer
demonstrate the criterion are being met on an on-going basis.
Historical data must show that the analyzer remains in
agreement with the grab sample method over a period of two
consecutive weeks without analyzer maintenance or calibration
adjustment. Agreement is defined as being within ± 0.1 mg/L
or ± 15% (whichever is larger) of the grab sample
measurement. The following procedures must be completed
prior to using the analyzer for compliance monitoring.

10.2.2.1.1. Verify the calibration of the grab sample

measurement according to 10.1.1.

10.2.2.1.2. Each field sampler must complete the IDC

requirements for the grab sample measurement
according to 10.1.2.

10.2.2.1.3. Calibration of the on-line chlorine analyzer must be

verified according to 10.2.1 after the grab sample
IDC is completed.

10.2.2.1.4. Proceed to 10.2.3.

10.2.2.2. When multiple on-line chlorine analyzers are being installed,

the primacy agency may allow the IDC to be shortened under
the following conditions.

10.2.2.2.1. The same model analyzer is installed at each

location.

10.2.2.2.2. The water quality characteristics and treatment

processes are equivalent at each location.

10.2.2.2.3. A successful IDC (Section 10.2.2.3) is completed

for the first analyzer that is placed in service.

10.2.2.2.4. The IDC for subsequent analyzers can be shortened

to 7 consecutive days (or 7 consecutive business
days) of daily grab sample comparisons. The
analyzer reading must be within ± 0.1 mg/L or ±
15% (whichever is larger) of the grab sample
measurement for each data pair. When you obtain 7
consecutive days (or business days) of data pairs

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 that meet the acceptance criterion, proceed to
10.2.3.

10.2.2.3. Compare the concentration determined by the on-line chlorine

analyzer with grab sample analyses collected at least daily for
14 days. (If samples cannot be collected during the weekend,
14 consecutive business days is acceptable.) During the 14
days, grab samples should be collected at concentrations that
represent highs and lows, as indicated by the analyzer. (e.g., if
the analyzer indicates the chlorine concentration varies
between 0.5 mg/L and 1.0 mg/L, grab samples should be
collected to verify accuracy at both of these concentrations.)
The analyzer reading must be within ± 0.1 mg/L or ± 15%
(whichever is larger) of the grab sample measurement for each
data pair. If this criterion is not met, determine the source of
the problem, take corrective action and continue collecting
daily grab samples. When you obtain 14 consecutive days (or
business days) of data pairs that meet the acceptance criterion,
proceed to 10.2.3.

10.2.2.4. If you are unable to meet the criterion in 10.2.2.3, verify you
have chosen an appropriate analyzer for your water quality and
operating conditions. An on-line chlorine analyzer that cannot
meet the criterion in 10.2.2.3 may be used for compliance
monitoring only if grab sample comparisons are conducted
daily or at a frequency approved by the primacy agency.

10.2.3. Upon successful completion of the IDC, the analyzer can be put into
service for compliance monitoring. Control or warning limits should be
established for the analyzer readings, so that operators are immediately
alerted to unexpected changes in the chlorine measurements. For remote
installations, interfacing the analyzer with a SCADA system, automated
phone dialer, or a similar notification system is a critical consideration.

10.2.4. A routine schedule for grab sample comparisons can be established

based on the results from intense monitoring over the course of the first
few months of operation. The maximum time between grab samples
must not exceed once every seven days. (Appendix A provides an
optional systematic approach for establishing a routine schedule for grab
sample comparisons. Alternative approaches may be used to determine
the optimum frequency of grab sample comparisons.)

10.2.5. All manufacturers’ recommendations for routine maintenance should be

followed. When maintenance is performed, the accuracy of the analyzer
must be verified with a grab sample comparison after the analyzer is
placed back in service. The accuracy must be verified again after one
day of operation (Section 11.2). If the accuracy criteria are not met and

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 the analyzer is operating properly, adjust the analyzer calibration
according to the procedure in Sections 11.2.3 – 11.2.7.

11. ROUTINE PROCEDURES

11.1 ROUTINE CALIBRATION CHECK FOR THE GRAB SAMPLE METHOD –

Prepare an aqueous calibration check standard at a concentration near the
expected concentration of the water samples. (Over time, vary the grab sample
calibration check standard concentration when multiple analyzers are being
verified and the drinking water chlorine concentration at each analyzer is
different.) The grab sample measured concentration of the calibration check
standard must be within ± 15% of the expected value. If this criterion is not met,
the analyst must identify and resolve the problem with the grab sample method
prior to proceeding with analyses of grab samples to verify the on-line chlorine
analyzer accuracy. The results from analyses of calibration check standards must
be recorded and maintained according to the requirements of the primacy agency.

11.1.1. A check standard must be analyzed:

11.1.1.1. when the grab sample measurement is used to adjust the

calibration of the on-line chlorine analyzer

11.1.1.2. a minimum of once quarterly.

11.1.2. Analysis of secondary standards is an easy way to verify the

spectrophotometer is operating properly for colorimetric methods.
Analysis of secondary standards does not replace the analysis of aqueous
check standards. Each secondary standard must be within ± 10% of its
expected concentration.

11.2 ROUTINE CALIBRATION CHECK FOR ON-LINE CHLORINE ANALYZER

– The accuracy of the on-line chlorine analyzer is monitored during routine use by
periodic comparisons of the analyzer readings to grab sample measurements. The
maximum time between grab samples must not exceed once every 7 days (i.e., a
weekly grab sample). The analyzer concentration must be within ± 0.1 mg/L or ±
15% (whichever is larger) of the grab sample measurement. (Section 15 – Table
4 and Flowchart 3 summarize the routine QC for on-line chlorine analyzers.) All
data from these comparisons must be recorded and maintained according to the
requirements of the primacy agency.

11.2.1. Disagreement between the grab sample and analyzer measurements may
indicate a need for maintenance on the analyzer (e.g., flow adjustment,
pH adjustment, cleaning, new membrane, fresh reagents, etc.) The
operator must conduct trouble-shooting activities and rule out problems
with the analyzer prior to making calibration adjustments.

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 11.2.1.1. The operator may perform a second comparison between the
analyzer and a grab sample to rule out variability in the grab
sample as the cause for disagreement.

11.2.1.2. Follow the manufacturer’s instructions for troubleshooting

problems with the analyzer.

11.2.2. If the analyzer is operating properly, verify that the grab sample
measurement is accurate by analyzing a grab sample calibration check
standard (Section 11.1).

11.2.2.1. For remote sites, the accuracy of the grab sample measurement
can initially be verified using secondary standards that have
been tested for accuracy according to Section 10.1.1.3. The
secondary standards must be within ± 10% of their expected
concentration.

11.2.2.2. If secondary standards are used in the field, a grab sample

calibration check standard should be analyzed using the same
lot of reagents within 24 hours unless an alternative time frame
is approved by the primacy agency.

11.2.3. After the accuracy of the grab sample measurement is verified, follow
the manufacturer’s instructions to adjust the calibration of the analyzer
so it gives the same value as the grab sample analysis.

11.2.4. Confirm that the calibration adjustment is accurate by analyzing another

grab sample and comparing the result to the reading from the analyzer.

11.2.5. Repeat steps 11.2.3 and 11.2.4 until the on-line chlorine analyzer
measurement agrees with the grab sample measurement. (The two
measurements should be as close as possible. Note that during routine
operation of the analyzer, the readings must be within ± 0.1 mg/L or ±
15% of the grab sample measurement. Use that criterion as a guide for
deciding when the analyzer calibration is properly adjusted.)

11.2.6. An additional grab sample must be collected and analyzed after one day
of operation in order to verify that the calibration adjustment was
performed accurately. If the criterion is not met, follow 11.2.3 -11.2.6 to
adjust the calibration of the analyzer or take other corrective steps
consistent with manufacturer instructions.

11.2.7. Return to the routine schedule for grab sample comparisons. A grab
sample must be analyzed at least once each week.

11.3 NON-ROUTINE CALIBRATION CHECK FOR ON-LINE CHLORINE

ANALYZER – Certain conditions may trigger the need to compare the analyzer
reading to a grab sample measurement outside the routine schedule. When a non-

14
 routine comparison is made, the analyzer concentration must be within ± 0.1
mg/L or ± 15% (whichever is larger) of the grab sample measurement. If this
criterion is not met, the operator must take corrective action to bring the analyzer
back into agreement with the grab sample measurement. The steps in Section
11.2 must be followed. Problems with the analyzer must be ruled out or fixed
prior to any calibration adjustment to the on-line chlorine analyzer.

11.3.1. The on-line chlorine analyzer measurement must be compared to a grab

sample measurement when routine maintenance (such as cleaning,
replenishment of reagents, membrane replacement, adjustment of flow
rate, pH calibration, etc.) is performed on the analyzer.

11.3.2. If the analyzer measurements indicate a gradual drift upward or

downward when no changes in chlorine concentration are expected, a
grab sample measurement should be performed.

11.4 EMERGENCY CALIBRATION CHECK FOR ON-LINE CHLORINE

ANALYZER – If the on-line chlorine analyzer indicates a large (≥ 50%)
unexpected change in chlorine residual concentration (based on process control
and water quality conditions), a grab sample should be collected and analyzed as
soon as possible. When an emergency comparison is made, the analyzer
concentration must be within ± 0.1 mg/L or ± 15% (whichever is larger) of the
grab sample measurement. If this criterion is not met, the operator must take
corrective action to bring the analyzer back into agreement with the grab sample
measurement. The steps in Section 11.2 must be followed. Problems with the
analyzer must be ruled out or fixed prior to any calibration adjustment to the on-
line chlorine analyzer.

11.5 RETURNING AN ON-LINE CHLORINE ANALYZER TO SERVICE – After a

major repair or after replacement of the on-line chlorine analyzer with an
equivalent model, follow all start-up procedures outlined in the operator’s manual.
Calibrate according to the procedure in Section 10.2.1. Return to the routine
schedule for grab sample comparisons (Section 11.2) after verifying the accuracy
of the analyzer on a daily basis for 7 consecutive days (or business days) or for a
period specified by the primacy agency.

12. POLLUTION PREVENTION

12.1 Pollution prevention encompasses any technique that reduces or eliminates the
quantity or toxicity of waste at the point of generation. Numerous opportunities
for pollution prevention exist in laboratory operation. EPA has established a
preferred hierarchy of environmental management techniques that places
pollution prevention as the management option of first choice. Whenever feasible,
laboratory personnel should use pollution prevention techniques to address their
waste generation. When wastes cannot be feasibly reduced at the source, the
Agency recommends recycling as the next best option.

15
 12.2 Quantity of a chemical purchased should be based on expected usage during its
shelf-life and disposal cost of unused material. Actual reagent preparation
volumes should reflect anticipated usage and reagent stability.

12.3 For information about pollution prevention that may be applicable to laboratory
operations, consult “Less is Better: Guide to Minimizing Waste in Laboratories.” 7

13. WASTE MANAGEMENT

13.1 The analytical procedures described in this method generate relatively small
amounts of waste since only small amounts of reagents are used. The matrices of
concern are drinking water. However, the Agency requires that waste
management practices be conducted consistent with all applicable rules and
regulations, and that the air, water, and land is protected by minimizing and
controlling all releases from bench operations. Also, compliance is required with
any sewage discharge permits and regulations, particularly the hazardous waste
identification rules and land disposal restrictions.

14. REFERENCES

1. Standard Methods for the Examination of Water and Wastewater. 21st Edition.
American Public Health Association. Washington DC. 2005.

2. Safety in Academic Chemistry Laboratories. Vol 1. 7th Edition. American

Chemical Society Publication; Committee on Chemical Safety, Washington DC,
2003. (available for download at http://membership.acs.org/C/CCS/pub_3.htm).

3. Chemical Safety Manual for Small Businesses. 3rd Edition. American Chemical
Society, Committee on Chemical Safety, Washington DC, 2009. (available for
download at http://membership.acs.org/C/CCS/pub_5.htm).

4. Occupational Safety and Health Administration (OSHA), Hazard

Communication. 29 CFR 1910.1200.

5. Occupational Safety and Health Administration (OSHA), Occupational Exposure

to Hazardous Chemicals in Laboratories. 29 CFR 1910.1450.

6. Standard Test Method for Residual Chlorine in Water. ASTM D 1253-03. ASTM
International, West Conshohocken, PA. 2003.

7. Less is Better: Guide to Minimizing Waste in Laboratories. American Chemical

Society, Task Force on Laboratory Environment, Health, & Safety, Washington
DC, 2002. (available for download at
http://membership.acs.org/C/CCS/pub_9.htm).

16
15. TABLES AND FLOWCHARTS

Table 1. Summary of Start-up QC for Grab Sample Methodology

Method
Requirement Specification Acceptance Criteria
Reference
10.1.1.2 Generate or Analyze method blank & 3 Each standard is within
validate calibration standards that span ±15% of its expected
calibration concentration range (Lowest concentration when
curve standard ≤ 0.2 mg/L or the compared to curve
minimum required by primacy
agency.)
10.1.1.3 Verify Analyze secondary standards on Each secondary standard is
accuracy of each meter for which they will be within ±10% of its expected
secondary used. concentration
standards
10.1.2.1 Initial Analyze method blank & 5 Method blank ≤ ⅓
Demonstration replicate independent reference concentration of lowest
of Capability samples fortified at a calibration standard;
(IDC) - concentration near the drinking Average of 5 replicates is
Accuracy water concentration within ±15% of expected
concentration
10.1.2.2 Initial Calculate relative standard RSD ≤ 15%
Demonstration deviation (RSD) for 5
of Capability independent reference sample
(IDC) - replicate analyses
Precision
10.1.3 Field Sampler Each sampler must successfully
IDC complete 10.1.2.1 and 10.1.2.2
(IDC samples may be prepared by
laboratory personnel for analyses
by field samplers.)

Table 2. Summary of Start-up QC for On-line Chlorine Analyzer

Method
Requirement Specification and Frequency Acceptance Criteria
Reference
10.2.1 Verify or adjust Analyze grab sample & compare Analyzer reading is within ±
analyzer to analyzer reading; Adjust 0.1 mg/L or ± 15%
calibration analyzer to agree with grab (whichever is larger) of grab
sample measurement; Iterative sample measurement
process until agreement is reached
10.2.2 Initial Compare analyzer measurement Analyzer reading must be
Demonstration to a grab sample analysis on a within ± 0.1 mg/L or ± 15%
of Capability daily basis for 14 consecutive (whichever is larger) of the
(IDC) days (or business days) grab sample measurement
for each data pair

17
Table 3. Routine QC for Grab Sample Methodology
Method
Requirement Specification and Frequency Acceptance Criteria
Reference
11.1.1 Routine Analyze a check standard: Standard is within ±15% of
calibration • When calibration of the on-line its expected concentration
check chlorine analyzer is adjusted
• At least quarterly
11.1.2 Secondary Recommended: analyze each day Each secondary standard is
standards grab sample method is used within ±10% of its expected
(This is only applicable to concentration
methods that use a
spectrophotometer/colorimeter.)

Table 4. QC for On-line Chlorine Analyzer

Method
Requirement Specification and Frequency Acceptance Criteria
Reference
11.2 Routine Compare analyzer measurement Analyzer reading must be
calibration to a grab sample analysis: within ± 0.1 mg/L or ± 15%
check • on a routine basis (at least once (whichever is larger) of the
each week) grab sample measurement
• immediately after analyzer
calibration is adjusted
• one day after analyzer
calibration is adjusted
11.3 Non-routine Compare analyzer measurement Analyzer reading must be
calibration to a grab sample analysis: within ± 0.1 mg/L or ± 15%
check • after routine maintenance (whichever is larger) of the
• when analyzer drifts upward or grab sample measurement
downward without explanation
(recommended)
11.4 Emergency If the analyzer indicates a large Analyzer reading must be
calibration (≥ 50%) unexpected change in within ± 0.1 mg/L or ± 15%
check chlorine residual, compare (whichever is larger) of the
analyzer measurement to a grab grab sample measurement
sample analysis as soon as
possible

18
 Flowchart 1. Start-up Procedure for Grab Sample Method

Select an approved grab sample method

from tabular listing in regulation (e.g., DPD
colorimetric, amperometric titration)
(Section 1.2)

Calibrate or verify calibration for each

This shows that the
spectrometer/colorimeter or titrator
meter/titrator is
(Analyze a blank + 3 standards)
accurate.
(Section 10.1.1)

Verify accuracy of secondary

standards on each colorimeter
(Section 10.1.1.3)

Initial demonstration of capability (IDC)

This shows that the
for each sampler
sampler can use the
(Analyze a blank + 5 replicate independent
method properly.
reference samples) (Section 10.1.2)

Determine source of problem & fix

No Is accuracy &
precision
criterion met?

Yes

Ready to use grab sample method for

verifying accuracy of on-line chlorine
analyzer

19
 Flowchart 2. Start-up QC for On-line Chlorine Analyzer

Install on-line chlorine analyzer

& follow manufacturers' start-up
procedures

Verify analyzer calibration

(Compare analyzer reading to
result from a grab sample
analysis)

Adjust analyzer calibration

according to manufacturers'
If you must use this analyzer for instructions
compliance monitoring, then
daily grab sample comparisons Do they No
will be needed agree?

No Yes

Analyzer Initial Demonstration

Yes of Capability (IDC)
Try again?
(Daily grab sample comparisons
for 2 weeks)

Identify problem & take No Do they

meet
corrective action
criteria?

Yes

Analyzer is ready for

compliance monitoring

20
 Flowchart 3. Routine QC for On-line Chlorine Analyzer

Verify analyzer calibration

(Compare analyzer reading to
result from a grab sample
analysis)

Continue under routine grab

sample schedule unless analyzer
Do they Yes
shows unexpected change
agree?
(at least one grab sample
each week)

No

Check for problems with

the analyzer A second grab sample analysis
(follow manufacturers' will rule out variability problems
recommendations for in grab sample measurement
troubleshooting)

Is analyzer
Resolve problem according to No
operating
manufacturers' instructions
properly?

Yes

Verify grab sample accuracy

(Analyze check standard)

Is grab
Resolve problem with grab No
sample
sample method
accurate?

Yes

Adjust analyzer calibration

(follow manufacturers'
instructions)

Verify analyzer calibration

(Compare analyzer reading to
result from a grab sample
analysis)

No Do they
agree?

Yes
Verify analyzer calibration after
one day of operation
(Compare analyzer reading to
result from a grab sample
analysis)

Check for problems with

the analyzer
Do they No
(follow manufacturers'
agree?
recommendations for
troubleshooting)

Yes

Return to routine grab sample

schedule

21
 METHOD 334.0 APPENDIX A

OPTIONAL PROCESS FOR ESTABLISHING A SCHEDULE FOR ROUTINE GRAB

SAMPLE COMPARISONS TO ON-LINE CHLORINE ANALYZER READINGS

A. Historical data can be used to establish a routine schedule for comparing grab sample
measurements to the results from the on-line chlorine analyzer. The data must
demonstrate that the grab sample measurements are frequent enough to detect problems
with the analyzer within a reasonable period of time after the problems occur. The
following protocol is presented as a conservative approach to developing a routine
schedule when historical data are not available. The acceptance criterion that must be
met in each step is that the on-line chlorine analyzer reading is within ± 0.1 mg/L or ±
15% (whichever is larger) of the grab sample measurement. (Section B provides a
flowchart of this process.)

A.1 The data from the on-line analyzer IDC (See Section 10.2.2) can be used as the
initial data set. If the on-line chlorine analyzer and grab sample results meet the
acceptance criteria over the 14 day period of the IDC, compare the concentration
determined by the on-line chlorine analyzer with grab sample analyses collected
every three days for 9 days.

A.2 If the on-line chlorine analyzer continues to meet acceptance criteria over the
above 9 day period, the grab sample interval can be extended to once every four
days for 12 days.

A.3 As long as the acceptance criterion is met, continue extending the interval
between grab samples using the same pattern as established in A.2 (i.e., once
every 5 days for 15 days, once every 6 days for 18 days, etc). Collect a minimum
of three grab samples each time the interval is extended by one day. The
maximum time between grab samples must not exceed once every 7 days (i.e.,
a weekly grab sample).

A.4 When the on-line analyzer fails to meet the acceptance criteria, resolve the
problem following the protocol in Section 11.2. After the analyzer/grab sample
agreement has been reestablished, examine the data collected in steps A.2 to A.3
to decide whether to continue extending the time between grab samples or to
establish a schedule based on the existing data. Continue extending the time
intervals between grab samples beginning with the interval that was being used
prior to when the on-line analyzer failed to meet the acceptance criteria.

A.5 Establish the routine grab sample frequency at an interval which is no greater than
one seventh of the average length of time between observed failures. The
maximum time between grab samples must not exceed once every seven days.

22
B. Process for Establishing Frequency of Routine Grab Sample Comparisons to Analyzer Readings

Analyze IDC
Daily grab samples Set grab sample
for 14 days frequency at daily
No

Yes
Adjust frequency Done?
Grab samples on alternate
days for 1 week

Set grab sample Find & resolve problem

Criteria No
frequency at daily or on Verify accuracy with a grab sample
Met?
alternate days
No
Yes
Yes
Done?
Adjust frequency
Grab samples every third day
for 9 days
Set grab sample
frequency at alternate or
every third day
Find & resolve problem
Verify accuracy with a grab sample No Criteria No
Verify accuracy after 24 hrs with Met?
another grab sample
Yes
Done?
Yes

Adjust frequency
Grab samples every fourth
day for 12 days

Yes
Set grab sample
frequency at every third
Find & resolve problem
or fourth day
Criteria No Verify accuracy with a grab sample
Met? Verify accuracy after 24 hrs with
No
another grab sample

Yes Yes
Done?

Adjust frequency
Grab samples every fifth day
for 15 days

Find & resolve problem

Verify accuracy with a grab sample No Criteria Set grab sample
Verify accuracy after 24 hrs with Met? frequency at every fourth
another grab sample or fifth day

Yes No

Yes
Adjust frequency Done?
Grab samples every sixth day
for 18 days

Set grab sample Find & resolve problem

frequency at every fifth Criteria No Verify accuracy with a grab sample
or sixth day Met? Verify accuracy after 24 hrs with
No another grab sample

Yes
Yes
Done?
Adjust frequency
Grab samples every seventh
day for 21 days

Find & resolve problem

Verify accuracy with a grab sample No Criteria
Verify accuracy after 24 hrs with Met?
another grab sample

Yes

Set grab sample frequency

at every seventh day

23