United States
Environmental Protection
Agency
Research and Development
Environmental Monitoring and
Systems Laboratory
Cincinnati, OH 45268
Revised August 1991
oEPA Test Method
The Determination of
Inorganic Anions in
Water by Ion Chromatography -
Method 300.0
John D. Raff, Carol A. Brockhoff, and James W. O'Dell
1. Scope and Application
1.1 Jhis method covers the determina-
tion of the following inorganic anions.
Method A.
Bromide
Chloride
Fluoride
Nitrate-N
Nitrite-N
Ortho-Phosphate-P
Sulfate
Method B.
Chlorite
Chlorate
Bromate
Storet No.
(Total)
71870
00940
00951
00620
00615
70507
00945
Storet No.
(Total)
50074
1.2	The matrices applicable to each
method are shown below:
A.	Drinking water, surface water, mixed
domestic and industrial wastewaters,
groundwater, reagent waters, solids
(after extraction 2.3), leachates (when
no acetic acid is used 2.4)
B.	Drinking water and reagent waters.
1.3	The Single Laboratory Method
Detection Limit (MDL, defined in
Section 13) for the above analytes is
listed in Tables 1A and 1B. The MDL for
a specific matrix may differ from those
listed, depending upon the nature of the
sample.
1.4 Method A is recommended for
drinking and waste waters. The
multilaboratory range tested for each
anion is as follows in mg/L:
Bromide
Chloride
Fluoride
Nitrate-N
Nitrite-N
Ortho-P
Sulfate
0.63-21.0
0.78 - 26.0
0.26 - 8.49
0.42 - 14.0
0.36 - 12.0
0.69-23.1
2.85 - 95.0
1.5	This method is recommended for
use only by or under the supervision of
analysts experienced in the use of ion
chromatography and in the interpreta-
tion of the resulting ion chromatogram.
Each analyst must demonstrate the
ability to generate acceptable results
with this method, using the procedure
described in Section 10.2.
1.6	When this method is used to
analyze unfamiliar samples for any of
the above anions, anion identification
should be supported by the use of
300.0-1
August 1991
LPN 0003 10M 9/91

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fortified sample matrix covering the
anions of interest. The fortification
procedure is described in Section 11.6.
2.	Summary of Method
2.1	A small volume of sample, typically
2 to 3 mL, is introduced into an ion
chromatograph. The anions of interest
are separated and measured, using a
system comprised of a guard column,
separator column, suppressor device,
and conductivity detector.
2.2	The main differences between
Method A and B are the separator
columns, guard columns and eluents.
Sections 6 and 7 will elicit the differ-
ences.
2.3	In order to use this method for
solids an extraction procedure must be
performed (See 11.7).
3.	Definitions
3.1	Stock standard solution - a
concentrated solution containing a
single certified standard that is a
method analyte. Stock standard
solutions are used to prepare calibra-
tion standards.
3.2	Calibration standards (CAL) - a
solution of analytes prepared in the
laboratory from stock standard solutions
and diluted as needed and used to
calibrate the instrument response with
respect to analytic concentration.
3.3	Quality control sample (QCS) - a
solution containing known concentra-
tions of analytes, prepared by a
laboratory other than the laboratory
performing the analysis. The analyzing
laboratory uses this solution to demon-
strate that it can obtain acceptable
identifications and measurements with
a method.
3.4	Performance evaluation sample
(PE) - a solution of method analytes
distributed by the Quality Assurance
Research Division (QARD), Environ-
mental Monitoring Systems Laboratory
(EMSL-Cincinnati), USEPA, Cincinnati,
Ohio, to multiple laboratories for
analysis. A volume of the solution is
added to a known volume of reagent
water and analyzed with procedures
used for samples. Results of analyses
are used by the QARD to determine
statistically the accuracy and precision
that can be expected when a method is
performed by a competent analyst.
Analyte true values are unknown to the
analyst.
3.5	Laboratory performance check
standards (LPC) - a solution of
analytes prepared in the laboratory by
adding appropriate volumes of the stock
standard solutions to reagent water
used to evaluate the performance of the
instrument system with respect to a
defined set of method criteria.
3.6	Laboratory duplicates (LD) - two
aliquots of the same sample that are
treated exactly the same throughout
laboratory analytical procedures.
Analyses of laboratory duplicates
indicate precision associated with
laboratory procedures but not the
sample collection, preservation, or
storage procedures.
3.7	Field duplicates (FD) - two
samples taken at the same time and
placed under identical circumstances
and treated exactly the same through-
out field and laboratory procedures.
Analyses of field duplicates indicate the
precision associated with sample
collection, preservation and storage, as
well as with laboratory procedures.
3.8	Laboratory fortified sample matrix
(LFM) - An aliquot of an environmental
sample to which known quantities of the
method analytes are added in the
laboratory. TTie LFM is analyzed exactly
like a sample, and its purpose is to
determine whether the sample matrix
contributes bias to the analytical results.
The background concentrations of the
analytes in the sample matrix must be
determined in a separate aliquot and
the measured values in the LFM
corrected for background concentra-
tions.
3.9	Laboratory fortified blank (LFB) -
An aliquot of reagent water to which
known quantities of the method
analytes are added in the laboratory.
The LFB is analyzed exactly like a
sample, and its purpose is to determine
whether the methodology is in control,
and whether the laboratory is capable
of making accurate and precise meas-
urements at the required method de-
tection limit.
4. Interferences
4.1 Interferences can be caused by
substances with retention times that are
similar to and overlap those of the anion
of interest. Large amounts of an anion
can interfere with the peak resolution of
an adjacent anion. Sample dilution
and/or fortification can be used to solve
most interference problems.
300.0-2	August 1991
4.2	The water dip or negative peak that
elutes near and can interfere with the
fluoride peak can usually be eliminated
by the addition of the equivalent of 1 mL
of concentrated eluent (7.3 100X) to
100 mL of each standard and sample.
4.3	Method interferences may be
caused by contaminants in the reagent
water, reagents, glassware, and other
sample processing apparatus that lead
to discrete artifacts or elevated baseline
in ion chromatograms.
4.4	Samples that contain particles
larger than 0.45 microns and reagent
solutions that contain particles larger
than 0.20 microns require filtration to
prevent damage to instrument columns
and flow systems.
4.5	Any anion that is not retained by
the column or only slightly retained will
elute in the area of fluoride and inter-
fere. Known coelution is caused by
carbonate and other small organic
anions. At concentrations of fluoride
above 1.5 mg/Lthis interference may
not be significant, however, it is the
responsibility of the user to generate
precision and accuracy information in
each sample matrix.
4.6	The acetate anion elutes early
during the chromatographic run. The
retention times of the anions also seem
to differ when large amounts of acetate
are present. Therefore, this method is
not recommended for leachates of solid
samples when acetic acid is used for
pH adjustment.
4.7	The quantitation of unretained
peaks should be avoided, such as low
molecular weight organic acids (for-
mate, acetate, propionate, etc.) which
are conductive and coelute with or near
fluoride and would bias the fluoride
quantitation in some drinking and most
waste waters.
5.	Safety
5.1 Normal, accepted laboratory safety
practices should be followed during
reagent preparation and instrument
operation. No known carcinogenic
materials are used in this method.
6.	Apparatus and Materials
6.1 Balance - Analytical, capable of
accurately weighing to the nearest
0.0001 g.

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6.2	Ion chromatograph - Analytical
system complete with ion chromato-
graph and all required accessories
including syringes, analytical columns,
compressed gasses and detectors.
6.2.1	Anion guard column: A protector
of the separator column. If omitted from
the system the retention times will be
shorter. Usually packed with a substrate
the same as that in the separator
column.
6.2.2	Anion separator column: This
column produces the separation shown
in Figures 1 and 2.
6.2.2.1	Anion separator column
(Method A): The separation shown in
Figure 1 was generated using a Dionex
AS4A column (P/N 37041). An optional
column may be used if comparable
resolution of peaks is obtained, and the
requirements of section 10.2 can be
met.
6.2.2.2	Anion separator column
(Method B). The separation shown in
Figure 2 was generated using a Dionex
AS9 column (P/N 42025). An optional
column may be used if comparable
resolution of peaks is obtained and the
requirements of section 10.2 can be
met.
6.2.3	Anion suppressor device: The
data presented in this method was
generated using a Dionex Anion Micro-
Membrane Suppressor (P/N 37106).
6.2.4	Detector - Conductivity cell:
approximately 1.25 jxL internal volume,
(Dionex, or equivalent) capable of
providing data as required in section
10.2. v
6.3	The Dionex AI-450 Data Chroma-
tography Software was used to gener-
ate all the data in the attached tables.
Systems using a stripchart recorder and
integrator or other computer based data
system may achieve approximately the
same MDL's but the user should
demonstrate this by the procedure
outlined in Section 10.2.
7. Reagents and Consumable
Materials
7.1	Sample bottles: Glass or polyethyl-
ene of sufficient volume to allow
replicate analyses of anions of interest.
7.2	Reagent water: Distilled or deion-
ized water, free of the anions of
interest. Water should contain particles
no larger than 0.20 microns.
7.3	Eluent solution (Method A and
Method B): Sodium bicarbonate (CAS
RN 144-55-8) 1.7 mM, sodium carbon-
ate (CAS RN 497-19-8) 1.8 mM.
Dissolve 0.2856 g sodium bicarbonate
(NaHC03) and 0.3816 g of sodium
carbonate (Na2C03) in reagent water
(7.2) and dilute to 2 liters.
7.4	Regeneration solution (MicroMem-
brane Suppressor): Sulfuric acid (CAS
RN-7664-93-9) 0.025N. Dilute 2.8 mL
conc. sulfuric acid (H2S04) to 4 liters
with reagent water.
7.5	Stock standard solutions, 1000 mg/
L (1 mg/ml): Stock standard solutions
may be purchased as certified solutions
or prepared from ACS reagent grade
materials (dried at 105°C for 30 min.) as
listed below.
7.5.1	Bromide (Br) 1000 mg/L:
Dissolve 1.2876 g sodium bromide
(NaBr, CAS RN 7647-15-6) in reagent
water and dilute to 1 liter.
7.5.2	Bromate (Br03~) 1000 mg/L: .
Dissolve 1.3057 g of potassium
bromate (KBr03, CAS RN 7758-01 -2) in
reagent water and dilute to 1 liter.
7.5.3	Chlorate (CI03") 1000 mg/L:
Dissolve 1.2753 g sodium chlorate
(NaCI03, CAS RN 7775-09-9) in
reagent water and dilute to 1 liter.
7.5.4	Chloride (CI") 1000 mg/L:
Dissolve 1.6485 g sodium chloride
(NaCI, CAS RN 7647-14-5) in reagent
water and dilute to 1 liter.
7.5.5	Chlorite (CI02~) 1000 mg/L:
Dissolve 1.3410 g of sodium chlorite
(NaCI02, CAS RN 7758-19-2) in
reagent water and dilute to 1 liter.
7.5.6	Fluoride (F") 1000 mg/L: Dissolve
2.21 OOg sodium fluoride (NaF, CAS RN
7681-49-4) in reagent water and dilute
to 1 liter.
7.5.7	Nitrate (N03"-N) 1000 mg/L:
Dissolve 6.0679 g sodium nitrate
(NaN03, CAS RN 7631-99-4) in reagent
water and dilute to 1 liter.
7.5.8	Nitrite (NCXf-N) 1000 mg/L:
Dissolve 4.9257 g sodium nitrite
(NaN02, CAS RN 7632-00-0) in reagent
water and dilute to 1 liter.
7.5.9	Phosphate<(HPO„2--P) 1000 mg/
L: Dissolve 4.3937 g potassium
phosphate, monobasic (KH2P04, CAS
RN 7778-77-0) in reagent water and
dilute to 1 liter.
7.5.10	Sulfate (SO/-) 1000 mg/L:
Dissolve 1.8141 g potassium sulfate
(K2S04, CAS RN 7778-80-5) in reagent
water and dilute to 1 liter.
Note: Stability of standards: Stock
standards (7.5) are stable for at least
one month when stored at 4°C. Dilute
working standards should be prepared
weekly, except those that contain nitrite
and phosphate should be prepared
fresh daily.
8. Sample Collection, Preserva-
tion and Storage
8.1 Samples should be collected in
scrupulously clean glass or polyethyl-
ene bottles.
8.2 Sample preservation and holding
times for the anions that can be deter-
mined by this method are as follow.
Analyte
Preservation
Holding


Time
Bromate
None required
28 days
Bromide
None required
28 days
Chlorate
None required
28 days
Chloride
None required
28 days
Chlorite
Cool to 4° C
immed.
Fluoride
None required
28 days
Nitrate-N


chlorinated
Cool to 4° C
28 days
nonchlorinated
conc. H.SO.
14 days

pH < 2

Nitrite-N
Cool to 4° C
48 hours
O-Phosphate-P
Cool to 4° C
48 hours
Sulfate
Cool to 4° C
28 days
8.3 The method of preservation and
the holding time for samples analyzed
by this method are determined by the
anions of interest. In a given sample,
the anion that requires the most preser-
vation treatment and the shortest hold-
ing time will determine the preservation
treatment. It is recommended that all
samples be cooled to 4° C and held no
longer than 28 days for Method A and
analyzed immediately for Method B.
9. Calibration and Standardiza-
tion
9.1 Establish ion chromatographic
operating parameters equivalent to
those indicated in Table 1A or 1B.
300.0-3
August 1991

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9.2	For each analyte of interest, pre-
pare calibration standards at a minimum
of three concentration levels and a
blank by adding accurately measured
volumes of one or more stock standards
(7.5) to a volumetric flask and diluting to
volume with reagent water. If a sample
analyte concentration exceeds the
calibration range the sample may be
diluted to fall within the range. If this is
not possible then three new calibration
concentrations must be chosen, two of
which must bracket the concentration of
the sample analyte of interest. Each
attenuation range of the instrument
used to analyze a sample must be
calibrated individually.
9.3	Using injections of 0.1 to 1.0 mL
(determined by injection loop volume) of
each calibration standard, tabulate peak
height or area responses against the
concentration. The results are used to
prepare a calibration curve for each
analyte. During this procedure, reten-
tion times must be recorded.
9.4	The calibration curve must be
verified on each working day, or
whenever the anion eluent is changed,
and after every 20 samples. If the
response or retention time for any
analyte varies from the expected values
by more than ±10%, the test must be
repeated, using fresh calibration
standards. If the results are still more
than ±10%, a new calibration curve
must be prepared for that analyte.
9.5	Non-linear response can result
when the separator column capacity is
exceeded (overloading). The response
of the detector to the sample when
diluted 1:1, and when not diluted,
should be compared. If the calculated
responses are the same, samples of
this total anionic concentration need not
be diluted.
10. Quality Control
10.1 Each laboratory using this method
should have a formal quality control
program. The minimum requirements of
this program consist of an initial
demonstration of laboratory capability
(10.2) and the analysis of fortified
samples as a continuing check on
performance. The laboratory should
maintain performance records to define
and document the quality of data that
are generated.
10.1.1 In recognition of the rapid
advances occurring in chromatography,
the analyst is permitted certain options
to improve the separations or lower the
cost of measurements. Each time such
modifications to the method are made,
the analyst is required to repeat the
procedure in Section 10.2.
10.1.2 The laboratory should fortify and
analyze a minimum of 10% of all
samples to monitor continuing labora-
tory performance. A minimum of 10% of
all samples should be run in duplicate.
10.2	Before performing any analyses,
the analyst should demonstrate the
ability to generate acceptable accuracy
and precision with this method, using a
laboratory performance standard.
10.2.1	Select a representative check
concentration for each analyte to be
measured. Using stock standards,
prepare a laboratory performance check
sample concentrate in reagent water
100 times more concentrated than the
selected concentrations.
10.2.2	Using a pipet, add. 1.00 mL of
the check sample concentrate (10.2.1)
to each of a minimum of four 100-mL
aliquots of reagent water. Analyze the
aliquots according to the procedure in
Section 11.
10.2.3	Calculate the average percent
recovery, (R), and the standard
deviation(s) of the percent recovery, for
the results.
10.2.4	Using the appropriate data from
Table 2, determine the recovery and
single operator precision expected for
the method, and compare these results
to the values calculated in Section
10.2.3. If the data are not comparable
within control limits (10.3.1), review
potential problem areas and repeat the
test.
10.3	The analyst must calculate
method performance criteria and define
the performance of the laboratory for
each fortified concentration of analyte
being measured.
10.3.1 Calculate upper and lower
control limits for method performance
as follows:
Upper Control Limit (UCL) = R + 3 s
Lower Control Limit (LCL) = R - 3 s
where R and s are calculated as in
Section 10.2.3. The UCL and LCL can
be used to construct control charts that
are useful in observing trends in
performance.
10.4	The laboratory should develop
and maintain separate accuracy
statements of laboratory performance
for each matrix being analyzed by the
laboratory. An accuracy statement for
the method is defined as R ± s. The
accuracy statement should be devel-
oped by the analyses of four aliquots of
water or wastewater, as described in
Section 10.2.2, followed by the calcula-
tion of R and s.
10.5	Before processing any samples,
the analyst must demonstrate through
the analysis of an aliquot of reagent
water that all glassware and reagent
interferences are under control. Each
time there is a change in reagents, a
laboratory reagent blank must be
processed as a safeguard against
laboratory contamination.
10.6	It is recommended that the
laboratory adopt additional quality
assurance practices for use with this
method. The specific practices that are
most productive depend upon the
needs of the laboratory and the nature
of the samples. Field duplicates may be
analyzed to monitor the precision of the
sampling technique. When doubt exists
over the identification of a peak in the
chromatogram, confirmatory techniques
such as sample dilution and fortification,
must be used. Whenever possible, the
laboratory should perform analysis of
quality control check samples and
participate in relevant performance
evaluation sample studies.
10.7	In order to verify that standards
have been prepared correctly a
reference standard check should be
performed using a standard of known
concentration prepared by an independ-
ent source.
10.8	With each batch of samples
processed analyze a single laboratory
fortified blank containing each analyte
of concern at a concentration at or near
those used in the reagent water data in
Tables 2A or 2B. If more than 20
samples are run in a batch analyze one
LFB for every 20 samples. Evaluate the
accuracy by compairing to Tables 2A of
2B. If acceptable data cannot be
obtained, locate the problem and
correct it.
10.9	At least quarterly, replicates of
LFBs should be analyzed to determine
the precision of the laboratory measure-
ments. Add these results to the on-
going control charts to document data
quality.
300.0-4
August 1991

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10.10 When using Part B, the analyst
should be aware of the purity of the
reagents used to prepare standards.
Allowances must be made when the
solid materials are less than 99% pure.
11. Procedure
11.1	Tables 1A and 1B summarize the
recommended operating conditions for
the ion chromatograph. Included in this
table are estimated retention times that
can be achieved by this method. Other
columns, chromatographic conditions,
or detectors may be used if the require-
ments of Section 10.2 are met.
11.2	Check system calibration daily
and , if required, recalibrate as de-
scribed in Section 9.
11.3	Load and inject a fixed amount of
well mixed sample. Flush injection loop
thoroughly, using each new sample.
Use the same size loop for standards
and samples. Record the resulting peak
size in area or peak height units. An
automated constant volume injection
system may also be used.
11.4	The width of the retention time
window used to make identifications
should be based upon measurements
of actual retention time variations of
standards over the course of a day.
Three times the standard deviation of a
retention time can be used to calculate
a suggested window size for each
analyte. However, the experience of the
analyst should weigh heavily in the
interpretation of chromatograms.
11.5	If the response for the peak
exceeds the working range of the
system, dilute the sample with an
appropriate amount of reagent water
and reanalyze.
11.6	If the resulting chromatogram fails
to produce adequate resolution, or if
identification of specific anions is
questionable, fortify the sample with an
appropriate amount of standard and
reanalyze.
Note: Retention time is inversely
proportional to concentration. Nitrate
and sulfate exhibit the greatest amount
of change, although all anions are
affected to some degree. In some
cases this peak migration may produce
poor resolution or identification.
11.7	The following extraction should be
used for solid materials. Add an amount
of reagent water equal to ten times the
weight of dry solid material taken as a
sample. This slurry is mixed together for
ten minutes using a magnetic stirring
device. Filter the resulting slurry before
injecting using a 0.45 p. membrane type
filter. This can be the type that attaches
directly to the end of the syringe. Care
should be taken to show that good
recovery and identification of peaks is
obtained with the users matrix through
the use of spikes.
12.	Calculation
12.1	Prepare separate calibration
curves for each anion of interest by
plotting peak size in area, or peak
height units of standards against
concentration values. Compute sample
concentration by comparing sample
peak response with the standard curve.
12.2	Report results in mg/L.
12.3	Report N02~ as N
N03- as N
HP042" as P
13.	Precision and Accuracy -
Method Detection Limit
14.	References
14.1	"Determination of Inorganic
Disinfection By-Products by Ion
Chromatography", J. Pfaff, C. Brockhoff.
J. Am. Water Works Assoc., Vol 82, No.
4, pg 192.
14.2	Standard Methods for the
Examination of Water and Wastewater,
Method 4110B, "Anions by Ion Chroma-
tography" proposed for the supplement
17th Edition of Standard Methods.
14.3	Dionex, System 4000 Operation
and Maintenance Manual, Dionex
Corp., Sunnyvale, California 94086.
1988.
14.4	Method Detection Limit (MDL) as
described in "Trace Analyses for
Wastewater," J. Glaser, D. Foerst, G.
McKee, S. Quave, W. Budde, Environ-
mental Science and Technology, Vol.
15,	Number 12, page 1426, December
1981.
Copies of this method provided
courtesy Dionex Corporation.
13.1	The method detection limit (MDL)
is defined as the minimum concentra-
tion of a substance that can be meas-
ured and reported with 99% confidence
that the value is above zero. The MDL
concentrations listed in Table 1A and
1B were obtained using reagent waters.
13.2	Single operator accuracy and
precision for reagent, drinking and
surface water, and mixed domestic and
industrial wastewater are listed in Table
2A and 2B.
13.3 Multiple laboratory accuracy and
precision data for reagent, drinking and
waste water using method A are given
for each anion in tables 3 through 9.
Data from nineteen laboratories were
used for this data.
13.4 Some of the bias statements, for
example chloride and sulfate, may be
misleading due to spiking small
increments of the anion into large
naturally occuring concentrations of the
same anion.
300.0-5
August 1991

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Table 1 A. Chromatographic Conditions and Detection Limits in Reagent Water (Method A)
Retention	MDL
Analyte
Peak#
Time (min)
(mg/L)
Fluoride
1
1.2
0.01
Chloride
2
1.7
0.02
Nitrite-N
3
2.0
0.004
Bromide
4
2.9
0.01
Nitrate-N
5
3.2
0.002
O-Phosphate-P
6
5.4
0.003
Sulfate
7
6.9
0.02
Standard Conditions:
Columns: as specified in 6.2.2.1
Detector: as specified in 6.2.4	Pump Rate: 2.0 mL/min.
Eluent: as specified in 7.3.1	Sample Loop: 50 ^L
MDL calculated from data system using a y-axis selection of 1000 ns and with a stripchart recorder with an
attenuator setting of 1, uMHO full scale.
* See figure 1
Table 1B. Chromatographic Conditions and Detection Limits in Reagent Water (Method B)

*
Retention
MDL
Analyte
Peak #
Time (min)
(mg/L)
Chlorite
1
2.8
0.01
Bromate
2
3.2
0.02
Chlorate
4
7.1
0.003
Standard Conditions:
Column: as specified in 6.2.2.2
Detector: as specified in 6.2.4	Pump Rate: 1.0 mL/min.
Eluent: as specified in 7.3	Sample Loop: 50 n.L
Attentuation -1
y- axis -500 ns
*See figure 2
300.0-6
August 1991

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Table 2A. Single-Operator Accuracy and Precision of Standard Anions (Method A)
Analyte
Sample
Type
Spike
(mg/L)
Number
of
Replicates
Mean
Recovery
%
Standard
Deviation
(mg/L)
Bromide
Chloride
Fluoride
Nitrate-N
Nitrite^N
O-Phosphate-P
Sulfate
RW
DW
SW
WW
GW
SD
RW
DW
SW
WW
GW
SD
RW
DW
SW
WW
GW
SD
RW
DW
SW
WW
GW
SD
RW
DW
SW
WW
GW
SD
RW
DW
SW
WW
GW
RW
DW
SW
WW
GW
5.0
5.0
5.0
5.0
5.0
2.0
20.0
20.0
10.0
20.0
20.0
20.0
2.0
1.0
1.0
1.0
0.4
5.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
5.0
5.0
10.0
2.0
10.0
10.0
10.0
10.0
10.0
20.0
50.0
40.0
40.0
40.0
99
105
95
105
92
82
96
108
86
101
114
90
91
92
73
87
95
101
103
104
93
101
97
82
97
121
92
91
96
98
99
99
98
106
95
99
105
95
102
112
0.08
0.10
0.13
0.34
0.34
0.06
0.35
1.19
0.33
5.2
1.3
0.32
0.05
0.06
0.05
0.07
0.07
0.35
0.21
0.27
0.17
0.82
0.47
0.28
0.14
0.25
0.14
0.50
0.35
0.08
0.17
0.26
0.22
0.85
0.33
0.40
3.35
1.7
6.4
3.2
RW = Reagent Water WW = Mixed Domestic and Industrial Wastewater
DW = Drinking Water GW = Groundwater
SW = Surface Water SD = USEPA QC Solid (Shale)
300.0-7
August 1991

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Table 2B. Single-Operator Accuracy and precision of By-Products (Method B)
Number	Mean	Standard
Sample Spike Spike	of Recovery	Deviation
Analyte Type (mg/L) Replicates	%	(mg/L)
Bromate RW 5.0	7	103	0.07
1.0	7	98	0.04
0.1	7	155	0.005
0.05	7	122	0.01
DW 5.0	7	95	0.04
1.0	7	85	0.02
0.1	7	98	0.005
0.05	7	98	0.005
Chlorate RW 5.0	7	101	0.06
1.0	7	97	0.01
0.1	7	100	0.01
0.05	7	119	0.05
DW 5.0	7	101	0.04
1.0	7	115	0.01
0.1	7	121	0.005
0.05	7	110	0.01
Chlorite RW 5.0	7	100	0.04
1.0	7	98	0.01
0.1	7	86	0.01
0.05	7	94	0.01
DW 5.0	7	96	0.03
1.0	7	100	0.02
0.1	7	76	0.00
0.05	7	96	0.01
RW = Reagent Water
DW = Drinking Water
300.0-8
August 1991

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Table 3. Determination of Bias for Fluoride
Water	Am't Added Am't Found	St	S0	Bias
mg/L	mg/L	%
Reagent 0.26	0.25	0.08	0.11 -3.8
0.34	0.29	0.11	-14.7
2.12	2.12	0.07	0.12 0.0
2.55	2.48	0.14	-2.7
6.79	6.76	0.20	0.19 -0.4
8.49	8.46	0.30	-0.4
Drinking 0.26	0.24	0.08	0.05 -7.7
0.34	0.34	0.11	0.0
2.12	2.09	0.18	0.06 -1.4
2.55	2.55	0.16	0.0
6.79	6.84	0.54	0.25 +0.7
8.49	8.37	0.75	-1.4
Waste 0.26	0.25	0.15	0.06 -3.8
0.34	0.32	0.08	-5.9
2.12	2.13	0.22	0.15 +0.5
2.55	2.48	0.16	-2.7
6.79	6.65	0.41	0.20 -2.1
8.49	8.27	0.36	-2.6
Table 4. Determination of Bias for Chloride
Water	Am't Added Am't Found	St	S0	Bias
mg/L	mg/L	%
Reagent 0.78	0.79
1.04	1.12
6.50	6.31
7.80	7.76
20.8	20.7
26.0	25.9 ,
Drinking 0.78	0.54
1.04	0.51
6.50	5.24
7.80	6.02
20.8	20.0
26.0	24.0
Waste 0.78	0.43
1.04	0.65
6.50	4.59
7.80	5.45
20.8	18.3
26.0	23.0
0.17	0.29 +1.3
0.46	+7.7
0.27	0.14 -2.9
0.39	-0.5
0.54	0.62 -0.5
0.58	-0.4
0.35	0.20 -30.8
0.38	-51.0
1.35	1.48 -19.4
1.90	-22.8
2.26	1.14 -3.8
2.65	-7.7
0.32	0.39 -44.9
0.48	-37.5
1.82	0.83 -29.4
2.02	-30.1
2.41	1.57 -11.8
2.50	-11.5
300.0-9
August 1991

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Table 5. Determination of Bias for Nitrite - Nitrogen
Water	Am't Added Am't Found	St	SQ	Bias
mg/L	mg/L	%
Reagent 0.36	0.37	0.04	0.04 +2.8
0.48	0.48	0.06	0.0
3.00	3.18	0.12	0.06 +6.0
3.60	3.83	0.12	+6.4
9.60	9.84	0.36	0.26 +2.5
12.0	12.1	0.27	+0.6
Drinking 0.36	0.30	0.13	0.03 -16.7
0.48	0.40	0.14	-16.7
3.00	3.02	0.23	0.12 +0.7
3.60	3.62	0.22	+0.6
9.60	9.59	0.44	0.28 -0.1
12.0	11.6	0.59	-3.1
Waste 0.36	0.34	0.06	0.04 -5.6
0.48	0.46	0.07	-4.2
3.00	3.18	0.13	0.10 +6.0
3.60	3.76	0.18	+4.4
9.60	9.74	0.49	0.26 +1.5
12.0	12.0	0.56	+0.3
Table 6. Determination of Bias for Bromide
Water	Am't Added Am't Found	S.	S0	Bias
mg/L	mg/L	%
Reagent 0.63 0.69	0.11	0.05	+9.5
0.84 0.85	0.12	+1.2
5.24 5.21	0.22	0.21	-0.6
6.29 6.17	0.35 .	-1.9
16.8	17.1	0.70	0.36 +1.6
21.0	21.3	0.93	+1.5
Drinking 0.63 0.63	0.13	0.04	0.0
0.84 0.81	0.13	-3.6
5.24 5.11	0.23	0.13	-2.5
6.29 6.18	0.30	-1.7
16.8	17.0	0.55	0.57 +0.9
21.0	20.9	0.65	-0.4
Waste 0.63 0.63	0.15	0.09	0.0
0.84 0.85	0.15	+1.2
5.24 5.23	0.36	0.11	-0.2
6.29 6.27	0.46	-0.3
16.8	16.6	0.69	0.43 -1.0
21.0	21.1	0.63	+0.3
300.0-10
August 1991

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Table 7. Determination of Bias for Nitrite - Nitrogen
Water
Am't Added
Am't Found
st
s0
Bias

mg/L
mg/L


%
Reagent
0.42
0.42
0.04
0.02
0.0

0.56
0.56
0.06

0.0

3.51
3.34
0.15
0.08
-4.8

4.21
4.05
0.28

-3.8

11.2
11.1
0.47
0.34
-1.1

14.0
14.4
0.61

+2.6
Drinking
0.42
0.46
0.08
0.03
+9.5

0.56
0.58
0.09

+3.6

3.51
3.45
0.27
0.10
-1.7

4.21
4.21
0.38

0.0

11.2
11.5
0.50
0.48
+2.3

14.0
14.2
0.70

+1.6
Waste
0.42
0.36
0.07
0.06
-14.6

0.56
0.40
0.16

-28.6

3.51
3.19
0.31
0.07
-9.1

4.21
3.84
0.28

-8.8

11.2
10.9
0.35
0.51
-3.0

14.0
14.1
0.74

+0.4
Table 8. Determination of Bias for Ortho-Phosphate


Water
Am't Added
Am't Found
s,
s0
Bias

mg/L
mg/L


%
Reagent
0.69
0.69
0.06
0.06
0.0

0.92
0.98
0.15

+6.5

5.77
5.72
0.36
0.18
-0.9

6.92
6.78
0.42

-2.0

18.4
18.8
1.04
0.63
+2.1

23.1
23.2
0.35

+0.4
Drinking
0.69
0.70
0.17
0.17
+1.4

0.92
0.96
0.20

+4.3

5.77
5.43
0.52
0.40
-5.9

6.92
6.29
0.72

-9.1

18.4
18.0
0.68
0.59
-2.2

23.1
22.6
1.07

-2.0
Waste
0.68
0.64
0.26
0.09
-7.2

0.92
0.82
0.28

-10.9

5.77
5.18
0.66
0.34
-10.2

6.92
6.24
0.74

-9.8

18.4
17.6
2.08
1.27
-4.1

23.1
22.4
0.87

-3.0
300.0-11
August 1991

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Table 9. Determination of Bias for Sulfate
Water	Am't Added Am't Found	St	S0	Bias
mg/L	mg/L	%
Reagent 2.85	2.83	0.32	0.52 -0.7
3.80	3.83	0.92	+0.8
23.8	24.0	1.67	0,68 +0.8
28.5	28.5	1.56	-0.1
76.0	76.8	3.42	2.33 +1.1
95.0	95.7	3.59	+0.7
Drinking 2.85	1.12	0.37	0.41 -60.7
3.80	2.26	0.97	-40.3
23.8	21.8	1.26	0.51 -8.4
28.5	25.9	2.48	-9.1
76.0	74.5	4.63	2.70 -2.0
95.0	92.3	5.19	-2.8
Waste 2.85	1.89	0.37	0.24 -33.7
3.80	2.10	1.25	-44.7
23.8	20.3	3.19	0.58 -14.7
28.5	24.5	3.24	-14.0
76.0	71.4	5.65	3.39 -6.1
95.0	90.3	6.80	-5.0
300.0-12
August 1991

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Method A
Peak
Ret. Time
Ion
mg/L
1
1.17
F"
2
2
1.73
ci-
20
3
2.02
NO-
2
4
2.95
B r
2
5
3.20
NOj"
10
6
5.38
hpo42-
2
7
6.92
so42-
60
7
5 .	A
0	2	4	6	8
Minutes
Figure 1. Chromatogram showing separation using the AS4A column
Method B
Peak
Ret. Time
Ion
mg/L
1
2.75
cio2-
0.1
2
3.23
Br03"
0.1
3
3.63
ci-
0.1
4
7.08
CI03-
0.1
0	2	4	6	8
Minutes
Figure 2. Chromatogram showing separation using the AS9 column
300.0-13
August 1991

-------