Method 300-1 1997
Method 300-1 1997
Method 300-1 1997
Revision 1.0
Daniel P. Hautman (USEPA, Office of Water) and David J. Munch (USEPA, Office of Water)
Method 300.1, (1997)
300.1-1
METHOD 300.1
CHROMATOGRAPHY
1.1 This method covers the determination of the following inorganic anions in reagent
water, surface water, ground water, and finished drinking water. As a result of
different specified injection volumes (See conditions in Tables 1A and 1B), these
anions are divided between the common anions listed in Part A and the inorganic
disinfection by-products listed in Part B. These different injection volumes are
required in order to compensate for the relative concentrations of these anions in
drinking water and maintain good chromatographic peak shape throughout the
expected dynamic range of the detector. Bromide is included in both Part A, due to
its importance as a common anion, as well as Part B due to its critical role as a
disinfection by-product precursor.
Bromide Nitrite
Chloride ortho-Phosphate-P
Fluoride Sulfate
Nitrate
Bromate Chlorite
Bromide Chlorate
1.2 The single laboratory Method Detection Limits (MDL, defined in Sect. 3.11) for the
above analytes are listed in Tables 1A, 1B and 1C. The MDL for a specific matrix
may differ from those listed, depending upon the nature of the sample and the specific
instrumentation employed.
1.3 This method is recommended for use only by or under the supervision of analysts
experienced in the use of ion chromatography and in the interpretation of the
resulting ion chromatograms.
300.1-2
1.4 When this method is used to analyze unfamiliar samples for any of the above anions,
anion identification should be supported by the use of a fortified sample matrix
covering the anions of interest. The fortification procedure is described in Sect.
9.4.1.
1.5 Users of the method data should state the data-quality objectives prior to analysis.
Users of the method must demonstrate the ability to generate acceptable results with
this method, using the procedures described in Sect. 9.0.
1.6 Bromide and nitrite react with most oxidants employed as disinfectants. The utility
of measuring these anions in treated water should be considered prior to conducting
the analysis.
2.1 A small volume of sample, 10 µL for Part A and 50 µL for Part B, is introduced into
an ion chromatograph. The anions of interest are separated and measured, using a
system comprised of a guard column, analytical column, suppressor device, and
conductivity detector.
2.2 The ONLY difference between Parts A and B is the volume of sample analyzed by
the ion chromatographic system. The separator columns and guard columns as well
as eluent conditions are identical.
3.0 DEFINITIONS
3.1 ANALYSIS BATCH -- A group of no more than 20 field samples (Field sample
analyses include only those samples derived from a field sample matrix. These
include the initial and duplicate field samples as well as all Laboratory Fortified
Sample Matrices). The analysis batch must include an Initial Calibration Check
Standard, an End Calibration Check Standard, Laboratory Reagent Blank, and a
Laboratory Fortified Blank. Within an ANALYSIS BATCH, for every group of ten
field samples, at least one Laboratory Fortified Matrix (LFM) and either a Field
Duplicate, a Laboratory Duplicate or a duplicate of the LFM must be analyzed.
When more than 10 field samples are analyzed, a Continuing Calibration Check
Standard must be analyzed after the tenth field sample analysis.
300.1-3
3.3 FIELD DUPLICATES -- Two separate samples collected at the same time and place
under identical circumstances and treated exactly the same throughout field and
laboratory procedures. Analyses of field duplicates indicate the precision associated
with sample collection, preservation and storage, as well as with laboratory
procedures.
3.5 LABORATORY DUPLICATE -- Two sample aliquots, taken in the laboratory from
a single sample bottle, and analyzed separately with identical procedures. Analyses
of LD1 and LD2 indicate precision associated specifically with the laboratory
procedures, removing any associated variables attributed by sample collection,
preservation, or storage procedures.
300.1-4
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
concentrations.
3.9 LINEAR CALIBRATION RANGE (LCR) -- The concentration range over which
the instrument response is linear.
3.12 MINIMUM REPORTING LEVEL (MRL) -- The minimum concentration that can
be reported for an anion in a sample following analysis. This defined concentration
can be no lower than the concentration of the lowest calibration standard and can
only be used if acceptable quality control criteria for this standard are met.
300.1-5
4.0 INTERFERENCES
4.1 Interferences can be divided into three different categories: direct chromatographic
coelution, where an analyte response is observed at very nearly the same retention
time as the target anion; concentration dependant coelution, which is observed when
the response of higher than typical concentrations of the neighboring peak overlap
into the retention window of the target anion; and, ionic character displacement,
where retention times may significantly shift due to the influence of high ionic
strength matrices (high mineral content or hardness) overloading the exchange sites
in the column and significantly shortening target analyte's retention times.
4.1.2 Sample dilution may resolve some of the difficulties if the interference is the
result of either concentration dependant coelution or ionic character
displacement, but it must be clarified that sample dilution will alter your
Minimum Reporting Limit (MRL) by a proportion equivalent to that of
the dilution. Therefore, careful consideration of project objectives should be
given prior to performing such a dilution. An alternative to sample dilution,
may be dilution of the eluent as outlined in 11.9.
300.1-6
4.2 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 baselines in an ion chromatogram. These interferences can lead to false
positive results for target analytes as well as reduced detection limits as a
consequence of elevated baseline noise.
4.3 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.
4.4 Any anion that is only weakly retained by the column may elute in the retention time
window of fluoride and potentially interfere. At concentrations of fluoride above 1.5
mg/L, this interference may not be significant, however, it is the responsibility of the
user to generate precision and accuracy information in each sample matrix.
4.5 Close attention should be given to the potential for carry over peaks from one
analysis which will effect the proper detection of analytes of interest in a second,
subsequent analysis. Normally, the elution of sulfate (retention time of 13.8 min.)
indicates the end of a chromatographic run, but, in the ozonated and chlorine dioxide
matrices, which were included as part of the single operator accuracy and bias study
(See Table 2B), a small response (200 nS baseline rise) was observed for a very late
eluting unknown peak at approximately 23 minutes. Consequently, a run time of 25
minutes is recommended to allow for the proper elution of any potentially interferant
late peaks. It is the responsibility of the user to confirm that no late eluting peaks
have carried over into a subsequent analysis thereby compromising the integrity of
the analytical results.
4.6 Any residual chlorine dioxide present in the sample will result in the formation of
additional chlorite prior to analysis. If any concentration of chlorine dioxide is
suspected in the sample, the sample must be purged with an inert gas (helium, argon
or nitrogen) for approximately five minutes or until no chlorine dioxide remains. This
sparging must be conducted prior to ethylenediamine preservation and at time of
sample collection.
5.0 SAFETY
5.1 The toxicity or carcinogenicity of each reagent used in this method have not been
fully established. Each chemical should be regarded as a potential health hazard and
300.1-7
5.2 Each laboratory is responsible for maintaining a current awareness file of OSHA
regulations regarding the safe handling of the chemicals specified in this method. A
reference file of Material Safety Data Sheets (MSDS) should be made available to all
personnel involved in the chemical analysis. The preparation of a formal safety plan
is also advisable.
5.3 The following chemicals have the potential to be highly toxic or hazardous, consult
MSDS.
6.1 Ion chromatograph -- Analytical system complete with ion chromatograph and all
required accessories including syringes, analytical columns, compressed gasses and a
conductivity detector.
300.1-8
6.1.3 Anion suppressor device: The data presented in this method were generated
using a Dionex Anion Self Regenerating Suppressor (ASRS, P/N 43187).
An equivalent suppressor device may be utilized provided comparable
detection limits are achieved and adequate baseline stability is attained as
measured by a combined baseline drift/noise of no more than 5 nS per minute
over the background conductivity.
6.2 The Dionex Peaknet Data Chromatography Software was used to generate all the
data in the attached tables. Systems using a strip chart 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 Sect. 9.2.
6.3 Analytical balance, ±0.1 mg sensitivity. Used to accurately weigh target analyte salts
for stock standard preparation.
6.4 Top loading balance, ±10 mg sensitivity. Used to accurately weigh reagents to
prepare eluents.
6.8 Bottles, high density polyethylene (HDPE), opaque or glass, amber, 30 mL, 125 mL,
250 mL. For sampling and storage of calibration solutions. Opaque or amber due to
the photoreactivity of chlorite anion.
300.1-9
7.1 Reagent water: Distilled or deionized water, free of the anions of interest. Water
should contain particles no larger than 0.20 microns.
7.2 Eluent solution : Sodium carbonate (CASRN 497-19-8) 9.0 mM. Dissolve 1.91 g
sodium carbonate (Na2CO3) in reagent water and dilute to 2 L.
7.2.1 This eluent solution must be purged for 10 minutes with helium prior to use
to remove dissolved gases which may form micro bubbles in the IC
compromising system performance and adversely effecting the integrity of
the data.
7.3 Stock standard solutions, 1000 mg/L (1 mg/mL): Stock standard solutions may be
purchased as certified solutions or prepared from ACS reagent grade, potassium or
sodium salts as listed below, for most analytes. Chlorite requires careful
consideration as outline below in 7.3.5.1.
7.3.1 Bromide (Br-) 1000 mg/L: Dissolve 0.1288 g sodium bromide (NaBr,
CASRN 7647-15-6) in reagent water and dilute to 100 mL in a volumetric
flask.
7.3.4 Chloride (Cl-) 1000 mg/L: Dissolve 0.1649 g sodium chloride (NaCl,
CASRN 7647-14-5) in reagent water and dilute to 100 mL in a volumetric
flask.
300.1-10
7.3.6 Fluoride (F-) 1000 mg/L: Dissolve 0.2210 g sodium fluoride (NaF, CASRN
7681-49-4) in reagent water and dilute to 100 mL in a volumetric flask.
7.3.7 Nitrate (NO-3 -N) 1000 mg/L: Dissolve 0.6068 g sodium nitrate (NaNO3,
CASRN 7631-99-4) in reagent water and dilute to 100 mL in a volumetric
flask.
7.3.8 Nitrite (NO-2 -N) 1000 mg/L: Dissolve 0.4926 g sodium nitrite (NaNO2,
CASRN 7632-00-0) in reagent water and dilute to 100 mL in a volumetric
flask.
7.3.10 Sulfate (SO4 2-) 1000 mg/L: Dissolve 0.1814 g potassium sulfate (K2SO4,
CASRN 7778-80-5) in reagent water and dilute to 100 mL in a volumetric
flask.
NOTE: Stability of standards: Stock standards (7.3) for most anions are stable for at
least 6 months when stored at 4EC. Except for the chlorite standard which is
only stable for two weeks when stored protected from light at 4EC, and
nitrite and phosphate which are only stable for 1 month when stored at 4EC.
Dilute working standards should be prepared monthly, except those that
contain chlorite, or nitrite and phosphate which should be prepared fresh
daily.
300.1-11
7.5.2 Prepare this solution fresh every 3 months or sooner if signs of degradation
are present.
8.1 Samples should be collected in plastic or glass bottles. All bottles must be
thoroughly cleaned and rinsed with reagent water. Volume collected should be
sufficient to insure a representative sample, allow for replicate analysis, if required,
and minimize waste disposal.
8.2.1 Sample bottles used for chlorite analysis must be opaque to protect the
sample from light.
8.2.2 When preparing the LFM, be aware that chlorite is an oxidant and may react
with the natural organic matter in an untreated drinking water matrix as a
result of oxidative demand. If untreated water is collected for chlorite
analysis, and subsequently used for the LFM, EDA preservation will not
control this demand and reduced chlorite recoveries may be observed.
8.3 Sample preservation and holding times for the anions that can be determined by this
method are as follows:
300.1-12
8.4 When collecting a sample from a treatment plant employing chlorine dioxide, the
sample must be sparged with an inert gas (helium, argon, nitrogen) prior to addition
of the EDA preservative at time of sample collection.
8.5 All four anions, in Part B, can be analyzed in a sample matrix which has been
preserved with EDA. Add a sufficient volume of the EDA preservation solution
(Sect. 7.4) such that the final concentration is 50 mg/L in the sample. This would be
equivalent to adding 0.5 mL of the EDA preservation solution to 1 L of sample.
9.1 Each laboratory using this method is required to operate a formal quality control
(QC) program. The requirements of this program consist of an initial demonstration
of laboratory performance, and subsequent analysis in each analysis batch (Sect. 3.1)
of a Laboratory Reagent Blank, Laboratory Fortified Blank, Instrument Performance
Check Standard, calibration check standards, Laboratory Fortified Sample Matrices
(LFM) and either Field, Laboratory or LFM duplicate sample analyses. This section
details the specific requirements for each of these QC parameters. The laboratory is
required to maintain performance records that define the quality of the data that are
generated.
300.1-13
9.2.2 Quality Control Sample (QCS) -- When beginning the use of this method, on
a quarterly basis or as required to meet data-quality needs, verify the
calibration standards and acceptable instrument performance with the
preparation and analyses of a QCS. If the determined concentrations are not
within ± 15% of the stated values, performance of the determinative step of
the method is unacceptable. The source of the problem must be identified
and corrected before either proceeding with the initial determination of
MDLs or continuing with on-going analyses.
9.2.3 Method Detection Limit (MDL) -- MDLs must be established for all
analytes, using reagent water (blank) fortified at a concentration of three to
five times the estimated instrument detection limit.(6) To determine MDL
values, take seven replicate aliquots of the fortified reagent water and
process through the entire analytical method over at least three separate
days. Perform all calculations defined in the method and report the
concentration values in the appropriate units. Calculate the MDL as follows:
9.3.1 Laboratory Reagent Blank (LRB) -- The laboratory must analyze at least one
LRB with each analysis batch (defined Sect 3.1). Data produced are used to
assess contamination from the laboratory environment. Values that exceed
the MDL indicate laboratory or reagent contamination should be suspected
and corrective actions must be taken before continuing the analysis.
300.1-14
9.3.1.1 If conducting analysis for the Part B anions, EDA must be added
to the LRB at 50 mg/L. By including EDA in the LRB, any bias
as a consequence of the EDA which may be observed in the field
samples, particularly in terms of background contamination, will
be identified.
9.3.2.1 If conducting analysis for the Part B anions, EDA must be added
to the LFB at 50 mg/L. The addition of EDA to all reagent water
prepared calibration and quality control samples is required not as
a preservative but rather as a means to normalize any bias
attributed by the presence of EDA in the field samples.
9.3.2.3 The laboratory must use the LRB to assess laboratory perfor
mance against the required control limits listed in 9.3.2.2. When
sufficient internal performance data become available (usually a
minimum of 20-30 analyses), optional control limits can be
developed from the percent mean recovery (x) and the standard
deviation (S) of the mean recovery. These data can be used to
establish the upper and lower control limits as follows:
300.1-15
recent 20-30 data points. Also, the standard deviation (S) data
should be used to establish an on-going precision statement for the
level of concentrations monitored. These data must be kept on file
and be available for review.
1.83 x W(1/2)
PGF = -----------------------
W(1/10)
9.3.3.1 The PGF must fall between 0.80 and 1.15 in order to demonstrate
proper instrument performance.
9.3.3.2 The retention time for the surrogate in the IPC must be closely
monitored on each day of analysis and throughout the lifetime of
the analytical column. Small variations in retention time can be
anticipated when a new solution of eluent is prepared but if shifts
of more than 2% are observed in the surrogate retention time,
some type of instrument problem is present. Potential problems
include improperly prepared eluent, erroneous method parameters
programmed such as flow rate or some other system problem. The
chromatographic profile (elution order) of the target anions
following an ion chromatographic analysis should closely replicate
the profile displayed in the test chromatogram that was shipped
when the column was purchased. As a column ages, it is normal to
see a gradual shift and shortening of retention times, but if after
several years of use, extensive use over less than a year, or use
with harsh samples, this retention time has noticeably shifted to
any less than 80% of the original recorded value, the column may
require cleaning or replacement. Particularly if resolution
problems are beginning to become common between previously
resolved peaks. A laboratory must retain a historic record of
300.1-16
retention times for the surrogate and all the target anions to
provide evidence of an analytical columns vitality.
9.4.1 Laboratory Fortified Sample Matrix (LFM) -- The laboratory must add a
known amount of analyte to a minimum of 10% of the field samples within
an analysis batch. The LFM sample must be prepared from a sample matrix
which has been analyzed prior to fortification. The analyte concentration
must be high enough to be detected above the original sample and should
adhere to the requirement of 9.4.1.2. It is recommended that the solutions
used to fortify the LFM be prepared from the same stocks used to prepare
the calibration standards and not from external source stocks. This will
remove the bias contributed by an externally prepared stock and focus on any
potential bias introduced by the field sample matrix.
9.4.1.3 Calculate the percent recovery for each analyte, corrected for
concentrations measured in the unfortified sample. Percent
recovery should be calculated using the following equation:
Cs - C
R = -------- x 100
s
300.1-17
9.4.1.5 If the recovery of any analyte falls outside the designated LFM
recovery range and the laboratory performance for that analyte is
shown to be in control (Sect. 9.3), the recovery problem
encountered with the LFM is judged to be either matrix or
solution related, not system related.
SRC
R = --------- x 100
SFC
300.1-18
(IC - Dc)
%Diff = -------------- X 100
([IC + Dc]/2)
9.4.3.3 If the %Diff fails to meet these criteria, the samples must be
reanalyzed.
9.4.4 Where reference materials are available, they should be analyzed to provide
additional performance data. The analysis of reference samples is a valuable
tool for demonstrating the ability to perform the method acceptably.
300.1-19
10.2 Estimate the Linear Calibration Range (LCR) -- The LCR should cover the expected
concentration range of the field samples and should not extend over more than 2
orders of magnitude in concentration (For example, if quantitating nitrate in the
expected range of 1.0 mg/L to 10 mg/L, 2 orders of magnitude would permit the
minimum and maximum calibration standards of 0.20 mg/L and 20 mg/L,
respectively.) The restriction of 2 orders of magnitude is prescribed since beyond this
it is difficult to maintain linearity throughout the entire calibration range.
10.2.1 If quantification is desired over a larger range, then two separate calibration
curves should be prepared.
10.3 Prepare the calibration standards by carefully adding measured volumes of one or
more stock standards (7.3) to a volumetric flask and diluting to volume with reagent
water.
10.3.1 For the Part B anions, EDA must be added to the calibration standards at 50
mg/L. The addition of EDA to all reagent water prepared calibration and
quality control samples is required not as a preservative but rather as a means
to normalize any bias attributed by the presence of EDA in the field samples.
300.1-20
10.4.1 Peak areas are strongly recommended since they have been found to be more
consistent, in terms of quantitation, than peak heights. Peak height can tend
to be suppressed as a result of high levels of common anions in a given
matrix which can compete for exchange sites. Using peak areas, it is the
analyst responsibility to review all chromatograms to insure accurate baseline
integration of target analyte peaks since poorly drawn baselines will more
significantly influence peak areas than peak heights.
10.5 Once the calibration curves have been established they must be verified prior to
conducting any sample analysis using an initial calibration check standard (3.2.2).
This verification must be performed on each analysis day or whenever fresh eluent
has been prepared. A continuing calibration check standard (3.2.3) must be analyzed
after every tenth sample and at the end of the analysis set as an end calibration check
standard (3.2.4). The response for the initial, continuing and end calibration check
must satisfy the criteria listed in 10.5.1. If during the analysis set, the response differs
by more than the calibration verification criteria shown in 10.5.1., or the retention
times shift more than ± 5% from the expected values for any analyte, the test must be
repeated, using fresh calibration standards. If the results are still outside these
criteria, sample analysis must be discontinued, the cause determined and/or in the
case of drift, the instrument recalibrated. All samples following the last acceptable
calibration check standard must be reanalyzed.
10.5.1.1 These control limits only apply if the MRL is established within a
factor of 10 times the MDL. Otherwise, the limits are set at 85%
to 115%.
300.1-21
10.5.3 After satisfying the requirement of 10.5.2, the levels selected for the other
calibration check standards should be varied between a middle calibration
level and the highest calibration level.
11.0 Procedure
11.1 Tables 1A and 1B summarize the recommended operating conditions for the ion
chromatograph. Included in these tables are estimated retention times that can be
achieved by this method. Other columns, chromatographic conditions, or detectors
may be used if the requirements of Sect. 9.2 are met.
11.2 Check system calibration daily and, if required, recalibrate as described in Sect. 10.
11.3.1 For refrigerated or samples arriving to the laboratory cold, ensure the
samples have come to room temperature prior to conducting sample analysis
by allowing the samples to warm on the bench for at least 1 hour.
11.3.2 Prepare a 10.0 mL aliquot of surrogate fortified sample which can be held for
direct manual injection or used to fill an autosampler vial. Add 20 µL of the
surrogate solution (7.5) to a 20 mL disposable plastic micro beaker. Using a
10.0 mL disposable pipet, place exactly 10.0 mL of sample into the micro
beaker and mix. Sample is now ready for analysis.
11.3.2.1 The less than 1% dilution error introduced by the addition of the
surrogate is considered insignificant.
11.4 Using a Luer lock, plastic 10 mL syringe, withdraw the sample from the micro
beaker and attach a 0.45 µm particulate filter (demonstrated to be free of ionic
contaminants) directly to the syringe. Filter the sample into an autosampler vial (If
vial is not designed to automatically filter) or manually load the injection loop
injecting a fixed amount of well mixed sample. If using a manually loaded injection
loop, flush the loop thoroughly between sample analysis using sufficient volumes of
each new sample matrix.
300.1-22
Tabulate peak area responses against the concentration. During this procedure,
retention times must be recorded. Use the same size loop for standards and samples.
Record the resulting peak size in area units. An automated constant volume injection
system may also be used.
11.6 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.
11.7 If the response of a sample analyte exceeds the calibration range, the sample may be
diluted with an appropriate amount of reagent water and reanalyzed. If this is not
possible then three new calibration concentrations must be employed to create a
separate high concentration curve, one standard near the estimated concentration
and the other two bracketing around an interval equivalent to ± 25% the estimated
concentration. The latter procedure involves significantly more time than a simple
sample dilution therefore, it is advisable to collect sufficient sample to allow for
sample dilution or sample reanalysis, if required.
11.9 Should more complete resolution be needed between any two coeluting peaks, the
eluent (7.2) can be diluted. This will spread out the run, however, and will cause late
eluting anions to be retained even longer. The analyst must determine to what extent
the eluent is diluted. This dilution is not be considered a deviation from the method.
If an eluent dilution is performed, section 9.2 must be repeated.
11.9.1 Eluent dilution will reduce the overall response of an anion due to
chromatographic band broadening which will be evident by shortened and
broadened peaks. This will adversely effect the MDLs for each analyte.
12.1 Prepare a calibration curve for each analyte by plotting instrument response, as peak
area, against standard concentration. Compute sample concentration by comparing
sample response with the standard curve. If a sample has been diluted, multiply the
response by the appropriate dilution factor.
12.2 Report ONLY those values that fall between the lowest and the highest calibration
standards. Samples with target analyte responses exceeding the highest standard
300.1-23
should be diluted and reanalyzed. Samples with target analytes identified but
quantitated below the concentration established by the lowest calibration standard
cannot be reported since the lowest calibrated concentration is the minimum
reporting limit (MRL).
12.3 Report results for Part A anions in mg/L and for Part B anions in µg/L.
NO3- as N
HPO4= as P
13.1 Tables 1A, 1B, and 1C give the single laboratory (OW OGWDW TSC-Cincinnati)
retention times, standard conditions and MDL determined for each anion included in
the method. MDLs for the Part A anions were determined in reagent water on the 2
mm column (Table 1A). MDLs for the Part B anions were conducted not only in
reagent water but also a simulated high ionic strength water (HIW) on the 2 mm
column (Table 1B) and in reagent water on the 4 mm column (Table 1C). HIW is
designed to simulate a high ionic strength field sample. It was prepared from reagent
water which was fortified with the common anions of chloride at 100 mg/L,
carbonate at 100 mg/L, nitrate at 10.0 mg/L as nitrogen, phosphate at 10.0 mg/L as
phosphorous, and sulfate at 100 mg/L.
13.2 Tables 2A and 2B give the single laboratory (OW OGWDW TSC-Cincinnati)
standard deviation for each anion included in the method in a variety of waters for the
standard conditions identified in Table 1A and 1B, respectively.
13.3 Tables 3A and 3B shown stability data for the Part A and B anions, respectively.
Each data point in these tables represent the mean percent recovery following
triplicate analysis. These data were used to formulate the holding times shown in
Sect. 8.3.
14.1 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. The 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
300.1-24
generation. When wastes cannot be feasibly reduced at the source, the Agency
recommends recycling as the next best option.
14.2 Quantity of the chemicals 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.
14.3 For information about pollution prevention that may be applicable to laboratories
and research institutions, consult "Less is Better: Laboratory Chemical Management
for Waste Reduction," available from the American Chemical Society's Department
of Government Regulations and Science Policy, 1155 16th Street N.W., Washington
D.C. 20036,
(202) 872-4477.
15.1 The Environmental Protection Agency requires that laboratory waste management
practices be conducted consistent with all applicable rules and regulations. Excess
reagents, samples and method process wastes should be characterized and disposed
of in an acceptable manner. The Agency urges laboratories to protect the air, water,
and land by minimizing and controlling all releases from hoods and bench operations,
complying with the letter and spirit of any waste discharge permit and regulations,
and by complying with all solid and hazardous waste regulations, particularly the
hazardous waste identification rules and land disposal restrictions. For further
information on waste management consult the "Waste Management Manual for
Laboratory Personnel," available from the American Chemical Society at the address
listed in Sect. 14.3.
300.1-25
16.0 REFERENCES
2. Standard Methods for the Examination of Water and Wastewater, Method 4110B,
"Anions by Ion Chromatography", 18th Edition of Standard Methods (1992).
5. American Society for Testing and Materials. Test Method for Anions in Water by
Chemically-Suppressed Ion Chromatography D4327-91. Annual Book of Standards,
Vol 11.01 (1993).
8. Standard Methods for the Examination of Water and Wastewater, Method 4500
ClO 2,C "Amperometric Method I" (for the determination of Chlorine Dioxide), 19th
Edition of Standard Methods (1995).
300.1-26
MDL DETERMINATION
Fort Conc, number DI
RETENTION TIME mg/L of MDL
ANALYTE PEAK # (1) (MIN.) Replicates mg/L
Fluoride 1 2.53 0.020 7 0.009
Chloride 2 4.67 0.020 7 0.004
Nitrite-N 3 6.01 0.010 7 0.001
Surrogate: DCA 4 7.03
Bromide 5 8.21 0.040 7 0.014
Nitrate-N 6 9.84 0.010 7 0.008
ortho-Phosphate-P 7 11.98 0.040 7 0.019
Sulfate 8 13.49 0.040 7 0.019
Standard Conditions:
300.1-27
MDL DETERMINATION
Fort number DI HIW(2)
RETENTION Conc, of MDL MDL
(1)
ANALYTE PEAK # TIME µg/L Replica µg/L µg/L
(MIN.) tes
Chlorite 1 3.63 2.00 7 0.89 0.45
Bromate 2 4.19 2.00 7 1.44 1.28
Surrogate: 4 7.28
DCA
Bromide 5 8.48 2.00 7 1.44 2.51
Chlorate 6 9.28 2.00 7 1.31 0.78
Standard Conditions:
(2) HIW indicates High Ionic Strength Water which is a simulated drinking water prepared
from reagent water and fortified with chloride at 100 mg/L, carbonate at 100 mg/L, nitrate
at 10.0 mg/L as nitrogen, phosphate at 10.0 mg/L as phosphorous, and sulfate at 100 mg/L.
300.1-28
MDL DETERMINATION
Fort number DI
RETENTION Conc, of MDL
ANALYTE PEAK # TIME µg/L Replica µg/L
(MIN.) tes
Chlorite 1 4.43 2.00 7 1.44
Bromate 2 5.10 2.00 7 1.32
Surrogate: 4 8.82
DCA
Bromide 5 10.11 2.00 7 0.98
Chlorate 6 10.94 2.00 7 2.55
Standard Conditions:
300.1-29
TABLE 2A. SINGLE-OPERATOR PRECISION AND RECOVERY FOR THE COMMON ANIONS
(PART A).
UNFORT FORT #
MATRIX CONC OF MEAN MEAN
ANALYTE MATRIX CONC., mg/L REPLC mg/L %REC SD(n-1) %RSD
mg/L
Fluoride RW <DL(1) 2.00 9 1.79 89.7 0.02 1.18
SW 0.139 2.00 9 1.75 80.4 0.01 0.56
GW 0.280 2.00 9 1.97 84.3 0.02 0.85
CDW 0.807 2.00 9 2.59 89.0 0.01 0.46
Chloride RW 0.029 50.0 9 49.4 98.7 0.03 0.10
SW 12.1 50.0 9 58.7 93.3 0.04 0.10
GW 56.6 50.0 9 100. --(2) 0.22 0.22
CDW 16.0 50.0 9 64.9 97.8 0.11 0.16
Nitrite-N RW <DL 1.00 9 0.851 85.1 0.00 0.51
SW <DL 1.00 9 0.780 78.0 0.00 0.40
GW 0.013 1.00 9 0.879 86.6 0.01 0.77
CDW <DL 1.00 9 0.720 72.0 0.00 0.55
Bromide RW <DL 0.500 9 0.480 96.1 0.00 0.92
SW 0.028 0.500 9 0.469 88.1 0.00 0.94
GW 0.153 0.500 9 0.634 96.3 0.00 0.52
CDW <DL 0.500 9 0.431 86.2 0.01 1.28
Nitrate-N RW <DL 10.0 9 9.50 95.0 0.01 0.14
SW 2.12 10.0 9 10.9 87.7 0.03 0.30
GW 0.016 10.0 9 9.64 96.3 0.03 0.27
CDW 1.64 10.0 9 10.9 92.4 0.04 0.41
Phosphate-P RW <DL 10.0 9 9.62 96.2 0.01 0.14
SW <DL 10.0 9 8.70 87.0 0.02 0.18
GW <DL 10.0 9 6.12 61.2 0.28 4.66
CDW <DL 10.0 9 9.15 91.5 0.04 0.42
Sulfate RW <DL 50.0 9 44.8 89.5 0.05 0.11
SW 47.8 50.0 9 92.1 88.6 0.21 0.23
GW 105 50.0 9 154 --(2) 0.60 0.39
CDW 57.8 50.0 9 105 --(2) 0.33 0.32
Surrogate: RW --- 5.00 9 5.12 102.3 0.50 0.49
SW --- 5.00 9 5.09 102.3 1.12 1.09
GW --- 5.00 9 5.16 101.8 0.67 0.66
CDW --- 5.00 9 5.17 103.1 1.36 1.32
300.1-30
UNFORT FORT #
CONC. CONC OF MEAN MEAN
ANALYTE MATRIX µg/L µg/L REPLC µg/L %REC SD(n-1) %RSD
Chlorite RW <DL(1) 100 9 96.2 96.2 0.95 0.99
500 9 523 105 3.13 0.60
HIW <DL 100 9 102 102 2.19 2.15
500 9 520 104 3.64 0.70
SW <DL 100 9 91.4 91.4 1.22 1.33
500 9 495 99.0 7.54 1.52
GW <DL 100 9 92.9 92.9 1.65 1.77
500 9 490 98.1 3.40 0.69
ClW <DL 100 9 87.4 87.4 0.59 0.68
500 9 485 97.1 6.36 1.31
CDW 292 100 9 396 --(2) 1.64 0.41
500 9 811 104 4.00 0.49
O3W <DL 100 9 84.4 84.4 0.46 0.54
500 9 481 96.1 3.24 0.67
300.1-31
UNFORT FORT #
CONC. CONC OF MEAN MEAN
ANALYTE MATRIX µg/L µg/L REPLC µg/L %REC SD(n-1) %RSD
Bromide RW <DL(1) 20.0 9 20.9 104 0.80 3.82
100 9 107 107 0.60 0.56
HIW 3.24 20.0 9 21.8 92.5 0.79 3.63
100 9 105 102 1.05 1
SW 31.0 20.0 9 51.3 --(2) 0.97 1.9
100 9 140. 109 1.88 1.35
GW 151 20.0 9 172 --(2) 0.78 0.45
100 9 265 --(2) 2.18 0.82
ClW 16.3 20.0 9 39.3 115 0.64 1.62
100 9 125 109 2.00 1.6
CDW 11.5 20.0 9 34.4 115 0.76 2.22
100 9 125 113 1.24 0.99
O3W 39.8 20.0 9 65.4 --(2) 128 3.67 5.61
100 9 153 113 1.00 0.65
300.1-32
FORT #
CONC OF MEAN MEAN
ANALYTE MATRIX mg/L REPLC mg/L %REC SD(n-1) %RSD
Surrogate: DCA RW 5.00 9 5.11 102 0.93 0.91
NOTE: The surrogate DCA was fortified at 5 mg/L but due to concerns about measuring trace
concentrations of bromide with such high concentration of the neighboring surrogate peak,
the recommended fortified concentration for the surrogate has been reduced to 1.00 mg/L.
300.1-33
TABLE 3A. STABILITY STUDY RESULTS FOR THE COMMON ANIONS (PART A).
UNFORT FORT Analyte % Recovery
CONC. CONC
Day Day Day See
ANALYTE Preservative Matrix mg/L mg/L
0 14 28 Note
Fluoride None RW <DL 2.00 89.8 88.3 88.4
SW 0.140 2.00 79.9 80.2 80.0
GW 0.280 2.00 84.7 87.8 87.0
CDW 0.929 2.00 82.9 83.6 81.6
Chloride None RW <DL 50.0 98.8 99.1 98.1
SW 12.0 50.0 93.4 93.5 92.8
GW 56.6 50.0 87.6 87.6 86.5
CDW 16.0 50.0 97.9 98.4 97.8
Nitrite-N None RW <DL 1.00 85.2 85.5 83.6
SW <DL 1.00 77.8 76.6 11.9 (1)
GW <DL 1.00 88.2 85.4 56.1 (1)
CDW <DL 1.00 71.9 71.7 73.9 (2)
Bromide None RW <DL 0.500 95.5 97.0 96.2
SW 0.028 0.500 87.5 88.3 86.7
GW 0.153 0.500 96.9 96.0 96.1
CDW <DL 0.500 85.7 87.1 89.2 (2)
Nitrate-N None RW <DL 10.0 94.9 94.7 94.2
SW 2.12 10.0 87.6 87.0 88.7
GW <DL 10.0 96.5 96.5 95.5
CDW 1.64 10.0 92.3 93.3 91.9
Phosphate-P None RW <DL 10.0 96.3 95.8 95.2
SW <DL 10.0 86.9 86.4 85.1
GW <DL 10.0 62.8 93.1 89.5 (3)
CDW <DL 10.0 91.6 91.4 90.8
Sulfate None RW <DL 50.0 89.6 89.3 89.1
SW 47.8 50.0 89.0 89.0 88.1
GW 105 50.0 97.5 97.3 96.5
CDW 57.8 50.0 94.3 94.9 93.8
NOTES:
(1) Degradation apparent.
(2) Analyte recovery will be adversely effected by reactions with free chlorine.
(3) Phosphate recovery on day 0 is believed to have been adversely effected by biological degradation
since the sample sat in the autosampler for 18 hrs prior to analysis
300.1-34
(PART B).
UNFORT FORT Analyte % Recovery
CONC. CONC
Day Day Day Day See
ANALYTE Preservative Matrix µg/L µg/L
0 3 10 30 Note
Chlorite None RW <DL 500 99.8 100 104 94.3
HIW <DL 500 99.3 98.5 106 89.3
SW <DL 500 92 88.5 82.3 75.1 (1)
GW <DL 500 93.9 94.5 96.1 91.7
ClW <DL 500 93.7 NA(1 90.3 84.7 (2,3)
CDW 286 500 98.6 101 91.7 77.5 (1,3)
O3W <DL 500 10 NA 82.5 90.5 (2)
Chlorite EDA RW <DL 500 101 101 104 95.3
HIW <DL 500 98.4 98.7 104 95.4
SW <DL 500 98.3 97.3 97.8 92.7
GW <DL 500 97.7 97.1 97.5 92.6
ClW <DL 500 98.9 NA 96.9 92.6 (2)
CDW 297 500 103 107 102 94.5
O3W <DL 500 105 NA 96.3 91.9 (2)
Bromate None RW <DL 25.0 93.6 94.1 110 96.1
HIW <DL 25.0 100 86.0 105 87.7
SW <DL 25.0 98.7 95.1 105 102
GW <DL 25.0 79.4 92.4 77.8 82.2
ClW <DL 25.0 102 NA 101 103 (2)
CDW <DL 25.0 104 96.8 98.9 92.1
O3W 2.27 25.0 87.3 NA 84.3 99.9 (2)
Bromate EDA RW <DL 25.0 97.3 95.3 99.5 102
HIW <DL 25.0 86.9 86.1 107 91.2
SW <DL 25.0 100 104 103 94.9
GW <DL 25.0 83.2 101 88.4 88.3
ClW <DL 25.0 105 NA 101 102 (2)
CDW <DL 25.0 117 97.3 98.1 83.9
O3W 2.32 25.0 92.6 NA 84.5 88.9 (2)
300.1-35
300.1-36
Figure 1. Chromatogram showing separation of the Part A common anions on the AS9-HC column. See Table 1A for
analysis conditions.
Figure 2 Chromatogram showing separation of the Part B inorganic DBPs and bromide on the AS9-HC column. See
Table 1B for analysis conditions.
Figure 3. Chromatogram of the inorganic DBPs and bromide (Part B) during the MDL determination in reagent water.
See Table 1B for analysis conditions.
Figure 4. Chromatogram of the inorganic DBPs and bromide (Part B) in high ionic strength water (HIW). See Table
1B for analysis conditions.
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