Test Methods for Evaluating Solid Waste
Physical/Chemical Methods
Final (Promulgated) Updates II and MA
Volume 2
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METHOD 8000A
GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Gas chromatography is a quantitative technique useful for the
analysis of organic compounds capable of being volatilized without being
decomposed or chemically rearranged. Gas chromatography (GC), also known as
vapor phase chromatography (VPC), has two subcategories distinguished by: gas-
solid chromatography (GSC), and gas-liquid chromatography (GLC) or gas-liquid
partition chromatography (GLPC). This last group is the most commonly used,
distinguished by type of column adsorbent or packing.
1.2 The chromatographic methods are recommended for use only by, or under
the close supervision of, experienced residue analysts.
2.0 SUMMARY OF METHOD
2.1 Each organic analytical method that follows provides a recommended
technique for extraction, cleanup, and occasionally, derivatization of the
samples to be analyzed. Before the prepared sample is introduced into the GC,
a procedure for standardization must be followed to determine the recovery and
the/ limits of detection for the analytes of interest. Following sample
introduction into the GC, analysis proceeds with a comparison of sample values
with standard values. Quantitative analysis is achieved through integration of
peak area or measurement of peak height.
3,0 INTERFERENCES
3.1 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed. To reduce carryover, the
sample syringe or purging device must be rinsed out between samples with water
or solvent. Whenever an unusually concentrated sample is encountered, it should
be r followed by an analysis of a solvent blank or of water to check for cross
cb'ritami nation. For volatile samples containing large amounts of water-soluble
materials, suspended solids, high boiling compounds or high organohalide
concentrations, it may be necessary to wash out the syringe or purging device
with a detergent solution, rinse it with distilled water, and then dry it in a
2 oven between analyses.
4,0 APPARATUS AND MATERIALS
4.1 Gas chromatograph - Analytical system complete with gas chromatograph
suitable for on-column injections and all required accessories, including
.detectors, column supplies, recorder, gases, and syringes. A data system for
measuring peak height and/or peak areas is recommended.
4.2
Other packed or capi
Gas chromatographic columns - See the specific determinative method.
or capillary (open-tubular) columns may be used if the requirements
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of Section 8.6 are met.
5.0 REAGENTS
5.1 See the specific determinative method for the reagents needed.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Extraction - Adhere to those procedures specified in the referring
determinative method.
7.2 Cleanup and separation - Adhere to those procedures specified in the
referring determinative method.
7,3 The recommended gas chromatographic columns and operating conditions
for the instrument are specified in the referring determinative method.
7.4 Calibration
7.4.1 Establish gas chromatographic operating parameters equivalent
to those indicated in Section 7.0 of the determinative method of interest.
Prepare calibration standards using the procedures indicated in
Section 5.0 of the determinative method of interest. Calibrate the
chromatographic system using either the external standard technique
(Section 7.4.2) or the internal standard technique (Section 7.4.3).
7.4.2 External standard calibration procedure
7.4.2.1 For each analyte of interest, prepare calibration
standards at a minimum of five concentrations by adding volumes of
one or more stock standards to a volumetric flask and diluting to
volume with an appropriate solvent. One of the external standards
should be at a concentration near, but above, the method detection
limit. The other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the detector.
7.4.2.2 Inject each calibration standard using the
technique that will be used to introduce the actual samples into the
gas chromatograph (e.g. 2-5 /xL injections, purge-and-trap, etc.).
Tabulate peak height or area responses against the mass injected.
The results can be used to prepare a calibration curve for each
analyte. Alternatively, for samples that are introduced into the
gas chromatograph using a syringe, the ratio of the response to the
amount injected, defined as the calibration factor (CF), can be
calculated for each analyte at each standard concentration. If the
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percent relative standard deviation (%RSD) of the calibration factor
is less than 20% over the working range, linearity through the
origin can be assumed, and the average calibration factor can be
used in place of a calibration curve.
C.Hbr.t1« factor ° *
ograms)
* For multi response pesticides/PCBs, use the total area of
all peaks used for quantitation.
7.4.2.3 The working calibration curve or calibration
factor must be verified on each working day by the injection of one
or more calibration standards. The frequency of verification is
dependent on the detector. Detectors, such as the electron capture
detector, that operate in the sub-nanogram range are more
susceptible to changes in detector response caused by GC column and
sample effects. Therefore, more frequent verification of
calibration is necessary. The flame ionization detector is much
less sensitive and requires less frequent verification. If the
response for any analyte varies from the predicted response by more
than + 15%, a new calibration curve must be prepared for that
analyte. For methods 8010, 8020, and 8030, see Table 3 in each
method for calibration and quality control acceptance criteria.
Percent Difference = - x 100
*i
where:
R, = Calibration Factor from first analysis.
R2 = Calibration Factor from succeeding analyses.
7.4.3 Internal standard calibration procedure
7.4.3.1 To use this approach, the analyst must select one
or more internal standards that are similar in analytical behavior
to the compounds of interest. The analyst must further demonstrate
that the measurement of the internal standard is not affected by
method or matrix interferences. Due to these limitations, no
internal standard applicable to all samples can be suggested.
7.4.3.2 Prepare calibration standards at a minimum of five
concentrations for each analyte of interest by adding volumes of one
or more stock standards to a volumetric flask. To each calibration
standard, add a known constant amount of one or more internal
standards and dilute to volume with an appropriate solvent. One of
the standards should be at a concentration near, but above, the
method detection limit. The other concentrations should correspond
to the expected range of concentrations found in real samples or
should define the working range of the detector.
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7.4.3.3 Inject each calibration standard using the same
Introduction technique that will be applied to the actual samples
(e.g. 2 to 5 pi Injection, purge-and-trap, etc.). Tabulate the peak
height or area responses against the concentration of each compound
and internal standard. Calculate response factors (RF) for each
compound as follows:
RF « (AsCis)/(AisCs)
where:
As » Response for the analyte to be measured.
Ajs » Response for the internal standard.
CJ8 * Concentration of the internal standard, M9/L.
C. » Concentration of the analyte to be measured,
M9/L.
If the RF value over the working range is constant (< 20%
RSD), the RF can be assumed to be invariant, and the average RF can
be used for calculations. Alternatively, the results can be used to
plot a calibration curve of response ratios, As/Ais versus RF.
7.4.3.4 The working calibration curve or RF must be
verified on each working day by the measurement of one or more
calibration standards. The frequency of verification is dependent
on the detector. Detectors, such as the electron capture detector,
that operate in the sub-nanogram range are more susceptible to
changes in detector response caused by GC column and sample effects.
Therefore, more frequent verification of calibration is necessary.
The flame ionization detector is much less sensitive and requires
less frequent verification. If the response for any analyte varies
from the predicted response by more than ± 15%, a new calibration
curve must be prepared for that compound. For methods 8010, 8020,
and 8030, see Table 3 in each method for calibration and quality
control acceptance criteria.
7.5 Retention time windows
7.5.1 Before establishing windows, make sure the GC system is within
optimum operating conditions.' Make three injections of all single
component standard mixtures and multiresponse products (i.e. PCBs)
throughout the course of a 72 hour period. Serial injections over less
than a 72 hour period result in retention time windows that are too tight.
7.5.2 Calculate the standard deviation of the three retention times
(use any function of retention time; including absolute retention time, or
relative retention time) for each single component standard. For
multiresponse products, choose one major peak from the envelope and
calculate the standard deviation of the three retention times for that
peak. The peak chosen should be fairly immune to losses due to
degradation and weathering in samples.
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7.5.2.1 Plus or minus three times the standard deviation
of the retention times for each standard will be used to define the
retention time window; however, the experience of the analyst should
weigh heavily in the interpretation of chromatograms. For
multiresponse analytes (i.e. PCBs), the analyst should use the
retention time window, but should primarily rely on pattern
recognition.
7.5.2.2 In those cases where the standard deviation for a
particular standard is zero, the laboratory must substitute the
standard deviation of a close eluting, similar compound to develop
a valid retention time window.
7.5.3 The laboratory must calculate retention time windows for each
standard on each GC column and whenever a new GC column is installed. The
data must be retained by the laboratory.
7.6 Gas chromatographic analysis
7.5.1 Introduction of organic compounds into the gas chromatograph
varies depending on the volatility of the compound. Volatile organics are
primarily introduced by purge-and-trap (Method 5030). However, there are
limited applications (in Method 5030) where direct injection is
acceptable. Use of Method 3810 or 3820 as a screening technique for
volatile organic analysis may be valuable with some sample matrices to
prevent overloading and contamination of the GC systems. Semi volatile
organics are introduced by direct injection.
7.6.2 The appropriate detector(s) is given in the specific method.
7.6.3 Samples are analyzed in a set referred to as an analysis
sequence. The sequence begins with instrument calibration followed by
sample extracts interspersed with multi-concentration calibration
standards. The sequence ends when the set of samples has been injected or
when qualitative and/or quantitative QC criteria are exceeded.
7.6.4 Direct Injection - Inject 2-5 /nL of the sample extract using
the solvent flush technique, if the extract is manually injected. Smaller
volumes (1.0 /uL) can be injected, and the solvent flush technique is not
required, if automatic devices are employed. Record the volume injected
to the nearest 0.05 pi and the resulting peak size in area units or peak
height.
7.6.5 If the responses exceed the linear range of the system, dilute
the extract and reanalyze. It is recommended that extracts be diluted so
that all peaks are on scale. Overlapping peaks are not always evident
when peaks are off scale. Computer reproduction of chromatograms,
manipulated to ensure all peaks are on scale over a 100-fold range, are
acceptable if linearity is demonstrated. Peak height measurements are
recommended over peak area integration when overlapping peaks cause errors
in area integration.
7.6.6 If peak detection is prevented by the presence of
interferences, further cleanup is required.
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7.6.7 Examples of chromatograms for the compounds of interest are
frequently available in the referring analytical method.
7.6.8 Calibrate the system immediately prior to conducting any
analyses (see Section 7.4), A mid-concentration standard must also be
injected at intervals specified in the method and at the end of the
analysis sequence. The calibration factor for each analyte to be
quantitated, must not exceed a 15% difference when compared to the initial
standard of the analysis sequence. When this criterion is exceeded,
inspect the GC system to determine the cause and perform whatever
maintenance is necessary (see Section 7.7) before recalibrating and
proceeding with sample analysis. All samples that were injected after the
standard exceeding the criterion must be reinjected to avoid errors in
quantitation, if the initial analysis indicated the presence of the
specific target analytes that exceeded the criterion.
7.6.9 Establish daily retention time windows for each analyte. Use
the retention time for each analyte from Section 7.6.8 as the midpoint of
the window for that day. The daily retention time window equals the
midpoint ± three times the standard deviation determined in Section 7.5.
7.6.9.1 Tentative identification of an analyte occurs when
a peak from a sample extract falls withtn the daily retention time
window. Normally, confirmation is required: on a second GC column,
by GC/MS if concentration permits, or by other recognized
confirmation techniques. Confirmation may not be necessary if the
composition of the sample matrix is well established by prior
analyses.
7.6.9.2 Validation of GC system qualitative performance:
Use the mid-concentration standards interspersed throughout the
analysis sequence (Section 7.6.8) to evaluate this criterion. If
any of the standards fall outside their daily retention time window,
the system is out of control. Determine the cause of the problem
and correct it (see Section 7.7). All samples that were injected
after the standard exceeding the criteria must be reinjected to
avoid false negatives and possibly false positives.
7.7 Suggested chromatography system maintenance - Corrective measures may
require any one or more of the following remedial actions.
7.7.1 Packed columns - For instruments with injection port traps,
replace the demister trap, clean, and deactivate the glass injection port
insert or replace with a cleaned and deactivated insert. Inspect the
injection end of the column and remove any foreign material (broken glass
from the rim of the column or pieces of septa). Replace the glass wool
with fresh deactivated glass wool. Also, it may be necessary to remove
the first few millimeters of the packing material if any discoloration is
noted, also swab out the inside walls of the column if any residue is
noted. If these procedures fail to eliminate the degradation problem, it
may be necessary to deactivate the metal injector body (described in
Section 7.7.3) and/or repack/replace the column.
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7.7.2 Capillary columns - Clean and deactivate the glass injection
port insert or replace with a cleaned and deactivated insert. Break off
the first few inches, up to one foot, of the injection port side of the
column. Remove the column and solvent backflush according to the
manufacturer's instructions. If these procedures fail to eliminate the
degradation problem, it may be necessary to deactivate the metal injector
body and/or replace the column.
7.7.3 Metal injector body - Turn off the oven and remove the
analytical column when the oven has cooled. Remove the glass injection
port insert (instruments with off-column injection or Grob). Lower the
injection port temperature to room temperature. Inspect the injection
port and remove any noticeable foreign material.
7.7.3.1 Place a beaker beneath the injector port inside
the GC oven. Using a wash bottle, serially rinse the entire inside
of the injector port with acetone and then toluene; catching the
rinsate in the beaker.
7.7.3.2 Prepare a solution of deactivating agent (Sylon-CT
or equivalent) following manufacturer's directions. After all metal
surfaces inside the injector body have been thoroughly coated with
the deactivation solution, serially rinse the injector body with
toluene, methanol, acetone, and hexane. Reassemble the injector and
replace the GC column.
7.8 Calculations
7.8.1 External standard calibration - The concentration of each
analyte in the sample may be determined by calculating the amount of
standard purged or injected, from the peak response, using the calibration
curve or the calibration factor determined in Section 7.4.2. The
concentration of a specific analyte is calculated as follows:
Aqueoussamples
Concentration (Mg/L) = [(Ax)(A)(Vt)(D)]/[(As)(V,)(V,}]
where:
Ax = Response for the analyte in the sample, units may be in
area counts or peak height.
A » Amount of standard injected or purged, ng.
A » Response for the external standard, units same as for
AX-
V, » Volume of extract injected, fiL. For purge-and-trap
analysis, V( is not applicable and therefore - 1.
Dilution factor, if dilution was made on the sample
prior to analysis. If no dilution was made, 0=1,
dimensionless.
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Vt - Volume of total extract, /nL. For purge-and-trap
analysis, Vt is not applicable and therefore - 1.
Vt - Volume of sample extracted or purged, ml.
Nonaoueous samples
Concentration (Mg/kg) - [(Ax)(A)(Vl)(D)]/[(A.)(V,)(W)]
where:
W - Weight of sample extracted or purged, g. The wet weight
or dry weight may be used, depending upon the specific
applications of the data.
Ax, At, A, Vt, D, and V, have the same definition as for aqueous
samples when a solid sample is purged (e.g., low concentration soil) for
volatile organic analysis or for semi volatile organic and pesticide
extracts. When the nonaqueous sample is extracted for purge and trap
analysis, V, - volume of methanol extract added to reagent water for purge
and trap analysis.
7.8.2 Internal standard calibration - For each analyte of interest,
the concentration of that analyte in the sample is calculated as follows:
Aqueous samples
Concentration (Mg/L) - [(A8)(C,.)(0)]/[(Aii)(RF)(V1)]
where:
Ax - Response of the analyte being measured, units may be in
area counts or peak height.
Cia - Amount of internal standard added to extract or volume
purged, ng.
D - Dilution factor, if a dilution was made on the sample
prior to analysis. If no dilution was made, D = 1,
dimensionless.
Ais - Response of the internal standard, units same as Ax.
RF - Response factor for analyte, as determined in Section
7.4.3.3.
•Vt - Volume of water extracted or purged, ml.
Nonaaueous samples
Concentration (Mg/kg) - [(As)(Cis)(D)]/[(Ais)(RF)(Ws)]
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where:
Ws - Weight of sample extracted, g. Either a dry weight or
wet weight may be used, depending upon the specific
application of the data.
AS» Cis, D, Ajs, and RF have the same definition as for aqueous
samples.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program consist
of an initial demonstration of laboratory capability and an ongoing analysis of
spiked samples to evaluate and document quality data. The laboratory should
maintain records to document the quality of the data generated. Ongoing data
quality checks are compared with established performance criteria to determine
if the results of analyses meet the performance characteristics of the method.
When results of sample spikes indicate atypical method performance, a quality
control check standard should be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a reagent blank, that interferences from the analytical
system, glassware, and reagents are under control. Each time a set of samples
is extracted or. there is a change in reagents, an organic-free reagent water
blank should be processed as a safeguard against chronic laboratory
contamination. The blank samples should be carried through all stages of the
sample preparation and measurement steps.
8.3 For each analytical batch (up to 20 samples), a reagent blank, matrix
spike, and duplicate or matrix spike duplicate should be analyzed (the frequency
of the spikes may be different for different monitoring programs). The blank and
spiked samples should be carried through all stages of the sample preparation and
measurement steps.
8.4 The experience of the analyst performing gas chromatography is
invaluable to the success of the methods. Each day that analysis is performed,
the daily calibration sample should be evaluated to determine if the
chromatographic system is operating properly. Questions that should be asked
are: Do the peaks look normal?; Is the response obtained comparable to the
response from previous calibrations? Careful examination of the standard
chromatogram can indicate whether the column is still good, the injector is
leaking, the injector septum needs replacing, etc. If any changes are made to
the system (e.g. column changed), recalibration of the system should take place.
8.5 Required instrument QC
8.5.1 Step 7.4 requires that the %RSD vary by < 20% when comparing
calibration factors to determine if a five point calibration curve is
linear.
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8.5.2 Section 7.4 sets a limit of ±15% difference when comparing
daily response of a given analyte versus the initial response. For
Methods 8010, 8020, and 8030, follow the guidance on limits specified in
Section 7.4.3.4. If the limit is exceeded, a new standard curve should be
prepared unless instrument maintenance corrects the problem for that
particular analyte.
8,5.3 Step 7.5 requires the establishment of retention time windows.
8.5.4 Section 7.6.8 sets a limit of ± 15% difference when comparing
the response from the continuing calibration standard of a given analyte
versus any succeeding standards analyzed during an analysis sequence.
8.5.5 Step 7,6.9.2 requires that all succeeding standards in an
analysis sequence should fall within the daily retention time window
established by the first standard of the sequence.
8.6 To establish the ability to generate acceptable accuracy and
precision, the analyst should perform the following operations.
8.6.1 A quality control (QC) check sample concentrate is required
containing each analyte of interest. The QC check sample concentrate may
be prepared from pure standard materials, or purchased as certified
solutions. If prepared by the laboratory, the QC check sample concentrate
should be made using stock standards prepared independently from those
used for calibration.
8.6.1.1 The .concentration of the QC check sample
concentrate is highly dependent upon the analytes being
investigated. Therefore, refer to Method 3500, Section 8.0 for the
required concentration of the QC check sample concentrate.
8.6.2 Preparation of QC check samples
8.6.2.1 Volatile organic analytes (Methods 8010, 8020, and
8030) - The QC check sample is prepared by adding 200 ptL of the QC
check sample concentrate (Step 8.6.1) to 100 ml of water.
8.6.2.2 Semivolatile organic analytes (Methods 8040, 8060,
8070, 8080, 8090, 8100, 8110, and 8120) - The QC check sample is
prepared by adding 1.0 ml of the QC check sample concentrate (Step
8.6.1) to each of four 1-L aliquots of water.
8.6.3 Four aliquots of the well-mixed QC check sample are analyzed
by the same procedures used to analyze actual samples (Section 7.0 of each
of the methods). For volatile organics, the preparation/analysis process
is purge-and-trap/gas chromatography. For semivolatile organics, the QC
check samples should undergo solvent extraction (see Method 3500) prior to
chromatographic analysis.
8.6.4 Calculate the average recovery (x) in u.g/L, and the standard
deviation of the recovery (s) in u.g/U for each analyte of interest using
the four results.
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8.6.5 For each analyte compare s and x with the corresponding
acceptance criteria for precision and accuracy, respectively, given the QC
Acceptance Criteria Table at the end of each of the determinative methods.
If s and x for all analytes of interest meet the acceptance criteria, the
system performance is acceptable and analysis of actual samples can_begin.
If any individual s exceeds the precision limit or any individual x falls
outside the range for accuracy, then the system performance is
unacceptable for that analyte.
NOTE; The large number of analytes in each of the QC Acceptance
Criteria Tables present a substantial probability that one or
more will fail at least one of the acceptance criteria when
all analytes of a given method are determined.
8.6.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst should proceed according to Step
8.6.6.1 or 8.6.6.2.
8.6.6.1 Locate and correct the source of the problem and
repeat the test for all analytes of interest beginning with
Step 8.6.2.
8.6.6.2 Beginning with Step 8.6.2, repeat the test only
for those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with
Step 8.6.2.
8.7 The laboratory should, on an ongoing basis, analyze a reagent blank
and a matrix spiked duplicate for each analytical batch (up to a maximum of 20
samples/batch) to assess accuracy. For soil and waste samples where detectable
amounts of organics are present, replicate samples may be appropriate in place
of spiked duplicates. For laboratories analyzing one to ten samples per month,
at least one spiked sample per month is required.
8.7.1 The. concentration of the spike in the sample should be
determined as follows:
8.7.1.1 If, as in compliance monitoring, the concentration
of a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at that limit,
or 1 to 5 times higher than the background concentration determined
in Step 8.7.2, whichever concentration would be larger.
8.7.1.2 If the concentration of a specific analyte in a
water sample is not being checked against a limit specific to that
analyte, the spike should be at the same concentration as the QC
reference sample (Step 8.6.2} or 1 to 5 times higher than the
background concentration determined in Step 8.7.2, whichever
concentration would be larger. For other matrices, the recommended
spiking concentration is 20 times the EQL.
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8.7.1.3 For semivolatile organics, it may not be possible
to determine the background concentration levels prior to spiking
(e.g. maximum holding times will be exceeded). If this is the case,
the spike concentration should be (1) the regulatory concentration
limit, if any; or, if none (2) the larger of either 5 times higher
than the expected background concentration or the QC reference
sample concentration (Step 8.6.2). For other matrices, the
recommended spiking concentration is 20 times the EQL.
8.7.2 Analyze one unspiked and one spiked sample aliquot to
determine percent recovery of each of the spiked compounds.
8.7.2.1 Volatile organics - Analyze one 5-mL sample
aliquot to determine the background concentration (B) of each
analyte. If necessary, prepare a new QC reference sample
concentrate (Step 8.6.1) appropriate for the background
concentration in the sample. Spike a second 5-mL sample aliquot
with 10 nl of the QC reference sample concentrate and analyze it to
determine the concentration after spiking (A) of each analyte.
Calculate each percent recovery (p) as 100(A - B)%/T, where T is the
known true value of the spike.
8.7.2.2 Semivolatile organics - Analyze one sample aliquot
(extract of 1-L sample) to determine the background concentration
(B) of each analyte. If necessary, prepare a new QC reference
sample concentrate (Step 8.6.1) appropriate for the background
concentration in the sample. Spike a second 1-L sample aliquot with
1.0 mL of the QC reference sample concentrate and analyze it to
determine the concentration after spiking (A) of each analyte.
Calculate each percent recovery (p) as 100(A - B)%/T, where T is the
known true value of the spike.
8.7.3 Compare the percent recovery (p) for each analyte in a water
sample with the corresponding criteria presented in the QC Acceptance
Criteria Table found at the end of each of the determinative methods.
These acceptance criteria were calculated to include an allowance for
error in measurement of both the background and spike concentrations,
assuming a spike to background ratio of 5:1. This error will be accounted
for to the extent that the analyst's spike to background ratio approaches
5:1. If spiking was performed at a concentration lower than the QC
reference sample concentration (Step 8.6.2), the analyst should use either
the QC acceptance criteria presented in the Tables, or optional QC
acceptance criteria calculated for the specific spike concentration. To
calculate optional acceptance criteria for the recovery of an analyte:
(1) Calculate accuracy (x;) using the equation found in the Method
Accuracy and Precision as a Function of Concentration Table (appears at
the end of each determinative method), substituting the spike
concentration (T) for C; (2) calculate overall_precision (S') using the
equation in the same Table, substituting x' for x; (3) calculate the range
for recovery at the spike concentration as (100x'/T) ± 2.44(100S'/T)%.
8.7.4 If any individual p falls outside the designated range for
recovery, that analyte has failed the acceptance criteria. A check
standard containing each analyte that failed the criteria should be
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analyzed as described in Step 8.8.
8.8 If any analyte in a water sample fails the acceptance criteria for
recovery in Step 8.7, a QC reference standard containing each analyte that failed
should be prepared and analyzed.
NOTE: The frequency for the required analysis of a QC reference standard
will depend upon the number of analytes being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory. If the entire list of analytes given in a method should
be measured in the sample in Step 8.7, the probability that the
analysis of a QC check standard will be required is high. In this
case, the QC check standard should be routinely analyzed with the
spiked sample.
8.8.1 Preparation of the QC check sample - For volatile organics,
add 10 ML of the QC check sample concentrate (Step 8.6.1 or 8.7.2) to 5
ml of water. For semivolatile organics, add 1.0 ml of the QC check sample
concentrate (Step 8.6.1 or 8.7.2) to 1 L of water. The QC check sample
needs only to contain the analytes that failed criteria in the test in
Step 8.7. Prepare the QC check sample for analysis following the
guidelines given in Method 3500 (e.g. purge-and-trap, extraction, etc.).
8.8.2 Analyze the QC check sample to determine the concentration
measured (A) of each analyte. Calculate each percent recovery (ps) as
100(A/T)%, where T is the true value of the standard concentration.
8.8.3 Compare the percent recovery (ps) for each analyte with the
corresponding QC acceptance criteria found in the appropriate Table in
each of the methods. Only analytes that failed the test in Step 8.7 need
to be compared with these criteria. If the recovery of any such analyte
falls outside the designated range, the laboratory performance for that
analyte is judged to be out of control, and the problem should be
immediately identified and corrected. The result for that analyte in the
unspiked sample is suspect and may not be reported for regulatory
compliance purposes.
8.9 As part of'the QC program for the laboratory, method accuracy for
each matrix studied should be assessed and records should be maintained. After
the analysis of five spiked samples (of the same matrix type) as in Step 8.7,
calculate the average percent recovery (p) and the standard deviation of the
percent recovery (s ). Express the accuracy assessment as a percent recovery
interval from p - 2s to p + 2s . If p = 90% and s = 10%, for example, the
accuracy interval is expressed as 70-110%. Update the accuracy assessment for
each analyte on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.10 Calculate surrogate control limits as follows:
8.10.1 For each sample analyzed, calculate the percent recovery
of each surrogate in the sample.
8.10.2 Calculate the average percent recovery (p) and standard
deviation of the percent recovery (s) for each of the surrogates when
8000A - 13 Revision 1
July 1992
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surrogate data from 25 to 30 samples for each matrix is available.
8.10.3 For a given matrix, calculate the upper and lower
control limit for method performance for each surrogate standard. This
should be done as follows:
Upper Control Limit (UCL) » p + 3s
Lower Control Limit (LCL) = p - 3s
8.10.4 For aqueous and soil matrices, these laboratory
established surrogate control limits should, if applicable, be compared
with the control limits in Tables A and B of Methods 8240 and 8270,
respectively. The limits given in these methods are multi-laboratory
performance based limits for soil and aqueous samples, and therefore, the
single-laboratory limits established in Step 8.10.3 should fall within
those given in Tables A and B for these matrices.
8.10.5 If recovery is not within limits, the following is
required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are a
problem or flag the data as "estimated concentration."
8.10.6 At a minimum, each laboratory should update surrogate
recovery limits on a matrix-by-matrix basis, annually.
8.11 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 assess the precision of the
environmental measurements. When doubt exists over the identification of a peak
on the chromatogram, confirmatory techniques such as gas chromatography with a
dissimilar column, specific element detector, or mass spectrometer should be
used. Whenever possible, the laboratory should analyze standard reference
materials and participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero. The MDL concentrations listed in the
referring analytical methods were obtained using water. Similar results were
achieved using representative wastewaters. The MDL actually achieved in a given
analysis will vary depending on instrument sensitivity and matrix effects.
8000A - 14 Revision 1
July 1992
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9.2 Refer to the determinative method for specific method performance
information.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
Final Rule and Proposed Rule," October 26, 1984.
2. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
8000A - 15 Revision 1
July 1992
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METHOD 8000A
GAS CHROMATOGRAPHY
Start
7 1 Refer to
determinative
procedure for
extraction
procedure
recommendation
7 2 R.f.r to
determinative
procedure far
cl.4nup and
preparation
proc.dur.
recommendations
Internal Standard
External Standard
7 4 1 C*tabli*h
chromatographic
condi 1 1 ons
7431 Select
internal standards
having behavior
similar to
compounds of
in teres t
7432 Prepar.
c» 1 ibr it ion
s tandards
7433 Inj.ct
calibration
standards .
calculate RF
7434 Verify
•orking calibration
curve or RF each
day
7421 Prepare
calibration
standards for each
compound of
interest
7422 Inject
cal ibralion
standards, prepare
calibration curve
or calculate
calibration factor
7423 Verify
uorlting calibration
curve each day
7 S Calculate
r.t.nIion Iimi
•indo-i
8000A - 16
Revision 1
July 1992
-------
METHOD 8000A
continued
vol»ti!•»
7 6.1 If
neceaiary,
screen aajaple*
by M.thod 3810
or 3820
761 Introduce
conpounda into CC
by purgei-and-trap
or direct injection
(Method S030)
I
761 Introduce
CC by direct
injection
7 6 * Inject
laraplea uting
to 1venl fluih
technique.
record voluae
7 6 5
Ooe> retponte
e»ceed linear
range of
• yatee,?
la peak
deteclion
prevented by
interference7
7 D S Dilute
extract and
reanalyie
' 6 6 Do
further
c1eanup
7
68 Calibrate
*yatea
laaiediately
prior Io
analytea
7 6 9 Eit.bU.h
daily retention
time iindo.i
for each
analyte
7 7 Perform
chrona tography
• ya tem
oaintenance . i f
needed
7 8 Calculate
concentration of
each analyte ujing
appropriate formula
for matnv and type
of ilandard
Stop
8000A - 17
Revision 1
July 1992
-------
00
o
M*
o
03
-------
METHOD 8010B
HALOGENATED VOLATILE ORGANICS BY GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 8010 is used to determine the concentration of various
volatile halogenated organic compounds. The following compounds can be
determined by this method:
Appropriate Technique
Compound Name
Allyl chloride
Benzyl chloride
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl ) ether
Bromoacetone
Bromobenzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Chloromethane
Chloromethyl methyl ether
Chloroprene
4-Chlorotoluene
Di bromochl oromethane
1 , 2-Dibromo-3-chloropropane
Dibromomethane
1 , 2-Di chl orobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
l,4-Dichloro-2-butene
Di chl orodi fl uoromethane
1, 1-Dichloroethane
1,2-Dichloroethane
1, 1-Dichloroethene
trans-l,2-Dichloroethene
Di chl oromethane
1,2-Dichloropropane
l,3-Dichloro-2-propanol
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Epichlorhydrin
CAS No.a
107-05-1
100-44-7
111-91-1
39638-32-9
598-31-2
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
108-90-7
75-00-3
107-07-03
110-75-8
67-66-3
544-10-5
74-87-3
107-30-2
126-99-8
106-43-4
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
106-46-7
764-41-0
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
96-23-1
10061-01-5
10061-02-6
106-89-8
Purge-and-Trap
b
PP
PP
b
PP
b
b
b
b
b
b
b
PP
b
b
pc
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
PP
b
b
PP
Direct
Injection
b
b
pc
b
b
b
b
b
b
b
b
b
b
b
b
pc
b
pc
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
8010B - 1
Revision 2
September 1994
-------
Compound Name
CAS No.'
Appropriate Technique
Direct
Purge-and-Trap Injection
Ethylene dibromide
Methyl iodide
1, 1,2,2-Tetrachloroethane
1,1,1 , 2-Tetrachl oroethane
Tetrachloroethene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
Vinyl Chloride
a Chemical Abstract Servi
b Adequate response using
pp Poor purging efficiency
106-93-4
74-88-4
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
75-01-4
ces Registry Number
this technique
, resulting in high EQLs
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
pc Poor chromatographic performance.
1.2 Table 1 indicates compounds that may be analyzed by this method and
lists the method detection limit for each compound in organic-free reagent water.
Table 2 lists the estimated quantitation limit for other matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8010 provides gas chromatographic conditions for the
detection of halogenated volatile organic compounds. Samples can be introduced
into the GC using direct injection or purge-and-trap (Method 5030). Ground water
samples must be analyzed using Method 5030. A temperature program is used in the
gas chromatograph to separate the organic compounds. Detection is achieved by
a electrolytic conductivity detector (HECD).
2.2 The method provides an optional gas chromatographic column that may
be helpful in resolving the analytes from co-eluting non-target compounds and for
analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Methods 5030 and 8000.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A trip blank prepared from
organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.
8010B - 2
Revision 2
September 1994
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4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas chromatograph - analytical system complete with gas
chromatograph suitable for on-column injections or purge-and-trap sample
introduction and all required accessories, including detector, analytical
columns, recorder, gases, and syringes. A data system for measuring peak
heights and/or peak areas is recommended.
4.1.2 Columns
4.1.2.1 Column 1 - 8 ft x 0.1 in. ID stainless steel or
glass column packed with 1% SP-1000 on Carbopack-B 60/80 mesh or
equivalent.
4.1.2.2 Column 2 - 6 ft x 0.1 in. ID stainless steel or
glass column packed with chemically bonded n-octane on Porasil-C
100/120 mesh (Durapak) or equivalent.
4.1.3 Detector - Electrolytic conductivity (HECD).
4.2 Sample introduction apparatus, refer to Method 5030 for the
appropriate equipment for sample introduction purposes.
4.3 Syringes, 5 ml Luerlok glass hypodermic and a 5 ml, gas-tight with
shutoff valve.
4.4 Volumetric flask, Class A, Appropriate sizes with ground glass
stoppers.
4.5 Microsyringe, 10 and 25 /xL with a 0.006 in. ID needle (Hamilton 702N
or equivalent) and a 100 j^L.
4.6 Analytical balance - 0.0001 g.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall 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 ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Methanol, CH3OH. Pesticide quality or equivalent. Store away from
other solvents.
8010B - 3 Revision 2
September 1994
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5.4 Stock standards - Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standards in
methanol using assayed liquids or gases, as appropriate. Because of the toxicity
of some of the organohalides, primary dilutions of these materials should be
prepared in a hood.
5.4.1 Place about 9.8 ml of methanol in a 10 ml tared ground glass
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes until all alcohol-wetted surfaces have dried. Weigh the
flask to the nearest 0.0001 g.
5.4.2 Add the assayed reference material, as described below.
5.4.2.1 Liquids. Using a 100 /xL syringe, immediately add
two or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5.4.2.2 Gases. To prepare standards for any compounds
that boil below 30°C (e.g. bromomethane, chloroethane,
chloromethane, dichlorodifluoromethane, trichlorofluoromethane,
vinyl chloride), fill a 5 ml valved gas-tight syringe with the
reference standard to the 5.0 ml mark. Lower the needle to 5 mm
above the methanol meniscus. Slowly introduce the reference
standard above the surface of the liquid. The heavy gas rapidly
dissolves in the methanol. This may also be accomplished by using
a lecture bottle equipped with a Hamilton Lecture Bottle Septum
(#86600). Attach Teflon tubing to the side-arm relief valve and
direct a gentle stream of gas into the methanol meniscus.
5.4.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in milligrams per
liter (mg/L) from the net gain in weight. When compound purity is assayed
to be 96% or greater, the weight may be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.4.4 Transfer the stock standard solution into a bottle with a
Teflon lined screw-cap. Store, with minimal headspace, at -10°C to -20°C
and protect from light.
5.4.5 Prepare fresh stock standards for gases weekly or sooner if
comparison with check standards indicates a problem. Reactive compounds
such as 2-chloroethyl vinyl ether may need to be prepared more frequently.
All other standards must be replaced after six months. Both gas and
liquid standards must be monitored closely by comparison to the initial
calibration curve and by comparison to QC check standards. It may be
necessary to replace the standards more frequently if either check exceeds
a 20% drift.
5.4.6 Optionally calibration using a certified gaseous mixture can
be accomplished daily utilizing commercially available gaseous analyte
8010B - 4 Revision 2
September 1994
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mixture of bromomethane, chloromethane, chloroethane, vinyl chloride,
dichlorodifluoromethane and trichlorofluoromethane in nitrogen. These
mixtures of documented quality are stable for as long as six months
without refrigeration. (VOA-CYL III, RESTEK Corporation, Cat. #20194 or
equivalent).
5.5 Secondary dilution standards. Using stock standard solutions,
prepare secondary dilution standards in methanol, as needed, containing the
compounds of interest, either singly or mixed together. The secondary dilution
standards should be prepared at concentrations such that the aqueous calibration
standards prepared in Sec. 5.6 will bracket the working range of the analytical
system. Secondary dilution standards should be stored with minimal headspace for
volatiles and should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards from them.
5.6 Calibration standards. Prepare calibration standards in
organic-free reagent water from the secondary dilution of the stock standards,
at a minimum of five concentrations. One of the concentrations should be at a
concentration near, but above, the method detection limit. The remaining
concentrations should correspond to the expected range of the concentrations
found in real samples or should define the working range of the GC. Each
standard should contain each analyte for detection by this method (e.g. some or
all of the compounds listed in Table 1 may be included). In order to prepare
accurate aqueous standard solutions, the following precautions must be observed.
5.6.1 Do not inject more than 20 /iL of alcoholic standards into
100 ml of water.
5.6.2 Use a 25 juL Hamilton 702N microsyringe or equivalent
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of methanolic standards into water).
5.6.3 Rapidly inject the alcoholic standard into the filled
volumetric flask. Remove the needle as fast as possible after injection.
5.6.4 Mix aqueous standards by inverting the flask three times only.
5.6.5 Fill the sample syringe from the standard solution contained
in the expanded area of the flask (do not use any solution contained in
the neck of the flask).
5.6.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.6.7 Aqueous standards are not stable and should be discarded after
one hour, unless properly sealed and stored. The aqueous standards can
be stored up to 24 hours, if held in sealed vials with zero headspace.
5.7 Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
8010B - 5 Revision 2
September 1994
-------
internal standard can be suggested that is applicable to all samples. The
compounds recommended for use as surrogate spikes (Sec. 5.8) have been used
successfully as internal standards, because of their generally unique retention
times.
5.7.1 Prepare calibration standards at a minimum of five
concentrations for each analyte of interest as described in Sec. 5.6.
5.7.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in Sees. 5.4 and 5.5. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 ng/juL of each internal standard compound. The
addition of 10 p,i of this standard to 5.0 ml of sample or calibration
standard would be equivalent to 30 M9A-
5.7.3 Analyze each calibration standard according to Sec. 7.0,
adding 10 /nL of internal standard spiking solution directly to the
syringe.
5.8 Surrogate standards - The analyst should monitor both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix by spiking each sample, standard, and
organic-free reagent water blank with surrogate halocarbons. A combination of
bromochloromethane, bromochlorobenzene and bromofluorobenzene is recommended to
encompass the range of temperature program used in this method. From stock
standard solutions prepared as in Sec. 5.4, add a volume to give 750 /xg of each
surrogate to 45 ml of organic-free reagent water contained in a 50 mL volumetric
flask, mix, and dilute to volume for a concentration of 15 ng//iL. Add 10 juL of
this surrogate spiking solution directly into the 5 ml syringe with every sample
and reference standard analyzed. If the internal standard calibration procedure
is used, the surrogate compounds may be added directly to the internal standard
spiking solution (Sec. 5.7.2).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this Chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
7.1 Volatile compounds are introduced into the gas chromatograph using
either direct injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-concentration contaminated soils and
sediments. For medium-concentration soils or sediments, methanolic extraction,
as described in Method 5030, may be necessary prior to purge-and-trap analysis.
7.2 Gas chromatographic conditions (Recommended)
7.2.1 Column 1:
Helium flow rate = 40 mL/min
8010B - 6 Revision 2
September 1994
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Temperature program:
Initial temperature = 45°C, hold for 3 minutes
Program = 45°C to 220°C at 8°C/min
Final temperature = 220°C, hold for 15 minutes.
7.2.2 Column 2:
Helium flow rate = 40 mL/min
Temperature program:
Initial temperature = 50°C, hold for 3 minutes
Program = 50°C to 170°C at 6°C/min
Final temperature = 170°C, hold for 4 minutes.
7.3 Calibration. The procedure for internal or external calibration may
be used. Refer to Method 8000 for a description of each of these procedures. Use
Table 1 and Table 2 for guidance on selecting the lowest point on the calibration
curve.
7.3.1 Calibration must take place using the same sample introduction
method that will be used to analyze actual samples (see Sec. 7.4.1).
7.4 Gas chromatographic analysis
7.4.1 Introduce volatile compounds into the gas chromatograph using
either Method 5030 (purge-and-trap) or the direct injection method (see
Sec. 7.4.1.1). If the internal standard calibration technique is used,
add 10 n\. of internal standard to the sample prior to purging.
7.4.1.1 In very limited applications (e.g. aqueous process
wastes) direct injection of the sample onto the GC column with a
10 juL syringe may be appropriate. The detection limit is very high
(approximately 10,000 M9/L) therefore, it is only permitted where
concentrations in excess of 10,000 M9/L are expected or for water-
soluble compounds that do not purge. The system must be calibrated
by direct injection (bypassing the purge-and-trap device).
7.4.2 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria. Include a mid-concentration standard after each
group of 10 samples in the analysis sequence.
7.4.3 Table 1 summarizes the estimated retention times on the two
columns for a number of organic compounds analyzable using this method.
An example of the separation achieved by Column 1 is shown in Figure 1.
7.4.4 Record the sample volume purged or injected and the resulting
peak sizes (in area units or peak heights).
7.4.5 Refer to Method 8000 for guidance on calculation of
concentration.
7.4.6 If analytical interferences are suspected, or for the purpose
of confirmation, analysis using the second GC column is recommended.
8010B - 7 Revision 2
September 1994
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7.4.7 If the response for a peak is off-scale, i.e., beyond the
calibration range of the standards, prepare a dilution of the sample with
organic-free reagent water. The dilution must be performed on a second
aliquot of the sample which has been properly sealed and stored prior to
use.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.
8.2 Quality control required to validate the GC system operation is
found in Method 8000.
8.2.1 The quality control check sample concentrate (Method 8000)
should contain each analyte of interest at a concentration of 10 mg/L in
methanol.
8.2.2 Table 3 indicates the calibration and QC acceptance criteria,
for water samples, for this method. Table 4 gives method accuracy and
precision as functions of concentration, for water samples, for the
analytes of interest. The contents of both Tables should be used to
evaluate a laboratory's ability to perform and generate acceptable data
by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (limits established by performing
QC procedure outlined in Method 8000).
8.3.1 If recovery is not within limits, the following is required:
• Check to be sure that there are no errors in
calculations, surrogate solutions and internal standards. Also,
check instrument performance.
• Recalculate the data and/or re-analyze the sample if
any of the above checks reveal a problem.
• Re-extract and re-analyze the sample if none of the
above are a problem or flag the data as "estimated concentration".
9.0 METHOD PERFORMANCE
9.1 This method was tested by 20 laboratories using organic-free reagent
water, drinking water, surface water, and three industrial wastewaters spiked at
six concentrations over the range 8.0-500 /^g/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to the
concentration of the analyte, and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 4.
8010B - 8 Revision 2
September 1994
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9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and by the calibration procedure used.
9.3 The method detection limits reported in Table 1 were generated under
optimum analytical conditions by an Agency contractor (Ref. 6) as guidance, and
may not be readily achievable by all laboratories at all times.
10.0 REFERENCES
1. Bellar, T.A.; Lichtenberg, J.J. jh Amer. Water Works Assoc. 1974, 66(12),
pp. 739-744.
2. Bellar, T.A.; Lichtenberg, J.J., Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds, Measurement of Organic Pollutants in Water and Wastewater; Van
Hall, Ed.; ASTM STP 686, pp 108-129, 1979.
3. "Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters: Category 11 - Purgeables and Category 12 -
Acrolein, Acrylonitrile, and Dichlorodifluoromethane"; report for EPA
Contract 68-03-2635.
4. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act: Final Rule and Interim
Final Rule and Proposed Rule", October 26, 1984.
5. "EPA Method Validation Study 23, Method 601 (Purgeable Halocarbons)";
report for EPA Contract 68-03-2856.
6. Gebhart, J.E., S.V. Lucas, S.J. Naber, A.M. Berry, T.H. Danison and H.M.
Burkholder, "Validation of SW-846 Methods 8010, 8015, and 8020"; Report
for EPA Contract 68-03-1760, Work Assignment 2-15; US EPA, EMSL-
Cincinnati, 1987.
8010B - 9 Revision 2
September 1994
-------
TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
FOR HALOGENATED VOLATILE ORGANICS
Compound
Ally! chloride*^
Benzyl chloride*'0
Bis(2-chloroethoxy)methane*
Bis(2-chloroisopropyl ) ether*
Bromobenzene
Bromodichloromethane
Bromoform*
Bromomethane*
Carbon tetrachloride*
Chi oroacet aldehyde*
Chlorobenzene*
Chl oroethane
Chloroform*
1-Chlorohexane
2-Chloroethyl^vinyl ether*
Chloromethane*
Chloromethyl methyl ether*
4-Chlorotoluene
Dibromochloromethane
1 , 2-Dibromo-3-chl oropropane*
Dibromomethane*
1 , 2-Di chl orobenzene*
1, 3 -Di chlorobenzene*
1 ,4-Dichl orobenzene*
l,4-Dichloro-2-butene*
Di chl orodi f 1 uoromethane*'d
1,1-Dichloroethane*
1,2-Dichloroethane*
1,1-Dichloroethene*
trans - 1 , 2-Di chl oroethene*
Dichloromethane*
1, 2-Di chl oropropane*
trans - 1 , 3-Di chl oropropene*
Ethylene dibromide
1,1,2 , 2-Tetrachl oroethane*
1,1, 1, 2-Tetrachl oroethane*
Tetrachl oroethene*
1 , 1 , 1 -Tri chl oroethane^
1, 1, 2 -Tri chl oroethane*
CAS
Registry
Number
107-05-1
100-44-7
111-91-1
39638-32-9
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
107-20-0
108-90-7
75-00-3
67-66-3
544-10-5
110-75-8
74-87-3
107-30-2
106-43-4
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
106-46-7
764-41-0
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
10061-02-5
106-93-4
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
Retention Time
(minutes)
Column 1 Column 2
10.17
30.29
38.60
34.79
29.05
15.44
21.12
2.90
14.58
(b)
25.49
5.18
12.62
26.26
19.23
1.40
8.88
34.46
18.22
28.09
13.83
37.96
36.88
38.64
23.45
3.68
11.21
13.14
10.04
11.97
7.56
16.69
16.97e
19.59
23.12
21.10
23.05
14.48
18.27
(b)
(b)
(b)
(b)
(b)
14.62
19.17
7.05
11.07
(b)
18.83
8.68
12.08
(b)
(b)
5.28
(b)
(b)
16.62
(b)
14.92
23.52
22.43
22.33
(b)
(b)
12.57
15.35
7.72
9.38
10.12
16.62
16.60
(b)
(b)
21.70
14.97
13.10
18.07
Method
Detection
Limit3
(M9/L)
(b)
(b)
(b)
(b)
(b)
0.002
0.020
0.030
0.003
(b)
0.001
0.008
0.002
(b)
0.130
0.010
(b)
(b)
(b)
0.030
(b)
(b)
(b)
(b)
(b)
(b)
0.002
0.002
0.003
0.002
(b)
(b)
0.340
(b)
0.010
(b)
0.001
0.003
0.007
8010B - 10
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TABLE 1.
Continued
Compound
CAS
Registry
Number
Retention Time
(minutes)
Column 1 Column
Method
Detection
Limit9
(M9/L)
Trichloroethene*
Trichlorofluoromethane*
1,2,3-Trichloropropane*
Vinyl Chloride*
79-01-6
75-69-4
96-18-4
75-01-4
17.40
9.26
22.95
3.25
13.12
(b)
(b)
5.28
0.001
(b)
(b)
0.006
a =
b =
* =
c =
d =
e =
Using purge-and-trap method (Method 5030). See Sec. 9.3.
Not determined
Appendix VIII compounds
Demonstrated very erratic results when tested by purge-and-trap
See Sec. 4.10.2 of Method 5030 for guidance on selection of trapping
material
Estimated retention time
TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
FOR VARIOUS MATRICES3
Matrix
Factor
Ground water 10
Low-concentration soil 10
Water miscible liquid waste 500
High-concentration soil and sludge 1250
Non-water miscible waste 1250
EQL = [Method detection limit (see Table 1)] X [Factor found in
this table]. For non-aqueous samples, the factor is on a wet-
weight basis. Sample EQLs are highly matrix-dependent. The EQLs
listed herein are provided for guidance and may not always be
achievable.
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TABLE 3.
CALIBRATION AND QC ACCEPTANCE CRITERIA3
Range Limit
for Q for S
Analyte
Bromodi chloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethylvinyl ether
Chloroform
Chloromethane
Di bromochl oromethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Di chlorobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
Dichloromethane
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chl orof 1 uoromethane
Vinyl chloride
(M9/L) (M9/L)
15.2-24.8
14.7-25.3
11.7-28.3
13.7-26.3
14.4-25.6
15.4-24.6
12.0-28.0
15.0-25.0
11.9-28.1
13.1-26.9
14.0-26.0
9.9-30.1
13.9-26.1
16.8-23.2
14.3-25.7
12.6-27.4
12.8-27.2
15.5-24.5
14.8-25.2
12.8-27.2
12.8-27.2
9.8-30.2
14.0-26.0
14.2-25.8
15.7-24.3
15.4-24.6
13.3-26.7
13.7-26.3
4.3
4.7
7.6
5.6
5.0
4.4
8.3
4.5
7.4
6.3
5.5
9.1
5.5
3.2
5.2
6.6
6.4
4.0
5.2
7.3
7.3
9.2
5.4
4.9
3.9
4.2
6.0
5.7
Q = Concentration measured in QC check sampl
Range
for x
(M9/L)
10.7-32.0
5.0-29.3
3.4-24.5
11.8-25.3
10.2-27.4
11.3-25.2
4.5-35.5
12.4-24.0
D-34.9
7.9-35.1
1.7-38.9
6.2-32.6
11.5-25.5
11.2-24.6
13.0-26.5
10.2-27.3
11.4-27.1
7.0-27.6
10.1-29.9
6.2-33.8
6.2-33.8
6.6-31.8
8.1-29.6
10.8-24.8
9.6-25.4
9.2-26.6
7.4-28.1
8.2-29.9
e, in M9/L.
S = Standard deviation of four recovery measurements, in
x = Average recovery
P, Ps = Percent recovery
D = Detected; result
a r •; •§• o *« i r» -Pv»/->m At\ rco Dn
Range
P>oPs
42-172
13-159
D-144
43-143
38-150
46-137
14-186
49-133
D-193
24-191
D-208
7-187
42-143
47-132
51-147
28-167
38-155
25-162
44-156
22-178
22-178
8-184
26-162
41-138
39-136
35-146
21-156
28-163
M9/L.
for four recovery measurements, in /ng/L.
measured.
must be greater
n+ 1 TC fnv Mat hn.
than zero.
A Cm on
f\ lilQV^Q ^ol^Mll
3 "H or! srciiminn
a QC check sample concentration of 20 p.g/1.
8010B - 12
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TABLE 4.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Analyte
Bromodichl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl etherb
Chloroform
Chloromethane
Di bromochl oromethane
1 ,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1 ,1-Dichloroethane
1 ,2-Dichloroethane
1 ,1-Dichloroethene
trans-l,2-Dichloroethene
Dichl oromethane
l,2-Dichloropropaneb
cis-l,3-Dichloropropeneb
trans-1 ,3-Dichloropropeneb
1 , 1,2, 2-Tetrachloroethane
Tetrachloroethene
1,1,1-Tri chloroethane
1, 1, 2 -Tri chloroethane
Trichloroethene
Trichlorofl uoromethane
Vinyl chloride
Accuracy, as
recovery, x'
(M9A)
1.12C-1.02
0.96C-2.05
0.76C-1.27
0.98C-1.04
l.OOC-1.23
0.99C-1.53
l.OOC
0.93C-0.39
0.77C+0.18
0.94C+2.72
0.93C+1.70
0.95C+0.43
0.93C-0.09
0.95C-1.08
1.04C-1.06
0.98C-0.87
0.97C-0.16
0.91C-0.93
l.OOC
l.OOC
l.OOC
0.95C+0.19
0.94C+0.06
0.90C-0.16
0.86C+0.30
0.87C+0.48
0.89C-0.07
0.97C-0.36
Single analyst
precision, s '
(M9/L)
0.11X+0.04
0.12X+0.58
0.28X+0.27
0.15X+0.38
0.15X-0.02
0.14X-0.13
0.20X
0.13X+0.15
0.28X-0.31
0.11X+1.10
0.20X+0.97
0.14X+2.33
0.15X+0.29
0.08X+0.17
0.11X+0.70
0.21X-0.23
0.11X+1.46
0.11X+0.33
0.13X
0.18X
0.18X
0.14X+2.41
0.14X+0.38
0.15X+0.04
0.13X-0.14
0.13X-0.03
0.15X+0.67
0.13X+0.65
Overall
precision,
S' (Mg/L)
0.20X+1.00
0.21X+2.41
0.36X+0.94
0.20X+0.39
0.18X+1.21
0.17X+0.63
0.35X
0.19X-0.02
0.52X+1.31
0.24X+1.68
0.13X+6.13
0.26X+2.34
0.20X+0.41
0.14X+0.94
0.15X+0.94
0.29X-0.04
0.17X+1.46
0.21X+1.43
0.23X
0.32X
0.32X
0.23X+2.79
0.18X+2.21
0.20X+0.37
0.19X+0.67
0.23X+0.30
0.26X+0.91
0.27X+0.40
x' = Expected recovery for one or more measurements of a sample containing
a concentration of C, in M9/L-
sr'= Expected single analyst standard deviation of measurements at an
average concentration of x, in ng/L.
S' = Expected interlaboratory standard deviation of measurements at an
average concentration found of x, in M9/L-
C = True value for the concentration, in M9/L-
X = Average recovery found for measurements of samples containing a
concentration of C, in M9/L.
a From 40 CFR Part 136 for Method 601.
b Estimates based upon the performance in a single laboratory.
8010B - 13
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FIGURE 1.
GAS CHROMATOGRAM OF HALOGENATED VOLATILE ORGANICS
CoI urn: 1% SP-1000 on Carbopack-B
Program: 45"C-3 Minutes, 8'C/Minute to 220CC
Detector: Hall 700-A Electrolytic Conductivity
• 10 12 M l« It 20 n
METCWTION TMC MIIIUTHI
8010B - 14
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METHOD 8010B
HALOGENATED VOLATILE ORGANICS BY GAS CHROMATOGRAPHY
Start
7.1 Introduce compounds
into gas chromatograph
by direct injection or
purge-end-trap
(Method 5030)
7.2 Set gas
chromatograph
condition.
7.3 Calibrate
(refer to Method 8000)
7.4.1 Introduce
volatile compounds
into gas chromatograph
by purge-and-trap or
direct injection.
7.4.2 Follow Method
8000 for analysis
sequence, etc.
7.4.4 Record volume
purged or injected
and peak sizes.
7.4.5 Calculate
concentration
(refer to Method 8000)
7.4.6 Are
analytical
interferences
suspected?
7.4.7 Is
response for
a peak
off-scale?
7.4.6 Analyze using
second GC column.
7.4.7 Dilute second
aliquot of sample.
8010B - 15
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METHOD 8011
1.2-DIBROMOETHANE AND 1,2-DIBROMO-3-CHLOROPROPANE
BY MICROEXTRACTION AND GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 This method is applicable to the determination of the following
compounds in drinking water and ground water:
Compound Name CAS No."
1,2-Dibromoethane (EDB) 106-93-4
l,2-Dibromo-3-chloropropane (DBCP) 96-12-8
8 Chemical Abstract Services Registry Number.
1.2 For compounds and matrices other than those listed in Section 1.1,
the laboratory must demonstrate the usefulness of the method by collecting
precision and accuracy data on actual samples and provide qualitative
confirmation of results by gas chromatography/mass spectrometry (GC/MS).
1.3 The experimentally determined method detection limits (MDL) for EOB
and DBCP were calculated to be 0.01 M9/L. The method has been shown to be
useful for these analytes over a concentration range of approximately 0.03 to 200
/ig/L. Actual detection limits are highly dependent upon the characteristics of
the gas chromatographic system, sample matrix, and calibration.
1.4 This method is restricted to use by or under the Supervision of
analysts experienced in the use of gas chromatography and in the interpretation
of gas chromatograms. Each analyst must demonstrate the ability to generate
acceptable results with this method using the procedure described in Section 8.2.
1.5 1,2-Dibromoethane and l,2-Dibromo-3-chloropropane have been
tentatively classified as known or suspected human or mammalian carcinogens.
Pure standard materials and stock standard solutions of these compounds should
be handled in a hood. A NIOSH/MESA approved toxic gas respirator should be worn
when the analyst handles high concentrations of these toxic compounds.
2.0 SUMMARY OF METHOD
2.1 Thirty five ml of sample are extracted with 2 ml of hexane. Two jiL
of the extract are then injected into a gas chromatograph equipped with a
linearized electron capture detector for separation and analysis. Aqueous matrix
spikes are extracted and analyzed in an identical manner as the samples in order
to compensate for possible extraction losses.
2.2 The extraction and analysis time is 30 to 50 minutes per sample
8011 - 1 Revision 0
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depending upon the analytical conditions chosen. See Table 1 and Figure 1.
2.3 Confirmatory evidence is obtained using a different column (Table 1).
3.0 INTERFERENCES
3.1 Impurities contained in the extracting solvent (hexane) usually
account for the majority of the analytical problems. Reagent blanks should be
analyzed for each new bottle of hexane before use. Indirect dally checks on the
hexane are obtained by monitoring the reagent blanks. Whenever an Interference
is noted in the method or instrument blank, the laboratory should reanalyze the
hexane. Low level interferences generally can be removed by distillation or
column chromatography, however, it is generally more economical to obtain a new
source of hexane solvent. Interference-free hexane is defined as containing less
than 0.01 pg/L of the analytes. Protect interference-free hexane by storing it
in an area known to be free of organochlorine solvents.
3.2 Several Instances of accidental sample contamination have been
attributed to diffusion of volatile organics through the septum seal Into the
sample bottle during shipment and storage. Trip blanks must be used to monitor
for this problem.
3.3 This liquid/liquid extraction technique extracts a wide boiling range
of non-polar organic compounds and, in addition, extracts some polar organic
compounds.
3.4 EDB at low concentrations may be masked by very high concentrations
of dibromochloromethane (DBCM), a common chlorinated drinking water contaminant,
when using the confirmation column.
4.0 APPARATUS AND MATERIALS
4.1 Microsyringe - 10, 25, and 100 pi with a 2 in. x 0.006 1n. needle
(Hamilton 702N or equivalent).
4.2 Gas Chromatograph
4.2.1 The GC must be capable of temperature programming and should
be equipped with a linearized electron capture detector and a capillary
column splitless injector.
4.2.2 Columns
4.2.2.1 Column A - 0.32 mm ID x 30 m fused silica
capillary with dimethyl silicone mixed phase (Durawax-DX 3, 0.25 urn
film, or equivalent).
4.2.2.2 Column B (confirmation column) - 0.32 mm ID x 30 m
fused silica capillary with methyl polysiloxane phase (DB-1, 0.25 ^m
film, or equivalent).
4.3 Volumetric flasks, Class A - 10 mL.
8011 - 2 Revision 0
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4.4 Glass bottles - 15 ml, with Teflon lined screw caps or crimp tops.
4.5 Analytical balance - 0.0001 g.
4.6 Graduated cylinder - 50 ml.
4.7 Transfer pipet.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall 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
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5,3 Hexane, C6HU - UV grade (Burdick and Jackson 1216 or equivalent).
5.4 Methyl alcohol, CH3OH - Demonstrated to be free of analytes.
5.5 Sodium chloride, NaCl - Pulverize a batch of NaCl and place 1t in a
muffle furnace at room temperature. Increase the temperature to 400°C for
30 minutes. Store in a capped bottle.
5.6 1,2-Dibromoethane (99%), C2H4Br2, (Aldrich Chemical Company, or
equivalent).
5.7 l,2-Dibromo-3-chloropropane (99.4%), C3H5Br2Cl, (AMVAC Chemical
Corporation, Los Angeles, California, or equivalent).
5.8 Stock standards - These solutions may be purchased as certified
solutions or prepared from pure standards using the following procedures:
5.8.1 Place about 9.8 ml of methanol into a 10 ml ground glass
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes and weigh to the nearest 0.0001 g.
5.8.2 Use a 25 pi syringe and immediately add two or more drops
(= 10 pi) of standard to the flask. Be sure that the standard falls
directly into the alcohol without contacting the neck of the flask.
5.8.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in milligrams per
liter (mg/L) from the net gain in weight. When compound purity is assayed
to be 96% or greater, the weight may be used without correction to
calculate the concentration of the stock standard.
5.8.4 Store stock standards in 15 ml bottles equipped with Teflon
lined screw-caps or crimp tops. Stock standards are stable for at least
8011 - 3 Revision 0
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four weeks when stored at 4°C and away from light.
5.9 Intermediate standard - Use stock standards to prepare an
intermediate standard that contains both analytes in methanol. The intermediate
standard should be prepared at a concentration that can be easily diluted to
prepare aqueous calibration standards that will bracket the working concentration
range. Store the intermediate standard with minimal headspace and check
frequently for signs of deterioration or evaporation, especially just before
preparing calibration standards. The storage time described for stock standards
also applies to the intermediate standard.
5.10 Quality control (QC) reference sample - Prepare a QC reference sample
concentrate at 0.25 mg/L of both analytes from standards from a different source
than the standards used for the stock standard.
5.11 Check standard - Add an appropriate volume of the intermediate
standard to an aliquot of organic-free reagent water in a volumetric flask. Do
not add more than 20 /iL of an alcoholic intermediate standard to the water or
poor precision will result. Use a 25 juL microsyringe and rapidly inject the
alcoholic intermediate standard into the expanded area of the almost filled
volumetric flask. Remove the needle as quickly as possible after injection. Mix
by inverting the flask several times. Discard the contents contained in the neck
of the flask. Aqueous calibration standards should be prepared every 8 hours.
6.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Recommended Chromatographic Conditions
Two gas chromatography columns are recommended. Column A is a highly
efficient column that provides separations for EDB and DBCP without interferences
from trihalomethanes. 'Column A should be used as the primary analytical column
unless routinely occurring analytes are not adequately resolved. Column B is
recommended for use as a confirmatory column when GC/MS confirmation is not
available. Retention times for EDB and DBCP on these columns are presented in
Table 1.
Column A:
Injector temperature: 200 C.
Detector temperature: 290°C.
Carrier gas (Helium) Linear velocity: 25 cm/sec.
Temperature program:
Initial temperature: 40°C, hold for 4 min.
Program: 40°C to 190°C at 8°C/min.
Final temperature: 190°C, hold for 25 min., or
until all expected analytes
have eluted.
8011 - 4 Revision 0
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See Figure 1 for a sample chromatogram and Table 1 for retention data.
Column B:
Injector temperature: 200°C.
Detector temperature: 290°C.
Carrier gas (Helium) Linear velocity: 25 cm/sec.
Temperature program:
Initial temperature: 40°C, hold for 4 min.
Program: 40°C to 270°C at 10°C/min.
Final temperature: 270°C, hold for 10 min., or
until all expected analytes
have eluted.
See Table 1 for retention data.
7.2 Calibration
7.2.1 Prepare at least five calibration standards. One should
contain EDB and DBCP at a concentration near, but greater than, the method
detection limit (Table 1) for each compound. The others should be at
concentrations that bracket the range expected in the samples. For
example, if the HDL is 0.01 M9/L. and a sample expected to contain
approximately 0.10 /ug/L is to be analyzed, aqueous calibration standards
should be prepared at concentrations of 0.03 /ug/L, 0.05 M9/U 0.10 M9/U
0.15 M9/U and 0.20 /ig/L.
7.2.2 Analyze each calibration standard and tabulate peak height or
area response versus the concentration in the standard. Prepare a
calibration curve for each compound. Alternatively, if the ratio of
response to concentration (calibration factor) is a constant over the
working range (< 10% relative standard deviation), linearity can be
assumed and the average ratio or calibration factor can be used in place
of a calibration curve.
7.3 Sample preparation
7.3.1 Remove samples and standards from storage and allow them to
reach room temperature.
7.3.2 For samples and field blanks contained in 40 ml bottles,
remove the container cap. Discard a 5 ml volume using a 5 ml transfer
pipet. Replace the container cap and weigh the container with contents to
the nearest 0.1 g and record this weight for subsequent sample volume
determination.
7.3.3 For calibration standards, check standards, QC reference
samples, and blanks, measure a 35 mi volume using a 50 ml graduated
cylinder and transfer it to a 40 ml sample container.
7.4 Extraction
7.4.1 Remove the container cap and add 7 g of NaCl to all samples.
8011 - 5 Revision 0
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7.4.2 Recap the sample container and dissolve the NaCl by shaking by
hand for about 20 seconds.
7.4.3 Remove the cap and using a transfer pi pet, add 2.0 ml of
hexane. Recap and shake vigorously by hand for 1 minute. Allow the water
and hexane phases to separate. If stored at this stage, keep the
container upside down.
7.4.4 Remove the cap and carefully transfer a sufficient amount
(0.5-1.0 ml) of the hexane layer into a vial using a disposable glass
pipet.
7.4.5 Transfer the remaining hexane phase, being careful not to
include any of the water phase, into a second vial. Reserve this second
vial at 4°C for reanalysis if necessary.
7.5 Analysis
7.5.1 Transfer the first sample vial to an autosampler set up to
inject 2.0 uL portions into the gas chromatograph for analysis.
Alternately, 2 n(. portions of samples, blanks and standards may be
manually injected, using the solvent flush technique, although an auto
sampler is strongly recommended.
7.6 Determination of sample volume
7.6.1 For samples and field blanks, remove the cap from the sample
container. Discard the remaining sample/hexane mixture. Shake off the
remaining few drops using short, brisk wrist movements. Reweigh the empty
container with original cap and calculate the net weight of sample by
difference to the nearest 0.1 g. This net weight is equivalent to the
volume of water extracted.
7.7 Calculations
7.7.1 Identify EDB and DBCP in the sample chromatogram by comparing
the retention time of the suspect peak to retention times generated by the
calibration standards and the check standard.
7.7.2 Use the calibration curve or calibration factor to directly
calculate the uncorrected concentration (C;) of each analyte in the sample
(e.g. calibration factor x response).
7.7.3 Calculate the sample volume (Vs) as equal to the net sample
weight:
Vs (ml) = gross weight (grams) - bottle tare (grams)
7.7.4 Calculate the corrected sample concentration as:
Concentration (^9/L) = C, x 35
7.7.5 Report the results for the unknown samples in M9/L- Round the
8011 - 6 Revision 0
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results to the nearest 0.01 M9/L or two significant figures.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses this method is required to operate a formal
quality control program.
8.1.1 The laboratory must make an initial determination of the
method detection limits and demonstrate the ability to generate acceptable
accuracy and precision with this method. This is established as described
in Section 8.2.
8.1.2 In recognition of laboratory advances that are occurring in
chromatography, the laboratory is permitted certain options to improve the
separations or lower the cost of measurements. Each time such a
modification is made to the method, the analyst is required to repeat the
procedure in Section 7.1 and 8.2.
8.1.3 The laboratory must analyze a reagent and calibration blank to
demonstrate that interferences from the analytical system are under
control every twenty samples or per analytical batch, whichever is more
frequent.
8.1.4 The laboratory must, on an ongoing basis, demonstrate through
the analyses of QC reference samples and check standards that the
operation of the measurement system is in control. The frequency of the
check standard analyses is equivalent to 5% of all samples or every
analytical batch, whichever is more frequent. On a weekly basis, the QC
reference sample must be run.
8.2 To establ ish the abil ity to achieve low detection 1 imits and generate
acceptable accuracy and precision, the analyst must perform the following
operations:
8.2.1 Prepare seven samples each at a concentration of 0.03 pg/L.
8.2.2 Analyze the samples according to the method beginning in
Section 7.0.
8.2.3 Calculate the average concentration (X) in ^g/L and the
standard deviation of the concentrations (s) in ^g/L, for each analyte
using the seven results. Then calculate the MDL at 99% confidence level
for seven replicates as 3.143s.
8.2.4 For each analyte in an aqueous matrix sample, X must be
between 60% and 140% of the true value. Additionally, the MDL may not
exceed the 0.03 jig/L spiked concentration. If both analytes meet the
acceptance criteria, the system performance is acceptable and analysis of
actual samples can begin. If either analyte fails to meet a criterion,
repeat the test. It is recommended that the laboratory repeat the MDL
determination on a regular basis.
8.3 The laboratory must demonstrate on a frequency equivalent to 5% of
8011 - 7 Revision 0
July 1992
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the sample load or once per analytical batch, whichever is more frequent, that
the measurement system is in control by analyzing a check standard of both
analytes at 0.25
8.3.1 Prepare a check standard (0.25 jig/L) by diluting the
intermediate standard with water to 0.25 ng/L.
8.3.2 Analyze the sample according to Section 7.0 and calculate the
recovery for each analyte. The recovery must be between 60% and 140% of
the expected value for aqueous matrices. For non-aqueous matrices, the
U.S. EPA will set criteria after more interlaboratory data are gathered.
8.3.3 If the recovery for either analyte falls outside the
designated range, the analyte fails the acceptance criteria. A second
calibration verification standard containing each analyte that failed must
be analyzed. Repeated failure, however, will confirm a general problem
with the measurement system. If this occurs, locate and correct the
source of the problem and repeat the test.
8.4 On a weekly basis, the laboratory must demonstrate the ability to
analyze a QC reference sample.
8.4.1 Prepare a QC reference sample at 0.10 yg/L by diluting the QC
reference sample concentrate (Section 5.9).
8.4.2 For each analyte in an aqueous matrix, the recovery must be
between 60% and 140% of the expected value. When either analyte fails the
test, the analyst must repeat the test only for that analyte which failed
to meet the criteria. Repeated failure, however, will confirm a genera\
problem with the measurement system or faulty samples and/or standards.
If this occurs, locate and correct the source of the problem and repeat
the test. For non-aqueous matrices, the U.S. EPA will set criteria after
more interlaboratory data are gathered.
8.5 Instrument performance - Check the performance of the entire
analytical system daily using data gathered from analyses of blanks, standards,
and replicate samples.
8.5.1 Peak tailing significantly in excess of that shown in the
chromatogram (Figure 1) must be corrected. Tailing problems are generally
traceable to active sites on the GC column or to the detector operation.
8.5.2 Check the precision between replicate analyses. A properly
operating system should perform with an average relative standard
deviation of less than 10%. Poor precision is generally traceable to
pneumatic leaks, especially at the injection port.
9.0 METHOD PERFORMANCE
9.1 Method detection limits are presented in Table 1. Single laboratory
accuracy and precision at several concentrations in tap water are presented in
Table 2.
8011 - 8 Revision 0
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9.2 In a preservation study extending over a 4 week period, the average
percent recoveries and relative standard deviations presented in Table 3 were
observed for organic-free reagent water (acidified), tap water and ground water.
The results for acidified and non-acidified samples were not significantly
different.
10.0 REFERENCES
1. Optimization of Liquid-Liquid Extraction Methods for Analysis of Orqanics
in Water. EPA-600/S4-83-052, 1984.
2. Henderson, J.E.; Peyton, G.R.; Glaze, W.H. Identification and Analysis of
Organic Pollutants in Water; Keith, L.H., Ed; Ann Arbor Sci.: Ann Arbor,
MI; 1976.
3. Richard J.J.; Junk, G.A. Journal AWWA 1977, 69, 62.
4. Budde, W.L.; Eichelberger, J.W. Organic Analyses Using Gas Chromatography-
Mass Soectrometrv; Ann Arbor Science: Ann Arbor, MI; 1978.
5. Glaser, J.A.; et al. Environmental Science and Technology 1981, 15, 1426.
6. Methods for the Determination of Organic Compounds in Finished Drinking
Water and Raw Source Water; U.S. Environmental Protection Agency. Office
of Research and Development. Environmental Monitoring and Support
Laboratory. ORD Publication Offices of Center for Environmental Research
Information: Cincinnati, OH 1986.
8011 - 9 Revision 0
July 1992
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TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION
LIMITS (MDL) FOR 1,2-OIBROMOETHANE (EDB) AND
l,2-DIBROMO-3-CHLOROPROPANE (DBCP)
Analyte
Retention Time. Minutes
Column A Column B MDL (ng/l)
EDB
DBCP
9.5
17.3
8.9
15.0
0.01
0.01
Column A: Durawax-DX 3
Column B: DB-1
TABLE 2.
SINGLE LABORATORY ACCURACY AND PRECISION
FOR EDB AND DBCP IN TAP WATER
Analyte
EDB
DBCP
Number
of
Samples
7
7
7
7
7
7
Spike
Concentration
(MA)
0.03
0.24
50.0
0.03
0.24
50.0
Average
Recovery
(*)
114
98
95
90
102
94
Relative
Standard
Deviation
(%)
9.5
11.8
4.7
11.4
8.3
4.8
8011 - 10
Revision 0
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TABLE 3.
ACCURACY AND PRECISION AT 2.0
OVER A 4-WEEK STUDY PERIOD
Analyte
EOB
DBCP
Matrix1
RW-A
GW
GW-A
TW
TW-A
RW-A
GW
GW-A
TW
TW-A
Number
of Samples
16
15
16
16
16
16
16
16
16
16
Average
Accuracy
(% Recovery)
104
101
96
93
93
105
105
101
95
94
Relative
Std. Dev.
(%)
4.7
2.5
4.7
6.3
6.1
8.2
6.2
8.4
10.1
6.9
RW-A =* Organic-free reagent water at pH 2
GW = Ground water, ambient pH
GW-A = Ground water at pH 2
TW = Tap water, ambient pH
TW-A = Tap water at pH 2
8011 - 11 Revision 0
July 1992
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FIGURE 1.
SAMPLE CHROMATOGRAM FOR EXTRACT OF WATER SPIKED
AT 0.114 M9/L WITH ED8 AND DBCP
COLUMN: Fused silica capillary
LIQUID PHASE: Durawax-OX3
FILM THICKNESS: 0.25 \m
COLUMN DIMENSIONS: 30 M x 0.317
ID
10 IS 14 !• It
TIME (MIN)
20 22 24
8011 - 12
Revision 0
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METHOD 8011
1,2-DIBROMOETHANE AND 1,2-OIBROMO-3-CHLOROPROPANE
BY MICROEXTRACTION AND GAS CHROMATOGRAPHY
Start
7 2 Calibrate
in* t r unent
prepa re
calibra tion
curve
7 2 Chick
in* t r un*jn t
performance
7 3 Pr«par«
lample*
7 4. 1 Add
VaCl ta
sampl•*
7 « 3 Add
h»»«n« and
• x t ract
lamp 1•
7 4 4 Put
pair t of
tulracl in
vial
? < 5 Sav,
remainder of
•Mtract for
poiiibl*.
raana i y>i*
7 S Analyze
by CC
7 6 Determine
•ample
volume
7 7 Calculate
concentration*
Stop
8011 - 13
Revision 0
July 1992
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00
o
KS*
-------
METHOD 80ISA
NONHALOGENATED VOLATILE ORGANICS BY GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 8015 is used to determine the concentration of various
nonhalogenated volatile organic compounds. The following compounds can be
determined by this method:
Appropriate Technique
Direct
Compound Name CAS No." Purge-and-Trap Injection
Diethyl ether
Ethanol
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
60-29-7
64-17-5
78-93-3
108-10-1
b
i
PP
PP
b
b
b
b
a Chemical Abstract Services Registry Number.
b Adequate response using this technique
i Inappropriate technique for this analyte
pp Poor purging efficiency, resulting in high EQLs
2.0 SUMMARY OF METHOD
2.1 Method 8015 provides gas chromatographic conditions for the detection
of certain nonhalogenated volatile organic compounds. Samples may be introduced
into the GC using direct injection or purge-and-trap (Method 5030). Ground water
samples must be analyzed by Method 5030. A temperature program is used in the
gas chromatograph to separate the organic compounds. Detection is achieved by
a flame ionization detector (FID).
2.2 The method provides an optional gas chromatographic column that may
be helpful in resolving the analytes from co-eluting non-target compounds and for
analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Method 5030 and 8000.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A trip blank prepared from
organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.
8015A - 1 Revision 1
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4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas Chromatograph - Analytical system complete with gas
chromatograph suitable for on-column injections or purge-and-trap sample
introduction and all required accessories, including detectors, column
supplies, recorder, gases, and syringes. A data system for measuring peak
heights and/or peak areas is recommended.
4.1.2 Columns
4.1.2.1 Column 1 - 8 ft x 0.1 in. ID stainless steel or
glass column packed with 1% SP-1000 on Carbopack-B 60/80 mesh or
equivalent.
4.1.2.2 Column 2 - 6 ft x 0.1 in. ID stainless steel or
glass column packed with n-octane on Porasil-C 100/120 mesh
(Durapak) or equivalent.
4.1.3 Detector - Flame ionization (FID).
4.2 Sample introduction apparatus - Refer to Method 5030 for the
appropriate equipment for sample introduction purposes.
4.3 Syringes - A 5 ml Luerlok glass hypodermic and a 5 ml, gas-tight with
shutoff valve.
4.4 Volumetric flasks, Class A - Appropriate sizes with ground glass
stoppers.
4.5 Microsyringes - 10 and 25 nl with a 0.006 in. ID needle (Hamilton
702N or equivalent) and a 100 nl.
4.6 Analytical balance - 0.0001 g.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall 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
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Methanol, CH3OH. Pesticide quality or equivalent. Store away from
other solvents.
5.4 Stock standards - Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standards in
8015A - 2 Revision 1
July 1992
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methanol using assayed liquids.
5.4.1 Place about 9.8 ml of methanol in a 10 ml tared, ground-glass
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes or until all alcohol wetted surfaces have dried. Weigh
the flask to the nearest 0.0001 g.
5.4.2 Using a 100 nl syringe, immediately add two or more drops of
assayed reference material to the flask; then reweigh. The liquid must
fall directly into the alcohol without contacting the neck of the flask.
5.4.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in milligrams per
liter (mg/L) from the net gain in weight. When compound purity is assayed
to be 96% or greater, the weight may be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.4.4 Transfer the stock standard solution into a bottle with a
Teflon lined screw-cap. Store, with minimal headspace, at -10°C to -20°C
and protect from light.
5.4.5 Standards must be replaced after 6 months, or sooner if
comparison with check standards indicates a problem.
5.5 Secondary dilution standards - Using stock standard solutions, pre-
pare in methanol secondary dilution standards, as needed, that contain the
compounds of interest, either singly or mixed together. The secondary dilution
standards should be prepared at concentrations such that the aqueous calibration
standards prepared in Section 5.5 will bracket the working range of the
analytical system. Secondary dilution standards should be stored with minimal
headspace for volatiles and should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards from
them.
5.6 Calibration standards - Calibration standards at a minimum of five
concentrations are prepared in water from the secondary dilution of the stock
standards. One of the concentrations should be at. a concentration near, but
above, the method detection limit. The remaining concentrations should
correspond to the expected range of concentrations found in real samples or
should define the working range of the GC. Each standard should contain each
analyte for detection by this method (e.g. some or all of the compounds listed
in Section 1.1 may be included). In order*to prepare accurate aqueous standard
solutions, the following precautions must be observed:
5.6.1 Do not inject more than 20 ^L of alcoholic standards into
100 ml of water.
5.6.2 Use a 25 ^L Hamilton 702N microsyringe or equivalent
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of methanolic standards into water).
5.6.3 Rapidly inject the alcoholic standard into the filled
8015A - 3 Revision 1
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volumetric flask. Remove the needle as fast as possible after injection.
5.6.4 Mix aqueous standards by inverting the flask three times only.
5.6.5 Fill the sample syringe from the standard solution contained
in the expanded area of the flask (do not use any solution contained in
the neck of the flask).
5.6.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.6.7 Aqueous standards are not stable and should be discarded after
1 hour, unless properly sealed and stored. The aqueous standards can be
stored up to 24 hours, if held in sealed vials with zero headspace.
5.7 Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.7.1 Prepare calibration standards at a minimum of five
concentrations for each parameter of interest as described in Section 5.6.
5.7.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in Sections 5.4 and 5,5. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 ng//xL of each internal standard compound. The
addition of 10 pi of this standard to 5.0 ml of sample or calibration
standard would be equivalent to 30
5.7.3 Analyze each calibration standard according to Section 7.0,
adding 10 pi. of internal standard spiking solution directly to the
syringe.
5.8 Surrogate standards - The analyst should monitor both the performance
of the analytical system and the effectiveness of the method in dealing with each
sample matrix by spiking each sample, standard, and water blank with one or two
surrogate compounds recommended to encompass the range of temperature program
used in this method. From stock standard solutions prepared as in Section 5.4,
add a volume to give 750 ng of each surrogate to 45 ml of water contained in a
50 ml volumetric flask, mix, and dilute to volume for a concentration of
15 ng//iL. Add 10 nl of this surrogate spiking solution directly into the 5 ml
syringe with every sample and reference standard analyzed. If the internal
standard calibration procedure is used, the surrogate compounds may be added
directly to the internal standard spiking solution (Section 5.7.2).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this Chapter, Organic Analytes,
Section 4.1.
8015A - 4 Revision 1
July 1992
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7.0 PROCEDURE
7.1 Volatile compounds are introduced into the gas chromatograph either
by direct injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-concentration contaminated soils and
sediments. For high-concentration soils or sediments, methanolic extraction, as
described in Method 5030, may be necessary prior to purge-and-trap analysis.
Method 5030 also provides guidance on the analysis of aqueous miscible and non-
aqueous miscible liquid wastes (see Section 7.4.1.1).
7.2 Chromatographic conditions (Recommended)
7.2.1 Column 1
Carrier gas (Helium) flow rate: 40 mL/min
Temperature program:
Initial temperature: 45°C, hold for 3 minutes
Program: 45°C to 220°C at 8°C/nnn
Final temperature: 220°C, hold for 15 minutes.
7.2.2 Column 2
Carrier gas (Helium) flow rate: 40 mL/min
Temperature program:
Initial temperature: 50°C, hold for 3 minutes
Program: 50°C to 170°C at 6°C/min
Final temperature: 170°C, hold for 4 minutes.
7.3 Calibration - Refer to Method 8000 for proper calibration techniques.
7.3.1 Calibration must take place using the same sample introduction
method that will be used to analyze actual samples (see Section 7.4.1).
7.3.2 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these procedures.
7.4 Gas chromatographic analysis
7.4.1 Introduce volatile compounds into the gas chromatograph using
either Method 5030 (purge-and-trap method) or the direct injection method.
If the internal standard calibration technique is used, add 10 jiL of
internal standard to the sample prior to purging.
7.4.1.1 Direct injection - In very limited applications
(e.g. aqueous process wastes), direct injection of the sample into
the GC system with a 10 pi syringe may be appropriate. One such
application is for verification of the alcohol content of an aqueous
sample prior to determining if the sample is ignitable (Methods 1010
or 1020). In this case, it is suggested that direct injection be
used. The detection limit is very high (approximately 10,000 M9/L);
therefore, it is only permitted when concentrations in excess of
10,000 A*9/L are expected or for water-soluble compounds that do not
purge. The system must be calibrated by direct injection (bypassing
the purge-and-trap device).
8015A - 5 Revision 1
July 1992
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Non-aqueous miscible wastes may also be analyzed by direct
injection if the concentration of target, analytes in the sample
falls within the calibration range. If dilution of the sample is
necessary, follow the guidance for High Concentration samples in
Method 5030, Section 7.3.3.2.
7.4.2 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria. Include a mid-concentration standard after each
group of 10 samples in the analysis sequence.*
7.4.3 Record the sample volume purged or injected and the resulting
peak sizes (in area units or peak heights).
7.4.4 Calculation of concentration is covered in Method 8000.
7.4.5 If analytical interferences are suspected, or for the purpose
of confirmation, analysis using the second GC column is recommended.
7.4.6 If the response for a peak is off-scale, prepare a dilution of
the sample with water. The dilution must be performed on a second aliquot
of the sample which has been properly sealed and stored prior to use.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.
8.2 Quality control required to validate the GC system operation is found
in Method 8000, Section 8.6.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (limits established by performing
QC procedure outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following is required:
• Check to be sure that there are no errors in calculations,
surrogate solutions, and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Re-extract and re-analyze the sample if none of the above are
a problem or flag the data as "estimated concentration".
9.0 METHOD PERFORMANCE
9.1 The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and calibration procedures used.
8015A - 6 Revision 1
July 1992
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9.2 Specific
becomes available.
method performance information will be provided as it
10.0 REFERENCES
1. Bellar, T.A., and J.J. Lichtenberg, Determining Volatile Organics at
Microgram-per-Liter Levels by Gas Chromatography, J. Amer. Water Works
Assoc., 66(121. pp. 739-744 (1974).
2. Bellar, T.A., and J.J. Lichtenberg, Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds, in Van Hall, ed., Measurement of Organic Pollutants in Water
and Wastewater, ASTM STP 686, pp. 108-129, 1979.
3. Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters: Category 11 - Purgeables and Category 12 -
Acrolein, Acrylonitrile, and Dichlorodifluoromethane, Report for EPA
Contract 68-03-2635 (in preparation).
8015A - 7
Revision 1
July 1992
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METHOD 8015A
NONHALOGENATED VOLATILE ORGANICS BY GAS CHROMATOGRAPHY
voluae purged
chroma, tog r a phi c
7 1 5 Calculate
concentration*
7 4. 4 Are
analytical
interference*
iuapeeled?
746 Analyie
sample
aeeonot CC
eeluan
•emple into CC
purge-and-trap
7 4 7 la peak
reaponae off
tea!.'
8015A - 8
Revision 1
July 1992
-------
METHOD 8015B
NONHALOGENATED ORGANICS USING GC/FID
1.0 SCOPE AND APPLICATION
1.1 Method 8015 is used to determine the concentration of various nonhalogenated volatile
organic compounds and semivolatile organic compounds by gas chromatography. The following
compounds can be determined quantitatively by this method:
Appropriate Techniaue
Compound Name
Acetone
Acetonitrile
Acrolein
Acrylonitrile
Allyl alcohol
1-Butanol (n-Butyl alcohol)
t-Butyl alcohol
2-Chloroacrylonitrile (I.S.)
Crotonaldehyde
Diethyl ether
1 ,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Ethylene oxide
Hexafluoro-2-propanol (I.S.)
Hexafluoro-2-methyl-
2-propanol (I.S.)
Isobutyl alcohol
Isopropyl alcohol
Methanol
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
N-Nitroso-di-n-butylamine
Paraldehyde
2-Pentanone
2-Picoline
1-Propanol
Propionitrile
CAS No.8
67-64-1
75-05-8
107-02-8
107-13-1
107-18-6
71-36-3
75-65-0
920-37-6
123-73-9
60-29-7
123-91-1
64-17-5
141-78-6
107-21-1
75-21-8
920-66-1
515-14-6
78-83-1
67-63-0
67-56-1
78-93-3
108-10-1
924-16-3
123-63-7
107-87-9
109-06-8
71-23-8
107-12-0
Purge-and-
Trap
PP
PP
PP
PP
ht
ht
PP
NA
PP
b
PP
I
I
I
I
NA
NA
PP
PP
I
PP
PP
PP
PP
PP
PP
PP
ht
Direct
Injection
b,d
b,d
b.d
b,d
b,d
b,d
b,d
d
b,d
b
b,d
b,d
b,d
b
b,d
d
d
b,d
b,d
b,d
b,d
b,d
b,d
b,d
b.d
b,d
b.d
d
Solvent
Extraction
h
JA
NA
NA
I
I
I
I
I
b
I
I
I
I
I
CD-ROM
8015B-1
Revision 2
December 1996
-------
Appropriate Technique
Compound Name Purge-and- Direct Solvent
CAS No.a Trap Injection Extraction
Pyridine 110-86-1 I b,d b
o-Toluidine 95-53-4 I b,d b
8 Chemical Abstract Services Registry Number.
b Adequate response using this technique
d Amenable to concentration by azeotropic distillation (Method 5031)
ht Method analyte only when purged at 80°C
I Inappropriate technique for this analyte
pp Poor purging efficiency, resulting in high EQLs
NA Not available
I.S. Internal standard appropriate for Method 5031
1.2 This method may also be applicable to the analysis of petroleum hydrocarbons, including
gasoline range organics (GROs) and diesel range organics (DROs). GROs correspond to the range
of alkanes from C6 to C10and covering a boiling point range of approximately 60°C - 170°C
(Reference 6). DROs correspond to the range of alkanes from C10 to C28 and covering a boiling point
range of approximately 170°C - 430°C (Reference 6). The identification of specific fuel types may
be complicated by environmental processes such as evaporation, biodegradation, or when more
than one fuel type is present. Methods from other sources may be more appropriate for GROs and
DROs since these hydrocarbons are not regulated under RCRA. Consult State and local regulatory
authorities for specific requirements.
1.3 This method is restricted for use by, or under the supervision of, analysts experienced
in the use of gas chromatographs and skilled in the interpretation of gas chromatograms. In addition,
if this method is used for the analysis of petroleum hydrocarbons, it is limited to analysts experienced
in the interpretation of hydrocarbon data. Each analyst must demonstrate the ability to generate
acceptable results with this method.
1.4 The method can also be used as a screening tool (for both volatile and semivolatile
organics) to obtain semiquantitative data for the prevention of sample overload during quantitative
analysis on a GC/MS system. This may be accomplished using an automated (Method 5021)
headspace method or by direct injection if a solvent extraction method has been utilized for sample
preparation. Single point calibration would be acceptable in this situation. Performance data are
not provided for screening.
2.0 SUMMARY OF METHOD
2.1 Method 8015 provides gas chromatographic conditions for the detection of certain
nonhalogenated volatile and semivolatile organic compounds.
2.1.1 Samples may be introduced into the GC:
following solvent extraction (Methods 3510, 3520, 3540, 3541, 3545, 3550, or
3560)
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by direct injection (aqueous samples) including the concentration of analytes by
azeotropic distillation (Method 5031)
by purge-and-trap (Methods 5030 or 5035), or
by vacuum distillation (Method 5032)
2.1.2 Ground or surface water samples must generally be analyzed in conjunction with
Methods 5030, 5031, 5032, 3510, 3520, or other appropriate preparatory methods to obtain
the necessary quantitation limits. Method 3535 (solid-phase extraction) may also be applicable
to the target analytes, but has not yet been validated by EPA in conjunction with Method 8015.
2.1.3 Diesel range organics (DROs) may be prepared by an appropriate solvent
extraction method.
2.1.4 Gasoline range organics (GROs) may be introduced into the GC/FID by purge-
and-trap, automated headspace, vacuum distillation, or other appropriate technique.
2.2 An appropriate column and temperature program is used in the gas chromatograph to
separate the organic compounds. Detection is achieved by a flame ionization detector (FID).
2.3 The method allows the use of packed or capillary columns for the analysis and
confirmation of the non-halogenated individual analytes. Columns and conditions listed have been
demonstrated to provide separation of those target analytes. Analysts may change these conditions
as long as they demonstrate adequate performance.
2.4 Fused silica capillary columns are necessary for the analysis of petroleum hydrocarbons.
3.0 INTERFERENCES
3.1 When analyzing for volatile organics, samples can be contaminated by diffusion of volatile
organics (particularly chlorofluorocarbons and methylene chloride) through the sample container
septum during shipment and storage. A trip blank prepared from organic-free reagent water and
carried through sampling and subsequent storage and handling must serve as a check on such
contamination.
3.2 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are analyzed in sequence. To reduce the potential for carryover, the
sample syringe or purging device must be rinsed out between samples with an appropriate solvent.
Whenever an unusually concentrated sample is encountered, it should be followed by injection of
a solvent blank to check for cross contamination.
3.2.1 Clean purging vessels with a detergent solution, rinse with distilled water, and
then dry in a 105°C oven between analyses. Clean syringes or autosamplers by flushing all
surfaces that contact samples using appropriate solvents.
3.2.2 All glassware must be scrupulously cleaned. Clean all glassware as soon as
possible after use by rinsing with the last solvent used. This should be followed by detergent
washing with hot water, and rinses with tap water and organic-free reagent water. Drain the
glassware and dry in an oven at 130°C for several hours or rinse with methanol and drain.
Store dry glassware in a clean environment.
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3.3 The flame ionization detector (FID) is a non-selective detector. There is a potential for
many non-target compounds present in samples to interfere with this analysis.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas Chromatograph - Analytical system complete with gas chromatograph
suitable for solvent injections or purge-and-trap sample introduction and all required
accessories, including detectors, column supplies, recorder, gases, and syringes. A data
system for measuring peak heights and/or peak areas is recommended.
4.1.2 Recommended GC Columns
4.1.2.1 Column 1 - 8 ft x 0.1 in. ID stainless steel or glass column packed with
1% SP-1000 on Carbopack-B 60/80 mesh or equivalent.
4.1.2.2 Column 2 - 6 ft x 0.1 in. ID stainless steel or glass column packed with
n-octane on Porasil-C 100/120 mesh (Durapak) or equivalent.
4.1.2.3 Column 3 - 30 m x 0.53 mm ID fused silica capillary column bonded with
DB-Wax (or equivalent), 1-um film thickness.
4.1.2.4 Column 4 - 30 m x 0.53 mm ID fused silica capillary column chemically
bonded with 5% methyl silicone (DB-5, SPB-5, RTx, or equivalent), 1.5-um film thickness.
4.1.2.4.1 Capillary columns are needed for petroleum hydrocarbon
analyses. Laboratories may use other capillary columns (e.g. 0.25-0.32 mm ID
capillary columns) if they document method performance data (e.g.
chromatographic resolution and MDLs) if appropriate for the intended use of the
data.
4.1.2.4.2 Wide-bore columns should be installed in 1/4-inch
injectors, with deactivated liners designed specifically for use with these columns.
4.1.3 Detector - Flame ionization (FID)
4.2 Sample introduction and preparation apparatus
4.2.1 Refer to the 5000 series sample preparation methods for the appropriate
apparatus.
4.2.2 Samples may also be introduced into the GC via injection of solvent extracts or
direct injection of aqueous samples.
4.3 Syringes
4.3.1 A 5-mL Luer-Lok glass hypodermic and a 5-mL gas-tight syringe with shutoff
valve for volatile analytes.
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4.3.2 Microsyringes - 10- and 25-ul_ with a 0.006 in. ID needle (Hamilton 702N or
equivalent) and 100-uL
4.4 Volumetric flasks, Class A - Appropriate sizes with ground glass stoppers.
4.5 Analytical balance - 0 -160 g capacity, capable of measuring differences of 0.0001 g.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used whenever possible. Unless otherwise indicated,
it is intended that all reagents shall 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 ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method refer to organic-free
reagent water, as defined in Chapter One.
5.3 Methanol, CH3OH. Pesticide quality or equivalent. Store away from other solvents.
5.4 Fuels, e.g., gasoline or diesel. Purchase from a commercial source. Low boiling
components in fuel evaporate quickly. If available, obtain fuel from the leaking tank on site.
5.5 Alkane standard. A standard containing a homologous series of n-alkanes for
establishing retention times (e.g., C10-C32 for diesel).
5.6 Stock standards - Stock solutions may be prepared from pure standard materials or
purchased as certified solutions. When methanol is a target analyte or when using azeotropic
distillation for sample preparation, standards should not be prepared in methanol. Standards must
be replaced after 6 months or sooner, if comparison with check standards indicates a problem.
5.7 Secondary dilution standards - Using stock standard solutions, prepare secondary dilution
standards, as needed, that contain the compounds of interest, either singly or mixed together. The
secondary dilution standards should be prepared at concentrations such that the aqueous calibration
standards prepared in Sec. 5.8 will bracket the working range of the analytical system. Secondary
dilution standards should be stored with minimal headspace for volatiles and should be checked
frequently for signs of degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.8 Calibration standards - Calibration standards at a minimum of five different concentrations
are prepared in water (purge-and-trap or direct injection) or in methylene chloride (solvent injection)
from the secondary dilution of the stock standards. One of the standards should be at or below the
concentration equivalent to the appropriate quantitation limit for the project. The remaining
concentrations should correspond to the expected range of concentrations found in real samples or
should define the working range of the GC. Each standard should contain each analyte for detection
by this method (e.g., some or all of the compounds listed in Sec. 1.1 may be included). Volatile
organic standards are prepared in organic-free reagent water. In order to prepare accurate aqueous
standard solutions, the following precautions must be observed:
5.8.1 Do not inject more than 20 uL of methanolic standards into 100 mL of water.
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5.8.2 Use a 25-pL Hamilton 702N microsyringe or equivalent (variations in needle
geometry will adversely affect the ability to deliver reproducible volumes of methanolic
standards into water).
5.8.3 Rapidly inject the primary standard into the filled volumetric flask. Remove the
needle as fast as possible after injection.
5.8.4 Mix diluted standards by inverting the flask three times only.
5.8.5 Fill the sample syringe from the standard solution contained in the expanded area
of the flask (do not use any solution contained in the neck of the flask).
5.8.6 Never use pipets to dilute or transfer samples or aqueous standards when diluting
volatile organic standards.
5.8.7 Aqueous standards used for purge-and-trap analyses (Method 5030) are not
stable and should be discarded after 1 hour, unless held in sealed vials with zero headspace.
If so stored, they may be held for up to 24 hours. Aqueous standards used for azeotropic
distillation (Method 5031) may be stored for up to a month in polytetrafluoroethylene (PTFE)-
sealed screw-cap bottles with minimal headspace, at 4°C, and protected from light.
5.9 Internal standards (if internal standard calibration is used) - To use this approach, the
analyst must select one or more internal standards that are similar in analytical behavior to the
compounds of interest. The analyst must further demonstrate that the measurement of the internal
standard is not affected by method or matrix interferences. Because of these limitations, no internal
standard can be suggested that is applicable to all samples. The following internal standards are
recommended when preparing samples by azeotropic distillation: 2-chloroacrytonitrile,
hexafluoro-2-propanol and hexafluoro-2-methyl-2-propanol.
5.10 Surrogate standards - Whenever possible, the analyst should monitor both the
performance of the analytical system and the effectiveness of the method in dealing with each
sample matrix by spiking each sample, standard, and blank with one or two surrogate compounds
which are not affected by method interferences.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See the introductory material to this chapter, Organic Analytes, Sec. 4.1.
7.0 PROCEDURE
7.1 Introduction/preparation methods
Various alternate methods are provided for sample introduction. All internal standards,
surrogates, and matrix spikes (when applicable) must be added to samples before introduction into
the GC/FID system. Follow the introduction method on when to add standards.
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7.1.1 Direct injection - This involves direct syringe injection into the GC injection port.
7.1.1.1 Volatile organics (includes gasoline range organics [GROs])
This may involve injection of an aqueous sample containing a very high
concentration of analytes; injection of aqueous concentrates from Method 5031
(azeotropic distillation for nonpurgeable volatile organics); and injection of an organic
solvent waste. Direct injection of aqueous samples (non-concentrated) has very limited
applications. It is only permitted for the determination of volatiles at the toxicity
characteristic (TC) regulatory limits or at concentrations in excess of 10,000 ug/L. It may
also be used in conjunction with the test for ignitability in aqueous samples (along with
Methods 1010 and 1020) to determine if alcohol is present at > 24%.
7.1.1.2 Semivolatile organics (includes diesel range organics [DROs])
This may involve syringe injection of extracts of aqueous samples prepared by
Methods 3510 or 3520 or extracts of soil/solids prepared by Methods 3540, 3541, 3545,
3550 or 3560.
WARNING: Ultrasonic extraction (Method 3550) is not as rigorous a method as
the other extraction methods for soil/solids. This means it is very
critical that the method be followed explicitly to achieve extraction
efficiency which approaches that of Soxhlet extraction. Consult
Method 3550 for information on the critical aspects of this extraction
procedure.
7.1.2 Purge and trap - this includes purge and trap for aqueous samples (Method 5030)
and purge and trap for solid samples (Method 5035). Method 5035 also provides techniques
for extraction of solid and oily waste samples by methanol (and other water miscible solvents)
with subsequent purge and trap from an aqueous matrix using Method 5030. Normally purge
and trap for aqueous samples is performed at ambient temperatures while soil/solid samples
utilize a 40°C purge to improve extraction efficiency. Occasionally, there may be a need to
perform a heated purge for aqueous samples to lower detection limits; however, a 25-mL
sample should provide the sensitivity needed in most situations.
7.1.3 Vacuum distillation - this is a device for the introduction of volatile organics from
aqueous, solid or tissue samples (Method 5032) into the GC/FID system.
7.1.4 Automated static headspace - this is a device for the introduction of volatile
organics from solid samples (Method 5021) into the GC/FID system.
7.2 Chromatographic conditions (recommended)
7.2.1 Column 1
Carrier gas (Helium) flow rate: 40 mL/min
Temperature program:
Initial temperature: 45°C, hold for 3 minutes
Program: 45°C to 220°C at 8°C/min
Final temperature: 220°C, hold for 15 minutes.
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7.2.2 Column 2
Carrier gas (Helium) flow rate:
Temperature program:
Initial temperature:
Program:
Final temperature:
7.2.3 Column 3
Carrier gas (Helium) flow rate:
Temperature program:
Initial temperature:
Program:
Final temperature:
7.2.4 Column 4 (DROs)
Carrier gas (Helium) flow rate:
Makeup gas (Helium) flow rate:
Injector temperature:
Detector temperature:
Temperature program:
Initial temperature:
Program:
Final temperature:
7.2.5 Column 4 (GROs)
Carrier gas (Helium) flow rate:
Makeup gas (Helium) flow rate:
Injector temperature:
Detector temperature:
Temperature program:
Initial temperature:
Program:
Final temperature:
Final hold:
7.3 Initial calibration
40 mL/min
50°C, hold for 3 minutes
50°C to 170°C at 6°C/min
170°C, hold for 4 minutes.
15 mL/min
45°C, hold for 4 minutes
45°C to 220°C at 12°C/min
220°C, hold for 3 minutes.
5-7 mL/minute
30 mL/min
200°C
340°C
45°C, hold 3 minute
45°Cto275°Cat12°C/min
275°C, hold 12 min
5-7 mL/minute
30 mL/min
200°C
340°C
45°C, hold 1 minute
45°Cto100°Cat5°C/min
100°C to 275°C, at 8°C/min
5 min
7.3.1 Set up the sample introduction system as outlined in the method of choice (see
Sec. 7.1). A different calibration curve is necessary for each sample introduction mode
because of the differences in conditions and equipment. Establish chromatographic operating
parameters that provide instrument performance equivalent to that documented in this method.
Prepare calibration standards using the procedures described above (Sec. 5.8). The external
standard technique is described below. Analysts wishing to use the internal standard
technique are referred to Method 8000. Recommended internal standards for the
non-purgeable volatiles include hexafluoro-2-propanol, hexafluoro-2-methyl-2-propanol, and
2-chloroacrylonitrile.
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7.3.2 External standard calibration procedure for single component analytes
7.3.2.1 For each analyte and surrogate of interest, prepare calibration standards
at a minimum of five different concentrations by adding volumes of one or more stock
standards to a volumetric flask and diluting to volume with an appropriate solvent. One
of the external standards should be at a concentration at or below the quantitation limit
necessary for the project (based on the concentration in the final volume specified in the
preparation method, with no dilutions). The other concentrations should correspond to
the expected range of concentrations found in real samples or should define the working
range of the detector.
7.3.2.2 Introduce each calibration standard using the technique that will be used
to introduce the actual samples into the gas chromatograph. Tabulate peak height or
area responses against the mass injected. Calculate the calibration factor (CF) for each
single component analyte as described in Method 8000.
7.3.3 External standard calibration procedure for DROs and GROs
The calibration of DROs and GROs is markedly different from that for single component
analytes. In particular, the response used for calibration must represent the entire area of the
chromatogram within the retention time range for the fuel type (DROs or GROs), including the
unresolved complex mixture that lies below the individual peaks. See Sec. 7.7.2 for
information on calculating this area.
7.3.3.1 For each fuel type, prepare calibration standards at a minimum of five
different concentrations by adding volumes of one or more stock standards to a
volumetric flask and diluting to volume with an appropriate solvent. One of the external
standards should be at a concentration at or below the quantitation limit necessary for
the project (based on the concentration in the final volume specified in the preparation
method, with no dilutions). The other concentrations should correspond to the expected
range of concentrations found in real samples or should define the working range of the
detector.
NOTE: Whenever possible, the calibration should be performed using the
specific fuel that is contaminating the site (e.g., a sample of the fuel
remaining in the tank suspected of leaking). Where such samples are
not available or not known, use recently purchased commercially-
available fuel. A qualitative screening injection and GC run may be
performed to identify unknown fuels.
7.3.3.2 Introduce each calibration standard using the technique that will be used
to introduce the actual samples into the gas chromatograph. Determine the area of the
response as described in Sec. 7.7.2. Calculate the calibration factor (CF) for each fuel
type as shown below:
~ ... .. ,_ . Total Area within Retention Time Range
Calibrator! Factor = Mgss jnjected (jp nanograms)
7.3.4 Calibration linearity
The linearity of the calibration must be assessed. This applies to both the single
component analytes and the fuel types.
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7.3.4.1 If the percent relative standard deviation (%RSD) of the calibration
factor is less than 20% over the working range, linearity through the origin can be
assumed, and the average calibration factor can be used in place of a calibration curve.
7.3.4.2 If the % RSD is more than 20% over the working range, linearity through
the origin cannot be assumed. See Method 8000 for other calibration options that may
be employed.
7.4 Retention time windows
Single component target analytes (see Sec. 1.1) are identified on the basis of retention
time windows. GROs and DROs are distinguished on the basis of the ranges of retention
times for characteristic components in each type of fuel.
7.4.1 Before establishing retention time windows, make sure that the chromatographic
system is functioning reliably and that the operating parameters have been optimized for the
target analytes and surrogates in the sample matrix to be analyzed. Establish the retention
time windows for single component target analytes using the procedure described in Sec. 7.0
of Method 8000.
7.4.2 The retention time range for GROs is defined during initial calibration. Two
specific gasoline components are used to establish the range, 2-methylpentane and 1,2,4-
trimethylbenzene. Use the procedure described in Sec. 7.0 of Method 8000 to establish the
retention time windows for these two components. The retention time range is then calculated
based on the lower limit of the RT window for the first eluting component and the upper limit
of the RT window for the last eluting component.
7.4.3 The retention time range for DROs is defined during initial calibration. The range
is established from the retention times of the C10 and C 2a alkanes. Use the procedure
described in Sec. 7.0 of Method 8000 to establish the retention time windows for these two
components. The retention time range is then calculated based on the lower limit of the RT
window for the first eluting component and the upper limit of the RT window for the last eluting
component.
7.5 Calibration verification
7.5.1 The working calibration curve, and retention times must be verified at the
beginning of each 12-hour work shift as a minimum requirement. Verification is accomplished
by the measurement of one or more calibration standards (normally mid-concentration) that
contain all of the target analytes and surrogates when individual target analytes are being
analyzed. Verification is accomplished by the measurement of the fuel standard and the
hydrocarbon retention time standard when petroleum hydrocarbons are being analyzed.
Additional analyses of the verification standard(s) throughout a 12-hour shift are strongly
recommended, especially for samples that contain visible concentrations of oily material. See
Sec. 7.0 "calibration verification" of Method 8000 for more detailed information.
7.5.2 Calculate the % difference as detailed in Sec. 7.0 of Method 8000. If the
response for any analyte is within ±15% of the response obtained during the initial calibration,
then the initial calibration is considered still valid, and analyst may continue to use the mean
CF or RF values from the initial calibration to quantitate sample results. For analyses
employing azeotropic distillation as the sample introduction technique, the % difference may
be up to ±20%. If the response for any analyte varies from the predicted response by more
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than ±15% (±20% for azeotropic distillation), corrective action must be taken to restore the
system or a new calibration curve must be prepared for that compound.
7.5.3 All target analytes and surrogates or n-alkanes in the calibration verification
analyses must fall within previously established retention time windows. If the retention time
of any analyte does not fall within the ± 3o window, corrective action must be taken to restore
the system or a new calibration curve must be prepared for that compound.
7.5.4 Solvent blanks and any method blanks should be run with calibration verification
analyses to confirm that laboratory contamination does not cause false positives.
7.6 Gas chromatographic analysis
7.6.1 Samples are analyzed in a set referred to as an analysis sequence. The
sequence begins with calibration verification followed by sample extract analyses. Additional
analyses of the verification standard(s) throughout a 12-hour shift are strongly recommended,
especially for samples that contain visible concentrations of oily material. A verification
standard is also necessary at the end of a set. The sequence ends when the set of samples
has been injected or when retention time and/or % difference QC criteria are exceeded.
If the criteria are exceeded, inspect the gas chromatographic system to determine the
cause and perform whatever maintenance is necessary before recalibrating and proceeding
with sample analysis. All sample analyses performed using external standard calibration must
be bracketed with acceptable data quality analyses (e.g., calibration and retention time criteria).
Therefore, all samples must be reanalyzed that fall within the standard that exceeded criteria
and the last standard that was acceptable.
7.6.2 Samples are analyzed with the same instrument configuration as is used during
calibration. When using Method 5030 for sample introduction, analysts are cautioned that
opening a sample vial or drawing an aliquot from a sealed vial (thus creating headspace) will
compromise samples analyzed for volatiles. Therefore, it is recommended that analysts
prepare two samples for purge-and-trap analysis. The second sample can be stored for 24
hours to ensure that an uncompromised sample is available for analysis or dilution, if the
analysis of the first sample is unsuccessful or if results exceed the calibration range of the
instrument. Distillates from Method 5031 may be split into two portions and held at 4°C prior
to analysis. It is recommended that the distillate be analyzed within 24 hours of distillation.
Distillates must be analyzed within 7 days of distillation.
7.6.3 Sample concentrations are calculated by comparing sample response data with
the initial calibration of the system (Sec. 7.3). Therefore, if sample response exceeds the limits
of the initial calibration range, a dilution of the sample must be analyzed. For volatile organic
aqueous samples, the dilution must be performed on a second aliquot of the sample which has
been properly sealed and stored prior to use and reanalysis. Extracts should be diluted so that
all peaks are on scale, as overlapping peaks are not always evident when peaks are off scale.
Computer reproduction of chromatograms, manipulated to ensure all peaks are on scale over
a 100-fold range, are acceptable as long as calibration limits are not exceeded. Peak height
measurements are recommended over peak area integration when overlapping peaks cause
errors in area integration.
7.6.4 Tentative identification of a single component analyte occurs when a peak from
a sample extract falls within the daily retention time window. Confirmation is required on a
second column or by GC/MS. Since the flame ionization detector is non-specific, it is highly
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recommended that GC/MS confirmation be performed on single component analytes unless
historical data are available to support the identification(s).
7.6.5 Second column confirmation is generally not necessary for petroleum
hydrocarbon analysis. However, if analytical interferences are indicated, analysis using the
second GC column is required. Also, the analyst must ensure that the sample hydrocarbons
fall within the retention time range established during the initial calibration.
NOTE: Identification of fuels, especially gasoline, is complicated by their inherent
volatility. The early eluting compounds in fuels are obviously the most volatile
and the most likely to have weathered unless sampled immediately following
a spill. The most highly volatile fraction of gasoline constitutes 50% of the
total peak area of a gasoline chromatogram. This fraction is least likely to be
present in an environmental sample or present in only very low concentration
in relation to the remainder of a gasoline chromatogram.
7.6.6 The performance of the entire analytical system should be checked every 12
hours, using data gathered from analyses of blanks, standards, and replicate samples.
Significant peak tailing must be corrected. Tailing problems are generally traceable to active
sites on the column, cold spots in a GC, the detector operation, or leaks in the system. See
Sec. 7.9 for GC/FID system maintenance. Follow manufacturer's instructions for maintenance
of the introduction device.
7.7 Calculations
7.7.1 The concentration of each analyte in the sample may be determined by
calculating the amount of standard purged or injected, from the peak response, using the
calibration curve or the mean CF or RF from the initial curve.
7.7.2 While both diesel fuel and gasoline contain a large number of compounds that
will produce well resolved peaks in a GC/FID chromatogram, both fuels contain many other
components that are not chromatographically resolved. This unresolved complex mixture
results in the "hump" in the chromatogram that is characteristic of these fuels. In addition,
although the resolved peaks are important for the identification of the specific fuel type, the
area of the unresolved complex mixture contributes a significant portion of the area of the total
response.
7.7.2.1 For the analysis of DROs, sum the area of all peaks eluting between C10
and C^. This area is generated by projecting a horizontal baseline between the retention
times of C10 and C28.
7.7.2.2 Because the chromatographic conditions employed for DRO analysis
can result in significant column bleed and a resulting rise in the baseline, it is appropriate
to perform a subtraction of the column bleed from the area of the DRO chromatogram.
In order to accomplish this subtraction, a methylene chloride blank should be analyzed
during each 12-hour analytical shift during which samples are analyzed for DROs. The
area of this chromatogram is measured in the same fashion as is used for samples (see
Sec. 7.7.2.1), by projecting a horizontal baseline across the retention time range for
DROs. This area is then subtracted from the area measured for the sample and the
difference in areas is used to calculate the DRO concentration, using the equations in
Method 8000.
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7.7.2.3 For the analysis of GROs, sum the area of all peaks eluting between 2-
methylpentane and 1,2,4-trimethyl benzene. This area is used to calculate the GRO
concentration, using the equations in Method 8000. Column bleed subtraction is not
generally required for GRO analysis.
7.7.3 Refer to Method 8000, Sec. 7.0 for calculation formulae. The formulae cover
external and internal standard calibration, aqueous and non-aqueous samples and linear and
non-linear calibration curves.
7.8 Screening
7.8.1 Method 8015 with single-point calibration can also be used for GC/FID screening
in order to reduce instrument down-time when highly contaminated samples are analyzed using
GC/MS (e.g., Methods 8260 and 8270).
7.8.2 The same configuration of introduction device interfaced to the GC/MS may be
utilized for the GC/FID or alternative configurations are acceptable.
7.8.3 Establish that the system response and chromatographic retention times are
stable. Analyze the high-point GC/MS calibration standard.
7.8.4 Analyze samples or sample extracts. Compare peak heights in the sample
chromatograms with the high-point standard to establish that no compound with the same
retention time as a target analyte exceeds the calibration range. However, the FID is much
less sensitive to halogenated compounds than the GC/MS system, therefore, the above
comparison is not an absolute certainty.
7.8.5 It is recommended that the high-point standard should be run at least every 12
hours to confirm the stability of instrument response and chromatographic retention times.
However, there is no QC requirement for screening.
7.9 Instrument Maintenance
7.9.1 Injection of sample extracts from waste sites often leaves a high boiling residue
in: the injection port area, splitters when used, and the injection port end of the
chromatographic column. This residue effects chromatography in many ways (i.e., peak tailing,
retention time shifts, analyte degradation, etc.) and, therefore, instrument maintenance is very
important. Residue buildup in a splitter may limit flow through one leg and therefore change
the split ratios. If this occurs during an analytical run, the quantitative data may be incorrect.
Proper cleanup techniques will minimize the problem and instrument QC will indicate when
instrument maintenance is required.
7.9.2 Suggested chromatograph maintenance
Corrective measures may require any one or more of the following remedial actions. Also
see Sec. 7.0 in Method 8000 for additional guidance on corrective action for capillary columns
and the injection port.
7.9.2.1 Splitter connections - For dual columns which are connected using a
press-fit Y-shaped glass splitter or a Y-shaped fused-silica connector, clean and
deactivate the splitter or replace with a cleaned and deactivated splitter. Break off the
first few inches (up to one foot) of the injection port side of the column. Remove the
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columns and solvent backflush according to the manufacturer's instructions. If these
procedures fail to eliminate the degradation problem, it may be necessary to deactivate
the metal injector body and/or replace the columns.
7.9.2.2 Column rinsing - The column should be rinsed with several column
volumes of an appropriate solvent. Both polar and nonpolar solvents are recommended.
Depending on the nature of the sample residues expected, the first rinse might be water,
followed by methanol and acetone; methylene chloride is a satisfactory final rinse and in
some cases may be the only solvent required. The column should then be filled with
methylene chloride and allowed to remain flooded overnight to allow materials within the
stationary phase to migrate into the solvent. The column is then flushed with fresh
methylene chloride, drained, and dried at room temperature with a stream of ultrapure
nitrogen passing through the column.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 8000 for specific quality control (QC) procedures.
Quality control procedures to ensure the proper operation of the various sample preparation and/or
sample introduction techniques can be found in Methods 3500 and 5000. Each laboratory should
maintain a formal quality assurance program. The laboratory should also maintain records to
document the quality of the data generated.
8.2 Quality control procedures necessary to evaluate the GC system operation are found in
Method 8000, Sec. 7.0 and include evaluation of retention time windows, calibration verification and
chromatographic analysis of samples.
8.3 Initial Demonstration of Proficiency - Each laboratory must demonstrate initial proficiency
with each sample preparation and determinative method combination it utilizes, by generating data
of acceptable accuracy and precision for target analytes in a clean matrix. The laboratory must also
repeat the following operations whenever new staff are trained or significant changes in
instrumentation are made. See Method 8000, Sec. 8.0 for information on how to accomplish this
demonstration.
8.4 Sample Quality Control for Preparation and Analysis - The laboratory must also have
procedures for documenting the effect of the matrix on method performance (precision, accuracy,
and detection limit). At a minimum, this includes the analysis of QC samples including a method
blank, a matrix spike, a duplicate, and a laboratory control sample (LCS) in each analytical batch and
the addition of surrogates to each field sample and QC sample.
8.4.1 Documenting the effect of the matrix should include the analysis of at least one
matrix spike and one duplicate unspiked sample or one matrix spike/matrix spike duplicate pair.
The decision on whether to prepare and analyze duplicate samples or a matrix spike/matrix
spike duplicate must be based on a knowledge of the samples in the sample batch. If samples
are expected to contain target analytes, then laboratories may use one matrix spike and a
duplicate analysis of an unspiked field sample. If samples are not expected to contain target
analytes, laboratories should use a matrix spike and matrix spike duplicate pair.
8.4.2 A Laboratory Control Sample (LCS) should be included with each analytical batch.
The LCS consists of an aliquot of a clean (control) matrix similar to the sample matrix and of
the same weight or volume. The LCS is spiked with the same analytes at the same
concentrations as the matrix spike. When the results of the matrix spike analysis indicate a
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potential problem due to the sample matrix itself, the LCS results are used to verify that the
laboratory can perform the analysis in a clean matrix.
8.4.3 See Method 8000, Sec. 8.0 for the details on carrying out sample quality control
procedures for preparation and analysis.
8.5 Surrogate recoveries - The laboratory must evaluate surrogate recovery data from
individual samples versus the surrogate control limits developed by the laboratory. See Method
8000, Sec. 8.0 for information on evaluating surrogate data and developing and updating surrogate
limits.
8.6 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. Whenever possible, the laboratory should analyze
standard reference materials and participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 Specific method performance information for non-purgeable volatiles prepared using the
azeotropic microdistillation technique from Method 5031 is included in Tables 1, 3 and 4 for aqueous
matrices and in Tables 2 and 5 for solid matrices.
9.2 Specific method performance information is provided for diesel fuel spiked into soil in
Tables 6 and 7.
10.0 REFERENCES
1. Bellar, T.A., and J.J. Lichtenberg. "Determining Volatile Organics at Microgram-per-Liter Levels
by Gas Chromatography", J. Amer. Water Works Assoc., 66(12V pp. 739-744 (1974).
2. Bellar, T.A., and J.J. Lichtenberg. "Semi-Automated Headspace Analysis of Drinking Waters
and Industrial Waters for Purgeable Volatile Organic Compounds", in Van Hall, ed.,
Measurement of Organic Pollutants in Water and Wastewater, ASTM STP 686, pp. 108-129,
1979.
3. Development and Application of Test Procedures for Specific Organic Toxic Substances in
Wastewaters: Category 11 - Purgeables and Category 12 - Acrolein, Acrylonitrile, and
Dichlorodifluoromethane, Report for EPA Contract 68-03-2635.
4. Bruce, M.L., R.P. Lee, and M.W. Stevens. "Concentration of Water Soluble Volatile Organic
Compounds from Aqueous Samples by Azeotropic Microdistillation", Environ. Sci. Technol.
1992, 26., 160-163.
5. Tsang, S.F., N. Chau, P.J. Marsden, and K.R. Carter. "Evaluation of the EnSys PETRO RISc.
kitforTPH", Report for Ensys, Inc., Research Triangle Park, NC, 27709,1992.
6. "Intertaboratory Study of Three Methods for Analyzing Petroleum Hydrocarbons in Soils," API
Publication Number 4599, American Petroleum Institute, March 1994.
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TABLE 1
METHOD DETECTION LIMITS FOR NON-PURGEABLE VOLATILE COMPOUNDS
IN AQUEOUS MATRICES BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)
Analyte
Acetone"
Acetonitrile
Acrolein
Acrylonitrile
1-Butanol
t-Butyl alcohol
1 ,4-Dioxane
Ethanol
Ethyl acetate
Ethylene oxide
Isobutyl alcohol
Isopropyl alcohol
Methanol
Methyl ethyl ketone
Methyl isobutyl ketone
2-Pentanone
1-Propanol
Propionitrile
Pyridine
Reagent Water
48
15
13
8
14
8
12
18
9
8
11
18
21
4
4
2
—
10
11
MDL (ua/L)a
Ground Water
16
6
15
9
8
7
15
12
8
9
8
17
21
5
2
2
7
6
9
TCLP Leachate
63
14
7
14
7
17
16
13
16
10
4
7
22
9
8
7
—
13
21
" Produced by analysis of 7 aliquots of water spiked at 25 UQ/L. using internal standard
calibration.
b Problematic due to transient laboratory contamination.
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TABLE 2
METHOD DETECTION LIMITS FOR NON-PURGEABLE VOLATILE COMPOUNDS
IN SOLID MATRICES BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)
MDL fma/kcri
Analyte Incinerator Ash Kaolin
Acrylonitrile
1-Butanol
t-Butyl alcohol
1,4-Dioxane
Ethanol
Ethyl acetate
Isopropyl alcohol
Methanol
Methyl ethyl ketone
Methyl isobutyl ketone
2-Pentanone
Pyridine
0.42
0.23
0.34
0.31
0.47
0.18
0.40
0.46
0.27
0.12
0.16
0.20
0.09
0.09
0.13
0.16
0.19
0.07
0.19
0.31
0.12
0.05
0.07
0.08
The MDLs calculated for this table were produced by the analysis of 7 replicates spiked at 0.50
mg/kg, using internal standard calibration.
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TABLE 3
METHOD PERFORMANCE DATA FOR NON-PURGEABLE VOLATILES IN GROUND
WATER BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)
Compound
Acetone*
Acetonitrile
Acrolein
Acrylonitrile
1-Butanol
t-Butyl alcohol
1 ,4-Dioxane
Ethanol
Ethyl Acetate
Ethylene oxide
Isobutyl alcohol
Isopropyl alcohol
Methanol
Methyl ethyl ketone
Methyl isobutyl ketone
2-Pentanone
1-Propanol
Propionitrile
Pyridine
Low Gone.8
Average"
%Rec %RSD
126 17
147 5
146 13
179 7
127 8
122 7
124 16
152 10
142 7
114 10
122 8
167 13
166 14
105 6
66 4
94 3
N/A
135 5
92 12
Medium Cone."
Average"
%Rec %RSD
N/A
105
120
143
86
N/A
96
N/A
135
N/A
87
.N/A
94
N/A
N/A
N/A
91
102
N/A
8
27
28
8
—
10
—
33
—
13
—
9
—
—
—
7
14
~~
High Conc.c
Average"
%Rec
N/A
92
80
94
90
N/A
99
N/A
92
N/A
89
N/A
95
N/A
N/A
N/A
91
90
N/A
%RSD
9
20
21
9
—
8
~
25
—
13
~
7
—
—
—
7
14
«.
8 25 ug/L spikes, using internal calibration.
b 100 ug/L spikes,
c 750 pg/L spikes,
using internal calibration.
using internal calibration.
6 Average of 7 replicates
e Problematic due
to transient laboratory contamination.
N/A Data not available
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TABLE 4
METHOD PERFORMANCE DATA FOR NON-PURGEABLE VOLATILES IN TCLP
LEACHATE BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)
Compound
Acetone8
Acetonitrile
Acrolein
Acrylonitrile
1-Butanol
t-Butyl alcohol
1 ,4-Dioxane
Ethanol
Ethyl Acetate
Ethylene oxide
Isobutyl alcohol
Isopropyl alcohol
Methanol
Methyl ethyl ketone
Methyl isobutyl ketone
2-Pentanone
1-Propanol
Propionitrile
Pyridine
Low Cone.8
Average1'
%Rec %RSD
99 91
107 17
88 10
133 13
119 7
70 31
103 20
122 13
164 12
111 12
115 4
114 8
107 10
87 13
78 13
101 8
N/A
100 16
46 59
Medium Cone."
Average"
%Rec
N/A
111
109
123
89
N/A
103
N/A
119
N/A
86
N/A
102
N/A
N/A
N/A
98
100
N/A
%RSD
10
29
29
12
~
16
—
29
~
13
~
6
~
~
—
10
11
•"•
High Conc.c
Average"
%Rec
N/A
95
87
103
86
N/A
102
N/A
107
N/A
82
N/A
N/A
N/A
N/A
N/A
89
90
N/A
%RSD
11
41
38
8
—
7
—
41
—
13
—
—
—
—
—
7
17
~—
a 25 ug/L spikes, using internal calibration.
b 100 ug/L spikes,
c 750 ug/L spikes,
using internal calibration.
using internal calibration.
d Average of 7 replicates
8 Problematic due
to transient laboratory contamination.
N/A Data not available
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TABLE 5
METHOD PERFORMANCE DATA FOR NON-PURGEABLE VOLATILE COMPOUNDS
IN SOLID MATRICES BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)
Incinerator Ash
Low Cone.8 High Cone."
Average0 Average0
%Rec %RSD %Rec
Acrylonitrile
1-Butanol
t-Butyl alcohol
1 ,4-Dioxane
Ethanol
Ethyl acetate
Isopropyl alcohol
Methanol
Methyl ethyl ketone
Methyl isobutyl ketone
2-Pentanone
Pyridine
8 0.5 mg/kg spikes
b OC rvm/lx^i t?v\ilsr\e*
50
105
101
106
117
62
119
55
81
68
79
52
, using
i i*»!rt/*» i
53
14
21
19
25
19
21
53
21
11
13
24
internal
*"» + *"M»*"* « 1
10
61
60
48
52
39
61
33
40
57
54
44
%RSD
31
12
13
18
20
12
15
28
12
14
10
20
Kaolin
Low Cone.8
Average0
%Rec
102
108
97
105
108
90
108
117
91
71
91
50
High Cone."
Average0
%RSD %Rec
6
5
9
10
11
5
11
17
8
5
5
10
12
58
59
48
48
41
58
37
42
55
54
49
%RSD
52
25
23
25
24
25
24
22
20
23
19
31
calibration.
^^ \i\^**%btf\n
Average of 7 replicates
CD-ROM
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TABLE 6
RESULTS FROM ANALYSIS8 OF LOW AROMATIC DIESEL" BY GC/FID
(5 replicates/test)
Spike Concentration
12.5 ppm
75 ppm
105 ppm
150 ppm
1000 ppm
Analysis Results
ND
54 ± 7 ppm
90 ± 15 ppm
125 ± 12 ppm
960 ± 1 05 ppm
Samples were prepared using 2 g aliquots of sandy loam soil spiked with known
amounts of low aromatic diesel. Extractions were accomplished using methylene
chloride as a solvent (Method 3550, high concentration option).
Low aromatic diese! is sold in California (Section 2256, CCR). For this study it was
purchased at a gas station in San Diego, California.
TABLE 7
RESULTS FROM ANALYSIS8 OF LOW AROMATIC DIESEL" BY GC/FID
(5 replicates/test)
Spike Concentration
25 ppm
75 ppm
125 ppm
150 ppm
Analysis Results
51. 2 ±6.4 ppm
75.9 ± 7.8 ppm
98.9 ± 5.2 ppm
162± 10.4 ppm
Samples were prepared using 10 g aliquots of sandy loam soil spiked with known
amounts of regular #2 diesel purchased at a gas station in Northern Virginia.
Extractions were accomplished using methylene chloride as a solvent (Method 3550).
CD-ROM
8015B-21
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CHROMATOGRAM OF A 300 PPM GASOLINE STANDARD
80000
60000
40000
20000
SF;
."JUW
£.
1 • i ' ' ' ' i ' '
2.00 3.00
N 5
jU
•n"1
5.00
\ i | i i i i'| i i i r^-rn
6.QO 7.00 8.00
It!
fie. . A
e
m
9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00 21.00
Time 0.00
1 ' I '
1.00
1 > i ' '
4.00
CD-ROM
8015B-22
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FIGURE 2
CHROMATOGRAM OF A 30 PPM DIESEL STANDARD
abundance
35000-
30000-
25000-
20000-
15000-
10000-
'.
5000-
TIC: 523002.D
0-
o-Terphenyl
(surrogate)
rime-->0.00 5.00 10.00 15.00 20.00 25.00 30.00
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FIGURE 3
CHROMATOGRAM OF A 30 PPM DIESEL STANDARD WITH THE
BASELINE PROJECTED BETWEEN C10 AND C18
10.00
20.00
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FIGURE 4
CHROMATOGRAM OF SEVERAL NONPURGEABLE VOLATILE COMPOUNDS IN
SPIKED REAGENT WATER USING AZEOTROPIC MICRODISTILLATION (METHOD 5031)
OUBdOjdOS|OJOn|JBX6l| 'S'l
louejnq-1. i
louedojd-(.-
8U6XO|p-t' I
J
euojaoe
— 10
Mix 1:
Conditions:
Analytes distilled at 0.25mg/L, Internal Stds. at 2.5 mg/L
J&W DB-Wax column with 0.53 ID
Temperature program: 30°C for 2 min.
3°C/min. to 100°C and held for 0 min.
25°C/min. to 200°C and held for 4 min.
CD-ROM
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December 1996
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FIGURE 5
CHROMATOGRAM OF SEVERAL NONPURGEABLE VOLATILE COMPOUNDS IN
SPIKED REAGENT WATER USING AZEOTROPIC MICRODISTILLATION (METHOD 5031)
Mix 2: Analytes distilled at 0.25mg/L, Internal Stds. at 2.5 mg/L
Conditions: J&W DB-Wax column with 0.53 ID
Temperature program: 30°C for 2 min.
3°C/min. to 100°C and held for 0 min.
25°C/min. to 200°C and held for 4 min.
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METHOD 8015B
NONHALOGENATED ORGANICS USING GC/FID
1
7.2
f
Set chromatographic conditions.
7.3.2 and 7.3.3 SBO Method
8000 for guidance on
external standard calibration.
7.3
Initial
Calibration;
Internal or
External?
Analysis
lor individual
analytes or
fuels?
7.3.3.1 Prepare 5
initial calibration standards
for each fuel type.
7.3.3.2 Introduce each
standard into GC using
technique to be used for
actual samples. Calculate
CF.
7.3 1 See Method 8000
for guidance on internal
standard calibration.
7.3.2.1 Prepare 5
initial calibration standards
containing each analyta
of interest
7.3.2.2 Introduce each
standard into GC using
technique to be used for
actual samples. Calculate
CF.
< 20% over
the working
range?
What is
the percent
relative std.
deviation
of the
CF?
7.3.4.1 Use the
average calibration
(actor from initial
calibration.
> 20% over
the working
range?
7.3.4.2 See Method
8000 for other
calibration options.
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METHOD 8015B
(continued)
7.4 Establish RT windows for
individual compounds or
establish RT ranges for
GROs and DROs.
>
t
7.6.1 Perform
chromatographic
analysis of samples.
Recalibrate instruments,
see Method 8000.
Check system and
reanalyze. Saa Method
8000 for additional
guidance.
7.6.3
Does sample
response exceed
limits of initial
calibration?
7.6.3 Dilute sample
and reanalyze.
Individual
Analysis \ Analytes
of individual
analytes or
fuels?
7.6.4 Confirm ID of
individual compounds
on a 2nd column or
GC/MS.
7.6.5 If analytical
interferences are
indicated, analyze on a
2nd column.
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00
o
-------
METHOD 8020
AROMATIC VOLATILE ORGANICS
1.0 SCOPE AND APPLICATION
1.1 Method 8020 1s used to determine the concentration of various
aromatic volatile organic compounds. Table 1 Indicates compounds which may be
determined by this method and lists the method detection limit for each
compound 1n reagent water. Table 2 lists the practical quantltation limit
(PQL) for other matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8020 provides chromatographlc conditions for the detection of
aromatic volatile compounds. Samples can be analyzed using direct Injection
or purge-and-trap (Method 5030). Ground water samples must be determined
using Method 5030. A temperature program 1s used 1n the gas chromatograph to
separate the organic compounds. Detection 1s achieved by a photo-1on1zation
detector (PID).
2.2 If Interferences are encountered, the method provides an optional
gas chromatographlc column that may be helpful 1n resolving the analytes from
the interferences and for analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Method 5030 and 8000.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A field sample blank prepared
from reagent water and carried through sampling and subsequent storage and
handling can serve as a check on such contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph:
4.1.1 Gas Chromatograph: Analytical system complete with gas
chromatograph suitable for on-column injections or purge-and-trap sample
introduction and all required accessories, Including detectors, column
supplies, recorder, gases, and syringes. A data system for measuring
peak heights and/or peak areas is recommended.
8020 - 1
Revision 0
Date September 1986
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TABLE 1. CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS FOR AROMATIC
VOLATILE ORGANICS
Compound
Benzene
Chlorobenzene
1 ,4-Dichlorobenzene
1 , 3-Dichlorobenzene
1,2-Dichlorobenzene
Ethyl Benzene
Toluene
Xylenes
Retention
(m1n)
Col. 1
3.33
9.17
16.8
18.2
25.9
8.25
5.75
time
Col. 2
2.75
8.02
16.2
15.0
19.4
6.25
4.25
Method
detection
limit3
(ug/L)
0.2
0.2
0.3
0.4
0.4
0.2
0.2
a Using purge-and-trap method (Method 5030).
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES3
Matrix Factorb
Ground water 10
Low-level soil 10
Water miscible liquid waste 500
High-level soil and sludge 1250
Non-water miscible waste 1250
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
bPQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor 1s on a wet-weight basis.
8020 - 2
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4.1.2 Columns:
4.1.2.1 Column 1: 6-ft x 0.082-1n I.D. 1304 stainless steel
or glass column packed with 5% SP-1200 and 1.75% Bentone-34 on
100/120 mesh Supelcort or equivalent.
4.1.2.2 Column 2: 8-ft x O.l-1n I.D. stainless steel or glass
column packed with 5% 1,2,3-Tr1s(2-cyanoethoxy)propane on 60/80 mesh
Chromosorb W-AW or equivalent.
4.1.3 Detector: Photoion1zat1on (PID) (h-Nu Systems, Inc. Model
PI-51-02 or equivalent).
4.2 Sample introduction apparatus; Refer to Method 5030 for the
appropriate equipment for sample introduction purposes.
4.3 Syringes; A 5-mL Luerlok glass hypodermic and a 5-mL, gas-tight
with shutoff valve.
4.4 Volumetric flask: 10-, 50-, 100-, 500-, and 1,000-mL with a ground-
glass stopper.
4.5 Microsyringe; 10- and 25-uL with a 0.006-1n I.D. needle (Hamilton
702N or equivalent) and a 100-uL.
5.0 REAGENTS
5.1 Reagent water; Reagent water 1s defined as
interferent is not observed at the method detection
parameters of interest.
a water in which an
limit (MOL) of the
5.2 Stock standards: Stock solutions may be prepared from pure standard
materials or .purchased as certified solutions. Prepare stock standards in
methanol using assayed liquids. Because of the toxlclty of benzene and 1,4-
dichlorobenzene, primary dilutions of these materials should be prepared in a
hood.
5.2.1 Place about 9.8 ml of methanol 1n a 10-mL tared ground-glass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 min or until all alcohol-wetted surfaces have dried. Weigh the
flask to the nearest 0.1 mg.
5.2.2 Using a 100-uL syringe, Immediately add two or more drops of
assayed reference material to the flask; then rewelgh. The liquid must
fall directly into the alcohol without contacting the neck of the flask.
5,2.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in micrograms per
microliter (ug/uL) from the net gain in weight. When compound purity is
assayed to be 96% or greater, the weight may be used without correction
8020 - 3
Revision 0
Date September 1986
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to calculate the concentration of the stock standard. Commercially
prepared stock standards may be used at any concentration if they are
certified by the manufacturer or by an independent source.
5.2.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store, with minimal headspace, at 4*C and protect from
light.
5.2.5 All standards must be replaced after 6 months, or sooner if
comparison with check standards indicates a problem.
5.3 Secondary dilution standards: Using stock standard solutions, pre-
pare in methanol secondarydilution standards, as needed, that contain the
compounds of interest, either singly or mixed together. The secondary
dilution standards should be prepared at concentrations such that the aqueous
calibration standards prepared in Paragraph 5.4 will bracket the working range
of the analytical system. Secondary dilution standards should be stored with
minimal headspace for volatiles and should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.4 Calibration standards; Calibration standards at a minimum of five
concentration levels are prepared in reagent water from the secondary dilution
of the stock standards. One of the concentration levels should be at a
concentration near, but above, the method detection limit. The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should define the working range of the GC. Each
standard should contain each analyte for detection by this method (e.g., some
or all of "the compounds listed in Table 1 may be included). In order to
prepare accurate aqueous standard solutions, the following precautions must be
observed.
5.4.1 Do not inject more than 20 uL of alcoholic standards Into 100
ml of reagent water.
5.4.2 Use a 25-uL Hamilton 702N microsyringe or equivalent
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of methanolic standards into water).
5.4.3 Rapidly inject the alcoholic standard into the filled
volumetric flask. Remove the needle as fast as possible after injection.
5.4.4 Mix aqueous standards by inverting the flask three times
only.
5.4.5 Fill the sample syringe from the standard solution contained
in the expanded area of the flask (do not use any solution contained in
the neck of the flask).
8020 - 4
Revision 0
Date September 1986
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5.4.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.4.7 Aqueous standards are not stable and should be discarded
after 1 hr, unless properly sealed and stored. The aqueous standards can
be stored up to 24 hr, if held in sealed vials with zero headspace.
5.5 Internal standards (If Internal standard calibration 1s used): To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of Interest. The analyst
must further demonstrate that the measurement of the Internal standard is not
affected by method or matrix interferences. Because of these limitations, no
Internal standard can be suggested that is applicable to all samples. The
compound, alpha,alpha,alpha-trifluorotoluene recommended for use as a
surrogate spiking compound (Paragraph 5.6) has been used successfully as an
internal standards.
5.5.1 Prepare calibration standards at a minimum of five
concentration levels for each parameter of interest as described in
Section 5.4.
5.5.2 Prepare a spiking solution containing each of the internal
standards using the procedures described In Sections 5.2 and 5.3. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 ug/mL of each Internal standard compound. The
addition of 10 uL of this standard to 5.0 ml of sample or calibration
standard would be equivalent to 30 ug/L.
5.5.3 Analyze each calibration standard according to Section 7.0,
adding 10 uL of internal standard spiking solution directly to the
syringe.
5.6 Surrogate standards; The analyst should monitor both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix by spiking each sample, standard, and reagent
water blank with surrogate compounds (e.g, alpha,alpha,alpha-trifluorotoluene)
recommended to encompass the range of the temperature program used in this
method. From stock standard solutions prepared as in Section 5.2, add a
volume to give 750 ug of each surrogate to 45 ml of reagent water contained in
a 50-mL volumetric flask, mix, and dilute to volume for a concentration of
15 ng/uL. Add 10 uL of this surrogate spiking solution directly into the 5-mL
syringe with every sample and reference standard analyzed. If the internal
standard calibration procedure is used, the1 surrogate compounds may be added
directly to the internal standard spiking solution (Paragraph 5.5.2).
5.7 Methanol; pesticide quality or equivalent. Store away from other
solvents.
8020 - 5
Revision 0
Date September 1986
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6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Volatile compounds are Introduced Into the gas chromatograph either
by direct Injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-level contaminated soils and
sediments. For medium-level soils or sediments, methanollc extraction, as
described 1n Method 5030, may be necessary prior to purge-and-trap analysis.
7.2 Gas chromatography conditions (Recommended);
7.2.1 Column 1: Set helium gas flow at 36 mL/m1n flow rate. The
temperature program sequences are as follows: For lower boiling
compounds, operate at 50*C Isothermal for 2 m1n; then program at 6*C/m1n
to 90*C and hold until all compounds have eluted. For higher boiling
range of compounds, operate at 50*C Isothermal for 2 m1n; then program at
3*C/m1n to 110*C and hold until all compounds have eluted. Column 1
provides outstanding separations for a wide variety of aromatic
hydrocarbons. Column 1 should be used as the primary analytical column
because of Its unique ability to resolve para-, meta-, and ortho-aromatic
Isomers.
7.2.2 Column 2: Set helium gas flow at 30 mL/m1n flow rate. The
temperature program sequence 1s as follows: 40*C Isothermal for 2 nrin;
then 2*C/m1n to 100'C and hold until all compounds have eluted. Column
2, an extremely high-polarity column, has been used for a number of years
to resolve aromatic hydrocarbons from alkanes 1n complex samples.
However, because resolution between some of the aromatlcs 1s not as
efficient as with Column 1, Column 2 should be used as a confirmatory
column.
7.3 Calibration; Refer to Method 8000 for proper calibration
techniques. Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 Calibration must take place using the same sample
Introduction method that will be used to analyze actual samples (see
Section 7.4.1).
7.3.2 The procedure for Internal or external calibration may be
used. Refer to Method 8000 for a description of each of these
procedures.
8020 - 6
Revision
Date September 1986
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7.4 Gas chromatographic analysis;
7.4.1 Introduce volatile compounds Into the gas chromatograph using
either Method 5030 (purge-and-trap method) or the direct injection
method. If the internal standard calibration technique is used, add
10 uL of internal standard to the sample prior to purging.
7.4.1.1 Direct Injection; In very limited applications (e.g.,
aqueous process wastes), direct Injection of the sample Into the GC
system with a 10 uL syringe may be appropriate. The detection limit
is very high (approximately 10,000 ug/L); therefore, it is only
permitted when concentrations in excess of 10,000 ug/L are expected
or for water-soluble compounds that do not purge. The system must
be calibrated by direct Injection (bypassing the purge-and-trap
device).
7.4.2 Follow Section 7.6 of Method 8000 for Instructions on the
analysis sequence, appropriate dilutions, establishing dally retention
time windows, and identification criteria. Include a mid-level standard
after each group of 10 samples 1n the analysis sequence.
7.4.3 Table 1 summarizes the estimated retention times and
detection limits for a number of organic compounds analyzable using this
method. An example of the separation achieved by Column 1 1s shown in
Figure 1. Figure 2 shows an example of the separation achieved using
Column 2.
7.4.4 Record the sample volume purged or Injected and the resulting
peak sizes (1n area units or peak heights).
7.4.5 Calculation of concentration 1s covered ir Section 7.8 of
Method 8000.
7.4.6 If analytical interferences are suspected, or for the purpose
of confirmation, analysis using the second GC column 1s recommended.
7.4.7 If the response for a peak is off-scale, prepare a dilution
of the sample with reagent water. The dilution must be performed on a
second aliquot of the sample which has been properly sealed and stored
prior to use.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.
8.2 Mandatory quality control to validate the GC system operation is
found in Method 8000, Section 8.6.
8020 - 7
Revision 0
Date September 1986
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Column: 6% SP-1200/1.75% Bottom 34
Program. 60°C-2 Minum. 6°C/Min. to 00°C
D«ttctor: Phototoniiation
Sample: 0.40 pg/1 Standard Mixture
CO
o
rv>
o
CO
n>
GO O
fO 3
cr
a to 12 M
RETENTION TIME (MINUTES)
16
18
20
vo
CO
Figure 1. Chromatogram of aromatic volatile organic* (column 1 conditions).
-------
Column: S* 1 JJ-Trii (2-Cvanecthoxy)
Prooww on Chromotorb—W
Program: 40°C-2 MinutM 2»C/M»n. to 100°C
Ovnetor: fttotoionization
Scmpit: 2.0^8/1 Sundard Mixturt
I 12 16
RETENTION TIME (MINUTES)
24
Figurt 2. Chrprwogrim of iromf tic volatile organic* (column 2 conditioru).
8020 - 9
Revision 0
Date September 1986
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8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each parameter of Interest at a concentration
of 10 ug/mL in methanol.
8.2.2 Table 3 indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as
functions of concentration for the analytes of interest. The contents of
both Tables should be used to evaluate a laboratory's ability to perform
and generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (limits established by
performing QC procedure outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following is required.
• Check to be sure there are no errors in calculations,
surrogate solutions and Internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample 1f none of the above are
a problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 This method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked at six
concentrations over the range 2.1-500 ug/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to
the concentration of the parameter and essentially Independent of the sample
matrix. Linear equations to describe these relationships are presented in
Table 4.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and by the calibration procedure used.
10.0 REFERENCES
1. Bellar, T.A., and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
pp. 739-744, 1974.
2. Bellar, T.A., and J.J. Lichtenberg, Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds, in Van Hall (ed.), Measurement of Organic Pollutants in Water and
Wastewater, ASTM STP 686, pp. 108-129, 1979.
8020 - 10
Revision 0
Date September 1986
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3. Dowty, B.J., S.R. Antolne, and J.L. Laseter, "Quantitative and Qualitative
Analysis of Purgeable Organlcs by High Resolution Gas Chromatography and Flame
lonization Detection," 1n Van Hall, ed., Measurement of Organic Pollutants 1n
Water and Wastewater. ASTM STP 686, pp. 24-35, 1979.
4. Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters. Category 11 - Purgeables and Category 12 -
Acroleln, Acrylon1tr1le, and D1chlorod1fluoromethane. Report for EPA Contract
68-03-2635 (1n preparation).
5. "EPA Method Validation Study 24, Method 602 (Purgeable Aromatlcs)," Report
for EPA Contract 68-03-2856 (in preparation).
6. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
7. Provost, L.P., and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 1_5, pp. 58-63, 1983.
8020 - 11
Revision
Date September 1986
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TABLE 3. CALIBRATION AND QC ACCEPTANCE CRITERIA3
Parameter
Benzene
Chlorobenzene
l,2-D1chlorobenzene
1,3-Di chlorobenzene
l,4-D1chlorobenzene
Ethylbenzene
Toluene
Range
for Q
(ug/L)
15.4-24.6
16.1-23.9
13.6-26.4
14.5-25.5
13.9-26.1
12.6-27.4
15.5-24.5
L1ra1t
for s
(ug/L)
4.1
3.5
5.8
5.0
5.5
6.7
4.0
Range
for 7.
(ug/L)
10.0-27.9
12.7-25.4
10.6-27,6
12.8-25.5
11.6-25.5
10.0-28.2
11.2-27.7
Range
P. PS
(X)
39-150
55-135
37-154
50-141
42-143
32-160
46-148
Q = Concentration measured 1n QC check sample, 1n ug/L.
s = Standard deviation of four recovery measurements, 1n ug/L.
7 = Average recovery for four recovery measurements, 1n ug/L.
P, PS = Percent recovery measured.
aCr1ter1a are from 40 CFR Part 136 for Method 602 and were calculated
assuming a QC check sample concentration of 20 ug/L. These criteria are based
directly upon the method performance data 1n Table 4. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 1.
8020 - 12
Revision 0
Date September 1986
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TABLE 4. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION
Parameter
Benzene
Chlorobenzene
l,2-D1chlorobenzene
l,3-D1chlorobenzene
1 , 4-D1 ch 1 orobenzene
Ethyl benzene
Toluene
Accuracy, as
recovery, x1
(ug/L)
0.92C+0.57
0.95C+0.02
0.93C+0.52
0.96C-0.04
0.93C-0.09
0.94C+0.31
0.94C+0.65
Single analyst Overall
precision, sr'
(ug/U
0.097+0.59
0.097+0.23
0.177-0.04
0.157-0.10
0.157+0.28
0.177+0.46
0.097+0.48
precision,
S1 (ug/L)
0.217+0.56
0.177+0.10
0.227+0.53
0.197+0.09
0.207+0.41
0.267+0.23
0.187-0.71
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, in ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, in ug/L.
S' = Expected interlaboratory standard deviation of measurements at an
average concentration found of 7, in ug/L.
C = True value for the concentration, in ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
8020 - 13
Revision 0
Date September 1986
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METHOD 6020
AROMATIC VOLATILE O«SANICS
C •— )
7. 1
Introduce compounds
into g«i
Chrom»tOOr«e»n by
Orect injection or
|M«tnoO 5030;
7.2
o
Set g*c
oimtog^i
condition
7.3
Ciliortte
(refer tc
603C!
7.41
Introouc* vol»tllt
eomoounai into g*>
cnrom»tOQr»ph ty
Mttnoo 5030 o-
a>r«ct injection
7.4.2
Folio-
Section 7.6
in Mitnoa 0000
for «n»ly«l»
•cauenee. etc.
volume puro«O
or tnjecteo «no
Calculate
concentration
(Section 7 . B.
eooo)
Arp •ntlytlol
inter!«r«nc»»
•UlOCCtf07
Anilyit ullng
•econa GC
COlumn
Dilute tecona
•1louot
O
8020 - 14
Revision 0
Date September 1986
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00
o
-------
METHOD 8020A
AROMATIC VOLATILE ORGAN ICS BY GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 8020 is used to determine the concentration of various
aromatic volatile organic compounds. The following compounds can be determined
by this method:
Appropriate Technique
Direct
Compound Name CAS No.a Purge-and-Trap Injection
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1, 4 -Di chlorobenzene
Ethyl benzene
Toluene
Xylenes
a Chemical Abstract
b adequate response
71-43-2
108-90-7
95-50-1
541-73-1
106-46-7
100-41-4
108-88-3
Services Registry Number.
by this technique.
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
1.2 Table 1 lists the method detection limit for each target analyte in
organic-free reagent water. Table 2 lists the estimated quantitation limit (EQL)
for other matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8020 provides chromatographic conditions for the detection of
aromatic volatile compounds. Samples can be introduced into the GC using direct
injection or purge-and-trap (Method 5030). Ground water samples must be
determined using Method 5030. A temperature program is used in the gas
chromatograph to separate the organic compounds. Detection is achieved by a
photo-ionization detector (PID).
2.2 If interferences are encountered, the method provides an optional gas
chromatographic column that may be helpful in resolving the analytes from the
interferences and for analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Method 5030 and 8000.
8020A - 1 Revision 1
September 1994
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3.2 Samples can be contaminated by diffusion of volatile organics
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A field sample blank prepared from
organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas Chromatograph - Analytical system complete with gas
chromatograph suitable for on-column injections or purge-and-trap sample
introduction and all required accessories, including detectors, column
supplies, recorder, gases, and syringes. A data system for measuring peak
heights and/or peak areas is recommended.
4.1.2 Columns
4.1.2.1 Column 1: 6 ft x 0.082 in ID #304 stainless steel
or glass column packed with 5% SP-1200 and 1.75% Bentone-34 on
100/120 mesh Supelcoport, or equivalent.
4.1.2.2 Column 2: 8 ft x 0.1 in ID stainless steel or
glass column packed with 5% l,2,3-Tris(2-cyanoethoxy)propane on
60/80 mesh Chromosorb W-AW, or equivalent.
4.1.3 Detector - Photoionization (PID) (h-Nu Systems, Inc. Model
PI-51-02 or equivalent).
4.2 Sample introduction apparatus - Refer to Method 5030 for the
appropriate equipment for sample introduction purposes.
4.3 Syringes - A 5 ml Luerlok glass hypodermic and a 5 ml, gas-tight with
shutoff valve.
4.4 Volumetric flask, Class A - Appropriate sizes with ground glass
stoppers.
4.5 Microsyringe - 10 and 25 p.1 with a 0.006 in ID needle (Hamilton 702N
or equivalent) and a 100 juL.
4.6 Analytical balance - 0.0001 g.
5.0 REAGENTS
5.1 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2 Methanol (CH3OH) - pesticide quality or equivalent. Store away from
other solvents.
8020A - 2 Revision 1
September 1994
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5.3 Stock standards - Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standards in
methanol using assayed liquids. Because of the toxicity of benzene and
1,4-dichlorobenzene, primary dilutions of these materials should be prepared in
a hood.
5.3.1 Place about 9.8 ml of methanol in a 10 ml tared ground glass
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 min or until all alcohol wetted surfaces have dried. Weigh the
flask to the nearest 0.0001 g.
5.3.2 Using a 100 /xL syringe, immediately add two or more drops of
assayed reference material to the flask; then reweigh. The liquid must
fall directly into the alcohol without contacting the neck of the flask.
5.3.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in milligrams per
liter (mg/L) from the net gain in weight. When compound purity is assayed
to be 96% or greater, the weight may be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.3.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store, with minimal headspace, at 4°C and protect from
light.
5.3.5 All standards must be replaced after 6 months, or sooner if
comparison with check standards indicates a problem.
5.4 Secondary dilution standards: Using stock standard solutions,
prepare in methanol secondary dilution standards, as needed, that contain the
compounds of interest, either singly or mixed together. The secondary dilution
standards should be prepared at concentrations such that the aqueous calibration
standards prepared in Section 5.5 will bracket the working range of the
analytical system. Secondary dilution standards should be stored with minimal
headspace for volatiles and should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards from
them.
5.5 Calibration standards: Calibration standards at a minimum of five
concentrations are prepared in organic-free reagent water from the secondary
dilution of the stock standards. One of .the concentrations should be at a
concentration near, but above, the method detection limit. The remaining
concentrations should correspond to the expected range of concentrations found
in real samples or should define the working range of the GC. Each standard
should contain each analyte for detection by this method (e.g., some or all of
the compounds listed in the target analyte list may be included). In order to
prepare accurate aqueous standard solutions, the following precautions must be
observed.
8020A - 3 Revision 1
September 1994
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5.5.1 Do not inject more than 20 juL of alcoholic standards into
100 ml of organic-free reagent water.
5.5.2 Use a 25 /iL Hamilton 702N microsyringe or equivalent
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of methanolic standards into water).
5.5.3 Rapidly inject the alcoholic standard into the filled
volumetric flask. Remove the needle as fast as possible after injection.
5.5.4 Mix aqueous standards by inverting the flask three times only.
5.5.5 Fill the sample syringe from the standard solution contained
in the expanded area of the flask (do not use any solution contained in
the neck of the flask) .
5.5.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.5.7 Aqueous standards are not stable and should be discarded after
1 hr, unless properly sealed and stored. The aqueous standards can be
stored up to 24 hr, if held in sealed vials with zero headspace.
5.6 Internal standards (if internal standard calibration is used): To
use this approach, the analyst must select -one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
Alpha, alpha, alpha-trifluorotoluene has been used successfully as an internal
standard.
5.6.1 Prepare calibration standards at a minimum of five
concentrations for each parameter of interest as described in Section 5.5.
5.6.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in Sections 5.3 and 5.4. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 mg/L of each internal standard compound. The addition
of 10 /iL of this standard to 5.0 ml of sample or calibration standard
would be equivalent to 30
5.6.3 Analyze each calibration standard according to Section 7.0,
adding 10 juL of internal standard spiking solution directly to the
syringe.
5.7 Surrogate standards: The analyst should monitor both the performance
of the analytical system and the effectiveness of the method in dealing with each
sample matrix by spiking each sample, standard, and organic-free reagent water
blank with surrogate compounds (bromochlorobenzene, bromofluorobenzene, 1,1,1-
tri fl uorotol uene, fluorobenzene, and difluorobenzene are recommended) which
encompass the range of the temperature program used in this method. From stock
8020A - 4 Revision 1
September 1994
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standard solutions prepared as in Section 5.3, add a volume to give 750 /jg of
each surrogate to 45 mi of organic-free reagent water contained in a 50 ml
volumetric flask, mix, and dilute to volume for a concentration of 15 ng//zL.
Add 10 juL of this surrogate spiking solution directly into the 5 ml syringe with
every sample and reference standard analyzed. If the internal standard
calibration procedure is used, the surrogate compounds may be added directly to
the internal standard spiking solution (Section 5,6.2).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Volatile compounds are introduced into the gas chromatograph either
by direct injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-concentration contaminated soils and
sediments. For medium-concentration soils or sediments, methanolic extraction,
as described in Method 5030, may be necessary prior to purge-and-trap analysis.
Method 5030 also provides guidance on the analysis of aqueous miscible and non-
aqueous miscible liquid wastes (see Section 7.4.1.1 below).
7.2 Gas chromatography conditions (Recommended):
7.2.1 Column 1:
Carrier gas (He) flow rate:
For lower boiling compounds
Initial temperature:
Temperature program:
36 mL/min
50°C, hold for 2
50°C to 90°C at
hold until
mm;
6°C/mi n,
all compounds have eluted.
For higher boiling range of compounds:
Initial temperature: 50°C, hold for 2 min;
Temperature program: 50°C to 110°C at 3°C/min, hold until
all compounds have eluted
Column i pruv11
aromatic hydrocarbons
column because of --i~
aromatic isomers
1 provides outstanding separations for a wide variety of
ocarbons. Column 1 should be used as the primary analytical
e of its unique ability to resolve para-, meta-, and ortho-
ers.
7.2.2 Column 2:
Carrier gas (He) flow
Initial temperature:
Temperature program:
rate: 30 mL/min
40°C, hold for 2 min;
40°C to 100°C at 2°C/min, hold until
all compounds have eluted.
8020A - 5
Revision 1
September 1994
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Column 2, an extremely high polarity column, has been used for a
number of years to resolve aromatic hydrocarbons from alkanes in complex
samples. However, because resolution between some of the aromatics is not
as efficient as with Column 1, Column 2 should be used as a confirmatory
column.
7.3 Calibration: Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.
7.3.1 Calibration must take place using the same sample introduction
method that will be used to analyze actual samples (see Section 7.4.1).
7.3.2 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these procedures.
7.4 Gas chromatographic analysis:
7.4.1 Introduce volatile compounds into the gas chromatograph using
either Method 5030 (purge-and-trap method) or the direct injection method.
If the internal standard calibration technique is used, add 10 p,l of
internal standard to the sample prior to purging.
7.4.1.1 Direct injection: In very limited applications
(e.g., aqueous process wastes),- direct injection of the sample into
the GC system with a 10 /iL syringe may be appropriate. The
detection limit is very high (approximately 10,000 juQ/L); therefore,
it is only permitted when concentrations in excess of 10,000 /zg/L
are expected or for water soluble compounds that do not purge. The
system must be calibrated by direct injection (bypassing the purge-
and-trap device).
Non-aqueous miscible wastes may also be analyzed by direct
injection if the concentration of target analytes in the sample
falls within the calibration range. If dilution of the sample is
necessary, follow the guidance for High Concentration samples in
Method 5030, Section 7.3.3.2.
7.4.2 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria. Include a mid-concentration standard after each
group of 10 samples in the analysis sequence.
7.4.3 Table 1 summarizes the estimated retention times and detection
limits for a number of organic compounds analyzable using this method. An
example of the separation achieved by Column 1 is shown in Figure 1.
Figure 2 shows an example of the separation achieved using Column 2.
7.4.4 Record the sample volume purged or injected and the resulting
peak sizes (in area units or peak heights).
7.4.5 Calculation of concentration is covered in Method 8000.
8020A - 6 Revision 1
September 1994
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7.4.6 If analytical interferences are suspected, or for the purpose
of confirmation, analysis using the second GC column is recommended.
7.4.7 If the response for a peak is off scale, i.e., beyond the
calibration range of the standards, prepare a dilution of the sample with
organic-free reagent water. The dilution must be performed on a second
aliquot of the sample which has been properly sealed and stored prior to
use.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.
8.2 Quality control required to validate the GC system operation is found
in Method 8000.
8.2.1 The quality control check sample concentrate (Method 8000)
should contain each parameter of interest at a concentration of 10 mg/L
in methanol.
8.2.2 Table 3 indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as functions
of concentration for the analytes of interest. The contents of both
tables should be used to evaluate a laboratory's ability to perform and
generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (limits established by performing
QC procedure outlined in Method 8000).
8.3.1 If recovery is not within limits, the following is required.
• Check to be sure that there are no errors in
calculations, surrogate solutions and internal
standards. Also, check instrument performance.
• Recalculate the data and/or reanalyze the extract if any
of the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above
are a problem or flag the data as "estimated
concentration".
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9.0 METHOD PERFORMANCE
9.1 This method was tested by 20 laboratories using organic-free reagent
water, drinking water, surface water, and three industrial wastewaters spiked at
six concentrations over the range 2.1 - 500 jug/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to the
concentration of the parameter and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 4.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and by the calibration procedure used.
9.3 The method detection limits reported in Table 1 were generated under
optimum analytical conditions by an Agency contractor (Ref. 7) as guidance, and
may not be readily achievable by all laboratories at all times.
10.0 REFERENCES
1.
2.
3.
4.
5.
6.
7.
Bellar, T.A.
pp. 739-744,
and J.J.
1974.
Lichtenberg, J. Amer. Water Works Assoc., 66(12),
Bellar, T.A., and J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds", in Van Hall (ed.), Measurement of Organic Pollutants in Water
and Wastewater, ASTM STP 686, pp. 108-129, 1979.
Dowty, B.J., S.R. Antoine, and J.L. Laseter, "Quantitative and Qualitative
Analysis of Purgeable Organics by High Resolution Gas Chromatography and
Flame lonization Detection", in Van Hall, ed., Measurement of Organic
Pollutants in Water and Wastewater. ASTM STP 686, pp. 24-35, 1979.
Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters. Category 11 - Purgeables and Category 12 -
Acrolein, Acrylonitrile, and Dichlorodifluoromethane. Report for EPA
Contract 68-03-2635.
"EPA Method Validation Study 24, Method 602 (Purgeable Aromatics)", report
for EPA Contract 68-03-2856.
U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
Final Rule and Proposed Rule", October 26, 1984.
Gebhart, J.E., S.V. Lucas, S.J. Naber, A.M. Berry, T.H. Danison and H.M.
Burkholder, "Validation of SW-846 Methods 8010, 8015, and 8020"; Report
for EPA Contract 68-03-1760, Work Assignment 2-15; US EPA, EMSL-
Cincinnati, 1987."
8020A - 8
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TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
FOR AROMATIC VOLATILE ORGANICS
Compound
Benzene
Chlorobenzeneb
1,4-Dichlorobenzene
1,3-Dichlorobenzene
1,2-Dichlorobenzene
Ethyl Benzene
Toluene
Xylenes
Retention
(min)
Col . 1
3.33
9.17
16.8
18.2
25.9
8.25
5.75
time
Col . 2
2.75
8.02
1-6.2
15.0
19.4
6.25
4.25
Method
detection
limit8
(M9/L)
0.2
0.2
0.3
0.4
0.4
0.2
0.2
a Using purge-and-trap method (Method 5030). See Sec. 9.3
b Chlorobenzene and m-xylene may co-elute on some columns
TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQLs)
FOR VARIOUS MATRICES8
Matrix
Factor
Ground water
Low-concentration soil
Water miscible liquid waste
High-concentration soil and sludge
Non-water miscible waste
10
10
500
1250
1250
EQL = [Method detection limit (see Table 1)] X [Factor found in this
table]. For non-aqueous samples, the factor is on a wet-weight basis.
Sample EQLs are highly matrix-dependent. The EQLs determined herein are
provided for guidance and may not always be achievable.
8020A - 9
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TABLE 3.
QC ACCEPTANCE CRITERIA8
Parameter
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1, 3 -Di chlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
Toluene
Range
for Q
(M9/L)
15.4-24.6
16.1-23.9
13.6-26.4
14.5-25.5
13.9-26.1
12.6-27.4
15.5-24.5
Limit
for s
(M9/L)
4.1
3.5
5.8
5.0
5.5
6.7
4.0
Range
for x
(M9/L)
10.0-27.9
12.7-25.4
10.6-27.6
12.8-25.5
11.6-25.5
10.0-28.2
11.2-27.7
Range
P> PS
(%)
39-150
55-135
37-154
50-141
42-143
32-160
46-148
Q
s
x
P,
a
Concentration measured in QC check sample, in M9/L-
Standard deviation of four recovery measurements, in M9/L-
Average recovery for four recovery measurements, in ^g/L.
Percent recovery measured.
Criteria from 40 CFR Part 136 for Method 602, using packed columns, and
were calculated assuming a check sample concentration of 20 jug/L. These
criteria are based directly upon the method performance data in Table 4.
Where necessary, the limits for recovery have been broadened to assure
applicability of the limits to concentrations below those used to develop
Table 1. When capillary columns are used, see Method 8021 for performance
data.
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TABLE 4.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION
Parameter
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
Toluene
Accuracy, as
recovery, x'
(M9/L)
0.92C+0.57
0.95C+0.02
0.93C+0.52
0.96C-0.04
0.93C-0.09
0.94C+0.31
0.94C+0.65
Single analyst
precision, sf'
(M9/L)
0.09X+0.59
0.09X+0.23
0.17X-0.04
0.15X-0.10
0.15X+0.28
O.Ux+0.46
0.09X-I-0.48
Overall
precision,
S' (M9/L)
0.21X+0.56
0.17X+0.10
0.22X+0.53
0.19X+0.09
0.20X+0.41
0.26X+0.23
O.lSx+0.71
sr'
S'
C
x
Expected recovery for one or more measurements of a sample
containing concentration C, in jug/L.
Expected single analyst standard deviation of measurements at an
average concentration of x, in
Expected interlaboratory standard deviation of measurements at an
average concentration found of x, in
True value for the concentration, in /zg/L.
Average recovery found for measurements of samples containing a
concentration of C, in jug/L.
8020A - 11
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Figure 1
Chromatogram of Aromatic Volatile Organics
(column 1 conditions)
I
Column:
Program:
Detector
Sample:
5% SP-1200/1.75% Bentone 34
50°C-2 Minutes, 6°C/Min. to 90°C
Photoionization
0.40 lig/L Standard Mixture
U-J
i
8 10 12 14
RETENTION TIME (MINUTES)
16
ta
20
22
8020A - 12
Revision 1
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Figure 2
Chromatogram of Aromatic Volatile Organics
(column 2 conditions)
Column:
Program:
Detector:
Sample:
5% l,2,3-Tris(2-Cyanoethoxy)Propane on Chromosorb-W
40°C-2 Minutes, 2'C/Min. to lOO'C
Photoionization
2.0 ^g/L Standard Mixture
I 12 If 30
MffTtNTtON Tttlf (MINUTES)
24
8020A - 13
Revision 1
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METHOD 8020A
AROMATIC VOLATILE ORGANICS BY GAS CHROMATOGRAPHY
Start
7.1 Introduce compounds
into gas chromatograph
by direct injection or
purge-end-trap
(Method 5030)
7.2 Set gas
chromatograph
condition.
7.3 Calibrate
(refer to Method SOOO)
7.4.1 Introduce
volatile compounds
into gas chromatograph
by purge-and-trap or
direct injection.
7.4.2 Follow Method
8000 for analysis
sequence, etc.
7.4.4 R-ecord volume
purged or injected
and peak sizes.
7.4.5 Calculate
concentration
(refer to Method 8000)
7.4.6 Ar«
analytical
interferences
suspected?
7.4.7 Is
response for
a peak
off-scale?
7.4.6 Analyze using
second GC column.
7.4.7 Dilute second
aliquot of sample.
8020A -14
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00
o
-------
METHOD 8021
HALOGENATED VQLATILES BY GAS CHROMATOGRAPHY USING
PHOTOIONIZATIQN AND ELECTROLYTIC CONDUCTIVITY DETECTORS
IN SERIES: CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8021 is used to determine volatile organic compounds in a
variety of solid waste matrices. This method is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic liquors, acid liquors, waste solvents, oily wastes, mousses, tars,
fibrous wastes, polymeric emulsions, filter cakes, spent carbons, spent
catalysts, soils, and sediments. The following compounds can be determined by
this method:
Analyte
CAS No.a
Appropriate Technique
Direct
Purge-and-Trap Injection
Benzene
Bromobenzene
Bromochl oromethane
Bromodichloromethane
Bromoform
Bromome thane
n-Butylbenzene
sec-Butylbenzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chi orodi bromomethane
Chloroethane
Chloroform
Chi oromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2-Di bromo-3 -chl oropropane
1,2-Dibromoethane
Di bromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichlor'oethane
1,1-Oichloroethene
cis-l,2-Dichloroethene
trans -1,2-Oi chl oroethene
71-43-2
108-86-1
74-97-5
75-27-4
75-25-2
74-83-9
104-51-8
135-98-8
98-06-6
56-23-5
108-90-7
124-48-1
75-00-3
67-66-3
74-87-3
95-49-8
106-43-4
96-12-8
106-93-4
74-95-3
95-50-1
541-73-1
106-46-7
75-71-8
75-34-3
107-06-2
75-35-4
156-59-4
156-60-5
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
8021 - 1
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Analyte
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Oichloropropane
1, 1-Dichloropropene
cis-l,3-dichloropropene
trans-l,3-dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p-IsopropyKoluene
Methylene chloride
Naphthalene
n-Propylbenzene
Styrene
1,1,1 ,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
3 ,2,4-Trichlorobenzene
1,1, 1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
1,2, 4 -Tri methyl benzene
1, 3, 5 -Tri methyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
CAS No.'
78-87-5
142-28-9
590-20-7
563-58-6
10061-01-5
10061-02-6
100-41-4
87-68-3
98-82-8
99-87-6
75-09-2
91-20-3
103-65-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
87-61-6
120-82-1
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
95-63-6
108-67-8
75-01-4
95-47-6
108-38-3
106-42-3
AooroDriate
Purge-and-Trap
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
D
b
b
b
b
b
b
b
Technioue
Direct
Injection
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
a Chemical Abstract Services Registry Number.
b Adequate response by thi
pp Poor purging efficiency
i Inappropriate technique
s technique.
resulting in high
for this analyte.
EQLs.
pc Poor chromatographic behavior.
1.2 Method detection limits (MDLs) are compound dependent and vary with
purging efficiency and concentration. The MDLs for selected analytes are
presented in Table 1. The applicable concentration range of this method is
compound and Instrument dependent but is approximately 0.1 to 200 ng/L.'
Analytes that are inefficiently purged from water will not be detected when
present at low concentrations, but they can be measured with acceptable accuracy
and precision when present in sufficient amounts. Determination of some
structural isomers (i.e. xylenes) may be hampered by coelution.
8021 - 2 Revision 0
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1.3 The estimated quantisation limit (EQL) of Method 8021 for an
individual compound is approximately 1 MQ/kg (wet weight) for soil/sediment
samples, 0.1 mg/kg (wet weight) for wastes, and 1 ng/l for ground water (see
Table 3). EQLs will be proportionately higher for sample extracts and samples
that require dilution or reduced sample size to avoid saturation of the detector.
1.4 This method is recommended for use only by analysts experienced in
the measurement of purgeable organics at low ng/L concentrations, or by
experienced technicians under the close supervision of a qualified analyst.
1.5 The toxicity or carcinogenicity of chemicals used in this method has
not been precisely defined. Each chemical should be treated as a potential
health hazard, and exposure to these chemicals should be minimized. Each
laboratory is responsible for maintaining awareness of OSHA regulations regarding
safe handling of chemicals used in this method. Additional references to
laboratory safety are available for the information of the analyst (references
4 and 6).
1.6 The following method analytes have been tentatively classified as
known or suspected human or mammalian carcinogens: benzene, carbon tetrachloride,
1,4-dichlorobenzene, 1,2-dichloroethane, hexachloro-butadiene, 1,1,2,2-
tetrachloroethane, 1,1,2-trichloroethane, chloroform, 1,2-dibromoethane,
tetrachloroethene, trichloroethene, and vinyl chloride. Pure standard materials
and stock standard solutions of these compounds should be handled in a hood. A
NIOSH/MESA approved toxic gas respirator should be worn when the analyst handles
high concentrations of these toxic compounds.
2.0 SUMMARY OF METHOD
2.1 Method 8021 provides gas chromatographic conditions for the detection
of halogenated and aromatic volatile organic compounds. Samples can be analyzed
using direct injection or purge-and-trap (Method 5030). Ground water samples
must be analyzed using Method 5030 {where applicable). A temperature program is
used in the gas chromatograph to separate the organic compounds. Detection is
achieved by a photoionization detector (PID) and an electrolytic conductivity
detector (HECD) in series.
2.2 Tentative Identifications are obtained by analyzing standards under
the same conditions used for samples and comparing resultant GC retention times.
Confirmatory information can be gained by comparing the relative response from
the two detectors. Concentrations of the identified components are measured by
relating the response produced for that compound to the response produced by a
compound that is used as an internal standard.
3.0 INTERFERENCES
3,1 Refer to Methods 5030 and 8000.
3.2 Samples can be contaminated by diffusion of volatile organics
{particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A trip blank prepared from
organic-free reagent water and carried through sampling and subsequent storage
8021 - 3 Revision 0
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and handling can serve as a check on such contamination.
4.0 APPARATUS AND MATERIALS
4.1 Sample introduction apparatus - Refer to Method 5030 for the
appropriate equipment for sample introduction purposes.
4.2 Gas Chromatograph - capable of temperature programming; equipped with
variable-constant differential flow controllers, subambient oven controller,
photoionization and electrolytic conductivity detectors connected with a short
piece of uncoated capillary tubing, 0.32-0.5 mm ID, and data system.
4.2.1 Column - 60 m x 0.75 mm 10 VOCOL wide-bore capillary column
with 1.5 jim film thickness (Supelco Inc., or equivalent).
4.2.2 Photoionization detector (PID) (Tracer Model 703, or
equivalent).
4.2.3 Electrolytic conductivity detector (HECD) (Tracor Hall Model
700-A, or equivalent).
4.3 Syringes - 5 ml glass hypodermic with Luer-Lok tips.
4.4 Syringe valves - 2-way with Luer ends (Teflon or Kel-F).
4.5 Microsyringe - 25 nL with a 2 in. x 0.006 in. ID, 22° bevel needle
(Hamilton #702N or equivalent).
4.6 Microsyringes - 10, 100 jil.
4.7 Syringes - 0.5, 1.0, and 5 ml, gas tight with sliut-off valve.
4.8 Bottles - 15 ml, Teflon lined with screw-cap or crimp top.
4.9 Analytical balance - 0.0001 g.
4.10 Refrigerator.
4.11 Volumetric flasks, Class A - 10 to 1000 ml.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all inorganic reagents shall 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 ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
8021 - 4 Revision 0
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5.3 Methanol, CH3OH - Pesticide quality or equivalent, demonstrated to
be free of analytes. Store away from other solvents.
5.4 Vinyl chloride, (99.9% pure), CH2=CHC1. Vinyl chloride is available
from Ideal Gas Products, Inc., Edison, New Jersey and from Matheson, East
Rutherford, New Jersey, as well as from other sources. Certified mixtures of
vinyl chloride in nitrogen at 1.0 and 10.0 ppm (v/v) are available from several
sources.
5.5 Stock standards - Stock solutions may either be prepared from pure
standard materials or purchased as certified solutions. Prepare stock standards
in methanol using assayed liquids or gases, as appropriate. Because of the
toxicity of some of the organohalides, primary dilutions of these materials of
the toxicity should be prepared in a hood.
5.5.1 Place about 9.8 ml of methanol in a 10 mL tared ground glass
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes until all alcohol-wetted surfaces have dried. Weigh the
flask to the nearest 0.1 mg.
5.5.2 Add the assayed reference material, as described below.
5.5.2.1 Liquids: Using a 100 ^l syringe, immediately add
two or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5.5.2.2 Gases: To prepare standards for any compounds
that boil below 30°C (e.g. bromomethane, chloroethane, chloromethane,
dichlorodifluoromethane, trichlorofluoromethane, vinyl chloride),
fill a 5 ml valved gas-tight syringe with the reference standard to
the 5.0 ml mark. Lower the needle to 5 mm above the methanol
meniscus. Slowly introduce the reference standard above the surface
of the liquid. The heavy gas rapidly dissolves in the methanol.
This may also be accomplished by using a lecture bottle equipped with
a Hamilton Lecture Bottle Septum (#86600). Attach Teflon tubing to
the side-arm relief valve and direct a gentle stream of gas into the
methanol meniscus.
5.5.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in milligrams per
liter (mg/L) from the net gain in weight. When compound purity is assayed
to be 96% or greater, the weight may be used without correction to
calculate the concentration of the .stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.5.4 Transfer the stock standard solution into a bottle with a
Teflon lined screw-cap or crimp top. Store, with minimal headspace, at -
10°C to -20°C and protect from light.
5.5.5 Prepare fresh stock standards every two months for gases.
Reactive compounds such as 2-chloroethyl vinyl ether and styrene may need
to be prepared more frequently. All other standards must be replaced
8021 - 5 Revision 0
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after six months. Both gas and liquid standards must be monitored closely
by comparison to the initial calibration curve and by comparison to QC
reference samples. It may be necessary to replace the standards more
frequently if either check exceeds a 25% difference.
5.6 Prepare secondary dilution standards, using stock standard solutions,
in methanol, as needed, that contain the compounds of interest, either singly or
mixed together. The secondary dilution standards should be prepared at
concentrations such that the aqueous calibration standards prepared in Section
5.7 will bracket the working range of the analytical system. Secondary dilution
standards should be stored with minimal headspace for volatiles and should be
checked frequently for signs of degradation or evaporation, especially just prior
to preparing calibration standards from them.
5.7 Calibration standards, at a minimum of five concentrations are
prepared in organic-free reagent water from the secondary dilution of the stock
standards. One of the concentrations should be at a concentration near, but
above, the method detection limit. The remaining concentrations should
correspond to the expected range of the concentrations found in real samples or
should define the working range of the GC. Standards (one or more) should
contain each analyte for detection by this method (e.g. some or all of the target
analytes may be included). In order to prepare accurate aqueous standard
solutions, the following precautions must be observed.
5.7.1 Do not inject more than 20 pi of alcoholic standards into
100 ml of water.
5.7.2 Use a 25 »\. Hamilton 702N microsyringe or equivalent
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of methanolic standards into water).
5.7.3 Rapidly inject the alcoholic standard into the filled
volumetric flask. Remove the needle as fast as possible after injection.
5.7.4 Mix aqueous standards by inverting the flask three times.
5.7.5 Fill the sample syringe from the standard solution contained
in the expanded area of the flask (do not use any solution contained in
the neck of the flask).
5.7.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.7.7 Aqueous standards are not stable and should be discarded after
one hour, unless properly sealed and stored. The aqueous standards can
be stored up to 12 hours, if held in sealed vials with zero headspace.
5.8 Internal standards - Prepare a spiking solution containing
fluorobenzene and 2-bromo-l-chloropropane in methanol, using the procedures
described in Sections 5.5 and 5.6. It is recommended that the secondary dilution
standard be prepared at a concentration of 5 mg/L of each internal standard
compound. The addition of 10 nl of such a standard to 5.0 ml of sample or
calibration standard would be equivalent to 10 M9/L.
8021 - 6 Revision 0
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5.9 Surrogate standards - The analyst should monitor both the performance
of the analytical system and the effectiveness of the method in dealing with each
sample matrix by spiking each sample, standard, and reagent blank with two or
more surrogate compounds. A combination of bromochloromethane, 2-bromo-l-
chloropropane and 1,4-dichlorobutane is recommended to encompass the range of the
temperature program used in this method. From stock standard solutions prepared
as in Section 5.5, add a volume to give 750 fig of each surrogate to 45 ml of
organic-free reagent water contained in a 50 ml volumetric flask, mix, and dilute
to volume for a concentration of 15 ng/juL. Add 10 nl of this surrogate spiking
solution directly into the 5 ml syringe with every sample and reference standard
analyzed. If the internal standard calibration procedure is used, the surrogate
compounds may be added directly to the internal standard spiking solution
(Section 5.8).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Volatile compounds are introduced into the gas chromatograph either
by direct injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-concentration contaminated soils and
sediments. For medium-concentration soils or sediments, methanolic extraction,
as described in Method 5030, may be necessary prior to purge-and-trap analysis.
Method 5030 also provides guidance on the analysis of aqueous miscible and non-
aqueous miscible liquid wastes (see Section 7.4.1.1 below).
7.2 Gas chromatography conditions (Recommended)
7.2.1 Set up the gas chromatograph system so that the
photoionization detector (PID) is in series with the electrolytic
conductivity detector (HECD).
7.2.2 Oven settings:
Carrier gas (Helium) Flow rate: 6 mL/min.
Temperature program
Initial temperature: 10°C, hold for 8 minutes
Program: 10°C to 180°C at 4°C/min
Final temperature: 180°C, hold until all expected
compounds have eluted.
7.2.3 The carrier gas flow is augmented with an additional 24 ml of
helium flow before entering the photoionization detector. This make-up
gas is necessary to ensure optimal response from both detectors.
7.2.4 These halogen-specific systems eliminate misidentifications
due to non-organohalides which are coextracted during the purge step. A
8021 - 7 Revision 0
July 1992
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Tracer Hall Model 700-A detector was used to gather the single laboratory
accuracy and precision data presented in Table 2. The operating
conditions used to collect these data are:
Reactor tube: Nickel, 1/16 in 00
Reactor temperature: 810°C
Reactor base temperature: 250°C
Electrolyte: 100% n-Propyl alcohol
Electrolyte flow rate: 0.8 mL/min
Reaction gas: Hydrogen at 40 mL/min
Carrier gas plus make-up gas: Helium at 30 mL/min
7.2.5 A sample chromatogram obtained with this column is presented
in Figure 5. This column was used to develop the method performance
statements in Section 9.0. Estimated retention times and MOLs that can
be achieved under these conditions are given in Table 1. Other columns
or element specific detectors may be used if the requirements of Section
8.0 are met.
7.3 Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.
7.3.1 Calibration must take place using the same sample introduction
method that will be used to analyze actual samples (see Section 7.4.1).
7.3.2 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these procedures.
7.4 Gas chromatographic analysis
7.4.1 Introduce volatile compounds into the gas chromatograph using
either Method 5030 (purge-and-trap method) or the direct injection method
(see Section 7.4.1.1). If the internal standard calibration technique is
used, add 10 juL of internal standard to the sample prior to purging.
7.4.1.1 Direct injection - In very limited applications
(e.g. aqueous process wastes) direct injection of the sample into the
GC system with a 10 nl syringe may be appropriate. The detection
limit is very high (approximately 10,000 M9/L), therefore, it is
only permitted where concentrations in excess of 10,000 ng/l are
expected or for water-soluble compounds that do not purge. The
system must be calibrated by direct injection (bypassing the purge-
and-trap device).
Non-aqueous miscible wastes may also be analyzed by direct
injection if the concentration of target analytes in the sample falls
within the calibration range. If dilution of the sample is
necessary, follow the guidance for High Concentration samples in
Method 5030, Section 7.3.3.2.
7.4.2 Follow in Method 8000 for instructions on the analysis
sequence, appropriate dilutions, establishing daily retention time
8021 - 8 Revision 0
July 1992
-------
windows, and identification criteria. Include a mid-concentration
standard after each group of 10 samples in the analysis sequence.
7.4.3 Table 1 summarizes the estimated retention times on the two
detectors for a number of organic compounds analyzable using this method.
7.4.4 Record the sample volume purged or injected and the resulting
peak sizes (in area units or peak heights).
7.4.5 Calculation of concentration is covered in Method 8000.
7.4.6 If analytical interferences are suspected, or for the purpose
of confirmation, analysis using a second GC column is recommended.
7.4.7 If the response for a peak is off-scale, prepare a dilution of
the sample with organic-free reagent water. The dilution must be
performed on a second aliquot of the sample which has been properly sealed
and stored prior to use.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures, and
Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.
8.2 Quality control required to validate the GC system operation is found
in Method 8000, Section 8.6.
8.2.1 The quality control reference sample (Method 8000, Step 8.6)
should contain each parameter of interest at a concentration of 10 mg/L
in methanol.
8.2.2 Table 2 gives method accuracy and precision as functions of
concentration for the analytes of interest.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (limits established by performing
QC procedure outlined in Method 8000, Section 8.10).
If recovery is not within limits, the following is required.
• Check to be sure there are no errors in calculations, surrogate
solutions and internal standards. Also check instrument performance.
• Recalculate the data and/or reanalyze the extract if any of the above
checks reveal a problem.
• Re-extract and re-analyze the sample if none of the above are a
problem or flag the data as "estimated concentration".
8021 - 9 Revision 0
July 1992
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9.0 METHOD PERFORMANCE
9.1 Method detection limits for these analytes have been calculated from
data collected by spiking organic-free reagent water at 0.1 ng/L. These data
are presented in Table 1.
9.2 This method was tested in a sinjgle laboratory using organic-free
reagent water spiked at 10 jigA- Single laboratory precision and accuracy data
for each detector are presented for the method analytes in Table 2.
10.0 REFERENCES
1. Volatile Organic Compounds in Water by Purqe-and-Trap Capillary Column Gas
Chromatoaraphv with Photoionization and Electrolytic Conductivity
Detectors in Series. Method 502.2; U.S. Environmental Protection Agency.
Environmental Monitoring and Support Laboratory: Cincinnati, OH,
September, 1986.
2. The Determination of Haloqenated Chemicals in Water bv the Purge and Trap
Method. Method 502.1; Environmental Protection Agency, Environmental
Monitoring and Support Laboratory: Cincinnati, Ohio 45268, September,
1986.
3. Volatile Aromatic and Unsaturated Organic Compounds in Water by Purge and
Trap Gas Chromatograohv. Method 503.1; Environmental Protection Agency,
Environmental Monitoring and Support Laboratory: Cincinnati, Ohio,
September, 1986.
4. Glaser, J.A.; Forest, D.L.; McKee, G.D.; Quave, S.A.; Budde, W.L. "Trace
Analyses for Wastewaters"; Environ. Sci. Techno!. 1981, 15, 1426.
5. Bellar, T.A.; Lichtenberg, J.J. The Determination of Synthetic Organic
Compounds in Water by Purge and Sequential Trapping Capillary Column Gas
Chromatographv; U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory: Cincinnati, Ohio, 45268.
8021 - 10 Revision 0
July 1992
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TABLE 1.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL) FOR
VOLATILE ORGANIC COMPOUNDS ON PHOTOION IZATION DETECTION (PID) AND
HALL ELECTROLYTIC CONDUCTIVITY DETECTOR (HECD) DETECTORS
Analyte
Di chl orodi f 1 uoromethane
Chloromethane
Vinyl Chloride
Bromomethane
Chloroethane
Tri chl orof 1 uoromethane
1,1-Dichloroethene
Methyl ene Chloride
trans-1 ,2-Dichloroethene
1,1-Dichloroethane
2,2-Dichloropropane
cis-1, 2 -Di chl oroethane
Chloroform
Bromochl oromethane
1,1,1 -Trichl oroethane
1,1-Dichloropropene
Carbon Tetrachloride
Benzene
1,2-Dichloroethane
Trichloroethene
1,2-Dichloropropane
Bromodi chl oromethane
Dibromomethane
Toluene
1 , 1 , 2-Trichl oroethane
Tetrachloroethene
1,3-Dichloropropane
Di bromochl oromethane
1,2-Dibromoethane
Chlorobenzene
Ethyl benzene
1,1,1, 2 -Tetrachl oroethane
m-Xylene
p-Xylene
o-Xylene
Styrene
Isopropyl benzene
Bromoform
1,1, 2, 2 -Tetrachl oroethane
1 , 2 , 3-Trichl oropropane
PID
Ret. Time8
minute
_b
-
9.88
-
_
_
16.14
-
19.30
-
-
23.11
-
.
-
25.21
-
26.10
-
27.99
-
-
_
31.95
-
33.88
-
-
-
36.56
36.72
-
36.98
36.98
38.39
38.57
39.58
-
-
-
8021 - 11
HECD
Ret. Time
minute
8.47
9.47
9.93
11.95
12.37
13.49
16.18
18.39
19.33
20.99
22.88
23.14
23.64
24.16
24.77
25.24
25.47
-
26.27
28.02
28.66
29.43
29.59
-
33.21
33.90
34.00
34.73
35.34
36.59
-
36.80
-
-
-
-
-
39.75
40.35
40.81
PID
MDL
M9A
0.02
NDC
0.05
0.02
0.02
0.009
0.02
0.01
0.05
0.003
0.005
0.01
0.01
0.02
0.01
0.05
HECD
MDL
M9A
0.05
0.03
0.04
1.1
0.1
0.03
0.07
0.02
0.06
0.07
0.05
0.01
0.02
0.01
0.03
0.02
0.01
0.03
0.01
0.006
0.02
2.2
ND
0.04
0.03
0.03
0.8
0.01
0.005
1.6
0.01
0.4
Revision 0
July 1992
-------
TABLE 1.
(Continued)
Analyte
PIO
Ret. Time8
minute
HECO
Ret. Time
minute
PID
MDL
M9/L
HECO
MDL
M9/L
n-Propylbenzene 40.87
Bromobenzene 40.99
1,3,5-Trimethylbenzene 41.41
2-Chlorotoluene 41.41
4-Chlorotoluene 41.60
tert-Butylbenzene 42.92
1,2,4-Trimethy]benzene 42.71
sec-Butyl benzene 43.31
p-Isopropyltoluene 43.81
1,3-Dichlorobenzene 44.08
1,4-Dichlorobenzene 44.43
n-Butyl benzene 45.20
1,2-Dichlorobenzene 45.71
l,2-Dibromo-3-Chloropropane
1,2,4-Trichlorobenzene 51.43
Hexachlorobutadiene 51.92
Naphthalene 52.38
1,2,3-Trichlorobenzene 53.34
Internal Standards
Fluorobenzene 26.84
2-Bromo-1-chloropropane
41.03
41.45
41.63
44.11
44.47
45.74
48.57
51.46
51.96
53.37
33.08
0.
0.
0.
0.004
0.006
0.004
NO
0.02
.06
,05
.02
0.01
0.02
0.007
0.02
0.05
0.02
0.06
0.06
ND
0.03
0.01
0.01
0.02
0.01
0.02
3.0
.03
.02
0.
0.
0.03
a Retention times determined on 60 m x 0.75 mm ID VOCOL capillary column.
Program: Hold at 10°C for 8 minutes, then program at 4°C/min to 180°C, and
hold until all expected compounds have eluted.
b Dash (-) indicates detector does not respond.
c ND = Not determined.
8021 - 12
Revision 0
July 1992
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TABLE1 2.
SINGLE LABORATORY ACCURACY AND PRECISION DATA
FOR VOLATILE ORGANIC COMPOUNDS IN WATERd
Photoionization
Detector
Analyte
Benzene
Bromobenzene
Bromochl oromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butylbenzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chi oromethane
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-chloropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Dichl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1,2 Dichloroethene
trans -1,2-Dichloroethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
I sopropyl benzene
p- Isopropyl tol uene
Recovery,8
%
99
99
-
-
-
-
100
97
98
-
100
-
.
-
NDC
101
-
-
-
.
102
104
103
-
-
-
100
ND
93
-
-
-
103
101
99
98
98
Standard
Deviation
of Recovery
1.2
1.7
-
-
-
_
4.4
2.6
2.3
-
1.0
-
_
-
ND
1.0
-
-
-
-
2.1
1.7
2.2
-
-
-
2.4
ND
3.7
-
-
-
3.6
1.4
9.5
0.9
2.4
Hall Electrolytic
Conductivity Detector
Standard
Recovery,8 Deviation
% of Recovery
_b
97
96
97
106
97
-
-
-
92
103
96
98
96
97
97
86
102
97
109
100
106
98
89
100
100
103
105
99
103
100
105
103
-
98
-
-
2.7
3.0
2.9
5.5
3.7
-
-
-
3.3
3.7
3.8
2.5
8.9
2.6
3.1
9.9
3.3
2.7
7.4
1.5
4.3
2.3
5.9
5.7
3.8
2.9
3.5
3.7
3.8
3.4
3.6
3.4
-
8.3
-
-
8021 - 13
Revision 0
July 1992
-------
TABLE 2.
(Continued)
Analyte
Photoionizat
Detector
Recovery,"
%
ion
Standard
Deviation
of Recovery
Hall Electrolytic
Conductivity Detector
Standard
Recovery,8 Deviation
% of Recovery
Methyl ene chloride
Naphthalene
n-Propyl benzene
Styrene
1,1, 1 ,2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1 , 1 , 1-Trichl oroethane
1,1,2-Trichl oroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
1, 2, 4-Trimethyl benzene
1,3, 5- Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
-
102
103
104
-
-
101
99
106
104
-
-
100
-
-
99
101
109
99
100
99
-
6.3
2.0
1.4
-
-
1.8
0.8
1.9
2.2
-
-
0.78
-
-
1.2
1.4
5.4
0.8
1.4
0.9
97
-
-
-
99
99
97
-
98
102
104
109
96
96
99
-
-
95
-
-
~
2.8
-
-
-
2.3
6.8
2.4
.
3.1
2.1
3.4
6.2
3.5
3.4
2.3
-
-
5.6
-
-
a Recoveries and standard deviations were determined from seven samples and spiked at
10 M9/L of each analyte. Recoveries were determined by internal standard method. Internal
standards were: Fluorobenzene for PID, 2-Bromo-l-chloropropane for HECD.
b Detector does not respond.
c ND = Not determined.
This method was tested
reference 8).
in a single laboratory using water spiked at 10 ^g/L (see
8021 - 14
Revision 0
July 1992
-------
TABLE 3.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
FOR VARIOUS MATRICES"
Matrix Factor6
Ground water 10
Low-concentration soil 10
Water miscible liquid waste 500
High-concentration soil and sludge 1250
Non-water miscible waste 1250
Sample EQLs are highly matrix dependent. The EQLs listed herein
are provided for guidance and may not always be achievable.
EQL = [Method detection limit (Table 1)] X [Factor (Table 2)].
For non-aqueous samples, the factor is on a wet-weight basis.
8021 - 15 Revision 0
July 1992
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FIGURE 1.
PURGING DEVICE
. on «• • oo
FIGURE 2.
TRAP PACKINGS AND CONSTRUCTION TO INCLUDE DESORB CAPABILITY
»«CXMO OVTA*.
8021 - 16
Revision 0
July 1992
-------
FIGURE 3.
PURGE-AND-TRAP SYSTEM - PURGE MODE
CAMWMOA*
NOT*
*U. LJMS MTVMCN TH**
*MO QC SMOMO M HCATV
rowx.
FIGURE 4.
SCHEMATIC OF PURGE-AND-TRAP DEVICE - DESORB MODE
HOTt
*u. UNCS WTWUN nv*
AM3 OC V4XLD M >**!»
8021 - 17
Revision 0
July 1992
-------
COLUMNI 6O METER x O.73 MM I.D. VOCOL CAPILLARY
(•UftCC AMD THAT VOC'm WITH HALL ft PIO IN SERIES
•*m i*n no « f»*5 l^-> — B lOMHi—araiQ m«« a «a
MN iw> »— H Ka »- o E iii»-M<5-«n a ONO) <3 »•*
Snux rs n O-. (ucrnr^ r-.
MOQ Kl »! ^ (X\JOJI-» •
00
o
rv>
oo
o
5>
to
yuL PID
•n 30
m
O en
O
30
CD
HECD
-------
METHOD 8021
HALOGENATED VOLATILES BY GAS CHROMATOGRAPHY USING
PHOTOIONIZATION AND ELECTROLYTIC CONDUCTIVITY DETECTORS IN SERIES:
CAPILLARY COLUMN TECHNIQUE
7 3 R.f.r to
Method 8000
for
calibration
t«chniqu««.
741 Introduce
aa»ple into CC
\»ing direct
injection or
purge-and-trip
744 Record
t*mpl» foluam
introduced
into CC and
7 IS R.f.r
to Method
8000 for
caIculat
746 An
analytical
int«rf«c«nc«»
•uap«et«d?
• acapla
>«eond CC
coluan
Dilul* and
r«analy>>
••cond
aliquot of
8021 - 19
Revision 0
July 1992
-------
00
©
-------
METHOD 8021A
HAL06ENATED VOLATILES BY GAS CHROMATOGRAPHY USING
PHOTOIONIZATION AND ELECTROLYTIC CONDUCTIVITY DETECTORS
IN SERIES: CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8021 is used to determine volatile organic compounds in a
variety of solid waste matrices. This method is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic liquors, acid liquors, waste solvents, oily wastes,
fibrous wastes, polymeric emulsions, filter cakes, spent
catalysts, soils, and sediments. The following compounds can
this method:
mousses, tars,
carbons, spent
be determined by
Analyte
Appropriate Technique
CAS No.a Purge-and-Trap
Direct
Injection
Benzene
Bromobenzene
Bromochl oromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butylbenzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chlorodibromomethane
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Dichlorodifluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans-l,2-Dichloroethene
71-43-2
108-86-1
74-97-5
75-27-4
75-25-2
74-83-9
104-51-8
135-98-8
98-06-6
56-23-5
108-90-7
124-48-1
75-00-3
67-66-3
74-87-3
95-49-8
106-43-4
96-12-8
106-93-4
74-95-3
95-50-1
541-73-1
106-46-7
75-71-8
75-34-3
107-06-2
75-35-4
156-59-4
156-60-5
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
8021A - 1
Revision 1
September 1994
-------
Analyte
CAS No.'
Appropriate Technique
Direct
Purge-and-Trap Injection
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
cis-l,3-dichloropropene
trans-1 ,3-dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyl toluene
Methylene chloride
Naphthalene
n-Propylbenzene
Styrene
1,1,1, 2 -Tetrachl oroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Tol uene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chl orof 1 uoromethane
1,2,3-Trichloropropane
1, 2, 4-Tri methyl benzene
1,3, 5 -Tri methyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
78-87-5
142-28-9
590-20-7
563-58-6
10061-01-5
10061-02-6
100-41-4
87-68-3
98-82-8
99-87-6
75-09-2
91-20-3
103-65-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
87-61-6
120-82-1
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
95-63-6
108-67-8
75-01-4
95-47-6
108-38-3
106-42-3
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
a Chemical Abstract Services Registry Number.
b Adequate response by thi
pp Poor purging efficiency
s technique.
resulting in high EQLs.
1.2 Method detection limits (MDLs) are compound dependent and vary with
purging efficiency and concentration. The MDLs for selected analytes are
presented in Table 1. The applicable concentration range of this method is
compound and instrument dependent but is approximately 0.1 to 200 p.g/1,
Analytes that are inefficiently purged from water will not be detected when
present at low concentrations, but they can be measured with acceptable accuracy
and precision when present in sufficient amounts. Determination of some
structural isomers (i.e. xylenes) may be hampered by coelution.
8021A - 2
Revision 1
September 1994
-------
1.3 The estimated quantitation limit (EQL) of Method 8021A for an
individual compound is approximately 1 jug/kg (wet weight) for soil/sediment
samples, 0.1 mg/kg (wet weight) for wastes, and 1 p.g/1 for ground water (see
Table 3). EQLs will be proportionately higher for sample extracts and samples
that require dilution or reduced sample size to avoid saturation of the detector.
1.4 This method is recommended for use only by analysts experienced in
the measurement of purgeable organics at the low p-g/L level or by experienced
technicians under the close supervision of a qualified analyst.
1.5 The toxicity or carcinogenicity of chemicals used in this method has
not been precisely defined. Each chemical should be treated as a potential
health hazard, and exposure to these chemicals should be minimized. Each
laboratory is responsible for maintaining awareness of OSHA regulations regarding
safe handling of chemicals used in this method. Additional references to
laboratory safety are available for the information of the analyst (references
4 and 6).
1.6 The following method analytes have been tentatively classified as
known or suspected human or mammalian carcinogens: benzene, carbon tetrachloride,
1,4-dichlorobenzene, 1,2-dichloroethane, hexachloro-butadiene, 1,1,2,2-
tetrachloroethane, 1,1,2-trichloroethane, chloroform, 1,2-dibromoethane,
tetrachloroethene, trichloroethene, and vinyl chloride. Pure standard materials
and stock standard solutions of these compounds should be handled in a hood. A
NIOSH/MESA approved toxic gas respirator should be worn when the analyst handles
high concentrations of these toxic compounds.
2.0 SUMMARY OF METHOD
2.1 Method 8021 provides gas chromatographic conditions for the
detection of halogenated and aromatic volatile organic compounds. Samples can
be analyzed using direct injection or purge-and-trap (Method 5030). Ground water
samples must be analyzed using Method 5030 (where applicable). A temperature
program is used in the gas chromatograph to separate the organic compounds.
Detection is achieved by a photoionization detector (PID) and an electrolytic
conductivity detector (HECO) in series.
2.2 Tentative identifications are obtained by analyzing standards under
the same conditions used for samples and comparing resultant GC retention times.
Confirmatory information can be gained by comparing the relative response from
the two detectors. Concentrations of the identified components are measured by
relating the response produced for that compound to the response produced by a
compound that is used as an internal standard.
3.0 INTERFERENCES
3.1 Refer to Methods 5030 and 8000.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A trip blank prepared from
8021A - 3 Revision 1
September 1994
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organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.
3.3 Sulfur dioxide is a potential interferant in the analysis for vinyl
chloride.
4.0 APPARATUS AND MATERIALS
4.1 Sample introduction apparatus - Refer to Method 5030 for the
appropriate equipment for sample introduction purposes.
4.2 Gas Chromatograph - capable of temperature programming; equipped
with variable-constant differential flow controllers, subambient oven controller,
photoionization and electrolytic conductivity detectors connected with a short
piece of uncoated capillary tubing, 0.32-0.5 mm ID, and data system.
4.2.1 Column - 60 m x 0.75 mm ID VOCOL wide-bore capillary column
with 1.5 fj.m film thickness (Supelco Inc., or equivalent).
4.2.2 Photoionization detector (PID) (Tracer Model 703, or
equivalent).
4.2.3 Electrolytic conductivity detector (HECD) (Tracor Hall Model
700-A, or equivalent).
4.3 Syringes - 5 ml glass hypodermic with Luer-Lok tips.
4.4 Syringe valves - 2-way with Luer ends (Teflon or Kel-F).
4.5 Microsyringe - 25 fj,l with a 2 in. x 0.006 in. ID, 22° bevel needle
(Hamilton #702N or equivalent).
4.6 Microsyringes - 10, 100 /iL.
4.7 Syringes - 0.5, 1.0, and 5 ml, gas-tight with shut-off valve.
4.8 Bottles - 15 ml, Teflon lined with screw-cap or crimp top.
4.9 Analytical balance - 0.0001 g.
4.10 Refrigerator.
4.11 Volumetric flasks, Class A - Appropriate sizes with ground glass
stoppers.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all inorganic reagents shall
conform to the specifications of the Committee on Analytical Reagents of the
American Chemical Society, where such specifications are available. Other grades
8021A - 4 Revision 1
September 1994
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may be used, provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of the
determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Methanol, CH3OH - Pesticide quality or equivalent, demonstrated to
be free of analytes. Store away from other solvents.
5.4 Vinyl chloride, (99.9% pure), CH2=CHC1. Vinyl chloride is available
from Ideal Gas Products, Inc., Edison, New Jersey and from Matheson, East
Rutherford, New Jersey, as well as from other sources. Certified mixtures of
vinyl chloride in nitrogen at 1.0 and 10.0 ppm (v/v) are available from several
sources.
5.5 Stock standards - Stock solutions may either be prepared from pure
standard materials or purchased as certified solutions. Prepare stock standards
in methanol using assayed liquids or gases, as appropriate. Because of the
toxicity of some of the organohalides, primary dilutions of these materials of
the toxicity should be prepared in a hood.
NOTE: If direct injection is used, the solvent system of standards must
match that of the sample. It is not necessary to prepare high
concentration aqueous mixed standards when using direct injection.
5.5.1 Place about 9.8 ml of methanol in a 10 ml tared ground glass
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes until all alcohol-wetted surfaces have dried. Weigh the
flask to the nearest 0.1 mg.
5.5.2 Add the assayed reference material, as described below.
5.5.2.1 Liquids: Using a 100 /A syringe, immediately add
two or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5.5.2.2 Gases: To prepare standards for any compounds
that boil below 30°C (e.g. bromomethane, chloroethane,
chloromethane, dichlorodifluoromethane, trichlorofluoromethane,
vinyl chloride), fill a 5 mL valved gas-tight syringe with the
reference standard to the 5.0 ml mark. Lower the needle to 5 mm
above the methanol meniscus. Slowly introduce the reference
standard above the surface of the liquid. The heavy gas rapidly
dissolves in the methanol. This may also be accomplished by using
a lecture bottle equipped with a Hamilton Lecture Bottle Septum
(#86600). Attach Teflon tubing to the side-arm relief valve and
direct a gentle stream of gas into the methanol meniscus.
5.5.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in milligrams per
liter (mg/L) from the net gain in weight. When compound purity is assayed
8021A - 5 Revision 1
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to be 96% or greater, the weight may be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.5.4 Transfer the stock standard solution into a bottle with a
Teflon lined screw-cap or crimp top. Store, with minimal headspace, at
-10°C to -20°C and protect from light.
5.5.5 Prepare fresh stock standards for gases weekly or sooner if
comparison with check standards indicates a problem. Reactive compounds
such as 2-chloroethyl vinyl ether and styrene may need to be prepared more
frequently. All other standards must be replaced after six months. Both
gas and liquid standards must be monitored closely by comparison to the
initial calibration curve and by comparison to QC check standards. It may
be necessary to replace the standards more frequently if either check
exceeds a 20% drift.
5.6 Prepare secondary dilution standards, using stock standard
solutions, in methanol, as needed, that contain the compounds of interest, either
singly or mixed together. The secondary dilution standards should be prepared
at concentrations such that the aqueous calibration standards prepared in Sec.
5.7 will bracket the working range of the analytical system. Secondary dilution
standards should be stored with minimal headspace for volatiles and should be
checked frequently for signs of degradation.or evaporation, especially just prior
to preparing calibration standards from them.
5.7 Calibration standards, at a minimum of five concentration levels are
prepared in organic-free reagent water from the secondary dilution of the stock
standards. One of the concentration levels should be at a concentration near,
but above, the method detection limit. The remaining concentration levels should
correspond to the expected range of the concentrations found in real samples or
should define the working range of the GC. Standards (one or more) should
contain each analyte for detection by this method. In order to prepare accurate
aqueous standard solutions, the following precautions must be observed.
NOTE: Prepare calibration solutions for use with direct injection analyses
in water at the concentrations required.
5.7.1 Do not inject more than 20 /xL of alcoholic standards into
100 ml of water.
5.7.2 Use a 25 /uL Hamilton 702N microsyringe or equivalent
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of methanolic standards into water).
5.7.3 Rapidly inject the alcoholic standard into the filled
volumetric flask. Remove the needle as fast as possible after injection.
5.7.4 Mix aqueous standards by inverting the flask three times.
8021A - 6 Revision 1
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5.7.5 Fill the sample syringe from the standard solution contained
in the expanded area of the flask (do not use any solution contained in
the neck of the flask).
5.7.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.7.7 Aqueous standards are not stable and should be discarded after
one hour, unless properly sealed and stored. The aqueous standards can
be stored up to 12 hours, if held in sealed vials with zero headspace.
5.7.8 Optionally calibration using a certified gaseous mixture can
be accomplished daily utilizing commercially available gaseous analyte
mixture of bromomethane, chloromethane, chloroethane, vinyl chloride,
dichlorodifluoromethane and trichlorofluoromethane in nitrogen. These
mixtures of documented quality are stable for as long as six months
without refrigeration. (VOA-CYL III, RESTEK Corporation, Cat. #20194 or
equivalent).
5.8 Internal standards - Prepare a spiking solution containing
fluorobenzene and 2-bromo-l-chloropropane in methanol, using the procedures
described in Sees. 5.5 and 5.6. It is recommended that the secondary dilution
standard be prepared at a concentration of 5 mg/L of each internal standard
compound. The addition of 10 /jL of such a standard to 5.0 ml of sample or
calibration standard would be equivalent to 10 jug/L.
5.9 Surrogate standards - The analyst should monitor both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix by spiking each sample, standard, and reagent
blank with two or more surrogate compounds. A combination of 1,4-dichlorobutane
and bromochlorobenzene is recommended to encompass the range of the temperature
program used in this method. From stock standard solutions prepared as in Sec.
5.5, add a volume to give 750 /ig of each surrogate to 45 ml of organic-free
reagent water contained in a 50 ml volumetric flask, mix, and dilute to volume
for a concentration of 15 ng/juL. Add 10 /LtL of this surrogate spiking solution
directly into the 5 ml syringe with every sample and reference standard analyzed.
If the internal standard calibration procedure is used, the surrogate compounds
may be added directly to the internal standard spiking solution (Sec. 5.8).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
7.1 Volatile compounds are introduced into the gas chromatograph either
by direct injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-concentration contaminated soils and
sediments. For medium-concentration soils or sediments, methanolic extraction,
as described in Method 5030, may be necessary prior to purge-and-trap analysis.
8021A - 7 Revision 1
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7.2 Gas chromatography conditions (Recommended)
7.2.1 Set up the gas chromatograph system so that the
photoionization detector (PID) is in series with the electrolytic
conductivity detector (HECD).
7.2.2 Oven settings:
Carrier gas (Helium) Flow rate: 6 mL/min.
Temperature program
Initial temperature: 10°C, hold for 8 minutes at
Program: 10°C to 180°C at 4°C/miri
Final temperature: 180°C, hold until all expected
compounds have eluted.
7.2.3 The carrier gas flow is augmented with an additional 24 ml of
helium flow before entering the photoionization detector. This make-up
gas is necessary to ensure optimal response from both detectors.
7.2.4 These halogen-specific systems eliminate misidentifications
due to non-organohalides which are coextracted during the purge step. A
Tracer Hall Model 700-A detector was used to gather the single laboratory
accuracy and precision data presented in Table 2. The operating
conditions used to collect these data are:
Reactor tube: Nickel, 1/16 in OD
Reactor temperature: 810°C
Reactor base temperature: 250°C
Electrolyte: 100% n-Propyl alcohol
Electrolyte flow rate: 0.8 mL/min
Reaction gas: Hydrogen at 40 mL/min
Carrier gas plus make-up gas: Helium at 30 mL/min
7.2.5 A sample chromatogram obtained with this column is presented
in Figure 5. This column was used to develop the method performance
statements in Sec. 9.0. Estimated retention times and MDLs that can be
achieved under these conditions are given in Table 1. Other columns or
element specific detectors may be used if the requirements of Sec. 8.0 are
met.
7.3 Calibration - Refer to Method 8000 for proper calibration
techniques. Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 Calibration must take place using the same sample introduction
method that will be used to analyze actual samples (see Sec. 7.4.1).
7.3.2 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these procedures.
7.4 Gas chromatographic analysis
8021A - 8 Revision 1
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7.4.1 Introduce volatile compounds into the gas chromatograph using
either Method 5030 (purge-and-trap method) or the direct injection method
(see Sec. 7.4.1.1). If the internal standard calibration technique is
used, add 10 /nL of internal standard to the sample prior to purging.
7.4.1.1 Direct injection - In very limited applications
(e.g. aqueous process wastes) direct injection of the sample into
the GC system with a 10 juL syringe may be appropriate. The
detection limit is very high (approximately 10,000 Mg/L), therefore,
it is only permitted where concentrations in excess of 10,000 /Ltg/L
are expected or for water-soluble compounds that do not purge. The
system must be calibrated by direct injection (bypassing the purge-
and-trap device).
7.4.2 Follow Sec. 7.6 in Method 8000 for instructions on the
analysis sequence, appropriate dilutions, establishing daily retention
time windows, and identification criteria. Include a mid-concentration
standard after each group of 10 samples in the analysis sequence.
7.4.3 Table 1 summarizes the estimated retention times on the two
detectors for a number of organic compounds analyzable using this method.
7.4.4 Record the sample volume purged or injected and the resulting
peak sizes (in area units or peak heights).
7.4.5 Calculation of concentration is covered in Method 8000.
7.4.6 If analytical interferences are suspected, or for the purpose
of confirmation, analysis using a second GC column is recommended.
7.4.7 If the response for a peak is off-scale, i.e., beyond the
calibration range of the standards, prepare a dilution of the sample with
organic-free reagent water. The dilution must be performed on a second
aliquot of the sample which has been properly sealed and stored prior to
use.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.
8.2 Quality control required to validate the GC system operation is
found in Method 8000.
8.2.1 The quality control reference sample (Method 8000) should
contain each parameter of interest at a concentration of 10 mg/L in
methanol.
8.2.2 Table 2 gives method accuracy and precision as functions of
concentration for the analytes of interest.
8021A - 9 Revision 1
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8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (limits established by performing
QC procedure outlined in Method 8000).
8.3.1 If recovery is not within limits, the following is required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any
of the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above
are a problem or flag the data as "estimated
concentration".
9.0 METHOD PERFORMANCE
9.1 Method detection limits for these analytes have been calculated from
data collected by spiking organic-free reagent water at 0.1 fj.g/1. These data
are presented in Table 1.
9.2 This method was tested in a single laboratory using organic-free
reagent water spiked at 10 jug/L. Single laboratory precision and accuracy data
for each detector are presented for the method analytes in Table 2.
10.0 REFERENCES
1. Volatile Organic Compounds^in Hater by Purqe-and-Trap Capillary Column Gas
Chromatography with Photoionization and Electrolytic Conduct ivity
Detectors in Series. Method 502.2. Rev. 2.0 (1989)
Determination of Organic Compounds in
Monitoring Systems Laboratory, Cincinnati
1988
Methods for the
Drinking Water", Environmental
, OH, EPA/600/4-88/039, December,
The Determination of Halogenated Chemicals in Water by the Purge and Trap
Method, Method 502.1; Environmental Protection Agency, Environmental
Monitoring and Support Laboratory: Cincinnati, Ohio 45268, September,
1986.
Volatile Aromatic and Unsaturated Organic Compounds in Water by Purge and
Trap Gas Chromatography, Method 503.1; Environmental Protection Agency,
Laboratory:
Environmental Monitoring
September, 1986.
and Support
Cincinnati, Ohio,
Glaser, J.A.; Forest, D.L.; McKee, G.D.; Quave, S.A.; Budde, W.L. "Trace
Analyses for Wastewaters"; Environ. Sci. Technol. 1981, 15, 1426.
8021A - 10
Revision 1
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5. Bellar, T.A.; Lichtenberg, J.J. The Determination of Synthetic Organic
Compounds In Water by Purge and Sequential Trapping Capillary Column Gas
Chromatoqraph.y; U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory: Cincinnati, Ohio, 45268.
8021A - 11 Revision 1
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TABLE 1.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL) FOR
VOLATILE ORGANIC COMPOUNDS ON PHOTOIONIZATION DETECTION (PID) AND
HALL ELECTROLYTIC CONDUCTIVITY DETECTOR (HECD) DETECTORS
Analyte
Dichlorodifluoromethane
Chloromethane
Vinyl Chloride
Bromomethane
Chloroethane
Tri chl orof 1 uoromethane
1,1-Dichloroethene
Methylene Chloride
trans-l,2-Dichloroethene
1,1-Dichloroethane
2,2-Dichloropropane
cis-l,2-Di chloroethane
Chloroform
Bromochloromethane
1 ,1,1 -Tri chloroethane
1,1-Dichloropropene
Carbon Tetrachloride
Benzene
1,2-Dichloroethane
Trichloroethene
1,2-Dichloropropane
Bromod ichl oromethane
Dibromomethane
Toluene
1,1, 2 -Tri chloroethane
Tetrachloroethene
1,3-Dichloropropane
Dibromochl oromethane
1,2-Dibromoethane
Chlorobenzene
Ethylbenzene
1,1,1 , 2-Tetrachloroethane
m-Xylene
p-Xylene
o-Xylene
Styrene
Isopropyl benzene
Bromoform
1,1, 2, 2-Tetrachloroethane
1,2,3-Trichloropropane
PID
Ret. Time8
minute
b
-
9.88
-
-
-
16.14
-
19.30
-
-
23.11
-
-
-
25.21
-
26.10
-
27.99
-
-
-
31.95
-
33.88
-
-
-
36.56
36.72
-
36.98
36.98
38.39
38.57
39.58
-
-
-
HECD
Ret. Time
minute
8.47
9.47
9.93
11.95
12.37
13.49
16.18
18.39
19.33
20.99
22.88
23.14
23.64
24.16
24.77
25.24
25.47
-
26.27
28.02
28.66
29.43
29.59
-
33.21
33.90
34.00
34.73
35.34
36.59
-
36.80
-
-
-
-
-
39.75
40.35
40.81
PID
MDL
M9/L
0.02
NDC
0.05
0.02
0.02
0.009
0.02
0.01
0.05
0.003
0.005
0.01
0.01
0.02
0.01
0.05
HECD
MDL
M9/L
0.05
0.03
0.04
1.1
0.1
0.03
0.07
0.02
0.06
0.07
0.05
0.01
0.02
0.01
0.03
0.02
0.01
0.03
0.01
0.006
0.02
2.2
ND
0.04
0.03
0.03
0.8
0.01
0.005
1.6
0.01
0.4
8021A - 12
Revision 1
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TABLE 1.
(Continued)
Analyte
PID
Ret. Time8
minute
HECD
Ret. Time
minute
PID
MDL
M9/L
HECD
MDL
M9/L
n-Propylbenzene 40.87
Bromobenzene 40.99
1,3,5-Trimethylbenzene 41.41
2-Chlorotoluene 41.41
4-Chlorotoluene 41.60
tert-Butylbenzene 42.92
1,2,4-Trimethylbenzene 42.71
sec-Butyl benzene 43.31
p-Isopropyltoluene 43.81
1,3-Dichlorobenzene 44.08
1,4-Dichlorobenzene 44.43
n-Butylbenzene 45.20
1,2-Dichlorobenzene 45.71
l,2-Dibromo-3-Chloropropane
1,2,4-Trichlorobenzene 51.43
Hexachlorobutadiene 51.92
Naphthalene 52.38
1,2,3-Trichlorobenzene 53.34
Internal Standards
Fluorobenzene 26.84
2-Bromo-l-chloropropane
41.03
41.45
41.63
44.11
44.47
45.74
48.57
51.46
51.96
53.37
33.08
0.004
0.006
0.004
ND
0.02
0.06
0.05
0.02
0.01
0.02
0.007
0.02
0.05
0.02
0.06
0.06
ND
0.03
0.01
0.01
0.02
0.01
0.02
3.0
0.03
0.02
0.03
Retention times determined on 60 m x 0.75 mm ID
Program: Hold at 10°C for 8 minutes, then program
hold until all expected compounds have eluted.
Dash (-) indicates detector does not respond.
ND = Not determined.
VOCOL capillary column.
at 4°C/min to 180°C, and
8021A - 13
Revision 1
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TABLE 2.
SINGLE LABORATORY ACCURACY AND PRECISION DATA
FOR VOLATILE ORGANIC COMPOUNDS IN WATERd
Photoionization
Detector
Analyte
Benzene
Bromobenzene
Bromochloromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
1 ,2-Dibromo-3-chloropropane
Dibromochloromethane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Dichlorodifluoromethane
1, 1-Dichloroethane
1,2-Dichloroethane
1 ,1-Dichloroethene
cis-1,2 Dichloroethene
trans-l,2-Dichloroethene
1 ,2-Dichloropropane
1 ,3-Dichloropropane
2,2-Dichloropropane
1 , 1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
I sopropyl benzene
p-Isopropyltoluene
Recovery,8
%
99
99
-
-
-
-
100
97
98
-
100
-
-
-
NDC
101
-
-
-
-
102
104
103
-
-
-
100
ND
93
-
-
-
103
101
99
98
98
Standard
Deviation
of Recovery
1.2
1.7
-
-
-
-
4.4
2.6
2.3
-
1.0
-
-
-
ND
1.0
-
-
-
-
2.1
1.7
2.2
-
-
-
2.4
ND
3.7
-
-
-
3.6
1.4
9.5
0.9
2.4
Hall Electrolytic
Conductivity Detector
Standard
Recovery,8 Deviation
% of Recovery
_b
97
96
97
106
97
-
-
-
92
103
96
98
96
97
97
86
102
97
109
100
106
98
89
100
100
103
105
99
103
100
105
103
-
98
-
-
.
2.7
3.0
2.9
5.5
3.7
-
-
-
3.3
3.7
3.8
2.5
8.9
2.6
3.1
9.9
3.3
2.7
7.4
1.5
4.3
2.3
5.9
5.7
3.8
2.9
3.5
3.7
3.8
3.4
3.6
3.4
-
8.3
-
-
8021A - 14
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TABLE 2.
(Continued)
Analyte
Photoionization
Detector
Standard
Recovery,8 Deviation
% of Recovery
Hall Electrolytic
Conductivity Detector
Standard
Recovery,8 Deviation
% of Recovery
Methylene chloride
Naphthalene
n-Propylbenzene
Styrene
1,1, 1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1, 1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
1,2, 4 -Tri methyl benzene
1,3, 5 -Tri methyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
102
103
104
-
-
101
99
106
104
-
-
100
-
-
99
101
109
99
100
99
6.3
2.0
1.4
-
-
1.8
0.8
1.9
2.2
-
-
0.78
-
-
1.2
1.4
5.4
0.8
1.4
0.9
97
-
-
-
99
99
97
-
98
102
104
109
96
96
99
-
-
95
-
-
~
2.8
-
-
-
2.3
6.8
2.4
-
3.1
2.1
3.4
6.2
3.5
3.4
2.3
-
5.6
-
~
Recoveries and standard deviations were determined from seven samples and spiked at
10 /xg/L of each analyte. Recoveries were determined by internal standard method. Internal
standards were: Fluorobenzene for PID, 2-Bromo-l-chloropropane for HECD.
b Detector does not respond.
0 ND = Not determined.
This method was tested
reference 5).
in a single laboratory using water spiked at 10
(see
8021A - 15
Revision 1
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TABLE 3.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
FOR VARIOUS MATRICES3
Matrix Factor
Ground water 10
Low-concentration soil 10
Water miscible liquid waste 500
High-concentration soil and sludge 1250
Non-water miscible waste 1250
EQL = [Method detection limit (see Table 1)] X [Factor found in
this table]. For non-aqueous samples, the factor is on a wet-
weight basis. Sample EQLs are highly matrix-dependent. The EQLs
listed herein are provided for guidance and may not always be
achievable.
8021A - 16 Revision 1
September 1994
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FIGURE 1.
PURGING DEVICE
OPTIONM.
POAMTTM*
OUT i<4 M 0.0
•— 14 MM 00
INLET 1M IN 00
Exrr IK IN. o.o
10 MM GLASS FRTT
MEDIUM
SAMPLf INLET
J4VAY SYAINGC VALVC
17 CM 20 GAUGE SVKNGC NEEDLE
MM 0 0 RU8KR SCFTUM
INLET 1M IN 0 0
1'ie IN 00
^ STAINLESS STEEL
'3X
MOLECULAR SIEVE
GAS
GAS
Fl.CV< CONTHOt
8021A - 17
Revision 1
September 1994
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FIGURE 2.
TRAP PACKINGS AND CONSTRUCTION TO INCLUDE DESORB CAPABILITY
PACKING DETAIL
i UUO>38 "OX
CM S4UO G£L
CONSTRUCTOR OFTAJL
3C
=T
• CM JX Ov-t
5 MM il>S8 WOOL
n*iNG a CM
a'06 IN. iD
0 '» it*. 00.
8021A - 18
Revision 1
September 1994
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FIGURE 3.
PURGE-AND-TRAP SYSTEM - PURGE MODE
CAPWERGAS
FLOW CONTROL
— uowo INJECTION PO«TS
COLUMN OVEN
COCUMN
PXWGCGAS
PLOW CONTROL
SIEVE RLTER
COLUMN
OPTIONAL 4^O*TT COLUMN
SELKTDON VALVE
». /- TRAP INLET
TRAP
22 *C
NOTE.
ALL UNtS 8€TWEEN
ANO QC SHOULD K H€AfEO
TO«3*C.
8021A - 19
Revision 1
September 1994
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FIGURE 4.
SCHEMATIC OF PURGE-ANO-TRAP DEVICE - DESORB MODE
CARRIER GAS
FLOW CONTROL
PRESSURE
REGULATOR
PURGE GAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
r- UOWO INJECTION PORTS
} r— COLUMN OVEN
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
OPTIONAL 4PORT COLUMN
SELECTION VALVE
TRAP INLET
TRAP
200*C
if PURGING
1 OCVCC
won.
ALL UNES BETWEEN TRAP
AMD GC SHOULD BE HEATED
8021A - 20
Revision 1
September 1994
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FIGURE 5.
GAS CHROMATOGRAM OF VOLATILE ORGANICS
COLUMN I 60 METER M 0. 73 MM I.D. VOCOL CAPILLARY
AM) TWA* VOC'l WITH MM.L t *IO IN SCRIES
;= n sa
s t
2*28
Sf^S
8 S
^v wtinnHt n
1
JU
JUUUL PID
KSCO
8021A - 21
Revision 1
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METHOD 8021A
HALOGENATED VOLATILES BY GAS CHROMATOGRAPHY USING PHOTOIONIZATION
AND ELECTROLYTIC CONDUCTIVITY DETECTORS IN SERIES:
CAPILLARY COLUMN TECHNIQUE
( Start J
7.2 Set
chromatographic
conditions.
7.3 Refer to
Method 8000 for
calibration techniques.
7.4.1 Introduce
sample into GC using
direct injection or
purge-snd-trap.
7.4.4 Record
sample volume
introduced into GC
and peak sizes.
7.4.5 Refer
to Method 8000 for
calculations.
7.4.6 Are
analytical
interferences
suspected?
7.4.7 Is peak
response off
scale?
Reanalyze sample
using second GC
column.
Dilute and reanalyze
second aliquot of
sample.
8021A - 22
Revision 1
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00
o
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METHOD 8030A
ACROLEIN AND ACRYLONITRILE BY GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 8030 is used to determine the concentration of the following
volatile organic compounds:
Compound Name CAS No.8
Acrolein (Propenal) 107-02-8
Acrylonitrile 107-13-1
a Chemical Abstract Services Registry Number.
1.2 Table 1 lists chromatographic conditions and method detection limits
for acrolein and acrylonitrile in organic-free reagent water. Table 2 lists the
estimated quantitation limit (EQL) for other matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8030 provides gas chromatographic conditions for the detection
of the target analytes. Samples can be analyzed using direct injection or purge-
and-trap (Method 5030). Tenax should be used as the trap packing material.
Ground water samples must be analyzed using Method 5030. A temperature program
is used in the gas chromatograph to separate the organic compounds. Detection
is achieved by a flame ionization detector (FID).
2.2 The method provides an optional gas chromatographic column that may
be helpful in resolving the analytes from co-eluting non-target compounds and for
analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Methods 5030 and 8000.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A trip blank prepared from
organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.
8030A - 1 Revision 1
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4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4,1.1 Gas Chromatograph - Analytical system complete with gas
chromatograph suitable for on-column injections or purge-and-trap sample
introduction and all required accessories, including detectors, column
supplies, recorder, gases, and syringes. A data system for measuring peak
height and/or peak area is recommended.
4.1.2 Columns
4.1.2.1 Column 1 - 10 ft x 2 mm ID stainless steel or
glass packed with Porapak-QS (80/100 mesh) or equivalent.
4.1.2.2 Column 2 - 6 ft x 0.1 in. ID stainless steel or
glass packed with Chromosorb 101 (60/80 mesh) or equivalent.
4.1.3 Detector - Flame ionization (FID).
4.2 Sample introduction apparatus - Refer to Method 5030 for the
appropriate equipment for sample introduction purposes.
4.3 Syringes - A 5 mL Luer-lok glass hypodermic and a 5 ml, gas-tight
with shutoff valve.
4.4 Volumetric flasks, Class A - Appropriate sizes with ground glass
stoppers.
4.5 Microsyringes - 10 and 25 pi with a 0.006 in. ID needle
(Hamilton 702N, or equivalent) and a 100 /iL.
4.6 Analytical balance - 0.0001 g.
5.0 REAGENTS
5.1 Reagent grade chemicals'shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall 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
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
5.2 Organic-free reagent water: All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5,3 Hydrochloric acid, HC1 - 1:1 (v/v).
5.4 Sodium hydroxide, NaOH - ION solution. Dissolve 40 g NaOH in
organic-free reagent water and dilute to 100 mL.
5.5 Stock standards - Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standards in
8030A - 2 Revision 1
July 1992
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organic-free reagent water using assayed liquids. Because acrolein and
acrylonitrile are lachrymators, primary dilutions of these compounds should be
prepared in a hood.
5.5.1 Place about 9.8 ml of organic-free reagent water in a 10
ml tared ground-glass stoppered volumetric flask. For acrolein standards
the water must be adjusted to pH 4-5 using hydrochloric acid (1:1 v/v) or
sodium hydroxide (ION),, if necessary. Weigh the flask to the nearest
0.0001 g.
5.5.2 Using a 100 /iL syringe, immediately add two or more drops
of assayed reference material to the flask, then reweigh. The liquid must
fall directly into the water without contacting the neck of the flask.
5.5.3 Reweigh, dilute to volume, stopper, and then mix by
inverting the flask several times. Calculate the concentration in
milligrams per liter (mg/L) from the net gain in weight. When compound
purity is assayed to be 96% or greater, the weight may be used without
correction to calculate the concentration of the stock standard.
Commercially prepared stock standards may be used at any concentration, if
they are certified by the manufacturer or by an independent source.
5.5.4 Transfer the stock standard solution into a bottle with
a Teflon lined screw-cap. Store, with minimal headspace, at 4°C and
protect from light.
5.5.5 Prepare fresh standards daily.
5.6 Secondary dilution standards - Prepare secondary dilution standards
as needed, in organic-free reagent water, from the stock standard solutions. The
secondary dilution standards must contain the compounds of interest, either
singly or mixed together. The secondary dilution standards should be prepared
at concentrations such that the aqueous calibration standards prepared in Section
5.7 will bracket the working range of the analytical system. Secondary dilution
standards should be stored with minimal headspace, and should be checked
frequently for signs of degradation or evaporation, especially just prior to
preparing calibration standards from them.
5.7 Cal ibration standards - Prepare cal ibration standards in organic-free
reagent water from the secondary dilution standards at a minimum of five
concentrations. One of the concentrations should be at a concentration near, but
above, the method detection limit. The remaining concentrations should
correspond to the expected range of concentrations found in real samples, or
should define the working range of the GC. Each standard should contain each
analyte for detection by this method. In order to prepare accurate aqueous
standard solutions, the following precautions must be observed.
5.7.1 Use a 25 pi Hamilton 702N microsyringe, or equivalent,
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of standards into water).
5.7.2 Never use pipets to dilute or transfer samples or aqueous
standards.
8030A - 3 Revision 1
July 1992
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5.7.3 Standards must be prepared daily.
5.8 Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.8.1 Prepare calibration standards at a minimum of five
concentrations for each parameter of interest, as described in Section
5.7.
5.8.2 Prepare a spiking solution containing each of the internal
standards, using the procedures described in Sections 5.5 and 5.6. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 mg/L of each internal standard compound. The addition
of 10 ML of this standard to 5.0 ml of sample or calibration standard
would be equivalent to 30
5.8.3 Analyze each calibration standard according to Section
7.0, adding 10 ML of internal standard spiking solution directly to the
syringe.
5.9 Surrogate standards - The analyst should monitor both the performance
of the analytical system and the effectiveness of the method in dealing with each
sample matrix by spiking each sample, standard, and organic-free reagent water
blank with one or two surrogate compounds (e.g. compounds similar in analytical
behavior to the analytes of interest but which are not expected to be present in
the sample) recommended to encompass the range of the temperature program used
in this method. From stock standard solutions prepared as in Section 5.5, add
a volume to give 750 /ug of each surrogate to 45 mL of organic-free reagent water
contained in a 50 mL volumetric flask, mix, and dilute to volume for a
concentration of 15 ng//iL. Add 10 nl of this surrogate spiking solution
directly into the 5 mL syringe with every sample and reference standard analyzed.
If the internal standard calibration procedure is used, the surrogate compounds
may be added directly to the internal standard spiking solution (Section 5.8.2).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Volatile compounds are introduced into the gas chromatograph either
by direct injection or heated purge-and-trap (Method 5030). Method 5030 may be
used directly on ground water samples or low-concentration contaminated soils and
sediments. For high-concentration soils or sediments, methanolic extraction, as
described in Method 5030, may be necessary prior to purge-and-trap analysis.
8030A - 4 Revision 1
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7.2 Gas chromatographic conditions (Recommended)
7.2.1 Column 1:
Helium flow rate = 30 mL/min
Temperature program:
Initial temperature - 110°C, hold for 1.5 minutes
Program - 110°C to 150°C, heating as
rapidly as possible
Final temperature = 150°C, hold for 20 minutes.
7.2.2 Column 2:
Helium flow rate = 40 mL/min
Temperature program:
Initial temperature - 80°C, hold for 4 minutes
Program - 80°C to 120°C at 50°C/min
Final temperature » 120°C, hold for 12 minutes.
7.3 Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.
7.3.1 Calibration must take place using the same sample
introduction method that will' be used to analyze actual samples (see
Section 7.4.1).
7.3.2 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these procedures.
7.4 Gas chromatographic analysis
7.4.1 Introduce volatile compounds into the gas chromatograph
using either Method 5030 (heated purge-and-trap method using Tenax as the
trap packing material) or the direct injection method. If the internal
standard calibration technique is used, add 10 ni of the internal standard
to the sample prior to purging.
7.4.1.1 Direct injection - In very limited applications
(e.g. aqueous process wastes), direct injection of the sample into
the GC system with a 10 pi syringe may be appropriate. The
detection limit is very high (approximately 10,000 M9A)> therefore,
it is only permitted when concentrations in excess of 10,000 /^g/L
are expected or for water-soluble compounds that do not purge. The
system must be calibrated by direct injection (bypassing the purge-
and-trap device).
7.4.2 Follow Method 8000 for instructions on the analysis
sequence, appropriate dilutions, establishing daily retention time
windows, and identification criteria. Include a mid-concentration
standard after each group of 10 samples in the analysis sequence.
7.4.3 Table 1 summarizes the estimated retention times and
detection limits for a number of organic compounds analyzable using this
8030A - 5 Revision 1
July 1992
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method. Figure 1 illustrates the chromatographic separation of acrolein
and of aeryfonitrile using Column 1.
7.4.4 Record the sample volume purged or injected and the
resulting peak sizes (in area units or peak heights).
7.4.5 Calculation of concentration is covered in Method 8000.
7.4.6 If analytical interferences are suspected, or for the
purpose of confirmation, analysis using the second GC column is
recommended.
7.4.7 If the response for a peak is off-scale, prepare a
dilution of the sample with organic-free reagent water. The dilution must
be performed on a second aliquot of the sample which has been properly
sealed and stored prior to use.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.
8.2 Procedures to check the GC system operation are found in Method 8000,
Section 8.6.
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each parameter of interest at a concentration
of 25 mg/L in water.
8.2.2 Table 3 indicates the calibration and QC acceptance
criteria for this method. Table 4 gives single laboratory accuracy and
precision for the analytes of interest. The contents of both Tables
should be used to evaluate a laboratory's ability to perform and generate
acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (limits established by performing
QC procedure outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following is
required.
• Check to be sure that there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of the
above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are a
problem or flag the data as "estimated concentration".
8030A - 6 Revision 1
July 1992
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9.0 METHOD PERFORMANCE
9.1 In a single laboratory, the average recoveries and standard
deviations presented in Table 4 were obtained using Method 5030. Seven replicate
samples were analyzed at each spike concentration.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and by the calibration procedure used.
10.0 REFERENCES
1. Bellar, T.A. and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12).
pp. 739-744, 1974.
2. Bellar, T.A. and J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Water
and Wastewater, ASTM STP 686, pp. 108-129, 1979.
3. Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters, Category 11: Purgeables and Category 12:
Acrolein, Acrylonitrile, and Dichlorodifluoromethane, Report for EPA
Contract 68-03-2635 (in preparation).
4. Going, J., et al., Environmental Monitoring Near Industrial Sites -
Acrylonitrile, Office of Toxic Substances, U.S. EPA, Washington, DC, EPA
560/6-79-003, 1979.
5. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
Final Rule and Proposed Rule," October 26, 1984.
6. Kerns, E.H., et al. "Determination of Acrolein and Acrylonitrile in Water
by Heated Purge and Trap Technique," U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268,
1980.
7. "Evaluation of Method 603," Final Report for EPA Contract 68-03-1760 (in
preparation).
8030A - 7 Revision 1
July 1992
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TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
Retention time (min) Method detection
Compound Col. 1 Col. 2 limit8 (M9/L)
Acrolein
Acrylonitrile
10.6
12.7
8.2
9.8
0.7
0.5
8 Based on using purge-and-trap, Method 5030.
TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION
LIMITS (EQLs) FOR VARIOUS MATRICES"
Matrix Factor6
Ground water 10
Low-concentration soil 10
Water miscible liquid waste 500
High-concentration soil and sludge 1250
Non-water miscible waste 1250
Sample EQLs are highly matrix dependent. The EQLs listed herein
are provided for guidance and may not always be achievable.
EQL * [Method detection limit (Table 1)] X [Factor (Table 2)].
For non-aqueous samples, the factor is on a wet-weight basis.
8030A - 8 Revision 1
July 1992
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TABLE 3.
CALIBRATION AND QC ACCEPTANCE CRITERIA8
Analyte
Acrolein
Acrylonitrile
Range
for Q
(M9/L)
45.9 - 54.1
41.2 - 58.8
Limit
for S
(M9/L)
4.6
9.9
Range
for x
(Atg/L)
42.9 - 60.1
33.1 - 69.9
Range
P> Ps
(%)
88-118
71-135
Q = Concentration measured in QC check sample, in M9/L.
S = Standard deviation of four recovery measurements, in fj.g/1.
R = Average recovery for four recovery measurements, in /ig/L.
P, Ps = Percent recovery measured.
" Criteria from 40 CFR Part 136 for Method 603 and were calculated
assuming a QC check sample concentration of 50 M9/L-
TABLE 4.
SINGLE LABORATORY ACCURACY AND PRECISION
Parameter
Acrolein
Acrylonitrile
AW
POTW
Spike
cone.
UgA)
5.0
50.0
5.0
50.0
5.0
100.0
5.0
50.0
20.0
100.0
10.0
100.0
ASTM Type
Average
recovery
(M9/L)
5.2
51.4
4.0
44.4
0.1
9.3
4.2
51.4
20.1
101.3
9.1
104.0
II water.
Standard
deviation
(M9/L)
0.2
0.7
0.2
0.8
0.1
1.1
0.2
1.5
0.8
1.5
0.8
3.2
Prechlori nation secondary effluent
Average
percent
recovery
104
103
80
89
2
9
84
103
100
101
91
104
from a muni
Sample
matrix
AW
AW
POTW
POTW
IW
IW
AW
AW
POTW
POTW
IW
IW
cipal sewage
IW
treatment plant.
Industrial wastewater containing an unidentified acrolein
reactant.
8030A - 9
Revision 1
July 1992
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Figure 1
Gas Chromatogram of Acrolein and Acrylonitrile
Column: Po< Ap«fc OS
HO*C
-------
METHOD 8030A
ACROLEIN AND ACRYLONITRILE BY GAS CHROMATOGRAPHY
Start
7 1 Introduce
compounds into ga s
chromatograph by
direct injection or
purge-and-trap
(Method 5030)
7 2 Set gas
chroma tograpn
cond 111on
1 3 Calibrate
(refer to Method
8000]
7 4 1 In t r oduce
volatile compounds
into gas
chromatograph by
purg«-and-trap or
direct injection
7 4 2 Pol low Method
8000 for analysis
sequence, etc
7 4 4 Record volume
purged or injected
and peak sizes
? 4 5 Calculate
concent ration
(refer to Method
8000)
Yesl
^
J
7 4 & Analyze using
second CC col umn
7 4 7 Oil
jle second
aliquot of sample -1
8030A - 11
Revision 1
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00
o
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METHOD 8031
ACRYLONITRILE BY GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 8031 is used to determine the concentration of acrylonitrile
in water. This method may also be applicable to other matrices. The following
compound can be determined by this method:
Compound Name CAS No.'
Acrylonitrile 107-13-1
8 Chemical Abstract Services Registry Number.
1.2 The estimated quantitation limit of Method 8031 for determining the
concentration of acrylonitrile in water is approximately 10 jug/L.
1.3 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatographs and skilled in the
interpretation of gas chromatograms. Each analyst must demonstrate the ability
to generate acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 A measured sample volume is micro-extracted with methyl tert-butyl
ether. The extract is separated by gas chromatography and measured with a
Nitrogen/Phosphorus detector.
3.0 INTERFERENCES
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that leads to discrete
artifacts and/or elevated baselines in gas chromatograms. All of these materials
must be routinely demonstrated to be free from interferences under the conditions
of the analysis by running laboratory reagent blanks.
3.2 Samples can be contaminated by diffusion of volatile organics around
the septum seal into the sample during handling and storage. A field blank
should be prepared from organic-free reagent water and carried through the
sampling and sample handling protocol to serve as a check on such contamination.
3.3 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed. To reduce carryover, the
8031 - 1 Revision 0
September 1994
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sample syringe must be rinsed out between samples with solvent. Whenever an
unusually concentrated sample is encountered, it should be followed by the
analysis of solvent to check for cross contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph system
4.1.1 Gas chromatograph, analytical system complete with gas
chromatograph suitable for on-column injections and all required
accessories, including detector, analytical columns, recorder, gases, and
syringes. A data system for measuring peak heights and/or peak areas is
recommended.
4.1.2 Column: Porapak Q - 6 ft., 80/10 Mesh, glass column, or
equivalent.
4.1.3 Nitrogen/Phosphorus detector.
4.2 Materials
4.2.1 Grab sample bottles - 40 ml VOA bottles.
4.2.2 Mixing bottles - 90 mL bottle with a Teflon lined cap.
4.2.3 Syringes - 10 y.1 and 50 ^L.
4.2.4 Volumetric flask (Class A) - 100 ml.
4.2.5 Graduated cylinder - 50 ml.
4.2.6 Pipet (Class A) - 5, 15, and 50 ml.
4.2.7 Vials - 10 ml.
4.3 Preparation
4.3.1 Prepare all materials to be used as described in Chapter 4 for
volatile organics.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall 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
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
8031 - 2 Revision 0
September 1994
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5.2 General
5.2.1 Methanol, CH3OH - Pesticide quality, or equivalent.
5.2.2 Organic-free reagent water. All references to water in this
method refer to organic-free reagent water, as defined in Chapter One.
5.2.3 Methyl tert-butyl ether, CH3Ot-C4H9 - Pesticide quality, or
equivalent.
5.2.4 Acrylonitrile, H2C:CHCN, 98%.
5.3 Stock standard solution
5.3.1 Stock standard solutions - Can be prepared from pure standard
materials or can be purchased as certified solutions. Prepare stock
standards in organic-free reagent water using assayed liquids.
5.3.2 The stock standard solution may be prepared by volume or by
weight. Stock solutions must be replaced after one year, or sooner if
comparison with the check standards indicates a problem.
CAUTION: Acrylonitrile is toxic. Standard preparation should be
performed in a laboratory fume hood.
5.3.2.1 To prepare the stock standard solution by volume:
inject 10 ul of acrylonitrile (98%) into a 100 ml volumetric flask
with a syringe. Make up to volume with methanol.
5.3.2.2 To prepare the stock standard solution by weight:
Place about 9.8 ml of organic-free reagent water into a 10 ml
volumetric flask before weighing the flask and stopper. Weigh the
flask and record the weight to the nearest 0.0001 g. Add two drops
of pure acrylonitrile, using a 50 ^L syringe, to the flask. The
liquid must fall directly into the water, without contacting the
inside wall of the flask. Stopper the flask and then reweigh.
Dilute to volume with organic-free reagent water. Calculate the
concentration from the net gain in weight.
5.4 Working standard solutions
5.4.1 Prepare a minimum of 5 working standard solutions that cover
the range of analyte concentrations -expected in the samples. Working
standards of 20, 40, 60, 80, and 100 j-tg/L may be prepared by injecting 10,
20, 30, 40, and 50 jul of the stock standard solution prepared in Sec.
5.3.2.1 into 5 separate 90 ml mixing bottles containing 40 ml of organic-
free reagent water.
5.4.2 Inject 15 ml of methyl tert-butyl ether into each mixing
bottle, shake vigorously, and let stand 5 minutes, or until layers have
separated.
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5.4.3 Remove 5 ml of top layer by pipet, and place in a 10 ml vial.
5.4.4 Keep all standard solutions below 4°C until used.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
7.1 Sample Extraction
7.1.1 Pour 40 mL of the sample into a 90 mL mixing bottle. Pipet 15
ml of Methyl, tert-butyl ether into the mixing bottle. Shake vigorously
for about 2 min. and let stand for about 5 min. Remove about 5 mL of the
top layer and store in a 10 mL vial.
7.2 Chromatographic Conditions (Recommended)
Carrier Gas (He) flow rate:
Column Temperature:
Injection port temperature:
Detector temperature:
Detector Current (DC):
Gases:
7.3 Calibration of GC
35 mL/min.
180° C, Isothermal
250° C
250° C
18 volts
Hydrogen, 3 mL/min; Air, 290 mL/min.
7.3.1 On a daily basis, inject 3 /xL of methyl tert-butyl ether
directly into the GC to flush the system. Also purge the system with
methyl tert-butyl ether injections between injections of standards and
samples.
7.3.2 Inject 3 ^L of a sample blank (organic-free reagent water
carried through the sample storage procedures and extracted with methyl
tert-butyl ether).
7.3.3 Inject 3 yuL of at least five standard solutions: one should
be near the detection limit; one should be near, but below, the expected
concentrations of the analyte; one should be near, but above, the expected
concentrations of the analyte. The range of standard solution
concentrations used should not exceed the working range of the GC system.
7.3.4 Prepare a calibration curve using the peak areas of the
standards (retention time of acrylonitrile under the conditions of Sec.
7.2 is approximately 2.3 minutes). If the calibration curve deviates
significantly from a straight line, prepare a new calibration curve with
the existing standards, or, prepare new standards and a new calibration
curve. See Method 8000, Sec. 7.4.2, for additional guidance on
calibration by the external standard method.
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7.4 Sample Analysis
7.4.1 Inject 3 ^L of the sample extract, using the same
chromatographic conditions used to prepare the standard curve. Calculate
the concentration of acrylonitrile in the extract, using the area of the
peak, against the calibration curve prepared in Sec. 7.3.4.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 8000 for specific quality control
procedures.
8.2 Prior to preparation of stock solutions, methanol and methyl
tert-butyl ether reagents should be analyzed gas chromatographically under the
conditions described in Sec. 7.2, to determine possible interferences with the
acrylonitrile peak. If the solvent blanks show contamination, a different batch
of solvents should be used.
9.0 METHOD PERFORMANCE
9.1 Method 8031 was tested in a single laboratory over a period of days.
Duplicate samples and one spiked sample were run for each calculation. The GC
was calibrated daily. Results are presented in Table 1.
10.0 REFERENCES
1. K.L. Anderson, "The Determination of Trace Amounts of Acrylonitrile in
Water by Specific Nitrogen Detector Gas Chromatograph", American Cynamid
Report No. WI-88-13, 1988.
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TABLE 1
SINGLE LABORATORY METHOD PERFORMANCE
CONCENTRATION
SAMPLE SPIKE (ng/L) % RECOVERY
A 60 100
B 60 105
C 40 86
D 40 100
E 40 88
F 60 94
Average 96
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METHOD 8031
ACRYLONITRILE BY GAS CHROMATOGRAPHY
Start
7.1.1 Extract 40 mL
of sample with methyl
t-butyl ether in 90 mL
bottle.
>
1
7.2 Set
Chromatographic
conditions.
^
r
7.3.1 Flush GC
system with 30 uL
methyl t-butyl ether.
>
f
7.3.2 Analyze 3 uL
of sample blank.
^
r
7.3.3 - 7.3.4 Establish
calibration curve with
at least 5 stds.
^l
r
7.4 Sample Analysis
x
r
Stop
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METHOD 8032
ACRYLAMIDE BY GAS CHROMAT06RAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 8032 is used to determine trace amounts of acrylamide monomer
in aqueous matrices. This method may be applicable to other matrices. The
following compound can be determined by this method:
Compound Name CAS No."
Acrylamide 79-06-01
a Chemical Abstract Services Registry Number.
1.2 The method detection limit (MDL) in clean water is 0.032
1.3 This method is restricted to use by, or under the supervision of,
analysts experienced in the use of gas chromatographs and skilled in the
interpretation of gas chromatograms. Each analyst must demonstrate the ability
to generate acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 Method 8032 is based on bromination of the acrylamide double bond.
The reaction product (2,3-dibromopropionamide) is extracted from the reaction
mixture with ethyl acetate, after salting out with sodium sulfate. The extract
is cleaned up using a Florisil column, and analyzed by gas chromatography with
electron capture detection (GC/ECD).
2.2 Compound identification should be supported by at least one
additional qualitative technique. Analysis using a second gas chromatographic
column or gas chromatography/mass spectrometry may be used for compound
confirmation.
3.0 INTERFERENCES
3.1 No interference is observed from sea water or in the presence of 8.0%
of ammonium ions derived from ammonium bromide. Impurities from potassium
bromide are removed by the Florisil clean up procedure.
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4.0 APPARATUS AND MATERIALS
4,1 Gas chromatographic System
4.1.1 Gas chromatograph suitable for on-column injections with all
required accessories, including detector, analytical columns, recorder,
gases, and syringes. A data system for measuring peak heights and/or peak
areas is recommended.
4.1.2 Column: 2 m x 3 mm glass column, 5% FFAP (free fatty acid
polyester) on 60-80 mesh acid washed Chromosorb W, or equivalent.
4.1.3 Detector: electron capture detector.
4.2 Kuderna-Danish (K-D) apparatus.
4.2.1 Concentrator tube - 10 mL graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.2.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.2.3 Snyder column - Three .ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.2.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.3 Separatory funnel - 150 ml.
4.4 Volumetric flask (Class A) - 100 ml, with ground glass stopper;
25 ml, amber, with ground glass stopper.
4.5 Syringe - 5 ml.
4.6 Microsyringes - 5 ^i, 100 /^L.
4.7 Pipets (Class A).
4.8 Glass column (30 cm x 2 cm).
4.9 Mechanical shaker.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
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such specifications are available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Solvents
5.3.1 Ethyl acetate, C2H5C02C2H5. Pesticide quality, or equivalent.
5.3.2 Diethyl ether, C2H5OC2H5. Pesticide quality, or equivalent.
Must be free of peroxides as indicated by test strips (EM Quant, or
equivalent). Procedures for removal of peroxides are provided with the
test strips. After cleanup, 20 ml of ethyl alcohol preservative must be
added to each liter of ether.
5.3.3 Methanol, CH3OH. Pesticide quality, or equivalent.
5.3.4 Benzene, C6H6. Pesticide quality, or equivalent.
5.3.5 Acetone, CH3COCH3. Pesticide quality, or equivalent.
5.4 Saturated bromine water. Prepare by shaking organic-free reagent
water with bromine and allowing to stand for 1 hour, in the dark, at 4°C. Use
the aqueous phase.
5.5 Sodium sulfate (anhydrous, granular), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.6 Sodium thiosulfate, Na2S203, 1 M aqueous solution.
5.7 Potassium bromide, KBr, prepared for infrared analysis.
5.8 Concentrated hydrobromic acid, HBr, specific gravity 1.48.
5.9 Acrylamide monomer, H2C:CHCONH2, electrophoresis reagent grade,
minimum 95% purity.
5.10 Dimethyl phthalate, C6H4(COOCH3)2, 99.0% purity.
5.11 Florisil (60/100 mesh): Prepare Florisil by activating at 130°C for
at least 16 hours. Alternatively, store Florisil in an oven at 130°C. Before
use, cool the Florisil in a desiccator. Pack 5 g of the Florisil, suspended in
benzene, in a glass column (Sec. 4.8).
5.12 Stock standard solutions
5.12.1 Prepare a stock standard solution of acrylamide monomer
as specified in Sec. 5.12.1.1. When compound purity is assayed to be 96%
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or greater, the weight can be used without correction to calculate the
concentration of the stock standard. Commercially prepared standards can
be used at any concentration if they are certified by the manufacturer or
by an independent source.
5.12.1.1 Dissolve 105.3 mg of acrylamide monomer in
organic-free reagent water in a 100 ml volumetric flask, and dilute
to the mark with organic-free reagent water. Dilute the solution of
acrylamide monomer so as to obtain standard solutions containing
0.1 - 10 mg/L of aery1 amide monomer.
5.13 Calibration standards
5.13.1 Dilute the acrylamide stock solution with organic-free
reagent water to produce standard solutions containing 0.1-5 mg/L of
acrylamide. Prior to injection the calibration standards are reacted and
extracted in the same manner as environmental samples (Sec. 7).
5.14 Internal standards
5.14.1 The suggested internal standard is dimethyl phthalate.
Prepare a solution containing 100 mg/L of dimethyl phthalate in ethyl
acetate. The concentration of dimethyl phthalate in the sample extracts
and calibration standards should be 4 mg/L.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
7.1 Bromination
7.1.1 Pipet 50 mL of sample into a 100 mL glass stoppered flask.
Dissolve 7.5 g of potassium bromide into the sample, with stirring.
7.1.2 Adjust the pH of the solution with concentrated hydrobromic
acid until the pH is between 1 and 3.
7.1.3 Wrap the flask with aluminum foil in order to exclude light.
Add 2.5 mL of saturated bromine water, with stirring. Store the flask and
contents in the dark, at 0°C, for at least 1 hour.
7.1.4 After reacting the solution for at least an hour, decompose
the excess of bromine by adding 1 M sodium thiosulfate solution, dropwise,
until the color of the solution is discharged.
7.1.5 Add 15 g of sodium sulfate, using a magnetic stirrer to effect
vigorous stirring.
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7.2 Extraction
7.2.1 Transfer the solution into a 150 mL separatory funnel. Rinse
the reaction flask three times with 1 ml aliquots of organic-free reagent
water. Transfer the rinsings into the separatory funnel.
7.2.2 Extract the aqueous solution with two 10 ml portions of ethyl
acetate for 2 min each, using a mechanical shaker (240 strokes per min).
Dry the organic phase with 1 g of sodium sulfate.
7.2.3 Transfer the organic phase into a 25 ml amber volumetric
flask. Rinse the sodium sulfate with three 1.5 ml portions of ethyl
acetate and combine the rinsings with the organic phase.
7.2.4 Add exactly 100 /ig of dimethyl phthalate to the flask and make
the solution up to the 25 ml mark with ethyl acetate. Inject 5 /LtL
portions of this solution into the gas chromatograph.
7.3 Florisil cleanup: Whenever interferences are observed, the samples
should be cleaned up as follows.
7.3.1 Transfer the dried extract into a Kuderna-Danish evaporator
with 15 ml of benzene. Evaporate the solvent at 70°C under reduced
pressure, and concentrate the solution to about 3 ml.
7.3.2 Add 50 ml of benzene and subject the solution to Florisil
column chromatography at a flow rate of 3 mL/min. Elute the column first
with 50 ml of diethyl ether/benzene (1:4) at a flow rate of 5 mL/min, and
then with 25 ml of acetone/benzene (2:1) at a flow rate of 2 mL/min.
Discard all of the first eluate and the initial 9 ml portion of the second
eluate, and use the remainder for the determination, using dimethyl
phthalate (4 mg/L) as an internal standard.
NOTE: Benzene is toxic, and should be only be used under a
ventilated laboratory hood.
7.4 Gas chromatographic conditions:
Nitrogen carrier gas flow rate: 40 mL/min
Column temperature: 165°C.
Injector temperature: 180°C
Detector temperature: 185°C.
Injection volume: 5 ^l
7.5 Calibration:
7.5.1 Inject 5 p.1 of a sample blank (organic-free reagent water
carried through all sample storage, handling, bromination and extraction
procedures).
7.5.2 Prepare standard solutions of acrylamide as described in Sec.
5.13.1. Brominate and extract each standard solution as described in
Sees. 7.1 and 7.2.
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7.5.2.1 Inject 5 ^L of each of a minimum of five standard
solutions: one should be near the detection limit; one should be
near, but below, the expected concentrations of the analyte; one
should be near, but above, the expected concentrations of the
analyte.
7.5.2.2 Prepare a calibration curve using the peak areas
of the standards. If the calibration curve deviates significantly
from a straight line, prepare a new calibration curve with the
existing standards, or, prepare new standards and a new calibration
curve. See Method 8000, Sec. 7.4.3, for additional guidance on
calibration by the internal standard method.
7.5.2.3 Calculate the response factor for each standard
according to Equation 1.
(Ps) (MJ
RF = Equation 1
(Pis) (MA)
RF = Response factor
Ps = Peak height of acrylamide
Mis = Amount of internal standard injected (ng)
Pis = Peak height of internal standard
MA = Amount of acrylamide injected (ng)
7.5.3 Calculate the mean response factor according to Equation 2.
n
ri
RF = Equation 2
n
RF = Mean response factor
RF = Response factors from standard analyses
(calculated in Equation 1)
n = Number of analyses
7.6 Gas chromatographic analysis:
7.6.1 Inject 5 ^l portions of each sample (containing 4 mg/L
internal standard) into the gas chromatograph. An example GC/ECD
chromatogram is shown in Figure 1.
7.6.2 The concentration of acrylamide monomer in the sample is given
by Equation 3.
[A] = - = - Equation 3
(Pis) (RF) (V,) (V.)
[A] = Concentration of acrylamide monomer in sample (mg/L)
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PA = Peak height of acrylamide monomer
Mjs = Amount of internal standard injected (ng)
Vs = Total volume of sample (mL)
P^ = Peak height of internal standard
RF = Mean response factor from Equation 2
V| = Injection volume
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 8000 for specific quality control
procedures.
9.0 METHOD PERFORMANCE
9.1 The following performance data have been generated under the
conditions described in this method:
9.1.1 The calibration curve for Method 8032 is linear over the range
0-5 M9/L of acrylamide monomer.
9.1.2 The limit of detection for an aqueous solution is 0.032 M9/L.
9.1.3 The yields of the brominated compound are 85.2 + 3.3% and 83.3
+ 0.9%, at fortification concentrations of 1.0 and 5.0 M9/L. respectively.
9.2 Table 1 provides the recoveries of acrylamide monomer from river
water, sewage effluent, and sea water.
9.3 The recovery of the bromination product as a function of the amount
of potassium bromide and hydrobromic acid added to the sample is shown in
Figure 2.
9.4 The effect of the reaction time on the recovery of the bromination
product is shown in Figure 3. The yield was constant when the reaction time was
more than 1 hour.
9.5 Figure 4 shows the recovery of the bromination product as a function
of the initial pH from 1 to 7.35. The yield was constant within this pH range.
The use of conventional buffer solutions, such as sodium acetate - acetic acid
solution or phosphate solution, caused a significant decrease in yield.
10.0 REFERENCES
1. Hashimoto, A., "Improved Method for the Determination of Acrylamide
Monomer in Water by Means of Gas-Liquid Chromatography with an Electron-
capture Detector," Analyst, 101:932-938, 1976.
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TABLE 1
RECOVERY OF ACRYLAMIDE FROM WATER SAMPLES AS
2,3-DIBROMOPROPIONAMIDE
Sample
Matrix
Standard
River Water
Sewage
Effluent
Sea Water
Acryl amide
Monomer
Spiked//ng
0.05
0.20
0.25
0.20
0.20
0.20
Amount of 2
Calculated
0.162
0.649
0.812
0.649
0.649
0.649
,3-DBPAa/Mg
Found0
0.138
0.535
0.677
0.531
0.542
0.524
Overall
Bromination
Recovery
%b
85.2
82.4
83.3
81.8
83.5
80.7
Recovery of
Acryl amide
Monomer, %b
—
99.4
101.3
98.8
Coefficient
of
Variation
3.3
1.0
0.9
2.5
3.0
3.5
a 2,3-Dibromopropionamide
b Mean of five replicate determinations
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Figure 1
s
JS
A
B
• I 10 12 U
Timt/min
Typical gas chromatograms of the bromination product obtained from aqueous
acrylamide monomer solution:
A. Untreated
B. With Florisil cleanup
BL. Chromatogram of blank, concentrated five-fold before gas chromatographic
analysis.
Peaks:
1.
2.
4-7.
2,3-Dibromopropionamide
Dimethyl phthalate
Impurities from potassium bromide
Sample size = 100 ml; acrylamide monomer = 0.1
8032 - 9
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Figure 2
§
V
cc
5 10 IS 20 25
Amount of KBr/g ptr SO ml
i . I • ' « n
0 2 4 6 8 10
Amount of H8f/ml ptr 50 ml
Effect of (A) potassium bromide and (B) hydrobromic acid on the yield of
bromination. Sample size « 50 ml; acrylamide monomer = 0.25 /*g
8032 - 10
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Figure 3
24
Effect of reaction time on the bromination. Reaction conditions:
50 ml of sample;
0.25 ng of acrylamide monomer;
7.5 g of potassium bromide;
2.5 ml of saturated bromine water
Extraction conditions:
15 g of sodium sulfate;
extraction at pH 2;
solvent = 10 ml of ethyl acetate (X2)
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Figure 4
100
50
01 2 349671
PM
Effect of initial pH on the bromination. Reaction and extraction conditions as
in Figure 3. The pH was adjusted to below 3 with concentrated hydrobromic acid,
and to 4-5 with dilute hydrobromic acid. Reaction at pH 6 was in distilled
water, pH 7.35 was achieved by careful addition of dilute sodium hydroxide
solution. The broken line shows the result obtained by the use of sodium acetate
- acetic acid buffer solution.
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METHOD 8032
ACRYLAMIOE BY GAS CHROMATOGRAPHY
Start
T
7.1 Bromination
1
7.1 .1 Dissolve 7.5 g KBr into
50 ml sample in flask.
i
7. 1.2 Adjust soln. pHwith
concentrated HBr to between
1 and 3.
1
7. 1.3 Wrap soln. flask with
aluminum. Add 2.5 ml satd.
bromine water, stir, store at
0 C for 1 hr.
1
7. 1.4 Add 1 M sodium
thiosulfate dropwise to flask to
decompose excess bromine.
I
7. 1. 5 Add 15 g sodium
sulfate, and stir.
1
7.2 Extraction
i
7.2.1 Transfer flask soln. to
sap. funnel along with rinses.
i
7.2.2 Extract soln. twice w/ethyl
acetate. Dry organic phase
using sodium sulfate.
1
7.2.3 Transfer organic phase
and rinses into amber
glass flask.
1
7.2.4 Add 100 ug dimethyl
phthalate to flask, dilute to
mark Inject 5 uL into GC.
1
7.3 Florisil Cleanup
1
7.3.1 Transfer dried extract to
K-D assembly w/benzene
Concentrate to 3 ml at 70 C
under reduced pressure.
7.3.2 Add 50 ml benzene to
solution. Pass soln. through
Florisil column. Elute with
diethyl ether/benzene, then
acetone/benzene. Collect
the second elution train (less
initial 9 ml) for analysis.
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METHOD 8032
continued
7.4 GC Conditions
7.5 Calibration
7.5.1 Inject 5 uL sample blank.
7.5.2 Brominate and extract std.
solns. similar to the samples.
. 1 Inject 5 uL of each of the
minimum 5 stds.
.2 Plot peak are vs. [).
.3 Calculate response factor
(RF) for each [ ].
7.5.3 Calculate mean RF from
eqn. 2.
I
7.6 GC Analysis
1
7.6.1 Inject 5 uL sample containing
internal std. into GC.
\
7.6.2 Calculate acrylamide monomer
concentration in sample using
eqn. 3.
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o
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METHOD 8040A
PHENOLS BY GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 8040 is used to determine the concentration of various
phenolic compounds. The following compounds can be determined by this method:
Compound Name
Appropriate Technique
CAS No.a 3510 3520 3540 3550 3580
2-sec-Butyl-4,6-dinitrophenol
(DNBP, Dinoseb)
4-Chloro-3-methylphenol
2-Chlorophenol
Cresols (methyl phenols)
2-Cyclohexyl-4,6-dinitrophenol
2,4-Dichlorophenol
2,6-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitropheno]
4-Nitrophenol
Pentachlorophenol
Phenol
Tetrachlorophenols
Trichlorophenols
2,4,6-Trichlorophenol
88-85-7 X NO NO NO X
-59-50-7 X X X X X
95-57-8 X X X X X
1319-77-3 X ND NO ND X
131-89-5 X ND ND ND LR
120-83-2 X X X X X
87-65-0 X ND ND ND X
105-67-9 X X X X X
51-28-5 X X X X X
534-52-1 X X X X X
88-75-5 X X X X X
100-02-7 X X X X X
87-86-5 X X X X X
108-95-2 DC(28) X X X X
25167-83-3 X ND ND ND X
25167-82-2 X X X X X
88-06-2 X X X X X
a Chemical Abstract Services Registry Number.
DC = Unfavorable distribution coefficient (number in parenthesis is percent
recovery).
LR = Low response.
ND = Not determined.
X = Greater than 70 percent recovery by this technique.
1.2 Table 1 lists the method detection limit for the target analytes in
water. Table 2 lists the estimated quantitation limit (EQL) for all matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8040 provides gas chromatographic conditions for the detection
of phenolic compounds. Prior to analysis, samples must be extracted using
appropriate techniques (see Chapter Two for guidance). Both neat and diluted
organic liquids (Method 3580, Waste Dilution) may be analyzed by direct
8040A - 1
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injection. A 2 to 5 p.1 sample is injected into a gas chromatograph using the
solvent flush technique, and compounds in the GC effluent are detected fay a flame
ionization detector (FID).
2.2 Method 8040 also provides for the preparation of pentafluorobenzyl-
bromide (PFB) derivatives, with additional cleanup procedures for electron
capture gas chromatography. This is to lower the detection limits of some
phenols and to aid the analyst in the elimination of interferences.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms. All of these materials must be demonstrated to be free
from interferences, under the conditions of the analysis, by analyzing reagent
blanks. Specific selection of reagents and purification of solvents by
distillation in all-glass systems may be required.
3.3 Interferences coextracted from samples will vary considerably from
source to source, depending upon the waste being sampled. Although general
cleanup techniques are recommended as part of this method, unique samples may
require additional cleanup.
3.4 The decomposition of some analytes under basic extraction conditions
has been demonstrated. Specifically, phenols may react to form tannates. These
reactions increase with increasing pH, and are decreased by the shorter reaction
times available in Method 3510.
3.5 The flame ionization detector (FID) is very susceptible to false
positives caused by the presence of hydrocarbons commonly found in samples from
waste sites. The problem may be minimized by applying acid-base cleanup (Method
3650) and/or alumina column chromatography (Method 3611) prior to GC/FID analysis
or using the derivatization technique and analyzing by GC/electron capture
detector. Initial site investigation should always be performed utilizing GC/MS
analysis to characterize the site and determine the feasibility of utilizing
Method 8040 with a GC/FID.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas Chromatograph - Analytical system complete with gas
chromatograph suitable for on-column injections and all required
accessories, including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak areas and/or peak heights is
recommended.
4.1.2 Columns
4.1.2.1 Column for underivatized phenols - 1.8 m x 2.0 mm
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ID glass column packed with 1% SP-1240DA on Supelcoport 80/100 mesh,
or equivalent.
4.1.2.2 Column for derivatized phenols - 1.8 m x 2 mm ID
glass column packed with 5% OV-17 on Chromosorb W-AW-DMCS 80/100
mesh, or equivalent.
4.1.3 Detectors - Flame ionization (FID) and electron capture (ECD).
4.2 Reaction vial - 20 ml, with Teflon lined screw-cap or crimp top.
4.3 Volumetric flask, Class A - Appropriate sizes with ground-glass
stoppers.
4.4 Kuderna-Danish (K-D) apparatus
4.4.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts.
4.4.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps or
equivalent.
4.4.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.4.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.4.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.5 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.6 Water bath - Heated, with concentric ring cover, capable of
temperature control (± 5°C). The bath should be used in a hood.
4.7 Microsyringe - 10 u.L.
4.8 Syringe - 5 ml.
4.9 Balance - analytical, 0.0001 g..
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall 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
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
8040A - 3 Revision 1
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5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Hexane, CH3(CH2)4CH3 - Pesticide quality or equivalent.
5.4 2-Propanol, (CH3)2CHOH - Pesticide quality or equivalent.
5.5 Toluene, C6H5CH3 - Pesticide quality or equivalent.
5.6 Derivatization reagent - Add 1 ml pentafluorobenzyl bromide and 1 g
18-crown-6-ether to a 50 mi volumetric flask and dilute to volume with
2-propanol. Prepare fresh weekly. This operation should be carried out in a
hood. Store at 4°C and protect from light.
5.6.1 Pentafluorobenzyl bromide (alpha-Bromopentafluorotoluene),
C6F5CH2Br. 97% minimum purity.
NOTE: This chemical is a lachrymator.
5.6.2 18-crown-6-ether (1,4,7,10,13,16-Hexaoxacyclooctadecane) -
98% minimum purity.
NOTE; This chemical is highly toxic.
5.7 Potassium carbonate (Powdered)., K2C03.
5.8 Stock standard solutions
5.8.1 Prepare stock standard solution at a concentration of
1000 mg/L by dissolving 0.0100 g of assayed reference material in
2-propanol and diluting to volume in a 10 ml volumetric flask. Larger
volumes can be used at the convenience of the analyst. When compound
purity is assayed to be 96% or greater, the weight can be used without
correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration if
they are certified by the manufacturer or by an independent source.
5.8.2 Transfer the stock standard solutions into bottles with Teflon
lined screw-caps or crimp tops. Store at 4°C and protect from light.
Stock standards should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards
from them.
5.8.3 Stock standard solutions must be replaced after one year, or
sooner if comparison with check standards indicates a problem.
5.9 Calibration standards - Prepare calibration standards at a minimum
of five concentrations through dilution of the stock standards with 2-propanol.
One of the concentrations should be at a concentration near, but above, the
method detection limit. The remaining concentrations should correspond to the
expected range of concentrations found in real samples or should define the
working range of the GC. Calibration solutions must be replaced after six
months, or sooner, if comparison with check standards indicates a problem.
8040A - 4 Revision 1
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5.10 Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.10.1 Prepare calibration standards at a minimum of five
concentrations for each analyte as described in Section 5.9.
5.10.2 To each calibration standard, add a known constant
amount of one or more internal standards, and dilute to volume with 2-
propanol.
5.10.3 Analyze each calibration standard according to Section
7.0.
5.11 Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (if necessary), and analytical system and the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and organic-free reagent water blank with phenolic surrogates
(e.g. 2-fluorophenol and 2,4,6-tribromophenol) recommended to encompass the range
of the temperature program used in this method. Method 3500 details instructions
on the preparation of acid surrogates. Deuterated analogs of analytes should not
be used as surrogates for gas chromatographic analysis due to coelution problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and analyzed within 40
days of extraction.
7.0 PROCEDURE
7.1 Extraction
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a pH of
less than or equal to 2 with methylene chloride, using either Method 3510
or 3520. Solid samples are extracted using either Method 3540 or 3550,
and non-aqueous samples using Method 3580. Extracts obtained from
application of either Method 3540 or 3550 should undergo Acid-Base
Partition Cleanup, using Method 3650.
7.1.2 Prior to gas chromatographic analysis, the extraction solvent
must be exchanged to 2-propanol. The exchange is performed as follows:
7.1.2.1 Following concentration of the extract to 1 mL
using the macro-Snyder column, allow the apparatus to cool and drain
for at least 10 minutes.
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7.1.2.2 Remove the micro-Snyder column and rinse its lower
joint into the concentrator tube with a minimum amount of 2-
propanol. Adjust the extract volume to 1.0 ml. Stopper the
concentrator tube and store refrigerated at 4°C if further
processing will not be performed immediately. If the extract will
be stored longer than two days, it should be transferred to a vial
with a Teflon lined screw-cap or crimp top. If the extract requires
no further derivatization or cleanup, proceed with gas
chromatographic analysis.
7.2 Gas chromatographic conditions (Recommended)
7.2.1 Column for underivatized phenols -
Carrier gas (N2) flow rate: 30 ml/min
Initial temperature: 80°C
Temperature program: 80°C to 150°C at 8°C/min
Final Temperature: 150°C, hold until all compounds have
eluted.
7.2.2 Column for derivatized phenols -
Carrier gas (5% methane/95% argon)
flow rate: 30 mL/min
Initial temperature: 200°C
Temperature program: isothermal, hold until all
compounds have eluted.
7.3 Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.
7.3.1 The procedure for internal or external calibration may be used
for the underivatized phenols. Refer to Method 8000 for a description of
each of these procedures. If derivatization of the phenols is required,
the method of external calibration should be used by injecting five or
more concentrations of calibration standards that have also undergone
derivatization and cleanup prior to instrument calibration.
7.4 Gas chromatographic analysis
7.4.1 Refer to Method 8000. If the internal standard calibration
technique is used, add 10 jiL of internal standard to the sample prior to
injection.
7.4.2 Phenols are to be determined on a gas chromatograph equipped
with a flame ionization detector according to the conditions listed for
the 1% SP-1240DA column (Section 7.2.1). Table 1 summarizes estimated
retention times and sensitivities that should be achieved by this method
for clean water samples. Estimated quantitation limits for other
matrices are list in Table 2.
7.4.3 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
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Identification criteria. Include a mid-concentration standard after each
group of 10 samples in the analysis sequence.
7.4.4 An example of a GC/FID chromatogram for certain phenols is
shown in Figure 1. Other packed or capillary (open-tubular) columns,
chromatographic conditions, or detectors may be used if the requirements
of Section 8.2 are met.
7.4.5 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).
7.4.6 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes. See Method 8000 for calculation equations.
7.4.7 If peak detection using the SP-1240DA column with the flame
ionization detector is prevented by interferences, PFB derivatives of the
phenols should be analyzed on a gas chromatograph equipped with an
electron capture detector according to the conditions listed for the 5%
OV-17 column (Section 7.2.2). The derivatization and cleanup procedure
is outlined in Sections 7.5 through 7.6. Table 3 summarizes estimated
retention times for derivatives of some phenols using the conditions of
this method.
7.4.8 Figure 2 shows a GC/ECD chromatogram of PFB derivatives of
certain phenols.
7.4.9 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).
7.4.10 Determine the identity and quantity of each component
peak in the sample chromatogram which corresponds to the compounds used
for calibration purposes. The method of external calibration should be
used (see Method 8000 for guidance). The concentration of the individual
compounds in the sample is calculated as follows:
Concentration (/ig/L) =
where:
A » Mass of underivatized phenol represented by area of peak
in sample chromatogram, determined from calibration
curve (see Method 8000), ng.
Vt - Total amount of column eluate or combined fractions from
which V,. was taken, ML.
B = Total volume of hexane added in Section 7.5.5, ml.
D - Total volume of 2-propanol extract prior to
derivatization, ml.
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V, * Volume injected, /nL.
X * Volume of water extracted, ml, or weight of nonaqueous
sample extracted, g, from Section 7.1. Either the dry
or wet weight of the nonaqueous sample may be used,
depending upon the specific application of the data.
C » Volume of hexane sample solution added to cleanup column
(Method 3630), ml.
E = Volume of 2-propanol extract carried through
derivatization in Section 7.5.1, ml.
7.5 Derivatization - If interferences prevent measurement of peak area
during analysis of the extract by flame ionization gas chromatography, the
phenols must be derivatized and analyzed by electron capture gas chromatography.
7.5.1 Pipet a 1.0 ml aliquot of the 2-propanol stock standard
solution or of the sample extract into a glass reaction vial. Add 1.0 ml
derivatization reagent (Section 5.3). This amount of reagent is
sufficient to derivatize a solution whose total phenolic content does not
exceed 300 mg/L.
7.5.2 Add approximately 0.003 g of potassium carbonate to the
solution and shake gently.
7.5.3 Cap the mixture and heat it for 4 hours at 80°C in a hot water
bath.
7.5.4 Remove the solution from the hot water bath and allow it to
cool.
7.5.5 Add 10 mi hexane to the reaction vial and shake vigorously for
1 minute. Add 3.0 ml organic-free reagent water to the reaction vial and
shake for 2 minutes.
7.5.6 Decant the organic layer into a concentrator tube and cap with
a glass stopper. Proceed with cleanup procedure.
7.6 Cleanup
7.6.1 Cleanup of the derivatized extracts takes place using Method
3630 (Silica Gel Cleanup), in which specific instructions for cleanup of
the derivatized phenols appear.
7.6.2 Following column cleanup, analyze the samples using GC/ECD, as
described starting in Section 7.4.7.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
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the extraction method used. If extract cleanup was performed, follow the QC in
Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method 8000,
Section 8.6.
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each analyte of interest at a concentration
of 100 mg/L in 2-propanol.
8.2.2 Table 4 indicates the calibration and QC acceptance criteria
for this method. Table 5 gives method accuracy and precision as
functions of concentration for the analytes. The contents of both tables
should be used to evaluate a laboratory's ability to perform and generate
acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following is required.
• Check to be sure that there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are a
problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 The method was tested by 20 laboratories using organic-free reagent
water, drinking water, surface water, and three industrial wastewaters spiked at
six concentrations over the range 12 to 450 M9/L- Single operator precision,
overall precision, and method accuracy were found to be directly related to the
concentration of the analyte and essentially independent of the sample matrix.
Linear equations to describe these relationships for a flame ionization detector
are presented in Table 5.
9.2 The accuracy and precision obtained will be affected by the sample
matrix, sample-preparation technique, and calibration procedures used.
10.0 REFERENCES
1. Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters. Category 3 - Chlorinated Hydrocarbons and
Category 8 - Phenols. Report for EPA Contract 68-03-2625 (in
preparation).
804-OA - 9 Revision 1
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U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for
the Analysis of Pollutants Under the Clean Water Act; Final Rule and
Interim Final Rule and Proposed Rule," October 26, 1984.
"Determination of Phenols in Industrial and Municipal Wastewaters,"
Report for EPA Contract 68-03-2625 (in preparation).
"EPA Method Validation Study Test Method 604 (Phenols)," Report for EPA
Contract 68-03-2625 (in preparation).
Kawahara, F.K. "Microdetermination of Derivatives of Phenols and
Mercaptans by Means of Electron Capture Gas Chromatography," Analytical
Chemistry, 40, 1009, 1968.
Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
8040A - 10 Revision 1
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TABLE 1.
FLAME IONIZATION GAS CHROMATOGRAPHY OF PHENOLS*
Method
Retention time Detection
Analyte (minutes) limit
2-sec-Butyl -4,6-dinitrophenol (DNBP)
4-Chloro-3-methyl phenol 7.50 0.36
2-Chlorophenol 1.70 0.31
Cresols (methyl phenols)
2-Cyclohexyl -4,6-dinitrophenol
2,4-Dichlorophenol 4.30 0.39
2,6-Dichlorophenol
2,4-Dimethylphenol 4.03 0.32
2,4-Dinitrophenol 10.00 13.0
2-Methyl -4,6-dinitrophenol 10.24 16.0
2-Nitrophenol 2.00 0.45
4-Nitrophenol 24.25 2.8
Pentachlorophenol 12.42 7.4
Phenol 3.01 0.14
Tetrachl orophenol s
Trichlorophenols
2,4,6-Trichlorophenol 6.05 0.64
a - 1% SP-1240DA on Supelcoport 80/100 mesh column.
TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION
LIMITS (EQLs) FOR VARIOUS MATRICES"
Matrix Factor6
Ground water 10
Low-concentration soil by sonication with GPC cleanup 670
High-concentration soil and sludges by sonication 10,000
Non-water miscible waste 100,000
a Sample EQLs are highly matrix-dependent. The EQLs listed herein are provided
for guidance and may not always be achievable.
b EQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor is on a wet-weight basis.
8040A - 11 Revision 1
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TABLE 3.
ELECTRON CAPTURE GAS CHROMATOGRAPHY OF PFB DERIVATIVES8
Parent compound
4-Chl oro-2-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2, 4-Dimethyl phenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Retention
time
(min)
4.8
3.3
5.8
2.9
46.9
36.6
9.1
14.0
28.8
1.8
7.0
Method
detection
limit (jug/L)
1.8
0.58
0.68
0.63
0.77
0.70
0.59
2.2
0.58
- 5% OV-17 on Chromosorb W-AW-OMCS 80/100 mesh column,
8040A - 12 Revision 1
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TABLE 4.
QC ACCEPTANCE CRITERIA'
Analyte
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
s - Standard deviation of
x =• Average recovery for
Test
cone.
(M9/L)
100
100
100
100
100
100
100
100
100
100
100
four recovery
four recovery
Limit
for s
(M9/L)
16.6
27.0
25.1
33.3
25.0
36.0
22.5
19.0
32.4
14.1
16.6
measurements
measurements,
Range
for x
(M9/L)
56.7-113.4
54.1-110.2
59.7-103.3
50.4-100.0
42.4-123.6
31.7-125.1
56.6-103.8
22.7-100.0
56.7-113.5
32.4-100.0
60.8-110.4
, in M9/L.
in M9/L.
Recovery
Range
(%)
99-122
38-126
44-119
24-118
30-136
12-145
43-117
13-110
36-134
23-108
53-119
a Criteria from 40 CFR Part 136 for Method 604. These criteria are based
directly upon the method performance data in Table 5. Where necessary, the
limits for recovery have been broadened to assure applicability of the
limits to concentrations below those used to develop Table 5.
8040A - 13 Revision 1
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TABLE 5.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION*
Analyte
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Accuracy, as
recovery, x'
(M9/U
0.87C-1.97
0.83C-0.84
0.81C+0.48
0.62C-1.64
0.84C-1.01
0.80C-1.58
0.81C-0.76
0.46C+0.18
0.83C+2.07
0.43C+0.11
0.86C-0.40
Single analyst
precision, s '
(M9/L)
O.llx-0.21
O.lSx+0.20
0.17X-0.02
0.30X-0.89
O.lBx+1.25
0.27X-1.15
0.15X+0.44
0.17X+2.43
0.22X-0.58
0.20X-0.88
O.lOx+0.53
Overall
precision,
S' (M9/L)
0.16X+1.41
0.21X+0.75
0.18X+0.62
0.25X+0.48
0.19X+5.85
0.29X+4.51
0.14x+3.84
0.19X+4.79
0.23X+0.57
0.17X+0.77
0.13X+2.40
X'
C
X
Expected recovery for one or more measurements of a sample
containing a concentration of C, in /ug/L.
Expected single analyst standard deviation of measurements at an
average concentration of x, in /ig/L.
Expected interlaboratory standard deviation of measurements at an
average concentration found of x, in /ig/L.
True value for the concentration, in jug/l.
Average recovery found for measurements of samples containing a
concentration of C, in /jg/L.
"From 40 CFR Part 136 for Method 604.
8040A - 14
Revision 1
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Figure 1
Gas Chromatogram of Phenols
Column: 1% Sf-12*00A on Supdcooort
Program: 80°C 0 MinutM 8°/Minute to 150°C
0«ttcxer: Fl«m« formation
1
i
I 12 18 20 24
RCTINT1ON TIME (MINUTES)
21
8040A - 15
Revision 1
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Figure 2
Gas Chromatogram of PFB Derivatives of Phenols
Column: 5% OV-17 on Giromaiorb W-AW
T«mpof«unj: 200°C
Octoetor: Iloetroft Cwtvrc
A_
« « » 24
ftlTfNTtON TIMI (MINUTQ)
2t
31
8040A - 16
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METHOD 8040A
PHENOLS BY GAS CHROMATOGRAPHY
7 1 1 Cho
appr opr i
ex t r ac t1
me thod {r
to Chapte
se
I*
n
f.r
21
7 1 2
Enchange
ex traction
jo 1ven t Lo
2-propjnol
^ 2 Set gaj
chroma tography
condition*
7 3 Refar to
Method 8000
for propar
calibration
technique!
7 3 1 Inject at
lea.t S
concen t ra11oni
of ca11bra 11on
>tandard>
7 4 Perform
CC analy»ia
(see He thod
8000)
7 4 analyze
using CC/FIO
8040A - 17
Revision 1
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METHOD 8040A
(Continued)
7 S Pr«p»r«
d«rivativ«t
No
749 Record
J*mpl* volum*
in j«ct*d and
1 6 Cleanup
using Method
3630
7 1 10
IdvnIitify and
quantital« each
componvnl pvalc
7 4 7 Analyi.
PFB
d«riva tiv«a
ujing CC/ECD
7 4 10
Calculate
conc«nt ration
Stop
8040A - 18
Revision 1
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00
o
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METHOD 8061
PHTHALATE ESTERS BY CAPILLARY GAS CHROMATOGRAPHY
WITH ELECTRON CAPTURE DETECTION (GC/ECD)
1.0 SCOPE AND APPLICATION
1.1 Method 8061 is used to determine the identities and concentrations
of various phthalate esters in liquid, solid and sludge matrices. The following
compounds can be determined by this method:
Compound Name CAS No.8
Benzyl benzoate (I.S.) 120-51-4
Bis(2-ethylhexyl) phthalate 117-81-7
Butyl benzyl phthalate 85-68-7
Di-n-butyl phthalate 84-74-2
Diethyl phthalate 84-66-2
Dimethyl phthalate 131-11-3
Di-n-octyl phthalate 117-84-0
8 Chemical Abstract Services Registry Number.
1.2 Table 1 lists the method detection limits (MDL) for the target
analytes in a water matrix. The MDLs for the components of a specific sample may
differ from those listed in Table 1 because MDLs depend on the nature of
interferences in the sample matrix. Table 2 lists the estimated quantitation
limits (EQL) for other matrices.
1.3 When this method is used to analyze for any or all of the target
analytes, compound identification should be supported by at least one additional
qualitative technique. This method describes conditions for parallel column,
dual electron capture detector analysis which fulfills the above requirement.
Retention time information obtained on two megabore fused-silica open tubular
columns is given in Table 1. Alternatively, gas chromatography/mass spectrometry
could be used for compound confirmation.
1.4 The following compounds, bis(2-n-butoxyethyl) phthalate, bis(2-
ethoxyethyl) phthalate, bis(2-methoxyethyl) phthalate, bis(4-tnethyl-2-pentyl)
phthalate, diamyl phthalate, dicyclohexyl phthalate, dihexyl phthalate,
diisobutyl phthalate, dinonyl phthalate, and hexyl 2-ethylhexyl phthalate can
also be analyzed by this method and may be used as surrogates.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatographs and skilled in the
interpretation of gas chromatograms. Each analyst must demonstrate the ability
to generate acceptable results with this method.
8061 - 1 Revision 0
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2.0 SUMMARY OF METHOD
2.1 A measured volume or weight of sample (approximately 1 liter for
liquids, 10 to 30 grams for solids and sludges) is extracted by using the
appropriate sample extraction technique specified in Methods 3510, 3540, 3541,
and 3550. Method 3520 is not recommended for the extraction of aqueous samples
because the longer chain esters (dihexyl phthalate, bis(2-ethylhexyl) phthalate,
di-n-octyl phthalate, and dinonyl phthalate) tend to adsorb to the glassware and
consequently, their extraction recoveries are <40 percent. Aqueous samples are
extracted at a pH of 5 to 7, with methylene chloride, in a separatory funnel
(Method 3510). Alternatively, particulate-free aqueous samples could be filtered
through membrane disks that contain C18-bonded silica. The phthalate esters are
retained by the silica and, later eluted with acetonitrile. Solid samples are
extracted with hexane/acetone (1:1) or methylene chloride/acetone (1:1) in a
Soxhlet extractor (Methods 3540/3541) or with an ultrasonic extractor (Method
3550). After cleanup, the extract is analyzed by gas chromatography with
electron capture detection (GC/ECD).
2.2 The sensitivity of Method 8061 usually depends on the level of
interferences rather than on instrumental limitations. If interferences prevent
detection of the analytes, cleanup of the sample extracts is necessary. Either
Method 3610 or 3620 alone or followed by Method 3660, Sulfur Cleanup, may be used
to eliminate interferences in the analysis. Method 3640, Gel Permeation Cleanup,
is applicable for samples that contain high amounts of lipids and waxes.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 Interferences coextracted from the samples will vary considerably
from waste to waste. While general cleanup techniques are referenced or provided
as part of this method, unique samples may require additional cleanup approaches
to achieve desired sensitivities for the target analytes.
3.3 Glassware must be scrupulously clean. All glassware require
treatment in a muffle furnace at 400 "C for 2 to 4 hrs, or thorough rinsing with
pesticide-grade solvent, prior to use. Refer to Chapter 4, Sec. 4.1.4, for
further details regarding the cleaning of glassware. Volumetric glassware should
not be heated in a muffle furnace.
If Soxhlet extractors are baked in the muffle furnace, care must be taken
to ensure that they are dry (breakage may result if any water is left in the
side-arm). Thorough rinsing with hot tap water, followed by deionized water and
acetone is not an adequate decontamination procedure. Even after a Soxhlet
extractor was refluxed with acetone for three days, with daily solvent changes,
the concentrations of bis(2-ethylhexyl) phthalate were as high as 500 ng per
washing. Storage of glassware in the laboratory introduces contamination, even
if the glassware is wrapped in aluminum foil. Therefore, any glassware used in
Method 8061 should be cleaned immediately prior to use.
3.4 Florisil and alumina may be contaminated with phthalate esters and,
therefore, use of these materials in sample cleanup should be employed
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cautiously. If these materials are used, they must be obtained packaged in glass
(plastic packaging will contribute to contamination with phthalate esters).
Washing of these materials prior to use with the solvent(s) used for elution
during extract cleanup was found helpful, however, heating at 320 °C for Florisil
and 210 °C for alumina is recommended. Phthalate esters were detected in
Florisil cartridge method blanks at concentrations ranging from 10 to 460 ng,
with 5 phthalate esters in the 105 to 460 ng range. Complete removal of the
phthalate esters from Florisil cartridges does not seem possible, and it is
therefore desirable to keep the steps involved in sample preparation to a
minimum.
3.5 Paper thimbles and filter paper must be exhaustively washed with the
solvent that will be used in the sample extraction. Soxhlet extraction of paper
thimbles and filter paper for 12 hrs with fresh solvent should be repeated for
a minimum of three times. Method blanks should be obtained before any of the
precleaned thimbles or filter papers are used. Storage of precleaned thimbles
and filter paper in precleaned glass jars covered with aluminum foil is
recommended.
3.6 Glass wool used in any step of sample preparation should be a
specially treated pyrex wool, pesticide grade, and must be baked at 400°C for
4 hrs. immediately prior to use.
3.7 Sodium sulfate must be obtained packaged in glass (plastic packaging
will contribute to contamination with phthalate esters), and must be purified by
heating at 400 °C for 4 hrs. in a shallow tray, or by precleaning with methylene
chloride (Sec. 5.3). To avoid recontamination, the precleaned material must be
stored in glass-stoppered glass bottles, or glass bottles covered with precleaned
aluminum foil. The storage period should not exceed two weeks. To minimize
contamination, extracts should be dried directly in the glassware in which they
are collected by adding small amounts of precleaned sodium sulfate until an
excess of free flowing material is noted.
3.8 The presence of elemental sulfur will result in large peaks which
often mask the region of the compounds eluting before dicyclohexyl phthalate
(Compound No. 14) in the gas chromatograms shown in Figure 1. Method 3660 is
suggested for removal of sulfur.
3.9 Waxes and lipids can be removed by Gel Permeation Chromatography
(Method 3640). Extracts containing high concentrations of lipids are viscous,
and may even solidify at room temperature.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatography
4.1.1 Gas chromatograph, analytical system complete with gas
chromatograph suitable for on-column and split/splitless injections and
all required accessories, including detector, analytical columns,
recorder, gases, and syringes. A data system for measuring peak heights
and/or peak areas is recommended.
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4.1.1.1 Eight inch injection tee (Supelco, Inc., Catalog
No. 2-3665, or equivalent) or glass Y splitter for megabore columns
(J&W Scientific,-"press-fit", Catalog No. 705-0733, or equivalent).
4.1.2 Columns
4.1.2.1 Column 1, 30 m x 0.53 mm ID, 5% phenyl/95% methyl
silicone fused-silica open tubular column (DB-5, J&W Scientific, or
equivalent), 1.5 p,m film thickness.
4.1.2.2 Column 2, 30 m x 0.53 mm ID, 14% cyanopropyl
phenyl silicone fused-silica open tubular column (DB-1701, J&W
Scientific, or equivalent), 1.0 fj,m film thickness.
4.1.3 Detector - Dual electron capture detector (ECD)
4.2 Glassware, see Methods 3510, 3540, 3541, 3550, 3610, 3620, 3640, and
3660 for specifications.
4.3 Kuderna-Danish (K-D) apparatus.
4.3.1 Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500 mL (Kontes K-570001-500 or equiva-
lent). Attach to concentrator tube with springs, clamps, or equivalent.
4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.4 Boiling chips, approximately 10/40 mesh. Heat to 400 °C for 30 min,
or Soxhlet-extract with methylene chloride prior to use.
4.5 Water bath, heated, with concentric ring cover, capable of
temperature control (+ 2°C).
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall 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 ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
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5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400 °C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.4 Solvents:
5.4.1 Hexane, C6H14 - Pesticide quality, or equivalent.
5.4.2 Methylene chloride, CH2C12 - Pesticide quality, or equivalent.
5.4.3 Acetone, CH3COCH3 - Pesticide quality, or equivalent.
5.4.4 Acetonitrile, CH3CN - HPLC grade.
5.4.5 Methanol, CH3OH - HPLC grade.
5.4.6 Diethyl Ether, C2H5OC2H5 - Pesticide quality, or equivalent.
Must be free of peroxides, as indicated by test strips (EM Quant, or
equivalent). Procedures for removal of peroxides are provided with the
test strips. After cleanup, 20 ml of ethyl alcohol preservative must be
added to each liter of ether.
5.5 Stock standard solutions:
5.5.1 Prepare stock standard solutions at a concentration of
1000 mg/L by dissolving 0.0100 g of assayed reference material in hexane,
and diluting to volume in a 10 ml volumetric flask. When compound purity
is assayed to be 96 percent or greater, the weight can be used without
correction to calculate the concentration of the stock standard.
Commercially prepared stock standard solutions can be used at any
concentration if they are certified by the manufacturer or by an
independent source.
5.5.2 Transfer the stock standard solutions into glass vials with
Teflon lined screw-caps or crimp tops. Store at 4 °C and protect from
light. Stock standard solutions should be checked periodically by gas
chromatography for signs of degradation or evaporation, especially just
prior to preparation of calibration standards.
5.5.3 Stock standard solutions must be replaced after 6 months, or
sooner if comparison with check standards indicates a problem.
5.6 Calibration standards: Calibration standards are prepared at a
minimum of five concentrations for each parameter of interest through dilution
of the stock standard solutions with hexane. One of the concentrations should
be at a concentration near, but above, the method detection limit. The remaining
concentrations should correspond to the expected range of concentrations found
in real samples, or should define the working range of the GC. Calibration
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solutions must be replaced after 1 to 2 months, or sooner if comparison with
calibration verification standards indicates a problem.
5.7 Internal standards (if internal standard calibration is used): To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Benzyl benzoate has been tested and
found appropriate for Method 8061.
5.7.1 Prepare a spiking solution of benzyl benzoate in hexane at
5000 mg/L. Addition of 10 juL of this solution to 1 ml of sample extract
is recommended. The spiking concentration of the internal standard should
be kept constant for all samples and calibration standards. Store the
internal standard spiking solution at 4 °C in glass vials with Teflon
lined screw-caps or crimp tops. Standard solutions should be replaced
when ongoing QC (Sec. 8) indicates a problem.
5.8 Surrogate standards: The analyst should monitor the performance of
the extraction, cleanup (when used), analytical system, and the effectiveness of
the method in dealing with each sample matrix by spiking each sample, standard,
and blank with surrogate compounds. Three surrogates may be used for Method 8061
in addition to those listed in Sec. 1.4: diphenyl phthalate, diphenyl
isophthalate, and dibenzyl phthalate. However, the compounds listed in Sec. 1.4
are recommended.
5.8.1 Prepare a surrogate standard spiking solution, in acetone,
which contains 50 ng/juL of each compound. Addition of 500 /iL of this
solution to 1 L of water or 30 g solid sample is equivalent to 25 ^tg/L of
water or 830 M9A9 °f solid sample. The spiking concentration of the
surrogate standards may be adjusted accordingly, if the final volume of
extract is reduced below 2 ml for water samples or 10 ml for solid
samples. Store the surrogate spiking solution at 4 °C in glass vials with
Teflon lined screw-caps or crimp tops. The solution must be replaced
after 6 months, or sooner if ongoing QC (Sec. 8) indicates problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
7.1 Extraction:
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a pH of
5 to 7 with methylene chloride in a separatory funnel (Method 3510).
Method 3520 is not recommended for the extraction of aqueous samples
because the longer chain esters (dihexyl phthalate bis(2-ethylhexyl)
phthalate, di-n-octyl phthalate, and dinonyl phthalate) tend to adsorb to
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the glassware and consequently, their extraction recoveries are
<40 percent. Solid samples are extracted with hexane/acetone (1:1) or
methylene chloride/acetone (1:1) in a Soxhlet extractor (Methods
3540/3541) or with an ultrasonic extractor (Method 3550). Immediately
prior to extraction, spike 500 p,l of the surrogate standard spiking
solution (concentration = 50 ng//iL) into 1 L aqueous sample or 30 g solid
sample.
7.1.2 Extraction of particulate-free aqueous samples using
C18-extraction disks (optional):
7.1.2.1 Disk preconditioning: Place the C18-extraction disk
into the filtration apparatus and prewash the disk with 10 to 20 ml
of acetonitrile. Apply vacuum to pull the solvent through the disk.
Maintain vacuum to pull air through for 5 min. Follow with 10 ml of
methanol. Apply vacuum and pull most of the methanol through the
disk. Release vacuum before the disk gets dry. Follow with 10 ml
organic-free reagent water. Apply vacuum and pull most of the water
through the disk. Release the vacuum before the disk gets dry.
7.1.2.2 Sample preconcentration: Add 2.5 ml of methanol to
the 500 ml aqueous sample in order to get reproducible results.
Pour the sample into the filtration apparatus. Adjust vacuum so
that it takes approximately 20 min to process the entire sample.
After all of the sample has passed through the membrane disk, pull
air through the disk for 5 to 10 min. to remove any residual water.
7.1.2.3 Sample elution: Break the vacuum and place the tip
of the filter base into the test tube that is contained inside the
suction flask. Add 10 ml of acetonitrile to the graduated funnel,
making sure to rinse the walls of the graduated funnel with the
solvent. Apply vacuum to pass the acetonitrile through the membrane
disk.
7.1.2.4 Extract concentration (if necessary): Concentrate
the extract to 2 ml or less, using either the micro Snyder column
technique (Sec. 7.1.2.4.1) or nitrogen blowdown technique (Sec.
7.1.2.4.2).
7.1.2.4.1 Micro Snyder Column Technique
7.1.2.4.1.1 Add one or two clean boiling chips to
the concentrator tube and attach a two ball micro Snyder
column. Prewet the column by adding about 0.5 ml of
acetonitrile to the top of the column. Place the K-D
apparatus in a hot water bath (15-20°C above the boiling
point of the solvent) so that the concentrator tube is
partially immersed in the hot water and the entire lower
rounded surface of the flask is bathed with hot vapor.
Adjust the vertical position of the apparatus and the
water temperature, as required, to complete the
concentration in 5-10 minutes. At the proper rate of
distillation the balls of the column will actively
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chatter, but the chambers will not flood. When the
apparent volume of liquid reaches 0.5 mL, remove the K-D
apparatus from the water bath and allow it to drain and
cool for at least 10 minutes. Remove the Snyder column
and rinse the flask and its lower joints with about
0.2 ml of solvent and add to the concentrator tube.
Adjust the final volume to 1.0-2.0 ml with solvent.
7.1.2.4.2 Nitrogen Slowdown Technique
7.1.2.4.2.1 Place the concentrator tube in a warm
water bath (approximately 35 °C) and evaporate the
solvent volume to the required level using a gentle
stream of clean, dry nitrogen (filtered through a column
of activated carbon).
CAUTION: Do not use plasticized tubing between
the carbon trap and the sample.
7.1.2.4.2.2 The internal wall of the tube must be
rinsed down several times with acetonitrile during the
operation. During evaporation, the solvent level in the
tube must be positioned to prevent water from condensing
into the sample (i.e., the solvent level should be below
the level of the water bath). Under normal operating
conditions, the extract should not be allowed to become
dry.
7.2 Solvent Exchange: Prior to Florisil cleanup or gas chromatographic
analysis, the methylene chloride and methylene chloride/acetone extracts obtained
in Sec. 7.1.1 must be exchanged to hexane, as described in Sees. 7.2.1 through
7.2.3. Exchange is not required for the acetonitrile extracts obtained in
Sec. 7.1.2.4.
7.2.1 Add one or two clean boiling chips to the flask and attach a
three ball Snyder column. Concentrate the extract as described in Sec.
7.1.2.4.1, using 1 ml of methylene chloride to prewet the column, and
completing the concentration in 10-20 minutes. When the apparent volume
of liquid reaches 1-2 ml, remove the K-D apparatus from the water bath and
allow it to drain and cool for at least 10 minutes.
7.2.2 Momentarily remove the Snyder column, add 50 ml of hexane, a
new boiling chip, and attach the macro Snyder column. Concentrate the
extract as described in Sec. 7.1.2.4.1, using 1 ml of hexane to prewet the
Snyder column, raising the temperature of the water bath, if necessary, to
maintain proper distillation, and completing the concentration in 10-20
minutes. When the apparent volume of liquid reaches 1-2 ml, remove the
K-D apparatus and allow it to drain and cool for at least 10 min.
7.2.3 Remove the Snyder column and rinse the flask and its lower
joint into the concentrator tube with 1 to 2 mL hexane. A 5 ml syringe is
recommended for this operation. Adjust the extract volume to 2 mL for
water samples, using either the micro Snyder column technique (Sec.
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7.1.2.4.1) or nitrogen blowdown technique {Sec. 7.1.2.4.2), or 10 ml for
solid samples. Stopper the concentrator tube and store at 4 °C if further
processing will be performed immediately. If the extract will be stored
for two days or longer, it should be transferred to a glass vial with a
Teflon lined screw-cap or crimp top. Proceed with the gas chromatographic
analysis.
7.3 Cleanup/Fractionation:
7.3.1 Cleanup may not be necessary for extracts from a relatively
clean sample matrix. If polychlorinated biphenyls (PCBs) and
organochlorine pesticides are known to be present in the sample, use the
procedure outlined in Methods 3610 or 3620. When using column cleanup,
collect Fraction 1 by eluting with 140 ml (Method 3610) or 100 ml
(Method 3620) of 20-percent diethyl ether in hexane. Note that, under
these conditions, bis(2-methoxyethyl) phthalate, bis(2-ethoxyethyl)
phthalate, and bis(2-n-butoxyethyl) phthalate are not recovered from the
Florisil column. The elution patterns and compound recoveries are given
in Table 3.
7.3.2 Methods 3610 and 3620 also describe procedures for sample
cleanup using Alumina and Florisil Cartridges. With this method,
bis(2-methoxyethyl) phthalate, bis(2-ethoxyethyl) phthalate, and
bis(2-n-butoxyethyl) phthalate are recovered quantitatively.
7.4 Gas chromatographic conditions (recommended):
7.4.1 Column 1 and Column 2 (Sec. 4.1.2):
Carrier gas (He) = 6 inL/min.
Injector temperature = 250 °C.
Detector temperature = 320 °C.
Column temperature:
Initial temperature = 150 °C, hold for 0.5 min.
Temperature program = 150 °C to 220 °C at 5 °C/min.,
followed by 220 °C to 275 °C at 3
°C/min.
Final temperature = 275 °C hold for 13 min.
7.4.2 Table 1 gives the retention times and MDLs that can be
achieved by this method for the 16 phthalate esters. An example of the
separations achieved with the DB-5 and DB-1701 fused-silica open tubular
columns is shown in Figure 1.
7.5 Calibration:
7.5.1 Refer to Method 8000 for proper calibration techniques. Use
Tables 1 and 2 for guidance on selecting the lowest point on the
calibration curve.
7.5.2 The procedure for internal or external calibration may be
used. Refer to Method 8000 for the description of each of these
procedures.
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7.6 Gas chromatographic analysis:
7.6.1 Refer to Method 8000. If the internal standard calibration
technique is used, add 10 //L of internal standard solution at 5000 mg/L
to the sample prior to injection.
7.6.2 Follow Method 8000 for instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria.
7.6.3 Record the sample volume injected and the resulting peak
areas.
7.6.4 Using either the internal or the external calibration
procedure (Method 8000), determine the identity and the quantity of each
component peak in the sample chromatogram which corresponds to the
compounds used for calibration purposes.
7.6.5 If the response of a peak exceeds the working range of the
system, dilute the extract and reanalyze.
7.6.6 Identify compounds in the sample by comparing the retention
times of the peaks in the sample chromatogram with those of the peaks in
standard chromatograms. The retention time window used to make
identifications is based upon measurements of actual retention time
variations over the course of 10 consecutive injections. Three times the
standard deviation of the retention time can be used to calculate a
suggested window size.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized. If extract cleanup was performed, follow the QC
specified in Method 3600 and in the specific cleanup method.
8.2 Quality control required to evaluate the GC system operation is found
in Method 8000.
8.2.1 The quality control check sample concentrate (Method 8000)
should contain the test compounds at 5 to 10 ng/^L.
8.3 Calculate the recoveries of the surrogate compounds for all samples,
method blanks, and method spikes. Determine if the recoveries are within limits
established by performing QC procedures outlined in Method 8000.
8.3.1 If the recoveries are not within limits, the following are
required:
8.3.1.1 Make sure there are no errors in calculations,
surrogate solutions and internal standards. Also check instrument
performance.
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8.3.1.2 Recalculate the data and/or reanalyze the extract
if any of the above checks reveal a problem.
8.3.1.3 Reextract and reanalyze the sample if none of the
above are a problem, or flag the data as "estimated concentration."
8.4 An internal standard peak area check must be performed on all
samples. The internal standard must be evaluated for acceptance by determining
whether the measured area for the internal standard deviates by more than 30
percent from the average area for the internal standard in the calibration
standards. When the internal standard peak area is outside that limit, all
samples that fall outside the QC criteria must be reanalyzed.
8.5 GC/MS confirmation: Any compounds confirmed by two columns may also
be confirmed by GC/MS if the concentration is sufficient for detection by GC/MS
as determined by the laboratory-generated detection limits.
8.5.1 The GC/MS would normally require a minimum concentration of 10
ng//nL in the final extract for each single-component compound.
8.5.2 The sample extract and associated blank should be analyzed by
GC/MS as per Sec. 7.0 of Method 8270. Normally, analysis of a blank is
not required for confirmation analysis, however, analysis for phthalates
is a special case because of the possibility for sample contamination
through septum punctures, etc.
8.5.3 A reference standard of the compound must also be analyzed by
GC/MS. The concentration of the reference standard must be at a
concentration that would demonstrate the ability to confirm the phthalate
esters identified by GC/ECD.
8.6 Include a mid-concentration calibration standard after each group of
20 samples in the analysis sequence. The response factors for the
mid-concentration calibration must be within + 15 percent of the average values
for the multiconcentration calibration.
8.7 Demonstrate through the analyses of standards that the Florisil
fractionation scheme is reproducible. When using the fractionation schemes given
in Methods 3610 or 3620, batch-to-batch variations in the composition of the
alumina or Florisil material may cause variations in the recoveries of the
phthalate esters.
9.0 METHOD PERFORMANCE
9.1 The MDL is defined in Chapter One. The MDL concentrations listed in
Table 1 were obtained using organic-free reagent water. Details on how to
determine MDLs are given in Chapter One. The MDL actually achieved in a given
analysis will vary, as it is dependent on instrument sensitivity and matrix
effects.
9.2 This method has been tested in a single laboratory by using different
types of aqueous samples and solid samples which were fortified with the test
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compounds at two concentrations. Single-operator precision, overall precision,
and method accuracy were found to be related to the concentration of the
compounds and the type of matrix. Results of the single-laboratory method
evaluation are presented in Tables 4 and 5.
9.3 The accuracy and precision obtained is determined by the sample
matrix, sample preparation technique, cleanup techniques, and calibration
procedures used.
10.0 REFERENCES
1. Glazer, J.A.; Foerst, G.D.; McKee, G.D.; Quave, S.A., and Budde, W.L.,
"Trace Analyses for Wastewaters," Environ. Sci. and Techno!. 15: 1426,
1981.
2. Lopez-Avila, V., Baldin, E., Benedicto, J., Milanes, J., and Beckert,
W.F., "Application of Open-Tubular Columns to SW-846 GC Methods", EMSL-Las
Vegas, 1990.
3. Beckert, W.F. and Lopez-Avila, V., "Evaluation of SW-846 Method 8060 for
Phthalate Esters", Proceedings of Fifth Annual Testing and Quality
Assurance Symposium, USEPA, 1989.
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TABLE 1.
GAS CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS FOR THE PHTHALATE ESTERS8
Compound
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
IS
SU-1
SU-2
SU-3
Compound name
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Butyl benzyl phthalate
Bis(2-n-butoxyethyl ) phthalate
Bis(2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Benzyl benzoate
Diphenyl phthalate
Diphenyl isophthalate
Dibenzyl phthalate
Chemical
Abstract
Registry
No.
131-11-3
84-66-2
84-69-5
84-74-2
146-50-9
117-82-8
131-18-0
605-54-9
75673-16-4
84-75-3
85-68-7
117-83-9
117-81-7
84-61-7
117-84-0
84-76-4
120-51-4
84-62-8
744-45-6
523-31-9
Retention time8
(min)
Column 1
7.06
9.30
14.44
16.26
18.77
17.02
20.25
19.43
21.07
24.57
24.86
27.56
29.23
28.88
33.33
38.80
12.71
29.46
32.99
34.40
Column 2
6.37
8.45
12.91
14.66
16.27
16.41
18.08
18.21
18.97
21.85
23.08
25.24
25.67
26.35
29.83
33.84
11.07
28.32
31.37
32.65
MDLb
Liquid
(ng/L)
640
250
120
330
370
510
110
270
130
68
42
84
270
22
49
22
c
c
c
c
8061 - 13
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Table 1. (continued)
Column 1 is a 30 m x 0.53 mm ID DB-5 fused-silica open tubular column (1.5 //m film thickness).
Column 2 is a 30 m 0.53 mm ID DB-1701 fused-silica open tubular column (1.0 urn film thickness).
Temperature program is 150°C (0.5 min hold) to 220°C at 5°C/min, then to 275'C (13 min hold) at
3°C/min. An 8-in Supelco injection tee or a J&W Scientific press fit glass inlet splitter is used
to connect the two columns to the injection port of a gas chromatograph. Carrier gas helium at
6 mL/min; makeup gas nitrogen at 20 mL/min; injector temperature 250°C; detector temperature
320°C.
MDL is the method detection limit. The MDL was determined from the analysis of seven replicate
aliquots of organic-free reagent water processed through the entire analytical method (extraction,
Florisil cartridge cleanup, and GC/ECD analysis using the single column approach: DB-5 fused-
silica capillary column). MDL = t(lvl 099) x SD where t(n.., 0991 is the student's t value appropriate
for a 99 percent confidence interval and a standard deviation with n-1 degrees of freedom, and SD
is the standard deviation of the seven replicate measurements. Values measured were not corrected
for method blanks.
Not applicable.
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TABLE 2.
ESTIMATED QUANTITATION LIMITS (EQL) FOR VARIOUS MATRICES6
Matrix Factor
Groundwater 10
Low-concentration soil by ultrasonic extraction 670
with GPC cleanup
High-concentration soil and sludges by ultrasonic 10,000
extraction
Non-water miscible waste 100,000
EQL = [Method detection limit (see Table 1)] X [Factor found in this
table]. For non-aqueous samples, the factor is on a wet-weight basis.
Sample EQLs are highly matrix-dependent. The EQLs determined herein are
provided for guidance and may not always be achievable.
8061 - 15 Revision 0
September 1994
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TABLE 3.
AVERAGE RECOVERIES OF METHOD 8061 COMPOUNDS USING METHODS 3610 AND 3620
Compound
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Benzyl butyl phthalate
Bis(2-n-butoxyethyl) phthalate
Bis(2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Alumina
col umn8
64.5
62.5
77.0
76.5
89.5
70.5
75.0
67.0
90.5
73.0
87.0
62.5
91.0
84.5
108
71.0
Florisil
column"
40.0
57.0
80.0
85.0
84.5
0
81.5
0
105
74.5
90.0
0
82.0
83.5
115
72.5
Alumina
cartridge6
101
103
104
108
103
64.1°
103
111
101
108
103
108
97.6
97.5
112
97.3
Florisil
cartridge6
89.4
97.3
91.8
102
105
78. 3e
94.5
93.6
96.0
96.8
98.6
91.5
97.5
90.5
97.1
105
a 2 determinations; alumina and Florisil chromatography performed according
to Methods 3610 and 3620, respectively.
b 2 determinations, using 1 g alumina cartridges; Fraction 1 was eluted with
5 ml of 20-percent acetone in hexane. 40 jug of each component was spiked
per cartridge.
c 36.8 percent was recovered by elution with an additional 5 ml of
20-percent acetone in hexane.
d 2 determinations, using 1 g Florisil cartridges; Fraction 1 was eluted
with 5 ml of 10-percent acetone in hexane. 40 /^g of each component was
spiked per cartridge.
e 14.4 percent was recovered by elution with an additional 5 ml of
10-percent acetone in hexane.
8061 - 16
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September 1994
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TABLE 4.
ACCURACY AND PRECISION DATA FOR METHOD 3510 AND METHOD 8061£
Spike Concentration
(20 uq/U
Estuarine
Compound
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Benzyl butyl phthalate
Bis(2-n-butoxyethyl) phthalate
Bis(2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Surrogates:
Diphenyl phthalate
Diphenyl isophthalate
Dibenzyl phthalate
water
84.0
71.2
76.0
83.2
78.6
73.8
78.2
75.6
84.7
79.8
84.1
78.5
81.4
77.4
74.9
59.5
98.5
95.8
93.9
(4.1)
(3.8)
(6.5)
(6.5)
(2.6)
(1.0)
(7.3)
(3.3)
(5.3)
(7.2)
(6.4)
(3.5)
(4.1)
(6.5)
(4.9)
(6.1)
(2.6)
(1.9)
(4.4)
Leachate
98.9
82.8
95.3
97.5
87.3
87.2
92.1
90.8
91.1
102
105
92.3
93.0
88.2
87.5
77.3
113
112
112
(19.6)
(19.3)
(16.9)
(22.3)
(18.2)
(21.7)
(21.5)
(22.4)
(27.5)
(21.5)
(20.5)
(16.1)
(15.0)
(13.2)
(18.7)
(4.2)
(14.9)
(11-7)
(14.0)
Estuarine
Groundwater
87.1
88.5
92.7
91.0
92.6
82.4
88.8
86.4
81.4
90.9
89.6
89.3
90.5
91.7
87.2
67.2
110
109
106
(8.1)
(15.3)
(17.1)
(10-7)
(13.7)
(4.4)
(7.5)
(5.8)
(17.6)
(7.6)
(6.1)
(3.6)
(4.9)
(15.2)
(3.7)
(8.0)
(3.3)
(3.3)
(3.8)
Sp
water
87.1
71.0
99.1
87.0
97.4
82.5
89.2
88.7
107
90.1
92.7
86.1
86.5
87.7
85.1
97.2
110
104
111
(7.5)
(7.7)
(19.0)
(8.0)
(15.0)
(5.5)
(2.8)
(4.9)
(16.8)
(2.4)
(5.6)
(6.2)
(6.9)
(9.6)
(8.3)
(7.0)
(12.4)
(5.9)
(5.9)
ike Concentration
(60 uq/L)
Leachate
112
88.5
100
106
107
99.0
112
109
117
109
117
107
108
102
105
108
95.1
97.1
93.3
(17-5)
(17.9)
(9.6)
(17.4)
(13.3)
(13.7)
(14.2)
(14.6)
(11.4)
(20.7)
(24.7)
(15.3)
(15.1)
(14.3)
(17.7)
(17.9)
(7.2)
(7.1)
(9.5)
Groundwater
90.9 (4.5)
75.3 (3.5)
83.2 (3.3)
87.7 (2.7)
87.6 (2.9)
76.9 (6.6)
92.5 (1.8)
84.8 (5.9)
80.1 (4.1)
88.9 (2.4)
93.0 (2.0)
92.4 (0.6)
91.1 (3.0)
71.9 (2.4)
90.4 (2.0)
90.1 (1.1)
107 (2.4)
106 (2.8)
105 (2.4)
The number of determinations was 3.
the average recoveries.
The values given in parentheses are the percent relative standard deviations of
8061 - 17
Revision 0
September 1994
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TABLE 5.
ACCURACY AND PRECISION DATA FOR METHOD 3550 AND METHOD 8061a
Spike Concentration
(1 mq/kq)
Compound
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Benzyl butyl phthalate
Bis(2-n-butoxyethyl ) phthalate
Bis(2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Estuarine
sediment
77.9
68.4
103
121
108
26.6
95.0
C
c
103
113
114
C
36.6
C
c
(42.8)
(1.7)
(3.1)
(25.8)
(57.4)
(26.8)
(10.2)
(3.6)
(12.8)
(21.1)
(48.8)
Municipal
sludge
52.1
68.6
106
86.3
97.3
72.7
81.9
66.6
114
96.4
82.8
74.0
76.6
65.8
93.3
80.0
(35.5)
(9.1)
(5.3)
(17.7)
(7.4)
(8.3)
(7.1)
(4.9)
(10.5)
(10.7)
(7.8)
(15.6)
(10.6)
(15.7)
(14.6)
(41.1)
Sandy loam
soil
c
54.7
70.3
72.6
c
0
81.9
c
57.7
77.9
56.5
c
99.2
92.8
84.7
64.2
(6.2)
(3-7)
(3.7)
(15.9)
(2.8)
(2.4)
(5-1)
(25.3)
(35.9)
(9.3)
(17.2)
Spike Concentration
(3 uq/q)
Estuarine
sediment
136
60.2
74.8
74.6
104
19.5
77.3
21.7
72.7
75.5
72.9
38.3
59.5
33.9
36.8
c
(9.6)
(12.5)
(6.0)
(3.9)
(1.5)
(14.8)
(4.0)
(22.8)
(11.3)
(6.8)
(3.4)
(25.1)
(18.3)
(66.1)
(16.4)
Municipal
sludge
64.8
72.8
84.0
113
150
59.9
116
57.5
26.6
80.3
76.8
98.0
85.8
68.5
88.4
156
(11.5)
(10.0)
(4.6)
(5.8)
(6.1)
(5.4)
(3-7)
(9.2)
(47.6)
(4.7)
(10.3)
(6.4)
(6.4)
(9.6)
(7.4)
(8.6)
Sandy loam
soil
70.2 (2.0)
67.0 (15.1)
79.2 (0.1)
70.9 (5.5)
83.9 (11.8)
0
82.1 (15.5)
84.7 (8.5)
28.4 (4.3)
79.5 (2.7)
67.3 (3.8)
62.0 (3.4)
65.4 (2.8)
62.2 (19.1)
115 (29.2)
115 (13.2)
a The number of determinations was 3. The values given in parentheses are the percent relative standard deviations of the
average recoveries. All samples were subjected to Florisil cartridge cleanup.
b The estuarine sediment extract (Florisil, Fraction 1) was subjected to sulfur cleanup (Method 3660 with
tetrabutylammonium sulfite reagent).
c Not able to determine because of matrix interferant.
8061 - 18
Revision 0
September 1994
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Figure 1
OB-5
30 m x 0.53 mm 10
1.S~um Rim
IS
11 12 SU-1 SU-2 SU-3
v«w_*A'
16
O
LU
u
IS
JL
10
DB-1701
SU-2 SU-3 30 m x 0.53 mm ID
II 1 0— urn Film
12 SU-1 15 1 T
13
10
20
TIME (min)
30
40
GC/ECD chromatograms of a composite phthalate esters standard (concentration
10 ng//iL per compound) analyzed on a DB-5 and a DB-1701 fused-silica open
tubular column. Temperature program: 150°C (0.5 min hold) to 220°C at
5°C/min, then to 275°C (13 min hold) at 3°C/nnn.
8061 - 19
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METHOD 8061
PHTHALATE ESTERS BY CAPILLARY GAS CHROMATOGRAPHY
WITH ELECTRON CAPTURE DETECTION (GC/ECD)
7 1 Extraction
711 Refer to Chapter 2 for
guidance on choosing
an extraction procedure.
Recommendations given.
7.1.2 Determine spike sample
recovery and detection limit
for each new sample matrix
and a given extraction
procedure.
713 Aqueous sample extraction
with C18 disks:
1 Precondition disks using
solvent train.
2 Concentrate sample
analytes on disk.
3 Elute sample analytes
with acetonitrile.
.4 Concentrate extract:
1 Micro-Snyder Column
Technique
2 Nitrogen Slowdown
Technique
1 Evaporate solvent to
desired level
2 Rinse tube walls
frequently and avoid
evaporating todryness.
I
7 2 Solvent Exchange to Hexane
7 2.1 Evaporate extract volume to
1 -2 ml using K-D assembly
7 2.2 Add hexane to K-D assembly
and evaporate to 1-2 mL
7 23 Rinse K-D components and
adjust volume to desired level.
7 3 Cleanup/FracoonaOon
73.1 Cleanup may not be
necessary tor extracts with
clean sample matrices
Fraction collection and
methods outlined tor other
compd groups of interest.
7.3.2 Flonsil Cartridge Cleanup
1 Check each lot of Rorisil
cartridges for analyte
recovery by eluting and
analyzing a composite std
2 Wash and adjust solvent
flow through cartridges.
3 Place culture tubes or 5 mL
vol. flasks for eluate
collection.
4 Transfer appropriate extract
volume on cartridge
5 Elute the cartridges and
dilute to mark on flask
Transfer eluate to glass
vials for concentration.
733 Collect 2 fractions it PCBs
and organochlorme pesticides
are known to be present
7 4 Gas Chromatograph
7 41 Set GC operating parameters
7.4 2 Table 1 and Figure 1 show
MOLs and analyte retention
times.
8061 - 20
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September 1994
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METHOD 8061
(CONTINUED)
9
75 Calibration
751 See Method 8000 for
calibration technique.
7.52 Refer to Method 8000 tor
internal/external std.
procedure.
7 6 GC Analysis
7 6 i Refer (o Memod 8000
762 Follow Section 76 in
Method 8000 for
instructions on analysis
sequence, dilutions.
retention time windows.
and identification criteria
7 6.3 Record injection volume
and sample peak areas
7 64 Identify and quantify each
component peak using the
internal or external std
procedure.
765 Dilute extracts which
show analyte levels
outside of the calibration
range.
766 Identify compounds in the
sample by comparing
retention times in the
sample and the standard
chromatograms
8061 - 21
Revi sion 0
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00
o
-------
METHOD 8070
NITROSAMINES BY GAS CHROMATQGRAPHY
1.0 SCOPE AND APPLICATION
1.1 This method covers the determination of certain nitrosamines. The
following compounds can be determined by this method:
Appropriate Technique
Compound Name CAS No.a 3510 3520 3540 3550 3580
N-Nitrosodimethylamine 62-75-9 X X X X
N-Nitrosodiphenylamine 86-30-6 X X X X
N-Nitrosodi-n-propylamine 621-64-7 X X X X
X
X
X
a Chemical Abstract Services Registry Number.
X Greater than 70 percent recovery by this preparation technique.
1.2 This is a gas chromatographic (GC) method applicable to the
determination of the parameters listed above in municipal and industrial
discharges. When this method is used to analyze unfamiliar samples for any or
all of the compounds above, compound identifications should be supported by at
least one additional qualitative technique. This method describes analytical
conditions for a second gas chromatographic column that can be used to confirm
measurements made with the primary column. Method 8270 provides gas
chromatograph/mass spectrometer (GC/MS) conditions appropriate for the
qualitative and quantitative confirmation of results for
N-nitrosodi-n-propylamine. In order to confirm the presence of
N-nitrosodiphenylamine, the cleanup procedure specified in Section 7.3.3 or 7.3.4
must be used. In order to confirm the presence of N-nitrosodimethylamine by
GC/MS, chromatographic column 1 of this method must be substituted for the column
recommended in Method 82-70. Confirmation of these parameters using GC-high
resolution mass spectrometry or a Thermal Energy Analyzer is also recommended
practice.
1.3 The method detection limit (MDL) for each parameter is listed in
Table 1. The MOL for a specific wastewater may differ from those listed,
depending upon the nature of interferences in the sample matrix. Table 2 lists
the Estimated Quantitation Limits (EQLs) for various matrices.
1.4 The toxicity or carcinogenicity of each reagent used in this method
has not been precisely defined. However, each chemical compound should be
treated as a potential health hazard. From this viewpoint, exposure to these
chemicals must be reduced to the lowest possible concentration by whatever means
available. The 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 data handling sheets should also
8070 - 1 Revision 0
July 1992
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be made available to all personnel involved in the chemical analysis.
1.5 These nitrosamines are known carcinogens. Therefore, utmost care
must be exercised in the handling of these materials. Nitrosamine reference
standards and standard solutions should be handled and prepared in a ventilated
glove box within a properly ventilated room.
1.6 N-Nitrosodiphenylamine is reported to undergo transnitrosation
reactions. Care must be exercised in the heating or concentrating of solutions
containing this compound in the presence of reactive amines.
2.0 SUMMARY OF METHOD
2.1 A measured volume of aqueous sample, approximately one liter, is
solvent extracted with methylene chloride using a separatory funnel. The
methylene chloride extract is washed with dilute HC1 to remove free amines,
dried, and concentrated to a volume of 10 mi or less. Gas chromatographic
conditions are described which permit the separation and measurement of the
compounds in the extract after it has been exchanged to methanol.
2.2 Method 8070 provides gas chromatographic conditions for the detection
of ppb concentrations of nitrosamines. Prior to use of this method, appropriate
sample extraction techniques must be used. • Both neat and diluted.organic liquids
(Method 3580, Waste Dilution) may be analyzed by direct injection. A 2 to 5 pi
aliquot of the extract is injected into a gas chromatograph (GC) using the
solvent flush technique, and compounds in the GC effluent are detected by a
nitrogen-phosphorus detector (NPD) or a Thermal Energy Analyzer and the reductive
Hall detector.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and diversity of
the industrial complex or municipality being sampled. The cleanup procedures
(Methods 3610 or 3620) can be used to overcome many of these interferences, but
unique samples may require additional cleanup approaches to achieve the MDL
listed in Table 1.
3.3 Nitrosamines contaminate many types of products commonly found in the
laboratory. The analyst must demonstrate that no nitrosamine residues
contaminate the sample or solvent extract under the conditions of analysis.
Plastics, in particular, must be avoided because nitrosamines are commonly used
as plasticizers and are easily extracted from plastic materials. Serious
nitrosamine contamination may result at any time if consistent quality control
is not practiced.
3.4 The sensitive and selective Thermal Energy Analyzer and the reductive
Hall detector may be used in place of the nitrogen-phosphorus detector when
8070 - 2 Revision 0
July 1992
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interferences are encountered. The Thermal Energy Analyzer offers tha highest
selectivity of the non-mass spectrometric detectors.
3.5 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms. All these materials must be demonstrated to be free from
interferences, under the conditions of the analysis, by analyzing reagent blanks.
Specific selection of reagents and purification of solvents by distillation in
all-glass systems may be required.
3.6 Interferences coextracted from samples will vary considerably from
source to source, depending upon the waste being sampled. Although general
cleanup techniques are recommended as part of this method, unique samples may
require additional cleanup.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph - An analytical system complete with temperature
programmable gas chromatograph suitable for on-column injection and all required
accessories including syringes, analytical columns, gases, detector, and strip-
chart recorder. A data system is recommended for measuring peak areas.
4.1.1 Column !-1.8mx4mmID Pyrex glass, packed with Chromosorb
W AW, (80/100 mesh) coated with 10% Carbowax 20 M/2% KOH or equivalent.
This column was used to develop the method performance statements in
Section 9.0. Guidelines for the use of alternate column packings are
provided in Section 7.3.2.
4.1.2 Column 2 - 1.8 m x 4 mm ID Pyrex glass, packed with
Supelcoport (100/120 mesh) coated with 10% SP-2250, or equivalent.
4.1.3 Detector - Nitrogen-Phosphorus, reductive Hall or Thermal
Energy Analyzer. These detectors have proven effective in the analysis of
wastewaters for the parameters listed in the scope. A nitrogen-phosphorus
detector was used to develop the method performance statements in Section
9.0. Guidelines for the use of alternate detectors are provided in
Section 7.3.2.
4.2 Kuderna-Danish (K-D) apparatus
4.2.1 Concentrator tube - 10 mL, graduated (Kontes K-570050-1025 or
equivalent). Calibration must be checked at the volumes employed in the
test. A ground glass stopper is used to prevent evaporation of extracts.
4.2.2 Evaporation flask - 500 mL (Kontes K-570001-0500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.2.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
8070 - 3 Revision 0
July 1992
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equivalent).
4.2.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.3 Boiling chips - Approximately 10/40 mesh. Heat to 400°C for
30 minutes or Soxhlet extract with methylene chloride.
4.4 Water bath - Heated, with concentric ring cover, capable of
temperature control (± 2°C). The bath should be used in a hood.
top.
4.5 Balance - Analytical, 0.0001 g.
4.6 Vials - 10 to 15 ml, amber glass with Teflon lined screw-cap or crimp
4.7 Volumetric flasks, Class A, Appropriate sizes with ground glass
stoppers.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all inorganic reagents shall 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 ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Methanol, CH3OH - Pesticide quality or equivalent.
5.4 Isooctane, (CH3)3CCH2CH(CH3}2 - Pesticide quality or equivalent.
5.5 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.6 Stock standard solutions (1000 mg/L) - Stock standard solutions can
be prepared from pure standard materials or purchased as certified solutions.
5.6.1 Prepare stock standard solutions by accurately weighing
0.1000 ± 0.0010 g of pure material. Dissolve the material in pesticide
quality methanol and dilute to volume in a 100 ml volumetric flask.
Larger volumes can be used at the convenience of the analyst. If compound
purity is certified at 96% or greater, the weight can be used without
correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration if
they are certified by the manufacturer or by an independent source.
5.6,2 Transfer the stock standard solutions into bottles with Teflon
lined screw-caps or crimp tops. Store at 4°C and protect from light.
8070 - 4 Revision 0
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Stock standard solutions should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.6.3 Stock standard solutions must be replaced after six months, or
sooner if comparison with check standards indicates a problem.
5.7 Calibration standards - A minimum of five concentrations should be
prepared through dilution of the stock standards with isooctane. One of the
concentrations should be at a concentration near, but above, the method detection
limit. The remaining concentrations should correspond to the expected range of
concentrations found in real samples or should define the working range of the
GC. Calibration solutions must be replaced after six months, or sooner if
comparison with check standards indicates a problem.
5.8 Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.8.1 Prepare calibration standards at a minimum of five
concentrations for each analyte of interest, as described in Section 5.7.
5.8.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with isooctane.
5.8.3 Analyze each calibration standard according to Section 7.0.
5.9 Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (when used), and analytical system and the effectiveness
of the method in dealing with each sample matrix by spiking each sample,
standard, and reagent blank with one or two surrogates (e.g. nitrosamines that
are not expected to be in the sample) recommended to encompass the range of the
temperature program used in this method. Method 3500 details instructions on the
preparation of base/neutral surrogates. Deuterated analogs of analytes should
not be used as surrogates for gas chromatographic analysis due to coelution
problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored at 4°C and analyzed within 40 days of
extraction.
8070 - 5 Revision 0
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7.0 PROCEDURE
7.1 Extraction
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral, or as is, pH with methylene chloride, using either Method 3510 or
3520. Solid samples are extracted using either Method 3540 or 3550.
7.1.2 Prior to gas chromatographic analysis, the extraction solvent
must be exchanged to methanol. The exchange is performed during the K-D
procedures listed in all of the extraction methods. The exchange is
performed as follows.
7.1.2.1 Following K-D of the methylene chloride extract to
1 ml using the macro-Snyder column, allow the apparatus to cool and drain
for at least 10 minutes.
7.1.2.2 Momentarily remove the Snyder column, add 50 ml of
methanol, a new boiling chip, and reattach the macro-Snyder column.
Concentrate the extract using 1 ml of methanol to prewet the Snyder
column. Place the K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration in 5-10 minutes. At the proper
rate of distillation the balls of the column will actively chatter,
but the chambers will not flood. When the apparent volume of liquid
reaches 1 ml, remove the K-D apparatus and allow it to drain and
cool for at least 10 minutes. The extract will be handled
differently at this point, depending on whether or not cleanup is
needed. If cleanup is not required, proceed to Section 7.1.2.3. If
cleanup is needed, proceed to Section 7.1.2.4.
7.1.2.3 If cleanup of the extract is not required, remove
the Snyder column and rinse the flask and its lower joint into the
concentrator tube with 1-2 ml of methanol. A 5 ml syringe is
recommended for this operation. Adjust the extract volume to
10.0 ml. Stopper the concentrator tube and store refrigerated at
4°C if further processing will not be performed immediately. If the
extract will be stored longer than two days, it should be
transferred to a vial with a Teflon lined screw-cap or crimp top.
Proceed with gas chromatographic analysis.
7.1.2.4 If cleanup of the extract is required, remove the
Snyder column and rinse the flask and its lower joint into the
concentrator tube with a minimum amount of methylene chloride. A 5
ml syringe is recommended for this operation. Add a clean boiling
chip to the concentrator tube and attach a two ball micro-Snyder
column. Prewet the column by adding about 0.5 ml of methylene
chloride to the top. Place the micro K-D apparatus on the water
bath (80°C) so that the concentrator tube is partially immersed in
the hot water. Adjust the vertical position of the apparatus and
the water temperature, as required, to complete concentration in 5-
8070 - 6 Revision 0
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10 minutes. At the proper rate of distillation the balls of the
column will actively chatter, but the chambers will not flood. When
the apparent volume of liquid reaches 0.5 ml, remove the K--D
apparatus and allow it to drain and cool for at least 10 minutes.
7.1.2.5 Remove the micro-Snyder column and rinse the flask
and its lower joint into the concentrator tube with 0.2 ml of
methylene chloride. Adjust the extract volume to 2.0 ml and proceed
with either Method 3610, 3620, or 3640.
7.1.3 If N-nitrosodiphenylamine is to be measured by gas
chromatography, the analyst must first use a cleanup column to eliminate
diphenylamine interference (Methods 3610 or 3620). If N-
nitrosodiphenylamine is of no interest, the analyst may proceed directly
with gas chromatographic analysis (Section 7.3).
7.2 Cleanup
7.2.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix. The cleanup procedure recommended in this method has been
used for the analysis of various clean waters and industrial effluents. If
particular circumstances demand the use of an alternative cleanup
procedure, the analyst must determine the elution profile and demonstrate
that the recovery of each compound of interest is no less than 85%.
Diphenylamine, if present in the original sample extract must be separate
from the nitrosatnines if N-nitrosodiphenylamine is to be determined by
this method.
7.2.2 Proceed with either Method 3610 or 3620, using the 2 ml
methylene chloride extracts obtained from Section 7.1.2.5.
7.2.3 Following cleanup, the extracts should be analyzed by GC, as
described in the previous paragraphs and in Method 8000.
7.3 Gas Chromatography
7.3.1 N-nitrosodiphenylamine completely reacts to form diphenylamine
at the normal operating temperatures of a GC injection port (200 to 250°C).
Thus, N-nitrosodiphenylamine is chromatographed and detected as
diphenylamine. Accurate determination depends on removal of diphenylamine
that may be present in the original extract prior to GC (see Section
7.1.3).
7.3.2 Table 1 summarizes the recommended operating conditions for
the gas chromatograph. This table includes retention times and MOLs that
were obtained under these conditions. Examples of the parameter
separations achieved by these columns are shown in Figures 1 and 2. Other
packed columns, chromatographic conditions, or detectors may be used if
the requirements of Section 8.2 are met. Capillary (open-tubular) columns
may also be used if the relative standard deviations of responses for
replicate injections are demonstrated to be less than 6% and the
requirements of Section 8.2 are met.
8070 - 7 Revision 0
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7.4 Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.
7.4.1 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these procedures.
7.4.2 If cleanup is performed on the samples, the analyst should
process a series of standards through the cleanup procedure and then
analyze the samples by GC. This will confirm elution patterns and the
absence of interferents from the reagents.
7.5 Gas chromatographic analysis
7.5.1 Refer to Method 8000. If the internal standard calibration
technique is used, add 10 pi of internal standard to the sample prior to
injection.
7.5.2 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria. Include a mid-concentration check standard after
each group of 10 samples in the analysis sequence.
7.5.3 Examples of GC/NPD chromatograms for nitrosamines are shown in
Figures 1 and 2.
7.5.4 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).
7.5.5 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each analyte peak in
the sample chromatogram. See Method 8000 for calculation equations.
7.5.6 If peak detection and identification are prevented due to
interferences, the hexane extract may undergo cleanup using either Method
3610 or 3620.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized. If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method 8000,
Section 8.6.
8.2.1 The quality control (QC) reference sample concentrate (Method
8000, Section 8.6) should contain each analyte of interest at 20 mg/L.
8.2.2 Table 3 indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as functions
8070 - 8 Revision 0
July 1992
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of concentration for the analytes of interest. The contents of both
Tables should be used to evaluate a laboratory's ability to perform and
generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following is required.
• Check to be sure that there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are a
problem or flag the data as "estimated concentration.
9.0 METHOD PERFORMANCE
9.1 This method has been tested for linearity of recovery from spiked
organic-free reagent water and has been demonstrated to be applicable for the
concentration range from 4 x MDL to 1000 x MOL.
9.2 In a single laboratory (Southwest Research Institute), using spiked
wastewater samples, the average recoveries presented in Table 2 were obtained.
Each spiked sample was analyzed in triplicate on three separate occasions. The
standard deviation of the percent recovery is also included in Table 2.
10.0 REFERENCES
1. Fed. Regist. 1984, 49, 43234; October 26.
2. "Determination of Nitrosamines in Industrial and Municipal Wastewaters";
Report for EPA Contract 68-03-2606, in preparation.
3. Burgess, E.M.; Lavanish, J.M. "Photochemical Decomposition of N-
nitrosamines"; Tetrahedron Letters 1964, 1221.
4. Methods for Chemical Analysis of Water and Wastes: U.S. Environmental
Protection Agency. Office of Research and Development. Environmental
Monitoring and Support Laboratory. ORD Publication Offices of Center for
Environmental Research Information: Cincinnati, OH, 1979; EPA-600/4-79-
020.
5. "Method Detection Limit and Analytical Curve Studies EPA Methods 606, 607,
608"; U.S. Environmental Protection Agency. Environmental Monitoring and
Support Laboratory, Cincinnati, OH, special letter report for EPA Contract
68-03-2606.
8070 - 9 Revision 0
July 1992
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TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
Analyte
Retention Time
(minutes)
Column 1 Column 2
Method
Detection Limit
N-Ni trosodimethyl ami ne
N-Nitrosodi-n-propyl amine
N-Ni trosodi phenyl ami ne*
4.1
12.1
12. 8b
0.88
4.2
6.4C
0.15
0.46
0.81
Column 1 conditions:
Carrier gas (He) flow rate:
Column temperature:
Column 2 conditions:
Carrier gas (He) flow rate:
Column temperature:
40 mL/min
Isothermal
indicated.
40 mL/min
Isotherma.1
indicated.
at 110°C, except as otherwise
at 120°C, except as otherwise
a Measured as diphenylamine.
b Determined isothermally at 220°C.
c Determined isothermally at 210°C.
TABLE 2.
SINGLE OPERATOR ACCURACY AND PRECISION
Average Standard Spike
Percent Deviation Range
Number
of Matrix
Analyte
Types
N-Nitrosodimethyl amine
N-Nitrosodiphenyl amine
N-Ni trosodi -n-propyl ami ne
Recovery % (MgA)
32
79
61
3.7
7.1
4.1
0.8
1.2
9.0
Analyses
29
29
29
5
5
5
8070 - 10
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TABLE 3.
QC ACCEPTANCE CRITERIA
Test Limit Range Recovery
Cone. for s for X Range
Analyte (jig/L)
N-Nitrosodimethylamine 20 3.4 4.6-20.0 13-109
N-Nitrosodiphenylamine 20 6.1 2.1-24.5 D-139
N-Nitrosodi-n-propylamine 20 5.7 11.5-26.8 45-146
s = Standard deviation for four recovery measurements, in pg/L.
X = Average recovery for four recovery measurements, in
D = Detected, result must be greater than zero.
8070 - 11 Revision 0
July 1992
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TABLE 4.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION
Analyte
N-Ni trosodimethyl ami ne
N-Ni trosodi phenyl ami ne
N-Ni troso-n-propyl ami ne
Accuracy, as
recovery, X'
(W/U
0.37C+0.06
0.64C+0.52
0.96C-0.07
Single
analyst
precision,
sr' (ng/L)
0.25X-0.04
0.36X-1.53
0.15X+0.13
Overall
precision,
S' (ng/L)
0.25X+0.11
0.46X-0.47
0.21X+0.15
c
X
Expected recovery for one or more measurements of a sample
containing a concentration of C, in [ig/L.
Expected single analyst standard deviation of measurements at an
average concentration found of X, in jig/L.
True value for the concentration, in ng/L.
Average recovery found for measurements of samples containing a
concentration of C, in yg/L.
8070 - 12
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FIGURE 1.
GAS CHROMATOGRAM OF NITROSAMINES
Column: 10% Csrbowtt 20M + 2%
KOH on Chromosorb W-AW
Timptftturt: 7/0°
Dittctor: Phosphorus/Nitrogin
_J I I I
2 4 S 8 10 12 !4
minute*
8070 - 13
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July 1992
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FIGURE 2.
GAS CHROMATOGRAM OF N-NITROSODIPHENYLAMINE AS DIPHENYLAMINE
Column- IO% CtrbowtJt 20M * 2% KQH on
Chromosorb W-4W
remptnturi: 220° C.
Dtttctor Phosphorus/Nitrogen
Q
0 2 4 6 8 tO 12 14 16 19
tim*. minvt**
8070 - 14
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July 1992
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METHOD 8070
NITROSAMINES BY GAS CHROMATOGRAPHY
7 1 i Chaota
apprpri«la
an t. raclion
procadura
7 1 2 P«cfoc»
olvanl ««cnan9a
u»in^ malhanol
'124 P.rfor.
•icro-K-D procadura
uiing mathylan*
chlorida p«r(ar«
Malhod 3610 or
3620. pcoca»d »iIh
CC analyai.1
7
I 2 3
Ho
Adjuit
procaad »
anal yaia or
nannar
th
• to r*
7 1 : P.rfor.
column cleanup
utino, Method 3610
or 3620
1 3 2 Rafar U
Tibia 1 for
raeo*aandad
oparatin?
condition* for tha
CC
4 RaCar to Malhod
3000 for propar
calibra Lion
Lachniqua*
7 $ 1 Rafar to
.lalhod 9000 for
9uidanca on CC
inalyt11
5 V 5 S Raeord
tav>pla vo 1 u*a
in]aelad and
fa«ulting paak
ilia/parforn
•ppcopriala
alcuUlioni Irafar
to Malhod 800G)
Stop
8070 - 15
Revision 0
July 1992
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00
©
00
o
-------
METHOD 8080
ORGANOCHLORINE PESTICIDES AND PCBs
1.0 SCOPE AND APPLICATION
1.1 Method 8080 1s used to determine the concentration of various
organochlorine pesticides and polychlorinated biphenyls (PCBs). Table 1
indicates compounds that may be determined by this method and lists the method
detection limit for each compound in reagent water. Table 2 lists the
practical quantitation limit (PQL) for other matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8080 provides gas chromatograpMc conditions for the
detection of ppb levels of certain organochlorine pesticides and PCBs. Prior
to the use of this method, appropriate sample extraction techniques must be
used. Both neat and diluted organic liquids (Method 3580, Waste Dilution) may
be analyzed by direct Injection. A 2- to 5-uL sample is injected into a gas
chromatograph (GC) using the solvent flush technique, and compounds in the GC
effluent are detected by an electron capture detector (ECD) or a halogen-
specific detector (HSD).
2.2 The sensitivity of Method 8080 usually depends on the level of
Interferences rather than on Instrumental limitations. If Interferences
prevent detection of the analytes, Method 8080 may also be performed on
samples that have undergone cleanup. Method 3620, Flor1s1l Column Cleanup, by
itself or followed by Method 3660, Sulfur Cleanup, may be used to eliminate
interferences in the analysis.
3.0 INTERFERENCES
3.1 Refer to Methods 3500 (Section 3.5, in particular), 3600, and 8000.
3.2 Interferences by phthalate esters can pose a major problem 1n
pesticide determinations when using the electron capture detector. These
compounds generally appear 1n the chromatogram as large late-eluting peaks,
especially in the 15% and 50% fractions from the Florisll cleanup. Common
flexible plastics contain varying amounts of phthalates. These phthalates are
easily extracted or leached from such materials during laboratory operations.
Cross contamination of clean glassware routinely occurs when plastics are
handled during extraction steps, especially when solvent-wetted surfaces are
handled. Interferences from phthalates can best be minimized by avoiding
contact with any plastic materials. Exhaustive cleanup of reagents and
glassware may be required to eliminate background phthalate contamination.
The contamination from phthalate esters can be completely eliminated with a
microcoulometrlc or electrolytic conductivity detector.
8080 - 1
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Date September 1986
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TABLE 1. GAS CHROMATOGRAPHY OF PESTICIDES AND PCBsa
Retention time (m1n)
Compound
Aldrln
a-BHC
£-BHC
ff-BHC
7-BHC (Llndane)
Chlordane (technical)
4,4'-DDD
4,4 '-DDE
4,4'-DDT
D1eldr1n
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrln
Endrln aldehyde
Heptachlor
Heptachlor epoxlde
Methoxychlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
aU.S. EPA. Method
Environmental Monitoring and
Col. 1
2.40
1.35
1.90
2.15
1.70
e
7.83
5.13
9.40
5.45
4.50
8.00
14.22
6.55
11.82
2.00
3.50
18.20
e
e
e
e
e
e
e
e
617.
Col. 2
4.10
1.82
1.97
2.20
2.13
e
9.08
7.15
11.75
7.23
6.20
8.28
10.70
8.10
9.30
3.35
5.00
26.60
e
e
e
e
e
e
e
e
Organochlorlde
Method
Detection
limit (ug/L)
0.004
0.003
0.006
0.009
0.004
0.014
0.011
0.004
0.012
0.002
0.014
0.004
0.066
0.006
0.023
0.003
0.083
0.176
0.24
nd
nd
nd
0.065
nd
nd
nd
Pesticides and PCBs.
Support Laboratory, Cincinnati, Ohio 45268.
e • Multiple peak response.
nd * not determined.
8080 - 2
Revision
Date September 1986
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TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES8
Matrix Factor*
Ground water 10
Low-level soil by sonlcatlon with GPC cleanup 670
High-level soil and sludges by sonlcatlon 10,000
Non-water mlsdble waste 100,000
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
bPQL - [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor 1s on a wet-weight basis.
8080 - 3
Revision
Date September 1986
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4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph:
4.1.1 Gas Chromatograph: Analytical system complete with gas
chromatograph suitable for on-column Injections and all required
accessories, Including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak heights and/or peak areas Is
recommended.
4.1.2 Columns:
4.1.2.1 Column 1: Supelcoport (100/120 mesh) coated with 1.5%
SP-2250/1.95% SP-2401 packed 1n a 1.8-m x 4-mm I.D. glass column or
equivalent.
4.1.2.2 Column 2: Supelcoport (100/120 mesh) coated with 3%
OV-1 1n a 1.8-m x 4-mm I.D. glass column or equivalent.
4.1.3 Detectors: Electron capture (ECD) or halogen specific (HSD)
(I.e., electrolytic conductivity detector).
4.2 Kuderna-Danlsh (K-D) apparatus;
4.2.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper 1s used to prevent evaporation of
extracts
4.2.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs,
4.2.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.3 BolHng chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.4 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used 1n a hood.
4.5 Volumetric flasks; 10-, 50-, and 100-mL, ground-glass stopper.
4.6 M1crosyr1nge; 10-uL.
4.7 Syringe: 5-mL.
4.8 Vials; Glass, 2-, 10-, and 20-mL capacity with Teflon-Hned screw
cap.
8080 - 4
Revision
Date September 1986
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5.0 REAGENTS
5.1 Solvents: Hexane, acetone, toluene, Isooctane {2,2,4-trimethyl-
pentane) (pesticide quality or equivalent).
5.2 Stock standard solutions;
5.2.1 Prepare stock standard solutions at a concentration of
1.00 ug/uL by dissolving 0.0100 g of assayed reference material in
Isooctane and diluting to volume 1n a 10-mL volumetric flask. A small
volume of toluene may be necessary to put some pesticides 1n solution.
Larger volumes can be used at the convenience of the analyst. When
compound purity 1s assayed to be 96% or greater, the weight can be used
without correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration 1f
they are certified by the manufacturer or by an Independent source.
5.2.2 Transfer the stock standard solutions Into Teflon-sealed
screw-cap bottles. Store at 4*C and protect from light. Stock standards
should be checked frequently for signs of degradation or evaporation,
especially just prior to preparing calibration standards from them.
5.2.3 Stock standard solutions must be replaced after one year, or
sooner if comparison with check standards Indicates a problem.
5.3 Calibration standards: Calibration standards at a minimum of five
concentration levelsTOTeach parameter of Interest are prepared through
dilution of the stock standards with Isooctane. One of the concentration
levels should be at a concentration near, but above, the method detection
limit. The remaining concentration levels should correspond to the expected
range of concentrations found in real samples or should define the working
range of the GC. Calibration solutions must be replaced after six months, or
sooner, 1f comparison with check standards Indicates a problem.
5.4 Internal standards (if internal standard calibration is used); To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the Internal standard 1s not
affected by method or matrix Interferences. Because of these limitations, no
internal standard can be suggested that 1s applicable to all samples.
5.4.1 Prepare calibration standards at a minimum of five
concentration levels for each analyte of interest as described in
Paragraph 5.3.
5.4.2 To each calibration standard, add a known constant amount of
one or more Internal standards, and dilute to volume with Isooctane.
5.4.3 Analyze each calibration standard according to Section 7.0.
8080 - 5
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Date September 1986
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5.5 Surrogate standards; The analyst should monitor the performance of
the extraction, cleanup(when used), and analytical .system and the effec-
tiveness of the method 1n dealing with each sample matrix by spiking each
sample, standard, and reagent water blank with pesticide surrogates. Becau'se
GC/ECD data are much more subject to Interference than GC/MS, a secondary
surrogate 1s to be used when sample Interference is apparent. Dibutyl-
chlorendate (DBC) 1s also subject to add and base degradation. Therefore,
two surrogate standards are added to each sample; however, only one need be
calculated for recovery. DBC 1s the primary surrogate and should be used
whenever possible. However, 1f DBC recovery 1s low or compounds interfere
with DBC, then the 2,4,5,6-tetrachloro-meta-xylene should be evaluated for
acceptance. Proceed with corrective action when both surrogates are out of
limits for a sample (Section 8.3). Method 3500, Section 5.3.2, Indicates the
proper procedure for preparing these surrogates.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and analyzed within
40 days of extraction.
7.0 PROCEDURE
7.1 Extraction:
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral, or as 1s, pH with methylene chloride, using either Method 3510
or 3520. Solid samples are extracted using either Method 3540 or 3550.
7.1.2 Prior to gas chromatographlc analysis, the extraction solvent
must be exchanged to hexane. The exchange Is performed during the K-D
procedures listed 1n all of the extraction methods. The exchange is
performed as follows.
7.1.2.1 Following K-D of the methylene chloride extract to
1 ml using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 min.
7.1.2.2 Increase the temperature of the hot water bath to
about 90*C. Momentarily remove the Snyder column, add 50 mL of
hexane, a new boiling chip, and reattach the macro-Snyder column.
Concentrate the extract using 1 mL of hexane to prewet the Snyder
column. Place the K-D apparatus on the water bath so that the
concentrator tube 1s partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration in 5-10 m1n. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches 1 mL, remove the K-D apparatus and allow it to drain and
cool for at least 10 m1n.
8080 - 6
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Date September 1986
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7.1.2.3 Remove the Snyder column and rinse the flask and its
lower joint Into the concentrator tube with 1-2 ml of hexane. A
5-mL syringe 1s recommended for this operation. Adjust the'extract
volume to 10.0 mL. Stopper the concentrator tube and store
refrigerated at
-------
7.4.3 Examples of GC/ECO chromatograms for various pesticides and
PCBs are shown in Figures 1 through 5.
7.4.4 Prime the column as per Paragraph 7.3.2.
7.4.5 DOT and endrfn are easily degraded In the Injection port ff
the Injection port or front of the column 1s dirty. This 1s the result
of buildup of high boiling residue from sample injection. Check for
degradation problems by injecting a mid-level standard containing only
4,4'-DDT and endrin. Look for the degradation products of 4,4'-DDT
(4,4'-DDE and 4,4'-DOD) and endrin (endrin ketone and endrin aldehyde).
If degradation of either DDT or endrin exceeds 20%, take corrective
action before proceeding with calibration, by following the GC system
maintenance outlined 1n Section 7.7 of Method 8000, Calculate percent
breakdown as follows:
% breakdown Total DDT degradation peak area (DDE + ODD) 1nn
for 4,4'-DDT Total DDT peak area (DDT + DDE + ODD] A iuu
X breakdown
for Endrin
Total endrin degradation peak area (endrin aldehyde + endrin ketone) .Qn
Total endrin peak ^rea (endrin + endrin aldehyde + endrin ketone)
7.4.6 Record the sample volume Injected and the resulting peak
sizes (In area units or peak heights).
7.4.7 Using either the Internal or external calibration procedure
(Method 8000), determine the Identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes.
7.4.8 If peak detection and Identification are prevented due to
Interferences, the hexane extract may need to undergo cleanup using
Method 3620. The resultant extract(s) may be analyzed by GC directly or
may undergo further cleanup to remove Sulfur using Method 3660.
7.5 Cleanup;
7.5.1 Proceed with Method 3620, followed by, if necessary, Method
3660, using the 10-mL hexane extracts obtained from Paragraph 7.1.2.3.
7.5.2 Following cleanup, the extracts should be analyzed by GC, as
described 1n the previous paragraphs and 1n Method 8000.
7.6 Calculations (exerpted from U.S. FDA, PAM):
7.6.1 Calculation of Certain Residues: Residues which are mixtures
of two or more components present problems in measurement. When they are
found together, e.g., toxaphene and DDT, the problem of quantitatlon
becomes even more difficult. In the following sections suggestions are
offered for handling toxaphene, chlordane, PCB, DDT, and BHC. A column
10% DC-200 stationary phase was used to obtain the chromatograms in
Figures 6-9.
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Column: 1.5% 9-2250*
1JS% SP-2401 en Suptlcopon
Ttmptrtiurt: 200° C
Dtuctor: Eltctron Ciotun
0 4 I 12
RETENTION TIME (MINUTES)
Figure 1. Gas chromatogram of pesticides.
8080 - 9
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Column: 1.5% SP-2250-
1.95\ S? 2401 on Swpticopon
Ttmpmturt 20C°C
Dructor: EUctron ClCtur*
> I t
0 4 8 12
RETENTION TIME (MINUTES)
Figure 2. Gas chromatogr»m of chlordane.
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Column; 1.S* 9-2250*
1J5N $P-2«01 en Sueticooon
TtfT»ptr»twrt. 200°C
Dmctor: Electron CiDtur*
10 14 18
HETENTION TIME (MINUTES)
22
26
Figure 3. Gas chromatogram of toxaphene.
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Column :1.5% SJ-2250*
US* SP 2401 on Sopticooon
Ttmotr»turt: 200° C
Otttctor: Electron CftDturt
I •
6 10 U
RETENTION TIME (MINUTES)
22
Figure 4. Gas chromatogram of PCS-1254.
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Column: 1.S\SP2250*
MS* SP-24C1 on Suwicooon
Ttmp«r«turt; 200eC
Octtcur: Eltctron Caeturt
t i
10 U 18 22
RETENTION TIME (MINUTES)
26
Figure 5. G«s chromatogrvn of PCB-1260.
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J..L
Fig. g—Basellne construction tor some typical gas chromatogrtphlc peaks.
a, symmetrical separated flat baseline; b and c, overlapping flat baseline;
d, separated (pen does not return to baseline between peaks); e, separated
sloping baseline; f, separated (pen goes below baseline between peaks);
i, «- andy.BHC sloping baseline; h.•-,£-. and Y-BHC sloping baseline;
i, chlordane flat baseline; ), heptachlor and heptachlor epoxide super-
Imposed on chlordane; k, chair-shaped peaks, unsymmetrical peak; 1,
p,p'-DOT superimposed on toxapnene.
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Fig. 7a—Baseline construction for multiple residues with standard
toxmphene.
Pig. 7b~B*»ehne construction for multiple residues with coxa.
phene, DOE and o.p'-, and p.p'-DOT.
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Fig. 6a-_Baseline construction for multiple residues: standard toxaphene.
Fig. 8fc— Baseline connructlon for multiple residues: rice bran with BHC,
toxephene, DOT, and meihoxychlor.
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Fig. 9»—Baseline construction for multiple residues: standard chlordtne.
Fig. 9b—Baseline construolcD for multiple residues: rice bran with chlordane, toxapbetw, and DOT.
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7.6.2 Toxaphene: Quantitative calculation of toxaphene or Strobane
is difficult, but reasonable accuracy can be obtained. To calculate
toxaphene on GC/ECD: (a) adjust sample size so that toxaphene major
peaks are 10-30% full-scale deflection (FSD); (b) inject a toxaphene
standard that is estimated to be within +10 ng of the sample; (c)
construct the baseline of standard toxaphene between it extremities; and
(d) construct the baseline under the sample, using the distances of the
peak troughs to baseline on the standard as a guide (Figures 7, 8, and
9). This procedure is made difficult by the fact that the relative
heights and widths of the peaks in the sample will probably not be
identical to the standard. A toxaphene standard that has been passed
through a Flqrisil column will show a shorter retention time for peak X
and an enlargement of peak Y.
7.6.3 Toxaphene and DDT: If DDT is present, it will superimpose
itself on toxaphene peak V. To determine the approximate baseline of the
DDT, draw a line connecting the trough of peaks U and V with the trough
of peaks W and X and construct another line parallel to this line which
will just cut the top of peak W (Figure 61). This procedure was tested
with ratios of standard toxaphene-DDT mixtures from 1:10 to 2:1 and the
results of added and calculated DDT and toxaphene by the "parallel lines-
method of baseline construction were within 10% of the actual values in
all cases.
7.6.3.1 A series of toxaphene residues have been calculated
using total peak area for comparison to the standard and also using
area of the last four peaks only 1n both sample and standard. The
agreement between the results obtained by the two methods justifies
the use of the latter method for calculating toxaphene in a sample
where the early eluting portion of the toxaphene chromatogram is
interfered with by other substances.
7.6.3.2 The baseline for methoxychlor superimposed on
toxaphene (Figure 8b) was constructed by overlaying the samples on a
toxaphene standard of approximately the same concentration (Figure
8a) and viewing the charts against a lighted background.
7.6.4 Chlordane 1s a technical mixture of at least 11 major
components and 30 or more minor ones. Gas chromatography-mass
spectrometry and nuclear magnetic resonance analytical techniques have
been applied to the elucidation of the chemical structures of the many
chlordane constituents. Figure 9a is a chromatogram of standard chlor-
dane. Peaks E and F are responses to trans- and cis-chlordane, respec-
tively. These are the two major components of technical chlordane, but
the exact percentage of each in the technical material is not completely
defined and is not consistent from batch to batch. Other labelled peaks
in Figure 9a are thought to represent: A, monochlorinated adduct of
pentachlorocyclopentadiene with cyclopentadiene; B, coelution of
heptachlor and o-chlordene; C, coelution of /J-chlordene and 7-chlordene;
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D, a chlordane analog; G, coelution of cis-nonachlor and "Compound K," a
chlordane Isomer. The right "shoulder" of peak F 1s caused by trans-
nonachlor.
7.6.4.1 The GC pattern of a chlordane residue may differ
considerably from that of the technical standard. Depending on the
sample substrate and Its history, residues of chlordane can consist
of almost any combination of: constituents from the technical
chlordane; plant and/or animal metabol1t1es; and products of
degradation caused by exposure to environmental factors such as
water and sunlight. Only limited information 1s available on which
residue GC patterns are likely to occur in which samples types, and
even this Information may not be applicable to a situation where the
route of exposure is unusual. For example, fish exposed to a recent
spill of technical chlordane will contain a residue drastically
different from a fish whose chlordane residue was accumulated by
1ngest1on of smaller fish or of vegetation, which 1n turn had
accumulated residues because chlordane was in the water from
agricultural runoff.
7.6.4.2 Because of this Inability to predict a chlordane
residue GC pattern, 1t is not possible to prescribe a single method
for the quantltatlon of chlordane residues. The analyst must judge
whether or not the residue's GC pattern 1s sufficiently similar to
that of a technical chlordane reference material to use the latter
as a reference standard for quantltatlon.
7.6.4.3 When the chlordane residue does not resemble technical
chlordane, but instead consists primarily of individual,
identifiable peaks, quantltate each peak separately against the
appropriate reference materials and report the Individual residues.
(Reference materials are available for at least 11 chlordane
constituents, metabolites or degradation products which may occur 1n
the residue.)
7.6.4.4 When the GC pattern of the residue resembles that of
technical chlordane, quantitate chlordane residues by comparing the
total area of the chlordane chromatogram from peaks A through F
(Figure 9a) 1n the sample versus the same part of the standard
chromatogram. Peak G may be obscured in a sample by the presence of
other pesticides. If G 1s not obscured, Include it In the
measurement for both standard and sample. If the heptachlor epoxide
peak 1s relatively small, include it as part of the total chlordane
area for calculation of the residue. If heptachlor and/or
heptachlor epoxide are much out of proportion as in Figure 6j,
calculate these separately and subtract their areas from total area
to give a corrected chlordane area. (Note that octachlor epoxide,
metabolite of chlordane, can easily be mistaken for heptachlor
epoxide on a nonpolar GC column.)
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7.6.4.5 T6 measure the total area of the chlordane
chromatogram, proceed as 1n Section 7.6.2 on toxaphene. Inject an
amount of technical chlordane standard which will produce a
chromatogram 1n which peaks E and F are approximately the same size
as those 1n the sample chromatograms. Construct the baseline
beneath the standard from the beginning of peak A to the end of peak
F as shown 1n Figure 9a. Use the distance from the trough between
peaks E and F to the baseline 1n the chromatogram of the standard to
construct the baseline In the chromatogram of the sample. Figure 9b
shows how the presence of toxaphene causes the baseline under
chlordane to take an upward angle. When the size of peaks E and F
1n standard and sample chromatograms are the same, the distance from
the trough of the peaks to the baselines should be the same.
Measurement of chlordane area should be done by total peak area 1f
possible.
NOTE: A comparison has been made of the total peak area
Integration method and the addition of peak heights method for
several samples containing chlordane. The peak heights A, B,
C, D, E, and F were measured 1n millimeters from peak maximum
of each to the baseline constructed under the total chlordane
area and were then added together. These results obtained by
the two techniques are too close to Ignore this method of "peak
height addition" as a means of calculating chlordane. The
technique has Inherent difficulties because not all the peaks
are symmetrical and not all are present 1n the same ratio In
standard and 1n sample. This method does offer a means of
calculating results 1f no means of measuring total area 1s
practical.
7.6.5 Polychlortnated blphenyls (PCBs): Quantltatlon of residues
of PCB Involves problems similar to those encountered In the quantltatlon
of toxaphene, Strobane, and chlordane: 1n each case, the chemical 1s
made up of numerous compounds and so the chromatograms are multi-peak;
also 1n each case the chromatogram of the residue may not match that of
the standard.
7.6.5.1 Mixtures of PCB of various chlorine contents were sold
for many years 1n the U.S. by the Monsanto Co. under the tradename
Aroclor (1200 series and 1016). Though these Aroclors are no longer
marketed, the PCBs remain 1n the environment and are sometime found
as residues In foods, especially fish.
7.6.5.2 PCB residues are quantltated by comparison to one or
more of the Aroclor materials, depending on the chromatographlc
pattern of the residue. A choice must be made as to which Aroclor
or mixture of Aroclors will produce a chromatogram most similar to
that of the residue. This may also Involve a judgment about what
proportion of the different Aroclors to combine to produce the
appropriate reference material.
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7.6.5.3 Quantltate PCB residues by comparing total area or
height of residue peaks to total area of height of peaks from
appropriate Aroclor(s) reference materials. Measure total area or
height response from common baseline under all peaks. Use only
those peaks from sample that can be attributed to chloroblphenyls.
These peaks must also be present 1n chromatogram of reference
materials. Mixture of Aroclors may be required to provide best
match of GC patterns of sample and reference.
7.6.6 DDT: DDT found 1n samples often consists of both o.p1- and
p,p'-DDT. Residues of DDE and TDE are also frequently present. Each
Isomer of DDT and Its metabolites should be quantHated using the pure
standard of that compound and reported as such.
7.6.7 Hexachlorocyclohexane (BHC, from the former name, benzene
hexachlorlde): Technical grade BHC is a cream-colored amorphous solid
with a very characteristic musty odor; 1t consists of a mixture of six
chemically distinct isomers and one or more heptachloro-cyclohexanes and
octachloro-cyclohexanes.
7.6.7.1 Commercial BHC preparations may show a wide variance
in the percentage of Individual Isomers present. The elimination
rate of the Isomers fed to rats was 3 weeks for the a-, 7-, and 5-
isomers and 14 weeks for the /Msomer. Thus 1t may be possible to
have any combination of the various isomers in different food
commodities. BHC found in dairy products usually has a large
percentage of /Msomer.
7.6.7.2 Individual Isomers (a, /J, 7, and 5) were Injected into
gas chromatographs equipped with flame 1on1zat1on, mlcrocoulometric,
and electron capture detectors. Response for the four Isomers 1s
very nearly the same whether flame ionlzatlon or mlcrocoulometric
GLC 1s used. The a-, 7-, and 5-1somers show equal electron
affinity. /J-BHC shows a much weaker electron affinity compared to
the others Isomers.
7.6.7.3 Quantltate each Isomer (a, /J, 7, and 6} separately
against a standard of the respective pure Isomer, using a GC column
which separates all the Isomers from one another.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered 1n Method 3500 and In
the extraction method utilized. If extract cleanup was performed, follow the
QC in Method 3600 and in the specific cleanup method.
8.2 Mandatory quality control to evaluate the GC system operation 1s
found in Method 8000, Section 8.6.
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8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each single-component parameter of Interest
at the following concentrations 1n acetone: 4,4'-DDD, 10 ug/mL; 4,4'-
DDT, 10 ug/mL; endosulfan II, 10 ug/mL; endosulfan sulfate, 10 ug/mL;
endrln, lOug/mL; and any other single-component pesticide, 2 ug/mL. If
this method 1s only to be used to analyze for PCBs, chlordane, or
toxaphene, the QC check sample concentrate should contain the most
representative millt1-component parameter at a concentration of 50 ug/mL
1n acetone.
8.2.2 Table 3 Indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as
functions of concentration for the analytes of Interest. The contents of
both Tables should be used to evaluate a laboratory's ability to perform
and generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine 1f the recovery 1s within limits (limits established by
performing QC procedures outlined 1n Method 8000, Section 8.10).
8.3.1 If recovery 1s not within limits, the following 1s required.
• Check to be sure there are no errors 1n calculations,
surrogate solutions and Internal standards. Also, check
Instrument performance.
• Recalculate the data and/or reanalyze the extract 1f any of
the above checks reveal a problem.
• Reextract and reanalyze the sample 1f none of the above are
a problem or flag the data as "estimated concentration."
8.4 GC/MS confirmation; Any compounds confirmed by two columns may also
be confirmed by GC/MST7the concentration Is sufficient for detection by
GC/MS as determined by the laboratory generated detection limits.
8.4.1 The GC/MS would normally require a minimum concentration of
10 ng/uL 1n the final extract, for each single-component compound.
8.4.2 The pesticide extract and associated blank should be analyzed
by GC/MS as per Section 7.0 of Method 8270.
8.4.3 The confirmation may be from the GC/MS analysis of the
base/neutral-add extractables extracts (sample and blank). However, 1f
the compounds are not detected 1n the base/neutral-add extract even
though the concentration 1s high enough, a GC/MS analysis of the
pesticide extract should be performed.
8.4.4 A reference standard of the compound must also be analyzed by
GC/MS. The concentration of the reference standard must be at a level
that would demonstrate the ability to confirm the pest1c1des/PCBs
Identified by GC/ECD.
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9.0 METHOD PERFORMANCE
9.1 The method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three Industrial wastewaters spiked at six
concentrations. Concentrations used 1n the study ranged from 0.5 to 30 ug/L
for single-component pesticides and from 8.5 to 400 ug/L for multl-component
parameters. Single operator precision, overall precision, and method accuracy
were found to be directly related to the concentration of the parameter and
essentially Independent of the sample matrix. Linear equations to describe
these relationships for a flame 1on1zat1on detector are presented 1n Table 4,
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, optional cleanup techniques, and
calibration procedures used.
10.0 REFERENCES
1. U.S. EPA, "Development and Application of Test Procedures for Specific
Organic Toxic Substances 1n Wastewaters, Category 10: Pesticides and PCBs,"
Report for EPA Contract 68-03-2605.
2. U.S. EPA, "Interim Methods for the Sampling and Analysis of Priority
Pollutants 1n Sediments and F1sh Tissue," Environmental Monitoring and Support
Laboratory, Cincinnati, OH 45268, October 1980.
3. Pressley, T.A., and J.E. Longbottom, "The Determination of Organohallde
Pesticides and PCBs 1n Industrial and Hunlcipal Wastewater: Method 617," U.S.
EPA/EMSL, Cincinnati, OH, EPA-600/4-84-006, 1982.
4. "Determination of Pesticides and PCB's in Industrial and Municipal
Wastewaters, U.S. Environmental Protection Agency," Environmental Monitoring
and Support Laboratory, Cincinnati, OH 45268, EPA-600/4-82-023, June 1982.
5. Goerlltz, D.F. and L.M. Law, Bulletin for Environmental Contamination and
Toxicology, 6, 9, 1971.
6. Burke, J.A., "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1955.
7. Webb, R.G. and A.C. McCall, "Quantitative PCB Standards for Electron
Capture Gas Chromatography," Journal of Chromatographlc Science, 11, 366,
1973.
8. Millar, J.D., R.E. Thomas and H.J. Schattenberg, "EPA Method Study 18,
Method 608: Organochlorine Pesticides and PCBs," U.S. EPA/EMSL, Research
Triangle Park, NC, EPA-600/4-84-061, 1984.
9. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
8080 - 23
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10. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, lj>, pp. 58-63, 1983.
11. U.S. Food and Drug Administration, Pesticide Analytical Manual, Vol. 1,
Oune 1979.
12. Sawyer, L.D., JAOAC, 56, 1015-1023 (1973), 61 272-281 (1978), 61 282-291
(1978).
13. Official Methods of Analysis of the Association of Official Analytical
Chemists, 12th Edition; Changes 1n Methods, JAOAC 61, 465-466 (1978), Sec.
29.018.
8080 - 24
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TABLE 3. QC ACCEPTANCE CRITERIA*
Parameter
Aldrln
a-BHC
tf-BHC
ff-BHC
7-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dleldrln
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrln
Heptachlor
Heptachlor epoxlde
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Test
cone.
(ug/L)
2.0
2.0
2.0
2.0
2.0
50
10
2.0
10
2.0
2.0
10
10
10
2.0
2.0
50
50
50
50
50
50
50
50
Limit
for s
(ug/L)
0.42
0.48
0.64
0.72
0.46
10.0
2.8
0.55
3.6
0.76
0.49
6.1
2.7
3.7
0.40
0.41
12.7
10.0
24.4
17.9
12.2
15.9
13.8
10.4
.tenge
for 7
(ug/L)
i. 08-2. 24
.98-2.44
U. 78-2. 60
1.01-2.37
0.86-2.32
27.6-54.3
4.8-12.6
1.08-2.60
4.6-13.7
1.15-2.49
1.14-2.82
2.2-17.1
3.8-13.2
5.1-12.6
0.86-2.00
1.13-2.63
27.8-55.6
30.5-51.5
22.1-75.2
14.0-98.5
24.8-69.6
29.0-70.2
22.2-57.9
18.7-54.9
Range
P, PS
(X)
42-122
37-134
17-147
19-140
32-127
45-119
31-141
30-145
25-160
36-146
45-153
D-202
26-144
30-147
34-111
37-142
41-126
50-114
15-178
10-215
39-150
38-158
29-131
8-127
s » Standard deviation of four recovery measurements, 1n .ug/L.
7 = Average recovery for four recovery measurements, 1n ug/L.
P, Ps = Percent recovery measured.
D = Detected; result must be greater than zero.
aCr1ter1a from 40 CFR Part 136 for Method 608. These criteria are based
directly upon the method performance data 1n Table 4. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 4.
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TABLE 4. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Aldrln
a-BHC
fl-BHC
6-BHC
7-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DOT
D1eldr1n
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrln
Heptachlor
Heptachlor epoxlde
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Accuracy, as
recovery, x'
(ug/L)
0.81C+0.04
0.84C+0.03
0.81C+0.07
0.81C+0.07
0.82C-0.05
0.82C-0.04
0.84C+0.30
0.85O0.14
0.93C-0.13
0.90C+0.02
0.97C+0.04
0.93C+0.34
0.89C-0.37
0.89C-0.04
0.69C+0.04
0.89C+0.10
0.80C+1.74
0.81C+0.50
0.96C+0.65
0.91C+10.79
0.93C+0.70
0.97C+1.06
0.76C+2.07
0.66C+3.76
Single analyst
precision, sr'
'(ug/L)
0.167-0.04
0.137+0.04
0.227+0.02
0.187+0.09
0.127+0.06
0.137+0.13
0.207-0.18
0.137+0.05
0.177+0.35
0.127+0.19
0.107+0.07
0.417-0.65
0.137+0.33
0.207+0.25
0.067+0.13
0.187-0.11
0.097+3.20
0.137+0.15
0.297-0.76
0.217-1.93
0.117+1.40
0.177+0.41
0.157+1.66
0.227-2.37
Overall
precision,
S' (ug/L)
0.207-0.01
0.237-0.00
0.337-0.95
0.257+0.03
0.227+0.04
0.187+0.18
0.277-0.14
0.28T-0.09
0.31x-0.21
0.167+0.16
0.187+0.08
0.477-0.20
0.247+0.35
0.247+0.25
0.167+0.08
0.257-0.08
0.207+0.22
0.157+0.45
0.357-0.62
0.317+3.50
0.217+1.52
0.257-0.37
0.177+3.62
0.397-4.86
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, in ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, in ug/L.
S1 = Expected interlaboratory standard deviation of measurements at an
average concentration found of 7, in ug/L.
C = True value for the concentration, in ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
8080 - 26
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METHOD 8080
ooG«MOCHLO*!NE PESTICIDES c PCB>
C --• )
7. i . 1
O
Cnoose
eppropr iete
extractIon
procedure
(cee Cnepter 2)
7.4
Perform CC
analysis (see
Method 8000)
7.1.8
Exchange
•xtr»ct-
lon solvent to
heiccne
during micro
K-D procedures
7.Z
Set g»«
chrometogr«pny
7.3
Befer to
Method 6OOO
'or proper
celloretlon
teennlaues
7.3.2
pe»K
detection 6 iden-
tification
prevent-
ed?
Cleanup
using Method
36ZO end 3660
if neeescery
Methods or
calculation of
toxepnene. cnioraane.
PCB. DOT. and One ere
handled in this
• ret Ion
Prieie or
deectivete
CC column
prior to deily
calibration
O
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00
o
00
o
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METHOD 8080A
ORGANOCHLORINE PESTICIDES AND POLYCHLORINATED BIPHENYLS
BY GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 8080 is used to determine the concentration of various
organochlorine pesticides and polychlorinated biphenyls (PCBs). The following
compounds can be determined by this method:
Compound Name
CAS No."
Aldrin
a-BHC
/3-BHC
5-BHC
7-BHC (Lindane)
Chlordane (technical)
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
4,4'-Methoxychlor
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
12789-03-6
72-54-8
72-55-9
50-29-3
60-57-1
959-98-8
33212-65-9
1031-07-8
72-20-8
7421-93-4
76-44-8
1024-57-3
72-43-5
8001-35-2
12674-11-2
1104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
a Chemical Abstract Services Registry Number.
1.2 Table 1 lists the method detection limit for each compound in
organic-free reagent water. Table 2 lists the estimated quantitation limit (EQL)
for other matrices.
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2.0 SUMMARY OF METHOD
2.1 Method 8080 provides gas chromatographic conditions for the detection
of ppb concentrations of certain organochlorine pesticides and PCBs. Prior to
the use of this method, appropriate sample extraction techniques must be used.
Both neat and diluted organic liquids (Method 3580, Waste Dilution) may be
analyzed by direct injection. A 2 to 5 ^L sample is injected into a gas
chromatograph (GC) using the solvent flush technique, and compounds in the GC
effluent are detected by an electron capture detector (ECD) or an electrolytic
conductivity detector (HECD).
2.2 The sensitivity of Method 8080 usually depends on the concentration
of interferences rather than on instrumental limitations. If interferences
prevent detection of the analytes, Method 8080 may also be performed on samples
that have undergone cleanup. Method 3620, Florisil Column Cleanup, by itself or
followed by Method 3660, Sulfur Cleanup, may be used to eliminate interferences
in the analysis.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 Interferences by phthalate esters can pose a major problem in
pesticide determinations when using the electron capture detector. These
compounds generally appear in the chromatogram as large late-eluting peaks,
especially in the 15% and 50% fractions from the Florisil cleanup. Common
flexible plastics contain varying amounts of phthalates. These phthalates are
easily extracted or leached from such materials during laboratory operations.
Cross contamination of clean glassware routinely occurs when plastics are handled
during extraction steps, especially when solvent-wetted surfaces are handled.
Interferences from phthalates can best be minimized by avoiding contact with any
plastic materials. Exhaustive cleanup of reagents and glassware may be required
to eliminate background phthalate contamination. The contamination from
phthalate esters can be completely eliminated with a microcoulometric or
electrolytic conductivity detector.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas Chromatograph: Analytical system complete with gas
chromatograph suitable for on-column injections and all required
accessories, including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak heights and/or peak areas is
recommended.
4.1.2 Columns
4.1.2.1 Column 1: Supelcoport (100/120 mesh) coated with
1.5% SP-2250/1.95% SP-2401 packed in a 1.8 m x 4 mm ID glass column
or equivalent.
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4.1.2.2 Column 2: Supelcoport (100/120 mesh) coated with
3% OV-1 in a 1.8 m x 4 mm ID glass column or equivalent.
4.1.3 Detectors: Electron capture (ECD) or electrolytic
conductivity detector (HECD).
4.2 Kuderna-Danish (K-D) apparatus:
4.2.1 Concentrator tube: 10 ml, graduated (Kontes K-570050-1025 or
equivalent). A ground-glass stopper is used to prevent evaporation of
extracts.
4.2.2 Evaporation flask: 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.2.3 Snyder column: Three ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column: Two ball micro (Kontes K-569001-0219 or
equivalent).
4.2.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.3 Boiling chips: Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.4 Water bath: Heated, with concentric ring cover, capable of
temperature control (±5°C). The bath should be used in a hood.
4.5 Volumetric flasks, Class A: sizes as appropriate with ground-glass
stoppers.
4.6 Microsyringe: 10 /nL.
4.7 Syringe: 5 ml.
4.8 Vials: Glass, 2, 10, and 20 ml capacity with Teflon-lined screw caps
or crimp tops.
4.9 Balances: Analytical, 0,0001 g and Top loading, 0.01 g.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall 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
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
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5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Solvents
5.3.1 Hexane, C6H14 - Pesticide quality or equivalent.
5.3.2 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.3.3 Toluene, C6H5CH3 - Pesticide quality or equivalent.
5.3.4 Isooctane, (CH3)3CCH2CH(CH3)2 - Pesticide quality or equivalent.
5.4 Stock standard solutions:
5.4.1 Prepare stock standard solutions at a concentration of
1000 mg/L by dissolving 0.0100 g of assayed reference material in
isooctane and diluting to volume in a 10 ml volumetric flask. A small
volume of toluene may be necessary to put some pesticides in solution.
Larger volumes can be used at the convenience of the analyst. When
compound purity is assayed to be 96% or greater, the weight can be used
without correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration if
they are certified by the manufacturer or by an independent source.
5.4.2 Transfer the stock standard solutions into vials with Teflon-
lined screw caps or crimp tops. Store at 4°C and protect from light.
Stock standards should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards from
them.
5.4.3 Stock standard solutions must be replaced after one year, or
sooner if comparison with check standards indicates a problem.
5.5 Calibration standards: Calibration standards at a minimum of five
concentrations for each parameter of interest are prepared through dilution of
the stock standards with isooctane. One of the concentrations should be at a
concentration near, but above, the method detection limit. The remaining
concentrations should correspond to the expected range of concentrations found
in real samples or should define the working range of the GC. Calibration
solutions must be replaced after six months, or sooner, if comparison with check
standards indicates a problem.
5.6 Internal standards (if internal standard calibration is used): To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.6.1 Prepare calibration standards at a minimum of five
concentrations for each analyte of interest as described in Sec. 5.5.
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5.6.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with isooctane.
5.6.3 Analyze each calibration standard according to Sec. 7.0.
5.7 Surrogate standards: The analyst should monitor the performance of
the extraction, cleanup (when used), and analytical system and the effectiveness
of the method in dealing with each sample matrix by spiking each sample,
standard, and organic-free reagent water blank with pesticide surrogates.
Because GC/ECD data are much more subject to interference than GC/MS, a secondary
surrogate is to be used when sample interference is apparent. Two surrogate
standards (tetrachloro-m-xylene (TCMX) and decachlorobiphenyl) are added to each
sample; however, only one need be calculated for recovery. Proceed with
corrective action when both surrogates are out of limits for a sample (Sec. 8.3).
Method 3500 indicates the proper procedure for preparing these surrogates.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes, Sec.
4.1. Extracts must be stored under refrigeration and analyzed within 40 days of
extraction.
7.0 PROCEDURE
7.1 Extraction:
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral, or as is, pH with methylene chloride, using either Method 3510 or
3520. Solid samples are extracted using Method 3540, 3541, or 3550.
7.1.2 Prior to gas chromatographic analysis, the extraction solvent
must be exchanged to hexane. The exchange is performed during the K-D
procedures listed in all of the extraction methods. The exchange is
performed as follows.
7.1.2.1 Following K-D of the methylene chloride extract to
1 mL using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 min.
7.1.2.2 Increase the temperature of the hot water bath to
about 90°C. Momentarily remove the Snyder column, add 50 mL of
hexane, a new boiling chip, and reattach the macro-Snyder column.
Concentrate the extract using 1 mL of hexane to prewet the Snyder
column. Place the K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration in 5-10 min. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
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reaches 1 ml, remove the K-D apparatus and allow it to drain and
cool for at least 10 min.
7.1.2.3 Remove the Snyder column and rinse the flask and
its lower joint into the concentrator tube with 1-2 mL of hexane.
A 5 ml syringe is recommended for this operation. Adjust the
extract volume to 10.0 ml. Stopper the concentrator tube and store
refrigerated at 4°C, if further processing will not be performed
immediately. If the extract will be stored longer than two days, it
should be transferred to a vial with a Teflon-lined screw cap or
crimp top. Proceed with gas chromatographic analysis if further
cleanup is not required.
7.2 Gas chromatography conditions (Recommended):
7.2.1 Column 1:
Carrier gas (5% methane/95% argon) flow rate: 60 mL/min
Column temperature: 200°C isothermal
When analyzing for the low molecular weight PCBs (PCB 1221-PCB
1248), it is advisable to set the oven temperature to 160°C.
7.2.2 Column 2:
Carrier gas (5% methane/95% argon) flow rate: 60 mL/min
Column temperature: 200°C isothermal
When analyzing for the low molecular weight PCBs (PCB 1221-PCB
1248), it is advisable to set the oven temperature to 140°C.
7.2.3 When analyzing for most or all of the analytes in this method,
adjust the oven temperature and column gas flow to provide sufficient
resolution for accurate quantitation of the analytes. This will normally
result in a retention time of 10 to 12 minutes for 4,4'-DDT, depending on
the packed column used.
7.3 Calibration: Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.
7.3.1 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these procedures.
7.3.2 Because of the low concentration of pesticide standards
injected on a GC/ECD, column adsorption may be a problem when the GC has
not been used for a day. Therefore, the GC column should be primed or
deactivated by injecting a PCB or pesticide standard mixture approximately
20 times more concentrated than the mid-concentration standard. Inject
this prior to beginning initial or daily calibration.
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7.4 Gas chromatographic analysis:
7.4.1 Refer to Method 8000. If the internal standard calibration
technique is used, add 10 /iL of internal standard to the sample prior to
injection.
7.4.2 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria. Include a mid-concentration standard after each
group of 10 samples in the analysis sequence.
NOTE: A 72 hour sequence is not required with this method.
7.4.3 Examples of GC/ECD chromatograms for various pesticides and
PCBs are shown in Figures 1 through 5.
7.4.4 Prime the column as per Sec. 7.3.2.
7.4.5 DDT and endrin are easily degraded in the injection port if
the injection port or front of the column is dirty. This is the result of
buildup of high boiling residue from sample injection. Check for
degradation problems by injecting a mid-concentration standard containing
only 4,4'-DDT and endrin. Look for the degradation products of 4,4'-DDT
(4,4'-DDE and 4,4'-DDD) and endrin (endrin ketone and endrin aldehyde).
If degradation of either DDT or endrin exceeds 20%, take corrective action
before proceeding with calibration, by following the GC system maintenance
outlined in of Method 8000. Calculate percent breakdown as follows:
Total DDT degradation peak area (DDE + ODD)
% breakdown = x 100
for 4,4'-DDT Total DDT peak area (DDT + DDE + ODD)
Total endrin degradation peak area
(endrin aldehyde + endrin ketone)
% breakdown = x 100
for Endrin Total endrin peak area (endrin +
endrin aldehyde + endrin ketone)
7.4.6 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).
7.4.7 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes.
7.4.8 If peak detection and identification are prevented due to
interferences, the hexane extract may need to undergo cleanup using Method
3620. The resultant extract(s) may be analyzed by GC directly or may
undergo further cleanup to remove sulfur using Method 3660.
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'0
7.5 Cleanup:
7.5.1 Proceed with Method 3620, followed by, if necessary, Method
3660, using the 10 ml hexane extracts obtained from Sec. 7.1.2.3.
7.5.2 Following cleanup, the extracts should be analyzed by GC, as
described in the previous sections and in Method 8000.
7.5.3 If only PCBs are to be measured in a sample, the sulfuric
acid/permanganate cleanup (Method 3665), followed by Silica Cleanup
(Method 3630) or Florisil Cleanup (Method 3620), is recommended.
7.6 Calculations (excerpted from U.S. FDA, RAM):
7.6.1 Calculation of Certain Residues: Residues which are mixtures
of two or more components present problems in measurement. When they are
found together, e.g., toxaphene and DDT, the problem of quantitation
becomes even more difficult. In the following sections suggestions are
offered for handling toxaphene, chlordane, PCB, DDT, and BHC. A 10%
DC-200 stationary phase column was used to obtain the chromatograms in
Figures 6-9.
7.6.2 Toxaphene: Quantitative calculation of toxaphene or Strobane
is difficult, but reasonable accuracy can be obtained. To calculate
toxaphene on GC/ECD: (a) adjust sample size so that toxaphene major peaks
are 10-30% full-scale deflection (FSD); (b) inject a toxaphene standard
that is estimated to be within +10 ng of the sample; (c) construct the
baseline of standard toxaphene between its extremities; and (d) construct
the baseline under the sample, using the distances of the peak troughs to
baseline on the standard as a guide (Figures 7, 8, and 9). This procedure
is made difficult by the fact that the relative heights and widths of the
peaks in the sample will probably not be identical to the standard. A
toxaphene standard that has been passed through a Florisil column will
show a shorter retention time for peak X and an enlargement of peak Y.
7.6.3 Toxaphene and DDT: If DDT is present, it will superimpose
itself on toxaphene peak V. To determine the approximate baseline of the
DDT, draw a line connecting the trough of peaks U and V with the trough of
peaks W and X and construct another line parallel to this line which will
just cut the top of peak W (Figure 61). This procedure was tested with
ratios of standard toxaphene-DDT mixtures from 1:10 to 2:1 and the results
of added and calculated DDT and toxaphene by the "parallel lines" method
of baseline construction were within 10% of the actual values in all
cases.
7.6.3.1 A series of toxaphene residues have been
calculated using total peak area for comparison to the standard and
also using area of the last four peaks only in both sample and
standard. The agreement between the results obtained by the two
methods justifies the use of the latter method for calculating
toxaphene in a sample where the early eluting portion of the
toxaphene chromatogram is interfered with by other substances.
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7.6.3.2 The baseline for methoxychlor superimposed on
toxaphene (Figure 8b) was constructed by overlaying the samples on
a toxaphene standard of approximately the same concentration (Figure
8a) and viewing the charts against a lighted background.
7.6.4 Chlordane is a technical mixture of at least 11 major
components and 30 or more minor ones. Gas chromatography-mass
spectrometry and nuclear magnetic resonance analytical techniques have
been applied to the elucidation of the chemical structures of the many
chlordane constituents. Figure 9a is a chromatogram of standard chlor-
dane. Peaks E and F are responses to trans- and cis-chlordane, respec-
tively. These are the two major components of technical chlordane, but
the exact percentage of each in the technical material is not completely
defined and is not consistent from batch to batch. Other labelled peaks
in Figure 9a are thought to represent: A, monochtorinated adduct of
pentachlorocyclopentadiene with cyclopentadiene; B, coelution of
heptachlor and a-chlordene; C, coelution of /3-chlordene and 7-chlordene;
D, a chlordane analog; G, coelution of cis-nonachlor and "Compound K," a
chlordane isomer. The right "shoulder" of peak F is caused by trans-
nonachlor.
7.6.4.1 The GC pattern of a chlordane residue may differ
considerably from that of the technical standard. Depending on the
sample substrate and its history, residues of chlordane can consist
of almost any combination of constituents from the technical
chlordane, plant and/or animal metabolites, and products of
degradation caused by exposure tc environmental factors such as
water and sunlight. Only limited information is available on which
residue GC patterns are likely to occur in which samples types, and
even this information may not be applicable to a situation where the
route of exposure is unusual. For example, fish exposed to a recent
spill of technical chlordane will contain a residue drastically
different from a fish whose chlordane residue was accumulated by
ingestion of smaller fish or of vegetation, which in turn had
accumulated residues because chlordane was in the water from
agricultural runoff.
7.6.4.2 Because of this inability to predict a chlordane
residue GC pattern, it is not possible to prescribe a single method
for the quantitation of chlordane residues. The analyst must judge
whether or not the residue's GC pattern is sufficiently similar to
that of a technical chlordane reference material to use the latter
as a reference standard for quantitation.
7.6.4.3 When the chlordane residue does not resemble
technical chlordane, but instead consists primarily of individual,
identifiable peaks, quantitate each peak separately against the
appropriate reference materials and report the individual residues.
(Reference materials are available for at least 11 chlordane
constituents, metabolites or degradation products which may occur in
the residue.)
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7.6.4.4 When the GC pattern of the residue resembles that
of technical chlordane, quantitate chlordane residues by comparing
the total area of the chlordane chromatogram from peaks A through F
(Figure 9a) in the sample versus the same part of the standard
chromatogram. Peak G may be obscured in a sample by the presence of
other pesticides. If G is not obscured, include it in the
measurement for both standard and sample. If the heptachlor epoxide
peak is relatively small, include it as part of the total chlordane
area for calculation of the residue. If heptachlor and/or
heptachlor epoxide are much out of proportion as in Figure 6j,
calculate these separately and subtract their areas from total area
to give a corrected chlordane area. (Note that octachlor epoxide,
a metabolite of chlordane, can easily be mistaken for heptachlor
epoxide on a nonpolar GC column.)
7.6.4.5 To measure the total area of the chlordane
chromatogram, proceed as in Sec. 7.6.2 on toxaphene. Inject an
amount of technical chlordane standard which will produce a
chromatogram in which peaks E and F are approximately the same size
as those in the sample chromatograms. Construct the baseline
beneath the standard from the beginning of peak A to the end of peak
F as shown in Figure 9a. Use the distance from the trough between
peaks E and F to the baseline in the chromatogram of the standard to
construct the baseline in the chromatogram of the sample. Figure 9b
shows how the presence of toxaphene causes the baseline under
chlordane to take an upward angle. When the size of peaks E and F
in standard and sample chromatograms are the same, the distance from
the trough of the peaks to the baselines should be the same.
Measurement of chlordane area should be done by total peak area if
possible.
NOTE: A comparison has been made of the total peak area
integration method and the addition of peak heights
method for several samples containing chlordane. The
peak heights A, B, C, D, E, and F were measured in
millimeters from peak maximum of each to the baseline
constructed under the total chlordane area and were then
added together. These results obtained by the two
techniques are too close to ignore this method of "peak
height addition" as a means of calculating chlordane.
The technique has inherent difficulties because not all
the peaks are symmetrical and not all are present in the
same ratio in standard and in sample. This method does
offer a means of calculating results if no means of
measuring total area is practical.
7.6.5 Polychlorinated biphenyls (PCBs): Quantitation of residues of
PCB involves problems similar to those encountered in the quantitation of
toxaphene, Strobane, and chlordane. In each case, the chemical is made up
of numerous compounds. So the chromatograms are multi-peak. Also in each
case, the chromatogram of the residue may not match that of the standard.
7.6.5.1 Mixtures of PCBs of various chlorine contents were
sold for many years in the U.S. by the Monsanto Co. under the
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tradename Aroclor (1200 series and 1016). Though these Aroclors are
no longer marketed, the PCBs remain in the environment and are
sometimes found as residues in foods, especially fish.
7.6.5.2 PCB residues are quantitated by comparison to one
or more of the Aroclor materials, depending on the chromatographic
pattern of the residue. A choice must be made as to which Aroclor
or mixture of Aroclors will produce a chromatogram most similar to
that of the residue. This may also involve a judgment about what
proportion of the different Aroclors to combine to produce the
appropriate reference material.
7.6.5.3 Quantitate PCB residues by comparing total area or
height of residue peaks to total area of height of peaks from
appropriate Aroclor(s) reference materials. Measure total area or
height response from common baseline under all peaks. Use only
those peaks from the sample that can be attributed to
chlorobiphenyls. These peaks must also be present in the
chromatogram of the reference materials. Mixtures of Aroclors may
be required to provide the best match of GC patterns of sample and
reference.
7.6.6 DDT: DDT found in samples often consists of both o,p'- and
p,p'-DDT. Residues of DDE and ODD are also frequently present. Each
isomer of DDT and its metabolites should be quantitated using the pure
standard of that compound and reported as such.
7.6.7 Hexachlorocyclohexane (BHC, from the former name, benzene
hexachloride): Technical grade BHC is a cream-colored amorphous solid
with a very characteristic musty odor; it consists of a mixture of six
chemically distinct isomers and one or more heptachloro-cyclohexanes and
octachloro-cyclohexanes.
7.6,7.1 Commercial BHC preparations may show a wide
variance in the percentage of individual isomers present. The
elimination rate of the isomers fed to rats was 3 weeks for the a-,
7-, and 6-isomers and 14 weeks for the 0-isomer. Thus it may be
possible to have any combination of the various isomers in different
food commodities. BHC found in dairy products usually has a large
percentage of /3-isomer.
7.6.7.2 Individual isomers (a, fi, 7, and s) were injected
into gas chromatographs equipped with flame ionization,
microcoulometric, and electron capture detectors. Response for the
four isomers is very nearly the same whether flame ionization or
microcoulometric GLC is used. The a-, 7-, and (5-isomers show equal
electron affinity. /3-BHC shows a much weaker electron affinity
compared to the other isomers.
7.6.7.3 Quantitate each isomer (a, 0, 7, and 6)
separately against a standard of the respective pure isomer, using
a GC column which separates all the isomers from one another.
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8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized. If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
8.2 Quality control required to evaluate the GC system operation is found
in Method 8000.
8.2.1 The quality control check sample concentrate (Method 8000)
should contain each single-component parameter of interest at the
following concentrations in acetone or other water miscible solvent:
4,4'-ODD, 10 mg/L; 4,4'-DDT, 10 mg/L; endosulfan II, 10 mg/L; endosulfan
sulfate, 10 mg/L; endrin, 10 mg/L; and any other single-component
pesticide, 2 mg/L. If this method is only to be used to analyze for PCBs,
chlordane, or toxaphene, the QC check sample concentrate should contain
the most representative multi-component parameter at a concentration of 50
mg/L in acetone.
8.2.2 Table 3 indicates the QC acceptance criteria for this method.
Table 4 gives method accuracy and precision as functions of concentration
for the analytes of interest. The contents of both Tables should be used
to evaluate a laboratory's ability to perform and generate acceptable data
by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000).
8.3.1 If recovery is not within limits, the following is required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any
of the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above
are a problem or flag the data as "estimated
concentration".
8.4 GC/MS confirmation: Any compounds confirmed by two columns may also
be confirmed by GC/MS if the concentration is sufficient for detection by GC/MS
as determined by the laboratory generated detection limits.
8.4.1 The GC/MS would normally require a minimum concentration of 10
r\g/p,l in the final extract, for each single-component compound.
8.4.2 The pesticide extract and associated blank should be analyzed
by GC/MS as per Sec. 7.0 of Method 8270.
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8.4.3 The confirmation may be from the GC/MS analysis of the
base/neutral-acid extractables extracts (sample and blank). However, if
the compounds are not detected in the base/neutral-acid extract even
though the concentration is high enough, a GC/MS analysis of the pesticide
extract should be performed.
8.4.4 A reference standard of the compound must also be analyzed by
GC/MS. The concentration of the reference standard must be at a level
that would demonstrate the ability to confirm the pesticides/PCBs
identified by GC/ECD.
9.0 METHOD PERFORMANCE
9.1 The method was tested by 20 laboratories using organic-free reagent
water, drinking water, surface water, and three industrial wastewaters spiked at
six concentrations. Concentrations used in the study ranged from 0.5 to 30 /ug/L
for single-component pesticides and from 8.5 to 400 ng/L for multi-component
parameters. Single operator precision, overall precision, and method accuracy
were found to be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to describe these
relationships for an electron capture detector are presented in Table 4.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, optional cleanup techniques, and
calibration procedures used.
10.0 REFERENCES
1. U.S. EPA, "Development and Application of Test Procedures for Specific
Organic Toxic Substances in Wastewaters, Category 10: Pesticides and
PCBs," Report for EPA Contract 68-03-2605.
2. U.S. EPA, "Interim Methods for the Sampling and Analysis of Priority
Pollutants in Sediments and Fish Tissue," Environmental Monitoring and
Support Laboratory, Cincinnati, OH 45268, October 1980.
3. Pressley, T.A., and O.E. Longbottom, "The Determination of Organohalide
Pesticides and PCBs in Industrial and Municipal Wastewater: Method 617,"
U.S. EPA/EMSL, Cincinnati, OH, EPA-600/4-84-006, 1982.
4. "Determination of Pesticides and PCB's in Industrial and Municipal
Wastewaters, U.S. Environmental Protection Agency," Environmental
Monitoring and Support Laboratory, Cincinnati, OH 45268, EPA-600/4-82-023,
June 1982.
5. Goerlitz, D.F. and L.M. Law, Bulletin for Environmental Contamination and
Toxicology, 6, 9, 1971.
6. Burke, J.A., "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
8080A - 13 Revision 1
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7. Webb, R.G. and A.C. McCall, "Quantitative PCB Standards for Electron
Capture Gas Chromatography," Journal of Chromatographic Science, H, 366,
1973.
8. Millar, J.D., R.E. Thomas and H.J. Schattenberg, "EPA Method Study 18,
Method 608: Organochlorine Pesticides and PCBs," U.S. EPA/EMSL, Research
Triangle Park, NC, EPA-600/4-84-061, 1984.
9. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
Final Rule and Proposed Rule," October 26, 1984.
11. U.S. Food and Drug Administration, Pesticide Analytical Manual, Vol. 1,
June 1979.
12. Sawyer, L.D., JAOAC, 56, 1015-1023 (1973), 61 272-281 (1978), 61 282-291
(1978).
13. Stewart, J. "EPA Verification Experiment for Validation of the SOXTEC® PCB
Extraction Procedure"; Oak Ridge National Laboratory, Oak Ridge, TN,
37831-6138; October 1988.
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TABLE 1.
GAS CHROMATOGRAPHY OF PESTICIDES AND PCBs"
Analyte
Aldrin
a-BHC
jS-BHC
5-BHC
7-BHC (Lindane)
Chlordane (technical)
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Methoxychlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Retention
Col. 1
2.40
1.35
1.90
2.15
1.70
e
7.83
5.13
9.40
5.45
4.50
8.00
14.22
6.55
11.82
2.00
3.50
18.20
e
e
e
e
e
e
e
e
time (min)
Col. 2
4.10
1.82
1.97
2.20
2.13
e
9.08
7.15
11.75
7.23
6.20
8.28
10.70
8.10
9.30
3.35
5.00
26.60
e
e
e
e
e
e
e
e
Method
Detection
limit (M9/L)
0.004
0.003
0.006
0.009
0.004
0.014
0.011
0.004
0.012
0.002
0.014
0.004
0.066
0.006
0.023
0.003
0.083
0.176
0.24
nd
nd
nd
0.065
nd
nd
nd
aU.S. EPA. Method 617. Organochlorine Pesticides and PCBs.
Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
e = Multiple peak response.
nd = not determined.
Environmental
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TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQLs) FOR VARIOUS MATRICES8
Matrix Factor
Ground water 10
Low-concentration soil by sonication with GPC cleanup 670
High-concentration soil and sludges by sonication 10,000
Non-water miscible waste 100,000
EQL = [Method detection limit (see Table 1)] X [Factor found in this
table]. For non-aqueous samples, the factor is on a wet-weight
basis. Sample EQLs are highly matrix-dependent. The EQLs listed
herein are provided for guidance and may not always be achievable.
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TABLE 3.
QC ACCEPTANCE CRITERIA3
Analyte
Aldrin
a-BHC
0-BHC
5-BHC
7-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan
Endosulfan
Endosulfan
Endrin
Heptachlor
Heptachlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
g =
x
P, Ps =
D
Test
cone.
(M9A)
2.0
2.0
2.0
2.0
2.0
50
10
2.0
10
2.0
I 2.0
II 10
Sulfate 10
10
2.0
epoxide 2.0
50
50
50
50
50
50
50
50
Standard deviation of
Average recovery for
Limit
for s
(M9/L)
0.42
0.48
0.64
0.72
0.46
10.0
2.8
0.55
3.6
0.76
0.49
6.1
2.7
3.7
0.40
0.41
12.7
10.0
24.4
17.9
12.2
15.9
13.8
10.4
four recovery
four recovery
Range
for x
(M9A)
1.08-2.24
0.98-2.44
0.78-2.60
1.01-2.37
0.86-2.32
27.6-54.3
4.8-12.6
1.08-2.60
4.6-13.7
1.15-2.49
1.14-2.82
2.2-17.1
3.8-13.2
5.1-12.6
0.86-2.00
1.13-2.63
27.8-55.6
30.5-51.5
22.1-75.2
14.0-98.5
24.8-69.6
29.0-70.2
22.2-57.9
18.7-54.9
measurements, in /
measurements, in ^
Range
P> PS
(%)
42-122
37-134
17-147
19-140
32-127
45-119
31-141
30-145
25-160
36-146
45-153
D-202
26-144
30-147
34-111
37-142
41-126
50-114
15-178
10-215
39-150
38-158
29-131
8-127
3/ *
Percent recovery measured.
Detected; result must
be greater than zero.
"Criteria from 40 CFR Part 136 for Method 608. These criteria are based directly
upon the method performance data in Table 4. Where necessary, the limits for
recovery have been broadened to assure applicability of the limits to
concentrations below those used to develop Table 4.
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TABLE 4.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION"
Analyte
Aldrin
a-BHC
0-BHC
5-BHC
7-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrin
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Accuracy, as
recovery, x'
(M9/L)
0.81C+0.04
0.84C+0.03
0.81C+0.07
0.81C+0.07
0.82C-0.05
0.82C-0.04
0.84C+0.30
0.85C+0.14
0.93C-0.13
0.90C+0.02
0.97C+0.04
0.93C+0.34
0.89C-0.37
0.89C-0.04
0.69C+0.04
0.89C+0.10
0.80C+1.74
0.81C+0.50
0.96C+0.65
0.91C+10.79
0.91C+10.79
0.91C+10.79
0.91C+10.79
0.91C+10.79
Single analyst
precision, s/
(M9/L)
0.16X-0.04
0.13X+0.04
0.22X+0.02
0.18X+0.09
0.12X+0.06
0.13X+0.13
O.ZOx-0.18
0.13X+0.06
0.17X+0.39
0.12X+O.I9
O.lOx+0.07
0.41X-0.65
0.13X+0.33
0.20X+0.25
0.06X+0.13
O.lSx-0.11
0.09X+3.20
0.13X+0.15
0.29X-0.76
0.21X-1.93
O.Zlx-1.93
0.21X-1.93
0.21X-1.93
fl.21x-l.93
Overall
precision,
S' (M9/L)
0.20X-0.01
0.23X-0.00
0.33X-0.95
0.25X+0.03
0.22x-t-0.04
O.lSx+0.18
0.27X-0.14
0.28X-0.09
0.31X-0.21
0.16X+0.16
0.18X+0.08
0.47X-0.20
0.24X+0.35
0.24X+0.25
0.16X+0.08
0.25X-0.08
0.20X+0.22
0.15X+0.45
0.35X-0.62
0.31X+3.50
0.31X+3.50
0.31X+3.50
0.31X+3.50
0.31X+3.50
X'
S'
C
x
Expected recovery for one or more measurements of a sample
containing concentration C, in /Lig/L.
Expected single analyst standard deviation of measurements at an
average concentration of x, in M9/L-
Expected interlaboratory standard deviation of measurements at an
average concentration found of x, in
True value for the concentration, in /zg/L.
Average recovery found for measurements of samples containing a
concentration of C, in M9A-
8080A - 18
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Figure 1
Gas Chromatogram of Pesticides
Column: 1.5% SP-2250+
1.95% SP-2401 on Supelcoport
Temperature: 200°C
Detector: Electron Capture
• 12
MfTiNTION TIME (MINUTES)
8080A - 19
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Figure 2
Gas Chromatogram of Chlordane
Column: 1.5% SP-2250+
1.95% SP-2401 on Supelcoport
Temperature: 200°C
Detector: Electron Capture
4 I 12
RETENTION TIME (MINUTES)
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Figure 3
Gas Chromatogram of Toxaphene
Column: 1.5% SP-2250+
1.95% SP-2401 on Supelcoport
Temperature: 200°C
Detector: Electron Capture
10 H II
HfTtNTION TIMI (MINUTIS)
22
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Figure 4
Gas Chromatogram of Aroclor 1254
Column: 1.5% SP-2250+
1.95% SP-2401 on Supelcoport
Temperature: 200°C
Detector: Electron Capture
6 10 14
ftCTINTlON TIME (MINUTIS)
II
22
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Figure 5
Gas Chromatogram of Aroclor 1260
Column: 1.5% SP-2250+
1.95% SP-2401 on Supelcoport
Temperature: 200°C
Detector: Electron Capture
10 14 II
ftfTINTtON T1MI (MINUTIS)
22
2f
8080A - 23
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Figure 6
J..L
Fig.6--Baseline construction for some typical gas chromotagraphic peaks.
a: symmetrical separated flat baseline; b and c: overlapp flat baseline;
d: separated (pen does not return to baseline between peaks); e: separated
sloping baseline; f: separated (pen goes below baseline between peaks);
g: a- and 7-BHC sloping baseline; h: a-,ft- and 7-BHC sloping baseline;
i: chlordane flat baseline; j: heptachlor and heptachlor epoxide super-
imposed on chlordane; k: chair-shaped peaks, unsymmetrical peak;
1: p,p'-DDT superimposed on toxaphene.
8080A - 24
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Figure 7
Fig.- 7a - - Baseline construction for multiple residues with standard
toxaphene.
Fig.- 7b -- Baseline construction for multiple residues with toxaphene,
DDE and o,p'-, and p,p'-DDT
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Figure 8
Fig.- 8a -- Baseline construction for multiple residues: standard toxaphene.
Pig.- 8b -- Baseline construction for multiple residues: rice bran with BHC,
toxaphene, DDT, and methoxychlor.
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Figure 9
Pig.- 9a -- Baseline construction for multiple residues: standard chlordane.
Fig.- 9b -- Baseline construction for multiple residues: rice bran with
chlordane, toxaphene, and DDT.
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METHOD 8080A
ORGANOCHLORINE PESTICIDES AND POLYCHLORINATED BIPHENYLS
BY GAS CHROMATOGRAPHY
Start
7.1.1 Choos«
appropriate extraction
procedure.
7.1.2 Exchange
extraction solvent
to hexane.
7.2 Set
chromatographic
conditions.
7.3 Refer to
Method 8000 for
proper calibration
techniques.
7.3.2 Prime or
deactivate the GC
column prior to
daily calibration.
7.4 Perform
GC analysis.
7.4.8
is peak
detection and
identification
prevented?
7.6.1 Do
residues have
two or more
components?
7.5.1 Cleanup
using Method 3620
or 3660 if necessary.
7.6 Calculate
concentrations.
8080A - 28
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00
o
00
-------
METHOD 8081
ORGANOCHLORINE PESTICIDES AND PCBs AS AROCLORS BY GAS
CHROMATOGRAPHY: CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8081 is used to determine the concentrations of various
organochlorine pesticides and polychlorinated biphenyls (PCBs) as Aroclors, in
extracts from solid and liquid matrices. Open-tubular, capillary columns were
employed with electron capture detectors (ECD) or electrolytic conductivity
detectors (ELCD). When compared to the packed columns, these fused-sil ica, open-
tubular columns offer improved resolution, better selectivity, increased
sensitivity, and faster analysis. The list below is annotated to show whether a
single- or dual-column analysis system was used to identify each target analyte.
Compound Name
CAS Registry No.
Aldrin8-"
Aroclor-1016a'b
Aroclor-1221a'b
Aroclor-1232a'b
Aroclor-1242a'b
Aroclor-1248a-b
Aroclor-1254a'b
Aroclor-1260a'b
a-BHCa'b
/3-BHCa'b
-y-BHC (Lindane)a-b
5-BHCa-b
Chlorobenzilateb
a-Chlordaneb
T-Chlordanea-b
DBCPb
4,4'-DDDa'b
4,4'-DDEa'b
4,4'-DDTa'b
Diallate6
Dieldrina-b
Endosulfan Pb
Endosulfan IPb
Endosulfan sulfatea'b
Endrina'b
Endrin aldehydea'b
Endrin ketoneb
309-00-2
12674-11-2
1104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
319-84-6
319-85-7
58-89-9
319-86-8
510-15-6
5103-71-9
5103-74-2
96-12-8
72-54-8
72-55-9
50-29-3
2303-16-4
60-57-1
959-98-8
33213-65-9
1031-07-8
72-20-8
7421-93-4
53494-70-5
8081 - 1
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Compound Name CAS Registry No.
Heptachlora'b 76-44-8
Heptachlor epoxide"'b 1024-57-3
Hexachlorobenzeneb 118-74-1
Hexachlorocyclopentadieneb 77-47-4
Isodrinb 465-73-6
Keponeb 143-50-0
Methoxychlora'b 72-43-5
Toxaphenea'b 8001-35-2
Single-column analysis
Dual-column analysis
1.2 The analyst must select columns, detectors and calibration procedures
most appropriate for the specific analytes of interest in a study. Matrix-
specific performance data must be established and the stability of the analytical
system and instrument calibration must be established for each analytical matrix
(e.g., hexane solutions from sample extractions, diluted oil samples, etc.).
1.3 Although performance data are presented for many of the listed
chemicals, it is unlikely that all of them could be determined in a single
analysis. This limitation results because the chemical and chromatographic
behavior of many of these chemicals can result in co-elution. Several
cleanup/fractionation schemes are provided in this method and in Method 3600.
Any chemical is a potential method interference when it is not a target analyte.
1.4 Several multi-component mixtures (i.e., Aroclors and Toxaphene) are
listed as target compounds. When samples contain more than one multi-component
analyte, a higher level of analyst expertise is required to attain acceptable
levels of qualitative and quantitative analysis. The same is true of multi-
component analytes that have been subjected to environmental degradation or
degradation by treatment technologies. These result in "weathered" Aroclors (or
any other multi-component mixtures) that may have significant differences in peak
patterns than those of standards. In these cases, individual congener analyses
may be preferred over total mixture analyses.
1.5 Compound identification based on single column analysis should be
confirmed on a second column, or should be supported by at least one other
qualitative technique. This method describes analytical conditions for a second
gas chromatographic column that can be used to confirm the measurements made with
the primary column. GC/MS Method 8270 is also recommended as a confirmation
technique if sensitivity permits (Sec. 8).
1.6 This method describes a dual column option. The option allows a
hardware configuration of two analytical columns joined to a single injection
port. The option allows one injection to be used for dual column analysis.
8081 - 2 Revision 0
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Analysts are cautioned that the dual column option may not be appropriate when
the instrument is subject to mechanical stress, many samples are to be run in a
short period, or when contaminated samples are analyzed.
1.7 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph (GC) and in the
interpretation of gas chromatograms. Each analyst must demonstrate the ability
to generate acceptable results with this method.
1.8 Extracts suitable for analysis by this method may also be analyzed
for organophosphorus pesticides (Method 8141). Some extracts may also be
suitable for triazine herbicide analysis, if low recoveries (normally samples
taken for triazine analysis must be preserved) are not a problem.
1.9 The following compounds may also be determined using this method:
Compound Name
CAS Registry No.
Alachlor8-6
Captafolb
Captanb
Chloroneb6
Chloropropylateb
Chlorothalonilb
DCPAb
Dichlone6
Dicofolb
Etridiazoleb
Halowax-1000b
Halowax-1001b
Halowax-1013b
Halowax-1014b
Halowax-1051b
Halowax-1099b
Mirexb
Nitrofenb
PCNB"
Perthaneb
Propachlor6
Strobaneb
trans-Nonachlorb
trans-Permethrinb
Trifluralinb
15972-60-8
2425-06-1
133-06-2
2675-77-6
99516-95-7
1897-45-6
1861-32-1
117-80-6
115-32-2
2593-15-9
58718-66-4
58718-67-5
12616-35-2
12616-36-3
2234-13-1
39450-05-0
2385-85-5
1836-75-5
82-68-8
72-56-0
1918-16-17
8001-50-1
39765-80-5
51877-74-8
1582-09-8
Single-column analysis
Dual-column analysis
8081 - 3
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2.0 SUMMARY OF METHOD
2.1 A measured volume or weight of sample (approximately 1 L for 1 iquids,
2 g to 30 g for solids) is extracted using the appropriate sample extraction
technique. Liquid samples are extracted at neutral pH with methylene chloride
using either a separatory funnel (Method 3510) or a continuous liquid-liquid
extractor (Method 3520). Solid samples are extracted with hexane-acetone (1:1)
or methylene chloride-acetone (1:1) using either Soxhlet extraction (Method
3540), Automated Soxhlet (Method 3541), or Ultrasonic Extraction (Method 3550).
A variety of cleanup steps may be applied to the extract, depending on (1) the
nature of the coextracted matrix interferences and (2) the target analytes.
After cleanup, the extract is analyzed by injecting a 1-^1- sample into a gas
chromatograph with a narrow- or wide-bore fused silica capillary column and
electron capture detector (GC/ECD) or an electrolytic conductivity detector
(GC/ELCD).
3.0 INTERFERENCES
3.1 Refer to Methods 3500 (Sec. 3, in particular), 3600, and 8000.
3.2 Sources of interference in this method can be grouped into three
broad categories: contaminated solvents, reagents or sample processing hardware;
contaminated GC carrier gas, parts, column surfaces or detector surfaces; and the
presence of coeluting compounds in the sample matrix to which the ECD will
respond. Interferences coextracted from the samples will vary considerably from
waste to waste. While general cleanup techniques are referenced or provided as
part of this method, unique samples may require additional cleanup approaches to
achieve desired degrees of discrimination and quantitation.
3.3 Interferences by phthalate esters introduced during sample
preparation can pose a major problem in pesticide determinations. These
materials may be removed prior to analysis using Gel Permeation Cleanup -
pesticide option (Method 3640) or as Fraction III of the silica gel cleanup
procedure (Method 3630). Common flexible plastics contain varying amounts of
phthalate esters which are easily extracted or leached from such materials during
laboratory operations. Cross-contamination of clean glassware routinely occurs
when plastics are handled during extraction steps, especially when solvent-wetted
surfaces are handled. Interferences from phthalate esters can best be minimized
by avoiding contact with any plastic materials and checking all solvents and
reagents for phthalate contamination. Exhaustive cleanup of solvents, reagents
and glassware may be required to eliminate background phthalate ester
contamination.
3.4 Glassware must be scrupulously cleaned. Clean all glassware as soon
as possible after use by rinsing with the last solvent used. This should be
followed by detergent washing with hot water, and rinses with tap water and
organic-free reagent water. Drain the glassware and dry in an oven at 130°C for
several hours or rinse with methanol and drain. Store dry glassware in a clean
environment.
3.5 The presence of elemental sulfur will result in broad peaks that
interfere with the detection of early-eluting organochlorine pesticides. Sulfur
8081 - 4 Revision 0
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contamination should be expected with sediment samples. Method 3660 is suggested
for removal of sulfur. Since the recovery of Endrin aldehyde (using the TBA
procedure) is drastically reduced, this compound must be determined prior to
sulfur cleanup.
3.6 Waxes, lipids, and other high molecular weight co-extractables can
be removed by Gel-Permeation Cleanup (Method 3640).
3.7 It may be difficult to quantitate Aroclor patterns and single
component pesticides together. Some pesticides can be removed by sulfuric
acid/permanganate cleanup (Method 3665} and silica fractionation (Method 3630).
Guidance on the identification of PCBs Is given in Sec. 7.
3.8 The following target analytes coelute using single column analysis:
DB 608 Trifluralin/Diallate isomers
PCNP/Dichlone/Isodrin
DDD/Endosulfan II
DB 1701 Captan/Chlorobenzilate
Captafol/Mirex
DDD/Endosulfan II
Methoxychlor/Endosulfan sulfate
3.8.1 Other halogenated pesticides or industrial chemicals may
interfere with the analysis of pesticides. Certain co-eluting
organophosphorus pesticides are eliminated by the Gel Permeation
Chromatography cleanup - pesticide option (Method 3640). Co-eluting
chlorophenols are eliminated by Silica gel (Method 3630), Florisil (Method
3620), or Alumina (Method 3610) cleanup.
3.9 The following compounds coelute using the dual column analysis. Two
temperature programs are provided for the same pair of columns as option 1 and
option 2 for dual column analysis. In general, the DB-5 column resolves fewer
compounds that the DB-1701:
3.9.1 DB-5/DB-1701, thin film, slow ramp: See Sec. 7 and Table 6.
DB-5 trans-Permethrin/Heptachlor epoxide
Endosulfan I/a-Chlordane
Perthane/Endrin
Endosulfan II/Chloropropylate/Chiorobenzi1 ate
4,4'-DDT/Endosulfan sulfate
Methoxychlor/Dicofol
Perthane/Endrin and Chiorobenzilate/Endosulfan II/Chloropropylate
will also co-elute on DB-5 after moderate deterioration in column
performance.
8081 - 5 Revision 0
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DB-1701 Chlorothalonil/8-BHC
£-BHC/DCPA/tra/7s-Permethrin
a-Chlordane/tra/?s-Nonachlor
Captan/Dieldrin
Chiorobenzi1 ate/Chioropropylate
Chlorothalonil/G-BHC and or-Chlordane/trans-Nonachlor will co-elute
on the DB-1701 column after moderate deterioration in column performance.
Nitrofen, Dichlone, Carbophenothion, Dichloran and Kepone were
removed from the composite mixture because of extensive peak tailing on
both columns. Simazine and Atrazine give poor responses on the ECD
detector. Triazine compounds should be analyzed using Method 8141 (NPD
option).
3.9.2 DB-5/DB-1701, thick film, fast ramp: See Sec. 7 and Table 7.
DB-5 Diallate/o-BHC
Perthane/Endosulfan II
Chiorobenzi1 ate/Chioropropylate
Endrin/Nitrofen
4,4'-DDT/Endosulfan sulfate
Methoxychlor/Dicolfol
DB-1701 a-Chlordane/ferans-Nonachlor {partially resolved)
4,4'-DDD/Endosulfan II (partially resolved)
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph: an analytical system complete with gas
chromatograph suitable for on-column and split-splitless injection and all
required accessories including syringes, analytical columns, gases, electron
capture detectors (ECD), and recorder/integrator or data system.
The columns listed in this section were used to develop the method
performance data. Their specification is not intended to prevent laboratories
from using columns that are developed after promulgation of the method.
Laboratories may use other capillary columns if they document method performance
data (e.g. chromatographic resolution, analyte breakdown, and MDLs) equal to or
better than those provided with the method.
4.1.1 Single-column Analysis:
4.1.1.1 Narrow-bore columns:
4.1.1.1.1 Column 1 - 30 m x 0.25 or 0.32 mm internal
diameter (ID) fused silica capillary column chemically bonded
with SE-54 (DB 5 or equivalent), 1 /urn film thickness.
4.1.1.1.2 Column 2 - 30 m x 0.25 mm ID fused silica
capillary column chemically bonded with 35 percent phenyl
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methylpolysiloxane (DB 608, SPB 608, or equivalent), 25 pm
coating thickness, 1 jitm film thickness.
4.1.1.1.3 Narrow bore columns should be installed in
split/splitless (Grob-type) injectors.
4.1.1.2 Wide-bore columns
4.1.1.2.1 Column 1 - 30 m x 0.53 mm ID fused silica
capillary column chemically bonded with 35 percent phenyl
methylpolysiloxane (OB 608, SPB 608, RTx-35, or equivalent),
0.5 jLtm or 0.83 urn film thickness.
4.1.1.2.2 Column 2 - 30 m x 0.53 mm ID fused silica
capillary column chemically bonded with 50 percent phenyl
methylpolysiloxane (DB 1701, or equivalent), 1.0 jum film
thickness.
4.1.1.2.3 Column 3 - 30 m x 0.53 mm ID fused silica
capillary column chemically bonded with SE-54 (DB 5, SPB 5,
RTx5, or equivalent), 1.5 ^m film thickness.
4.1.1.2.4 Wide-bore columns should be installed in 1/4
inch injectors, with deactivated liners designed specifically
for use with these columns.
4.1.2 Dual Column Analysis:
4.1.2.1 Column pair 1 :
4.1.2.1.1 J&W Scientific press-fit Y-shaped glass 3-
way union splitter (J&W Scientific, Catalog no. 705-0733) or
Restek Y-shaped fused-silica connector (Restek, Catalog no.
20405), or equivalent.
4.1.2.1.2 30 m x 0.53 m ID DB-5 (J&W Scientific),
1.5 /iiti film thickness, or equivalent.
4.1.2.1.3 30 m x 0.53 mm ID DB-1701 (J&W Scientific),
1.0 fj.m film thickness, or equivalent.
4.1.2.2 Column pair 2:
4.1.2.2.1 Splitter 2 - Supelco 8 in. glass injection
tee, deactivated (Supelco, Catalog no. 2-3665M), or
equivalent.
4.1.2.2.2 30 m x 0.53 m ID OB-5 (J&W Scientific),
0.83 /Ltm film thickness, or equivalent.
4.1.2.2.3 30 m x 0.53 mm ID DB-1701 (J&W Scientific),
1.0 y,m film thickness, or equivalent.
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4.1.3 Column rinsing kit: Bonded-phase column rinse kit (J&W
Scientific, Catalog no. 430-3000 or equivalent).
4.2 Glassware (see Methods 3510, 3520, 3540, 3541, 3550, 3630, 3640,
3660, and 3665 for specifications).
4.3 Kuderna-Danish (K-D) apparatus. See extraction methods for specifics.
5.0 REAGENTS
5.1 Reagent or pesticide grade chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all reagents shall conform to
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 ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
NOTE: Store the standard solutions (stock, composite, calibration,
internal, and surrogate) at 4°C in Teflon-sealed containers in the
dark. When a lot of standards is prepared, it is recommended that
aliquots of that lot be stored in individual small vials. All stock
standard solutions must be replaced after one year or sooner if
routine QC (Sec. 8) indicates a problem. All other standard
solutions must be replaced after six months or sooner if routine QC
(Sec. 8) indicates a problem.
5.2 Solvents and reagents: As appropriate for Method 3510, 3520, 3540,
3541, 3550, 3630, 3640, 3660, or 3665: n-hexane, diethyl ether, methylene
chloride, acetone, ethyl acetate, and isooctane (2,2,4-tnmethylpentane). All
solvents should be pesticide quality or equivalent, and each lot of solvent
should be determined to be phthalate free. Solvents must be exchanged to hexane
or isooctane prior to analysis.
5.2.1 Organic-free reagent water: All references to water in this
method refer to organic-free reagent water as defined in Chapter One.
5.3 Stock standard solutions (1000 mg/L): Can be prepared from pure
standard materials or can be purchased as certified solutions.
5.3.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure compound. Dissolve the compound in isooctane or hexane
and dilute to volume in a 10-mL volumetric flask. If compound purity is
96 percent or greater, the weight can be used without correction to
calculate the concentration of the stock standard solution. Commercially
prepared stock standard solutions can be used at any concentration if they
are certified by the manufacturer or by an independent source.
5.3.2 6-BHC, Dieldrin, and some other standards may not be
adequately soluble in isooctane. A small amount of acetone or toluene
should be used to dissolve these compounds during the preparation of the
stock standard solutions.
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5.4 Composite stock standard: Can be prepared from individual stock
solutions. For composite stock standards containing less than 25 components,
take exactly 1 ml of each individual stock solution at 1000 mg/L, add solvent,
and mix the solutions in a 25-mL volumetric flask. For example, for a composite
containing 20 individual standards, the resulting concentration of each component
in the mixture, after the volume is adjusted to 25 ml, will be 1 mg/25 ml. This
composite solution can be further diluted to obtain the desired concentrations.
For composite stock standards containing more than 25 components, use volumetric
flasks of the appropriate volume (e.g., 50 ml, 100 ml).
5.5 Calibration standards should be prepared at a minimum of five
concentrations by dilution of the composite stock standard with isooctane or
hexane. The concentrations should correspond to the expected range of
concentrations found in real samples and should bracket the linear range of the
detector.
5.5.1 Although all single component analytes can be resolved on a
new 35 percent phenyl methyl silicone column (e.g., DB-608), two
calibration mixtures should be prepared for the single component analytes
of this method.
5.5.2 This procedure is established to (1) minimize potential
resolution and quantitation problems on confirmation columns or on older
35 percent phenyl methyl silicone (e.g. DB-608) columns and (2) allow
determination of Endrin and DDT breakdown for method QC (Sec. 8).
5.5.3 Separate calibration standards are required for each multi-
component target analyte, with the exception of Aroclors 1016 and 1260,
which can be run as a mixture.
5.6 Internal standard (optional):
5.6.1 Pentachloronitrobenzene is suggested as an internal standard
for the single column analysis, when it is not considered to be a target
analyte. l-Bromo-2-nitrobenzene is a suggested option. Prepare the
standard to complement the concentrations found in Sec. 5.5.
5.6.2 Make a solution of 1000 mg/L of l-bromo-2-nitrobenzene for
dual-column analysis. Dilute it to 500 ng/>L for spiking, then use a
spiking volume of 10 nl/ml of extract.
5.7 Surrogate standards: The performance of the method should be
monitored using surrogate compounds. Surrogate standards are added to all
samples, method blanks, matrix spikes, and calibration standards.
5.7.1 For the single column analysis, use decachlorobiphenyl as the
primary surrogate. However, if recovery is low, or late-eluting compounds
interfere with decachlorobiphenyl, then tetrachloro-m-xylene should be
evaluated as a surrogate. Proceed with corrective action when both
surrogates are out of limits for a sample (Sec. 8.2). Method 3500, Sec.
5, indicates the proper procedure for preparing these surrogates.
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5.7.2 For the dual column analysis make a solution of 1000 mg/L of
4-chloro-3-nitrobenzotrifluoride and dilute to 500 ng//iL. Use a spiking
volume of 100 /iL for all aqueous sample. Store the spiking solutions
at 4°C in Teflon-sealed containers in the dark.
6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING
6.1 See Chapter 4, Organic Analytes, Sec. 4.
6.2 Extracts must be stored under refrigeration in the dark and analyzed
within 40 days of extraction.
7.0 PROCEDURE
7.1 Extraction:
7.1.1 Refer to Chapter Two and Method 3500 for guidance in choosing
the appropriate extraction procedure. In general, water samples are
extracted at a neutral pH with methylene chloride as a solvent using a
separatory funnel (Method 3510} or a continuous liquid-liquid extractor
(Method 3520). Extract solid samples with hexane-acetone (1:1) using one
of the Soxhlet extraction (Method 3540 or 3541) or ultrasonic extraction
(Method 3550) procedures.
NOTE: Hexane/acetone (1:1) may be more effective as an extraction
solvent for organochlorine pesticides and PCBs in some
environmental and waste matrices than is methylene
chloride/acetone (1:1). Use of hexane/acetone generally
reduces the amount of co-extracted interferences and improves
signal/noise.
7.1.2 Spiked samples are used to verify the applicability of the
chosen extraction technique to each new sample type. Each sample type
must be spiked with the compounds of interest to determine the percent
recovery and the limit of detection for that sample (Sec. 5). See Method
8000 for guidance on demonstration of initial method proficiency as well
as guidance on matrix spikes for routine sample analysis.
7.2 Cleanup/Fractionation:
7.2.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix, but most extracts from environmental and waste samples will
require additional preparation before analysis. The specific cleanup
procedure used will depend on the nature of the sample to be analyzed and
the data quality objectives for the measurements. General guidance for
sample extract cleanup is provided in this section and in Method 3600.
7.2.1.1 If a sample is of biological origin, or contains
high molecular weight materials, the use of GPC cleanup/pesticide
option (Method 3640) is recommended. Frequently, one of the
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adsorption chromatographic cleanups may also be required following
the GPC cleanup.
7.2.1.2 If only PCBs are to be measured in a sample, the
sulfuric acid/permanganate cleanup (Method 3665) is recommended.
Additional cleanup/fractionation by Alumina Cleanup (Method 3610),
Silica-Gel Cleanup (Method 3630), or Florisil Cleanup (Method 3620),
may be necessary.
7.2.1.3 If both PCBs and pesticides are to be measured in
the sample, isolation of the PCB fraction by Silica Cleanup (Method
3630) is recommended.
7.2.1.4 If only pesticides are to be measured, cleanup by
Method 3620 or Method 3630 is recommended.
7.2.1.5 Elemental sulfur, which may appear in certain
sediments and industrial wastes, interferes with the electron
capture gas chromatography of certain pesticides. Sulfur should be
removed by the technique described in Method 3660, Sulfur Cleanup.
7.3 GC Conditions: This method allows the analyst to choose between
a single column or a dual column configuration in the injector port. Either
wide- or narrow-bore columns may be used. Identifications based on retention
times from a single column must be confirmed on a second column or with an
alternative qualitative technique.
7.3.1 Single Column Analysis:
7.3.1.1 This capillary GC/ECD method allows the analyst
the option of using 0.25-0.32 mm ID capillary columns (narrow-bore)
or 0.53 mm ID capillary columns (wide-bore). Performance data are
provided for both options. Figures 1-6 provide example
chromatograms.
7.3.1.2 The use of narrow-bore columns is recommended when
the analyst requires greater chromatographic resolution. Use of
narrow-bore columns is suitable for relatively clean samples or for
extracts that have been prepared with one or more of the clean-up
options referenced in the method. Wide-bore columns (0.53 mm) are
suitable for more complex environmental and waste matrices.
7.3.1.3 For the single column method of analysis, using
wide-bore capillary columns, Table 1 lists average retention times
and method detection limits (MDLs) for the target analytes in water
and soil matrices. For the single column method of analysis, using
narrow-bore capillary columns, Table 2 lists average retention times
and method detection limits (MDLs) for the target analytes in water
and soil matrices. The MDLs for the components of a specific sample
may differ from those listed in Tables 1 and 2 because they are
dependent upon the nature of interferences in the sample matrix.
Table 3 lists the Estimated Quantitation Limits (EQLs) for other
matrices. Table 4 lists the GC operating conditions for the single
column method of analysis.
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7.3.2 Dual Column Analysis:
7.3.2.1 The dual-column/dual-detector approach involves
the use of two 30 m x 0.53 mm ID fused-silica open-tubular columns
of different polarities, thus different selectivities towards the
target compounds. The columns are connected to an injection tee and
ECD detectors. Retention times for the organochlorine analytes on
dual columns are in Table 5. The GC operating conditions for the
compounds in Table 5 are in Table 6. Multicomponent mixtures of
Toxaphene and Strobane were analyzed separately (Figures 7 and 8)
using the GC operating conditions found in Table 7. Seven Aroclor
mixtures and six Halowax mixtures were analyzed under the conditions
outlined in Table 7 (Figures 9 through 21). Figure 22 is a sample
chromatogram for a mixture of organochlorine pesticides. The
retention times of the individual components detected in these
mixtures are given in Tables 8 and 9.
7.3.2.1.1 Operating conditions for a more heavily
loaded DB-5/DB-1701 pair are given in Table 7. This column
pair was used for the detection of multicomponent
organochlorine compounds.
7.3.2.1.2 Operating conditions for a DB-5/DB-1701
column pair with thinner films, a different type of splitter,
and a slower temperature programming rate are provided in
Table 6. These conditions gave better peak shapes for
compounds such as Nitrofen and Dicofol. Table 5 lists the
retention times for the compounds detected on this column
pair.
7.4 Calibration:
7.4.1 Prepare calibration standards using the procedures in Sec. 5.
Refer to Method 8000 (Sec. 7) for proper calibration techniques for both
initial calibration and calibration verification. The procedure for
either internal or external calibration may be used, however, in most
cases external standard calibration is used with Method 8081. This is
because of the sensitivity of the electron capture detector and the
probability of the internal standard being affected by interferences.
Because several of the pesticides may co-elute on any single column,
analysts should use two calibration mixtures (see Sec. 3.8). The specific
mixture should be selected to minimize the problem of peak overlap.
NOTE: Because of the sensitivity of the electron capture detector,
the injection port and column should always be cleaned prior
to performing the initial calibration.
7.4.1.1 Method 8081 has many multi-component target
analytes. For this reason, the target analytes chosen for
calibration should be limited to those specified in the project
plan. For instance, some sites may require analysis for the
organochlorine pesticides only or the PCBs only. Toxaphene and/or
technical Chlordane may not be specified at certain sites. In
addition, where PCBs are specified in the project plan, a mixture of
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Aroclors 1016 and 1260 will suffice for the initial calibration of
all Aroclors, since they include all congeners present in the
different regulated Aroclors. A mid-point calibration standard of
all Aroclors (for Aroclor pattern recognition) must be included with
the initial calibration so that the analyst is familiar with each
Aroclor pattern and retention times on each column.
7.4.1.2 For calibration verification (each 12 hr shift)
all target analytes required in the project plan must be injected
with the following exception for the Aroclors. For sites that
require PCB analysis, include only the Aroclors that are expected to
be found at the site. If PCBs are required, but it is unknown which
Aroclors may be present, the mid-concentration Aroclors 1016/1260
mixture only, may be injected. However, if specific Aroclors are
found at the site during the initial screening, it is required that
the samples containing Aroclors be reinjected with the proper mid-
concentration Aroclor standards.
7.4.2 Because of the low concentration of pesticide standards
injected on a GC/ECD, column adsorption may be a problem when the GC has
not been used for a day or more. Therefore, the GC column should be
primed or deactivated by injecting a PCB or pesticide standard mixture
approximately 20 times more concentrated than the mid-concentration
standard. Inject this standard mixture prior to beginning the initial
calibration or calibration verification.
CAUTION: Several analytes, including Aldrin, may be observed in
the injection just following this system priming.
Always run an acceptable blank prior to running any
standards or samples.
7.4.3 Retention time windows:
7.4.3.1 Before establishing the retention time windows,
make sure the gas chromatographic system is within optimum operating
conditions. The width of the retention time window should be based
upon actual retention times of standards measured over the course of
72 hours. See Method 8000 for details.
7.4.3.2 Retention time windows shall be defined as plus or
minus three times the standard deviation of the absolute retention
times for each standard. However, the experience of the analyst
should weigh heavily in the interpretation of the chromatograms.
For multicomponent standards (i.e., PCBs), the analyst should use
the retention time window but should primarily rely on pattern
recognition. Sec. 7.5.4 provides guidance on the establishment of
absolute retention time windows.
7.4.3.3 Certain analytes, particularly Kepone, are subject
to changes in retention times. Dry Kepone standards prepared in
hexane or isooctane can produce gaussian peaks. However, Kepone
extracted from samples or standards exposed to water or methanol may
produce peaks with broad tails that elute later than the standard
(0-1 minute). This shift is presumably the result of the formation
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of a hemi-acetal from the ketone functionality. Method 8270 is
recommended for Kepone.
7.5 Gas chromatographic analysis:
7.5.1 Set up the GC system using the conditions described in Tables
4, 6, or 7. An initial oven temperature at or below 140-150°C is required
to resolve the four BHC isomers. A final temperature of 240-270°C is
required to elute decachlorobiphenyl. Use of injector pressure
programming will improve the chromatography of late eluting peaks.
7.5.2 Verify calibration each 12 hour shift by injecting calibration
verification standards prior to conducting any analyses. See Sec. 7.4.1.2
for special guidance on calibration verification of PCBs. A calibration
standard must also be injected at intervals of not less than once every
twenty samples (after every 10 samples is recommended to minimize the
number of samples requiring re-injection when QC limits are exceeded) and
at the end of the analysis sequence. The calibration factor for each
analyte to be quantitated must not exceed a +15 percent difference when
compared to the initial calibration curve. When this criterion is
exceeded, inspect the gas chromatographic system to determine the cause
and perform whatever maintenance is necessary before verifying calibration
and proceeding with sample analysis. If routine maintenance does not
return the instrument performance to meet the QC requirements {Sec. 8.2}
based on the last initial calibration, then a new initial calibration must
be performed.
7.5.2.1 Analysts should use high and low concentrations of
mixtures of single-component analytes and multi-component analytes
for calibration verification.
7.5.3 Sample injection may continue for as long as the calibration
verification standards and standards interspersed with the samples meet
instrument QC requirements. It is recommended that standards be analyzed
after every 10 (required after every 20 samples), and at the end of a set.
The sequence ends when the set of samples has been injected or when
qualitative and/or quantitative QC criteria are exceeded.
7.5.3.1 Each sample analysis must be bracketed with an
acceptable initial calibration, calibration verification standard(s)
(each 12 hr shift), or calibration standards interspersed within the
samples. All samples that were injected after the standard that
last met the QC criteria must be reinjected.
7.5.3.2 Although analysis of a single mid-concentration
standard (standard mixture or multi-component analyte) will satisfy
the minimum requirements, analysts are urged to use different
calibration verification standards during organochlorine
pesticide/PCB analyses. Also, multi-level standards (mixtures or
multi-component analytes) are highly recommended to ensure that
detector response remains stable for all analytes over the
calibration range.
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7.5.4 Establish absolute retention time windows for each analyte.
Use the absolute retention time for each analyte from standards analyzed
during that 12 hour shift as the midpoint of the window. The daily
retention time window equals the midpoint + three times the standard
deviations.
7.5.4.1 Tentative identification of an analyte occurs when
a peak from a sample extract falls within the daily retention time
window.
7.5.4.2 Validation of gas chromatographic system
qualitative performance: Use the calibration standards analyzed
during the sequence to evaluate retention time stability. If any of
the standards fall outside their daily retention time windows, the
system is out of control. Determine the cause of the problem and
correct it.
7.5.5 Record the volume injected to the nearest 0.05 yuL and the
resulting peak size in area units. Using either the internal or the
external calibration procedure (Method 8000), determine the identity and
the quantity of each component peak in the sample chromatogram which
corresponds to the compounds used for calibration purposes.
7.5.5.1 If the responses exceed the calibration range of
the system, dilute the extract and reanalyze. Peak height
measurements are recommended over peak area integration when
overlapping peaks cause errors in area integration.
7.5.5.2 If partially overlapping or coeluting peaks are
found, change columns or try GC/MS quantitation, see Sec. 8 and
Method 8270.
7.5.5.3 If the peak response is less than 2.5 times the
baseline noise level, the validity of the quantitative result may be
questionable. The analyst should consult with the source of the
sample to determine whether further concentration of the sample is
warranted.
7.5.6 Identification of mixtures {i.e. PCBs and Toxaphene) is based
on the characteristic "fingerprint" retention time and shape of the
indicator peak(s); and quantitation is based on the area under the
characteristic peaks as compared to the area under the corresponding
calibration peak(s) of the same retention time and shape generated using
either internal or external calibratibn procedures.
7.5.7 Quantitation of the target compounds is based on: 1) a
reproducible response of the ECD or ELCD within the calibration range; and
2} a direct proportionality between the magnitude of response of the
detector to peaks in the sample extract and the calibration standards.
Proper quantitation requires the appropriate selection of a baseline from
which the area or height of the characteristic peak(s) can be determined.
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7.5.8 If compound identification or quantitation is precluded due to
interference (e.g., broad, rounded peaks or ill-defined baselines are
present) cleanup of the extract or replacement of the capillary column or
detector is warranted. Rerun the sample on another instrument to
determine if the problem results from analytical hardware or the sample
matrix. Refer to Method 3600 for the procedures to be followed in sample
cleanup.
7.6 Quantitation of Multiple Component Analytes:
7.6.1 Multi-component analytes present problems in measurement.
Suggestions are offered in the following sections for handing Toxaphene,
Chlordane, PCBs, DDT, and BHC.
7.6.2 Toxaphene: Toxaphene is manufactured by the chlorination of
camphenes, whereas Strobane results from the chlorination of a mixture of
camphenes and pinenes. Quantitative calculation of Toxaphene or Strobane
is difficult, but reasonable accuracy can be obtained. To calculate
Toxaphene on GC/ECD: (a) adjust the sample size so that the major
Toxaphene peaks are 10-70% of full-scale deflection (FSD); (b) inject a
Toxaphene standard that is estimated to be within ±10 ng of the sample;
(c) quantitate using the five major peaks or the total area of the
Toxaphene pattern.
7.6.2.1 To measure total area, construct the baseline of
standard Toxaphene between its extremities; and construct the
baseline under the sample, using the distances of the peak troughs
to baseline on the standard as a guide. This procedure is made
difficult by the fact that the relative heights and widths of the
peaks in the sample will probably not be identical to the standard.
7,6.2.2 A series of Toxaphene residues have been
calculated using the total peak area for comparison to the standard
and also using the area of the last four peaks only, in both sample
and standard. The agreement between the results obtained by the two
methods justifies the use of the latter method for calculating
Toxaphene in a sample where the early eluting portion of the
Toxaphene chromatogram shows interferences from other substances
such as DDT.
7.6.3 Chlordane is a technical mixture of at least 11 major
components and 30 or more minor components. Trans- and C7's-Chlordane (a
and 7, respectively), are the two major components of technical Chlordane.
However, the exact percentage of each in the technical material is not
completely defined, and is not consistent from batch to batch.
7.6.3.1 The GC pattern of a Chlordane residue may differ
considerably from that of the technical standard. Depending on the
sample substrate and its history, residues of Chlordane can consist
of almost any combination of: constituents from the technical
Chlordane, plant and/or animal metabolites, and products of
degradation caused by exposure to environmental factors such as
water and sunlight.
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7.6.3.2 Whenever possible, when a Chlordane residue does
not resemble technical Chlordane, the analyst should quantitate the
peaks of a-Chlordane, 7-Chlordane, and Heptachlor separately against
the appropriate reference materials, and report the individual
residues.
7.6.3.3 When the GC pattern of the residue resembles that
of technical Chlordane, the analyst may quantitate Chlordane
residues by comparing the total area of the Chlordane chromatogram
using the five major peaks or the total area. If the Heptachlor
epoxide peak is relatively small, include it as part of the total
Chlordane area for calculation of the residue. If Heptachlor and/or
Heptachlor epoxide are much out of proportion, calculate these
separately and subtract their areas from the total area to give a
corrected Chlordane area. (Note that octachloro epoxide, a
metabolite of Chlordane, can easily be mistaken for Heptachlor
epoxide on a nonpolar GC column.)
7.6.3.4 To measure the total area of the Chlordane
chromatogram, inject an amount of technical Chlordane standard which
will produce a chromatogram in which the major peaks are
approximately the same size as those in the sample chromatograms,
7.6.4 Polychlorinated biphenyls (PCBs): Quantitation of residues of
PCBs involves problems similar to those encountered in the quantitation of
Toxaphene, Strobane, and Chlordane. In each case, the material is made up
of numerous compounds which generate multi-peak chromatograms. Also, in
each case, the chromatogram of the residue may not match that of the
standard.
7.6.4.1 Mixtures of PCBs of various chlorine contents were
sold for many years in the U.S. by the Monsanto Co. under the trade
name Aroclor (1200 series and 1016). Although these Aroclors are no
longer marketed, the PCBs remain in the environment and are
sometimes found as residues in foods, especially fish. The Aroclors
most commonly found in the environment are 1242, 1254, and 1260.
7.6.4.2 PCB residues are generally quantitated by
comparison to the most similar Aroclor standard. A choice must be
made as to which Aroclor is most similar to that of the residue and
whether that standard is truly representative of the PCBs in the
sample.
7.6.4.3 PCB Quantitation option #1- Quantitate the PCB
residues by comparing the total area of the chlorinated biphenyl
peaks to the total area of peaks from the appropriate Aroclor
reference material. Measure the total area or height response from
the common baseline under all the peaks. Use only those peaks from
the sample that can be attributed to chlorobiphenyls. These peaks
must also be present in the chromatogram of the reference materials.
Option #1 should not be used if there are interference peaks within
the Aroclor pattern, especially if they overlap PCB congeners.
8081 - 17 Revision 0
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7.6.4.4 PCB Quantitation option #2- Quantitate the PCB
residues by comparing the responses of 3 to 5 major peaks in each
appropriate Aroclor standard with the peaks obtained from the
chlorinated biphenyls in the sample extract. The amount of Aroclor
is calculated using an individual response factor for each of the
major peaks. The results of the 3 to 5 determinations are averaged.
Major peaks are defined as those peaks in the Aroclor standards that
are at least 25% of the height of the largest Aroclor peak. Late-
eluting Aroclor peaks are generally the most stable in the
environment.
7.6.4.5 When samples appear to contain weathered PCBs,
treated PCBs, or mixtures of Aroclors, the use of Aroclor standards
is not appropriate. Several diagnostic peaks useful for identifying
non-Aroclor PCBs are given in Table 10. Analysts should examine
chromatograms containing these peaks carefully, as these samples may
contain PCBs. PCB concentrations may be estimated from specific
congeners by adding the concentration of the congener peaks listed
in Table 11. The congeners are analyzed as single components. This
approach will provide reasonable accuracy for Aroclors 1016, 1232,
1242 and 1248 but will underestimate the concentrations of Aroclors
1254, 1260 and 1221. It is highly recommended that heavily
weathered, treated, or mixed Aroclors be analyzed using GC/MS if
concentration permits.
7.6.5 Hexachlorocyclohexane (BHC, from the former name, benzene
hexachloride): Technical grade BHC is a cream-colored amorphous solid
with a very characteristic musty odor; it consists of a mixture of six
chemically distinct isomers and one or more heptachlorocyclohexanes and
octachlorocyclohexanes. Commercial BHC preparations may show a wide
variance in the percentage of individual isomers present. Quantitate
each isomer (a, /3, 7, and 6) separately against a standard of the
respective pure isomer.
7.6.6 DDT: Technical DDT consists primarily of a mixture of 4,4'-
DDT (approximately 75%) and 2,4'-DDT (approximately 25%). As DDT
weathers, 4,4'-DDE, 2,4'-DDE, 4,4'-DDD, and 2,4'-DDD are formed. Since
the 4,4'-isomers of DDT, DDE, and ODD predominate in the environment,
these are the isomers normally regulated by US EPA and should be
quantitated against standards of the respective pure isomer.
7.7 Suggested chromatography maintenance: Corrective measures may require
any one or more of the following remedial actions.
7.7.1 Splitter connections: For dual columns which are connected
using a press-fit Y-shaped glass splitter or a Y-shaped fused-silica
connector (J&W Scientific or Restek), clean and deactivate the splitter
port insert or replace with a cleaned and deactivated splitter. Break off
the first few inches (up to one foot) of the injection port side of the
column. Remove the columns and solvent backflush according to the
manufacturer's instructions. If these procedures fail to eliminate the
degradation problem, it may be necessary to deactivate the metal injector
body and/or replace the columns.
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7.7.1.1 GC injector ports can be of critical concern,
especially in the analysis of DDT and Endrin. Injectors that are
contaminated, chemically active, or too hot can cause the
degradation ("breakdown") of the analytes. Endrin and DDT breakdown
to Endrin aldehyde, Endrin ketone, ODD, or DDE. When such breakdown
is observed, clean and deactivate the injector port, break off at
least 0.5 M of the column and remount it. Check the injector
temperature and lower it to 205°C, if required. Endrin and DDT
breakdown is less of a problem when ambient on-column injectors are
used.
7.7.2 Metal injector body: Turn off the oven and remove the
analytical columns when the oven has cooled. Remove the glass injection
port insert (instruments with on-column injection). Lower the injection
port temperature to room temperature. Inspect the injection port and
remove any noticeable foreign material.
7.7.2.1 Place a beaker beneath the injector port inside
the oven. Using a wash bottle, serially rinse the entire inside of
the injector port with acetone and then toluene; catch the rinsate
in the beaker.
7.7.2.2 Prepare a solution of a deactivating agent (Sylon-
CT or equivalent) following manufacturer's directions. After all
metal surfaces inside the injector body have been thoroughly coated
with the deactivation solution, rinse the injector body with
toluene, methanol, acetone, then hexane. Reassemble the injector
and replace the columns.
7.7.3 Column rinsing: The column should be rinsed with several
column volumes of an appropriate solvent. Both polar and nonpolar
solvents are recommended. Depending on the nature of the sample residues
expected, the first rinse might be water, followed by methanol and
acetone; methylene chloride is a good final rinse and in some cases may be
the only solvent required. The column should then be filled with
methylene chloride and allowed to stand flooded overnight to allow
materials within the stationary phase to migrate into the solvent. The
column is then flushed with fresh methylene chloride, drained, and dried
at room temperature with a stream of ultrapure nitrogen.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control (QC) procedures
including matrix spikes, duplicates and blanks. Quality control to validate
sample extraction is covered in Method 3500 and in the extraction method
utilized. If an extract cleanup was performed, follow the QC in Method 3600 and
in the specific cleanup method.
8.2 Quality control requirements for the GC system, including cal ibration
and corrective actions, are found in Method 8000. The following steps are
recommended as additional method QC.
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8.2.1 The QC Reference Sample concentrate (Method 3500} should
contain the organochlorine pesticides at 10 mg/L for water samples. If
this method is to be used for analysis of Aroclors, Chlordane, or
Toxaphene only, the QC Reference Sample should contain the most
representative multi-component mixture at a concentration of 50 mg/L in
acetone. The frequency of analysis of the QC reference sample analysis is
equivalent to a minimum of 1 per 20 samples or 1 per batch if less than 20
samples. If the recovery of any compound found in the QC reference sample
is less than 80 percent or greater than 120 percent of the certified
value, the laboratory performance is judged to be out of control, and the
problem must be corrected. A new set of calibration standards should be
prepared and analyzed.
8.2.2 Calculate surrogate standard recovery on all samples, blanks,
and spikes. Determine if the recovery is within limits (limits
established by performing QC procedures outlined in Method 8000).
If recovery is not within limits, the following are required:
8.2.2.1 Confirm that there are no errors in calculations,
surrogate solutions and internal standards. Also, check instrument
performance.
8.2.2.2 Examine chromatograms for interfering peaks and
for integrated areas.
8.2.2.3 Recalculate the data and/or reanalyze the extract
if any of the above checks reveal a problem.
8.2.2.4 Reextract and reanalyze the sample if none of the
above are a problem or flag the data as "estimated concentration."
8.2.3 Include a calibration standard after each group of 20 samples
(it is recommended that a calibration standard be included after every 10
samples to minimize the number of repeat injections) in the analysis
sequence as a calibration check. The response factors for the calibration
should be within 15 percent of the initial calibration. When this
continuing calibration is out of this acceptance window, the laboratory
should stop analyses and take corrective action.
8.2.4 Whenever quantitation is accomplished using an internal
standard, internal standards must be evaluated for acceptance. The
measured area of the internal standard must be no more than 50 percent
different from the average area calculated during calibration. When the
internal standard peak area is outside the limit, all samples that fall
outside the QC criteria must be reanalyzed.
8.3 DDT and Endrin are easily degraded in the injection port. Breakdown
occurs when the injection port liner is contaminated high boiling residue from
sample injection or when the injector contains metal fittings. Check for
degradation problems by injecting a standard containing only 4,4'-DDT and Endrin.
Presence of 4,4'-DDE, 4,4'-ODD, Endrin ketone or Endrin indicates breakdown. If
degradation of either DDT or Endrin exceeds 15%, take corrective action before
proceeding with calibration.
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8.3.1 Calculate percent breakdown as follows:
% breakdown Total DDT degradation peak area (DDE + ODD)
for 4,4'-DDT = x 100
peak areas (DDT + DDE + ODD)
Total endrin degradation peak area
% breakdown (Endrin aldehyde + Endrin ketone)
for Endrin = x 100
peak areas (Endrin + aldehyde + ketone)
8.3.2 The breakdown of DDT and Endrin should be measured before
samples are analyzed and at the beginning of each 12 hour shift. Injector
maintenance and recalibration should be completed if the breakdown is
greater than 15% for either compound (Sec. 8.2.3).
8.4 GC/MS confirmation may be used for single column analysis. In
addition, any compounds confirmed by two columns should also be confirmed by
GC/MS if the concentration is sufficient for detection by GC/MS.
8.4.1 Full-scan GC/MS will normally require a minimum concentration
near 10 ng//j,L in the final extract for each single-component compound.
Ion trap or selected ion monitoring will normally require a minimum
concentration near 1 ng//xl_.
8.4.2 The GC/MS must be calibrated for the specific target
pesticides when it is used for quantitative analysis.
8.4.3 GC/MS may not be used for single column confirmation when
concentrations are below 1 ng/|xL.
8.4.4 GC/MS confirmation should be accomplished by analyzing the
same extract used for GC/ECD analysis and the associated blank.
8.4.5 Use of the base/neutral-acid extract and associated blank may
be used if the surrogates and internal standards do not interfere and it
is demonstrated that the analyte is stable during acid/base partitioning.
However, if the compounds are not detected in the base/neutral-acid
extract even though the concentrations are high enough, a GC/MS analysis
of the pesticide extract should be performed.
8.4.6 A QC reference sample of the compound must also be analyzed by
GC/MS. The concentration of the QC reference standard must demonstrate
the ability to confirm the pesticides/Aroclors identified by GC/ECD.
8.5 Whenever silica gel (Method 3630) or Florisil (Method 3620) cleanup
is used, the analyst must demonstrate that the fractionation scheme is
reproducible. Batch to batch variation in the composition of the silica gel
material or overloading the column may cause a change in the distribution
patterns of the organochlorine pesticides and PCBs. When compounds are found in
two fractions, add the concentrations in the fractions, and corrections for any
additional dilution.
8081 - 21 Revision 0
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9.0 METHOD PERFORMANCE
9.1 The MDL is defined in Chapter One. The MDL concentrations listed in
Tables 1 and 2 were obtained using organic-free reagent water and sandy loam
soil.
9.2 The chromatographic separations in this method have been tested in
a single laboratory by using clean hexane and liquid and solid waste extracts
that were spiked with the test compounds at three concentrations. Single-
operator precision, overall precision, and method accuracy were found to be
related to the concentration of the compound and the type of matrix.
9.3 This method has been applied in a variety of commercial laboratories
for environmental and waste matrices. Performance data were obtained for a
limited number of target analytes spiked into sewage sludge and dichloroethene
still bottoms at high concentration levels. These data are provided in Tables
12 and 13.
9.4 The accuracy and precision obtainable with this method depend on the
sample matrix, sample preparation technique, optional cleanup techniques, and
calibration procedures used.
9.5 Single laboratory accuracy data were obtained for organochlorine
pesticides in a clay soil. The spiking concentration was 500 M9A9- The
spiking solution was mixed into the soil and -then immediately transferred to the
extraction device and immersed in the extraction solvent. The spiked sample was
then extracted by Method 3541 (Automated Soxhlet). The data represent a single
determination. Analysis was by capillary column gas chromatography/electron
capture detector following Method 8081 for the organochlorine pesticides. These
data are listed in Table 14 and were taken from Reference 14.
9.6 Single laboratory recovery data were obtained for PCBs in clay and
soil. Oak Ridge National Laboratory spiked Aroclors 1254 and 1260 at
concentrations of 5 and 50 ppm into portions of clay and soil samples and
extracted these spiked samples using the procedure outlined in Method 3541.
Multiple extractions using two different extractors were performed. The extracts
were analyzed by Method 8081. The data are listed in Table 15 and were taken
from Reference 15.
9.7 Multi-laboratory accuracy and precision data were obtained for PCBs
in soil. Eight laboratories spiked Aroclors 1254 and 1260 into three portions
of 10 g of Fuller's Earth on three non-consecutive days, followed by immediate
extraction using Method 3541. Six of the laboratories spiked each Aroclor at 5
and 50 mg/kg and two laboratories spiked each Aroclor at 50 and 500 mg/kg. All
extracts were analyzed by Oak Ridge National Laboratory, Oak Ridge, TN, using
Method 8081. These data are listed in Table 16 and were taken from Reference 13.
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10.0 REFERENCES
1. Lopez-Avila, V.; Baldin, E.; Benedicto, J; Milanes, J.; Beckert. W. F.
Application of Open-Tubular Columns to SW-846 GC Methods"; final report to
the U.S. Environmental Protection Agency on Contract 68-03-3511; Mid-
Pacific Environmental Laboratory, Mountain View, CA, 1990.
2. Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters. Category 10 - Pesticides and PCB Report for
the U.S. Environmental Protection Agency on Contract 68-03-2606.
3. Goerlitz, D.F.; Law, L.M. "Removal of Elemental Sulfur Interferences from
Sediment Extracts for Pesticide Analysis"; Bull. Environ. Contam. Toxicol.
1971, 6, 9.
4. Ahnoff, M.; Josefsson, B. "Cleanup Procedures for PCB Analysis on River
Water Extracts"; Bull. Environ. Contam. Toxicol. 1975, 13, 159.
5. Jensen, S.; Renberg, L.; Reutergardth, L. "Residue Analysis of Sediment
and Sewage Sludge for Organochlorines in the Presence of Elemental
Sulfur"; Anal. Chem. 1977, 49, 316-318.
6. Wise, R.H.; Bishop, D.F.; Williams, R.T.; Austern, B.M. "Gel Permeation
Chromatography in the GC/MS Analysis of Organics in Sludges"; U.S.
Environmental Research Laboratory. Cincinnati, OH 45268.
7. Pionke, H.B.; Chesters, G.; Armstrong, D.E. "Extraction of Chlorinated
Hydrocarbon Insecticides from Soil"; Agron. J. 1968, 60, 289.
8. Burke, J.A.; Mills, P.A.; Bostwick, D.C. "Experiments with Evaporation of
Solutions of Chlorinated Pesticides"; J. Assoc. Off. Anal. Chem. 1966, 49,
999.
9. Glazer, J.A., et al. "Trace Analyses for Wastewaters"; Environ. Sci. and
Technol. 1981, 15, 1426.
10. Marsden, P.J., "Performance Data for SW-846 Methods 8270, 8081, and 8141,"
EMSL-LV, EPA/600/4-90/015.
11. Marsden, P.O., "Analysis of PCBs", EMSL-LV, EPA/600/8-90/004
12. Erickson, M. Analytical Chemistry of PCBs, Butterworth Publishers, Ann
Arbor Science Book (1986).
13. Stewart, J. "EPA Verification Experiment for Validation of the SOXTEC* PCB
Extraction Procedure"; Oak Ridge National Laboratory, Oak Ridge, TN,
37831-6138; October 1988.
14. Lopez-Avila, V. (Beckert, W., Project Officer), "Development of a Soxtec
Extraction Procedure for Extracting Organic Compounds from Soils and
Sediments", EPA 600/X-91/140, US EPA, Environmental Monitoring Systems
Laboratory-Las Vegas, October 1991.
8081 - 23 Revision 0
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15. Stewart, J.H.; Bayne, C.K.; Holmes, R.L.; Rogers, W.F.; and Maskarinec,
M.P., "Evaluation of a Rapid Quantitative Organic Extraction System for
Determining the Concentration of PCB in Soils", Proceedings of the USEPA
Symposium on Waste Testing and Quality Assurance, Oak Ridge National
Laboratory, Oak Ridge, TN 37831-6131; July 11-15, 1988.
8081 - 24 Revision 0
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TABLE 1
GAS CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION
LIMITS FOR THE ORGANOCHLORINE PESTICIDES AND PCBs AS AROCLORS
USING WIDE-BORE CAPILLARY COLUMNS
SINGLE COLUMN METHOD OF ANALYSIS
Compound
Aldrin
ff-BHC
6-BHC
£-BHC
7-BHC (Lindane)
a-Chlordane
7-Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Methoxychlor
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Water = Organic-
Retention
DB 608b
11.84
8.14
9.86
11.20
9.52
15.24
14.63
18.43
16.34
19.48
16.41
15.25
18.45
20.21
17.80
19.72
10.66
13.97
22.80
MR
MR
MR
MR
MR
MR
MR
MR
free reagent
Time (min)
DB 1701b
12.50
9.46
13.58
14.39
10.84
16.48
16.20
19.56
16.76
20.10
17.32
15.96
19.72
22.36
18.06
21.18
11.56
15.03
22.34
MR
MR
MR
MR
MR
MR
MR
MR
water.
MDLa Water
(M9/L)
0.034
0.035
0.023
0.024
0.025
0.008
0.037
0.050
0.058
0.081
0.044
0.030
0.040
0.035
0.039
0.050
0.040
0.032
0.086
NA
0.054
NA
NA
NA
NA
NA
0.90
MDL° Soil
(M9/kg)
2.2
1.9
3.3
1.1
2.0
1.5
4.2
2.5
3.6
NA
2.1
2.4
3.6
3.6
1.6
2.0
2.1
5.7
NA
57.0
NA
NA
NA
NA
NA
70.0
Soil = Sandy loam soil .
MR = Multiple
NA = Data not
peak responses.
available.
MDL is the method detection limit. MDL
was determi
ned from
the
analysis of seven replicate aliquots of each matrix processed
through the entire analytical method (extraction, silica gel
cleanup, and GC/ECD analysis). MDL = t(n-l, 0.99) x SD, where t(n-
1, 0.99) is the Student's t value appropriate for a 99% confidence
interval and a standard deviation with n-1 degrees of freedom, and
SD is the standard deviation of the seven replicate measurements.
See Table 4 for GC operating conditions.
8081 - 25
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TABLE 2
GAS CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION
LIMITS FOR THE ORGANOCHLORINE PESTICIDES AND PCBs AS AROCLORS
USING NARROW-BORE CAPILLARY COLUMNS
SINGLE COLUMN METHOD OF ANALYSIS
Compound
Retention Time (min)
DB 608b DB 5b
MDLa Water MDLa Soil
(M9/L)
Aldrin
o-BHC
B-BHC
-------
TABLE 2
(Continued)
MDL is the method detection limit. MDL was determined from the
analysis of seven replicate aliquots of each matrix processed
through the entire analytical method (extraction, cleanup, and
GC/ECD analysis). MDL = t(n-l, 0.99) x SD, where t(n-l, 0.99) is
the Student's t value appropriate for a 99% confidence interval and
a standard deviation with n-1 degrees of freedom, and SD is the
standard deviation of the seven replicate measurements.
30 m x 0.25 mm ID DB-608 1 pm film thickness, see Table 4 for GC
operating conditions.
30 m x 0.25 mm ID DB-5 1 jitm film thickness, see Table 4 for GC
operating conditions.
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TABLE 3
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQLs) FOR VARIOUS MATRICES8
Matrix Factor
Ground water 10
Low-concentration soil by sonication with GPC cleanup 670
High-concentration soil and sludges by sonication 10,000
Non-water miscible waste 100,000
EQL = [Method detection limit for water (see Table 1 or Table 2) wide-
bore or narrow-bore options] x [Factor found in this table]. For
nonaqueous samples, the factor is on a wet-weight basis. Sample EQLs
are highly matrix-dependent. The EQLs to be determined herein are
provided for guidance and may not always be achievable.
8081 - 28 Revision 0
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TABLE 4
GC OPERATING CONDITIONS FOR ORGANOCHLORINE COMPOUNDS
SINGLE COLUMN ANALYSIS
Narrow-bore columns:
Narrow-bore Column 1 - 30 m x 0.25 or 0.32 mm internal diameter (ID) fused
silica capillary column chemically bonded with SE-54 (DB-5 or equivalent), 1
jum film thickness.
Carrier gas (He)
Injector temperature
Detector temperature
Initial temperature
Temperature program
Final temperature
16 psi
225°C
300°C
100°C, hold 2 minutes
100°C to 160°C at 15°C/min, followed
by 160°C to 270°C at 5°C/min
270°C
Narrow-bore Column 2 - 30 m x 0.25 mm ID fused silica capillary column
chemically bonded with 35 percent phenyl methylpolysiloxane (DB-608, SPB-608,
or equivalent), 25 jum coating thickness, 1 /xm film thickness
Carrier gas (N2)
Injector temperature
Detector temperature
Initial temperature
Temperature program
Final temperature
20 psi
225°C
300°C
160°C,
160°C
290°C,
hold 2 minutes
to 290°C at 5°C/min
hold 1 min
Wide-bore columns:
Wide-bore Column 1 - 30 m x 0.53 mm ID fused silica capillary column
chemically bonded with 35 percent phenyl methylpolysiloxane (DB-608, SPB-608,
RTx-35, or equivalent), 0.5 urn or 0.83 fj.m film thickness.
Wide-bore Column 2 - 30 m x 0.53 mm ID fused silica capillary column
chemically bonded with 50 percent phenyl methylpolysiloxane (DB-1701, or
equivalent), 1.0 /urn film thickness.
Carrier gas (He)
Makeup gas
argon/methane (P-5 or P-10) or N2
Injector temperature
Detector temperature
Initial temperature
Temperature program
Final temperature
5-7 mL/minute
30 mL/min
250°C
290°C
150°C, hold 0.5 minute
150°C to 270°C at 5°C/min
270°C, hold 10 min
(continued)
8081 - 29
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September 1994
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TABLE 4 (Continued)
GC OPERATING CONDITIONS FOR ORGANOCHLORINE COMPOUNDS
SINGLE COLUMN ANALYSIS
Wide-bore Columns (continued)
Wide-bore Column 3 - 30 m x 0.53 mm ID fused silica capillary column
chemically bonded with SE-54 (DB-5, SPB-5, RTx-5, or equivalent), 1.5 JLUTI film
thickness.
Carrier gas (He)
Makeup gas
argon/methane (P-5 or P-10) or N2
Injector temperature
Detector temperature
Initial temperature
Temperature program
Final temperature
6 mL/minute
30 mL/min
205°C
290°C
140°C, hold 2 min
140°C to 240°C at 10°C/nriri»
hold 5 minutes at 240°C,
240°C to 265°C at 5°C/min
265°C, hold 18 min
8081 - 30
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TABLE 5
RETENTION TIMES OF THE ORGANOCHLORINE PESTICIDES"
DUAL COLUMN METHOD OF ANALYSIS
Compound
DBCP
Hexachl orocycl open tad i ene
Etridiazole
Chloroneb
Hexachl orobenzene
Diallate
Propachlor
Trifluralin
a-BHC
PCNB
y-BHC
Heptachlor
Aldrin
Alachlor
Chlorothalonil
Alachlor
0-BHC
Isodrin
DC PA
S-BHC
Heptachlor epoxide
Endosulfan-I
7-Chlordane
a-Chlordane
trans-Nonachlor
4,4'-DDE
Dleldrin
Captan
Perthane
Endrin
Chloropropylate
Chlorobenzllate
Nitrofen
4,4'-DDD
Endosulfan II
4,4'-DDT
Endrin aldehyde
Mi rex
Endosulfan sulfate
CAS No.
96-12-8
77-47-4
2593-15-9
2675-77-6
118-74-1
2303-16-4
1918-16-17
1582-09-8
319-84-6
82-68-8
58-89-9
76-44-8
309-00-2
15972-60-8
1897-45-6
15972-60-8
319-85-7
465-73-6
1861-32-1
319-86-8
1024-57-3
959-98-8
5103-74-2
5103-71-9
39765-80-5
72-55-9
60-57-1
133-06-2
72-56-0
72-20-8
99516-95-7
510-15-6
1836-75-5
72-54-8
33213-65-9
50-29-3
7421-93-4
2385-85-5
1031-07-8
DB-5
RT(min)
2.14
4.49
6.38
7.46
12.79
12.35
9.96
11.87
12.35
14.47
14.14
18.34
20.37
18.58
15.81
18.58
13.80
22.08
21.38
15.49
22.83
25.00
24.29
25.25
25.58
26.80
26.60
23.29
28.45
27.86
28.92
28.92
27.86
29.32
28.45
31.62
29.63
37.15
31.62
DB-1701
RT(min)
2.84
4.88
8.42
10.60
14.58
15.07
15.43
16.26
17.42
18.20
20.00
21.16
22.78
24.18
24.42
24.18
25.04
25.29
26.11
26.37
27.31
28.88
29.32
29.82
30.01
30.40
31.20
31.47
32.18
32.44
34.14
34.42
34.42
35.32
35.51
36.30
38.08
38.79
40.05
continued
8081 - 31
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Compound
Methoxychlor
Captafol
Endrin ketone
trans-Permethrin
Kepone
Dicofol
Dichlone
a, or -Dibromo-m-xylene
2-Bromobiphenyl
TABLE 5
(Continued)
CAS No.
72-43-5
2425-06-1
53494-70-5
51877-74-8
143-50-0
115-32-2
117-80-6
DB-5
RT(min)
35.33
32.65
33.79
41.50
31.10
35.33
15.17
9.17
8.54
DB-1701
RT(min)
40.31
41.42
42.26
45.81
b
b
b
11.51
12.49
3The GC operating conditions were as follows: 30-m x 0.53-mm ID DB-5
(0.83-jum film thickness) and 30-m x 0.53-mm ID DB-1701 (1.0-jum film
thickness) connected to an 8-in injection tee (Supelco Inc.). Temperature
program: 140°C (2-min hold) to 270°C (1-min hold) at 2.8°C/min; injector
temperature 250°C; detector temperature 320°C; helium carrier gas 6 mL/min;
nitrogen makeup gas 20 mL/min.
bNot detected at 2 ng per injection.
8081 - 32
Revision 0
September 1994
-------
Column 1
TABLE 6
GC OPERATING CONDITIONS FOR ORGANOCHLORINE PESTICIDES
FOR DUAL COLUMN METHOD OF ANALYSIS
LOW TEMPERATURE, THIN FILM
Type: DB-1701 (J&W) or equivalent
Dimensions: 30 m x 0.53 mm ID
Film Thickness (urn): 1.0
Column 2;
Type: DB-5 (J&W) or equivalent
Dimensions: 30 m x 0.53 mm ID
Film Thickness (y^m): 0.83
Carrier gas flowrate (mL/min): 6 (Helium)
Makeup gas flowrate (mL/min): 20 (Nitrogen)
Temperature program: 140°C (2 min hold) to 270°C (1 min hold) at 2.8°C/min
Injector temperature: 250°C
Detector temperature: 320°C
Injection volume: 2 pi
Solvent: Hexane
Type of injector: Flash vaporization
Detector type: Dual ECD
Range: 10
Attenuation: 64 (DB-1701)/32 (DB-5)
Type of splitter: Supelco 8 in injection tee
8081 - 33 Revision 0
September 1994
-------
Column 1:
TABLE 7
GC OPERATING CONDITIONS FOR ORGANOCHLORINE PESTICIDES
FOR THE DUAL COLUMN METHOD OF ANALYSIS
HIGH TEMPERATURE, THICK FILM
Type: DB-1701 (J&W) or equivalent
Dimensions: 30 m x 0.53 mm ID
Film Thickness: 1.0 n\n
Column 2:
Type: DB-5 (J&W) or equivalent
Dimensions: 30 m x 0.53 mm ID
Film Thickness: 1.5 jum
Carrier gas flowrate (mL/min): 6 (Helium)
Makeup gas flowrate (mL/min): 20 (Nitrogen)
Temperature program: 150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min
then to 275°C (10 min hold) at 4°C/imn.
Injector temperature: 250°C
Detector temperature: 320°C
Injection volume: 2 fj.1
Solvent: Hexane
Type of injector: Flash vaporization
Detector type: Dual ECD
Range: 10
Attenuation: 64 (DB-1701J/64 (DB-5)
Type of splitter: J&W Scientific press-fit Y-shaped inlet splitter
8081 - 34 Revision 0
September 1994
-------
TABLE 8 SUMMARY OF RETENTION TIMES (MIN) OF AROCLORS
ON THE OB-5 COLUMN8
DUAL SYSTEM OF ANALYSIS
Peak
No.6
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
Aroclor
1016
8.41
8.77
8.98
9.71
10.49
10.58
10.90
11.23
11.88
11.99
12.27
12.66
12.98
13.18
13.61
13.80
13.96
14.48
14.63
14.99
15.35
16.01
16.27
Aroclor Aroclor
1221 1232
5.85 5.85
7.63 7.64
8.43 8.43
8.77 8.78
8.99 9.00
10.50 10.50
10.59 10.59
10.91
11.24 11.24
11.90
12.00
12.29 12.29
12.68 12.69
12.99 13.00
13.19
13.63
13.82
13.97
14.50
14.64
15.02
15.36
16.14
16.29
17.04
17.22
17.46
18.41
18.58
18.83
19.33
20.03
21.18
Aroclor
1242
7.57
8.37
8.73
8.94
9.66
10.44
10.53
10.86
11.18
11.84
11.95
12.24
12.64
12.95
13.14
13.58
13.77
13.93
14.46
14.60
14.98
15.32
15.96
16,08
16.26
17.19
17.43
17.92
18.16
18.37
18.56
18.80
19.30
19.97
20.46
20.85
21.14
22.08
Aroclor
1248
8.95
10.45
10.85
11.18
11.85
12.24
12.64
12.95
13.15
13.58
13.77
13.93
14.45
14.60
14.97
15.31
16.08
16.24
16.99
17.19
17.43
17.69
17,91
18.14
18.36
18.55
18.78
19.29
19.92
20.45
20.83
21.12
21,36
22.05
Aroclor
1254
13.59
13.78
13.90
14.46
14.98
15.32
16.10
16.25
16.53
16.96
17.19
17.44
17.69
17.91
18.14
18.36
18.55
18.78
19.29
19.48
19.81
19.92
20.28
20.57
20.83
20.98
21.38
21.78
22.04
22.38
22.74
22.96
23.23
23.75
Aroclor
1260
13.59
16.26
16.97
17.21
18.37
18.68
18.79
19.29
19.48
19.80
20.28
20.57
20.83
21.38
21.78
22.03
22.37
22.73
22.95
23.23
23.42
23.73
Pesticide eluting at same
retention time
Chlorothaloni I (11.18)
Captan (16.21)
gamma-Chlordane (16.95)
4,4'-DDE (18.38)
Dieldrin (18.59)
Chloropropylate (19.91)
Endosulfan II (19.91)
Kepone (20.99)
4,4'-ODT (21.75)
Endosulfan sulfate (21.75)
Captafol (22.71)
Endrin ketone (23.73)
'The GC operating conditions are given in Table 7.
(continued)
8081 - 35
Revision 0
September 1994
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TABLE 8 CONTINUED
Peak
No.
56
57
58
59
60
61
62
63
64
65
66
67
68
69
Aroclor Aroclor Aroclor Aroclor Aroclor Aroclor
1016 1221 1232 1242 1248 1254
23.99
24.27
24.61
24.93
26.22
Aroclor Pesticide eluting at same
1260 retention time
23.97
24.16
Methoxychlor (24.29)
Dicofol (24.29)
24.45
24.62
24.91
25.44
26.19 Mi rex (26.19)
26.52
26.75
27.41
28.07
28.35
29.00
"The GC operating conditions are given in Table 7.
"These are sequentially numbered from elution order and are not isomer numbers
8081 - 36
Revision 0
September 1994
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TABLE 9 SUMMARY OF RETENTION TIMES (MIN) OF AROCLORS
ON THE DB-1701 COLUMN"
DUAL SYSTEM OF ANALYSIS
Peak Aroclor Aroclor Aroclor
No.b 1016 1221 1232
1 4.45 4.45
2 5.38
3 5.78
4 5.86 5.86
5 6.33 6.31 6.34
6 6.78 6.78 6.79
7 6.96 6.96 6.96
8 7.64
9 8.23 8.23 8.23
10 8.62 8.63 8.63
11 8.88 8.89
12 9.05 9.06 9.06
13 9.46 9.47
14 9.77 9.79 9.78
15 10.27 10.29 10.29
16 10.64 10.65 10.66
17
18 11.01 11.02
19 11.09 11.10
20 11.98 11.99
21 12.39 12.39
22 12.77
23 12.92
24 12.99 13.00
25 13.14 13.16
26
27 13.49
28 13.58
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
13.49
13.61
14.08
14.30
14.49
15.38
15.65
15.78
16.13
16.77
17.13
Aroclor
1242
6.28
6.72
6.90
7.59
8.15
8.57
8.83
8.99
9.40
9.71
10.21
10.59
10.96
11.02
11.94
12.33
12.71
12.94
13.09
13.44
13.54
13.67
14.03
14.26
14.46
15.33
15.62
15.74
16.10
16.73
17.09
17.46
17.69
18.48
19.13
Aroclor
1248
6.91
8.16
8.83
8.99
9.41
9.71
10.21
10.59
10.95
11.03
11.93
12.33
12.69
12.93
13.09
13.44
13.54
14.03
14.24
14.39
14.46
15.10
15.32
15.62
15.74
16.10
16.74
17.07
17.44
17.69
18.19
18.49
19.13
Aroclor
1254
10.95
11.93
12.33
13.10
13.24
13.51
13.68
14.03
14.24
14.36
14.56
15.10
15.32
15.61
15.74
16.08
16.34
16.44
16.55
16.77
17.07
17.29
17.43
17.68
18.17
18.42
18.59
18.86
19.10
19.42
Aroclor Pesticide eluting at same
1260 retention time
Trifluralin (6.96)
13.52
14.02
14.25
14.56
Chlordane (15.32)
16.61 4,4'-DDE (15.67)
15.79
16.19
16.34
16.45
16.77 Perthane (16.71)
17.08
17.31
17.43
17.68
18.18
18.40
18.86
19.09 Endosutfan II (19.05)
19.43
"The GC operating conditions are given in Table 7.
(continued)
8081 - 37
Revision 0
September 1994
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TABLE 9 CONTINUED
Peak
No.
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
Aroclor Aroclor Aroclor Aroclor Aroclor Aroclor
1016 1221 1232 1242 1248 1254
19.55
20.20
20.34
20.57 20.55
20.62
20.88
21.53
21.83
23.31
Aroclor Pesticide eluting at same
1260 retention time
19.59 4.4'-DDT (19.54)
20.21
20.43
20.66 Endrin aldehyde (20.69)
20.87
21.03
21.53
21.81
23.27
23.85
24.11
24.46
24.59
24.87
25.85
27.05
27.72
"The GC operating conditions are given in Table 7.
"These are sequentially numbered from elution order and are not isomer numbers
8081 - 38
Revision 0
September 1994
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TABLE 10
PEAKS DIAGNOSTIC OF PCBs OBSERVED IN 0.53 mm ID COLUMN
SINGLE COLUMN ANALYSIS
Peak RT on RT on Elution
No.c DB 608s DB 1701" Aroclor" Order
I479047661221Before TCmX
II 7.15 6.96 1221, 1232, 1248 Before a-BHC
III 7.89 7.65 1061, 1221, 1232, 1242, Before a-BHC
IV 9.38 9.00 1016, 1232, 1242, 1248, just after a-BHC on
DB-1701;just before
7-BHC on DB-608
V 10.69 10.54 1016. 1232, 1242. 1248 a-BHC and
heptachlor on DB-1701;
just after heptachlor
on DB-608
VI 14.24 14.12 1248, 1254 7-BHC and heptachlor
epoxide on DB-1701;
heptachlor epoxide and
7-Chlordane on DB-608
VII 14.81 14.77 1254 Heptachlor epoxide and
7-Chlordane on
DB-1701; a- and
7-Chlordane on DB-608
VIII 16.71 16.38 1254 DDE and Dieldrin on
DB-1701; Dieldrin and
Endrin on DB-608
IX 19.27 18.95 1254, 1260 Endosulfan II on
DB-1701; DDT on DB-608
Continued
8081 - 39 Revision 0
September 1994
-------
TABLE 10 (Continued)
PEAKS DIAGNOSTIC OF PCBs OBSERVED IN 0.53 mm ID COLUMN
SINGLE COLUMN ANALYSIS
Peak RT on RT on Elution
No. DB 60S8 DB 1701" Aroclorb Order
X 21.22 21.23 1260 Endrin aldehyde and
Endosulfan sulfate on
DB-1701; Endosulfan
sulfate and
Methoxychlor on
on DB-608
XI 22.89 22.46 1260 Just before endrin
ketone on DB-1701;
after endrin ketone on
DB-608
0 Temperature program: Tj = 150°C, hold 30 seconds; increase temperature at
5°C/minutes to 275°C.
b Underlined Aroclor indicates the largest peak in the pattern.
c These are sequentially numbered from elution order and are not isotner
numbers
8081 - 40 Revision 0
September 1994
-------
TABLE 11 SPECIFIC PCB CONGENERS IN AROCLORS
Congener
IUPAC number
Aroclor
1016 1221 1232 1242 1248 1254 1260
Biphenyl
2CB
23DCB
34DC8
244'TCB
22'35'TCB
23'44'TCB
233'4'6PCB
23'44'5PCB
22'44'55'HCB
1
5
12
28*
44
66*
110
118*
153
X
XXX
XXX
X X
X X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
22'344'5'HCB 138
22'344'55'HpCB 180
22'33'44'5HpCB 170
X
X
X
*apparent co-elution of two major peaks:
28 with 31 {2,4',5 trichloro)
66 with 95 (2,2',3,5',6 pentachloro)
118 with 149 (2,2',3,4',5',6 hexachloro)
8081 - 41
Revision 0
September 1994
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TABLE 12 ANALYTE RECOVERY FROM SEWAGE SLUDGE
Compound
Sonication
Soxhlet
Hexachloroethane
2-Chloronapthalene
4-Bromodiphenyl ether
a-BHC
7-BHC
Heptachlor
Aldrin
0-BHC
-------
TABLE 13 ANALYTE RECOVERY FROM DCE STILL BOTTOMS
Compound
Sonication
Soxhlet
Hexachloroethane
2-Chloronapthalene
4-Bromodiphenyl ether
a-BHC
0-BHC
Heptachlor
Aldrin
j8-BHC
5-BHC
Heptachlor epoxide
Endosulfan I
7-Chlordane
a-Chlordane
DDE
Dieldrin
Endrin
Endosulfan II
DDT
Endrin aldehyde
ODD
Tetrachloro-m-xylene
Decachl orobi phenyl
%Recovery
70
59
159
55
43
48
48
51
43
47
47
48
45
45
45
50
49
49
40
48
49
17
%RSD
2
3
14
7
6
6
5
7
4
6
4
5
5
4
5
6
5
4
4
5
2
29
%Recovery
50
35
128
47
30
55
200
75
119
66
41
47
37
70
58
41
46
40
29
35
176
104
%RSD
30
35
137
25
30
18
258
42
129
34
18
13
21
40
24
23
17
29
20
21
211
93
Concentration spiked in the sample: 500-1000 ng/g
Three replicates/sample
Extraction solvent, Method 3540 - methylene chloride
Extraction solvent, Method 3550 - methylene chloride/acetone (1:1)
Cleanup - Method 3640
GC column - DB-608, 30M X 0.53 mm ID
8081 - 43
Revision 0
September 1994
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TABLE 14
SINGLE LABORATORY ACCURACY DATA FOR THE EXTRACTION OF
ORGANOCHLORINE PESTICIDES FROM SPIKED CLAY SOIL BY METHOD 3541
(AUTOMATED SOXHLET)8
Compound Name Spike Level % Recovery
DB-5 DB-1701
a-BHC
/3-BHC
Heptachlor
Aldrin
Heptachlor epoxide
trans-Chlordane
Endosulfan I
Dieldrin
Endrin
Endosulfan II
4, 4' -DDT
Mirex
500
500
500
500
500
500
500
500
500
500
500
500
89
86
94
b
97
94
92
b
111
104
b
108
94
b
95
92
97
95
92
113
104
104
b
102
a The operating conditions for the automated Soxhlet were as follows:
immersion time 45 min; extraction time 45 min; the sample size was 10 g
clay soil, extraction solvent, 1:1 acetone/hexane. No equilibration time
following spiking.
b Not able to determine because of interference.
Data taken from Reference 14.
8081 - 44 Revision 0
September 1994
-------
TABLE 15
SINGLE LABORATORY RECOVERY DATA FOR EXTRACTION OF
PCBS FROM CLAY AND SOIL BY METHOD 3541" (AUTOMATED SOXHLET)
Matrix Compound Spike Level
(ppm)
Clay Aroclor-1254 5
Clay Aroclor-1254 50
Clay Aroclor-1260 5
Clay Aroclor-1260 50
Soil Aroclor-1254 5
Soil Aroclor-1254 50
Trial
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
1
2
3
4
5
6
Percent
Recovery6
87.0
92.7
93.8
98.6
79.4
28.3
65.3
72.6
97.2
79.6
49.8
59.1
87.3
74.6
60.8
93.8
96.9
113.1
73.5
70.1
92.4
88.9
90.2
67.3
69.7
89.1
91.8
83.2
62.5
84.0
77.5
91.8
66.5
82.3
61.6
(continued)
8081 - 45
Revision 0
September 1994
-------
TABLE 15
(continued)
Matrix Compound Spike Level
(ppm)
Soil Aroclor-1260 5
Soil Aroclor-1260 50
Trial
1
2
3
4
5
6
7
1
2
3
4
5
6
Percent
Recovery6
83.9
82.8
81.6
96.2
93.7
93.8
97.5
76.9
69.4
92.6
81.6
83.1
76.0
a The operating conditions for the automated Soxhlet were as follows:
immersion time 60 min; reflux time 60 min.
b Multiple results from two different extractors.
Data from Reference 15.
8081 - 46
Revision 0
September 1994
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TABLE 16. MULTI-LABORATORY PRECISION AND ACCURACY DATA
FOR THE EXTRACTION OF PCBS FROM SPIKED SOIL
BY METHOD 3541 (AUTOMATED SOXHLET)
Laboratory
Lab 1
Lab 2
Lab 3
Lab 4
Lab 5
. .
Lab 6
Lab 7
Lab 8
All
Laboratories
Num
Average
St Dev
Num
Average
St Dev
Num
Average
St Dev
Num
Average
St Dev
Num
Average
St Dev
Num
Average
St Dev
Num
Average
St Dev
Num
Average
St Dev
Num
Average
St Dev
•
PCB Percent Recovery
Aroclor
12.54
PCB Level
0
3.0
101.2
34.9
3.0
72.8
10.8
6.0
112.6
18.2
2.0
140.9
4.3
3.0
100.1
17.9
3.0
65.0
16.0
20.0
98.8
28.7
50
3.0
74.0
41.8
6.0
56.5
7.0
3.0
63.3
8.3
6.0
144.3
30.4
3.0
97.1
8.7
3.0
127.7
15.5
3.0
123.4
14.6
3.0
38.3
21.9
30.0
92.5
42.9
500
6.0
66.9
15.4
3.0
80.1
5.1
9.0
71.3
14.1
1260
PCB Level
5
3.0
83.9
7.4
3.0
70.6
2.5
6.0
100.3
13.3
....
3.0
138.7
15.5
3.0
82.1
7.9
3.0
92.8
36.5
21.0
95.5
25.3
50
3.0
78.5
7.4
6.0
70.1
14.5
3.0
57.2
5.6
6.0
84.8
3.8
3.0
79.5
3.1
4.0
105.9
7.9
3.0
94.1
5.2
3.0
51.9
12.8
31.0
78.6
18.0
500
6.0
74.5
10.3
3.0
77.0
9 4
.r. :.".
9.0
75.3
9.5
All
Levels
12.0
84.4
26.0
24.0
67.0
13.3
12.0
66.0
9.1
24.0
110.5
28.5
12.0
83.5
10.3
12.0
125.4
18.4
12.0
99.9
19.0
12.0
62.0
29.1
120.0
87.6
29.7
Data from Reference 13.
8081 - 47
Revision 0
September 1994
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FIGURE 1.
GAS CHROMATOGRAM OF THE MIXED ORGANOCHLORINE PESTICIDE STANDARD
Surt I'W : 0.00 min
Scale factor: 0
End Tint : 33.00 Kin
Plot Off»*t: 20 n«
Low Paine : 20.00 nV
Plat Sc«U: 100 UN
Hijn Point : 420.00 M
Response [mV]
o-
:o
j
I I I I I I I I I I I I
=-7 . 99
9.93
-23.18
23.80
26.23
•=-28.64
Column:
Temperature program:
—0.95
-8.60
— 30.19
30 m x 0.25 mm ID, DB-5
100°C (hold 2 minutes) to 160°C at 15°C/min, then at
5°C/min to 270°C; carrier He at 16 psi.
8081 - 48
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FIGURE 2.
GAS CHROMATOGRAM OF INDIVIDUAL ORGANOCHLORINE PESTICIDE STANDARD MIX A
Start Time : 0.00 min End lime : 53.00 *in Lou Point : 20.00 «V mgn Point : 270.CO mv
Scale factor: 0 Plot offset: 20 .w Plot Scale: 250 mv
Response [mV]
o-
LP
o
o
o
(Ji
o
O
O
I I I I I I I I I I I I I I I I I
ro
(_n
O
I | I I I I I
2.
D
o'
H
3'
0)
to
-
•7.93
I. 60
-14.27
-17.08
0.22
1.77
22.68
-23.73
--28.52
-4.95
-12.33
-9.86
-17.54
-18.47
-19.78
-19.24
-21.13
-23.03
-30.05
Column:
Temperature program:
30 m x 0.25 mm ID, DB-5
100°C (hold 2 minutes) to 160°C at 15°C/min, then at
5°C/min to 270°C; carrier He at 16 psi.
8081 - 49
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FIGURE 3
GAS CHROMATOGRAM OF INDIVIDUAL ORGANOCHLORINE PESTICIDE STANDARD MIX B
Start rifne : 0.00 mm
Scale Factor: 0
End Ti« : JJ.OO "in
Plot Offset: 20 ">V
Low Point : 20.00 mv
Plot Scale: 250 mV
?:r". : 270.?C mv
Response [mV]
o-
o
I i i i i
-i -» K)
O Ui O
000
I I I I I I I I I I I
to
(_n
O
I'll
0)
3
o' ->_!
3
CD
•2.74
-6.97
tL-9.60
--10.71
-14.27
. 24
^20.69
22.00
-11.73
-14.84
-16.23
—17.OS
-17.63
-18.31
19.54
-20.19
21.03
--22.68
-4.95
-30.04
Column:
Temperature program:
30 m x 0.25 mm ID, DB-5
100°C (hold 2 minutes) to 160°C at 15°C/min, then at
50C/min to 270°C; carrier He at 16 psi.
8081 - 50
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FIGURE 4.
GAS CHROMATOGRAM OF THE TOXAPHENE STANDARD
Start Hint : 0.00 mm
Sole Factor: 0
End lime : 33.00 nin
Plot Offset: 20 i«v
low Point : 20.00 mV
Plot Scale: 60 inv
KijH Point : 80.00 mv
Response [mV]
K> (_J -f* <_fl O> -J
o o o o o o
lii ill 11 ii 11 ii 1111 ill it H lii ill 1111 lini 111 ill mi 111111 mi
§SH
'I'
1 ' ro
z! °"
KJ
Ul"
O
',99
24 . 32
Column:
Temperature program:
30 m x 0.25 mm ID, DB-5
100°C (hold 2 minutes) to 160°C at 15°C/min, then at
50C/min to 270°C; carrier He at 16 psi.
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FIGURE 5.
GAS CHROMATOGRAM OF THE AROCLOR-1016 STANDARD
Start lime : 0.00 min End lime : 33.00 min Low Point : 20.00 Hi "<9K Point : UO.OO mv
Scale Factor: 0 Plot Offset: 20 mv Plot Sole: 100 mv
Response [mV]
o-
N> ^ O) CO O
O O O O O
I 1111 111 I) 11 111 1111 111 1111 1111 111 1111 111 1111 111 111
on—
O~
' f-o
"
L-1"
'-••I
-1.81
9. 83
12.95
-1.03
Column:
Temperature program:
30 m x 0.25 mm ID DB-5 fused silica capillary.
100°C (hold 2 minutes) to 160°C at 15°C/min, then at
5°C/min to 270°C; carrier He at 16 psi.
8081 - 52
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FIGURE 6.
GAS CHROMATOGRAM OF THE TECHNICAL CHLORDANE STANDARD
Start rime : 0.00 mm End lime : J3.00 Bin Low Point : 20.00 mV High Point : 220.00 off
Scale Factor; 0 Plot Offset: 20 mv Plot Sc«lt: 200 nv
Response [mV]
mow
o a o
i i j I i i i i I i i i i i
tO
o
o
i i i I i i
O"
.11
ftl
LH"
4.59
4.33
=-5.83
-8.87
13.60
38
-0.97
17. 11
17.65
Column:
Temperature program:
30 m x 0.25 mm ID DB-5 fused silica capillary.
100°C (hold 2 minutes) to 160°C at 15°C/min, then at
5°C/min to 270°C; carrier He at 16 psi.
8081 - 53
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r-
Ll
OB-1701
DB-5
FIGURE 7. GC/ECD chromatogram of Toxaphene analyzed on a DB-5/DB-1701 fused-
silica open-tubular column pair. The GC operating conditions were
as follows: 30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and 30
m x 0.53 mm ID DB-1701 (1.0-jun film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/mn.
8081 - 54
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0
DB-1701
0-
r-
DB-5
!•»
«•
tfl
&
•14 t lit
um a- s> — AJ . .
M ru i>«
I-AT
>
FIGURE 8. GC/ECD chromatogram of Strobane analyzed on a DB-5/DB-1701 fused-
silica open-tubular column pair. The GC operating conditions were
as follows: 30 m x 0.53 mm ID DB-5 {1.5-jum film thickness) and 30
m x 0.53 mm ID DB-1701 (1.0-/im film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/niin.
8081 - 55
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If
0
ra
10-O
> f-
o
lUl'4
a* •
r- u
FIGURE 9. GC/ECD chromatogram of Aroclor 1016 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-^m film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/niin then to 275°C
(10 min hold) at 40C/min.
8081 - 56
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r-to .
f^O- *•
DB-1701
Or-
C-0
•CO
'v/v
OB-5
FIGURE 10. GC/ECD chromatogram of Aroclor 1221 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-/im film thickness) and
30 m x 0.53 mm ID DB-1701 (l.Q-pm film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/nrin.
808] - 57
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DB-1701
r
OB-5
FIGURE 11. GC/ECD chromatogram of Aroclor 1232 analyzed on a DB-5/D8-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-jum film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
8081 - 58
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-------
0
(u
in
tn
r«
OD-bu tl)
-111
IJL
I
m t
uW
DB-1701
r\i
rv
ID K)
DB-5
a) tr.
C. M
FIGURE 13. GC/ECD chromatogram of Aroclor 1248 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-/itn film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-^m film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
8081 - 60
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CD
in
m
DB-1701
u
DB-5
0 C«'l u Ui M
FIGURE 14. GC/ECD chromatogram of Aroclor 1254 analyzed on a DB-5/OB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and
30 m x 0.53 mm ID D8-1701 (1.0-jum film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/nnn then to 275°C
(10 min hold) at 4°C/min.
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DB-1701
DB-5
FIGURE 15. GC/ECD chromatogram of Aroclor 1260 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-^m film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-/*m film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/imn.
8081 - 62
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DB-1701
orvi r- —
(mrr o -
OOT'IO T
Q-T
CD
y irrn
0>
o
K> rn
n ®
— 01
r-
01
DB-5
FIGURE 16. GC/ECD chromatogram of Halowax 1000 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-/im film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/nun then to 275°C
(10 min hold) at 4°C/min.
8081 - 63
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08-1701
FIGURE 17. GC/ECD chromatogram of Halowax 1001 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-/nm film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-jum film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/nnn then to 275°C
(10 min hold) at 4°C/nnn.
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OB-1701
•a
»
9-
II
DB-5
•o
FIGURE 18. GC/ECD chromatogram of Halowax.1099 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-/um film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-^m film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/niin.
8081 - 65
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u — K
_ |. t«
• 0 »
DB-1701
•0
0
e
o
DB-5
HI
•t
FIGURE 19. GC/ECD chromatogram of Halowax 1013 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (LS-^m film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-fim film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 120C/min then to 275°C
(10 min hold) at 40C/min.
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DB-1701
. .1
LT^T -. -. %
r-fl -.-" " *>
FIGURE 20. GC/ECD chromatogram of Halowax 1014 analyzed on a DB-5/DB-1701
fused-silica open-tubular column'pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-^m film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-^cm film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
8081 - 67
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DB-1701
•» I • * 9W
J I"" -•."••
"••» •• - f
— — -— "•« t* f
DB-5
i
Ju, : : ;f
liii
FIGURE 21. GC/ECD chromatogram of Halowax 1051 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-/im film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/nnn then to 275°C
(10 min hold) at 4°C/min.
8081 - 68
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IS SU
DB-5
a
24
2»
34 33 42
'14
37
3S
43
DB-1701
12 1 4 SU IS (
10 II 12 It
14
32
4 34 )» 4
43
20.
FIGURE 22. GC/ECD chromatogram of the organochlorine pesticides analyzed on a
DB-5/DB-1701 fused-silica open-tubular column pair. The GC
operating conditions were as follows: 30 m x 0.53 mm ID DB-5 (0.83-
jjm film thickness) and 30 m x 0.53 mm ID DB-1701 (1.0-/im film
thickness) connected to an 8 in injection tee (Supelco Inc.).
Temperature program: 140°C (2 min hold) to 270°C (1 min hold) at
2.8°C/Tiin.
8081 - 69
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METHOD 8081
ORGANOCHLORINE PESTICIDES AND PCBs AS AROCLORS BY GAS
CHROMATOGRAPHY: CAPILLARY COLUMN TECHNIQUE
7.1.1 ChooM
appropriate extraction
technique (sea Ctiaptar 2)
7.1. 2 Add specified
matlx spfca to sample.
7.2 Routine cleanup/
fractfonation.
7.3 Set chromatograpNc
cendHtens.
i
7.4 Refer lo Method 8000
tor proper caJbratfon
techniques.
7.4.2 Prime or deactivate GC
column prior to caHbraVon.
E
7.5 Perform GC analysis (s
MettKxJSOOO)
7.5.8 AddtkanaJ
cteanuprtracttonatton
(saeSectfon7.2)
7.6 Calculation of
toxapheoe, crtoroane, PCBs.
DDT, and BHC done here.
8081 - 70
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LIST OF TABLES
Table 1 Gas chromatographic retention times and method detection limits for
the Organochlorine Pesticides and PCBs as Aroclors using wide-bore
capillary columns, single column analysis
Table 2 Gas chromatographic retention times and method detection limits for
the Organochlorine pesticides and PCBs as Aroclors using narrow-bore
capillary columns, single column analysis
Table 3 Estimated quantitation limits (EQL) for various matrices
Table 4 GC Operating conditions for Organochlorine compounds, single column
analysis
Table 5 Retention times of the Organochlorine pesticides, dual column method
of analysis
Table 6 GC operating conditions for Organochlorine pesticides, dual column
method of analysis, low temperature, thin film
Table 7 GC operating conditions for Organochlorine pesticides, dual column
method of analysis, high temperature, thick film
Table 8 Summary of retention times (min) of Aroclors on the DB 5 column,
dual system of analysis
Table 9 Summary of retention times (min) of Aroclors on the DB 1701 column,
dual system of analysis
Table 10 Peaks diagnostic of PCBs observed in 0.53 mm ID column, single
column system of analysis
Table 11 Specific Congeners in Aroclors
Table 12 Recovery from Sewage Sludge
Table 13 Recovery DCE still bottoms
Table 14 Single Laboratory Accuracy Data for the Extraction of Organochlorine
Pesticides from Spiked Clay Soil by Method 3541 (Automated Soxhlet)
Table 15 Single Laboratory Recovery Data for Extraction of PCBs from Clay and
Soil by Method 3541 (Automated Soxhlet)
Table 16 Multi-laboratory Precision and Accuracy Data for the Extraction of
PCBs from Spiked Soil by Method 3541 (Automated Soxhlet)
8081 - 71
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LIST OF FIGURES
Figure 1. GC of the Mixed Organochlorine Pesticide Standard. The GC operating
conditions were as follows: 30 m x 0.25 mm ID DB-5 column.
Temperature program: 100°C (hold 2 minutes) to 160°C at 15°C/min,
then at 5°C/min to 270°C; carrier He at 16 psi.
Figure 2. GC of Individual Organochlorine Pesticide Standard Mix A. The GC
operating conditions were as follows: 30 m x 0.25 mm ID DB-5
column. Temperature program: 100°C (hold 2 minutes) to 160°C at
15°C/min, then at 5°C/nnn to 270°C; carrier He at 16 psi.
Figure 3. GC of Individual Organochlorine Pesticide Standard Mix B. The GC
operating conditions were as follows: 30 m x 0.25 mm ID DB-5
column. Temperature program: 100°C (hold 2 minutes) to 160°C at
15°C/min, then at 5°C/min to 270°C; carrier He at 16 psi.
Figure 4. GC of the Toxaphene Standard. The GC operating conditions were as
follows: 30 m x 0.25 mm ID DB-5 column. Temperature program:
100°C (hold 2 minutes) to 160°C at 15°C/min> then at 5°C/min to 270°C;
carrier He at 16 psi.
Figure 5. GC of the Aroclor-1016 Standard. The GC operating conditions were
as follows: 30 m x 0.25 mm ID .DB-5 fused silica capillary column.
Temperature program: 100°C (hold 2 minutes) to 160°C at 15°C/min,
then at 5°C/min to 270°C; carrier He at 16 psi.
Figure 6. GC of the Technical Chlordane Standard. The GC operating conditions
were as follows: 30 m x 0.25 mm ID DB-5 fused silica capillary
column. Temperature program: 100°C (hold 2 minutes) to 160°C at
15°C/min, then at 5°C/rnin to 270°C; carrier He at 16 psi.
Figure 7. GC/ECD chromatogram of Toxaphene analyzed on a DB-5/DB-1701 fused-
silica open-tubular column pair. The GC operating conditions were
as follows: 30 m x 0.53 mm ID DB-5 {1.5-jum film thickness) and 30
m x 0.53 mm ID DB-1701 (1.0-/xm film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
Figure 8. GC/ECD chromatogram of Strobane analyzed on a DB-5/DB-1701 fused-
silica open-tubular column pair. The GC operating conditions were
as follows: 30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and 30
m x 0.53 mm ID DB-1701 (1.0-jum film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/nrin then to 275°C
(10 min hold) at 4°C/min.
8081 - 72
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Figure 9. GC/ECD chromatogram of Aroclor 1016 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-^tm film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-^m film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
{10 min hold) at 4°C/min.
Figure 10. GC/ECO chromatogram of Aroclor 1221 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-/im film thickness) and
30 m x 0.53 mm ID DB-1701 (l-D-^m film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
Figure 11. GC/ECD chromatogram of Aroclor 1232 analyzed on a DB-5/OB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-jiim film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-p film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
Figure 12. GC/ECD chromatogram of Aroclor 1242 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-/im film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-^m film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
Figure 13. GC/ECD chromatogram of Aroclor 1248 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-/im film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 120C/min then to 275°C
(10 min hold) at 4°C/nnn.
Figure 14. GC/ECD chromatogram of Aroclor 1254 analyzed on a DB-5/D8-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-/um film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/imn.
8081 - 73
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Figure 15. GC/ECD chromatogram of Aroclor 1260 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-/nm film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-Mm film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at \2°C/mir\ then to 275°C
(10 min hold) at 4°C/min.
Figure 16. GC/ECD chromatogram of Halowax 1000 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-^m film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-/im film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/nun then to 275°C
(10 min hold) at 4°C/min.
Figure 17. GC/ECD chromatogram of, Halowax 1001 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-jim film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
Figure 18. GC/ECD chromatogram of Halowax 1099 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID D6-5 (1.5-/itn film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-/^m film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
Figure 19. GC/ECD chromatogram of Halowax 1013 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-^m film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-/xm film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
Figure 20. GC/ECD chromatogram of Halowax 1014 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and
30 m x 0.53 mm ID DB-1701 (1.0-^m film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
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Figure 21. GC/ECD chromatogram of Halowax 1051 analyzed on a DB-5/DB-1701
fused-silica open-tubular column pair. The GC operating conditions
were as follows: 30 m x 0.53 mm ID DB-5 (1.5-^m film thickness) and
30 m x 0.53 mm ID OB-1701 (1.0-/im film thickness) connected to a J&W
Scientific press-fit Y-shaped inlet splitter. Temperature program:
150°C (0.5 min hold) to 190°C (2 min hold) at 12°C/min then to 275°C
(10 min hold) at 4°C/min.
Figure 22. GC/ECD chromatogram of the organochlorine pesticides analyzed on a
DB-5/DB-1701 fused-silica open-tubular column pair. The GC
operating conditions were as follows: 30 m x 0.53 mm ID DB-5 (0.83-
jLim film thickness) and 30 m x 0.53 mm ID DB-1701 (1.0-/^m film
thickness) connected to an 8 in injection tee (Supelco Inc.).
Temperature program: 140°C (2 min hold) to 270°C (1 min hold) at
2.8°C/min.
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00
>_t
I—*
o
-------
METHOD 8110
HALOETHERS BY GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 This method covers the determination of certain haloethers. The
following compounds can be determined by this method:
Appropriate Technique
Compound Name CAS No.a 3510 3520 3540 3550 3580
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bts(2-chloroisopropyl) ether
4-Bromophenyl phenyl ether
4-Chlorophenyl phenyl ether
111-91-1
111-44-4
108-60-1
101-55-3
7005-72-3
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
a Chemical Abstract Services Registry Number.
X Greater than 70 percent recovery by this technique.
1.2 This is a gas chromatographic (GC) method applicable to the
determination of the compounds listed above in municipal and industrial
discharges. When this method is used to analyze unfamiliar samples for any or
all of the compounds above, compound identifications should be supported by at
least one additional qualitative technique. This method describes analytical
conditions of a second GC column that can be used to confirm measurements made
with the primary column. Method 8270 provides gas chromatograph/mass
spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative
confirmation of results for all of the parameters listed above, using the extract
from this method.
1.3 The method detection limit (MDL, defined in Section 9.1) for each
parameter is listed in Table 1. The MDL for a specific wastewater may differ
from that listed, depending upon the nature of interferences in the sample
matrix.
1.4 This method is restricted to- use by or under the supervision of
analysts experienced in the use of gas chromatography and in the interpretation
of gas chromatograms. Each analyst must demonstrate the ability to generate
acceptable results with this method using the procedure described in Section 8.2.
1.5 The toxicity or carcinogenicity of each reagent used in this method
has not been precisely defined. However, each chemical compound should be
treated as a potential health hazard. From this viewpoint, exposure to these
chemicals must be reduced to the lowest possible level by whatever means
available. The 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 data handling sheets should also
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be made available to all personnel involved in the chemical analysis. Additional
references to laboratory safety are available and have been identified.
2.0 SUMMARY OF METHOD
2.1 A measured volume of sample, approximately one-liter, is solvent
extracted with methylene chloride using a separatory funnel. The methylene
chloride extract is dried and exchanged to hexane during concentration to a
volume of 10 mL or less. GC conditions are described which permit the separation
and measurement of the compounds in the extract using a halide specific detector.
2.2 Method 8110 provides gas chromatographic conditions for the detection
of ppb concentrations of haloethers. Prior to use of this method, appropriate
sample extraction techniques must be used. Both neat and diluted organic liquids
(Method 3580, Waste Dilution) may be analyzed by direct injection. A 2 to 5 jiL
aliquot of the extract is injected into a gas chromatograph (GC) using the
solvent flush technique, and compounds in the GC effluent are detected by an
electrolytic conductivity detector (HECD).
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and diversity of
the industrial complex or municipality being sampled. The cleanup procedures in
Section 7.3 can be used to overcome many of these interferences, but unique
samples may require additional cleanup approaches to achieve the MDL listed in
Table 1.
3.3 Dichlorobenzenes are known to coelute with haloethers under some gas
chromatographic conditions. If these materials are present in a sample, it may
be necessary to analyze the extract with two different column packings to
completely resolve all of the compounds.
3.4 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms. All these materials must be demonstrated to be free from
interferences under the conditions of the analysis, by analyzing reagent blanks.
Specific selection of reagents and purification of solvents by distillation in
all-glass systems may be required.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas chromatograph - An analytical system complete with
temperature programmable gas chromatograph suitable for on-column
injection and all required accessories including syringes, analytical
columns, gases, detector, and strip-chart recorder. A data system is
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recommended for measuring peak areas,
4.1.2 Columns
4.1.2.1 Column 1 - 1.8 m x 2 mm ID pyrex glass, packed
with Supelcoport, (100/120 mesh) coated with 3% SP-1000 or
equivalent. This column was used to develop the method performance
statements in Section 9.0. Guidelines for the use of alternate
column packings are provided in Section 7.3.1.
4.1.2.2 Column 2 - 1.8 m x 2 mm ID pyrex glass, packed
with 2,6-diphenylene oxide polymer {Tenax-GC 60/80 mesh) or
equivalent.
4.1.3 Detector - Electrolytic conductivity or microcoulometric.
These detectors have proven effective in the analysis of wastewaters for
the parameters listed in the scope of this method. The Hall conductivity
detector (HECD) was used to develop the method performance statements in
Section 9.0. Guidelines for the use of alternate detectors are provided
in Section 7.3.1. Although less selective, an electron capture detector
(ECD) is an acceptable alternative.
4.2 Kuderna-Danish (K-D) apparatus
4.2.1 Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.2.2 Evaporation flask - 500 mL (Kontes K-570001-0500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.2.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.3 Vials - Amber glass, 10 to 15 ml capacity, with Teflon lined screw-
cap or crimp top.
4.4 Boiling chips - Approximately 10/40 mesh. Heat to 400°C for
30 minutes or Soxhlet extract with methylene chloride.
4.5 Water bath - Heated, with 'concentric ring cover, capable of
temperature control (± 2°C). The bath should be used in a hood.
4.6 Balance - Analytical, 0.0001 g.
4.7 Volumetric flasks, Class A - Appropriate sizes with ground glass
stoppers.
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5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all inorganic reagents shall 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 ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.4 Hexane, C6HU - Pesticide quality or equivalent.
5.5 Isooctane, (CH3)3CCH2CH(CH3)2 - Pesticide quality or equivalent.
5.6 Stock standard solutions (1000 mg/L) - Stock standard solutions can
be prepared from pure standard materials or purchased as certified solutions.
5.6.1 Prepare stock standard solutions by accurately weighing
0.1000 ± 0.0010 g of pure material. Dissolve the material in pesticide
quality acetone and dilute to volume in a 100 ml volumetric flask. Larger
volumes can be used at the convenience of the analyst. If compound purity
is certified at 96% or greater, the weight can be used without correction
to calculate the concentration of the stock standard. Commercially
prepared stock standards can be used at any concentration if they are
certified by the manufacturer or by an independent source.
5.6.2 Transfer the stock standard solutions into bottles with Teflon
lined screw-caps or crimp tops. Store at 4°C and protect from light.
Stock standard solutions should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.6.3 Stock standard solutions must be replaced after six months, or
sooner if comparison with check standards indicates a problem.
5.7 Calibration standards - Calibration standards at a minimum of five
concentrations should be prepared through dilution of the stock standards with
isooctane. One of the concentrations should be at a concentration near, but
above, the method detection limit. The remaining concentrations should
correspond to the expected range of concentrations found in real samples or
should define the working range of the GC. Calibration solutions must be
replaced after six months, or sooner if comparison with check standards indicates
a problem.
5.8 Internal standards (if internal standard calibration is used) - To
use'this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to" the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
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5.8.1 Prepare calibration standards at a minimum of five
concentrations for each analyte of interest as described in Section 5.7.
5,8.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with isooctane.
5.8.3 Analyze each calibration standard according to Section 7.0.
5.9 Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (when used), and analytical system and the effectiveness
of the method in dealing with each sample matrix by spiking each sample,
standard, and reagent blank with one or two surrogates {e.g. haloethers that are
not expected to be in the sample) recommended to encompass the range of the
temperature program used in this method. Method 3500 details instructions on the
preparation of base/neutral surrogates. Deuterated analogs of analytes should
not be used as surrogates for gas chromatographic analysis due to coelution
problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored at 4°C and analyzed within 40 days of
extraction.
7.0 PROCEDURE
7.1 Extraction
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral, or as is, pH with methylene chloride, using either Method 3510 or
3520. Solid samples are extracted using either Method 3540 or 3550.
NOTE: Some of the haloethers are very volatile and significant
losses will occur in concentration steps if care is not
exercised. It is important to maintain a constant gentle
evaporation rate and not to allow the liquid volume to fall
below 1 to 2 mL before removing the K-D apparatus from the hot
water bath.
7.1.2 Prior to gas chromatographic analysis, the extraction solvent
must be exchanged to hexane. The exchange is performed during the K-D
procedures listed in all of the extraction methods. The exchange is
performed as follows.
7.1.2.1 Following K-D of the methylene chloride extract to
1 mL using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 minutes.
7.1.2.2 Momentarily remove the Snyder column, add 50 mL of
hexane, a new boiling chip, and reattach the macro-Snyder column.
Concentrate the extract using 1 mL of hexane to prewet the Snyder
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column. Place the K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration in 5-10 minutes. At the proper
rate of distillation the balls of the column will actively chatter,
but the chambers will not flood. When the apparent volume of liquid
reaches 1 ml, remove the K-D apparatus and allow it to drain and
cool for at least 10 minutes. The extract will be handled
differently at this point, depending on whether or not cleanup is
needed. If cleanup is not required, proceed to Section 7.1.2.3. If
cleanup is needed, proceed to Section 7.1.2.4.
7.1.2.3 If cleanup of the extract is not required, remove
the Snyder column and rinse the flask and its lower joint into the
concentrator tube with 1-2 ml of hexane. A 5 ml syringe is
recommended for this operation. Adjust the extract volume to
10.0 ml. Stopper the concentrator tube and store refrigerated at
4°C if further processing will not be performed immediately. If the
extract will be stored longer than two days, it should be
transferred to a Teflon lined screw-cap vial. Proceed with gas
chromatographic analysis.
7.1.2.4 If cleanup of the extract is required, remove the
Snyder column and rinse the flask and its lower joint into the
concentrator tube with a minimum amount of hexane. A 5 ml syringe
is recommended for this operation. Add a clean boiling chip to the
concentrator tube and attach a two ball micro-Snyder column. Prewet
the column by adding about 0.5 ml of hexane to the top. Place the
micro-K-D apparatus on the water bath (80°C) so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration in 5-10 minutes. At the proper
rate of distillation the balls of the column will actively chatter,
but the chambers will not flood. When the apparent volume of liquid
reaches 0.5 ml, remove the K-D apparatus and allow it to drain and
cool for at least 10 minutes.
7.1.2.5 Remove the micro-Snyder column and rinse the flask
and its lower joint into the concentrator tube with 0.2 ml of
hexane. Adjust the extract volume to 2.0 ml and proceed with either
Method 3610 or 3620.
7.2 Cleanup
7.2.1 Proceed with Method 3620, using the 2 ml hexane extracts
obtained from Section 7.1.2.5.
7.2.2 Following cleanup, the extracts should be analyzed by GC, as
described in the previous paragraphs and in Method 8000.
7.3 Gas Chromatography Conditions
7.3.1 Table 1 summarizes the recommended operating conditions for
the gas chromatograph. This table includes retention times and MDLs that
8110 - 6 Revision 0
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were obtained under these conditions. , Examples of the parameter
separations achieved by these columns are shown in Figures 1 and 2. Other
packed columns, chromatographic conditions, or detectors may be used if
the requirements of Section 8.2 are met. Capillary (open-tubular) columns
may also be used if the relative standard deviations of responses for
replicate injections are demonstrated to be less than 6% and the
requirements of Section 8.2 are met.
7.4 Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.
7.4.1 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these procedures.
7.4.2 If cleanup is performed on the samples, the analyst should
process a series of standards through the cleanup procedure and then
analyze the samples by GC. This will confirm elution patterns and the
absence of interferents from the reagents.
7.5 Gas chromatographic analysis
7.5.1 Refer to Method 8000. If the internal standard calibration
technique is used, add 10 nL of internal standard to the sample prior to
injection.
7.5.2 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria. Include a mid-concentration check standard after
each group of 10 samples in the analysis sequence.
7.5.3 Examples of GC/HECD chromatograms for haloethers are shown in
Figures 1 and 2.
7.5.4 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).
7.5.5 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each analyte peak in
the sample chromatogram. See Method 8000 for calculation equations.
7.5.6 If peak detection and identification are prevented due to
interferences, the hexane extract may undergo cleanup using either Method
3610 or 3620.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized. If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
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8.2 Procedures to check the GC system operation are found in Method 8000,
Section 8.6.
8.2.1 The quality control (QC) reference sample concentrate (Method
8000, Section 8.6) should contain each analyte of interest at 20 mg/L.
8.2.2 Table 1 indicates the recommended operating conditions,
retention times, and MDLs that were obtained under these conditions.
Table 2 gives method accuracy and precision for the analytes of interest.
The contents of both Tables should be used to evaluate a laboratory's
ability to perform and generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following is required.
• Check to be sure that there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are a
problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 This method has been tested for linearity of recovery from spiked
organic-free reagent water and has been demonstrated to be applicable for the
concentration range from 4 x MOL to 1000 x MDL.
9.2 In a single laboratory (Monsanto Research Center), using spiked
wastewater samples, the average recoveries presented in Table 2 were obtained.
Each spiked sample was analyzed in triplicate on three separate occasions. The
standard deviation of the percent recovery is also included in Table 2.
10.0 REFERENCES
1. Fed. Reoist. 1984, 49_, 43234; October 26.
2. Mills, P.A. "Variation of Florisil Activity: Simple Method for Measuring
Absorbent Capacity and Its Use in Standardizing Florisil Columns"; Journal
of the Association of Official Analytical Chemists 1968, 51, 29.
3. Handbook of Analytical Quality Control in Water and Wastewater
Laboratories; U.S. Environmental Protection Agency. Office of Research and
Development. Environmental Monitoring and Support Laboratory. ORD
Publication Offices of Center for Environmental Research Information:
Cincinnati, OH, 1979; EPA-600/4-79-019.
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4. Methods for Chemical Analysis of Water and Wastes; U.S. Environmental
Protection Agency. Office of Research and Development. Environmental
Monitoring and Support Laboratory. ORD Publication Offices of Center for
Environmental Research Information: Cincinnati, OH, 1983; EPA-600/4-79-
020.
5. Burke, J.A. "Gas Cnromatography for Pesticide Residue Analysis; Some
Practical Aspects"; Journal of the Association o_f Official Analytical
Chemists 1965, 48, 1037.
6. "EPA Method Validation Study 21 Methods 611 (Haloethers)," Report for EPA
Contract 68-03-2633.
7. "Determination of Haloethers in Industrial and Municipal Wastewaters";
Report for EPA Contract 68-03-2633 (In preparation).
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TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
Analyte
Retention Time
(minutes)
Column 1 Column 2
Method
Detection Limit
(M9/L)
Bis(2-chloroisopropyl) ether
Bis(2-chloroethyl) ether
Bis(2-chloroethoxy)methane
4-Chlorophenyl phenyl ether
4-Bromophenyl phenyl ether
8.4
9.4
13.1
19.4
21.2
9.7
9.1
10.0
15.0
16.2
0.8
0.3
0.5
3.9
2.3
Column 1 conditions:
Carrier gas (He) flow rate:
Initial temperature:
Temperature program:
Final temperature:
40 mL/min
60°C, hold for 2 minutes
60°C to 230°C at 8°C/min
230°C, hold for 4 minutes
Under these conditions the retention time for aldrin is 22.6 minutes.
Column 2 conditions:
Carrier gas (He) flow
Initial temperature:
Temperature program:
Final temperature:
rate: 40 mL/min
150°C, hold for 4 minutes
150°C to 310°C at 16°C/nnn
310°C
Under these conditions the retention time for aldrin is 18.4 minutes.
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TABLE 2.
SINGLE OPERATOR ACCURACY AND PRECISION
Average Standard Spike Number
Percent Deviation Range of Matrix
Analyte Recovery % (M9/L) Analyses Types
Bis(2-chloroethoxy)methane62571f38273
Bis(2-chloroethyl) ether 59 4.5 97 27 3
Bis(2-chloroisopropyl) ether 67 4.0 54 27 3
4-Bromophenyl phenyl ether 78 3.5 14 27 3
4-Chlorophenyl phenyl ether 73 4.5 30 27 3
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FIGURE 1.
GAS CHROMATOGRAM OF HALOETHERS
Column: 3% SP-TOOO on Suptlcopon
Prognm: 60*C. -2 minutit i*/minut» to 23O*C.
Dtttctor: Hull tltctrolytic conductivity
1C
24 6 8 10 12 14 IS 18 20 22 24
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FIGURE 2.
GAS CHROMATOGRAM OF HALOETHERS
Column: T»n»x GC
Prognm: JSO°C.-4 minuttt 16"/minut» to 310°C.
Dtttftar: Hill ultctrolytie conductivity
I
9 12 16
ftttintiofi timt.
20
24
8110 - 13
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METHOD 8110
HALOETHERS BY GAS CHROMATOGRAPHY
Start
7124 Perform
nvicra-K-D procedure
using hexan*.
proceed wilh Method
3610 or 3620
Yes
7 I I ChooJQ
aopropria Ie
ett t rac 11 art
procadu r»
712 Perform
solvent exchange
us ing hexane
No
7123 Adjust
extract volume and
pr oceed *itn
ana Lysis or store
in appropriate
manner
7 3 1 Hcfer '.:
Taole 1 :or
r ecommcnded
opera 11.19
conditions IDT '.
7 4 Ref or I o Me (.hod
30CO for proper
c a I i-Dration
techniques
7 S 1 Refer to
Method 8000 for
guidance on CC
anal/Si >
7 5 4 Record sample
volume injected and
resulting peak size
7 S S Perform
aopropridte
1cula tions |ref (
to Method 30CO]
5'. op
8110 - 14
Revision 0
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00
-------
METHOD 8120A
CHLORINATED HYDROCARBONS BY GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 8120 is used to determine the
chlorinated hydrocarbons. The following compounds
method:
concentration of certain
can be determined by this
Compounds
Appropriate Preparation Techniques
CAS No8 3510 3520 3540/ 3550 3580
3541
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl ohexane
Hexachl orocycl opentadi ene
Hexachl oroethane
Pentachlorohexane
Tetrachl orobenzenes
1,2,4-Trichlorobenzene
91-58-7
95-50-1
541-73-1
106-46-7
118-74-1
87-68-3
608-73-1
77-47-4
67-72-1
120-82-1
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
a Chemical Abstract Services Registry Number.
x Greater than 70 percent recovery by this technique
ND Not determined.
1.2 Table 1 indicates compounds that may be determined by this method and
lists the method detection limit for each compound in organic-free reagent water.
Table 2 lists the estimated quantitation limit (EQL) for other matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8120 provides gas chromatographic conditions for the detection
of ppb concentrations of certain chlorinated hydrocarbons. Prior to use of this
metho'd, appropriate sample extraction techniques must be used. Both neat and
diluted organic liquids (Method 3580, Waste Dilution) may be analyzed by direct
injection. A 2 to 5 juL aliquot of the extract is injected into a gas
chromatograph (GC), and compounds in the GC effluent are detected by an electron
capture detector (ECD).
8120A - 1
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2.2 If interferences are encountered in the analysis, Method 8120 may
also be performed on extracts that have undergone cleanup using Method 3620.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms. All of these materials must be demonstrated to be free
from interferences, under the conditions of the analysis, by analyzing method
blanks. Specific selection of reagents and purification of solvents by
distillation in all glass systems may be required.
3.3 Interferences coextracted from samples will vary considerably from
source to source, depending upon the waste being sampled. Although general
cleanup techniques are recommended as part of this method, unique samples may
require additional cleanup.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas chromatograph - Analytical system complete with gas
chromatograph suitable for on-column injections and all required
accessories, including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak areas and/or peak heights is
recommended.
4.1.2 Columns
4.1.2.1 Column 1 - 1.8 m x 2 mm ID glass column packed
with 1% SP-1000 on Supelcoport (100/120 mesh) or equivalent.
4.1.2.2 Column 2 - 1.8 m x 2 mm ID glass column packed
with 1.5% OV-1/2.4% OV-225 on Supelcoport (80/100 mesh) or
equivalent.
4.2
4.1.3 Detector - Electron capture (ECD).
Kuderna-Danish (K-D) apparatus
4.2.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts
4.2.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps or
equivalent.
4.2.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
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4.2.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.2.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.3 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.4 Water bath - Heated, with concentric ring cover, capable of
temperature control (+ 5°C). The bath should be used in a hood.
4.5 Volumetric flasks - 10, 50, and 100 ml, with ground glass stoppers.
4.6 Microsyringe - 10 juL.
4.7 Syringe - 5 ml.
4.8 Vials - Glass, 2, 10, and 20 ml capacity with Teflon lined screw-
caps or crimp tops.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall 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 ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Solvents
5.3.1 Hexane, C6H14. Pesticide quality or equivalent.
5.3.2 Acetone, CH3COCH3. Pesticide quality or equivalent.
5.3.3 Isooctane, C8H18. Pesticide quality or equivalent.
5.4 Stock standard solutions
5.4.1 Prepare stock standard solutions at a concentration of 1000
mg/l by dissolving 0.0100 g of assayed reference material in isooctane or
hexane and diluting to volume in a 10 ml volumetric flask. Larger volumes
can be used at the convenience of the analyst. When compound purity is
assayed to be 96% or greater, the weight can be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards can be used at any concentration if they are certified by
the manufacturer or by an independent source.
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5.4.2 Transfer the stock standard solutions into vials with Teflon
lined screw caps or crimp tops. Store at 4°C and protect from light.
Stock standards should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards.
5.4.3 Stock standard solutions must be replaced after one year, or
sooner if comparison with check standards indicates a problem.
5.5 Calibration standards - Calibration standards at a minimum of five
concentrations should be prepared through dilution of the stock standards with
isooctane or hexane. One of the concentrations should be at a concentration
near, but above, the method detection limit. The remaining concentrations should
correspond to the expected range of concentrations found in real samples or
should define the working range of the GC. Calibration solutions must be
replaced after six months, or sooner if comparison with check standards indicates
a problem.
5.6 Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.6.1 Prepare calibration standards at a minimum of five
concentrations for each analyte of interest as described in Sec. 5.5.
5.6.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with isooctane or
hexane.
5.6.3 Analyze each calibration standard according to Sec. 7.0.
5.7 Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (when used), and analytical system and the effectiveness
of the method in dealing with each sample matrix by spiking each sample,
standard, and organic-free reagent water blank with one or two surrogates (e.g.
chlorinated hydrocarbons that are not expected to be in the sample) recommended
to encompass the range of the temperature program used in this method. Method
3500 details instructions on the preparation of base/neutral surrogates.
Deuterated analogs of analytes should not be used as surrogates for gas
chromatographic analysis due to coelution problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes, Sec.
4.1.
6.2 Extracts must be stored under refrigeration and analyzed within 40
days of extraction.
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7.0 PROCEDURE
7.1 Extraction
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral, or as is, pH with methylene chloride, using either Method 3510 or
3520. Solid samples are extracted using either Methods 3540/3541 or 3550.
7.1.2 Prior to gas chromatographic analysis, the extraction solvent
must be exchanged to hexane. The exchange is performed during the K-D
procedures listed in all of the extraction methods. The exchange is
performed as follows.
7.1.2.1 Following K-D of the methylene chloride extract
to 1 ml using the macro Snyder column, allow the apparatus to cool
and drain for at least 10 minutes.
7.1.2.2 Momentarily remove the Snyder column, add 50 ml
of hexane, a new boiling chip, and reattach the macro Snyder column.
Concentrate the extract using 1 ml of hexane to prewet the Snyder
column. Place the K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration in 5-10 minutes. At the proper
rate of distillation the balls of the column will actively chatter,
but the chambers will not flood. When the apparent volume of liquid
reaches 1 ml, remove the K-D apparatus and allow it to drain and
cool for at least 10 minutes. The extract will be handled
differently at this point, depending on whether or not cleanup is
needed. If cleanup is not required, proceed to Sec. 7.1.2.3. If
cleanup is needed, proceed to Sec. 7.1.2.4.
7.1.2.3 If cleanup of the extract is not required, remove
the Snyder column and rinse the flask and its lower joint into the
concentrator tube with 1-2 ml of hexane. A 5 ml syringe is
recommended for this operation. Adjust the extract volume to
10.0 ml. Stopper the concentrator tube and store refrigerated at 4°C
if further processing will not be performed immediately. If the
extract will be stored longer than two days, it should be
transferred to a vial with a Teflon lined screw cap or crimp top.
Proceed with gas chromatographic analysis.
7.1.2.4 If cleanup of the extract is required, remove the
Snyder column and rinse the flask and its lower joint into the
concentrator tube with a minimum amount of hexane. A 5 ml syringe
is recommended for this operation. Add a clean boiling chip to the
concentrator tube and attach a two ball micro Snyder column. Prewet
the column by adding about 0.5 ml of hexane to the top. Place the
micro K-D apparatus on the water bath (80°C) so that the concentrator
tube is partially immersed in the hot water. Adjust the vertical
position of the apparatus and the water temperature, as required, to
complete concentration in 5-10 minutes. At the proper rate of
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distillation the balls of the column will actively chatter, but the
chambers will not flood. When the apparent volume of liquid reaches
0.5 mL, remove the K-D apparatus and allow it to drain and cool for
at least 10 minutes.
7.1.2.5 Remove the micro Snyder column and rinse the flask
and its lower joint into the concentrator tube with 0.2 ml of
hexane. Adjust the extract volume to 2.0 ml and proceed with Method
3620.
7.2 Gas chromatographic conditions (Recommended)
7.2.1 Column 1
Carrier gas (5% methane/95% argon) flow rate = 25 mL/min
Column temperature = 65°C isothermal, unless otherwise specified
(see Table 1).
7.2.2 Column 2
Carrier gas (5% methane/95% argon) flow rate = 25 mL/min
Column temperature = 75°C isothermal, unless otherwise specified
(see Table 1).
7.3 Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.
7.3.1 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these procedures.
7.3.2 If cleanup is performed on the samples, the analyst should
process a series of standards through the cleanup procedure and then
analyze the samples by GC. This will validate elution patterns and the
absence of interferents from the reagents.
7.4 Gas chromatographic analysis
7.4.1 Refer to Method 8000. If the internal standard calibration
technique is used, add 10 /uL of internal standard to the sample prior to
injecting.
7.4.2 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria. Include a mid-concentration standard after each
group of 10 samples in the analysis sequence.
7.4.3 Examples of GC/ECD chromatograms for certain chlorinated
hydrocarbons are shown in Figures 1 and 2.
7.4.4 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).
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7.4.5 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes. See Method 8000 for calculation equations.
7.4.6 If peak detection and identification are prevented due to
interferences, the hexane extract may undergo cleanup using Method 3620.
7.5 Cleanup: If required, the samples may be cleaned up using the Methods
presented in Chapter 4.
7.5.1 Proceed with Method 3620 using the 2 mL hexane extracts
obtained from Sec. 7.1.2.5.
7.5.2 Following cleanup, the extracts should be analyzed by GC, as
described in the previous paragraphs and in Method 8000.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized. If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method 8000.
8.2.1 The quality control check sample concentrate (Method 8000)
should contain each parameter of interest at the following concentrations
in acetone: hexachloro-substituted hydrocarbon, 10 mg/L; and any other
chlorinated hydrocarbon, 100 mg/L.
8.2.2 Table 3 indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as functions
of concentration for the analytes of interest. The contents of both
Tables should be used to evaluate a laboratory's ability to perform and
generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000).
8.3.1 If recovery is not within limits, the following procedures are
required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also,
check instrument performance.
• Recalculate the data and/or reanalyze the extract if
any of the above checks reveal a problem.
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Reextract and reanalyze the sample if none of the above
are a problem or flag the data as "estimated
concentration".
9.0 METHOD PERFORMANCE
9.1 The method was tested by 20 laboratories using organic-free reagent
water, drinking water, surface water, and three industrial wastewaters spiked at
six concentrations over the range 1.0 to 356 p,g/l. Single operator precision,
overall precision, and method accuracy were found to be directly related to the
concentration of the parameter and essentially independent of the sample matrix.
Linear equations to describe these relationships for a flame ionization detector
are presented in Table 4.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample preparation technique, and calibration procedures used.
10.0 REFERENCES
1, "Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters. Category 3 - Chlorinated Hydrocarbons, and
Category 8 - Phenols," Report for EPA Contract 68-03-2625.
2. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
3. "EPA Method Validation Study 22, Method 612 (Chlorinated Hydrocarbons),"
Report for EPA Contract 68-03-2625.
4. "Method Performance for Hexachlorocyclopentadiene by Method 612,"
Memorandum from R. Slater, U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268,
December 7, 1983.
5. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
Final Rule and Proposed Rule," October 26, 1984.
6. "Determination of Chlorinated Hydrocarbons in Industrial and Municipal
Wastewaters," Report for EPA Contract 68-03-2625.
8120A - 8 Revision 1
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TABLE 1.
GAS CHROMATOGRAPHY OF CHLORINATED HYDROCARBONS
Compound
Retention time (min)
Col. 1 Col. 2
Method
Detection
limit (M9/I-)
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachl orobutadi ene
Hexachl orocycl ohexane
Hexachl orocycl opentadi ene
Hexachl oroethane
Pentachlorohexane
Tetrachlorobenzenes
1,2,4-Trichlorobenzene
2.7a
6.6
4.5
5.2
5.6a
7.7
ND
4.9
--
15.5
3.6b
9.3
6.8
7.6
10. lb
20.0
16. 5C
8.3
22.3
0.94
1.14
1.19
1.34
0.05
0.34
0.40
0.03
--
--
0.05
ND = Not determined.
8150°C column temperature.
b!65°C column temperature.
C100°C column temperature.
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TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION
LIMITS (EQL) FOR VARIOUS MATRICES"
Matrix Factor
Ground water 10
Low-concentration soil by ultrasonic extraction with GPC cleanup 670
High-concentration soil and sludges by ultrasonic extraction 10,000
Non-water miscible waste 100,000
a EQL = [Method detection limit (see Table 1)] X [Factor found in this
table]. For non-aqueous samples, the factor is on a wet weight basis.
Sample EQLs are highly matrix dependent. The EQLs to be determined
herein are provided for guidance and may not always be achievable.
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TABLE 3.
QC ACCEPTANCE CRITERIA"
Parameter
2-Chloronaphthalene
1,2-Dichlorobenzene
1 , 3-Di chl orobenzene
1,4-Dichlorobenzene
Hexachl orobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachl oroethane
1, 2, 4-Tri chl orobenzene
Test
cone.
(M9/L)
100
100
100
100
10
10
10
10
100
Limit Range
for s for x
(M9/L) (M9/L)
37.3 29.5-126.9
28.3 23.5-145.1
26.4 7.2-138.6
20.8 22.7-126.9
2.4 2.6-14.8
2.2 D-12.7
2.5 D-10.4
3.3 2.4-12.3
31.6 20.2-133.7
Range
P. PS
(%)
9-148
9-160
D-150
13-137
15-159
D-139
0-111
8-139
5-149
s = Standard deviation of four recovery measurements, in /^g/L.
x = Average recovery
P,PS = Percent recovery
D = Detected; result
a Criteria from 40
for four recovery
measured.
measurements, in ng/L.
must be greater than zero.
CFR Part 136 for
Method 612. These cri
teria are
based directly upon the method performance data in Table 4. Where
necessary, the limits for recovery have been broadened to assure
applicability of the limits to concentrations below those used to
develop Table 4.
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TABLE 4.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION8
Parameter
Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachl orobenzene
Hexachlorobutadiene
Hexachl orocyclopentadiene"
Hexachl oroethane
1, 2, 4-Trichl orobenzene
Accuracy, as
recovery, x'
(M9/L)
0.75C+3.21
0.85C-0.70
0.72C+0.87
0.72C+2.80
0.87C-0.02
0.61C+0.03
0.47C
0.74C-0.02
0.76C+0.98
Single analyst
precision, sr'
(M9/L)
0.28X-1.17
0.22X-2.95
0.21X-1.03
0.16X-0.48
0.14X+0.07
O.lSx+0.08
0.24x
0.23X+0.07
0.23X-0.44
Overall
precision,
S' (/ig/L)
0.38X-1.39
0.41x-3.92
0.49X-3.98
0.35X-0.57
0.36X-0.19
0.53X-0.12
O.SOx
0.36X-0.00
0.40X-1.37
X'
V
S'
C
x
Expected recovery for one or more measurements of a sample
containing a concentration of C, in /zg/L.
Expected single analyst standard deviation of measurements at an
average concentration of x, in /zg/L.
Expected interlaboratory standajrd deviation of measurements at an
average concentration found of x, in /zg/L.
True value for the concentration, in /ug/L.
Average recovery found for measurements of samples containing a
concentration of C, in jug/L.
Estimates based upon the performance in a single laboratory.
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FIGURE 1
Column: 1.5% OV-1 +1.5% OV-225 on Gas Chrom. Q
Temperature: 75°C
Detector: Electron Capture
I
t « t i «
4 I 12 16
RETENTION TIME (MINUTES)
20
Gas chromatagram of chlorinated hydrocarbons (high molecular weight compounds).
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FIGURE 2
I I
Column: 1.5V OV-1 + 1.5% OV-225 on Gas Chrom. Q
Temperature: 160°C
Detector: Electron Capture
i t «
0 4 • 12 16
RETENTION TIME (MINUTES)
Gas chromatagram of chlorinated hydrocarbons (low molecular weight compounds).
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METHOD 8120A
CHLORINATED HYDROCARBONS BY GAS CHROMATOGRAPHY
7.1.1 Choose
appropriate
extraction
procedure (see
Chapter 2).
7.1.2 Exchange
extraction solvent
to hexane during
K-D procedures.
7.2 Set gas
chromatography
conditions.
7.3 Refer to Method
8000 for proper
calibration
techniques.
7.3.2 Is
cleanup
necessary?
7.3.2 Process a
series of standards
through cleanup
procedure; analyze
by GC.
7.4 Perform GC
analysis (see
Method 8000).
7.4.5
Is identification
& detection
prevented by
interferences?
7.5.1 Cleanup using
Method 3620.
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00
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METHOD 8121
CHLORINATED HYDROCARBONS BY GAS CHROMATOGRAPHY: CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8121 describes the determination of chlorinated hydrocarbons
in extracts prepared from environmental samples and RCRA wastes. It describes
wide-bore open-tubular, capillary column gas chromatography procedures using both
single column/single detector and dual-column/dual-detector approaches. The
following compounds can be determined by this method:
Compound Name CAS Registry No.8
Benzal chloride
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachl orobutadi ene
a-Hexachlorocyclohexane (a-BHC)
j6-Hexachlorocyclohexane (0-BHC)
7-Hexachlorocyclohexane (y-BHC)
-------
the nature of interferences in the sample matrix. Table 2 lists the estimated
quantitation limits (EQL) for other matrices.
1.4 Table 3 lists the compounds that have been determined by this method
and their retention times using the single column technique. Table 4 lists dual
column/dual detector retention time data. Figures 1 and 2 are chromatograms
showing the single column technique. Figure 3 shows a chromatogram of the target
analytes eluted from a pair of DB-5/DB-1701 columns and detected with electron
capture detectors (ECD) under the prescribed GC conditions listed in Table 2.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the use of a gas chromatograph and in the interpretation
of gas chromatograms.
2.0 SUMMARY OF METHOD
2.1 Method 8121 provides gas chromatographic conditions for the detection
of ppb concentrations of chlorinated hydrocarbons in water and soil or ppm
concentrations in waste samples. Prior to use of this method, appropriate sample
extraction techniques must be used for environmental samples (refer to Chapt. 2).
Both neat and diluted organic liquids (Method 3580) may be analyzed by direct
injection. Spiked samples are used to verify the applicability of the chosen
extraction technique to each new sample type. Analysis is accomplished by gas
chromatography utilizing an instrument equipped with wide bore capillary columns
and single or dual electron capture detectors.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 The electron capture detector responds to all electronegative
compounds. Therefore, interferences are possible by other halogenated compounds,
as well as phthalates and other oxygenated compounds, and, organonitrogen,
organosulfur and organophosphorus compounds. Second column confirmation or GC/MS
confirmation are necessary to ensure proper analyte identification unless
previous characterization of the sample source will ensure proper identification.
3.3 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed. To reduce carryover, the
syringe used for injection must be rinsed out between samples with solvent.
Whenever an extract concentration exceeds that of the highest calibration
standard, it should be followed by the analysis of a solvent blank to check for
cross-contamination. Additional solvent blanks interspersed with the sample
extracts should be considered whenever the analysis of a solvent blank indicates
cross-contamination problems.
3.4 Phthalate esters, if present in a sample, will interfere only with
the BHC isomers because they elute in Fraction 2 of the Florisil procedure
described in Method 3620. The presence of phthalate esters can usually be
minimized by avoiding contact with any plastic materials and by following
standard decontamination procedures of reagents and glassware.
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3.5 The presence of elemental sulfur will result in large peaks, and can
often mask the region of compounds eluting after 1,2,4,5-tetrachlorobenzene. The
tetrabutylammonium (TBA)-sulfite procedure (Method 3660) works well for the
removal of elemental sulfur.
3.6 In certain cases some compounds coelute on either one or both
columns. In these cases the compounds must be reported as coeluting. The
mixture can be reanalyzed by GC/MS techniques, see Sec. 8.7 and Method 8270.
3.6.1 Using the dual column system of analysis the following
compounds coeluted:
DB-5 1,4-dichlorobenzene/benzyl chloride
l,2,3,5-tetrachlorobenzene/l,2,4,5-tetrachlorobenzene
l,2,3,4-tetrachlorobenzene/2-chloronaphthalene
DB-1701 benzyl chloride/1,2-dichlorobenzene/hexachloroethane
benzal chloride/1,2,4-trichlorobenzene/
hexachlorobutadiene
Some of the injections showed a separation of 1,2,4-trichlorobenzene
from the other two compounds, however, this is not always the case, so the
compounds are listed as coeluting.
3.7 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms. All these materials must be demonstrated to be free from
interferences under the conditions of the analysis, by analyzing reagent blanks.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph: An analytical system complete with a gas
chromatograph suitable for on-column and spl it-splitless injection, and all
required accessories, including syringes, analytical columns, gases, and two
electron capture detectors. A data system for measuring peak areas, and dual
display of chromatograms is recommended. A GC equipped with a single GC column
and detector are acceptable, however, second column confirmation is obviously
more time consuming. Following are the single and dual column configurations
used for developing the retention time data presented in the method. The columns
listed in the dual column configuration may also be used for single column
analysis.
4.1.1 Single Column Analysis:
4.1.1.1 Column 1 - 30 m x 0.53 mm ID fused-silica
capillary column chemically bonded with trifluoropropyl methyl
silicone (DB-210 or equivalent).
4.1.1.2 Column 2 - 30 m x 0.53 mm ID fused-silica
capillary column chemically bonded with polyethylene glycol (DB-WAX
or equivalent).
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4.1.2 Dual Column Analysis:
4.1.2.1 Column 1 - 30 m x 0.53 mm ID fused-silica
open-tubular column, cross!inked and chemically bonded with 95
percent dimethyl and 5 percent diphenyl-polysiloxane (DB-5, RTx-5,
SPB-5, or equivalent), 0.83 /xm or 1.5 jum film thickness.
4.1.2.2 Column 2 - 30 m x 0.53 mm ID fused-silica
open-tubular column crosslinked and chemically bonded with 14
percent cyanopropylphenyl and 86 percent dimethyl-polysiloxane
(DB-1701, RTX-1701, or equivalent), 1.0 /xm film thickness.
4.1.3 Splitter: If the splitter approach to dual column injection
is chosen, following are three suggested splitters. An equivalent
splitter is acceptable. See Sec. 7.5.1 for a caution on the use of
splitters.
4.1.3.1 Splitter 1 - J&W Scientific press-fit Y-shaped
glass 3-way union splitter (J&W Scientific, Catalog no. 705-0733).
4.1.3.2 Splitter 2 - Supelco 8 in. glass injection tee,
deactivated (Supelco, Catalog no. 2-3665M).
4.1.3.3 Splitter 3 - Restek Y-shaped fused-silica
connector (Restek, Catalog no. 20405).
4.1.4 Column rinsing kit (optional): Bonded-phase column rinse kit
(J&W Scientific, Catalog no. 430-3000 or equivalent).
4.1.5 Microsyringes - 100 /xL, 50 /xL, 10 JJ.L (Hamilton 701 N or
equivalent), and 50 /xL (Blunted, Hamilton 705SNR or equivalent).
4.1.6 Balances - Analytical, 0.0001 g.
4.1.7 Volumetric flasks, Class A - 10 ml to 1000 ml.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall 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 ascertained that the chemicals are of sufficiently high
purity to permit their use without affecting the accuracy of the determinations.
NOTE: Store the standard solutions (stock, composite, calibration,
internal, and surrogate) at 4°C in Teflon-sealed containers in the
dark. All standard solutions must be replaced after six months or
sooner if routine QC (Sec. 8) indicates a problem.
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5.2 Solvents
5.2.1 Hexane, C6H14 - Pesticide quality or equivalent.
5.2.2 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.2.3 Isooctane, (CH3)3CCH2CH(CH3)2 - Pesticide quality or equivalent.
5.3 Stock standard solutions (1000 mg/L): Can be prepared from pure
standard materials or can be purchased as certified solutions.
5.3.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure compound. Dissolve the compound in isooctane or hexane
and dilute to volume in a 10 ml volumetric flask. If compound purity is
96 percent or greater, the weight can be used without correction to
calculate the concentration of the stock standard solution. Commercially
prepared stock standard solutions can be used at any concentration if they
are certified by the manufacturer or by an independent source.
5.3.2 For those compounds which are not adequately soluble in hexane
or isooctane, mixtures of acetone and hexane are recommended.
5.4 Composite stock standard: Can be prepared from individual stock
solutions. For composite stock standards containing less than 25 components,
take exactly 1 mL of each individual stock solution at 1000 mg/L, add solvent,
and mix the solutions in a 25 mL volumetric flask. For example, for a composite
containing 20 individual standards, the resulting concentration of each component
in the mixture, after the volume is adjusted to 25 mL, will be 40 mg/L. This
composite solution can be further diluted to obtain the desired concentrations.
5.5 Calibration standards should be prepared at a minimum of five
concentrations by dilution of the composite stock standard with isooctane or
hexane. The concentrations should correspond to the expected range of
concentrations found in real samples and should bracket the linear range of the
detector. A suggested list of calibration solution standards is found in Table
7.
5.6 Recommended internal standard: Make a solution of 1000 mg/L of
1,3,5-tnbromobenzene. (Two other internal standards, 2,5-dibromotoluene and
alpha,alpha'-dibromo-m-xylene, are suggested if matrix interferences are a
problem.) For spiking, dilute this solution to 50 ng//nL. Use a spiking volume
of 10 jiL/mL of extract. The spiking concentration of the internal standards
should be kept constant for all samples and calibration standards. Store the
internal standard spiking solutions at 4°C in Teflon-sealed containers in the
dark.
5.7 Recommended surrogate standards: Monitor the performance of the
method using surrogate compounds. Surrogate standards are added to all samples,
method blanks, matrix spikes, and calibration standards. Make a solution of
1000 mg/L of 1,4-dichloronaphthalene and dilute it to 100 ng/^l. Use a spiking
volume of 100 yuL for a 1 L aqueous sample. If matrix interferences are a
8121 - 5 Revision 0
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problem, two alternative surrogates are: alpha, 2,6-trichlorotoluene or
2,3,4,5,6-pentachlorotoluene.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this Chapter, Organic Analytes, Sec.
4.1.
6.2 Extracts must be stored at 4 °C and analyzed within 40 days of
extraction.
7.0 PROCEDURE
7.1 Extraction and Cleanup:
7.1.1 Refer to Chapter Two and Method 3500 for guidance on choosing
the appropriate extraction procedure. In general, water samples are
extracted at a neutral, or as is, pH with methylene chloride, using either
Method 3510 or 3520. Solid samples are extracted using either Methods
3540, 3541, or 3550 with methylene chloride/acetone (1:1) as the
extraction solvent.
7.1.2 If required, the samples may be cleaned up using Method 3620
(Florisil) and/or Method 3640 (Gel Permeation Chromatography). See
Chapter Two, Sec. 2.3.2 and Method 3600 for general guidance on cleanup
and method selection. Method 3660 is used for sulfur removal.
7.1.3 Prior to gas chromatographic analysis, the extraction solvent
must exchanged into hexane using the Kuderna-Danish concentration step
found in any of the extraction methods. Any methylene chloride remaining
in the extract will cause a very broad solvent peak.
7.2 Gas Chromatographic Conditions:
7.2.1 Retention time information for each of the analytes is
presented in Tables 3 and 4. The recommended GC operating conditions are
provided in Tables 5 and 6. Figures 1, 2 and 3 illustrate typical
chromatography of the method analytes for both the single column approach
and the dual column approach when operated at the conditions specified in
Tables 5 and 6.
7.3 Calibration:
7.3.1 Prepare calibration standards using the procedures in Sec.
5.0. Refer to Method 8000 for proper calibration procedures. The
procedure for internal or external calibration may be used.
7.3.2 Refer to Method 8000 for the establishment of retention time
windows.
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7.4 Gas chromatographic analysis:
7.4.1 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria.
7.4.2 Automatic injections of 1 /xL are recommended. Hand injections
of no more than 2 /uL may be used if the analyst demonstrates quantitation
precision of < 10 percent relative standard deviation. The solvent flush
technique may be used if the amount of solvent is kept at a minimum. If
the internal standard calibration technique is used, add 10 pi of the
internal standard to each mL of sample extract prior to injection.
7.4.3 Tentative identification of an analyte occurs when a peak from
a sample extract falls within the daily retention time window.
7.4.4 Validation of gas chromatographic system qualitative
performance: Use the midconcentration standards interspersed throughout
the analysis sequence (Sec. 7.3) to evaluate this criterion. If any of
the standards fall outside their daily retention time windows, the system
is out of control. Determine the cause of the problem and correct it (see
Sec. 7.5).
7.4.5 Record the volume injected to the nearest 0.05 /iL and the
resulting peak size in peak height or area units. Using either the
internal or the external calibration procedure (Method 8000), determine
the identity and the quantity of each component peak in the sample
chromatogram which corresponds to the compounds used for calibration
purposes. See Method 8000 for calculation equations.
7.4.6 If the responses exceed the linear range of the system, dilute
the extract and reanalyze. Peak height measurements are recommended over
peak area integration when overlapping peaks cause errors in area
integration.
7.4.7 If partially overlapping or coeluting peaks are found, change
columns or try a GC/MS technique (see Sec. 8.7 and Method 8270).
Interferences that prevent analyte identification and/or quantitation may
be removed by the cleanup techniques mentioned above.
7.4.8 If the peak response is less than 2.5 times the baseline noise
level, the validity of the quantitative result may be questionable. The
analyst should consult with the source of the sample to determine whether
further concentration of the sample is warranted.
7.5 Instrument Maintenance:
7.5.1 Injection of sample extracts from waste sites often leaves a
high boiling residue in: the injection port area, splitters when used, and
the injection port end of the chromatographic column. This residue
effects chromatography in many ways (i.e., peak tailing, retention time
shifts, analyte degradation, etc.) and, therefore, instrument maintenance
8121 - 7 Revision 0
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is very important. Residue buildup in a splitter may limit flow through
one leg and therefore change the split ratios. If this occurs during an
analytical run, the quantitative data may be incorrect. Proper cleanup
techniques will minimize the problem and instrument QC will indicate when
instrument maintenance is required.
7.5.2 Suggested chromatograph maintenance: Corrective measures may
require any one or more of the following remedial actions. Also see Sec.
7 in Method 8000 for additional guidance on corrective action for
capillary columns and the injection port.
7.5.2.1 Splitter connections: For dual columns which are
connected using a press-fit Y-shaped glass splitter or a Y-shaped
fused-silica connector, clean and deactivate the splitter or replace
with a cleaned and deactivated splitter. Break off the first few
inches (up to one foot) of the injection port side of the column.
Remove the columns and solvent backflush according to the
manufacturer's instructions. If these procedures fail to eliminate
the degradation problem, it may be necessary to deactivate the metal
injector body and/or replace the columns.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 8000 for specific quality control
procedures. Quality control to validate sample extraction is covered in Method
3500 and in the extraction method utilized. If extract cleanup was performed,
follow the QC in Method 3600 and in the specific cleanup method.
8.2 Quality control required to evaluate the GC system operation is found
in Method 8000, Sec. 8.3.
8.3 Calculate surrogate standard recoveries for all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000, Sec. 8). If the recovery is
not within limits, the following are required:
8.3.1 Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check instrument
performance.
8.3.2 Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
8.3.3 Reextract and reanalyze the sample if none of the above are
a problem, or flag the data as "estimated concentrations".
8.4 Data from systems that automatically identify target analytes on the
basis of retention time or retention time indices should be reviewed by an
experienced analyst before they are reported.
8.5 When using the internal standard calibration technique, an internal
standard peak area check must be performed on all samples. The internal standard
8121 - 8 Revision 0
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must be evaluated for acceptance by determining whether the measured area for the
internal standard deviates by more than 50 percent from the average area for the
internal standard in the calibration standards. When the internal standard peak
area is outside that limit, all samples that fall outside the QC criteria must
be reanalyzed.
8.6 Include a mid-concentration calibration standard after each group of
20 samples in the analysis sequence. The response factors for the
mid-concentration calibration must be within + 15 percent of the average values
for the multiconcentration calibration. When the response factors fall outside
that limit, all samples analyzed after that mid-concentration calibration
standard must be reanalyzed after performing instrument maintenance to correct
the usual source of the problem. If this fails to correct the problem, a new
calibration curve must be established.
8.7 GC/MS confirmation:
8.7.1 GC/MS techniques should be judiciously employed to support
qualitative identifications made with this method. Follow the GC/MS
operating requirements specified in Method 8270. Ensure that there is
sufficient concentration of the analyte(s) to be confirmed, in the extract
for GC/MS analysis.
8.7.2 When available, chemical ionization mass spectra may be
employed to aid in the qualitative identification process.
8.7.3 To confirm an identification of a compound, the background
corrected mass spectrum of the compound must be obtained from the sample
extract and must be compared with a mass spectrum from a stock or
calibration standard analyzed under the same chromatographic conditions.
At least 25 ng of material should be injected into the GC/MS. The
identification criteria specified in Method 8270 must be met for
qualitative confirmation.
8.7.3.1 Should the MS procedure fail to provide
satisfactory results, additional steps may be taken before
reanalysis. These steps may include the use of alternate packed or
capillary GC columns or additional sample cleanup.
9.0 METHOD PERFORMANCE
9.1 The MDL is defined in Chapter One. The MDLs listed in Table 1 were
obtained by using organic-free reagent water. Details on how to determine MDLs
are given in Chapter One. The MDLs actually achieved in a given analysis will
vary since they depend on instrument sensitivity and matrix effects.
9.2 This method has been tested in a single laboratory by using
organic-free reagent water, sandy loam samples and extracts which were spiked
with the test compounds at one concentration. Single-operator precision and
method accuracy were found to be related to the concentration of compound and the
type of matrix.
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9.3 Single laboratory accuracy data were obtained for chlorinated
hydrocarbons in a clay soil. The spiking concentrations ranged from 500 to 5000
M9/kg, depending on the sensitivity of the analyte to the electron capture
detector. The spiking solution was mixed into the soil during addition and then
immediatly transferred to the extraction device and immersed in the extraction
solvent. The spiked sample was then extracted by Method 3541 (Automated
Soxhlet). The data represents a single determination. Analysis was by capillary
column gas chromatography/electron capture detector following Method 8121 for the
chlorinated hydrocarbons. These data are listed in Table 9 and were taken from
Reference 4.
10.0 REFERENCES
1. Lopez-Avila, V., N.S. Dodhiwala, and J. Milanes, "Single Laboratory
Evaluation of Method 8120, Chlorinated Hydrocarbons", 1988, EPA Contract
Numbers 68-03-3226 and 68-03-3511.
2. Glazer, J.A., G.D. Foerst, G.D. McKee, S.A. Quave, and W.L. Budde, "Trace
Analyses for Wastewaters," Environ. Sci. and Techno!. 15:1426-1431, 1981.
3. Lopez-Avila, V.; Baldin, E.; Benedicto, J; Milanes, J.; Beckert, W. F.
"Application of Open-Tubular Columns to SW 846 GC Methods"; final report
to the U.S. Environmental Protection Agency on Contract 68-03-3511;
Mid-Pacific Environmental Laboratory, Mountain View, CA, 1990.
4. Lopez-Avila, V. (Beckert, W., Project Officer), "Development of a Soxtec
Extraction Procedure for Extracting Organic Compounds from Soils and
Sediments", EPA 600/X-91/140, US EPA, Environmental Monitoring Systems
Laboratory-Las Vegas, October 1991.
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TABLE 1
METHOD DETECTION LIMITS FOR CHLORINATED HYDROCARBONS
SINGLE COLUMN METHOD OF ANALYSIS
Compound name
Benzal chloride
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1 ,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadiene
a-Hexachlorocyclohexane (a-BHC)
/3-Hexachlorocyclohexane (/3-BHC)
y-Hexachlorocyclohexane (y-BHC)
5-Hexachlorocyclohexane (5-BHC)
Hexachl orocycl opentadi ene
Hexachloroethane
Pentachl orobenzene
1,2, 3, 4-Tetrachl orobenzene
1,2,4 , 5-Tetrachl orobenzene
1,2,3 , 5-Tetrachl orobenzene
1, 2, 4-Trichl orobenzene
1, 2, 3-Trichl orobenzene
1,3, 5 -Trichl orobenzene
CAS Reg. No.
98-87-3
98-07-7
100-44-7
91-58-7
95-50-1
541-73-1
106-46-1
118-74-1
87-68-3
319-84-6
319-85-7
58-89-9
319-86-8
77-47-4
67-72-1
608-93-5
634-66-2
95-94-2
634-90-2
120-82-1
87-61-6
108-70-3
MDLa
(ng/L)
2-5b
6.0
180
1,300
270
250
890
5.6
1.4
11
31
23
20
240
1.6
38
11
9.5
8.1
130
39
12
MDL is the method detection limit for organic-free reagent water. MDL
was determined from the analysis of eight replicate aliquots processed
through the entire analytical method (extraction, Florisil cartridge
cleanup, and GC/ECD analysis).
MDL - T/DC(n.1>B = .99,(s)
where t(n.1099) is the student's t value appropriate for a 99 percent
confidence interval and a standard deviation with n-1 degrees of
freedom, and SD is the standard deviation of the eight replicate
measurements.
Estimated from the instrument detection limit.
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TABLE 2
ESTIMATED QUANTITATION LIMIT (EQL) FACTORS FOR VARIOUS MATRICES"
Matrix Factor
Ground water 10
Low-concentration soil by ultrasonic extraction 670
with GPC cleanup
High-concentration soil and sludges by ultrasonic 10,000
extraction
Waste not miscible with water 100,000
8 EQL = [Method detection limit (see Table 1)] x [Factor found in this
table]. For nonaqueous samples, the factor is on a wet-weight basis.
Sample EQLs are highly matrix-dependent. The EQLs listed herein are
provided for guidance and may not always be achievable.
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TABLE 3
GAS CHROMATOGRAPHIC RETENTION TIMES FOR CHLORINATED HYDROCARBONS: SINGLE
COLUMN METHOD OF ANALYSIS
Compound name
Retention time (min)
DB-2108DB-WAX"
Benzal chloride
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1 , 2-Di chl orobenzene
1,3-Dichlorobenzene
1, 4- Di chl orobenzene
Hexachl orobenzene
Hexachl orobutadi ene
a-BHC
K-BHC
tf-BHC
Hexachl orocycl opentadi ene
Hexachl oroethane
Pent achl orobenzene
1,2,3,4-Tetrachlorobenzene
1,2,4, 5-Tetrachl orobenzene
1,2,3 , 5-Tetrachl orobenzene
1 ,2,4-Trichlorobenzene
1,2, 3 -Tri chl orobenzene
1, 3, 5-Tri chl orobenzene
6.86
7.85
4.59
13.45
4.44
3.66
3.80
19.23
5.77
25.54
24.07
26.16
8.86
3.35
14.86
11.90
10.18
10.18
6.86
8.14
5.45
15.91
15.44
10.37
23.75
9.58
7.73
8.49
29.16
9.98
33.84
54.30
33.79
c
8.13
23.75
21.17
17.81
17.50
13.74
16.00
10.37
Internal Standards
2,5-Dibromotoluene
1,3,5-Tribromobenzene
a,a'-Di bromo-meta-xyl ene
Surrogates
9.55
11.68
18.43
(7,2,6-Trichlorotoluene 12.96
1,4-Dichloronaphthalene 17.43
2,3,4,5,6-Pentachlorotoluene 18.96
18.55
22.60
35.94
22.53
26.83
27.91
GC operating conditions: 30 m x 0.53 mm ID DB-210 fused-silica
capillary column; 1 jum film thickness; carrier gas helium at 10 mL/min;
makeup gas is nitrogen at 40 mL/min; temperature program from 65°C to
175°C (hold 20 minutes) at 4°C/min; injector temperature 220°C; detector
temperature 250°C.
GC operating conditions: 30 m x 0.53 mm ID DB-WAX fused-silica
capillary column; 1 jiim film thickness; carrier gas helium at 10 mL/min;
makeup gas is nitrogen at 40 mL/min; temperature program from 60°C to
170°C (hold 30 minutes) at 4°C/min; injector temperature 200°C; detector
temperature 230°C.
Compound decomposes on-column.
8121 - 13
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TABLE 4
RETENTION TIMES OF THE CHLORINATED HYDROCARBONS'
DUAL COLUMN METHOD OF ANALYSIS
Compound
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Benzyl chloride
1,2-Dichlorobenzene
Hexachloroethane
1,3,5-Trichlorobenzene
Benzal chloride
1,2,4-Trichlorobenzene
1,2,3-Trichlorobenzene
Hexachl orobutadi ene
Benzotrichloride
1,2,3 , 5-Tetrachl orobenzene
1,2,4,5-Tetrachlorobenzene
Hexachl orocycl opentad i ene
1,2, 3, 4-Tetrachl orobenzene
2-Chloronaphthalene
Pentachl orobenzene
a-BHC
Hexachl orobenzene
/3-BHC
7-BHC
5-BHC
DB-5
RT(min)
5.82
6.00
6.00
6.64
7.91
10.07
10.27
11.97
13.58
13.88
14.09
19.35
19.35
19.85
21.97
21.77
29.02
34.64
34.98
35.99
36.25
37.39
DB-1701
RT(min)
7.22
7.53
8.47
8.58
8.58
11.55
14.41
14.54
16.93
14.41
17.12
21.85
22.07
21.17
25.71
26.60
31.05
38.79
36.52
43.77
40.59
44.62
Internal Standard
1,3,5-Tribromobenzene 11.83 13.34
Surrogate
1,4-Dichloronaphthalene 15.42 17.71
"The GC operating conditions were as follows: 30 m x 0.53 mm ID DB-5
(0.83-/xm film thickness) and 30 m x 0.53 mm ID DB-1701 (1.0 /xm film
thickness) connected to an 8-in injection tee (Supelco Inc.). Temperature
program: 80°C (1.5 min hold) to 125°C (1 min hold) at 2°C/min then to 240°C
(2 min hold) at 5°C/m7n; injector temperature 250°C; detector temperature
320°C; helium carrier gas 6 mL/min; nitrogen makeup gas 20 mL/min.
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TABLE 5
GC OPERATING CONDITIONS FOR CHLOROHYDROCARBONS
SINGLE COLUMN METHOD OF ANALYSIS
Column 1: DB-210 30 m x 0.53 mm ID fused-silica capillary column
chemically bonded with trifluoropropyl methyl silicone
Carrier gas (He) 10 mL/min
Column temperature:
Initial temperature 65°C
Temperature program 65°C to 175°C at 4°C/min
Final temperature 175°C, hold 20 minutes.
Injector temperature 220°C
Detector temperature 250°C
Injection volume 1-2 pL
Column 2: DB-WAX 30 m x 0.53 mm ID fused-silica capillary column
chemically bonded with polyethylene glycol
Carrier gas (He) 10 mL/min
Column temperature:
Initial temperature 60°C
Temperature program 60°C to 170°C at 4°C/min
Final temperature 170°C, hold 30 minutes.
Injector temperature 200°C
Detector temperature 230°C
Injection volume 1-2 tit
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Column 1:
Column 2:
TABLE 6
GC OPERATING CONDITIONS FOR CHLORINATED HYDROCARBONS
DUAL COLUMN METHOD OF ANALYSIS
Type: DB-1701 (J&W Scientific) or equivalent
Dimensions: 30 m x 0.53 mm ID
Film Thickness: 1.0 (/urn)
Type: DB-5 (J&W Scientific) or equivalent
Dimensions: 30 m x 0.53 mm ID
Film Thickness: 0.83
Carrier gas flowrate (mL/min): 6 (Helium)
Makeup gas flowrate (mL/min): 20 (Nitrogen)
Temperature program: 80°C (1.5 min hold) to 125"C (1 min hold) at 2°C/min
then to 240°C (2 min hold) at 5eC/min.
Injector temperature: 250°C
Detector temperature: 320eC
Injection volume: 2 jiL
Solvent: Hexane
Type of injector: Flash vaporization
Detector type: Dual ECD
Range: 10
Attenuation: 32 (DB-1701)/32 (DB-5)
Type of splitter: Supelco 8-in injection tee
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TABLE 7
SUGGESTED CONCENTRATIONS FOR THE CALIBRATION SOLUTIONS8
Concentration (ng//zL)
Benzal chloride
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1, 4- Dichl orobenzene
Hexachlorobenzene
Hexachl orobutadi ene
a-BHC
j8-BHC
7-BHC
6-BHC
Hexachl orocycl opentadi ene
Hexachl oroethane
Pentachl orobenzene
1,2,3,4-Tetrachlorobenzene
1 , 2 , 4, 5-Tetrachl orobenzene
1,2,3 , 5-Tetrachl orobenzene
1, 2, 4-Trichl orobenzene
1 ,2, 3 -Trichl orobenzene
1, 3, 5-Trichl orobenzene
0.1
0.1
0.1
2.0
1.0
1.0
1.0
0.01
0.01
0.1
0.1
0.1
0.1
0.01
0.01
0.01
0.1
0.1
0.1
0.1
0.1
0.1
0.2
0.2
0.2
4.0
2.0
2.0
2.0
0.02
0.02
0.2
0.2
0.2
0.2
0.02
0.02
0.02
0.2
0.2
0.2
0.2
0.2
0.2
0.5
0.5
0.5
10
5.0
5.0
5.0
0.05
0.05
0.5
0.5
0.5
0.5
0.05
0.05
0.05
0.5
0.5
0.5
0.5
0.5
0.5
0.8
0.8
0.8
16
8.0
8.0
8.0
0.08
0.08
0.8
0.8
0.8
0.8
0.08
0.08
0.08
0.8
0.8
0.8
0.8
0.8
0.8
1.0
1.0
1.0
20
10
10
10
0.1
0.1
1.0
1.0
1.0
1.0
0.1
0.1
0.1
1.0
1.0
1.0
1.0
1.0
1.0
Surrogates
a,2,6-Trichlorotoluene 0.02 0.05 0.1 0.15 0.2
1,4-Dichloronaphthalene 0.2 0.5 1.0 1.5 2.0
2,3,4,5,6-Pentachlorotoluene 0.02 0.05 0.1 0.15 0.2
One or more internal standards should be spiked prior to GC/ECD
analysis into all calibration solutions. The spike concentration of
the internal standards should be kept constant for all calibration
solutions.
8121 - 17
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TABLE 8
ELUTION PATTERNS OF CHLORINATED HYDROCARBONS
FROM THE FLORISIL COLUMN BY ELUTION WITH PETROLEUM ETHER (FRACTION 1)
AND 1:1 PETROLEUM ETHER/DIETHYL ETHER (FRACTION 2)
Compound
Benzal chlorided
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachl orobenzene
Hexachl orobutadi ene
a-BHC
j3-BHC
7-BHC
5-BHC
Hexachl orocycl opentadi ene
Hexachl oroethane
Pentachl orobenzene
1,2, 3, 4-Tetrachl orobenzene
1 , 2 , 4 , 5-Tetrachl orobenzene8
1,2,3, 5-Tetrachl orobenzene6
1, 2, 4-Trichl orobenzene
1 , 2 , 3-Tri chl orobenzene
1 ,3 , 5-Tri chl orobenzene
Amount
(M9)
10
10
100
200
100
100
100
1.0
1.0
10
10
10
10
1.0
1.0
1.0
10
10
10
10
10
10
Recovery
Fraction 1"
0
0
82
115
102
103
104
116
101
93
100
129
104
102
102
59
96
102
(percent)"
Fraction 2C
0
0
16
95
108
105
71
Values given represent average values of duplicate experiments.
Fraction 1 was eluted with 200 mL petroleum ether.
Fraction 2 was eluted with 200 mL petroleum ether/diethyl ether (1:1).
This compound coelutes with 1,2,4-trichlorobenzene; separate
experiments were performed with benzal- chloride to verify that this
compound is not recovered from the Florisil cleanup in either fraction.
This pair cannot be resolved on the DB-210 fused-silica capillary
columns.
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TABLE 9
SINGLE LABORATORY ACCURACY DATA FOR THE EXTRACTION OF
CHLORINATED HYDROCARBONS FROM SPIKED CLAY SOIL BY METHOD 3541
(AUTOMATED SOXHLET)8
Compound Name
Spike Level
% Recovery
DB-5
DB-1701
1, 3 -Dichl orobenzene
1,2-Dichlorobenzene
Benzal chloride
Benzotrichloride
Hexachl orocycl opentadi ene
Pentachl orobenzene
alpha-BHC
delta-BHC
Hexachl orobenzene
5000
5000
500
500
500
500
500
500
500
b
94
61
48
30
76
89
86
84
39
77
66
53
32
73
94
b
88
a The operating conditions for the automated Soxhlet were as follows:
immersion time 45 min; extraction time 45 min; the sample size was 10 g
clay soil, extraction solvent, 1:1 acetone/hexane. No equilibration time
following spiking.
b Not able to determine because of interference.
Data taken from Reference 4.
8121 - 19
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1
30
IT
14
JU
10
73
K>
IS
T1MI (mtoi)
20
30
Figure 1. GC/ECD chromatogram of Method 8121 composite standard analyzed on a
30 m x 0.53 mm ID DB-210 fused-sH1ca capillary column. GC
operating conditions are given 1n Section 7.4. See Table 3 for
compound Identification.
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17
11
13
10 15
20 25 30 36 40 45 50 55
Figure 2. GC/ECD chromatogram of Method 8121 composite standard analyzed on a
30 m x 0.53 mm ID DB-UAX fused-silica capillary column. GC
operating conditions are given in Section 7.4. See Table 3 for
compound Identification.
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DB-S
it
[
ik
DB-1701
10
i
7 .11 14 II I* IS 17 M It II II to
If
uu
JU
Figure 3. GC/ECD chromatogram of chlorinated hydrocarbons analyzed on a DB
5/DB 1701 fused-silica, open-tubular column pair. The GC operating
conditions were as follows: 30 m x 0.53 mm ID DB 5 (0.83 /xm film
thickness) and 30 m x 0.53 mm ID DB 1701 (1.0 Mm film thickness)
connected to an 8 in injection tee (Supelco Inc.). Temperature
program: 80°C (1.5 min hold) to 125°C (1 min hold) at 2°C/nrin, then
to 240°C (2 min hold) at 5°C/m1n.
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METHOD 8121
CHLORINATED HYDROCARBONS BY GAS CHROMATOGRAPHY: CAPILLARY COLUMN TECHNIQUE
7.1.1 Chooee approon**
extraction procedure
7.12 Add appropriate spiting
c^ii^>ufi4li to uiiijii prior
to extraction procedure
I
7.2 Exchange extrecoon
eofvent to hexane dicing
K-D procedure
7.2.1 Following concentration of
methytene crtoride allow K-O
apparatus to drain vx) cool
7^.2 IOCTMM MmpwMur* o! hot
w«Mr tath; «dd hcauw: *tt*ch
Snyd«r column: olco* «pcw«tu« on wiMr
twti: ooncflntniM; remove from
«MM»r twth; cool
I
72.3 Remove column; ririM Imak
e/xl jointo with hexine; exljtut
•xtmct volume
7.3 Choote •ppropriate deejxjp
technique, if neceteery;
(looroul cteeriup w recommended
Refer to Method 3620 or to
Section 7.3.2
7^.3 Tnvwfer extract to
Teflon teemed icrew-cip
v«l»; refrigerate
7.2.3 Will further
proceuJnebe
performed withJn
twodcyi?
73.3 GPC
cleanup
required?
7.3.4 Elemental
tuttur removeJ
required?
7.3.4 Refer to
Method 3880,
Section 7.3
7.33 Refer to
Method 3640
No
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METHOD 8121
(continued)
7.2.3 Stopper concentrator
and refrigerate
7.4.1 Set column 1 conditions
7.4.2 Set column 2 conditions
7.5.1 Refer to Method 8000 for
calibration techniques; select
lowest point on calibration curve
I
7.5.2 Choose and perform
internal or external calibration
(refer to Method 8000)
7.6.1 Add internal standard
if necessary
7.6.2 Establish daily retention time
windows, analysis sequence,
dilutions, and identification criteria
8121 - 24
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METHOD 8121
(concluded)
0
7.6.3 Record sample volume
Injected and resulting peak
sizes
7.6.4 Determine identity and
quantity of each component peak
that corresponds to compound
used for calibration
7.6.5
Does peak
exceed working
range of
system?
7.6.5 Dilute extract reanalyze
7.6.6 Compare standard and
sample retention times;
identify compounds
8121 - 25
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00
-------
METHOD 8141
ORGANOPHOSPHORUS COMPOUNDS BY GAS CHROMATOGRAPHY:
CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8141 is a gas chromatographic (GC) method used to determine
the concentration of various organophosphorus compounds. The following compounds
can be determined by this method:
Compound Name
CAS No.8
Azinphos-methyl
Bolstar (Sulprofos)
Chlorpyrifos
Coumaphos
Demeton, -0 and -S
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfothion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Stirophos (Tetrachlorovinphos)
Tokuthion (Protothiofos)
Trichloronate
86-50-0
35400-43-2
2921-88-2
56-72-4
8065-48-3
333-41-5
62-73-7
60-51-5
298-04-4
2104-64-5
13194-48-4
115-90-2
55-38-9
121-75-5
150-50-5
7786-34-7
6923-22-4
300-76-5
56-38-2
298-00-0
298-02-2
299-84-3
3689-24-5
21646-99-1
22248-79-9
34643-46-4
327-98-0
a Chemical Abstract Services Registry Number.
1.2 Table 1 lists method detection limits (MDL) for each compound in a
water and a soil matrix. Table 2 lists the estimated quantitation limits (EQLs)
for other matrices.
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1.3 Analytical difficulties encountered with specific organophosphorus
compounds may include (but are not limited to) the following:
1.3.1 Tetraethyl pyrophosphate (TEPP) is an unstable diphosphate
which is readily hydrolyzed in water and is thermally labile (TEPP
decomposes at 170°C). Care must be taken to minimize loss during GC
analysis and during sample preparation. Identification of bad standard
lots is difficult since the electron impact mass spectrum of TEPP is nearly
identical to its major breakdown product, triethyl phosphate.
1.3.2 The water solubility of dichlorvos is 10 g/L at 20°C, and
recovery is poor from aqueous solution.
1.3.3 Naled is converted to Dichlorvos on column by debromination.
This reaction may also occur during sample workup. The extent of
debromination will depend on the nature of the matrix being analyzed. The
analyst must consider the potential for debromination when Naled is to be
determined.
1.3.4 Trichlorofon (not determined by this method) rearranges and is
dehydrochlorinated in acidic, neutral, or basic media to form dichlorvos
and hydrochloric acid. If this method is to be used for the determination
of organophosphates in the presence of Trichlorofon, the analyst should be
aware of the possibility of rearrangement to Dichlorvos to prevent
misidentification.
1.3.5 Demeton is a mixture of two compounds;
0,0-Diethyl 0-[2-(ethylthio)ethyl] phosphorothioate (Demeton-0) and
0,0-Diethyl S-[2-(ethylthio)ethyl] phosphorothioate (Demeton-S). Standards
for the individual isomers are no longer available through the EPA
repository, and two peaks will be observed in all mixed Demeton standards.
It is recommended that the early eluting compound (Demeton-S) be used for
quantitation.
1.3.6 Tributyl phosphorotrithioite (Merphos) is a single component
compound that is readily oxidized in the environment and during storage to
the phosphorotrithioate. The analyst may observe two peaks in the
chromatograms of merphos standards.
1.4 Recoveries for some additional organophosphorus compounds have been
determined for water. They include:
Azinphos-ethyl HMPA
Carbofenthion Leptophos
Chlorfenvinphos Phosmet
Dioxathion Phosphamidion
Ethion Terbuphos
Famphur TOCP
As Method 8141 has not been fully validated for the determination of these
compounds, the analyst must demonstrate recoveries of greater than 70 percent
with precision of no more than 15 percent RSD before Method 8141 is used for
these or any additional analytes.
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1.5 When Method 8141 is used to analyze unfamiliar samples, compound
identifications should be supported by at least two additional qualitative
techniques if mass spectroscopy is not employed. Section 8.4 provides gas
chromatograph/mass spectrometer (GC/MS) criteria appropriate for the qualitative
confirmation of compound identifications.
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatography and in the interpretation
of chromatograms.
1.7 The use of Gel Permeation Cleanup (Method 3640) for sample cleanup has
been demonstrated to yield recoveries of less than 85 percent for many method
analytes and is therefore not recommended for use with this method.
2.0 SUMMARY OF METHOD
2.1 Method 8141 provides gas chromatographic conditions for the detection
of ppb concentrations of organophosphorus compounds. Prior to the use of this
method, appropriate sample preparation techniques must be used. Water samples
are extracted at a neutral pH with methylene chloride as a solvent by using a
separatory funnel (Method 3510) or a continuous liquid-liquid extractor (Method
3520). Soxhlet extraction (Method 3540) or ultrasonic extraction (Method 3550)
using methylene chloride/acetone (1:1) are used for solid samples. Both neat and
diluted organic liquids (Method 3580, Waste Dilution) may be analyzed by direct
injection. Spiked samples are used to verify the applicability of the chosen
extraction technique to each new sample type. A gas chromatograph with a flame
photometric or nitrogen-phosphorus detector is used for this multiresidue
procedure.
2.2 If interferences are encountered in the analysis, Method 8141 may also
be performed on extracts that have undergone cleanup using Method 3620 or Method
3660.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 The use of Florisil cleanup materials (Method 3620) for some of the
compounds in this method has been demonstrated to yield recoveries less than 85%
and is therefore not recommended for all compounds. Refer to Table 2 of Method
3620 for recoveries of organophosphorus compounds as a function of Florisil
fractions. Use of phosphorus or halogen specific detectors, however, often
obviates the necessity for cleanup for relatively clean sample matrices. If
particular circumstances demand the use of an alternative cleanup procedure, the
analyst must determine the elution profile and demonstrate that the recovery of
each analyte is no less than 85%.
3.3 Use of a flame photometric detector in the phosphorus mode will
minimize interferences from materials that do not contain phosphorus. Elemental
sulfur, however, may interfere with the determination of certain organophosphorus
compounds by flame photometric gas chromatography. Sulfur cleanup using Method
3660 may alleviate this interference.
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3.4 A halogen specific detector (i.e. electrolytic conductivity or
microcoulometric) is very selective for the halogen containing compounds and may
be used for the determination of Chlorpyrifos, Ronnel, Coumaphos, Tokuthion,
Trichloronate, Dichlorvos, EPN, Naled, and Stirophos only.
3.5 Please note in Table 3 that a few analytes coelute on certain columns.
Therefore, select a second column for confirmation where coelution of the
analytes of interest does no.t occur.
3.6 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to discrete
artifacts or elevated baselines in gas chromatograms. All these materials must
be routinely demonstrated to be free from interferences under the conditions of
the analysis by analyzing reagent blanks (refer to Section 8.1).
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas chromatograph, analytical system complete with gas
chromatograph and all required accessories including syringes, analytical
columns, gases, detector and data system, integrator or stripchart
recorder. A data system or integrator is recommended for measuring peak
areas and/or peak heights.
4.1.2 Columns
4.1.2.1 Column 1 - 15 m x 0.53 mm megabore capillary
column, 1.0 urn film thickness, DB-210 (J&W Scientific or equivalent.)
4.1.2.2 Column 2 - 15 m x 0.53 mm megabore capillary
column, 1.5 pm film thickness, SPB-608 (Supelco, Inc. or equivalent.)
4.1.2.3 Column 3 - 15 m x 0.53 mm megabore capillary
column, 1.0 pm film thickness, DB-5 (J&W Scientific or equivalent.)
4.1.3 Detector - These detectors have proven effective in analysis
for all analytes listed in Table 1 and Section 1.4 and were used to develop
the accuracy and precision statements in Section 9.0.
4.1.3.1 Nitrogen Phosphorus Detector (NPD) operated in the
phosphorus specific mode is recommended.
4.1.3.2 Flame Photometric Detector (FPD) operated in the
phosphorus specific mode is recommended.
4.1.3.3 Halogen specific detectors (electrolytic
conductivity or microcoulometric) may be used if only halogenated or
sulfur analytes are to be determined.
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4.2 Kuderna-Danish (K-D) apparatus:
4.2.1 Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.2.2 Evaporation flask - 500 mL (Kontes K-570001-500 or equivalent).
Attach to concentrator tube with springs, clamps or equivalent.
4.2.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.2.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.3 Vials - 10 ml, glass with Teflon lined screw-caps or crimp tops.
4.4 Water bath - Heated with concentric ring cover, capable of temperature
control (± 2°C). The bath should be used in a hood.
4.5 Balance - Analytical, capable of accurately weighing to the nearest
0.0001 g.
4.6 Boiling chips - Solvent extracted with methylene chloride,
approximately 10/40 mesh (silicon carbide or equivalent).
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all inorganic reagents shall 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 ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
5.2 Hexane, C6HU - Pesticide quality or equivalent.
5.3 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.4 Isooctane, C8H18 - Pesticide quality or equivalent.
5.5 Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (when used), and analytical system and the effectiveness
of the method in dealing with each sample matrix by spiking each sample,
standard, and blank with one or two surrogates (e.g. organophosphorus compounds
not expected to be present in the sample) recommended to encompass the range of
the temperature program used in this method. Deuterated analogs of analytes
should not be used as surrogates for gas chromatographic analysis due to
coelution problems.
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5.6 Stock standard solutions - Can be prepared from pure standard
materials or can be purchased as certified solutions. Commercially prepared
stock standards can be used if they are verified against EPA standards. If EPA
standards are not available for verification, then standards certified by the
manufacturer and verified against a standard made from pure material is
acceptable.
5.6.1 Prepare stock standard solutions by accurately weighing
0.0100 g of pure material. Dissolve the material in hexane or other
suitable solvent and dilute to known volume in a volumetric flask. If
compound purity is certified at 96% or greater, the weight can be used
without correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration if
the are certified by the manufacturer or by an independent source.
5.6.2 Transfer the stock standard solutions into bottles with Teflon
lined screw-caps or crimp tops. Store at 4°C and protect from light.
Stock standard solutions should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.6.3 Stock standard solutions must be replaced after six months or
sooner if comparison with check standards indicates a problem. All stock
standards must be stored in a freezer at 4°C.
5.7 Calibration standards - A minimum of five concentrations for each
analyte of interest should be prepared through dilution of the stock standards
with isooctane. One of the concentrations should be at a concentration near, but
above, the MDL. The remaining concentrations should correspond to the expected
range of concentrations found in real samples or should define the working range
of the GC. Calibration standards must be replaced after one to two months, or
sooner if comparison with check standards indicates a problem.
5.8 Internal standards should only be used on well characterized samples.
To use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.8.1 Prepare calibration standards at a minimum of five
concentrations for each analyte of interest as described in Section 5.7.
5.8.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with hexane or other
suitable solvent.
5.8.3 Analyze each calibration standard according to Section 7.0.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
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6.2 Extracts are to be refrigerated at 4°C and analyzed within 40 days of
extraction.
7.0 PROCEDURE
7.1 Extraction
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a neutral
pH with methylene chloride, using either Method 3510 or 3520. Solid
samples are extracted using either Method 3540 or 3550 with methylene
chloride/acetone (1:1) as the extraction solvent.
7.1.2 Prior to gas chromatographic analysis, the extraction solvent
may be exchanged to hexane. The exchange is performed during the K-D
procedures listed in all of the extraction methods. The analyst must
ensure quantitative transfer of the extract concentrate. Single laboratory
data indicates that samples should not be transferred with 100 percent
hexane during sample workup as the more water soluble organophosphorus
compounds may be lost. This transfer is best accomplished with a
hexane/acetone solvent mixture. The exchange is performed as follows:
7.1.2.1 Following K-D concentration of the methylene
chloride extract to 1 ml using the macro Snyder column, allow the
apparatus to cool and drain for at least 10 minutes.
7.1.2.2 Momentarily remove the Snyder column, add 50 mL
of hexane/acetone solvent mixture, a new glass bead or boiling chip,
and attach the micro Snyder column. Concentrate the extract using
1 ml of hexane to prewet the Snyder column. Place the K-D apparatus
on the water bath so that the concentrator tube is partially immersed
in the hot water. Adjust the vertical position of the apparatus and
the water temperature, as required, to complete concentration in
5-10 minutes. At the proper rate of distillation the balls of the
column will actively chatter, but the chambers will not flood. When
the apparent volume of liquid reaches 1 ml, remove the K-D apparatus
and allow it to drain and cool for at least 10 minutes.
7.1.2.3 Remove the Snyder column and rinse the flask and
its lower joint with 1-2 ml of hexane into the concentrator tube. A
5 ml syringe is recommended for this operation. Adjust the extract
volume to 10 ml. Stopper the concentrator tube and store
refrigerated at 4°C if further processing will not be performed
immediately. If the extract will be stored longer than two days, it
should be transferred to a vial with a Teflon lined screw-cap or
crimp top. Proceed with gas chromatographic analysis if further
cleanup is not required.
7.2 Gas chromatographic conditions (recommended): Three megabore
capillary columns are included for analysis of organophosphates by this method.
Column 1 (DB-210 or equivalent) and Column 2 (SPB-608 or equivalent) are
recommended if a large number of organophosphorus analytes are to be determined.
If the superior resolution offered by Column 1 and Column 2 is not required,
Column 3 (DB-5 or equivalent) may be used.
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7.2.1 Columns 1 and 2
Carrier gas (He) flow rate » 5 mL/min
Initial temperature = 50°C, hold for 1 minute
Temperature program - 50°C to 140°C at 50C/min, hold for 10
minutes, followed by 140°C to 240°C
at 10°C/min, hold for 10 minutes (or
a sufficient amount of time for last
compound to elute).
7.2.2' Column 3
Carrier gas (He) flow rate = 5 mL/min
Initial temperature - 130°C, hold for 3 minutes
Temperature program = 130°C to 180°C at 5°C/min, hold for 10
minutes, followed by 180°C to 250°C
at 2°C/min, hold for 15 minutes (or a
sufficient amount of time for last
compound to elute).
7.2.3 Retention times for all analytes on each column are presented
in Table 3. The analyst should note that several method analytes coelute
on column 3.
7.3 Calibration: Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.
7.3.1 The procedure for internal or external calibration may be used.
Refer to Method 8000 for a description of each of these procedures.
7.3.2 If cleanup is performed on the samples, the analyst should
process a series of standards through the cleanup procedure and then
analyze the samples by GC. This will confirm elution patterns and the
absence of interferences from the reagents.
7.4 Gas chromatographic analysis
7.4.1 Refer to Method 8000. If the internal standard calibration
technique is used, add 10 jtiL of internal standard to the sample prior to
injection.
7.4.2 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria.
7.4.3 For megabore capillary columns, automatic injections of 1 Mi-
are recommended. Hand injections of no more than 2 pi may be used if the
analyst demonstrates quantitation precision of <; 10 percent relative
standard deviation. The solvent flush technique may be used if the amount
of solvent is kept at a minimum.
7.4.4 Examples of chromatograms for various organophosphorus
compounds are shown in Figures 1 through 4.
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7.4.5 Record the sample volume injected to the nearest 0.05 p.1 and
the resulting peak sizes (in area units or peak heights).
7.4.6 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes. See Method 8000 for calculation equations.
7.4.7 If peak detection and identification is prevented by the
presence of interferences, further cleanup is required. Before using any
cleanup procedure, the analyst must process a series of calibration
standards through the procedure to establish elution patterns and to
determine recovery of target compounds. The absence of interference from
reagents must be demonstrated by routine processing of reagent blanks
through the chosen cleanup procedure.
7.4.8 Naled has been reported to be converted to DDVP on some columns
by debromination. If this process is demonstrated on the GC system that
is used for analysis, clean the injector and break off several inches of
a megabore column or change the glass wool of a packed column prior to
analyzing samples. If subsequent injections of Naled give DDVP, report
Naled as DDVP, but, in this instance, both Naled and DDVP may not be
reported in the same sample.
7.5 Cleanup
7.5.1 Proceed with Florisil column Cleanup (Method 3620), followed
by, if necessary, Sulfur Cleanup (Method 3660), using the 10 mL hexane
extracts obtained from Section 7.1.2.3.
NOTE: The use of Gel Permeation (Method 3640) for sample cleanup has
been demonstrated to yield recoveries of less than 85 percent
for many method analytes and is therefore not recommended for
use with this method.
7.5.2 Following cleanup, the extracts should be analyzed by GC, as
described in the previous Sections and in Method 8000.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures. Include
a mid-level check standard after each group of 10 samples in the analysis
sequence. Quality control to validate sample extraction is covered in Method
3500 and in the extraction method utilized. If extract cleanup was performed,
follow the QC in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method 8000,
Section 8.6.
8.3 GC/MS confirmation
8.3.1 GC/MS techniques should be judiciously employed to support
qualitative identifications made with this method. Follow the GC/MS
8141 - 9 Revision 0
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operating requirements specified in Method 8270.
8.3.2 When available, chemical ionization mass spectra may be
employed to aid in the qualitative identification process.
8.3.3 To confirm an identification of a compound, the background-
corrected mass spectrum of the compound must be obtained from the sample
extract and must be compared with a mass spectrum from a stock or
calibration standard analyzed under the same chromatographic conditions.
At least 25 ng of material should be injected into the GC/MS. The
following criteria must be met for qualitative confirmation:
The molecular ion and all other ions present above 20 percent
relative abundance in the mass spectrum of the standard must be present in
the mass spectrum of the sample with agreement to ± 20 percent. For
example, if the relative abundance of an ion is 30 percent in the mass
spectrum of the standard, the allowable limits for the relative abundances
of that ion in the mass spectrum for the sample would be 20 to 40 percent.
The retention time of the compound in the sample must be within six
seconds of the retention time for the same compound in the standard
solution.
Compounds that have very similar mass spectra can be explicitly
identified by GC/MS only on the basis of retention time data.
8.3.4 Where available, chemical ionization mass spectra may be
employed to aid in the qualitative identification process because of the
extensive fragmentation of organophosphorus compounds during electron
impact MS processes.
8.3.5 Should the MS procedure fail to provide satisfactory results,
additional steps may be taken before reanalysis. These steps may include
the use of alternate packed or capillary GC columns or additional sample
cleanup.
9.0 METHOD PERFORMANCE
9.1 Estimated MDLs and associated chromatographic conditions for water and
clean soil (uncontaminated with synthetic organics) are listed in Table 1. As
detection limit will vary with the particular matrix to be analyzed, guidance for
estimating EQLs is given in Table 2.
9.2 Single operator accuracy and precision studies have been conducted
with spiked water and soil samples. The results of these studies are presented
in Tables 4-7.
10.0 REFERENCES
1. Taylor, V.; Hickey, D.M.; Marsden, P.O. "Single Laboratory Validation of
EPA Method 8140"; U.S. Environmental Protection Agency. Environmental
Monitoring Systems Laboratory. Office of Research and Development, Las
8141 - 10 Revision 0
July 1992
-------
Vegas, NV, 1987; EPA-600/4-87-009.
Pressley, T.A; Longbottom, J.E. "The Determination of Organophosphorus
Pesticides in Industrial and Municipal Wastewater: Method 614"; U.S.
Environmental Protection Agency. Environmental Monitoring and Support
Laboratory. Cincinnati, OH, 1982; EPA-600/4-82-004.
"Analysis of Volatile Hazardous Substances by 6C/MS: Pesticide Methods
Evaluation"; Letter Reports 6, 12A, and 14 to the U.S.Environmental
Protection Agency on Contract 68-03-2697, 1982.
"Method 622, Organophosphorus Pesticides"; U.S. Environmental Protection
Agency. Environmental Monitoring Systems Laboratory. Cincinnati, OH 45268.
Chau, A.S.Y.; Afghan, B.K. Analysis of Pesticides in Water. Vol. II;
"Chlorine and Phosphorus-Containing Pesticides"; CRC: Boca Raton, FL, 1982,
pp 91-113, 238.
Hild, J.; Schulte, E; Thier, H.P. "Separation of Organophosphorus
Pesticides and Their Metabolites on Glass-Capillary Columns";
Chromatographia, 1978, 11-17.
Luke, M.A.; Froberg, J.E.; Doose, G.M.; Masumoto, H.T. "Improved
Multiresidue Gas Chromatographic Determination of Organophosphorus,
Organonitrogen, and Organohalogen Pesticides in Produce, Using Flame
Photometric and Electrolytic Conductivity Detectors"; vh. Assoc. Off. Anal.
Chem. 1981, 1187. 64.
Sherma, J.; Berzoa, M. "Analysis of Pesticide Residues in Human and
Environmental Samples"; U.S. Environmental Protection Agency. Research
Triangle Park, NC; EPA-600/8-80-038.
Desmarchelier, J.M.; Wustner, D.A.; Fukuto, T.R. "Mass Spectra of
Organophosphorus Esters and Their Alteration Products"; Residue Reviews.
1974, pp 63, 77.
8141 - 11 Revision 0
July 1992
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TABLE 1.
METHOD DETECTION LIMITS IN A WATER AND A SOIL
MATRIX USING A FLAME PHOTOMETRIC DETECTOR
Compound
Reagent
Water (3510)8
(M9/L)
Soil (3540)
Azinphos-methyl
Bolstar (Sulprofos)
Chlorpyrifos
Coumaphos
Demeton, -0, -S
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfothion
Fenthion
Malathion
Merphos
Mevinphos
Naled
Parathion-ethyl
Parathion-methyl
Phorate
Ronnel
Sulfotep
TEPPC
Tetrachlorovinphos
Tokuthion (Protothiofos)0
Trichloronatec
0.10
0.07
0.07
0.20
0.12
0.20
0.80
0.26
0.07
0.04
0.20
0.08
0.08
0.11
0.20
0.50
0.50
0.06
0.12
0.04
0.07
0.07
0.80
0.80
0.07
0.80
5.0
3.5
5.0
10.0
6.0
10.0
40.0
13.0
3.5
2.0
10.0
4.0
5.0
5.5
10.0
25.0
25.0
3.0
6.0
2.0
3.5
3.5
40.0
40.0
5.5
40.0
a Sample extracted using Method 3510, Separatory Funnel Liquid-Liquid
Extraction.
b Sample extracted using Method 3540, Soxhlet Extraction.
c Purity of these standards not established by the EPA Pesticides and
Industrial Chemicals Repository, RTP, NC.
8141 - 12
Revision 0
July 1992
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TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS
(EQL) FOR VARIOUS MATRICES8
Matrix Factor6
Ground water (Methods 3510 or 3520) 10
Low-concentration soil by Soxhlet and no cleanup 10°
Low-concentration soil by ultrasonic extraction with GPC cleanup 6.7C
High-concentration soil and sludges by ultrasonic extraction 500C
Non-water miscible waste (Method 3580) 1000C
Sample EQLs are highly matrix dependent. The EQLs listed herein are provided
for guidance and may not always be achievable.
EQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor is on a wet-weight basis.
Multiply this factor times the soil MDL.
8141 - 13 Revision 0
July 1992
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TABLE 3.
RETENTION TIMES FOR METHOD 8141 ANALYTES
Compound
TEPP
Dichlorvos
Mevinphos
Demeton, -0 and -S
Ethoprop
Naled
Phorate
Monocrotophos
Sul f otep
Dimethoate
Disulfoton
Diazinon
Merphos
Ronnel
Chlorpyrifos
Malathion
Parathion, methyl
Parathion, ethyl
Trichloronate
Tetrachlorovinphos
Tokuthion (Protothiofos)
Fensulfothion
Bolstar^Sulprofos)
Famphur
EPN
Azinphos-methyl
Fenthion
Coumaphos
*Method 8141 has not been fully val
Initial temperature
Initial time
Program 1 rate
Program 1 final temperature
Program 1 hold
Program 2 rate
Program 2 final temperature
Program 2 hold
Capil
DBS
6.44
9.63
14.178
18.31
18.618
19.01
19.94
20.04
20.11
20.636
23.71
24.27
26.82
29.23
31.17
31.72
31.84
31.85
32.19
34.65
34.67
35.85
36.34
36.40
37.80
38.342
38.83
39.83
larv Column
SPB608
5.12
7.91
12.88
15.90
16.48
17.40
17.52
20.11
18.02
20.18
19.96
20.02
21.73
22.98
26.88
28.78
23.71
27.62
28.41
32.99
24.58
35.20
35.08
36.93
36.71
38.04
29.45
38.87
DB210
10.66
12.79
18.44
17.24
18.67
19.35
18.19
31.42
19.58
27.96
20.66
19.68
32.44
23.19
25.18
32.58
32.17
33.39
29.95
33.68
39.913
36.80
37.55
37.86
36.74
37.24
28.86
39.47
idated for Famphur.
130°C
3 minutes
5°C/niin
180°C
10 minutes
2°C/min
250°C
15 minutes
50°C
1 minute
5°C/min
140°C
10 minutes
10°C/min
240°C
10 minutes
50°C
1 minute
5°C/min
140°C
10 minutes
10°C/min
240°C
10 minutes
8141 - 14
Revision 0
July 1992
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TABLE 4.
RECOVERY OF 27 ORGANOPHOSPHATES BY SEPARATORY FUNNEL EXTRACTION
Compound
Azinphos-methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
126
134
7
103
33
136
80
NR
48
113
82
84
NR
127
NR
NR
NR
NR
101
NR
94
67
87
96
79
NR
NR
Medium
143 + 8
141 + 8
89 + 6
90 + 6
67 + 11
121 + 9.5
79 + 11
47 + 3
92 + 7
125 + 9
90 + 6
82 + 12
48 + 10
92 + 6
79
NR
18 + 4
NR
94 + 5
46 + 4
77 + 6
97 + 5
85 + 4
55 + 72
90 + 7
45 + 3
35
High
101
101
86
96
74
82
72
101
84
97
80
96
89
86
81
55
NR
NR
86
44
73
87
83
63
80
90
94
NR = Not recovered.
8141 - 15
Revision 0
July 1992
-------
TABLE 5.
RECOVERY OF 27 ORGANOPHOSPHATES BY CONTINUOUS LIQUID EXTRACTION
Compound
Azinphos-methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Famphur
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
NR
NR
13
94
38
NR
81
NR
94
NR
39
--
90
8
105
NR
NR
NR
NR
106
NR
84
82
40
39
56
132
NR
Medium
129
126
82 + 4
79 + 1
23 + 3
128 + 37
32 + 1
10 + 8
69 + 5
104 + 18
76 + 2
63 + 15
67 + 26
32 + 2
87 + 4
80
87
30
NR
81 + 1
50 + 30
63+3
83 + 7
77 + 1
18 + 7
70 + 14
32 + 14
NR
High
122
128
88
89
41
118
74
102
81
119
83
--
90
86
86
79
49
1
74
87
43
74
89
85
70
83
90
21
NR = Not recovered.
8141 - 16
Revision 0
July 1992
-------
TABLE 6.
RECOVERY OF 27 ORGANOPHOSPHATES BY SOXHLET EXTRACTION
Compound
Azinphos -methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion., ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
156
102
NR
93
169
87
84
NR
78
114
65
72
NR
100
62
NR
NR
NR
75
NR
75
NR
67
36
50
NR
56
Medium
110 + 6
103 + 15
66 + 17
89 + 11
64 + 6
96 + 3
39 + 21
48 + 7
78 + 6
93 + 8
70 + 7
81 + 18
43 + 7
81 + 8
53
71
NR
48
80 + 8
41+3
77 + 6
83 + 12
72 + 8
34 + 33
81 + 7
40 + 6
53
High
87
79
79
90
75
75
71
98
76
82
75
111
89
81
60
63
NR
NR
80
28
78
79
78
63
83
89
53
NR = Not recovered.
8141 - 17
Revision 0
July 1992
-------
TABLE 7.
RECOVERY OF 27 ORGANOPHOSPHATES BY ULTRASONIC EXTRACTION
Compound
Azinphos-methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
NR
NR
NR
NR
NR
NR
41
NR
30
14
19
NR
NR
55
NR
NR
NR
82
NR
63
NR
70
NR
43
NR
NR
NR
Medium
27 + 10
103 + 15
79 + 7
60
NR
90 + 14
13 + 9
67
44 + 22
86 + 38
34 + 26
37
35
67
71
NR
NR
40
74 + 13
NR
51+9
84+8
68 + 10
7
47 + 24
NR
NR
High
21
114
77
15
16
78
27
NR
69
105
35
2
84
31
155
23
NR
33
75
17
64
81
76
3
69
82
31
NR =. Not recovered.
8141 - 18 Revision 0
July 1992
-------
FIGURE 1.
CHARACTERISTIC RESPONSE OF ORGANOPHOSPHATES ON OB210 WITH FPD DETECTOR
300.00
250.00
200.00-
150.00
100.00
50.00
0.00
8
t
f- ...»-..
13579
1
L
i
m
S
°
(
i
(
<
i
1
1 1 1
Is
1 II
• . i
„
1
u.
1
I
1
$
1 1
2 8
1 1
e
s
v... jt
A
S
U
\
11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45
8141 - 19
Revision 0
July 1992
-------
FIGURE 2.
CHARACTERISTIC RESPONSE OF OR6ANOPHOSPHATES ON DB210 WITH NPD DETECTOR
300.00
250.00
200.00 -i
150.00-^
100.00-
50.00-
0.00 -J
III
rf I I I | I I I | I lf|l fl|l»|MI|lll|ii||tli||ii|iM|iii|llTJ Tiipiinii|«TrjTi»|»t-i|1i»)
5 7 9 11 13 15 17 19 21 23 25 27 29 31 33. 35 37 39 41 43 45
8141 - 20
Revision 0
July 1992
-------
FIGURE 3.
CHROMATOGRAM OF ORGANOPHOSPHATES ON DB210 WITH FPD DETECTOR
300.00
i
Q
250.00
200.00
150.00
100.00
50.00
II .'
\
-------
FIGURE 4.
CHROMATOGRAM OF ORGANOPHOSPHATES ON DB210 WITH NPO DETECTOR
300.00-,
250.00-
200.00-
150.00-
100.00-
50.00-^ .
;_JJL_jtL_
|
i
VI
to..
0.00 •'-i • i»" 11"!»"».' M...|...|.. .,,,.,,..,,,.,
13 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45
8141 - 22
Revision 0
July 1992
-------
METHOD 8141
ORGANOPHOSPHORUS COMPOUNDS BY GAS CHROMATOGRAPHY: CAPILLARY COLUMN TECHNIQUE
7.1.1 Choose
appropriate
extraction procedure
(see Chapter 2)
7.1.2 Exchange
extraction solvent to
hexane during
K-D procedures
1
7.2 Set gas
OvomatDgrapny
conditions
7.3 Refer to
Metfiod 8000 tor
proper calibration
techniques
7.3.2 Process a
series of stds through
cleanup procedure.
analyze by GC
7.4 Perform
QC analysis
(see Method 8000)
7.5.1 Cleanup using
erod 3620 and 3630
if necessary
8141 - 23
Revision 0
July 1992
-------
00
-------
METHOD 8141A
ORGANOPHOSPHORUS COMPOUNDS BY GAS CHRQMATOGRAPHY:
CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8141 is a capillary gas chromatographic (GC) method used to
determine the concentration of organophosphorus (OP) compounds. The fused-
silica, open-tubular columns specified in this method offer improved resolution,
better selectivity, increased sensitivity, and faster analysis than packed
columns. The compounds listed in the table below can be determined by GC using
capillary columns with a flame photometric detector (FPD) or a nitrogen-
phosphorus detector (NPD). Triazine herbicides can also be determined with this
method when the NPD is used. Although performance data are presented for each
of the listed chemicals, it is unlikely that all of them could be determined in
a single analysis. This limitation results because the chemical and
chromatographic behavior of many of these chemicals can result in co-elution.
The analyst must select columns, detectors and calibration procedures for the
specific analytes of interest in a study. Any listed chemical is a potential
method interference when it is not a target analyte.
Compound Name
8141A - 1
CAS Registry No.
OP Pesticides
Aspon,b
Azinphos-methyl
Azinphos-ethyT
Bolstar (Sulprofos)
Carbophenothion8
Chlorfenvinphos8
Chlorpyrifos
Chlorpyrifos methyl8
Coumaphos
Crotoxyphos8
Demeton-0°
Demeton-Sc
Diazinon
Dichlorofenthion8
Dichlorvos (DDVP)
Dicrotophos8
Dimethoate
Dioxathion8'0
Disulfoton
EPN
Ethion0
Ethoprop
Famphur8
Fenitrothion8
Fensulfothion
3244-90-4
86-50-0
2642-71-9
35400-43-2
786-19-6
470-90-6
2921-88-2
5598-13-0
56-72-4
7700-17-6
8065-48-3
8065-48-3
333-41-5
97-17-6
62-73-7
141-66-2
60-51-5
78-34-2
298-04-4
2104-64-5
563-12-2
13194-48-4
52-85-7
122-14-5
115-90-2
Revision 1
September 1994
-------
Compound Name
CAS Registry No.
Fonophos8
Fenthion
Leptophosa'd
Malathion
Merphos0
Mevinphos6
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Phosmet8
Phosphamidon8
Ronnel
Stirophos (Tetrachlorovinphos)
Sulfotepp
TEPPd
Terbufos8
Thionazina-b (Zinophos)
Tokuthionb (Protothiofos)
Trichlorfon8
Trichloronate6
944-22-9
55-38-9
21609-90-5
121-75-5
150-50-5
7786-34-7
6923-22-4
300-76-5
56-38-2
298-00-0
298-02-2
732-11-6
13171-21-6
299-84-3
22248-79-9
3689-24-5
21646-99-1
13071-79-9
297-97-2
34643-46-4
52-68-6
327-98-0
Industrial Chemicals
Hexamethylphosphoramide8 (HMPA)
Tri-o-cresylphosphatea'd (TOCP)
Triazine Herbicides (NPD only)
Atrazine8
Simazine8
680-31-9
78-30-8
1912-24-9
122-34-9
a This analyte has been evaluated using a 30-m column only.
b Production discontinued in the U.S., standard not readily available,
c Standards may have multiple components because of oxidation.
d Compound is extremely toxic or neurotoxic.
e Adjacent major/minor peaks can be observed due to cis/trans isomers.
1.2 A dual-column/dual-detector approach may be used for the analysis of
relatively clean extracts. Two 15- or 30-m x 0.53-mm ID fused-silica, open-
tubular columns of different polarities are connected to an injection tee and
each is connected to a detector. Analysts are cautioned regarding the use of a
dual column configuration when their instrument is subject to mechanical stress,
8141A - 2
Revision 1
September 1994
-------
when many samples are analyzed over a short time, or when extracts of
contaminated samples are analyzed.
1.3 Two detectors can be used for the listed OP chemicals. The FPD works
by measuring the emission of phosphorus- or sulfur-containing species. Detector
performance is optimized by selecting the proper optical filter and adjusting the
hydrogen and air flows to the flame. The NPD is a flame ionization detector with
a rubidium ceramic flame tip which enhances the response of phosphorus- and
nitrogen-containing analytes. The FPD is more sensitive and more selective, but
is a less common detector in environmental laboratories.
1.4 Table 1 lists method detection limits (MDLs) for the target analytes,
using 15-m columns and FPD, for water and soil matrices. Table 2 lists the
estimated quantitation limits (EQLs) for other matrices. MDLs and EQLs using 30-
m columns will be very similar to those obtained from 15-m columns.
1.5 The use of a 15-m column system has not been fully validated for the
determination of the following compounds. The analyst must demonstrate
chromatographic resolution of all analytes, recoveries of greater than 70
percent, with precision of no more than 15 percent RSD, before data generated on
the 15-m column system can be reported for these, or any additional, analytes:
Azinphos-ethyl Ethion Phosmet
Carbophenothion Famphur Phosphamidon
Chlorfenvinphos HMPA Terbufos
Dioxathion Leptophos TOCP
1.6 When Method 8141 is used to analyze unfamiliar samples, compound
identifications should be supported by confirmatory analysis. Sec. 8.0 provides
gas chromatograph/mass spectrometer (GC/MS) criteria appropriate for the
qualitative confirmation of compound identifications.
1.7 This method is restricted to use by, or under the supervision of,
analysts experienced in the use of capillary gas chromatography and in the
interpretation of chromatograms.
2.0 SUMMARY OF METHOD
2.1 Method 8141 provides gas chromatographic conditions for the detection
of ppb concentrations of organophosphorus compounds. Prior to the use of this
method, appropriate sample preparation techniques must be used. Water samples
are extracted at a neutral pH with methylene chloride by using a separatory
funnel (Method 3510) or a continuous liquid-liquid extractor (Method 3520).
Soxhlet extraction (Method 3540) or automated Soxhlet extraction (Method 3541)
using methylene chloride/acetone (1:1) are used for solid samples. Both neat and
diluted organic liquids (Method 3580, Waste Dilution) may be analyzed by direct
injection. Spiked samples are used to verify the applicability of the chosen
extraction technique to each new sample type. A gas chromatograph with a flame
photometric or nitrogen-phosphorus detector is used for this multiresidue
procedure.
8141A - 3 Revision 1
September 1994
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2.2 Organophosphorus esters and thioesters can hydrolyze under both acid
and base conditions. Samples prepared using acid and base partitioning
procedures are not suitable for analysis by Method 8141.
2.3 Ultrasonic Extraction (Method 3550) is not an appropriate sample
preparation method for Method 8141 and should not be used because of the
potential for destruction of target analytes during the ultrasonic extraction
process.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000, as well as to Sec. 1.1.
3.2 The use of Florisil Cleanup (Method 3620) for some of the compounds
in this method has been demonstrated to yield recoveries less than 85 percent and
is therefore not recommended for all compounds. Refer to Table 2 of Method 3620
for recoveries of organophosphorus compounds. Use of an FPD often eliminates the
need for sample cleanup. If particular circumstances demand the use of an
alternative cleanup procedure, the analyst must determine the elution profile and
demonstrate that the recovery of each analyte is not less than 85 percent.
3.3 The use of Gel Permeation Cleanup (GPC) (Method 3640) for sample
cleanup has been demonstrated to yield recoveries of less than 85 percent for
many method analytes because they elute before bis-(2-ethylhexyl) phthalate.
Method 3640 is therefore not recommended for use with this method, unless
analytes of interest are listed in Method 3640 or are demonstrated to give
greater than 85 percent recovery.
3.4 Use of a flame photometric detector in the phosphorus mode will
minimize interferences from materials that do not contain phosphorus or sulfur.
Elemental sulfur will interfere with the determination of certain
organophosphorus compounds by flame photometric gas chromatography. If Method
3660 is used for sulfur cleanup, only the tetrabutylammonium (TBA)-sulfite option
should be employed, since copper and mercury may destroy OP pesticides. The
stability of each analyte must be tested to ensure that the recovery from the
TBA-sulfite sulfur cleanup step is not less than 85 percent.
3.5 A halogen-specific detector (i.e., electrolytic conductivity or
microcoulometry) is very selective for the halogen-containing compounds and may
be used for the determination of Chlorpyrifos, Ronnel, Coumaphos, Tokuthion,
Trichloronate, Dichlorvos, EPN, Naled, and Stirophos only. Many of the OP
pesticides may also be detected by the electron capture detector (ECD); however,
the ECD is not as specific as the NPD or FPD. The ECD should only be used when
previous analyses have demonstrated that interferences will not adversely effect
quantitation, and that the detector sensitivity is sufficient to meet regulatory
1imits.
3.6 Certain analytes will coelute, particularly on 15-m columns (Table
3). If coelution is observed, analysts should (1) select a second column of
different polarity for confirmation, (2) use 30-m x 0.53-mm columns, or (3) use
0.25- or 0.32-mm ID columns. See Figures 1 through 4 for combinations of
compounds that do not coelute on 15-m columns.
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3.7 The following pairs coeluted on the DB-5/DB-210 30-m column pair:
DB-5 Terbufos/tri-o-cresyl phosphate
Naled/Simazine/Atrazine
Dichlorofenthion/Demeton-0
Trichloronate/Aspon
Bolstar/Stirophos/Carbophenothion
Phosphamidon/Crotoxyphos
Fensulfothion/EPN
DB-210 Terbufos/tri-o-cresyl phosphate
Dichlorofenthion/Phosphamidon
Chlorpyrifos, methyl/Parathion, methyl
Chlorpyrifos/Parathion, ethyl
Aspon/Fenthion
Demeton-0/Dimethoate
Leptophos/Azinphos-methyl
EPN/Phosmet
Famphur/Carbophenothi on
See Table 4 for retention times of these compounds on 30-m columns.
3.8 Analytical difficulties encountered for target analytes include:
3.8.1 Tetraethyl pyrophosphate (TEPP) is an unstable diphosphate
which is readily hydrolyzed in water and is thermally labile (TEPP
decomposes at 170°C). Care must be taken to minimize loss during GC
analysis and during sample preparation. Identification of bad standard
lots is difficult since the electron impact (El) mass spectrum of TEPP is
nearly identical to its major breakdown product, triethyl phosphate.
3.8.2 The water solubility of Dichlorvos (DDVP) is 10 g/L at 20°C,
and recovery is poor from aqueous solution.
3.8.3 Naled is converted to Dichlorvos (DDVP) on column by
debromination. This reaction may also occur during sample workup. The
extent of debromination will depend on the nature of the matrix being
analyzed. The analyst must consider the potential for debromination when
Naled is to be determined.
3.8.4 Trichlorfon rearranges and is dehydrochlorinated in acidic,
neutral, or basic media to form Dichlorvos (DDVP) and hydrochloric acid.
If this method is to be used for the determination of organophosphates in
the presence of Trichlorfon, the' analyst should be aware of the
possibility of rearrangement to Dichlorvos to prevent misidentification.
3.8.5 Demeton (Systox) is a mixture of two compounds; 0,0-diethyl
0-[2-(ethylthio)ethyl]phosphorothioate (Demeton-0) and 0,0-diethyl S-[2-
(ethylthio)ethyl]phosphorothioate (Demeton-S). Two peaks are observed in
all the chromatograms corresponding to these two isomers. It is
recommended that the early eluting compound (Demeton-S) be used for
quantitation.
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3.8.6 Dioxathion is a single-component pesticide. However, several
extra peaks are observed in the chromatograms of standards. These peaks
appear to be the result of spontaneous oxygen-sulfur isomerization.
Because of this, Dioxathion is not included in composite standard
mixtures.
3.8.7 Merphos (tributyl phosphorotrithioite) is a single-component
pesticide that is readily oxidized to its phosphorotrithioate (Merphos
oxone). Chromatographic analysis of Merphos almost always results two
peaks (unoxidized Merphos elutes first). As the relative amounts of
oxidation of the sample and the standard are probably different,
quantitation based on the sum of both peaks may be most appropriate.
3.8.8 Retention times of some analytes, particularly Monocrotophos,
may increase with increasing concentrations in the injector. Analysts
should check for retention time shifts in highly contaminated samples.
3.8.9 Many analytes will degrade on reactive sites in the
chromatographic system. Analysts must ensure that injectors and splitters
are free from contamination and are silanized. Columns should be
installed and maintained properly.
3.8.10 Performance of chromatographic systems will degrade with
time. Column resolution, analyte breakdown and baselines may be improved
by column washing (Sec. 7). Oxidation of columns is not reversible.
3.9 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to discrete
artifacts or elevated baselines in gas chromatograms. All these materials must
be routinely demonstrated to be free from interferences under the conditions of
the analysis by analyzing reagent blanks (Sec. 8.0).
3.10 NP Detector interferences: Triazine herbicides, such as Atrazine
and Simazine, and other nitrogen-containing compounds may interfere.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph: An analytical system complete with a gas
chromatograph suitable for on-column or spl it/splitless injection, and all
required accessories, including syringes, analytical columns, gases, suitable
detector(s), and a recording device. The analyst should select the detector for
the specific measurement application, either the flame photometric detector or
the nitrogen-phosphorus detector. A data'system for measuring peak areas and
dual display of chromatograms is highly recommended.
4.1.1 Capillary Columns (0.53-mm, 0.32-mm, or 0.25-mm ID x 15-m or
30-m length, depending on the resolution required). Columns of 0.53-mm ID
are recommended for most environmental and waste analysis applications.
Dual-column, single-injector analysis requires columns of equal length and
bore. See Sec. 3.0 and Figures 1 through 4 for guidance on selecting the
proper length and diameter for the column(s).
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4.1.1.1 Column 1 - 15- or 30-m x 0.53-mm wide-bore
capillary column, l.Q-/j,m film thickness, chemically bonded with 50%
trifluoropropyl polysiloxane, 50% methyl polysiloxane (DB-210), or
equivalent.
4.1.1.2 Column 2 - 15- or 30-m x 0.53-mm wide-bore
capillary column, 0.83-/zm film thickness, chemically bonded with
35% phenyl methyl polysiloxane (DB-608, SPB-608, RTx-35), or
equivalent.
4.1.1.3 Column 3 - 15- or 30-m x 0.53-mm wide-bore
capillary column, 1.0 p,m film thickness, chemically bonded with 5%
phenyl polysiloxane, 95% methyl polysiloxane (DB-5, SPB-5, RTx-5),
or equivalent.
4.1.1.4 Column 4 - 15- or 30-m x 0.53-mm ID fused-silica
open-tubular column, chemically bonded with methyl polysiloxane
(DB-1, SPB-1, or equivalent), 1.0-/Lim or 1.5-/um film thickness.
4.1.1.5 (optional) Column rinsing kit: Bonded-phase column
rinse kit (J&W Scientific, Catalog no. 430-3000 or equivalent).
4.1.2 Splitter: If a dual-column, single-injector configuration is
used, the open tubular columns should be connected to one of the following
splitters, or equivalent:
4.1.2.1 Splitter 1 - J&W Scientific press-fit Y-shaped
glass 3-way union splitter (J&W Scientific, Catalog no. 705-0733).
4.1.2.2 Splitter 2 - Supelco 8-in glass injection tee,
deactivated (Supelco, Catalog no. 2-3665M).
4.1.2.3 Splitter 3 - Restek Y-shaped fused-silica
connector (Restek, Catalog no. 20405).
4.1.3 Injectors:
4.1.3.1 Packed column, 1/4-in injector port with hourglass
liner are recommended for 0.53-mm column. These injector ports can
be fitted with splitters (Sec. 4.0) for dual-column analysis.
4.1.3.2 Split/splitless capillary injectors operated in
the split mode are required for 0.25-mm and 0.32-mm columns.
4.1.4 Detectors:
4.1.4.1 Flame Photometric Detector (FPD) operated in the
phosphorus-specific mode is recommended.
4.1.4.2 Nitrogen-Phosphorus Detector (NPD) operated in the
phosphorus-specific mode is less selective but can detect triazine
herbicides.
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4.1.4.3 Halogen-Specific Detectors (electrolytic
conductivity or microcoulometry) may be used only for a limited
number of halogenated or sulfur-containing analytes (Sec. 3.0).
4.1.4.4 Electron-capture detectors may be used for a
limited number of analytes (Sec. 3.0).
4.1.5 Data system:
4.1.5.1 Data system capable of presenting chromatograms,
retention time, and peak integration data is strongly recommended.
4.1.5.2 Use of a data system that allows storage of raw
chromatographic data is strongly recommended.
5.0 REAGENTS
5.1 Solvents
5.1.1 Isooctane, (CH3)3CCH2CH(CH3)2 - Pesticide quality or equivalent.
5.1.2 Hexane, C6H14 - Pesticide quality or equivalent.
5.1.3 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.1.4 Tetrahydrofuran (THF), C4H80 - Pesticide quality or equivalent
(for triazine standards only).
5.1.5 Methyl tert-butyl-ether (MTBE), CH3Ot-C4H9 - Pesticide quality
or equivalent (for triazine standards only).
5.2 Stock standard solutions (1000 mg/L): Can be prepared from pure
standard materials or can be purchased as certified solutions.
5.2.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure compounds. Dissolve the compounds in suitable mixtures
of acetone and hexane and dilute to volume in a 10-mL volumetric flask.
If compound purity is 96 percent or greater, the weight can be used
without correction to calculate the concentration of the stock standard
solution. Commercially prepared stock standard solutions can be used at
any concentration if they are certified by the manufacturer or by an
independent source.
5.2.2 Both Simazine and Atrazine have low solubilities in hexane.
If Simazine and Atrazine standards are required, Atrazine should be
dissolved in MTBE, and Simazine should be dissolved in acetone/MTBE/THF
(1:3:1).
5.2.3 Composite stock standard: This standard can be prepared from
individual stock solutions. The analyst must demonstrate that the
individual analytes and common oxidation products are resolved by the
chromatographic system. For composite stock standards containing less
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than 25 components, take exactly 1 ml of each individual stock solution at
1000 mg/L, add solvent, and mix the solutions in a 25-mL volumetric flask.
For example, for a composite containing 20 individual standards, the
resulting concentration of each component in the mixture, after the volume
is adjusted to 25 ml, will be 40 mg/L. This composite solution can be
further diluted to obtain the desired concentrations. Composite stock
standards containing more than 25 components are not recommended.
5.2.4 Store the standard solutions (stock, composite, calibration,
internal, and surrogate) at 4°C in Teflon-sealed containers in the dark.
All standard solutions should be replaced after two months, or sooner if
routine QC (Sec. 8.0) indicates a problem. Standards for easily
hydrolyzed chemicals including TEPP, Methyl Parathion, and Merphos should
be checked every 30 days.
5.2.5 It is recommended that lots of standards be subdivided and
stored in small vials. Individual vials should be used as working
standards to minimize the potential for contamination or hydrolysis of the
entire lot.
5.3 Calibration standards should be prepared at a minimum of five
concentrations by dilution of the composite stock standard with isooctane or
hexane. The concentrations should correspond to the expected range of
concentrations found in real samples and should bracket the linear range of the
detector. Organophosphorus calibration standards should be replaced after one
or two months, or sooner if comparison with check samples or historical data
indicates that there is a problem. Laboratories may wish to prepare separate
calibration solutions for the easily hydrolyzed standards identified above.
5.4 Internal standard: Internal standards should only be used on well-
characterized samples by analysts experienced in the technique. Use of internal
standards is complicated by co-elution of some OP pesticides and by the
differences in detector response to dissimilar chemicals.
5.4.1 FPD response for organophosphorus compounds is enhanced by the
presence of sulfur atoms bonded to the phosphorus atom. It has not been
established that a thiophosphate can be used as an internal standard for
an OP with a different numbers of sulfur atoms (e.g., phosphorothioates
[P=S] as an internal standard for phosphates [P04]) or phosphorodithioates
[P=S2]).
5.4.2 If internal standards are to be used, the analyst must select
one or more internal standards that are similar in analytical behavior to
the compounds of interest. The analyst must further demonstrate that the
measurement of the internal standard is not affected by method or matrix
interferences.
5.4.3 When 15-m columns are used, it may be difficult to fully
resolve internal standards from target analytes, method interferences and
matrix interferences. The analyst must demonstrate that the measurement
of the internal standard is not affected by method or matrix
interferences.
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5.4.4 The following NPD internal standard has been used for a 30-m
column pair. Make a solution of 1000 mg/L of l-bromo-2-nitrobenzene. For
spiking, dilute this solution to 5 mg/L. Use a spiking volume of 10 /iL/mL
of extract. The spiking concentration of the internal standards should be
kept constant for all samples and calibration standards. Since its FPD
response is small, l-bromo-2-nitrobenzene is not an appropriate internal
standard for that detector. No FPD internal standard is suggested.
5.5 Surrogate standard spiking solutions - The analyst should monitor the
performance of the extraction, cleanup (when used), and analytical system, and
the effectiveness of the method in dealing with each sample matrix, by spiking
each sample, standard, and blank with one or two surrogates (e.g.,
organophosphorus compounds not expected to be present in the sample). If
multiple analytes are to be measured, two surrogates (an early and a late eluter)
are recommended. Deuterated analogs of analytes are not appropriate surrogates
for gas chromatographic/FPD/NPD analysis.
5.5.1 If surrogates are to be used, the analyst must select one or
more compounds that are similar in analytical behavior to the compounds of
interest. The analyst must further demonstrate that the measurement of a
surrogate is not affected by method or matrix interferences. General
guidance on the selection and use of surrogates is provided in Sec. 5.0 of
Method 3500.
5.5.2 Tributyl phosphate and triphenyl phosphate are used as FPD and
NPD surrogates. A volume of 1.0 mL of a 1-^g/L spiking solution (1 ng of
surrogate) is added to each water sample and each soil/sediment sample.
If there is a co-elution problem, 4-chloro-3-nitrobenzo-trifluoride has
also been used as an NPD-only surrogate.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to Chapter Four, "Organic Analytes,"
Sec. 4.0.
6.2 Extracts are to be refrigerated at 4°C and analyzed within 40 days
of extraction. See Sec. 5.2.4 for storage of standards.
6.3 Organophosphorus esters will hydrolyze under acidic or basic
conditions. Adjust samples to a pH of 5 to 8 using sodium hydroxide or sulfuric
acid solution as soon as possible after sample collection. Record the volume
used.
6.4 Even with storage at 4°C and use of mercuric chloride as a
preservative, most OPs in groundwater samples collected for the national
pesticide survey degraded within a 14-day period. Begin sample extraction within
7 days of collection.
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7.0 PROCEDURE
7.1 Extraction and cleanup:
7.1.1 Refer to Chapter Two and Method 8140 for guidance on choosing
the appropriate extraction procedure. In general, water samples are
extracted at a neutral pH with methylene chloride, using either Method
3510 or 3520. Solid samples are extracted using either Method 3540 or
3541 with methylene chloride/acetone (1:1 v/v) or hexane/acetone (1:1 v/v)
as the extraction solvent. Method 3550 is an inappropriate extraction
technique for the target analytes of this method (See Sec. 2.3).
7.1.2 Extraction and cleanup procedures that use solutions below pH
4 or above pH 8 are not appropriate for this method.
7.1.3 If required, the samples may be cleaned up using the Methods
presented in Chapter Four, Sec. 2. Florisil Column Cleanup (Method 3620)
and Sulfur Cleanup (Method 3660, TBA-sulfite option) may have particular
application for OPs. Gel Permeation Cleanup (Method 3640) should not
generally be used for OP pesticides.
7.1.3.1 If sulfur cleanup by Method 3660 is required, do
not use mercury or copper.
7.1.3.2 GPC may only be employed if all target OP
pesticides are listed as analytes of Method 3640, or if the
laboratory has demonstrated a recovery of greater than 85 percent
for target OPs at a concentration not greater than 5 times the
regulatory action level. Laboratories must retain data
demonstrating acceptable recovery.
7.1.4 Prior to gas chromatographic analysis, the extraction solvent
may be exchanged to hexane. The analyst must ensure quantitative transfer
of the extract concentrate. Single-laboratory data indicate that samples
should not be transferred with 100-percent hexane during sample workup, as
the more polar organophosphorus compounds may be lost. Transfer of
organophosphorus esters is best accomplished using methylene chloride or
a hexane/acetone solvent mixture.
7.1.5 Methylene chloride may be used as an injection solvent with
both the FPD and the NPD.
NOTE: Follow manufacturer's instructions as to suitability of using
methylene chloride with any specific detector.
7.2 Gas chromatographic conditions:
7.2.1 Four 0.53-mm ID capillary columns are suggested for the
determination of organophosphates by this method. Column 1 (DB-210 or
equivalent) and Column 2 (SPB-608 or equivalent) of 30-m length are
recommended if a large number of organophosphorus analytes are to be
determined. If superior chromatographic resolution is not required, 15-m
lengths columns may be appropriate. Operating conditions for 15-m columns
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are listed in Table 5. Operating conditions for 30-m columns are listed
in Table 6.
7.2.2 Retention times for analytes on each set of columns are
presented in Tables 3 and 4.
7.3 Calibration: Refer to Method 8000 for proper calibration techniques.
Use Table 5 and Table 6 for establishing the proper operating parameters for the
set of columns being employed in the analyses.
7.4 Gas chromatographic analysis: Method 8000 provides instructions on
the analysis sequence, appropriate dilutions, establishing daily retention time
windows and identification criteria.
7.4.1 Automatic injections of 1 /uL are recommended. Hand injections
of no more than 2 /it may be used if the analyst demonstrates quantitation
precision of < 10 percent relative standard deviation. The solvent flush
technique may be used if the amount of solvent is kept at a minimum. If
the internal standard calibration technique is used, add 10 /iL of internal
standard to each mL of sample prior to injection. Chromatograms of the
target organophosphorus compounds are shown in Figures 1 through 4.
7.4.2 Figures 5 and 6 show chromatograms with and without Simazine,
Atrazine, and Carbophenothion on 30-m columns.
7.5 Record the sample volume injected to the nearest 0.05 jiL and the
resulting peak sizes (in area units or peak heights). Using either the internal
or external calibration procedure (Method 8000), determine the identity and
quantity of each component peak in the sample chromatogram which corresponds to
the compounds used for calibration purposes. See Method 8000 for calculation
equations.
7.5.1 If peak detection and identification is prevented by the
presence of interferences, the use of an FPD or further sample cleanup is
required. Before using any cleanup procedure, the analyst must process a
series of calibration standards through the procedure to establish elution
patterns and to determine recovery of target compounds. The absence of
interference from reagents must be demonstrated by routine processing of
reagent blanks through the chosen cleanup procedure. Refer to Sec. 3.0
for interferences.
7.5.2 If the responses exceed the linear range of the system, dilute
the extract and reanalyze. It is recommended that extracts be diluted so
that all peaks are on scale. Overlapping peaks are not always evident
when peaks are off-scale. Computer reproduction of chromatograms,
manipulated to ensure all peaks are on scale over a 100-fold range, are
acceptable if linearity is demonstrated. Peak height measurements are
recommended over peak area integration when overlapping peaks cause errors
in area integration.
7.5.3 If the peak response is less than 2.5 times the baseline noise
level, the validity of the quantitative result may be questionable. The
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analyst should consult with the source of the sample to determine whether
further concentration of the sample extract is warranted.
7.5.4 If partially overlapping or coeluting peaks are found, change
columns or try a GC/MS technique. Refer to Sec. 8.0 and Method 8270.
7.6 Suggested chromatograph maintenance: Corrective measures may require
any one or more of the following remedial actions.
7.6.1 Refer to Method 8000 for general information on the
maintenance of capillary columns and injectors.
7.6.2 Splitter connections: For dual columns which are connected
using a press-fit Y-shaped glass splitter or a Y-shaped fused-silica
connector (J&W Scientific, Restek, or equivalent), clean and deactivate
the splitter. Reattach the columns after cleanly cutting off at least one
foot from the injection port side of the column using a capillary cutting
tool or scribe. The accumulation of high boiling residues can change
split ratios between dual columns and thereby change calibration factors.
7.6.3 Columns will be damaged permanently and irreversibly by
contact with oxygen at elevated temperature. Oxygen can enter the column
during a septum change, when oxygen traps are exhausted, through neoprene
diaphragms of regulators, and through leaks in the gas manifold. Polar
columns including the DB-210 and DB-608 are more prone to oxidation.
Oxidized columns will exhibit baselines that rise rapidly during
temperature programming.
7.6.4 Peak tailing for all components will be exacerbated by dirty
injectors, pre-columns, and glass "Y"s. Additionally, cleaning of this
equipment (or replacement/clipping, as appropriate) will greatly reduce
the peak tailing. Components such as Fensulfothion, Naled, Azinphos-
methyl, and Dimethoate are very good indicators of system performance.
7.7 Detector maintenance:
7.7.1 Older FPDs may be susceptible to stray light in the
photomultiplier tube compartment. This stray light will decrease the
sensitivity and the linearity of the detector. Analysts can check for
leaks by initiating an analysis in a dark room and turning on the lights.
A shift in the baseline indicates that light may be leaking into the
photomultiplier tube compartment. Additional shielding should be applied
to eliminate light leaks and minimize stray light interference.
7.7.2 The bead of the NPD will become exhausted with time, which
will decrease the sensitivity and the selectivity of the detector. The
collector may become contaminated which decreased detector sensitivity.
7.7.3 Both types of detectors use a flame to generate a response.
Flow rates of air and hydrogen should be optimized to give the most
sensitive, linear detector response for target analytes.
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8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Include a mid-level check standard after each group of 10 samples in the analysis
sequence. Quality control to validate sample extraction is covered in Method
3500 and in the extraction method utilized. If extract cleanup was performed,
follow the QC in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method 8000.
8.3 GC/MS confirmation
8.3.1 GC/MS techniques should be judiciously employed to support
qualitative identifications made with this method. Follow the GC/MS
operating requirements specified in Method 8270.
8.3.2 When available, chemical ionization mass spectra may be
employed to aid in the qualitative identification process.
8.3.3 To confirm an identification of a compound, the background-
corrected mass spectrum of the compound must be obtained from the sample
extract and must be compared with a mass spectrum from a stock or
calibration standard analyzed under the same chromatographic conditions.
At least 25 ng of material should be injected into the GC/MS. The
following criteria must be met for qualitative confirmation:
8.3.3.1 The qualitative identification of compounds
determined by this method is based on retention time, and on
comparison of the sample mass spectrum, after background correction,
with characteristic ions in a reference mass spectrum. The
reference mass spectrum must be generated by the laboratory using
the conditions of this method. The characteristic ions from the
reference mass spectrum are defined to be the three ions of greatest
relative intensity, or any ions over 30% relative intensity if less
than three such ions occur in the reference spectrum. Compounds
should be identified as present when the criteria below are met.
8.3.3.1.1 The intensities of the characteristic ions
of a compound maximize in the same scan or within one scan of
each other. Selection of a peak by a data system target
compound search routine where the search is based on the
presence of a target chromatographic peak containing ions
specific for the target compound at a compound-specific
retention time will be accepted as meeting this criterion.
8.3.3.1.2 The RRT of the sample component is within
± 0.06 RRT units of the RRT of the standard component.
8.3.3.1.3 The relative intensities of the
characteristic ions agree within 30% of the relative
intensities of these ions in the reference spectrum.
(Example: For an ion with an abundance of 50% in the
reference spectrum, the corresponding abundance in a sample
spectrum can range between 20% and 80%.)
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8.3.3.1.4 Structural isomers that produce very similar
mass spectra should be identified as individual isomers if
they have sufficiently different GC retention times.
Sufficient GC resolution is achieved if the height of the
valley between two isomer peaks is less than 25% of the sum of
the two peak heights. Otherwise, structural isomers are
identified as isomeric pairs.
8.3.3.1.5 Identification is hampered when sample
components are not resolved chromatographically and produce
mass spectra containing ions contributed by more than one
analyte. When gas chromatographic peaks obviously represent
more than one sample component (i.e., a broadened peak with
shoulder(s) or a valley between two or more maxima),
appropriate selection of analyte spectra and background
spectra is important. Examination of extracted ion current
profiles of appropriate ions can aid in the selection of
spectra, and in qualitative identification of compounds. When
analytes coelute (i.e., only one chromatographic peak is
apparent), the identification criteria can be met, but each
analyte spectrum will contain extraneous ions contributed by
the coeluting compound.
8.3.3.2 For samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the purpose of the
analyses being conducted. Computer generated library search
routines should not use normalization routines that would
misrepresent the library or unknown spectra when compared to each
other. For example, the RCRA permit or waste delisting requirements
may require the reporting of nontarget analytes. Only after visual
comparison of sample spectra with the nearest library searches will
the mass spectral interpretation specialist assign a tentative
identification. Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should be present in
the sample spectrum.
(2) The relative intensities of the major ions should agree
within + 20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%.)
(3) Molecular ions present in the reference spectrum should
be present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible background
contamination or presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible subtraction from the
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sample spectrum because of background contamination or coeluting
peaks. Data system library reduction programs can sometimes create
these discrepancies.
8.3.4 Where available, chemical ionization mass spectra may be
employed to aid in the qualitative identification process because of the
extensive fragmentation of organophosphorus pesticides during electron
impact MS processes.
8.3.5 Should the MS procedure fail to provide satisfactory results,
additional steps may be taken before reanalysis. These steps may include
the use of alternate packed or capillary GC columns or additional sample
cleanup.
9.0 METHOD PERFORMANCE
9.1 Estimated MDLs and associated chromatographic conditions for water
and clean soil (uncontaminated with synthetic organics) are listed in Table 1.
As detection limits will vary with the particular matrix to be analyzed, guidance
for determining EQLs is given in Table 2. Recoveries for several method analytes
are provided in Tables 5, 6, and 7.
10.0 REFERENCES
1. Taylor, V.; Hickey, D.M.; Marsden, P.J. "Single Laboratory Validation of
EPA Method 8140"; U.S. Environmental Protection Agency, Environmental
Monitoring Systems Laboratory, Office of Research and Development, Las
Vegas, NV, 1987; EPA-600/4-87-009.
2. Pressley, T.A; Longbottom, J.E. "The Determination of Organophosphorus
Pesticides in Industrial and Municipal Wastewater: Method 614"; U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, OH, 1982; EPA-600/4-82-004.
3. "Analysis of Volatile Hazardous Substances by GC/MS: Pesticide Methods
Evaluation"; Letter Reports 6, 12A, and 14 to the U.S. Environmental
Protection Agency on Contract 68-03-2697, 1982.
4. "Method 622, Organophosphorus Pesticides"; U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati, OH
45268.
5. Lopez-Avila, V.; Baldin, E.; Benedicto, J; Milanes, J.; Beckert, W. F.
"Application of Open-Tubular Columns to SW-846 GC Methods"; final report
to the U.S. Environmental Protection Agency on Contract 68-03-3511; Mid-
Pacific Environmental Laboratory, Mountain View, CA, 1990.
6. Hatcher, M.D.; Hickey, D.M.; Marsden, P.O.; and Betowski, L.D.;
"Development of a GC/MS Module for RCRA Method 8141"; final report to the
U.S. EPA Environmental Protection Agency on Contract 68-03-1958; S-Cubed,
San Diego, CA, 1988.
8141A - 16 Revision 1
September 1994
-------
7. Chau, A.S.Y.; Afghan, B.K. Analysis of Pesticides in Water; "Chlorine and
Phosphorus-Containing Pesticides"; CRC: Boca Raton, FL, 1982, Vol. 2, pp
91-113, 238.
8. Hild, J.; Schulte, E; Thier, H.P. "Separation of Organophosphorus
Pesticides and Their Metabolites on Glass-Capillary Columns";
Chromatographia, 1978, 11-17.
9. Luke, M.A.; Froberg, J.E.; Doose, G.M.; Masumoto, H.T. "Improved
Multiresidue Gas Chromatographic Determination of Organophosphorus,
Organonitrogen, and Organohalogen Pesticides in Produce, Using Flame
Photometric and Electrolytic Conductivity Detectors"; J. Assoc, Off. Anal.
Chem. 1981, 1187, 64.
10. Sherma, J.; Berzoa, M. "Analysis of Pesticide Residues in Human and
Environmental Samples"; U.S. Environmental Protection Agency, Research
• Triangle Park, NC; EPA-600/8-80-038.
11. Desmarchelier, J.M.; Wustner, D.A.; Fukuto, T.R. "Mass Spectra of
Organophosphorus Esters and Their Alteration Products"; Residue Reviews,
1974, pp 63, 77.
12. Munch, D.J. and Frebis, C.P., "Analyte Stability Studies Conducted during
the National Pesticide Survey", ES & T, 1992, vol 26, 921-925.
13. T.L. Jones, "Organophosphorus Pesticide Standards: Stability Study", EMSL-
LV Research Report, EPA 600/X-92/040, April, 1992
14. Kotronarou, A., et al., "Decomposition of Parathion in Aqueous Solution by
Ultrasonic Irradiation," ES&T, 1992, Vol. 26, 1460-1462.
8141A - 17 Revision 1
September 1994
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TABLE 1
METHOD DETECTION LIMITS IN A WATER AND A SOIL
MATRIX USING 15-m COLUMNS AND A FLAME PHOTOMETRIC DETECTOR
Compound
Reagent
Water (3510)"
Soil (3540)
Azinphos-methyl
Bolstar (Sulprofos)
Chlorpyrifos
Coumaphos
Demeton, -0, -S
Diazinon
Dichlorvos (DDVP)
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfothion
Fenthion
Malathion
Merphos
Mevinphos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotepp
TEPPC
Tetrachlorovinphos
Tokuthion (Protothiofos)0
Trichloronatec
0.10
0.07
0.07
0.20
0.12
0.20
0.80
0.26
0.07
0.04
0.20
0.08
0.08
0.11
0.20
0.50
0.50
0.06
0.12
0.04
0.07
0.07
0.80
0.80
0.07
0.80
5.0
3.5
5.0
10.0
6.0
10.0
40.0
13.0
3.5
2.0
10.0
4.0
5.0
5.5
10.0
25.0
25.0
3.0
6.0
2.0
3.5
3.5
40.0
40.0
5.5
40.0
Sample extracted using Method 3510, Separatory Funnel Liquid-Liquid
Extraction.
Sample extracted using Method 3540, Soxhlet Extraction.
Purity of these standards not established by the EPA Pesticides and
Industrial Chemicals Repository, Research Triangle Park, NC.
8141A - 18
Revision 1
September 1994
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TABLE 2
DETERMINATION OF ESTIMATED QUANTITATION LIMITS
(EQLs) FOR VARIOUS MATRICES8
Matrix Factor
Ground water (Methods 3510 or 3520) 10
Low-concentration soil by Soxhlet and no cleanup 10
Non-water miscible waste (Method 3580) 1000
a EQL = [Method detection limit (see Table 1)] X [Factor found in this table].
For non-aqueous samples, the factor is on a wet-weight basis. Sample EQLs are
highly matrix dependent. The EQLs to be determined herein are for guidance and
may not always be achievable.
b Multiply this factor times the reagent water MDL in Table 1.
c Multiply this factor times the soil MDL in Table 1.
8141A - 19 Revision 1
September 1994
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TABLE 3.
RETENTION TIMES FOR METHOD 8141A ANALYTES
EMPLOYING 15-m COLUMNS
TEPP
Dichlorvos (DDVP)
Mevinphos
Demeton, -0 and -S
Ethoprop
Naled
Phorate
Monochrotophos
Sulfotepp
Dimethoate
Disulfoton
Diazinon
Merphos
Ronnel
Chlorpyrifos
Malathion
Parathion, methyl
Parathion, ethyl
Trichloronate
Tetrachlorovinphos
Tokuthion (Protothiofos)
Fensulfothion
Bolstari (Sulprofos)
Famphur"
EPN
Azinphos-methyl
Fenthion
Coumaphos
Method 8141A has not been fully
Initial temperature
Initial time
Program 1 rate
Program 1 final temp.
Program 1 hold
Program 2 rate
Program 2 final temp.
Program 2 hold
Capi
Compound
9.63
14.18
18.31
18.62
19.94
20.04
20.11
20.64
23.71
24.27
26.82
29.23
31.17
31.72
31.84
31.85
32.19
34.65
34.67
35.85
36.34
36.40
38.34
38.83
39.83
llary Column
DB-5
6.44
7.91
12.88
15.90
16.48
19.01
17.52
20.11
18.02
20.18
19.96
20.02
21.73
22.98
26.88
28,78
23.71
27.62
28.41
32.99
24.58
35.20
35.08
36.93
37.80
38.04
29.45
38.87
SPB-608
5.12
12.79
18.44
17.24
18.67
17.40
18.19
31.42
19.58
27.96
20.66
19.68
32.44
23.19
25.18
32.58
32.17
33.39
29.95
33.68
39.91
36.80
37.55
37.86
36.71
37.24
28.86
39.47
DB-210
10.66
19.35
36.74
val idated- for Famphur.
130°C
3 minutes
5°C/min
180°C
10 minutes
2°C/min
250°C
15 minutes
50°C
1 minute
5°C/min
140°C
10 minutes
10°C/min
240°C
10 minutes
50°C
1 minute
5°C/min
140°C
10 minutes
10°C/min
240°C
10 minutes
8141A - 20
Revision 1
September 1994
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TABLE 4.
RETENTION TIMES FOR METHOD 8141A ANALYTES
EMPLOYING 30-m COLUMNS8
Compound
DB-5
RT (min)
DB-210 DB-608
DB-1
Trimethyl phosphate
Dichlorvos (DDVP)
Hexamethylphosphoramide
Trichlorfon
TEPP
Thionazin
Mevinphos
Ethoprop
Diazinon
Sulfotepp
Terbufos
Tri-o-cresyl phosphate
Naled
Phorate
Fonophos
Disulfoton
Merphos
Oxidized Merphos
Dichlorofenthion
Chlorpyrifos, methyl
Ronnel
Chlorpyrifos
Trichloronate
Aspon
Fenthion
Demeton-S
Demeton-0
Monocrotophosc
Dimethoate
Tokuthion
Malathion
Parathion, methyl
Fenithrothion
Chlorfenvinphos
Parathion, ethyl
Bolstar
Stirophos
Ethion
b
7.45
b
11.22
b
12.32
12.20
12.57
13.23
13.39
13.69
13.69
14.18
12.27
14.44
14.74
14.89
20.25
15.55
15.94
16.30
17.06
17.29
17.29
17.87
11.10
15.57
19.08
18.11
19.29
19.83
20.15
20 .£3
21.07
21.38
22.09
22.06
22.55
2.36
6.99
7.97
11.63
13.82
24.71
10.82
15.29
18.60
16.32
18.23
18.23
15.85
16.57
18.38
18.84
23.22
24.87
20.09
20.45
21.01
22.22
22.73
21.98
22.11
14.86
17.21
15.98
17.21
24.77
21.75
20.45
21.42
23.66
22.22
27.57
24.63
27.12
6.56
12.69
11.85
18.69
24.03
20.04
22.97
18.92
20.12
23.89
35.16
26.11
26.29
27.33
29.48
30.44
29.14
21.40
17.70
19.62
20.59
33.30
28.87
25.98
32.05
29.29
38.10
33.40
37.61
10.43
14.45
18.52
21.87
19.60
18.78
19.65
21.73
26.23
23.67
24.85
24.63
20.18
19.3
19.87
27.63
24.57
22.97
24.82
29.53
26.90
(continued)
8141A - 21
Revision 1
September 1994
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TABLE 4. (Continued)
Compound
DB-5
RT (min)
DB-210 DB-608 DB-1
Phosphamidon
Crotoxyphos
Leptophos
Fensulfothion
EPN
Phosmet
Azinphos-methyl
Azinphos-ethyl
Famphur
Coumaphos
Atrazine
Simazine
Carbophenothion
Dioxathion
Trithion methyl
Dicrotophos
Internal Standard
l-Bromo-2-nitrobenzene
Surrogates
Tributyl phosphate
Triphenyl phosphate
4-C1-3-nitrobenzotrifluoride
22.77
22.77
24.62
27.54
27.58
27.89
28.70
29.27
29.41
33.22
13.98
13.85
22.14
d
8.11
5.73
20.09
23.85
31.32
26.76
29.99
29.89
31.25
32.36
27.79
33.64
17.63
17.41
27.92
9.07
5.40
25.88
32.65
44.32
36.58
41.94
41.24
43.33
45.55
38.24
48.02
22.24
36.62
19.33
11.1
33.4
28.58
31.60
32.33
34.82
a The GC operating conditions were as follows:
DB-5 and DB-210 - 30-m x 0.53-mm ID column, DB-5 (1.50- m film thickness) and
DB-210 (1.0- m film thickness). Both connected to a press-fit Y-shaped inlet
splitter. Temperature program: 120°C (3-min hold) to 270"C (10-min hold) at
5°C/min; injector temperature 250°C; detector temperature 300°C; bead temperature
400"C; bias voltage 4.0; hydrogen gas pressure 20 psi; helium carrier gas 6
mL/min; helium makeup gas 20 mL/min.
DB-608 - 30-m x 0.53-mm ID column, DB-608 (1.50- m film thickness) installed in
an 0.25-in packed-column inlet. Temperature program: 110°C (0.5-min hold) to
250°C (4-min hold) at 3°C/min; injector temperature 250°C; helium carrier gas 5
mL/min; flame photometric detector.
DB-1 30-m x 0.32-mm ID column, DB-1 (0.25- m film thickness) split/splitless with
head pressure of 10 psi, split valve closure at 45 sec, injector temp. 250°C,
50°C (1-min hold) to 280°C (2-min hold) at 6°C/min, mass spectrometer full scan
35-550 amu.
b Not detected at 20 ng per injection.
c Retention times may shift to longer times with larger amounts injected (shifts
of over 30 seconds have been observed, Hatcher et. al.)
d Shows multiple peaks; therefore, not included in the composite.
8141A - 22
Revision 1
September 1994
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TABLE 5.
PERCENT RECOVERY OF 27 ORGANOPHOSPHATES BY SEPARATORY FUNNEL EXTRACTION
Compound
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
126
134
7
103
33
136
80
NR
48
113
82
84
NR
127
NR
NR
NR
NR
101
NR
94
67
87
96
79
NR
NR
Percent Recovery
Medium
143 + 8
141 + 8
89 + 6
90 + 6
67 + 11
121 + 9.5
79 + 11
47 + 3
92 + 7
125 + 9
90 + 6
82 + 12
48 + 10
92 + 6
79
NR
18 + 4
NR
94 + 5
46 + 4
77 + 6
97 + 5
85 + 4
55 + 72
90 + 7
45 + 3
35
High
101
101
86
96
74
82
72
101
84
97
80
96
89
86
81
55
NR
NR
86
44
73
87
83
63
80
90
94
NR = Not recovered.
8141A - 23
Revision 1
September 1994
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TABLE 6.
PERCENT RECOVERY OF 27 ORGANOPHOSPHATES BY CONTINUOUS LIQUID-LIQUID EXTRACTION
Percent Recovery
Compound
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Famphur
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
NR
NR
13
94
38
NR
81
NR
94
NR
39
._
90
8
105
NR
NR
NR
NR
106
NR
84
82
40
39
56
132
NR
Medium
129
126
82 + 4
79 + 1
23 + 3
128 + 37
32 + 1
10 + 8
69 + 5
104 + 18
76 + 2
63 + 15
67 + 26
32 + 2
87 + 4
80
87
30
NR
81 + 1
50 + 30
63 + 3
83 + 7
77 + 1
18 + 7
70 + 14
32 + 14
NR
High
122
128
88
89
41
118
74
102
81
119
83
--
90
86
86
79
49
1
74
87
43
74
89
85
70
83
90
21
NR = Not recovered.
8141A - 24
Revision 1
September 1994
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TABLE 7.
PERCENT RECOVERY OF 27 ORGANOPHOSPHATES BY SOXHLET EXTRACTION
Percent Recovery
Compound
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
156
102
NR
93
169
87
84
NR
78
114
65
72
NR
100
62
NR
NR
NR
75
NR
75
NR
67
36
50
NR
56
Medium
110 + 6
103 + 15
66 + 17
89 + 11
64 + 6
96 + 3
39 + 21
48+7
78 + 6
93 + 8
70 + 7
81 + 18
43 + 7
81 + 8
53
71
NR
48
80 + 8
41 + 3
77 + 6
83 + 12
72 + 8
34 + 33
81 + 7
40 + 6
53
High
87
79
79
90
75
75
71
98
76
82
75
111
89
81
60
63
NR
NR
80
28
78
79
78
63
83
89
53
NR = Not recovered.
8141A - 25
Revision 1
September 1994
-------
TABLE 8.
SUGGESTED OPERATING CONDITIONS FOR 15-m COLUMNS
Columns 1 and 2 (DB-210 and SPB-608 or their equivalent)
Carrier gas (He) flow rate
Initial temperature =
Temperature program =
Column 3 (DB-5 or equivalent)
Carrier gas (He) flow rate =
Initial temperature =
Temperature program =
5 mL/min
50°C, hold for 1 minute
50°C to 140°C at 5°C/min, hold for
10 minutes, followed by 140°C to
240°C at 10°C/min, hold for 10
minutes (or a sufficient amount of
time for last compound to elute).
5 mL/min
130°C, hold for 3 minutes
130°C to 180°C at 5°C/min, hold for
10 minutes, followed by 180°C to
250°C at 2°C/min, hold for 15
minutes (or a sufficient amount of
time for last compound to elute).
8141A - 26
Revision 1
September 1994
-------
TABLE 9
SUGGESTED OPERATING CONDITIONS FOR 30-m COLUMNS
Column 1:
Type: DB-210
Dimensions: 30-m x 0.53-mm ID
Film Thickness (jum): 1.0
Column 2:
Type: DB-5
Dimensions: 30-m x 0.53-mm ID
Film Thickness (p.m): 1.5
Carrier gas flowrate (mL/min): 6 (Helium)
Makeup gas flowrate (mL/min): 20 (Helium)
Temperature program: 120°C (3-min hold) to 270°C (10-min hold) at 5°C/min
Injector temperature: 250°C
Detector temperature: 300°C
Injection volume: 2 /^L
Solvent: Hexane
Type of injector: Flash vaporization
Detector type: Dual NPD
Range: 1
Attenuation: 64
Type of splitter: Y-shaped or Tee
Data system: Integrator
Hydrogen gas pressure: 20 psi
Bead temperature: 400°C
Bias voltage: 4
8141A - 27 Revision 1
September 1994
-------
TABLE 10
QUANTITATION AND CHARACTERISTIC IONS FOR OP PESTICIDES
Compound Name
Quantitation ions
Characteristic ions
Azinphos-methyl
Bolstar (Sulprofos)
Chlorpyrifos
Coumaphos
Demeton-S
Diazinon
Dichlorvos (DDVP)
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfothion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Stirophos
Sulfotepp
TEPP
Tokuthion
160
156
197
109
88
137
109
87
88
157
158
293
278
173
209
127
127
109
291
109
75
285
109
322
99
113
77,132
140,143,113,33
97,199,125.314
97,226,362,21
60,114,170
179,152,93,199,304
79,185,145
93,125,58,143
89,60,61,97,142
169,141,63,185
43,97,41,126
97,125,141,109,308
125,109,93,169
125,127,93,158
57,153,41,298
109,67,192
67,97,192,109
145,147,79
97,109,139,155
125,263,79
121,97,47,260
125,287,79,109
329,331,79
97,65,93,121,202
155,127,81,109
43,162,267,309
8141A - 28
Revision 1
September 1994
-------
300.X
250.00
200.00-
150.00
100.00
50.00
0.00
I
faratmnn eim/i
Tetrachlorovinphos
Fensulfothion
• ' V... Ji
A „.
11.. I ... 11. 111 » I •. 111 • I,.,.,,,. ,1. • I 11, (,.. p ,,,.,, I ,., I,,.,,., I ...,. , ,, ... I ..,,.,.,.,,,
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45
Figure 1. Chromatogram of target organophosphorus compounds from a 15-m DB-210
column with FPD detector. More compounds are shown in Figure 2. See Table 3 for
retention times.
8141A - 29
Revision 1
September 1994
-------
300.00
250.00
200.00
150.00
100.00
50.00
0.00
o
i
o
\
(A
O
Q.
O
O
I
0.
lil
>.
I
Q.
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45
Figure 2. Chromatogram of target organophosphorus compounds from a 15-m DB-210
column with FPD detector. More compounds are shown in Figure 1. See Table 3 for
retention times.
8141A - 30
Revision 1
September 1994
-------
300.00
250.00
200.00 H
150.00 H
100.00 H
50.00 H
0.00-
t-p-iTT rrrrt-rrriTrptT|i t ij t . i; n T p > »rTTT t1T T I" ' I '" I ' " I "TT T" I" ' I"M ' T'
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45
Figure 3. Chromatogram of target organophosphorus compounds from a 15-m DB-210
column with NPD detector. More compounds are shown in Figure 4. See Table 3 tor
retention times.
8141A - 31
Revision 1
September 1994
-------
300.00 -,
250.00-
200.00-
150.00-
100.00-
50.00-
0.00-
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45
Figure 4. Chromatogram of target organophosphorus compounds from a 15-m DB-210
column with NPD detector. More compounds are shown in Figure 3. See Table 3 for
retention times.
8141A - 32
Revision 1
September 1994
-------
-f
DB-210
OB-5
Figure 5. Chromatogram of target organophosphorus compounds on a 30-m DB-5/DB-210
column pair with NPD detector, without Simazine, Atrazine and Carbophenothion. See
Table 4 for retention times and for GC operating conditions.
8141A - 33
Revision 1
September 1994
-------
-r
DB-210
It
It
It
r-fcvN
I <
^•« f—JWtAi
DB-5
Figure 6. Chromatogram of target organophosphorus compounds on a 30-m DB-5/DB-210
column pair with NPD detector, with Simazine, Atrazine and Carbophenothion. See
Table 4 for retention times and for GC operating conditions.
8141A - 34
Revision 1
September 1994
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METHOD 8141A
ORGANOPHOSPHORUS COMPOUNDS BY GAS CHROMATOGRAPHY:
CAPILLARY COLUMN TECHNIQUE
Start
I
7.1.1 Refer to Chapter
Two for guidance on
choosing the appropriate
extraction procedure.
7.1 .2 Perform
solvent exchange
during K-D
procedures in all
extraction methods.
I
7.2 Select GC
conditions.
7.3 Refer to Method
8000 for
calibration techniques.
7.3.1 Internal or
external
calibration may
be used.
I
7.4.1 Add internal
standard to sample
if necessary.
7.4.2 Refer to
Method 8OOO, Sec.
7.6 for instructions
on analysis sequence,
dilutions, retention times,
and identification
criteria.
7.4.3 Inject sample.
7.4.5 Record sample
volume injected and
resulting peak sizes.
7.4.6 Determine
identity and
quantity of each
component peak;
refer to Method
8000, Sec. 7.8 for
calculation equations.
7.4.7
Is paak
detection and
identification
prevented b'y
interfer
encos?
7.5.1 Perform
appropriate cleanup.
7.5.2 Reanalyze by
GC.
c
1
Stop
8141A - 35
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00
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I/I
o
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METHOD 8150A
CHLORINATED HERBICIDES BY GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 8150 is a gas chromatographic (GC) method for determining
certain chlorinated acid herbicides. The following compounds can be determined
by this method:
Compound Name CAS No.a
2,4-0 94-75-7
2,4-DB 94-82-6
2,4,5-TP (Silvex) 93-72-1
2,4,5-T 93-76-5
Dalapon 75-99-0
Dicamba 1918-00-9
Dichlorprop 120-36-5
Dinoseb 88-85-7
MCPA 94-74-6
MCPP 93-65-2
a Chemical Abstract Services Registry Number.
1.2 Table 1 lists the method detection limit for each compound in
organic-free reagent water. Table 2 lists the estimated quantitation limit (EQL)
for other matrices.
1.3 When Method 8150 is used to analyze unfamiliar samples, compound
identifications should be supported by at least one additional qualitative
technique. This method describes analytical conditions for a second gas
chromatographic column that can be used to confirm measurements made with the
primary column. Section 8.4 provides gas chromatograph/mass spectrometer (GC/MS)
criteria appropriate for the qualitative confirmation of compound
identifications.
1.4 Only experienced analysts should be allowed to work with diazomethane
due to the potential hazards associated with its use (the compound is explosive
and carcinogenic).
2.0 SUMMARY OF METHOD
2.1 Method 8150 provides extraction, esterification, and gas
chromatographic conditions for the analysis of chlorinated acid herbicides.
Spiked samples are used to verify the applicability of the chosen extraction
technique to each new sample type. The esters are hydrolyzed with potassium
hydroxide, and extraneous organic material is removed by a solvent wash. After
8150A - 1 Revision 1
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acidification, the acids are extracted with solvent and converted to their methyl
esters using diazomethane as the derivatizing agent. After excess reagent is
removed, the esters are determined by gas chromatography employing an electron
capture detector, microcoulometric detector, or electrolytic conductivity
detector (Goerlitz and Lamar, 1967). The results are reported as the acid
equivalents.
2.2 The sensitivity of Method 8150 usually depends on the level of
interferences rather than on instrumental limitations.
3.0 INTERFERENCES
3.1 Refer to Method 8000.
3.2 Organic acids, especially chlorinated acids, cause the most direct
interference with the determination. Phenols, including chlorophenols, may also
interfere with this procedure.
3.3 Alkaline hydrolysis and subsequent extraction of the basic solution
remove many chlorinated hydrocarbons and phthalate esters that might otherwise
interfere with the electron capture analysis.
3.4 The herbicides, being .strong organic acids, react readily with
alkaline substances and may be lost during analysis. Therefore, glassware and
glass wool must be acid rinsed, and sodium sulfate must be acidified with
sulfuric acid prior to use to avoid this possibility.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas chromatograph, analytical system complete with gas
chromatograph suitable for on-column injections and all required
accessories, including detectors, analytical columns, recorder, gases, and
syringes. A data system for measuring peak heights and/or peak areas is
recommended.
4.1.2 Columns
4.1.2.1 Column la and Ib - 1.8 m x 4 mm ID glass, packed
with 1.5% SP-2250/1.95% SP-2401 on Supelcoport (100/120 mesh) or
equivalent.
4.1.2.2 Column 2 - 1.8 m x 4 mm ID glass, packed with 5%
OV-210 on Gas Chrom Q (100/120 mesh) or equivalent.
4.1.2.3 Column 3 - 1.98 m x 2 mm ID glass, packed with
0.1% SP-1000 on 80/100 mesh Carbopack C or equivalent.
4.1.3 Detector - Electron capture (ECD).
4.2 Erlenmeyer flasks - 250 and 500 mL Pyrex, with 24/40 ground glass
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joint.
4.3 Beaker - 500 ml.
4.4 Diazomethane generator - Refer to Section 7.4 to determine which
method of diazomethane generation should be used for a particular application.
4.4.1 Diazald kit - recommended for the generation of diazomethane
using the procedure given in Section 7.4.2 (Aldrich Chemical Co., Cat. No.
210,025-2 or equivalent).
4.4.2 Assemble from two 20 x 150 mm test tubes, two Neoprene rubber
stoppers, and a source of nitrogen. Use Neoprene rubber stoppers with
holes drilled in them to accommodate glass delivery tubes. The exit tube
must be drawn to a point to bubble diazomethane through the sample extract.
The generator assembly is shown in Figure 1. The procedure for use of this
type of generator is given in Section 7.4.3.
4.5 Vials - 10 to 15 ml, amber glass, with Teflon lined screw cap or
crimp top.
4.6 Separatory funnel - 2000 ml, 125 ml, and 60 ml.
4.7 Drying column - 400 mm x 20 mm ID Pyrex chromatographic column with
Pyrex glass wool at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without
frits may be purchased. Use a small pad of Pyrex glass wool to
retain the adsorbent. Prewash the glass wool pad with 50 ml of
acetone followed by 50 ml of elution solvent prior to packing the
column with adsorbent.
4.8 Kuderna-Danish (K-D) apparatus
4.8.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts
4.8.2 Evaporation flask - 500 ml (Kontes K-570001-500 or equivalent).
Attach to concentrator tube with springs, clamps or equivalent.
4.8.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.8.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.8.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.9 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.10 Water bath - Heated, with concentric ring cover, capable of
8150A - 3 Revision 1
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temperature control (* 5°C). The bath should be used in a hood.
4.11 Microsyringe - 10 ^L.
4.12 Wrist shaker - Burrell Model 75 or equivalent.
4.13 Glass wool - Pyrex, acid washed.
4.14 Balance - Analytical, capable of accurately weighing to the nearest
0.0001 g.
4.15 Syringe - 5 ml.
4.16 Glass rod.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall 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 ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sulfuric acid solution
5.3.1 ((1:1) (v/v)) - Slowly add 50 ml H2S04 (sp. gr. 1.84) to 50 ml
of organic-free reagent water.
5.3.2 ((1:3) (v/v)) - Slowly add 25 ml H2S04 (sp. gr. 1.84) to 75 ml
of organic-free reagent water.
5.4 Hydrochloric acid ((1:9) (v/v)),HCl. Add one volume of concentrated
HC1 to 9 volumes of organic-free reagent water.
5.5 Potassium hydroxide solution (KOH) - 37% aqueous solution (w/v).
Dissolve 37 g potassium hydroxide pellets in organic-free reagent water, and
dilute to 100 ml.
5.6 Carbitol (Diethylene glycol monoethyl ether), C2H5OCH2CH2OCH2CH2OH.
Available from Aldrich Chemical Co.
5.7 Solvents
5.7.1 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.7.2 Methanol, CH3OH - Pesticide quality or equivalent.
5.7.3 Hexane, C6HU - Pesticide quality or equivalent.
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5.7.4 Diethyl Ether, C2H5OC2H5. Pesticide quality or equivalent.
Must be free of peroxides as indicated by test strips (EM Quant, or
equivalent). Procedures for removal of peroxides are provided with the
test strips. After cleanup, 20 ml of ethyl alcohol preservative must be
added to each liter of ether.
5.8 Sodium sulfate (granular, anhydrous), Na2SO,. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.9 N-Methyl-N-nitroso-p-toluenesulfonamide(Diazald),CH3C6H4S02N(CH3)NO.
Available from Aldrich Chemical Co.
5.10 Silicic acid. Chromatographic grade, nominal 100 mesh. Store at
130°C.
5.11 Stock standard solutions - Stock standard solutions can be prepared
from pure standard materials or purchased as certified solutions.
5.11.1 Prepare stock standard solutions by accurately weighing
about 0.0100 g of pure acids. Dissolve the material in pesticide quality
diethyl ether and dilute to volume in a 10 ml volumetric flask. Larger
volumes can be used at the convenience of the analyst. If compound purity
is certified at 96% or greater, the weight can be used without correction
to calculate the concentration of the stock standard. Commercially
prepared stock standards can be used at any concentration if they are
certified by the manufacturer or by an independent source.
5.11.2 Transfer the stock standard solutions into vials with
Teflon lined screw caps or crimp tops. Store at 4°C and protect from
light. Stock standard solutions should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.11.3 Stock standard solutions must be replaced after 1 year,
or sooner if comparison with check standards indicates a problem.
5.12 Calibration standards - A minimum of five calibration standards for
each parameter of interest should be prepared through dilution of the stock
standards with diethyl ether. One of the concentrations should be at a
concentration near, but above, the method detection limit. The remaining
concentrations should correspond to the expected range of concentrations found
in real samples or should define the working range of the GC. Calibration
solutions must be replaced after six months, or sooner if comparison with check
standards indicates a problem.
5.13 Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
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5.13.1 Prepare calibration standards at a minimum of five
concentrations for each parameter of interest as described in Section 5.12.
5.13.2 To each calibration standard, add a known constant
amount of one or more internal standards, and dilute to volume with diethyl
ether.
5.13.3 Analyze each calibration standard according to Section
7.0.
5.14 Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (when used), and analytical system and the effectiveness
of the method in dealing with each sample matrix by spiking each sample,
standard, and organic-free reagent water blank with one or two herbicide
surrogates (e.g. herbicides that are not expected to be present in the sample).
The surrogates selected should elute over the range of the temperature program
used in this method. Deuterated analogs of analytes should not be used as
surrogates for gas chromatographic analysis due to coelution problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this Chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and analyzed within 40
days of extraction.
7.0 PROCEDURE
7.1 Preparation of waste samples
7.1.1 Extraction
7.1.1.1 Follow Method 3580 except use diethyl ether as the
dilution solvent, acidified anhydrous sodium sulfate, and acidified
glass wool.
7.1.1.2 Transfer 1.0 mL (a lesser volume or a dilution may
be required if herbicide concentrations are high) to a 250 mL ground
glass-stoppered Erlenmeyer flask. Proceed to Section 7.2.2
hydrolysis.
7.2 Preparation of soil, sediment, and other solid samples
7.2.1 Extraction
7.2.1.1 To a 500 mL, wide mouth Erlenmeyer flask add 50
g (dry weight) of the well mixed, moist solid sample. Adjust the pH
to 2 with concentrated HC1 and monitor the pH for 15 minutes with
occasional stirring. If necessary, add additional HC1 until the pH
remains at 2.
7.2.1.2 Add 20 mL acetone to the flask and mix the
contents with the wrist shaker for 20 minutes. Add 80 mL diethyl
8150A - 6 Revision 1
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ether to the same flask and shake again for 20 minutes. Decant the
extract and measure the volume of solvent recovered.
7.2.1.3 Extract the sample twice more using 20 mL of
acetone followed by 80 ml of diethyl ether. After addition of each
solvent, the mixture should be shaken with the wrist shaker for
10 minutes and the acetone-ether extract decanted.
7.2.1.4 After the third extraction, the volume of extract
recovered should be at least 75% of the volume of added solvent. If
this is not the case, additional extractions may be necessary.
Combine the extracts in a 2 liter separatory funnel containing 250 ml
of 5% acidified sodium sulfate. If an emulsion forms, slowly add 5
g of acidified sodium sulfate (anhydrous) until the solvent-water
mixture separates. A quantity of acidified sodium sulfate equal to
the weight of the sample may be added, if necessary.
7.2.1.5 Check the pH of the extract. If it is not at or
below pH 2, add more concentrated HC1 until stabilized at the desired
pH. Gently mix the contents of the separatory funnel for 1 minute
and allow the layers to separate. Collect the aqueous phase in a
clean beaker and the extract phase (top layer) in a 500 ml ground
glass-stoppered Erlenmeyer flask. Place the aqueous phase back into
the separatory funnel and re-extract using 25 ml of diethyl ether.
Allow the layers to separate and discard the aqueous layer. Combine
the ether extracts in the 500 ml Erlenmeyer flask.
7.2.2 Hydrolysis
7.2.2.1 Add 30 mL of organic-free reagent water, 5 ml of
37% KOH, and one or two clean boiling chips to the flask. Place a
three ball Snyder column on the flask, evaporate the diethyl ether
on a water bath, and continue to heat for a total of 90 minutes.
7.2.2.2 Remove the flask from the water bath and allow to
cool. Transfer the water solution to a 125 ml separatory funnel and
extract the basic solutions once with 40 mL and then twice with 20 ml
of diethyl ether. Allow sufficient time for the layers to separate
and discard the ether layer each time. The phenoxy-acid herbicides
remain soluble in the aqueous phase as potassium salts.
7.2.3 Solvent cleanup
7.2.3.1 Adjust the pH to 2 by adding 5 mL cold (4°C) sulfuric
acid (1:3) to the separatory funnel. Be sure to check the pH at this
point. Extract the herbicides once with 40 mL and twice with 20 mL of
diethyl ether. Discard the aqueous phase.
7.2.3.2 Combine ether extracts in a 125 mL Erlenmeyer
flask containing 5-7 g of acidified anhydrous sodium sulfate.
Stopper and allow the extract to remain in contact with the acidified
sodium sulfate. If concentration and esterification are not to be
performed immediately, store the sample overnight in the
refrigerator.
8150A - 7 Revision 1
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NOTE: The drying step is very critical to ensuring complete
esterification. Any moisture remaining in the ether
will result in low herbicide recoveries. The amount of
sodium sulfate is adequate if some free flowing crystals
are visible when swirling the flask. If all the sodium
sulfate solidifies in a cake, add a few additional grams
of acidified sodium sulfate and again test by swirling.
The 2 hour drying time is a minimum, however, the
extracts may be held overnight in contact with the
sodium sulfate.
7.2.3.3 Transfer the ether extract, through a funnel
plugged with acid washed glass wool, into a 500 ml K-D flask equipped
with a 10 ml concentrator tube. Use a glass rod to crush caked
sodium sulfate during the transfer. Rinse the Erlenmeyer flask and
column with 20-30 ml of diethyl ether to complete the quantitative
transfer.
7.2.3.4 Add one or two clean boiling chips to the flask
and attach a three ball Snyder column. Prewet the Snyder column by
adding about 1 mL of diethyl ether to the top. Place the apparatus
on a hot water bath (60°-65°C) so that the concentrator tube is
partially immersed in the hot water and the entire lower rounded
surface of the flask is bathed in vapor. Adjust the vertical
position of the apparatus and the water temperature, as required, to
complete the concentration in 15-20 minutes. At the proper rate of
distillation the balls of the column will actively chatter, but the
chambers will not flood. When the apparent volume of liquid reaches
1 ml, remove the K-D apparatus from the water bath and allow it to
drain and cool for at least 10 minutes.
7.2.3.5 Remove the Snyder column and rinse the flask and
its lower joints into the concentrator tube with 1-2 mL of diethyl
ether. A 5 ml syringe is recommended for this operation. Add a
fresh boiling chip, attach a micro Snyder column to the concentrator
tube, and prewet the column by adding 0.5 ml of ethyl ether to the
top. Place the micro K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust the
vertical position of the apparatus and the water temperature as
required to complete concentration in 5-10 minutes. When the
apparent volume of the liquid reaches 0.5 mL, remove the micro K-D
from the bath and allow it to drain and cool. Remove the Snyder
column and add 0.1 mL of methanol. Rinse the walls of the
concentrator tube while adjusting the extract volume to 1.0 mL with
diethyl ether. Proceed to Section 7.4 for esterification.
7.3 Preparation of aqueous samples
7.3.1 Extraction
7.3.1.1 Using a 1 liter graduated cylinder, measure 1
liter (nominal) of sample, record the sample volume to the nearest
5 mL, and transfer it to the separatory funnel. If high
concentrations are anticipated, a smaller volume may be used and then
8150A - 8 Revision 1
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diluted with organic-free reagent water to 1 liter. Adjust the pH
to less than 2 with sulfuric acid (1:1).
7.3.1.2 Add 150 ml of diethyl ether to the sample bottle,
seal, and shake for 30 seconds to rinse the walls. Transfer the
solvent wash to the separatory funnel and extract the sample by
shaking the funnel for 2 minutes with periodic venting to release
excess pressure. Allow the organic layer to separate from the water
layer for a minimum of 10 minutes. If the emulsion interface between
layers is more than one third the size of the solvent layer, the
analyst must employ mechanical techniques to complete the phase
separation. The optimum technique depends upon the sample and may
include stirring, filtration of the emulsion through glass wool,
centrifugation, or other physical methods. Drain the aqueous phase
into a 1 liter Erlenmeyer flask. Collect the solvent extract in a
250 ml ground glass Erlenmeyer flask containing 2 ml of 37% KOH.
Approximately 80 ml of the diethyl ether will remain dissolved in the
aqueous phase.
7.3.1.3 Repeat the extraction two more times using 50 ml
of diethyl ether each time. Combine the extracts in the Erlenmeyer
flask. (Rinse the 1 liter flask with each additional aliquot of
extracting solvent.)
7.3.2 Hydrolysis
7.3.2.1 Add one or two clean boiling chips and 15 ml of
organic-free reagent water to the 250 ml flask and attach a three
ball Snyder column. Prewet the Snyder column by adding about 1 ml
of diethyl ether to the top of the column. Place the apparatus on
a hot water bath (60°-65°C) so that the bottom of the flask is bathed
with hot water vapor. Although the diethyl ether will evaporate in
about 15 minutes, continue heating for a total of 60 minutes,
beginning from the time the flask is placed in the water bath.
Remove the apparatus and let stand at room temperature for at least
10 minutes.
7.3.2.2 Transfer the solution to a 60 ml separatory funnel
using 5-10 ml of organic-free reagent water. Wash the basic solution
twice by shaking for 1 minute with 20 ml portions of diethyl ether.
Discard the organic phase. The herbicides remain in the aqueous
phase.
7.3.3 Solvent cleanup
7.3.3.1 Acidify the contents of the separatory funnel to
pH 2 by adding 2 ml of cold (4°C) sulfuric acid (1:3). Test with pH
indicator paper. Add 20 ml diethyl ether and shake vigorously for
2 minutes. Drain the aqueous layer into a 250 ml Erlenmeyer flask,
and pour the organic layer into a 125 ml Erlenmeyer flask containing
about 5-7 g of acidified sodium sulfate. Repeat the extraction twice
more with 10 ml aliquots of diethyl ether, combining all solvent in
the 125 ml flask. Allow the extract to remain in contact with the
sodium sulfate for approximately 2 hours.
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NOTE: The drying step is very critical to ensuring complete
esterification. Any moisture remaining in the ether
will result in low herbicide recoveries. The amount of
sodium sulfate is adequate if some free flowing crystals
are visible when swirling the flask. If all the sodium
sulfate solidifies in a cake, add a few additional grams
of acidified sodium sulfate and again test by swirling.
The 2 hour drying time is a minimum, however, the
extracts may be held overnight in contact with the
sodium sulfate.
7.3.3.2 Transfer the ether extract, through a funnel
plugged with acid washed glass wool, into a 500 ml K-D flask equipped
with a 10 ml concentrator tube. Use a glass rod to crush caked
sodium sulfate during the transfer. Rinse the Erlenmeyer flask and
column with 20-30 ml of diethyl ether to complete the quantitative
transfer.
7.3.3.3 Add one or two clean boiling chips to the flask
and attach a three ball Snyder column. Prewet the Snyder column by
adding about 1 ml of diethyl ether to the top. Place the apparatus
on a hot water bath (60°-65°C) so that the concentrator tube is
partially immersed in the hot water and the entire lower rounded
surface of the flask is bathed in vapor. Adjust the vertical
position of the apparatus and the water temperature, as required, to
complete the concentration in 15-20 minutes. At the proper rate of
distillation the balls of the column will actively chatter, but the
chambers will not flood. When the apparent volume of liquid reaches
1 ml, remove the K-D apparatus from the water bath and allow it to
drain and cool for at least 10 minutes.
7.3.3.4 Remove the Snyder column and rinse the flask and
its lower joints into the concentrator tube with 1-2 ml of diethyl
ether. A 5 mL syringe is recommended for this operation. Add a
fresh boiling chip, attach a micro Snyder column to the concentrator
tube, and prewet the column by adding 0.5 ml of ethyl ether to the
top. Place the micro K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust the
vertical position of the apparatus and the water temperature as
required to complete concentration in 5-10 minutes. When the
apparent volume of the liquid reaches 0.5 ml, remove the micro K-D
from the bath and allow it to drain and cool. Remove the Snyder
column and add 0.1 ml of methanol. Rinse the walls of the
concentrator tube while adjusting the extract volume to 1.0 ml with
diethyl ether.
7.4 Esterification
7.4.1 Two methods may be used for the generation of diazomethane:
the bubbler method (set up shown in Figure 1) and the Diazald kit method.
The bubbler method is suggested when small batches (10-15) of samples
require esterification. The bubbler method works well with samples that
have low concentrations of herbicides (e.g. aqueous samples) and is safer
to use than the Diazald kit procedure. The Diazald kit method is good for
8150A - 10 Revision 1
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are
large quantities of samples needing esterification. The Oiazald kit method
is more effective than the bubbler method for soils or samples that may
contain high concentrations of herbicides (e.g. samples such as soils that
may result in yellow extracts following hydrolysis may be difficult to
handle by the bubbler method). The diazomethane derivatization (U.S. EPA,
1971) procedures, described below, will react efficiently with all of the
chlorinated herbicides described in this method and should be used only by
experienced analysts, due to the potential hazards associated with its use.
The following precautions should be taken:
CAUTION: Diazomethane is a carcinogen and can explode under
certain conditions.
Use a safety screen.
Use mechanical pipetting aides.
Do not heat above 90°C -- EXPLOSION may result.
Avoid grinding surfaces, ground glass joints, sleeve bearings,
glass stirrers -- EXPLOSION may result.
Store away from alkali metals -- EXPLOSION may result.
Solutions of diazomethane decompose rapidly in the presence of
solid materials such as copper powder, calcium chloride, and
boiling chips.
7.4.2 Diazald kit method - Instructions for preparing diazomethane
provided with the generator kit.
7.4.2.1 Add 2 ml of diazomethane solution and let sample
stand for 10 minutes with occasional swirling.
7.4.2.2 Rinse inside wall of ampule with several hundred
pi of diethyl ether. Allow solvent to evaporate spontaneously at
room temperature to about 2 mL.
7.4.2.3 Dissolve the residue in 5 mL of hexane. Analyze
by gas chromatography.
7.4.3 Bubbler method - Assemble the diazomethane bubbler (see
Figure 1).
7.4.3.1 Add 5 mL of diethyl ether to the first test tube.
Add 1 mL of diethyl ether, 1 mL of carbitol, 1.5 mL of 37% KOH, and
0.1-0.2 g Diazald to the second test tube. Immediately place the
exit tube into the concentrator tube containing the sample extract.
Apply nitrogen flow (10 mL/min) to bubble diazomethane through
the extract for 10 minutes or until the yellow color of diazomethane
persists. The amount of Diazald used is sufficient for
esterification of approximately three sample extracts. An additional
0.1-0.2 g of Diazald may be added (after the initial Diazald is
consumed) to extend the generation of the diazomethane. There is
sufficient KOH present in the original solution to perform a maximum
of approximately 20 minutes of total esterification.
7.4.3.2 Remove the concentrator tube and seal it with a
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Neoprene or Teflon stopper. Store at room temperature in a hood for
20 minutes.
7.4.3.3 Destroy any unreacted diazomethane by adding
0.1-0.2 g silicic acid to the concentrator tube. Allow to stand
until the evolution of nitrogen gas has stopped. Adjust the sample
volume to 10.0 mL with hexane. Stopper the concentrator tube and
store refrigerated if further processing will not be performed
immediately. It is recommended that the methylated extracts be
analyzed immediately to minimize the trans-esterification and other
potential reactions that may occur. Analyze by gas chromatography.
7.5 Gas chromatographic conditions (Recommended)
7.5.1 Column la
Carrier gas (5% methane/95% argon) flow rate: 70 mL/min
Temperature program: 185°C, isothermal.
7.5.2 Column Ib
Carrier gas (5% methane/95% argon) flow rate: 70 mL/min
Initial temperature: 140°C, hold for 6 minutes
Temperature program: 140°C to 200°C at 10°C/min, hold until last
compound has eluted.
7.5.3 Column 2
Carrier gas (5% methane/95% argon) flow rate: 70 mL/min
Temperature program: 185°C, isothermal.
7.5.4 Column 3
Carrier gas (ultra-high purity N2) flow rate: 25 mL/min
Initial temperature: 100°C, no hold
Temperature program: 100°C to 150°C at 10°C/min, hold until last
compound has eluted.
7.6 Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.
7.6.1 The procedure for internal or external calibration may be used.
Refer to Method 8000 for a description of each of these procedures.
7.6.2 The following gas chromatographic columns are recommended for
the compounds indicated:
Analyte
Dicamba
2,4-D
2,4,5-TP
2,4,5-T
2,4-DB
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Daiapon 3
MCPP lb
MCPA lb
Dichloroprop lb
Oinoseb lb
7.7 Gas chromatographic analysis
7.7.1 Refer to Method 8000. If the internal standard calibration
technique is used, add 10 pi of internal standard to the sample prior to
injection.
7.7.2 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria. Include a mid-concentration check standard after
each group of 10 samples in the analysis sequence.
7.7.3 Examples of chromatograms for various chloro-phenoxy herbicides
are shown in Figures 2 through 4.
7.7.4 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).
7.7.5 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak-
in the sample chromatogram which corresponds to the compounds used for
calibration purposes.
7.7.6 If calibration standards have been analyzed in the same manner
as the samples (e.g. have undergone hydrolysis and esterification), then
the calculation of concentration given in Method 8000 should be used.
However, if calibration is done using standards made from methyl ester
compounds (compounds not esterified by application of this method), then
the calculation of concentration must include a correction for the
molecular weight of the methyl ester versus the acid herbicide.
7.7.7 If peak detection and identification are prevented due to
interferences, further cleanup is required. Before using any cleanup
procedure, the analyst must process a series of standards through the
procedure to validate elution patterns and the absence of interferences
from reagents.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized. If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method 8000,
Section 8.6.
8.2.1 Select a representative spike concentration for each compound
8150A - 13 Revision 1
July 1992
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(acid or ester) to be measured. Using stock standards, prepare a quality
control check sample concentrate in acetone 1,000 times more concentrated
than the selected concentrations.
8.2.2 Table 3 indicates Single Operator Accuracy and Precision for
this method. Compare the results obtained with the results given in
Table 3 to determine if the data quality is acceptable.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following procedures are
required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are a
problem or flag the data as "estimated concentration".
8.4 GC/MS confirmation
8.4.1 GC/MS techniques should be judiciously employed to support
qualitative identifications made with this method. Refer to Method 8270
for the appropriate GC/MS operating conditions and analysis procedures.
8.4.2 When available, chemical ionization mass spectra may be
employed to aid the qualitative identification process.
8.4.3 Should these MS procedures fail to provide satisfactory
results, additional steps may be taken before reanalysis. These steps may
include the use of alternate packed or capillary GC columns or additional
cleanup.
9.0 METHOD PERFORMANCE
9.1 In a single laboratory, using organic-free reagent water and
effluents from publicly owned treatment works (POTW), the average recoveries
presented in Table 3 were obtained. The standard deviations of the percent
recoveries of these measurements are also included in Table 3.
10.0 REFERENCES
1. U.S. EPA, National Pollutant Discharge Elimination System, Appendix A, Fed.
Reg., 38, No. 75, Pt. II, Method for Chlorinated Phenoxy Acid Herbicides
in Industrial Effluents, Cincinnati, Ohio, 1971.
8150A - 14 Revision 1
July 1992
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Goerlitz, D.G., and W.L. Lamar, "Determination of Phenoxy Acid Herbicides
in Water by Electron Capture and Microcoulometric Gas Chromatography,"
U.S. Geol. Survey Water Supply Paper, 1817-C, 1967.
3. Burke, J.A., "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
4. U.S. EPA, "Extraction and Cleanup Procedure for the Determination of
Phenoxy Acid Herbicides in Sediment," EPA Toxicant and Analysis Center, Bay
St. Louis, Mississippi, 1972.
5. "Pesticide Methods Evaluation," Letter Report #33 for EPA Contract No. 68-
03-2697. Available from U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
6. Eichelberger, J.W., L.E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurement in Gas Chromatography-Mass
Spectrometry," Analytical Chemistry, 47, 995, 1975.
7. Glaser, J.A. et.al., "Trace Analysis for Wastewaters," Environmental
Science & Technology, 15, 1426, 1981.
8. U.S. EPA, "Method 615. The Determination of Chlorinated Herbicides in
Industrial and Municipal Wastewater," Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio, 45268, June 1982.
8150A - 15 Revision 1
July 1992
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TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND DETECTION LIMITS
FOR CHLORINATED HERBICIDES
Retention
Compound
2,4-D
2,4-DB
2,4,5-T
2,4,5-TP (Silvex)
Dalapon
Dicamba
Dichloroprop
Dinoseb
MCPA
MCPP
Col. la
2.0
4.1
3.4
2.7
-
1.2
-
-
-
-
Col.lb
.
-
-
-
-
-
4.8
11.2
4.1
3.4
time (rnin)8
Col. 2 Col. 3
1.6
-
2.4
2.0
5.0
1.0
-
-
-
- -
Method
detection
1 imit (M9/U
1.2
0.91
0.20
0.17
5.8
0.27
0.65
0.07
249
192
Column conditions are given in Sections 4.1 and 7.5.
TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION
LIMITS (EQL) FOR VARIOUS MATRICES8
Matrix
Factor
Ground water (based on one liter sample size)
Soil/sediment and other solids
Waste samples
10
200
100,000
"Sample EQLs are highly matrix dependent. The EQLs listed herein are provided for
guidance and may not always be achievable.
bEQL - [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-aqueous
samples, the factor is on a wet weight basis.
8150A - 16
Revision 1
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TABLE 3.
SINGLE OPERATOR ACCURACY AND PRECISION8
Compound
2,4-D
Dalapon
2,4-DB
Dicamba
Dichlorprop
Dinoseb
MCPA
MCPP
2,4,5-T
2,4,5-TP
Sample
Type
DW
MM
MW
OW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
Spike
(M9/D
10.9
10.1
200
23.4
23.4
468
10.3
10.4
208
1.2
1.1
22.2
10.7
10.7
213
0.5
102
2020
2020
21400
2080
2100
20440
1.1
1.3
25.5
1.0
1.3
25.0
Mean
Recovery
(%)
75
77
65
66
96
81
93
93
77
79
86
82
97
72
100
86
81
98
73
97
94
97
95
85
83
78
88
88
72
Standard
deviation
W
4
4
5
8
13
9
3
3
6
7
9
6
2
3
2
4
3
4
3
2
4
3
2
6
4
5
5
4
5
"All results based upon seven replicate analyses. Esterification performed using
the bubbler method. Data obtained from reference 9.
DW = ASTM Type II
MW - Municipal water
8150A - 17
Revision 1
July 1992
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FIGURE 1.
DIAZOMETHANE GENERATOR
gloss lubing
nitrogen
rubber stopper
tube 1
lubo 2
8150A - 18
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FIGURE 2.
GAS CHROMATOGRAM OF CHLORINATED HERBICIDES
Column: 1.5% 9-2250/1.95% SP-2401 on Soptlcopon (100/120 M«*>
Ttmp«rttur«: ItottMrmal it 18S°C
D«ttctor: Electron C*ptjr«
012345
HCTENTION TIME (MINUTES)
8150A - 19
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FIGURE 3.
GAS CHROMATOGRAM OF CHLORINATED HERBICIDES
Column: 1.5% SP-2250/1.95% SP-2401 on Suptlcoport (100/120 M«*)
Program: 140°C for 6 Min. 10°C/Minuti to 200°C
Ottcctor: Electron Capturt
468
RETENTION TIME (MINUTES)
10
12
8150A - 20
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FIGURE 4.
GAS CHROMATOGRAM OF DALAPON, COLUMN 3
I
Column: 0.1% 9-1000 en 10/100 M«h Ortxxnk C
100°C, 10°C/Min to 150°C
: Electron Captur*
I
0246
ftfTfMTION T1MC (MINUTES)
8150A - 21
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METHOD 8150A
CHLORINATED HERBICIDES BY GAS CHROMATOGRAPHY
7211
Adjust sample
pH with HC1
7212 Extract
sample three
times with
acetone and
diethyl ether
7214
Combine
extracts
7215 Check
pH of extract.
adjust if
necessary.
Separate layers
Mas te
sample
7215
Re-extract
and discard
aqueous
phase
7 1 1 1 Folio.
Method 3580 for
extraction, using
diethyl ether.
acidified anhydrous
sodium sulfate and
acidified glass
wool
7 2 2 Proceed
with
hydro lysis
? 1 L 2 Use
V 0 ml of
sampl• for
hydrolysis
7 2 3 Proceed
«ith 101v«n t
cleanup
7 3 1 Extract
three times
• ith dielhyi
olh.r
7313
Combine
ax tracts
7 3 2 Proceed
with
hydr o1ys u
733 Proceed
with solvent
cleanup
8150A - 22
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METHOD 8150A
(Continued)
?43 Axsembe
diazomethane
oubb1«r.
genera ie
dla zome thane
7 5 Sal
chroma tograohic
cond 111on»
7 6 Clatbra*. e
acco rdi ng '.o
Mathod 8000
7 6 2 Choose
appropriate
CC column
742 Preoara
d la z om« lhan*
acco rding to
' tanda rds
through syj t*m
c I aanup
8150A - 23
Revision 1
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00
o
w
-------
METHOD 8150B
CHLORINATED HERBICIDES BY GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 8150 is a gas chromatographic (GC) method for determining
certain chlorinated acid herbicides. The following compounds can be determined
by this method:
Compound Name CAS No.'
2,4-D 94-75-7
2,4-DB 94-82-6
2,4,5-TP (Silvex) 93-72-1
2,4,5-T 93-76-5
Dalapon 75-99-0
Dicamba 1918-00-9
Dichloroprop 120-36-5
Dinoseb 88-85-7
MCPA 94-74-6
MCPP 93-65-2
a Chemical Abstract Services Registry Number.
1.2 Table 1 lists the method detection limit for each compound in
organic-free reagent water. Table 2 lists the estimated quantitation limit (EQL)
for other matrices.
1.3 When Method 8150 is used to analyze unfamiliar samples, compound
identifications should be supported by at least one additional qualitative
technique. This method describes analytical conditions for a second gas
chromatographic column that can be used to confirm measurements made with the
primary column. Sec. 8.4 provides gas chromatograph/mass spectrometer (GC/MS)
criteria appropriate for the qualitative confirmation of compound
identifications.
1.4 Only experienced analysts should be allowed to work with
diazomethane due to the potential hazards associated with its use (the compound
is explosive and carcinogenic).
2.0 SUMMARY OF METHOD
2.1 Method 8150 provides extraction, esterification, and gas
chromatographic conditions for the analysis of chlorinated acid herbicides.
Spiked samples are used to verify the applicability of the chosen extraction
technique to each new sample type. The esters are hydrolyzed with potassium
8150B - 1 Revision 2
September 1994
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hydroxide, and extraneous organic material is removed by a solvent wash. After
acidification, the acids are extracted with solvent and converted to their methyl
esters using diazomethane as the derivatizing agent. After excess reagent is
removed, the esters are determined by gas chromatography employing an electron
capture detector, microcoulometric detector, or electrolytic conductivity
detector (Goerlitz and Lamar, 1967). The results are reported as the acid
equivalents.
2.2 The sensitivity of Method 8150 usually depends on the level of
interferences rather than on instrumental limitations.
3.0 INTERFERENCES
3.1 Refer to Method 8000.
3.2 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to discrete
artifacts or elevated baselines in gas chromatograms. All these materials must
be routinely demonstrated to be free from interferences under the conditions of
the analysis, by analyzing reagent blanks.
3.2.1 Glassware must be scrupulously cleaned. Clean each piece of
glassware as soon as possible after use by rinsing it with the last
solvent used in it. This should be followed by detergent washing with hot
water and rinses with tap water, then with organic-free reagent water.
Glassware should be solvent-rinsed with acetone and pesticide-quality
hexane. After rinsing and drying, glassware should be sealed and stored
in a clean environment to prevent any accumulation of dust or other
contaminants. Store glassware inverted or capped with aluminum foil.
Immediately prior to use, glassware should be rinsed with the next solvent
to be used.
3.2.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.3 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences will vary
considerably from waste to waste, depending upon the nature and diversity of the
waste being sampled.
3.4 Organic acids, especially chlorinated acids, cause the most direct
interference with the determination. Phenols, including chlorophenols, may also
interfere with this procedure.
3.5 Alkaline hydrolysis and subsequent extraction of the basic solution
remove many chlorinated hydrocarbons and phthalate esters that might otherwise
interfere with the electron capture analysis.
3.6 The herbicides, being strong organic acids, react readily with
alkaline substances and may be lost during analysis. Therefore, glassware and
glass wool must be acid rinsed, and sodium sulfate must be acidified with
sulfuric acid prior to use to avoid this possibility.
8150B - 2 Revision 2
September 1994
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3.7 Sample extracts should be dry prior to methylation or else poor
recoveries will be obtained.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas chromatograph, analytical system complete with gas
chromatograph suitable for on-column injections and all required
accessories, including detectors, analytical columns, recorder, gases, and
syringes. A data system for measuring peak heights and/or peak areas is
recommended.
4.1.2 Columns
4.1.2.1 Column la and Ib - 1.8 m x 4 mm ID glass, packed
with 1.5% SP-2250/1.95% SP-2401 on Supelcoport (100/120 mesh) or
equivalent.
4.1.2.2 Column 2 - 1.8 m x 4 mm ID glass, packed with 5%
OV-210 on Gas Chrom Q (100/120 mesh) or equivalent.
4.1.2.3 Column 3 - 1.98 m x 2 mm ID glass, packed with
0.1% SP-1000 on 80/100 mesh Carbopack C or equivalent.
4.1.3 Detector - Electron capture (ECD).
4.2 Erlenmeyer flasks - 250 and 500 ml Pyrex, with 24/40 ground glass
joint.
4.3 Beaker - 500 ml.
4.4 Diazomethane generator - Refer to Sec. 7.4 to determine which method
of diazomethane generation should be used for a particular application.
4.4.1 Diazald kit - recommended for the generation of diazomethane
using the procedure given in Sec. 7.4.2 (Aldrich Chemical Co., Cat. No.
210,025-2 or equivalent).
4.4.2 Assemble from two 20 x 150 mm test tubes, two Neoprene rubber
stoppers, and a source of nitrogen. Use Neoprene rubber stoppers with
holes drilled in them to accommodate glass delivery tubes. The exit tube
must be drawn to a point to bubble diazomethane through the sample
extract. The generator assembly is shown in Figure 1. The procedure for
use of this type of generator is given in Sec. 7.4.3.
4.5 Vials - 10 to 15 ml, amber glass, with Teflon lined screw cap or
crimp top.
4.6 Separatory funnel - 2000 ml, 125 ml, and 60 ml.
4.7 Drying column - 400 mm x 20 mm ID Pyrex chromatographic column with
Pyrex glass wool at bottom and a Teflon stopcock.
8150B - 3 Revision 2
September 1994
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NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without
frits may be purchased. Use a small pad of Pyrex glass wool to
retain the adsorbent. Prewash the glass wool pad with 50 mL of
acetone followed by 50 mL of elution solvent prior to packing the
column with adsorbent.
4.8 Kuderna-Danish (K-D) apparatus
4.8.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts
4.8.2 Evaporation flask - 500 mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps or
equivalent.
4.8.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.8.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.8.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.9 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.10 Water bath - Heated, with concentric ring cover, capable of
temperature control (+ 5°C). The bath should be used in a hood.
4.11 Microsyringe - 10 /xL.
4.12 Wrist shaker - Burrell Model 75 or equivalent.
4.13 Glass wool - Pyrex, acid washed.
4.14 Balance - Analytical, capable of accurately weighing to 0.0001 g.
4.15 Syringe - 5 mL.
4.16 Glass rod.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all reagents shall 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 ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
8150B - 4 Revision 2
September 1994
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5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sulfuric acid solution
5.3.1 ((1:1) (v/v)) - Slowly add 50 mL H2S04 (sp. gr. 1.84) to 50 ml
of organic-free reagent water.
5.3.2 ((1:3) (v/v)) - Slowly add 25 ml H2S04 (sp. gr. 1.84) to 75 ml
of organic-free reagent water.
5,4 Hydrochloric acid ((1:9) (v/v)), HC1. Add one volume of
concentrated HC1 to 9 volumes of organic-free reagent water.
5.5 Potassium hydroxide solution (KOH) - 37% aqueous solution (w/v).
Dissolve 37 g potassium hydroxide pellets in organic-free reagent water, and
dilute to 100 mL.
5.6 Carbitol (Diethylene glycol monoethyl ether), C2H5OCH2CH2OCH2CH2OH.
Available from Aldrich Chemical Co.
5.7 Solvents
5.7.1 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.7.2 Methanol, CH3OH - Pesticide quality or equivalent.
5.7.3 Isooctane, (CH3)3CCH2CH(CH3)2 - Pesticide quality or
equivalent.
5.7.4 Hexane, C6H14 - Pesticide quality or equivalent.
5.7.5 Diethyl Ether, C2H5OC2H5. Pesticide quality or equivalent.
Must be free of peroxides as indicated by test strips (EM Quant, or
equivalent). Procedures for removal of peroxides are provided with the
test strips. After cleanup, 20 ml of ethyl alcohol preservative must be
added to each liter of ether.
5.8 Sodium sulfate (granular, acidified, anhydrous), Na2S04. Purify by
heating at 400°C for 4 hours in a shallow tray, or by precleaning the sodium
sulfate with methylene chloride. If the sodium sulfate is precleaned with
methylene chloride, a method blank must be analyzed, demonstrating that there is
no interference from the sodium sulfate. 'Acidify by slurrying 100 g sodium
sulfate with enough diethyl ether to just cover the solid; then add 0.1 ml of
concentrated sulfuric acid and mix thoroughly. Remove the ether under a vacuum.
Mix 1 g of the resulting solid with 5 ml of organic-free reagent water and
measure the pH of the mixture. It must be below a pH of 4. Store at 130°C.
5.9 N-Methyl-N-nitroso-p-toluenesulfonamide (Diazald), CH3C6H4S02N(CH3)NO.
Available from Aldrich Chemical Co.
5.10 Silicic acid. Chromatographic grade, nominal 100 mesh. Store at
130°C.
8150B - 5 Revision 2
September 1994
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5.11 Stock standard solutions - Stock standard solutions can be prepared
from pure standard materials or purchased as certified solutions.
5.11.1 Prepare stock standard solutions by accurately weighing
about 0.0100 g of pure acids. Dissolve the acids in pesticide quality
acetone and dissolve the esters in 10% acetone/isooctane (v/v) and dilute
to volume in a 10 mL volumetric flask. Larger volumes can be used at the
convenience of the analyst. If compound purity is certified at 96% or
greater, the weight can be used without correction to calculate the
concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
manufacturer or by an independent source.
5.11.2 Transfer the stock standard solutions into vials with
Teflon lined screw caps or crimp tops. Store at 4°C and protect from
light. Stock standard solutions should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.11.3 Stock standard solutions of the derivatized acids must
be replaced after 1 year, or sooner, if comparison with check standards
indicates a problem. Stock standard solutions of the free acids degrade
more quickly and should be replaced after two months, or sooner if
comparison with check standards indicates a problem.
5.12 Calibration standards - A minimum of five calibration standards for
each parameter of interest should be prepared through dilution of the stock
standards with diethyl ether. One of the concentrations should be at a
concentration near, but above, the method detection limit. The remaining
concentrations should correspond to the expected range of concentrations found
in real samples or should define the working range of the GC. Calibration
solutions must be replaced after six months, or sooner if comparison with check
standards indicates a problem.
5.13 Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.13.1 Prepare calibration standards at a minimum of five
concentrations for each parameter of interest as described in Sec. 5.12.
5.13.2 To each calibration standard, add a known constant
amount of one or more internal standards, and dilute to volume with
hexane.
5.13.3 Analyze each calibration standard per Sec. 7.0.
5.14 Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (when used), and analytical system, and the effectiveness
of the method in dealing with each sample matrix by spiking each sample,
8150B - 6 Revision 2
September 1994
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standard, and organic-free reagent water blank with one or two herbicide
surrogates (e.g. herbicides that are not expected to be present in the sample).
The surrogates selected should elute over the range of the temperature program
used in this method. 2,4-Dichlorophenylacetic acid (DCAA) is recommended as a
surrogate compound. Deuterated analogs of analytes should not be used as
surrogates for gas chromatographic analysis due to coelution problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this Chapter, Organic Analytes,
Sec. 4.1. Extracts must be stored under refrigeration and analyzed within 40
days of extraction.
7.0 PROCEDURE
7.1 Preparation of waste samples
7.1.1 Extraction
7.1.1.1 Follow Method 3580 except use diethyl ether as the
dilution solvent, acidified anhydrous sodium sulfate, and acidified
glass wool.
7.1.1.2 Transfer 1.0 mL (a lesser volume or a dilution may
be required if herbicide concentrations are high) to a 250 mL ground
glass-stoppered Erlenmeyer flask. Proceed to Sec. 7.2.2 hydrolysis.
7.2 Preparation of soil, sediment, and other solid samples
7.2.1 Extraction
7.2.1.1 To a 500 mL, wide mouth Erlenmeyer flask add 50
g (dry weight as determined in Method 3540, Sec. 7.2.1) of the well
mixed, moist solid sample. Adjust the pH to 2 (See Method 9045)
with concentrated HC1 and monitor the pH for 15 minutes with
occasional stirring. If necessary, add additional HC1 until the pH
remains at 2.
7.2.1.2 Add 20 mL acetone to the flask and mix the
contents with the wrist shaker for 20 minutes. Add 80 mL diethyl
ether to the same flask and shake again for 20 minutes. Decant the
extract and measure the volume of solvent recovered.
7.2.1.3 Extract the sample twice more using 20 mL of
acetone followed by 80 mL of diethyl ether. After addition of each
solvent, the mixture should be shaken with the wrist shaker for
10 minutes and the acetone-ether extract decanted.
7.2.1.4 After the third extraction, the volume of extract
recovered should be at least 75% of the volume of added solvent.
If this is not the case, additional extractions may be necessary.
Combine the extracts in a 2 liter separatory funnel containing
8150B - 7 Revision 2
September 1994
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250 ml of reagent water. If an emulsion forms, slowly add 5 g of
acidified sodium sulfate (anhydrous) until the solvent-water mixture
separates. A quantity of acidified sodium sulfate equal to the
weight of the sample may be added, if necessary.
7.2.1.5 Check the pH of the extract. If it is not at or
below pH 2, add more concentrated HC1 until stabilized at the
desired pH. Gently mix the contents of the separatory funnel for
1 minute and allow the layers to separate. Collect the aqueous
phase in a clean beaker and the extract phase (top layer) in a
500 mL ground glass-stoppered Erlenmeyer flask. Place the aqueous
phase back into the separatory funnel and re-extract using 25 ml of
diethyl ether. Allow the layers to separate and discard the aqueous
layer. Combine the ether extracts in the 500 ml Erlenmeyer flask.
7.2.1.6 An alternative extraction procedure using
ultrasonic extraction can be found in Sec. 7.2 of Method 8151.
7.2.2 Hydrolysis
7.2.2.1 Add 30 ml of organic-free reagent water, 5 ml of
37% KOH, and one or two clean boiling chips to the flask. Place a
three ball Snyder column on the flask, evaporate the diethyl ether
on a water bath, and continue to heat until the hydrolysis step is
completed (usually 1 to 2 hours).
7.2.2.2 Remove the flask from the water bath and allow to
cool. Transfer the water solution to a 125 ml separatory funnel and
extract the basic solutions once with 40 ml and then twice with
20 ml of diethyl ether. Allow sufficient time for the layers to
separate and discard the ether layer each time. The phenoxy-acid
herbicides remain soluble in the aqueous phase as potassium salts.
7.2.3 Solvent cleanup
7.2.3.1 Adjust the pH to 2 by adding 5 ml cold (4°C)
sulfuric acid (1:3) to the separatory funnel. Be sure to check the
pH at this point. Extract the herbicides once with 40 mL and twice
with 20 ml of diethyl ether. Discard the aqueous phase.
7.2.3.2 Combine ether extracts in a 125 ml Erlenmeyer
flask containing 5-7 g of acidified anhydrous sodium sulfate.
Stopper and allow the extract to remain in contact with the
acidified sodium sulfate. If concentration and esterification are
not to be performed immediately, store the sample overnight in the
refrigerator.
NOTE: The drying step is very critical to ensuring complete
esterification. Any moisture remaining in the ether
will result in low herbicide recoveries. The amount of
sodium sulfate is adequate if some free=flowing
crystals are visible when swirling the flask. If all
the sodium sulfate solidifies in a cake, add a few
8150B - 8 Revision 2
September 1994
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additional grams of acidified sodium sulfate and again
test by swirling. The 2 hour drying time is a minimum,
however, the extracts may be held overnight in contact
with the sodium sulfate.
7.2.3.3 Transfer the ether extract, through a funnel
plugged with acid washed glass wool, into a 500 ml K-D flask
equipped with a 10 ml concentrator tube. Use a glass rod to crush
caked sodium sulfate during the transfer. Rinse the Erlenmeyer
flask and column with 20-30 ml of diethyl ether to complete the
quantitative transfer.
7.2.3.4 Add one or two clean boiling chips to the flask
and attach a three ball Snyder column. Prewet the Snyder column by
adding about 1 ml of diethyl ether to the top. Place the apparatus
on a hot water bath (60°-65°C) so that the concentrator tube is
partially immersed in the hot water and the entire lower rounded
surface of the flask is bathed in vapor. Adjust the vertical
position of the apparatus and the water temperature, as required,
to complete the concentration in 15-20 minutes. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches 1 ml, remove the K-D apparatus from the water bath and allow
it to drain and cool for at least 10 minutes.
7.2.3.5 Remove the Snyder column and rinse the flask and
its lower joints into the concentrator tube with 1-2 ml of diethyl
ether. A 5 mL syringe is recommended for this operation. Add a
fresh boiling chip, attach a micro Snyder column to the concentrator
tube, and prewet the column by adding 0.5 ml of ethyl ether to the
top. Place the micro K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature as
required to complete concentration in 5-10 minutes. When the
apparent volume of the liquid reaches 0.5 ml, remove the micro K-D
from the bath and allow it to drain and cool. Remove the Snyder
column and add 0.1 ml of methanol. Rinse the walls of the
concentrator tube while adjusting the extract volume to 1.0 ml with
diethyl ether. Proceed to Sec. 7.4 for esterification.
7.3 Preparation of aqueous samples
7.3.1 Extraction
7.3.1.1 Using a 1 liter graduated cylinder, measure 1
liter (nominal) of sample, record the sample volume to the nearest
5 ml, and quantitatively transfer it to the separatory funnel. If
high concentrations are anticipated, a smaller volume may be used
and then diluted with organic-free reagent water to 1 liter. Adjust
the pH to less than 2. with sulfuric acid (1:1).
7.3.1.2 Add 150 ml of diethyl ether to the sample bottle,
seal, and shake for 30 seconds to rinse the walls. Transfer the
8150B - 9 Revision 2
September 1994
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solvent wash to the separatory funnel and extract the sample by
shaking the funnel for 2 minutes with periodic venting to release
excess pressure. Allow the organic layer to separate from the water
layer for a minimum of 10 minutes. If the emulsion interface
between layers is more than one third the size of the solvent layer,
the analyst must employ mechanical techniques to complete the phase
separation. The optimum technique depends upon the sample and may
include stirring, filtration of the emulsion through glass wool,
centrifugation, or other physical methods. Drain the aqueous phase
into a 1 liter Erlenmeyer flask. Collect the solvent extract in a
250 ml ground glass Erlenmeyer flask containing 2 ml of 37% KOH.
Approximately 80 ml of the diethyl ether will remain dissolved in
the aqueous phase.
7.3.1.3 Repeat the extraction two more times using 50 ml
of diethyl ether each time. Combine the extracts in the Erlenmeyer
flask. (Rinse the 1 liter flask with each additional aliquot of
extracting solvent.)
7.3.2 Hydrolysis
7.3.2.1 Add one or two clean boiling chips and 15 ml of
organic-free reagent water to the 250 ml flask and attach a three
ball Snyder column. Prewet the Snyder column by adding about 1 ml
of diethyl ether to the top of the column. Place the apparatus on
a hot water bath (60°-65°C) so that the bottom of the flask is bathed
with hot water vapor. Although the diethyl ether will evaporate in
about 15 minutes, continue heating until the hydrolysis step is
completed (usually 1 to 2 hours). Remove the apparatus and let
stand at room temperature for at least 10 minutes.
7.3.2.2 Transfer the solution to a 60 ml separatory funnel
using 5-10 ml of organic-free reagent water. Wash the basic
solution twice by shaking for 1 minute with 20 ml portions of
diethyl ether. Discard the organic phase. The herbicides remain
in the aqueous phase.
7.3.3 Solvent cleanup
7.3.3.1 Acidify the contents of the separatory funnel to
pH 2 by adding 2 ml of cold (4°C) sulfuric acid (1:3). Test with pH
indicator paper. Add 20 ml diethyl ether and shake vigorously for
2 minutes. Drain the aqueous,layer into a 250 ml Erlenmeyer flask,
and pour the organic layer into a 125 mL Erlenmeyer flask containing
about 5-7 g of acidified sodium sulfate. Repeat the extraction
twice more with 10 mL aliquots of diethyl ether, combining all
solvent in the 125 ml flask. Allow the extract to remain in contact
with the sodium sulfate for approximately 2 hours.
NOTE: The drying step is very critical to ensuring complete
esterification. Any moisture remaining in the ether
will result in low herbicide recoveries. The amount of
sodium sulfate is adequate if some free flowing
8150B - 10 Revision 2
September 1994
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crystals are visible when swirling the flask. If all
the sodium sulfate solidifies in a cake, add a few
additional grams of acidified sodium sulfate and again
test by swirling. The 2 hour drying time is a minimum,
however, the extracts may be held overnight in contact
with the sodium sulfate.
7.3.3.2 Transfer the ether extract, through a funnel
plugged with acid washed glass wool, into a 500 ml K-D flask
equipped with a 10 mL concentrator tube. Use a glass rod to crush
caked sodium sulfate during the transfer. Rinse the Erlenmeyer
flask and column with 20-30 mL of diethyl ether to complete the
quantitative transfer.
7.3.3.3 Add one or two clean boiling chips to the flask
and attach a three ball Snyder column. Prewet the Snyder column by
adding about 1 mL of diethyl ether to the top. Place the apparatus
on a hot water bath (60°-65°C) so that the concentrator tube is
partially immersed in the hot water and the entire lower rounded
surface of the flask is bathed in vapor. Adjust the vertical
position of the apparatus and the water temperature, as required,
to complete the concentration in 15-20 minutes. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches 1 mL, remove the K-D apparatus from the water bath and allow
it to drain and cool for at least 10 minutes.
7.3.3.4 Remove the Snyder column and rinse the flask and
its lower joints into the concentrator tube with 1-2 mL of diethyl
ether. A 5 mL syringe is recommended for this operation. Add a
fresh boiling chip, attach a micro Snyder column to the concentrator
tube, and prewet the column by adding 0.5 mL of ethyl ether to the
top. Place the micro K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature as
required to complete concentration in 5-10 minutes. When the
apparent volume of the liquid reaches 0.5 mL, remove the micro K-D
from the bath and allow it to drain and cool. Remove the Snyder
column and add 0.1 mL of methanol. Rinse the walls of the
concentrator tube while adjusting the extract volume to 1.0 mL with
diethyl ether.
7.4 Esterification
7.4.1 Two methods may be used for the generation of diazomethane:
the bubbler method (set up shown in Figure 1) and the Diazald kit method.
The bubbler method is suggested when small batches (10-15) of samples
require esterification. The bubbler method works well with samples that
have low concentrations of herbicides (e.g. aqueous samples) and is safer
to use than the Diazald kit procedure. The Diazald kit method is good for
large quantities of samples needing esterification. The Diazald kit
method is more effective than the bubbler method for soils or samples that
may contain high concentrations of herbicides (e.g., samples such as soils
8150B - 11 Revision 2
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that result in yellow extracts following hydrolysis may be difficult to
handle by the bubbler method). The diazomethane derivatization (U.S. EPA,
1971) procedures, described below, will react efficiently with all of the
chlorinated herbicides described in this method and should be used only by
experienced analysts, due to the potential hazards associated with its
use. The following precautions should be taken:
CAUTION: Diazomethane is a carcinogen and can explode under
certain conditions.
Use a safety screen.
Use mechanical pipetting aides.
Do not heat above 90°C -- EXPLOSION may result.
Avoid grinding surfaces, ground glass joints, sleeve
bearings, glass stirrers -- EXPLOSION may result.
Store away from alkali metals -- EXPLOSION may result.
Solutions of diazomethane decompose rapidly in the
presence of solid materials such as copper powder,
calcium chloride, and boiling chips.
7.4.2 Diazald kit method - Instructions for preparing diazomethane
are provided with the generator kit.
7.4.2.1 Add 2 mL of diazomethane solution and let sample
stand for 10 minutes with occasional swirling.
7.4.2.2 Rinse inside wall of the ampule with several
hundred /uL of diethyl ether. Allow solvent to evaporate
spontaneously at room temperature to about 2 mL.
7.4.2.3 Dissolve the residue in 5 mL of hexane. Analyze
by gas chromatography.
7.4.3 Bubbler method - Assemble the diazomethane bubbler (see
Figure 1).
7.4.3.1 Add 5 mL of diethyl ether to the first test tube.
Add 1 mL of diethyl ether, 1 mL of carbitol, 1.5 mL of 37% KOH, and
0.1-0.2 g Diazald to the second test tube. Immediately place the
exit tube into the concentrator tube containing the sample extract.
Apply nitrogen flow (10 mL/min) to bubble diazomethane through
the extract for 10 minutes or until the yellow color of diazomethane
persists. The amount of Diazald used is sufficient for
esterification of approximately three sample extracts. An
additional 0.1-0.2 g of Diazald may be added (after the initial
Diazald is consumed) to extend the generation of the diazomethane.
There is sufficient KOH present in the original solution to perform
a maximum of approximately 20 minutes of total esterification.
7.4.3.2 Remove the concentrator tube and seal it with a
Neoprene or Teflon stopper. Store at room temperature in a hood for
20 minutes.
8150B - 12 Revision 2
September 1994
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7.4.3.3 Destroy any unreacted diazomethane by adding
0.1-0.2 g silicic acid to the concentrator tube. Allow to stand
until the evolution of nitrogen gas has stopped. Adjust the sample
volume to 10.0 mi with hexane. Stopper the concentrator tube and
store refrigerated if further processing will not be performed
immediately. It is recommended that the methylated extracts be
analyzed immediately to minimize the trans-esterification and other
potential reactions that may occur. Analyze by gas chromatography.
7.5 Gas chromatographic conditions (Recommended)
7.5.1 Column la
Carrier gas (5% methane/95% argon) flow rate: 70 mL/min
Temperature program: 185°C, isothermal.
7.5.2 Column Ib
Carrier gas (5% methane/95% argon) flow rate: 70 mL/min
Initial temperature: 140°C, hold for 6 minutes
Temperature program: 140°C to 200°C at 10°C/min, hold until last
compound has eluted.
7.5.3 Column 2
Carrier gas (5% methane/95% argon) flow rate: 70 mL/min
Temperature program: 185°C, isothermal.
7.5.4 Column 3
Carrier gas (ultra-high purity N2) flow rate: 25 mL/min
Initial temperature: 100°C, no hold
Temperature program: 100°C to 150°C at 10°C/min, hold until last
compound has eluted.
7.6 Calibration - Refer to Method 8000 for proper calibration
techniques. Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.6.1 The procedure for internal or external calibration may be
used. Refer to Method 8.000 for a description of each of these procedures.
7.6.2 The following gas chromatographic columns are recommended for
the compounds indicated:
Analyte Column Analyte Column
Dicamba la,2 Dalapon 3
2,4-D la,2 MCPP Ib
2,4,5-TP la,2 MCPA Ib
2,4,5-T la,2 Dichloroprop Ib
2,4-DB la Dinoseb Ib
8150B - 13 Revision 2
September 1994
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7.7 Gas chromatographic analysis
7.7.1 Refer to Method 8000. If the internal standard calibration
technique is used, add 10 jiL of internal standard to the sample prior to
injection.
7.7.2 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria. Include a mid-concentration check standard after
each group of 10 samples in the analysis sequence.
7.7.3 Examples of chromatograms for various chlorophenoxy acid
herbicides are shown in Figures 2 through 4.
7.7.4 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).
7.7.5 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes.
7.7.6 If calibration standards have been analyzed in the same manner
as the samples (e.g. have undergone hydrolysis and esterification), then
the calculation of concentration given in Method 8000 should be used.
However, if calibration is done using standards made from methyl ester
compounds (compounds not esterified by application of this method), then
the calculation of concentration must include a correction for the
molecular weight of the methyl ester versus the acid herbicide.
7.7.7 If peak detection and identification are prevented due to
interferences, further cleanup is required. Before using any cleanup
procedure, the analyst must process a series of standards through the
procedure to validate elution patterns and the absence of interferences
from reagents.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized. If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method
8000.
8.2.1 Select a representative spike concentration for each compound
(acid or ester) to be measured. Using stock standards, prepare a quality
control check sample concentrate in acetone 1,000 times more concentrated
than the selected concentrations.
8150B - 14 Revision 2
September 1994
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8.2.2 Table 3 indicates single operator accuracy and precision for
this method. Compare the results obtained with the results given in
Table 3 to determine if the data quality is acceptable.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000).
8.3.1 If recovery is not within limits, the following procedures are
required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also,
check instrument performance.
• Recalculate the data and/or reanalyze the extract if
none of the above checks reveal a problem.
• Re-extract and re-analyze the sample if none of the
above are a problem or flag the data as "estimated
concentration".
8.4 GC/MS confirmation
8.4.1 GC/MS techniques should be judiciously employed to support
qualitative identifications made with this method. Refer to Method 8270
for the appropriate GC/MS operating conditions and analysis procedures.
8.4.2 When available, chemical ionization mass spectra may be
employed to aid the qualitative identification process.
8.4.3 Should these MS procedures fail to provide satisfactory
results, additional steps may be taken before reanalysis. These steps may
include the use of alternate packed or capillary GC columns or additional
cleanup.
9.0 METHOD PERFORMANCE
9.1 In a single laboratory, using organic-free reagent water and
effluents from publicly owned treatment works (POTW), the average recoveries
presented in Table 3 were obtained. The standard deviations of the percent
recoveries of these measurements are also included in Table 3.
10.0 REFERENCES
1. U.S. EPA, National Pollutant Discharge Elimination System, Appendix A,
Fed. Reg., 38, No. 75, Pt. II, Method for Chlorinated Phenoxy Acid
Herbicides in Industrial Effluents, Cincinnati, Ohio, 1971.
2. Goerlitz, D.G., and W.L. Lamar, "Determination of Phenoxy Acid Herbicides
in Water by Electron Capture and Microcoulometric Gas Chromatography,"
U.S. Geol. Survey Water Supply Paper, 1817-C, 1967.
8150B - 15 Revision 2
September 1994
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Burke, J.A., "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
U.S. EPA, "Extraction and Cleanup Procedure for the Determination of
Phenoxy Acid Herbicides in Sediment," EPA Toxicant and Analysis Center,
Bay St. Louis, Mississippi, 1972.
"Pesticide Methods Evaluation," Letter Report #33 for EPA Contract No. 68-
03-2697. Available from U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
Eichelberger, J.W., L.E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurement in Gas Chromatography-Mass
Spectrometry," Analytical Chemistry, 47, 995, 1975.
Glaser, J.A. et.al., "Trace Analysis for Wastewaters," Environmental
Science & Technology, 15, 1426, 1981.
Gurka, D.F, Shore, F.L., Pan, S-T, "Single Laboratory Validation of EPA
Method 8150 for Determination of Chlorinated Herbicides in Hazardous
Waste", JAOAC, 69, 970, 1986.
U.S. EPA, "Method 615. The Determination of Chlorinated Herbicides in
Industrial and Municipal Wastewater," Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio, 45268, June 1982.
8150B - 16 Revision 2
September 1994
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TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND DETECTION LIMITS
FOR CHLORINATED HERBICIDES
Compound
Retention time (min)a
Col.la Col.lb Col.2 Col.3
"Column conditions are given in Sees. 4.1 and 7.5.
TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION
LIMITS (EQL) FOR VARIOUS MATRICES8
Method
detection
limit (M9/L)
2,4-D
2,4-DB
2,4,5-T
2,4,5-TP (Silvex)
Dalapon
Dicamba
Dichloroprop
Dinoseb
MCPA
MCPP
2.0
4.1
3.4
2.7
-
1.2
-
-
-
-
-
-
-
-
-
4.8
11.2
4.1
3.4
1.6
-
2.4
2.0
5.0
1.0
-
-
-
-
1.2
0.91
0.20
0.17
5.8
0.27
0.65
0.07
249
192
Matrix
Factor
Ground water (based on one liter sample si?e)
Soil/sediment and other solids
Waste samples
10
200
100,000
aEQL = [Method detection limit (see Table 1)] X [Factor found in this table].
For non-aqueous samples, the factor is on a wet weight basis. Sample EQLs are
highly matrix dependent. The EQLs to be determined herein are provided for
guidance and may not always be achievable.
8150B - 17
Revision 2
September 1994
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TABLE 3.
SINGLE OPERATOR ACCURACY AND PRECISION'
Compound
2,4-D
Dalapon
2,4-DB
Dicamba
Dichlorprop
Dinoseb
MCPA
MCPP
2,4,5-T
2,4,5-TP
Sample
Type
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
Spike
10.9
10.1
200
23.4
23.4
468
10.3
10.4
208
1.2
1.1
22.2
10.7
10.7
213
0.5
102
2020
2020
21400
2080
2100
20440
1.1
1.3
25.5
1.0
1.3
25.0
Mean
Recovery
75
77
65
66
96
81
93
93
77
79
86
82
97
72
100
86
81
98
73
97
94
97
95
85
83
78
88
88
72
Standard
deviation
4
4
5
8
13
9
3
3
6
7
9
6
2
3
2
4
3
4
3
2
4
3
2
6
4
5
5
4
5
aAll results based upon seven replicate analyses. Esterification performed using
the bubbler method. Data obtained from reference 8.
DW = ASTM Type II
MW = Municipal water
8150B - 18
Revision 2
September 1994
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FIGURE 1.
DIAZOMETHANE GENERATOR
nitrogen
TIE
rubber stopper
U
lube 1
a*
tube 2
glass tubing
8150B - 19
Revision 2
September 1994
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FIGURE 2.
GAS CHROMATOGRAM OF CHLORINATED HERBICIDES
Column: 1.5% SP-2250/1.95* SF-2401 on Suptteopoa (100/120 Mt*)
Ttmparatura: Isothermal at 18S°C
Dtttctor: Electron Capturt
0 12346
RETENTION TIME (MINUTES)
8150B - 20
Revision 2
September 1994
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FIGURE 3.
GAS CHROMATOGRAM OF CHLORINATED HERBICIDES
Column: 1.5% SP-2260/1.95% SP-2401 on Suotlcoport (100/120
Program: UO°C for 6 Min. 10°C/Minuti to 200°C
Dtuctor: Electron Capturt
468
RETENTION TIME (MINUTES)
10
12
81508 - 21
Revision 2
September 1994
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FIGURE 4.
GAS CHROMATOGRAM OF DALAPON, COLUMN 3
J
Column: 0.1% 9-1000 on 80/100 Mmh C*rtoop«k C
Program: 100°C, 10°C/Min to 1BO°C
Otnetor: Etoctron Capture
0246
RETENTION TIME (MINUTES)
8150B - 22
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METHOD 81 SOB
CHLORINATED HERBICIDES BY GAS CHROMATOGRAPHY
7.2.1.1
Adjust lampla
pH with HCI.
Solid
Sample
7.2.1.2 Extract
sample with
acetona and
diethyl ethar.
7.2.1.3 Extract
twica more.
7.2.1.4
Combine
extract*.
7.2.1.5 Check
pH of extract,
adjust if
necessary.
Separata layer*.
7.2.1.5
Re-extract
and discard
aqueous
phase.
7.1.1 Follow
Method 3580 for
extraction, u»mg
diethyl ether,
acidified anhydrous
aodium sulfata and
acidified glass
wool.
7.2.2 Proceed
with
hydrolysis.
7.1.1.2 Use
1.0 mL of
cample for
hydrolysis.
7.2.3 Proceed
with solvent
cleanup.
V
7.3.1.1 Adjust
sample pH
with H2S04.
7.3.1.2 Extract
with diethyl
ether.
7.3.1.3
Extract twica more,
and combine
extracts.
7.3.2 Proceed
with
hydrolysis.
7.3.3 Proceed
with solvent
cleanup.
8150B - 23
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September 1994
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METHOD 81BOB
(Continued)
7.4.3 Assemble
diazomethane
bubbler;
generate
diazomethane.
7.4
Choose
method for
esterification
7.4.2 Prepare
diazomethane
according to
kit
instructions.
7.5 Set
chromatographic
conditions.
7.6 Claibrate
according to
Method 8000.
I
7.6.2 Choose
appropriate
GC column.
7.7 Analyze
by GC (refer
to Method
8000).
7.7.7 Do
interferences
prevent peak
detection?
7.7.7 Process
series of
stendards
through system
cleanup.
8150B - 24
Revision 2
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00
-------
METHOD 8151
CHLORINATED HERBICIDES BY GC USING METHYLATION OR PENTAFLUOROBENZYLATION
DERIVATIZATION: CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8151 is a capillary gas chromatographic (GC) method for
determining certain chlorinated acid herbicides and related compounds in aqueous,
soil and waste matrices. Specifically, Method 8151 may be used to determine the
following compounds:
Compound Name CAS No."
2,4-D 94-75-7
2,4-DB 94-82-6
2,4,5-TP (Silvex) 93-72-1
2,4,5-T 93-76-5
Dalapon 75-99-0
Dicamba 1918-00-9
Dichloroprop 120-36-5
Dinoseb 88-85-7
MCPA 94-74-6
MCPP 93-65-2
4-Nitrophenol 100-02-1
Pentachlorophenol 87-86-5
a Chemical Abstract Services Registry Number.
Because these compounds are produced and used in various forms (i.e., acid,
salt, ester, etc.), Method 8151 describes a hydrolysis step that can be used to
convert herbicide esters into the acid form prior to analysis. Herbicide esters
generally have a half-life of less than one week in soil.
1.2 When Method 8151 is used to analyze unfamiliar samples, compound
identifications should be supported by at least one additional qualitative
technique. Sec. 8.4 provides gas chromatograph/mass spectrometer (GC/MS)
criteria appropriate for the qualitative confirmation of compound
identifications.
1.3 The estimated detection limits for each of the compounds in aqueous
and soil matrices are listed in Table 1. The detection limits for a specific
waste sample may differ from those listed, depending upon the nature of the
interferences and the sample matrix.
8151 - 1 Revision 0
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1.4 The following compounds may also be determined using this method:
Compound Name CAS No."
Acifluorfen 50594-66-6
Bentazon 25057-89-0
Chloramben 133-90-4
DCPA diacidb 2136-79-0
3,5-Dichlorobenzoic acid 51-36-5
5-Hydroxydicamba 7600-50-2
Picloram 1918-02-1
Chemical Abstract Services Registry Number.
DCPA monoacid and diacid metabolites included in method scope; DCPA
diacid metabolite used for validation studies. DCPA is a dimethyl
ester.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatography and skilled in the
interpretation of gas chromatograms. Each analyst must demonstrate the ability
to generate acceptable results with this method.
1.6 Only experienced analysts should be allowed to work with diazomethane
due to the potential hazards associated with its use (explosive, carcinogenic).
2.0 SUMMARY OF METHOD
2.1 Method 8151 provides extraction, derivatization, and gas
chromatographic conditions for the analysis of chlorinated acid herbicides in
water, soil, and waste samples. An option for the hydrolysis of esters is also
described.
2.1.1 Water samples are extracted with diethyl ether and then
esterified with either diazomethane or pentafluorobenzyl bromide. The
derivatives are determined by gas chromatography with an electron capture
detector (GC/ECD). The results are reported as acid equivalents.
2.1.2 Soil and waste samples are extracted and esterified with
either diazomethane or pentafluorobenzyl bromide. The derivatives are
determined by gas chromatography with an electron capture detector
(GC/ECD). The results are reported as acid equivalents.
2.1.3 If herbicide esters are to be determined using this method,
hydrolysis conditions for the esters in water and soil extracts are
described.
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2.2 The sensitivity of Method 8151 depends on the level of interferences
in addition to instrumental limitations. Table 1 lists the GC/ECD and GC/MS
detection limits that can be obtained in aqueous and soil matrices in the absence
of interferences. Detection limits for a typical waste sample should be higher.
3.0 INTERFERENCES
3.1 Refer to Method 8000.
3.2 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to discrete
artifacts or elevated baselines in gas chromatograms. All these materials must
be routinely demonstrated to be free from interferences under the conditions of
the analysis, by analyzing reagent blanks.
3.2.1 Glassware must be scrupulously cleaned. Clean each piece of
glassware as soon as possible after use by rinsing it with the last
solvent used in it. This should be followed by detergent washing with hot
water and rinses with tap water, then with organic-free reagent water.
Glassware should be solvent-rinsed with acetone and pesticide-quality
hexane. After rinsing and drying, glassware should be sealed and stored
in a clean environment to prevent any accumulation of dust or other
contaminants. Store glassware inverted or capped with aluminum foil.
Immediately prior to use, glassware should be rinsed with the next solvent
to be used.
3.2.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required.
3.3 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences will vary
considerably from waste to waste, depending upon the nature and diversity of the
waste being sampled.
3.4 Organic acids, especially chlorinated acids, cause the most direct
interference with the determination by methylation. Phenols, including
chlorophenols, may also interfere with this procedure. The determination using
pentafluorobenzylation is more sensitive, and more prone to interferences from
the presence of organic acids or phenols than by methylation.
3.5 Alkaline hydrolysis and subsequent extraction of the basic solution
removes many chlorinated hydrocarbons and phthalate esters that might otherwise
interfere with the electron capture analysis. However, hydrolysis may result in
the loss of dinoseb and the formation of aldol condensation products if any
residual acetone remains from the extraction of solids.
3.6 The herbicides, being strong organic acids, react readily with
alkaline substances and may be lost during analysis. Therefore, glassware must
be acid-rinsed and then rinsed to constant pH with organic-free reagent water.
Sodium sulfate must be acidified.
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3.7 Sample extracts should be dry prior to methylation or else poor
recoveries will be obtained.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4.1.1 Gas chromatograph - Analytical system complete with gas
chromatograph suitable for Grob-type injection using capillary columns,
and all required accessories including detector, capillary analytical
columns, recorder, gases, and syringes. A data system for measuring peak
heights and/or peak areas is recommended.
4.1.2 Columns
4.1.2.1 Narrow Bore Columns
4.1.2.1.1 Primary Column 1 - 30 m x 0.25 mm, 5%
phenyl/95% methyl silicone (DB-5, J&W Scientific, or
equivalent), 0.25 p.m film thickness.
4.1.2.1.2 Primary Column la (GC/MS) - 30 m x 0.32 mm,
5% phenyl/95% methyl silicone, (DB-5, J&W Scientific, or
equivalent), 1 ^m film thickness.
4.1.2.1.3 Column 2 - 30 m x 0.25 mm DB-608 (J&W
Scientific or equivalent) with a 25 /Ltm film thickness.
4.1.2.1.4 Confirmation Column - 30 m x 0.25 mm, 14%
cyanopropyl phenyl silicone, (DB-1701, J&W Scientific, or
equivalent), 0.25 /xm film thickness.
4.1.2.2 Wide-bore Columns
4.1.2.2.1 Primary Column - 30 m x 0.53 mm DB-608 (J&W
Scientific or equivalent) with 0.83 /urn film thickness.
4.1.2.2.2 Confirmation Column - 30 m x 0.53 mm, 14%
cyanopropyl phenyl silicone, (DB-1701, J&W Scientific, or
equivalent), 1.0 jum film thickness.
4.1.3 Detector - Electron Capture Detector (ECD)
4.2 Kuderna-Danish (K-D) apparatus
4.2.1 Concentrator tube - 10 mL graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.2.2 Evaporation flask - 500 mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
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4.2.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.2.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.3 Diazomethane Generator: Refer to Sec. 7.5 to determine which method
of diazomethane generation should be used for a particular generation.
4.3.1 Diazald Kit - Recommended for the generation of diazomethane
(Aldrich Chemical Co., Cat No. 210,025-0, or equivalent).
4.3.2 As an alternative, assemble from two 20 mm x 150 mm test
tubes, two Neoprene rubber stoppers, and a source of nitrogen. Use
Neoprene rubber stoppers with holes drilled in them to accommodate glass
delivery tubes. The exit tube must be drawn to a point to bubble
diazomethane through the sample extract. The generator assembly is shown
in Figure 1. The procedure for use of this type of generator is given in
Sec. 7.5.
4.4 Other Glassware
4.4.1 Beaker - 400 ml, thick walled.
4.4.2 Funnel - 75 mm diameter.
4.4.3 Separatory funnel - 500 ml, with Teflon stopcock.
4.4.4 Centrifuge bottle - 500 ml (Pyrex 1260 or equivalent).
4.4.5 Centrifuge bottle - 24/40 500 ml
4.4.6 Continuous Extractor (Hershberg-Wolfe type, Lab Glass No. LG-
6915, or equivalent)
4.4.7 Pipet - Pasteur, glass, disposable (140 mm x 5 mm ID).
4.4.8 Vials - 10 ml, glass, with Teflon lined screw-caps.
4.4.9 Volumetric flasks, Class A - 10 ml to 1000 ml.
4.5 Filter paper - 15 cm diameter (Whatman No. 1 or equivalent).
4.6 Glass Wool - Pyrex, acid washed.
4.7 Boiling chips - Solvent extracted with methylene
chloride,approximately 10/40 mesh (silicon carbide or equivalent).
4.8 Water bath - Heated, with concentric ring cover, capable of
temperature control (+ 2°C). The bath should be used in a hood.
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4.9 Balance - Analytical, capable of accurately weighing to 0.0001 g.
4.10 Centrifuge.
4.11 Ultrasonic preparation - A horn-type device equipped with a titanium
tip, or a device that will give equivalent performance, shall be used.
4.11.1 Ultrasonic Disrupter - The disrupter must have a minimum
power wattage of 300 watts, with pulsing capability. A device designed to
reduce the cavitation sound is recommended. Follow the manufacturers
instructions for preparing the disrupter for extraction of samples. Use
a 3/4" horn for most samples.
4.12 Sonabox - Recommended with above disrupters for decreasing cavitation
sound (Heat Systems - Ultrasonics, Inc., Model 432B or equivalent).
4.13 pH paper.
4.14 Silica gel cleanup column (Bond Elut™ - Analytichem, Harbor City, CA
or equivalent).
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall 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 ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free water, as defined in Chapter One.
5.3 Sodium hydroxide solution (0.1 N), NaOH. Dissolve 4 g NaOH in
organic-free reagent water and dilute to 1.0 L.
5.4 Potassium hydroxide solution (37% aqueous solution (w/v)), KOH.
Dissolve 37 g potassium hydroxide pellets in organic-free reagent water and
dilute to 100 mL.
5.5 Phosphate buffer pH = 2.5 (0.1 M). Dissolve 12 g sodium phosphate
(NaH2P04) in organic-free reagent water and dilute to 1.0 L. Add phosphoric acid
to adjust the pH to 2.5.
5.6 N-methyl-N-nitroso-p-toluenesulfonamide (Diazald). High purity,
available from Aldrich Chemical Co. or equivalent.
5.7 Silicic acid, H2SiOs. 100 mesh powder, store at 130°C.
5.8 Potassium carbonate, K2C03.
5.9 2,3,4,5,6-Pentafluorobenzyl bromide (PFBBr), C6F5CH2Br. Pesticide
quality or equivalent.
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5.10 Sodium sulfate (granular, acidified, anhydrous), Na2S04. Purify by
heating at 400°C for 4 hours in a shallow tray, or by precleaning the sodium
sulfate with methylene chloride. If the sodium sulfate is precleaned with
methylene chloride, a method blank must be analyzed, demonstrating that there is
no interference from the sodium sulfate. Acidify by slurrying 100 g sodium
sulfate with enough diethyl ether to just cover the solid; then add 0.1 ml of
concentrated sulfuric acid and mix thoroughly. Remove the ether under vacuum.
Mix 1 g of the resulting solid with 5 ml of organic-free reagent water and
measure the pH of the mixture. It must be below a pH of 4. Store the remaining
solid at 130°C.
5.11 Solvents
5.11.1
equivalent.
5.11.2
5.11.3
5.11.4
Methylene chloride, CH2C12. Pesticide quality or
Acetone, CH3COCH3. Pesticide quality or equivalent.
Methanol, CH3OH. Pesticide quality or equivalent.
Toluene, C6H5CH3. Pesticide quality or equivalent.
5.11.5 Diethyl Ether, C2H5OC2H5. Pesticide quality or
equivalent. Must be free of peroxides as indicated by test strips (EM
Quant, or equivalent). Procedures for removal of peroxides are provided
with the test strips. After cleanup, 20 ml of ethyl alcohol preservative
must be added to each liter of ether.
5.11.6
equivalent.
5.11.7
5.11.8
Isooctane, (CH3)3CH2CH(CH3)2. Pesticide quality or
Hexane, C6H14. Pesticide quality or equivalent.
Ethanol, absolute. C2H5OH
5.11.9 Carbitol (diethylene glycol monoethyl ether),
C2H5OCH2CH2OCH2CH20 - optional for producing alcohol-free diazomethane.
5.12 Stock standard solutions (1000 tng/L) - Can be prepared from pure
standard materials or can be purchased as certified solutions.
5.12.1 Prepare stock standard solutions by accurately weighing
about 0.010 g of pure acid. Dissolve the material in pesticide quality
acetone and dilute to volume in a 10 ml volumetric flask. Stocks prepared
from pure methyl esters are dissolved in 10% acetone/isooctane (v/v).
Larger volumes may be used at the convenience of the analyst. If compound
purity is certified at 96% or greater, the weight may be used without
correction to calculate the concentration of the stock standard.
5.12.2 Transfer the stock standard solutions to vials with
Teflon lined screw-caps. Store at 4°C, protected from light. Stock
standard solutions should be checked frequently for signs of degradation
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or evaporation, especially immediately prior to preparing calibration
standards from them.
5.12.3 Stock standard solutions of the derivatized acids must
be replaced after 1 year, or sooner, if comparison with check standards
indicates a problem. Stock standard solutions of the free acids degrade
more quickly and should be replaced after two months, or sooner if
comparison with check standards indicates a problem.
5.13 Internal Standard Spiking Solution (if internal standard calibration
is used) - To use this approach, the analyst must select one or more internal
standards that are similar in analytical behavior to the compounds of interest.
The analyst must further demonstrate that the measurement of the internal
standard is not affected by method or matrix interferences. The compound 4,4'-
dibromooctafluorobiphenyl (DBOB) has been shown to be an effective internal
standard, but other compounds, such as 1,4-dichlorobenzene, may be used if there
is a DBOB interference.
5.13.1 Prepare an internal standard spiking solution by
accurately weighing approximately 0.0025 g of pure DBOB. Dissolve the
DBOB in acetone and dilute to volume in a 10 ml volumetric flask.
Transfer the internal standard spiking solution to a vial with a Teflon
lined screw-cap, and store at room temperature. Addition of 10 juL of the
internal standard spiking solution to 10 ml of sample extract results in
a final internal standard concentration of 0.25 M9/L. The solution should
be replaced if there is a change in internal standard response greater
than 20 percent of the original response recorded.
5.14 Calibration standards - Calibration standards, at a minimum of five
concentrations for each parameter of interest, should be prepared through
dilution of the stock standards with diethyl ether or hexane. One of the
concentrations should be at a concentration near, but above, the method detection
limit. The remaining concentrations should correspond to the expected range of
concentrations found in real samples or should define the working range of the
GC. Calibration solutions must be replaced after six months, or sooner if
comparison with check standards indicates a problem.
5.14.1 Derivatize each calibration standard prepared from free
acids in a 10 ml K-D concentrator tube, according to the procedures
beginning at Sec. 7.5.
5.14.2 Add a known, constant amount of one or more internal
standards to each derivatized calibration standard, and dilute to volume
with the solvent indicated in the derivative option used.
5.15 Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (when used), and determinative step, and the
effectiveness of the method in dealing with each sample matrix, by spiking each
sample, standard, and blank with one or two herbicide surrogates (e.g.,
herbicides that are not expected to be present in the sample) recommended to
encompass the range of the temperature program used in this method. Deuterated
analogs of analytes should not be used as surrogates in gas chromatographic
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analysis due to coelution problems. The surrogate standard recommended for use
is 2,4-Dichlorophenylacetic acid (DCAA).
5.15.1 Prepare a surrogate standard spiking solution by
accurately weighing approximately 0.001 g of pure DCAA. Dissolve the DCAA
in acetone, and dilute to volume in a 10 ml volumetric flask. Transfer
the surrogate standard spiking solution to a vial with a Teflon lined
screw-cap, and store at room temperature. Addition of 50 juL of the
surrogate standard spiking solution to 1 L of sample, prior to extraction,
results in a final concentration in the extract of 0.5 mg/L.
5.16 pH Adjustment Solutions
5.16.1 Sodium hydroxide, NaOH, 6 N.
5.16.2 Sulfuric acid, H2S04, 12 N.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1. 1 L samples should be collected.
6.2 Extracts must be stored under refrigeration (4°C).
7.0 PROCEDURE
7.1 Preparation of High Concentration Waste Samples
7.1.1 Extraction
7.1.1.1 Follow Method 3580, Waste Dilution, with the
following exceptions:
• use diethyl ether as the dilution solvent,
• use acidified anhydrous sodium sulfate, and acidified
glass wool,
• spike the sample with surrogate compound(s) according to
Sec. 5.16.1.
7.1.1.2 If the sample is to be analyzed for both herbicide
esters and acids, then the sample extract must be hydrolyzed. In
this case, transfer 1.0 mL (a smaller volume or a dilution may be
required if herbicide concentrations are large) to a 250 mL ground
glass Erlenmeyer flask. Proceed to Sec. 7.2.1.8. If the analysis
is for acid herbicides only, proceed to Sec. 7.4.5 for
derivatization by diazomethane (if PFB derivatization is selected,
reduce the volume of diethyl ether to 0.1 - 0.5 mL as per Sec. 7.4.2
and then dilute to 4 mL with acetone).
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7.2 Preparation of Soil, Sediment, and Other Solid Samples
7.2.1 Extraction
7.2.1.1 To a 400 ml, thick-wall beaker add 30 g (dry
weight as determined in Method 3540, Sec. 7.2.1) of the well-mixed
solid sample. Adjust the pH to 2 with concentrated hydrochloric
acid or acidify solids in each beaker with 85 ml of 0.1 M phosphate
buffer (pH = 2.5) and thoroughly mix the contents with a glass
stirring rod. Spike the sample with surrogate compound(s) according
to Sec. 5.16.1.
7.2.1.2 The ultrasonic extraction of solids must be
optimized for each type of sample. In order for the ultrasonic
extractor to efficiently extract solid samples, the sample must be
free flowing when the solvent is added. Acidified anhydrous sodium
sulfate should be added to clay type soils (normally 1:1), or any
other solid that is not a free flowing sandy mixture, until a free
flowing mixture is obtained.
7.2.1.3 Add 100 ml of methylene chloride/acetone (1:1
v/v) to the beaker. Perform ultrasonic extraction for 3 minutes,
with output control knob set at 10 (full power) and with mode switch
on Pulse (pulsing energy rather than continuous energy) and percent-
duty cycle knob set at 50% (energy on 50% of time and off 50% of
time). Allow the solids to settle. Transfer the organic layer into
a 500 mL centrifuge bottle.
7.2.1.4 Ultrasonically extract the sample twice more using
100 ml of methylene chloride and the same ultrasonic conditions.
7.2.1.5 Combine the three organic extracts from the sample
in the centrifuge bottle and centrifuge 10 minutes to settle the
fine particles. Filter the combined extract through filter paper
(Whatman #1, or equivalent) containing 7-10 g of acidified sodium
sulfate into a 500 ml 24/40 Erlenmeyer flask. Add 10 g of acidified
anhydrous sodium sulfate. Periodically, vigorously shake the
extract and drying agent and allow the drying agent to remain in
contact with the extract for a minimum of 2 hours. See NOTE in Sec.
7.3.1.6 that emphasizes the need for a dry extract prior to
esterification.
7.2.1.6 Quantitatively transfer the contents of the flask
to a 500-mL Kuderna-Danish fTask with a 10-mL concentrator tube
attached. Add boiling chips and attach the macro Snyder column.
Evaporate the extract on the water bath to a volume of approximately
5 ml. Remove the flasks from the water bath and allow them to cool.
7.2.1.7 If hydrolysis or additional cleanup is not
required and the sample is dry, proceed to Sec. 7.4.4 - Nitrogen
Slowdown.
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7.2.1.8 Use this step only if herbicide esters in addition
to herbicide acids are to be determined:
7.2.1.8.1 Add 5 ml of 37% aqueous potassium hydroxide
and 30 ml of water to the extract. Add additional boiling
chips to the flask. Reflux the mixture on a water bath at
60-65°C until the hydrolysis step is completed (usually 1 to
2 hours). Remove the flasks from the water bath and cool to
room temperature. CAUTION - the presence of residual acetone
will result in the formation of aldol condensation products
which will cause GC interference.
7.2.1.8.2 Transfer the hydrolyzed aqueous solution to
a 500 ml separatory funnel and extract the solution three
times with 100 ml portions of methylene chloride. Discard the
methylene chloride phase. At this point the basic (aqueous)
solution contains the herbicide salts.
7.2.1.8.3 Adjust the pH of the solution to <2 with
cold (4°C) sulfuric acid (1:3) and extract once with 40 ml of
diethyl ether and twice with 20 ml portions of ether. Combine
the extracts and pour them through a pre-rinsed drying column
containing 7 to 10 cm of acidified anhydrous sodium sulfate.
Collect the dried extracts in a 500 ml Erlenmeyer flask (with
a 24/40 joint) containing 10 g of acidified anhydrous sodium
sulfate. Periodically, vigorously shake the extract and
drying agent and allow the drying agent to remain in contact
with the extract for a minimum of 2 hours. See NOTE in Sec.
7.3.1.6 that emphasizes the need for a dry extract prior to
esterification. Quantitatively transfer the contents of the
flask to a 500-mL Kuderna-Danish flask with a 10-mL
concentrator tube attached when the extract is known to be
dry.
7.2.1.8.4 Proceed to Sec. 7.4, Extract Concentration.
If additional cleanup is required, proceed to Sec. 7.2.1.9.
7.2.1.9 Use this step if additional cleanup of the non-
hydrolyzed herbicides is required:
7.2.1.9.1 Partition the herbicides by extracting the
methylene chloride from 7.2.1.7 (or diethyl ether from
7.2.1.8.4) with 3 x 15 ml portions of aqueous base prepared
by carefully mixing 30 ml of reagent water into 15 ml of 37%
aqueous potassium hydroxide. Discard the methylene chloride
or ether phase. At this point the basic (aqueous) solution
contains the herbicide salts.
7.2.1.9.2 Adjust the pH of the solution to <2 with
cold (4°C) sulfuric acid (1:3) and extract once with 40 ml of
diethyl ether and twice with 20 ml portions of ether. Combine
the extracts and pour them through a pre-rinsed drying column
containing 7 to 10 cm of acidified anhydrous sodium sulfate.
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Collect the dried extracts in a 500 ml Erlenmeyer flask (with
a 24/40 joint) containing 10 g of acidified anhydrous sodium
sulfate. Periodically, vigorously shake the extract and
drying agent and allow the drying agent to remain in contact
with the extract for a minimum of 2 hours. See NOTE in Sec.
7.3.1.6 that emphasizes the need for a dry extract prior to
esterification. Quantitatively transfer the contents of the
flask to a 500-mL Kuderna-Danish flask with a 10-mL
concentrator tube attached when the extract is known to be
dry.
7.2.1.9.3 Proceed to section 7.4 for extract
concentration.
7.2.1.10 An alternative wrist-shaker extraction procedure
can be found in Sec. 7.2 of Method 8150.
7.3 Preparation of Aqueous Samples
7.3.1 Separatory Funnel
7.3.1.1 Using a graduated cylinder, measure out a 1-L
sample and transfer it into a 2-L separatory funnel. Spike the
sample with surrogate compound(s) according to Sec. 5.15.1.
7.3.1.2 Add 250 g of NaCl to the sample, seal, and shake
to dissolve the salt.
7.3.1.3 Use this step only if herbicide esters in addition
to herbicide acids, are to be determined:
7.3.1.3.1 Add 17 mL of 6 N NaOH to the sample, seal,
and shake. Check the pH of the sample with pH paper; if the
sample does not have a pH greater than or equal to 12, adjust
the pH by adding more 6 N NaOH. Let the sample sit at room
temperature until the hydrolysis step is completed (usually 1
to 2 hours), shaking the separatory funnel and contents
periodically.
7.3.1.3.2 Add 60 mL of methylene chloride to the
sample bottle and rinse both the bottle and the graduated
cylinder. Transfer the methylene chloride to the separatory
funnel and extract the sample by vigorously shaking the funnel
for 2 minutes, with periodic venting to release excess
pressure. Allow the organic layer to separate from the water
phase for a minimum of 10 minutes. If the emulsion interface
between the layers is more than one-third the volume of the
solvent layer, the analyst must employ mechanical techniques
to complete the phase separation. The optimum technique
depends upon the sample, but may include stirring, filtration
through glass wool, centrifugation, or other physical methods.
Discard the methylene chloride phase.
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7.3.1.3.3 Add a second 60 mL volume of methylene
chloride to the separatory funnel and repeat the extraction
procedure a second time, discarding the methylene chloride
layer. Perform a third extraction in the same manner.
7.3.1.4 Add 17 mL of cold (4°C) 12 N sulfuric acid to the
sample (or hydrolyzed sample), seal, and shake to mix. Check the pH
of the sample with pH paper: if the sample does not have a pH less
than or equal to 2, adjust the pH by adding more acid.
7.3.1.5 Add 120 mL diethyl ether to the sample, seal, and
extract the sample by vigorously shaking the funnel for 2 min with
periodic venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of 10 min. If
the emulsion interface between layers is more than one third the
volume of the solvent layer, the analyst must employ mechanical
techniques to complete the phase separation. The optimum techniques
to complete the phase separation depends upon the sample, but may
include stirring, filtration through glass wool, centrifugation, or
other physical methods. Remove the aqueous phase to a 2 L
Erlenmeyer flask and collect the ether phase in a 500 mL Erlenmeyer
flask containing approximately 10 g of acidified anhydrous sodium
sulfate. Periodically, vigorously shake the extract and drying
agent.
7.3.1.6 Return the aqueous phase to the separatory funnel,
add 60 mL of diethyl ether to the sample, and repeat the extraction
procedure a second time, combining the extracts in the 500 mL
Erlenmeyer flask. Perform a third extraction with 60 mL diethyl
ether in the same manner. Allow the extract to remain in contact
with the sodium sulfate for approximately 2 hours.
NOTE: The drying step is very critical to ensuring
complete esterification. Any moisture remaining
in the ether will result in low herbicide
recoveries. The amount of sodium sulfate is
adequate if some free flowing crystals are
visible when swirling the flask. If all of the
sodium sulfate solidifies in a cake, add a few
additional grams of acidified sodium sulfate and
again test by swirling. The 2 hour drying time
is a minimum, however, the extracts may be held
in contact with the sodium sulfate overnight.
7.3.1.7 Pour the dried extract through a funnel plugged
with acid washed glass wool, and collect the extract in the K-D
concentrator. Use a glass rod to crush any caked sodium sulfate
during the transfer. Rinse the Erlenmeyer flask and funnel with 20
to 30 mL of diethyl ether to complete the quantitative transfer.
Proceed to Sec. 7.4 for extract concentration.
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7.4 Extract Concentration
7.4.1 Add one or two clean boiling chips to the flask and attach a
three ball Snyder column. Prewet the Snyder column by adding about 1 ml
of diethyl ether to the top of the column. Place the K-D apparatus on a
hot water bath (15-20°C above the boiling point of the solvent) so that the
concentrator tube is partially immersed in the hot water and the entire
lower rounded surface of the flask is bathed with hot vapor. Adjust the
vertical position of the apparatus and the water temperature, as required,
to complete the concentration in 10-20 minutes. At the proper rate of
distillation the balls of the column will actively chatter, but the
chambers will not flood. When the apparent volume of liquid reaches 1 ml,
remove the K-D apparatus from the water bath and allow it to drain and
cool for at least 10 minutes.
7.4.2 Remove the Snyder column and rinse the flask and its lower
joints into the concentrator tube with 1-2 ml of diethyl ether. The
extract may be further concentrated by using either the micro Snyder
column technique (Sec. 7.4.3) or nitrogen blowdown technique (Sec. 7.4.4).
7.4.3 Micro Snyder Column Technique
7.4.3.1 Add another one or two clean boiling chips to the
concentrator tube and attach a two ball micro Snyder column. Prewet
the column by adding about 0.5 ml of diethyl ether to the top of the
column. Place the K-D apparatus in a hot water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete the concentration in 5-10 minutes. At the
proper rate of distillation the balls of the column will actively
chatter, but the chambers will not flood. When the apparent volume
of liquid reaches 0.5 ml, remove the K-D apparatus from the water
bath and allow it to drain and cool for at least 10 minutes. Remove
the Snyder column and rinse the flask and its lower joints with
about 0.2 ml of diethyl ether and add to the concentrator tube.
Proceed to Sec. 7.4.5.
7.4.4 Nitrogen Blowdown Technique
7.4.4.1 Place the concentrator tube in a warm water bath
(approximately 35°C) and evaporate the solvent volume to the
required level using a gentle stream of clean, dry nitrogen
(filtered through a column of activated carbon).
CAUTION: Do not use plasticized tubing between the carbon
trap and the sample.
7.4.4.2 The internal wall of the tube must be rinsed down
several times with diethyl ether during the operation. During
evaporation, the solvent level in the tube must be positioned to
prevent water from condensing into the sample (i.e., the solvent
level should be below the level of the water bath). Under normal
8151 - 14 Revision 0
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operating conditions, the extract should not be allowed to become
dry. Proceed to Sec. 7.4.5.
7.4.5 Dilute the extract with 1 ml of isooctane and 0.5 mL of
methanol. Dilute to a final volume of 4 mL with diethyl ether. The
sample is now ready for methylation with diazomethane. If PFB derivation
is being performed, dilute to 4 ml with acetone.
7.5 Esterification - For diazomethane derivatization proceed with Sec.
7.5.1. For PFB derivatization proceed with Sec. 7.5.2.
7.5.1 Diazomethane Derivatization - Two methods may be used for the
generation of diazomethane: the bubbler method (see Figure 1), Sec.
7.5.1.1, and the Diazald kit method, Sec. 7.5.1.2.
CAUTION: Diazomethane is a carcinogen
certain conditions.
and can explode under
The bubbler method is suggested when small batches of samples
(10-15) require esterification. The bubbler method works well with
samples that have low concentrations of herbicides (e.g., aqueous samples)
and is safer to use than the Diazald kit procedure. The Diazald kit
method is good for large quantities of samples needing esterification.
The Diazald kit method is more effective than the bubbler method for soils
or samples that may contain high concentrations of herbicides (e.g.,
samples such as soils that may result in yellow extracts following
hydrolysis may be difficult to handle by the bubbler method). The
diazomethane derivatization (U.S.EPA, 1971) procedures, described below,
will react efficiently with all of the chlorinated herbicides described in
this method and should be used only by experienced analysts, due to the
potential hazards associated with its use. The following precautions
should be taken:
Use a safety screen.
Use mechanical pipetting aides.
Do not heat above 90°C - EXPLOSION may result.
Avoid grinding surfaces, ground-glass joints, sleeve bearings,
and glass stirrers - EXPLOSION may result.
Store away from alkali metals - EXPLOSION may result.
Solutions of diazomethane decompose rapidly in the presence of
solid materials such as copper powder, calcium chloride, and
boiling chips.
7.5.1.1
(see Figure 1).
Bubbler method - Assemble the diazomethane bubbler
7.5.1.1.1 Add 5 mL of diethyl ether to the first test
tube. Add 1 mL of diethyl ether, 1 mL of carbitol, 1.5 mL of
37% KOH, and 0.1-0.2 g of Diazald to the second test tube.
Immediately place the exit tube into the concentrator tube
containing the sample extract. Apply nitrogen flow
(10 mL/min) to bubble diazomethane through the extract for
10 minutes or until the yellow color of diazomethane persists.
8151 - 15
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The amount of Diazald used is sufficient for esterification of
approximately three sample extracts. An additional 0.1-0.2 g
of Diazald may be added (after the initial Diazald is
consumed) to extend the generation of the diazomethane. There
is sufficient KOH present in the original solution to perform
a maximum of approximately 20 minutes of total esterification.
7.5.1.1.2 Remove the concentrator tube and seal it
with a Neoprene or Teflon stopper. Store at room temperature
in a hood for 20 minutes.
7.5.1.1.3 Destroy any unreacted di azomethane by adding
0.1-0.2 g of silicic acid to the concentrator tube. Allow to
stand until the evolution of nitrogen gas has stopped. Adjust
the sample volume to 10.0 mL with hexane. Stopper the
concentrator tube or transfer 1 ml of sample to a GC vial, and
store refrigerated if further processing will not be performed
immediately. Analyze by gas chromatography.
7.5.1.1.4 Extracts should be stored at 4°C away from
light. Preservation study results indicate that most analytes
are stable for 28 days; however, it is recommended that the
methylated extracts be analyzed immediately to minimize the
trans-esterification and other potential reactions that may
occur.
7.5.1.2 Diazald kit method - Instructions for preparing
diazomethane are provided with the generator kit.
7.5.1.2.1 Add 2 mL of diazomethane solution and let
the sample stand for 10 minutes with occasional swirling. The
yellow color of diazomethane should be evident and should
persist for this period.
7.5.1.2.2 Rinse the inside wall of the ampule with 700
/iL of diethyl ether. Reduce the sample volume to
approximately 2 ml to remove excess diazomethane by allowing
the solvent to evaporate spontaneously at room temperature.
Alternatively, 10 mg of silicic acid can be added to destroy
the excess diazomethane.
7.5.1.2.3 Dilute the sample to 10.0 ml with hexane.
Analyze by gas chromatography. It is recommended that the
methylated extracts be analyzed immediately to minimize the
trans-esterification and other potential reactions that may
occur.
7.5.2 PFB Method
7.5.2.1 Add 30 /zL of 10% K2C03 and 200 /zL of 3% PFBBr in
acetone. Close the tube with a glass stopper and mix on a vortex
mixer. Heat the tube at 60°C for 3 hours.
8151 - 16 Revision 0
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7.5.2.2 Evaporate the solution to 0.5 ml with a gentle
stream of nitrogen. Add 2 mL of hexane and repeat evaporation just
to dryness at ambient temperature.
7.5.2.3 Redissolve the residue in 2 ml of toluene:hexane
(1:6) for column cleanup.
7.5.2.4 Top a silica column (Bond Elut™ or equivalent)
with 0.5 cm of anhydrous sodium sulfate. Prewet the column with 5
ml hexane and let the solvent drain to the top of the adsorbent.
Quantitatively transfer the reaction residue to the column with
several rinsings of the toluene:hexane solution (total 2-3 mL).
7.5.2.5 Elute the column with sufficient toluene:hexane to
collect 8 ml of eluent. Discard this fraction, which contains
excess reagent.
7.5.2.6 Elute the column with toluene:hexane (9:1) to
collect 8 ml of eluent containing PFB derivatives in a 10 mL
volumetric flask. Dilute to 10 mL with hexane. Analyze by GC/ECD.
7.6 Gas chromatographic conditions (recommended):
7.6.1 Narrow Bore
7.6.1.1 Primary Column 1:
Temperature program: 60°C to 300°C, at 4°C/min
Helium carrier flow: 30 cm/sec
Injection volume: 2 /iL, splitless, 45 sec delay
Injector temperature: 250°C
Detector temperature: 320°C
7.6.1.2 Primary Column la:
Temperature program: 60°C to 300°C, at 4°C/min
Helium carrier flow: 30 cm/sec
Injection volume: 2 juL, splitless, 45 sec delay
Injector temperature: 250°C
Detector temperature: 320°C
7.6.1.3 Column 2:
Temperature program: 60°C to 300°C, at 4°C/min
Helium carrier flow: 30 cm/sec
Injection volume: 2 juL, splitless, 45 sec delay
Injector temperature: 250°C
Detector temperature: 320°C
8151 - 17 Revision 0
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7.6.1.4 Confirmation Column:
Temperature program: 60°C to 300°C, at 4°C/min
Helium carrier flow: 30 cm/sec
Injection volume: 2 jiiL, splitless, 45 sec delay
Injector temperature: 250°C
Detector temperature: 320°C
7.6.2 Wide-bore
7.6.2.1 Primary Column:
Temperature program: 0.5 minute at 150°C, 150°C to 270°C at
5°C/min
Helium carrier flow: 7 mL/min
Injection volume: 1 /xL
7.6.2.2 Confirmatory Column:
Temperature program: 0.5 minute at 150°C, 150°C to 270°C at
5°C/min
Helium carrier flow: 7 mL/min
Injection volume: 1 p,l
7.7 Calibration
7.7.1 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these procedures.
Use Table 1 for guidance on selecting the lowest point on the calibration
curve.
7.8 Gas chromatographic analysis
7.8.1 Refer to Method 8000. If the internal standard calibration
technique is used, add 10 /zL of internal standard to the sample prior to
injection.
7.8.2 Follow Method 8000 for instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria. Include a mid-concentration standard after each
group of 10 samples in the analysis sequence.
7.8.3 An example of a chromatogram for a methylated chlorophenoxy
herbicide is shown in Figure 2. Tables 2 and 3 present retention times
for the target analytes after esterification, using the diazomethane
derivatization procedure and the PFB derivatization procedure,
respectively.
7.8.4 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).
7.8.5 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
8151 - 18 Revision 0
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in the sample chromatogram which corresponds to the compounds used for
calibration purposes.
7.8.6 If calibration standards have been analyzed in the same manner
as the samples (e.g. have undergone hydrolysis and esterification), then
the calculation of concentration given in Method 8000 should be used.
However, if calibration is performed using standards made from methyl
ester compounds (compounds not esterified by application of this method),
then the calculation of concentration must include a correction for the
molecular weight of the methyl ester versus the acid herbicide.
7.8.7 If peak detection and identification are prevented due to
interferences, further cleanup is required. Before using any cleanup
procedure, the analyst must process a series of standards through the
procedure to validate elution patterns and the absence of interferences
from reagents.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized. If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method 8000.
8.2.1 Select a representative spike concentration for each compound
(acid or ester) to be measured. Using stock standards, prepare a quality
control check sample concentrate, in acetone, that is 1000 times more
concentrated than the selected concentrations. Use this quality control
check sample concentrate to prepare quality control check samples.
8.2.2 Tables 4 and 5 present bias and precision data for water and
clay matrices, using the diazomethane derivatization procedure. Table 6
presents relative recovery data generated using the PFB derivatization
procedure and water samples. Compare the results obtained with the results
given in these Tables to determine if the data quality is acceptable.
8.3 Calculate surrogate standard recovery on all standards, samples,
blanks, and spikes. Determine if the recovery is within limits (limits
established by performing QC procedures outlined in Method 8000).
8.3.1 If recovery is not within limits, the following procedures are
required:
8.3.1.1 Check to be sure there are no errors in
calculations, surrogate solutions and internal standards. Also,
check instrument performance.
8.3.1.2 Recalculate the data and/or reanalyze the extract
if any of the above checks reveal a problem.
8151 - 19 Revision 0
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8.3.1.3 Reextract and reanalyze the sample if none of the
above are a problem or flag the data as "estimated concentration."
8.4 GC/MS confirmation
8.4.1 GC/MS techniques should be judiciously employed to support
qualitative identifications made with this method. Refer to Method 8270
for the appropriate GC/MS operating conditions and analysis procedures.
8.4.2 When available, chemical ionization mass spectra may be
employed to aid the qualitative identification process.
8.4.3 Should these MS procedures fail to provide satisfactory
results, additional steps may be taken before reanalysis. These steps may
include the use of alternate packed or capillary GC columns or additional
cleanup.
9.0 METHOD PERFORMANCE
9.1 In single laboratory studies using organic-free reagent water and
clay/still bottom samples, the mean recoveries presented in Tables 4 and 5 were
obtained for diazomethane derivatization. The standard deviations of the percent
recoveries of these measurements are also in Tables 4 and 5.
9.2 Table 6 presents relative recoveries of the target analytes obtained
using the PFB derivatization procedure with spiked water samples.
10.0 REFERENCES
1. Fed. Reg. 1971, 38, No. 75, Pt. II.
2. Goerlitz, D. G.; Lamar, W.L., "Determination of Phenoxy Acid Herbicides in
Water by Electron Capture and Microcoulometric Gas Chromatography,". U.S.
Geol. Survey Water Supply Paper 1967, 1817-C.
3. Burke, J. A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects, J. Assoc. Off Anal. Chem. 1965, 48, 1037.
4. "Extraction and Cleanup Procedures for the Determination of Phenoxy Acid
Herbicides in Sediment"; U.S. Environmental Protection Agency. EPA
Toxicant and Analysis Center: Bay St. Louis, MS, 1972.
5. Shore, F.L.; Amick, E.N.; Pan, S. T. "Single Laboratory Validation of EPA
Method 8151 for the Analysis of Chlorinated Herbicides in Hazardous
Waste"; U.S. Environmental Protection Agency. Environmental Monitoring
Systems Laboratory. Office of Research and Development, Las Vegas, NV,
1985; EPA-60014-85-060.
6. Method 515.1, "Determination of Chlorinated Acids in Water by Gas
Chromatography with an Electron Capture Detector", Revision 4.0, USEPA,
Office of Research and Development, Environmental Monitoring Systems
Laboratory, Cincinnati, Ohio.
8151 - 20 Revision 0
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7. Method 1618, "Organo-halide and Organo-phosphorus Pesticides and Phenoxy-
acid Herbicides by Wide Bore Capillary Column Gas Chromatography with
Selective Detectors", Revision A, July 1989, USEPA, Office of Water
Regulations and Standards, Washington, DC.
8. Gurka, D.F, Shore, F.L., Pan, S-T, "Single Laboratory Validation of EPA
Method 8150 for Determination of Chlorinated Herbicides in Hazardous
Waste", JAOAC, 69, 970, 1986.
8151 - 21 Revision 0
September 1994
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Figure 1
DIAZOMETHANE GENERATOR
nitrogen
rubber (topper
gloss tubing
tube 1
tube 2
8151 - 22
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September 1994
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Figure 2
CHROMATOGRAM OF METHYL ESTERS OF CHLOROPHENOXYACIDS
100.0
RIC-
200 400
3:2O 6:40
600
10:OO
Dalapon. methyl ester
Dicamba. methyl ester
MCPP. methyl estsr
MCPA. methyl ester
Dichlorprop. methyl ester
2.4.-D. methyl ester
Silver, nieihyl ester
2.4.6 T. methyl ester
2.4 OB. methyl ester
Oinoseli. methyl ether
1200
20:00
Scan Time
8151 - 23
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TABLE 1
ESTIMATED METHOD DETECTION LIMITS FOR METHOD 8151,
DIAZOMETHANE DERIVATIZATION
Aqueous Samples
Analyte
Acifluorfen
Bentazon
Chloramben
2,4-0
Dalapon
2,4-DB
DCPA diacid"
Dicamba
3,5-Dichlorobenzoic acid
Dichloroprop
Dinoseb
5-Hydroxydicamba
MCPP
MCPA
4-Nitrophenol
Pentachlorophenol
Picloram
2,4,5-T
2,4,5-TP
GC/ECD
Estimated
Detection
Limit8
(M9/L)
0.096
0.2
0.093
0.2
1.3
0.8
0.02
0.081
0.061
0.26
0.19
0.04
0.09d
0.056d
0.13
0.076
0.14
0.08
0.075
Soil Samples
GC/ECD
Estimated
Detection
Limitb
(/*g/kg)
4.0
0.11
0.12
0.38
66
43
0.34
0.16
0.28
GC/MS
Estimated
Identification
Limit0
(ng)
1.7
1.25
0.5
0.65
0.43
0.3
0.44
1.3
4.5
a EDL = estimated detection limit; defined as either the MDL (40 CFR Part 136,
Appendix B, Revision 1.11 ), or a concentration of analyte in a sample
yielding a peak in the final extract with signal-to-noise ratio of
approximately 5, whichever value is higher.
b Detection limits determined from standard solutions corrected back to 50 g
samples, extracted and concentrated to 10 mL, with 5 /xL injected.
Chromatography using narrow bore capillary column, 0.25 ^m film,
5% pnenyl/95% methyl silicone.
c The minimum amount of analyte to give a Finnigan INCOS FIT value of 800 as
the methyl derivative vs. the spectrum obtained from 50 ng of the respective
free acid herbicide.
40 CFR Part 136, Appendix B (49 FR 43234).
capillary column.
Chromatography using wide-bore
e DCPA monoacid and diacid metabolites included in method scope; DCPA diacid
metabolite used for validation studies. DCPA is a dimethyl ester.
8151 - 24
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TABLE 2
RETENTION TIMES (MINUTES) OF METHYL DERIVATIVES OF CHLORINATED HERBICIDES
Megabore Columns
Narrow Bore Columns
Wide-bore Columns
Analyte
Dalapon
3,5-Dichlorobenzoic
4-Nitrophenol
DCAA (surrogate)
Dicamba
Dichloroprop
2,4-D
DBOB (internal std.
Pentachlorophenol
Chloramben
2,4,5-TP
5-Hydroxydicamba
2,4,5-T
2,4-DB
Dinoseb
Bentazon
Picloram
DCPA diacidc
Acifluorfen
MCPP
MCPA
Primary8
Column
3.4
acid 18.6
18.6
22.0
22.1
25.0
25.5
) 27.5
28.3
29.7
29.7
30.0
30.5
32.2
32.4
33.3
34.4
35.8
41.5
Confirmation8
Column
4.7
17.7
20.5
14.9
22.6
25.6
27.0
27.6
27.0
32.8
29.5
30.7
30.9
32.2
34.1
34.6
37.5
37.8
42.8
Primary6
Column
4.39
5.15
5.85
6.97
7.92
8.74
4.24
4.74
Confirmation5
Column
4.39
5.46
6.05
7.37
8.20
9.02
4.55
4.94
Primary Column:
Confirmation Column:
Temperature program:
Helium carrier flow:
Injection volume:
Injector temperature:
Detector temperature;
Primary Column:
Confirmatory Column:
Temperature program:
Helium carrier flow:
Injection volume:
5% phenyl/95% methyl silicone
14% cyanopropyl phenyl silicone
60°C to 300°C, at 4°C/min
30 cm/sec
2 juL, splitless, 45 sec delay
250°C
320°C
DB-608
14% cyanopropyl phenyl silicone
0.5 minute at 150°C,
150°C to 270°C, at 5°C/min
7 mL/min
1
111 JCV- I I Ull VUIUIIIG. 1 JU,I-
DCPA monoacid and diacid metabolites included in method scope; DCPA diacid
metabolite used for validation studies. DCPA is a dimethyl ester.
8151 - 25
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TABLE 3
RETENTION TIMES (MINUTES) OF PFB DERIVATIVES OF CHLORINATED HERBICIDES
Herbicide
Gas Chromatographic Column
Thin-film DB-5a
SP-2250*
Thick-film DB-5C
Dalapon
MCPP
Dicamba
MCPA
Dichloroprop
2,4-D
Silvex
2,4,5-T
Dinoseb
2,4-DB
10.41
18.22
18.73
18.88
19.10
19.84
21.00
22.03
22.11
23.85
12.94
22.30
23.57
23.95
24.10
26.33
27.90
31.45
28.93
35.61
13.54
22.98
23.94
24.18
24.70
26.20
29.02
31.36
31.57
35.97
a DB-5 capillary column, 0.25 /zm film thickness, 0.25 mm ID x 30 m long.
Column temperature, programmed: 70°C for 1 minute, program 10°C/min. to
240°C, hold for 17 minutes.
b SP-2550 capillary column, 0.25 pirn film thickness, 0.25 mm ID x 30 m long.
Column temperature, programmed: 70°C for i minute, program 10°C/min. to
240°C, hold for 10 minutes.
c DB-5 capillary column, 1.0 /urn film thickness, 0.32 mm ID x 30 m long.
Column temperature, programmed: 70°C for 1 minute, program 10°C/min. to
240°C, hold for 10 minutes.
8151 - 26
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TABLE 4
ACCURACY AND PRECISION FOR METHOD 8151
DIAZOMETHANE DERIVATIZATION, ORGANIC-FREE REAGENT WATER MATRIX
Analyte
Acifluorfen
Bentazon
Chloramben
2,4-D
Dalapon
2,4-DB
DCPA diacidb
Dicamba
3,5-Dichlorobenzoic acid
Dichloroprop
Dinoseb
5-Hydroxydicamba
4-Nitrophenol
Pentachlorophenol
Picloram
2,4,5-TP
2,4,5-T
Spike
Concentration
(M9/L)
0.2
1
0.4
1
10
4
0.2
0.4
0.6
2
0.4
0.2
1
0.04
0.6
0.4
0.2
Mean8 Standard
Percent Deviation of
Recovery Percent Recovery
121
120
111
131
100
87
74
135
102
107
42
103
131
130
91
117
134
15.7
16.8
14.4
27.5
20.0
13.1
9.7
32.4
16.3
20.3
14.3
16.5
23.6
31.2
15.5
16.4
30.8
Mean percent recovery calculated from 7-8 determinations of spiked
organic-free reagent water.
DCPA monoacid and diacid metabolites included in method scope; DCPA
diacid metabolite used for validation studies. DCPA is a dimethyl ester.
8151 - 27
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TABLE 5
ACCURACY AND PRECISION FOR METHOD 8151
DIAZOMETHANE DERIVATIZATION, CLAY MATRIX
Analyte
Mean
Percent Recovery8
Linear
Concentration
Rangeb
(ng/g)
Percent
Relative
Standard Deviation0
(n-20)
Dicamba
MCPP
MCPA
Dichloroprop
2,4-D
2,4,5-TP
2,4,5-T
2,4-DB
Dinoseb
95.7
98.3
96.9
97.3
84.3
94.5
83.1
90.7
93.7
0.52
620
620
1.5
1.2
0.42
0.42
4.0
0.82
- 104
- 61,800
- 61,200
- 3,000
- 2,440
- 828
- 828
- 8,060
- 1,620
7.5
3.4
5.3
5.0
5.3
5.7
7.3
7.6
8.7
Mean percent recovery calculated from 10 determinations of spiked clay
and clay/still bottom samples over the linear concentration range.
Linear concentration range was determined using standard solutions and
corrected to 50 g solid samples.
Percent relative standard deviation was calculated using standard
solutions, 10 samples high in the linear concentration range, and 10
samples low in the range.
8151 - 28
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TABLE 6
RELATIVE RECOVERIES OF PFB DERIVATIVES OF HERBICIDES8
Standard
Concentration
Relative recoveries, %
Analyte
MCPP
Dicamba
MCPA
Dichloroprop
2,4-D
Silvex
2,4,5-T
2,4-DB
Mean
mg/L
5.
3.
10.
6.
9.
10.
12.
20.
1
9
1
0
8
4
8
1
1
95.6
91.4
89.6
88.4
55.6
95.3
78.6
99.8
86.8
2
88.8
99.2
79.7
80.3
90.3
85.8
65.6
96.3
85.7
3
97.1
100
87.0
89.5
100
91.5
69.2
100
91.8
4
100
92.7
100
100
65.9
100
100
88.4
93.4
5
95.5
84.0
89.5
85.2
58.3
91.3
81.6
97.1
85.3
6
97.2
93.0
84.9
87.9
61.6
95.0
90.1
92.4
89.0
7
98.1
91.1
92.3
84.5
60.8
91.1
84.3
91.6
87.1
8
98.2
90.1
98.6
90.5
67.6
96.0
98.5
91.6
91.4
Mean
96.3
92.7
90.2
88.3
70.0
93.3
83.5
95.0
Percent recovery determinations made using eight spiked water samples.
8151 - 29
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METHOD 8151
CHLORINATED HERBICIDES BY GC USING METHYLATION OR PENTAFLUOROBENZYLATION
DERIVATIZATION: CAPILLARY COLUMN TECHNIQUE
Extraction/Hydrolysis of Waste and Soil Samples
NO
1
Concentrate and/or
dilute based on
whether derivatization
is by dlazomethane
orPFB
7.0 Does
sample con
tain a hign
cone of
waste?
72.1.1 Weigh sample
and add to beaker;
add add and spike;
mix wed.
7.1.1.2
Does analysis
include herbicide
esters?
72.1.2 Optimize
ultrasonic solid extrac
Son for each matrix
7.2.1.8.1 AddKOHand
water Reflux for 2 hrs.
Allow to cod.
72.1.3 AddMeCI/
acetone to sample 4
extract 3 mm ; let
serte & decant extract
7.2.1.8.2 Transfer the
hydrofyzed solutton to a
sep funnel and extract 3
times with MeCI.
Discard extracts.
7.2.1.445 Ultra-
soracalty extract sample
2 more times with MeCI
7.2.1.8.3 Acidify and
extract 3 times with
diethyl efter. Combine
and dry the extracts 2 hrs
72.15 Combine organic
extracts, centrifuge, and
filter extract. Dry for
2 hrs
Is additional
cleanup
required?
7.2.1.6 Concentrate
extract to about 5 ml
with Snyder column.
7.2.1.8.4 Proceed to
Section 7.4 to concentrate
extract
72.1.9.1 Extract 3 times
with KOH. Discard the
MeCI.
72.1.9.2 Acidify and
extract 3 times with
diethyl ether. Combine
and dry the extracts 2 hrs
72.17
Does analysis
include herbicide
esters?
If hydrolysis is not
required, proceed to Section
7.4.4, Nitrogen Slowdown.
8151 - 30
Revision 0
September 1994
-------
METHOD 8151
(continued)
Extraction/Hydrolysis of Aqueous Samples and Extract Concentration
73.1.1 Measure 1 Lot
sample and transfer to
a 2L sep. funnel.
7.3.1.2 Add2SOgNad
to sample and shake
to dissolve
7.3.1.3
Does analysts
include hetxoda esters?
7.3.1.4 Add 12N sulfunc
acid and shake. Add
until pH < 2
7.3.1.5 Adddfettyl
ether to sample and
extract Save both
phases
73.1.3.1 AddSNNaOHto
sample and shake. Add
until pH > 12. Let stand
1 hr.
7.3.1.3.2 AddMeCland
extract by shaking for
Zmin. Discard MeCI.
73.1.6 Return aqueous phase
to separately runnel and repeat
extraction 2 more times, combine
extracts, and allow extract to
remain in contact with sodium
sulfats for 2 hrs.
Does
difficult
emulsion form
>1/3 solvent
volume?
Employ mechanical techniques
to complete phase separation
(e.g. stirring, filtration through
glass wool, centritugatlon, or
other physical methods).
Discard MeCI.
7.3.1.3.3 Repeat
extraction twice more.
Discard MeCI.
Employ mechanical techniques
to oompMta phase separation
(e.g. stirring, filtration through
glass wool, centritugation. or
other physical methods).
Save both phases.
7.3.1.7 Pour extract
through glass wool and
proceed to Section 7.4.1
7.4.1 Place K-D apparatus
in water bath, concentrate
and cool
7 4.2 • 7.4.4 Complete
concentration with micro-
Snyder column or nitrogen
blow down.
74.5 Dilute extract
with 1 mL isooctane and
0 SmLmethanol
8151 - 31
Revision 0
September 1994
-------
METHOD 8151
(continued)
Extract Derlvatization
7.4.5 Dilute extract
to 4 ml with acetone
7.5.2.1 Add potassium
carbonate and PFBBr.
Close tube, mix 4 heat
7.5.2.2 Evaporate with
nitrogen to 0.5 ml. Add
2 mL hexane and repeat
75.23 Redissorve the
residue in 2 mL toluene:
hexane (1 6)
7.5.14 Load sodium
sulfate / silica cleanup
column with residue.
.4.5 Will
PFB or dlaio-
metiane deriva
zatkxibe
used?
7.4.5 OiluM extract
to 4 mL with dietfiyl
ether
7.5.1
WHIlrw \ DiazaW
Bubbler or the\ Kit
DiazaMKlt
metxidbe
used?
7.5.1 1 Assemble the
diazomethane bubbler
(Rgure 1)
7.5.1.1.1 Add 5 mL to 1st test
tube. Add 1 mL dtethyl ether.
1 mL carbitol, 1.5 mL of 37% KOH
and 0.1 • 0.2 g DlazakJ to the
2nd tube. Bubble wrth nitrogen
for 10 min or until yellow persists
7.5.1 2 Read kit
instructions
7.5.1.2.1 Add2mL
diazomethane soiuoon
Let stand for 10 min
and swirl
7.5.1.1.2 Remove con
centra tor tube and seal
it Store at room temp.
7.5.2.5 Bute column
with enough toluene:
hexane to collect 8 mL
eluant
7526 Discard 1st fraction
and continue edition with
enough toluene : hexane (1 :9)
to collect 8 mL more eluant
Transfer to a 10 mL volumetric
flask and dilute to the mark
with hexane
7.5.1.1.3 Add silicic acid to
concentrator tube and let stand
until nitrogen evolution has
stopped. Adjust sample volume
to 10 mL with hexane. Stopper.
Immediate analysis is recommended
7.5.1.2.2 Rinse ampule with
diethyl ether and evaporate
to 2 mL to remove diazomettiane
Alternatively, silicic acid
may be added.
75.1.1.5 If necessary
store at 4 C in the dark
for a max of 28 days.
7.5.1.2.3 Dilute sample
to 10 mL with hexane
7.6.1 47.6.2 SetGC
conditions
8151 - 32
Revision 0
September 1994
-------
METHOD 8151
(continued)
Analysis by Gas Chromatography
7.7 Internal or external
calibration may be used
(See method 8000).
7.8.1 Add 10 uL internal
standard to the sample
prior to injection.
7.8.2 See method 8000 for
analysis sequence, appropriate
dilutions, establishing daily
retention time windows, and
identification criteria. Check
stds every 10 samples.
7.84 Record volume
Injected and the resulting
peak sizes.
7.8.5 Determine the
identity and quantify
component peaks.
7.8.6
Have stds
and samples
been prepared and
analyzed the
way?
Calculate the correction
for molecular weight of
methyl ester vs herbicide
7.8.6 Calculate con-
centration using procedure
in Method 8000.
7.8.7 Perform further
cleanup if necessary
i
8151 - 33
Revision 0
September 1994
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00
N>
4X
O
-------
METHOD 8240A
VOLATILE ORGANICS BY GAS CHROMATOGRAPHY/HASS SPECTROMETRY fGC/HS)
1.0 SCOPE AND APPLICATION
1.1 Method 8240 is used to determine volatile organic compounds in a
variety of solid waste matrices. This method is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic liquors, acid liquors, waste solvents, oily wastes, mousses, tars,
fibrous wastes, polymeric emulsions, filter cakes, spent carbons, spent
catalysts, soils, and sediments. The following compounds can be determined by
this method:
Analyte
CAS No.
Appropriate Technique
Direct
Purge-and-Trap Injection
Acetone
Acetonitrile
Acrolein
Acrylonitrile
Ally! alcohol
Ally! chloride
Benzene
Benzyl chloride
Bromoacetone
Bromochloromethane (I.S.)
Bromodichloromethane
4-Bromofluorobenzene (surr.)
Bromoform
Bromomethane
2-Butanone
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chlorobenzene-de (I.S.)
Chi orodi bromomethane
Chloroethane
2-Chloroethanol
2-ChToroethyl vinyl ether
Chloroform
Chloromethane
Chloroprene
3 -Chi oropropi oni tri 1 e
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Oi bromomethane
l,4-Dichloro-2-butene
Dichl orodi fluoromethane
1,1-Dichloroethane
67-64-1
75-05-8
107-02-8
107-13-1
107-18-6
107-05-1
71-43-2
100-44-7
598-31-2
74-97-5
75-27-4
460-00-4
75-25-2
74-83-9
78-93-3
75-15-0
56-23-5
108-90-7
108-90-7
124-48-1
75-00-3
107-07-3
110-75-8
67-66-3
74-87-3
126-99-8
542-76-7
96-12-8
106-93-4
74-95-3
764-41-0
75-71-8
75-34-3
PP
PP
PP
PP
PP
a
a
PP
PP
a
a
a
a
a
PP
PP
a
a
a
a
a
PP
a
a
a
a
ND
PP
a
a
PP
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
pc
pc
a
a
a
a
a
a
8240A - 1
Revision 1
July 1992
-------
Appropriate Technique
Analyte
1,2-Dichloroethane
1, 2 -Dichl oroethane -djsurr.)
1, 1-Dichloroethene
trans -l,2-Dichloroethenec
1,2-Dichloropropane
l,3-Dichloro-2-propanol
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,2,3,4-Diepoxybutane
1,4-Difluorobenzene (I.S.)
1,4-Dioxane
Epichlorohydrin
Ethanol
Ethyl benzene
Ethylene oxide
Ethyl methacrylate
2-Hexanone
2-Hydroxypropionitrile
lodomethane
Isobutyl alcohol
Malononitrile
Methacrylonitrile
Methyl ene chloride
Methyl iodide
Methyl methacrylate
4-Methyl -2-pentanone
Pentachlproethane
2-Picoline
Propargyl alcohol
B-Propiolactone
Propionitrile
n-Propylamine
Pyridine
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
Toluene-d8 (surr.)
1,1,1-Trichl oroethane
1 , 1 ,2-Trichl oroethane
Trichloroethene
Trichlorofluoromethane
1 , 2 , 3-Tri chl oropropane
Vinyl acetate
Vinyl chloride
Xylene (Total)
CAS No.b
107-06-2
107-06-2
75-35-4
156-60-5
78-87-5
96-23-1
10061-01-5
10061-02-6
1464-53-5
540-36-3
123-91-1
106-89-8
64-17-5
100-41-4
75-21-8
97-63-2
591-78-6
78-97-7
74-88-4
78-83-1
109-77-3
126-98-7
75-09-2
74-88-4
80-62-6
108-10-1
76-01-7
109-06-8
107-19-7
57-57-8
107-12-0
107-10-8
110-86-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
108-88-3
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
108-05-4
75-01-4
1330-20-7
8240A - 2
Purge-and-Trap
a
a
a
a
a
PP
a
a
a
a
PP
i
i
a
PP
a
PP
NO
a
PP
PP
PP
a
a
a
PP
i
PP
PP
PP
PP
a
i
a
a
a
a
a
a
a
a
a
a
a
a
a
a
Direct
Injection
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
pc
a
a
a
a
a
a
a
a
pc
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
Revision 1
July 1992
-------
Adequate response by this technique.
Chemical Abstract Services Registry Number.
cis- and trans-1,2-dichloroethene may coelute on packed columns. For better
separation of these two compounds use Method 8260.
pp Poor purging efficiency resulting in high EQLs.
i Inappropriate technique for this analyte.
pc Poor chromatographic behavior.
1.2 Method 8240 can be used to quantitate most volatile organic compounds
that have boiling points below 200°C and that are insoluble or slightly soluble
in water. Volatile water-soluble compounds can be included in this analytical
technique. However, for the more soluble compounds, quantitation limits are
approximately ten times higher because of poor purging efficiency. The method
is also limited to compounds that elute as sharp peaks from a GC column packed
with graphitized carbon lightly coated with a carbowax. Such compounds include
low molecular weight halogenated hydrocarbons, aromatics, ketones, nitriles,
acetates, acrylates, ethers, and sulfides. See Table 1 for a list of compounds,
retention times, and their characteristic ions that have been evaluated on a
purge-and-trap GC/MS system.
1.3 The estimated quantitation limit (EQL) of Method 8240 for an
individual compound is approximately 5 jug/kg (wet weight) for soil/sediment
samples, 0,5 mg/kg (wet weight) for wastes, and 5 yug/L for ground water (see
Table 2). EQLs will be proportionately higher for sample extracts and samples
that require dilution or reduced sample size to avoid saturation of the detector,
1.4 Method 8240 is based upon a purge-and-trap, gas chromatographic/mass
spectrometric (GC/MS) procedure. This method is restricted to use by, or under
the supervision of, analysts experienced in the use of purge-and-trap systems and
gas chromatograph/mass spectrometers, and skilled in the interpretation of mass
spectra and their use as a quantitative tool.
1.5 To increase purging efficiencies of acrylonitrile and acrolein, refer
to Methods 5030 and 8030 for proper purge-and-trap conditions.
2.0 SUMMARY OF METHOD
2.1 The volatile compounds are introduced into the gas chromatograph by
the purge-and-trap method or by direct injection (in limited applications). The
components are separated via the gas chromatograph and detected using a mass
spectrometer, which is used to provide both qualitative and quantitative
information. The chromatographic conditions, as well as typical mass
spectrometer operating parameters, are given.
2.2 If the above sample introduction techniques are not applicable, a
portion of the sample is dispersed in methanol to dissolve the volatile organic
constituents. A portion of the methanolic solution is combined with organic-free
reagent water in a specially designed purging chamber. It is then analyzed by
purge-and-trap GC/MS following the normal water method.
2.3 The purge-and-trap process - An inert gas is bubbled through the
solution at ambient temperature, and the volatile components are efficiently
transferred from the aqueous phase to the vapor phase. The vapor is swept
8240A - 3 Revision 1
July 1992
-------
through a sorbent column where the volatile components are trapped. After
purging is completed, the sorbent column is heated and backflushed with inert gas
to desorb the components onto a gas chromatographic column. The gas
chromatographic column is heated to elute the components, which are detected with
a mass spectrometer.
3.0 INTERFERENCES
3.1 Interferences purged or coextracted from the samples will vary
considerably from source to source, depending upon the particular sample or
extract being tested. The analytical system, however, should be checked to
ensure freedom from interferences, under the analysis conditions, by analyzing
method blanks.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal into
the sample during shipment and storage. A trip blank, prepared from organic-free
reagent water and carried through the sampling and handling protocol, can serve
as a check on such contamination.
3.3 Cross contamination can occur whenever high-concentration and low-
concentration samples are analyzed sequentially. Whenever an unusually
concentrated sample is analyzed, it should be followed by the analysis of
organic-free reagent water to check for cross contamination. The purge-and-trap
system may require extensive bake-out and cleaning after a high-concentration
sample.
3.4 The laboratory where volatile analysis is performed should be
completely free of solvents.
3.5 Impurities in the purge gas and from organic compounds out-gassing
from the plumbing ahead of the trap account for the majority of contamination
problems. The analytical system must be demonstrated to be free from
contamination under the conditions of the analysis by running reagent blanks.
The use of non-TFE plastic coating, non-TFE thread sealants, or flow controllers
with rubber components in the purging device should be avoided.
4.0 APPARATUS AND MATERIALS
4.1 Microsyringes - 10 /iL, 25 /nl_, 100 /uL, 250 /iL, 500 juL, and 1,000 ^l.
These syringes should be equipped with a 20 gauge (0.006 in. ID) needle having
a length sufficient to extend from the sample inlet to within 1 cm of the glass
frit in the purging device. The needle length will depend upon the dimensions
of the purging device employed.
4.2 Syringe valve - Two-way, with Luer ends (three each), if applicable
to the purging device.
4.3 Syringe - 5 ml, gas-tight with shutoff valve.
4.4 Balances - Analytical, 0.0001 g, and top-loading, 0.1 g.
8240A - 4 Revision 1
July 1992
-------
4.5 Glass scintillation vials - 20 ml, with screw caps and Teflon liners
or glass culture tubes with a screw cap and Teflon liner.
4.6 Volumetric flasks, Class A - 10 mL and 100 ml, with ground-glass
stoppers.
4.7 Vials - 2 ml, for GC autosampler.
4.8 Spatula - Stainless steel.
4.9 Disposable pipets - Pasteur.
4.10 Heater or heated oil bath - Should be capable of maintaining the
purging chamber to within 1°C over the temperature range of ambient to 100°C.
4.11 Purge-and-trap device - The purge-and-trap device consists of three
separate pieces of equipment: the sample purger, the trap, and the desorber.
Several complete devices are commercially available.
4.11.1 The recommended purging chamber is designed to accept 5 ml
samples with a water column at least 3 cm deep. The gaseous headspace
between the water column and the trap must have a total volume of less than
15 ml. The purge gas must pass through the water column as finely divided
bubbles with a diameter of less than 3 mm at the origin. The purge gas
must be introduced no more than 5 mm from the base of the water column.
The sample purger, illustrated in Figure 1, meets these design criteria.
Alternate sample purge devices may be utilized, provided equivalent
performance is demonstrated.
4.11.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 in. Starting from the inlet, the trap must
contain the following amounts of adsorbents: 1/3 of 2,6-diphenylene oxide
polymer, 1/3 of silica gel, and 1/3 of coconut charcoal. It is recommended
that 1.0 cm of methyl silicone coated packing be inserted at the inlet to
extend the life of the trap (see Figure 2). If it is not necessary to
analyze for dichlorodifluoromethane or other fluorocarbons of similar
volatility, the charcoal can be eliminated and the polymer increased to
fill 2/3 of the trap. If only compounds boiling above 35°C are to be
analyzed, both the silica gel and charcoal can be eliminated and the
polymer increased to fill the entire trap. Before initial use, the trap
should be conditioned overnight at 180°C by backflushing with an inert gas
flow of at least 20 mL/min. Vent the trap effluent to the room, not to the
analytical column. Prior to daily use, the trap should be conditioned for
10 minutes at 180°C with backflushing. The trap may be vented to the
analytical column during daily conditioning. However, the column must be
run through the temperature program prior to analysis of samples.
4.11.3 The desorber should be capable of rapidly heating the trap to
180°C for desorption. The polymer section of the trap should not be heated
higher than 180 C, and the remaining sections should not exceed 220°C during
bake out mode. The desorber design illustrated in Figure 2 meets these
criteria.
8240A - 5 Revision 1
July 1992
-------
4.11.4 The purge-and-trap device may be assembled as a separate unit
or may be coupled to a gas chromatograph, as shown in Figures 3 and 4.
4.11.5 Trap Packing Materials
4.11.5.1 2,6-Diphenylene oxide polymer - 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
4.11.5.2 Methyl silicone packing - OV-1 (3%) on
Chromosorb-W, 60/80 mesh or equivalent.
4.11.5.3 Silica gel - 35/60 mesh, Davison, grade 15 or
equivalent.
4.11.5.4 Coconut charcoal - Prepare from Barnebey Cheney,
CA-580-26, lot #M-2649, by crushing through 26 mesh screen (or
equivalent).
4.12 Gas chromatograph/mass spectrometer system
4.12.1 Gas chromatograph - An analytical system complete with a
temperature programmable gas chromatograph and all required accessories
including syringes, analytical columns, and gases.
4.12.2 Column - 6 ft x 0.1 in. ID glass, packed with 1% SP-1000 orr
Carbopack-B (60/80 mesh) or equivalent.
4.12.3 Mass spectrometer - Capable of scanning from 35-260 amu every
3 seconds or less, using 70 volts (nominal) electron energy in the electron
impact mode and producing a mass spectrum that meets all the criteria in
Table 3 when 50 ng of 4-bromofluorobenzene (BFB) are injected through the
gas chromatograph inlet.
4.12.4 GC/MS interface - Any GC-to-MS interface that gives acceptable
calibration points at 50 ng or less per injection for each of the analytes
and achieves all acceptable performance criteria (see Table 3) may be used.
GC-to-MS interfaces constructed entirely of glass or of glass-lined
materials are recommended. Glass can be deactivated by silanizing with
di chlorodimethyl si 1ane.
4.12.5 Data system - A computer system that allows the continuous
acquisition and storage on machine readable media of all mass spectra
obtained throughout the duration of the chromatographic program must be
interfaced to the mass spectrometer. The computer must have software that
allows searching any GC/MS data file for ions of a specified mass and
plotting such ion abundances versus time or scan number. This type of plot
is defined as an Extracted Ion Current Profile (EICP). Software must also
be available that allows integrating the abundances in any EICP between
specified time or scan number limits. The most recent version of the
EPA/NIST Mass Spectral Library should also be available.
8240A - 6 Revision 1
July 1992
-------
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall 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 ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Stock solutions - Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standard solutions
in methanol, using assayed liquids or gases, as appropriate.
5.3.1 Place about 9.8 ml of methanol in a 10 ml tared ground-glass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes or until all alcohol wetted surfaces have dried. Weigh
the flask to the nearest 0.0001 g.
5.3.2 Add the assayed reference material, as described below.
5.3.2.1 Liquids - Using a 100 /iL syringe, immediately add
two or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5.3.2.2 Gases - To prepare standards for any compounds
that boil below 30°C (e.g. bromomethane, chloroethane, chloromethane,
or vinyl chloride), fill a 5 ml valved gas-tight syringe with the
reference standard to the 5.0 ml mark. Lower the needle to 5 mm
above the methanol meniscus. Slowly introduce the reference standard
above the surface of the liquid. The heavy gas will rapidly dissolve
in the methanol. Standards may also be prepared by using a lecture
bottle equipped with a Hamilton Lecture Bottle Septum (#86600).
Attach Teflon tubing to the side-arm relief valve and direct a gentle
stream of gas into the methanol meniscus.
5.3.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in milligrams per
liter (mg/L) from the net gain in weight. When compound purity is assayed
to be 96% or greater, the weight may be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.3.4 Transfer the stock standard solution into a Teflon sealed
screw cap bottle. Store, with minimal headspace, at -10°C to -20°C and
protect from 1ight.
5.3.5 Prepare fresh standards every two months for gases. Reactive
compounds such as 2-chloroethylvinyl ether and styrene may need to be
prepared more frequently. All other standards must be replaced after six
8240A - 7 Revision 1
July 1992
-------
months. Both gas and liquid standards must be monitored closely by
comparison to the initial calibration curve and by comparison to QC check
standards. It may be necessary to replace the standards more frequently if
either check exceeds a 25% difference.
5.4 Secondary dilution standards - Using stock standard solutions, prepare
in methanol, secondary dilution standards containing the compounds of interest,
either singly or mixed together. Secondary dilution standards must be stored
with minimal headspace and should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards from
them.
5.5 Surrogate standards - The surrogates recommended are toluene-da,
4-bromofluorobenzene, and l,2-dichloroethane-d4. Other compounds may be used as
surrogates, depending upon the analysis requirements. A stock surrogate solution
in methanol should be prepared as described in Section 5.3, and a surrogate
standard spiking solution should be prepared from the stock at a concentration
of 250 M9/10 mL in methanol. Each sample undergoing GC/MS analysis must be
spiked with 10 (j.1 of the surrogate spiking solution prior to analys.is.
5.6 Internal standards - The recommended internal standards are
bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-d5. Other compounds
may be used as internal standards as long as they have retention times similar
to the compounds being detected by GC/MS. Prepare internal standard stock and
secondary dilution standards in methanol using the procedures described in-
Sections 5.3 and 5.4. It is recommended that the secondary dilution standard
should be prepared at a concentration of 25 mg/L of each internal standard
compound. Addition of 10 y.1 of this standard to 5.0 ml of sample or calibration
standard would be the equivalent of 50 M9/L.
5.7 4-Bromofluorobenzene (BFB) standard - A standard solution containing
25 ng/jil_ of BFB in methanol should be prepared.
5.8 Calibration standards - Calibration standards at a minimum of five
concentrations should be prepared from the secondary dilution of stock standards
(see Sections 5.3 and 5.4). Prepare these solutions in organic-free reagent
water. One of the concentrations should be at a concentration near, but above,
the method detection limit. The remaining concentrations should correspond to the
expected range of concentrations found in real samples but should not exceed the
working range of the GC/MS system. Each standard should contain each analyte for
detection by this method (e.g. some or all of the target analytes may be
included). Calibration standards must be prepared daily.
5.9 Matrix spiking standards - Matrix spiking standards should be prepared
from volatile organic compounds which will be representative of the compounds
being investigated. The suggested compounds are 1,1-dichloroethene,
trichloroethene, chlorobenzene, toluene, and benzene. The standard should be
prepared in methanol, with each compound present at a concentration of
250 /jg/10.0 ml.
5.10 Great care must be taken to maintain the integrity of all standard
solutions. It is recommended that all standards in methanol be stored at -10°C'
to -20°C in screw cap amber bottles with Teflon liners.
8240A - 8 Revision 1
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5.11 Methanol, CH3OH. Pesticide quality or equivalent. Store apart from
other solvents.
5.12 Reagent Tetraglyme - Reagent tetraglyme is defined as tetraglyme in
which interference is not observed at the method detection limit of compounds of
interest.
5.12.1 Tetraglyme (tetraethylene glycol dimethyl ether, Aldrich #17,
240-5 or equivalent), CgH^Oj. Purify by treatment at reduced pressure in a
rotary evaporator. The tetraglyme should have a peroxide content of less
than 5 ppm as indicated by EM Quant Test Strips (available from Scientific
Products Co., Catalog No. P1126-8 or equivalent).
CAUTION: Glycol ethers are suspected carcinogens. All solvent
handling should be done in a hood while using proper
protective equipment to minimize exposure to liquid and
vapor.
Peroxides may be removed by passing the tetraglyme through a column
of activated alumina. The tetraglyme is placed in a round bottom flask
equipped with a standard taper joint, and the flask is affixed to a rotary
evaporator. The flask is immersed in a water bath at 90-100°C and a vacuum
is maintained at < 10 mm Hg for at least two hours using a two stage
mechanical pump. The vacuum system is equipped with an all glass trap,
which is maintained in a dry ice/methanol bath. Cool the tetraglyme to
ambient temperature and add 100 mg/L of 2,6-di-tert-butyl-4-methy1-phenol
to prevent peroxide formation. Store the tetraglyme in a tightly sealed
screw cap bottle in an area that is not contaminated by solvent vapors.
5.12.2 In order to demonstrate that all interfering volatiles have
been removed from the tetraglyme, an organic-free reagent water/tetraglyme
blank must be analyzed.
5.13 Polyethylene glycol, H(OCH2CH2)nOH. Free of interferences at the
detection limit of the analytes.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Direct injection - In very limited applications (e.g. aqueous process
wastes), direct injection of the sample into the GC/MS system with a 10 /xL
syringe may be appropriate. One such application is for verification of the
alcohol content of an aqueous sample prior to determining if the sample is
ignitable (Methods 1010 or 1020). In this case, it is suggested that direct
injection be used. The detection limit is very high (approximately 10,000 M9/L);
therefore, it is only permitted when concentrations in excess of 10,000 M9/L are
expected or for water soluble compounds that do not purge. The system must be
calibrated by direct injection (bypassing the purge-and-trap device).
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7.2 Initial calibration for purge-and-trap procedure
7.2.1 Recommended GC/MS operating conditions
Electron energy: 70 volts (nominal).
Mass range: 35-260 amu.
Scan time: To give 5 scans/peak, but not to
exceed 7 sec/scan.
Initial column temperature: 45°C.
Initial column holding time: 3 minutes.
Column temperature program: 8°C/minute.
Final column temperature: 220°C.
Final column holding time: 15 minutes.
Injector temperature: 200-225°C.
Source temperature: According to manufacturer's
specifications.
Transfer line temperature: 250-300°C.
Carrier gas: Hydrogen at 50 cm/sec or helium at 30
cm/sec.
7.2.2 Each GC/MS system must be hardware tuned to meet the criteria
in Table 3 for a 50 ng injection or purging of 4-bromofluorobenzene (2 Mi-
injection of the BFB standard). Analyses must not begin until these
criteria are met.
7.2.3 Assemble a purge-and-trap device that meets the specification
in Section 4.11. Condition the trap overnight at 180°C in the purge mode
with an inert gas flow of at least 20 mL/min. Prior to use, condition the
trap daily for 10 min while backflushing at 180°C with the column at 220°C.
7.2.4 Connect the purge-and-trap device to a gas chromatograph.
7.2.5 Prepare the final solutions containing the required
concentrations of calibration standards, including surrogate standards,
directly in the purging device (use freshly prepared stock solutions when
preparing the calibration standards for the initial calibration.) Add
5.0 ml of organic-free reagent water to the purging device. The organic-
free reagent water is added to the purging device using a 5 ml glass
syringe fitted with a 15 cm, 20 gauge needle. The needle is inserted
through the sample inlet shown in Figure 1. The internal diameter of the
14 gauge needle that forms the sample inlet will permit insertion of the 20
gauge needle. Next, using a 10 yuL or 25 nl microsyringe equipped with a
long needle (Section 4.1), take a volume of the secondary dilution solution
containing appropriate concentrations of the calibration standards (Section
5.8). Add the aliquot of calibration solution directly to the organic-free
reagent water in the purging device by inserting the needle through the
sample inlet. When discharging the contents of the microsyringe, be sure
that the end of the syringe needle is well beneath the surface of the
organic-free reagent water. Similarly, add 10 ^L of the internal standard
solution (Section 5.6). Close the 2 way syringe valve at the sample inlet.
7.2.6 Carry out the purge-and-trap analysis procedure as described
in Section 7.4.1.
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7.2.7 Tabulate the area response of the characteristic ions (see
Table 1) against concentration for each compound and each internal
standard. Calculate response factors (RF) for each compound relative to
one of the internal standards. The internal standard selected for the
calculation of the RF for a compound should be the internal standard that
has a retention time closest to the compound being measured (Section
7.5.2). The RF is calculated as follows:
where:
Ax = Area of the characteristic ion for the compound being
measured.
Ajs = Area of the characteristic ion for the specific internal
standard.
Cis = Concentration of the specific internal standard.
Cx = Concentration of the compound being measured.
7.2.8 The average RF must be calculated for each compound. A system
performance check should be made before this calibration curve is used.
Five compounds (the System Performance Check Compounds, or SPCCs) are
checked for a minimum average response factor. These compounds are
chloromethane, 1,1-dichloroethane, bromoform, 1,1,2,2-tetrachloroethane,
and chlorobenzene. The minimum acceptable average RF for these compounds
should be 0.300 (0.250 for bromoform) . These compounds typically have RFs
of 0.4-0.6 and are used to check compound instability and to check for
degradation caused by contaminated lines or active sites in the system.
Examples' of these occurrences are:
7.2.8.1 Chloromethane - This compound is the most likely
compound to be lost if the purge flow is too fast.
7.2.8.2 Bromoform - This compound is one of the compounds
most likely to be purged very poorly if the purge flow is too slow.
Cold spots and/or active sites in the transfer lines may adversely
affect response. Response of the quantitation ion (m/z 173) is
directly affected by the tuning of BFB at ions m/z 174/176.
Increasing the m/z 174/176 ratio may improve bromoform response.
7.2.8.3 Tetrachloroethane and 1,1-dichloroethane - These
compounds are degraded by contaminated transfer lines in purge-and-
trap systems and/or active sites in trapping materials.
7.2.9 Using the RFs from the initial calibration, calculate the
percent relative standard deviation (%RSD) for Calibration Check Compounds
(CCCs).
SD
%RSD = - x 100
where:
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RSO = relative standard deviation.
x = mean of 5 initial RFs for a compound.
SO = standard deviation of average RFs for a compound.
N (x,-
£
Ni=l N
-x)2
- 1
SO
The %RSD for each individual CCC should be less than 30 percent.
This criterion must be met in order for the individual calibration to be
valid. The CCCs are:
1,1-Dichloroethene,
Chloroform,
1,2-Dichloropropane,
Toluene,
Ethyl benzene, and
Vinyl chloride.
7.3 Daily GC/MS calibration
7.3.1 Prior to the analysis of samples, inject or purge 50 ng of the
4-bromofluorobenzene standard. The resultant mass spectra for the BFB must
meet all of the criteria given in Table 3 before sample analysis begins,.
These criteria must be demonstrated each 12 hour shift.
7.3.2 The initial calibration curve (Section 7.2) for each compound
of interest must be checked and verified once every 12 hours of analysis
time. This is accomplished by analyzing a calibration standard that is at
a concentration near the midpoint concentration for the working range of
the GC/MS by checking the SPCC (Section 7.3.3) and CCC (Section 7.3.4).
7.3.3 System Performance Check Compounds (SPCCs) - A system
performance check must be made each 12 hours. If the SPCC criteria are
met, a comparison of response factors is made for all compounds. This is
the same check that is applied during the initial calibration. If the
minimum response factors are not met, the system must be evaluated, and
corrective action must be taken before sample analysis begins. The minimum
response factor for volatile SPCCs is 0.300 (0.250 for Bromoform). Some
possible problems are standard mixture degradation, injection port inlet
contamination, contamination at the front end of the analytical column, and
active sites in the column or chromatographic system.
7.3.4 Calibration Check Compounds (CCCs): After the system
performance check is met, CCCs listed in Section 7.2.9 are used to check
the validity of the initial calibration. Calculate the percent difference
using:
RF, - RFC
% Difference = = x 100
RF,
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where:
RF = average response factor from initial calibration
(Section 7.2).
RF = response factor from current verification check
standard.
If the percent difference for any compound is greater than 20, the
laboratory should consider this a warning limit. If the percent difference
for each CCC is less than 25%, the initial calibration is assumed to be
valid. If the criterion is not met (> 25% difference), for any one CCC,
corrective action MUST be taken. Problems similar to those listed under
SPCCs could affect this criterion. If no source of the problem can be
determined after corrective action has been taken, a new five point
calibration MUST be generated. This criterion MUST be met before
quantitative sample analysis begins.
7.3.5 The internal standard responses and retention times in the
check calibration standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard changes
by more than 30 seconds from the last daily calibration (Section 7.3), the
chromatographic system must be inspected for malfunctions and corrections
must be made, as required. If the EICP area for any of the internal
standards changes by a factor of two (- 50% to + 100%) from the last daily
calibration standard check, the mass spectrometer must be inspected for
malfunctions and corrections must be made, as appropriate. When
corrections are made, reanalysis of samples analyzed while the system was
malfunctioning are necessary.
7.4 GC/MS analysis
7.4.1 Water samples
7.4.1.1 Screening of the sample prior to purge-and-trap
analysis will provide guidance on whether sample dilution is
necessary and will prevent contamination of the purge-and-trap
system. Two screening techniques that can be used are: the
headspace sampler (Method 3810) using a gas chromatograph (GC)
equipped with a photo ionization detector (PID) in series with an
electrolytic conductivity detector (HECD); and extraction of the
sample with hexadecane and.analysis of the extract on a GC with a FID
and/or an ECD (Method 3820).
7.4.1.2 All samples and standard solutions must be allowed
to warm to ambient temperature before analysis.
7.4.1.3 Set up the GC/MS system as outlined in Section
7.2.1.
7.4.1.4 BFB tuning criteria and daily GC/MS calibration
criteria must be met (Section 7.3) before analyzing samples.
7.4.1.5 Adjust the purge gas (helium) flow rate to 25-
40 ml/min on the purge-and-trap device. Optimize the flow rate to
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provide the best response for chloromethane and bromoform, if these
compounds are analytes. Excessive flow rate reduces chloromethane
response, whereas insufficient flow reduces bromoform response (see
Section 7.2.8).
7.4.1.6 Remove the plunger from a 5 ml syringe and attach
a closed syringe valve. Open the sample or standard bottle, which
has been allowed to come to ambient temperature, and carefully pour
the sample into the syringe barrel to just short of overflowing.
Replace the syringe plunger and compress the sample. Open the
syringe valve and vent any residual air while adjusting the sample
volume to 5.0 ml. This process of taking an aliquot destroys the
validity of the liquid sample for future analysis; therefore, if
there is only one VOA vial, the analyst should fill a second syringe
at this time to protect against possible loss of sample integrity.
This second sample is maintained only until such time when the
analyst has determined that the first sample has been analyzed
properly. Filling one 20 mL syringe would allow the use of only one
syringe. If a second analysis is needed from a syringe, it must be
analyzed within 24 hours. Care must be taken to prevent air from
leaking into the syringe.
7.4.1.7 The following procedure is appropriate for
diluting purgeable samples. All steps must be performed without
delays until the diluted sample is in a gas tight syringe.
7.4.1.7.1 Dilutions may be made in volumetric flasks
(10 to 100 mL). Select the volumetric flask that will allow
for the necessary dilution. Intermediate dilutions may be
necessary for extremely large dilutions.
7.4.1.7.2 Calculate the approximate volume of organic-
free reagent water to be added to the volumetric flask
selected and add slightly less than this quantity of organic-
free reagent water to the flask.
7.4.1.7.3 Inject the proper aliquot of samples from
the syringe prepared in Section 7.4.1.6 into the flask.
Aliquots of less than 1 mL are not recommended. Dilute the
sample to the mark with organic-free reagent water. Cap the
flask, invert, and shake three times. Repeat above procedure
for additional dilutions.
7.4.1.7.4 Fill a 5 ml syringe with the diluted sample
as in Section 7.4.1.6.
7.4.1.8 Add 10.0 p.1 of surrogate spiking solution (Section
5.5) and 10 /*L of internal standard spiking solution (Section 5.6)
through the valve bore of the syringe; then close the valve. The
surrogate and internal standards may be mixed and added as a single
spiking solution. The addition of 10 pi of the surrogate spiking
solution to 5 mL of sample is equivalent to a concentration of
50 jjg/L of each surrogate standard.
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7.4.1.9 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the syringe valves and
inject the sample into the purging chamber.
7.4.1.10 Close both valves and purge the sample for 11.0 ±
0.1 minutes at ambient temperature.
7.4.1.11 At the conclusion of the purge time, attach the
trap to the chromatograph, adjust the device to the desorb mode, and
begin the gas chromatographic temperature program and GC/MS data
acquisition. Concurrently, introduce the trapped materials to the gas
chromatographic column by rapidly heating the trap to 180°C while
backflushing the trap with inert gas between 20 and 60 mL/min for
4 minutes. If this rapid heating requirement cannot be met, the gas
chromatographic column must be used as a secondary trap by cooling it
to 30°C (or subambient, if problems persist) instead of the
recommended initial program temperature of 45°C.
7.4.1.12 While the trap is being desorbed into the gas
chromatograph, empty the purging chamber. Wash the chamber with a
minimum of two 5 mL flushes of organic-free reagent water (or
methanol followed by organic-free reagent water) to avoid carryover
of pollutant compounds into subsequent analyses.
7.4.1.13 After desorbing the sample for 4 minutes,
recondition the trap by returning the purge-and-trap device to the
purge mode. Wait 15 seconds; then close the syringe valve on the
purging device to begin gas flow through the trap. The trap
temperature should be maintained at 180°C. Trap temperatures up to
220 C may be employed; however, the higher temperature will shorten
the useful life of the trap. After approximately 7 minutes, turn off
the trap heater and open the syringe valve to stop the gas flow
through the trap. When cool, the trap is ready for the next sample.
7.4.1.14 If the initial analysis of a sample or a dilution
of the sample has a concentration of analytes that exceeds the
initial calibration range, the sample must be reanalyzed at a higher
dilution. Secondary ion quantitation is allowed only when there are
sample interferences with the primary ion. When a sample is analyzed
that has saturated ions from a compound, this analysis must be
followed by a blank organic-free reagent water analysis. If the
blank analysis is not free of interferences, the system must be
decontaminated. Sample analysis may not resume until a blank can be
analyzed that is free of interferences.
7.4.1.15 For matrix spike analysis, add 10 juL of the matrix
spike solution (Section 5.9) to the 5 ml of sample to be purged.
Disregarding any dilutions, this is equivalent to a concentration of
50 jig/L of each matrix spike standard.
7.4.1.16 All dilutions should keep the response of the
major constituents (previously saturated peaks) in the upper half of
the linear range of the curve. Proceed to Sections 7.5.1 and 7.5.2
for qualitative and quantitative analysis.
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7.4.2 Water miscible liquids
7.4.2.1 Water miscible liquids are analyzed as water
samples after first diluting them at least 50 fold with organic-free
reagent water.
7.4.2.2 Initial and serial dilutions can be prepared by
pipetting 2 mL of the sample to a 100 mi volumetric flask and
diluting to volume with organic-free reagent water. Transfer
immediately to a 5 mL gas tight syringe.
7.4.2.3 Alternatively, prepare dilutions directly in a 5
ml syringe filled with organic-free reagent water by adding at least
20 /iL, but not more than 100 /uL of liquid sample. The sample is
ready for addition of internal and surrogate standards.
7.4.3 Sediment/soil and waste samples - It is highly recommended
that all samples of this type be screened prior to the purge-and-trap GC/MS
analysis. The headspace method (Method 3810) or the hexadecane extraction
and screening method (Method 3820) may be used for this purpose. These
samples may contain percent quantities of purgeable organics that will
contaminate the purge-and-trap system, and require extensive cleanup and
instrument downtime. Use the screening data to determine whether to use
the low-concentration method (0.005-1 mg/kg) or the high-concentration
method (> 1 mg/kg).
7.4.3.1 Low-concentration method - This is designed for
samples containing individual purgeable compounds of < 1 mg/kg. It
is limited to sediment/soil samples and waste that is of a similar
consistency (granular and porous). The low-concentration method is
based on purging a heated sediment/soil sample mixed with organic-
free reagent water containing the surrogate and internal standards.
Analyze all reagent blanks and standards under the same conditions as
the samples. See Figure 5 for an illustration of a low soils
impinger.
7.4.3.1.1 Use a 5 g sample if the expected
concentration is < 0.1 mg/kg or a 1 g sample for expected
concentrations between 0.1 and 1 mg/kg.
7.4.3.1.2 The GC/MS system should be set up as in
Sections 7.4.1.2-7.4.1.4. This should be done prior to the
preparation of the sample to avoid loss of volatiles from
standards and samples.- A heated purge calibration curve must
be prepared and used for the quantitation of all samples
analyzed with the low-concentration method. Follow the
initial and daily calibration instructions, except for the
addition of a 40°C purge temperature.
7.4.3.1.3 Remove the plunger from a 5 mL Luerlock type
syringe equipped with a syringe valve and fill until
overflowing with water. Replace the plunger and compress the
water to vent trapped air. Adjust the volume to 5.0 mL. Add
10 juL each of surrogate spiking solution (Section 5.5) and
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internal standard solution (Section 5.6) to the syringe
through the valve. (Surrogate spiking solution and internal
standard solution may be mixed together.) The addition of 10
Ml of the surrogate spiking solution to 5 g of sediment/soil
is equivalent to 50 jug/kg of each surrogate standard.
7.4.3.1.4 The sample (for volatile organics) consists
of the entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents of the
sample container with a narrow metal spatula. Weigh the
amount determined in Section 7.4.3.1.1 into a tared purge
device. Note and record the actual weight to the nearest 0.1
9-
7.4.3.1.5 Determine the percent dry weight of the
soil/sediment sample. This includes waste samples that are
amenable to percent dry weight determination. Other wastes
should be reported on a wet-weight basis.
7.5.3.1.5.1 Immediately after weighing the sample
for extraction, weigh 5-10 g of the sample into a tared
crucible. Determine the % dry weight of the sample by
drying overnight at 105°C. Allow to cool in a
desiccator before re-weighing. Concentrations of
individual analytes are reported relative to the dry
weight of sample.
WARNING: The drying oven should be contained
in a hood or vented. Significant
laboratory contamination may result
from a heavily contaminated hazardous
waste sample.
% dry weight = g of dry sample x 100
g of sample
7.4.3.1.6 Add the spiked water to the purge device,
which contains the weighed amount of sample, and connect the
device to the purge-and-trap system.
NOTE: Prior to the attachment of the purge device, the
procedures in Sections 7.4.3.1.4 and 7.4.3.1.6
must be performed rapidly and without
interruption to avoid loss of volatile organics.
These steps must be performed in a laboratory
free of solvent fumes.
7.4.3.1.7 Heat the sample to 40°C ± 1°C and purge the
sample for 11.0 +.0.1 minute.
7.4.3.1.8 Proceed with the analysis as outlined in
Sections 7.4.1.11-7.4.1.16. Use 5 ml of the same organic-free
reagent water as in the reagent blank. If saturated peaks
occurred or would occur if a 1 g sample were analyzed, the
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high-concentration method must be followed.
7.4.3.1.9 For low-concentration sediment/soils add
10 nl of the matrix spike solution (Section 5.9) to the 5 mL
of organic-free reage'nt water (Section 7.4.3.1.3). The
concentration for a 5 g sample would be equivalent to 50 jug/kg
of each matrix spike standard.
7.4.3.2 High-concentration method - The method is based on
extracting the sediment/soil with methanol. A waste sample is either
extracted or diluted, depending on its solubility in methanol.
Wastes (i.e. petroleum and coke wastes) that are insoluble in
methanol are diluted with reagent tetraglyme or possibly polyethylene
glycol (PEG). An aliquot of the extract is added to organic-free
reagent water containing internal standards. This is purged at
ambient temperature. All samples with an expected concentration of
> 1.0 mg/kg should be analyzed by this method.
7.4.3.2.1 The sample (for volatile organics) consists
of the entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents of the
sample container with a narrow metal spatula. For
sediment/soil and solid wastes that are insoluble in methanol,
weigh 4 g (wet weight) of sample into a tared 20 ml vial. Use
a top loading balance. Note and record the actual weight to
0.1 gram and determine the percent dry weight of the sample
using the procedure in Section 7.4.3.1.5. For waste that is
soluble in methanol, tetraglyme, or PEG, weigh 1 g (wet
weight) into a tared scintillation vial or culture tube or a
10 ml volumetric flask. (If a vial or tube is used, it must
be calibrated prior to use. Pipet 10.0 mL of solvent into the
vial and mark the bottom of the meniscus. Discard this
solvent.)
7.4.3.2.2 For sediment/soil or solid waste, quickly
add 9.0 mL of appropriate solvent, then add 1.0 mL of the
surrogate spiking solution to the vial. For a solvent
miscible sample, dilute the sample to 10 mL with the
appropriate solvent after adding 1.0 mL of the surrogate
spiking solution. Cap and shake for 2 minutes.
NOTE: Sections 7.4.3.2.1 and 7.4.3.2.2 must be
performed rapidly and without interruption to
avoid loss- of volatile organics. These steps
must be performed in a laboratory free from
solvent fumes.
7.4.3.2.3 Pipet approximately 1 mL of the extract to
a GC vial for storage, using a disposable pipet. The
remainder may be disposed of. Transfer approximately 1 mL of
appropriate solvent to a separate GC vial for use as the
method blank for each set of samples. These extracts may be
stored at 4°C in the dark, prior to analysis. The addition of
a 100 /LtL aliquot of each of these extracts in Section
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7.4.3.2.6 will give a concentration equivalent to 6,200
of each surrogate standard.
7.4.3.2.4 The GC/MS system should be set up as in
Sections 7.4.1.2-7.4.1.4. This should be done prior to the
addition of the solvent extract to organic-free reagent water.
7.4.3.2.5 Table 4 can be used to determine the volume
of solvent extract to add to the 5 ml of organic-free reagent
water for analysis. If a screening procedure was followed
(Method 3810 or 3820), use the estimated concentration to
determine the appropriate volume. Otherwise, estimate the
concentration range of the sample from the low-concentration
analysis to determine the appropriate volume. If the sample
was submitted as a high-concentration sample, start with 100
/iL. All dilutions must keep the response of the major
constituents (previously saturated peaks) in the upper half of
the linear range of the curve.
7.4.3.2.6 Remove the plunger from a 5.0 mL Luerlock
type syringe equipped with a syringe valve and fill until
overflowing with water. Replace the plunger and compress the
water to vent trapped air. Adjust the volume to 4.9 ml. Pull
the plunger back to 5.0 mL to allow volume for the addition of
the sample extract and of standards. Add 10 /iL of internal
standard solution. Also add the volume of solvent extract
determined in Section 7.4.3.2.5 and a volume of extraction or
dissolution solvent to total 100 nl (excluding methanol in
standards).
7.4.3.2.7 Attach the syringe-syringe valve assembly to
the syringe valve on the purging device. Open the syringe
valve and inject the organic-free reagent water/methanol
sample into the purging chamber.
7.4.3.2.8 Proceed with the analysis as outlined in
Section 7.4.1.11-7.4.1.16. Analyze all reagent blanks on the
same instrument as that use for the samples. The standards
and blanks should also contain 100 nl of solvent to simulate
the sample conditions.
7.4.3.2.9 For a matrix spike in the high-concentration
sediment/soil samples, add 8.0 ml of methanol, 1.0 ml of
surrogate spike solution (Section 5.5), and 1.0 ml of matrix
spike solution (Section 5.9) as in Section 7.4.3.2.2. This
results in a 6,200 jig/kg concentration of each matrix spike
standard when added to a 4 g sample. Add a 100 /xL aliquot of
this extract to 5 ml of organic-free reagent water for purging
(as per Section 7.4.3.2.6).
7.5 Data interpretation
7.5.1 Qualitative analysis
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7.5.1.1 An analyte (e.g. those listed in Table 1) is
identified by comparison of the sample mass spectrum with the mass
spectrum of a standard of the suspected compound (standard reference
spectrum). Mass spectra for standard reference should be obtained on
the user's GC/MS within the same 12 hours as the sample analysis.
These standard reference spectra may be obtained through analysis of
the calibration standards. Two criteria must be satisfied to verify
identification: (1) elation of sample component at the same GC
relative retention time (RRT) as those of the standard component; and
(2) correspondence of the sample component and the standard component
mass spectrum.
7.5.1.1.1 The sample component RRT must compare within
±0.06 RRT units of the RRT of the standard component. For
reference, the standard must be run within the same 12 hours
as the sample. If coelution of interfering components
prohibits accurate assignment of the sample component RRT from
the total ion chromatogram, the RRT should be assigned by
using extracted ion current profiles for ions unique to the
component of interest.
7.5.1.1.2 (1) All ions present in the standard mass
spectra at a relative intensity greater than 10% (most
abundant ion in the spectrum equals 100% must be present in
the sample spectrum). (2) The relative intensities of ions
specified in (1) must agree within plus or minus 20% between
the standard and sample spectra. (Example: For an ion with
an abundance of 50% in the standard spectra, the corresponding
sample abundance must be between 30 and 70 percent.
7.5.1.2 For samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the type of analyses
being conducted. Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should be present in
the sample spectrum.
(2) The relative intensities of the major ions should agree
within + 20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%).
(3) Molecular ions present in the reference spectrum should
be present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible background
contamination or presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible subtraction from the
8240A - 20 Revision 1
July 1992
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sample spectrum because of background contamination or coeluting
peaks. Data system library reduction programs can sometimes create
these discrepancies.
Computer generated library search routines should not use
normalization routines that would misrepresent the library or unknown
spectra when compared to each other. Only after visual comparison of
sample with the nearest library searches will the mass spectral
interpretation specialist assign a tentative identification.
7.5.2 Quantitative analysis
7.5.2.1 When a compound has been identified, the
quantitation of that compound will be based on the integrated
abundance from the EICP of the primary characteristic ion.
Quantitation will take place using the internal standard technique.
The internal standard used shall be the one nearest the retention
time of that of a given analyte (e.g. see Table 5).
7.5.2.2 Calculate the concentration of each identified
analyte in the sample as follows:
Water and Water-Miscible Waste:
concentration (ng/l) =
(A,.)(RF)(V0)
where:
Ax * Area of characteristic ion for compound being
measured.
Is = Amount of internal standard injected (ng).
Ais = Area of characteristic ion for the internal
standard.
RF = Response factor for compound being measured
(Section 7.2.7).
V0 =» Volume of water purged (ml), taking into
consideration any dilutions made.
Sediment/Soil, Sludge, and Waste:
High-concentration:
(A, )(!,) (Vt)
concentration (jug/kg)
(A,.)(RF)(Vf)(H,)
Low-concentration:
(Ax )(I.)
concentration (jig/kg)
(Ais)(RF)(Ws)
8240A - 21 Revision 1
July 1992
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Ax, Is, Ajs, RF = Same as in water and water-miscible waste
above.
where :
Vt = Volume of total extract (pi) (use 10,000 juL or a
factor of this when dilutions are made).
Vf = Volume of extract added (/iL) for purging.
Ws = Weight of sample extracted or purged (g). The
wet weight or dry weight may be used, depending
upon the specific applications of the data.
7.5.2.3 Sediment/soil samples are generally reported on a
dry weight basis, while sludges and wastes are reported on a wet
weight basis. The percent dry weight of the sample (as calculated in
Section 7.4.3.1.5) should be reported along with the data in either
instance.
7.5.2.4 Where applicable, an estimate of concentration for
noncalibrated components in the sample should be made. The formulae
given above should be used with the following modifications: The
areas A and Ais should be from the total ion chromatograms, and the
RF for the compound should be assumed to be 1. The concentration
obtained should be reported indicating (1) that the value is an
estimate and (2) which internal standard was used to determine
concentration. Use the nearest internal standard free of
interferences.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program consist
of an initial demonstration of laboratory capability and an ongoing analysis of
spiked samples to evaluate and document quality data. The laboratory should
maintain records to document the quality of the data generated. Ongoing data
quality checks are compared with established performance criteria to determine
if the results of analyses meet the performance characteristics of the method.
When results of sample spikes indicate atypical method performance, a quality
control reference sample should be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.2 Before processing any samples, the analyst should demonstrate, through
the analysis of a calibration blank, that interferences from the analytical
system, glassware, and reagents are under control. Each time a set of samples
is extracted or there is a change in reagents, a reagent blank should be
processed as a safeguard against chronic laboratory contamination. The blank
samples should be carried through all stages of sample preparation and
measurement.
8.3 The experience of the analyst performing GC/MS analyses is invaluable
to the success of the methods. Each day that analysis is performed, the daily
calibration standard should be evaluated to determine if the chromatographic
system is operating properly. Questions that should be asked are: Do the peaks
look normal?; Is the response obtained comparable to the response from previous
8240A - 22 Revision 1
July 1992
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calibrations? Careful examination of the standard chromatogram can indicate
whether the column is still useable, the injector is leaking, the injector septum
needs replacing, etc. If any changes are made to the system (e.g. column
changed), recalibration of the system should take place.
8.4 Required instrument QC is found in the following section:
8.4.1 The GC/MS system should be tuned to meet the BFB
specifications in Section 7.2.2.
8.4.2 There should be an initial calibration of the GC/MS system as
specified in Section 7.2.
8.4.3 The GC/MS system should meet the SPCC criteria specified in
Section 7.3.3 and the CCC criteria in Section 7.3.4, each 12 hours.
8.5 To establish the ability to generate acceptable accuracy and
precision, the analyst should perform the following operations.
8.5.1 A quality control (QC) reference sample concentrate is
required containing each analyte at a concentration of 10 mg/L in methanol.
The QC reference sample concentrate may be prepared from pure standard
materials or purchased as certified solutions. If prepared by the
laboratory, the QC reference sample concentrate should be made using stock
standards prepared independently from those used for calibration.
8.5.2 Prepare a QC reference sample to contain 20 M9/L of each
analyte by adding 200 /A of QC reference sample concentrate to 100 ml of
water.
8.5.3 Four 5 ml aliquots of the well mixed QC reference sample are
analyzed according to the method beginning in Section 7.4.1.
8.5.4 Calculate the average recovery (x) in M9/U and the standard
deviation of the recovery (s) in M9/L, for each analyte using the four
results.
8.5.5 For each analyte compare s and x with the corresponding
acceptance criteria_for precision and accuracy, respectively, found in
Table 6. If s and x for all analytes meet the acceptance criteria, the
system performance is acceptable and analysis of actual samples can_begirr.
If any individual s exceeds the precision limit or any individual x falls
outside the range for accuracy, then the system performance is unacceptable
for that analyte.
NOTE: The large number of analytes in Table 6 present a substantial
probability that one or more will fail at least one of the
acceptance criteria when all analytes of a given method are
determined,
8.5.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst should proceed according to Section
8.5.6.1 or 8.5.6.2.
8240A - 23 Revision 1
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8.5.6.1 Locate and correct the source of the problem and
repeat the test for all analytes beginning with Section 8.5.2.
8.5.6.2 Beginning with Section 8.5.2, repeat the test only
for those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Section
8.5.2.
8.6 The laboratory should, on an ongoing basis, analyze a reagent blank
and a spiked replicate for each analytical batch (up to a maximum of 20
samples/batch) to assess accuracy. For soil and waste samples where detectable
amounts of organics are present, replicate samples may be appropriate in place
of spiked replicates. For laboratories analyzing one to ten samples per month,
at least one spiked sample per month is required.
8.6.1 The concentration of the spike in the sample should be
determined as follows:
8.6.1.1 If, as in compliance monitoring, the concentration
of a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at that limit or
1 to 5 times higher than the background concentration determined in
Step 8.6.2, whichever concentration would be larger.
8.6.1.2 If the concentration of a specific analyte in a
water sample is not being checked against a specific limit, the spike
should be at 20 jig/L or 1 to 5 times higher than the background
concentration determined in Section 8.6.2, whichever concentration
would be larger. For other matrices, recommended spiking
concentration is 10 times the EQL.
8.6.2 Analyze one 5-mL sample aliquot to determine the background
concentration (B) of each analyte. If necessary, prepare a new QC
reference sample concentrate (Step 8.5.1) appropriate for the background
concentration in the sample. Spike a second 5-mL sample aliquot with 10 \il
of the QC reference sample concentrate and analyze it to determine the
concentration after spiking (A) of each analyte. Calculate each percent
recovery (p) as 100(A-B)%/T, where T is the known true value of the spike.
8.6.3 Compare the percent recovery (p) for each analyte in a water
sample with the corresponding QC acceptance criteria found in Table 6.
These acceptance criteria were calculated to include an allowance for error
in measurement of both the background and spike concentrations, assuming a
spike to background ratio of 5:1. This error will be accounted for to the
extent that the analyst's spike to background ratio approaches 5:1. If
spiking was performed at a concentration lower than 20 ng/L, the analyst
should use either the QC acceptance criteria presented in Table 6, or
optional QC acceptance criteria calculated for the specific spike
concentration. To calculate optional acceptance criteria for the recovery
of an analyte: (1) Calculate accuracy (x') using the equation found in
Table 7, substituting the spike concentration (T) for C; (2) calculate
overall precision (S') using the equation in Table 7, substituting x' for
8240A - 24 Revision 1
July 1992
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x; (3) calculate the range for recovery at the spike concentration as
(lOOx'/T) ± 2.44(100S'/T)%.
8.6.4 If any individual p falls outside the designated range for
recovery, that analyte has failed the acceptance criteria. A check
standard containing each analyte that failed the criteria should be
analyzed as described in Section 8.7.
8.7 If any analyte in a water sample fails the acceptance criteria for
recovery in Section 8.6, a QC reference sample containing each analyte that
failed should be prepared and analyzed.
NOTE: The frequency for the required analysis of a QC reference sample will
depend upon the number of analytes being simultaneously tested, the
complexity of the sample matrix, and the performance of the
laboratory. If the entire list of analytes in Table 6 should be
measured in the sample in Section 8.6, the probability that the
analysis of a QC reference sample will be required is high. In this
case the QC reference sample should be routinely analyzed with the
spiked sample.
8.7.1 Prepare the QC reference sample by adding 10 |iL of the QC
reference sample concentrate (Section 8.5.1 or 8.6.2) to 5 ml of reagent
water. The QC reference sample needs only to contain the analytes that
failed criteria in the test in Section 8.6.
8.7.2 Analyze the QC reference sample to determine the concentration
measured (A) of each analyte. Calculate each percent recovery (ps) as
100(A/T)%, where T is the true value of the standard concentration.
8.7.3 Compare the percent recovery (ps) for each analyte with the
corresponding QC acceptance criteria found in Table 6. Only analytes that
failed the test in Step 8.6 need to be compared with these criteria. If
the recovery of any such analyte falls outside the designated range, the
laboratory performance for that analyte is judged to be out of control, and
the problem should be immediately identified and corrected. The result for
that analyte in the unspiked sample is suspect and may not be reported for
regulatory compliance purposes.
8.8 As part of the QC program for the laboratory, method accuracy for each
matrix studied should be assessed and records should be maintained. After the
analysis of five spiked samples (of the same matrix) as in Section 8.6, calculate
the average percent recovery (p) and the standard deviation of the percent
recovery (s ). Express the accuracy assessment as a percent recovery interval
from p - 2s to p + 2s . If p = 90% and s = 10%, for example, the accuracy
interval is expressed as 70-110%. Update the accuracy assessment for each
analyte on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.9 To determine acceptable accuracy and precision limits for surrogate
standards the following procedure should be performed.
8240A -25 Revision 1
July 1992
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8.9.1 For each sample analyzed, calculate the percent recovery of
each surrogate in the sample.
8.9.2 Once a minimum of thirty samples of the same matrix have been
analyzed, calculate the average percent recovery (p) and standard deviation
of the percent recovery (s) for each of the surrogates.
8.9.3 For a given matrix, calculate the upper and lower control
limit for method performance for each surrogate standard. This should be
done as follows:
Upper Control Limit (UCL) = p + 3s
Lower Control Limit (LCL) = p - 3s
8.9.4 For aqueous and soil matrices, these laboratory established
surrogate control limits should, if applicable, be compared with the
control limits listed in Table 8. The limits given in Table 8 are multi-
laboratory performance based limits for soil and aqueous samples, and
therefore, the single-laboratory limits established in Step 8.9.3 should
fall within those given in Table 8 for these matrices.
8.9.5 If recovery is not within limits, the following procedures are
required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are a
problem or flag the data as "estimated concentration".
8.9.6 At a minimum, each laboratory should update surrogate recovery
limits on a matrix-by-matrix basis, annually.
8.10 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 assess the precision of the
environmental measurements. When doubt exists over the identification of a peak
on the chromatogram, confirmatory techniques such as gas chromatography with a
dissimilar column or a different ionizatioji mode using a mass spectrometer should
be used. Whenever possible, the laboratory should analyze standard reference
materials and participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 This method was tested by 15 laboratories using organic-free reagent
water, drinking water, surface water, and industrial wastewaters spiked at six
concentrations over the range 5-600 fj,g/l. Single operator precision, overall
precision, and method accuracy were found to be directly related to the
8240A - 26 Revision 1
July 1992
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concentration o* r.he ana'yte and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 7.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136. "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act, Method 624," October 26,
1984.
2. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
3. Bellar, T.A., and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
739-744, 1974.
4. Bellar, T.A., and J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Water
and Wastewater, ASTM STP 686, pp. 108-129, 1979.
5. Budde, W.L. and J.W. Eichelberger, "Performance Tests for the Evaluation of
Computerized Gas Chromatography/Mass Spectrometry Equipment and
Laboratories," EPA-600/4-79-020, U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268,
April 1980.
6. Eichelberger, J.W., L.E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurement in Gas Chromatography-Mass Spectrometry
Systems," Analytical Chemistry, 47, 995-1000, 1975.
7. "Method Detection Limit for Methods 624 and 625," Olynyk, P., W.L. Budde,
and J.W. Eichelberger, Unpublished report, October 1980.
8. "Interlaboratory Method Study for EPA Method 624-Purgeables," Final Report
for EPA Contract 68-03-3102.
9. "Method Performance Data for Method 624," Memorandum from R. Slater and T.
Pressley, U.S. Environmental Protection Agency, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio 45268, January 17, 1984.
10. Gebhart, J.E.; Lucas, S.V.; Naber, S.J.; Berry, A.M.; Danison, T.H.;
Burkholder, H.M. "Validation of SW-846 Methods 8010, 8015, and 8020"; U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Old 45268, July 1987, Contract No. 68-03-1760.
11. Lucas, S.V.; Kornfeld, R.A. "GC-MS Suitability Testing of RCRA Appendix
VIII and Michigan List Analytes "; U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, OH 45268,
February 20, 1987, Contract No. 68-03-3224.
8240A - 27 Revision 1
July 1992
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TABLE 1.
RETENTION TIMES AND CHARACTERISTIC IONS FOR VOLATILE COMPOUNDS
Compound
Retention
Time (minutes)
Primary Ion Secondary Ion(s)
Ethylene oxide
Chloromethane
Dichlorodifluoromethane
Bromomethane
Vinyl chloride
Acetonitrile
Chloroethane
Methyl iodide
Methylene chloride
Carbon disulfide
Trichlorofluoromethane
Propionitrile
Ally! chloride
1,1-Dichloroethene
Bromochloromethane (I.S.)
Ally! alcohol
trans- 1,2-Dichloroethene
1,2-Dichloroethane
Propargyl alcohol
Chloroform
l,2-Dichloroethane-d4(surr)
2-Butanone
Methacrylonitrile
Dibrornomethane
2-Chloroethanol
b-Propiolactone
Epichlorohydrin
1,1,1-Tri chloroethane
Carbon tetrachloride
1,4-Dioxane
Isobutyl alcohol
Bromodi Chloromethane
Chloroprene
l,2:3,4-Diepoxybutane
1,2-Dichloropropane
cis-l,3-Dichloropropene
Bromoacetone
Trichloroethene
Benzene
trans-l,3-Dichloropropene
1,1,2-Trichloroethane
3-Chloropropionitrile
1,2-Dibromoethane
Pyridine
1.30
2.30
2.47
3.10
3.80
3.97
4.60
5.37
6.40
7.47
8.30
8.53
8.83
9.00
9.30
9.77
10.00
10.10
10.77
11.40
12.10
12.20
12.37
12.53
12.93
13.00
13.10
13.40
13.70
13.70
13.80
14.30
14.77
14.87
15.70
15.90
16.33
16.50
17.00
17.20
17.20
17.37
18.40
18.57
44
50
85
94
62
41
64
142
84
76
101
54
76
96
128
57
96
62
55
83
65
72
41
93
49
42
57
97
117
88
43
83
53
55
63
75
136
130
78
75
97
54
107
79
44, 43, 42
52, 49
85, 87, 101, 103
96, 79
64, 61
41, 40, 39
66, 49
142, 127, 141
49, 51, 86
76, 78, 44
103, 66
54, 52, 55, 40
76, 41, 39, 78
61, 98
49, 130, 51
57, 58, 39
61, 98
64, 98
55, 39, 38, 53
85, 47
102
43, 72
41, 67, 39, 52, 66
93, 174, 95, 172, 176
49, 44, 43, 51, 80
42, 43, 44
57, 49, 62, 51
99, 117
119, 121
88, 58, 43, 57
43, 41, 42, 74
85, 129
53, 88, 90, 51
55, 57, 56
62, 41
77, 39
43, 136, 138, 93, 95
95, 97, 132
52, 71
77, 39
83, 85, 99
54, 49, 89, 91
107, 109, 93, 188
79, 52, 51, 50
8240A - 28
Revision 1
July 1992
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TABLE 1.
(Continued)
Compound
Retention
Time (minutes)
Primary Ion Secondary Ion(s)
2-Chloroethyl vinyl ether
2-Hydroxypropionitrile
1,4-Difluorobenzene (I.S.)
Malononitrile
Methyl methacrylate
Bromoform
1,1,1 , 2-Tetrachl oroethane
l,3-Oichloro-2-propanol
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
1,2,3-Trichloropropane
l,4-Dichloro-2-butene
n-Propylamine
2-Picoline
Toluene
Ethyl methacrylate
Chlorobenzene
Pentachl oroethane8
Ethyl benzene
l,2-Dibromo-3-chloropropane
4-Bromofluorobenzene (surr.)
Benzyl chloride
Styrene
Acetone
Acrolein
Acrylonitrile
Chlorobenzene-dc (I.S.)
Chlorodibromomethane
1,1-Dichloroethane
Ethanol
2-Hexanone
lodomethane
4-Methyl -2-pentanone
Toluene-do (surr.)
Vinyl acetate
Xylene (Total)
18.60
18.97
19.60
19.60
19.77
19.80
20.33
21.83
22.10
22.20
22.20
22.73
23.00
23.20
23.50
23.53
24.60
24.83
26.40
27.23
28.30
29.50
30.83
--
--
::
--
-.
--
--
--
-.
• -
63
44
114
66
69
173
131
79
83
164
75
75
59
93
92
69
112
167
106
157
95
91
104
43
56
53
117
129
63
31
43
142
43
98
43
106
65,106
44,43,42,53
63,88
66,39,65,38
69,41,100,39
171,175,252
131,133,117,119,95
79,43,81,49
85,131,133
129,131,166
75,77,110,112,97
75,53,77,124,89
59,41,39
93,66,92,78
91,65
69,41,99,86,114
114,77
167,130,132,165,169
91
157,75,155,77
174,176
91,126,65,128
104,103,78,51,77
58
55,58
52,51
82,119
208,206
65,83
45,27,46
58,57, 100
127,141
58,57,100
70,100
86
91
a The base peak at m/e 117 was not used due to an interference at that mass with
a nearly coeluting internal standard, chlorobenzene-d5.
8240A - 29
Revision 1
July 1992
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TABLE 2.
ESTIMATED QUANTITATION LIMITS (EQL) FOR VOLATILE ORGANICS3
Estimated
Quantitation
Limits"
Ground water
Volatiles p.g/1
Acetone
Acetonitrile
Allyl chloride
Benzene
Benzyl chloride
Bromodichloromethane
Bromoform
Bromomethane
2-Butanone
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chi orodi bromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Chloroprene
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Di bromomethane
l,
-------
TABLE 2.
(Continued)
Estimated
Quantitation
Limits6
Ground water Low Soil/Sediment
Volatiles ng/l M9/kg
Propionitrile
Styrene
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
1,2,3-Trichloropropane
Vinyl acetate
Vinyl chloride
Xylene (Total)
100
5
5
5
5
5
5
5
5
5
50
10
5
100
5
5
5
5
5
5
5
5
5
50
10
5
a Sample EQLs are highly matrix dependent. The EQLs listed herein are provided
for guidance and may not always be achievable. See the following information
for further guidance on matrix dependent EQLs.
b EQLs listed for soil/sediment are based on wet weight. Normally data is
reported on a dry weight basis; therefore, EQLs will be higher, based on the
percent dry weight of each sample.
Other Matrices Factor0
Water miscible liquid was'te 50
High-concentration soil and sludge 125
Non-water miscible waste 500
CEQL = [EQL for low soil sediment (Table 2)] X [Factor], For non-aqueous
samples, the factor is on a wet weight basis.
8240A - 31 Revision 1
July 1992
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TABLE 3.
BFB KEY ION ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
50 15 to 40% of mass 95
75 30 to 60% of mass 95
95 base peak, 100% relative abundance
96 5 to 9% of mass 95
173 0% to less than 2% of mass 174
174 greater than 50% of mass 95
175 5 to 9% of mass 174
176 greater than 95% but less than 101% of mass 174
177 5 to 9% of mass 176
TABLE 4.
QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS
OF HIGH-CONCENTRATION SOILS/SEDIMENTS
Approximate Volume of
Concentration Range Methanol Extract*
500- 10,000 ng/kg 100 /*L
1,000- 20,000 Mg/kg 50 ML
5,000-100,000 Mg/kg 10 ML
25,000-500,000 Mg/kg 100 ML of 1/50 dilution"
Calculate appropriate dilution factor for concentrations exceeding this
table.
a The volume of methanol added to 5 mL of water being purged should be kept
constant. Therefore, add to the 5 mL syringe whatever volume of methanol
is necessary to maintain a volume of 100 ML added to the syringe.
b Dilute and aliquot of the methanol extract and then take 100 ML for
analysis.
8240A - 32 Revision 1
July 1992
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TABLE 5.
VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES ASSIGNED
FOR QUANTITATION
Bromochloromethane
Acetone
Acrolein
Acrylonitrile
Bromomethane
Carbon disulfide
Chloroethane
Chloroform
Chloromethane
Di chlorodi fluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
l,2-Dichloroethane-d4 (surrogate)
1,1-Dichloroethene
trans-1,2-Dichloroethene
lodomethane
Methylene chloride
Tri chlorof1uoromethane
Vinyl chloride
1,4-Difluorobenzene
Benzene
Bromodichloromethane
Bromoform
2-Butanone
Carbon tetrachloride
Chlorodi bromomethane
2-Chloroethyl vinyl ether
Dibromomethane
l,4-Dichloro-2-butene
1,2-Dichloropropane
cis^l,3-Dichloropropene
trans-l,3-Dichloropropene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Vinyl acetate
Chlorobenzene-dc
Bromofluorobenzene (surrogate)
Chlorobenzene
Ethyl benzene
Ethyl methacrylate
2-Hexanone
4-Methyl-2-pentanone
Styrene
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
Toluene-d8 (surrogate)
1,2,3-Trichloropropane
Xylene
8240A - 33
Revision 1
July 1992
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TABLE 6.
CALIBRATION AND QC ACCEPTANCE CRITERIA3
Parameter
Benzene
Bromodi Chloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
2-Chloroethylvinyl ether
Chloroform
Chloromethane
Dibromochloromethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans -1,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethyl benzene
Methylene chloride
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
Vinyl chloride
Range
for Q
(M9/L)
12.8-27.2
13.1-26.9
14.2-25.8
2.8-37.2
14.6-25.4
13.2-26.8
0-44.8
13.5-26.5
D-40.8
13.5-26.5
12.6-27.4
14.6-a5.4
12.6-27.4
14.5-25.5
13.6-26.4
10.1-29.9
13.9-26.1
6.8-33.2
4.8-35.2
10.0-30.0
11.8-28.2
12.1-27.9
12.1-27.9
14.7-25.3
14.9-25.1
15.0-25.0
14.2-25.8
13.3-26.7
9.6-30.4
0.8-39.2
Q = Concentration measured in QC check
s = Standard deviation of four recovery
x = Average recovery
p, ps = Percent recovery
D = Detected; result
for four recovery
measured.
Limi t
for s
(M9/L)
6.9
6.4
5.4
17.9
5.2
6.3
25.9
6.1
19.8
6.1
7.1
5.5
7.1
5.1
6.0
9.1
5.7
13.8
15.8
10.4
7.5
7.4
7.4
5.0
4.8
4.6
5.5
6.6
10.0
20.0
sample,
Range
for x
(M9/L)
15.2-26.0
10.1-28.0
11.4-31.1
D-41.2
17.2-23.5
16.4-27.4
D-50.4
13.7-24.2
D-45.9
13.8-26.6
11.8-34.7
17.0-28.8
11.8-34.7
14.2-28.4
14.3-27.4
3.7-42.3
13.6-28.4
3.8-36.2
1.0-39.0
7.6-32.4
17.4-26.7
D-41.0
13.5-27.2
17.0-26.6
16.6-26.7
13.7-30.1
14.3-27.1
18.5-27.6
8.9-31.5
D-43.5
in ng/L.
Range
P,PS
37-151
35-155
45-169
0-242
70-140
37-160
0-305
51-138
0-273
53-149
18-190
59-156
18-190
59-155
49-155
0-234
54-156
0-210
0-227
17-183
37-162
D-221
46-157
64-148
47-150
52-162
52-150
71-157
17-181
D-251
measurements, in /ug/L.
measurements, in /ug/L.
must be greater than zero.
Criteria from 40 CFR Part 136 for Method 624 and were calculated assuming a
QC check sample concentration of 20 /ug/L- These criteria are based directly
upon the method performance data in Table 7. Where necessary, the limits for
recovery have been broadened to assure applicability of the limits to
concentrations below those used to develop Table 7.
8240A - 34
Revision 1
July 1992
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TABLE 7.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Accuracy, as
recovery, x'
(M9/L)
Single analyst Overall
precision, s ' precision.
(M9/L) S' (Mg/L)
Benzene
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl ether3
Chloroform
Chloromethane
Di bromochl oromethane
l,2-Dich1orobenzeneb
1,3-Dichlorobenzene
1,4-Di chlorobenzene6
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2,-Dichloroethene
l,2-Dich1oropropanea
cis-l,3-Dichloropropenea
trans -1,3-Di chl oropropene3
Ethyl benzene
Methyl ene chloride
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chl orof 1 uoromethane
Vinyl chloride
0.93C+2.00
1.03C-1.58
1.18C-2.35
l.OOC
1.10C-1.68
0.98C+2.28
1.18C+0.81
l.OOC
0.93C+0.33
1.03C-1.81
1.01C-0.03
0.94C+4.47
1.06C+1.68
0.94C+4.47
1.05C+0.36
1.02C+0.45
1.12C+0.61
1.05C+0.03
l.OOC
l.OOC
l.OOC
0.98C+2.48
0.87C+1.88
0.93C+1.76
1.06C+0.60
0.98C+2.03
1.06C+0.73
0.95C+1.71
1.04C+2.27
0.99C+0.39
l.OOC
0.26X-1.74
0.15X+0.59
0.12X+0.34
0.43x
0.12X+0.25
0.16X-0.09
0.14X+2.78
0.62x
0.16X+0.22
0.37X+2.14
0.17x-0.18
0.22X-1.45
0.14X-0.48
0.22X-1.45
0.13X-0.05
0.17X-0.32
O.Ux+1.06
0.14X+0.09
0.33x
0.38x
0.25x
0.14X+1.00
O.lBx+1.07
0.16X+0.69
0.13X-0.18
O.lBx-0.71
0.12X-0.15
0.14X+0.02
0.13X+0.36
0.33X-1.48
0.48x
0.25X-1.33
0.20x+1.13
0.17x+1.38
0.58x
O.llx+0.37
0.26x-1.92
0.29X+1.75
0.84x
O.lSx+0.16
0.58x+0,43
0.17X+0.49
O.SOx-1.20
O.lSx-0.82
fl.30x-l.20
0.16X+0.47
0.21X-0.38
0.43X-0.22
0.19X+0.17
0.45x
0.52X
0.34X
0.26X-1.72
0.32X+4.00
0. 20X+0.41
0.16X-0.45
0.22X-1.71
0.21X-0.39
0.18X+0.00
0.12X+0.59
0.34X-0.39
0.65x
x' = Expected recovery for one or more measurements of a sample
containing a concentration of C, in M9/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of x, in /ig/L.
S' = Expected interlaboratory standajd deviation of measurements at an
average concentration found of x, in /zg/L.
C = True value for the concentration, in Mg/L.
x = Average recovery found for measurements of samples containing a
concentration of C, in ng/L.
a Estimates based upon the performance in a single laboratory.
b Due to chromatographic resolution problems, performance statements for
these isomers are based upon the sums of their concentrations.
8240A - 35
Revision 1
July 1992
-------
TABLE 8.
SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Low/High Low/High
Surrogate Compound Water Soil/Sediment
4-Bromofluorobenzene 86-115 74-121
1,2-Dichloroethane-d, 76-114 70-121
Toluene-dfl 88-110 81-117
8240A - 36 Revision 1
July 1992
-------
FIGURE 1.
PURGING CHAMBER
OPTIONAL
FOAM TRAP jH Exit * lnch °- °
Inch 0. 0. Exit
10 mm Glass Frit
Medium PorotitY
14 mm 0. 0.
Inlet 'A Inch 0. 0.
Sample Inlet
2-Way Syringe Valve
17 cm, 20 Gauge Syringe Needle
6 mm 0. D. Rubber Septum
— 10 mm 0 D.
Inlet
4 Inch 0. D.
1/16 Inch 0 D
Stainless Ste«:
13x Molecular
Sieve Purge
Gas Filter
Purge Gas
Flow Control
8240A - 37
Revision 1
July 1992
-------
FIGURE 2.
TRAP PACKINGS AND CONSTRUCTION TO INCLUDE
DESORB CAPABILITY FOR METHOD 8240A
Packing Procedure
Construction
Glass Wool 5 mm
t
Silica G«l Bern
Ttn»x 15cm
3%OV-1 lemj
Glut Wool 5 mm
Compression
Pitting Nut
and Ferrules
14 Ft. ?n/Foot
Rtsittanet Wire
Wrapptd Solid
Thirmocouple/
Controiltr
Electronic
Ttmptratun
Control *nd
Tubing 25 cm
0.105 In. l.D.
0.125 In. O.D.
Stiinlw Stt«l
Trap Inlet
8240A - 38
Revision 1
July 1992
-------
FIGURE 3.
SCHEMATIC OF PURGE-AND-TRAP DEVICE - PURGE MODE FOR METHOD 8240A
CMMMOAS
*JOM CONT1XX
4TOMV
TO OCTtCTOA
»
*»- AHUtmCAl OOUIMN
HOTl
AU. UM
ANO OC SHOULD M HCATW
8240A - 39
Revision 1
July 1992
-------
FIGURE 4.
SCHEMATIC OF PURGE-ANO-TRAP DEVICE - OESOR8 MODE FOR METHOD 8240A
r- uouo MJCCTOH "ours
CCUAMOCM
fOOCTKTOI
AKH.TTCA1. CtXUMM
AM) (K SHOUU) M HCAHO
TOWX.
8240A - 40
Revision 1
July 1992
-------
FIGURE 5.
LOW SOILS IMPINGER
PU*GE INLET rrrnwo
J • I mm o D CLASS TUHKC
8240A - 41
Revision 1
July 1992
-------
METHOD 8240A
VOLATILE ORGANICS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)
Purg«-and-trap
Dir«ct
In)«cI ion
Selvcl
procedure for
in t roducing
•ample into
CC/MS
'.2 1 S.t
CC/MS
opvnting
cortdi 11 oni
724 Connvct
purg»-ind-trap
d«vic« to CC
' I 6 P.rform
purgcand- trap
analytii
' 2 8
Caleulat* RF«
for S SPCC.
7 3 P.rfor.
daily
calibration
u«ing SPCCt
and CCC.
8240A - 42
Revision 1
July 1992
-------
METHOD 8240A
(continued)
Low concentra*. ian
sail /sediment
Medium concentration
•oil/sediment
?421
Dilute sample
a', lea si 50%
with water
Hater and Ma ter
miscible liquids
7411
Screen sampl•
us ing Method
3810 or 3820
7417
Perform
secondary
di1ution»
7418 Add
internal standard
and surrogate
spilt ing solution*
7 4 1 10
Per form
purge-and•t rap
procedure
I ' I
74311
Choo»* sample
size based on
es tima ted
concen t ra tion
7 4 3 1 3 Add
internal standard
and surrogate
spiking solutions
74315
Determine
percent dry
weight of
sample
74317
Perform
purge-and-trap
procedure
7 4 1 11
Attach trap
*.o CC and
perform
analyst!
7432 Choose
sol ven t for
•itraction or
dilution Weigh
sample
7511 Identify
anaiytes by
comparing the
sample and standard
mass spectra
7 4 3 2 2 Add
jo 1 vent.
shake
7522 Calculate
lh« concent rat von
of each identified
analyle
74327
Per form
purge•and * t rap
procedure
7525
Report all
resu1ts
Stop
8240A - 43
Revision 1
July 1992
-------
00
o
03
-------
METHOD 8240B
VOLATILE ORGANIC COMPOUNDS BY GAS CHRQMATOGRAPHY/MASS SPECTROMETRY (GC/MS1
1.0 SCOPE AND APPLICATION
1.1 Method 8240 is used to determine volatile organic compounds in a
variety of solid waste matrices. This method is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic liquors, acid liquors, waste solvents, oily wastes,
fibrous wastes, polymeric emulsions, filter cakes, spent
catalysts, soils, and sediments. The following compounds can
this method:
mousses, tars,
carbons, spent
be determined by
ApproDriate Technique
Analyte
Acetone
Acetonitrile
Acrolein (Propenal)
Acrylonitrile
Allyl alcohol
Allyl chloride
Benzene
Benzyl chloride
Bromoacetone
Bromochloromethane (I.S.)
Bromodichloromethane
4-Bromofluorobenzene (surr.)
Bromoform
Bromomethane
2-Butanone (MEK)
Carbon disulfide
Carbon tetrachloride
Chloral hydrate
Chlorobenzene
Chlorobenzene-d5 (I.S.)
Chi orodi bromomethane
Chloroethane
2-Chloroethanol
bis-(2-Chloroethyl) sulfide
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Chloroprene
3-Chloropropionitrile
1 , 2-Dibromo-3-chl oropropane
1,2-Dibromoethane
CAS No.b
67-64-1
75-05-8
107-02-8
107-13-1
107-18-6
107-05-1
71-43-2
100-44-7
598-31-2
74-97-5
75-27-4
460-00-4
75-25-2
74-83-9
78-93-3
75-15-0
56-23-5
302-17-0
108-90-7
3114-55-4
124-48-1
75-00-3
107-07-3
505-60-2
110-75-8
67-66-3
74-87-3
126-99-8
542-76-7
96-12-8
106-93-4
Purge-and-Trap
PP
PP
PP
PP
PP
a
a
PP
PP
a
a
a
a
a
PP
PP
a
PP
a
a
a
a
PP
PP
a
a
a
a
ND
PP
a
Direct
Injection
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
pc
pc
a
a
8240B - 1
Revision 2
September 1994
-------
Appropriate Technique
Analyte
Dibromomethane
l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
l,2-Dichloroethane-d4(surr.)
1,1-Dichloroethene
trans -1 ,2-Dichloroethene
1,2-Dichloropropane
l,3-Dichloro-2-propanol
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,2,3,4-Diepoxybutane
1,4-Difluorobenzene (I.S.)
1,4-Dioxane
Epichlorohydrin
Ethanol
Ethyl benzene
Ethylene oxide
Ethyl methacrylate
2-Hexanone
2-Hydroxypropionitrile
lodomethane
Isobutyl alcohol
Malononitrile
Methacrylonitrile
Methylene chloride
Methyl iodide
Methyl methacrylate
4-Methyl -2-pentanone
Pentachloroethane
2-Picol ine
Propargyl alcohol
B-Propiolactone
Propionitrile
n-Propylamine
Pyridine
Styrene
1,1,1, 2 -Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
Toluene-d8 (surr.)
1,1,1-Trichloroethane
1, 1, 2 -Tri chl oroethane
Trichloroethene
Trichlorofl uoromethane
CAS No.b
74-95-3
764-41-0
75-71-8
75-34-3
107-06-2
107-06-2
75-35-4
156-60-5
78-87-5
96-23-1
10061-01-5
10061-02-6
1464-53-5
540-36-3
123-91-1
106-89-8
64-17-5
100-41-4
75-21-8
97-63-2
591-78-6
78-97-7
74-88-4
78-83-1
109-77-3
126-98-7
75-09-2
74-88-4
80-62-6
108-10-1
76-01-7
109-06-8
107-19-7
57-57-8
107-12-0
107-10-8
110-86-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
2037-26-5
71-55-6
79-00-5
79-01-6
75-69-4
Purge-and-Trap
a
PP
a
a
a
a
a
a
a
PP
a
a
a
a
PP
i
i
a
PP
a
PP
ND
a
PP
PP
PP
a
a
a
PP
i
PP
PP
PP
PP
a
i
a
a
a
a
a
a
a
a
a
a
Direct
Injection
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
pc
a
a
a
a
a
a
a
a
pc
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
8240B - 2
Revision 2
September 1994
-------
Appropriate Technique
Direct
Analyte CAS No.b Purge-and-Trap Injection
1,2,3-Trichloropropane
Vinyl acetate
Vinyl chloride
Xylene (Total)
96-18-4
108-05-4
75-01-4
1330-20-7
a
a
a
a
a
a
a
a
a Adequate response by this technique.
b Chemical Abstract Services Registry Number.
pp Poor purging efficiency resulting in high EQLs.
i Inappropriate technique for this analyte.
pc Poor chromatographic behavior.
surr Surrogate
I.S. Internal Standard
ND Not determined
1.2 Method 8240 can be used to quantitate most volatile organic
compounds that have boiling points below 200°C and that are insoluble or slightly
soluble in water. Volatile water-soluble compounds can be included in this
analytical technique. However, for the more soluble compounds, quantitation
limits are approximately ten times higher because of poor purging efficiency.
The method is also limited to compounds that elute as sharp peaks from a GC
column packed with graphitized carbon lightly coated with a carbowax. Such
compounds include low molecular weight halogenated hydrocarbons, aromatics,
ketones, nitriles, acetates, acrylates, ethers, and sulfides. See Table 1 for
a list of compounds, retention times, and their characteristic ions that have
been evaluated on a purge-and-trap GC/MS system.
1.3 The estimated quantitation limit (EQL) of Method 8240 for an
individual compound is approximately 5 /jg/kg (wet weight) for soil/sediment
samples, 0.5 mg/kg (wet weight) for wastes, and 5 jug/L for ground water (see
Table 2). EQLs will be proportionately higher for sample extracts and samples
that require dilution or reduced sample size to avoid saturation of the detector.
1.4 This method is restricted to use by, or under the supervision of,
analysts experienced in the use of purge-and-trap systems and gas
chromatograph/mass spectrometers, and skilled in the interpretation of mass
spectra and their use as a quantitative tool.
1.5 To increase purging efficiencies of acrylonitrile and acrolein,
refer to Methods 5030 and 8030 for proper purge-and-trap conditions.
2.0 SUMMARY OF METHOD
2.1 The volatile compounds are introduced into the gas chromatograph by
the purge-and-trap method or by direct injection (in limited applications). The
8240B - 3 Revision 2
September 1994
-------
components are separated via the gas chromatograph and detected using a mass
spectrometer, which is used to provide both qualitative and quantitative
information. The chromatographic conditions, as well as typical mass
spectrometer operating parameters, are given.
2.2 If the above sample introduction techniques are not applicable, a
portion of the sample is dispersed in methanol to dissolve the volatile organic
constituents. A portion of the methanolic solution is combined with organic-free
reagent water in a specially designed purging chamber. It is then analyzed by
purge-and-trap GC/MS following the normal water method.
2.3 The purge-and-trap process - An inert gas is bubbled through the
solution at ambient temperature, and the volatile components are efficiently
transferred from the aqueous phase to the vapor phase. The vapor is swept
through a sorbent column where the volatile components are trapped. After
purging is completed, the sorbent column is heated and backflushed with inert gas
to desorb the components onto a gas chromatographic column. The gas
chromatographic column is heated to elute the components, which are detected with
a mass spectrometer.
3.0 INTERFERENCES
3.1 Interferences purged or coextracted from the samples will vary
considerably from source to source, depending upon the particular sample or
extract being tested. The analytical system, however, should be checked to
ensure freedom from interferences, under the analysis conditions, by analyzing
method blanks.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal into
the sample during shipment and storage. A trip blank, prepared from organic-free
reagent water and carried through the sampling and handling protocol, can serve
as a check on such contamination.
3.3 Cross contamination can occur whenever high-concentration and low-
concentration samples are analyzed sequentially. Whenever an unusually
concentrated sample is analyzed, it should be followed by the analysis of
organic-free reagent water to check for cross contamination. The purge-and-trap
system may require extensive bake-out and cleaning after a high-concentration
sample.
3.4 The laboratory where volatile analysis is performed should be
completely free of solvents.
3.5 Impurities in the purge gas and from organic compounds out-gassing
from the plumbing ahead of the trap account for the majority of contamination
problems. The analytical system must be demonstrated to be free from
contamination under the conditions of the analysis by running calibration and
reagent blanks. The use of non-TFE plastic coating, non-TFE thread sealants, or
flow controllers with rubber components in the purging device should be avoided.
8240B - 4 Revision 2
September 1994
-------
4.0 APPARATUS AND MATERIALS
4.1 Microsyringes - 10 /xL, 25 txL, 100 /xL, 250 /xL, 500 /xL, and 1,000 /xL.
These syringes should be equipped with a 20 gauge (0.006 in. ID) needle having
a length sufficient to extend from the sample inlet to within 1 cm of the glass
frit in the purging device. The needle length will depend upon the dimensions
of the purging device employed.
4.2 Syringe valve - Two-way, with Luer ends (three each), if applicable
to the purging device.
4.3 Syringe - 5 ml, gas-tight with shutoff valve.
4.4 Balances - Analytical, 0.0001 g, and top-loading, 0.1 g.
4.5 Glass scintillation vials - 20 ml, with screw caps and Teflon liners
or glass culture tubes with a screw cap and Teflon liner.
4.6 Volumetric flasks, Class A - 10 ml and 100 ml, with ground-glass
stoppers.
4.7 Vials - 2 ml, for GC autosampler.
4.8 Spatula - Stainless steel.
4.9 Disposable pipets - Pasteur.
4.10 Heater or heated oil bath - Should be capable of maintaining the
purging chamber to within 1°C over the temperature range of ambient to 100°C.
4.11 Purge-and-trap device - The purge-and-trap device consists of three
separate pieces of equipment: the sample purger, the trap, and the desorber.
Several complete devices are commercially available.
4.11.1 The recommended purging chamber is designed to accept
5 ml samples with a water column at least 3 cm deep. The gaseous
headspace between the water column and the trap must have a total volume
of less than 15 ml. The purge gas must pass through the water column as
finely divided bubbles with a diameter of less than 3 mm at the origin.
The purge gas must be introduced no more than 5 mm from the base of the
water column. The sample purger, illustrated in Figure 1, meets these
design criteria. Alternate sample purge devices may be utilized, provided
equivalent performance is demonstrated.
4.11.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 in. Starting from the inlet, the trap should
contain the following amounts of adsorbents: 1/3 of 2,6-diphenylene oxide
polymer, 1/3 of silica gel, and 1/3 of coconut charcoal. It is
recommended that 1.0 cm of methyl silicone coated packing be inserted at
the inlet to extend the life of the trap (see Figure 2). If it is not
necessary to analyze for dichlorodifluoromethane or other fluorocarbons
of similar volatility, the charcoal can be eliminated and the polymer
increased to fill 2/3 of the trap. If only compounds boiling above 35°C
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are to be analyzed, both the silica gel and charcoal can be eliminated
and the polymer increased to fill the entire trap. Before initial use,
the trap should be conditioned overnight at 180°C by backflushing with an
inert gas flow of at least 20 mL/min. Vent the trap effluent to the room,
not to the analytical column. Prior to daily use, the trap should be
conditioned for 10 minutes at 180°C with backflushing. The trap may be
vented to the analytical column during daily conditioning. However, the
column must be run through the temperature program prior to analysis of
samples.
4.11.3 The desorber should be capable of rapidly heating the
trap to 180°C for desorption. The polymer section of the trap should not
be heated higher than 180°C, and the remaining sections should not exceed
220°C during bake out mode. The desorber design illustrated in Figure 2
meets these criteria.
4.11.4 The purge-and-trap device may be assembled as a separate
unit or may be coupled to a gas chromatograph, as shown in Figures 3
and 4.
4.11.5 Trap Packing Materials
4.11.5.1 2,6-Diphenylene oxide polymer - 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
4.11.5.2 Methyl silicone packing - OV-1 (3%) on
Chromosorb-W, 60/80 mesh or equivalent.
4.11.5.3 Silica gel - 35/60 mesh, Davison, grade 15 or
equivalent.
4.11.5.4 Coconut charcoal - Prepare from Barnebey Cheney,
CA-580-26, lot #M-2649, by crushing through 26 mesh screen (or
equivalent).
4.12 Gas chromatograph/mass spectrometer system
4.12.1 Gas chromatograph - An analytical system complete with
a temperature programmable gas chromatograph and all required accessories
including syringes, analytical columns, and gases.
4.12.2 Column - 6 ft x 0.1 in. ID glass, packed with 1% SP-1000
on Carbopack-B (60/80 mesh) or equivalent.
4.12.3 Mass spectrometer - Capable of scanning from 35-260 amu
every 3 seconds or less, using 70 volts (nominal) electron energy in the
electron impact mode and producing a mass spectrum that meets all the
criteria in Table 3 when 50 ng of 4-bromofluorobenzene (BFB) are injected
through the gas chromatograph inlet.
4.12.4 GC/MS interface - Any GC-to-MS interface that gives
acceptable calibration points at 50 ng or less per injection for each of
the analytes and achieves all acceptable performance criteria (see
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Table 3) may be used. GC-to-MS interfaces constructed entirely of glass
or of glass-lined materials are recommended. Glass can be deactivated by
silanizing with dichlorodimethylsilane.
4.12.5 Data system - A computer system that allows the
continuous acquisition and storage on machine readable media of all mass
spectra obtained throughout the duration of the chromatographic program
must be interfaced to the mass spectrometer. The computer must have
software that allows searching any GC/MS data file for ions of a specified
mass and plotting such ion abundances versus time or scan number. This
type of plot is defined as an Extracted Ion Current Profile (EICP).
Software must also be available that allows integrating the abundances in
any EICP between specified time or scan number limits. The most recent
version of the EPA/NIST Mass Spectral Library should also be available.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall 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 ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Stock solutions - Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standard solutions
in methanol, using assayed liquids or gases, as appropriate.
5.3.1 Place about 9.8 ml of methanol in a 10 ml tared ground-glass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes or until all alcohol wetted surfaces have dried. Weigh
the flask to the nearest 0.0001 g.
5.3.2 Add the assayed reference material, as described below.
5.3.2.1 Liquids - Using a 100 ^L syringe, immediately add
two or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5.3.2.2 Gases - To prepare standards for any compounds
that boil below 30°C (e.g. bromomethane, chloroethane,
chloromethane, or vinyl chloride), fill a 5 ml valved gas-tight
syringe with the reference standard to the 5.0 ml mark. Lower the
needle to 5 mm above the methanol meniscus. Slowly introduce the
reference standard above the surface of the liquid. The heavy gas
will rapidly dissolve in the methanol. Standards may also be
prepared by using a lecture bottle equipped with a Hamilton Lecture
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Bottle Septum (#86600). Attach Teflon tubing to the side-arm relief
valve and direct a gentle stream of gas into the methanol meniscus.
5.3.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in milligrams per
liter (mg/L) from the net gain in weight. When compound purity is assayed
to be 96% or greater, the weight may be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.3.4 Transfer the stock standard solution into a Teflon sealed
screw cap bottle. Store, with minimal headspace, at -10°C to -20°C and
protect from light.
5.3.5 Prepare fresh stock standards for gases weekly or sooner if
comparison with check standards indicates a problem. Reactive compounds
such as 2-chloroethyl vinyl ether and styrene may need to be prepared more
frequently. All other standards must be replaced after six months. Both
gas and liquid standards must be monitored closely by comparison to the
initial calibration curve and by comparison to QC check standards. It may
be necessary to replace the standards more frequently if either check
exceeds a 20% drift.
5.3.6 Optionally, calibration using a certified gaseous mixture can
be accomplished daily utilizing commercially available gaseous analyte
mixture of bromomethane, chloromethane, chloroethane, vinyl chloride,
dichlorodifluoromethane and trichlorofluoromethane in nitrogen. These
mixtures of documented quality are stable for as long as six months
without refrigeration. (VOA-CYL III, RESTEK Corporation, Cat. #20194 or
equivalent).
5.4 Secondary dilution standards - Using stock standard solutions,
prepare in methanol, secondary dilution standards containing the compounds of
interest, either singly or mixed together. Secondary dilution standards must be
stored with minimal headspace and should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.5 Surrogate standards - The surrogates recommended are toluene-d8,
4-bromofluorobenzene, and l,2-dichloroethane-d4. Other compounds may be used
as surrogates, depending upon the analysis requirements. A stock surrogate
solution in methanol should be prepared as described in Sec. 5.3, and a surrogate
standard spiking solution should be prepared from the stock at a concentration
of 250 /itg/10 ml in methanol. Each water sample undergoing GC/MS analysis must
be spiked with 10 /A of the surrogate spiking solution prior to analysis.
5.6 Internal standards - The recommended internal standards are
bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-d5. Other compounds
may be used as internal standards as long as they have retention times similar
to the compounds being detected by GC/MS. Prepare internal standard stock and
secondary dilution standards in methanol using the procedures described in Sees.
5.3 and 5.4. It is recommended that the secondary dilution standard should be
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prepared at a concentration of 25 mg/L of each internal standard compound.
Addition of 10 juL of this standard to 5.0 mL of sample or calibration standard
would be the equivalent of 50
5.7 4-Bromof)uorobenzene (BFB) standard - A standard solution containing
25 ng/^L of BFB in methanol should be prepared.
5.8 Calibration standards - Calibration standards at a minimum of five
concentrations should be prepared from the secondary dilution of stock standards
(see Sees. 5.3 and 5.4). Prepare these solutions in organic-free reagent water.
One of the concentrations should be at a concentration near, but above, the
method detection limit. The remaining concentrations should correspond to the
expected range of concentrations found in real samples but should not exceed the
working range of the GC/MS system. Each standard should contain each analyte for
detection by this method. It is EPA's intent that all target analytes for a
particular analysis be included in the calibration standard(s). However, these
target analytes may not include the entire List of Analytes (Sec. 1.1) for which
the method has been demonstrated. However, the laboratory shall not report a
quantitative result for a target analyte that was not included in the calibration
standard(s). Calibration standards must be prepared daily.
5.9 Matrix spiking standards - Matrix spiking standards should be
prepared from volatile organic compounds which will be representative of the
compounds being investigated. The suggested compounds are 1,1-dichloroethene,
trichloroethene, chlorobenzene, toluene, and benzene. The standard should be
prepared in methanol, with each compound present at a concentration of
250 /ig/10.0 mL.
5.10 Great care must be taken to maintain the integrity of all standard
solutions. It is recommended that all standards in methanol be stored at -10°C
to -20°C in screw cap amber bottles with Teflon liners.
5.11 Methanol, CH3OH. Pesticide quality or equivalent. Store apart from
other solvents.
5.12 Reagent Tetraglyme - Reagent tetraglyme is defined as tetraglyme in
which interference is not observed at the method detection limit of compounds of
interest.
5.12.1 Tetraglyme (tetraethylene glycol dimethyl ether, Aldrich
#17, 240-5 or equivalent), C8H1805. Purify by treatment at reduced pressure
in a rotary evaporator. The tetraglyme should have a peroxide content of
less than 5 ppm as indicated by EM Quant Test Strips (available from
Scientific Products Co., Catalog No. P1126-8 or equivalent).
CAUTION: Glycol ethers are suspected carcinogens. All solvent
handling should be done in a hood while using proper
protective equipment to minimize exposure to liquid and
vapor.
Peroxides may be removed by passing the tetraglyme through a column
of activated alumina. The tetraglyme is placed in a round bottom flask
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equipped with a standard taper joint, and the flask is affixed to a rotary
evaporator. The flask is immersed in a water bath at 90-100°C and a vacuum
is maintained at < 10 mm Hg for at least two hours using a two stage
mechanical pump. The vacuum system is equipped with an all glass trap,
which is maintained in a dry ice/methanol bath. Cool the tetraglyme to
ambient temperature and add 100 mg/L of 2,6-di-tert-butyl-4-methyl-phenol
to prevent peroxide formation. Store the tetraglyme in a tightly sealed
screw cap bottle in an area that is not contaminated by solvent vapors.
5.12.2 In order to demonstrate that all interfering volatiles
have been removed from the tetraglyme, an organic-free reagent
water/tetraglyme blank must be analyzed.
5.13 Polyethylene glycol, H(OCH2CH2)nOH. Free of interferences at the
detection limit of the analytes.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
Samples may be introduced into the GC by either direct injection or purge-
and-trap procedures. Whichever procedure is used, the instrument calibration and
sample introduction must be performed by the same procedure.
Regardless of which sample introduction procedure is employed, establish
GC/MS operating conditions using the following recommendations as guidance.
Recommended GC/MS operating conditions:
Electron energy: 70 volts (nominal).
Mass range: 35-260 amu.
Scan time: To give 5 scans/peak, but not to
exceed 1 sec/scan.
Initial column temperature: 45°C.
Initial column holding time: 3 minutes.
Column temperature program: 8°C/minute.
Final column temperature: 220°C.
Final column holding time: .15 minutes.
Injector temperature: 200-225°C.
Source temperature: According to manufacturer's
specifications.
Transfer line temperature: 250-300°C.
Carrier gas: Hydrogen at 50 cm/sec or helium at 30
cm/sec.
7.1 Direct injection - In very limited applications (e.g. aqueous
process wastes), direct injection of the sample into the GC/MS system with a 10
//L syringe may be appropriate. One such application is for verification of the
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alcohol content of an aqueous sample prior to determining if the sample is
ignitable (Methods 1010 or 1020). In this case, it is suggested that direct
injection be used. The detection limit is very high (approximately 10,000 /^g/L);
therefore, it is only permitted when concentrations in excess of 10,000 /zg/L are
expected or for water soluble compounds that do not purge. The system must be
calibrated by direct injection using the procedures described in Sec. 7.2,, but
bypassing the purge-and-trap device.
7.2 Initial calibration for purge-and-trap procedure
7.2.1 Establish the GC/MS operating conditions, using the
recommendations in Sec. 7.0 as guidance.
7.2.2 Each GC/MS system must be hardware tuned to meet the criteria
in Table 3 for a 50 ng injection or purging of 4-bromofluorobenzene (2 juL
injection of the BFB standard). Analyses must not begin until these
criteria are met.
7.2.3 Assemble a purge-and-trap device that meets the specification
in Sec. 4.11. Condition the trap overnight at 180°C in the purge mode
with an inert gas flow of at least 20 mL/min. Prior to use, condition the
trap daily for 10 min while backflushing at 180°C with the column at 220°C.
7.2.4 Connect the purge-and-trap device to a gas chromatograph.
7.2.5 Prepare the final solutions containing the required
concentrations of calibration standards, including surrogate standards,
directly in the purging device (use freshly prepared stock solutions when
preparing the calibration standards for the initial calibration.) Add
5.0 ml of organic-free reagent water to the purging device. The organic-
free reagent water is added to the purging device using a 5 mL glass
syringe fitted with a 15 cm, 20 gauge needle. The needle is inserted
through the sample inlet shown in Figure 1. The internal diameter of the
14 gauge needle that forms the sample inlet will permit insertion of the
20 gauge needle. Next, using a 10 pi or 25 yul microsyringe equipped with
a long needle (Sec. 4.1), take a volume of the secondary dilution solution
containing appropriate concentrations of the calibration standards (Sec.
5.6). Add the aliquot of calibration solution directly to the organic-
free reagent water in the purging device by inserting the needle through
the sample inlet. When discharging the contents of the microsyringe, be
sure that the end of the syringe needle is well beneath the surface of the
organic-free reagent water. Similarly, add 10 /uL of the internal standard
solution (Sec. 5.4). Close the 2 way syringe valve at the sample inlet.
7.2.6 Carry out the purge-and-trap analysis procedure as described
in Sec. 7.4.1.
7.2.7 Tabulate the area response of the characteristic ions (see
Table 1) against concentration for each compound and each internal
standard. Calculate response factors (RF) for each compound relative to
one of the internal standards. The internal standard selected for the
calculation of the RF for a compound should be the internal standard that
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has a retention time closest to the compound being measured (Sec. 7.5.2).
The RF is calculated as follows:
RF - (AxCis)/(AisCx)
where:
Ax = Area of the characteristic ion for the compound being
measured.
Ais = Area of the characteristic ion for the specific internal
standard.
Cis = Concentration of the specific internal standard.
Cx = Concentration of the compound being measured.
7.2.8 The average RF must be calculated for each compound using the
5 RF values calculated for each compound from the initial (5-point)
calibration curve. A system performance check should be made before this
calibration curve is used. Five compounds (the System Performance Check
Compounds, or SPCCs) are checked for a minimum average relative response
factor. These compounds are chloromethane, 1,1-dichloroethane, bromoform,
1,1,2,2-tetrachloroethane, and chlorobenzene. The minimum acceptable
average RF for these compounds should be 0.300 (>0.10 for bromoform).
These compounds typically have RFs of 0.4-0.6 and are used to check
compound instability and to check for degradation caused by contaminated
lines or active sites in the system. Examples of these occurrences are:
7.2.8.1 Chloromethane - This compound is the most likely
compound to be lost if the purge flow is too fast.
7.2.8.2 Bromoform - This compound is one of the compounds
most likely to be purged very poorly if the purge flow is too slow.
Cold spots and/or active sites in the transfer lines may adversely
affect response. Response of the quantitation ion (m/z 173) is
directly affected by the tuning of BFB at ions m/z 174/176.
Increasing the m/z 174/176 relative to m/z 95 ratio may improve
bromoform response.
7.2.8.3 Tetrachloroethane and 1,1-dichloroethane - These
compounds are degraded by contaminated transfer lines in purge-and-
trap systems and/or active sites in trapping materials.
7.2.9 Using the RFs from the initial calibration, calculate and
record the percent relative standard deviation (%RSD) for all compounds.
The percent RSD is calculated as follows:
SD
%RSD =———- x 100
RF
where:
RSD = relative standard deviation.
RF = mean of 5 initial RFs for a compound.
SD = standard deviation of average RFs for a compound.
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SD =
N (RFj - RF)
I
i=l N - 1
2
where:
RFj = RF for each of the 5 calibration levels
N = Number of RF values (i.e., 5)
The percent relative standard deviation should be less than 15% for
each compound. However, the %RSD for each individual Calibration Check
Compound (CCC) must be less than 30%. Late-eluting compounds usually have
much better agreement. The CCCs are:
1,1-Dichloroethene,
Chloroform,
1,2-Dichloropropane,
Toluene,
Ethylbenzene, and
Vinyl chloride.
7.2.9.1 If a %RSD greater than 30 percent is measured for
any CCC, then corrective action to eliminate a system leak and/or
column reactive sites is required before reattempting calibration.
7.2.10 Linearity - If the %RSD of any compound is 15% or less,
then the relative response factor is assumed to be constant over the
calibration range, and the average relative response factor may be used
for quantitation (Sec. 7.5.2.2).
7.2.10.1 If the %RSD of any compound is greater than 15%,
construct calibration curves of area ratio (A/Ais) versus
concentration using first or higher order regression fit of the five
calibration points. The analyst should select the regression order
which introduces the least calibration error into the quantitation
(Sec. 7.5.2.4). The use of calibration curves is a recommended
alternative to average response factor calibration, and a useful
diagnostic of standard preparation accuracy and absorption activity
in the chromatographic system.
7.2.11 These curves are verified each shift by purging a
performance standard. Recalibration is required only if calibration and
on-going performance criteria cannot-be met.
7.3 Daily GC/MS calibration
7.3.1 Prior to the analysis of samples, inject or purge 50 ng of the
4-bromofluorobenzene standard. The resultant mass spectra for the BFB
must meet all of the criteria given in Table 3 before sample analysis
begins. These criteria must be demonstrated each 12 hour shift.
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7.3.2 The initial calibration curve (Sec. 7.2) for each compound of
interest must be checked and verified once every 12 hours of analysis
time. This is accomplished by analyzing a calibration standard that is
at a concentration near the midpoint concentration for the working range
of the GC/MS and checking the SPCC (Sec. 7.3.3) and CCC (Sec. 7.3.4).
7.3.3 System Performance Check Compounds (SPCCs) - A system
performance check must be made each 12 hours. If the SPCC criteria are
met, a comparison of relative response factors is made for all compounds.
This is the same check that is applied during the initial calibration.
If the minimum relative response factors are not met, the system must be
evaluated, and corrective action must be taken before sample analysis
begins. The minimum relative response factor for volatile SPCCs is 0.300
(>0.10 for Bromoform). Some possible problems are standard mixture
degradation, injection port inlet contamination, contamination at the
front end of the analytical column, and active sites in the column or
chromatographic system.
7.3.4 Calibration Check Compounds (CCCs): After the system
performance check is met, CCCs listed in Sec. 7.2.9 are used to check the
validity of the initial calibration.
Calculate the percent drift using the following equation:
c, - cc
% Drift = x 100
where:
C,
C, = Calibration Check Compound standard concentration.
Cc = Measured concentration using selected quantitation method.
If the percent difference for each CCC is less than 20%, the initial
calibration is assumed to be valid. If the criterion is not met (> 20%
drift), for any one CCC, corrective action must be taken. Problems
similar to those listed under SPCCs could affect this criterion. If no
source of the problem can be determined after corrective action has been
taken, a new five point calibration MUST be generated. This criterion
MUST be met before quantitative sample analysis begins. If the CCCs are
not required analytes by the permit, then all required analytes must meet
the 20% drift criterion.
7.3.5 The internal standard responses and retention times in the
check calibration standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard changes
by more than 30 seconds from the last calibration check (12 hours), the
chromatographic system must be inspected for malfunctions and corrections
must be made, as required. If the EICP area for any of the internal
standards changes by a factor of two (- 50% to + 100%) from the last daily
calibration check standard, the mass spectrometer must be inspected for
malfunctions and corrections must be made, as appropriate. When
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corrections are made, reanalysis of samples analyzed while the system was
malfunctioning is necessary.
7.4 GC/MS analysis
7.4.1 Water samples
7.4.1.1 Screening of the sample prior to purge-and-trap
analysis will provide guidance on whether sample dilution is
necessary and will prevent contamination of the purge-and-trap
system. Two screening techniques that can be used are: the
headspace sampler (Method 3810) using a gas chromatograph (GC)
equipped with a photo ionization detector (PID) in series with an
electrolytic conductivity detector (HECD); and extraction of the
sample with hexadecane and analysis of the extract on a GC with a
FID and/or an ECD (Method 3820).
7.4.1.2 All samples and standard solutions must be allowed
to warm to ambient temperature before analysis.
7.4.1.3 Set up the GC/MS system as outlined in Sec. 7.2.1.
7.4.1.4 BFB tuning criteria and daily GC/MS calibration
criteria must be met (Sec. 7.3) before analyzing samples.
7.4.1.5 Adjust the purge gas (helium) flow rate to 25-
40 mL/min on the purge-and-trap device. Optimize the flow rate to
provide the best response for chloromethane and bromoform, if these
compounds are analytes. Excessive flow rate reduces chloromethane
response, whereas insufficient flow reduces bromoform response (see
Sec. 7.2.8).
7.4.1.6 Remove the plunger from a 5 ml syringe and attach
a closed syringe valve. Open the sample or standard bottle, which
has been allowed to come to ambient temperature, and carefully pour
the sample into the syringe barrel to just short of overflowing.
Replace the syringe plunger and compress the sample. Open the
syringe valve and vent any residual air while adjusting the sample
volume to 5.0 ml. This process of taking an aliquot destroys the
validity of the liquid sample for future analysis; therefore, if
there is only one VGA vial, the analyst should fill a second syringe
at this time to protect against possible loss of sample integrity.
This second sample is maintained only until such time when the
analyst has determined that the first sample has been analyzed
properly. Filling one 20 ml syringe would allow the use of only one
syringe. If a second analysis is needed from a syringe, it must be
analyzed within 24 hours. Care must be taken to prevent air from
leaking into the syringe.
7.4.1.7 The following procedure is appropriate for
diluting purgeable samples. All steps must be performed without
delays until the diluted sample is in a gas tight syringe.
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7.4.1.7.1 Dilutions may be made in volumetric flasks
(10 to 100 ml). Select the volumetric flask that will allow
for the necessary dilution. Intermediate dilutions may be
necessary for extremely large dilutions.
7.4.1.7.2 Calculate the approximate volume of organic-
free reagent water to be added to the volumetric flask
selected and add slightly less than this quantity of organic-
free reagent water to the flask.
7.4.1.7.3 Inject the proper aliquot of samples from
the syringe prepared in Sec. 7.4.1.6 into the flask.
Aliquots of less than 1 ml are not recommended. Dilute the
sample to the mark with organic-free reagent water. Cap the
flask, invert, and shake three times. Repeat above procedure
for additional dilutions.
7.4.1.7.4 Fill a 5 ml syringe with the diluted sample
as in Sec. 7.4.1.6.
7.4.1.8 Add 10.0 /iL of surrogate spiking solution (Sec.
5.5) and 10 fj,l of internal standard spiking solution (Sec. 5.6)
through the valve bore of the syringe; then close the valve. The
surrogate and internal standards may be mixed and added as a single
spiking solution. The addition of 10 fj.L of the surrogate spiking
solution to 5 ml of sample is equivalent to a concentration of
50 /zg/L of each surrogate standard.
7.4.1.9 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the syringe valves and
inject the sample into the purging chamber.
7.4.1.10 Close both valves and purge the sample for
11.0 + 0.1 minutes at ambient temperature.
7.4.1.11 At the conclusion of the purge time, attach the
trap to the chromatograph, adjust the device to the desorb mode, and
begin the gas chromatographic temperature program and GC/MS data
acquisition. Concurrently, introduce the trapped materials to the
gas chromatographic column by rapidly heating the trap to 180°C
while backflushing the trap with inert gas between 20 and 60 ml/min
for 4 minutes. If this rapid heating requirement cannot be met, the
gas chromatographic column must be used as a secondary trap by
cooling it to 30°C (or subambient, if problems persist) instead of
the recommended initial program temperature of 45°C.
7.4.1.12 While the trap is being desorbed into the gas
chromatograph, empty the purging chamber. Wash the chamber with a
minimum of two 5 ml flushes of organic-free reagent water (or
methanol followed by organic-free reagent water) to avoid carryover
of pollutant compounds into subsequent analyses.
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7.4.1.13 After desorbing the sample for 4 minutes,
recondition the trap by returning the purge-and-trap device to the
purge mode. Wait 15 seconds; then close the syringe valve on the
purging device to begin gas flow through the trap. The trap
temperature should be maintained at 180°C. Trap temperatures up to
220°C may be employed; however, the higher temperature will shorten
the useful life of the trap. After approximately 7 minutes, turn
off the trap heater and open the syringe valve to stop the gas flow
through the trap. When cool, the trap is ready for the next sample.
7.4.1.14 If the initial analysis of a sample or a dilution
of the sample has a concentration of analytes that exceeds the
initial calibration range, the sample must be reanalyzed at a higher
dilution. Secondary ion quantitation is allowed only when there are
sample interferences with the primary ion. When a sample is
analyzed that has saturated ions from a compound, this analysis must
be followed by a blank organic-free reagent water analysis. If the
blank analysis is not free of interferences, the system must be
decontaminated. Sample analysis may not resume until a blank can
be analyzed that is free of interferences.
7.4.1.15 For matrix spike analysis, add 10 fj,l of the matrix
spike solution (Sec. 5.9) to the 5 ml of sample to be purged.
Disregarding any dilutions, this is equivalent to a concentration
of 50 M9/L of each matrix spike standard.
7.4.1.16 All dilutions should keep the response of the
major constituents (previously saturated peaks) in the upper half
of the linear range of the curve. Proceed to Sees. 7.5.1 and 7.5.2
for qualitative and quantitative analysis.
7.4.2 Water miscible liquids
7.4.2.1 Water miscible liquids are analyzed as water
samples after first diluting them at least 50 fold with organic-free
reagent water.
7.4.2.2 Initial and serial dilutions can be prepared by
pipetting 2 mL of the sample to a 100 ml volumetric flask and
diluting to volume with organic-free reagent water. Transfer
immediately to a 5 ml gas tight syringe.
7.4.2.3 Alternatively,, prepare dilutions directly in a 5
ml syringe filled with organic-free reagent water by adding at least
20 /xL, but not more than 100 pi of liquid sample. The sample is
ready for addition of internal and surrogate standards.
7.4.3 Sediment/soil and waste samples - It is highly recommended
that all samples of this type be screened prior to the purge-and-trap
GC/MS analysis. The headspace method (Method 3810) or the hexadecane
extraction and screening method (Method 3820) may be used for this
purpose. These samples may contain percent quantities of purgeable
organics that will contaminate the purge-and-trap system, and require
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extensive cleanup and instrument downtime. Use the screening data to
determine whether to use the low-concentration method (0.005-1 mg/kg) or
the high-concentration method (> 1 mg/kg).
7.4.3.1 Low-concentration method - This is designed for
samples containing individual purgeable compounds of < 1 mg/kg. It
is limited to sediment/soil samples and waste that is of a similar
consistency (granular and porous). The low-concentration method is
based on purging a heated sediment/soil sample mixed with organic-
free reagent water containing the surrogate and internal standards.
Analyze all reagent blanks and standards under the same conditions
as the samples. See Figure 5 for an illustration of a low soils
impinger.
7.4.3.1.1 Use a 5 g sample if the expected
concentration is < 0.1 mg/kg or a 1 g sample for expected
concentrations between 0.1 and 1 mg/kg.
7.4.3.1.2 The GC/MS system should be set up as in
Sees. 7.4.1.2-7.4.1.4. This should be done prior to the
preparation of the sample to avoid loss of volatiles from
standards and samples. A heated purge calibration curve must
be prepared and used for the quantitation of all samples
analyzed with the low-concentration method. Follow the
initial and daily calibration instructions, except for the
addition of a 40°C purge temperature.
7.4.3.1.3 Remove the plunger from a 5 ml Luerlock type
syringe equipped with a syringe valve and fill until
overflowing with organic-free reagent water. Replace the
plunger and compress the water to vent trapped air. Adjust
the volume to 5.0 ml. Add 10 /j.1 each of surrogate spiking
solution (Sec. 5.5) and internal standard solution (Sec. 5.6)
to the syringe through the valve. (Surrogate spiking
solution and internal standard solution may be mixed
together.) The addition of 10 /nL of the surrogate spiking
solution to 5 g of sediment/soil is equivalent to 50 /ig/kg of
each surrogate standard.
7.4.3.1.4 The sample (for volatile organics) consists
of the entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents of the
sample container with a. narrow metal spatula. Weigh the
amount determined in Sec. 7.4.3.1.1 into a tared purge
device. Note and record the actual weight to the nearest 0.1
9-
7.4.3.1.5 Determine the percent dry weight of the
soil/sediment sample. This includes waste samples that are
amenable to percent dry weight determination. Other wastes
should be reported on a wet-weight basis.
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7.4.3.1.5.1 Immediately after weighing the sample
for extraction, weigh 5-10 g of the sample into a tared
crucible. Determine the % dry weight of the sample by
drying overnight at 105°C. Allow to cool in a
desiccator before re-weighing. Concentrations of
individual analytes are reported relative to the dry
weight of sample.
WARNING: The drying oven should be contained
in a hood or vented. Significant
laboratory contamination may result
from a heavily contaminated hazardous
waste sample.
% dry weight = g of dry sample x 100
g of sample
7.4.3.1.6 Add the spiked water to the purge device,
which contains the weighed amount of sample, and connect the
device to the purge-and-trap system.
NOTE: Prior to the attachment of the purge device, the
procedures in Sees. 7.4.3.1.4 and 7.4.3.1.6 must
be performed rapidly and without interruption to
avoid loss of volatile organics. These steps
must be performed in a laboratory free of solvent
fumes.
7.4.3.1.7 Heat the sample to 40°C + 1°C and purge the
sample for 11.0 + 0.1 minute.
7.4.3.1.8 Proceed with the analysis as outlined in
Sees. 7.4.1.11-7.4.1.16. Use 5 ml of the same organic-free
reagent water as in the reagent blank. If saturated peaks
occurred or would occur if a 1 g sample were analyzed, the
high-concentration method must be followed.
7.4.3.1.9 For low-concentration sediment/soils add
1C pi of the matrix spike solution (Sec. 5.9) to the 5 ml of
organic-free reagent water (Sec. 7.4.3.1.3). The
concentration for a 5 g sample would be equivalent to 50
/ig/kg of each matrix spike standard.
7.4.3.2 High-concentration method - The method is based on
extracting the sediment/soil with methanol. A waste sample is
either extracted or diluted, depending on its solubility in
methanol. Wastes (i.e. petroleum and coke wastes) that are
insoluble in methanol are diluted with reagent tetraglyme or
possibly polyethylene glycol (PEG). An aliquot of the extract is
added to organic-free reagent water containing internal standards.
This is purged at ambient temperature. All samples with an expected
concentration of > 1.0 mg/kg should be analyzed by this method.
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7.4.3.2.1 The sample (for volatile organics) consists
of the entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents of the
sample container with a narrow metal spatula. For
sediment/soil and solid wastes that are insoluble in
methanol, weigh 4 g (wet weight) of sample into a tared 20 ml
vial. Use a top loading balance. Note and record the actual
weight to 0.1 gram and determine the percent dry weight of
the sample using the procedure in Sec. 7.4.3.1.5. For waste
that is soluble in methanol, tetraglyme, or PEG, weigh 1 g
(wet weight) into a.tared scintillation vial or culture tube
or a 10 mL volumetric flask. (If a vial or tube is used, it
must be calibrated prior to use. Pipet 10.0 ml of solvent
into the vial and mark the bottom of the meniscus. Discard
this solvent.)
7.4.3.2.2 Quickly add 9.0 ml of appropriate solvent;
then add 1.0 mL of the surrogate spiking solution to the
vial. Cap and shake for 2 minutes.
NOTE: Sees. 7.4.3.2.1 and 7.4.3.2.2 must be performed
rapidly and without interruption to avoid loss of
volatile organics. These steps must be performed
in a laboratory free from solvent fumes.
7.4.3.2.3 Pipet approximately 1 ml of the extract to
a GC vial for storage, using a disposable pipet. The
remainder may be disposed of. Transfer approximately 1 ml of
appropriate solvent to a separate GC vial for use as the
method blank for each set of samples. These extracts may be
stored at 4°C in the dark, prior to analysis. The addition
of a 100 /^L aliquot of each of these extracts in Sec.
7.4.3.2.6 will give a concentration equivalent to 6,200 M9/kg
of each surrogate standard.
7.4.3.2.4 The GC/MS system should be set up as in
Sees. 7.4.1.2-7.4.1.4. This should be done prior to the
addition of the solvent extract to organic-free reagent
water.
7.4.3.2.5 Table 4 can be used to determine the volume
of solvent extract to add to the 5 mL of organic-free reagent
water for analysis. If a screening procedure was followed
(Method 3810 or 3820), use the estimated concentration to
determine the appropriate volume. Otherwise, estimate the
concentration range of the sample from the low-concentration
analysis to determine the appropriate volume. If the sample
was submitted as a high-concentration sample, start with
100 juL. All dilutions must keep the response of the major
constituents (previously saturated peaks) in the upper half
of the linear range of the curve.
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7.4.3.2.6 Remove the plunger from a 5.0 ml Luerlock
type syringe equipped with a syringe valve and fill until
overflowing with organic-free reagent water. Replace the
plunger and compress the water to vent trapped air. Adjust
the volume to 4.9 ml. Pull the plunger back to 5.0 mL to
allow volume for the addition of the sample extract and of
standards. Add 10 juL of internal standard solution. Also
add the volume of solvent extract determined in Sec.
7.4.3.2.5 and a volume of extraction or dissolution solvent
to total 100 jut. (excluding methanol in standards).
7.4.3.2.7 Attach the syringe-syringe valve assembly to
the syringe valve on the purging device. Open the syringe
valve and inject the organic-free reagent water/methanol
sample into the purging chamber.
7.4.3.2.8 Proceed with the analysis as outlined in
Sec. 7.4.1.11-7.4.1.16. Analyze all reagent blanks on the
same instrument as that use for the samples. The standards
and blanks should also contain 100 /A of solvent to simulate
the sample conditions.
7.4.3.2.9 For a matrix spike in the high-concentration
sediment/soil samples, add 8.0 ml of methanol, 1.0 ml of
surrogate spike solution (Sec. 5.5), and 1.0 ml of matrix
spike solution (Sec. 5.9) as in Sec. 7.4.3.2.2. This results
in a 6,200 jug/kg concentration of each matrix spike standard
when added to a 4 g sample. Add a 100 /jL aliquot of this
extract to 5 ml of organic-free reagent water for purging (as
per Sec. 7.4.3.2.6).
7.5 Data interpretation
7.5.1 Qualitative analysis
7.5.1.1 The qualitative identification of compounds
determined by this method is based on retention time, and on
comparison of the sample mass spectrum, after background correction,
with characteristic ions in a reference mass spectrum. The
reference mass spectrum must be generated by the laboratory using
the conditions of this method. The characteristic ions from the
reference mass spectrum are defined to be the three ions of greatest
relative intensity, or any ions over 30% relative intensity if less
than three such ions occur in -the reference spectrum. Compounds
should be identified as present when the criteria below, are met.
7.5.1.1.1 The intensities of the characteristic ions
of a compound maximize in the same scan or within one scan of
each other. Selection of a peak by a data system target
compound search routine where the search is based on the
presence of a target chromatographic peak containing ions
specific for the target compound at a compound-specific
retention time will be accepted as meeting this criterion.
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7.5.1.1.2 The RRT of the sample component is within
+ 0.06 RRT units of the RRT of the standard component.
7.5.1.1.3 The relative intensities of the
characteristic ions agree within 30% of the relative
intensities of these ions in the reference spectrum.
(Example: For an ion with an abundance of 50% in the
reference spectrum, the corresponding abundance in a sample
spectrum can range between 20% and 80%.)
7.5.1.1.4 Structural isomers that produce very similar
mass spectra should be identified as individual isomers if
they have sufficiently different GC retention times.
Sufficient GC resolution is achieved if the height of the
valley between two isomer peaks is less than 25% of the sum
of the two peak heights. Otherwise, structural isomers are
identified as isomeric pairs.
7.5.1.1.5 Identification is hampered when sample
components are not resolved chromatographically and produce
mass spectra containing ions contributed by more than one
analyte. When gas chromatographic peaks obviously represent
more than one sample component (i.e., a broadened peak with
shoulder(s) or a valley between two or more maxima),
appropriate selection of analyte spectra and background
spectra is important. Examination of extracted ion current
profiles of appropriate ions can aid in the selection of
spectra, and in qualitative identification of compounds.
When analytes coelute (i.e., only one chromatographic peak is
apparent), the identification criteria can be met, but each
analyte spectrum will contain extraneous ions contributed by
the coeluting compound.
7.5.1.2 For samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the type of analyses
being conducted. Guidelines for making tentative identification
are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should be present in
the sample spectrum.
(2) The relative intensities of the major ions should agree
within + 20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%).
(3) Molecular ions present in the reference spectrum should
be present in the sample spectrum.
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(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible background
contamination or presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or coeluting
peaks. Data system library reduction programs can sometimes create
these discrepancies.
Computer generated library search routines should not use
normalization routines that would misrepresent the library or
unknown spectra when compared to each other. Only after visual
comparison of sample with the nearest library searches will the mass
spectral interpretation specialist assign a tentative
identification.
7.5.2 Quantitative analysis
7.5.2.1 When a compound has been identified, the
quantitation of that compound will be based on the integrated
abundance from the EICP of the primary characteristic ion.
Quantitation will take place using the internal standard technique.
The internal standard used shall be the one nearest the retention
time of that of a given analyte (e.g. see Table 5).
7.5.2.2 When linearity exists, as per Sec. 7.2.10,
calculate the concentration of each identified analyte in the sample
as follows:
Water
(A,) (I.)
concentration (^g/L) =
(AJ(RF)(V0)
where:
Ax = Area of characteristic ion for compound being
measured.
Is = Amount of internal standard injected (ng).
Ais = Area of characteristic ion for the internal
standard.
RF = Mean relative response factor for compound being
measured (Sec. 7.2.8).
V0 = Volume of water purged (ml_), taking into
consideration any dilutions made.
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Sediment/Soil Sludge (on a dry-weight basis) and Waste
(normally on a wet-weight basis)
concentration (M9/kg) =
(Ais)(RF)(Vi)(Ws)(D)
where:
Ax> ^s' Ais> Rf:» = Same as f°r water.
Vt = Volume of total extract (jzL) (use 10,000 /xL or a
factor of this when dilutions are made).
V, = Volume of extract added (/iL) for purging.
Ws = Weight of sample extracted or purged (g).
D = % dry weight of sample/100, or 1 for a wet-weight
basis.
7.5.2.3 Where applicable, an estimate of concentration for
noncal ibrated components in the sample should be made. The formulae
given above should be used with the following modifications: The
areas Ax and Ais should be from the total ion chromatograms, and the
RF for the compound should be assumed to be 1. The concentration
obtained should be reported indicating (1) that the value is an
estimate and (2) which internal standard was used to determine
concentration. Use the nearest internal standard free of
interferences.
7.5.2.4 Alternatively, the regression line fitted to the
initial calibration (Sec. 7.2.10.1) may be used for determination
of analyte concentration.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program consist
of an initial demonstration of laboratory capability and an ongoing analysis of
spiked samples to evaluate and document data quality. The laboratory must
maintain records to document the quality of the data generated. Ongoing data
quality checks are compared with established performance criteria to determine
if the results of analyses meet the performance characteristics of the method.
When results of sample spikes indicate atypical method performance, a quality
control reference sample must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a method blank, that interferences from the analytical
system, glassware, and reagents are under control. Each time a set of samples
is extracted or there is a change in reagents, a method blank should be processed
as a safeguard against chronic laboratory contamination. The blank samples
should be carried through all stages of sample preparation and measurement.
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8.3 The experience of the analyst performing GC/MS analyses is
invaluable to the success of the methods. Each day that analysis is performed,
the daily calibration standard should be evaluated to determine if the
chromatographic system is operating properly. Questions that should be asked
are: Do the peaks look normal?; Is the response obtained comparable to the
response from previous calibrations? Careful examination of the standard
chromatogram can indicate whether the column is still useable, the injector is
leaking, the injector septum needs replacing, etc. If any changes are made to
the system (e.g. column changed), recalibration of the system must take place.
8.4 Required instrument QC is found in the following section:
8.4.1 The GC/MS system must be tuned to meet the BFB specifications
in Sec. 7.2.2.
8.4.2 There must be an initial calibration of the GC/MS system as
specified in Sec. 7.2.
8.4.3 The GC/MS system must meet the SPCC criteria specified in Step
7.3.3 and the CCC criteria in Sec. 7.3.4, each 12 hours.
8.5 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.5.1 A quality control (QC) reference sample concentrate is
required containing each analyte at a concentration of 10 mg/L in
methanol. The QC reference sample concentrate may be prepared from pure
standard materials or purchased as certified solutions. If prepared by
the laboratory, the QC reference sample concentrate must be made using
stock standards prepared independently from those used for calibration.
8.5.2 Prepare a QC reference sample to contain 20 jug/L of each
analyte by adding 200 juL of QC reference sample concentrate to 100 ml of
water.
8.5.3 Four 5-mL aliquots of the well mixed QC reference sample are
analyzed according to the method beginning in Sec. 7.4.1.
8.5,4 Calculate the average recovery (x) in jug/L, and the standard
deviation of the recovery (s) in /j.g/1, for each analyte using the four
results.
8.5.5 For each analyte compare s and x with the corresponding
acceptance criteria_for precision and accuracy, respectively, found in
Table 6. If s and x for all analytes meet the acceptance criteria, the
system performance is acceptable and analysis of actual samples can_begin.
If any individual s exceeds the precision limit or any individual x falls
outside the range for accuracy, then the system performance is
unacceptable for that analyte.
NOTE: The large number of analytes in Table 6 present a substantial
probability that one or more will fail at least one of the
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acceptance criteria when all analytes of a given method are
determined.
8.5.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst must proceed according to Sec.
8.5.6.1 or 8.5.6.2.
8.5.6.1 Locate and correct the source of the problem and
repeat the test for all analytes beginning with Sec. 8.5.2.
8.5.6.2 Beginning with Sec. 8.5.2, repeat the test only
for those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Sec.
8.5.2.
8.6 The laboratory must, on an ongoing basis, analyze a method blank and
a spiked replicate for each analytical batch (up to a maximum of 20
samples/batch) to assess accuracy. For soil and waste samples where detectable
amounts of organics are present, replicate samples may be appropriate in place
of spiked replicates. For laboratories analyzing one to ten samples per month,
at least one spiked sample per month is required.
8.6.1 The concentration of the spike in the sample should be
determined as follows:
8.6.1.1 If, as in compliance monitoring, the concentration
of a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at that limit
or 1 to 5 times higher than the background concentration determined
in Sec. 8.6.2, whichever concentration would be larger.
8.6.1.2 If the concentration of a specific analyte in a
water sample is not being checked against a specific limit, the
spike should be at 20 /ug/L or 1 to 5 times higher than the
background concentration determined in Sec. 8.6.2, whichever
concentration would be larger. For other matrices, recommended
spiking concentration is 10 times the EQL.
8.6.2 Analyze one 5-mL sample aliquot to determine the background
concentration (B) of each analyte. If necessary, prepare a new QC
reference sample concentrate (Sec. 8.5.1) appropriate for the background
concentration in the sample. Spike a second 5-mL sample aliquot with
10 p,L of the QC reference sample concentrate and analyze it to determine
the concentration after spiking (A) of each analyte. Calculate each
percent recovery (p) as 100(A-B)%/T, where T is the known true value of
the spike.
8.6.3 Compare the percent recovery (p) for each analyte in a water
sample with the corresponding QC acceptance criteria found in Table 6.
These acceptance criteria were calculated to include an allowance for
error in measurement of both the background and spike concentrations,
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assuming a spike to background ratio of 5:1. This error will be accounted
for to the extent that the analyst's spike to background ratio approaches
5:1. If spiking was performed at a concentration lower than 20 M9/L, the
analyst must use either the QC acceptance criteria presented in Table 6,
or optional QC acceptance criteria calculated for the specific spike
concentration. To calculate optional acceptance criteria for the recovery
of an analyte: (1) Calculate accuracy (x') using the equation found in
Table 7, substituting the spike concentration (T) for C; (2) calculate
overall precision (S') using the equation in Table 7, substituting x' for
x; (3) calculate the range for recovery at the spike concentration as
(100x'/T) + 2.44(100S'/T)%.
8.6.4 If any individual p falls outside the designated range for
recovery, that analyte has failed the acceptance criteria. A check
standard containing each analyte that failed the criteria must be analyzed
as described in Sec. 8.7.
8.7 If any analyte in a water sample fails the acceptance criteria for
recovery in Sec. 8.6, a QC reference sample containing each analyte that failed
must be prepared and analyzed.
NOTE: The frequency for the required analysis of a QC reference sample
will depend upon the number of analytes being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory. If the entire list of analytes in Table 6 must be
measured in the sample in Sec. 8.6, the probability that the
analysis of a QC reference sample will be required is high. In this
case, the QC reference sample should be routinely analyzed with the
spiked sample.
8.7.1 Prepare the QC reference sample by adding 10 p,l of the QC
reference sample concentrate (Sec. 8.5.1 or 8.6.2) to 5 ml of reagent
water. The QC reference sample needs only to contain the analytes that
failed criteria in the test in Sec. 8.6.
8.7.2 Analyze the QC reference sample to determine the concentration
measured (A) of each analyte. Calculate each percent recovery (ps) as
100(A/T)%, where T is the true value of the standard concentration.
8.7.3 Compare the percent recovery (pj for each analyte with the
corresponding QC acceptance criteria found in Table 6. Only analytes that
failed the test in Sec. 8.6 need to be compared with these criteria. If
the recovery of any such analyte falls outside the designated range, the
laboratory performance for that analyte is judged to be out of control,
and the problem must be immediately identified and corrected. The result
for that analyte in the unspiked sample is suspect and may not be reported
for regulatory compliance purposes.
8.8 As part of the QC program for the laboratory, method accuracy for
each matrix studied must be assessed and records must be maintained. After the
analysis of five spiked samplesJof the same matrix) as in Sec. 8.6, calculate
the average percent recovery (p) and the standard deviation of the percent
recovery (sp). Express the accuracy assessment as a percent recovery interval
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from p - 2sp to p + 2sp. If p = 90% and sp = 10%, for example, the accuracy
interval is expressed as 70-110%. Update the accuracy assessment for each
analyte on a regular basis (e.g., after each five to ten new accuracy
measurements).
8.9 To determine acceptable accuracy and precision limits for surrogate
standards the following procedure should be performed.
8.9.1 For each sample analyzed, calculate the percent recovery of
each surrogate in the sample.
8.9.2 Once a minimum of thirty samples of the same matrix have been
analyzed, calculate the average percent recovery (P) and standard
deviation of the percent recovery (s) for each of the surrogates.
8.9.3 For a given matrix, calculate the upper and lower control
limit for method performance for each surrogate standard. This should be
done as follows:
Upper Control Limit (UCL) = P + 3s
Lower Control Limit (LCL) = P - 3s
8.9.4 For aqueous and soil matrices, these laboratory established
surrogate control limits should, if applicable, be compared with the
control limits listed in Table 8. The limits given in Table 8 are multi-
laboratory performance based limits for soil and aqueous samples, and
therefore, the single-laboratory limits established in Sec. 8.9.3 must
fall within those given in Table 8 for these matrices.
8.9.5 If recovery is not within limits, the following procedures are
required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration".
8.9.6 At a minimum, each laboratory should update surrogate recovery
limits on a matrix-by-matrix basis, annually.
8.10 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 assess the precision of the
environmental measurements. When doubt exists over the identification of a peak
on the chromatogram, confirmatory techniques such as gas chromatography with a
dissimilar column or a different ionization mode using a mass spectrometer must
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be used. Whenever possible, the laboratory should analyze standard reference
materials and participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 This method was tested by 15 "laboratories using organic-free reagent
water, drinking water, surface water, and industrial wastewaters spiked at six
concentrations over the range 5-600 ng/L. Single operator precision, overall
precision, and method accuracy were found to be directly related to the
concentration of the analyte and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 7.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act, Method 624,"
October 26, 1984.
2. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
3. Bellar, T.A., and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
739-744, 1974.
4. Bellar, T.A., and J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Water
and Wastewater, ASTM STP 686, pp. 108-129, 1979.
5. Budde, W.L. and J.W. Eichelberger, "Performance Tests for the Evaluation
of Computerized Gas Chromatography/Mass Spectrometry Equipment and
Laboratories," EPA-600/4-79-020, U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268,
April 1980.
6. Eichelberger, J.W., L.E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurement in Gas Chromatography-Mass
Spectrometry Systems," Analytical Chemistry, 47, 995-1000, 1975.
7. "Method Detection Limit for Methods 624 and 625," Olynyk, P., W.L. Budde,
and J.W. Eichelberger, Unpublished report, October 1980.
8. "Interlaboratory Method Study for EPA Method 624-Purgeables," Final Report
for EPA Contract 68-03-3102.
9. "Method Performance Data for Method 624," Memorandum from R. Slater and
T. Pressley, U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio 45268, January 17,
1984.
8240B - 29 Revision 2
September 1994
-------
10. Gebhart, J.E.; Lucas, S.V.; Naber, S.J.; Berry, A.M.; Danison, T.H.;
Burkholder, H.M. "Validation of SW-846 Methods 8010, 8015, and 8020"; U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Old 45268, July 1987, Contract No. 68-03-1760.
11. Lucas, S.V.; Kornfeld, R.A. "GC-MS Suitability Testing of RCRA Appendix
VIII and Michigan List Analytes "; U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, OH 45268,
February 20, 1987, Contract No. 68-03-3224.
8240B - 30 Revision 2
September 1994
-------
TABLE 1.
RETENTION TIMES AND CHARACTERISTIC IONS FOR VOLATILE COMPOUNDS
Compound
Retention
Time (minutes)
Primary Ion Secondary Ion(s)
Ethylene oxide
Chloromethane
Di chl orodi f 1 uoromethane
Bromomethane
Vinyl chloride
Acetonitrile
Chloroethane
Methyl iodide
Methylene chloride
Carbon disulfide
Trichlorofl uoromethane
Propionitrile
Allyl chloride
1,1-Dichloroethene
Bromochloromethane (I.S.)
Allyl alcohol
trans-l,2-Dichloroethene
1,2-Dichloroethane
Propargyl alcohol
Chloroform
l,2-Dichloroethane-d4(surr)
2-Butanone
Methacrylonitrile
Dibromomethane
2-Chloroethanol
b-Propiolactone
Epichlorohydrin
1,1,1-Trichloroethane
Carbon tetrachloride
1,4-Dioxane
Isobutyl alcohol
Bromodi chloromethane
Chloroprene
l,2:3,4-Diepoxybutane
1,2-Dichloropropane
Chloral hydrate (b)
cis-l,3-Dich1oropropene
Bromoacetone
Trichloroethene
Benzene
trans-l,3-Dichloropropene
1, 1, 2 -Tri chloroethane
3-Chloropropionitrile
1,2-Dibromoethane
Pyridine
1.30
2.30
2.47
3.10
3.80
3.97
4.60
5.37
6.40
7.47
8.30
8.53
8.83
9.00
9.30
9.77
10.00
10.10
10.77
11.40
12.10
12.20
12.37
12.53
12.93
13.00
13.10
13.40
13.70
13.70
13.80
14.30
14.77
14.87
15.70
15.77
15.90
16.33
16.50
17.00
17.20
17.20
17.37
18.40
18.57
44
50
85
94
62
41
64
142
84
76
101
54
76
96
128
57
96
62
55
83
65
72
41
93
49
42
57
97
117
88
43
83
53
55
63
82
75
136
130
78
75
97
54
107
79
44, 43, 42
52, 49
85, 87, 101, 103
96, 79
64, 61
41, 40, 39
66, 49
142, 127, 141
49, 51, 86
76, 78, 44
103, 66
54, 52, 55, 40
76, 41, 39, 78
61, 98
49, 130, 51
57, 58, 39
61, 98
64, 98
55, 39, 38, 53
85, 47
102
43, 72
41, 67, 39, 52, 66
93, 174, 95, 172, 176
49, 44, 43, 51, 80
42, 43, 44
57, 49, 62, 51
99, 117
119, 121
88, 58, 43, 57
43, 41, 42, 74
85, 129
53, 88, 90, 51
55, 57, 56
62, 41
44, 84, 86, 111
77, 39
43, 136, 138, 93, 95
95, 97, 132
52, 71
77, 39
83, 85, 99
54, 49, 89, 91
107, 109, 93, 188
79, 52, 51, 50
8240B - 31
Revision 2
September 1994
-------
TABLE 1.
(Continued)
Compound
Retention
Time (minutes)
Primary Ion Secondary Ion(s)
2-Chloroethyl vinyl ether
2-Hydroxypropionitrile
1,4-Difluorobenzene (I.S.)
Malononitrile
Methyl methacrylate
Bromoform
1,1,1 , 2-Tetrachl oroethane
l,3-Dichloro-2-propanol
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
1,2,3-Trichloropropane
l,4-Dichloro-2-butene
n-Propylamine
2-Picoline
Toluene
Ethyl methacrylate
Chlorobenzene
Pentachl oroethane8
Ethyl benzene
l,2-Dibromo-3-chloropropane
4-Bromofluorobenzene (surr.)
Benzyl chloride
Styrene
bis-(2-Chloroethyl) sulfide(b)
Acetone
Acrolein
Acrylonitrile
Chlorobenzene-d5 (I.S.)
Chlorodibromomethane
1,1-Dichloroethane
Ethanol
2-Hexanone
lodomethane
4-Methyl -2-pentanone
Toluene-d8 (surr.)
Vinyl acetate
Xylene (Total)
18.60
18.97
19.60
19.60
19.77
19.80
20.33
21.83
22.10
22.20
22.20
22.73
23.00
23.20
23.50
23.53
24.60
24.83
26.40
27.23
28.30
29.50
30.83
33.53
--
--
--
--
--
--
--
--
--
63
44
114
66
69
173
131
79
83
164
75
75
59
93
92
69
112
167
106
157
95
91
104
109
43
56
53
117
129
63
31
43
142
43
98
43
106
65,106
44,43,42,53
63,88
66,39,65,38
69,41,100,39
171,175,252
131,133,117,119,95
79,43,81,49
85,131,133
129,131,166
75,77,110,112,97
75,53,77,124,89
59,41,39
93,66,92,78
91,65
69,41,99,86,114
114,77
167,130,132,165,169
91
157,75,155,77
174,176
91,126,65,128
104,103,78,51,77
111, 158, 160
58
55,58
52,51
82,119
208,206
65,83
45,27,46
58,57, 100
127,141
58,57,100
70,100
86
91
a The base peak at m/e 117 was not used due to an interference at that mass with
a nearly coeluting internal standard, chlorobenzene-d5.
b Response factor judged to be too low (less than 0.02) for practical use.
(I.S.) = Internal Standard
(surr) = Surrogate
8240B - 32
Revision 2
September 1994
-------
TABLE 2.
ESTIMATED QUANTITATION LIMITS (EQL) FOR VOLATILE ORGANICS
Estimated
Quantitation
Limits8
Ground water
Volatiles /ig/L
Acetone
Acetonitrile
Allyl chloride
Benzene
Benzyl chloride
Bromodi chl oromethane
Bromoform
Bromomethane
2-Butanone
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chl orodi bromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
Chloroprene
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Di bromomethane
l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1 Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethyl benzene
Ethyl methacrylate
2-Hexanone
Isobutyl alcohol
Methacrylonitrile
Methyl ene chloride
Methyl iodide
Methyl methacrylate
4-Methyl -2-pentanone
Pentachloroethane
100
100
5
5
100
5
5
10
100
100
5
5
5
10
10
5
10
5
100
5
5
100
5
5
5
5
5
5
5
5
5
5
50
100
100
5
5
5
50
10
Low Soil/Sediment6
M9/kg
100
100
5
5
100
5
5
10
100
100
5
5
5
10
10
5
10
5
100
5
5
100
5
5
5
5
5
5
5
5
5
5
50
100
100
5
5
50
50
10
8240B - 33 Revision 2
September 1994
-------
TABLE 2.
(Continued)
Estimated
Quantitation
Limits"
Ground water Low Soil/Sediment15
Volatiles M9/L M9A9
Propionitrile
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,1 , 1-Trichl oroethane
1 , 1 , 2-Tri chl oroethane
Trichloroethene
1,2,3-Trichloropropane
Vinyl acetate
Vinyl chloride
Xylene (Total)
100
5
5
5
5
5
5
5
5
5
50
10
5
100
5
5
5
5
5
5
5
5
5
50
10
5
a Sample EQLs are highly matrix dependent. The EQLs listed herein are provided
for guidance and may not always be achievable.
b EQLs listed for soil/sediment are based on wet weight. Normally data are
reported on a dry weight basis; therefore, EQLs will be higher, based on the
percent dry weight of each sample.
Other Matrices Factor0
Water miscible liquid waste 50
High-concentration soil and,sludge 125
Non-water miscible waste 500
CEQL = [EQL for low soil/sediment (see Table 2)] X [Factor found in this
table]. For non-aqueous samples, the factor is on a wet weight basis.
8240B - 34 Revision 2
September 1994
-------
TABLE 3.
BFB KEY ION ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
50 15 to 40% of mass 95
75 30 to 60% of mass 95
95 base peak, 100% relative abundance
96 5 to 9% of mass 95
173 less than 2% of mass 174
174 greater than 50% of mass 95
175 5 to 9% of mass 174
176 greater than 95% but less than 101% of mass 174
177 5 to 9% of mass 176
TABLE 4.
QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS
OF HIGH-CONCENTRATION SOILS/SEDIMENTS
Approximate Volume of
Concentration Range Methanol Extract8
500- 10,000 Mg/kg 100 ML
1,000- 20,000 M9/kg 50 /uL
5,000-100,000 Mg/kg 10 /zL
25,000-500,000 Mg/kg 100 ML of 1/50 dilution6
Calculate appropriate dilution factor for concentrations exceeding this
table.
a The volume of methanol added to 5 mL of water being purged should be kept
constant. Therefore, add to the 5 mL syringe whatever volume of methanol
is necessary to maintain a volume of 100 ML added to the syringe.
b Dilute and aliquot of the methanol extract and then take 100 ML for
analysis.
8240B - 35 Revision 2
September 1994
-------
TABLE 5.
VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES ASSIGNED
FOR QUANTITATION
Bromochloromethane
Acetone
Acrolein
Acrylonitrile
Bromomethane
Carbon disulfide
Chloroethane
Chloroform
Chioromethane
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
l,2-Dichloroethane-d4 (surrogate)
1,1-Dichloroethene
trans-l,2-Dichloroethene
lodomethane
Methylene chloride
Tri chlorof1uoromethane
Vinyl chloride
1,4-Difluorobenzene
Benzene
Bromodi chloromethane
Bromoform
2-Butanone
Carbon tetrachloride
Chlorodi bromomethane
2-Chloroethyl vinyl ether
Dibromomethane
l,4-Dichloro-2-butene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Vinyl acetate
Chlorobenzene-d,;
Bromofluorobenzene (surrogate)
Chlorobenzene
Ethyl benzene
Ethyl methacrylate
2-Hexanone
4-Methyl-2-pentanone
Styrene
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
Toluene-d8 (surrogate)
1,2,3-Trichloropropane
Xylene
8240B - 36
Revision 2
September 1994
-------
TABLE 6.
CALIBRATION AND QC ACCEPTANCE CRITERIA8
Parameter
Benzene
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
Di bromochl oromethane
1,2-Dichlorobenzene
1,3-Di chlorobenzene
1,4-Dichlorobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans- 1,2-Di chl oroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans- 1 , 3-Di chl oropropene
Ethyl benzene
Methyl ene chloride
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1 , 1 , 1 -Tr i chl oroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
Vinyl chloride
Range
for Q
(M9A)
12.8-27.2
13.1-26.9
14.2-25.8
2.8-37.2
14.6-25.4
13.2-26.8
D-44.8
13.5-26.5
D-40.8
13.5-26.5
12.6-27.4
14.6-25.4
12.6-27.4
14.5-25.5
13.6-26.4
10.1-29.9
13.9-26.1
6.8-33.2
4.8-35.2
10.0-30.0
11.8-28.2
12.1-27.9
12.1-27.9
14.7-25.3
14.9-25.1
15.0-25.0
14.2-25.8
13.3-26.7
9.6-30.4
0.8-39.2
Q = Concentration measured in QC check
s = Standard deviati
x = Average recovery
p, ps = Percent recovery
D = Detected; result
Limit
for s
(M9/L)
6.9
6.4
5.4
17.9
5.2
6.3
25.9
6.1
19.8
6.1
7.1
5.5
7.1
5.1
6.0
9.1
5.7
13.8
15.8
10.4
7.5
7.4
7.4
5.0
4.8
4.6
5.5
6.6
10.0
20.0
sample,
Range
for x
(M9/L)
15.2-26.0
10.1-28.0
11.4-31.1
D-41.2
17.2-23.5
16.4-27.4
D-50.4
13.7-24.2
D-45.9
13.8-26.6
11.8-34.7
17.0-28.8
11.8-34.7
14.2-28.4
14.3-27.4
3.7-42.3
13.6-28.4
3.8-36.2
1.0-39.0
7.6-32.4
17.4-26.7
D-41.0
13.5-27.2
17.0-26.6
16.6-26.7
13.7-30.1
14.3-27.1
18.5-27.6
8.9-31.5
D-43.5
in jug/L.
Range
P>Ps
(*)
37-151
35-155
45-169
D-242
70-140
37-160
D-305
51-138
D-273
53-149
18-190
59-156
18-190
59-155
49-155
D-234
54-156
D-210
D-227
17-183
37-162
D-221
46-157
64-148
47-150
52-162
52-150
71-157
17-181
D-251
on of four recovery measurements, in M9/L.
for four recovery
measured.
measurements, in M9/L.
must be greater than zero.
Criteria from 40 CFR Part 136 for Method 624 and were calculated assuming a
QC check sample concentration of 20 M9/L- These criteria are based directly
upon the method performance data in Table 7. Where necessary, the limits for
recovery have been broadened to assure applicability of the limits to
concentrations below those used to develop Table 7.
8240B - 37
Revision 2
September 1994
-------
TABLE 7.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION8
Parameter
Benzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethylvinyl ether8
Chloroform
Chloromethane
Di bromochl oromethane
l,2-Dichlorobenzeneb
1,3-Dichlorobenzene
l,4-Dichlorobenzeneb
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2,-Dichloroethene
1 , 2-Di chl oropropane8
cis-l,3-Dichloropropene8
trans-l,3-Dichloropropenea
Ethyl benzene
Methylene chloride
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,1,1-Tri chl oroethane
1,1,2-Tri chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
Vinyl chloride
Accuracy, as
recovery, x'
(09A)
0.93C+2.00
1.03C-1.58
1.18C-2.35
l.OOC
1.10C-1.68
0.98C+2.28
1.18C+0.81
l.OOC
0.93C+0.33
1.03C-1.81
1.01C-0.03
0.94C+4.47
1.06C+1.68
0.94C+4.47
1.05C+0.36
1.02C+0.45
1.12C+0.61
1.05C+0.03
l.OOC
l.OOC
l.OOC
0.98C+2.48
0.87C+1.88
0.93C+1.76
1.06C+0.60
0.98C+2.03
1.06C+0.73
0.95C+1.71
1.04C+2.27
0.99C+0.39
l.OOC
Single analyst
precision, sr'
(M/L)
0.26X-1.74
O.lSx+0.59
0.12X+0.34
0.43x
0.12X+0.25
0.16X-0.09
0.14X+2.78
0.62X
O.lGx+0.22
0.37X+2.14
0.17X-0.18
0.22X-1.45
0.14X-0.48
0.22X-1.45
0.13x-0.05
0.17X-0.32
0.17X+1.06
0.14X+0.09
0.33x
0.38x
0.25x
0.14X+1.00
0.15X+1.07
0.16X+0.69
0.13X-0.18
0.15X-0.71
0.12X-0.15
0.14X+0.02
0.13X+0.36
0.33X-1.48
0.48x
Overall
precision,
S' (ftg/i)
0.25X-1.33
0.20X+1.13
O.Ux+1.38
0.58x
O.llx+0.37
0.26X-1.92
0.29X+1.75
0.84X
0. 18X+0.16
0.58X+0.43
0.17X+0.49
0.30X-1.20
O.lSx-0.82
O.SOx-1.20
0.16x+0.47
0.21X-0.38
0.43X-0.22
0.19X+0.17
0.45x
0.52x
0.34x
0.26X-1.72
0.32X+4.00
0.20X+0.41
0.16X-0.45
0.22X-1.71
0.21x-0.39
O.lSx+O.OO
0.12X+0.59
0.34X-0.39
0.65x
x' = Expected recovery for one or more measurements of a sample
containing a concentration of C, in M9/L.
s/ = Expected single analyst standard deviation of measurements at an
average concentration of x, in ng/i.
S' = Expected interlaboratory standard deviation of measurements at an
average concentration found of x, in fj.g/1.
C = True value for the concentration, in jug/L.
x = Average recovery found for measurements of samples containing a
concentration of C, in /ig/L.
a Estimates based upon the performance in a single laboratory.
b Due to chromatographic resolution problems, performance statements for
these isomers are based upon the sums of their concentrations.
8240B - 38
Revision 2
September 1994
-------
TABLE 8.
SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Low/High Low/High
Surrogate Compound Water Soil/Sediment
4-Bromofluorobenzene 86-115 74-121
l,2-Dichloroethane-d4 76-114 70-121
Toluene-do 88-110 81-117
8240B - 39 Revision 2
September 1994
-------
FIGURE 1.
PURGING CHAMBER
FOAMTIMP
GOT 1M IN
M MM 00.
INLET 1M IN. O.O.
EXIT 1M IN. O.O
10 MM QLASS FNT
MEDIUM POM06TTY
SAMPLE INUTT
24MAV SYNNOE VALVC
17 CM 20 OAUOE SVHNQf NC£DU
« MM 0.0. RUMCR SCPTUM
INLET 1M IN O 0.
_ 1/16 IN O 0
/^ STAINUSS STffi.
13X
MOCECULAA SIEVE
PU«OE GAS FKTCT
PWWEOAS
n.ov» CONTROL
8240B - 40
Revision 2
September 1994
-------
FIGURE 2.
TRAP PACKINGS AND CONSTRUCTION TO INCLUDE
DESORB CAPABILITY FOR METHOD 8240B
OCTM.
-tMMOLMi
CONSTRUCTION OCTM.
*CMTUu»QC
8240B - 41
Revision 2
September 1994
-------
FIGURE 3.
SCHEMATIC OF PURGE-AND-TRAP DEVICE - PURGE MODE FOR METHOD 8240B
CARRIER GAS
FLOW CONTROL
PRESSURE
REGULATOR
PURGE OAS
PLOW CONTROL
13X MOLECULAR
SIEVE FILTER
UOUIO INJECTION PORTS
l— COLUMN OVEN
UW-,
UUTJV-
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
OPTIONAL ^PORT COLUMN
SELECTION VALVE
^ y- TRAP INLET
TRAP
22*C
PURGING
DEVICE
NOTE
ALL LINES BETWEEN TRAP
AND QC SHOULD K HEATED
TO
8240B - 42
Revision 2
September 1994
-------
FIGURE 4.
SCHEMATIC OF PURGE-AND-TRAP DEVICE - DESORB MODE FOR METHOD 82408
OARER OAS
FlOW CONTROL
PRESSURE
REGULATOR
PURGE GAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
LJOWO INJECTION PORTS
p- COLUMN OVEN
UUUV-
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
OPTIONAL 4*ORT COLUMN
SELECTION VALVE
/-TRAP INLET
TRAP
200*C
i PURGING
41 DEVICE
NOTE.
ALL LINES BETWEEN TRAP
AND OC SHOULD BE HEATED
TO UPC.
8240B - 43
Revision 2
September 1994
-------
FIGURE 5.
LOW SOILS IMPINGER
—-1
PURGE INLET FITTING
SAMPLE OUTLET FITTING
3" « 6mm 0 D GLASS TUBING
SEPTUM
CAP
40ml VIAL
8240B - 44
Revision 2
September 1994
-------
METHOD 8240B
VOLATILE ORGANICS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)
7.1
Select
procedure for
introducing
sample into
GC/MS.
Direct
Injection
Purge-and-trap
7.2.1
Set GC/MS
operating
conditions.
7.2.4 Connect
purge-and-trap
device to GC.
7.2.6 Perform
purge-and-trap
analysis.
7.2.8
Calculate RFs
for 6 SPCCs.
7.3 Perform
daily
calibration
using SPCCs
and CCCs.
Soil/Sediment
Miscible
Liquids
and Waste
Samples
7.4.2.1
Dilute sample
at least 50
fold with
water.
7.4.3 Screen
sample using
Method 3810
or 3820.
screening
method for the
waste
matrix.
Water
Samples
7.4.1.1
Screen sample
using Method
3810 or 3820.
7.4.1.7
Perform
secondary
dilutions.
7.4.1.8 Add
internal standard
and surrogate
spiking solutions.
7.4.1.10
Perform
purge-and-trap
procedure.
8240B - 45
Revision 2
September 1994
-------
METHOD 8240B
(continued)
7.4.3
Is
concentration
> 1 mg/Kg?
7.4.3.1.1
Choose sample
size based on
estimated
concentration.
7.4.3.1.3 Add
internal standard
and surrogate
spiking solutions.
7.4.3.1.5
Determine
percent dry
weight of
sample.
7.4.3.1.7
Perform
purge-and-trap
procedure.
7.4.3.2 Choose
solvent for
extraction or
dilution. Weigh
sample.
7.4.1.1 1
Attach trap
to GC and
perform
analysis.
7.4.3.2.2 Add
solvent,
shake.
7.5.1.1 Indentify
analytes by
comparing the
sample retention
time and sample
mass spectra.
7.4.3.2.7
Perform
purge-and-trap
procedure.
7.5.2.2 Calculate
the concentration
of each identified
analyte.
7.5.2.4
Report all
results.
C Stop J
8240B - 46
Revision 2
September 1994
-------
8
-------
METHOD 8250A
SEMIVOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)
1.0 SCOPE AND APPLICATION
1.1 Method 8250 is used to determine the concentration of semi volatile
organic compounds in extracts prepared from all types of solid waste matrices,
soils, and ground water. Direct injection of a sample may be used in limited
applications. The following compounds can be determined by this method:
Appropriate Preparation Techniques
Compounds
CAS No" 3510
8250A - 1
3520 3540/ 3550 3580
3541
Acenaphthene
Acenaphthene-d10 (I.S.)
Acenaphthylene
Acetophenone
Aldrin
4-Aminobiphenyl
Aniline
Anthracene
Aroclor - 1016 (PCB-1016)
Aroclor - 1221 (PCB-1221)
Aroclor - 1232 (PCB-1232)
Aroclor - 1242 (PCB-1242)
Aroclor - 1248 (PCB-1248)
Aroclor - 1254 (PCB-1254)
Aroclor - 1260 (PCB-1260)
Benzidine
Benzoic acid
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzyl alcohol
a-BHC
0-BHC
5-BHC
7-BHC (Lindane)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
83-32-9
208-96-8
98-86-2
309-00-2
92-67-1
62-53-3
120-12-7
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
92-87-5
65-85-0
56-55-3
205-99-2
207-08-9
191-24-2
50-32-8
100-51-6
319-84-6
319-85-7
319-86-8
58-89-9
111-91-1
111-44-4
108-60-1
117-81-7
101-55-3
85-68-7
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
NO
X
ND
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
X
X
X
X
X
X
X
X
CP
ND
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
ND
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Revision 1
September 1994
-------
Appropriate Preparation Techniaues
Compounds
Chlordane (technical)
4-Chloroaniline
1-Chloronaphthalene
2-Chloronaphthalene
4-Chloro -3 -methyl phenol
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-d12 (I.S.)
4,4'-DDD
4,4'-DDT
4,4'-DOE
Dibenz(a, j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
l,4-Dichlorobenzene-d4 (I.S)
3,3' -Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dieldrin
Diethyl phthalate
Dimethyl aminoazobenzene
7,12-Dimethylbenz(a)-
anthracene
a,a-Dimethylphenethylamine
2,4-Dimethylphenol
Dimethyl phthalate
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di phenyl ami ne
1,2-Di phenyl hydrazine
Di-n-octyl phthalate
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
Ethyl methanesulfonate
CAS Noa
57-74-9
106-47-8
90-13-1
91-58-7
59-50-7
95-57-8
7005-72-3
218-01-9
72-54-8
50-29-3
72-55-9
224-42-0
53-70-3
132-64-9
84-74-2
95-50-1
541-73-1
106-46-7
3855-82-1
91-94-1
120-83-2
87-65-0
60-57-1
84-66-2
60-11-7
57-97-6
122-09-8
105-67-9
131-11-3
534-52-1
51-28-5
121-14-2
606-20-2
122-39-4
122-66-7
117-84-0
959-98-8
33213-65-9
1031-07-8
72-20-8
7421-93-4
53494-70-5
62-50-0
3510
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP(45)
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
3520
X
ND
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
ND
X
X
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
3540/
3541
X
ND
X
X
X
X
X
X
X
X
X
ND
X
ND
X
X
X
X
X
X
X
ND
X
X
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
ND
3550
X
ND
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
ND
X
X
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
3580
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
8250A - 2
Revision 1
September 1994
-------
Compounds
Appropriate Preparation Techniques
CAS Noa 3510 3520 3540/ 3550 3580
3541
Fluoranthene
Fluorene
2-Fluorobiphenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
Indeno(l,2,3-cd}pyrene
Isophorone
Methoxychlor
3-Methylchol anthrene
Methyl methanesulfonate
2 -Methyl naphthalene
2-Methylphenol
4-Methylphenol
Naphthalene
Naphthalene-d8 (I.S.)
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
Nitrobenzene-dg (surr.)
2-Nitrophenol
4-Nitrophenol
N -Nitrosodi butyl ami ne
N-Nitrosodi methyl ami ne
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
N-Nitrosopi peri dine
Pentachlorobenzene
Pentachloronitrobenzene
Pentachlorophenol
Perylene-d12 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-d10 (I.S.)
Phenol
Phenol -d6 (surr.)
2-Picoline
Pronamide
206-44-0
86-73-7
321-60-8
367-12-4
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
193-39-5
78-59-1
72-43-5
56-49-5
66-27-3
91-57-6
95-48-7
106-44-5
91-20-3
1146-65-2
134-32-7
91-59-8
88-74-4
99-09-2
100-01-6
98-95-3
4165-60-0
88-75-5
100-02-7
924-16-3
62-75-9
86-30-6
621-64-7
100-75-4
608-93-5
82-68-8
87-86-5
198-55-0
62-44-2
85-01-8
108-95-2
13127-88-3
109-06-8
23950-58-5
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
OS(44)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
DC(28)
DC(28)
NO
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
X
ND
ND
X
X
ND
ND
X
X
X
X
X
X
X
ND
X
X
X
ND
ND
ND
X
X
ND
X
X
X
X
ND
ND
X
X
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
X
X
X
X
ND
X
X
X
ND
ND
ND
X
X
ND
X
X
X
X
ND
ND
X
X
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
X
ND
ND
X
X
ND
ND
X
X
X
X
X
X
X
ND
X
X
X
ND
ND
ND
X
X
ND
X
X
X
X
ND
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
8250A - 3
Revision 1
September 1994
-------
Appropriate Preparation Techniques
Compounds CAS Noa 3510 3520 3540/ 3550 3580
3541
Pyrene
Terpheny1-d14(surr.)
1,2,4 , 5-Tetrachl orobenzene
2,3,4,6-Tetrachlorophenol
Toxaphene
2,4,6-Tribromophenol (surr. )
1,2, 4 -Trichl orobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
129-00-0
1718-51-0
95-94-3
58-90-2
8001-35-2
118-79-6
120-82-1
95-95-4
88-06-2
X
X
X
X
X
X
X
X
X
X
X
ND
ND
X
X
X
X
X
X
ND
ND
ND
X
X
X
ND
X
X
X
ND
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
8 Chemical Abstract Service Registry Number.
CP = Nonreproducible chromatographic performance.
DC = Unfavorable distribution coefficient (number in parenthesis is
percent recovery).
ND = Not determined.
OS = Oxidation during storage (number in parenthesis is percent
stability).
X = Greater than 70 percent recovery by this technique.
1.2 Method 8250 can be used to quantitate most neutral, acidic, and
basic organic compounds that are soluble in methylene chloride and capable of
being eluted without derivatization as sharp peaks from a gas chromatographic
packed column. Such compounds include polynuclear aromatic hydrocarbons,
chlorinated hydrocarbons and pesticides, phthalate esters, organophosphate
esters, nitrosamines, haloethers, aldehydes, ethers, ketones, anilines,
pyridines, quinolines, aromatic nitro compounds, and phenols, including
nitrophenols. See Table 1 for a list of compounds and their characteristic ions
that have been evaluated on the specified GC/MS system.
1.3 The following compounds may require special treatment when being
determined by this method. Benzidine can be subject to oxidative losses during
solvent concentration. Also, chromatography is poor. Under the alkaline
conditions of the extraction step, a-BHC, 7-BHC, endosulfan I and II, and endrin
are subject to decomposition. Neutral extraction should be performed if these
compounds are expected and are not being determined by Method 8080.
Hexachlorocyclopentadiene is subject to thermal decomposition in the inlet of the
gas chromatograph, chemical reaction in acetone solution, and photochemical
decomposition. N-nitrosodimethylamine is difficult to separate from the solvent
under the chromatographic conditions described. N-nitrosodiphenylamine
decomposes in the gas chromatographic inlet and cannot be separated from
diphenylamine. Pentachlorophenol, 2,4-dinitrophenol, 4-nitrophenol, 4,6-dinitro-
2-methylphenol, 4-chloro-3-methylphenol, benzoic acid, 2-nitroaniline,
8250A - 4 Revision 1
September 1994
-------
3-nitroaniline, 4-chloroaniline, and benzyl alcohol are subject to erratic
chromatographic behavior, especially if the GC system is contaminated with high
boil ing material.
1.4 The estimated quantitation limit (EQL) of Method 8250 for
determining an individual compound is approximately 1 mg/kg (wet weight) for
soil/sediment samples, 1-200 mg/kg for wastes (dependent on matrix and method of
preparation), and 10 /xg/L for ground water samples (see Table 2). EQLs will be
proportionately higher for sample extracts that require dilution to avoid
saturation of the detector.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatograph/mass spectrometers and
skilled in the interpretation of mass spectra. Each analyst must demonstrate the
ability to generate acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 Prior to using this method, the samples should be prepared for
chromatography using the appropriate sample preparation and cleanup methods.
This method describes chromatographic conditions that will allow for the
separation of the compounds in the extract.
3.0 INTERFERENCES
3.1 Raw GC/MS data from all blanks, samples, and spikes must be
evaluated for interferences. Determine if the source of interference is in the
preparation and/or cleanup of the samples and take corrective action to eliminate
the problem.
3.2 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed. To reduce carryover, the
sample syringe must be rinsed out between samples with solvent. Whenever an
unusually concentrated sample is encountered, it should be followed by the
analysis of solvent to check for cross contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph/mass spectrometer system
4.1.1 Gas chromatograph - An analytical system complete with a
temperature-programmable gas chromatograph suitable for splitless
injection and all required accessories, including syringes, analytical
columns, and gases.
4.1.2 Columns
4.1.2.1 For base/neutral compound detection - 2 m x 2
mm ID stainless or glass, packed with 3% SP-2250-DB on 100/120 mesh
Supelcoport or equivalent.
8250A - 5 Revision 1
September 1994
-------
4.1.2.2 For acid compound detection - 2 m x 2 mm ID glass,
packed with 1% SP-1240-DA on 100/120 mesh Supelcoport or equivalent.
4.1.3 Mass spectrometer - Capable of scanning from 35 to 500 amu
every 1 second or less, using 70 volts (nominal) electron energy in the
electron impact ionization mode. The mass spectrometer must be capable
of producing a mass spectrum for decafluorotriphenylphosphine (DFTPP)
which meets all of the criteria in Table 3 when 1 /uL of the GC/MS tuning
standard is injected through the GC (50 ng of DFTPP).
4.1.4 GC/MS interface - Any GC-to-MS interface that gives acceptable
calibration points at 50 ng per injection for each compound of interest
and achieves acceptable tuning performance criteria may be used. GC-to-MS
interfaces constructed entirely of glass or glass-lined materials are
recommended. Glass may be deactivated by silanizing with
di chlorodimethylsi 1ane.
4.1.5 Data system - A computer system must be interfaced to the mass
spectrometer. The system must allow the continuous acquisition and
storage on machine-readable media of all mass spectra obtained throughout
the duration of the chromatographic program. The computer must have
software that can search any GC/MS data file for ions of a specific mass
and that can plot such ion abundances versus time or scan number. This
type of plot is defined as an Extracted Ion Current Profile (EICP).
Software must also be available that allows integrating the abundances in
any EICP between specified time or scan-number limits. The most recent
version of the EPA/NIH Mass Spectral Library should also be available.
4.2 Syringe - 10 /xL.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall 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
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Stock standard solutions (lOO'O mg/L) - Standard solutions can be
prepared from pure standard materials or purchased as certified solutions.
5.3.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in pesticide quality
acetone or other suitable solvent and dilute to volume in a 10 ml
volumetric flask. Larger volumes can be used at the convenience of the
analyst. When compound purity is assayed to be 96% or greater, the weight
may be used without correction to calculate the concentration of the stock
standard. Commercially prepared stock standards may be used at any
8250A - 6 Revision 1
September 1994
-------
concentration if they are certified by the manufacturer or by an
independent source.
5.3.2 Transfer the stock standard solutions into bottles with Teflon
lined screw-caps or crimp tops. Store at -10°C to -20°C or less and
protect from light. Stock standard solutions should be checked frequently
for signs of degradation or evaporation, especially just prior to
preparing calibration standards from them.
5.3.3 Stock standard solutions must be replaced after 1 year or
sooner if comparison with quality control check samples indicates a
problem.
5.4 Internal standard solutions - The internal standards recommended are
l,4-dichlorobenzene-d4, naphthalene-d8, acenaphthene-d10, phenanthrene-d10,
chrysene-d12, and perylene-d12. Other compounds may be used as internal standards
as long as the requirements given in Sec. 7.3.2 are met. Dissolve 200 mg of each
compound with a small volume of carbon disulfide. Transfer to a 50 ml volumetric
flask and dilute to volume with methylene chloride so that the final solvent is
approximately 20% carbon disulfide. Most of the compounds are also soluble in
small volumes of methanol, acetone, or toluene, except for perylene-d12. The
resulting solution will contain each standard at a concentration of 4,000 ng//xL.
Each 1 ml sample extract undergoing analysis should be spiked with 10 fj,L of the
internal standard solution, resulting in a concentration of 40 ng/nl of each
internal standard. Store at -10°C to -20°C or less when not being used.
5.5 GC/MS tuning standard - A methylene chloride solution containing
50 ng/VL of decafluorotriphenylphosphine (DFTPP) should be prepared. The
standard should also contain 50 ng/^L each of 4,4'-DDT, pentachlorophenol, and
benzidine to verify injection port inertness and GC column performance. Store
at 4°C or less when not being used.
5.6 Calibration standards - Calibration standards at a minimum of five
concentrations should be prepared. One of the calibration standards should be
at a concentration near, but above, the method detection limit; the others should
correspond to the range of concentrations found in real samples but should not
exceed the working range of the GC/MS system. Each standard should contain each
analyte for detection by this method (e.g. some or all of the compounds listed
in Table 1 may be included). Each 1 mL aliquot of calibration standard should
be spiked with 10 ^L of the internal standard solution prior to analysis. All
standards should be stored at -10°C to -20°C and should be freshly prepared once
a year, or sooner if check standards indicate a problem. The daily calibration
standard should be prepared weekly and stored at 4°C.
5.7 Surrogate standards - The recommended surrogate standards are
phenol-d6, 2-fluorophenol, 2,4,6-tribromophenol, nitrobenzene-d5, 2-
fluorobiphenyl, and p-terphenyl-d14. See Method 3500 for the instructions on
preparing the surrogate standards. Determine what concentration should be in the
blank extracts after all extraction, cleanup, and concentration steps. Inject
this concentration into the GC/MS to determine recovery of surrogate standards
in all blanks, spikes, and sample extracts. Take into account all dilutions of
sample extracts.
8250A - 7 Revision 1
September 1994
-------
5,8 Matrix spike standards - See Method 3500 for instructions on
preparing the matrix spike standard. Determine what concentration should be in
the blank extracts after all extraction, cleanup, and concentration steps.
Inject this concentration into the GC/MS to determine recovery of standards in
all matrix spikes. Take into account all dilutions of sample extracts.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
7.1 Sample preparation - Samples must be prepared
following methods prior to GC/MS analysis.
by one of the
Matrix
Water
Soil/sediment
Waste
Methods
3510, 3520
3540, 3541, 3550
3540, 3541, 3550, 3580
7.1.1 Direct injection - In very limited applications direct
injection of the sample into the GC/MS system with a 10 /xL syringe may be
appropriate. The detection limit is very high (approximately
10,000 M9/L); therefore, it is only permitted where concentrations in
excess of 10,000 /xg/L are expected. The system must be calibrated by
direct injection.
7.2 Extract cleanup - Extracts
methods prior to GC/MS analysis.
may be cleaned up by any of the following
Compounds
Phenols
Phthalate esters
Nitrosamines
Organochlorine pesticides & PCBs
Nitroaromatics and cyclic ketones
Polynuclear aromatic hydrocarbons
Haloethers
Chlorinated hydrocarbons
Organophosphorus pesticides
Petroleum waste
All basic, neutral, and acidic
Priority Pollutants
Methods
3630, 3640, 8040°
3610, 3620, 3640
3610, 3620, 3640
3620, 3640, 3660
3620, 3640
3611, 3630, 3640
3620, 3640
3620, 3640
3620
3611, 3650
3640
"Method 8040 includes a derivatization technique followed by GC/ECD analysis, if
interferences are encountered on GC/FID.
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7.3 Recommended GC/MS operating conditions
Electron energy: 70 volts (nominal)
Mass range: 35-500 amu
Scan time: 1 sec/scan
Injector temperature: 250-300°C
Transfer line temperature: 250-300°C
Source temperature: According to manufacturer's specifications
Injector: Grob-type, splitless
Sample volume: 1-2 juL
Carrier gas: Helium at 30 mL/min
Conditions for base/neutral analysis (3% SP-2250-DB):
Initial column temperature and hold time: 50°C for 4 minutes
Column temperature program: 50-300°C at 8°C/min
Final column temperature hold: 300°C for 20 minutes
Conditions for acid analysis (1% SP-1240-DA):
Initial column temperature and hold time: 70°C for 2 minutes
Column temperature program: 70-200°C at 8°C/min
Final column temperature hold: 200°C for 20 minutes
7.4 Initial calibration
7,4.1 Each GC/MS system must be hardware-tuned to meet the criteria
in Table 3 for a 50 ng injection of DFTPP. Analyses should not begin
until all these criteria are met. Background subtraction should be
straightforward and designed only to eliminate column bleed or instrument
background ions. The GC/MS tuning standard should also be used to assess
GC column performance and injection port inertness. Degradation of DDT
to DDE and ODD should not exceed 20% (See Sec. 7.4.5 of Method 8080).
Benzidine and pentachlorophenol should be present at their normal
responses, and no peak tailing should be visible. If degradation is
excessive and/or poor chromatography is noted, the injection port may
require cleaning.
7.4.2 The internal standards selected in Sec. 5.1 should permit most
of the components of interest in a chromatogram to have retention times
of 0.80-1.20 relative to one of the internal standards. Use the base peak
ion from the specific internal standard as the primary ion for
quantitation (see Table 1). If interferences are noted, use the next most
intense ion as the quantitation ion (i.e. for l,4-dichlorobenzene-d4 use
m/z 152 for quantitation).
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7.4.3 Analyze 1 /j,l of each calibration standard (containing internal
standards) and tabulate the area of the primary characteristic ion against
concentration for each compound (as indicated in Table 1). Calculate
response factors (RFs) for each compound relative to the internal standard
as follows:
RF = (AxCis)/(AisCJ
where:
Ax = Area of the characteristic ion for the compound being
measured.
Ais = Area of the characteristic ion for the specific internal
standard.
Cx = Concentration of the compound being measured (ng//iL).
Cis = Concentration of the specific internal standard (ng/^L).
7.4.4 A system performance check must be performed to ensure that
minimum average response factors, calculated as the mean of the 5
individual relative response factors, are met before the calibration curve
is used. For semivolatiles, the System Performance Check Compounds
(SPCCs) are: N-nitroso-di-n-propylamine; hexachlorocyclopentadiene;
2,4-dinitrophenol; and 4-nitrophenol. The minimum acceptable average RF
for these compounds is 0.050. These SPCCs typically have very low RFs
(0.1-0.2) and tend to decrease in response as the chromatographic system
begins to deteriorate or the standard material begins to deteriorate.
They are usually the first to show poor performance. Therefore, they must
meet the minimum requirement when the system is calibrated.
7.4.4.1 The percent relative standard deviation should be
less than 15% for each compound. However, the %RSD for each
individual Calibration Check Compound (CCC) (see Table 4) must be
less than 30%. The relative retention times of each compound in
each calibration run should agree within 0.06 relative retention
time units. Late-eluting compounds usually have much better
agreement.
SD
%RSD = — x 100
RF
where:
RSD = relative standard deviation.
RF = mean of 5 initial RFs for a compound.
SD = standard deviation of average RFs for a compound.
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SD =
N (RFj - RF):
I
1=1 N - 1
where:
RFi = RF for each of the 5 calibration levels
N = Number of RF values (i.e., 5)
7.4.4.2 If the %RSD of any CCC is 30% or greater, then the
chromatographic system is too reactive for analysis to begin. Clean
or replace the injector liner and/or capillary column, then repeat
the calibration procedure beginning with Sec. 7.4.
7.4.5 Linearity - If the %RSD of any compound is 15% or less, then
the relative response factor is assumed to be constant over the
calibration range, and the average relative response factor may be used
for quantitation (Sec. 7.7.2).
7.4.5.1 If the %RSD of any compound is greater than 15%,
construct calibration curves of area ratio (A/Ais) versus
concentration using first or higher order regression fit of the five
calibration points. The analyst should select the regression order
which introduces the least calibration error into the quantitation
(Sees. 7.7.2.2 and 7.7.2.3). The use of calibration curves is a
recommended alternative to average response factor calibration, and
a useful diagnostic of standard preparation accuracy and absorption
activity in the chromatographic system.
7.5 Daily GC/MS calibration
7.5.1 Prior to analysis of samples, the GC/MS tuning standard must
be analyzed. A 50 ng injection of DFTPP must result in a mass spectrum
for DFTPP which meets the criteria given in Table 3. These criteria must
be demonstrated during each 12 hour shift.
7.5.2 A calibration standard(s) at mid-concentration containing all
semivolatile analytes, including all required surrogates, must be
analyzed every 12 hours during analysis. Compare the instrument response
factor from the standards every 12 hours with the SPCC (Sec. 7.5.3) and
CCC (Sec. 7.5.4) criteria.
7.5.3 System Performance Check Compounds (SPCCs) - A system
performance check must be made during every 12 hour shift. If the SPCC
criteria are met, a comparison of response factors is made for all
compounds. This is the same check that is applied during the initial
calibration. If the minimum response factors are not met, the system must
be evaluated, and corrective action must be taken before sample analysis
begins. The minimum RF for semivolatile SPCCs is 0.050. Some possible
problems are standard mixture degradation, injection port inlet
contamination, contamination at the front end of the analytical column,
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and active sites in the column or chromatographic system. This check must
be met before analysis begins.
7.5.4 Calibration Check Compounds (CCCs): After the system
performance check is met, CCCs listed in Table 4 are used to check the
validity of the initial calibration.
Calculate the percent drift using:
c, - cc
% Drift = x 100
where:
C,
C, = Calibration Check Compound standard concentration.
Cc = Measured concentration using selected quantitation method.
If the percent difference for each CCC is less than or equal to 20%,
the initial calibration is assumed to be valid. If the criterion is not
met (> 20% drift) for any one CCC, corrective action must be taken.
Problems similar to those listed under SPCCs could affect this criterion.
If no source of the problem can be determined after corrective action has
been taken, a new five-point calibration must be generated. This
criterion must be met before sample analysis begins. If the CCCs are not
analytes required by the permit, then all required analytes must meet the
20% drift criterion.
7.5.5 The internal standard responses and retention times in the
calibration check standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard changes
by more than 30 seconds from the last daily calibration (Sec. 7.4), the
chromatographic system must be inspected for malfunctions and corrections
must be made, as required. If the EICP area for any of the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration check standard, the mass spectrometer must be inspected for
malfunctions and corrections must be made, as appropriate.
7.6 GC/MS analysis
7.6.1 It is highly recommended that the extract be screened on a
GC/FID or GC/PID using the same type of column. This will minimize
contamination of the GC/MS system from unexpectedly high concentrations
of organic compounds.
7.6.2 Spike the 1 mL extract obtained from sample preparation with
10 /iL of the internal standard solution (Sec. 5.4) just prior to analysis.
7.6.3 Analyze the 1 ml extract by GC/MS using the appropriate column
(as specified in Sec. 4.1.2). The recommended GC/MS operating conditions
to be used are specified in Sec. 7.3.
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7.6.4 If the response for any quantitation ion exceeds the initial
calibration curve range of the GC/MS system, extract dilution must take
place. Additional internal standard must be added to the diluted extract
to maintain the required 40 ng//xL of each internal standard in the
extracted volume. The diluted extract must be reanalyzed.
7.6.5 Perform all qualitative and quantitative measurements as
described in Sec. 7.7. Store the extracts at 4°C, protected from light
in screw-cap vials equipped with unpierced Teflon lined septa.
7,7 Data interpretation
7.7.1 Qualitative analysis
7.7.1.1 The qualitative identification of compounds
determined by this method is based on retention time, and on
comparison of the sample mass spectrum, after background correction,
with characteristic ions in a reference mass spectrum. The
reference mass spectrum must be generated by the laboratory using
the conditions of this method. The characteristic ions from the
reference mass spectrum are defined to be the three ions of greatest
relative intensity, or any ions over 30% relative intensity if less
than three such ions occur in the reference spectrum. Compounds
should be identified as present when the criteria below are met.
7.7.1.1.1 The intensities of the characteristic ions
of a compound maximize in the same scan or within one scan of
each other. Selection of a peak by a data system target
compound search routine where the search is based on the
presence of a target chromatographic peak containing ions
specific for the target compound at a compound-specific
retention time will be accepted as meeting this criterion.
7.7.1.1.2 The RRT of the sample component is within
± 0.06 RRT units of the RRT of the standard component.
7.7.1.1.3 The relative intensities of the
characteristic ions agree within 30% of the relative
intensities of these ions in the reference spectrum.
(Example: For an ion with an abundance of 50% in the
reference spectrum, the corresponding abundance in a sample
spectrum can range between 20% and 80%.)
7.7.1.1.4 Structural isomers that produce very
similar mass spectra should be identified as individual
isomers if they have sufficiently different GC retention
times. Sufficient GC resolution is achieved if the height of
the valley between two isomer peaks is less than 25% of the
sum of the two peak heights. Otherwise, structural isomers
are identified as isomeric pairs.
7.7.1.1.5 Identification is hampered when sample
components are not resolved chromatographically and produce
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mass spectra containing ions contributed by more than one
analyte. When gas chromatographic peaks obviously represent
more than one sample component (i.e., a broadened peak with
shoulder(s) or a valley between two or more maxima),
appropriate selection of analyte spectra and background
spectra is important. Examination of extracted ion current
profiles of appropriate ions can aid in the selection of
spectra, and in qualitative identification of compounds. When
analytes coelute (i.e., only one chromatographic peak is
apparent), the identification criteria can be met, but each
analyte spectrum will contain extraneous ions contributed by
the coeluting compound.
7.7.1.2 For samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the purpose of the
analyses being conducted. Computer generated library search
routines should not use normalization routines that would
misrepresent the library or unknown spectra when compared to each
other. For example, the RCRA permit or waste delisting requirements
may require the reporting of nontarget analytes. Only after visual
comparison of sample spectra with the nearest library searches will
the mass spectral interpretation specialist assign a tentative
identification. Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should be present in
the sample spectrum.
(2) The relative intensities of the major ions should agree
within + 20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%.)
(3) Molecular ions present in the reference spectrum should
be present in sample the spectrum.
(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible background
contamination or presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or coeluting
peaks. Data system library reduction programs can sometimes create
these discrepancies.
7.7.2 Quantitative Analysis
7.7.2.1 When a compound has been identified, the
quantitation of that compound will be based on the integrated
abundance from the EICP of the primary characteristic ion.
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7.7.2.2 If the %RSD of a compound's relative response
factor is 15% or less, then the concentration in the extract may be
determined using the average response factor (RF) from initial
calibration data (Sec. 7.4.3) and the following equation:
(Ax x Cis)
C
ex
(Ais x RF)
where Cex is the concentration of the compound in the extract,
and the other terms are as defined in Sec. 7.4.3.
7.7.2.3 Alternatively, the regression line fitted to the
initial calibration (Sec. 7.4.6.1) may be used for determination of
the extract concentration.
7.7.2.4 Compute the concentration of the analyte in the
sample using the equations in Sees. 7.7.2.4.1 and 7.7.2.4.2.
7.7.2.4.1 The concentration of the analyte in the
liquid phase of the sample is calculated using the
concentration of the analyte in the extract and the volume of
liquid extracted, as follows:
Concentration in liquid (/j.g/1) = i_C.v x V9J
o
where:
Vex = extract volume, in mL
V0 = volume of liquid extracted, in L.
7.7.2.4.2 The concentration of the analyte in the
solid phase of the sample is calculated using the
concentration of the pollutant in the extract and the weight
of the solids, as follows:
Concentration in solid (M9Ag) = .(£.„ x VBX)
s
where:
Vex = extract volume, in ml
Ws = sample weight, in kg.
7.7.2.5 Where applicable, an estimate of concentration for
noncalibrated components in the sample should be made. The formulae
given above should be used with the following modifications: The
areas Ax and Ais should be from the total ion chromatograms and the
RF for the compound should be assumed to be 1. The concentration
obtained should be reported indicating (1) that the value is an
estimate and (2) which internal standard was used to determine
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concentration. Use the nearest internal standard free of
interferences.
7.7.2.6 Quantitation of multicomponent compounds (e.g.
Aroclors) is beyond the scope of Method 8250A. Normally,
quantisation is performed using a GC/ECD by Method 8080.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program consist
of an initial demonstration of laboratory capability and an ongoing analysis of
spiked samples to evaluate and document data quality. The laboratory must
maintain records to document the quality of the data generated. Ongoing data
quality checks are compared with established performance criteria to determine
if the results of analyses meet the performance characteristics of the method.
When results of sample spikes indicate atypical method performance, a quality
control check standard must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a reagent water blank, that interferences from the
analytical system, glassware, and reagents are under control. Each time a set
of samples is extracted or there is a change in reagents, a reagent water blank
should be processed as a safeguard against chronic laboratory contamination. The
blank samples should be carried through all stages of the sample preparation and
measurement steps.
8.3 The experience of the analyst performing GC/MS analyses is
invaluable to the success of the methods. Each day that analysis is performed,
the daily calibration standard should be evaluated to determine if the
chromatographic system is operating properly. Questions that should be asked
are: Do the peaks look normal?; Is the response obtained comparable to the
response from previous calibrations? Careful examination of the standard
chromatogram can indicate whether the column is still good, the injector is
leaking, the injector septum needs replacing, etc. If any changes are made to
the system (e.g. column changed), recal ibration of the system must take place.
8.4 Required instrument QC is found in the following section:
8.4.1 The GC/MS system must be tuned to meet the DFTPP
specifications in Sec. 7.3.1 and 7.4.1.
8.4.2 There must be an initial calibration of the GC/MS system as
specified in Sec. 7.4.
8.4.3 The GC/MS system must meet the SPCC criteria specified in Sec.
7.5.3 and the CCC criteria in Sec. 7.5.4, each 12 hr.
8.5 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
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8.5.1 A quality control (QC) check sample concentrate is required
containing each analyte at a concentration of 100 mg/L in acetone. The
QC check sample concentrate may be prepared from pure standard materials
or purchased as certified solutions. If prepared by the laboratory, the
QC check sample concentrate must be made using stock standards prepared
independently from those used for calibration.
8.5.2 Using a pipet, prepare QC check samples at a concentration of
100 jug/L by adding 1.00 ml of QC check sample concentrate to each of four
1-L aliquots of organic-free reagent water.
8.5.3 Analyze the well-mixed QC check samples according to the
method beginning in Sec. 7.1 with extraction of the samples.
8.5.4 Calculate the average recovery (x) in jiig/L, and the standard
deviation of the recovery (s) in /Ltg/L, for each analyte using the four
results.
8.5.5 For each analyte compare s and x with the corresponding
acceptance criteria jfor precision and accuracy, respectively, found in
Table 6. If s and x for all analytes of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or any
individual x falls outside the range for accuracy, then the system
performance is unacceptable for that analyte.
NOTE: The large number of analytes in Table 6 present a substantial
probability that one or more will fail at least one of the
acceptance criteria when all analytes of a given method are
analyzed.
8.5.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst must proceed according to Sees.
8.5.6.1 or 8.5.6.2.
8.5.6.1 Locate and correct the source of the problem and
repeat the test for all analytes of interest beginning with Sec.
8.5.2.
8.5.6.2 Beginning with Sec. 8.5.2, repeat the test only
for those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Sec.
8.5.2.
8.6 The laboratory must, on an ongoing basis, analyze a method blank,
a matrix spike, and a matrix spike/duplicate for each analytical batch (up to a
maximum of 20 samples/batch) to assess accuracy. For laboratories analyzing one
to ten samples per month, at least one spiked sample per month is required.
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8.6.1 The concentration of. the spike in the sample should be
determined as follows:
8.6.1.1 If, as in compliance monitoring, the concentration
of a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at that limit
or 1 to 5 times higher than the background concentration determined
in Sec. 8.6.2, whichever concentration would be larger.
8.6.1.2 If the concentration of a specific analyte in the
sample is not being checked against a limit specific to that
analyte, the spike should be at 100 /ng/L or 1 to 5 times higher than
the background concentration determined in Sec. 8.6.2, whichever
concentration would be larger.
8.6.1.3 If it is impractical to determine background
levels before spiking (e.g., maximum holding times will be
exceeded), the spike concentration should be at (1) the regulatory
concentration limit, if any; or, if none (2) the larger of either
5 times higher than the expected background concentration or
100
8.6.2 Analyze one sample aliquot to determine the background
concentration (B) of each analyte. If necessary, prepare a new QC check
sample concentrate (Sec. 8.5.1) appropriate for the background
concentration in the sample. Spike a second sample aliquot with 1.00 ml
of the QC reference sample concentrate and analyze it to determine the
concentration after spiking (A) of each analyte. Calculate each percent
recovery (p) as 100(A-B)%/T, where T is the known true value of the spike.
8.6.3 Compare the percent recovery (p) for each analyte with the
corresponding QC acceptance criteria found in Table 6. These acceptance
criteria were calculated to include an allowance for error in measurement
of both the background and spike concentrations, assuming a spike to
background ratio of 5:1. This error will be accounted for to the extent
that the analyst's spike to background ratio approaches 5:1. If spiking
was performed at a concentration lower than 100 /xg/L, the analyst must use
either the QC acceptance criteria presented in Table 6, or optional QC
acceptance criteria calculated for the specific spike concentration. To
calculate optional acceptance criteria for the recovery of an analyte: (1)
Calculate accuracy (x') using the equation found in Table 7, substituting
the spike concentration (T) for C; (2) calculate overall precision (S')
using the equation in Table 7, substituting x' for x; (3) calculate the
range for recovery at the spike concentration as (100x'/T)
± 2.44(100S'/T)%.
8.6.4 If any individual p falls outside the designated range for
recovery, that analyte has failed the acceptance criteria. A check
standard containing each analyte that failed the criteria must be analyzed
as described in Sec. 8.7.
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8.7 If any analyte fails the acceptance criteria for recovery in Sec.
8.6, a QC check standard containing each analyte that failed must be prepared and
analyzed.
NOTE: The frequency for the required analysis of a QC check standard will
depend upon the number of analytes being simultaneously tested, the
complexity of the sample matrix, and the performance of the
laboratory. If the entire list of analytes in Table 6 must be
measured in the sample in Sec. 8.6, the probability that the
analysis of a QC check standard will be required is high. In this
case, the QC check standard should be routinely analyzed with the
spiked sample.
8.7.1 Prepare the QC reference sample by adding 1.0 ml of the QC
check sample concentrate (Sec. 8.5.1 or 8.6.2) to 1 L of reagent water.
The QC check standard needs only to contain the analytes that failed
criteria in the test in Sec. 8.6.
8.7.2 Analyze the QC check standard to determine the concentration
measured (A) of each analyte. Calculate each percent recovery (PJ as
100(A/T)%, where T is the true value of the standard concentration.
8.7.3 Compare the percent recovery (PJ for each analyte with the
corresponding QC acceptance criteria found in Table 6. Only analytes that
failed the test in Sec. 8.6 need to be compared with these criteria. If
the recovery of any such analyte falls outside the designated range, the
laboratory performance for that analyte is judged to be out of control,
and the problem must be immediately identified and corrected. The result
for that analyte in the unspiked sample is suspect and may not be reported
for regulatory compliance purposes.
8.8 As part of the QC program for the laboratory, method accuracy for
each matrix studied must be assessed and records must be maintained. After the
analysis of five spiked samples _(of the same matrix) as in Sec. 8.6, calculate
the average percent recovery (p) and the standard deviation of the percent
recovery (sp). Express the accuracy assessment as a percent recovery interval
from p - 2sp to p + 2sp. If p = 90% and sp = 10%, for example, the accuracy
interval is expressed as 70-110%. Update the accuracy assessment for each
analyte on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.9 To determine acceptable accuracy and precision limits for surrogate
standards the following procedure should be performed.
8.9.1 For each sample analyzed, calculate the percent recovery of
each surrogate in the sample.
8.9.2 Once a minimum of thirty samples of the same matrix have been
analyzed, calculate the average percent recovery (P) and standard
deviation of the percent recovery (s) for each of the surrogates.
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8.9.3 For a given matrix, calculate the upper and lower control
limit for method performance for each surrogate standard. This should be
done as follows:
Upper Control Limit (UCL) = P + 3s
Lower Control Limit (LCL) = P - 3s
8.9.4 For aqueous and soil matrices, these laboratory established
surrogate control limits should, if applicable, be compared with the
control limits listed in Table 8. The limits given in Table 8 are multi-
laboratory performance based limits for soil and aqueous samples, and
therefore, the single-laboratory limits established in Step 8.9.3 must
fall within those given in Table 8 for these matrices.
8.9.5 If recovery is not within limits, the following procedures are
required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration".
8.9.6 At a minimum, each laboratory should update surrogate recovery
limits on a matrix-by-matrix basis, annually.
8.10 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 assess the precision of the
environmental measurements. When doubt exists over the identification of a peak
on the chromatogram, confirmatory techniques such as gas chromatography with a
dissimilar column or mass spectrometry using other ionization modes must be used.
Whenever possible, the laboratory should analyze standard reference materials and
participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 Method 8250 was tested by 15 laboratories using organic-free reagent
water, drinking water, surface water, and industrial wastewaters spiked at six
concentrations over the range 5-1,300 ^g/L. Single operator accuracy and
precision, and method accuracy were found to be directly related to the
concentration of the analyte and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 7.
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10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act, Method 625," October 26,
1984.
2. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
3. Eichelberger, J.W., L.E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurement in Gas Chromatography-Mass
Spectrometry Systems," Analytical Chemistry, 47, 995-1000, 1975.
4. "Method Detection Limit for Methods 624 and 625," Olynyk, P., W.L. Budde,
and J.W. Eichelberger, Unpublished report, October 1980.
5. "Interlaboratory Method Study for EPA Method 625-Base/Neutrals, Acids, and
Pesticides," Final Report for EPA Contract 68-03-3102 (in preparation).
6. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
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TABLE 1.
CHROMATOGRAPHIC CONDITIONS, METHOD DETECTION LIMITS, AND
CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS
Compound
Acenaphthene
Acenaphthene-d10 (I.S.)
Acenaphthylene
Acetophenone
Aldrin
4-Aminobiphenyl
Aniline
Anthracene
Aroclor-1016b
Aroclor-1221b
Aroclor-1232b
Aroclor-1242b
Aroclor-1248b
Aroclor-1254b
Aroclor-1260b
Benzidine"
Benzoic acid
Benzo(a) anthracene
Benzo(b)fl uoranthene
Benzo(k)fl uoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzyl alcohol
a-BHCa
iS-BHC
5-BHC
7-BHC (Lindane)9
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl ) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
Chlordane6
4-Chloroaniline
1-Chloronaphthalene
2-Chloronaphthalene
4-Chl oro-3-methyl phenol
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-d12 (I.S.)
4,4'-DDD
Method
Retention Detection Primary Secondary
Time (min) limit (/zg/L) Ion Ion(s)
17.8
--
17.4
--
24.0
--
--
22.8
18-30
15-30
15-32
15-32
12-34
22-34
23-32
28.8
--
31.5
34.9
34.9
45.1
36.4
--
21.1
23.4
23.7
22.4
12.2
8.4
9.3
30.6
21.2
29.9
19-30
--
_.
15.9
13.2
5.9
19.5
31.5
--
28.6
1.9
--
3.5
--
1.9
--
--
1.9
30
36
--
44
--
7.8
4.8
2.5
4.1
2.5
--
--
4.2
3.1
--
5.3
5.7
5.7
2.5
1.9
2.5
--
--
--
1.9
3.0
3.3
4.2
2.5
--
2.8
154
164
152
105
66
169
93
178
222
190
190
222
292
292
360
184
122
228
252
252
276
252
108
183
181
183
183
93
93
45
149
248
149
373
127
162
162
107
128
204
228
240
235
153, 152
162, 160
151, 153
77, 51
263, 220
168, 170
66, 65
176, 179
260, 292
224, 260
224, 260
256, 292
362, 326
362, 326
362, 394
92, 185
105, 77
229, 226
253, 125
253, 125
138, 277
253, 125
79, 77
181, 109
183, 109
181, 109
181, 109
95, 123
63, 95
77, 121
167, 279
250, 141
91, 206
375, 377
129
127, 164
127, 164
144, 142
64, 130
206, 141
226, 229
120, 236
237, 165
8250A - 22
Revision 1
September 1994
-------
TABLE 1.
(Continued)
Compound
4,4'-DDT
4,4'-DDE
Dibenz(a,j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
l,4-Dichlorobenzene-d4 (I.S.)
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dieldrin
Diethyl phthalate
p-Dimethyl aminoazobenzene
7, 12-Dimethylbenz(a)anthracene
a-,a-Dimethylphenethylamine
2,4-Dimethylphenol
Dimethyl phthalate
4, 6-Dinitro- 2 -methyl phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
1,2-Diphenylhydrazine
Di-n-octyl phthalate
Endosulfan Ia
Endosulfan IT
Endosulfan sulfate
Endrina
Endrin aldehyde
Endrin ketone
Ethyl methanesulfonate
Fluoranthene
Fluorene
2-Fluorobiphenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene"
Hexachloroethane
Method
Retention Detection Primary Secondary
Time (min) Limit (/zg/L) Ion Ion(s)
29.3
27.2
43.2
24.7
8.4
7.4
7.8
--
32.2
9.8
--
27.2
20.1
--
--
--
9.4
18.3
16.2
15.9
19.8
18.7
--
--
32.5
26.4
28.6
29.8
27.9
--
--
--
26.5
19.5
--
--
23.4
25.6
21.0
11.4
13.9
8.4
4.7
--
--
2.5
--
2.5
1.9
1.9
4.4
--
16.5
2.7
--
2.5
1.9
--
--
--
2.7
1.6
24
42
5.7
1.9
--
2.5
--
--
5.6
--
--
--
--
2.2
1.9
--
--
1.9
2.2
1.9
0.9
--
1.6
235
246
279
278
168
149
146
146
146
152
252
162
162
79
149
120
256
58
122
163
198
184
165
165
169
77
149
195
337
272
263
67
317
79
202
166
172
112
100
353
284
225
237
117
237,
24,
280,
139,
139
150,
148,
148,
148,
150,
254,
164,
164,
263,
177,
225,
241,
91,
107,
194,
51,
63,
63,
63,
168,
105,
167,
339,
339,
387,
82,
345,
67,
109,
101,
165,
171
64
272,
355,
142,
223,
235,
201,
165
176
277
279
104
111
111
111
115
126
98
98
279
150
77
257
42
121
164
105
154
89
89
167
182
43
341
341
422
81
250
319
97
203
167
274
351
249
227
272
199
8250A - 23
Revision 1
September 1994
-------
TABLE 1.
(Continued)
Compound
Indeno(l,2,3-cd)pyrene
Isophorone
Methoxychlor
3-Methyl chol anthrene
Methyl methanesulfonate
2 -Methyl naphthalene
2-Methyl phenol
4-Methyl phenol
Naphthalene
Naphthalene-d8 (I.S.)
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-Nitroanil ine
4-Nitroanil ine
Nitrobenzene
Nitrobenzene-d5 (surr.)
2-Nitrophenol
4-Nitrophenol
N-Nitroso-di -n-butylamine
N-Nitrosodi methyl ami nea
N-Nitrosodiphenylaminea
N-Nitroso-di-n-propylamine
N-Nitrosopi peri dine
Pentachl orobenzene
Pentachloronitrobenzene
Pentachlorophenol
Perylene-d12 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-d10 (I.S.)
Phenol
Phenol -de (surr.)
2-Picoline
Pronamide
Pyrene
Terphenyl-d14 (surr.)
1,2,4, 5-Tetrachl orobenzene
2,3,4,6-Tetrachlorophenol
Method
Retention Detection Primary Secondary
Time (min) Limit (p.g/1) Ion Ion(s)
42.7
11.9
--
__
--
--
--
--
12.1
--
--
--
--
--
--
11.1
--
6.5
20.3
--
--
20.5
--
--
--
--
17.5
--
--
22.8
--
8.0
--
--
--
27.3
--
--
--
3.7
2.2
--
--
--
--
--
--
1.6
--
--
--
--
--
--
1.9
--
3.6
2.4
--
--
1.9
--
--
--
--
3.6
--
--
5.4
--
1.5
--
--
1.9
--
--
--
276
82
227
268
80
142
108
108
128
136
143
143
65
138
138
77
82
139
139
84
42
169
70
42
250
295
266
264
108
178
188
94
99
93
173
202
244
216
232
138,
95,
228
253,
79,
141
107,
107,
129,
68
115,
115,
92,
108,
108,
123,
128,
109,
109,
57,
74,
168,
130,
114,
252,
237,
264,
260,
109,
179,
94,
65,
42,
66,
175,
200,
122,
214,
230,
227
138
267
65
79
79
127
116
116
138
92
92
65
54
65
65
41
44
167
42
55
248
142
268
265
179
176
80
66
71
92
145
203
212
218
131
8250A - 24
Revision 1
September 1994
-------
TABLE 1.
(Continued)
Compound
Toxapheneb
2,4,6-Tribromophenol (surr.)
1,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Retention
Time (min)
25-34
--
11.6
--
11.8
Method
Detection
Limit (MQ/L)
— —
--
1.9
--
2.7
Primary
Ion
159
330
180
196
196
Secondary
Ion(s)
231, 233
332, 141
182, 145
198, 200
198, 200
"See Sec. 1.3
bThese compounds are mixtures of various isomers.
(I.S.) = Internal Standard
(surr). = Surrogate
TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
FOR VARIOUS MATRICES8
Matrix
Factor
Ground water 10
Low-concentration soil by ultrasonic extraction with GPC cleanup 670
High-concentration soil and sludges by ultrasonic extraction 10,000
Non-water miscible waste 100,000
EQL = [Method detection limit (see Table 1)] X [Factor found in this table].
For non-aqueous samples, the factor is on a wet-weight basis. Sample EQLs
are highly matrix-dependent. The EQLs to be determined herein are provided
for guidance and may not always be achievable.
8250A - 25
Revision 1
September 1994
-------
TABLE 3.
DFTPP KEY IONS AND ION ABUNDANCE CRITERIA"
Mass Ion Abundance Criteria
51 30-60% of mass 198
68 < 2% of mass 69
70 < 2% of mass 69
127 40-60% of mass 198
197 < 1% of mass 198
198 Base peak, 100% relative abundance
199 5-9% of mass 198
275 10-30% of mass 198
365 > 1% of mass 198
441 Present but less than mass 443
442 > 40% of mass 198
443 17-23% of mass 442
"See Reference 3.
8250A - 26 Revision 1
September 1994
-------
TABLE 4.
CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction Acid Fraction
Acenaphthene 4-Chloro-3-methylphenol
1,4-Dichlorobenzene 2,4-Dichlorophenol
Hexachlorobutadiene 2-Nitrophenol
N-Nitroso-di-n-phenylamine Phenol
Di-n-octyl phthalate Pentachlorophenol
Benzo(a)pyrene 2,4,6-Trichlorophenol
Fluoranthene
8250A - 27 Revision 1
September 1994
-------
TABLE 5.
SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION
1,4-Dichlorobenzene-D,,
Naphthalene-d8
Acenaphthene-d10
Aniline
Benzyl alcohol
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl)ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Di chlorobenzene
Ethyl methanesulfonate
2-Fluorophenol (surr.)
Hexachloroethane
Methyl methanesulfonate
2-Methylphenol
4-Methylphenol
N-Nitrosodimethylamine
N-Nitroso-di-n-propylamine
Phenol
Phenol-d6 (surr.)
2-Picoline
Acetophenone
Benzole acid
Bis(2-chloroethoxy)methane
4-Chloroaniline
4-Chloro-3-methyl phenol
2,4-Dichlorophenol
2,6-Dichlorophenol
a,a-Dimethylphenethylamine
2,4-Dimethylphenol
Hexachlorobutadiene
Isophorone
2-Methylnaphthalene
Naphthalene
Nitrobenzene
Nitrobenzene-d8 (surr.)
2-Nitrophenol
N-Nitroso-di-n-butyl amine
N-Nitrosopiperidine
1,2,4-Trichlorobenzene
Acenaphthene
Acenaphthylene
1-Chloronaphthalene
2-Chloronaphthalene
4-Chlorophenyl
phenyl ether
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Fluorene
2-Fluorobiphenyl
(surr.)
Hexachlorocyclo-
pentadiene
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-Nitroani1ine
4-Nitroaniline
4-Nitrophenol
Pentachlorobenzene
1,2,4,5-Tetrachloro-
benzene
2,3,4,6-Tetrachloro-
phenol
2,4,6-Tribromophenol
(Surr.)
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
(surr.) = surrogate
8250A - 28
Revision 1
September 1994
-------
TABLE 5.
SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION
(Continued)
Phenanthrene-d
10
Chrysene-d12
Perylene-d
12
4-Aminobiphenyl
Anthracene
4-Bromophenyl phenyl ether
Di-n-butyl phthalate
4,6-Dinitro-2-methyl phenol
Diphenylamine
1,2-Di phenylhydrazi ne
Fluoranthene
Hexachlorobenzene
N-Nitrosodiphenylamine
Pentachlorophenol
Pentachloronitrobenzene
Phenacetin
Phenanthrene
Pronamide
Benzidine
Benzo(a)anthracene
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Chrysene
3,3'-Dichlorobenzidine
p-Dimethylaminoazobenzene
Pyrene
Terphenyl-d14 (surr.)
Benzo(b)fluoranthene
Benzo(k) fl uoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
7,12-Dimethylbenz-
(a)anthracene
Di-n-octyl phthalate
Indeno(l,2,3-cd)pyrene
3-Methylcholanthrene
(surr,) = surrogate
8250A - 29
Revision 1
September 1994
-------
TABLE 6.
QC ACCEPTANCE CRITERIA"
Compound
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Butyl benzyl phthalate
6-BHC
(5-BHC
Bis(2-chloroethy1) ether
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo (a, h) anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Dieldrin
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fluoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachl orobutadi ene
Test
cone.
(M9/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(M9/L)
27.6
40.2
39.0
32.0
27.6
38.8
32.3
39.0
58.9
23.4
31.5
21.6
55.0
34.5
46.3
41.1
23.0
13.0
33.4
48.3
31.0
32.0
61.6
70.0
16.7
30.9
41.7
32.1
71.4
30.7
26.5
23.2
21.8
29.6'
31.4
16.7
32.5
32.8
20.7
37.2
54.7
24.9
26.3
Range
for x
(M9/L)
60.1-132.3
53.5-126.0
7.2-152.2
43.4-118.0
41.8-133.0
42.0-140.4
25.2-145.7
31.7-148.0
D-195.0
D-139.9
41.5-130.6
D-100.0
42.9-126.0
49.2-164.7
62.8-138.6
28.9-136.8
64.9-114.4
64.5-113.5
38.4-144.7
44.1-139.9
D-134.5
19.2-119.7
D-170.6
D-199.7
8.4-111.0
48.6-112.0
16.7-153.9
37.3-105.7
8.2-212.5
44.3-119.3
D-100.0
D-100.0
47.5-126.9
68.1-136.7
18.6-131.8
D-103.5
D-188.8
42.9-121.3
71.6-108.4
D-172.2
70.9-109.4
7.8-141.5
37.8-102.2
Range
P. Ps
(%)
47-145
33-145
D-166
27-133
33-143
24-159
11-162
17-163
D-219
D-152
24-149
D-110
12-158
33-184
36-166
8-158
53-127
60-118
25-158
17-168
D-145
4-136
D-203
D-227
1-118
32-129
D-172
20-124
D-262
29-136
D-114
D-112
39-139
50-158
4-146
D-107
D-209
26-137
59-121
D-192
26-155
D-152
24-116
8250A - 30
Revision 1
September 1994
-------
TABLE 6.
QC ACCEPTANCE CRITERIA"
(Continued)
Compound
Hexachloroethane
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitroso-di-n-propylamine
PCB-1260
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
4-Chloro-3 -methyl phenol
2-Chlorophenol
2,4-Chlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl -4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Test
cone.
(M9/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(^g/L)
24.5
44.6
63.3
30.1
39.3
55.4
54.2
20.6
25.2
28.1
37.2
28.7
26.4
26.1
49.8
93.2
35.2
47.2
48.9
22.6
31.7
s = Standard deviation of four recovery
x = Average recovery
p, ps = Percent recovery
D = Detected; result
a r v> -i 4- n\* •! •> ft»nm Af\ TCD D
for four
measured
must be
•,.*+ I'SC 4
recovery
•
Range
for x
(M9/L)
55.2-100.0
D-150.9
46.6-180.2
35.6-119.6
54.3-157.6
13.6-197.9
19.3-121.0
65.2-108.7
69.6-100.0
57.3-129.2
40.8-127.9
36.2-120.4
52.5-121.7
41.8-109.0
D-172.9
53.0-100.0
45.0-166.7
13.0-106.5
38.1-151.8
16.6-100.0
52.4-129.2
measurements,
measurements,
Range
P> Ps
(%)
40-113
D-171
21-196
21-133
35-180
D-230
D-164
54-120
52-115
44-142
22-147
23-134
39-135
32-119
D-191
D-181
29-182
D-132
14-176
5-112
37-144
in M9/L.
in jug/L-
greater than zero.
"f\i/« M *-i 4- U /-\ /-I
ao c TU<-» r- f* r*\
^-i+-r»v*-i^ -sv»n K-acarl
directly on the method performance data in Table 7. Where necessary, the
limits for recovery have been broadened to assure applicability of the
limits to concentrations below those used to develop Table 7.
8250A - 31
Revision 1
September 1994
-------
TABLE 7.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION8
Parameter
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benzo( a) anthracene
Chloroethane
Benzo ( b) fl uoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Butyl benzyl phthalate
B-BHC
£-BHC
Bis(2-chloroethyl) ether
Bis(2-chloroethoxy) methane
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo (a, h) anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Dieldrin
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fluoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachloroethane
Accuracy, as
recovery, x'
(M9/L)
0.96C+0.19
0.89C+0.74
0.78C+1.66
0.80C+0.68
0.88C-0.60
0.99C-1.53
0.93C-1.80
0.87C-1.56
0.90C-0.13
0.98C-0.86
0.66C-1.68
0.87C-0.94
0.29C-1.09
0.86C-1.54
1.12C-5.04
1.03C-2.31
0.84C-1.18
0.91C-1.34
0.89C+0.01
0.91C+0.53
0.93C-1.00
0.56C-0.40
0.70C-0.54
0.79C-3.28
0.88C+4.72
0.59C+0.71
0.80C+0.28
0.86C-0.70
0.73C-1.47
1.23C-12.65
0.82C-0.16
0.43C+1.00
0.20C+1.03
0.92C-4.81
1.06C-3.60
0.76C-0.79
0.39C+0.41
0.76C-3.86
0.81C+1.10
0.90C-0.00
0.87C-2.97
0.92C-1.87
0.74C+0.66
0.71C-1.01
0.73C-0.83
Single analyst
precision, s/
(M9/L)
0.15X-0.12
0.24X-1.06
0.27X-1.28
0.21X-0.32
0.15X+0.93
0.14X-0.13
0.22X+0.43
0.19X+1.03
0.22X+0.48
0.29X+2.40
O.lSx+0.94
0.20X-0.58
0.34X+0.86
0.35X-0.99
0.16X+1.34
0.24X+0.28
0.26X+0.73
0.13X+0.66
0.07X+0.52
0.20X-0.94
0.28X+0.13
0.29X-0.32
0.26X-1.17
0.42X+0.19
0.30X+8.51
O.lSx+1.16
0.20X+0.47
0.25X+0.68
0.24X+0.23
0.28X+7.33
0.20X-0.16
0.28X+1.44
0.54x+0'.19
0.12X+1.06
0.14X+1.26
0.21X+1.19
0.12X+2.47
O.lSx+3.91
0.22X-0.73
0.12X+0.26
0.24X-0.56
0.33X-0.46
0.18X-0.10
0.19X+0.92
0.17X+0.67
Overall
precision,
S' (M9A)
0.21X-0.67
0.26X-0.54
0.43X+1.13
0.27X-0.64
0.26X-0.21
0.17X-0.28
0.29X+0.96
0.35X+0.40
0.32X+1.35
0.51X-0.44
0.53X+0.92
0.30X+1.94
0.93X-0.17
0.35X+0.10
0.26X+2.01
0.25X+1.04
0.36X+0.67
0.16X+0.66
0.13X+0.34
0.30X-0.46
0.33X-0.09
0.66X-0.96
0.39X-1.04
0.65X-0.58
0.59X+0.25
0.39X+0.60
0.24X+0.39
0.41X+0.11
0.29X+0.36
0.47X+3.45
0.26X-0.07
0.52X+0.22
1.05X-0.92
0.21X+1.50
0.19X+0.35
0.37X+1.19
0.63X-1.03
0.73X-0.62
0.28X-0.60
0.13X+0.61
O.SOx-0.23
0.28X+0.64
0.43X-0.52
0.26X+0.49
0.17X+0.80
8250A - 32
Revision 1
September 1994
-------
TABLE 7.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION8
(Continued)
Parameter
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitroso-di-n-propylamine
PCB-1260
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
4-Chloro-3 -methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2 , 4 , 6-Tri chl orophenol
Accuracy, as
recovery, x'
(M9/L)
0.78C-3.10
1.12C+1.41
0.76C+1.58
1.09C-3.05
1.12C-6.22
0.81C-10.86
0.87C+0.06
0.84C-0.16
0.94C-0.79
0.84C+0.35
0.78C+0.29
0.87C-0.13
0.71C+4.41
0.81C-18.04
1.04C-28.04
0.07C-1.15
0.61C-1.22
0.93C+1.99
0.43C+1.26
0.91C-0.18
Single analyst
precision, sr'
(M9/L)
0.29X+1.46
0.27X+0.77
0.21X-0.41
0.19X+0.92
0.27X+0.68
0.35X+3.61
0.12X+0.57
0.16X+0.06
0.15X+0.85
0.23X+0.75
O.lSx+1.46
0.15X+1.25
0.16X+1.21
0.38X+2.36
O.lOx+42.29
0.16X+1.94
0.38X+2.57
0.24X+3.03
0.26x+0.73
0.16X+2.22
Overall
precision,
S' (M9/L)
O.BOx-0.44
0.33X+0.26
0.30X-0.68
0.27X+0.21
0.44X+0.47
0.43X+1.82
O.lBx+0.25
0.15X+0.31
0.21X+0.39
0.29X+1.31
0.28X+0.97
0.21X+1.28
0.22X+1.31
0.42X+26.29
0.26x+23.10
0.27X+2.60
0.44x+3.24
0.30X+4.33
0.35X+0.58
0.22X+1.81
X'
S'
C
x
Expected recovery for one or more measurements of a sample
containing a concentration of C, in M9/L-
Expected single analyst standard deviation of measurements at an
average concentration of x, in /xg/L.
Expected interlaboratory standard deviation of measurements at an
average concentration found of x, in M9/L.
True value for the concentration, in ng/l.
Average recovery found for measurements of samples containing a
concentration of C, in
8250A - 33
Revision 1
September 1994
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TABLE 8.
SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Low/Medium Low/Medium
Surrogate Compound Water Soil/Sediment
Nitrobenzene-d5 35-114 23-120
2-Fluorobiphenyl 43-116 30-115
Terphenyl-d14 33-141 18-137
Phenol-d6 10-94 24-113
2-Fluorophenol 21-100 25-121
2,4,6-Tribromophenol 10-123 19-122
8250A - 34 Revision 1
September 1994
-------
METHOD 8250A
SEMIVOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)
7.1 Prepare tampla
u*ing Method 3540,
3541. or 3550
7.1 Prepare (ample
u»mg Method 3510
or 3520
7.1 Prepare eample
uiing Method 3540,
3541, 3550, or 3580
7.2 Cleanup
extract
7.3
Recommended
GC/MS
operating
condition*.
7.4
Initial
Calibration.
7.5 Daily
calibration • Tune
GC/MS with TFTPP
and check SPCC &
CCC.
8250A - 35
Revision 1
September 1994
-------
METHOD 8250A
continued
7.6.1 Screen extract
in GC/FID or GC/PID to
eliminate too high
concentration*.
7.6.2 Spike
sample with
internal
standard.
7.6.3 Analyze
extract by GC/MS
using recommended
column and operating
conditions.
7.7.1 Identify
compounds by
comparing sample
retention time and
sample mass spectra
to standard*.
7.6.4
Does
response exceed
initial calibration
curve
range?
7.6.4 Dilute
extract.
7.7.2
Quantitata
samples using
internal std.
technique.
7.7.2.4 Report
results.
( Stop J
8250A - 36
Revision 1
September 1994
-------
oo
ks>
o\
o
-------
METHOD 8260
VOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)
CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8260 is used to determine volatile organic compounds in a
variety of solid waste matrices. This method is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic liquors, acid liquors, waste solvents, oily wastes, mousses, tars,
fibrous wastes, polymeric emulsions, filter cakes, spent carbons, spent
catalysts, soils, and sediments. The following compounds can be determined by
this method:
Analyte
CAS No.
Appropriate Technique
Direct
Purge-and-Trap Injection
Benzene
Bromobenzene
Bromochloromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chi orodi bromomethane
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Di bromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
1,3-Dichloropropane
71-43-2
108-86-1
74-97-5
75-27-4
75-25-2
74-83-9
104-51-8
135-98-8
98-06-6
56-23-5
108-90-7
124-48-1
75-00-3
67-66-3
74-87-3
95-49-8
106-43-4
96-12-8
106-93-4
74-95-3
95-50-1
541-73-1
106-46-7
75-71-8
75-34-3
107-06-2
75-35-4
156-59-2
156-60-5
78-87-5
142-28-9
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
PP
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
8260 - 1
Revision 0
July 1992
-------
Appropriate Technique
Analyte
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyltoluene
Methyl ene chloride
Naphthalene
n-Propylbenzene
Styrene
1,1,1 , 2-Tetrachl oroethane
1 , 1 ,2, 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,2, 3 -Tri chl orobenzene
1 , 2 , 4 -Tri chl orobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chl orofl uoromethane
1,2,3-Trichloropropane
1 , 2 , 4-Tri methyl benzene
1 ,3,5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
a Adequate response by thi
CAS No.b
594-20-7
563-58-6
100-41-4
87-68-3
98-82-8
99-87-6
75-09-2
91-20-3
103-65-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
87-61-6
120-82-1
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
95-63-6
108-67-8
75-01-4
95-47-6
108-38-3
106-42-3
s technique.
Purge-and-Trap
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
Direct
Injection
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
b Chemical Abstract Services Registry Number.
pp Poor purging efficiency
i Inappropriate technique
resulting in high
for this analyte.
EQLs.
pc Poor chromatographic behavior.
1.2 Method 8260 can be used to quantitate most volatile organic compounds
that have boiling points below 200°C and that are insoluble or slightly soluble
in water. Volatile water-soluble compounds can be included in this analytical
technique. However, for the more soluble compounds, quantitation limits are
approximately ten times higher because of poor purging efficiency. Such
compounds include low-molecular-weight halogenated hydrocarbons, aromatics,
ketones, nitriles, acetates, acrylates, ethers, and sulfides. See Tables 1 and
2 for lists of analytes and retention times that have been evaluated on a purge-
and-trap GC/MS system. Also, the method detection limits for 25 ml sample
volumes are presented.
8260 - 2
Revision 0
July 1992
-------
1.3 The estimated quantitation limit (EQL) of Method 8260 for an
individual compound is approximately 5 M9A9 (wgt weight) for soil/sediment
samples, 0.5 mg/kg (wet weight) for wastes, and 5 ^g/l for ground water (see
Table 3). EQLs will be proportionately higher for sample extracts and samples
that require dilution or reduced sample size to avoid saturation of the detector.
1.4 Method 8260 is based upon a purge-and-trap, gas chromatographic/mass
spectrometric (GC/MS) procedure. This method is restricted to use by, or under
the supervision of, analysts experienced in the use of purge-and-trap systems and
gas chromatograph/mass spectrometers, and skilled in the interpretation of mass
spectra and their use as a quantitative tool.
2.0 SUMMARY OF METHOD
2.1 The volatile compounds are introduced into the gas chromatograph by
•the purge-and-trap method or by direct injection (in limited applications).
Purged sample components are trapped in a tube containing suitable sorbent
materials. When purging is complete, the sorbent tube is heated and backflushed
with helium to desorb trapped sample components. The analytes are desorbed
directly to a large bore capillary or cryofocussed on a capillary precolumn
before being flash evaporated to a narrow bore capillary for analysis. The
column is temperature programmed to separate the analytes which are then detected
with a mass spectrometer (MS) interfaced to the gas chromatograph. Wide bore
capillary columns require a jet separator, whereas narrow bore capillary columns
can be directly interfaced to the ion source.
2.2 If the above sample introduction techniques are not applicable, a
portion of the sample is dispersed in solvent to dissolve the volatile organic
constituents. A portion of the solution is combined with organic-free reagent
water in the purge chamber. It is then analyzed by purge-and-trap GC/MS
following the normal water method.
2.3 Qualitative identifications are confirmed by analyzing standards under
the same conditions used for samples and comparing resultant mass spectra and GC
retention times. Each identified component is quantitated by relating the MS
response for an appropriate selected ion produced by that compound to the MS
response for another ion produced by an internal standard.
3.0 INTERFERENCES
3.1 Major contaminant sources are volatile materials in the laboratory and
impurities in the inert purging gas and in the sorbent trap. The use of non-
polytetrafluoroethylene (PTFE) thread sealants, plastic tubing, or flow
controllers with rubber components should be avoided since such materials out-gas
.organic compounds which will be concentrated in the trap during the purge
operation. Analyses of reagent blanks provide information about the presence of
contaminants. When potential interfering peaks are noted in blanks, the analyst
should change the purge gas source and regenerate the molecular sieve purge gas
filter (Figure 1). Subtracting blank values from sample results is not
permitted. If reporting values not corrected for blanks result in what the
laboratory feels is a false positive for a sample, this should be fully explained
in text accompanying the uncorrected data.
8260 - 3 Revision 0
July 1992
-------
3.2 Interfering contamination may occur when a sample containing low
concentrations of volatile organic compounds is analyzed immediately after a
sample containing high concentrations of volatile organic compounds. The
preventive technique is rinsing of the purging apparatus and sample syringes with
two portions of organic-free reagent water between samples. After analysis of
a sample containing high concentrations of volatile organic compounds, one or
more calibration blanks should be analyzed to check for cross contamination. For
samples containing large amounts of water soluble materials, suspended solids,
high boiling compounds or high concentrations of compounds being determined, it
may be necessary to wash the purging device with a soap solution, rinse it with
organic-free reagent water, and then dry the purging device in an oven at 105°C.
In extreme situations, the whole purge and trap device may require dismantling
and cleaning. Screening of the samples prior to purge and trap GC/MS analysis
is highly recommended to prevent contamination of the system. This is especially
true for soil and waste samples. Screening may be accomplished with an automated
headspace technique or by Method 3820 (Hexadecane Extraction and Screening of
Purgeable Organics).
3.3 Special precautions must be taken to analyze for methylene chloride.
The analytical and sample storage area should be isolated from all atmospheric
sources of methylene chloride. Otherwise random background levels will result.
Since methylene chloride will permeate through PTFE tubing, all gas
chromatography carrier gas lines and purge gas plumbing should be constructed
from stainless steel or copper tubing. Laboratory clothing worn by the analyst
should be clean since clothing previously exposed to methylene chloride fumes
during liquid/liquid extraction procedures can contribute to sample
contamination.
3.4 Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal into
the sample during shipment and storage. A trip blank prepared from organic-free
reagent water and carried through the sampling and handling protocol can serve
as a check on such contamination.
4.0 APPARATUS AND MATERIALS
4.1 Purge-and-trap device - The purge-and-trap device consists of three
separate pieces of equipment: the sample purger, the trap, and the desorber.
Several complete devices are commercially available.
4.1.1 The recommended purging chamber is designed to accept 5 ml (and
25 mL if the lowest detection limit is required) samples with a water
column at least 3 cm deep. The gaseous-headspace between the water column
and the trap must have a total volume of less than 15 mL. The purge gas
must pass through the water column as finely divided bubbles with a
diameter of less than 3 mm at the origin. The purge gas must be introduced
no more than 5 mm from the base of the water column. The sample purger,
illustrated in Figure 1, meets these design criteria. Alternate sample
purge devices (i.e. needle spargers), may be utilized, provided equivalent
performance is demonstrated.
4.1.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 in. Starting from the inlet, the trap must
8260 - 4 Revision 0
July 1992
-------
contain the following amounts of adsorbents: 1/3 of 2,6-diphenylene oxide
polymer, 1/3 of silica gel, and 1/3 of coconut charcoal. It is recommended
that 1.0 cm of methyl silicone-coated packing be inserted at the inlet to
extend the life of the trap (see Figure 2). If it is not necessary to
analyze for dichlorodifluoromethane or other fluorocarbons of similar
volatility, the charcoal can be eliminated and the polymer increased to
fill 2/3 of the trap. If only compounds boiling above 35°C are to be
analyzed, both the silica gel and charcoal can be eliminated and the
polymer increased to fill the entire trap. Before initial use, the trap
should be conditioned overnight at 180°C by backflushing with an inert gas
flow of at least 20 mL/min. Vent the trap effluent to the room, not to the
analytical column. Prior to daily use, the trap should be conditioned for
10 minutes at 180°C with backflushing. The trap may be vented to the
analytical column during daily conditioning; however, the column must be
run through the temperature program prior to analysis of samples. Traps
normally last 2-3 months when used daily. Some signs of a deteriorating
trap are: uncharacteristic recoveries of surrogates, especially toluene-d-;
a loss of the response of the internal standards during a 12 hour shift;
and/or a rise in the baseline in the early portion of the scan.
4.1.3 The desorber should be capable of rapidly heating the trap to
180°C for desorption. The trap bake-out temperature should not exceed
220°C. The desorber design illustrated in Figure 2 meets these criteria.
4.1.4 The purge-and-trap device may be assembled as a separate unit
or may be coupled to a gas chromatograph, as shown in Figures 3 and 4.
4.1.5 Trap Packing Materials
4.1.5.1 2,6-Diphenylene oxide polymer - 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
4.1.5.2 Methyl silicone packing - OV-1 (3%) on Chromosorb-
W, 60/80 mesh or equivalent.
4.1.5.3 Silica gel - 35/60 mesh, Davison, grade 15 or
equivalent.
4.1.5.4 Coconut charcoal - Prepare from Barnebey Cheney,
CA-580-26 lot #M-2649 by crushing through a 26 mesh screen (or
equivalent).
4.2 Heater or heated oil bath - Should be capable of maintaining the
purging chamber to within 1°C over the temperature range of ambient to 100°C.
4.3 Gas chromatography/mass spectrometer/data system
4.3.1 Gas chromatograph - An analytical system complete with a
temperature-programmable gas chromatograph suitable for splitless injection
and all required accessories, including syringes, analytical columns, and
gases. The GC should be equipped with variable constant differential flow
controllers so that the column flow rate will remain constant throughout
desorption and temperature program operation. For some column
configuration, the column oven must be cooled to < 30°C, therefore, a
8260 - 5 Revision 0
July 1992
-------
subambient oven controller may be required. The capillary column should be
directly coupled to the source.
4.3.1.1 Capillary precolumn interface when using cryogenic
cooling - This device interfaces the purge and trap concentrator to
the capillary gas chromatograph. The interface condenses the
desorbed sample components and focuses them into a narrow band on an
uncoated fused silica capillary precolumn. When the interface is
flash heated, the sample is transferred to the analytical capillary
column.
4.3.1.1.1 During the cryofocussing step, the
temperature of the fused silica in the interface is maintained
at -150°C under a stream of liquid nitrogen. After the
desorption period, the interface must be capable of rapid
heating to 250°C in 15 seconds or less to complete the
transfer of analytes.
4.3.2 Gas chromatographic columns (Recommended)
4.3.2.1 Column 1 - 60 m x 0.75 mm ID capillary column
coated with VOCOL (Supelco), 1.5 urn film thickness, or equivalent.
4.3.2.2 Column 2 - 30 m x 0.53 mm ID capillary column
coated with DB-624 (J&W Scientific) or VOCOL (Supelco), 3 ^m film.
thickness, or equivalent.
4.3.2.3 Column 3 - 30 m x 0.32 mm ID capillary column
coated with DB-5 (J&W Scientific) or SE-54 (Supelco), 1 urn film
thickness, or equivalent.
4.3.3 Mass spectrometer - Capable of scanning from 35 to 300 amu
every 2 sec or less, using 70 volts (nominal) electron energy in the
electron impact ionization mode. The mass spectrometer must be capable of
producing a mass spectrum for Bromofluorobenzene (BFB) which meets all of
the criteria in Table 4 when 50 ng of the GC/MS tuning standard (BFB) is
injected through the GC. To ensure sufficient precision of mass spectral
data, the desirable MS scan rate allows acquisition of at least five
spectra while a sample component elutes from the GC.
4.3.4 GC/MS interface - The GC is interfaced to the MS with an all
glass enrichment device and an all glass transfer line, but any enrichment
device or transfer line can be used if the performance specifications
described in Section 8.2 can be achieved. Any GC-to-MS interface that
gives acceptable calibration points at 50 ng or less per injection for each
of the analytes and achieves all acceptable performance criteria (see Table
4) may be used. GC-to-MS interfaces constructed entirely of glass or of
glass-lined materials are recommended. Glass can be deactivated by
silanizing with dichlorodimethylsilane. This interface is only needed for
the wide bore columns (> 0.53 mm ID).
4.3.5 Data system - A computer system that allows the continuous
acquisition and storage on machine-readable media of all mass spectra
obtained throughout the duration of the chromatographic program must be
8260 - 6 Revision 0
July 1992
-------
interfaced to the mass spectrometer. The computer must have software that
allows searching any GC/MS data file for ions of a specified mass and
plotting such ion abundances versus time or scan number. This type of plot
is defined as an Extracted Ion Current Profile (EICP). Software must also
be available that allows integrating the abundances in any EICP between
specified time or scan-number limits. The most recent version of the
EPA/NIST Mass Spectral Library should also be available.
4.5 Microsyringes - 10, 25, 100, 250, 500, and 1,000 nl.
4.6 Syringe valve - Two-way, with Luer ends (three each), if applicable
to the purging device.
4.7 Syringes - 5, 10, or 25 mL, gas-tight with shutoff valve.
4.8 Balance - Analytical, 0.0001 g, and top-loading, 0.1 g.
4.9 Glass scintillation vials - 20 mL, with Teflon lined screw-caps or
glass culture tubes with Teflon lined screw-caps.
4.10 Vials - 2 mL, for GC autosampler.
4.11 Disposable pipets - Pasteur.
4.12 Volumetric flasks, Class A - 10 mL and 100 ml, with ground-
glass stoppers.
4.13 Spatula - Stainless steel.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all inorganic reagents shall 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 ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Methanol, CH3OH - Pesticide quality or equivalent, demonstrated to be
free of analytes. Store apart from other solvents.
5.4 Reagent Tetraglyme - Reagent tetraglyme is defined as tetraglyme in
which interference is not observed at the method detection limit of compounds of
interest.
CAUTION: Glycol ethers are suspected carcinogens. All solvent handling
should be done in a hood while using proper protective
equipment to minimize exposure to liquid and vapor.
5.4.1 Tetraglyme (tetraethylene glycol dimethyl ether, Aldrich #17,
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240-5 or equivalent), C8H,aCL - Purify by treatment at reduced pressure in
a rotary evaporator. The telraglyme should have a peroxide content of less
than 5 ppm as indicated by EM Quant Test Strips (available from Scientific
Products Co., Catalog No. P1126-8 or equivalent).
5.4,1.1 Peroxides may be removed by passing the tetraglyme
through a column of activated alumina. The tetraglyme is placed in
a round bottom flask equipped with a standard taper joint, and the
flask is affixed to a rotary evaporator. The flask is immersed in a
water bath at 90-100°C and a vacuum is maintained at < 10 mm Hg for
at least two hours using a two-stage mechanical pump. The vacuum
system is equipped with an all-glass trap, which is maintained in a
dry ice/methanol bath. Cool the tetraglyme to ambient temperature
and add 100 mg/L of 2,6-di-tert-butyl-4-methyl-phenol to prevent
peroxide formation. Store the tetraglyme in a tightly sealed screw-
cap bottle in an area that is not contaminated by solvent vapors.
5.4.2 In order to demonstrate that all interfering volatiles have
been removed from the tetraglyme, an organic-free reagent water/tetraglyme
blank must be analyzed.
5.5 Polyethylene glycol, H(OCH2CH2)nOH - Free of interferences at the
detection limit of the target analytes.
5.6 Hydrochloric acid (1:1 v/v), HC1 - Carefully add a measured volume
of concentrated HC1 to an equal volume of organic-free reagent water.
5.7 Stock solutions - Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standard solutions
in methanol, using assayed liquids or gases, as appropriate.
5.7.1 Place about 9.8 ml of methanol in a 10 mL tared ground-glass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes or until all alcohol-wetted surfaces have dried. Weigh
the flask to the nearest 0.0001 g.
5.7.2 Add the assayed reference material, as described below.
5.7.2.1 Liquids - Using a 100 /iL syringe, immediately add
two or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5.7.2.2 Gases - To prepare standards for any compounds that
boil below 30°C (e.g. bromomethane, chloroethane, chloromethane, or
vinyl chloride), fill a 5 ml valved gas-tight syringe with the
reference standard to the 5.0 ml mark. Lower the needle to 5 mm
above the methanol meniscus. Slowly introduce the reference standard
above the surface of the liquid. The heavy gas will rapidly dissolve
in the methanol. Standards may also be prepared by using a lecture
bottle equipped with a Hamilton Lecture Bottle Septum (#86600).
Attach Teflon tubing to the side arm relief valve and direct a gentle
stream of gas into the methanol meniscus.
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5.7.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in milligrams per
liter (mg/L) from the net gain in weight. When compound purity is assayed
to be 96% or greater, the weight may be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.7.4 Transfer the stock standard solution into a bottle with a
Teflon lined screw-cap. Store, with minimal headspace, at -10°C to -20°C
and protect from light.
5.7.5 Prepare fresh standards for gases every two months or sooner
if comparison with check standards indicates a problem. Reactive compounds
such as 2-chloroethyl vinyl ether and styrene may need to be prepared more
frequently. All other standards must be replaced after six months, or
sooner if comparison with check standards indicates a problem. Both gas
and liquid standards must be monitored closely by comparison to the initial
calibration curve and by comparison to QC check standards. It may be
necessary to replace the standards more frequently if either check exceeds
a 25% difference.
5.8 Secondary dilution standards - Using stock standard solutions, prepare
in methanol, secondary dilution standards containing the compounds of interest,
either singly or mixed together. Secondary dilution standards must be stored
with minimal headspace and should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards from
them. Store in a vial with no headspace for one week only.
5.9 Surrogate standards - The surrogates recommended are toluene-d8,
4-bromofluorobenzene, and dibromofluoromethane. Other compounds may be used as
surrogates, depending upon the analysis requirements. A stock surrogate solution
in methanol should be prepared as described in Section 5.7, and a surrogate
standard spiking solution should be prepared from the stock at a concentration
of 50-250 M9/10 ml in methanol. Each sample undergoing GC/MS analysis must be
spiked with 10 /nL of the surrogate spiking solution prior to analysis.
5.10 Internal standards - The recommended internal standards are
chlorobenzene-d5, 1,4-difluorobenzene, 1,4-dichlorobenzene-d4, and
pentafluorobenzene. Other compounds may be used as internal standards as long
as they have retention times similar to the compounds being detected by GC/MS.
Prepare internal standard stock and secondary dilution standards in methanol
using the procedures described in Sections 5.7 and 5.8. It is recommended that
the secondary dilution standard should be prepared at a concentration of 25 mg/L
of each internal standard compound. Addition of 10 /xL of this standard to
5.0 mL of sample or calibration standard would be the equivalent of 50 p.g/1.
5.11 4-Bromofluorobenzene (BFB) standard - A standard solution containing
25 ng/jitL of BFB in methanol should be prepared.
-5.12 Calibration standards - Calibration standards at a minimum of five
concentrations should be prepared from the secondary dilution of stock standards
(see Sections 5.7 and 5.8). Prepare these solutions in organic-free reagent
water. One of the concentrations should be at a concentration near, but above,
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the method detection limit. The remaining concentrations should correspond to
the expected range of concentrations found in real samples but should not exceed
the working range of the GC/MS system. Each standard should contain each analyte
for detection by this method (e.g. some or all of the compounds listed in Table
1 may be included). Calibration standards must be prepared daily.
5.13 Matrix spiking standards - Matrix spiking standards should be prepared
from volatile organic compounds which will be representative of the compounds
being investigated. At a minimum, the matrix spike should include 1,1-
dichloroethene, trichloroethene, chlorobenzene, toluene, and benzene. It is
desirable to perform a matrix spike using compounds found in samples. Some
permits may require spiking specific compounds of interest, especially if they
are polar and would not be represented by the above listed compounds. The
standard should be prepared in methanol, with each compound present at a
concentration of 250 /ig/10.0 ml.
5.14 Great care must be taken to maintain the integrity of all standard
solutions. It is recommended all standards in methanol be stored at -10°C to
-20°C in amber bottles with Teflon lined screw-caps.
6.0 SAMPLE" COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Direct injection - In very limited applications (e.g. aqueous process
wastes) direct injection of the sample into the GC/MS system with a 10 /iL
syringe may be appropriate. One such application is for verification of the
alcohol content of an aqueous sample prior to determining if the sample is
ignitable (Methods 1010 or 1020). In this case, it is suggested that direct
injection be used. The detection limit is very high (approximately
10,000 M9/L). Therefore, it is only permitted when concentrations in excess of
10,000 p.g/1 are expected, or for water-soluble compounds that do not purge. The
system must be calibrated by direct injection using the same solvent (e.g. water)
for standards as the sample matrix (bypassing the purge-and-trap device).
7.2 Chromatographic conditions (Recommended)
7.2.1 General:
Injector temperature: 200-225°C
Transfer line temperature: 250-300°C
7.2.2 Column 1 (A sample chromatogram is presented in Figure 5)
Carrier gas (He) flow rate: 15 mL/min
Initial temperature: 10°C, hold for 5 minutes
Temperature program: 6°C/min to 160°C
Final temperature: 160°C, hold until all expected
compounds have eluted.
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7.2.3 Column 2, Cryogenic cooling (A sample chromatogram is presented
in Figure 6)
Carrier gas (He) flow rate:
Initial temperature:
Temperature program:
Final temperature:
15 mL/min
10°C, hold for 5 minutes
6°C/min to 160°C
160°C, hold until all
compounds have eluted.
expected
7.2.4 Column 2,
presented in Figure 7)
Non-cryogenic cooling (A sample chromatogram is
Carrier gas flow rate:
Initial temperature:
Temperature program:
Final temperature:
It is recommended that carrier gas flow and
split and make-up gases be set using
performance of standards as guidance. Set
the carrier gas head pressure to'» 10 psi
and the split to = 30 mL/min. Optimize the
make-up gas flow for the separator
(approximately 30 mL/min) by injecting BFB,
and determining the optimum response when
varying the make-up gas. This will require
several injections of BFB. Next, make
several injections of the volatile working
standard with all analytes of interest.
Adjust the carrier and split to provide
optimum chromatography and response. This
is an especially critical adjustment for the
volatile gas analytes. The head pressure
should optimize between 8-12 psi and the
split between 20-60 mL/min. The use of the
splitter is important to minimize the effect
of water on analyte response, to allow the
use of a larger volume of helium during trap
desorption, and to slow column flow.
45°C, hold for 2 minutes
8°C/min to 200°C
200°C, hold for 6 minutes.
A trap preheated to 150°C prior to trap desorption is required to
provide adequate chromatography of the gas analytes.
7.2.5 Column 3 (A sample chromatogram is presented in Figure 8)
Carrier gas (He) flow rate:
Initial temperature:
Temperature program:
Final temperature:
to
4 mL/min
10°C, hold for 5 minutes
6°C/min to 70°C, then 15°C/min
145°C
145°C, hold until all expected
compounds have eluted.
7.3 Initial calibration for purge-and-trap procedure
7.3.1 Each GC/MS system must be hardware-tuned to meet the criteria
in Table 4 for a 50 ng injection or purging of 4-bromofluorobenzene (2 /iL
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injection of the BF3 standard). Analyses Tiust not begin until these
criteria are met.
7.3.2 Assemble a purge-and-trap device that meets the specification
in Section 4.1. Condition the trap overnight at 1SO°C in the purge mode
with an inert gas flow of at least 20 mL/min. Prior to use, condition the
trap daily for 10 minutes while backflushing at 180°C with the column at
220bC.
7.3.3 Connect the purge-and-trap device to a gas chromatograph.
7.3.4 A set of at least five calibration standards containing the
method analytes is needed. One calibration standard should contain each
analyte at a concentration approaching but greater than the method
detection limit (Table 1) for that compound; the other calibration
standards should contain analytes at concentrations that define the range
of the method. The purging efficiency for 5 mL of water is greater than
for 25 ml. Therefore, develop the standard curve with whichever volume of
sample that will be analyzed. To prepare a calibration standard, add an
appropriate volume of a secondary dilution standard solution to an aliquot
of organic-free reagent water in a volumetric flask. Use a microsyringe
and rapidly inject the alcoholic standard into the expanded area of the
filled volumetric flask. Remove the needle as quickly as possible after
injection. Mix by inverting the flask three times only. Discard the
contents contained in the neck of the flask. Aqueous standards are not
stable and should be prepared daily. Transfer 5.0 ml (or 25 ml if lower
detection limits are required) of each standard to a gas tight syringe
along with 10 /ul_ of internal standard. Then transfer the contents to a
purging device.
7.3.5 Carry out the purge-and-trap analysis procedure as described
in Section 7.5.1.
7.3.6 Tabulate the area response of the characteristic ions (see
Table 5) against concentration for each compound and each internal
standard. Calculate response factors (RF) for each compound relative to
one of the internal standards. The internal standard selected for the
calculation of the RF for a compound should be the internal standard that
has a retention time closest to the compound being measured (Section
7.6.2). The RF is calculated as follows:
RF = (AXC,S)/(AJSCX)
where:
Ax = Area of the characteristic ion for the compound being
measured.
Ais = Area of the characteristic ion for the specific internal
standard.
Cis = Concentration of the specific internal standard.
Cx = Concentration of the compound being measured.
7.3.7 The average RF must be calculated and recorded for each
compound. A system performance check should be made before this
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calibration curve is used. Five compounds (the System Performance Check
Compounds, or SPCCs) are checked for a minimum average response factor.
These compounds are chloromethane; 1,1-dichloroethane; bromoform; 1,1,2,2-
tetrachloroethane; and chlorobenzene. The minimum acceptable average RF
for these compounds should be 0.300 (0.250 for bromoform). These compounds
typically have RFs of 0.4-0.6 and are used to check compound instability
and to check for degradation caused by contaminated lines or active sites
in the system. Examples of these occurrences are:
7.3.7.1 Chloromethane - This compound is the most likely
compound to be lost if the purge flow is too fast.
7.3.7.2 Bromoform - This compound is one of the compounds
most likely to be purged very poorly if the purge flow is too slow.
Cold spots and/or active sites in the transfer lines may adversely
affect response. Response of the quantitation ion (m/z 173) is
directly affected by the tuning of 8FB at ions m/z 174/176.
Increasing the m/z 174/176 ratio relative to m/z 95 may improve
bromoform response.
7.3.7.3 Tetrachloroethane and 1,1-dichloroethane - These
compounds are degraded by contaminated transfer lines in purge-and-
trap systems and/or active sites in trapping materials.
7.3.8 Using the RFs from the initial calibration, calculate the
percent relative standard deviation (%RSD) for Calibration Check Compounds
(CCCs). Record the %RSDs for all compounds. The percent RSD is calculated
as follows:
SD
%RSD = x 100
where:
RSD = Relative standard deviation.
x = Mean of 5 initial RFs for a compound.
SD = Standard deviation of average RFs for a compound.
SD
N (x,. - x)2
£
1-1 N - 1
The %RSD for each individual CCC must be less than 30 percent. This
criterion must be met for the individual calibration to be valid. The CCCs
are:
1,1-Dichloroethene,
Chloroform,
1,2-Dichloropropane,
Toluene,
Ethyl benzene, and
Vinyl chloride.
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7.4 DaHy GC/MS cal i brat ion
7.4.1 Prior to the analysis of samples, inject or purge 50 ng of the
4-bromofluorobenzene standard. The resultant mass spectra for the BFB must
meet all of the criteria given in Table 4 before sample analysis begins.
These criteria must be demonstrated each 12-hour shift.
7.4.2 The initial calibration curve (Section 7.3) for each compound
of interest must be checked and verified once every 12 hours of analysis
time. This is accomplished by analyzing a calibration standard that is at
a concentration near the midpoint concentration for the working range of
the GC/MS by checking the SPCC (Section 7.4.3) and CCC (Section 7.4.4).
7.4.3 System Performance Check Compounds (SPCCs) - A system
performance check must be made each 12 hours. If the SPCC criteria are
met, a comparison of response factors is made for all compounds. This is
the same check that is applied during the initial calibration. If the
minimum response factors are not met, the system must be evaluated, and
corrective action must be taken before sample analysis begins. The minimum
response factor for volatile SPCCs is 0.300 (0.250 for Bromoform). Some
possible problems are standard mixture degradation, injection port inlet
contamination, contamination at the front end of the analytical column, and
active sites in the column or chromatographic system.
7.4.4 Calibration Check Compounds (CCCs) - After the system
performance check is met, CCCs listed in Section 7.3.8 are used to check
the validity of the initial calibration. Calculate the percent difference
using the following equation:
RF. - RFC
% Difference = x 100
RF,
where:
RF, = Average response factor from initial calibration
(Section 7.3).
RFC = Response factor from current verification check
standard.
If the percent difference for any compound is greater than 20, the
laboratory should consider this a warning limit. If the percent difference
for each CCC is less than 25%, the initial calibration is assumed to be
valid. If the criterion is not met (> 25% difference), for any one CCC,
corrective action must be taken. Problems similar to those listed under
SPCCs could affect this criterion. If no source of the problem can be
determined after corrective ' action has been taken, a new five-point
calibration must be generated. This criterion must be met before
quantitative sample analysis begins. If the CCCs are not required analytes
by the permit, then all required analytes must meet the 25% difference
criterion.
7.4.5 The internal standard responses and retention times in the
check calibration standard must be evaluated immediately after or during
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data acquisition. If the retention time for any internal standard changes
by more than 30 seconds from the last daily calibration (Section 7.4), the
chromatographic system must be inspected for malfunctions and corrections
must be made, as required. If the EICP area for any of the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration standard check, the mass spectrometer must be inspected for
malfunctions and corrections must be made, as appropriate. When
corrections are made, reanalysis of samples analyzed while the system was
malfunctioning are necessary.
7.5 GC/MS analysis
7.5.1 Water samples
7.5.1.1 Screening of the sample prior to purge-and-trap
analysis will provide guidance on whether sample dilution is
necessary and will prevent contamination of the purge-and-trap
system. Two screening techniques that can be used are the headspace
sampler (Method 3810) using a gas chromatograph (GC) equipped with a
photo ionization detector (PID) in series with an electrolytic
conductivity detector (HECD), and extraction of the sample with
hexadecane and analysis of the extract on a GC with a FID and/or an
ECD (Method 3820).
7.5.1.2 All samples and standard solutions must be allowed
to warm to ambient temperature before analysis.
7.5.1.3 Set up the GC/MS system as outlined in Sections 4.3
and 7.2.
7.5.1.4 BFB tuning criteria and daily GC/MS calibration
criteria must be met (Section 7.4) before analyzing samples.
7.5.1.5 Adjust the purge gas (helium) flow rate to 25-
40 mL/min on the purge-and-trap device. Optimize the flow rate to
provide the best response for chloromethane and bromoform, if these
compounds are analytes. Excessive flow rate reduces chloromethane
response, whereas insufficient flow reduces bromoform response (see
Section 7.3.7).
7.5.1.6 Remove the plunger from a 5 ml syringe and attach
a closed syringe valve. If lower detection limits are required, use
a 25 ml syringe. Open the sample or standard bottle, which has been
allowed to come to ambient temperature, and carefully pour the sample
into the syringe barrel to just short of overflowing. Replace the
syringe plunger and compress the sample. Open the syringe valve and
vent any residual air while adjusting the sample volume to 5.0 mL.
This process of taking an aliquot destroys the validity of the liquid
sample for future analysis; therefore, if there is only one VOA vial,
the analyst should fill a second syringe at this time to protect
against possible loss of sample integrity. This second sample is
maintained only until such time when the analyst has determined that
the first sample has been analyzed properly. Filling one 20 ml
syringe would allow the use of only one syringe. If a second
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analysis is needed from a syringe, it must be analyzed within 24
hours. Care must be taken to prevent air from leaking into the
syringe.
7.5.1.7 The following procedure is appropriate for diluting
purgeable samples. All steps must be performed without delays until
the diluted sample is in a gas-tight syringe.
7.5.1.7.1 Dilutions may be made in volumetric flasks
(10 to 100 mL). Select the volumetric flask that will allow
for the necessary dilution. Intermediate dilutions may be
necessary for extremely large dilutions.
7.5.1.7.2 Calculate the approximate volume of organic-
free reagent water to be added to the volumetric flask
selected and add slightly less than this quantity of organic-
free reagent water to the flask.
7.5.1.7.3 Inject the proper aliquot of sample from the
syringe prepared in Section 7.5.1.6 into the flask. Aliquots
of less than 1 ml are not recommended. Dilute the sample to
the mark with organic-free reagent water. Cap the flask,
invert, and shake three times. Repeat above procedure for
additional dilutions.
7.5.1.7.4 Fill a 5 ml syringe with the diluted sample
as in Section 7.5.1.6.
7.5.1.8 Compositing samples prior to GC/MS analysis
7.5.1.8.1 Add 5 ml or equal larger amounts of each
sample (up to 5 samples are allowed) to a 25 ml glass syringe.
Special precautions must be made to maintain zero headspace in
the syringe.
7.5.1.8.2 The samples must be cooled at 4°C during this
step to minimize volatilization losses.
7.5.1.8.3 Mix well and draw out a 5 ml aliquot for
analysis.
7.5.1.8.4 Follow sample introduction, purging, and
desorption steps described in the method.
7.5.1.8.5 If less than five samples are used for
compositing, a proportionately smaller syringe may be used
unless a 25 ml sample is to be purged.
7.5.1.9 Add 10.0 /LtL of surrogate spiking solution
(Section 5.9) and 10 n\- of internal standard spiking solution
(Section 5.10) through the valve bore of the syringe; then close the
valve. The surrogate and internal standards may be mixed and added
as a single spiking solution. The addition of 10 /il_ of the surrogate
spiking solution to 5 ml of sample is equivalent to a concentration
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of 50 ug/l of each surrogate standard.
7.5.1.10 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the syringe valves and
inject the sample into the purging chamber.
7.5.1.11 Close both valves and purge the sample for 11.0 ±
0.1 minutes at ambient temperature. Be sure the trap is cooler than
25°C.
7.5.1.12 Sample desorption - The mode of sample desorption
is determined by the type of capillary column employed for the
analysis. When using a wide bore capillary column, follow the
desorption conditions of Section 7.5.1.13. The conditions for using
narrow bore columns are described in Section 7.5.1.14.
7.5.1.13 Sample desorption for wide bore capillary column.
Under most conditions, this type of column must be interfaced to the
MS through an all glass jet separator.
7.5.1.13.1 After the 11 minute purge, attach the trap
to the chromatograph, adjust the purge and trap system to the
desorb mode (Figure 4) and initiate the temperature program
sequence of the gas chromatograph and start data acquisition.
Introduce the trapped materials to the GC column by rapidly
heating the trap to 180°C while backflushing the trap with an
inert gas at 15 mL/min for 4 minutes. If the non-cryogenic
cooling technique is followed, the trap must be preheated to
150°C just prior to trap desorption at 180°C. While the purged
analytes are being introduced into the gas chromatograph,
empty the purging device using the sample syringe and wash the
chamber with two 5 ml or 25 ml portions of organic-free
reagent water depending on the size of the purge device.
After the purging device has been emptied, leave the syringe
valve open to allow the purge gas to vent through the sample
introduction needle.
7.5.1.13.2 Hold the column temperature at 10°C for
5 minutes, then program at 6°C/min to 160°C and hold until all
analytes elute.
7.5.1.13.3 After desorbing the sample for 4 minutes,
condition the trap by returning the purge-and-trap system to
the purge mode. Wait 15 seconds, then close the syringe valve
on the purging device to begin gas flow through the trap.
Maintain the trap temperature at 180°C. After approximately
7 minutes, turn off the trap heater and open the syringe valve
to stop the gas flow through the trap. When the trap is cool,
the next sample .can be analyzed.
7.5.1.14 Sample desorption for narrow bore capillary column.
Under normal operating conditions, most narrow bore capillary columns
can be interfaced directly to the MS without a jet separator.
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7.5.1.14.1 After the 11 minute purge, attach the trap
to the cryogenically cooled interface at -150°C and adjust the
purge-and-trap system to the desorb mode (Figure 4).
Introduce the trapped materials to the interface by rapidly
heating the trap to 180°C while backflushing the trap with an
inert gas at 4 mL/min for 5 minutes. While the extracted
sample is being introduced into the interface, empty the
purging device using the sample syringe and rinse the chamber
with two 5 ml or 25 ml portions of organic-free reagent water
depending on the size of the purging device. After the
purging device has been emptied, leave the syringe valve open
to allow the purge gas to vent through the sample introduction
needle. After desorbing for 5 minutes, flash heat the
interface to 250°C and quickly introduce the sample on the
chromatographic column. Start the temperature program
sequence, and initiate data acquisition.
7.5.1.14.2 Hold the column temperature at 10°C for
5 minutes, then program at 6°C/min to 70 C and then at 15°C/min
to 145°C. After desorbing the sample for 5 minutes,
recondition the trap by returning the purge-and-trap system to
the purge mode. Wait 15 seconds, then close the syringe valve
on the purging device to begin gas flow through the trap.
Maintain the trap temperature at 180°C. After approximately
15 minutes, turn off the trap heater and open the syringe
valve to stop the gas flow through the trap. When the trap is
cool, the next sample can be analyzed.
7.5.1.15 If the initial analysis of sample or a dilution of
the sample has a concentration of analytes that exceeds the initial
calibration range, the sample must be reanalyzed at a higher
dilution. Secondary ion quantitation is allowed only when there are
sample interferences with the primary ion. When a sample is analyzed
that has saturated ions from a compound, this analysis must be
followed by a blank organic-free reagent water analysis. If the
blank analysis is not free of interferences, the system must be
decontaminated. Sample analysis may not resume until a blank can be
analyzed that is free of interferences.
7.5.1.16 For matrix spike analysis, add 10 /xL of the matrix
spike solution (Section 5.13) to the 5 ml of sample to be purged.
Disregarding any dilutions, this is equivalent to a concentration of
50 jug/L of each matrix spike standard.
7.5.1.17 All dilutions should keep the response of the major
constituents (previously saturated peaks) in the upper half of the
linear range of the curve. Proceed to Sections 7.6.1 and 7.6.2 for
qualitative and quantitative analysis.
7.5.2 Water-miscible liquids
7.5.2.1 Water-miscible liquids are analyzed as water
samples after first diluting them at least 50 fold with organic-free
reagent water.
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7.5.2.2 Initial and serial dilutions can be prepared by
pipetting 2 ml of the sample to a 100 ml volumetric flask and
diluting to volume with organic-free reagent water. Transfer
immediately to a 5 ml gas-tight syringe.
7.5.2.3 Alternatively, prepare dilutions directly in a 5
ml syringe filled with organic-free reagent water by adding at least
20 ML, but not more than 100 nl of liquid sample. The sample is
ready for addition of internal and surrogate standards.
7.5.3 Sediment/soil and waste samples - It is highly recommended that
all samples of this type be screened prior to the purge-and-trap GC/MS
analysis. The headspace method (Method 3810) or the hexadecane extraction
and screening method (Method 3820) may used for this purpose. These
samples may contain percent quantities of purgeable organics that will
contaminate the purge-and-trap system, and require extensive cleanup and
instrument downtime. Use the screening data to determine whether to use
the low-concentration method (0.005-1 mg/kg) or the high-concentration
method (> 1 mg/kg).
7.5.3.1 Low-concentration method - This is designed for
samples containing individual purgeable compounds of < 1 mg/kg. It
is limited to sediment/soil samples and waste that is of a similar
consistency (granular and porous). The low-concentration method is
based on purging a heated sediment/soil sample mixed with organic-
free reagent water containing the surrogate and internal standards.
Analyze all blanks and standards under the same conditions as the
samples. See Figure 9 for an illustration of a low soils impinger.
7.5.3.1.1 Use a 5 g sample if the expected
concentration is < 0.1 mg/kg or a 1 g sample for expected
concentrations between 0.1 and 1 mg/kg.
7.5.3.1.2 The GC/MS system should be set .up as in
Sections 7.5.1.3-7.5.1.4. This should be done prior to the
preparation of the sample to avoid loss of volatiles from
standards and samples. A heated purge calibration curve must
be prepared and used for the quantitation of all samples
analyzed with the low-concentration method. Follow the
initial and daily calibration instructions, except for the
addition of a 40°C purge temperature.
7.5.3.1.3 Remove the plunger from a 5 ml Luerlock type
syringe equipped with a syringe valve and fill until
overflowing with water. Replace the plunger and compress the
water to vent trapped air. Adjust the volume to 5.0 ml. Add
10 ML each of surrogate spiking solution (Section 5.9) and
internal standard solution (Section 5.10) to the syringe
through the valve (surrogate spiking solution and internal
standard solution may be mixed together). The addition of
10 /.iL of the surrogate spiking solution to 5 g of
sediment/soil is equivalent to 50 M9A9 of each surrogate
standard.
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7.5.3.1.4 The sample (for volatile organics) consists
of the entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents of the
sample container with a narrow metal spatula. Weigh the
amount determined in Section 7.5.3.1.1 into a tared purge
device. Note and record the actual weight to the nearest 0.1
9-
7.5.3.1.5 Determine the percent dry weight of the
soil/sediment sample. This includes waste samples that are
amenable to percent dry weight determination. Other wastes
should be reported on a wet-weight basis.
7.5.3.1.5.1 Immediately after weighing the sample
for extraction, weigh 5-10 g of the sample into a tared
crucible. Determine the % dry weight of the sample by
drying overnight at 105°C. Allow to cool in a
desiccator before re-weighing. Concentrations of
individual analytes are reported relative to the dry
weight of sample.
WARNING: The drying oven should be contained
in a hood or vented. Significant
laboratory contamination may result
from a heavily contaminated hazardous-
waste sample.
% dry weight = g of dry sample x 100
g of sample
7.5.3.1.6 Add the spiked organic-free reagent water to
the purging device, which contains the weighed amount of
sample, and connect the device to the purge-and-trap system.
NOTE: Prior to the attachment of the purge device,
the procedures in Sections 7.5.3.1.4 and
7.5.3.1.6 must be performed rapidly and
without interruption to avoid loss of
volatile organics. These steps must be
performed in a laboratory free of solvent
fumes.
7.5.3.1.7 Heat the sample to 40°C + 1°C and purge the
sample for 11.0 + 0.1 minutes. Be sure the trap is cooler
than 25°C.
7.5.3.1.8 Proceed with the analysis as outlined in
Sections 7.5.1.12-7.5.1.17. Use 5 mL of the same organic-free
reagent water as in the blank. If saturated peaks occurred or
would occur if a 1 g sample were analyzed, the high-
concentration method must be followed.
7.5.3.1.9 For matrix spike analysis of low-
concentration sediment/soils, add 10 juL of the matrix spike
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solution (Section 5.7) to the 5 ml of organic-free reagent
water (Section 7.5.3.1.3). The concentration for a 5 g sample
would be equivalent to 50 /^g/kg of each matrix spike standard.
7.5.3.2 High-concentration method - The method is based on
extracting the sediment/soil with methanol. A waste sample is either
extracted or diluted, depending on its solubility in methanol.
Wastes (i.e. petroleum and coke wastes) that are insoluble in
methanol are diluted with tetraglyme or possibly polyethylene glycol
(PEG). An aliquot of the extract is added to organic-free reagent
water containing surrogate and internal standards. This is purged at
ambient temperature. All samples with an expected concentration of
> 1.0 mg/kg should be analyzed by this method.
7.5.3.2.1 The sample (for volatile organics) consists
of the entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents of the
sample container with a narrow metal spatula. For
sediment/soil and solid wastes that are insoluble in methanol
weigh 4 g (wet weight) of sample into a tared 20 ml vial. Use
a top-loading balance. Note and record the actual weight to
0.1 gram and determine the percent dry weight of the sample
using the procedure in Section 7.5.3.1.5. For waste that is
soluble in methanol, tetraglyme, or PEG, weigh 1 g (wet
weight) into a tared scintillation vial or culture tube or a
10 ml volumetric flask. (If a vial or tube is used, it must
be calibrated prior to use. Pipet 10.0 ml of solvent into the
vial and mark the bottom of the meniscus. Discard this
solvent.)
7.5.3.2.2 For sediment/soil or solid waste, quickly
add 9.0 ml of appropriate solvent; then add 1.0 ml of the
surrogate spiking solution to the vial. For a solvent
miscible sample, dilute the sample to 10 ml with the
appropriate solvent after adding 1.0 ml of the surrogate
spiking solution. Cap and shake for 2 minutes.
NOTE: Sections 7.5.3.2.1 and 7.5.3.2.2 must be
performed rapidly and without interruption
to avoid loss of volatile organics. These
steps must be performed in a laboratory free
from solvent fumes.
7.5.3.2.3 Pipet approximately 1 ml of the extract to
a GC vial for storage, using a disposable pipet. The
remainder may be disposed. Transfer approximately 1 ml of
appropriate solvent to a separate GC vial for use as the
method blank for each set of samples. These extracts may be
stored at 4°C in the dark, prior to analysis. The addition of
a 100 ML aliquot of each of these extracts in Section
7.5.3.2.6 will give a concentration equivalent to 6,200 M9/kg
of each surrogate standard.
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7.5.3.2.4 The GC/MS system should be set up as in
Sections 7.5.1.3-7.5.1.4. This should be done prior to the
addition of the solvent extract to organic-free reagent water.
7.5.3.2.5 The information in Table 10 can be used to
determine the volume of solvent extract to add to the 5 ml of
organic-free reagent water for analysis. If a screening
procedure was followed (Method 3810 or 3820), use the
estimated concentration to determine the appropriate volume.
Otherwise, estimate the concentration range of the sample from
the low-concentration analysis to determine the appropriate
volume. If the sample was submitted as a high-concentration
sample, start with 100 nl. All dilutions must keep the
response of the major constituents (previously saturated
peaks) in the upper half of the linear range of the curve.
7.5.3.2.6 Remove the plunger from a 5.0 ml Luerlock
type syringe equipped with a syringe valve and fill until
overflowing with water. Replace the plunger and compress the
water to vent trapped air. Adjust the volume to 4.9 ml. Pull
the plunger back to 5.0 ml to allow volume for the addition of
the sample extract and of standards. Add 10 /A of internal
standard solution. Also add the volume of solvent extract
determined in Section 7.5.3.2.5 and a volume of extraction or
dissolution solvent to total 100 /*L (excluding solvent in-
standards).
7.5.3.2.7 Attach the syringe-syringe valve assembly to
the syringe valve on the purging device. Open the syringe
valve and inject the water/solvent sample into the purging
chamber.
7.5.3.2.8 Proceed with the analysis as outlined in
Sections 7.5.1.12-7.5.1.17. Analyze all blanks on the same
instrument as that used for the samples. The standards and
blanks should also contain 100 /iL of the dilution solvent to
simulate the sample conditions.
7.5.3.2.9 For a matrix spike in the high-concentration
sediment/soil samples, add 8.0 ml of methanol, 1.0 ml of
surrogate spike solution (Section 5.9), and 1.0 ml of.matrix
spike solution (Section 5.13) as in Section 7.5.3.2.2. This
results in a 6,200 /ug/kg concentration of each matrix spike
standard when added to a-4 g sample. Add a 100 pi aliquot of
this extract to 5 ml of organic-free reagent water for purging
(as per Section 7.5.3.2.6).
7.6 Data interpretation
7.6.1 Qualitative analysis
7.6.1.1 An analyte (e.g. those listed in Table 1) is
identified by comparison of the sample mass spectrum with the mass
spectrum of a standard of the suspected compound (standard reference
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spectrum). Mass spectra for standard reference should be obtained on
the user's GC/MS within the same 12 hours as the sample analysis.
These standard reference spectra may be obtained through analysis of
the calibration standards. Two criteria must be satisfied to verify
identification: (1) elution of sample component at the same GC
relative retention time (RRT) as those of the standard component; and
(2) correspondence of the sample component and the standard component
mass spectrum.
7.6.1.1.1 The sample component RRT must compare within
+ 0.06 RRT units of the RRT of the standard component. For
reference, the standard must be run within the same 12 hours
as the sample. If coelution of interfering components
prohibits accurate assignment of the sample component RRT from
the total ion chromatogram, the RRT should be assigned by
using extracted ion current profiles for ions unique to the
component of interest.
7.6.1.1.2 (1) All ions present in the standard mass
spectra at a relative intensity greater than 10% (most
abundant ion in the spectrum equals 100% must be present in
the sample spectrum). (2) The relative intensities of ions
specified in (1) must agree within ± 20% between the standard
and sample spectra. Example: For an ion with an abundance of
50% in the standard spectra, the corresponding sample
abundance must be between 30 and 70 percent.
7.6.1.2 For samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the type of analyses
being conducted. Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should be present in
the sample spectrum.
(2) The relative intensities of the major ions should agree
within + 20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%).
(3) Molecular ions present in the reference spectrum should
be present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible background
contamination or presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or coeluting
peaks. Data system library reduction programs can sometimes create
these discrepancies.
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Computer generated library search routines should not use
normalization routines that would misrepresent the library or unknown
spectra when compared to each other. Only after visual comparison of
sample with the nearest library searches will the mass spectral
interpretation specialist assign a tentative identification.
7.6.2 Quantitative analysis
7.6.2.1 When a compound has been identified, the
quantitation of that compound will be based on the integrated
abundance from the EICP of the primary characteristic ion.
Quantitation will take place using the internal standard technique.
The internal standard used shall be the one nearest the retention
time of that of a given analyte (e.g. see Table 6).
7.6.2.2 Calculate the concentration of each identified
analyte in the sample as follows:
Water and Water-Miscible Waste:
(** HI.)
concentration (M9A) =
(AU)(RF)(V0)
where:
Ax = Area of characteristic ion for compound being
measured.
Is = Amount of internal standard injected (ng).
Ais = Area of characteristic ion for the internal
standard.
RF = Response factor for compound being measured
(Section 7.3.6).
Vo = Volume of water purged (ml), taking into
consideration any dilutions made.
Sediment/Soil, Sludge, and Waste:
High-concentration:
(*x HI.) (Vt)
concentration (M9/kg) =
(AU)(RF)(V,)(W.J
Low-concentration:
(A, HU
concentration (M9Ag) =
(AU)(RF)(W.)
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where:
A , L, Aic, RF = Same as in water and water-miscible waste
X S 1 S ,
above.
Vt = Volume of total extract (/iL) (use 10,000 juL or a
factor of this when dilutions are made).
Vj = Volume of extract added (/^L) for purging.
Wj = Weight of sample extracted or purged (g). The wet
weight or dry weight may be used, depending upon
the specific applications of the data.
7.6.2.3 Sediment/soil samples are generally reported on a
dry weight basis, while sludges and wastes are reported on a wet
weight basis. The percent dry weight of the sample (as calculated in
Section 7.5.3.1.5) should be reported along with the data in either
instance.
7.6.2.4 Where applicable, an estimate of concentration for
noncalibrated components in the sample should be made. The formulae
given above should be used with the following modifications: The
areas A and Ais should be from the total ion chromatograms, and the
RF for the compound should be assumed to be 1. The concentration
obtained should be reported indicating (1) that the value is an
estimate and (2) which internal standard was used to determine
concentration. Use the nearest internal standard free of
interferences.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program consist
of an initial demonstration of laboratory capability and an ongoing analysis of
spiked samples to evaluate and document quality data. The laboratory should
maintain records to document the quality of the data generated. Ongoing data
quality checks are compared with established performance criteria to determine
if the results of analyses meet the performance characteristics of the method.
When results of sample spikes indicate atypical method performance, a quality
control check sample should be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.2 Before processing any samples, the analyst should demonstrate, through
the analysis of a calibration blank, that interferences from the analytical
system, glassware, and reagents are under control. Each time a set of samples
is extracted or there is a change in reagents, a reagent blank should be
processed as a safeguard against chronic laboratory contamination. The blank
samples should be carried through all stages of sample preparation and
measurement.
8.3 The experience of the analyst performing GC/MS analyses is invaluable
to the success of the methods. Each day that analysis is performed, the daily
calibration standard should be evaluated to determine if the chromatographic
system is operating properly. Questions that should be asked are: Do the peaks
look normal?; Is the response obtained comparable to the response from previous
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calibrations? Careful examination of the standard chromatogram can indicate
whether the column is still useable, the injector is leaking, the injector septum
needs replacing, etc. If any changes are made to the system (e.g. column
changed), recal ibration of the system should take place.
8.4 Required instrument QC
8.4.1 The GC/MS system should be tuned to meet the BFB specifications
in Step 7.2.1.
8.4.2 There should be an initial calibration of the GC/MS system as
specified in Section 7.2.
8.4.3 The GC/MS system should meet the SPCC criteria specified in
Section 7.3.3 and the CCC criteria in Section 7.3.4, each 12 hours.
8.5 To establish the ability to generate acceptable accuracy and precision
on water samples, the analyst should perform the following operations.
8.5.1 A quality control (QC) reference sample concentrate is required
containing each analyte at a concentration of 10 mg/L in methanol . The QC
reference sample concentrate may be prepared from pure standard materials
or purchased as certified solutions. If prepared by the laboratory, the QC
reference sample concentrate should be made using stock standards prepared
independently from those used for calibration.
8.5.2 Prepare a QC reference sample to contain 20 /^g/L of each
analyte by adding 200 juL of QC reference sample concentrate to 100 ml of
water. For the low level 25 ml a sample, spike at 5
8.5.3 Four 5 mL aliquots (or 25 ml for low level) of the well-mixed
QC reference sample are analyzed according to the method beginning in Step
7.4.1.
8.5.4 Calculate the average recovery (R) and the standard deviation
of the recovery (SJ, for the results. Ground water background corrections
should be made before R and RR calculation.
8.5.5 Tables 7 and 8 provide single laboratory recovery and precision
data obtained for the method analytes from water. Similar results from
dosed water should be expected by any experienced laboratory. Compare
results obtained in Step 8.5.4 to the single laboratory recovery and
precision data. If the results are not comparable, review potential
problem areas and repeat the test. Results are comparable if the
calculated percent relative standard deviation (RSD) does not exceed 2.6
times the single laboratory RSD or 20%. whichever is greater and the mean
recovery lies within the interval R ± 3S or R ± 30%, whichever is greater.
8.5.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst should proceed according to Section
8.5.6.1 or 8.5.6.2.
8.5.6.1 Locate and correct the source of the problem and
repeat the test for all analytes beginning with Section 8.5.2.
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8.5.6.2 Beginning with Section 8.5.2, repeat the test only
for those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Section
8.5.2.
8.6 The laboratory should, on an ongoing basis, analyze a blank and spiked
replicates for each analytical batch (up to a maximum of 20 samples/batch) to
assess accuracy. For soil and waste samples where detectable amounts of organics
are present, replicate samples may be appropriate in place of spiked replicates.
For laboratories analyzing one to ten samples per month, at least one spiked
sample per month is required.
8.6.1 The concentration of the spike in the sample should be
determined as follows:
8.6.1.1 If, as in compliance monitoring, the concentration
of a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at that limit or
1 to 5 times higher than the background concentration determined in
Step 8.6.2, whichever concentration would be larger.
8.6.1.2 If the concentration of a specific analyte in a
water sample is not being checked against a specific limit, the spike
should be at 20 ^g/L (or 5 jig/I for low level) or 1 to 5 times higher
than the background concentration determined in Section 8.6.2,
whichever concentration would be larger. For other matrices, the
recommended spiking concentration is 10 times the EQL.
8.6.2 Analyze one 5 ml sample aliquot (or 25 ml for low level) to
determine the background concentration (B) of each analyte. If necessary,
prepare a new QC reference sample concentrate (Section 8.5.1) appropriate
for the background concentration in the sample. Spike a second 5 ml (or 25
ml for low level) sample aliquot with 10 nL of the QC reference sample
concentrate and analyze it to determine the concentration after spiking (A)
of each analyte. Calculate each percent recovery (p) as 100(A-B)%/T, where
T is the known true value of the spike.
8.6.2.1 Compare the percent recovery (R,.) for each analyte
with QC acceptance criteria established from the analyses of
laboratory control standards (Section 8.5). Monitor all data from
dosed samples. Analyte recoveries should fall within the established
control limits.
8.6.2.2 If recovery is not within limits, the following
procedures are required.
8.6.2.2.1 Check to be sure there are no errors in
calculations, matrix spike solutions and internal standards.
Also, check instrument performance.
8.6.2.2.2 Recalculate the data and/or reanalyze the
extract if any of the above checks reveal a problem.
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8.6.2.2.3 If the checks in 8.6.2.2.1 reveal no errors,
the recovery problem encountered with the dosed sample is
judged to be matrix-related, non system-related. The result
for that analyte in the unspiked sample is labeled
suspect/matrix to inform the user that the results are suspect
due to matrix effects.
8.7 As part of the QC program for the laboratory, method accuracy for each
matrix studied should be assessed and records should be maintained. After the
analysis of five spiked samples _(of the same matrix) as in Step 8.6, calculate
the average percent recovery (p) and the standard deviation of the percent
recovery (sp). Express the accuracy assessment as a percent recovery interval
from p - 2s to p + 2s . If p = 90% and s = 10%, for example, the accuracy
interval is expressed as 70-110%. Update the accuracy assessment for each
analyte on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.8 To determine acceptable accuracy and precision limits for surrogate
standards the following procedure should be performed.
8.8.1 For each sample analyzed, calculate the percent recovery of
each surrogate in the sample.
8.8.2 Once a minimum of thirty samples of the same matrix have been
analyzed, calculate the average percent recovery (p) and standard deviation
of the percent recovery (sp) for each of the surrogates.
8.8.3 For a given matrix, calculate the upper and lower control limit
for method performance for each surrogate standard. This should be done as
follows:
Upper Control Limit (UCL) = I + 3s
Lower Control Limit (LCL) = p - 3sp
8.8.4 For aqueous and soil matrices, these laboratory established
surrogate control limits should, if applicable, be compared with the
control limits listed in Table 9. The limits given in Table 9 are multi-
laboratory performance based limits for soil and aqueous samples, and
therefore, the single-laboratory limits established in Section 8.8.3 should
fall within those given in Table 9 for these matrices.
8.8.5 If recovery is not within limits, the following procedures are
required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are a
problem or flag the data as "estimated concentration".
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8.8.6 At a minimum, each laboratory should update surrogate recovery
limits on a matrix-by-matrix basis, annually.
8.9 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 assess the precision of the
environmental measurements. When doubt exists over the identification of a peak
on the chromatogram, confirmatory techniques such as gas chromatography with a
dissimilar column or a different ionization mode using a mass spectrometer should
be used. Whenever possible, the laboratory should analyze standard reference
materials and participate in relevant performance evaluation studies.
8.10 In recognition of the rapid advances occurring in chromatography, the
analyst is permitted to modify GC columns, GC conditions, or detectors to improve
the separations or lower the cost of the measurements. Each time such
modifications to the method are made, the analyst is required to repeat the
procedure in Section 8.4.
9.0 METHOD PERFORMANCE
9.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero. The MDL actually achieved in a given
analysis will vary depending on instrument sensitivity and matrix effects.
9.2 This method has been tested in a single laboratory using spiked
water. Using a wide-bore capillary column, water was spiked at concentrations
between 0.5 and 10 M9/L- Single laboratory accuracy and precision data are
presented for the method analytes in Table 7. Calculated MDLs are presented in
Table 1.
9.3 The method was tested using water spiked at 0.1 to 0.5 ng/L and
analyzed on a cryofocussed narrow-bore column. The accuracy and precision data
for these compounds are presented in Table 8. MDL values were also calculated
from these data and are presented in Table 2.
10.0 REFERENCES
1. Methods for the Determination of Organic Compounds in Finished Drinking
Water and Raw Source Water Method 524.2; U.S. Environmental Protection
Agency. Office of Research Development. Environmental Monitoring and
Support Laboratory: Cincinnati, OH 1986.
2. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
3. Bellar, T.A.; Lichtenberg, J.J. vL Amer. Water Works Assoc. 1974, 66(12),
739-744.
4. Bellar, T.A.; Lichtenberg, J.J. "Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
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Compounds"; in Van Hall, Ed.; Measurement of Organic Pollutants In Water
and Wastewater. ASTM STP 686, pp 108-129, 1979.
5. Budde, W.L.; Eichelberger, J.W. "Performance Tests for the Evaluation of
Computerized Gas Chromatography/Mass Spectrometry Equipment and
Laboratories"; U.S. Environmental Protection Agency. Environmental
Monitoring and Support Laboratory. Cincinnati, OH 45268, April 1980; EPA-
600/4-79-020.
6. Eichelberger, J.W.; Harris, L.E.; Budde, W.L. "Reference Compound to
Calibrate Ion Abundance Measurement in Gas Chromatography-Mass Spectrometry
Systems"; Analytical Chemistry 1975, 47, 995-1000.
7. Olynyk, P.; Budde, W.L.; Eichelberger, J.W. "Method Detection Limit for
Methods 624 and 625"; Unpublished report, October 1980.
8. Non Cryogenic Temperatures Program and Chromatogram, Private
Communications; Myron Stephenson and Frank Allen, EPA Region IV Laboratory,
Athens, GA.
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TABLE 1.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL)
FOR VOLATILE ORGANIC COMPOUNDS ON WIDE BORE CAPILLARY COLUMNS
ANALYTE
RETENTION TIME
(minutes)
MDLd
Di chl orodi f 1 uoromethane
Chl oromethane
Vinyl Chloride
Bromomethane
Chloroethane
Tri chl orof 1 uoromethane
1,1-Dichloroethene
Methyl ene chloride
trans -1,2-Di chl oroethene
1,1-Dichloroethane
2,2-Dichloropropane
cis- 1,2-Di chl oroethene
Chloroform
Bromochl oromethane
1,1, 1 -Trichl oroethane
Carbon tetrachloride
1,1-Dichloropropene
Benzene
1,2-Di chl oroethane
Trichloroethene
1,2-Dichloropropane
Bromodi chl oromethane
Dibromomethane
trans- 1,3-Dichloropropene
Toluene
cis- 1,3-Dichloropropene
1,1,2-Trichloroethane
Tetrachl oroethene
1,3-Dichloropropane
Di bromochl oromethane
1,2-Dibromoethane
1-Chlorohexane
Chlorobenzene
1,1,1 , 2-Tetrachl oroethane
Ethyl benzene
p-Xylene
m-Xylene
o-Xylene
Styrene
Bromoform
Isopropyl benzene
1,1,2, 2-Tetrachl oroethane
Column la
1.55
1.63
1.71
2.01
2.09
2.27
2.89
3.60
3.98
4.85
6.01
6.19
6.40
6.74
7.27
7.61
7.68
8.23
8.40
9.59
10.09
10.59
10.65
--
12.43
--
13.41
13.74
14.04
14.39
14.73
15.46
15.76
15.94
15.99
16.12
16.17
17.11
17.31
17.93
18.06
18.72
Column 2°
0.70
0.73
0.79
0.96
1.02
1.19
1.57
2.06
2.36
2.93
3.80
3.90
4.80
4.38
4.84
5.26
5.29
5.67
5.83
7.27
7.66
8.49
7.93
--
10.00
--
11.05
11.15
11.31
11.85
11.83
13.29
13.01
13.33
13.39
13.69
13.68
14.52
14.60
14.88
15.46
16.35
Column 2"
3.13
3.40
3.93
4.80
--
6.20
7.83
9.27
9.90
10.80
11.87
11.93
12.60
12.37
12.83
13.17
13.10
13.50
13.63
14.80
15.20
15.80
15.43
16.70
17.40
17.90
18.30
18.60
18.70
19.20
19.40
--
20.67
20.87
21.00
21.30
21.37
22.27
22.40
22.77
23.30
24.07
0.10
0.13
0.17
0.11
0.10
0.08
0.12
0.03
0.06
0.04
0.35
0.12
0.03
0.04
0.08
0.21
0.10
0.04
0.06
0.19
0.04
0.08
0.24
--
0.11
--
0.10
0.14
0.04
0.05
0.06
0.05
0.04
0.05
0.06
0.13
0.05
0.11
0.04
0.12
0.15
0.04
8260 - 31
Revision 0
July 1992
-------
TABLE 1.
(Continued)
ANALYTE
RETENTION TIME
(minutes)
Column T
Column 2 Column 2
/c
INTERNAL STANDARDS/SURROGATES
4-Bromofluorobenzene
18.63
15.71
23.63
MDL"
Bromobenzene
1,2,3-Trichloropropane
n-Propyl benzene
2-Chlorotoluene
1, 3 ,5-Tri methyl benzene
4-Chlorotoluene
tert-Butyl benzene
1 , 2 , 4-Trimethyl benzene
sec-Butyl benzene
p- I sopropyl toluene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
n-Butyl benzene
1,2-Dichlorobenzene
l,2-Dibromo-3-chloropropane
1,2,4-Trichlorobenzene
Hexachlorobutadiene
Naphthalene
1,2,3-Trichlorobenzene
18.95
19.02
19.06
19.34
19.47
19.50
20.28
20.34
20.79
21.20
21.22
21.55
22.22
22.52
24.53
26.55
26.99
27.17
27.78
15.86
16.23
16.41
16.42
16.90
16.72
17.57
17.70
18.09
18.52
18.14
18.39
19.49
19.17
21.08
23.08
23.68
23.52
24.18
24.00
24.13
24.33
24.53
24.83
24.77
26.60
31.50
26.13
26.50
26.37
26.60
27.32
27.43
--
31.50
32.07
32.20
32.97
0.03
0.32
0.04
0.04
0.05
0.06
0.14
0.13
0.13
0.12
0.12
0.03
0.11
0.03
0.26
0.04
0.11
0.04
0.03
a Column 1 - 60 meter x 0.75 mm ID VOCOL capillary. Hold at 10°C for 5 minutes,
then program to 160°C at 6°/nnn.
b Column 2 - 30 meter x 0.53 mm ID DB-624 wide-bore capillary using cryogenic
oven. Hold at 10°C for 5 minutes, then program to 160°C at 6°/min.
c Column 2' - 30 meter x 0.53 mm ID DB-624 wide-bore capillary, cooling GC oven
to ambient temperatures. Hold at 10°C for 6 minutes, program to 70°C at
10°/min, program to 120°C at 5°/min, then program to 180°C at 8°/min.
d MDL based on a 25 mL sample volume.
8260 - 32
Revision 0
July 1992
-------
TABLE 2.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL)
FOR VOLATILE ORGANIC COMPOUNDS ON NARROW BORE CAPILLARY COLUMNS
ANALYTE
Di chl orodi f 1 uoromethane
Chloromethane
Vinyl chloride
Bromomethane
Chloroethane
Tri chl orof 1 uoromethane
1,1-Dichloroethene
Methylene chloride
trans- 1,2-Di chl oroethene
1,1-Dichloroethane
cis- 1,2-Di chl oroethene
2,2-Dichloropropane
Chloroform
Bromochl oromethane
1,1,1 -Tri chl oroethane
1,2-Dichloroethane
1,1-Dichloropropene
Carbon tetrachloride
Benzene
1,2-Dichloropropane
Trichloroethene
Dibromomethane
Bromod i chl oromethane
Toluene
1,1,2-Trichloroethane
1,3-Dichloropropane
Di bromochl oromethane
Tetrachl oroethene
1,2-Di bromoethane
Chlorobenzene
1,1,1 , 2-Tetrachl oroethane
Ethyl benzene
p-Xylene
m-Xylene
Bromoform
o-Xylene
Styrene
1,1,2 , 2-Tetrachl oroethane
1,2, 3 -Tri chl oropropane
I sopropyl benzene
RETENTION TIME
(minutes)
Column 3
0.88
0.97
1.04
1.29
1.45
1.77
2.33
2.66
3.54
4.03
5.07
5.31
5.55
5.63
6.76
7.00
7.16
7.41
7.41
8.94
9.02
9.09
9.34
11.51
11.99
12.48
12.80
13.20
13.60
14.33
14.73
14.73
15.30
15.30
15.70
15.78
15.78
15.78
16.26
16.42
MDLb
(M9/L)
0.11
0.05
0.04
0.06
0.02
0.07
0.05
0.09
0.03
0.03
0.06
0.08
0.04
0.09
0.04
0.02
0.12
0.02
0.03
0.02
0.02
0.01
0.03
0.08
0.08
0.08
0.07
0.05
0.10
0.03
0.07
0.03
0.06
0.03
0.20
0.06
0.27
0.20
0.09
0.10
8260 - 33
Revision 0
July 1992
-------
ANALYTE
Bromobenzene
2-Chlorotoluene
n-Propyl benzene
4-Chlorotoluene
1 , 3 , 5-Trimethyl benzene
tert-Butyl benzene
1 , 2 , 4-Trimethyl benzene
sec-Butyl benzene
1,3-Dichlorobenzene
p- I sopropyl tol uene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
n-Butyl benzene
1 , 2-Di bromo-3-chl oropropane
1 , 2 , 4-Tri chl orobenzene
Naphthalene
Hexachl orobutadi ene
1 , 2 , 3-Tri chl orobenzene
TABLE 2.
(Continued)
RETENTION TIME
(minutes)
/* 1 M. *5«
Column 3
16.42
16.74
16.82
16.82
16.99
17.31
17.31
17.47
17.47
17.63
17.63
17.79
17.95
18.03
18.84
19.07
19.24
19.24
MDLb
(M9/L)
0.11
0.08
0.10
0.06
0.06
0.33
0.09
0.12
0.05
0.26
0.04
0.05
0.10
0.50
0.20
0.10
0.10
0.14
a Column 3 - 30 meter x 0.32 mm ID DB-5 capillary with 1
b MDL based on a 25 ml sample volume.
film thickness.
8260 - 34
Revision 0
July 1992
-------
TABLE 3.
ESTIMATED QUANTITATION LIMITS FOR VOLATILE ANALYTES3
Estimated
Quantitation
Limits
Ground waterLow Soil/Sediment0
Volume of water purged 5 mL 25 mL
All analytes in Table 1 5 1
Estimated Quantitation Limit (EQL) - The lowest concentration that can be
reliably achieved within specified limits of precision and accuracy during
routine laboratory operating conditions. The EQL is generally 5 to 10
times the MDL. However, it may be nominally chosen within these guidelines
to simplify data reporting. For many analytes the EQL analyte
concentration is selected for the lowest non-zero standard in the
calibration curve. Sample EQLs are highly matrix-dependent. The EQLs
listed herein are provided for guidance and may not always be achievable.
See the following information for further guidance on matrix-dependent
EQLs.
EQLs listed for soil/sediment are based on wet weight. Normally data is
reported on a dry weight basis; therefore, EQLs will be higher, based on
the percent dry weight in each sample.
Other Matrices Factor0
Water miscible liquid waste 50
High-concentration soil and sludge 125
Non-water miscible waste 500
CEQL = [EQL for low soil sediment (Table 3)] X [Factor]. For non-aqueous
samples, the factor is on a wet-weight basis.
8260 - 35 Revision 0
July 1992
-------
TABLE 4.
BFB MASS - INTENSITY SPECIFICATIONS (4-BROMOFLUOROBENZENE)
Mass Intensity Required (relative abundance)
50 15 to 40% of mass 95
75 30 to 60% of mass 95
95 base peak, 100% relative abundance
96 5 to 9% of mass 95
173 less than 2% of mass 174
174 greater than 50% of mass 95
175 5 to 9% of mass 174
176 greater than 95% but less than 101% of mass 174
177 5 to 9% of mass 176
8260 - 36 Revision 0
July 1992
-------
TABLE 5.
CHARACTERISTIC MASSES (M/Z) FOR PURGEABLE ORGANIC COMPOUNDS'
Primary Secondary
Characteristic Characteristic
Analyte Ion Ion(s)
Benzene
Bromobenzene
Bromochl oromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chi oromethane
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-chloropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1 , 2-Di chl orobenzene
1,3-Dichlorobenzene
1 ,4-Di chlorobenzene
Dichlorodi fluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-l,2-D'ch1oroethene
trans -1 , 2- Oichl oroethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyl toluene
Methylene chloride
Naphthalene
n-Propyl benzene
Styrene
1,1,1 , 2-Tetrachl oroethane
78
156
128
83
173
94
91
105
119
117
112
64
83
50
91
91
75
129
107
93
146
146
146
85
63
62
96
96
96
63
76
77
75
91
225
105
119
84
128
91
104
131
8260 - 37
.
77, 158
49, 130
85, 127
175, 254
96
92, 134
134
91, 134
119
77, 114
66
85
52
126
126
155, 157
127
109, 188
95, 174
111, 148
111, 148
111, 148
87
65, 83
98
61, 63
61, 98
61, 98
112
78
97
110, 77
106
223, 227
120
134, 91
86, 49
-
120
78
133, 119
Revision 0
July 1992
-------
TABLE 5.
(Continued)
Primary Secondary
Characteristic Characteristic
Analyte Ion Ion(s)
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1 -Trichl oroethane
1 , 1 , 2-Tri chl oroethane
Trichloroethene
Trichl orofluoromethane
1 ,2,3-Trichloropropane
1 , 2 , 4-Tri methyl benzene
1,3, 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
83
166
92
180
180
97
83
95
101
75
105
105
62
106
106
106
131,
168,
91
182,
182,
99,
97,
130,
103
77
120
120
64
91
91
91
85
129
145
145
61
85
132
INTERNAL STANDARDS/SURROGATES
4-Bromofluorobenzene 95 174, 176
Dibromofl loromethane 113
To1uene-d8 98
Pentafluorobenzene 168
1,4-Difluorobenzene 114
Ch1orobenzene-d5 117
l,4-Dichiorobenzene-d4 152
8260 - 38 Revision 0
July 1992
-------
TABLE 6.
VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION
Pentafluorobenzene
Acetone
Acrolein
Acrylonitrile
Bromochloromethane
Bromomethane
2-Butanone
Carbon dlsulfide
Chloroethane
Chloroform
Chloromethane
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,1-Dichloroethene
ci s-1,2-Dichloroethene
trans-1,2-Dichloroethene
2,2-Dichloropropane
lodomethane
Methylene chloride
1,1,1-Tri chloroethane
Tri chlorof1uoromethane
Vinyl acetate
Vinyl chloride
Chlorobenzene-dr
Bromoform
Chlorodibromomethane
Chlorobenzene
1,3-Dichloropropane
Ethyl benzene
2-Hexanone
Styrene
1,1,1,2-Tetrachloroethane
Tetrachloroethene
Xylene
1,4-Difluorobenzene
Benzene
Bromodichloromethane
Bromofluorobenzene (surrogate)
Carbon tetrachloride
2-Chloroethyl vinyl ether
1,2-Dibromoethane
Dibromomethane
1,2-Dichloroethane
1,2-Dichloroethane-d4 (surrogate)
1,2-Dichloropropane
1,1-Dichloropropene
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
4-Methyl-2-pentanone
Toluene
Toluene-d8 (surrogate)
1,1,2-Trichloroethane
Trichloroethene
1.4-Dichlorobenzene-d4
Bromobenzene
n-8utylbenzene
sec-Butylbenzene
tert-Butylbenzene
2-Chlorotoluene
4-Chlorotoluene
1,2-Di bromo-3-chloropropane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyltoluene
Naphthalene
n-Propylbenzene
1,1,2,2-Tetrachloroethane
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,2,3-Tri chloropropane
1,2,4-Trimethyl benzene
1,3,5-Trimethyl benzene
8260 - 39
Revision 0
July 1992
-------
TABLE 7.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR VOLATILE
ORGANIC COMPOUNDS IN WATER DETERMINED WITH A WIDE
BORE CAPILLARY COLUMN
Analyte
Benzene
Bromobenzene
Bromochl oromethane
Bromodi chl oromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert -Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chl oromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2-Dibromo-3-Ch1 oropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orod i f 1 uoromethane
l,l-Dichloroben?ene
1,2-Dichlorobenzene
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans- 1,2-Di chl oroethene
1,2-Dichl oropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachl orobutadi ene
I sopropyl benzene
p-Isopropyl toluene
Methylene chloride
Naphthalene
n-Propyl benzene
Cone. Number
Range, of Recovery,8
jig/L Samples %
0.1
0.1
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.5
0.5
0.5
0.1
0.1
0.5
0.1
0.5
0.5
0.1
0.5
0.2
0.5
0.5
0.1
0.1
0.5
0.1
0.1
0.1
0.5
0.5
0.1
0.5
0.5
0.1
0.1
0.1
0.1
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 20
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
-100
- 10
8260
31
30
24
30
18
18
18
16
18
24
31
24
24
23
31
31
24
31
24
24
31
24
31
18
24
31
34
18
30
30
3T
12
18
31
18
16
23
30
31
31
- 40
97
100
90
95
101
95
100
100
102
84
98
89
90
93
90
99
83
92
102
100
93
99
103
90
96
95
94
101
93
97
96
86
98
99
100
101
99
95
104
100
Standard Percent
Deviation Rel . Std.
of Recovery6 Dev.
6.5
5.5
5.7
5.7
6.4
7.8
7.6
7.6
7.4
7.4
5.8
8.0
5.5
8.3
5.6
8.2
16.6
6.5
4.0
5.5
5.8
6.8
6.6
6.9
5.1
5.1
6.3
6.7
5.2
5.9
5.7
14.6
8.7
8.4
6.8
7.7
6.7
5.0
8.6
5.8
5.7
5.5
6.4
6.1
6.3
8.2
7.6
7.6
7.3
8.8
5.9
9.0
6.1
8.9
6.2
8.3
19.9
7.0
3.9
5.6
6.2
6.9
6.4
7.7
5.3
5.4
6.7
6.7
5.6
6.1
6.0
16.9
8.9
8.6
6.8
7.6
6.7
5.3
8.2
5.8
Revision 0
July 1992
-------
TABLE 7.
(Continued)
Analyte
Cone. Number
Range, of
/ig/L Samples
Recovery,'
%
Standard
Deviation
of Recovery6
Percent
Rel. Std.
Dev.
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2, 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichl oroethane
1 , 1 , 2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
1 , 2, 4-Trimethyl benzene
1,3, 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
0.1
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.5
-100
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 31
- 10
- 10
39
24
30
24
18
18
18
18
18
24
24
16
18
23
18
18
31
18
102
90
91
89
102
109
108
98
104.
90
89
108
99
92
98
103
97
104
7.3
6.1
5.7
6.0
8.1
9.4
9.0
7.9
7.6
6.5
7.2
15.6
8.0
6.8
6.5
7.4
6.3
8.0
7.2
6.8
6.3
6.8
8.0
8.6
8.3
8.1
7.3
7.3
8.1
14.4
8.1
7.4
6.7
7.2
6.5
7.7
9 Recoveries were calculated using internal standard method. Internal
standard was fluorobenzene.
b Standard deviation was calculated by pooling data form three
concentrations.
8260 - 41
Revision 0
July 1992
-------
TABLE 8.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR
VOLATILE ORGANIC COMPOUNDS IN WATER DETERMINED
WITH A NARROW BORE CAPILLARY COLUMN
Analyte
Benzene
Bromobenzene
Bromochloromethane
Bromodichloromethane
Bromoform
Bromomethane
n -Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2-Di bromo-3-chl oropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1, 2-Di chl oroethene
trans - 1 , 2 -Di chl oroethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachl orobutadi ene
Isopropyl benzene
p- I sopropyl toluene
Methyl ene chloride
Naphthalene
n-Propylbenzene
Cone.
M9/L
0.1
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.1
0.1
0,5
0.5
0.5
0.5
0.1
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
Number
of
Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
8260 - 42
Recovery,8
%
99
97
97
100
101
99
94
110
110
108
91
100
105
101
99
96
92
99
97
93
97
101
106
99
98
100
95
100
98
96
99
99
102
99
100
102
113
97
98
99
Standard
Deviation
of Recovery
6.2
7.4
5.8
4.6
5.4
7.1
6.0
7.1
2.5
6.8
5.8
5.8
3.2
4.7
4.6
7.0
10.0
5.6
5.6
5.6
3.5
6.0
6.5
8.8
6.2
6.3
9.0
3.7
7.2
6.0
5.8
4.9
7.4
5.2
6.7
6.4
13.0
13.0
7.2
6.6
Percent
Rel. Std.
Dev.
6.3
7.6
6.0
4.6
5.3
7.2
6.4
6.5
2.3
6.3
6.4
5.8
3.0
4.7
4.6
7.3
10.9
5.7
5.8
6.0
3.6
5.9
6.1
8.9
6.3
6.3
9.5
3.7
7.3
6.3
5.9
4.9
7.3
5.3
6.7
6.3
11.5
13.4
7.3
6.7
Revision 0
July 1992
-------
TABLE 8.
(Continued)
Analyte
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1 -Tri chl oroethane
1 , 1 , 2-Trichl oroethane
Trichloroethene
Tr i chl orof 1 uoromethane
1,2,3-Trichloropropane
1 , 2 , 4-Trimethyl benzene
1,3 , 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
Cone.
M9/L
0.5
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.5
0.5
0.5
0.1
0.5
0.5
0.5
Number
of
Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Recovery,8
%
96
100
100
96
100
102
91
100
102
104
97
96
96
101
104
106
106
97
Standard
Deviation
of Recovery
19.0
4.7
12.0
5.0
5.9
8.9
16.0
4.0
4.9
2.0
4.6
6.5
6.5
4.2
0.2
7.5
4.6
6.1
Percent
Rel. Std.
Dev.
19.8
4.7
12.0
5.2
5.9
8.7
17.6
4.0
4.8
1.9
4.7
6.8
6.8
4.2
0.2
7.1
4.3
6.3
Recoveries were calculated
standard was fluorobenzene.
using internal standard method. Internal
8260 - 43
Revision 0
July 1992
-------
TABLE 9.
SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Surrogate Compound
4-Bromofl uorobenzene8
Di bromof 1 uoromethane8
Toluene-d8a
Low/High
Water
86-115
86-118
88-110
Low/High
Soil/Sediment
74-121
80-120
81-117
8 Single laboratory data for guidance only.
TABLE 10.
QUANTITY OF EXTRACT REQUIRED FOR ANALYSIS OF
HIGH-CONCENTRATION SAMPLES
Approximate Volume of
Concentration Range Extract8
500 - 10,000 /ig/kg 100
1,000 - 20,000 pig/kg 50
5,000 - 100,000 /ig/kg 10
25,000 - 500,000 /ig/kg 100 /xL of 1/50 dilution6
Calculate appropriate dilution factor for concentrations exceeding this table.
a The volume of solvent added to 5 mL of water being purged should be kept
constant. Therefore, add to the 5 mL syringe whatever volume of solvent
is necessary to maintain a volume of 100 nl added to the syringe.
b Dilute an aliquot of the solvent extract and then take 100 /uL for
analysis.
8260 - 44 Revision 0
July 1992
-------
FIGURE 1.
PURGING DEVICE
CUT <* « OA
FIGURE 2.
TRAP PACKING AND CONSTRUCTION TO INCLUDE DESORB CAPABILITY
0«0<1MO OtTM.
8260 - 45
Revision 0
July 1992
-------
FIGURE 3.
SCHEMATIC OF PURGE-ANO-TRAP DEVICE - PURGE MODE
CAWWOAS
aow CONTWOL
•UUCOAI
nowcoMTKx
mMOLfCULAft
MVf W.TCT
NOTt
»U. UHf» KTV«f W m»»
ANO oc SHOULD M MCATV
FIGURE 4.
SCHEMATIC OF PURGE-AND-TRAP DEVICE - DESORB MODE
CAANOOMI
FLOWCONTMX
COLUMN OVtN
conrmMATpm COLUMN
TO UtTCCTDft
*u uwts inxoH TIM*
AMD OC SHOULD M HtATB)
TOVC
8260 - 46
Revision 0
July 1992
-------
00
ro
en
o
JL.
COLUMN! &0 METER » O.73 NN I, O. VQCOl. Cf*PIt,UU*V
10 c FOR a HIN., TMSH 4 /KIN TO t&o C
2000
-. i .
24OO
NCTCNIIOM IMMf. MM.
o o>
c <
U? 3
\£>
r\J O
-------
00
ro
en
o
CO
PHOOHAHi IO C FOR 9 HIM.,
1MEN 6 /NIN TO I6O C
V«-| f r i I • i i
30
C-. (B
C <
AtlfMIIOM IMM. MM.
O
£75
tP
O C
-n po
o
33
CT>
^- O
VO 3
-------
R1C DATA: -JO»'S0423c.7 1843 SCANS 125 TO 900
04-23--87 y:2s:00 CALI: 46US042y8? 13
SAt-lFlE: 40t'OAST00423dr, 5UL.-5ML
CGHGS.: F4000,40-160X8,12,F4,30MLPURGE,TENSILGEL.Dee24.SWEEP35,10FS1
RANGE: G 1.1200 LABEL: H 0, 4.0 GUAM: A 0, 1.0 J 6 BASE: U 20, 3
lOO.O-i
oo
ro
cri
o
.p.
VD
R1C
73
' <
(/>
' O
i 3
a
1
"flfl
3«u
~~l
400
6:40
~]
500
9:20
—I
600
10:00
—I
700
11:40
—T""
800
13:20
264132.
oo
o
33
O
O
G1
o
1
»00> SCHl/
15:00 TIME
-------
1
00
ro
cr>
O
en
O
C_ (D
C <
U
$
M
si *
I 11 1
5
I. l.l-*OMlOMOrimiOlt
1.
• CMUMOT
» «.«.*-
ti. n
M(Mff1»)
II IfMOttAftOOMV
IJ IJ
«* VOUKMI
M. nNlUHMICMt
ft. t.»-V«UM(
1>.
•»
M
'00
X
—1
cr
I)
U
JL.
~ O
VO 3
ro O
-------
FIGURE 9.
LOW SOILS IMPINGER
PURGE INLET FITTING
SEPTUM
J i |mm 0 0 GLASS
40ml VIAL
8260 - 51
Revision 0
July 1992
-------
METHOD 8250
VOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS):
CAPILLARY COLUMN TECHNIQUE
Purge-and-trap
7 1
S.l.ct
pr ocedure for
in I reducing
•ample into
CC/MS
732 Tuna
CC/MS lyjtem
• Uh BF8
732/733
A»»embl •
purge•and•trap
device Conned
device to CC
734 Prepare
c-al i br* t 2 on
•tandardl
736 Perform
purge•and•trap
ana 1ysi*
7 3 7
Calculate RFi
for 5 SPCCi
7 3 8
Calculate
*RSD of Rr
for CCC»
7 4 Perform
daily
calibration
8260 - 52
Revision 0
July 1992
-------
METHOD 8260
(Continued)
Low concentratio
soil /seaiment
7 5 31.3 Prepare
aqueou* solution of
surrogate and
internal standard*
water and wa ter
mi scible 1 iquids
751/752 Screen
sample us ing Method
3810 or 382C
(Dilute
water-miscible
liquid* at least SO
fold ]
7 S 1 3 Add
internal standard
and surroga te
spitting solution*
7 5 1 10/7 £ 1 11
Par form
purge -and- 1 rap
pr oodur •
7 S3 22 Add
sol vent, internal
standard and
surrogate spiking
solution* Shake
7532 Store
portion of extract
for re-analy*i*
Prepare method
blank
7 5 1 12 Desorb trap
on to column Ana 1y xe
samole
chromatographically
7611 Identify
analytes by
coaparing the
sample and standard
mass spectra.
I
7622 Calculate
the concentration
of each identified
8260 - 53
Revision 0
July 1992
-------
00
to
-------
METHOD 8260A
VOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS):
CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8260 is used to determine volatile organic compounds in a
variety of solid waste matrices. This method is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic liquors, acid liquors, waste solvents, oily wastes
fibrous wastes, polymeric emulsions, filter cakes, spent
catalysts, soils, and sediments. The following compounds can
this method:
mousses, tars,
carbons, spent
be determined by
Analyte
CAS No.1
Appropriate Technique
Direct
Purge-and-Trap Injection
Acetone
Acetonitrile
Acrolein (Propenal)
Acrylonitrile
Allyl alcohol
Allyl chloride
Benzene
Benzyl chloride
Bromoacetone
Bromochloromethane (I.S.)
Bromodichloromethane
4-Bromofluorobenzene (surr.)
Bromoform
Bromomethane
n-Butanol
2-Butanone (MEK)
Carbon disulfide
Carbon tetrachloride
Chloral hydrate
Chlorobenzene
2-Chloro-l,3-butadiene
Chi orodi bromomethane
Chloroethane
2-Chloroethanol
bis-(2-Chloroethyl) sulfide
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Chloroprene
67-64-1
75-05-8
107-02-8
107-13-1
107-18-6
107-05-1
71-43-2
100-44-7
598-31-2
74-97-5
75-27-4
460-00-4
75-25-2
74-83-9
71-36-3
78-93-3
75-15-0
56-23-5
302-17-0
108-90-7
126-99-8
124-48-1
75-00-3
107-07-3
505-60-2
110-75-8
67-66-3
74-87-3
126-99-8
PP
PP
PP
PP
ht
a
a
a
PP
a
a
a
a
a
ht
PP
PP
a
PP
a
a
a
a
PP
PP
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
pc
8260A - 1
Revision 1
September 1994
-------
Appropriate Technique
Analyte
3-Chloropropene
3-Chloropropionitrile
1 , 2-Dibromo-3-chl oropropane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
cis-l,4-Dichloro-2-butene
trans -l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans -1,2-Di chl oroethene
1,2-Dichloropropane
l,3-Dichloro-2-propanol
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,2,3,4-Diepoxybutane
Di ethyl ether
1,4-Difluorobenzene (I.S.)
1,4-Dioxane
Epichlorohydrin
Ethanol
Ethyl acetate
Ethyl benzene
Ethylene oxide
Ethyl methacrylate
Hexachl orobutad i ene
Hexachloroethane
2-Hexanone
2-Hydroxypropionitrile
lodomethane
Isobutyl alcohol
Isopropyl benzene
Malononitrile
Methacrylonitrile
Methanol
Methylene chloride (DCM)
Methyl methacrylate
4-Methyl-2-pentanone (MIBK)
Naphthalene
Nitrobenzene
2-Nitropropane
CAS No.b
107-05-1
542-76-7
96-12-8
106-93-4
74-95-3
95-50-1
541-73-1
106-46-7
1476-11-5
110-57-6
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
78-87-5
96-23-1
10061-01-5
10061-02-6
1464-53-5
60-29-7
540-36-3
123-91-1
106-89-8
64-17-5
141-78-6
100-41-4
75-21-8
97-63-2
87-68-3
67-72-1
591-78-6
78-97-7
74-88-4
78-83-1
98-82-8
109-77-3
126-98-7
67-56-1
75-09-2
80-62-6
108-10-1
91-20-3
98-95-3
79-46-9
Purge-and-Trap
a
i
PP
a
a
a
a
a
a
PP
a
a
a
a
a
a
PP
a
a
a
a
a
PP
i
i
i
a
PP
a
a
i
PP
i
a
PP
a
PP
PP
i
a
a
PP
a
a
a
Direct
Injection
a
pc
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
pc
a
a
a
a
a
a
a
a
a
a
a
a
8260A - 2
Revision 1
September 1994
-------
AocroDriate Techniaue
Analyte
Pentachloroethane
2-Picol ine
Propargyl alcohol
B-Propiolactone
Propionitrile (ethyl cyanide)
n-Propylamine
Pyridine
Styrene
1,1,1 , 2-Tetrachl oroethane
1 , 1 , 2, 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1 , 2 , 4-Tri chl orobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
Vinyl acetate
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
a Adequate response by thi
CAS No.b
76-01-7
109-06-8
107-19-7
57-57-8
107-12-0
107-10-8
110-86-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
120-82-1
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
108-05-4
75-01-4
95-47-6
108-38-3
106-42-3
s technique.
Purge-and-Trap
i
PP
PP
PP
ht
a
i
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
Direct
Injection
a
a
a
a
pc
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
b Chemical Abstract Services Registry Number.
ht Method analyte only when
i Inappropriate technique
purged at 80°C
for this analyte.
pc Poor chromatographic behavior.
pp Poor purging efficiency
surr Surrogate
I.S. Internal Standard
resulting in high
EQLs.
1.2 Method 8260 can be used to quantitate most volatile organic compounds
that have boiling points below 200°C and that are insoluble or slightly soluble
in water. Volatile water-soluble compounds' can be included in this analytical
technique. However, for the more soluble compounds, quantitation limits are
approximately ten times higher because of poor purging efficiency. Such
compounds include low-molecular-weight halogenated hydrocarbons, aromatics,
ketones, nitriles, acetates, acrylates, ethers, and sulfides. See Tables 1 and
2 for lists of analytes and retention tines that have been evaluated on a purge-
8260A - 3 Revision 1
September 1994
-------
and-trap GC/MS system. Also, the method detection limits for 25 ml sample
volumes are presented. The following analytes are also amenable to analysis by
Method 8260:
Bromobenzene 1-Chlorohexane
n-Butylbenzene 2-Chlorotoluene
sec-Butyl benzene 4-Chlorotoluene
tert-Butylbenzene Crotonaldehyde
Chloroacetonitrile Dibromofluoromethane
1-Chlorobutane cis-l,2-Dichloroethene
1,3-Dichloropropane Methyl-t-butyl ether
2,2-Dichloropropane Pentafluorobenzene
1,1-Dichloropropene n-Propylbenzene
Fluorobenzene 1,2,3-Trichlorobenzene
p-1sopropyltoluene 1,2,4-Trimethyl benzene
Methyl acrylate 1,3,5-Trimethylbenzene
1.3 The estimated quantitation limit (EQL) of Method 8260 for an
individual compound is somewhat instrument dependent. Using standard quadrupole
instrumentation, limits should be approximately 5 M9/kg (wet weight) for
soil/sediment samples, 0.5 mg/kg (wet weight) for wastes, and 5 fj.g/1 for ground
water (see Table 3). Somewhat lower limits may be achieved using an ion trap
mass spectrometer or other instrumentation of improved design. No matter which
instrument is used, EQLs will be proportionately higher for sample extracts and
samples that require dilution or reduced sample size to avoid saturation of the
detector.
1.4 Method 8260 is based upon a purge-and-trap, gas chromatographic/mass
spectrometric (GC/MS) procedure. This method is restricted to use by, or under
the supervision of, analysts experienced in the use of purge-and-trap systems and
gas chromatograph/mass spectrometers, and skilled in the interpretation of mass
spectra and their use as a quantitative tool.
1.5 An additional method for sample introduction is direct injection.
This technique has been tested for the analysis of waste oil diluted with
hexadecane 1:1 (vol/vol) and may have application for the analysis of some
alcohols and aldehydes in aqueous samples.
2.0 SUMMARY OF METHOD
2.1 The volatile compounds are introduced into the gas chromatograph by
the purge-and-trap method or by direct injection (in limited applications).
Purged sample components are trapped in'a tube containing suitable sorbent
materials. When purging is complete, the sorbent tube is heated and backflushed
with helium to desorb trapped sample components. The analytes are desorbed
directly to a large bore capillary or cryofocussed on a capillary precolumn
before being flash evaporated to a narrow bore capillary for analysis. The
column is temperature programmed to separate the analytes which are then detected
with a mass spectrometer (MS) interfaced to the gas chromatograph. Wide bore
capillary columns require a jet separator, whereas narrow bore capillary columns
can be directly interfaced to the ion source.
8260A - 4 Revision 1
September 1994
-------
2.2 If the above sample introduction techniques are not applicable, a
portion of the sample is dispersed in solvent to dissolve the volatile organic
constituents. A portion of the solution is combined with organic-free reagent
water in the purge chamber. It is then analyzed by purge-and-trap GC/MS
following the normal water method.
2.3 Analytes eluted from the capillary column are introduced into the
mass spectrometer via a jet separator or a direct connection. Identification of
target analytes is accomplished by comparing their mass spectra with the electron
impact (or electron impact-like) spectra of authentic standards. Quantitation
is accomplished by comparing the response of a major (quantitation) ion relative
to an internal standard with a five-point calibration curve.
2.4 The method includes specific calibration and quality control steps
that replace the general requirements in Method 8000.
3.0 INTERFERENCES
3.1 Major contaminant sources are volatile materials in the laboratory
and impurities in the inert purging gas and in the sorbent trap. The use of non-
polytetrafluoroethylene (PTFE) thread sealants, plastic tubing, or flow
controllers with rubber components should be avoided since such materials out-gas
organic compounds which will be concentrated in the trap during the purge
operation. Analyses of calibration and reagent blanks provide information about
the presence of contaminants. When potential interfering peaks are noted in
blanks, the analyst should change the purge gas source and regenerate the
molecular sieve purge gas filter (Figure 1). Subtracting blank values from
sample results is not permitted. If reporting values not corrected for blanks
result in what the laboratory feels is a false positive for a sample, this should
be fully explained in text accompanying the uncorrected data.
3.2 Interfering contamination may occur when a sample containing low
concentrations of volatile organic compounds is analyzed immediately after a
sample containing high concentrations of volatile organic compounds. The
preventive technique is rinsing of the purging apparatus and sample syringes with
two portions of organic-free reagent water between samples. After analysis of
a sample containing high concentrations of volatile organic compounds, one or
more calibration blanks should be analyzed to check for cross contamination. For
samples containing large amounts of water soluble materials, suspended solids,
high boiling compounds or high concentrations of compounds being determined, it
may be necessary to wash the purging device with a soap solution, rinse it with
organic-free reagent water, and then dry the purging device in an oven at 105°C.
In extreme situations, the whole purge and "trap device may require dismantling
and cleaning. Screening of the samples prior to purge and trap GC/MS analysis
is highly recommended to prevent contamination of the system. This is especially
true for soil and waste samples. Screening may be accomplished with an automated
headspace technique or by Method 3820 (Hexadecane Extraction and Screening of
Purgeable Organics).
3.2.1 The low purging efficiency of many analytes from a 25 ml
sample often results in significant concentrations remaining in the sample
purge vessel after analysis. After removal of the analyzed sample aliquot
8260A - 5 Revision 1
September 1994
-------
and three rinses of the purge vessel with analyte free water, it is
required that the empty vessel be subjected to a heated purge cycle prior
to the analysis of another sample in the same purge vessel to reduce
sample to sample carryover.
3.3 Special precautions must be taken to analyze for methylene chloride.
The analytical and sample storage area should be isolated from all atmospheric
sources of methylene chloride. Otherwise random background levels will result.
Since methylene chloride will permeate through PTFE tubing, all gas
chromatography carrier gas lines and purge gas plumbing should be constructed
from stainless steel or copper tubing. Laboratory clothing worn by the analyst
should be clean since clothing previously exposed to methylene chloride fumes
during liquid/liquid extraction procedures can contribute to sample
contamination.
3.4 Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal into
the sample during shipment and storage. A trip blank prepared from organic-free
reagent water and carried through the sampling and handling protocol can serve
as a check on such contamination.
3.5 Use of sensitive mass spectrometers to achieve lower detection level
will increase the potential to detect laboratory contaminants as interferences.
3.6 Direct injection - Some contamination may be eliminated by baking out
the column between analyses. Changing the injector liner will reduce the
potential for cross-contamination. A portion of the analytical column may need
to be removed in the case of extreme contamination. Use of direct injection will
result in the need for more frequent instrument maintenance.
3.7 If hexadecane is added to samples or petroleum samples are analyzed,
some chromatographic peaks will elute after the target analytes. The oven
temperature program must include a post-analysis bake out period to ensure that
semi-volatile hydrocarbons are volatilized.
4.0 APPARATUS AND MATERIALS
4.1 Purge-and-trap device - aqueous samples, described in Method 5030.
4.2 Purge-and-trap device - solid samples, described in Method 5030.
4.3 Injection port liners (HP catalogue #18740-80200, or equivalent) are
modified for direct injection analysis by placing a 1-cm plug of pyrex wool
approximately 50-60 mm down the length
of the injection port towards the
oven. An 0.53 mm ID column is mounted septum so — eo o
1 cm into the liner from the oven side "^
of the injection port, according to
manufacturer's specifications. Modified Injector
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4.4 Gas chromatography/mass spectrometer/data system
4.4.1 Gas chromatograph - An analytical system complete with a
temperature-programmable gas chromatograph suitable for splitless
injection or interface to purge-and-trap apparatus. The system includes
all required accessories, including syringes, analytical columns, and
gases. The GC should be equipped with variable constant differential flow
controllers so that the column flow rate will remain constant throughout
desorption and temperature program operation. For some column
configurations, the column oven must be cooled to < 30°C, therefore, a
subambient oven controller may be required. The capillary column should
be directly coupled to the source.
4.4.1.1 Capillary precolumn interface when using cryogenic
cooling - This device interfaces the purge and trap concentrator to
the capillary gas chromatograph. The interface condenses the
desorbed sample components and focuses them into a narrow band on an
uncoated fused silica capillary precolumn. When the interface is
flash heated, the sample is transferred to the analytical capillary
column.
4.4.1.1.1 During the cryofocussing step, the
temperature of the fused silica in the interface is maintained
at -150°C under a stream of liquid nitrogen. After the
desorption period, the interface must be capable of rapid
heating to 250°C in 15 seconds or less to complete the
transfer of analytes.
4.4.2 Gas chromatographic columns
4.4.2.1 Column 1 - 60 m x 0.75 mm ID capillary column
coated with VOCOL (Supelco), 1.5 p,m film thickness, or equivalent.
4.4.2.2 Column 2 - 30 - 75 m x 0.53 mm ID capillary column
coated with DB-624 (J&W Scientific), Rtx-502.2 (RESTEK), or VOCOL
(Supelco), 3 /zm film thickness, or equivalent.
4.4.2.3 Column 3 - 30 m x 0.25 - 0.32 mm ID capillary
column coated with 95% dimethyl - 5% diphenyl polysiloxane (DB-5,
Rtx-5, SPB-5, or equivalent), 1 ^m film thickness.
4.4.2.4 Column 4 - 60 m x 0.32 mm ID capillary column
coated with DB-624 (J&W Scientific), 1.8 fj.m film thickness, or
equivalent.
4.4.3 Mass spectrometer - Capable of scanning from 35 to 300 amu
every 2 sec or less, using 70 volts (nominal) electron energy in the
electron impact ionization mode. The mass spectrometer must be capable of
producing a mass spectrum for p-Bromofluorobenzene (BFB) which meets all
of the criteria in Table 4 when 5-50 ng of the GC/MS tuning standard (BFB)
is injected through the GC. To ensure sufficient precision of mass
spectral data, the desirable MS scan rate allows acquisition of at least
five spectra while a sample component elutes from the GC.
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4.4.3.1 The ion trap mass spectrometer may be used if it
is capable of axial modulation to reduce ion-molecule reactions and
can produce electron impact-like spectra that match those in the
EPA/NIST Library. In an ion trap mass spectrometer, because ion-
molecule reactions with water and methanol may produce interferences
that coelute with chloromethane and chloroethane, the base peak for
both of these analytes will be at m/z 49. This ion should be used
as the quantitation ion in this case. The mass spectrometer must be
capable of producing a mass spectrum for BFB which meets all of the
criteria in Table 3 when 5 or 50 ng are introduced.
4.4.4 GC/MS interface - Two alternatives are used to interface the
GC to the mass spectrometer.
4.4.4.1 Direct coupling by inserting the column into the
mass spectrometer is generally used for 0.25-0.32 mm id columns.
4.4.4.2 A separator including an all-glass transfer line
and glass enrichment device or split interface is used with an
0.53 mm column.
4.4.4.3 Any enrichment device or transfer line can be used
if all of the performance specifications described in Sec. 8
(including acceptable calibration at 50 ng or less) can be achieved.
GC-to-MS interfaces constructed entirely of glass or of glass-lined
materials are recommended. Glass can be deactivated by silanizing
with dichlorodimethylsilane.
4.4.5 Data system - A computer system that allows the continuous
acquisition and storage on machine-readable media of all mass spectra
obtained throughout the duration of the chromatographic program must be
interfaced to the mass spectrometer. The computer must have software that
allows searching any GC/MS data file for ions of a specified mass and
plotting such ion abundances versus time or scan number. This type of
plot is defined as an Extracted Ion Current Profile (EICP). Software must
also be available that allows integrating the abundances in any EICP
between specified time or scan-number limits. The most recent version of
the EPA/NIST Mass Spectral Library should also be available.
4.5 Microsyringes - 10, 25, 100, 250, 500, and 1,000 /xL.
4.6 Syringe valve - Two-way, with Luer ends (three each), if applicable
to the purging device.
4.7 Syringes - 5, 10, or 25 ml, gas-tight with shutoff valve.
4.8 Balance - Analytical, 0.0001 g, and top-loading, 0.1 g.
4.9 Glass scintillation vials - 20 mL, with Teflon lined screw-caps or
glass culture tubes with Teflon lined screw-caps.
4.10 Vials - 2 mL, for GC autosampler.
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4.11 Disposable pipets - Pasteur.
4.12 Volumetric flasks, Class A - 10 ml and 100 ml, with ground-glass
stoppers.
4.13 Spatula - Stainless steel.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all inorganic reagents shall 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 ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Methanol, CH3OH - Pesticide quality or equivalent, demonstrated to
be free of analytes. Store apart from other solvents.
5.4 Reagent Hexadecane - Reagent hexadecane is defined as hexadecane in
which interference is not observed at the method detection limit of compounds of
interest.
5.4.1 In order to demonstrate that all interfering volatiles have
been removed from the hexadecane, a direct injection blank must be
analyzed.
5,5 Polyethylene glycol, H(OCH2CH2),,OH - Free of interferences at the
detection limit of the target analytes.
5.6 Hydrochloric acid (1:1 v/v), HC1 - Carefully add a measured volume
of concentrated HC1 to an equal volume of organic-free reagent water.
5.7 Stock solutions - Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standard solutions
in methanol, using assayed liquids or gases, as appropriate.
5.7.1 Place about 9.8 ml of methanol in a 10 ml tared ground-glass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes or until all alcohol-wetted surfaces have dried. Weigh
the flask to the nearest 0.0001 g.
5.7.2 Add the assayed reference material, as described below.
5.7.2.1 Liquids - Using a 100 /uL syringe, immediately add
two or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
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5.7.2.2 Gases - To prepare standards for any compounds
that boil below 30°C (e.g. bromomethane, chloroethane, chloromethane,
or vinyl chloride), fill a 5 mL valved gas-tight syringe with the
reference standard to the 5.0 ml mark. Lower the needle to 5 mm
above the methanol meniscus. Slowly introduce the reference standard
above the surface of the liquid. The heavy gas will rapidly dissolve
in the methanol. Standards may also be prepared by using a lecture
bottle equipped with a Hamilton Lecture Bottle Septum (#86600).
Attach Teflon tubing to the side arm relief valve and direct a gentle
stream of gas into the methanol meniscus.
5.7.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in milligrams per
liter (mg/L) from the net gain in weight. When compound purity is assayed
to be 96% or greater, the weight may be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.7.4 Transfer the stock standard solution into a bottle with a
Teflon lined screw-cap. Store, with minimal headspace, at -10°C to -20°C
and protect from light.
5.7.5 Prepare fresh standards for gases weekly or sooner if
comparison with check standards indicates a problem. Reactive compounds
such as 2-chloroethyl vinyl ether and styrene may need to be prepared more
frequently. All other standards must be replaced after six months, or
sooner if comparison with check standards indicates a problem. Both gas
and liquid standards must be monitored closely by comparison to the
initial calibration curve and by comparison to QC check standards. It may
be necessary to replace the standards more frequently if either check
exceeds a 20% drift.
5.7.6 Optionally calibration using a certified gaseous mixture can
be accomplished daily utilizing commercially available gaseous analyte
mixture of bromomethane, chloromethane, chloroethane, vinyl chloride,
dichlorodifluoromethane and trichlorofluoromethane in nitrogen. These
mixtures of documented quality are stable for as long as six months
without refrigeration. (VOA-CYL III, RESTEK Corporation, Cat. #20194 or
equivalent).
5.7.6.1 Preparation of Calibration Standards From a Gas
Mixture
5.7.6.1.1 Before removing the cylinder shipping cap,
be sure the valve is completely closed (turn clockwise). The
contents are under pressure and should be used in a well-
ventilated area.
5.7.6.1.2 Wrap the pipe thread end of the Luer fitting
with Teflon tape. Remove the shipping cap from the cylinder
and replace it with the Luer fitting.
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5.7.6.1.3 Transfer half the working standard containing
other analytes, internal standards, and surrogates to the
purge apparatus.
5.7.6.1.4 Purge the Luer fitting and stem on the gas
cylinder prior to sample removal using the following sequence:
a) Connect either the 100 /uL or 500 jxL Luer syringe
to the inlet fitting of the cylinder.
b) Make sure the on/off valve on the syringe is in
the open position.
c) Slowly open the valve on the cylinder and
withdraw a full syringe volume.
d) Be sure to close the valve on the cylinder before
you withdraw the syringe from the Luer fitting.
e) Expel the gas from the syringe into a well-
ventilated area.
f) Repeat steps a through e one more time to fully
purge the fitting.
5.7.6.1.5 Once the fitting and stem have been purged,
quickly withdraw the volume of gas you require using steps
5.6.6.1.4(a) through (d). Be sure to close the valve on the
cylinder and syringe before you withdraw the syringe from the
Luer fitting.
5.7.6.1.6 Open the syringe on/off valve for 5 seconds
to reduce the syringe pressure to atmospheric pressure. The
pressure in the cylinder is -30 psi.
5.7.6.1.7 The gas mixture should be quickly transferred
into the reagent water through the female Luer fitting located
above the purging vessel.
NOTE: Make sure the arrow on the 4-way valve is
pointing toward the female Luer fitting when
transferring the sample from the syringe. Be sure
to switch the 4-way valve back to the closed
position before removing the syringe from the
Luer fitting.
5.7.6.1.8 Transfer the remaining half of the working
standard into the purging vessel. This procedure insures that
the total volume of gas mix is flushed into the purging
vessel, with none remaining in the valve or lines.
5.7.6.1.9 Concentration of each compound in the
cylinder is typically 0.0025
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5.7.6.1.10 The fol 1 owi ng are the recommended gas vol umes
spiked into 5 ml of water to produce a typical 5-point
calibration:
Gas Calibration
Volume Concentration
40 ni 20 M9/L
100 Hi 50 M9/L
200 fti 100 M9/L
300 ML 150 M9/L
400 ML 200 M9/L
5.7.6.1.11 The following are the recommended gas volumes
spiked into 25 ml of water to produce a typical 5-point
calibration:
Gas Calibration
Volume Concentration
10 /LtL 1 M9/L
20 ML 2 M9/L
50 ML 5 M9/L
100 ML 10 M9/L
250 ML 25 M9/L
5.8 Secondary dilution standards - Using stock standard solutions,
prepare in methanol, secondary dilution standards containing the compounds of
interest, either singly or mixed together. Secondary dilution standards must be
stored with minimal headspace and should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them. Store in a vial with no headspace for one week only.
5.9 Surrogate standards - The surrogates recommended are toluene-d8,
4-bromofluorobenzene, l,2-dichloroethane-d4, and dibromofluoromethane. Other
compounds may be used as surrogates, depending upon the analysis requirements.
A stock surrogate solution in methanol should be prepared as described above, and
a surrogate standard spiking solution should be prepared from the stock at a
concentration of 50-250 M9/10 niL in methanol. Each water sample undergoing
GC/MS analysis must be spiked with 10 ML of the surrogate spiking solution prior
to analysis.
5.9.1 If a more sensitive mass spectrometer is employed to achieve
lower detection levels, more dilute surrogate solutions may be required.
5.10 Internal standards - The recommended internal standards are
fluorobenzene, chlorobenzene-d5, and l,4-dichlorobenzene-d4. Other compounds may
be used as internal standards as long as they have retention times similar to the
compounds being detected by GC/MS. Prepare internal standard stock and secondary
dilution standards in methanol using the procedures described in Sees. 5.7 and
5.8. It is recommended that the secondary dilution standard should be prepared
at a concentration of 25 mg/L of each internal standard compound. Addition of
10 ML of this standard to 5.0 ml of sample or calibration standard would be the
equivalent of 50 jtzg/L.
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5.10.1 If a more sensitive mass spectrometer is employed to
achieve lower detection levels, more dilute internal standard solutions
may be required. Area counts of the internal standard peaks should be
between 50-200% of the area of the target analytes in the mid-point
calibration analysis.
5.11 4-Bromofluorobenzene (BFB) standard - A standard solution containing
25 ng//iL of BFB in methanol should be prepared.
5.11.1 If a more sensitive mass spectrometer is employed to
achieve lower detection levels, a more dilute BFB standard solution may be
required.
5.12 Calibration standards - Calibration standards at a minimum of five
concentrations should be prepared from the secondary dilution of stock standards
(see Sees. 5.7 and 5.8). Prepare these solutions in organic-free reagent water.
One of the concentrations should be at a concentration near, but above, the
method detection limit. The remaining concentrations should correspond to the
expected range of concentrations found in real samples but should not exceed the
working range of the GC/MS system. Each standard should contain each analyte for
detection by this method. It is EPA's intent that all target analytes for a
particular analysis be included in the calibration standard(s). However, these
target analytes may not include the entire List of Analytes (Sec. 1.1) for which
the method has been demonstrated. However, the laboratory shall not report a
quantitative result for a target analyte that was not included in the calibration
standard(s). Calibration standards must be prepared daily.
5.13 Matrix spiking standards - Matrix spiking standards should be
prepared from volatile organic compounds which will be representative of the
compounds being investigated. At a minimum, the matrix spike should include 1,1-
dichloroethene, trichloroethene, chlorobenzene, toluene, and benzene. It is
desirable to perform a matrix spike using compounds found in samples. Some
permits may require spiking specific compounds of interest, especially if they
are polar and would not be represented by the above listed compounds. The
standard should be prepared in methanol, with each compound present at a
concentration of 250 jug/10.0 ml.
5.13.1 If a more sensitive mass spectrometer is employed to
achieve lower detection levels, more dilute matrix spiking solutions may
be required.
5.14 Great care must be taken to maintain the integrity of all standard
solutions. It is recommended all standards in methanol be stored at -10°C to
-20°C in amber bottles with Teflon lined screw-caps.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes, Sec.
4.1.
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7.0 PROCEDURE
7.1 Three alternate methods are provided for sample introduction. All
internal standards, surrogates, and matrix spikes (when applicable) must be added
to samples before introduction.
7.1.1 Direct injection - in very limited application, (e.g.,
volatiles in waste oil or aqueous process wastes) direct injection of
aqueous samples or samples diluted according to Method 3585 may be
appropriate. Direct injection has been used for the analysis of volatiles
in waste oil (diluted 1:1 with hexadecane) and for determining if the
sample is ignitable (aqueous injection, Methods 1010 or 1020). Direct
injection is only permitted for the determination of volatiles at the
toxicity characteristic (TC) regulatory limits, at concentrations in
excess of 10,000 M9/U or for water-soluble compounds that do not purge.
7.1.2 Purge-and-trap for aqueous samples, see Method 5030 for
details.
7.1.3 Purge-and-trap for solid samples, see Method 5030 for details.
7.2 Recommended Chromatographic conditions
7.2.1 General:
Injector temperature: 200-225°C
Transfer line temperature: 250-300°C
7.2.2 Column 1 (A sample chromatogram is presented in Figure 5)
Carrier gas (He) flow rate: 15 mL/min
Initial temperature: 10°C, hold for 5 minutes
Temperature program: 6°C/min to 160°C
Final temperature: 160°C, hold until all expected
compounds have eluted.
7.2.3 Column 2, Cryogenic cooling (A sample chromatogram is
presented in Figure 6)
Carrier gas (He) flow rate: 15 mL/min
Initial temperature: 10°C, hold for 5 minutes
Temperature program: 6°C/min to 160°C
Final temperature: 160°C, hold until all expected
compounds have eluted.
7.2.4 Column 2, Non-cryogenic cooling (A sample chromatogram is
presented in Figure 7). It is recommended that carrier gas flow and split
and make-up gases be set using performance of standards as guidance. Set
the carrier gas head pressure to <= 10 psi and the split to « 30 mL/min.
Optimize the make-up gas flow for the separator (approximately 30 mL/min)
by injecting BFB, and determining the optimum response when varying the
make-up gas. This will require several injections of BFB. Next, make
several injections of the volatile working standard with all analytes of
8260A - 14 Revision 1
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interest. Adjust the carrier and split to provide optimum chromatography
and response. This is an especially critical adjustment for the volatile
gas analytes. The head pressure should optimize between 8-12 psi and the
split between 20-60 mL/min. The use of the splitter is important to
minimize the effect of water on analyte response, to allow the use of a
larger volume of helium during trap desorption, and to slow column flow.
Initial temperature: 45°C, hold for 2 minutes
Temperature program: 8°C/min to 200°C
Final temperature: 200°C, hold for 6 minutes.
A trap preheated to 150°C prior to trap desorption is required to
provide adequate chromatography of the gas analytes.
7.2.5 Column 3 (A sample chromatogram is presented in Figure 8)
Carrier gas (He) flow rate: 4 mL/min
Initial temperature: 10°C, hold for 5 minutes
Temperature program: 6°C/min to 70°C, then 15°C/min
to 145°C
Final temperature: 145°C, hold until all expected
compounds have eluted.
7.2.6 Direct injection - Column 2
Carrier gas (He) flow rate: 4 mL/min
Column: J&W DB-624, 70m x 0.53 mm
Initial temperature: 40°C, hold for 3 minutes
Temperature program: 8°C/min
Final temperature: 260°C, hold until all expected
compounds have eluted.
Column Bake out (direct inj): 75 minutes
Injector temperature: 200-225°C
Transfer line temperature: 250-300°C
7.2.7 Direct Split Interface - Column 4
Carrier gas (He) flow rate: 1.5 mL/min
Initial temperature: 35°C, hold for 2 minutes
Temperature program: 4°C/min to 50°C
10'C/min to 220'C
Final temperature: 220°C, hold until all expected
compounds have eluted
Split ratio: 100:1
Injector temperature: 125°C
7.3 Initial calibration - the recommended MS operating conditions
Mass range: 35-260 amu
Scan time: 0.6-2 sec/scan
Source temperature: According to manufacturer's specifications
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Ion trap only: Set axial modulation, manifold temperature,
and emission current to manufacturer's
recommendations
7.3.1 Each GC/MS system must be hardware-tuned to meet the criteria
in Table 4 for a 5-50 ng injection or purging of 4-bromofluorobenzene
(2 IJ.L injection of the BFB standard). Analyses must not begin until these
criteria are met.
7.3.2 Set up the purge-and-trap system as outlined in Method 5030 if
purge-and-trap analysis is to be utilized. A set of at least five
calibration standards containing the method analytes is needed. One
calibration standard should contain each analyte at a concentration
approaching but greater than the method detection limit (Table 1) for that
compound; the other calibration standards should contain analytes at
concentrations that define the range of the method. Calibration should be
done using the sample introduction technique that will be used for
samples. For Method 5030, the purging efficiency for 5 ml of water is
greater than for 25 mL. Therefore, develop the standard curve with
whichever volume of sample that will be analyzed.
7.3.2.1 To prepare a calibration standard for purge-and-
trap or aqueous direct injection, add an appropriate volume of a
secondary dilution standard solution to an aliquot of organic-free
reagent water in a volumetric flask. Use a microsyringe and rapidly
inject the alcoholic standard into the expanded area of the filled
volumetric flask. Remove the needle as quickly as possible after
injection. Mix by inverting the flask three times only. Discard the
contents contained in the neck of the flask. Aqueous standards are
not stable and should be prepared daily. Transfer 5.0 ml (or 25 ml
if lower detection limits are required) of each standard to a gas
tight syringe along with 10 /xL of internal standard. Then transfer
the contents to a purging device or syringe. Perform purge-and-trap
or direct injection as outlined in Method 5030.
7.3.2.2 To prepare a calibration standard for direct
injection analysis of oil, dilute standards in hexadecane.
7.3.3 Tabulate the area response of the characteristic ions (see
Table 5) against concentration for each compound and each internal
standard. Calculate response factors (RF) for each compound relative to
one of the internal standards. The internal standard selected for the
calculation of the RF for a compound should be the internal standard that
has a retention time closest to the compound being measured (Sec. 7.6.2).
The RF is calculated as follows:
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RF = (AxCis)/(AisCx)
where:
Ax = Area of the characteristic ion for the compound being
measured.
Ais = Area of the characteristic ion for the specific
internal standard.
Cjs = Concentration of the specific internal standard.
Cx = Concentration of the compound being measured.
7.3.4 The average RF must be calculated and recorded for each
compound using the five RF values calculated for each compound from the
initial (5-point) calibration curve. A system performance check should be
made before this calibration curve is used. Five compounds (the System
Performance Check Compounds, or SPCCs) are checked for a minimum average
relative response factor. These compounds are chloromethane; 1,1-
dichloroethane; bromoform; 1,1,2,2-tetrachloroethane; and chlorobenzene.
These compounds are used to check compound instability and to check for
degradation caused by contaminated lines or active sites in the system.
Examples of these occurrences are:
7.3.4.1 Chloromethane - This compound is the most likely
compound to be lost if the purge flow is too fast.
7.3.4.2 Bromoform - This compound is one of the compounds
most likely to be purged very poorly if the purge flow is too slow.
Cold spots and/or active sites in the transfer lines may adversely
affect response. Response of the quantitation ion (m/z 173) is
directly affected by the tuning of BFB at ions m/z 174/176.
Increasing the m/z 174/176 ratio relative to m/z 95 may improve
bromoform response.
7.3.4.3 Tetrachloroethane and 1,1-dichloroethane - These
compounds are degraded by contaminated transfer lines in purge-and-
trap systems and/or active sites in trapping materials.
7.3.5 Using the RFs from the initial calibration, calculate and
record the percent relative standard deviation (%RSD) for all compounds.
The percent RSD is calculated as follows:
% RSD = -JH. x 100%
RFX
where:
RSD = Relative standard deviation.
RFX = mean of 5 initial RFs for a compound.
SD = standard deviation of the 5 initial RFs for a compound.
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SD =
A (RFi-RF):
n-l
where:
RFi = RF for each of the 5 calibration levels
N = number of RF values (i.e., 5)
The percent relative standard deviation should be less than 15% for
each compound. However, the %RSD for each individual Calibration Check
Compound (CCC) must be less than 30%. The CCCs are:
1,1-Dichloroethene,
Chloroform,
1,2-Dichloropropane,
Toluene,
Ethyl benzene, and
Vinyl chloride.
7.3.5.1 If a %RSD greater than 30 percent is measured for
any CCC, then corrective action to eliminate a system leak and/or
column reactive sites is required before reattempting calibration.
7.3.6 Linearity - If the %RSD of any compound is 15% or less, then
the relative response factor is assumed to be constant over the
calibration range, and the average relative response factor may be used
for quantitation.
7.3.6.1 If the %RSD of any compound is greater than 15%,
construct calibration curves of area ratio (A/Ais) versus
concentration using first or higher order regression fit of the five
calibration points. The analyst should select the regression order
which introduces the least calibration error into the quantitation.
The use of calibration curves is a recommended alternative to average
response factor calibration (Sec. 7.6.2.4), and a useful diagnostic
of standard preparation accuracy and absorption activity in the
chromatographic system.
7.3.7 These curves are verified each shift by purging a performance
standard. Recalibration is required only if calibration and on-going
performance criteria cannot be met.
7.4 GC/MS calibration verification
7.4.1 Prior to the analysis of samples, inject or purge 5-50 ng of
the 4-bromofluorobenzene standard following Method 5030. The resultant
mass spectra for the BFB must meet all of the criteria given in Table 4
before sample analysis begins. These criteria must be demonstrated each
12-hour shift.
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7.4.2 The initial calibration curve (Sec. 7.3) for each compound of
interest must be checked and verified once every 12 hours during analysis
with the introduction technique used for samples. This is accomplished by
analyzing a calibration standard that is at a concentration near the
midpoint concentration for the working range of the GC/MS by checking the
SPCC and CCC.
7.4.3 System Performance Check Compounds (SPCCs) - A system
performance check must be made each 12 hours. If the SPCC criteria are
met, a comparison of relative response factors is made for all compounds.
This is the same check that is applied during the initial calibration. If
the minimum relative response factors are not met, the system must be
evaluated, and corrective action must be taken before sample analysis
begins. Some possible problems are standard mixture degradation,
injection port inlet contamination, contamination at the front end of the
analytical column, and active sites in the column or chromatographic
system.
7.4.3.1 The minimum relative response factor for volatile
SPCCs are as follows:
Chloromethane 0.10
1,1-Dichloroethane 0.10
Bromoform >0.10
Chlorobenzene 0.30
1,1,2,2-Tetrachloroethane 0.30
7.4.4 Calibration Check Compounds (CCCs) - After the system
performance check is met, CCCs listed in Sec. 7.3.5 are used to check the
validity of the initial calibration.
Calculate the percent drift using the following equation:
% Drift = (C, - CC)/C, x 100
where:
C, = Calibration Check Compound standard concentration.
Cc = Measured concentration using selected quantitation method.
If the percent drift for each CCC is less than 20%, the initial
calibration is assumed to be valid. If the criterion is not met (> 20%
drift), for any one CCC, corrective action must be taken. Problems
similar to those listed under SPCCs could affect this criterion. If no
source of the problem can be determined after corrective action has been
taken, a new five point calibration MUST be generated. This criterion
MUST be met before quantitative sample analysis begins. If the CCCs are
not required analytes by the permit, then all required analytes must meet
the 20% drift criterion.
7.4.5 The internal standard responses and retention times in the
check calibration standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard changes
8260A - 19 Revision 1
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by more than 30 seconds from the last calibration check (12 hours), the
chromatographic system must be inspected for malfunctions and corrections
must be made, as required. If the EICP area for any of the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration check standard, the mass spectrometer must be inspected for
malfunctions and corrections must be made, as appropriate. When
corrections are made, reanalysis of samples analyzed while the system was
malfunctioning is necessary.
7.5 GC/MS analysis
7.5.1 It is highly recommended that the extract be screened on a
headspace-GC/FID (Methods 3810/8015), headspace-GC/PID/ELCD (Methods
3810/8021), or waste dilution-GC/PID/ELCD (Methods 3585/8021) using the
same type of capillary column. This will minimize contamination of the
GC/MS system from unexpectedly high concentrations of organic compounds.
Use of screening is particularly important when this method is used to
achieve low detection levels.
7.5.2 All samples and standard solutions must be allowed to warm to
ambient temperature before analysis. Set up the purge-and-trap system as
outlined in Method 5030 if purge-and-trap introduction will be used.
7.5.3 BFB tuning criteria and GC/MS calibration verification
criteria must be met before analyzing samples.
7.5.3.1 Remove the plunger from a 5 ml syringe and attach
a closed syringe valve. If lower detection limits are required, use
a 25 ml syringe. Open the sample or standard bottle, which has been
allowed to come to ambient temperature, and carefully pour the sample
into the syringe barrel to just short of overflowing. Replace the
syringe plunger and compress the sample. Open the syringe valve and
vent any residual air while adjusting the sample volume to 5.0 ml.
7.5.4 The process of taking an aliquot destroys the validity of
aqueous and soil samples for future analysis; therefore, if there is only
one VGA vial, the analyst should prepare a second aliquot for analysis at
this time to protect against possible loss of sample integrity. This
second sample is maintained only until such time when the analyst has
determined that the first sample has been analyzed properly. For aqueous
samples, filling one 20 ml syringe would require the use of only one
syringe. If a second analysis is needed from a syringe, it must be
analyzed within 24 hours. Care must be taken to prevent air from leaking
into the syringe.
7.5.4.1 The following procedure is appropriate for
diluting aqueous purgeable samples. All steps must be performed
without delays until the diluted sample is in a gas-tight syringe.
7.5.4.1.1 Dilutions may be made in volumetric flasks
(10 to 100 ml). Select the volumetric flask that will allow
for the necessary dilution. Intermediate dilutions may be
necessary for extremely large dilutions.
8260A - 20 Revision 1
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7.5.4.1.2 Calculate the approximate volume of organic-
free reagent water to be added to the volumetric flask
selected and add slightly less than this quantity of organic-
free reagent water to the flask.
7.5.4.1.3 Inject the proper aliquot of sample from the
syringe into the flask. Aliquots of less than 1 ml are not
recommended. Dilute the sample to the mark with organic-free
reagent water. Cap the flask, invert, and shake three times.
Repeat above procedure for additional dilutions.
7.5.4.1.4 Fill a 5 ml syringe with the diluted sample.
7.5.4.2 Compositing aqueous samples prior to GC/MS
analysis
7.5.4.2.1 Add 5 ml or equal larger amounts of each
sample (up to 5 samples are allowed) to a 25 mL glass syringe.
Special precautions must be made to maintain zero headspace in
the syringe.
7.5.4.2.2 The samples must be cooled at 4°C during this
step to minimize volatilization losses.
7.5.4.2.3 Mix well and draw out a 5 ml aliquot for
analysis.
7.5.4.2.4 Follow sample introduction, purging, and
desorption steps described in Method 5030.
7.5.4.2.5 If less than five samples are used for
compositing, a proportionately smaller syringe may be used
unless a 25 ml sample is to be purged.
7.5.5 Add 10.0 /xL of surrogate spiking solution and 10 p.1 of
internal standard spiking solution to each sample. The surrogate and
internal standards may be mixed and added as a single spiking solution.
The addition of 10 /j,l of the surrogate spiking solution to 5 ml of sample
is equivalent to a concentration of 50 /ig/L of each surrogate standard.
The addition of 10 jul of the surrogate spiking solution to 5 g of sample
is equivalent to a concentration of 50 M9/kg of each surrogate standard.
7.5.5.1 If a more sensitive mass spectrometer is employed
to achieve lower detection levels, more dilute surrogate and internal
standard solutions may be required.
7.5.6 Perform purge-and-trap or direct injection by Method 5030. If
the initial analysis of sample or a dilution of the sample has a
concentration of analytes that exceeds the initial calibration range, the
sample must be reanalyzed at a higher dilution. Secondary ion
quantitation is allowed only when there are sample interferences with the
primary ion. When a sample is analyzed that has saturated ions from a
compound, this analysis must be followed by a blank organic-free reagent
8260A - 21 Revision 1
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water analysis. If the blank analysis is not free of interferences, the
system must be decontaminated. Sample analysis may not resume until the
blank analysis is demonstrated to be free of interferences.
7.5.6.1. All dilutions should keep the response of the
major constituents (previously saturated peaks) in the upper half of
the linear range of the curve. Proceed to Sees. 7.6.1 and 7.6.2 for
qualitative and quantitative analysis.
7.5.7 For matrix spike analysis, add 10 juL of the matrix spike
solution (Sec. 5.13) to the 5 ml of sample to be purged. Disregarding any
dilutions, this is equivalent to a concentration of 50 jzg/L of each matrix
spike standard.
7.6 Data interpretation
7.6.1 Qualitative analysis
7.6.1.1 The qualitative identification of compounds
determined by this method is based on retention time, and on
comparison of the sample mass spectrum, after background correction,
with characteristic ions in a reference mass spectrum. The reference
mass spectrum must be generated by the laboratory using the
conditions of this method. The characteristic ions from the
reference mass spectrum are defined to be the three ions of greatest
relative intensity, or any ions over 30% relative intensity if less
than three such ions occur in the reference spectrum. Compounds
should be identified as present when the criteria below are met.
7.6.1.1.1 The intensities of the characteristic ions
of a compound maximize in the same scan or within one scan of
each other. Selection of a peak by a data system target
compound search routine where the search is based on the
presence of a target chromatographic peak containing ions
specific for the target compound at a compound-specific
retention time will be accepted as meeting this criterion.
7.6.1.1.2 The RRT of the sample component is within
± 0.06 RRT units of the RRT of the standard component.
7.6.1.1.3 The relative intensities of the
characteristic ions agree within 30% of the relative
intensities of these ions in the reference spectrum.
(Example: For an ion' with an abundance of 50% in the
reference spectrum, the corresponding abundance in a sample
spectrum can range between 20% and 80%.)
7.6.1.1.4 Structural isomers that produce very similar
mass spectra should be identified as individual isomers if
they have sufficiently different GC retention times.
Sufficient GC resolution is achieved if the height of the
valley between two isomer peaks is less than 25% of the sum of
8260A - 22 Revision 1
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the two peak heights. Otherwise, structural isomers are
identified as isomeric pairs.
7.6.1.1.5 Identification is hampered when sample
components are not resolved chromatographically and produce
mass spectra containing ions contributed by more than one
analyte. When gas chromatographic peaks obviously represent
more than one sample component (i.e., a broadened peak with
shoulder(s) or a valley between two or more maxima),
appropriate selection of analyte spectra and background
spectra is important. Examination of extracted ion current
profiles of appropriate ions can aid in the selection of
spectra, and in qualitative identification of compounds. When
analytes coelute (i.e., only one chromatographic peak is
apparent), the identification criteria can be met, but each
analyte spectrum will contain extraneous ions contributed by
the coeluting compound.
7.6.1.2 For samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the type of analyses
being conducted. Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should
be present in the sample spectrum.
(2) The relative intensities of the major ions should agree
within + 20%. (Example: For an ion with an abundance
of 50% in the standard spectrum, the corresponding
sample ion abundance must be between 30 and 70%).
(3) Molecular ions present in the reference spectrum should
be present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible
background contamination or presence of coeluting
compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible
subtraction from' the sample spectrum because of
background contamination or coeluting peaks. Data
system library reduction programs can sometimes create
these discrepancies.
Computer generated library search routines should not use
normalization routines that would misrepresent the library or unknown
spectra when compared to each other. Only after visual comparison
of sample with the nearest library searches will the mass spectral
interpretation specialist assign a tentative identification.
8260A - 23 Revision 1
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7.6.2 Quantitative analysis
7.6.2.1 When a compound has been identified, the
quantitation of that compound will be based on the integrated
abundance from the EICP of the primary characteristic ion.
Quantitation will take place using the internal standard technique.
The internal standard used shall be the one nearest the retention
time of that of a given analyte.
7.6.2.2 When MS response is linear and passes through the
origin, calculate the concentration of each identified analyte in the
sample as follows:
Water
(AJ(IS)
concentration (jug/L) = —
(Ais)(RF)(V0)
where:
Ax = Area of characteristic ion for compound being
measured.
Is = Amount of internal standard injected (ng).
Ais = Area of characteristic ion for the internal
standard.
RF = Mean relative response factor for compound being
measured.
V0 = Volume of water purged (mL), taking into
consideration any dilutions made.
Sediment/Soil Sludge (on a dry-weight basis) and Waste
(normally on a wet-weight basis)
(AJd.MV.)
concentration (M9/kg) =
(A,J(RF)(V,)(WS)(D)
where:
Ax, Is, Ais, RF, = Same as for water.
Vt = Volume of total extract (p.1) (use 10,000 fj.1 or a
factor of this when dilutions are made).
V| = Volume of extract added (/zL) for purging.
Ws = Weight of sample extracted or purged (g).
D = % dry weight of sample/100, or 1 for a wet-weight
basis.
7.6.2.3 Where appl icable, an estimate of concentration for
noncalibrated components in the sample should be made. The formulae
given above should be used with the following modifications: The
areas Ax and Ais should be from the total ion chromatograms, and the
RF for the compound should be assumed to be 1. The concentration
8260A - 24 Revision 1
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obtained should be reported indicating (1) that the value is an
estimate and (2) which internal standard was used to determine
concentration. Use the nearest internal standard free of
interferences.
7.6.2.4 Alternatively, the regression line fitted to the
initial calibration (Sec. 7.3.6.1) may be used for determination of
analyte concentration.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 8000 for general quality control
procedures.
8.2 Additional required instrument QC is found in the Sees. 7.3 and 7.4:
8.2.1 The GC/MS system must be tuned to meet the BFB specifications.
8.2.2 There must be an initial calibration of the GC/MS system
8.2.3 The GC/MS system must meet the SPCC criteria and the CCC
criteria, each 12 hours.
8.3 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.3.1 A quality control (QC) reference sample concentrate is
required containing each analyte at a concentration of 10 mg/L or less in
methanol. The QC reference sample concentrate may be prepared from pure
standard materials or purchased as certified solutions. If prepared by
the laboratory, the QC reference sample concentrate must be made using
stock standards prepared independently from those used for calibration.
8.3.2 Prepare a QC reference sample to contain 20 /ug/L or less of
each analyte by adding 200 /uL of QC reference sample concentrate to 100 mL
of organic-free reagent water.
8.3.3 Four 5-mL aliquots of the well mixed QC reference sample are
analyzed according to the method beginning in Sec. 7.5.1.
8.3.4 Calculate the average recovery (x) in /Ltg/L, and the standard
deviation of the recovery (s) in M9/U for each analyte using the four
results.
8.3.5 Tables 7 and 8 provide single laboratory recovery and
precision data obtained for the method analytes from water. Similar
results from dosed water should be expected by any experienced laboratory.
Compare s and x (Sec. 8.3.4) for each analyte to the single laboratory
recovery and precision data. Results are comparable if the calculated
standard deviation of the recovery does not exceed 2.6 times the single
laboratory RSD or 20%, whichever is greater, and the mean recovery lies
within the interval x ± 3s or x ± 30%, whichever is greater.
8260A - 25 Revision 1
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NOTE: The large number of analytes in Tables 7 and 8 present a
substantial probability that one or more will fail at least
one of the acceptance criteria when all analytes of a given
method are determined.
8.3.6 When one or more of the analytes tested are not comparable to
the data in Table 6 or 7, the analyst must proceed according to Sec.
8.3.6.1 or 8.3.6.2.
8.3.6.1 Locate and correct the source of the problem and
repeat the test for all analytes beginning with Sec. 8.3.2.
8.3.6.2 Beginning with Sec. 8.3.2, repeat the test only
for those analytes that are not comparable. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Sec.
8.3.2.
8.4 For aqueous and soil matrices, laboratory established surrogate
control limits should be compared with the control limits listed in Table 8.
8.4.1 If recovery is not within limits, the following procedures are
required.
8.4.1.1 Check to be sure that there are no errors in the
calculations, surrogate solutions or internal standards. If errors
are found, recalculate the data accordingly.
8.4.1.2 Check instrument performance. If an instrument
performance problem is identified, correct the problem and re-analyze
the extract.
8.4,1.3 If no problem is found, re-extract and re-analyze
the sample.
8.4.1.4 If, upon re-analysis, the recovery is again not
within limits, flag the data as "estimated concentration".
8.4.2 At a minimum, each laboratory should update surrogate recovery
limits on a matrix-by-matrix basis, annually.
9.0 METHOD PERFORMANCE
9.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero. The MDL actually achieved in a given
analysis will vary depending on instrument sensitivity and matrix effects.
9.2 This method has been tested in a single laboratory using spiked
water. Using a wide-bore capillary column, water was spiked at concentrations
between 0.5 and 10 ng/l. Single laboratory accuracy and precision data are
8260A - 26 Revision 1
September 1994
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presented for the method analytes in Table 6. Calculated MDLs are presented in
Table 1.
9.3 The method was tested using water spiked at 0.1 to 0.5 ng/l and
analyzed on a cryofocussed narrow-bore column. The accuracy and precision data
for these compounds are presented in Table 7. MDL values were also calculated
from these data and are presented in Table 2.
9.4 Direct injection has been used for the analysis of waste motor oil
samples using a wide-bore column. The accuracy and precision data for these
compounds are presented in Table 10.
10.0 REFERENCES
1. Methods for the Determination of Organic Compounds in Finished Drinking
Water and Raw Source Water Method 524.2; U.S. Environmental Protection
Agency. Office of Research Development, Environmental Monitoring and
Support Laboratory, Cincinnati, OH 1986.
2. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
3. Bellar, T.A.; J.J. Lichtenberg. J. Amer. Water Works Assoc. 1974, 66(12),
739-744.
4. Bellar, T.A.; J.J. Lichtenberg. "Semi -Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds"; in Van Hall, Ed.; Measurement of Organic Pollutants in Water
and Wastewater, ASTM STP 686, pp 108-129, 1979.
5. Budde, W.L.; J.W. Eichelberger. "Performance Tests for the Evaluation of
Computerized Gas Chromatography/Mass Spectrometry Equipment and
Laboratories"; U.S. Environmental Protection Agency. Environmental
Monitoring and Support Laboratory, Cincinnati, OH 45268, April 1980; EPA-
600/4-79-020.
6. Eichelberger, J.W.; L.E. Harris; W.L. Budde. "Reference Compound to
Calibrate Ion Abundance Measurement in Gas Chromatography-Mass
Spectrometry Systems"; Analytical Chemistry 1975, 47, 995-1000.
7. Olynyk, P.; W.L. Budde; J.W. Eichelberger. "Method Detection Limit for
Methods 624 and 625"; Unpublished report, October 1980.
8. Non Cryogenic Temperatures Program and Chromatogram, Private
Communications; Myron Stephenson and Frank Allen, EPA Region IV
Laboratory, Athens, GA.
9. Marsden, P.; C.L. Helms, B.N. Colby. "Analysis of Volatiles in Waste Oil";
report for B. Lesnik, OSW/EPA under EPA contract 68-W9-001, 6/92.
8260A - 27 Revision 1
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10. Methods for the Determination of Organic Compounds in Drinking Water,
Supplement II M6th_o_d_524.2; U.S. Environmental Protection Agency. Office
of Research and Development, Environmental Monitoring Systems Laboratory,
Cincinnati, OH 1992.
8260A - 28 Revision 1
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TABLE 1.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL)
FOR VOLATILE ORGANIC COMPOUNDS ON WIDE-BORE CAPILLARY COLUMNS
ANALYTE
RETENTION TIME
(minutes)
Column la Column 2° Column 2'
Di chl orodi f 1 uoromethane
Chloromethane
Vinyl Chloride
Bromomethane
Chloroethane
Tri chl orofl uoromethane
Acrolein
lodomethane
Acetonitrile
Carbon disulfide
Ally! chloride
Methyl ene chloride
1,1-Dichloroethene
Acetone
trans-l,2-Dichloroethene
Acrylonitrile
1,1-Dichloroethane
Vinyl acetate
2,2-Dichloropropane
2-Butanone
cis-l,2-Dichloroethene
Propionitrile
Chloroform
Bromochl oromethane
Methacrylonitrile
1,1,1-Trichloroethane
Carbon tetrachloride
1,1-Dichloropropene
Benzene
1,2-Dichloroethane
Trichloroethene
1,2-Dichloropropane
Bromodi chl oromethane
Dibromomethane
Methyl methacrylate
1,4-Dioxane
2-Chloroethyl vinyl ether
4-Methyl -2-pentanone
trans-l,3-Dichloropropene
Toluene
cis-l,3-Dichloropropene
1 , 1 , 2 -Tri chl oroethane
1.35
1.49
1.56
2.19
2.21
2.42
3.19
3.56
4.11
4.11
4.11
4.40
4.57
4.57
4.57
5.00
6.14
6.43
8.10
8.25
8.51
9.01
9.19
10.18
11.02
--
11.50
12.09
14.03
14.51
15.39
15.43
15.50
16.17
--
17.32
17.47
18.29
19.38
19.59
0.70
0.73
0.79
0.96
1.02
1.19
2.06
1.57
2.36
2.93
3.80
3.90
4.80
4.38
4.84
5.26
5.29
5.67
5.83
7.27
7.66
8.49
7.93
--
10.00
--
11.05
3.13
3.40
3.93
4.80
6.20
9.27
7.83
9.90
10.80
11.87
11.93
12.60
12.37
12.83
13.17
13.10
13.50
13.63
14.80
15.20
15.80
15.43
16.70
17.40
17.90
18.30
MDLd
(M9/L)
0.10
0.13
0.17
0.11
0.10
0.08
0.03
0.12
0.06
0.04
0.35
0.12
0.03
0.04
0.08
0.21
0.10
0.04
0.06
0.19
0.04
0.08
0.24
0.11
--
0.10
8260A - 29
Revision 1
September 1994
-------
TABLE 1.
(Continued)
ANALYTE
Ethyl methacrylate
2-Hexanone
Tetrachloroethene
1,3-Dichloropropane
Di bromochl oromethane
1,2-Dibromoethane
1-Chlorohexane
Chlorobenzene
1,1,1 , 2-Tetrachl oroethane
Ethyl benzene
p-Xylene
m-Xylene
o-Xylene
Styrene
Bromoform
Isopropyl benzene (Cumene)
cis-l,4-Dichloro-2-butene
1 , 1 , 2, 2-Tetrachl oroethane
Bromobenzene
1,2,3-Trichloropropane
n-Propyl benzene
2-Chlorotoluene
trans-l,4-Oichloro-2-butene
1, 3, 5 -Tri methyl benzene
4-Chlorotoluene
Pentachl oroethane
1, 2, 4-Trimethyl benzene
sec-Butyl benzene
tert-Butyl benzene
p- Isopropyl toluene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Benzyl chloride
n-Butyl benzene
1,2-Dichlorobenzene
1 ,2-Dibromo-3-chloropropane
1 ,2,4-Trichlorobenzene
Hexachl orobutadi ene
Naphthalene
1, 2, 3-Tri chlorobenzene
RETENTION TIME
Column 1"
20.01
20.30
20.26
20.51
21.19
21.52
--
23.17
23.36
23.38
23.54
23.54
25.16
25.30
26.23
26.37
27.12
27.29
27.46
27.55
27.58
28.19
28.26
28.31
28.33
29.41
29.47
30.25
30.59
30.59
30.56
31.22
32.00
32.23
32.31
35.30
38.19
38.57
39.05
40.01
(minutes)
Column 2"
11.15
11.31
11.85
11.83
13.29
13.01
13.33
13.39
13.69
13.68
14.52
14.60
14.88
15.46
16.35
15.86
16.23
16.41
16.42
16.90
16.72
17.70
18.09
17.57
18.52
18.14
18.39
19.49
19.17
21.08
23.08
23.68
23.52
24.18
Column 2'c
18.60
18.70
19.20
19.40
--
20.67
20.87
21.00
21.30
21.37
22.27
22.40
22.77
23.30
24.07
24.00
24.13
24.33
24.53
24.83
24.77
31.50
26.13
26.60
26.50
26.37
26.60
27.32
27.43
--
31.50
32.07
32.20
32.97
MDLd
(M9/L)
0.14
0.04
0.05
0.06
0.05
0.04
0.05
0.06
0.13
0.05
0.11
0.04
0.12
0.15
0.04
0.03
0.32
0.04
0.04
0.05
0.06
0.13
0.13
0.14
0.12
0.12
0.03
0.11
0.03
0.26
0.04
0.11
0.04
0.03
8260A - 30
Revision 1
September 1994
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TABLE 1.
(Continued)
ANALYTE RETENTION TIME MDLd
(minutes) (M9/U
Column 1"Column 2bColumn 2/c
INTERNAL STANDARDS/SURROGATES
1,4-Difluorobenzene
Chlorobenzene-d5
l,4-Dichlorobenzene-d4
4-Bromofl uorobenzene
1 , 2-Dichl orobenzene-d4
Dichloroethane-d4
Di bromof 1 uoromethane
Toluene-d8
Pentaf 1 uorobenzene
Fl uorobenzene
13.26
23.10
31.16
27.83
32.30
12.08
18.27
--
13.00
15.71 23.63
19.08 27.25
6.27 14.06
8 Column 1 - 60 meter x 0.75 mm ID VOCOL capillary. Hold at 10°C for 8 minutes,
then program to 180°C at 4%nn.
b Column 2-30 meter x 0.53 mm ID DB-624 wide-bore capillary using cryogenic
oven. Hold at 10°C for 5 minutes, then program to 160°C at 6°/min.
0 Column 2' - 30 meter x 0.53 mm ID DB-624 wide-bore capillary, cooling GC oven
to ambient temperatures. Hold at 10°C for 6 minutes, program to 70°C at
10°/min, program to 120°C at 5°/min, then program to 180°C at 8°/min.
d MDL based on a 25 mL sample volume.
8260A - 31 Revision 1
September 1994
-------
TABLE 2.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL)
FOR VOLATILE ORGANIC COMPOUNDS ON NARROW-BORE CAPILLARY COLUMNS
ANALYTE
RETENTION TIME
(minutes)
Column 3"
MDLb
Di chl orodi f 1 uoromethane
Chl oromethane
Vinyl chloride
Bromomethane
Chloroethane
Trichlorofl uoromethane
1,1-Dichloroethene
Methylene chloride
trans-l,2-Dichloroethene
1,1-Dichloroethane
cis-l,2-Dichloroethene
2,2-Dichloropropane
Chloroform
Bromochl oromethane
1,1,1-Tri chl oroethane
1,2-Dichloroethane
1,1-Dichloropropene
Carbon tetrachloride
Benzene
1,2-Dichloropropane
Trichloroethene
Dibromomethane
Bromodi chl oromethane
Toluene
1 , 1 , 2-Tri chl oroethane
1,3-Dichloropropane
Di bromochl oromethane
Tetrachloroethene
1,2-Dibromoethane
Chlorobenzene
1,1,1, 2-Tetrachl oroethane
Ethyl benzene
p-Xylene
m-Xylene
Bromoform
o-Xylene
Styrene
1,1,2 , 2-Tetrachl oroethane
1,2,3-Trichloropropane
Isopropyl benzene
0.88
0.97
1.04
1.29
1.45
1.77
2.33
2.66
3.54
4.03
5.07
5.31
5.55
5.63
6.76
7.00
7.16
7.41
7.41
8.94
9.02
9.09
9.34
11.51
11.99
12.48
12.80
13.20
13.60
14.33
14.73
14.73
15.30
15.30
15.70
15.78
15.78
15.78
16.26
16.42
0.11
0.05
0.04
0.06
0.02
0.07
0.05
0.09
0.03
0.03
0.06
0.08
0.04
0.09
0.04
0.02
0.12
0.02
0.03
0.02
0.02
0.01
0.03
0.08
0.08
0.08
0.07
0.05
0.10
0.03
0.07
0.03
0.06
0.03
0.20
0.06
0.27
0.20
0.09
0.10
8260A - 32
Revision 1
September 1994
-------
TABLE 2.
(Continued)
ANALYTE
RETENTION TIME
(minutes)
Column 3a
MDLb
(M9/L)
Bromobenzene
2-Chlorotoluene
n-Propyl benzene
4-Chlorotoluene
1,3, 5-Tri methyl benzene
tert-Butyl benzene
1 , 2 , 4-Trimethyl benzene
sec-Butyl benzene
1,3-Dichlorobenzene
p-Isopropyltoluene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
n-Butyl benzene
1 ,2-Dibromo-3-chloropropane
1,2,4-Trichlorobenzene
Naphthalene
Hexachlorobutadiene
1,2,3-Trichlorobenzene
16.42
16.74
16.82
16.82
16.99
17.31
17.31
17.47
17.47
17.63
17.63
17.79
17.95
18.03
18.84
19.07
19.24
19.24
0.11
0.08
0.10
0.06
0.06
0.33
0.09
0.12
0.05
0.26
0.04
0.05
0.10
0.50
0.20
0.10
0.10
0.14
a Column 3 - 30 meter x 0.32 mm ID DB-5 capillary with 1
b HDL based on a 25 ml sample volume.
film thickness,
8260A - 33
Revision 1
September 1994
-------
TABLE 3.
ESTIMATED QUANTITATION LIMITS FOR VOLATILE ANALYTES8
Estimated Quantitation Limits
(All Analytes in Table 1)
Ground water Low Soil/Sediment6
Purging 5 mL of water 5
Purging 25 mL of water 1
Soil/Sediment
Estimated Quantitation Limit (EQL) - The lowest concentration that can be
reliably achieved within specified limits of precision and accuracy during
routine laboratory operating conditions. The EQL is generally 5 to 10
times the MDL. However, it may be nominally chosen within these guidelines
to simplify data reporting. For many analytes the EQL is selected from the
lowest non-zero standard in the calibration curve. Sample EQLs are highly
matrix-dependent. The EQLs listed herein are provided for guidance and may
not always be achievable.
EQLs listed for soil/sediment are based on wet weight. Normally data are
reported on a dry weight basis; therefore, EQLs will be higher, based on
the percent dry weight in each sample.
Other Matrices Factor0
Water miscible liquid waste 50
High-concentration soil and sludge 125
Non-water miscible waste 500
CEQL = [EQL for low soil/sediment (see Table 3)] X [Factor], For non-aqueous
samples, the factor is on a wet-weight basis.
8260A - 34 Revision 1
September 1994
-------
TABLE 4.
BFB MASS - INTENSITY SPECIFICATIONS (4-BROMOFLUOROBENZENE)"
Mass Intensity Required (relative abundance)
50 15 to 40% of mass 95
75 30 to 60% of mass 95
95 base peak, 100% relative abundance
96 5 to 9% of mass 95
173 less than 2% of mass 174
174 greater than 50% of mass 95
175 5 to 9% of mass 174
176 greater than 95% but less than 101% of mass 174
177 5 to 9% of mass 176
Alternate tuning criteria may be used (e.g. CLP, Method 524.2, or
manufacturers' instructions), provided that method performance is not
adversely affected.
8260A - 35 Revision 1
September 1994
-------
TABLE 5.
CHARACTERISTIC MASSES (M/Z) FOR PURGEABLE ORGANIC COMPOUNDS
Analyte
Primary
Characteristic
Ion
Secondary
Characteristic
Ion(s)
Acetone
Acetonitrile
Acrolein
Acrylonitrile
Allyl alcohol
Ally! chloride
Benzene
Benzyl chloride
Bromoacetone
Bromobenzene
Bromochl oromethane
Bromodi chl oromethane
Bromoform
Bromomethane
iso-Butanol
n-Butanol
2-Butanone
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon disulfide
Carbon tetrachloride
Chloral hydrate
Chloroacetonitrile
Chlorobenzene
1-Chlorobutane
Chl orodi bromomethane
Chloroethane
2-Chloroethanol
bis-(Z-chloroethyl) sulfide
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
Chloroprene
3-Chloropropionitrile
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-chloropropane
Di bromochl oromethane
1,2-Dibromoethane
Di bromomethane
1,2-Dichlorobenzene
l,2-Dichlorobenzene-d4
58
41
56
53
57
76
78
91
136
156
128
83
173
94
74
56
72
91
105
119
76
117
82
48
112
56
129
64(49*)
49
109
63
83
50(49*)
53
54
91
91
75
129
107
93
146
152
43
41, 40, 39
55, 58
52, 51
57, 58, 39
76, 41, 39, 78
-
91, 126, 65, 128
43, 136, 138, 93, 95
77, 158
49, 130
85, 127
175, 254
96
43
41
43, 72
92, 134
134
91, 134
78
119
44, 84, 86, 111
75
77, 114
49
208, 206
66(51*)
49, 44, 43, 51, 80
111, 158, 160
65, 106
85
52(51*)
53, 88, 90, 51
54, 49, 89, 91
126
126
155, 157
127
109, 188
95, 174
111, 148
115, 150
8260A - 36
Revision 1
September 1994
-------
TABLE 5.(continued)
Analyte
Primary
Characteristic
Ion
Secondary
Characteristic
Ion(s)
1,3-Dichlorobenzene
1,4-Dichlorobenzene
cis-l,4-Dichloro-2-butene
trans-l,4-Dichloro-2-butene
Dichlorodifluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
l,3-Dichloro-2-propanol
1 ,1-Dichloropropene
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,2,3,4-Diepoxybutane
Diethyl ether
1,4-Dioxane
Epichlorohydrin
Ethanol
Ethyl acetate
Ethyl benzene
Ethylene oxide
Ethyl methacrylate
Hexachlorobutadiene
Hexachloroethane
2-Hexanone
2-Hydroxypropionitrile
lodomethane
Isobutyl alcohol
Isopropyl benzene
p-Isopropyltoluene
Malononitrile
Methacrylonitrile
Methyl acrylate
Methyl -t-butyl ether
Methylene chloride
Methyl ethyl ketone
Methyl iodide
Methyl methacrylate
4-Methyl -2-pentanone
Naphthalene
Nitrobenzene
146
146
75
53
85
63
62
96
96
96
63
76
77
79
75
75
75
55
74
88
57
31
88
91
44
69
225
201
43
44
142
43
105
119
66 '
41
55
73
84
72
142
69
100
128
123
111, 148
111, 148
75, 53, 77, 124,
88, 75
87
65, 83
98
61, 63
61, 98
61, 98
112
78
97
79, 43, 81, 49
110, 77
77, 39
77, 39
55, 57, 56
45, 59
88, 58, 43, 57
57, 49, 62, 51
45, 27, 46
43, 45, 61
106
44, 43, 42
69, 41, 99, 86,
223, 227
166, 199, 203
58, 57, 100
44, 43, 42, 53
127, 141
43, 41, 42, 74
120
134, 91
66, 39, 65, 38
41, 67, 39, 52,
85
57
86, 49
43
142, 127, 141
69, 41, 100, 39
43, 58, 85
-
51, 77
89
114
66
8260A - 37
Revision 1
September 1994
-------
TABLE 5.(continued)
Analyte
Primary
Characteristic
Ion
Secondary
Characteristic
Ion(s)
2-Nitropropane
2-Picoline
Pentachloroethane
Propargyl alcohol
6-Propiolactone
Propionitrile (ethyl cyanide)
n-Propylamine
n-Propyl benzene
Pyridine
Styrene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1 , 2-Tetrachloroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,1,1-Trichloroethane
1, 1, 2 -Trichl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
1,2,3-Trichloropropane
1, 2, 4-Trimethyl benzene
1,3, 5- Trimethyl benzene
Vinyl acetate
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
INTERNAL STANDARDS/SURROGATES
1,4-Difluorobenzene
Chlorobenzene-d5
l,4-Dichlorobenzene-d4
4-Bromofl uorobenzene
Di bromof 1 uoromethane
Dichloroethane-d4
Toluene-d8
Pentaf 1 uorobenzene
Fl uorobenzene
46
93
167
55
42
54
59
91
79
104
180
180
131
83
164
92
97
83
95
151
75
105
105
43
62
106
106
106
114
117
152
95
113'
102
98
168
96
.
93,
167,
55,
42,
54,
59,
120
52
78
182,
182,
133,
131,
129,
91
99,
97,
97,
101,
77
120
120
86
64
91
91
91
115,
174,
77
66, 92, 78
130, 132, 165, 169
39, 38, 53
43, 44
52, 55, 40
41, 39
145
145
119
85
131, 166
61
85
130, 132
153
150
176
* - characteristic ion for an ion trap mass spectrometer (to be used when
ion-molecule reactions are observed)
8260A - 38
Revision 1
September 1994
-------
TABLE 6.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR VOLATILE
ORGANIC COMPOUNDS IN WATER DETERMINED WITH A WIDE-
BORE CAPILLARY COLUMN
Analyte
Benzene
Bromobenzene
Bromochl oromethane
Bromodi chl oromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chl oromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2-Dibromo-3-Chl oropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1 , 2-Di chl orobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichlorobenzene
1,2-Dichlorobenzene
1,1-Dichloroethene
cis-1, 2-Di chl oroethene
trans -1, 2-Di chl oroethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachl orobutadi ene
Isopropyl benzene
p-Isopropyl toluene
Methylene chloride
Naphthalene
n-Propyl benzene
Styrene
Cone. Number
Range, of Recovery8
pig/L Samples %
0.1
0.1
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.5
0.5
0.5
0.1
0.1
0.5
0.1
0.5
0.5
0.1
0.5
0.2
0.5
0.5
0.1
0.1
0.5
0.1
0.1
0.1
0.5
0.5
0.1
C.5
0.5
0.1
0.1
0.1
0.1
0.1
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 20
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
-100
- 10
-100
31
30
24
30
18
18
18
16
18
24
31
24
24
23
31
31
24
31
24
24
31
24
31
18
24
31
34
18
30
30
31
12
18
31
18
16
23
30
31
31
39
97
100
90
95
101
95
100
100
102
84
98
89
90
93
90
99
83
92
102
100
93
99
103
90
96
95
94
101
93
97
96
86
98
99
100
101
99
95
104
100
102
Standard
Deviation Percent
of Recovery13 RSD
6.5
5.5
5.7
5.7
6.4
7.8
7.6
7.6
7.4
7.4
5.8
8.0
5.5
8.3
5.6
8.2
16.6
6.5
4.0
5.6
5.8
6.8
6.6
6.9
5.1
5.1
6.3
6.7
5.2
5.9
5.7
14.6
8.7
8.4
6.8
7.7
6.7
5.0
8.6
5.8
7.3
5.7
5.5
6.4
6.1
6.3
8.2
7.6
7.6
7.3
8.8
5.9
9.0
6.1
8.9
6.2
8.3
19.9
7.0
3.9
5.6
6.2
6.9
6.4
7.7
5.3
5.4
6.7
6.7
5.6
6.1
6.0
16.9
8.9
8.6
6.8
7.6
6.7
5.3
8.2
5.8
7.2
8260A - 39
Revision 1
September 1994
-------
TABLE 6.
(Continued)
Analyte
Cone.
Range,
M9A
Number
of Recovery8
Samples %
Standard
Deviation Percent
of Recovery15 RSD
1,1,1,2-Tetrachloroethane 0.5 - 10 24 90
1,1,2,2-Tetrachloroethane 0.1 - 10 30 91
Tetrachloroethene 0.5 - 10 24 89
Toluene 0.5 - 10 18 102
1,2,3-Trichlorobenzene 0.5 - 10 18 109
1,2,4-Trichlorobenzene 0.5 - 10 18 108
1,1,1-Trichloroethane 0.5 - 10 18 98
1,1,2-Trichloroethane 0.5 - 10 18 104
Trichloroethene 0.5 - 10 24 90
Trichlorofluoromethane 0.5 - 10 24 89
1,2,3-Trichloropropane 0.5 - 10 16 108
1,2,4-Trimethylbenzene 0.5-10 18 99
1,3,5-Trimethylbenzene 0.5 - 10 23 92
Vinyl chloride 0.5 - 10 18 98
o-Xylene 0.1 - 31 18 103
m-Xylene 0.1 - 10 31 97
p-Xylene 0.5 - 10 18 104
6.1
5.7
6.0
8.1
9.4
9.0
7.9
7.6
6.5
7.2
15.6
8.0
6.8
6.5
7.4
6,3
8.0
6.8
6.3
6.8
8.0
8.6
8.3
8.1
7.3
7.3
8.1
14.4
8.1
7.4
6.7
7.2
6.5
7.7
8 Recoveries were calculated using internal standard method. Internal standard
was fluorobenzene.
b Standard deviation was calculated by pooling data from three concentrations.
8260A - 40
Revision 1
September 1994
-------
TABLE 7.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR
VOLATILE ORGANIC COMPOUNDS IN WATER DETERMINED
WITH A NARROW-BORE CAPILLARY COLUMN
Analyte
Benzene
Bromobenzene
Bromochl oromethane
Bromodi chl oromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
1 ,2-Dibromo-3-chl oropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1, 2 -Di chlorobenzene
1 ,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
I sopropyl benzene
p-Isopropyltoluene
Methylene chloride
Naphthalene
n-Propyl benzene
Cone.
M9/L
0.1
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.5
0.1
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
Number
of
Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Recovery8
%
99
97
97
100
101
99
94
110
110
108
91
100
105
101
99
96
92
99
97
93
97
101
106
99
98
100
95
100
98
96
99
99
102
99
100
102
113
97
98
99
Standard
Deviation
of Recovery
6.2
7.4
5.8
4.6
5.4
7.1
6.0
7.1
2.5
6,8
5.8
5.8
3.2
4.7
4.6
7.0
10.0
5.6
5.6
5.6
3.5
6.0
6.5
8.8
6.2
6.3
9.0
3.7
7.2
6.0
5.8
4.9
7.4
5.2
6.7
6.4
13.0
13.0
7.2
6.6
Percent
RSD
6.3
7.6
6.0
4.6
5.3
7.2
6.4
6.5
2.3
6.3
6.4
5.8
3.0
4.7
4.6
7.3
10.9
5.7
5.8
6.0
3.6
5.9
6.1
8.9
6.3
6.3
9.5
3.7
7.3
6.3
5.9
4.9
7.3
5.3
6.7
6.3
11.5
13.4
7.3
6.7
8260A - 41
Revision 1
September 1994
-------
TABLE 7.
(Continued)
Analyte
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1 , 2 , 3-Tri chl orobenzene
1 , 2 , 4-Tr i chl orobenzene
1,1,1-Tri chl oroethane
1,1,2-Trichloroethane
Trichloroethene
Tr i chl orof 1 uoromethane
1,2, 3-Tri chl oropropane
1 , 2, 4-Trimethyl benzene
1 ,3 , 5-Tri methyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
Cone.
yug/L
0.5
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.5
0.5
0.5
0.1
0.5
0.5
0.5
Number
of
Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
1
1
1
1
7
Recovery"
%
96
100
100
96
100
102
91
100
102
104
97
96
96
101
104
106
106
97
Standard
Deviation
of Recovery
19.0
4.7
12.0
5.0
5.9
8.9
16.0
4.0
4.9
2.0
4.6
6.5
6.5
4.2
0.2
7.5
4.6
6.1
Percent
RSD
19.8
4.7
12.0
5.2
5.9
8.7
17.6
4.0
4.8
1.9
4.7
6.8
6.8
4.2
0.2
7.1
4.3
6.3
Recoveries were calculated using internal standard method. Internal standard
was fluorobenzene.
8260A - 42
Revision 1
September 1994
-------
TABLE 8.
SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Surrogate Compound
4-Bromofl uorobenzene8
Di bromof 1 uoromethane"
Toluene-d8a
Dichloroethane-d4a
Percent
Low/High
Water
86-115
86-118
88-110
80-120
Recovery
Low/High
Soil/Sediment
74-121
80-120
81-117
80-120
Single laboratory data, for guidance only.
TABLE 9.
QUANTITY OF EXTRACT REQUIRED FOR ANALYSIS OF
HIGH-CONCENTRATION SAMPLES
Approximate Volume of
Concentration Range Extract8
500 - 10,000 /xg/kg 100 ML
1,000 - 20,000 MQ/kg 50 /iL
5,000 - 100,000 jig/kg 10 ML
25,000 - 500,000 /ug/kg 100 /xL of 1/50 dilution15
Calculate appropriate dilution factor for concentrations exceeding this table.
a The volume of solvent added to 5 mL of water being purged should be kept
constant. Therefore, add to the 5 mL syringe whatever volume of solvent
is necessary to maintain a volume of 100 /xL added to the syringe.
b Dilute an aliquot of the solvent extract and then take 100 /j,i for
analysis.
8260A - 43 Revision 1
September 1994
-------
TABLE 10
DIRECT INJECTION ANALYSIS OF NEW OIL AT 5 PPM
Compound
Acetone
Benzene
n-Butanol*,**
iso-Butanol*,**
Carbon tetrachloride
Carbon disulfide**
Chlorobenzene
Chloroform
1,4-Dichlorobenzene
1,2-Dichloroethane
1,1-Dichloroethene
Di ethyl ether
Ethyl acetate
Ethyl benzene
Hexachloroethane
Methylene chloride
Methyl ethyl ketone
MIBK
Nitrobenzene
Pyridine
Tetrachloroethene
Recovery (%)
91
86
107
95
86
53
81
84
98
101
97
76
113
83
71
98
79
93
89
31
82
Trichlorofluoromethane 76
l,l,2-Cl3F3ethane
Toluene
Trichloroethene
Vinyl chloride
o-Xylene
m/p-Xylene
* Alternate mass
** T<^ nnant i t at i nr
69
73
66
63
83
84
employed
^
%RSD
14.8
21.3
27.8
19.5
44.7
22.3
29.3
29.3
24.9
23.1
45.3
24.3
27.4
30.1
30.3
45.3
24.6
31.4
30.3
35.9
27.1
27.6
29.2
21.9
28.0
35.2
29.5
29.5
Blank
(ppm)
1.9
0.1
0.5
0.9
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.2
0.0
0.0
0.4
0.0
0.0
0.0
0.0
0.0
0.0
0.6
0.0
0.0
0.4
0.6
Spike
(ppm)
5.0
0.5
5.0
5.0
0.5
5.0
5.0
6.0
7.5
0.5
0.7
5.0
5.0
5.0
3.0
5.0
5.0
5.0
2.0
5.0
0.7
5.0
5.0
5.0
0.5
0.2
5.0
10.0
Data are taken from Reference 9.
8260A - 44
Revision 1
September 1994
-------
FIGURE 1.
PURGING DEVICE
FOAM TIM*
EXrr IM m. 0.0.
GUT 1M M OJO.
14 MM O.O.
INLET 1M Ht. 0.0.
10 MM GLASS FWT
MCOUM
INLET
2-WAY SYMNOE VALVE
17 CM 20 GAUGE SYftMQE NEEDLE
• MM O.O. RUeKA SEPTUM
INLET 1M IN. O.O.
1DQ IN 00
/~ STAINLESS STEEL
13X
MOLECULAR SIEVE
PUBOE GAS FH.TCT
PUMQEGAS
fl.CV» CXXTWX
8260A - 45
Revision 1
September 1994
-------
FIGURE 2.
TRAP PACKING AND CONSTRUCTION TO INCLUDE DESORB CAPABILITY
PACKING DETAIL
i
ZjT SMMOLAS
CONSTRUCTION DETAIL
77 CM SnXA GEL
IS CM TOUX QC
•- i CM 3H OV-1
5 MM OLAM »VOCX
TH0MOCOUFIB
COMTNOU9
8260A - 46
Revision 1
September 1994
-------
FIGURE 3.
SCHEMATIC OF PURGE-AND-TRAP DEVICE - PURGE MODE
CARRIER GAS
FLOW CONTROL
PRESSURE
REGULATOR
PURGE OAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
UCMO INJECTION PORTS
COLUMN OVEN
L/in/v
CONFIRMATORY COLUMN
TO DETECTOR
> ANALYTICAL COLUMN
OPTIONAL 4^>ORT COLUMN
SELECTION VALVE
TRAP INLET
TRAP
PURGING
DEVICE
NOTE
ALL UN£S BETWEEN TRAP
ANO OC SHOULD BE HEATED
TO KTC
8260A - 47
Revision 1
September 1994
-------
FIGURE 4.
SCHEMATIC OF PURGE-AND-TRAP DEVICE - DESORB MODE
CARRKRGAS
FLOW CONTROL
PRESSURE
REGULATOR
LJQUK) INJECTION PORTS
r- COLUMN OVEN
OPTIONAL **ORT COLUMN
SELECTION VALVE
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
TRAP INLET
PURGE GAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
PURGING
DEVCE
NOTE
ALL UNES BETWEEN TRAP
AND OC SHOULD BE HEATED
TOCTC.
8260A - 48
Revision 1
September 1994
-------
FIGURE 5.
GAS CHROMATOGRAM OF VOLATILE ORGANICS
408
I 1C
999
1299
2008
24OO
COLUMNi £0 METER * O.73 MM l.O. VOCOL CAPILLARY
PROGRAM* 10 C FOR 9 MIN., THEN 6 /HIN TO ISO C
UJ
O
•_•
oc
O
*
J
z
2
*
u •-
5 *B s
T »-• Of fc
H *0 |
u o J *
g J?S u
O ^ *^ «p
" U «l A
« s!-2
i f I"
u. i
^
Id
O
oe
a
&
I I il ~ I I I % 111
.M>M.A.4'^"*.w.ff
2 4 6 8 18 12 14 16
Z it)
Ss
z d
a T
o P
or T
o a
i»
•-«
oe
H
I
«
N
-I
UJ
5
N
III
n
o
K
o
_i
u
TL
I
I
n
-------
FIGURE 6.
GAS CHROMATOGRAM OF VOLATILE ORGANICS
Column Z - 30m long x O.SJnw 10 06-624
•woe-bore col urn
PROGRAMi 10 C FOB 3 HIM.,
THEN 6 /MIN TO ISO C
ftCTIMttOM TIMI. MIN.
8260A - 50
Revision 1
September 1994
-------
FIGURE 7.
GAS CHROMATOGRAM OF VOLATILE ORGANICS
RIC
04.-'1-9'87 9:26:00
SuJJS 125 TO 900
Ctt.1: 40MS04238? «3
COItlS.: F4000.40-160X8.12,F4,3mPURGE.TEIKIl.&EL.06624.SHEEP35,18PSI
: G 1,1200 LftBEL: tl 8, 4.6 GUrtl: ft 8- 1.0 J 0 EASE: U 28, 3
100.8-1
F.1C
thane
oride
thane
thar.e
DC Et
lch
cme
roe
clilo
viny
brcr
chlo
C13
1
^
i—1
U
AAAJ'J
ij
ro
C
5H
X3 K *~*
Wo -> -I a«P
(NO o air<
fi
0) a
*
(I
li
VL-
I
~°§ <
ri& c
rH5? fl)
I-
o
667
643
705o
s
in
e.
a
u
»
2641W.
I'WJ
400
6:40
11:40
6C>0
iit>0 CJ'H(I
IS:00 HMf
8260A - 51
Revision 1
September 1994
-------
FIGURE 8.
GAS CHROMATOGRAM OF TEST MIXTURE
(OT.I
U
9
H
Q
O
KAMI
UN
0.5 g/L PER COMPOUND
1. 1,1-DICHLOROETHYLENE
2. METHYLENE CHLORIDE
3. TRANS-1.2-DICHLOROETHYLENE
4. 1,1 DICHLOROETHANE
5. ISOPROPYLETHER
6. CHLOROFORM
7. 1.1,1-TRICHLOROETHANE
8. 1,2-DICHLORORETHYLENE
9. CARBON TETRACHLORIDE
10. BENZENE
11. FLOUROBENZENE (INT. STD.)
12. TRICHLOROETHYENE
13.1,2-DICHLOROPROPAKE
14. BROMODICHLOROHETHANE
IS. TOLUENE
16. BROHOCHLOROPROPANE INT. STD.)
17. DIBROMOCHLOROHETHANE
18. TETRACHLOROETHYLENE
19. CHLOR08ENZENE
20. ETHYLBENZENE
21. 1,3-XYLENE
22. BROMOFORM
23. BROMOBENZENE
24. 1.4-DICHLOROBENZENE
25. 1,2,4-TRICHLOROBENZENE
26. NAPHTHALENE
8360A - 52
Revision 1
September 1994
-------
FIGURE 9.
LOW SOILS IMPINGER
—'
PURGE INLET FITTING
SAMPLE OUTLET PITTING
3- • 6mm 0 D CLASS TUBING
SEPTUM
CAP
40mi VIAL
8260A - 53
Revision 1
September 1994
-------
METHOD 8260A
VOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)
CAPILLARY COLUMN TECHNIQUE
Purge-and-trap
7.1
Select
procedure
for introducing
sample into
GC/MS.
Direct
Injection
^
7.2 Set GC/MS
operating
conditions.
7.3.1 Tune
GC/MS system
with BFB.
7.3.2 Assemble
purge-and-trap
device and prepare
calibration standards
7.3.2.1 Perform
purge-and-trap
analysis.
8260A - 54
7.3.4 Calculate
RFs for
5 SPCCs.
7.3.5 Calculate
%RSD of RF
for CCCs.
7.4 Perform
calibration
verification.
7.5 Perform GC/MS
analysis utilizing
Methods 5030
or 8260.
7.6.1 Identify
analytes by
comparing the
sample and standard
mass spectra.
7.6.2 Calculate the
concentration of
each identified
analyte.
7.6.2.3 Report
all results.
f Stop J
Revision 1
September 1994
-------
00
*o
-4
o
-------
METHOD 8270A
SEMIVOLATILE ORGANIC COMPOUNDS BY
GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS); CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8270 is used to determine the concentration of semivolatile
organic compounds in extracts prepared from all types of solid waste matrices,
soils, and ground water. Direct injection of a sample may be used in limited
applications. The following compounds can be determined by this method:
Compounds
Appropriate Preparation Techniques
CAS No8 3510 3520 3540 3550 3580
Acenaphthene
Acenaphthene-d10 (I.S.)
Acenaphthylene
Acetophenone
2-Acetyl ami nof 1 uorene
l-Acetyl-2-thiourea
Aldrin
2-Aminoanthraquinone
Aminoazobenzene
4-Aminobiphenyl
Anilazine
Aniline
o-Anisidine
Anthracene
Aramite
Aroclor - 1016
Aroclor - 1221
Aroclor - 1232
Aroclor - 1242
Aroclor - 1248
Aroclor - 1254
Aroclor - 1260
Azinphos-methyl
Barban
Benzidine
Benzoic acid
Benz(a)anthracene
Benzo (b)fl uoranthene
Benzo ( k) fl uoranthene
Benzo (g,h,i)perylene
Benzo(a)pyrene
p-Benzoquinone
Benzyl alcohol
83-32-9
208-96-8
98-86-2
53-96-3
591-08-2
309-00-2
117-79-3
60-09-3
92-67-1
101-05-3
62-53-3
90-04-0
120-12-7
140-57-8
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
86-50-0
101-27-9
92-87-5
65-85-0
56-55-3
205-99-2
207-08-9
191-24-2
50-32-8
106-51-4
100-51-6
X
X
X
X
X
LR
X
X
X
X
X
X
X
X
HS(43)
X
X
X
X
X
X
X
HS(62)
LR
CP
X
X
X
X
X
X
OE
X
X
X
X
NO
ND
ND
X
ND
ND
ND
ND
X
ND
X
ND
X
X
X
X
X
X
X
ND
ND
CP
X
X
X
X
X
X
ND
X
X
X
X
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
X
ND
X
X
X
X
X
X
X
ND
ND
CP
ND
X
X
X
X
X
ND
ND
X
X
X
ND
ND
ND
X
ND
ND
ND
ND
X
ND
X
ND
X
X
X
X
X
X
X
ND
ND
CP
X
X
X
X
X
X
ND
X
X
X
X
X
X
LR
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
CP
X
X
X
X
X
X
X
X
8270A - 1
Revision 1
July 1992
-------
Appropriate Preparation Techniaues
Compounds
a-BHC
/3-BHC
5-BHC
y-BHC (Lindane)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Bromoxynil
Butyl benzyl phthalate
Captafol
Captan
Carbaryl
Carbofuran
Carbophenothion
Chlordane
Chlorfenvinphos
4-Chloroaniline
Chi orobenzi late
5-Chl oro-2-methyl ani 1 i ne
4-Chloro-3-methyl phenol
3-(Chloromethyl )pyridine
hydrochloride
1-Chloronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-d12 (I.S.)
Coumaphos
p-Cresidine
Crotoxyphos
2-Cyclohexyl-4,6-dinitrophenol
4,4'-DDD
4,4'-DDE
4, 4 '-DDT
Oemeton-0
Demeton-S
Diallate (cis or trans)
2,4-Diaminotoluene
Dibenz(a,j)acridine
Dtbenz(a,h) anthracene
Oibenzofuran
Dibenzo(a,e)pyrene
Di-n-butyl phthalate
CAS Noa
319-84-6
319-85-7
319-86-8
58-89-9
111-91-1
111-44-4
108-60-1
117-81-7
101-55-3
1689-84-5
85-68-7
2425-06-1
133-06-2
63-25-2
1563-66-2
786-19-6
57-74-9
470-90-6
106-47-8
510-15-6
95-79-4
59-50-7
6959-48-4
90-13-1
91-58-7
95-57-8
7005-72-3
218-01-9
56-72-4
120-71-8
7700-17-6
131-89-5
72-54-8
72-55-9
50-29-3
298-03-3
126-75-0
2303-16-4
95-80-7
224-42-0
53-70-3
132-64-9
192-65-4
84-74-2
8270A - 2
3510
X
X
X
X
X
X
X
X
X
X
X
HS(55)
HS(40)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
HS(68)
X
X
DC,OE(42)
X
X
X
ND
X
3520
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
ND
ND
ND
X
ND
ND
ND
NO
X
ND
X
X
X
X
X
X
ND
ND
ND
ND
X
X
X
ND
ND
ND
ND
ND
X
X
ND
X
3540
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
X
ND
X
X
X
X
X
X
ND
ND
ND
ND
X
X
X
ND
ND
ND
ND
ND
X
ND
ND
X
3550
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
ND
ND
ND
X
ND
ND
ND
NO
X
ND
X
X
X
X
X
X
ND
ND
ND
ND
X
X
X
ND
ND
ND
ND
ND
X
X
ND
X
Revi
3580
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
X
X
X
X
X
X
X
X
X
X
X
X
sion 1
July 1992
-------
Compounds
Dichlone
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
l,4-Dichlorobenzene-d4 (I.S)
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos
Dicrotophos
Oieldrin
Diethyl phthalate
Diethylstilbestrol
Diethyl sulfate
Dimethoate
3,3'-Dimethoxybenzidine
Dimethyl ami noazobenzene
7,12-Dimethylbenz(a)-
anthracene
3,3' -Dimethylbenzidine
a, a -Dimethyl phenethyl ami ne
2,4-Dimethylphenol
Dimethyl phthalate
1,2-Dinitrobenzene
1,3-Dinitrobenzene
1,4-Dinitrobenzene
4,6-Dinitro-2-methylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap
Dinoseb
Diphenylamine
5,5-Diphenylhydantoin
1,2-Diphenylhydrazine
Di-n-octyl phthalate
Disulfoton
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
EPN
Ethion
Ethyl carbamate
t
CAS Noa
117-80-6
95-50-1
541-73-1
106-46-7
91-94-1
120-83-2
87-65-0
62-73-7
141-66-2
60-57-1
84-66-2
56-53-1
64-67-5
60-51-5
119-90-4
60-11-7
57-97-6
119-93-7
122-09-8
105-67-9
131-11-3
528-29-0
99-65-0
100-25-4
534-52-1
51-28-5
121-14-2
606-20-2
39300-45-3
88-85-7
122-39-4
57-41-0
122-66-7
117-84-0
298-04-4
959-98-8
33213-65-9
1031-07-8
72-20-8
7421-93-4
53494-70-5
2104-64-5
563-12-2
51-79-6
8270A - 3
yopropriate Preoaration Techniaues
3510
OE
X
X
X
X
X
X
X
X
X
X
X
AW,OS(67)
LR
HE,HS(31)
X
X
CP(45)
X
ND
X
X
X
X
HE(14)
X
X
X
X
CP,HS(28)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
DC(28)
3520
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
X
X
X
X
ND
ND
X
ND
X
X
ND
X
X
X
X
X
X
ND
ND
ND
3540
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
X
X
X
X
ND
ND
X
ND
X
X
ND
X
X
X
X
X
ND
ND
ND
ND
3550 3580
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
X
X
X
X
ND
ND
X
ND
X
X
ND
X
X
X
X
X
X
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
X
LR
X
CP
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Revision 1
July
1992
-------
Compounds
Ethyl methanesulfonate
Famphur
Fensulfothion
Fenthion
Fluchloralin
Fluoranthene
Fluorene
2-Fluorobiphenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
Hexachl orophene
Hexachl oropropene
Hexamethyl phosphorami de
Hydroquinone
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
Isosafrole
Kepone
Leptophos
Malathion
Maleic anhydride
Mestranol
Methapyrilene
Methoxychlor
3-Methylcholanthrene
4,4'-Methylenebis(2-chloranil
Methyl methanesulfonate
2-Methylnaphthalene
Methyl parathion
2-Methyl phenol
3-Methyl phenol
4-Methyl phenol
Mevinphos
Mexacarbate
Mirex
Monocrotophos
Naled
Naphthalene
Naphthalene-dg (I.S.)
1,4-Naphthoquinone
1-Naphthylamine
i
CAS Noa
62-50-0
52-85-7
115-90-2
55-38-9
33245-39-5
206-44-0
86-73-7
321-60-8
367-12-4
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
680-31-9
123-31-9
193-39-5
465-73-6
78-59-1
120-58-1
143-50-0
21609-90-5
121-75-5
108-31-6
72-33-3
91-80-5
72-43-5
56-49-5
ine) 101-14-4
66-27-3
91-57-6
298-00-0
95-48-7
108-39-4
106-44-5
7786-34-7
315-18-4
2385-85-5
6923-22-4
300-76-5
91-20-3
130-15-4
134-32-7
8270A - 4
\DDrooriate Preoaration Terhnioues
3510
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
AW,CP(62)
X
X
NO
X
X
X
DC(46)
X
X
HS(5)
HE
X
X
X
X
OE,OS(0)
X
X
X
X
X
X
X
HE,HS(68)
X
HE
X
X
X
X
OS(44)
3520
ND
NO
ND
NO
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
3540
ND
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
3550
ND
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
X
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
Revi
3580
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
si on 1
July 1992
-------
Appropriate Preoaration Techniaue<;
Compounds
2-Naphthylamine
Nicotine
5-Nitroacenaphthene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
5-Nitro-o-anisidine
Nitrobenzene
Nitrobenzene-dr (surr.)
4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
Nitroquinoline-1 -oxide
N-Nitrosodibutylamine
N-Nitrosodi ethyl ami ne
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
N-Ni trosomethyl ethyl ami ne
N-Nitrosomorphol ine
N-Nitrosopipendine
N-Nitrosopyrrol idine
5-Nitro-o-toluidine
Octamethyl pyrophosphoramide
4,4'-Oxydiani1ine
Parathion
Pentachlorobenzene
Pentachloronitrobenzene
Pentachlorophenol
Pery1ene-d12 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-d10 (I.S.)
Phenobarbital
Phenol
Phenol -d6 (surr.)
1,4-Phenylenediamine
Phorate
Phosalone
Phosmet
Phosphamidon
Phthalic anhydride
2-Picoline
Piperonyl sulfoxide
Pronamide
Propylthiouracil
CAS No8
91-59-8
54-11-5
602-87-9
88-74-4
99-09-2
100-01-6
99-59-2
98-95-3
92-93-3
1836-75-5
88-75-5
100-02-7
56-57-5
924-16-3
55-18-5
62-75-9
86-30-6
621-64-7
10595-95-6
59-89-2
100-75-4
930-55-2
99-55-8
152-16-9
101-80-4
56-38-2
608-93-5
82-68-8
87-86-5
62-44-2
85-01-8
50-06-6
108-95-2
106-50-3
298-02-2
2310-17-0
732-11-6
13171-21-6
85-44-9
109-06-8
120-62-7
23950-58-5
51-52-5
8270A - 5
3510
X
DE(67)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
LR
X
X
X
X
X
X
X
X
X
X
DC(28)
DC(28)
X
X
HS(65)
HS(15)
HE(63)
CP,ME(1)
ND
X
X
LR
3520
ND
ND
ND
X
X
X
ND
X
X
ND
ND
X
X
ND
ND
ND
X
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
X
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3540
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
X
X
ND
ND
ND
X
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
X
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3550
ND
ND
ND
X
X
X
ND
X
X
ND
ND
X
X
ND
ND
ND
X
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
X
X
ND
X
X
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
Revi
3580
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
ND
X
X
LR
sion 1
July 1992
-------
Compounds
Appropriate Preparation Techniques
CAS Noa 3510 3520 3540 3550 3580
Pyrene
Pyridine
Resorcinol
Safrole
Strychnine
Sul fall ate
Terbufos
Terphenyl-du(surr.)
1,2,4,5-Tetrachlorobenzene
2,3,4,6-Tetrachlorophenol
Tetrachlorvinphos (Stirophos)
Tetraethyl pyrophosphate
Thionazine
Thiophenol (Benzenethiol )
Toluene diisocyanate
o-Toluidine
Toxaphene
2,4,6-Tribromophenol (surr.)
1,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Trifluralin
2,4,5-Trime.thylani"! ine
Trimethyl phosphate
1,3,5-Trinitrobenzene
Tris(2,3-dibromopropyl) phosphate
Tri-p-tolyl phosphate
0,0,0-Triethyl phosphorothioate
129-00-0
110-86-1
108-46-3
94-59-7
60-41-3
95-06-7
13071-79-9
95-94-3
58-90-2
961-11-5
107-49-3
297-97-2
108-98-5
584-84-9
95-53-4
8001-35-2
120-82-1
95-95-4
88-06-2
1582-09-8
137-17-7
512-56-1
99-35-4
126-72-7
78-32-0
126-68-1
X
ND
DC.OE(IO)
X
AW,OS(55)
X
X
X
X
X
X
X
X
X
HE(6)
X
X
X
X
X
X
X
X
HE(60)
X
X
X
X
X
ND
NO
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
ND
X
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
ND
ND
ND
ND
ND
ND
ND
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
x
X
X
X
LR
X
X
a Chemical Abstract Service Registry Number.
AW = Adsorption to walls of glassware during extraction and storage.
CP = Nonreproducible chromatographic performance.
DC = Unfavorable distribution coefficient (number in parenthesis is percent
recovery).
HE = Hydrolysis during extraction accelerated by acidic or basic conditions
(number in parenthesis is percent recovery).
HS = Hydrolysis during storage (number in parenthesis is percent stability).
LR = Low response.
ND = Not determined.
OE = Oxidation during extraction accelerated by basic conditions (number in
parenthesis is percent recovery).
OS = Oxidation during storage (number in parenthesis is percent stability).
X = Greater than 70 percent recovery by this technique.
Percent Stability = Average Recovery (Day 7) x 100/Average Recovery (Day 0).
8270A - 6
Revision 1
July 1992
-------
1.2 Method 8270 can be used to quantitate most neutral, acidic, and basic
organic compounds that are soluble in methylene chloride and capable of being
eluted without derivatization as sharp peaks from a gas chromatographic fused-
silica capillary column coated with a slightly polar silicone. Such compounds
include polynuclear aromatic hydrocarbons, chlorinated hydrocarbons and
pesticides, phthalate esters, organophosphate esters, nitrosamines, haloethers,
aldehydes, ethers, ketones, anilines, pyridines, quinolines, aromatic nitro
compounds, and phenols, including nitrophenols. See Table 1 for a list of
compounds and their characteristic ions that have been evaluated on the specified
GC/MS system.
1.3 The following compounds may require special treatment when being
determined by this method. Benzidine can be subject to oxidative losses during
solvent concentration. Also, chromatography is poor. Under the alkaline
conditions of the extraction step, a-BHC, yBHC, Endosulfan I and II, and Endrin
are subject to decomposition. Neutral extraction should be performed if these
compounds are expected. Hexachlorocyclopentadiene is subject to thermal
decomposition in the inlet of the gas chromatograph, chemical reaction in acetone
solution, and photochemical decomposition. N-nitrosodimethylamine is difficult
to separate from the solvent under the chromatographic conditions described. N-
nitrosodiphenylamine decomposes in the gas chromatographic inlet and cannot be
separated from diphenylamine. Pentachlorophenol, 2,4-dinitrophenol,
4-nitrophenol, 4,6-dinitro-2-methylphenol,4-chloro-3-methylphenol, benzoicacid,
2-nitroaniline, 3-nitroaniline, 4-chloroaniline, and benzyl alcohol are subject
to erratic chromatographic behavior, especially if the GC system is contaminated
with high boiling material.
1.4 The estimated quantitation limit (EQL) of Method 8270 for determining
an individual compound is approximately 1 mg/kg (wet weight) for soil/sediment
samples, 1-200 mg/kg for wastes (dependent on matrix and method of preparation),
and 10 M9/L for ground water samples (see Table 2). EQts will be
proportionately higher for sample extracts that require dilution to avoid
saturation of the detector.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatograph/mass spectrometers and
skilled in the interpretation of mass spectra. Each analyst must demonstrate the
ability to generate acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 Prior to using this method, the samples should be prepared for
chromatography using the appropriate sample preparation and cleanup methods.
This method describes chromatographic conditions that will allow for the
separation of the compounds in the extract and for their qualitative and
quantitative analysis by mass spectrometry.
3.0 INTERFERENCES
3.1 Raw GC/MS data from all blanks, samples, and spikes must be evaluated
for interferences. Determine if the source of interference is in the preparation
8270A - 7 Revision 1
July 1992
-------
and/or cleanup of the samples and take corrective action to eliminate the
problem.
3.2 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed. To reduce carryover, the
sample syringe must be rinsed out between samples with solvent. Whenever an
unusually concentrated sample is encountered, it should be followed by the
analysis of solvent to check for cross contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph/mass spectrometer system
4.1.1 Gas chromatograph - An analytical system complete with a
temperature-programmable gas chromatograph suitable for splitless injection
and all required accessories, including syringes, analytical columns, and
gases. The capillary column should be directly coupled to the source.
4.1.2 Column - 30 m x 0.25 mm ID (or 0.32 mm ID) 1 jum film thickness
silicone-coated fused-silica capillary column (J&W Scientific DB-5 or
equivalent).
4.1.3 Mass spectrometer - Capable of scanning from 35 to 500 amu
every 1 sec or less, using 70 volts (nominal) electron energy in the
electron impact ionization mode. The mass spectrometer must be capable of
producing a mass spectrum for decafluorotriphenylphosphine (DFTPP) which
meets all of the criteria in Table 3 when 1 ML of the GC/MS tuning standard
is injected through the GC (50 ng of DFTPP).
4.1.4 GC/MS interface - Any GC-to-MS interface that gives acceptable
calibration points at 50 ng per injection for each compound of interest and
achieves acceptable tuning performance criteria may be used.
4.1,5 Data system - A computer system must be interfaced to the mass
spectrometer. The system must allow the continuous acquisition and storage
on machine-readable media of all mass spectra obtained throughout, the
duration of the chromatographic program. The computer must have software
that can search any GC/MS data file for ions of a specific mass and that
can plot such ion abundances versus time or scan number. This type of plot
is defined as an Extracted Ion Current Profile (EICP). Software must also
be available that allows integrating the abundances in any EICP between
specified time or scan-number limits. The most recent version of the
EPA/NIST Mass Spectral Library should also be available.
4.2 Syringe - 10 nl.
4.3 Volumetric flasks, Class A - Appropriate sizes with ground glass
stoppers.
4.4 Balance - Analytical, 0.0001 g.
4.5 Bottles - glass with Teflon-lined screw caps or crimp tops.
8270A - 8 Revision 1
July 1992
-------
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall 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 ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Stock standard solutions (1000 mg/L) - Standard solutions can be
prepared from pure standard materials or purchased as certified solutions.
5.3.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in pesticide quality
acetone or other suitable solvent and dilute to volume in a 10 ml
volumetric flask. Larger volumes can be used at the convenience of the
analyst. When compound purity is assayed to be 96% or greater, the weight
may be used without correction to calculate the concentration of the stock
standard. Commercially prepared stock standards may be used at any
concentration if they are certified by the manufacturer or by an
independent source.
5.3.2 Transfer the stock standard solutions into bottles with Teflon
lined screw-caps. Store at 4°C and protect from light. Stock standard
solutions should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards from
them.
5.3.3 Stock standard solutions must be replaced after 1 year or
sooner if comparison with quality control check samples indicates a
problem.
5.4 Internal standard solutions - The internal standards recommended are
1,4-dichlorobenzene-d,, naphthalene-d8, acenaphthene-d10, phenanthrene-d^,
chrysene-d12, and perylene-d12. Other compounds may be used as internal standards
as long as the requirements given in Section 7.3.2 are met. Dissolve 0.200 g of
each compound with a small volume of carbon disulfide. Transfer to a 50 ml
volumetric flask and dilute to volume with methylene chloride so that the final
solvent is approximately 20% carbon disulfide. Most of the compounds are also
soluble in small volumes of methanol, acetone, or toluene, except for
perylene-d<2. The resulting solution will contain each standard at a
concentration of 4,000 ng//j,L. Each 1 mL sample extract undergoing analysis
should be spiked with 10 /LtL (5 \il if a 2 \il injection is used) of the internal
standard solution, resulting in a concentration of 40 ng//iL of each internal
standard. Store at 4°C or less when not being used.
5.5 -GC/MS tuning standard - A methylene chloride solution containing
50 ng/^L (25 ng/jiL if a 2 \ii injection is used) of decafluorotriphenylphosphine
(DFTPP) should be prepared. The standard should also contain 50 ng//nL each of
4,4'-DDT, pentachlorophenol, and benz.idine to verify injection port inertness and
GC column perfo'rmance. Store at 4°C or less when not being used.
8270A - 9 Revision 1
July 1992
-------
5.6 Cal ibration standards - A minimum of five cal ibration standards should
be prepared. One of the calibration standards should be at a concentration near,
but above, the method detection limit; the others should correspond to the range
of concentrations found in real samples but should not exceed the working range
of the GC/MS system. Each standard should contain each analyte for detection by
this method (e.g. some or all of the compounds listed in Table 1 may be
included). Each 1 ml aliquot of calibration standard should be spiked with
10 pi (5 [iL if a 2 jiL injection is used) of the internal standard solution prior
to analysis. All standards should be stored at -10°C to -20°C and should be
freshly prepared once a year, or sooner if check standards indicate a problem.
The daily calibration standard should be prepared weekly and stored at 4°C.
5.7 Surrogate standards - The recommended surrogate standards are
phenol-d6, 2-fluorophenol, 2,4,6-tribromophenol, nitrobenzene-ds,
2-fluorobiphenyl, and p-terphenyl-d.4. See Method 3500 for the instructions on
preparing the surrogate standards. Determine what concentration should be in the
blank extracts after all extraction, cleanup, and concentration steps. Inject
this concentration into the GC/MS to determine recovery of surrogate standards
in all blanks, spikes, and sample extracts. Take into account all dilutions of
sample extracts.
5.8 Matrix spike standards - See Method 3500 for instructions on preparing
the matrix spike standard. Determine what concentration should be in the blank
extracts after all extraction, cleanup, and concentration steps. Inject this
concentration into the GC/MS to determine recovery of surrogate standards in all
matrix spikes. Take into account all dilutions of sample extracts.
5.9 Acetone, hexane, methylene chloride, isooctane, carbon disulfide,
toluene, and other appropriate solvents - Pesticide quality or equivalent
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Sample preparation - Samples must be prepared by one of the following
methods prior to GC/MS analysis.
Matrix Methods
Water 3510, 3520
Soil/sediment 3540, 3550
Waste 3540, 3550, 3580
7.1.1 Direct injection - In very limited applications direct
injection of the sample into the GC/MS system with a 10>L syringe may be
appropriate. The detection limit is very high (approximately 10,000 M9/L);
therefore, it is only permitted where concentrations in excess of
10,000 /zg/L are expected. The system must be calibrated by direct
injection.
8270A - 10 Revision 1
July 1992
-------
7.2 Extract cleanup - Extracts may be cleaned up by any of the following
methods prior to GC/MS analysis.
Compounds
Phenols
Phthalate esters
Nitrosamines
Organochlorine pesticides & PCBs
Nitroaromatics and cyclic ketones
Polynuclear aromatic hydrocarbons
Haloethers
Chlorinated hydrocarbons
Organophosphorus pesticides
Petroleum waste
All priority pollutant base,
neutral, and acids
Methods
3630, 3640, 8040a
3610, 3620, 3640
3610, 3620, 3640
3620, 3660
3620, 3640
3611, 3630, 3640
3620, 3640
3620, 3640
3620
3611, 3650
3640
"Method 8040 includes a derivatization technique followed by GC/ECD analysis,
interferences are encountered on GC/FID.
7.3 Initial calibration - The recommended GC/MS operating conditions:
if
Mass range:
Scan time:
Initial temperature:
Temperature program:
Final temperature:
injector temperature:
Transfer line temperature:
Source temperature:
Injector:
Sample volume:
Carrier gas:
35-500 amu
1 sec/scan
40°C, hold for 4 minutes
40-270°C at 10°C/min
270°C, hold until benzo[g,h,i]perylene has
eluted
250-300°C
250-300°C
According to manufacturer's specifications
Grob-type, splitless
1-2 ML
Hydrogen at 50 cm/sec or helium at 30
cm/sec
7.j.l Each GC/MS system must be hardware-tuned to meet the criteria
in Table 3 for a 50 ng injection of DFTPP. Analyses should not begin until
all these criteria are met. Background subtraction should be
straightforward and designed only to eliminate column bleed or instrument
background ions. The GC/MS tuning standard should also be used to ass.ess
GC column performance and injection port inertness. Degradation of DOT to
DDE and ODD should not exceed 20%. Benzidine and pentachlorophenol should
be present at their normal responses, and no peak tailing should be
visible. If degradation is excessive and/or poor chromatography is noted,
the injection port may require cleaning. It may also be necessary to break
off the first 6-12 in. of the capillary column.
7.3.2 The internal standards selected in Section 5.1 should permit
most of the components of interest in a chromatogram to have retention
times of 0.80-1.20 relative to one of the internal standards. Use the base
peak ion from the specific internal standard as the primary ion for
quantitation (see Table 1). If interferences are noted, use the next most
8270A - 11
Revision 1
July 1992
-------
intense ion as the quantitation ion (i.e. for l,4-dichlorobenzene-d4 use
m/z 152 for quantitation).
7.3.3 Analyze 1 pi of each calibration standard (containing internal
standards) and tabulate the area of the primary characteristic ion against
concentration for each compound (as indicated in Table 1). Figure 1 shows
a chromatogram of a calibration standard containing base/neutral and acid
analytes. Calculate response factors (RFs) for each compound as follows:
RF = (AxCit)/(A,.Cx)
where:
Ax = Area of the characteristic ion for the compound being
measured.
A-s = Area of the characteristic ion for the specific internal
standard.
Cjs = Concentration of the specific internal standard
Cx = Concentration of the compound being measured (ng//nL).
7.3.4 The average RF should be calculated for each compound. The
percent relative standard deviation (%RSD = 100[SD/RF]) should also be
calculated for each compound. The %RSD should be less than 30% for each
compound. However, the %RSO for each individual Calibration Check Compound
(CCC) (see Table 4) must be less than 30%. The relative retention times
of each compound in each calibration run should agree within 0.06 relative
retention time units. Late-eluting compounds usually have much better
agreement.
7.3.5 A system performance check must be performed to ensure that
minimum average RFs are met before the calibration curve is used. For
semivolatiles, the System Performance Check Compounds (SPCCs) are: N-
nitroso-di-n-propylamine; hexachlorocyclopentadiene; 2,4-dinitro-phenol ;
and 4-nitrophenol . The minimum acceptable average RF for these compounds
SPCCs is 0.050. These SPCCs typically have very low RFs (0.1-0.2) and tend
to decrease in response as the chromatographic system begins to deteriorate
or the standard material begins to deteriorate. They are usually the first
to show poor performance. Therefore, they must meet the minimum
requirement when the system is calibrated.
7.4 Daily GC/MS calibration
7.4.1 Prior to analysis of samples, the GC/MS tuning standard must
be analyzed. A 50 ng injection of DFTPP must result in a mass spectrum for
DFTPP which meets the criteria given in Table 3. These criteria must be
demonstrated during each 12 hour shift.
7.4.2 A calibration standard(s) at mid-concentration, containing
each compound of interest, including all required surrogates, must be
performed every 12 hours during analysis. Compare the response factor data
from the standards every 12 hours with the average response factor from the
8270A - 12 Revision 1
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initial calibration for a specific instrument as per the SPCC (Section
7.4.3) and CCC (Section 7.4.4) criteria.
7.4.3 System Performance Check Compounds (SPCCs): A system
performance check must be made during every 12 hour shift. If the SPCC
criteria are met, a comparison of response factors is made for all
compounds. This is the same check that is applied during the initial
calibration. If the minimum response factors are not met, the system must
be evaluated, and corrective action must be taken before sample analysis
begins. The minimum RF for semivolatile SPCCs is 0.050. Some possible
problems are standard mixture degradation, injection port inlet
contamination, contamination at the front end of the analytical column, and
active sites in the column or chromatographic system. This check must be
met before analysis begins.
7.4.4 Calibration Check Compounds (CCCs): After the system
performance check is met, CCCs listed in Table 4 are used to check the
validity of the initial calibration. Calculate the percent difference
using:
RF, - RFC
% Difference = x 100
RF,
where:
RFj = Average response factor from initial calibration
(Section 7.3).
RFC = Response factor from current verification check standard.
If the percent difference for any compound is greater than 20, the
laboratory should consider this a warning limit. If the percent difference
for each CCC is less than 30%, the initial calibration is assumed to be
valid. If the criterion is not met (> 30% difference) for any one CCC,
corrective action must be taken. Problems similar to those listed under
SPCCs could affect this criterion. If no source of the problem can be
determined after corrective action has been taken, a new five-point
calibration must be generated. This criterion must be met before sample
analysis begins.
7.4.5 The internal standard responses and retention times in the
calibration check standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard changes
by more than 30 seconds from the las-t daily calibration (Section 7.4), the
chromatographic system must be inspected for malfunctions and corrections
must be made, as required. If the EICP area for any of the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration standard check, the mass spectrometer must be inspected for
malfunctions and corrections must be made, as appropriate.
7.5 GC/MS analysis
7.5.1 It is highly recommended that the extract be screened on a
GC/FID or GC/PID using the same type of capillary column. This will
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minimize contamination of the GC/MS system from unexpectedly high
concentrations of organic compounds.
7.5.2 Spike the 1 ml extract obtained from sample preparation with
10 nl of the internal standard solution just prior to analysis.
7.5.3 Analyze the 1 ml extract by GC/MS using a 30 m x 0.25 mm (or
0.32 mm) silicone-coated fused-silica capillary column. The volume to be
injected should ideally contain 100 ng of base/neutral and 200 ng of acid
surrogates (for a 1 /iL injection). The recommended GC/MS operating
conditions to be used are specified in Section 7.3.
7.5.4 If the response for any quantitation ion exceeds the initial
calibration curve range of the GC/MS system, extract dilution must take
place. Additional internal standard must be added to the diluted extract
to maintain the required 40 ng//iL of each internal standard in the
extracted volume. The diluted extract must be reanalyzed.
7.5.5 Perform all qualitative and quantitative measurements as
described in Section 7.6. Store the extracts at 4°C, protected from light
in screw-cap vials equipped with unpierced Teflon lined septa.
7.6 Data interpretation
7.6.1 Qualitative analysis
7.6.1.1 An analyte (e.g. those listed in Table 1) is
identified by comparison of the sample mass spectrum with the mass
spectrum of a standard of the suspected compound (standard reference
spectrum). Mass spectra for standard reference should be obtained on
the isyr's GC/MS within the same 12 hours as the sample analysis.
These standard reference spectra may be obtained through analysis of
the calibration standards. Two criteria must be satisfied to verify
identification: (1) elution of sample component at the same GC
relative retention time (RRT) as the standard component; and (2)
correspondence of the sample component and the standard component
mass -.pectrum.
7.6.1.1.1 The sample component RRT must compare within
+ 0.06 RRT units of the RRT of the standard component. For
reference, the standard must be run within the same 12 hours
as the sample. If coelution of interfering components
prohibits accurate assignment of the sample component RRT from
the total ion chromatogram, the RRT should be assigned by
using extracted ion current profiles for ions unique to the
component of interest.
7.6.1.1.2 All ions present in the standard mass
spectrum at a relative intensity greater than 10% (most
abundant ion in the spectrum equals 100% must be present in
the sample spectrum.
7.6.1.1.3 The relative intensities of ions specified
in Section 7.6.1.1.2 must agree within plus or minus 20%
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between the standard and sample spectra. (Example: For an
ion with an abundance of 50% in the standard spectrum, the
corresponding sample abundance must be between 30 and 70
percent.)
7.6.1.2 For samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification' will be determined by the purpose of the
analyses being conducted. Computer generated library search routines
should not use normalization routines that would misrepresent the
library or unknown spectra when compared to each other. For example,
the RCRA permit or waste deli sting requirements may require the
reporting of nontarget analytes. Only after visual comparison of
sample spectra with the nearest library searches will the mass
spectral interpretation specialist assign a tentative identification.
Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should be present in
the sample spectrum.
(2) The relative intensities of the-major ions should agree
within ± 20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%.)
(3) Molecular ions present in the reference spectrum should be
present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible background
contamination or presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or coeluting
peaks. Data system library reduction programs can sometimes create
these discrepancies.
7.6.2 Quantitative analysis
7.6.2.1 When a compound has been identified, the
quantitation of that compound will be based on the integrated
abundance from the EICP of the primary characteristic ion.
Quantitation will take place using the internal standard technique.
The internal standard used shall be the one nearest the retention
time of that of a given analyte (e.g. see Table 5).
7.6.2.2 Calculate the concentration of each identified
analyte in the sample as follows:
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Water:
concentration (M9/L) =
(Ais)(RF)(Vo)(Vj)
where:
Ax = Area of characteristic ion for compound being
measured. •
Is = Amount of internal standard injected (ng).
Vt = Volume of total extract, taking into account
dilutions (i.e. a l-to-10 dilution of a 1 ml
extract will mean Vt = 10,000 /iL. If half the
base/neutral extract and half the acid extract
are combined, Vt = 2,000).
A.s = Area of characteristic ion for the internal
standard.
RF = Response factor for compound being measured
(Section 7.3.3).
V0 = Volume of water extracted (ml).
V = Volume of extract injected
Sediment/Soil Sludge (on a dry-weight basis) and Waste
(normally on a wet-weight basis):
concentration (/igAg) = —
(A
where:
AX' Is' vt> Ais> RF, V. = Same as for water.
Ws = Weight of sample extracted or diluted in grams.
0 = % dry weight of sample/100, or 1 for a wet-weight
basis.
7.6.2.3 Where appl icable, an estimate of concentration for
noncalibrated components in the sample should be made. The formulas
given above should be used with the following modifications: The
areas A and A. should be from the total ion chromatograms and the
RF for the compound should be assumed to be 1. The concentration
obtained should be reported indicating (1) that the value' is an
estimate and (2) which internal standard was used to determine
concentration. Use the nearest internal standard free of
interferences.
7.6.2.4 Quantitation of multicomponent compounds (e.g.
Aroclors) is beyond the scope of Method 8270A. Normally,
quantitation is performed using a GC/ECD by Method 8080.
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8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program consist
of an initial demonstration of laboratory capability and an ongoing analysis of
spiked samples to evaluate and document quality data. The laboratory must
maintain records to document the quality of the data generated. Ongoing data
quality checks are compared with established performance criteria to determine
if the results of analyses meet the performance characteristics of the method.
When results of sample spikes indicate atypical method performance, a quality
control reference sample must be analyzed to confirm that the measurements were
performed in an in-control mode of operation.
8.2 Before processing any samples, the analyst must demonstrate, through
the analysis of a reagent blank, that interferences from the analytical system,
glassware, and reagents are under control. Each time a set of samples is
extracted or there is a change in reagents, a reagent blank should be processed
as a safeguard against chronic laboratory contamination. The blank samples
should be carried through all stages of sample preparation and measurement.
8.3 The experience of the analyst performing GC/MS analyses is invaluable
to the success of the methods. Each day that analysis is performed, the daily
calibration standard should be evaluated to determine if the chromatographic
system is operating properly. Questions that should be asked are: Do the peaks
look normal?; Is the response obtained comparable to the response from previous
calibrations? Careful examination of the standard chromatogram can indicate
whether the column is still good, the injector is leaking, the injector septum
needs replacing, etc. If any changes are made to the system (e.g. column
changed), recalibration of the system must take place,
8.4 Required instrument QC is found in the following sections
8.4.1 The GC/MS system must be tuned to meet the DFTPP
specifications in Sections 7.3.1 and 7.4.1.
8.4,2 There must be an initial calibration of the GC/MS system as
specified in Section 7.3.
8.4.3 The GC/MS system must meet the SPCC criteria specified in
Section 7.4.3 and the CCC criteria in Section 7.4.4, each 12 hours.
8.5 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.5.1 A quality control (QC) reference sample concentrate is
required containing each analyte at a concentration of 100 mg/L in acetone.
The QC reference sample concentrate may be prepared from pure standard
materials or purchased as certified solutions. If prepared by the
laboratory, the QC reference sample concentrate must be made using stock
standards prepared independently from those used for calibration.
8.5.2 Using a pipet, prepare QC reference samples at a concentration
of 100 /ig/L by adding 1.00 mL of QC reference sample concentrate to each
of four 1-L aliquots of water.
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8.5.3 Analyze the well-mixed QC reference samples according to the
method beginning in Section 7.1. with extraction of the samples.
8.5.4 Calculate the average recovery (x) in /xg/L, and the standard
deviation of the recovery (s) in /ig/L, for each analyte using the four
results.
8.5.5 For each analyte compare s and x with the corresponding
acceptance criteria_for precision and accuracy, respectively, found in
Table 6. If s and x for all analytes meet the acceptance criteria, the
system performance is acceptable and analysis of actual samples can_begin.
If any individual s exceeds the precision limit or any individual x falls
outside the range for accuracy, then the system performance is unacceptable
for that analyte.
NOTE: The large number of analytes in Table 6 present a substantial
probability that one or more will fail at least one of the
acceptance criteria when all analytes of a given method are
analyzed.
8.5.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst must proceed according to Section
8.5.6.1 or 8.5.6.2.
8.5.6.1 Locate and correct the source of the problem and
repeat the test for all analytes beginning with Section 8.5.2.
8.5.6.2 Beginning with Section 8.5.2, repeat the test only
for those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If ^his occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Step
8.5.2.
8.6 The laboratory must, on an ongoing basis, analyze a reagent blank, a
matrix spike, end a replicate for each analytical batch (up to a maximum of 20
samples/batch) to assess accuracy. For soil and waste samples where detectable
amounts of organics are present, replicate samples may be appropriate if' place
of matrix spiked samples. For laboratories analyzing one to ten samples per
month, at least one spiked sample per month is required.
8.6.1 The concentration of the spike in the sample should be
determined as follows:
8.6.1.1 If, as in compliance monitoring, the concentration
of a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at that limit or
1 to 5 times higher than the background concentration determined in
Step 8.6.2, whichever concentration would be larger.
8.6.1.2 If the concentration of a specific analyte in a
water sample is not being checked against a limit specific to that
analyte, the spike should be at 100 jig/L or 1 to 5 times higher than
the background concentration determined in Step 8.6.2, whichever
8270A - 18 Revision 1
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concentration would be larger. For other matrices, recommended
spiking concentration is 20 times the EQL.
8.6.1.3 If it is impractical to determine background
levels before spiking (e.g. maximum holding times will be exceeded),
the spike concentration should be at (1) the regulatory concentration
limit, if any; or, if none (2) the larger of either 5 times higher
than the expected background concentration or 100 ng/1. For other
matrices, recommended spiking concentration is 20 times the EQL.
8.6.2 Analyze one sample aliquot to determine the background
concentration (B) of each analyte. If necessary, prepare a new QC
reference sample concentrate (Step 8.5.1) appropriate for the background
concentration in the sample. Spike a second sample aliquot with 1.00 ml
of the QC reference sample concentrate and analyze it to determine the
concentration after spiking (A) of each analyte. Calculate each percent
recovery (p) as 100(A-B)%/T, where T is the known true value of the spike.
8.6.3 Compare the percent recovery (p) for each analyte in a water
sample with the corresponding QC acceptance criteria found in Table 6.
These acceptance criteria were calculated to include an allowance for error
in measurement of both the background and spike concentrations, assuming
a spike to background ratio of 5:1. This error will be accounted for to
the extent that the analyst's spike to background ratio approaches 5:1.
If spiking was performed at a concentration lower than 100 fig/L, the
analyst must use either the QC acceptance criteria presented in Table 6,
or optional QC acceptance criteria calculated for the specific spike
concentration. To calculate optional acceptance criteria for the recovery
of an analyte: (1) Calculate accuracy (x') using the equation found in
Table 7, substituting the spike concentration (T) for C; (2) calculate
overall precision (S') using the equation in Table 7, substituting x' for
x; (3) calculate the range for recovery at the spike concentration as
(lOOx'/T) ± 2.44(100S7T)%.
8.6.4 If any individual p falls outside the designated range for
recovery, that analyte has failed the acceptance criteria. A check
standard containing each analyte that failed the criteria must be analyzed
as described in Section 8.7.
8.7 If any analyte in a water sample fails the acceptance criteria for
recovery in Section 8.6, a QC reference sample containing each analyte that
failed must be prepared and analyzed.
NOTE; The frequency for the required analysis of a QC reference
sample will depend upon the number of analytes being
simultaneously tested, the complexity of the sample matrix,
and the performance of the laboratory. If the entire list of
analytes in Table 6 must be measured in the sample in Section
8.6, the probability that the analysis of a QC reference
sample will be required is high. In this case the QC
reference sample should be routinely analyzed with the spiked
sample.
8270A - 19 Revision 1
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8.7.1 Prepare the QC reference sample by adding 1.0 ml of the QC
reference sample concentrate (Section 8.5.1 or 8.6.2) to 1 L of water. The
QC reference sample needs only to contain the analytes that failed criteria
in the test in Section 8.6.
8.7.2 Analyze the QC reference sample to determine the concentration
measured (A) of each analyte. Calculate each percent recovery (ps) as
100(A/T)%, where T is the true value of the standard concentration.
8.7.3 Compare the percent recovery (ps) for each analyte with the
corresponding QC acceptance criteria found in Table 6. Only analytes that
failed the test in Step 8.6 need to be compared with these criteria. If
the recovery of any such analyte falls outside the designated range, the
laboratory performance for that analyte is judged to be out of control, and
the problem must be immediately identified and corrected. The analytical
result for that analyte in the unspiked sample is suspect and may not be
reported for regulatory compliance purposes.
8.8 As part of the QC program for the laboratory, method accuracy for each
matrix studied must be assessed and records must be maintained. After the
analysis of five spiked samples (of the same matrix) as in Section 8.6, calculate
the average percent recovery (p) and the standard deviation of the percent
recovery (s ). Express the accuracy assessment as a percent recovery interval
from p - 2s to p + 2s . If p = 90% and s = 10%, for example, the accuracy
interval is expressed as 70-110%. Update the accuracy assessment for each
analyte on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.9 To determine acceptable accuracy and precision limits for surrogate
standards the following procedure should be performed.
8.9.1 For each sample analyzed, calculate the percent recovery of
each surrogate in the sample.
8.9.2 Once a minimum of thirty samples of the same matrix have been
analyzed, calculate the average percent recovery (p) and standard deviation
of the percent recovery (s) for each of the surrogates.
8.9.3 For a given matrix, calculate the upper and lower control
limit for method performance for each surrogate standard. This should be
done as follows:
Upper Control Limit (UCL) = p + 3s
Lower Control Limit (LCL) = p - 3s
8.9.4 For aqueous and soil matrices, these laboratory established
surrogate control limits should, if applicable, be compared with the
control limits listed in Table 8. The limits given in Table 8 are multi-
laboratory performance based limits for soil and aqueous samples, and
therefore, the single-laboratory limits established in Step 8.9.3 must fall
within those given in Table 8 for these matrices.
8270A - 20 Revision 1
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8.9.5 If recovery is not within limits, the following procedures are
required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are a
problem or flag the data as "estimated concentration".
8.9.6 At a minimum, each laboratory should update surrogate recovery
limits on a matrix-by-matrix basis, annually.
8.10 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 assess the precision of the
environmental measurements. When doubt exists over the identification of a peak
on the chromatogram, confirmatory techniques such as gas chromatography with a
dissimilar column, specific element detector, or mass spectrometer must be used.
Whenever possible, the laboratory should analyze standard reference materials and
participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 Method 8250 (the packed column version of Method 8270) was tested by
15 laboratories using Organic-free reagent water, drinking water, surface water,
and industrial wastewaters spiked at six concentrations over the range 5-
1,300 M9/L. Single operator accuracy and precision, and method accuracy were
found to be directly related to the concentration of the analyte and essentially
independent of the sample matrix. Linear equations to describe these
relationships are presented in Table 7. Method performance data for Method 8270
is being developed.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act, Method 625," October 26,
1984.
2. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
3. Eichelberger, J.W., L,E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurement in Gas Chromatography-Mass Spectrometry
Systems," Analytical Chemistry, 47, 995-1000, 1975.
4. "Method Detection Limit for Methods 624 and 625," Olynyk, P., W.L. Budde,
and J.W. Eichelberger, Unpublished report, October 1980.
8270A - 21 Revision 1
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5. "Inter-laboratory Method Study for EPA Method 625-Base/Neutrals, Acids, and
Pesticides," Final Report for EPA Contract 68-03-3102 (in preparation).
6. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
7. Lucas, S.V.; Kornfeld, R.A. "GC-MS Suitability Testing of RCRA Appendix
VIII and Michigan List Analytes "; U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, OH 45268,
February 20, 1987, Contract No. 68-03-3224.
8. Engel, T.M.; Kornfeld, R.A.; Warner, J.S.; Andrews, K.D. "Screening of
Semivolatile Organic Compounds for Extractabllity and Aqueous Stability by
SW-846, Method 3510"; U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Cincinnati, OH 45268, June 5, 1987,
Contract 68-03-3224.
8270A - 22 Revision 1
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TABLE 1.
CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS
Compound
2-Picoline
Aniline
Phenol
Bis(2-chloroethyl) ether
2-Chlorophenol
1,3-Dichlorobenzene
l,4-Dichlorobenzene-d4 (I.S.)
1,4-Dichlorobenzene
Benzyl alcohol
1,2-Dichlorobenzene
N-Ni trosomethyl ethyl ami ne
Bis(2-chloroisopropyl) ether
Ethyl carbamate
Thiophenol (Benzenethiol )
Methyl methanesulfonate
N-Nitrosodi -n-propylamine
Hexachloroethane
Maleic anhydride
Nitrobenzene
Isophorone
N-Nitrosodi ethyl ami ne
2-Nitrophenol
2,4-Dimethylphenol
p-Benzoquinone
Bis(2-chloroethoxy)methane
Benzoic acid
2,4-Dichlorophenol
Trimethyl phosphate
Ethyl methanesulfonate
1,2,4-Trichlorobenzene
Naphthalene-da (I.S.)
Naphthalene
Hexachl orobutadi ene
Tetraethyl pyrophosphate
Diethyl sulfate
4-Chl oro-3-methyl phenol
2-Methyl naphthalene
2-Methyl phenol
Hexachl oropropene
Hexachl orocycl opentadi ene
N-Nitrosopyrrol idine
Acetophenone
4-Methyl phenol
2,4,6-Trichlorophenol
o-Toluidine
3-Methylphenol
2-Chloronaphthalene
Retention
Time (min.)
3.75a
5.68
5.77
5.82
5.97
6.27
6.35
6.40
6.78
6.85
6.97
7.22
7.27
7.42
7.48
7.55
7.65
7.65
7.87
8.53
8.70
8.75
9.03
9.13
9.23
9.38
9.48
9.53
9.62
9.67
9.75
9.82
10.43
11.07
11.37
11.68
11-. 87
12.40
12.45
12.60
12.65
12.67
12.82
12.85
12.87
12.93
13.30
Primary
Ion
93
93
94
93
128
146
152
146
108
146
88
45
62
110
80
70
117
54
77
82
102
139
122
108
93
122
162
110
79
180
136
128
225
99
139
107
142
107
213
237
100
105
107
196
106
107
162
Secondary
Ion(s)
66,92
66,65
65,66
63,95
64,130
148,111
150,115
148,111
79,77
148,111
42,88,43,56
77,121
62,44,45,74
110,66,109,84
80,79,65,95
42,101,130
201,199
54,98,53,44
123,65
95,138
102,42,57,44,56
109,65
107,121
54,108,82,80
95,123
105,77
164,98
110,79,95,109,140
79,109,97,45,65
182,145
68
129,127
223,227
99,155,127,81,109
139,45,59,99,111,125
144,142
141
107,108,77,79,90
213,211,215,117,106,141
235,272
100,41,42,68,69
71,105,51,120
107,108,77,79,90
198,200
106,107,77,51,79
107,108,77,79,90
127,164
8270A - 23
Revision 1
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TABLE 1.
(Continued)
Compound
Retention
Time (min.)
Primary
Ion
Secondary
Ion(s)
N-Nitrosopiperidine 13.55
1,4-Phenylenediamine 13.62
1-Chloronaphthalene 13.658
2-Nitroaniline 13.75
5-Ch1oro-2-methylani1ine 14.28
Dimethyl phthalate 14.48
Acenaphthylene 14.57
2,6-Dinitrotoluene 14.62
Phthalic anhydride 14.62
o-Anisidine 15.00
3-Nitroaniline 15.02
Acenaphthene-d10 (I.S.) 15.05
Acenaphthene 15.13
2,4-Dinitrophenol 15.35
2,6-Dinitrophenol 15.47
4-Chloroaniline 15.50
Isosafrole 15.60
Dibenzofuran 15.63
2,4-Diaminotoluene 15.78
2,4-Dinitrotoluene 15.80
4-Nitrophenol 15.80
2-Naphthylamine 16.00a
1,4-Naphthoquinone 16.23
p-Cresidine 16.45
Oichlorovos 16.48
Diethyl phthalate 16.70
Fluorene 16.70
2,4,5-Trimethylaniline 16.70
N-Nitrosodibutylamine 16.73
4-Chlorophenyl phenyl ether 16.78
Hydroquinone 16.93
4,6-Dinitro-2-methylpheno1 17.05
Resorcinol 17.13
N-Nitrosodiphenylamine 17.17
Safrole 17.23
Hexamethyl phosphoramide 17.33
3-(Chloromethy1)pyridine hydrochloride!7,50
Diphenylamine 17.548
1,2,4,5-Tetrachlorobenzene 17.97
1-Naphthylamine 18.20
l-Acetyl-2-thiourea 18.22
4-Bromophenyl phenyl ether 18.27
Toluene diisocyanate 18.42
2,4,5-Trichlorophenol 18.47
Hexachlorobenzene 18.65
Nicotine 18.70
Pentachlorophenol 19.25
8270A - 24
114 42,114,55,56,41
108 108,80,53,54,52
162 127,164
65 92,138
106 106,141,140,77,89
163 194,164
152 151,153
165 63,89
104 104,76,50,148
108 80,108,123,52
138 108,92
164 162,160
154 153,152
184 63,154
162 162,164,126,98,63
127 127,129,65,92
162 162,131,104,77,51
168 139
121 121,122,94,77,104
165 63,89
139 109,65
143 115,116
158 158,104,102,76,50,130
122 122,94,137,77,93
109 109,185,79,145
149 177,150
166 165,167
120 120,135,134,91,77
84 84,57,41,116,158
204 206,141
110 110,81,53,55
198 51,105
110 110,81,82,53,69
169 168,167
162 162,162,104,77,103,135
135 135,44,179,92,42
92 92,127,129,65,39
169 168,167
216 216,214,179,108,143,218
143 143,115,89,63
118 43,118,42,76
248 250,141
174 174,145,173,146,132,91
196 196,198,97,132,99
284 142,249
84 84,133,161,162
266 264,268
Revision 1
July 1992
-------
TABLE 1.
(Continued)
Compound
Retention
Time (min.)
Primary Secondary
Ion Ion(s)
5-Nitro-o-toluidine
Thionazine
4-Nitroaniline
Phenanthrene-d10( i. s.)
Phenanthrene
Anthracene
1,4-Dinitrobenzene
Mevinphos
Naled
1,3-Oinitrobenzene
Diallate (cis or trans)
1,2-Dinitrobenzene
Diallate (trans or cis)
Pentachlorobenzene
5-Nitro-o-anisidine
Pentachloronitrobenzene
4-Nitroquinoline-1-oxide
Di-n-butyl phthalate
2,3,4,6-Tetrachlorophenol
Demeton-0
Fluoranthene
1,3,5-Trinitrobenzene
Dicrotophos
Benzidine
Trifluralin
Bromoxynil
Pyrene
Monocrotophos
Phorate
Sulfall ate
Demeton-S
Phenacetin
Dimethoate
Phenobarbital
Carbofuran
Octamethyl pyrophosphoramide
4-Aminobiphenyl
Terbufos
a,a-Oimethylphenylamine
Pronamide
Aminoazobenzene
Dichlone
Dinoseb
Disulfoton
Fluchloralin
Mexacarbate
4,4'-Oxydianiline
19.27 152 77,152,79,106,94
19.35 107 96,107,97,143,79,68
19.37 138 138,65,108,92,80,39
19.55 188 94,80
19.62 178 179,176
19.77 178 176,179
19.83 168 168,75,50,76,92,122
19.90 127 127,192,109,67,164
20.03 109 109,145,147,301,79,189
20.18 168 168,76,50,75,92,122
20.57 86 86,234,43,70
20.58 168 168,50,63,74
20.78 86 86,234,43,70
21.35 250 250,252,108,248,215,254
21.50 168 168,79,52,138,153,77
21.72 237 237,142,214,249,295,265
21.73 174 174,101,128,75,116
21.78 149 150,104
21.88 232 232,131,230,166,234,168
22.72 88 88,89,60,61,115,171
23.33 202 101,203
23.68 75 75,74,213,120,91,63
23.82 127 127,67,72,109,193,237
23.87 184 92,185
23.88 306 306,43,264,41,290
23.90 277 277,279,88,275,168
24.02 202 200,203
24.08 127 127,192,67,97,109
24.10 75 75,121,97,93,260
24.23 188 188,88,72,60,44
24.30 88 88,60,81,89,114,115
24.33 108 180,179,109,137,80
24.70 87 87,93,125,143,229
24.70 204 204,117,232,146,161
24.90 164 164,149,131,122
24.95 135 135,44,199,286,153,243
25.08 169 169,168,170,115
25.35 231 231,57,97,153,103
25.43 58 58,91,65,134,42
25.48 173 173,175,145,109,147
25.72 197 92,197,120,65,77
25.77 191 191,163,226,228,135,193
25.83 211 211,163,147,117,240
25.83 88 88,97,89,142,186
25.88 306 306,63,326,328,264,65
26.02 165 165,150,134,164,222
26.08 200 200,108,171,80.65
8270A - 25 Revision 1
July 1992
-------
TABLE 1.
(Continued)
Compound
Retention
Time (min.)
Primary Secondary
Ion Ion(s)
Butyl benzyl phthalate
4-Nitrobiphenyl
Phosphamidon
2-Cyclohexyl-4,6-Dinitrophenol
Methyl parathion
Carbaryl
Dimethyl aminoazobenzene
Propylthiouracil
Benz(a)anthracene
Chrysene-d12 (I.S.)
3,3'-Dichlorobenzidine
Chrysene
Malathion
Kepone
Fenthion
Parathion
Anilazine
Bis(2-ethylhexyl) phthalate
3,3'-Dimethylbenzidine
Carbophenothion
5-Nitroacenaphthene
Methapyrilene
Isodrin
Captan
Chlorfenvinphos
Crotoxyphos
Phosmet
EPN
Tetrachlorvinphos
Di-n-octyl phthalate
2-Ami noanthraqu i none
Barban
Aramite
Benzo(b)f1uoranthene
Nitrofen
Benzo(k)fl uoranthene
Chiorobenzilate
Fensulfothion
Ethion
Diethylstilbestrol
Famphur
Tri-p-tolyl phosphate
Benzo(a)pyrene
Perylene-d)2 (I.S.)
7,12-Dimetnylbenz(a)anthracene
5,5-Di phenylhydantoi n
Captafol
26.43 149 91,206
26.55 199 199,152,141,169,151
26.85 127 127,264,72,109,138
26.87 231 231,185,41,193,266
27.03 109 109,125,263,79,93
27.17 144 144,115,116,201
27.50 225 225,120,77,105,148,42
27.68 170 170,142,114,83
27.83 228 229,226
27.88 240 120,236
27.88 252 254,126
27.97 228 226,229
28.08 173 173,125,127,93,158
28.18 272 272,274,237,178,143,270
28.37 278 278,125,109,169,153
28.40 109 109,97,291,139,155
28.47 239 239,241,143,178,89
28.47 149 167,279
28.55 212 212,106,196,180
28.58 157 157,97,121,342,159,199
28.73 199 199,152,169,141,115
28.77 97 97,50,191,71
28.95 193 193,66,195,263,265,147
29.47 79 79,149,77,119,117
29.53 267 267,269,323,325.295
29.73 127 127,105,193,166
30.03 160 160,77,93,317,76
30.11 157 157,169,185,141,323
30.27 329 109,329,331,79,333
30.48 149 167,43
30.63 223 223,167,195
30.83 222 222,51,87,224,257,153
30.92 185 185,191,319,334,197,321
31.45 252 253,125
31.48 283 283,285,202,139,253
31.55 252 253,125
31.77 251 251,139,253,111,141
31.87 293 293,97,308,125,292
32.08 231 231,97,153,125,121
32.15 268 268,145,107,239,121,159
32.67 218 218,125,93,109,217
32.75 368 358,367,107,165,198
32.80 252 253,125
33.05 264 260,265
33.25 256 256,241,239,120
33.40 180 180,104,252,223,209
33.47 79 79,77,80,107
8270A - 26
Revision 1
July 1992
-------
TABLE 1.
(Continued)
Compound
Retention
Time (min.)
Primary Secondary
Ion Ion(s)
Dinocap
Methoxychlor
2-Acetylami nof1uorene
4,4'-Methylenebis(2-ch1oroaniline)
3,3'-Dimethoxybenzidine
3-Methylcholanthrene
Phosalone
Azinphos-methyl
Leptophos
Mirex
Tris(2,3-dibromopropyl) phosphate
Dibenz(a,j)acridine
Mestranol
Coumaphos
Indeno(l,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
l,2:4,5-Dibenzopyrene
Strychnine
Piperonyl sulfoxide
Hexachlorophene
Aldrin
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
a-BHC
0-BHC
5-BHC
Y-BHC (Lindane)
4,4'-DDD
4,4'-DDE
4,4/-ODT
Dieldrin
1,2-Diphenylhydrazine
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
2-Fluorobiphenyl (surr.)
2-Fluorophenol (surr.)
33.47 69 69,41,39
33.55 227 227,228,152,114,274,212
33.58 181 181,180,223,152
34.38 231 231,266,268,140,195
34.47 244 244,201,229
35.07 268 268,252,253,126,134,113
35.23 182 182,184,367,121,379
35.25 160 160,132,93,104,105
35.28 171 171,377,375,77,155,379
35.43 272 272,237,274,270,239,235
35.68 201 137,201,119,217,219,199
36.40 279 279,280,277,250
36.48 277 277,310,174,147,242
37.08 362 362,226,210,364,97,109
39.52 276 138,227
39.82 278 139,279
41.43 276 138,277
41.60 302 302,151,150,300
45.15 334 334,335,333
46.43 162 162,135,105,77
47.98 196 196,198,209,211,406,408
66 263,220
222 260,292
190 224,260
190 224,260
222 256,292
292 362,326
292 362,326
360 362,394
183 181,109
181 183,109
183 181,109
183 181,109
235 237,165
246 248,176
235 237,165
79 263,279
77 105,182
195 339,341
337 339,341
272 387,422
263 82,81
67 345,250
317 67,319
172 171
112 64
8270A - 27
Revision 1
July 1992
-------
TABLE 1.
(Continued)
Retention Primary Secondary
Compound Time (min.) Ion Ion(s)
Heptachlor -- 100 272,274
Heptachlor epoxide -- 353 355,351
Nitrobenzene-d5 (surr.) -- 82 128,54
N-Nitrosodimethylamine -- 42 74,44
Phenol-d, (surr.) -- 99 42,71
Terphenyl-du (surr.) -- 244 122,212
2,4,6-Tribromophenol (surr.) -- 330 332,141
Toxaphene -- 159 231,233
I.S. = internal standard.
surr. = surrogate.
8Estimated retention times.
Substitute for the non-specific mixture, tricresyl phosphate.
8270A - 28 Revision 1
July 1992
-------
TABLE 2.
ESTIMATED QUANTITATION LIMITS (EQLs) FOR SEMIVOLATILE ORGANICS8
Semivolatiles
Acenaphthene
Acenaphthylene
Acetophenone
2-Acetylaminofluorene
l-Acetyl-2-thiourea
2-Aminoanthraquinone
Aminoazobenzene
4-Anrinobiphenyl
Anilazine
o-Anisidine
Anthracene
Aramite
Azinphos-methyl
Barban
Benz( a) anthracene
Benzo(b)fluoranthene
Benzo ( k) fl uoranthene
Benzole acid
Benzo(g,h,i)perylene
Benzo(a)pyrene
p-Benzoquinone
Benzyl alcohol
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl ) ether
Bis(2-chloroisopropyl) ether
4-bromophenyl phenyl ether
Bromoxynil
Butyl benzyl phthalate
Captafol
Captan
Carbaryl
Carbofuran
Carbophenothion
Chlorfenvinphos
4-ChToroaniline
Chlorobenzilate
5-Chloro-2-methyl aniline
4-Chloro-3-methyl phenol
3-(Chloroniethyl)pyridine hydrochloride
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Coumaphos
Estimated
Quantitation
Limits6
Ground water Low Soi
M9/L
10
10
10
20
1000
20
10
20
100
10
10
20
100
200
10
10
10
50
10
10
10
20
10
10
10
10
10
10
20
50
10
10
10
20
20
10
10
20
100
10
10
10
10
40
I/Sediment'
M9/kg
660
660
NO
NO
ND
ND
ND
ND
ND
NO
660
ND
ND
ND
660
660
660
3300
660
660
ND
1300
660
660
660
660
ND
660
ND
ND
ND
ND
ND
ND
1300
ND
ND
1300
ND
660
660
660
660
ND
8270A - 29 Revision 1
July 1992
-------
TABLE 2.
(Continued)
Semivolatiles
p-Cresidine
Crotoxyphos
2-Cyclohexyl -4,6-dinitrophenol
Demeton-0
Demeton-S
Diallate (cis or trans)
Diallate (trans or cis)
2,4-Diaminotoluene
Dibenz(a,j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Dibenzo(a,e)pyrene
Di-n-butyl phthalate
Dichlone
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Oichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos
Dicrotophos
Diethyl phthalate
Diethylstilbestrol
Diethyl sulfate
Dimethoate
3,3'-Dimethoxybenzidine
Dimethyl aminoazobenzene
7, 12 -Dimethyl benz( a) anthracene
3,3'-Oimethylbenzidine
a , a-Di methyl phenethyl ami ne
2,4-Dimethylphenol
Dimethyl phthalate
1,2-Dinitrobenzene
1,3-Di nitrobenzene
1,4-Dinitrobenzene
4, 6-Dinitro-2-methyl phenol
2,4-D'initrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap
Dinoseb
5,5-Oiphenylhydantoin
Di-n-octyl phthalate
Estimated
Quantitation
Limits"
Ground water Low Soi
M9/L
10
20
100
10
10
10
10
20
10
10
10
10
10
NA
10
10
10
20
10
10
10
10
10
20
100
20
100
10
10
10
ND
10
10
40
20
40
50
50
10
10
100
20
20
10
1 /Sediment'
M9/kg
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
660
ND
ND
ND
660
660
660
1300
660
ND
ND
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
660
660
ND
ND
ND
3300
3300
660
660
NO
ND
ND
660
8270A - 30
Revision 1
July 1992
-------
Semivolatiles
Disulfoton
EPN
Ethion
Ethyl carbamate
Bis(2-ethylhexyl) phthalate
Ethyl methanesulfonate
Famphur
Fensulfothion
Fenthion
Fluchloral in
Fluoranthene
Fluorene
Hexachl orobenzene
Hexachlorobutadiene
Hexachl orocyclopentadiene
Hexachloroethane
Hexachlorophene
Hexachl oropropene
Hexamethylphosphoramide
Hydroquinone
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
Isosafrole
Kepone
Leptophos
Malathion
Maleic anhydride
Mestranol
Me.thapyrilene
Methoxychlor
3-Methyl chol anthrene
4,4' -Methylenebi.s(2-chloroani
Methyl methanesulfonate
2-Methylnaphthalene
Methyl parathion
2-Methyl phenol
3-Methyl phenol
4-Methyl phenol
Mevinphos
Mexacarbate
Mirex
Monocrotophos
Naled
TABLE 2.
(Continued)
Estimated
Quantisation
. Limits
Ground water Low Soi
M9/L
10
10
10
50
10
20
20
40
10
20
10
10
10
10
10
10
50
10
20
ND
10
20
10
10
20
10
50
NA
20
100
10
10
line) NA
10
10
10
10
10
10
10
20
10
40
20
I/Sediment1
MQAg
NO
ND
ND
ND
660
ND
ND
ND
ND
ND
660
660
660
660
660
660
ND
ND
ND
ND
660
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
ND
660
ND
660
ND
ND
ND
ND
ND
8270A - 31
Revision 1
July 1992
-------
Semivolatiles
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
Nicotine
5-Nitroacenaphthene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
5-Nitro-o-anisidine
Nitrobenzene
4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
5-Nitro-o-toluidine
4-Nitroquinoline-l-oxide
N-Ni trosodi butyl ami ne
N-Ni trosodi ethyl ami ne
N-Ni trosodi phenyl ami ne
N-Ni troso-di-n-propyl ami ne
N-Nitrosopiperidine
N-Nitrosopyrrol idine
Octamethyl pyrophosphoramide
4,4'-Oxydianiline
Parathion
Pentachlorobenzene
Pentachloronitrobenzene
Pentachlorophenol
Phenacetin
Phenanthrene
Phenobarbital
Phenol
1,4- Phenyl enedi ami ne
Phorate
Phosalone
Phosmet
Phosphamidon
Phthalic anhydride
2-Picoline
FMperonyl sulfoxide
Pronamide
Propylthiouracil
Pyrene
TABLE 2.
(Continued)
Estimated
Quantitation
Limits"
Ground water Low Soi
M9/L
10
10
10
10
20
10
50
50
20
10
10
10
20
10
50
10
40
10
20
10
10
20
40
200
20
10
10
20
50
20
10
10
10
10
10
100
40
100
100
NO
100
10
100
10
I/Sediment1
M9/kg
660
NO
NO
NO
NO
ND
3300
3300
ND
ND
660
ND
ND
660
3300
ND
ND
ND
ND
660
660
ND
ND
ND
ND
ND
ND
ND
3300
ND
660
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
8270A - 32
Revision 1
July 1992
-------
TABLE 2.
(Continued)
Estimated
Quantitation
Limits"
Ground water Low Soil/SedimenT
Semivolatiles M9/L
Pyridine
Resorcinol
Safrole
Strychnine
Sul fall ate
Terbufos
1,2,4 , 5-Tetrachl orobenzene
2,3,4,6-Tetrachlorophenol
Tetrachlorvinphos
Tetraethyl pyrophosphate
Thionazine
Thiophenol (Benzenethiol)
Toluene diisocyanate
o-Toluidine
1, 2, 4-Trichl orobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Trifluralin
. 2, 4, 5-Tri methyl aniline
Trimethyl phosphate
1,3, 5-Tri nitrobenzene
Tris(2,3-dibromopropyl ) phosphate
Tri-p-tolyl phosphate(h)
0,0,0-Tri ethyl phosphorothioate
ND
100
10
40
10
20
10
10
20
40
20
20
100
10
10
10
10
10
10
10
10
200
10
NT
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
660
660
ND
ND
ND
ND
ND
ND
ND
a EQLs listed for soil/sediment are based on wet weight. Normally data is
reported on a dry weight basis, therefore, EQLs will be higher based on the
% dry weight of each sample. This is based on a 30 g sample and gel
permeation chromatography cleanup.
b Sample EQLs are highly matrix-dependent. The EQLs listed herein are provided
for guidance and may not always be achievable.
ND = Not determined.
NA = Not applicable.
NT = Not tested.
Other Matrices Factor1
High-concentration soil and sludges by ultrasonic extractor 7.5
Non-water miscible waste 75
1EQL = [EQL for Low Soil/Sediment (Table 2)] X [Factor].
8270A - 33 Revision 1
July 1992
-------
TABLE 3.
DFTPP KEY IONS AND ION ABUNDANCE CRITERIA8
Mass
Ion Abundance Criteria
51
68
70
127
197
198
199
275
365
441
442
443
30-60% of mass 198
< 2% of mass 69
< 2% of mass 69
40-60% of mass 198
< 1% of mass 198
Base peak, 100% relative abundance
5-9% of mass 198
10-30% of mass 198
> 1% of mass 198
Present but less than mass 443
> 40% of mass 198
17-23% of mass 442
aSee Reference 4.
TABLE 4.
CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction
Acid Fraction
Acenaphthene
1,4-Dichlorobenzene
Hexachlorobutadiene
N-Nitrosodiphenylamine
Di-n-octyl phthalate
Fluoranthene
Benzo(a)pyrene
4-Chloro-3-methyl phenol
2,4-Dichlorophenol
2-Nitrophenol
Phenol
Pentachlorophenol
2,4,6-Trichlorophenol
8270A - 34
Revision 1
July 1992
-------
TABLE 5.
SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION
!,4-Dich1orobenzene-d4
Naphthalene-d.
Acenaphthene-d
10
Aniline
Benzyl alcohol
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
Ethyl methanesulfonate
2-Fluorophenol (surr.)
Hexachloroethane
Methyl methanesulfonate
2-Methylphenol
4-Methylphenol
N-Nitrosodimethylamine
N-Nitroso-di-n-propylamine
Phenol
Phenol-d6 (surr.)
2-Picoline
Acetophenone
Benzoic acid
Bis(2-chloroethoxy)methane
4-Chloroaniline
4-Chloro-3-methylphenol
2,4-Dichlorophenol
2,6-Dichlorophenol
a,a-Dimethyl-
phenethylamine
2,4-Dimethylphenol
Hexachlorobutadiene
Isophorone
2-Methylnaphtha!ene
Naphthalene
Nitrobenzene
Nitrobenzene-d8 (surr.)
2-Nitrophenol
N-Nitrosodibutyl amine
N-Nitrosopiperidine
1,2,4-Trichlorobenzene
Acenaphthene
Acenaphthylene
1-Chloronaphthalene
2-Chloronaphthalene
4-Chlorophenyl
phenyl ether
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Fluorene
2-Fluorobiphenyl
(surr.)
Hexachlorocyclo-
pentadiene
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
4-Nitrophenol
Pentachlorobenzene
1,2,4,5-Tetra-
chlorobenzene
2,3,4,6-Tetra-
chlorophenol
2,4,6-Tribromo-
phenol (surr.)
2,4,6-Trichloro-
phenol
2,4,5-Trichloro-
phenol
(surr.) = surrogate
8270A - 35
Revision 1
July 1992
-------
TABLE 5.
(Continued)
Phenanthrene-d
10
Chrysene-d12
Perylene-d
12
4-Aminobiphenyl
Anthracene
4-Bromophenyl phenyl ether
Di-n-butyl phthalate
4,6-Dinitro-2-methylphenol
Diphenylamine
1,2-Diphenylhydrazine
Fluoranthene
Hexachlorobenzene
N-Nitrosodiphenylamine
Pentachlorophenol
Pentachloroni trobenzene
Phenacetin
Phenanthrene
Pronamide
Benzidine
Benzo(a)anthracene
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Chrysene
3,3'-Dichlorobenzidine
p-Dimethyl aminoazobenzene
Pyrene
Terphenyl-d14 (surr.)
Benzo(b)fluor-
anthene
Benzo(k)fluor-
anthene
Benzo(g,h,i)
perylene
Benzo(a)pyrene
Dibenz(a,j)acridine
Dibenz(a,h)
anthracene
7,12-Dimethylbenz-
(a)anthracene
Di-n-octyl phthalate
Indeno(l,2,3-cd)
pyrene
3-Methylchol-
anthrene
(surr.) = surrogate
8270A - 36
Revision 1
July 1992
-------
TABLE 6.
QC ACCEPTANCE CRITERIA8
Compound
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Benzo(ghi )perylene
Benzyl butyl phthalate
/3-BHC
6-BHC
Bis(2-chloroethyl) ether
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl)ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo( a, h) anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Dieldrin
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fluoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachl orobutad i ene
Test
cone.
(M9/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(M9/L)
27.6
40.2
39.0
32.0
27.6
38.8
32.3
39.0
58.9
23.4
31.5
21.6
55.0
34.5
46.3
41.1
23.0
13.0
33.4
48.3
31.0
32.0
61.6
70.0
16.7
30.9
41.7
32.1
71.4
30.7
26.5
23.2
21.8
29.6
31.4
16.7
32.5
32.8
20.7
37.2
54.7
24.9
26.3
Range
for x
(M9/L)
60.1-132.3
53.5-126.0
7.2-152.2
43.4-118.0
41.8-133.0
42.0-140.4
25.2-145.7
31.7-148.0
D-195.0
D-139.9
41.5-130.6
D-100.0
42.9-126.0
49.2-164.7
62.8-138.6
28.9-136.8
64.9-114.4
64.5-113.5
38.4-144.7
44.1-139.9
D-134.5
19.2-119.7
D-170.6
D-199.7
8.4-111.0
48.6-112.0
16.7-153.9
37.3-105.7
8.2-212.5
44.3-119.3
D-100.0
D-100.0
47.5-126.9
68.1-136.7
18.6-131.8
D-103.5
D-188.8
42.9-121.3
71.6-108.4
D-172.2
70.9-109.4
7.8-141.5
37.8-102.2
Range
P» Ps
(%)
47-145
33-145
D-166
27-133
33-143
24-159
11-162
17-163
D-219
D-152
24-149
D-110
12-158
33-184
36-166
8-158
53-127
.60-118
25-158
17-168
D-145
4-136
D-203
D-227
1-118
32-129
D-172
20-124
D-262
29-136
D-114
D-112
39-139
50-158
4-146
D-107
D-209
26-137
59-121
D-192
26.155
D-152
24-116
8270A - 37
Revision 1
July 1992
-------
TABLE 6.
(Continued)
Compound
Test Limit
cone. for s
(/ig/L) (/ig/L)
Range
for x
(M9/L)
Range
P» Ps
(%)
Hexachloroethane 100 24.5
Indeno(l,2,3-cd)pyrene 100 44.6
Isophorone 100 63.3
Naphthalene 100 30.1
Nitrobenzene 100 39.3
N-Nitrosodi-n-propylamine 100 55.4
PCB-1260 100 54.2
Phenanthrene 100 20.6
Pyrene 100 25.2
1,2,4-Trichlorobenzene 100 28.1
4-Chloro-3-methylphenol 100 37.2
2-Chlorophenol 100 28.7
2,4-Chlorophenol 100 26.4
2,4-Dimethylphenol 100 26.1
2,4-Dinitrophenol 100 49.8
2-Methyl-4,6-dinitrophenol 100 93.2
2-Nitrophenol 100 35.2
4-Nitrophenol 100 47.2
Pentachlorophenol 100 48.9
Phenol 100 22.6
2,4,6-Trichlorophenol 100 31.7
55.2-100.0
D-150.9
46.6-180.2
35.6-119.6
54.3-157.6
13.6-197.9
19.3-121.0
65.2-108.7
69.6-100.0
57.3-129.2
40.8-127.9
36.2-120.4
52.5-121.7
41.8-109.0
D-172.9
53.0-100.0
45.0-166.7
13.0-106.5
38.1-151.8
16.6-100.0
52.4-129.2
40-113
D-171
21-196
21-133
35-180
D-230
D-164
54-120
52-115
44-142
22-147
23-134
39-135
32-119
D-191
D-181
29-182
D-132
14-176
5-112
37-144
s
X
p.
D
a
Standard deviation of four recovery measurements, in M9/L.
Average recovery for four recovery measurements, in M9A-
Percent recovery measured.
Detected; result must be greater than zero.
Criteria from 40 CFR Part 136 for Method 625. These criteria are based
directly on the method performance data in Table 7. Where necessary, the
limits for recovery have been broadened to assure applicability of the
limits to concentrations below those used to develop Table 7.
8270A - 38
Revision 1
July 1992
-------
TABLE 7.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION"
Compound
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benz(a)anthracene
Chloroethane
Benzo(b)fluoranthene
Benzo ( k) f 1 uoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Benzyl butyl phthalate
j9-BHC
6-BHC
Bis(2-chloroethyl) ether
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo (a, h) anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Dieldrin
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Accuracy, as
recovery, x'
(M9/L)
0.96C+0.19
0.89C+0.74
0.78C+1.66
0.80C+0.68
0.88C-0.60
0.99C-1.53
0.93C-1.80
0.87C-1.56
0.90C-0.13
0.98C-0.86
0.66C-1.68
0.87C-0.94
0.29C-1.09
0.86C-1.54
1.12C-5.04
1.03C-2.31
0.84C-1.18
0.91C-1.34
0.89C+0.01
0.91C+0.53
0.93C-1.00
0.56C-0.40
0.70C-0.54
0.79C-3.28
0.88C+4.72
0.59C+0.71
0.80C+0.28
0.86C-0.70
0.73C-1.47
1.23C-12.65
0.82C-0.16
0.43C+1.00
0.20C+1.03
0.92C-4.81
1.06C-3.60
0.76C-0.79
0.39C+0.41
0.76C-3.86
0.81C+1.10
0.90C-0.00
0.87C-2.97
0.92C-1.87
8270A - 39
Single analyst
precision, s'
(M9/L)
O.lBx-0.12
0.24X-1.06
0.27X-1.28
0.21X-0.32
O.lSx+0.93
0.14X-0.13
0.22X+0.43
0.19X+1.03
0.22X+0.48
0.29X+2.40
0.18X+0.94
0.20X-0.58
0.34X+0.86
0.35X-0.99
0.16X+1.34
0.24X+0.28
0.26X+0.73
O.lSx+0.66
0.07X+0.52
0.20X-0.94
0.28X+0.13
0.29X-0.32
0.26X-1.17
0.42X+0.19
0.30X+8.51
0.13X+1.16
0.20X+0.47
0.25X+0.68
0.24X+0.23
0.28X+7.33
0.20X-0.16
0.28X+1.44
0.54X+0.19
0.12x+1.06
0.14X+1.26
0.21X+1.19
0.12X+2.47
O.lSx+3.91
0.22X-0.73
0.12X+0.26
0.24X-0.56
0.33X-0.46
Overall
precision,
S' (M9/L)
0.21X-0.67
0.26x-0.54
0.43X+1.13
0.27X-0.64
0.26X-0.21
0.17X-0.28
0.29X+0.96
0.35X+0.40
0.32X+1.35
O.Slx-0.44
0.53X+0.92
0.30X+1.94
0.93X-0.17
0.35X+0.10
0.26X+2.01
0.25X+1.04
0.36X+0.67
0.16X+0.66
0.13X+0.34
0.30X-0.46
0.33X-0.09
0.66X-0.96
0.39X-1.04
0.65X-0.58
0.59X+0.25
0.39X+0.60
0.24X+0.39
0.41X+0.11
0.29X-I-0.36
0.47X+3.45
0.26X-0.07
0.52X+0.22
1.05X-0.92
0.21X+1.50
0.19X+0.35
0.37X+1.19
0.63X-1.03
0.73X-0.62
0.28X-0.60
0.13X+0.61
0.50X-0.23
0.28X+0.64
Revision 1
July 1992
-------
Compound
Hexachlorobenzene
Hexachlorobutadiene
Hexachloroethane
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitrosodi-n-propylamine
PCB-1260
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2, 4-Dimethyl phenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
TABLE 7.
(Continued)
Accuracy, as
recovery, x'
(M9/L)
0.74C+0.66
0.71C-1.01
0.73C-0.83
0.78C-3.10
1.12C+1.41
0.76C+1.58
1.09C-3.05
1.12C-6.22
0.81C-10.86
0.87C+0.06
0.84C-0.16
0.94C-0.79
0.84C+0.35
0.78C+0.29
0.87C-0.13
0.71C+4.41
0.81C-18.04
1.04C-28.04
0.07C-1.15
0.61C-1.22
0.93C+1.99
0.43C+1.26
0.91C-0.18
Single analyst
precision, s '
(M9/L)
O.lSx-0.10
0.19X+0.92
O.Ux+0.67
0.29X+1.46
0.27x+0.77
0.21X-0.41
0.19X+0.92
0.27X+0.68
0.35X+3.61
0.12X+0.57
0.16X+0.06
O.lSx+0.85
0.23X+0.75
O.lSx+1.46
O.lBx+1.25
Q.16X+1.21
0.38X+2.36
O.lOx+42.29
0.16X+1.94
0.38X+2.57
0.24X+3.03
0.26X+0.73
O.lSx+2.22
Overall
precision,
S' (M9/L)
0.43X-0.52
0.26X+0.49
0.17x+0.80
O.BOx-0.44
0.33x+0.26
0.30X-0.68
0.27X+0.21
0.44X+0.47
0.43X+1.82
O.lSx+0.25
O.lSx+0.31
0.21X+0.39
0.29X+1.31
0.28X+0.97
0.21X-I-1.28
0.22X+1.31
0.42X+26.29
0.26X+23.10
0.27X+2.60
0.44X+3.24
0.30x^4.33
0.35X+0.58
0.22X+1.81
X'
S'
C
x"
Expected recovery for one or more measurements of a sample
containing a concentration of C, in M9/L.
Expected single analyst s_tandard deviation of measurements at an
average concentration of x, in M9/L.
Expected interlaboratory standajd deviation of measurements at an
average concentration found of x, in /j.g/1.
True value for the concentration, in M9/L.
Average recovery found for measurements of samples containing a
concentration of C, in M9/L-
8270A - 40
Revision 1
July 1992
-------
TABLE 8.
SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Low/High Low/High
Surrogate Compound Water Soil/Sediment
Nitrobenzene-d5 35-114 23-120
2-Fluorobiphenyl 43-116 30-115
p-Terphenyl-du 33-141 18-137
Phenol-d, 10-94 24-113
2-Fluorophenol 21-100 25-121
2,4,6-Tribromophenol 10-123 19-122
8270A - 41 Revision 1
July 1992
-------
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-------
METHOD 8270A
SEMIVOLATILE ORGANIC COMPOUNDS BY
GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS): CAPILLARY COLUMN TECHNIQUE
^ 1 Prepare
*ampl« uiing
Method 3540
or 3550
7 1 Prepare
sample uiing
Method 3S10
or 3520
7 1 Prepare
samp 1• using
Method 3540.
3550 or 3580
1 S 1 Screen
extract on CC/fID
or CC/PID to
eliminate sampl«»
that are too
concent ra ted
7 2 Cleanup
ext ract
753 Analyze
extract by GC/MS.
using appripriate
fused•aiitea
capi1i a ry column
754 Dilute
• M tract
So
7 3 Set CC/MS
opera ting
condit L onj
Perform initia1
calibration
? 6 1 'r^ufy
a r. a . \ '. « o y
ca^urf ; i -9 *,Ke
sample ana standard
.•nass 9 o e c '. r a
7 4 Perform daily
calibration with
SPCCs »nd CCC»
prior to ana lysis
of sample*
7 6 2 Caic-iat*
concentration of
eac!*. individual
analyle 3 e u o r t
results
Stop
8270A - 43
Revision 1
July IS
32
-------
06
O
W
-------
METHOD 8270B
SEMIVOLATILE ORGANIC COMPOUNDS BY
GAS CHROMATOGRAPHY/MASS SPECTROMETRV (GC/MS): CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8270 is used to determine the concentration of semivolatile
organic compounds in extracts prepared from all types of solid waste matrices,
soils, and ground water. Direct injection of a sample may be used in limited
applications. The following compounds can be determined by this method:
Compounds
Appropriate Preparation Techniques
CAS Noa 3510
3540/
3520 3541 3550 3580
Acenaphthene
Acenaphthene-d10 (I.S.)
Acenaphthylene
Acetophenone
2-Acetylaminofluorene
l-Acetyl-2-thiourea
Aldrin
2-Aminoanthraquinone
Aminoazobenzene
4-Aminobiphenyl
3-Amino-9-ethylcarbazole
Anilazine
Aniline
o-Anisidine
Anthracene
Aramite
Aroclor - 1016
Aroclor - 1221
Aroclor - 1232
Aroclor - 1242
Aroclor - 1248
Aroclor - 1254
Aroclor - 1260
Azinphos-methyl
Barban
Benzidine
Benzoic acid
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo (g , h , i ) peryl ene
Benzo(a)pyrene
83-32-9
208-96-8
98-86-2
53-96-3
591-08-2
309-00-2
117-79-3
60-09-3
92-67-1
132-32-1
101-05-3
62-53-3
90-04-0
120-12-7
140-57-8
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
86-50-0
101-27-9
92-87-5
65-85-0
56-55-3
205-99-2
207-08-9
191-24-2
50-32-8
X
X
X
X
X
LR
X
X
X
X
X
X
X
X
X
HS(43)
X
X
X
X
X
X
X
HS(62)
LR
CP
X
X
X
X
X
X
X
X
X
ND
NO
ND
X
ND
ND
ND
X
ND
X
ND
X
ND
X
X
X
X
X
X
X
ND
ND
CP
X
X
X
X
X
X
X
X
X
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
X
ND
X
X
X
X
X
X
X
ND
ND
CP
ND
X
X
X
X
X
X
X
X
ND
ND
ND
X
ND
ND
ND
ND
ND
X
ND
X
ND
X
X
X
X
X
X
X
ND
ND
CP
X
X
X
X
X
X
X
X
X
X
X
LR
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
CP
X
X
X
X
X
X
8270B - 1
Revision 2
September 1994
-------
Appropriate Preparation Techniques
Compounds
p-Benzoquinone
Benzyl alcohol
a-BHC
jS-BHC
5-BHC
-y-BHC (Lindane)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(Z-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Bromoxynil
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol
Captafol
Captan
Carbaryl
Carbofuran
Carbophenothion
Chlordane
Chlorfenvinphos
4-Chloroaniline
Chlorobenzilate
5-Chloro- 2 -methyl aniline
4- Chi oro-3 -methyl phenol
3-(Chloromethyl )pyridine
hydrochloride
1-Chloronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chloro- 1,2- phenyl enedi ami ne
4 -Chi oro- 1,3 -phenyl enedi ami ne
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-d12 (I.S.)
Coumaphos
p-Cresidine
Crotoxyphos
2-Cyclohexyl-4,6-dinitro-phenol
4,4'-DDD
4,4'-DDE
4,4'-DDT
Demeton-0
Demeton-S
Oiallate (cis or trans)
2,4-Diaminotoluene
CAS Noa
106-51-4
100-51-6
319-84-6
319-85-7
319-86-8
58-89-9
111-91-1
111-44-4
108-60-1
117-81-7
101-55-3
1689-84-5
85-68-7
88-85-7
2425-06-1
133-06-2
63-25-2
1563-66-2
786-19-6
57-74-9
470-90-6
106-47-8
510-15-6
95-79-4
59-50-7
6959-48-4
90-13-1
91-58-7
95-57-8
95-83-0
5131-60-2
7005-72-3
218-01-9
56-72-4
120-71-8
7700-17-6
131-89-5
72-54-8
72-55-9
50-29-3
298-03-3
126-75-0
2303-16-4
95-80-7
3510
OE
X
X
X
X
X
X
X
X
X
X
X
X
X
HS(55)
HS(40)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
HS(68)
X
X
DC,OE(42)
3520
ND
X
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
X
ND
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
X
X
ND
ND
ND
ND
3540/
3541
ND
ND
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
X
ND
X
X
X
ND
ND
X
X
X
ND
ND
ND
ND
X
X
X
ND
ND
ND
ND
3550
ND
X
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
X
ND
X
X
X
ND
ND
X
X
X
ND
ND
ND
ND
X
X
X
ND
ND
ND
ND
3580
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
ND
X
X
X
X
X
X
LR
X
X
X
X
X
X
X
8270B - 2
Revision 2
September 1994
-------
Compounds
Appropriate Preparation Techniques
CAS No8 3510
3540/
3520 3541 3550 3580
Dibenz(a,j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Dibenzo(a,e)pyrene
l,2-Dibromo-3-chloropropane
Di-n-butyl phthalate
Dichlone
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
l,4-Dichlorobenzene-d4 (I.S)
3,3'-Dich1orobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos
Dicrotophos
Dieldrin
Diethyl phthalate
Diethylstilbestrol
Diethyl sulfate
Dihydrosaffrole
Dimethoate
3,3' -Dimethoxybenzidine
Dimethyl aminoazobenzene
7,12-Dimethylbenz(a)-
anthracene
3,3'-Dimethylbenzidine
a,a-Dimethylphenethylamine
2,4-Dimethylphenol
Dimethyl phthalate
1,2-Dinitrobenzene
1,3-Dinitrobenzene
1,4-Dinitrobenzene
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap
Dinoseb
Dioxathion
Diphenylamine
5,5-Diphenylhydantoin
1,2-Diphenylhydrazine
Di-n-octyl phthalate
Disulfoton
224-42-0
53-70-3
132-64-9
192-65-4
96-12-8
84-74-2
117-80-6
95-50-1
541-73-1
106-46-7
91-94-1
120-83-2
87-65-0
62-73-7
141-66-2
60-57-1
84-66-2
56-53-1
64-67-5
56312-13-1
60-51-5
119-90-4
60-11-7
57-97-6
119-93-7
122-09-8
105-67-9
131-11-3
528-29-0
99-65-0
100-25-4
534-52-1
51-28-5
121-14-2
606-20-2
39300-45-3
88-85-7
78-34-2
122-39-4
57-41-0
122-66-7
117-84-0
298-04-4
X
X
X
ND
X
X
OE
X
X
X
X
X
X
X
X
X
X
X
AW,OS(67)
LR
ND
HE,HS(31)
X
X
CP(45)
X
ND
X
X
X
X
HE(14)
X
X
X
X
CP,HS(28)
X
ND
X
X
X
X
X
ND
X
X
ND
X
X
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
X
X
X
X
ND
ND
ND
X
ND
X
X
ND
ND
X
ND
ND
ND
X
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
X
X
X
X
ND
ND
ND
X
ND
X
X
ND
ND
X
X
ND
ND
X
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
X
X
X
X
ND
ND
ND
X
ND
X
X
ND
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
ND
X
LR
X
CP
X
X
X
X
X
X
X
X
X
X
X
CP
X
ND
X
X
X
X
X
8270B - 3
Revision 2
September 1994
-------
Compounds
Appropriate Preparation_Technicities
CAS No8 3510
3540/
3520 3541 3550 3580
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
EPN
Ethion
Ethyl carbamate
Ethyl methanesulfonate
Ethyl parathion
Famphur
Fensulfothion
Fenthion
Fluchloral in
Fluoranthene
Fluorene
2-Fluorobiphenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachl orobutad i ene
Hexachlorocyclopentadiene
Hexachl oroethane
Hexachl orophene
Hexachl oropropene
Hexamethyl phosphoramide
Hydroquinone
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
Isosafrole
Kepone
Leptophos
Malathion
Maleic anhydride
Mestranol
Methapyrilene
Methoxychlor
3-Methyl chol anthrene
4,4'-Methylenebis
(2-chloroaniline)
4,4'-Methylenebis
(N,N-dimethylaniline)
959-98-8
33213-65-9
1031-07-8
72-20-8
7421-93-4
53494-70-5
2104-64-5
563-12-2
51-79-6
62-50-0
56-38-2
52-85-7
115-90-2
55-38-9
33245-39-5
206-44-0
86-73-7
321-60-8
367-12-4
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
680-31-9
123-31-9
193-39-5
465-73-6
78-59-1
120-58-1
143-50-0
21609-90-5
121-75-5
108-31-6
72-33-3
91-80-5
72-43-5
56-49-5
101-14-4
101-61-1
X
X
X
X
X
X
X
X
DC(28)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
AW,CP(62)
X
X
ND
X
X
X
DC(46)
X
X
HS(5)
HE
X
X
X
X
OE,OS(0)
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
ND
8270B - 4
Revision 2
September 1994
-------
Compounds
Appropriate Preparation Techniques
CAS Noa 3510
3540/
3520 3541 3550 3580
Methyl methanesulfonate
2-Methyl naphthalene
2-Methyl-5-nitroanil ine
Methyl parathion
2-Methylphenol
3-Methyl phenol
4-Methyl phenol
2-Methylpyridine
Mevinphos
Mexacarbate
Mi rex
Monocrotophos
Naled
Naphthalene
Naphthalene-d8 (I.S.)
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
Nicotine
5-Nitroacenaphthene
2-Nitroanil ine
3-Nitroanil ine
4-Nitroanil ine
5-Nitro-o-anisidine
Nitrobenzene
Nitrobenzene-d5 (surr.)
4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
5-Nitro-o-toluidine
Nitroquinoline-1 -oxide
N -N itrosodi butyl ami ne
N-Nitrosodi ethyl ami ne
N-Nitrosodimethylamine
N-Nitrosomethyl ethyl ami ne
N-Nitrosodiphenylamine
N-Nitrosodi -n-propylamine
N-Nitrosomorphol ine
N-Nitrosopiperidine
N-Nitrosopyrrol idine
Octamethyl pyrophosphoramide
4,4'-Oxydianil ine
Parathion
Pentachl orobenzene
66-27-3
91-57-6
99-55-8
298-00-0
95-48-7
108-39-4
106-44-5
109-06-8
7786-34-7
315-18-4
2385-85-5
6923-22-4
300-76-5
91-20-3
130-15-4
134-32-7
91-59-8
54-11-5
602-87-9
88-74-4
99-09-2
100-01-6
99-59-2
98-95-3
92-93-3
1836-75-5
88-75-5
100-02-7
99-55-8
56-57-5
924-16-3
55-18-5
62-75-9
10595-95-6
86-30-6
621-64-7
59-89-2
100-75-4
930-55-2
152-16-9
101-80-4
56-38-2
608-93-5
X
X
X
X
X
X
X
X
X
HE,HS(68)
X
HE
X
X
X
X
OS(44)
X
DE(67)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
LR
X
X
X
ND
X
X
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
X
X
X
ND
X
X
ND
ND
X
X
ND
ND
ND
ND
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
X
X
ND
ND
ND
ND
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
X
X
X
ND
X
X
ND
ND
X
X
ND
ND
ND
ND
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
X
X
ND
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
X
X
X
8270B - 5
Revision 2
September 1994
-------
Compounds
Appropriate Preparation Techniques
CAS No" 3510
3540/
3520 3541 3550 3580
Pentach.1 oroni trobenzene
Pentachlorophenol
Perylene-d12 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-d10 (I.S.)
Phenobarbital
Phenol
Phenol -d6 (surr.)
1,4-Phenylenediamine
Phorate
Phosalone
Phosmet
Phosphamidon
Phthalic anhydride
2-Picol ine
Piperonyl sulfoxide
Pronamide
Propylthiouracil
Pyrene
Pyridine
Resorcinol
Safrole
Strychnine
Sul fall ate
Terbufos
Terphenyl-d14(surr.)
1,2,4 , 5-Tetrachl orobenzene
2,3,4,6-Tetrachlorophenol
Tetrachlorvinphos
Tetraethyl dithiopyrophosphate
Tetraethyl pyrophosphate
Thionazine
Thiophenol (Benzenethiol )
Toluene diisocyanate
o-Toluidine
Toxaphene
2,4,6-Tribromophenol (surr.)
1,2, 4 -Trichl orobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Trifluralin
2,4,5-Trimethylaniline
Trimethyl phosphate
82-68-8
87-86-5
62-44-2
85-01-8
50-06-6
108-95-2
106-50-3
298-02-2
2310-17-0
732-11-6
13171-21-6
85-44-9
109-06-8
120-62-7
23950-58-5
51-52-5
129-00-0
110-86-1
108-46-3
94-59-7
60-41-3
95-06-7
13071-79-9
1718-51-0
95-94-3
58-90-2
961-11-5
3689-24-5
107-49-3
297-97-2
108-98-5
584-84-9
95-53-4
8001-35-2
120-82-1
95-95-4
88-06-2
1582-09-8
137-17-7
512-56-1
X
X
X
X
X
X
X
DC(28)
DC(28)
X
X
HS(65)
HS(15)
HE(63)
CP,HE(1)
ND
X
X
LR
X
ND
DC,OE(10)
X
AW,OS(55)
X
X
X
X
X
X
X
X
X
X
HE(6)
X
X
X
X
X
X
X
X
HE(60)
ND
X
X
ND
X
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
X
ND
ND
ND
ND
ND
X
X
X
X
X
ND
ND
ND
ND
X
X
ND
X
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
ND
X
ND
ND
ND
ND
X
X
ND
X
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
ND
X
X
LR
X
ND
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
8270B - 6
Revision 2
September 1994
-------
Appropriate Preparation Techniques
3540/
Compounds CAS No8 3510 3520 3541 3550 3580
1,3,5-Trinitrobenzene 99-35-4
Tris(2,3-dibromopropyl) phosphate 126-72-7
Tri-p-tolyl phosphate 78-32-0
0,0,0-Triethyl phosphorothioate 126-68-1
X
X
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
LR
X
X
a Chemical Abstract Service Registry Number.
AW = Adsorption to walls of glassware during extraction and storage.
CP = Nonreproducible chromatographic performance.
DC = Unfavorable distribution coefficient (number in parenthesis is percent
recovery).
HE = Hydrolysis during extraction accelerated by acidic or basic conditions
(number in parenthesis is percent recovery).
HS = Hydrolysis during storage (number in parenthesis is percent stability).
LR = Low response.
ND = Not determined.
OE = Oxidation during extraction accelerated by basic conditions (number in
parenthesis is percent recovery).
OS = Oxidation during storage (number in parenthesis is percent stability).
X = Greater than 70 percent recovery by this technique.
1.2 Method 8270 can be used to quantitate most neutral, acidic, and
basic organic compounds that are soluble in methylene chloride and capable of
being eluted without derivatization as sharp peaks from a gas chromatographic
fused-silica capillary column coated with a slightly polar silicone. Such
compounds include polynuclear aromatic hydrocarbons, chlorinated hydrocarbons and
pesticides, phthalate esters, organophosphate esters, nitrosamines, haloethers,
aldehydes, ethers, ketones, anilines, pyridines, quinolines, aromatic nitro
compounds, and phenols, including nitrophenols. See Table 1 for a list of
compounds and their characteristic ions that have been evaluated on the specified
GC/MS system.
1.3 The following compounds may require special treatment when being
determined by this method. Benzidine can be subject to oxidative losses during
solvent concentration. Also, chromatography is poor. Under the alkaline
conditions of the extraction step, a-BHC, 7-BHC, Endosulfan I and II, and Endrin
are subject to decomposition. Neutral extraction should be performed if these
compounds are expected. Hexachlorocyclopentadiene is subject to thermal
decomposition in the inlet of the gas chromatograph, chemical reaction in acetone
solution, and photochemical decomposition. N-nitrosodimethylamine is difficult
to separate from the solvent under the chromatographic conditions described.
N-nitrosodiphenylaroine decomposes in the gas chromatographic inlet and cannot be
separated from diphenylamine. Pentachlorophenol, 2,4-dinitrophenol,
8270B - 7 Revision 2
September 1994
-------
4-nitrophenol, 4,6-dinitro-2-methylpheno1,4-chloro-3-methylphenol, benzoicacid,
2-nitroaniline, 3-nitroanil ine, 4-chloroaniline, and benzyl alcohol are subject
to erratic chromatographic behavior, especially if the GC system is contaminated
with high boiling material.
1.4 The estimated quantitation limit (EQL) of Method 8270 for
determining an individual compound is approximately 1 mg/kg (wet weight) for
soil/sediment samples, 1-200 mg/kg for wastes (dependent on matrix and method of
preparation), and 10 /ug/L for ground water samples (see Table 2). EQLs will be
proportionately higher for sample extracts that require dilution to avoid
saturation of the detector.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatograph/mass spectrometers and
skilled in the interpretation of mass spectra. Each analyst must demonstrate the
ability to generate acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 Prior to using this method, the samples should be prepared for
chromatography using the appropriate sample preparation and cleanup methods.
This method describes chromatographic conditions that will allow for the
separation of the compounds in the extract and for their qualitative and
quantitative analysis by mass spectrometry.
3.0 INTERFERENCES
3.1 Raw GC/MS data from all blanks, samples, and spikes must be
evaluated for interferences. Determine if the source of interference is in the
preparation and/or cleanup of the samples and take corrective action to eliminate
the problem.
3.2 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed. To reduce carryover, the
sample syringe must be rinsed out between samples with solvent. Whenever an
unusually concentrated sample is encountered, it should be followed by the
analysis of solvent to check for cross contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph/mass spectrometer system
4.1.1 Gas chromatograph - An analytical system complete with a
temperature-programmable gas chromatograph suitable for splitless
injection and all required accessories, including syringes, analytical
columns, and gases. The capillary column should be directly coupled to
the source.
8270B - 8 Revision 2
September 1994
-------
4.1.2 Column - 30 m x 0.25 mm ID (or 0.32 mm ID) 1 ^m film thickness
silicone-coated fused-silica capillary column (J&W Scientific DB-5 or
equivalent).
4.1.3 Mass spectrometer - Capable of scanning from 35 to 500 amu
every 1 sec or less, using 70 volts (nominal) electron energy in the
electron impact ionization mode. The mass spectrometer must be capable
of producing a mass spectrum for decaf!uorotriphenylphosphine (DFTPP)
which meets all of the criteria in Table 3 when 1 ^L of the GC/MS tuning
standard is injected through the GC (50 ng of DFTPP).
4.1.4 GC/MS interface - Any GC-to-MS interface that gives acceptable
calibration points at 50 ng per injection for each compound of interest
and achieves acceptable tuning performance criteria may be used. For a
narrow-bore capillary column, the interface is usually capillary-direct
into the mass spectrometer source.
4.1.5 Data system - A computer system must be interfaced to the mass
spectrometer. The system must allow the continuous acquisition and
storage on machine-readable media of all mass spectra obtained throughout
the duration of the chromatographic program. The computer must have
software that can search any GC/MS data file for ions of a specific mass
and that can plot such ion abundances versus time or scan number. This
type of plot is defined as an Extracted Ion Current Profile (EICP).
Software must also be available that allows integrating the abundances in
any EICP between specified time or scan-number limits. The most recent
version of the EPA/NIST Mass Spectral Library should also be available.
4.1.6 Guard column (optional) (J&W Deactivated Fused Silica, 0.25
mm ID x 6 m, or equivalent) between the injecti'on port and the analytical
column joined with column joiners (Hewlett Packard No. 5062-3556, or
equivalent).
4.2 Syringe - 10 nl.
4.3 Volumetric flasks, Class A - Appropriate sizes with ground glass
stoppers.
4.4 Balance - Analytical, 0.0001 g.
4.5 Bottles - glass with Teflon-lined screw caps or crimp tops.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all reagents shall 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 ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
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5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Stock standard solutions (1000 mg/L) - Standard solutions can be
prepared from pure standard materials or purchased as certified solutions.
5.3.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in pesticide quality
acetone or other suitable solvent and dilute to volume in a 10 ml
volumetric flask. Larger volumes can be used at the convenience of the
analyst. When compound purity is assayed to be 96% or greater, the weight
may be used without correction to calculate the concentration of the stock
standard. Commercially prepared stock standards may be used at any
concentration if they are certified by the manufacturer or by an
independent source.
5.3.2 Transfer the stock standard solutions into bottles with Teflon
lined screw-caps. Store at -10°C to -20°C or less and protect from light.
Stock standard solutions should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.3.3 Stock standard solutions must be replaced after 1 year or
sooner if comparison with quality control check samples indicates a
problem.
5.4 Internal standard solutions - The internal standards recommended are
l,4-dichlorobenzene-d4, naphthalene-ds, acenaphthene-d10, phenanthrene-d10,
chrysene-d12, and perylene-d12 (see Table 5). Other compounds may be used as
internal standards as long as the requirements given in Sec. 7.3.2 are met.
Dissolve 0.200 g of each compound with a small volume of carbon disulfide.
Transfer to a 50 ml volumetric flask and dilute to volume with methylene chloride
so that the final solvent is approximately 20% carbon disulfide. Most of the
compounds are also soluble in small volumes of methanol, acetone, or toluene,
except for perylene-d12. The resulting solution will contain each standard at
a concentration of 4,000 ng/>L. Each 1 mi sample extract undergoing analysis
should be spiked with 10 /nL of the internal standard solution, resulting in a
concentration of 40 ng/juL of each internal standard. Store at -10°C to -20°C
or less when not being used.
5.5 GC/MS tuning standard - A methylene chloride solution containing
50 ng//zL of decafluorotriphenylphosphine (DFTPP) should be prepared. The
standard should also contain 50 ng/ptL each of 4,4'-DDT, pentachlorophenol, and
benzidine to verify injection port inertness and GC column performance. Store
at -10°C to -20°C or less when not being used.
5.6 Calibration standards - A minimum of five calibration standards
should be prepared. One of the calibration standards should be at a
concentration near, but above, the method detection limit; the others should
correspond to the range of concentrations found in real samples but should not
exceed the working range of the GC/MS system. Each standard should contain each
analyte for detection by this method (e.g. some or all of the compounds listed
in Table 1 may be included). Each 1 ml aliquot of calibration standard should
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be spiked with 10 juL of the internal standard solution prior to analysis. All
standards should be stored at -10°C to -20°C or less, and should be freshly
prepared once a year, or sooner if check standards indicate a problem. The daily
calibration standard should be prepared weekly and stored at 4°C.
5.7 Surrogate standards - The recommended surrogate standards are
phenol-d6, 2-fluorophenol, 2,4,6-tribromophenol, nitrobenzene-d5,
2-fluorobiphenyl, and p-terphenyl-du. See Method 3500 for the instructions on
preparing the surrogate standards. Determine what concentration should be in the
blank extracts after all extraction, cleanup, and concentration steps. Inject
this concentration into the GC/MS to determine recovery of surrogate standards
in all blanks, spikes, and sample extracts. Take into account all dilutions of
sample extracts.
5.8 Matrix spike standards - See Method 3500 for instructions on
preparing the matrix spike standard. Determine what concentration should be in
the blank extracts after all extraction, cleanup, and concentration steps.
Inject this concentration into the GC/MS to determine recovery of surrogate
standards in all matrix spikes. Take into account all dilutions of sample
extracts.
5.9 Acetone, hexane, methylene chloride, isooctane, carbon disulfide,
toluene, and other appropriate solvents - Pesticide quality or equivalent
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
7.1 Sample preparation - Samples must be prepared by one of the
following methods prior to GC/MS analysis.
Matrix Methods
Water 3510, 3520
Soil/sediment 3540, 3541, 3550
Waste 3540, 3541, 3550, 3580
7.1.1 Direct injection - In very limited applications direct
injection of the sample into the GC/MS system with a 10 juL syringe may be
appropriate. The detection limit is very high (approximately
10,000 /xg/L); therefore, it is only permitted where concentrations in
excess of 10,000 fj.g/1 are expected. The system must be calibrated by
direct injection.
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7.2 Extract cleanup - Extracts may be cleaned up by any of the following
methods prior to GC/MS analysis.
Compounds Methods
Phenols 3630, 3640, 8040"
Phthalate esters 3610, 3620, 3640
Nitrosamines 3610, 3620, 3640
Organochlorine pesticides & PCBs 3620, 3660
Nitroaromatics and cyclic ketones 3620, 3640
Polynuclear aromatic hydrocarbons 3611, 3630, 3640
Haloethers 3620, 3640
Chlorinated hydrocarbons 3620, 3640
Organophosphorus pesticides 3620
Petroleum waste 3611, 3650
All priority pollutant base,
neutral, and acids 3640
8 Method 8040 includes a derivatization technique followed by GC/ECD
analysis, if interferences are encountered on GC/FID.
7.3 Initial calibration - The recommended GC/MS operating conditions:
Mass range: 35-500 amu
Scan time: 1 sec/scan
Initial temperature: 40°C, hold for 4 minutes
Temperature program: 40-270°C at 10°C/min
Final temperature: 270°C, hold until benzo[g,h,i]perylene has eluted
Injector temperature: 250-300°C
Transfer line temperature: 250-300°C
Source temperature: According to manufacturer's specifications
Injector: Grob-type, splitless
Sample volume: 1-2 juL
Carrier gas: Hydrogen at 50 cm/sec or helium at 30 cm/sec
(Split injection is allowed if the sensitivity of the mass spectrometer
is sufficient).
7.3.1 Each GC/MS system must be hardware-tuned to meet the criteria
in Table 3 for a 50 ng injection of DFTPP. Analyses should not begin
until all these criteria are met. Background subtraction should be
straightforward and designed only to eliminate column bleed or instrument
background ions. The GC/MS tuning standard should also be used to assess
GC column performance and injection port inertness. Degradation of DDT
to DDE and ODD should not exceed 20%. (See Sec. 8.3.1 of Method 8081 for
the percent breakdown calculation). Benzidine and pentachlorophenol
should be present at their normal responses, and no peak tailing should
be visible. If degradation is excessive and/or poor chromatography is
noted, the injection port may require cleaning. It may also be necessary
to break off the first 6-12 in. of the capillary column. The use of a
guard column (Sec. 4.1.6) between the injection port and the analytical
column may help prolong analytical column performance.
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7.3.2 The internal standards selected in Sec. 5.4 should permit most
of the components of interest in a chromatogram to have retention times
of 0.80-1.20 relative to one of the internal standards. Use the base peak
ion from the specific internal standard as the primary ion for
quantitation (see Table 1). If interferences are noted, use the next most
intense ion as the quantitation ion (i.e. for l,4-dichlorobenzene-d4, use
152 m/z for quantitation).
7.3.3 Analyze 1 /iL of each calibration standard (containing internal
standards) and tabulate the area of the primary characteristic ion against
concentration for each compound (as indicated in Table 1). Figure 1 shows
a chromatogram of a calibration standard containing base/neutral and acid
analytes. Calculate response factors (RFs) for each compound relative to
one of the internal standards as follows:
RF = (AxCis)/(AisCx)
where:
Ax = Area of the characteristic ion for the compound being
measured.
Ais = Area of the characteristic ion for the specific internal
standard.
Cis = Concentration of the specific internal standard (ng/^L).
Cx = Concentration of the compound being measured (ng/^L).
7.3.4 A system performance check must be performed to ensure that
minimum average RFs are met before the calibration curve is used. For
semivolatiles, the System Performance Check Compounds (SPCCs) are:
N-nitroso-di-n-propylamine;hexachlorocyclopentadiene;2,4~dinitro-phenol;
and 4-nitrophenol. The minimum acceptable average RF for these compounds
is 0.050. These SPCCs typically have very low RFs (0.1-0.2) and tend to
decrease in response as the chromatographic system begins to deteriorate
or the standard material begins to deteriorate. They are usually the
first to show poor performance. Therefore, they must meet the minimum
requirement when the system is calibrated.
7.3.4.1 The percent relative standard deviation (%RSD)
should be less than 15% for each compound. However, the %RSD for
each individual Calibration Check Compound (CCC) (see Table 4) must
be less than 30%. The relative retention times of each compound in
each calibration run should agree within 0.06 relative retention
time units. Late-eluting compounds usually have much better
agreement.
SD
%RSD = _ x 100
RF
where:
RSD = relative standard deviation.
RF = mean of 5 initial RFs for a compound.
SD = standard deviation of average RFs for a compound.
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SD =
N (RFj - RF):
I
i=l N - 1
where:
RF> = RF for each of the 5 calibration levels
N = Number of RF values (i.e., 5)
7.3.4.2 If the %RSD of any CCC is 30% or greater, then the
chromatographic system is too reactive for analysis to begin. Clean
or replace the injector liner and/or capillary column, then repeat
the calibration procedure beginning with section 7.3.
7.3.5 Linearity - If the %RSD of any compound is 15% or less, then
the relative response factor is assumed to be constant over the
calibration range, and the average relative response factor may be used
for quantitation (Sec. 7.6.2).
7.3.5.1 If the %RSD of any compound is greater than 15%,
construct calibration curves of area ratio (A/Ajs) versus
concentration using first or higher order regression fit of the five
calibration points. The analyst should select the regression order
which introduces the least calibration error into the quantitation
(Sec. 7.6.2.2 and 7.6.2.3). The use of calibration curves is a
recommended alternative to average response factor calibration, and
a useful diagnostic of standard preparation accuracy and absorption
activity in the chromatographic system.
7.4 Daily GC/MS calibration
7.4.1 Prior to analysis of samples, the GC/MS tuning standard must
be analyzed. A 50 ng injection of DFTPP must result in a mass spectrum
for DFTPP which meets the criteria given in Table 3. These criteria must
be demonstrated during each 12 hour shift.
7.4.2 A calibration standard(s) at mid-concentration containing all
semivolatile analytes, including all required surrogates, must be
analyzed every 12 hours during analysis. Compare the instrument response
factor from the standards every 12 hours with the SPCC (Sec. 7.4.3) and
CCC (Sec. 7.4.4) criteria.
7.4.3 System Performance Check Compounds (SPCCs): A system
performance check must be made during every 12 hour shift. For each SPCC
compound in the daily calibration a minimum response factor of 0.050 must
be obtained. This is the same check that is applied during the initial
calibration. If the minimum response factors are not met, the system must
be evaluated, and corrective action must be taken before sample analysis
begins. The minimum RF for semivolatile SPCCs is 0.050. Some possible
problems are standard mixture degradation, injection port inlet
contamination, contamination at the front end of the analytical column,
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and active sites in the column or chromatographic system. This check must
be met before analysis begins.
7.4.4 Calibration Check Compounds (CCCs): After the system
performance check is met, CCCs listed in Table 4 are used to check the
validity of the initial calibration.
Calculate the percent drift using:
c - c
c
% Drift = - x 100
C,
where:
C, = Calibration Check Compound standard concentration.
Cc = Measured concentration using selected quantitation method.
If the percent difference for each CCC is less than or equal to 20%,
the initial calibration is assumed to be valid. If the criterion is not
met (> 20% drift) for any one CCC, corrective action must be taken.
Problems similar to those listed under SPCCs could affect this criterion.
If no source of the problem can be determined after corrective action has
been taken, a new five-point calibration must be generated. This
criterion must be met before sample analysis begins. If the CCCs are not
analytes required by the permit, then all required analytes must meet the
20% drift criterion.
7.4.5 The internal standard responses and retention times in the
calibration check standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard changes
by more than 30 seconds from the last calibration check (12 hours), the
chromatographic system must be inspected for malfunctions and corrections
must be made, as required. If the EICP area for any of the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration check standard, the mass spectrometer must be inspected for
malfunctions and corrections must be made, as appropriate. When
corrections are made, reanalysis of samples analyzed while the system was
malfunctioning is required.
7.5 GC/MS analysis
7.5.1 It is highly recommended that the extract be screened on a
6C/FID or GC/PID using the same type of capillary column. This will
minimize contamination of the GC/MS system from unexpectedly high
concentrations of organic compounds.
7.5.2 Spike the 1 ml extract obtained from sample preparation with
10 nL of the internal standard solution just prior to analysis.
7.5.3 Analyze the 1 mi extract by GC/MS using a 30 m x 0.25 mm (or
0.32 mm) silicone-coated fused-silica capillary column. The volume to be
injected should ideally contain 100 ng of base/neutral and 200 ng of acid
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surrogates (for a 1 p.1 injection). The recommended GC/MS operating
conditions to be used are specified in Sec. 7.3.
7.5.4 If the response for any quantitation ion exceeds the initial
calibration curve range of the GC/MS system, extract dilution must take
place. Additional internal standard must be added to the diluted extract
to maintain the required 40 ng//iL of each internal standard in the
extracted volume. The diluted extract must be reanalyzed.
7.5.5 Perform all qualitative and quantitative measurements as
described in Sec. 7.6. Store the extracts at 4°C, protected from light
in screw-cap vials equipped with unpierced Teflon lined septa.
7.6 Data interpretation
7.6.1 Qualitative analysis
7.6.1.1 The qualitative identification of compounds
determined by this method is based on retention time, and on
comparison of the sample mass spectrum, after background correction,
with characteristic ions in a reference mass spectrum. The
reference mass spectrum must be generated by the laboratory using
the conditions of this method. The characteristic ions from the
reference mass spectrum are defined to be the three ions of greatest
relative intensity, or any ions over 30% relative intensity if less
than three such ions occur in the reference spectrum. Compounds
should be identified as present when the criteria below are met.
7.6.1.1.1 The intensities of the characteristic ions
of a compound maximize in the same scan or within one scan of
each other. Selection of a peak by a data system target
compound search routine where the search is based on the
presence of a target chromatographic peak containing ions
specific for the target compound at a compound-specific
retention time will be accepted as meeting this criterion.
7.6.1.1.2 The RRT of the sample component is within
± 0.06 RRT units of the RRT of the standard component.
7.6.1.1.3 The relative intensities of the
characteristic ions agree within 30% of the relative
intensities of these ions in the reference spectrum.
(Example: For an ion with an abundance of 50% in the
reference spectrum, the' corresponding abundance in a sample
spectrum can range between 20% and 80%.)
7.6.1.1.4 Structural isomers that produce very similar
mass spectra should be identified as individual isomers if
they have sufficiently different GC retention times.
Sufficient GC resolution is achieved if the height of the
valley between two isomer peaks is less than 25% of the sum
of the two peak heights. Otherwise, structural isomers are
identified as isomeric pairs.
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7.6.1.1.5 Identification is hampered when sample
components are not resolved chromatographically and produce
mass spectra containing ions contributed by more than one
analyte. When gas chromatographic peaks obviously represent
more than one sample component (i.e., a broadened peak with
shoulder(s) or a valley between two or more maxima),
appropriate selection of analyte spectra and background
spectra is important. Examination of extracted ion current
profiles of appropriate ions can aid in the selection of
spectra, and in qualitative identification of compounds.
When analytes coelute (i.e., only one chromatographic peak is
apparent), the identification criteria can be met, but each
analyte spectrum will contain extraneous ions contributed by
the coeluting compound.
7.6.1.2 For samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the purpose of the
analyses being conducted. Computer generated library search
routines should not use normalization routines that would
misrepresent the library or unknown spectra when compared to each
other. For example, the RCRA permit or waste delisting requirements
may require the reporting of nontarget analytes. Only after visual
comparison of sample spectra with the nearest library searches will
the mass spectral interpretation specialist assign a tentative
identification. Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should be present in
the sample spectrum.
(2) The relative intensities of the major ions should agree
within ± 20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%.)
(3) Molecular ions present in the reference spectrum should
be present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible background
contamination or presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or coeluting
peaks. Data system library reduction programs can sometimes create
these discrepancies.
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7.6.2 Quantitative analysis
7.6.2.1 When a compound has been identified, the
quantitation of that compound will be based on the integrated
abundance from the EICP of the primary characteristic ion.
7.6.2.2 If the %RSD of a compound's relative response
factor is 15% or less, then the concentration in the extract may be
determined using the average response factor (RF) from initial
calibration data (7.4.5.2) and the following equation:.
(Ax x CJ
C
ex
(A,-, x RF)
where Cex is the concentration of the compound in the extract, and
the other terms are as defined in Sec. 7.4.3.
7.6.2.3 Alternatively, the regression line fitted to the
initial calibration (Sec. 7.3.5.1) may be used for determination of
the extract concentration.
7.6.2.4 Compute the concentration of the analyte in the
sample using the equations in Sees. 7.6.2.4.1 and 7.6.2.4.2.
7.6.2.4.1 The concentration of the analyte in the
liquid phase of the sample is calculated using the
concentration of the analyte in the extract and the volume of
liquid extracted, as follows:
Concentration in liquid (M9/L) = (Cex x_V8J
V0
where:
Vex = extract volume, in ml
V0 = volume of liquid extracted, in L.
7.6.2.4.2 The concentration of the analyte in the
solid phase of the sample is calculated using the
concentration of the pollutant in the extract and the weight
of the solids, as follows:
Concentration in solid (/zg/kg) = (C^ x _VBJ
where:
Vex = extract volume, in ml
Ws = sample weight, in kg.
7.6.2.5 Where applicable, an estimate of concentration for
noncalibrated components in the sample should be made. The formulae
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given above should be used with the following modifications: The
areas Ax and A. should be from the total ion chromatograms and the
RF for the compound should be assumed to be 1. The concentration
obtained should be reported indicating (1) that the value is an
estimate and (2) which internal standard was used to determine
concentration. Use the nearest internal standard free of
interferences.
7.6.2.6 Quantitation of multicomponent compounds (e.g.
Aroclors) is beyond the scope of Method 8270. Normally,
quantitation is performed using a GC/ECD by Method 8081.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program consist
of an initial demonstration of laboratory capability and an ongoing analysis of
spiked samples to evaluate and document quality data. The laboratory must
maintain records to document the quality of the data generated. Ongoing data
quality checks are compared with established performance criteria to determine
if the results of analyses meet the performance characteristics of the method.
When results of sample spikes indicate atypical method performance, a quality
control reference sample (Sec. 8.5.1) must be analyzed to confirm that the
measurements were performed in an in-control mode of operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a method blank, that interferences from the analytical
system, glassware, and reagents are under control. Each time a set of samples
is extracted or there is a change in reagents, a method blank should be processed
as a safeguard against chronic laboratory contamination. The blanks should be
carried through all stages of sample preparation and measurement.
8.3 The experience of the analyst performing GC/MS analyses is
invaluable to the success of the methods. Each day that analysis is performed,
the daily calibration standard should be evaluated to determine if the
chromatographic system is operating properly. Questions that should be asked
are: Do the peaks look normal?; Is the response obtained comparable to the
response from previous calibrations? Careful examination of the standard
chromatogram can indicate whether the column is still good, the injector is
leaking, the injector septum needs replacing, etc. If any changes are made to
the system (e.g. column changed), recal ibration of the system must take place.
8.4 Required instrument QC is found in the following sections
8.4.1 The GC/MS system must be tuned to meet the DFTPP
specifications in Sees. 7.3.1 and 7.4.1.
8.4.2 There must be an initial calibration of the GC/MS system as
specified in Sec. 7.3.
8.4.3 The GC/MS system must meet the SPCC criteria specified in Sec.
7.4.3 and the CCC criteria in Sec. 7.4.4, each 12 hours.
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8.5 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.5.1 A quality control (QC) reference sample concentrate is
required containing each base/neutral analyte at a concentration of 100
mg/L and each acid analyte at a concentration of 200 mg/L in acetone or
methanol. (See Sec. 5.5.1 of Method 3500 for minimum requirements.) The
QC reference sample concentrate may be prepared from pure standard
materials or purchased as certified solutions. If prepared by the
laboratory, the QC reference sample concentrate must be made using stock
standards prepared independently from those used for calibration.
8.5.2 Using a pipet, prepare QC reference samples at a concentration
of 100 /itg/L by adding 1.00 ml of QC reference sample concentrate to each
of four 1-L aliquots of water.
8.5.3 Analyze the well-mixed QC reference samples according to the
method beginning in Sec. 7.1 with extraction of the samples.
8.5.4 Calculate the average recovery (x) in /xg/L, and the standard
deviation of the recovery (s) in M9/U for each analyte of interest using
the four results.
8.5.5 For each analyte compare s and x with the corresponding
acceptance criteria_for precision and accuracy, respectively, found in
Table 6. If s and x for all analytes meet the acceptance criteria, the
system performance is acceptable and analysis of actual samples can_begin.
If any individual s exceeds the precision limit or any individual x falls
outside the range for accuracy, then the system performance is
unacceptable for that analyte.
NOTE: The large number of analytes in Table 6 present a substantial
probability that one or more will fail at least one of the
acceptance criteria when all analytes of a given method are
analyzed.
8.5.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst must proceed according to Sec.
8.5.6.1 or 8.5.6.2.
8.5.6.1 Locate and correct the source of the problem and
repeat the test for all analytes of interest beginning with Sec.
8.5.2.
8.5.6.2 Beginning with Sec. 8.5.2, repeat the test only
for those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Sec.
8.5.2.
8.6 The laboratory must, on an ongoing basis, analyze a method blank,
a matrix spike, and a replicate for each analytical batch (up to a maximum of 20
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samples/batch) to assess accuracy. For soil and waste samples where detectable
amounts of organics are present, replicate samples may be appropriate in place
of matrix spiked samples. For laboratories analyzing one to ten samples per
month, at least one spiked sample per month is required.
8.6.1 The concentration of the spike in the sample should be
determined as follows:
8.6.1.1 If, as in compliance monitoring, the concentration
of a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at that limit
or 1 to 5 times higher than the background concentration determined
in Sec. 8.6.2, whichever concentration would be larger.
8.6.1.2 If the concentration of a specific analyte in a
water sample is not being checked against a limit specific to that
analyte, the spike should be at 100 ^g/L or 1 to 5 times higher than
the background concentration determined in Step 8.6.2, whichever
concentration would be larger. For other matrices, recommended
spiking concentration is 20 times the EQL.
8.6.1.3 If it is impractical to determine background
levels before spiking (e.g. maximum holding times will be exceeded),
the spike concentration should be at (1) the regulatory
concentration limit, if any; or, if none (2) the larger of either
5 times higher than the expected background concentration or 100
M9/L. For other matrices, recommended spiking concentration is 20
times the EQL.
8.6.2 Analyze one sample aliquot to determine the background
concentration (B) of each analyte. If necessary, prepare a new QC
reference sample concentrate (Sec. 8.5.1) appropriate for the background
concentration in the sample. Spike a second sample aliquot with 1.00 ml
of the QC reference sample concentrate and analyze it to determine the
concentration after spiking (A) of each analyte. Calculate each percent
recovery (p) as 100(A-B)%/T, where T is the known true value of the spike.
8.6.3 Compare the percent recovery (p) for each analyte in a water
sample with the corresponding QC acceptance criteria found in Table 6.
These acceptance criteria were calculated to include an allowance for
error in measurement of both the background and spike concentrations,
assuming a spike to background ratio of 5:1. This error will be accounted
for to the extent that the analyst's spike to background ratio approaches
5:1. If spiking was performed at a concentration lower than 100 /zg/L, the
analyst must use either the QC acceptance criteria presented in Table 6,
or optional QC acceptance criteria calculated for the specific spike
concentration. To calculate optional acceptance criteria for the recovery
of an analyte: (1) Calculate accuracy (x') using the equation found in
Table 7, substituting the spike concentration (T) for C; (2) calculate
overall precision (S') using the equation in Table 7, substituting x' for
x; (3) calculate the range for recovery at the spike concentration as
(100x'/T) ± 2.44(100S'/T)%.
8270B - 21 Revision 2
September 1994
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8.6.4 If any individual p falls outside the designated range for
recovery, that analyte has failed the acceptance criteria. A check
standard containing each analyte that failed the criteria must be analyzed
as described in Sec. 8.7.
8.7 If any analyte in a sample fails the acceptance criteria for
recovery in Sec. 8.6, a QC reference sample containing each analyte that failed
must be prepared and analyzed.
NOTE: The frequency for the required analysis of a QC reference sample
will depend upon the number of analytes being simultaneously tested,
the complexity of the sample matrix, and the performance of the
laboratory. If the entire list of analytes in Table 6 must be
measured in the sample in Sec. 8.6, the probability that the
analysis of a QC reference sample will be required is high. In this
case, the QC reference sample should be routinely analyzed with the
spiked sample.
8.7.1 Prepare the QC reference sample by adding 1.0 mi of the QC
reference sample concentrate (Sec. 8.5.1 or 8.6.2) to 1 L of water. The
QC reference sample needs only to contain the analytes that failed
criteria in the test in Sec. 8.6.
8.7.2 Analyze the QC reference sample to determine the concentration
measured (A) of each analyte. Calculate each percent recovery (pj as
100(A/T)%, where T is the true value of the standard concentration.
8.7.3 Compare the percent recovery (ps) for each analyte with the
corresponding QC acceptance criteria found in Table 6. Only analytes that
failed the test in Sec. 8.6 need to be compared with these criteria. If
the recovery of any such analyte falls outside the designated range, the
laboratory performance for that analyte is judged to be out of control,
and the problem must be immediately identified and corrected. The
analytical result for that analyte in the unspiked sample is suspect and
may not be reported for regulatory compliance purposes.
8.8 As part of the QC program for the laboratory, method accuracy for
each matrix studied must be assessed and records must be maintained. After the
analysis of five spiked samplesjof the same matrix) as in Sec. 8.6, calculate
the average percent recovery (p) and the standard deviation of the percent
recovery (sp). Express the accuracy assessment as a percent recovery interval
from p - 2sp to p + 2sp. If p = 90% and sp = 10%, for example, the accuracy
interval is expressed as 70-110%. Update the accuracy assessment for each
analyte on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.9 The following procedure should be performed to determine acceptable
accuracy and precision limits for surrogate standards.
8.9.1 For each sample analyzed, calculate the percent recovery of
each surrogate in the sample.
8270B - 22 Revision 2
September 1994
-------
8.9.2 Once a minimum of thirty samples of the same matrix have been
analyzed, calculate the average percent recovery (P) and standard
deviation of the percent recovery (s) for each of the surrogates.
8.9.3 For a given matrix, calculate the upper and lower control
limit for method performance for each surrogate standard. This should be
done as follows:
Upper Control Limit (UCL) = P + 3s
Lower Control Limit (LCL) = P - 3s
8.9.4 For aqueous and soil matrices, these laboratory-established
surrogate control limits should, if applicable, be compared with the
control limits listed in Table 8. The limits given in Table 8 are multi-
laboratory performance-based limits for soil and aqueous samples, and
therefore, the single-laboratory limits established in Sec. 8.9.3 must
fall within those given in Table 8 for these matrices.
8.9.5 If recovery is not within limits, the following procedures are
required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration".
8.9.6 At a minimum, each laboratory should update surrogate recovery
limits on a matrix-by-matrix basis, annually.
8.10 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 assess the precision of the
environmental measurements. When doubt exists over the identification of a peak
on the chromatogram, confirmatory techniques such as gas chromatography with a
dissimilar column, specific element detector, or a mass spectrometer must be
used. Whenever possible, the laboratory should analyze standard reference
materials and participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 Method 8250 (the packed column version of Method 8270) was tested
by 15 laboratories using organic-free reagent water, drinking water, surface
water, and industrial wastewaters spiked at six concentrations over the range 5-
1,300 /Ltg/L. Single operator accuracy and precision, and method accuracy were
found to be directly related to the concentration of the analyte and essentially
8270B - 23 Revision 2
September 1994
-------
independent of the sample matrix. Linear equations to describe these
relationships are presented in Table 7.
9.2 Chromatograms from calibration standards analyzed with Day 0 and Day
7 samples were compared to detect possible deterioration of GC performance.
These recoveries (using Method 3510 extraction) are presented in Table 9.
9.3 Method performance data (using Method 3541 Automated Soxhlet
extraction) are presented in Table 10. Single laboratory accuracy and precision
data were obtained for semivolatile organics in a clay soil by spiking at a
concentration of 6 mg/kg for each compound. The spiking solution was mixed into
the soil during addition and then allowed to equilibrate for approximately 1 hr
prior to extraction. The spiked samples were then extracted by Method 3541
(Automated Soxhlet). Three determinations were performed and each extract was
analyzed by gas chromatography/ mass spectrometry following Method 8270. The low
recovery of the more volatile compounds is probably due to volatilization losses
during equilibration. These data are listed in Table 11 and were taken from
Reference 9.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act, Method 625," October 26,
1984.
2. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
3. Eichelberger, J.W., L.E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurement in Gas Chromatography-Mass
Spectrometry Systems," Analytical Chemistry, 47, 995-1000, 1975.
4. "Method Detection Limit for Methods 624 and 625," Olynyk, P., W.L. Budde,
and J.W. Eichelberger, Unpublished report, October 1980.
5. "Inter!aboratory Method Study for EPA Method 625-Base/Neutrals, Acids, and
Pesticides," Final Report for EPA Contract 68-03-3102 (in preparation).
6. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
7. Lucas, S.V.; Kornfeld, R.A. "GC-MS Suitability Testing of RCRA Appendix
VIII and Michigan List Analytes "; U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, OH 45268,
February 20, 1987, Contract No. 68-03-3224.
8. Engel, T.M.; Kornfeld, R.A.; Warner, J.S.; Andrews, K.D. "Screening of
Semivolatile Organic Compounds for Extractability and Aqueous Stability
by SW-846, Method 3510"; U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, OH 45268,
June 5, 1987, Contract 68-03-3224.
8270B - 24 Revision 2
September 1994
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9. Lopez-Avila, V. (W. Beckert, Project Officer); "Development of a Soxtec
Extraction Procedure for Extraction of Organic Compounds from Soils and
Sediments"; U.S. Environmental Protection Agency. Environmental
Monitoring and Support Laboratory. Las Vegas, NV, October 1991; EPA
600/X-91/140.
8270B - 25 Revision 2
September 1994
-------
TABLE 1.
CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS
Compound
Retention Primary Secondary
Time (min.) Ion Ion(s)
2-Picoline
Aniline
Phenol
Bis(2-chloroethy1) ether
2-Chlorophenol
1,3-Dichlorobenzene
l,4-Dichlorobenzene-d4 (I.S.)
1,4-Dichlorobenzene
Benzyl alcohol
1,2-Dichlorobenzene
N-Nitrosomethylethyl amine
Bis(2-chloroisopropyl) ether
Ethyl carbamate
Thiophenol (Benzenethiol)
Methyl methanesulfonate
N-Nitrosodi-n-propylamine
Hexachloroethane
Maleic anhydride
Nitrobenzene
Isophorone
N-Nitrosodiethyl amine
2-Nitrophenol
2,4-Dimethylphenol
p-Benzoquinone
Bis(2-chloroethoxy)methane
Benzoic acid
2,4-Dichlorophenol
Trimethyl phosphate
Ethyl methanesulfonate
1,2,4-Trichlorobenzene
Naphthalene-d8 (I.S.)
Naphthalene
Hexachlorobutadiene
Tetraethyl pyrophosphate
Diethyl sulfate
4-Chloro-3-methylphenol
2-Methylnaphthalene
2-Methylphenol
Hexachloropropene
Hexachlorocyclopentadiene
N-Nitrosopyrrolidine
Acetophenone
4-Methylphenol
2,4,6-Trichlorophenol
o-Toluidine
3-Methylphenol
3.75" 93 66,92
5.68 93 66,65
5.77 94 65,66
5.82 93 63,95
5.97 128 64,130
6.27 146 148,111
6.35 152 150,115
6.40 146 148,111
6.78 108 79,77
6.85 146 148,111
6.97 88 42,88,43,56
7.22 45 77,121
7.27 62 62,44,45,74
7.42 110 110,66,109,84
7.48 80 80,79,65,95
7.55 70 42,101,130
7.65 117 201,199
7.65 54 54,98,53,44
7.87 77 123,65
8.53 82 95,138
8.70 102 102,42,57,44,56
8.75 139 109,65
9.03 122 107,121
9.13 108 54,108,82,80
9.23 93 95,123
9.38 122 105,77
9.48 162 164,98
9.53 110 110,79,95,109,140
9.62 79 79,109,97,45,65
9.67 180 182,145
9.75 136 68
9.82 128 129,127
10.43 225 223,227
11.07 99 99,155,127,81,109
11.37 139 139,45,59,99,111,125
11.68 107 144,142
11.87 142 141
12.40 107 107,108,77,79,90
12.45 213 213,211,215,117,106,141
12.60 237 235,272
12.65 100 100,41,42,68,69
12.67 105 71,105,51,120
12.82 107 107,108,77,79,90
12.85 196 198,200
12.87 106 106,107,77,51,79
12.93 107 107,108,77,79,90
8270B - 26
Revision 2
September 1994
-------
TABLE 1.
(Continued)
Compound
Retention
Time (min.)
Primary
Ion
Secondary
Ion(s)
2-Chloronaphthalene
N-Nitrosopiperi dine
1,4-Phenylenediamine
1-Chioronaphthalene
2-Nitroaniline
5-Chloro-2-methyl aniline
Dimethyl phthalate
Acenaphthylene
2,6-Dinitrotoluene
Phthalic anhydride
o-Anisidine
3-Nitroaniline
Acenaphthene-d10 (I.S.)
Acenaphthene
2,4-Dinitrophenol
2,6-Dinitrophenol
4-Chloroaniline
Isosafrole
Dibenzofuran
2,4-Diaminotoluene
2,4-Dinitrotoluene
4-Nitrophenol
2-Naphthylamine
1,4-Naphthoquinone
p-Cresidine
Dichlorovos
Diethyl phthalate
Fluorene
2,4,5-Trimethyl aniline
N-Nitrosodibutylamine
4-Chlorophenyl phenyl ether
Hydroquinone
4,6-Dinitro-2-methylphenol
Resorcinol
N-Nitrosodiphenylamine
Safrole
Hexamethyl phosphoramide
3-(Chloromethyl)pyridine hydrochl
Diphenylamine
1,2,4,5-Tetrachlorobenzene
1-Naphthylamine
1-Acetyl-2-thiourea
4-Bromophenyl phenyl ether
Toluene diisocyanate
2,4,5-Trichlorophenol
Hexachlorobenzene
13.30 162 127,164
13.55 114 42,114,55,56,41
13.62 108 108,80,53,54,52
13.65a 162 127,164
13.75 65 92,138
14.28 106 106,141,140,77,89
14.48 163 194,164
14.57 152 151,153
14.62 165 63,89
14.62 104 104,76,50,148
15.00 108 80,108,123,52
15.02 138 108,92
15.05 164 162,160
15.13 154 153,152
15.35 184 63,154
15.47 162 162,164,126,98,63
15.50 127 127,129,65,92
15.60 162 162,131,104,77,51
15.63 168 139
15.78 121 121,122,94,77,104
15.80 165 63,89
15.80 139 109,65
16.00a 143 115,116
16.23 158 158,104,102,76,50,130
16.45 122 122,94,137,77,93
16.48 109 109,185,79,145
16.70 149 177,150
16.70 166 165,167
16.70 120 120,135,134,91,77
16.73 84 84,57,41,116,158
16.78 204 206,141
16.93 110 110,81,53,55
17.05 198 51,105
17.13 110 110,81,82,53,69
17.17 169 168,167
17.23 162 162,162,104,77,103,135
17.33 135 135,44,179,92,42
oride!7.50 92 92,127,129,65,39
17.54a 169 168,167
17.97 216 216,214,179,108,143,218
18.20 143 143,115,89,63
18.22 118 43,118,42,76
18.27 248 250,141
18.42 174 174,145,173,146,132,91
18.47 196 196,198,97,132,99
18.65 284 142,249
8270B - 27
Revision 2
September 1994
-------
TABLE 1.
(Continued)
Compound
Retention
Time (min.)
Primary
Ion
Secondary
Ion(s)
Nicotine
Pentachlorophenol
5-Nitro-o-toluidine
Thionazine
4-Nitroaniline
Phenanthrene-d10(i .s.)
Phenanthrene
Anthracene
1,4-Dinitrobenzene
Mevinphos
Naled
1,3-Dinitrobenzene
Diallate (cis or trans)
1,2-Dinitrobenzene
Diallate (trans or cis)
Pentachlorobenzene
5-Nitro-o-anisidine
Pentachloronitrobenzene
4-Nitroquinoline-l-oxide
Di-n-butyl phthalate
2,3,4,6-Tetrachlorophenol
Dihydrosaffrole
Demeton-0
Fluoranthene
1,3,5-Trinitrobenzene
Dicrotophos
Benzidine
Trifluralin
Bromoxynil
Pyrene
Monocrotophos
Phorate
Sulfall ate
Demeton-S
Phenacetin
Dimethoate
Phenobarbital
Carbofuran
Octamethyl pyrophosphoramide
4-Aminobiphenyl
Dioxathion
Terbufos
a,a-Dimethylphenylamine
Pronamide
Aminoazobenzene
Dichlone
18.70 84 84,133,161,162
19.25 266 264,268
19.27 152 77,152,79,106,94
19.35 107 96,107,97,143,79,68
19.37 138 138,65,108,92,80,39
19.55 188 94,80
19.62 178 179,176
19.77 178 176,179
19.83 168 168,75,50,76,92,122
19.90 127 127,192,109,67,164
20.03 109 109,145,147,301,79,189
20.18 168 168,76,50,75,92,122
20.57 86 86,234,43,70
20.58 168 168,50,63,74
20.78 86 86,234,43,70
21.35 250 250,252,108,248,215,254
21.50 168 168,79,52,138,153,77
21.72 237 237,142,214,249,295,265
21.73 174 174,101,128,75,116
21.78 149 150,104
21.88 232 232,131,230,166,234,168
22.42 135 135,64,77
22.72 88 88,89,60,61,115,171
23.33 202 101,203
23.68 75 75,74,213,120,91,63
23.82 127 127,67,72,109,193,237
23.87 184 92,185
23.88 306 306,43,264,41,290
23.90 277 277,279,88,275,168
24.02 202 200,203
24.08 127 127,192,67,97,109
24.10 75 75,121,97,93,260
24.23 188 188,88,72,60,44
24.30 88 88,60,81,89,114,115
24.33 108 180,179,109,137,80
24.70 87 87,93,125,143,229
24.70 204 204,117,232,146,161
24.90 164 164,149,131,122
24.95 135 135,44,199,286,153,243
25.08 169 169,168,170,115
25.25 97 97,125,270,153
25.35 231 231,57,97,153,103
25.43 58 58,91,65,134,42
25.48 173 173,175,145,109,147
25.72 197 92,197,120,65,77
25.77 191 191,163,226,228,135,193
8270B - 28
Revision 2
September 1994
-------
TABLE 1.
(Continued)
Compound
Retention
Time (min.)
Primary
Ion
Secondary
Ion(s)
Dinoseb
Disulfoton
Fluchloralin
Mexacarbate
4,4'-Oxydianiline
Butyl benzyl phthalate
4-Nitrobiphenyl
Phosphamidon
2-Cyclohexyl-4,6-Dinitrophenol
Methyl parathion
Carbaryl
Dimethyl aminoazobenzene
Propylthiouracil
Benz(a)anthracene
Chrysene-d12 (I.S.)
3,3'-Dichlorobenzidine
Chrysene
Malathion
Kepone
Fenthion
Parathion
Anilazine
Bis(2-ethylhexyl) phthalate
3,3'-Dimethylbenzidine
Carbophenothion
5-Nitroacenaphthene
Methapyrilene
Isodrin
Captan
Chlorfenvinphos
Crotoxyphos
Phosmet
EPN
Tetrachlorvinphos
Di-n-octyl phthalate
2-Aminoanthraquinone
Barban
Aramite
Benzo(b)fluoranthene
Nitrofen
Benzo(k)fluoranthene
Chiorobenzilate
Fensulfothion
Ethion
Diethylstilbestrol
Famphur
25.83 211 211,163,147,117,240
25.83 88 88,97,89,142,186
25.88 306 306,63,326,328,264,65
26.02 165 165,150,134,164,222
26.08 200 200,108,171,80,65
26.43 149 91,206
26.55 199 199,152,141,169,151
26.85 127 127,264,72,109,138
26.87 231 231,185,41,193,266
27.03 109 109,125,263,79,93
27.17 144 144,115,116,201
27.50 225 225,120,77,105,148,42
27.68 170 170,142,114,83
27.83 228 229,226
27.88 240 120,236
27.88 252 254,126
27.97 228 226,229
28.08 173 173,125,127,93,158
28.18 272 272,274,237,178,143,270
28.37 278 278,125,109,169,153
28.40 109 109,97,291,139,155
28.47 239 239,241,143,178,89
28.47 149 167,279
28.55 212 212,106,196,180
28.58 157 157,97,121,342,159,199
28.73 199 199,152,169,141,115
28.77 97 97,50,191,71
28.95 193 193,66,195,263,265,147
29.47 79 79,149,77,119,117
29.53 267 267,269,323,325,295
29.73 127 127,105,193,166
30.03 160 160,77,93,317,76
30.11 157 157,169,185,141,323
30.27 329 109,329,331,79,333
30.48 149 167,43
30.63 223 223,167,195
30.83 222 222,51,87,224,257,153
30.92 185 185,191,319,334,197,321
31.45 252 253,125
31.48 283 283,285,202,139,253
31.55 252 253,125
31.77 251 251,139,253,111,141
31.87 293 293,97,308,125,292
32.08 231 231,97,153,125,121
32.15 268 268,145,107,239,121,159
32.67 218 218,125,93,109,217
8270B - 29
Revision 2
September 1994
-------
TABLE 1.
(Continued)
Compound
Retention
Time (min.)
Primary Secondary
Ion Ion(s)
Tri-p-tolyl phosphate6 32.75 368
Benzo(a)pyrene 32.80 252
Perylene-d12 (I.S.) 33.05 264
7,12-Dimethylbenz(a)anthracene 33.25 256
5,5-Diphenylhydantoin 33.40 180
Captafol 33.47 79
Dinocap 33.47 69
Methoxychlor 33.55 227
2-Acetylaminofluorene 33.58 181
4,4'-Methylenebis(2-chloroani1ine) 34.38 231
3,3'-Dimethoxybenzidine 34.47 244
3-Methylcholanthrene 35.07 268
Phosalone 35.23 182
Azinphos-methyl 35.25 160
Leptophos 35.28 171
Mirex 35.43 272
Tris(2,3-dibromopropy1) phosphate 35.68 201
Dibenz(a,j)acridine 36.40 279
Mestranol 36.48 277
Coumaphos 37.08 362
Indeno(l,2,3-cd)pyrene 39.52 276
Dibenz(a,hjanthracene 39.82 278
Benzo(g,h,i)perylene 41.43 276
l,2:4,5-Dibenzopyrene 41.60 302
Strychnine 45.15 334
Piperonyl sulfoxide 46.43 162
Hexachlorophene 47.98 196
Aldrin -- 66
Aroclor-1016 -- 222
Aroclor-1221 -- 190
Aroclor-1232 -- 190
Aroclor-1242 -- 222
Aroclor-1248 -- 292
Aroclor-1254 -- 292
Aroclor-1260 -- 360
a-BHC -- 183
/3-BHC -- 181
-------
TABLE 1.
(Continued)
Retention Primary Secondary
Compound Time (min.) Ion Ion(s)
Endosulfan sulfate -- 272 387,422
Endrin -- 263 82,81
Endrin aldehyde -- 67 345,250
Endrin ketone -- 317 67,319
2-Fluorobiphenyl (surr.) -- 172 171
2-Fluorophenol (surr.) -- 112 64
Heptachlor -- 100 272,274
Heptachlor epoxide -- 353 355,351
Nitrobenzene-d5 (surr.) -- 82 128,54
N-Nitrosodimethylamine -- 42 74,44
Phenol-d6 (surr.) -- 99 42,71
Terphenyl-d14 (surr.) -- 244 122,212
2,4,6-Tribromophenol (surr.) -- 330 332,141
Toxaphene -- 159 231,233
I.S. = internal standard.
surr. = surrogate.
8Estimated retention times.
bSubstitute for the non-specific mixture, tricresyl phosphate.
82708 - 31 Revision 2
September 1994
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TABLE 2.
ESTIMATED QUANTITATION LIMITS (EQLs) FOR SEMIVOLATILE ORGANICS
Estimated
Quantitation
Limits"
Ground water
Semivolatiles M9/L
Acenaphthene
Acenaphthylene
Acetophenone
2-Acetyl ami nof 1 uorene
l-Acetyl-2-thiourea
2-Aminoanthraquinone
Aminoazobenzene
4-Aminobiphenyl
Anilazine
o-Anisidine
Anthracene
Aramite
Azinphos-methyl
Barban
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzoic acid
Benzo (g , h , i ) peryl ene
Benzo(a)pyrene
p-Benzoquinone
Benzyl alcohol
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
4-bromophenyl phenyl ether
Bromoxynil
Butyl benzyl phthalate
Captafol
Captan
Carbaryl
Carbofuran
Carbophenothion
Chlorfenvinphos
4-Chloroaniline
Chlorobenzilate
5- Chi oro- 2 -methyl aniline
4- Chi oro-3-methyl phenol
3-(Chloromethyl)pyridine hydrochloride
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Coumaphos
10
10
10
20
1000
20
10
20
100
10
10
20
100
200
10
10
10
50
10
10
10
20
10
10
10
10
10
10
20
50
10
10
10
20
20
10
10
20
100
10
10
10
10
40
Low Soil/Sediment"
M9/kg
660
660
ND
ND
ND
ND
ND
ND
ND
ND
660
ND
ND
ND
660
660
660
3300
660
660
ND
1300
660
660
660
660
NO
660
ND
ND
ND
ND
ND
ND
1300
ND
ND
1300
ND
660
660
660
660
ND
8270B - 32 Revision 2
September 1994
-------
Semivolatiles
p-Cresidine
Crotoxyphos
2-Cyclohexyl-4,6-dinitrophenol
Demeton-0
Demeton-S
Diallate (cis or trans)
Diallate (trans or cis)
2,4-Diaminotoluene
Dibenz(a, j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Dibenzo(a,e)pyrene
Di-n-butyl phthalate
Dichlone
1 , 2-Di chl orobenzene
1 ,3-Di chl orobenzene
1 , 4-Di chl orobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos
Dicrotophos
Diethyl phthalate
Diethylstilbestrol
Diethyl sulfate
Dimethoate
3,3'-Dimethoxybenzidine
Dimethyl aminoazobenzene
7, 12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine
a, a-Di methyl phenethyl amine
2,4-Dimethylphenol
Dimethyl phthalate
1,2-Dinitrobenzene
1,3-Dinitrobenzene
1,4-Dinitrobenzene
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap
Dinoseb
5,5-Diphenylhydantoin
Di-n-octyl phthalate
TABLE 2.
(Continued)
Ground
M9/1
10
20
100
10
10
10
10
20
10
10
10
10
10
NA
10
10
10
20
10
10
10
10
10
20
100
20
100
10
10
10
ND
10
10
40
20
40
50
50
10
10
100
20
20
10
Estimated
Quantitation
Limits"
water Low Soil/Sediment"
Mg/kg
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
660
ND
ND
ND
660
660
660
1300
660
ND
ND
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
660
660
ND
ND
ND
3300
3300
660
660
ND
ND
ND
660
8270B - 33
Revision 2
September 1994
-------
Semivolatiles
Disulfoton
EPN
Ethion
Ethyl carbamate
Bis(Z-ethylhexyl) phthalate
Ethyl methanesulfonate
Famphur
Fensulfothion
Fenthion
Fluchloralin
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
Hexachlorophene
Hexachl oropropene
Hexamethyl phosphorami de
Hydroquinone
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
Isosafrole
Kepone
Leptophos
Malathion
Maleic anhydride
Mestranol
Methapyrilene
Methoxychlor
3-Methyl chol anthrene
4,4'-Methylenebis(2-chloroanil
Methyl methanesulfonate
2 -Methyl naphthalene
Methyl parathion
2-Methyl phenol
3-Methylphenol
4-Methylphenol
Mevinphos
Mexacarbate
Mi rex
Monocrotophos
Naled
TABLE 2.
(Continued)
Estimated
Quantitation
Limits"
Ground water Low Soi
M9/L
10
10
10
50
10
20
20
40
10
20
10
10
10
10
10
10
50
10
20
ND
10
20
10
10
20
10
50
NA
20
100
10
10
ine) NA
10
10
10
10
10
10
10
20
10
40
20
l/Sedimentb
M9/kg
ND
ND
ND
ND
660
ND
ND
ND
ND
ND
660
660
660
660
660
660
ND
ND
ND
ND
660
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
ND
660
ND
660
ND
ND
ND
ND
ND
8270B - 34 Revision 2
September 1994
-------
Semivolatiles
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
Nicotine
5-Nitroacenaphthene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
5-Nitro-o-anisidine
Nitrobenzene
4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
5-Nitro-o-toluidine
4-Nitroquinoline-l -oxide
N-Nitrosodibutylamine
N-Nitrosodiethyl amine
N-Nitrosodiphenylamine
N-Nitroso-di -n-propylamine
N-Nitrosopiperidine
N-Nitrosopyrrol idine
Octamethyl pyrophosphoramide
4,4' -Oxydianil ine
Parathion
Pentachl orobenzene
Pentachl oronitrobenzene
Pentachl orophenol
Phenacetin
Phenanthrene
Phenobarbital
Phenol
1 , 4- Phenyl enedi ami ne
Phorate
Phosalone
Phosmet
Phosphamidon
Phthalic anhydride
2-Picoline
Piperonyl sulfoxide
Pronamide
Propylthiouracil
Pyrene
TABLE 2.
(Continued)
Estimated
Quantitation
Limits8
Ground water Low Soi
M9A
10
10
10
10
20
10
50
50
20
10
10
10
20
10
50
10
40
10
20
10
10
20
40
200
20
10
10
20
50
20
10
10
10
10
10
100
40
100
100
NO
100
10
100
10
l/Sedimentb
/xg/kg
660
ND
ND
ND
ND
ND
3300
3300
ND
ND
660
ND
ND
660
3300
ND
ND
ND
ND
660
660
ND
ND
ND
ND
ND
ND
ND
3300
ND
660
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
8270B - 35
Revision 2
September 1994
-------
TABLE 2.
(Continued)
Estimated
Quantitation
Limits'
Ground water Low Soil/Sedimervr
Semivolatiles /xg/L
Pyridine
Resorcinol
Safrole
Strychnine
Sul fall ate
Terbufos
1 , 2, 4, 5-Tetrachl orobenzene
2,3,4,6-Tetrachlorophenol
Tetrachlorvinphos
Tetraethyl pyrophosphate
Thionazine
Thiophenol (Benzenethiol)
Toluene diisocyanate
o-Toluidine
1, 2, 4-Trichl orobenzene
2,4,5-Trichlorophenol
2 , 4 , 6-Tr i chl orophenol
Trifluralin
2, 4, 5 -Tri methyl anil ine
Trimethyl phosphate
1,3,5-Trinitrobenzene
Tris(2,3-dibromopropyl ) phosphate
Tri-p-tolyl phosphate(h)
0,0,0-Triethyl phosphorothioate
ND
100
10
40
10
20
10
10
20
40
20
20
100
10
10
10
10
10
10
10
10
200
10
NT
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
660
660
ND
ND
ND
ND
ND
ND
ND
a Sample EQLs are highly matrix-dependent. The EQLs listed herein are provided
for guidance and may not always be achievable.
b EQLs listed for soil/sediment are based on wet weight. Normally data are
reported on a dry weight basis, therefore, EQLs will be higher based on the
% dry weight of each sample. These EQLs are based on a 30 g sample and gel
permeation chromatography cleanup.
ND = Not determined.
NA = Not applicable.
NT = Not tested.
Other Matrices Factor0
High-concentration soil and sludges by sonicator775
Non-water miscible waste 75
°EQL = (EQL for Low Soil/Sediment given above in Table 2) X (Factor).
8270B - 36 Revision 2
September 1994
-------
TABLE 3.
DFTPP KEY IONS AND ION ABUNDANCE CRITERIA"'6
Mass
Ion Abundance Criteria
51
68
70
127
197
198
199
275
365
441
442
443
30-60% of mass 198
< 2% of mass 69
< 2% of mass 69
40-60% of mass 198
< 1% of mass 198
Base peak, 100% relative abundance
5-9% of mass 198
10-30% of mass 198
> 1% of mass 198
Present but less than mass 443
> 40% of mass 198
17-23% of mass 442
a See Reference 3.
b Alternate tuning criteria may be used (e.g., CLP, Method 525, or
manufacturers' instructions), provided that method performance is not
adversely affected.
TABLE 4.
CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction
Acid Fraction
Acenaphthene
1,4-Dichlorobenzene
Hexachlorobutadiene
N-Nitrosodiphenylamine
Di-n-octyl phthalate
Fluoranthene
Benzo(a)pyrene
4-Chloro-3-methyl phenol
2,4-Dichlorophenol
2-Nitrophenol
Phenol
Pentachlorophenol
2,4,6-Trichlorophenol
8270B - 37
Revision 2
September 1994
-------
TABLE 5.
SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION
l,4-Dichlorobenzene-d4 Naphthalene-dE
Acenaphthene-d10
Aniline
Benzyl alcohol
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl)
ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
Ethyl methanesulfonate
2-Fluorophenol (surr.)
Hexachloroethane
Methyl methanesulfonate
2-Methylphenol
4-Methylphenol
N-Nitrosodimethyl amine
N-Nitroso-di-n-propyl-
amine
Phenol
Phenol-d6 (surr.)
2-Picoline
Acetophenone
Benzoic acid
Bis(2-chloroethoxy)methane
4-Chloroaniline
4-Chioro-3-methyl phenol
2,4-Dichlorophenol
2,6-Dichlorophenol
a,a-Dimethyl -
phenethylamine
2,4-Dimethylphenol
Hexachlorobutadiene
Isophorone
2-Methyl naphthalene
Naphthalene
Nitrobenzene
Nitrobenzene-d8 (surr.)
2-Nitrophenol
N-Nitrosodibutyl amine
N-Nitrosopiperi dine
1,2,4-Trichlorobenzene
Acenaphthene
Acenaphthylene
1-Chloronaphthalene
2-Chloronaphthalene
4-Chlorophenyl
phenyl ether
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Fluorene
2-Fluorobiphenyl
(surr.)
Hexachlorocyclo-
pentadiene
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
4-Nitrophenol
Pentachlorobenzene
1,2,4,5-Tetra-
chlorobenzene
2,3,4,6-Tetra-
chlorophenol
2,4,6-Tribromo-
phenol (surr.)
2,4,6-Trichloro-
phenol
2,4,5-Trichloro-
phenol
(surr.) = surrogate
8270B - 38
Revision 2
September 1994
-------
TABLE 5.
(Continued)
Phenanthrene-d
10
Chrysene-d12
Perylene-d
12
4-Aminobiphenyl
Anthracene
4-Bromophenyl phenyl
ether
Di-n-butyl phthalate
4,6-Dinitro-2-methyl-
phenol
Diphenylamine
Fluoranthene
Hexachlorobenzene
N-Nitrosodiphenylamine
Pentachlorophenol
Pentachloroni trobenzene
Phenacetin
Phenanthrene
Pronamide
Benzidine
Benzo(a)anthracene
Bis(2-ethylhexyl)
phthalate
Butyl benzyl phthalate
Chrysene
3,3'-Dichlorobenzidine
p-Dimethylaminoazobenzene
Pyrene
Terphenyl-d14 (surr.)
Benzo(b)fluor-
anthene
Benzo(k)fluor-
anthene
Benzo(g,h,i)-
perylene
Benzo(a)pyrene
Dibenz(a,j)acridine
Dibenz(a,h)-
anthracene
7,12-Dimethylbenz-
(a)anthracene
Di-n-octyl phthalate
Indeno(l,2,3-cd)
pyrene
3-Methylchol-
anthrene
(surr.) = surrogate
8270B - 39
Revision 2
September 1994
-------
TABLE 6.
QC ACCEPTANCE CRITERIA8
Compound
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fl uoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Benzyl butyl phthalate
/3-BHC
5-BHC
Bis(2-chloroethyl ) ether
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo( a, h) anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1 ,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Dieldrin
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Test
cone.
(M9/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(M9/L)
27.6
40.2
39.0
32.0
27.6
38.8
32.3
39.0
58.9
23.4
31.5
21.6
55.0
34.5
46.3
41.1
23.0
13.0
33.4
48.3
31.0
32.0
61.6
70.0
16.7
30.9
41.7
32.1
71.4
30.7
26.5
23.2
21.8
29.6
31.4
16.7
32.5
32.8
20.7
37.2
54.7
24.9
26.3
Range
for x
(M9/L)
60.1-132.3
53.5-126.0
7.2-152.2
43.4-118.0
41.8-133.0
42.0-140.4
25.2-145.7
31.7-148.0
D-195.0
D-139.9
41.5-130.6
D-100.0
42.9-126.0
49.2-164.7
62.8-138.6
28.9-136.8
64.9-114.4
64.5-113.5
38.4-144.7
44.1-139.9
D-134.5
19.2-119.7
D-170.6
D-199.7
8.4-111.0
48.6-112.0
16.7-153.9
37.3-105.7
8.2-212.5
44.3-119.3
D-100.0
D-100.0
47.5-126.9
68.1-136.7
18.6-131.8
D-103.5
D-188.8
42.9-121.3
71.6-108.4
D-172.2
70.9-109.4
7.8-141.5
37.8-102.2
Range
P, Ps
(%)
47-145
33-145
D-166
27-133
33-143
24-159
11-162
17-163
D-219
D-152
24-149
D-110
12-158
33-184
36-166
8-158
53-127
60-118
25-158
17-168
D-145
4-136
D-203
D-227
1-118
32-129
D-172
20-124
D-262
29-136
D-114
D-112
39-139
50-158
4-146
D-107
D-209
26-137
59-121
D-192
26.155
D-152
24-116
8270B - 40
Revision 2
September 1994
-------
Compound
Hexachloroethane
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Ni trosodi -n-propyl amine
PCB-1260
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
4-Chloro -3 -methyl phenol
2-Chlorophenol
2,4-Chlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl -4,6-dinitrophenol
2-Nitrophenol
4-NHrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
TABLE 6.
(Continued)
Test
cone.
(/*g/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(M9/L)
24.5
44.6
63.3
30.1
39.3
55.4
54.2
20.6
25.2
28.1
37.2
28.7
26.4
26.1
49.8
93.2
35.2
47.2
48.9
22.6
31.7
Range
for x
(M9/L)
55.2-100.0
D-150.9
46.6-180.2
35.6-119.6
54.3-157.6
13.6-197.9
19.3-121.0
65.2-108.7
69.6-100.0
57.3-129.2
40.8-127.9
36.2-120.4
52.5-121.7
41.8-109.0
D-172.9
53.0-100.0
45.0-166.7
13.0-106.5
38.1-151.8
16.6-100.0
52.4-129.2
Range
P» Ps
(%)
40-113
D-171
21-196
21-133
35-180
D-230
D-164
54-120
52-115
44-142
22-147
23-134
39-135
32-119
D-191
D-181
29-182
D-132
14-176
5-112
37-144
s = Standard deviation of four recovery measurements, in
x = Average recovery for four recovery measurements, in ju9/L.
p, ps = Percent recovery measured.
D = Detected; result must be greater than zero.
a Criteria from 40 CFR Part 136 for Method 625. These criteria are based
directly on the method performance data in Table 7. Where necessary, the
limits for recovery have been broadened to assure applicability of the
limits to concentrations below those used to develop Table 7.
8270B - 41
Revision 2
September 1994
-------
TABLE 7.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION"
Compound
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benz(a)anthracene
Chloroethane
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Benzyl butyl phthalate
0-BHC
5-BHC
Bis(2-chloroethyl) ether
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl )
ether
Bis(2-ethylhexyl)
phthalate
4-Bromophenyl phenyl
ether
2-Chloronaphthalene
4-Chlorophenyl phenyl
ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo( a, h) anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Dieldrin
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fluoranthene
Accuracy, as
recovery, x'
(M9/L)
0.96C+0.19
0.89C+0.74
0.78C+1.66
0.80C+0.68
0.88C-0.60
0.99C-1.53
0.93C-1.80
0.87C-1.56
0.90C-0.13
0.98C-0.86
0.66C-1.68
0.87C-0.94
0.29C-1.09
0.86C-1.54
1.12C-5.04
1.03C-2.31
0.84C-1.18
0.91C-1.34
0.89C+0.01
0.91C+0.53
0.93C-1.00
0.56C-0.40
0.70C-0.54
0.79C-3.28
0.88C+4.72
0.59C+0.71
0.80C+0.28
0.86C-0.70
0.73C-1.47
1.23C-12.65
0.82C-0.16
0.43C+1.00
0.20C+1.03
0.92C-4.81
1.06C-3.60
0.76C-0.79
0.39C+0.41
0.76C-3.86
0.81C+1.10
Single analyst
precision, s/
(M9A)
O.lSx-0.12
0.24x-1.06
0.27X-1.28
0.21X-0.32
O.lSx+0.93
0.14X-0.13
0.22X+0.43
0.19X+1.03
0.22X+0.48
0.29x4-2.40
0.18x4-0.94
0.20X-0.58
0.34X+0.86
0.35X-0.99
0.16X+1.34
0.24X+0.28
0.26X+0.73
0.13X+0.66
0.07X+0.52
0.20X-0.94
0.28X+0.13
0.29X-0.32
0.26X-1.17
0.42X+0.19
0.30X+8.51
0.13X+1.16
0.20X+0.47
0.25X+0.68
0.24X+0.23
0.28X+7.33
0.20X-0.16
0.28X+1.44
0.54X+0.19
0.12X+1.06
0.14X+1.26
0.21X+1.19
0.12X+2.47
0.18x+3.91
0.22X-0.73
Overall
precision,
S' (M9/L)
0.21X-0.67
0.26X-0.54
0.43X+1.13
0.27X-0.64
0.26X-0.21
0.17X-0.28
0.29X+0.96
0.35X+0.40
0.32X+1.35
0.51X-0.44
0.53X+0.92
0.30X+1.94
0.93X-0.17
0.35X+0.10
0.26X+2.01
0.25X+1.04
0.36X+0.67
0.16X+0.66
0.13X+0.34
0.30X-0.46
0.33X-0.09
0.66X-0.96
0.39X-1.04
0.65X-0.58
0.59X+0.25
0.39X+0.60
0.24X+0.39
0.41X+0.11
0.29X+0.36
0.47X+3.45
0.26X-0.07
0.52X+0.22
1.05X-0.92
0.21x4-1.50
0.19x4-0.35
0.37X+1.19
0.63X-1.03
0.73X-0.62
0.28X-0.60
8270B - 42
Revision 2
September 1994
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Compound
Fluorene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachloroethane
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitrosodi-n-propylamine
PCB-1260
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
4- Chi oro -3 -methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
TABLE 7.
(Continued)
Accuracy, as
recovery, x'
(M9/U
0.90C-0.00
0.87C-2.97
0.92C-1.87
0.74C+0.66
0.71C-1.01
0.73C-0.83
0.78C-3.10
1.12C+1.41
0.76C+1.58
1.09C-3.05
1.12C-6.22
0.81C-10.86
0.87C+0.06
0.84C-0.16
0.94C-0.79
0.84C+0.35
0.78C+0.29
0.87C-0.13
0.71C+4.41
0.81C-18.04
1.04C-28.04
0.07C-1.15
0.61C-1.22
0.93C+1.99
0.43C+1.26
0.91C-0.18
Single analyst
precision, sr'
(M9/L)
0.12x+0.26
0.24x-0.56
0.33X-0.46
0.18x-0.10
0.19x+0.92
0.17X+0.67
0.29X+1.46
0.27x+0.77
0.21x-0.41
0.19x+0.92
0.27x+0.68
0.35x4-3.61
0.12X+0.57
0.16x+0.06
0.15x+0.85
0.23x+0.75
0.18X+1.46
O.lSx+1.25
0.16X+1.21
0.38X+2.36
O.lOx+42.29
0.16X+1.94
0.38X+2.57
0.24x+3.03
0.26X+0.73
0.16x+2.22
Overall
precision,
S' (M9/L)
0.13X+0.61
O.SOx-0.23
0.28X+0.64
0.43X-0.52
0.26X+0.49
0.17X+0.80
O.SOx-0.44
0.33X+0.26
0.30X-0.68
0.27x+0.21
0.44x+0.47
0.43X+1.82
0.15X+0.25
0.15X+0.31
0.21X+0.39
0.29X+1.31
0.28x+0,97
0.21X+1.28
0.22X+1.31
0.42x4-26.29
0.26X+23.10
0.27X+2.60
0.44X+3.24
0.30X+4.33
0.35X+0.58
0.22X+1.81
X'
S'
C
x
Expected recovery for one or more measurements of a sample
containing a concentration of C, in fJ.g/1.
Expected single analyst s_tandard deviation of measurements at an
average concentration of x, in /j.g/1.
Expected interlaboratory standard deviation of measurements at an
average concentration found of x, in
True value for the concentration, in iJ.g/1.
Average recovery found for measurements of samples containing a
concentration of C, in M9/L.
8270B - 43
Revision 2
September 1994
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TABLE 8.
SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Surrogate Compound
Nitrobenzene-d5
2-Fluorobiphenyl
Terphenyl-du
Phenol -d6
2-Fluorophenol
2,4,6-Tribromophenol
Low/High
Water
35-114
43-116
33-141
10-94
21-100
10-123
Low/High
Soil/Sediment
23-120
30-115
18-137
24-113
25-121
19-122
TABLE 9.
EXTRACTION EFFICIENCY AND AQUEOUS STABILITY RESULTS
COMPOUND
PERCENT RECOVERY
ON DAY 0
AVG. RSD
PERCENT RECOVERY
ON DAY 7
AVG. RSD
3-Amino-9-ethylcarbazo1e 80
4-Ch1oro-l,2-phenylenediamine 91
4-Chloro-l,3-phenylenediamine 84
l,2-Dibromo-3-chloropropane 97
2-sec-Butyl-4,6-dinitrophenol 99
Ethyl parathion 100
4,4'-Methylenebis(N,N-dimethyl aniline) 108
2-Methyl-5-nitroaniline 99
2-Methylpyridine 80
Tetraethyl dithiopyrophosphate 92
8
1
3
2
3
2
4
10
4
7
73
108
70
98
97
103
90
93
83
70
3
4
3
5
6
4
4
4
4
1
Data from Reference 8.
8270B - 44
Revision 2
September 1994
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TABLE 10.
AVERAGE PERCENT RECOVERIES AND PERCENT RSDs FOR THE TARGET COMPOUNDS
FROM SPIKED CLAY SOIL AND TOPSOIL BY AUTOMATED SOXHLET EXTRACTION
WITH HEXANE-ACETONE (1:1)'
Clay Soil
Topsoil
Compound name
1,3-Dichlorobenzene
1,2-Dichlorobenzene
Nitrobenzene
Benzal chloride
Benzotrichloride
4-Chloro-2-nitrotoluene
Hexachl orocycl opentadi ene
2,4-Dichloronitrobenzene
3,4-Dichloronitrobenzene
Pentachl orobenzene
2,3,4,5-Tetrachloronitrobenzene
Benefin
alpha-BHC
Hexachl orobenzene
delta-BHC
Heptachlor
Aldrin
Isopropal in
Heptachlor epoxide
trans-Chlordane
Endosulfan I
Dieldrin
2,5-Dichlorophenyl-
4-nitrophenyl ether
Endrin
Endosulfan II
p,p'-DDT
2,3,6-Trichlorophenyl-
4'-nitrophenyl ether
2,3,4-Trichlorophenyl-
4'-nitrophenyl ether
Mi rex
Average
percent
recovery
0
0
0
0
0
0
4.1
35.2
34.9
13.7
55.9
62.6
58.2
26.9
95.8
46.9
97.7
102
90.4
90.1
96.3
129
110
102
104
134
110
112
104
Percent
RSD
_.
--
--
--
15
7.6
15
7.3
6.7
4.8
7.3
13
4.6
9.2
12
4.3
4.4
4.5
4.4
4.7
4.1
4.5
4.1
2.1
4.8
4.4
5.3
Average
percent
recovery
0
0
0
0
0
0
7.8
21.2
20.4
14.8
50.4
62.7
54.8
25.1
99.2
49.1
102
105
93.6
95.0
101
104
112
106
105
111
110
112
108
Percent
RSD
..
--
--
23
15
11
13
6.0
2.9
4.8
5.7
1.3
6.3
7.4
2.3
2.4
2.3
2.2
1.9
2.1
3.7
0.4
2.0
2.8
3.3
2.2
The operating conditions for the Soxtec apparatus were as follows:
immersion time 45 min; extraction time 45 min; the sample size was 10 g;
the spiking concentration was 500 ng/g, except for the surrogate compounds
at 1000 ng/g, compounds 23, 27, and 28 at 1500 ng/g, compound 3 at 2000
ng/g, and compounds 1 and 2 at 5000 ng/g.
8270B - 45
Revision 2
September 1994
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TABLE 11.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR THE EXTRACTION
OF SEMIVOLATILE ORGANICS FROM SPIKED CLAY BY
METHOD 3541 (AUTOMATED SOXHLET)8
Compound name
Phenol
Bis(2-chloroethyl)ether
2-Chlorophenol
Benzyl alcohol
2-Methyl phenol
Bis(2-chloroisopropyl )ether
4-Methyl phenol
N-Nitroso-di-n-propylamine
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
Benzole acid
Bis(2-chloroethoxy) methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
4-Chloroaniline
4-Chloro -3 -methyl phenol
2 -Methyl naphthalene
Hexachl orocycl opentad i ene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
2-Nitroaniline
Dimethyl phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diethyl phthalate
4-Chlorophenyl-phenyl ether
Fluorene
4-Nitroaniline
4, 6-Dinitro-2-methyl phenol
N-Nitrosodiphenylamine
4-Bromophenyl-phenyl ether
Average
percent
recovery
47.8
25.4
42.7
55.9
17.6
15.0
23.4
41.4
28.2
56.1
36.0
50.1
40.6
44.1
55.6
18.1
26.2
55.7
65.1
47.0
19.3
70.2
26.8
61.2
73.8
74.6
71.6
77.6
79.2
91.9
62.9
82.1
84.2
68.3
74.9
67.2
82.1
79.0
63.4
77.0
62.4
Percent
RSD
5.6
13
4.3
7.2
6.6
15
6.7
6.2
7.7
4.2
6.5
5.7
7.7
3.0
4.6
31
15
12
5.1
8.6
19
6.3
2.9
6.0
6.0
5.2
5.7
5.3
4.0
8.9
16
5.9
5.4
5.8
5.4
3.2
3.4
7.9
6.8
3.4
3.0
8270B - 46
Revision 2
September 1994
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Table 11. (Continued)
Compound name
Average
percent
recovery
Percent
RSD
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Butyl benzyl phthalate
3,3'-Dichlorobenzidine
Benzo(a)anthracene
Bis(2-ethylhexyl) phthalate
Chrysene
Di-n-octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachloroethane
Hexachlorobutadiene
72.6
62.7
83,
96.
78.
87.
102
66.
25.
73.4
77.2
76.2
83.1
.9
.3
.3
.7
.3
.2
82.7
71.7
71.7
72.2
66.7
63.9
0
0
0
0
0
3.7
6.1
5.4
3.9
40
6.9
0.8
5.2
11
3.8
4.8
4.4
4.8
5.0
4.1
4.1
4.3
6.3
8.0
a Number of determinations was three. The operating conditions for the
Soxtec apparatus were as follows: immersion time 45 min; extraction time
45 min; the sample size was 10 g clay soil; the spike concentration was
6 mg/kg per compound. The sample was allowed to equilibrate 1 hour after
spiking.
Data taken from Reference 9.
8270B - 47
Revision 2
September 1994
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FIGURE 1.
GAS CHROMATOGRAM OF BASE/NEUTRAL AND ACID CALIBRATION STANDARD
R1C
8:26:09
: BASE ACID STD. 2UL/!oNC- UL
CWCS.:
R*€E: C 1,2768 LflfcEU N 6. 4.8
CUT*: 5l&H*C«w786 kl
CHL!: 51BHS6S878S 13
SCANS 2ue TO 2786
0. 1.6 J 6 E»c£: U 28. 3
8270B - 48
Revision 2
September 1994
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METHOD 82708
SEMIVOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY
(GC/MS): CAPILLARY COLUMN TECHNIQUE
7.1 Prepare sample
using Method 3540,
3541, or 3550.
7.1 Prepare sample
using Method 3510
or 3520.
7.1 Prepare sample
using Method 3540,
3541, 3650, or 3580.
7.2 Cleanup
extract.
7.3 Set GC/MS
operating conditions;
perform initial
calibration.
7.4 Perform daily
calibration with SPCCs
and CCCs prior to
analysis of samples.
8270B - 49
Revision 2
September 1994
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METHOD 82708
(Continued)
7.5.1 Screen extract
on GC/FID or GC/PID to
eliminate samples that
are too concentrated.
7.5.3 Analyze extract
by GC/MS, using
appropriate fused-silica
capillary column.
7.5.4 Dilute
Extract.
7.5.4
Does response
exceed initial
calibration
curve?
7.6.1 Identify
analyte by comparing
the sample and standard
mass spectra.
^
r
7.6.2 Calculate
concentration of each
individual analyte;
report results.
>
f
( Stop J
8270B - 50
Revision 2
September 1994
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