PART A
PROTOCOL FOR THE ANALYSIS OF PURGEABLE ORGANIC PRIORITY POLLUTANTS
IN INDUSTRIAL AND MUNICIPAL WASTEWATER TREATMENT SLUDGE
Scope and Application
1.1 This method is used for the determination of purgeable (volatile) or
ganics. The complete list of compounds is provided in Table 1.
1.2 The method is for qualitative and quantitative analysis of these
compounds in municipal and industrial wastewater treatment sludges.
The procedure requires the use of a gas chromatography/mass spec-
trometer (GC/MS) as the final detector.
1.3 The method detection limit for each compound is very dependent on
the compound characteristics and the particular sludge analyzed.
However, typical detection limits are 2 to 5 Mg/liter for publicly
owned treatment works (POTW) sludges with 1 to 5% total solids.
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 GC/MS
and skilled in the interpretation of mass spectra. Each analyst
must demonstrate the ability to generate acceptable results with
this method using the procedure described in Section 8.
Summary of Method
2.1 An inert gas is bubbled through a 10-ml sludge aliquot contained in
a specially designed purging chamber at ambient temperature. The
purgeables are efficiently transferred from the aqueous phase to the
vapor phase. The vapor is swept through a sorbent column where the
purgeables are trapped. After purging is completed, the sorbent col
umn is heated and backflushed with the inert gas to desorb the purge
ables onto a gas chromatographic column. The gas chromatograph is
temperature programmed to separate the purgeables which are then de-
tected with a mass spectrometer.1,2
Interferences
3.1 Interferences coextracted from the samples will vary considerably
from source to source, depending upon the diversity of the indus-
trial complex or municipality being sampled. Impurities in the
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purge gas and organic compounds outgassing from the plumbing up-
stream of the trap account for the majority of contamination prob-
lems. The analytical system must be demonstrated to be free from
the interferences under the conditions of the analysis by running
method blanks. Method blanks are run by charging the purging device
with reagent water and analyzing it in the normal manner. The use
of non-TFE plastic tubing, non-TFE thread sealants, or flow control-
lers with rubber components in the purging device should be avoided.
3.2 Samples can be contaminated by diffusipn of volatile organic mate-
rials (particularly dichloromethane) through the septum seal into
the sample during shipment and storage. A field blank prepared from
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-level and low-level sam-
ples are analyzed sequentially. To reduce cross-contamination, it
is recommended that the purging device and sample syringe be rinsed
twice between samples with reagent water to check for cross-contami-
nation. For samples containing large amounts of water-soluble mate-
rials, suspended solids, high-boiling compounds or high organohalide
levels, it may be necessary to wash the purging device with a soap
solution, rinse with distilled water, and then dry in a 105°C oven
between analyses.
4. Safety
4.1 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 a current awareness file of OSHA regulations regard-
ing the safe handling of the chemicals specified in this method. A
reference file of material data handling sheets should also be made
available to all personnel involved in the chemical analysis. Addi-
tional references to laboratory safety are available and have been
identified3"5 for the information of the analyst.
4.2 The following parameters covered by this method have been tentatively
classified as known or suspected, human or mammalian carcinogens:
benzene, carbon tetrachloride, chloroform, 1,4-dichlorobenzene, and
vinyl chloride. Primary standards of these toxic compounds should
be prepared in a hood. A NIOSH/MESA approved toxic gas respirator
should be worn when the analyst handles high concentrations of these
toxic compounds.
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5. Apparatus and Materials
5.1 Sampling
5.1.1 Vial - 25-ml capacity or larger, equipped with a screw cap
with hole in center (Pierce No. 13075 or equivalent). Deter-
gent wash, rinse with tap and distilled water, and dry at
105°C before use.
5.1.2 Septum - Teflon-faced (Pierce No. 12722 or equivalent).
Detergent wash, rinse with tap and distilled water, and dry
at 105°C for 1 hr before use.
5.2 Sample Preparation
5.2.1 Purge and Trap System. Assemble the system as depicted in
Figures 1 and 2. A commercial version, such as the Tekmar
Liquid Sample Concentrator Model LSC-1, or its equivalent,
may be modified for use by replacing the standard purge tube
with the purge tube shown in Figure 3. The trap is packed
according to Figure 4. In order to function properly, the
trap must be packed in the following order: Place the glass
wool plug in the inlet end of the trap and follow with the
0V-1, Tenax®, silica gel, charcoal, and finally, a second
glass wool plug. Reversing the packing order, i.e., placing
the charcoal in the trap first, will cause the silica gel and
Tenax® layers to become contaminated with charcoal dust caus-
ing poor desorption efficiencies. Install the trap so that
the effluent from the purging device enters the Tenax® end of
the trap.
5.2.2 Glassware
5.2.2.1 Screw-cap vials, 40 ml with TFE-lined caps.
5.2.2.2 Graduated cylinder. 10 ml.
5.2.2.3 Volumetric flasks, 10 ml and 50 ml.
5.2.2.4 Round-bottom flask (optional), 250 ml for sample
compositing.
5.2.3 Analytical balance, for standards preparation.
5.2.4 Roller mill and 1/8-in. stainless steel ball bearings.
5.2.5 Catalytic gas purifier.
5.2.6 Purging gas, He or N2, water compressed, high-purity grade.
5.2.7 Syringes, 10 pi, 25 |Jl, 100 |Jl, 1 ml, and 10 ml gas tight.
5.2.8 Magnetic stirring motor with 2- to 2.5 cm TFE-coated spin bar.
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5.3 For Quantitation and Identification
Gas chromatograph/mass spectrometer/data system, Finnigan 4000 or
equivalent. The GC/MS interface should be a glass jet separator.
The computer system should allow acquisition and storage of repeti-
tive scan data throughout the GC/MS runs. Computer software should
he available to allow searching of GC/MS data for display of ex-
tracted ion current profiles (EICP) and integration of the peaks.
The GC/MS should be fitted with a stainless steel or glass column
packed with 0.2% Carbowaz 1500 on Carbopack C. Typical column di-
mensions are 1/8-in. 0D stainless steel or 2-mm ID glass and 2.4 to
2.8 m in length.
6. Reagents
6.1 Trap Packing Materials
6.1.1 3% 0V-1 on Chromosorb-W 60/80 mesh.
6.1.2 Tenax-GC®, 60/80 mesh.
6.1.3 Silica gel, Davison Grade 15, 35/60 mesh or equivalent.
6.1.4 Coconut charcoal, 26 mesh Barnaby Chaney No. CA-580-26, Lot
Ho. M-2649 or equivalent.
6.2 Reagent Water (purgeable organic-free). Generate organic-free water
by passing tap water through a carbon filter bed containing about 1
lb of activated carbon and purging overnight with prepurified nitro-
gen. A Millipore Super-Q Water System or its equivalent may be used
to generate organic-free deionized water. Organic-free water can
also be prepared by boiling distilled water for 15 min. While still
hot, transfer to a glass-stoppered bottle. Cool to room temperature.
Continuously purge the water during storage. Test organic-free water
daily by analyzing according to the method described in Section 10.
6.3 Methanol. "Distilled in Glass" or equivalent, stored in original
containers and used as received.
6.4 Analytical Standards
6.4.1 Primary Standards. Prepare standard stock solutions (at ap-
proximately 2 Mg/Ml) by adding, from a lOO-pl syringe, 1 to 2
drops of the 99+% pure reference standard to methanol (9.8 ml)
contained in a tared 10-ml volumetric flask (weighed to near-
est 0.1 mg). Add the component so that the two drops fall
into the alcohol and do not come in contact with the ueck of
the flask. Prepare gaseous standards, e.g., vinyl chloride,
in a similar maimer using a 10.0 ml valved gas-tight syringe
with a 2-in. needle. Fill the syringe (10.0 ml) with the gas-
eous compound. Weigh the 10-ml volumetric flask containing
9.8 ml of methyl alcohol to 0.1 mg. Lower the syringe needle
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to about 5 pn above the methyl alcohol meniscus and slowly
inject the standard into the flask. The gas rapidly dissolves
in the methyl alcohol. Reweigh the flask and use the weight
gain to calculate the concentration of the standard. Dilute
to volume, mix, and transfer to a 10-ml screw-cap vial with a
silicone rubber/TFE cap liner. Gas stock standards are gener-
ally stable for at least 1 week when maintained at less than
0°C. With the exception of 2-chloroethylvinyl ether, stock
standards of compounds that boil above room temperature are
generally stable for at least 4 weeks when stored at 4°C.
(Safety Caution: Because of the toxicity of most organohal-
ides, dilutions should be made in a glove box suitable for
handling carcinogens. It is advisable to use an approved
respirator when high concentrations of such materials must be
handled in a fume hood.)
6.4.2 Working Standards. From the primary dilutions, prepare 10 ml
of a multicomponent secondary dilution mixture in methyl alco-
hol at a concentration of 50 ng/|Jl containing each of the com-
pounds to be determined. Prepare 50 ml of a 50-ng/ml standard
from the 50 ng/pl standard by dosing 50.0 |Jl into 50.0 ml of
organic-free water. Additional working standards should be
prepared as required to bracket concentrations of compounds
for referee analyses.
6.5 Internal Standard Spiking Solution. From stock standard solutions
prepared as above, add a volume to give 1,000 jjg each of bromochloro-
methane, 2-bromo-l-chloropropane, and 1,4-dichlorobutane to 45 ml of
organic-free water (blank water) contained in a 50-ml volumetric
flask, mix, and dilute to volume. Dose 9.0 pi of this internal stan-
dard spiking solution into every sample and reference standard ana-
lyzed. Prepare a fresh method recovery spiking solution on a weekly
basis.
6.6 Surrogate Standard Spiking Solution. Select a minimum of three sur-
rogate compounds from Table 2. Prepare and store stock standard and
spiking solutions as described in Section 6.5
7. Calibration
7.1 Establish GC/MS operating parameters equivalent to those indicated
in Section 11. The purge-trap GC/MS system can be calibrated using
the external standard technique (Section 7.2) or the internal stan-
dard technique (Section 7.3).
7.2 External Standard Calibration Procedure
7.2.1 Prepare calibration standards at a minimum of three concen-
tration levels for each parameter of interest by adding vol-
umes of one or more stock standards to 10.0-ml aliquots of
reagent water. Analyze immediately. One of the external
standards should be at a concentration near, but above, the
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method detection limit, and the other concentrations should
correspond to the expected range of concentrations found in
real samples or should define the working range of the detec-
tor.
7.2.2 Analyze each calibration standard with the purge-trap GC/MS
system described in Section 11. Tabulate peak heights or
area responses against the concentration of the analyte in
the standard. The results can be used to prepare a calibra-
tion curve for each compound. Alternatively, if the ratio of
response to concentration analyzed (calibration factor) is a
constant over the working range (< 10% relative standard de-
viation, RSD), linearity through the origin can be assumed
and the average ratio or calibration factor can be used in
place of a calibration curve.
7.2.3 Verify the working calibration curve or calibration factor on
each working day by the measurement of one or more calibration
standards. If the response for any parameter varies from the
predicted response by more than ± 10%, the test must be re-
peated using a fresh calibration standard. Alternatively, a
new calibration curve or calibration factor must be prepared
for that compound.
7.3 Internal Standard Calibration Procedure. To use this approach,
select one or more internal standards that are similar in analytical
behavior to the compounds of interest. The analyst must demonstrate
that the measurement of the interaal standard is not affected by
method or matrix interferences. The internal standards used for this
procedure should include bromochloromethane, 2-bromo-l-chloropropane,
and 1,4-dichlorobutane. Because of the limitations, no additional
internal standards can be suggested that are applicable to all sam-
ples.
7.3.1 Prepare calibration standards at a minimum of three concen-
tration levels for each parameter of interest by adding vol-
umes of one or more stock standards to a 10.0-ml aliquot of
reagent water, add 9.0 |Jl of the internal standard spiking
solution, and analyze immediately. One of the standards
should be at a concentration near, but above, the method de-
tection limit and 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 Analyze each calibration standard with the purge-trap GC/MS
system described in Section 11. Tabulate peak height or area
responses against concentration for each compound and
internal standard. Calculate relative response factors (HHP)
for each compound using Equation 1.
RRF * CA8B.s)/CAisBs)
(Eq. 1)
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where: A = Response for the parameter to be measured,
s
A^s = Response for the internal standard.
B. = Mass of the internal standard (ng).
is
B = Mass of the parameter to be measured (ng).
S
If the RRF value over the working range is a constant (< 10%
RSD), the RRF can be assumed to be nonvariant and the average
RRF can be used for calculations. Alternatively, the results
can be used to plot a calibration curve of response ratios,
A /A. , vs. RRF.
s' is'
7.3.3 Verify the working calibration curve or RRF on each working
day by the measurement of one or more calibration standards.
If the response for any parameter varies from the predicted
response by more than ± 10%, the test must be repeated using
a fresh calibration standard. Alternatively, a new calibra-
tion curve must be prepared for that compound.
7.4 Daily Calibration of the Gas Chromatography-Mass Spectrometry
(GC/MS) System
7.4.1 Evaluate the system performance each day that it is used for
the analysis of samples or blanks by injecting 20 ng of £-
bromofluorobenzene (BFB) into the GC inlet. Check to be sure
that the performance criteria listed in Table 2 are met. If
the criteria are not met, the instrument must be retuned to
satisfy those criteria before continuing.
To perform the calibration test, the following instrumental
parameters are required.
Electron energy, 70 eV (nominal)
Mass range, m/e 20-275
Scan time, 5 sec or less.
7.4.2 At the beginning of each working day, verify the calibration
of the system by analyzing a standard (Section 7.3.3).
8. Quality Control
Each laboratory that uses this method is required to operate a formal
quality control program. The minimum requirements of this program con-
sist of an initial demonstration of laboratory capability and the analy-
sis of spiked samples as a continuing check on performance. The labora-
tory is required to maintain performance records to define the quality of
data that is generated. After January 1, 1982, ongoing performance checks
must be compared with established performance criteria to determine if
the results of anayses are within accuracy and precision limits expected
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of tiie method. Before performing any analyses, the analyst must demon-
strate the ability to generate acceptable accuracy and precision with this
method. This ability is established as described in Section 8.1. In rec-
ognition of the rapid advances that are occurring in chromatography, the
analyst is permitted certain options to improve the separations or lower
the cost of measurements. Each tine such modifications are made to the
method, analyst is required to repeat the procedure in Section 8.1.
The laboratory must spike all samples with surrogate standards to monitor
continuing laboratory performance. This procedure is described in Section
8.4.
8.1 Demonstrate Acceptable Performance. Before performing any analyses,
the analyst must demonstrate the ability to generate acceptable accu-
racy and precision with this procedure.
8.1.1 For each compound to be measured, select a spike concentra-
tion representative of the expected levels in the samples.
Using stock standards, prepare a quality control check stan-
dard in methanol 1,000 times more concentrated than the
selected concentrations.
8.1.2 Syringe 10.0 jjI of the check standard to each of a m-im'mum of
four 10.0-ml aliquots of reagent water. A representative
sludge can be used in place of the reagent water, but one or
more additional aliquots must be analyzed to determine back-
ground levels, and the spike level must exceed twice the back-
ground level for the test to be valid. Analyze the aliquots
according to the method beginning in Section 10.
8.1.3 Calculate average recovery (R) and standard deviation (s), in
percentage recovery, for the results. Sludge background cor-
rections must be made before R and s calculations are performed.
8.1.4 Using the appropriate data from Table 7, determine the recov-
ery and single operator precision expected for the method for
each parameter, and compare these results to the values cal-
culated in Section 8.1.3. If the data are not comparable,
the analyst must review potential problem areas and repeat
the test.
8.1.5 After January 1, 1982, the values for R and s must meet rigid
method performance criteria provided by the U.S. EPA, Environ-
mental Monitoring and Support Laboratory, Cincinnati, Ohio,
before any samples may be analyzed.
8.2 Precision and Accuracy Statement. The analyst must calculate method
performance criteria for each of the surrogate standards.
8.2.1 Calculate upper and lower control limits for method perfor-
mance for each surrogate standard, using the values for R and
s calculated in Section 8.1.3:
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Upper Control Limit (UCL) = R + 3 s
Lower Control Limit (LCL) = R - 3 s
The UCL and LCL can be used to construct control charts6 that
are useful in observing trends in performance. After January 1,
1982, the control limits above must be replaced by method per-
formance criteria provided by the U.S. Environmental Protection
Agency.
8.2.2 For each surrogate standard, the laboratory must develop and
maintain separate accuracy statements of laboratory perfor-
mance for wastewater samples. An accuracy statement for the
method is defined as R ± s. The accuracy statement should be
developed by the analysis of four aliquots of sludge as de-
scribed in Section 8.1.2, followed by the calculation of R
and s. Alternately, the analyst may use four sludge data
points gathered through the requirement for continuing quality
control in Section 8.4. The accuracy statements should be
updated regularly.6
8.3 Surrogate Spikes. The laboratory is required to spike all of their
samples with the surrogate standard spiking solution to monitor spike
recoveries. If the recovery for any surrogate standard does not fall
within the control limits for method performance, the results reported
for that sample must be qualified as described in Section 13.3. The
laboratory should monitor the frequency of suspect data to ensure
that it remains at or below 5%.
8.4 System Blanks. Analyze daily an organic-free water blank spiked with
75 ng of BFB prior to the analysis of samples. The intensities of
EICPs for the internal standards gives an overall check of the system
sensitivity. Check the spectrum obtained for BFB and adjust the mass
spectrometer tuning parameters as required to meet the ion abundance
criteria specified in Table 3.
8.5 Fortified and Duplicate Samples
8.5.1 Sample Selection. Analyze all samples in duplicate. Using
the procedures described in Section 8.5.2, spike and analyze
two additional aliquots. Analyze a third unspiked aliquot on
the same day that the spiked aliquots are analyzed.
8.5.2 Spiking Procedures. Determine the volume of an empty vial to
within 0.5 ml by filling the vial with volatile organics-free
water and then measuring the volume of water with a graduated
cylinder. Mark the volume on the vial and allow it to air-dry.
Add 3 to 5 precleaned ball bearings to the vial. Transfer the
sample to the vial and spike with all of the compounds identi-
fied and the representative purgeable compounds listed in
Table 4 at two times the concentration found in the unspiked
sample or at 10 times the lower limit of detection, whichever
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is greater. Seal the vial and place on a roller mill in a
4°C cold room; tumble the sample for 16 hr before analysis.
8.6 Field Bl?"ig«- Analyze a field blank for each day of sampling at each
plant if available.
8.7 Additional Quality Control. 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 perform analysis of reference materials and
participate in relevant performance evaluation studies.
9. Sampling and Preservation
9.1 Sampling. Samples must be collected in 40-ml screw-cap vials with
zero headspace and sealed with XFE-lined septa. Before using, wash
all sample bottles and TFE seals in detergent and rinse with tap
water and finally distilled water. Allow the bottles and seals to
air-dry at room temperature, heat in a 105°C oven for 1 hr, then al-
low to cool in an area known to, be free of organics.
NOTE: Do not heat the TFE seals for extended periods of time (more
than 1 hr) because the silicone layer slowly degrades at 105°C.
9.2 Preservation. As a general guideline, ice samples immediately after
collection, refrigerate at 4°C, and purge within 10 days. Desorb
and complete the analyses immediately after purging.
9.3 Special Preservation for Aromatics. Experimental evidence indicates
that some aromatic compounds, notably benzene, toluene, and ethyl
benzene are susceptible to rapid biological degradation under certain
environmental conditions.2 Refrigeration alone may not be adequate
to preserve these compounds in sludges for more than 7 days. For
this reason, a separate sample should be collected, acidified, and
analyzed when these aromatics are to be determined. Collect about
500 ml of sample in a clean container. Adjust the pH of the sample
to about 2 by adding HC1 (1+1) while stirring. Check pH with narrow
range (1.4 to 2.8) pfi paper. Fill a sample container as described
in Section 9.1. If chlorine residual is present, add sodium thio-
sulfate to another sample container and fill as in Section 9.1 and
mix thoroughly.
10. Sample Preparation and Purging
10-1 Sample Compositing. Sludge samples for the analysis of purgeable
compounds are typically collected as grab samples. Several samples
may be composited with minimal analyte losses. Chill the appropri-
ate sample vials and a clean 250-ml round-bottom flask by immersing
them in an ice bath. Gently pour the entire contents of each vial
into the flask and swirl gently. Vigorous mixing must be avoided
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to prevent analyte losses. Prepare a number of composite aliquots
sufficient for subsequent analysis by gently pouring the composited
sludge into precleaned 40-ml vials. Seal the vials with zero head-
space using TFE-lined septa and screw-caps. Store the composited
samples at 4°C.
10.2 Sample Purging. Condition the adsorbent trap at 200°C with nitro-
gen or helium flow. Allow the trap to cool to ambient room temper-
ature and turn off the gas flow through the trap and purge tube
before sample purging. Remove an aliqout of the sludge sample by
gently pouring the sludge into a 10-ml graduated cylinder. Fill
the cylinder just to the 10.0-ml mark. Dose the aliquot with 9 pi
of the internal standard spiking solution by slowly injecting the
solution (with a 10-jjI syringe) 3 to 4 cm under the surface of the
sludge. Gently pour the spiked sludge aliquot into the purge tube.
If solids adhere to the inner walls of the graduated cylinder,
rinse the cylinder with a small amount of organics-free water and
add the rinsings to the purge tube. Seal the purge tube and turn
on the purge gas flow (40 ml/min). Purge the sample for 12 min
while maintaining the sample and trap at ambient room temperature.
11• Analysis of the Sample Purge
Analyze the sample purge by GC/MS using the Carbowax 1500/Carbopack C
column described in Section 5.2 operated with a helium carrier gas flow
of 30 ml/min. Heat the trap to 180 to 200°C. Backflush it for 3 min
into the gas chromatograph, with the oven at 40°C. At the end of the
3-min period, program the column at 10°C/min to 170°C. Hold at this
temperature until all compounds have eluted. An example of the separa-
tion achieved by this column is shown in Figure 5. Relative retention
times for the purgeable compounds are listed in Table 5. The purging
device must be removed from the instrument and thoroughly rinsed with
volatile organic-free water between each sample. The trap must be con-
ditioned at 200°C with flow for 10 min between each sample.
12. Qualitative Identification
12.1 Obtain EICPs for the primary ion (Table 5) and, if available, at
least two secondary ions for each parameter of interest. The fol-
lowing criteria must be met to make a qualitative identification.
12.1.1 The characteristic ion of each parameter of interest must
maximize in the same or within one scan of each other.
12.1.2 The retention time must fall within ± 30 sec of the reten-
tion time of the authentic compound.
12.1.3 The relative peak heights of the three characteristic ions
in the EICPs must fall within ± 20% of the relative inten-
sities of these ions in a reference mass spectrum. The
reference mass spectrum can be obtained from a standard
analyzed in the GC/MS system or from a reference library.
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12.2 Structural isomers that have very similar mass spectra and less
rfran 30 sec difference in retention time, can be explicitly iden-
tified only if the resolution between authentic isomers in a stan-
dard mix is acceptable. Acceptable resolution is achieved if the
baseline to valley height between the isomers is less than 25% of
the sum of the two peak heights. Otherwise, structural isomers
are identified as isomeric pairs.
Calculations
13.1 When a parameter has been identified, the quantitation of that
parameter should be based on the integrated abundance from the
£1CP of the first listed characteristic ion given in Table 5. If
the sample produces an interference for the primary ion, use a sec-
ondary characteristic ion to quantitate. Quantitation may be per**
formed the external or internal standard techniques.
13.1.1 If the external standard calibration procedure is used,
calculate the concentration of the parameter being mea-
sured from the area of the characteristic ion using the
calibration curve or calibration factor in Section 7.2.
13.1.2 If the internal standard calibration procedure was used,
calculate the concentration in the sample using the rela-
tive response factor (RRF) determined in Section 7.3 and
Equation 2.
(A,KBis)
Concentration Mg/i = (i )({&?)(V) (E
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14. Method Performance
Performance data for the application of this method to both POTW and
industrial sludges are shown in Table 7. These data were generated by
analyzing duplicate aliquots of unspiked sludge and triplicate aliquots
of sludge spiked at 2, 20, and 200 times the typical detection limits
for representative purgeable compounds. The method was evaluated using
three POTW sludges and two industrial sludges. The recoveries and stan-
dard deviations represent the results from all determinations from each
sludge type. The mean RSD for triplicates illustrate the precision for
triplicate analyses. Although the recoveries observed were generally
good, many recovery determinations were influenced by relatively high
concentrations of the spiking compounds in the unspiked sludges. In most
cases, the results of recovery determinations for compounds present in
the unspiked aliquots at concentrations in excess of the spiking level
were not included in Table 7. The small mean RSD for triplicates observed
for most compounds indicate that the largest component of the method var-
iance can be attributed to differences in the characteristics of the test
sludges. These data represent the results from one laboratory.
15. References
1. Bellar, T. A., and J. J. Lichtenberg, Journal American Water Works
Association, 66, p. 739 (1964).
2. Bellar, T. A., and J. J. Lichtenberg, "Semi-Automated Headspace
Analysis of Drinking Waters and Industrial Waters for Purgeable
Volatile Organic Compounds," Measurement of Organic Pollutants in
Water and Wastewater, C. E. Van Hall, editor, American Society for
Testing and Materials, Philadelphia, PA. Special Technical Publi-
cation 686, 1978.
3. "Carcinogens - Working with Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute of Occupational Safety and Health,
Publication No. 77-206, August 1977.
4. "OSHA Safety and Health Standards, General Industry," (29CFR1910),
Occupational Safety and Health Administration, OSHA 2206 (Revised
January 1976).
5. "Safety in Academic Chemistry Laboratories," American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition,
1979.
6. "Handbook of Analytical Quality Control in Water and Wastewater
Laboratories," EPA-600/4-79-019, U.S. Environmental Monitoring and
Support Laboratory, Cincinnati, Ohio 45268, March 1979.
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Additional Sources
1. "Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants." U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati,
OH 45268, March 1977, Revised April 1977. Effluent Guidelines
Division, Washington, DC 20460.
2. "Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric,
DPD) for Chlorine, Total Residual," Methods for Chemical Analysis of
Water and Wastes, EPA 600/4-79-020, U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory - Cincinnati,
OH 45268. In preparation.
3. "Preservation and Maximum Holding Time for the Priority Pollutants,"
U.S. Environmental Protection Agency, Environmental Monitoring and
Support Laboratory, Cincinnati, OH 45268. In preparation.
4. Budde, W. L., and J. W. Eichelberger, "Performance Tests for the
Evaluation of Computerized Gas Chromatography/Mass Spectrometry
Equipment and Laboratories," EPA-600/4-80-025, U.S. Environmental
Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, OH 45268, p. 16, April 1980.
5. Kleopfer, R. D., "Priority Pollutant Methodology Quality Assurance
Review," U.S. Environmental Protection Agency, Region VII, Kansas
City, KS. Seminar for Analytical Methods for Priority Pollutants,
Norfolk, VA, January 17-18, 1980, U.S. Environmental Protection
Agency, Office of Water Programs, Effluent Guidelines Division,
Washington, D.C. 20460.
14
-------
TABLE 1. PURGEABLE ORGANIC PRIORITY POLLUTANTS
Compound
STORET No.
CAS No.
Acrolein
34210
107-02-8
Acrylonitrile
34215
107-13-1
Chioromethane
34418
74-87-3
Dichlorodifluoromethane
32105
75-71-8
Bromomethane
34413
74-83-9
Vinyl chloride
39175
75-01-4
Chloroethane
34311
75-00-3
Dichloromethane
34423
75-09-2
Trichlorofluoromethane
34488
75-69-4
1,1-Dichloroethene
34501
75-35-4
1,1-Dichloroethane
34496
75-34-3
trans-1,2-Dichloroethene
34546
540-59-0
Chloroform
32106
67-66-3
1,2-Dichloroethane
34531
107-06-2
1,1,1-Trichloroethane
34506
71-55-6
Carbon tetrachloride
32102
56-23-5
Bromodichloromethane
32101
75-27-4
1,2-Dichloropropane
34541
78-87-5
Benzene
34030
71-43-2
trans-1,3-Dichloropropene
34561
542-75-6
Trichloroethene
39180
79-01-6
cis-1,3-Dichloropropene
34561
542-75-6
Dibromochloromethane
34306
124-48-1
1,1,2-Trichloroethane
34511
79-00-5
2-Chloroethylvinyl ether
34576
110-75-8
Bromoform
32104
75-25-2
Tetrachloroethane
34516
127-18-4
Toluene
34010
108-88-3
1,1,2,2-Tetrachloroethane
34475
79-34-5
Chlorobenzene
34301
108-90-7
Ethylbenzene
34371
100-41-4
15
-------
TABLE 2
SUGGESTED SURROGATE AND INTERNAL STANDARDS
Retention
Time
Primary
Secondary
Compound
(minutes)
Ion
Ions
Surrogate Standards
Benzene d-6
17.0
84
*
4-Bromofluorobenzene
28.3
95
174, 176
1,2-Dichloroethane d-4
12.1
-
-
1,4-Difluorobenzene
19.6
114
63,88
Ethylbenzene d-5
26.4
-
-
Ethylbenzene d-10
26.4
98
- .
Fluorobenzene
18.4
96
70
Pentafluorobenzene
23.5
-
-
Internal Standards
B romochlo romethane
9.3
128
49, 130, 51
2-Bromo-l-chloropropane
ND
77
79, 156
1,4-Dichlorobutane
ND
55
90, 92
a For chromatographic conditions, see Table 5.
16
-------
TABLE 3. £-BROMOFLUOROBENZENE IONS AND
ION ABUNDANCE CRITERIA3
m/e Ion abundance criteria
50 25-40% of m/e 95
75 30-60% of m/e 95
95 base peak, 100% relative abundance
96 5-9% of m/e 95
173 < 2% of m/e 95
174 > 50% of m/e 95
175 5-9% of m/e 174
176 > 95% but < 101% of m/e 95
177 5-9% of m/e 176
a Eichelberger, J. W., L. E. Harris, and W. L. Budde,
"Reference Compound to Calibrate Ion Abundance
Measurement in Gas Chromatography-Mass Spectrom-
etry Systems," Analytical Chemistry, 47, 995-1000
(1979).
17
-------
TABLE 4. REPRESENTATIVE PURGEABLE COMPOUNDS
FOR RECOVERY STUDIES
Benzene
Carbon tetrachloride
Chlorobenzene
Chloroform
1,2-Dichloroethane
1,1-Dichloroethene
Ethyl benzene
Tetrachloroethene
1,1,1-Trichloroethane
Trlchloroethene
Vinyl chloride
18
-------
TABLE 5. RELATIVE RETENTION TIMES OF PURGEABLE PRIORITY" POLLUTANTSa
V
Compound RRT
Chloromethane 0.116
Bromomethane 0.146
Dichlorodifluoromethane 0.169
Vinyl chloride 0.179
Chloroethane 0.209
Dichloromethane 0.312
Trichlorofluoromethane 0.435
1,1-Dichloroethene 0.475
Bromochloromethane (IS) 0.502
1.1-Dichloroethane 0.545
trans-1,2-Dichloroethene 0.585
Chloroform 0.621
1.2-Dichloroethane 0.661
1.1.1-Trichloroethane 0.728
Carbon tetrachloride 0.751
Bromodichloromethane 0.784 c
Bis-chloromethyl ether Unknown
1,2-Dichloropropane 0.854
trans-1,3-Dichloropropene 0.870
Trichloroethene 0.900
Benzene 0.917
Dibromochloromethane 0.934
cis-1,3-Dichloropropene 0.937
1.1.2-Trichloroethane 0.937 ^
2-Chloroethylvinyl ether Unknown
2-Bromo-l-chloropropane (IS) 1.000
Bromoform 1.073
1,1,2,2-Tetrachloroethane 1.206
Tetrachloroethene 1.213
1,4-Dichlorobutane (IS) 1.236
Toluene 1.292
Chlorobenzene 1•412
Ethylbenzene 1.641 e
Acrolein Unknowne
Acrylonitrile Unknown
a These data were obtained under the following conditions: GC column -
glass, 8-ft long x 0.1 in. I.D. packed with Carbopack C (60/80 mesh),
coated with 0.2% Carbowax 1500; carrier flow - 30 ml/min; oven tempera-
ture - initial 40°C held for 3 min, programmed 10°C/min to 170°C and
held until all compounds eluted.
b Retention times relative to 2-bromo-l-chloropropane with an absolute
retention time of 903 sec.
c Bis-Chloromethyl ether has a half-life of about 10 sec in aqueous mixtures,
d 2-Chloroethylvinyl ether may be unstable in aqueous mixtures. Retention
time is unknown.
e Acrolein and acrylonitrile do not purge efficiently from aqueous mixtures.
Retention times under these conditions are not known.
19
-------
TABLE 6. CHARACTERISTIC IONS OF PURGEABLE ORGANICS
EI ions Ion used to
Compound (relative intensity) quantify
Chloromethane
50(100); 52(33)
50
B romomethane
94(100); 96(94)
94
Dichlorodifluoromethane
85(100); 87(33); 101(13); 103(9)
101
Vinyl chloride
62(100); 64(33)
62
Chloroethane
64(100); 66(33)
64
Dichloromethane
49(100); 51(33); 84(86); 86(55)
84
T richlo ro fluo romethane
101(100); 103(66)
101
1i1-Dichloroethene
61(100); 96(80); 98(53)
96
Bromochloromethane (IS)
49(100); 130(88); 128(70); 51(33)
128
1>1-Dichloroethane
63(100); 65(33); 83(13); 85(8); 98(7);
100(4)
63
trans-1.2-Dichloroethene
Chloroform
64(100); 96(90); 98(57)
96
83(100); 85(66)
83
1»2-Dichloroethane
62(100); 64(33); 98(23); 100(15)
98
1»1»1-Trichloroethane
98(100); 99(66); 117(17); 119(16)
97
Carbon tetrachloride
117(100); 119(96); 121(30)
117
Bromodi chlo romethane
83(100); 85(66); 127(13); 129(17)
127
Bis-chloromethvl ether
79(100); 81(33)
79
1,2-Di chlo rop ropane
63(100); 65(33); 112(4); 114(3)
112
trans-1.3-Dichloroorooene
75(100); 77(33)
75
Trichloroethene
95(100); 97(66); 130(90); 132(85)
130
Benzene
78(100); 52(15)
78
D ib r onto chl o rome thane
129(100); 127(78); 208(13); 206(10)
127
cis-l,3-Dichloropropene
75(100); 77(33)
75
1»1»2-Trichloroethane
83(95); 85(60); 97(100); 99(63);
132(9); 134(8)
97
2-Chloroethylvinyl ether
63(95); 65(32); 106(18)
106
2-Bromo-l-chloropropane (IS)
77(100); 79(33); 156(5)
77
Bromoform
171(50); 173(100); 175(50); 250(4);
252(11); 254(11); 256(4)
173
1»1,2,2-Tetrachloroethane
83(100); 85(66); 131(7); 133(7);
166(5); 168(6)
168
Tetrachloroethene
129(64); 131(62); 164(78); 166(100)
164
1,4-Dichlorobutane (IS)
55(100); 90(30); 92(10)
55
Toluene
91(100); 92(78)
92
Chlorobenzene
112(100); 114(33)
112
Ethylbenzene
91(100); 106(33)
106
Acrolein
26(49); 27(100); 55(64); 56(83)
56
Acrylonitrile
26(100); 51(32); 52(75); 53(99)
53
20
-------
TAHI.E 1. ACCUKACY AMI I'KKCI.SION FOR lUKIiKAHI.K OKtiANICS
Tli rco IDTW Sl«|i|ges
Sjiiiie Recovery
Mean
Co«|h>iiimI
Ihaetnin-
ations
Spike level
_ _
^({il Max
He an
(*)'.
Slawlanl
«lcv i si-
ll on
RSI) for
1 ri|>l.
(X)
DelerMii
alions
Benzene
17
1
100
160
55
16
15
Carhoii 1 nl raililnriili'
12
ino
1,000
0
-
-
12
ClilorolorM
21
2
200
100
58
20
17
1, l-l)i<:ltlnroelhaiie
27
5
500
170
53
15
15
Tel racliloroolliaiie
IS
.1
.100
150
33
16
12
Vinyl t-lilorl. _
Niii Max
lie an
<*>
Standard
ilcvia-
I i on
KSD lor
t ri|>l .
(X)
1
1(H)
«J8
25
16
100
i,om>
43
50
8
2
200
76
22
20
5
500
110
51
28
3
300
150
70
24
5
500
110
47
13
5
500
100
28
16
2
200
140
44
21
16
1,600
110
40
II
2
20U
160
62
14
5
500
150
55
14
-------
Carrier Gas
Pressure Flow Control
Regulator
> <
Purge Gas ~
Plow Control
To Gas Chromatograph
/-Trap Inlet (Tenax End)
/ ^-Resistance Wire
Heater
Control
Vent
^ Purging
Device
Note:
All Lines Between Trap and GC
Should be Heated to 80 °C
f
Figure 1. Schematic of Che purge-crap system in che purge mode.
22
-------
Carrier Gas
Pressure Flow Control
Regulator n
-+~4-
Purge Gas ~
Flow Control
6-Port
Valve
To Gas Chromatograph
^-Trap Inlet (Tenax End)
/ ~"Resistance Wire
©
Heater
Control
Vent
\
*
&
Purging
Device
Note:
All Lines Between Trap and GC
Should be Heated to 80 ®C
Figure 2. Schematic of the purge-trap system in the desorb mode.
23
-------
Figure 3. 3ottom fric purge tube.
24
-------
PACKING CONSTRUCTION
Glass Wool
Activated
Charcoal
Grade 15
Silica Gel
Tenax
3% OV-1 I
Glass Woof
Trap Inlet
Electronic
Temperature
Control and
Pyrometer
.^—Tubing, 25cm
0.105in. ID
0.125in. OD
Stainless Steel
70/Foot Resistance
Wire Wrapped Solid
(Double Layer)
15
Fitting
Nut and Ferrules
Thermocouple/
Controller
Sensor
7.0/Foof Resistance
Wire Wrapped Solid
(Single Layer)
Figure 4. Trap packings and construction.
25
-------
952320
20:00
23i0O TIME
Figure 5. GC/MS chromatogram for the purgeable compounds.
-------
PART B
PROTOCOL FOR TI£E ANALYSIS OF EXTRACTABLE ORGANIC PRIORITY POTTITTANT^
IN INDUSTRIAL AND MUNICIPAL WASTEWATER TREATMENT SLUDGE
I# Scope and Application
1.1 This method is used for the determination of the base, neutral, and
acid-extractable organic compounds listed in Table 1.
1.2 The method is for qualitative and quantitative analysis of these
compounds in municipal and industrial wastewater treatment sludees
requires the use of a gas chromatograph/mass spectrom-
eter (GC/MS) as the final detector.
1.3 The method detection limit for each compound is dependent on
the compound characteristics and the particular sludge analyzed.
However, typical detection limits are 200 to 300 |jg/liter for pub-
licly owned treatment works (POTW) sludges with 1 to 5% total solids.
1.4 This method is restricted to use by or under the close supervision
of experienced analysts. Each analyst must demonstrate the ability
to generate acceptable results with this method using the procedure
described in Section 8.
2. Summary of Method
This method (Figure 1) uses repetitive solvent extraction aided by a high-
speed homogenizer. The extract is separated by centrifugation and removed
with a pipette or syringe. Sludges are extracted at pH fc 11 to isolate
base/neutral compounds and at pH £ 2 to isolate acidic compounds. Extracts
containing base/neutral compounds are cleaned by silica gel or florisil
chromatography or by gel permeation chromatography (GPC). Extracts con-
taining the acidic compounds are cleaned by GPC. The organic priority
pollutants are determined in the cleaned extracts by capillary column or
packed column GC/MS. Option A is preferred since capillary GC/MS (HRGC/MS)
allows easier data interpretation. Qualitative identification of compounds
is performed using the retention time and the relative abundance of three
characteristic ions. Quantitative analysis is performed using external
or internal standard techniques with a single characteristic ion.
27
-------
3.- Interferences
3.1 Method interferences may be caused by contaminants in solvents, re-
agents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baselines in GC/MS chromatograms.
All of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running labora-
tory reagent blanks as described in Section 8.4.
3.1.1 Glassware must be scrupulously cleaned. All glassware should
be cleaned as soon as possible after use by rinsing with the
last solvent used in it. This should be followed by detergent
washing with hot water, and rinses with tap water and reagent
water. It should then be drained dry, and heated in a muffle
furnace at 400°C for 15 to 30 min. Some thermally stable ma-
terials, such as PCBs, may not be eliminated by this treat-
ment. Solvent rinses with acetone and pesticide quality di-
chloromethane may be substituted for the muffle furnace heat-
ing. Volumetric glassware should not be heated in a muffle
furnace. After drying and cooling, glassware should be sealed
and stored in a clean environment to prevent any accumulation
of dust or other contaminants. It should be stored inverted
or capped with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to mini-
mize interference problems. Purification of solvents by
distillation in all-glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are coex-
tracted from the sample. The extent of matrix interferences will
vary considerably from source to source, depending upon the nature
and diversity of the wastewater treatment system being sampled. The
cleanup procedures in Section 11 can be used to overcome many of
these interferences, but unique samples may require additional
cleanup approaches to achieve acceptable detection limits.
4. Safety
4.1 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 regard-,
ing the safe handling of the chemicals specified in this method. A
reference file of material data handling sheets should also be made
available to all personnel involved in the chemical analysis.
4.2 The following parameters covered by this method have been tentatively
classified as known or suspected, human or mamalian carcinogens;
benzo[a]anthracene, benzidine, 3,3'-dichlorobenzidine, benzo[a]pyrene,
Of-BHC, p-BHC, 6-BHC, y*BHC, dibenzo[a,h]anthracene, N-nitrosodimethyl-
amine, 4,4'-DDT, and polychlorinated biphenyls.
28
-------
5. Apparatus and Materials
5.1 Sampling, Extraction, and Extract Cleanup
5.1.1 Emulsifier-Tekmar Tissumizer® or equivalent, high capacity.
5-1.2 Centrifuge, capable of handling 200 ml bottles.
5.1.3 Centrifuge bottles with TFE lined screw caps, 200 ml.
5.1.4 Kuderna-Danish (K-D) glassware.
5.1.4.1 Snyder columns, 3 bulb, macro.
5.1.4.2 Snyder columns modified micro.
5.1.4.3 Evaporating flasks, 500 ml, 250 ml.
5.1.4.4 Receiver ampuls 5 and 10 ml, graduated, with spring
attachment.
5.1.4.5 Beakers, 100 ml.
5.1.5 Water or steam bath for Kuderna-Danish concentrations.
5.1.6 Chromatographic (drying) Column - Pyrex (400 mm x 20 mm ID)
without a fritted plate.
5.1.7 Separatory funnels, 500 ml with TFE stopcock.
5.1.8 Syringe, 100 ml, Pyrex, with long needle.
5.1.9 Graduated cylinder, 100 or 250 ml.
5.1.10 Vials, 2 ml, 4 ml, and 8 ml with TFE lined screw caps.
5.1.11 Sample bottles, 1,000 ml or 4,000 ml glass with TFE lined
screw caps.
5.1.12 Disposable pipettes, for transferring extracts.
5.1.13 Gel Permeation Chromatograph (GPC), Analytical Biochemical
Labs, Inc., GPC Autoprep 1002 or equivalent including:
5.1.13.1 Glass column 25 mm ID x 60-70 mm packed with 70 g of
Bio-Beads SX-3.
5.1.13.2 Chromatographic pump, operated at 5 ml/min with
350-700 millibars (5-10 psi).
5.1.13.3 Injector with loop.
29
-------
5.1.13.4 Syringe filter holder, stainless steel and TFE,
Gelman 4310 or equivalent.
5.1.13.5 Spectrophotometry chromatographic detector, 254 am,
with strip chart recorder (optional, for GPC cali-
bration) .
5.1.14 Chromatographic column, 200 mm x 20 mm ID, with solvent
reservoir (250 ml) and TFE stopcock.
5.1.15 Roller mill.
5.1.16 Bottles, 500 ml, brown glass.
5.2 For Identification and Quantitation
5.2.1 Gas chromatograph/mass spectrometer with data system, Finnigan
4000 or equivalent. The GC/MS interface should include a
glass jet separator and a direct capillary line. The computer
system should allow acquisition and storage of repetitive scan
data throughout the GC/MS runs. Computer software should be
available to allow searching of GC/MS data for display of ex-
tracted ion current profiles (EICPs) and integration of the
peaks. The GC should have injectors for both packed columns
and a splitless Grob-type capillary injector. GC columns re-
quired are:
5.2.1.1 0.9 to 1.8 m x 2 mm ID glass packed with 1% SP-1240-DA
on 100/120 mesh Supelcoport.
5.2.1.2 15-30 m x 0.2 mm ID wall coated open tubular capil-
lary column coated with SE-54 providing at least
25,000 effective theoretical plates, measured at C13,
or a 1.8 m x 2 mm ID glass packed with 3% SP-2250 on
100/120 mesh Supelcoport.
5.2.2 Gas chromatograph/flame ionization detector with the same GC
columns as for the GC/MS system.
6. Reagents
6.1 For Extraction and Extract Cleanup
6.1.1 Dichloromethane, "Distilled in Glass" or
equivalent, stored in original containers and used as received.
6.1.2 Hexane, "Distilled in Glass" or equivalent, stored in original
containers and used as received.
6.1.3 Acetone, "Distilled in Glass" or equivalent, stored in original
containers and used as received.
30
-------
6.1.A
Hydrochloric acid solution (6N). Slowly add 100 ml of HC1
(12N) to 100 ml of reagent water.
6.1.5 Sodium hydroxide solution (6N). Dissolve 24 g NaOH in re-
agent water and dilute to 100 ml.
6.1.6 Sodium sulfate (Na2S04), Anhydrous, granular. Clean by over-
night Soxhlet extraction with dichloromethane, drying in an
oven at 110 to 160°C oven, and then heating to 650°C for 2
hr. Store in a glass jar tightly sealed with TFE-lined screw
cap.
6.1.7 Silica gel, 75/150 mesh. Clean silica gel for 16 hr by
Soxhlet extraction with dichloromethane. Dry and activate
for 16 hr at 160°C. Deactivate by adding 3% water (by weight)
and mixing for at least 4 hr on a tumbler. Store at room tem-
perature in glass jars fitted with TFE lined screw caps.
6.1.8 Florisil 60/100 mesh, Floridan. Clean florisil for 16
hr by Soxhlet extraction with dichloromethane. Dry and acti-
vate for 16 hr at 160°C. Deactivate by adding 1% water by
weight and mixing for at least 4 hr on a tumbler. Store at
room temperature in glass jars fitted with TFE lined screw
caps.
6.1.9 Glass wool. Clean glass wool by thorough rinsing with hexane,
dried in a 100°C oven, and stored in a hexane rinsed glass
jar with TFE lined screw cap.
6.1.10 Boiling chips - silica or carborundum.
6.1.11 GPC Calibration Solutions
6.1.11.1 Corn oil, 200 mg/ml in dichloromethane.
6.1.11.2 Pentachlorophenol and di-n-octylphthalate,
4 mg/ml each in dichloromethane.
6.2 For Identification and Quantitation
6.2.1 Analytical Standards
6.2.1.1 Prepare stock solutions from the pure compounds by
dissolving 10 mg quantities into 10 ml of dichloro-
methane. If compound purity is certified at 96% or
greater, the weight can be used without correction
to calculate the concentration of the stock stan-
dard. Commercially prepared stock standards can be
used at any concentration if they are certified by
the manufacturer or by an independent source.
31
-------
6.2.1.2 Transfer the stock standard solutions into TFE
sealed screw cap bottles. Store at 4°C and protect
from light. Stock standard solutions should be
checked frequently for signs of degradation or evap-
oration, especially just prior to preparing calibra-
tion standards from them. Quality control check
standards are available from the U.S. Environmental
Protection Agency, Environmental Monitoring and Sup-
port Laboratory, Cincinnati, that can be used to de-
termine the accuracy of calibration standards.
6.2.1.3 Stock standard solutions must be replaced after
6 months, or sooner if comparison with check
standards indicate a problem.
6.2.1.4 Prepare mixed analytical standards by diluting ali-
quots of the stock solutions. Analytical standards
for all semivolatile compounds should be prepared in
three solutions. The acids standard should contain
each of the phenolic compounds at concentrations in
the range of 50 to 200 ng/pl. Base, neutral, and
pesticide (B/N/P) compounds should be split between
two solutions, both at concentrations in the range
of 20 to 100 ag/pl. One standard should contain the
more unstable B/N compounds listed in Table 2, and
the second should contain the remaining B/N/P com-
pounds. All working standards must include dio-
anthracene at 20 ag/|Jl.
6.2.1.5 Prepare mixed spiking solutions by serial dilution
from the individual stock solutions prepared above.
The specifications for spiking solutions for indi-
vidual samples are described in Section 8.3.2.
Method Calibration
7.1
7.2
tion levels for each parameter of interest by adding' volumes
of one or more stock standards to a volumetric flask and di-
luting to volume with dichloromethane. One of the external
standards should be at a concentration near, but above, the
method detection limit and the other concentrations should
correspond to the expected range of concentrations found in
real samples or should define the working range of the de-
tector.
Establish GC/MS operating parameters equivalent to those indicated
in Section 12. The GC/MS system can be calibrated using the external
standard technique or the internal standard technique.
External Standard Calibration Procedure
7.2.1 Prepare calibration tandards at a mini mum of three concentra-
32
-------
7.2.2 Using injections of -J. to 2 |Jl of each calibration standard,
tabulate peak height or area responses against the mass in-
jected. The results can be used to prepare a calibration
curve for each compound. Alternatively, if the ratio of re-
sponse to amount injected in the calibration factor is a con-
stant over the working range (< 10% relative standard devia-
tion RSD), linearity through the origin can be assumed and the
average ratio or calibration factor can be used in place of a
calibration curve.
7.2.3 Verify the working calibration curve or calibration factor on
each working day by the measurement of one or more calibration
standards. If the response for any parameter varies from the
predicted response by more than ± 10%, the test must be re-
peated using a fresh calibration standard. Alternatively, a
new calibration curve or calibration factor must be prepared
for that compound.
Internal Standard Calibration Procedure. To use this approach, se-
lect one or more internal standards that are similar in analytical
behavior to the compounds of interest. The analyst must demonstrate
that the measurement of the internal standard is not affected by
method or matrix interferences. The internal standards used for
this procedure must include dio-anthracene. Because of limitations
listed above, no additional internal standards can be suggested that
are applicable to all samples.
7.3.1 Prepare calibration standards at a minimum of three concen-
tration levels for each parameter of interest by adding vol-
umes 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 di-
chloromethane. One of the standards should be at a concen-
tration near, but above, the method detection limit, and 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 Using injections of 2 to 5 jjl of each calibration standard,
tabulate peak height or area responses against concentration
for each compound and internal standard, and calculate rela-
tive response factors (RRF) for each compound using Equation 1.
KRT = (AsBis)/(AisBs) (Eq. 1)
Response for the parameter to be measured.
Response for the internal standard.
where A„
s
33
-------
Big = Mass of the internal standard (ng).
B s Mass of the parameter to be measured (ng).
s
If the RET value over the working range is a constant (< 10%
RSD), the HBP can be assumed to be nonvariant and the average
REF can be used for calculations. Alternatively, the results
can be used to plot a calibration curve of response ratios,
A /A. vs. RET.
S IS
7.3.3 Verify the working calibration curve or KRF on each working
day by the measurement of one or more calibration standards.
If the response for any parameter varies from the predicted
response by more than £ 10%, the test must be repeated using
a fresh calibration standard. Alternatively, a new calibra-
tion curve must be prepared for that compound.
7.4 Daily Calibration of the GC/MS System
7.4.1 At the beginning of each day, check the calibration of the
GC/MS system and adjust if necessary to meet DFTPP specifi-
cations (Section 7.4.3). Each day base/neutrals are measured,
the column performance specification (Section 12) with benzi-
dine must be met. Each day the acids are measured, the column
performance specification (Section 12) with pentachlorophenol
must be met. DFTPP can be mixed in solution with either of
these compounds to complete two specifications with one in-
jection, if desired.
7.4.2 To perform the calibration test of the GC/MS system, the fol-
lowing instrumental parameters are required.
Electron energy, 70 eV (nominal)
Mass range, m/e 40-475
Scan time, 3 sec or less for acids or base/neutrals with the
packed column, 1 sec or less for base/neutrals with the capil-
lary column.
7.4.3 Evaluate the system performance each day that it is to be
used for the analysis of samples or blanks by examining the
mass spectrum of DFTPP. Inject a solution containing 50 ng
DFTPP and check to ensure that performance criteria listed in
Table 3 are met. If the system performance criteria are not
met, the analyst must retune the spectrometer and repeat the
performance check. The performance criteria must be met be-
fore any samples or standards may be analyzed.
7.4.4 At the beginning of each working day, verify the calibration
of the GC/MS system by injecting a standard mixture (Section
7.3.3).
34
-------
7-4.5 For instrument performance verification, to each acid and
base/neutral extract and each standard analyzed, add an
amount of dxo~anth?acene immediately prior to injection such
that 40 ± 4 ng will be injected.
8. Quality Control
8.1 Demonstrate Acceptable Performance
Before performing any analyses, the analyst must demonstrate the
ability to generate acceptable accuracy and precision with this pro-
cedure .
8.1.1 For each compound to be measured, select a spike concentra-
tion representative of the expected levels in the samples.
Using stock standards, prepare a quality control check stan-
dard in acetone 1,000 times more concentrated than the
selected concentrations.
8.1.2 Add 80 |Jl of the check standard to each of a minimum of four
80 ml aliquots of reagent water with a syringe. A representa-
tive sludge can be used in place of the reagent water, but
one or more additional aliquots must be analyzed to determine
background levels, and the spike level must exceed twice the
background level for the test to be valid. Analyze the ali-
quots according to the method beginning in Section 10.
8.1.3 Calculate average recovery (R) and standard deviation (s), in
percentage recovery, for the results. Sludge background cor-
rections must be made before R and s calculations are performed.
8.1.4 Using the appropriate data from Tables 13-15, determine the
recovery and single operator precision expected for the method
for each parameter, and compare these results to the values
calculated in Section 8.1.3. If the data are not comparable,
the analyst must review potential problem areas and repeat
the test.
8.1.5 After January 1, 1982, the values for R and s must be rigid
method performance criteria provided by the U.S. EPA, Environ-
mental Monitoring and Support Laboratory, Cincinnati, Ohio,
before any samples may be analyzed.
8.2 Precision and Accuracy Statement. The analyst must calculate method
performance criteria for each of the surrogate standards.
8.2.1 Calculate upper and lower control limits for method performane
for each surrogate standard, using the values for R and s cal-
culated in Section 8.1.3:
Upper Control Limit (UCL) = R + 3 s
Lower Control Limit (LCL) = R - 3 s
35
-------
The UCI and LCI can be used to construct control charts4
that are useful in observing trends in performance. After
January 1, 1982, the control limits above must be replaced
by method performance criteria provided by the U.S. Environ-
mental Protection Agency.
8.2.2 For each surrogate standard, the laboratory must develop and
maintain separate accuracy statements of laboratory perfor-
mance for wastewater samples. An accuracy statement for the
method is defined as R ± s. The accuracy statement should be
developed by the analysis of four aliquots of sludge as de-
scribed in Section 8.1.2, followed by the calculation of R
and s. Alternately, the analyst must use four sludge data
points gathered through the requirement for continuing qual-
ity control in Section 8.4. The accuracy statements should
be updated regularly.6
8.3 Surrogate Spikes. The laboratory is required to spike all of their
samples with the surrogate standard spiking solution to monitor spike
recoveries. Suggested surrogate compounds are listed in Table 5.
If the recovery for any surrogate standard does not fall within the
control limits for method performance, the results reported for that
sample oust be qualified as described in Section 14.3. The labo-
ratory should monitor the frequency of suspect data to ensure that
it remains at or below 5%.
8.4 Method Blank. Before processing any samples, the analyst should
demonstrate through the analysis of an 80 ml aliquot of reagent water,
that all glassware and reagents are interference free. Each time a
set of samples is extracted or there is a change in reagents, a la-
boratory reagent blank should be processed as a safeguard against
laboratory contamination.
8.5 Replicate and Spiked Samples
8.5.1 Analyze all samples in duplicate. Using the procedures de-
scribed in Section 8.3-2, spike and analyze two additional
aliquots. Analyze a third unspiked aliquot on the same day
that the spiked aliquots are analyzed.
8.5.2 Spike an 80 ml aliquot of sludge with all of the compounds
identified in the sample and the representative semivolatile
compounds listed in Table 4 at two times the observed concen-
tration or at 10 times the lower limit of detection, which-
ever is greater. Prepare the spike as two acetone solutions
with the acidic and neutral compounds in the first solution
and the basic compounds in the second solution. The concen-
trations of the spiking solutions should be such that 1 to 5
ml of each solution are added to the sludge sample to attain
the required spike concentration. Homogenize the spiked sam-
ple for 45 to 60 sec and store overnight at 4°C with tumbling
before extraction and analysis.
36
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Sampling. and Preservation
9.1 Sampling. Collect samples in glass containers (1,000 to 4,000 ml)
with a TFE lined screw cap. The container should be prewashed with
acetone and dried before use. Containers should be filled no more
than two-thirds full with sample to minimize breakage during freezing.
9.2 Preservation. Preferably, samples should be iced or refrigerated at
4°C for not more than 24 hr before extraction. Where extraction can-
not be performed within 24 hr, samples should be frozen. Samples
may be stored for up to 30 days at -20°C or indefinitely at -75°C.
In order to prevent breakage during storage, the containers should
not be slightly warmed and then recooled. The iced or defrosted
sample should be homogenized by mixing for 1 min with a Tissumizer®
before analysis.
Sample Extraction
10.1 Preparation of Drying Column. Immediately prior to extracting a
sample, prepare a drying tube for the extract. Place a small
glass wool plug in the bottom of the column and add anhydrous so-
dium sulfate to a depth of 10 to 15 cm.
10.2 pH Adjustment. Thoroughly mix the sludge sample by homogenizing
in the sample bottle for 1 min, then quickly remove a 80 ml aliquot
into a 250 ml graduated cylinder. Transfer the aliquot into a 250
ml centrifuge bottle. Basify to pH £ 11 with a 6 N sodium hydrox-
ide solution. Mix briefly with the homogenizer to ensure uniform
sample pH. (Note: If copious precipitation of carbonates is ob-
served when sodium hydroxide is added, make the sample slightly
acidic with 6 N hydrochloric acid and allow the carbon dioxide
evolution to cease before basifying the sample.)
10.3 Basic Extraction. Add 80 ml of dichloromethane to the centrifuge
bottle and homogenize for 45 to 60 sec. Do not homogenize more
than 60 sec to avoid heating the sample. Cap the centrifuge bot-
tles with TFE-lined screw caps and centrifuge at 2,500 to 3,000 rptn
for 30 min. Stir and repeat centrifugation if satisfactory phase
separation is not achieved. The mixture will separate into an
aqueous layer over the dichloromethane extract with a solids cake
at the water-dichloromethane interface. Withdraw the extract from
each centrifuge bottle with a 100 ml syringe. Discharge the ex-
tracts into a 500 ml separatory funnel. Drain the dichloromethane
through the drying column into a Kuderna-Danish evaporator. Retain
any aqueous layer and return it to the centrifuge bottle. Extract
the sample two more times to achieve three-fold extraction. Wash
the drying column with an additional 100 ml of dichloromethane and
combine the eluent with the dried extracts.
10.4 Extract Concentration. Add a boiling chip to the extract in the
Kuderna-Danish evaporator and concentrate the extract to 8 ml using
an 85°C bath or a steam bath. If the extract is only slightly col-
ored and not notably viscous, fit a modified Snyder column onto
37
-------
the Kuderna-Danish receiving tube and immerse the tube halfway in
a 35°C water bath. Direct a gentle stream of nitrogen directly on
the surface of the extract until the volume is 2 4 ml. Transfer
the extract to a clean vial, seal it with TFE lined screw cap, and
store the extract at 4°C. If the extract is highly colored, vis-
cous or solidifies when concentrating to 4 ml, dilute the extract
to 12.ml with dichloromethane, transfer to a clean vial, and store
as described above.
10.5 Acidic Extraction. Acidifiy the sludge sample portions to pH £ 2
with 6 N hydrochloric acid and extract the sample again by proce-
dures described in Sections 10.3 to 10.4. Discard the extracted
sludge aliquots.
Extract Cleanup
11.1 Base/Neutral Extracts. Clean the base/neutral sludge extracts by
adsorption chromatography on either florisil or silica gel. Al-
though there does not appear to be any significant difference in
the performance of these adsorbents, the adsorbent selected for
analyses of all quality assurance blanks, spiked blanks, and spiked
sludges associated with a specific sludge sample must be the same
as was selected for the original sample analysis. In cases where
the base/neutral extracts are to be analyzed by packed column GC/MS,
the GPC procedure (Section 11.2) may be used as an alternative
cleanup method.
11.1.1 Column Preparation. Prepare a 200 mm x 20 mm ID silica
gel or florisil column by pouring 20 g fresh 3% deactivated
silica gel or 1% deactivated florisil, no more.than 5 days
old, into a chromatographic column containing 60 to 70 ml
hexane. Tap the side of the clamped column with a stirring
rod to aid packing and air bubble escape. If clumping
should occur at the bottom of the solvent reservoir, a stir-
ring rod can be used to break the clumps. Add hexane as
needed. After most packing has settled, rinse down the
florisil or silica gel adhering to the column walls with
additional hexane. Wash the column with an additional 20
ml hexane until the solvent level is within 1 to 2 mm of
the top of the silica gel or florisil.
11.1.2 Column Calibration. Check the elution pattern for each
new batch of adsorbent prepared by chromatographing a
spiked blank. Mix 1 ml of a dichloromethane solution con-
taining 100 Mg of each of the specific analytes of interest
and the representative B/N/P compounds included in quality
assurance method spikes (described in Section 8.3) with
2 g of adsorbant. Evaporate the solvent with a gentle
stream of dry nitrogen and add the adsorbant to the column.
Elute the column with 20 ml of hexane (Fraction I), 50 ml
of 10% dichloromethane in hexane (Fraction II), 50 ml of 50%
dichloromethane in hexane (Fraction III), and then 150 ml
38
-------
of 5% acetone in dichloromethane (Fraction V). Maintain
the elution flow at 2 to 4 ml/min. Collect each fraction
in separate Kuderna-Danish evaporators and concentrate the
fractions according to the procedures described in Section
7.4. Analyze each fraction by GC/FID or GC/MS with the
SE-54 capillary or packed SP-2250 column. Determine the
recovery of each compound in each fraction by comparing
the detector responses with those from a duplicate aliquot
of the original spiked blank. Elution patterns and recover-
ies observed for selected compounds chromatographed on sil-
ica gel and florisil are shown in Tables 6 and 7. Increasing
the volume of Fraction I may be required to provide accept-
able cleanup for sludge extracts containing high concentra-
tions of aliphatic hydrocarbons or other non-polar compounds.
However, additional hexane may elute significant portions
of the chlorinated benzenes, hexachloroethane, hexachloro-
butadiene, hexachlorocyclopentadiene, 2-chloronaphthalene,
aldrin, and p,p'-DDE. The elution patterns and recoveries
observed for many B/N/P compounds chromatographed on silica
gel using 100 ml of hexane for Fraction I are shown in
Table 8. In cases where the volume of Fraction I must be
increased to achieve acceptable cleanup and the analytes
of interest include the compounds listed in this section,
Fraction I must be analyzed separately from Fraction II-IV.
11.1.3 Column Operation. Place 2 g of fresh 1% deactivated flor-
isil or 3% deactivated silica gel into a small beaker and
add the concentrated base/neutral extract. Dry the sample
with a gentle nitrogen stream with stirring to ensure fast
and uniform drying. Load dried florisil or silica gel con-
taining the sludge components into the column. Elute the
column as described in Section 11.1.2. Discard Fraction
I. Collect and composite in Kuderna-Danish evaporators
all fractions containing the compounds of interest such as
Fractions II through IV for all B/N/P compounds. Fraction
II frequently contains much higher levels of interfering
materials than to Fractions III or IV. As a result, it
should not be composited with Fractions III and IV if it
contains no compounds of interest. Fractions may be ana-
lyzed separately if desired. Concentrate all fractions
collected to 1 ml according to procedures described in
Section 10.4.
11.2 Acidic Fraction. Use gel permeation chromatography is used to re-
move triglycerides and fatty acids.
11.2.1 GPC Column Preparation. Place 70 g of Bio-Beads SX-3 in a
400 ml beaker. Cover the beads with dichloromethane and
allow the beads to swell overnight before packing the col-
umns . Transfer the swelled beads to the column and start
pumping solvent in this case, dichloromethane, through the
39
-------
column, with upward flow at 5.0 ml/min. After ~ 1 hr, ad-
just the pressure on the column to 350 to 700 millibars (5
to 10 psi) and pump an additional 4 hr to remove air from
the column. Adjust the column pressure periodically as
required to maintain 350 to 700 millibars.
11.2.2 Column Calibration. Calibrate the GPC column elution at
least once a week according to the following procedure.
Load 5 ml of the corn oil solution into sample loop No. 1
and 5 ml of the phthalate-phenol solution into loop No. 2.
Inject the corn oil and collect 10 ml fractions, for 36
min, changing the fraction at 2 min intervals. Inject the
phenols solution and collect 10-ml fractions for 1 hr.
Determine the com oil elution pattern by evaporation of
each fraction to dryness followed by a gravimetric deter-
mination of the residue. Analyze the phthalate-phenol
fractions by GC/FID on the SP-2250 and SP-1240-DA columns.
Plot the concentration of each component in each fraction
versus total eluent volume (or time) from the injection
points. Choose a "dump time" which allows & 85% removal
of the corn oil and 2 85% recovery of the di-n-octylphthal-
ate. Choose the "collect time" to extend at least 10 min
after the elution of pentachlorophenol. "Wash" the column
20 min between samples. Typical parameters selected are:
dump time, 20 min (100 ml); collect time, 30 min (150 ml);
and wash time, 20 min (100 ml). The column can also be
calibrated using a 254-nm UV detector to monitor the elu-
tion of the corn oil and the phenols. Measure the peak
areas at various elution times to determine appropriate
fractions.
11.2.3 Column Operation. Prefilter or load all extracts via the
filter holder to avoid particulates that might cause flow
stoppage. Load the £ 4-ml extracts into the 5-ml loops
with a clean solvent on both sides of the extract. Load
the * 12-ml extracts in three consecutive loops. Use suf-
ficient clean solvent after the extract to transfer the
entire aliquot into the loop. Between extracts, purge the
sample loading tubing thoroughly with clean solvent. After
especially dirty extracts, run a GPC blank using dichlo-
romethane to check for carry-over. Process the extracts
using the dump, collect, and wash parameters determined
from the calibration and collect the cleaned extracts in
250 ml brown bottles. Concentrate the cleaned extracts,
combining collected fractions from multiple injections, to
* 8 ml using Kuderna-Danish evaporators and then to S 4 ml
using modified Snyder columns and nitrogen blowdown.
Transfer the cleaned extracts to 8 ml graduated tubes and
dilute to 4 ml with dichloromethane. Store at 4°C for
GC/MS analysis. Intensely colored extracts may require a
second GPC cleanup.
40
-------
Note: Sample extracts must be in the same solvent used
for column elution. Injection of solutions in other sol-
vents can cause a significant change in the bead swell.
In extreme cases a traumatic pressure increase may damage
the column and cap, or even break the glass column.
Sample Extract Analysis
12.1 Base/Neutral/Pesticide Extracts. Analyze the B/N/P extracts by
GC/MS using the capillary column or packed column systems described
in Section 5.2.1 under the conditions shown below. The capillary
column GC/MS procedure is preferred because this procedure provides
more unambiguous interpretation of the resulting data. However,
if satisfactory performance of the column cannot be demonstrated
or if the required Grob-type injection system with direct capillary
GC/MS interface is not available, the packed column GC/MS procedure
may be used.
12.1.1 Capillary GC/MS with a SE-54 WCOT Column
12.1.1.1 Column Temperature: 50°C for 4 min, 50 to 320°C
at 4°C/min, and 320°C until after the elution
time for benzo[g,h,i]perylene.
GC/MS interface, 300°C
Carrier gas helium at 10 psi
Splitless injection for 30 sec
Injection size, 2 jjI
Examples of the separations achieved by this
column are shown in Figure 2. Relative retention
times for the base/neutral compounds on this col-
umn are listed in Table 9.
12.1.1.2 Capillary Column GC/MS Performance Checks
12.1.1.2.a Column Performance Screening. Fully evaluate
the performance of each new column by GC/FID
prior to installation in the GC/MS system.5
In addition, recheck columns that show a marked
decrease in performance on the GC/MS (as de-
scribed in Section 12.2.1.3) or that have not
been used the previous 2 weeks for GC/MS analy-
ses under this protocol. Install the capil-
lary column in a gas chromatograph equipped
with a Grob-type split/splitless injector and
flame ionization detector. Adjust carrier
gas at about 15 to 20 cm/sec for N2 or 30 to
40 cm/sec when He or hydrogen are used as the
41
-------
carrier gas. Set the splitter flow at 30 to
50 ml/min, makeup gas at 30 ml/min, and col-
umn oven temperature at 85 °C. Using split-
less injection, inject 2 fJl of a column per-
formance test mixture containing 20 ng each
of 2,6-dimethylphenol, 2,6-dimethylaniline,
1-octanol, 2-octanone, n-tridecane, and
n-tetradecane or an equivalent commercial test
mixture. Table 10 shows the contents of three
appropriate commercial mixtures. Measure the
pE of the column as the ratio of the peak
height of 2,6-dimethylaniline to that of 2,6*
dimethylphenol. A value of 0.5 to 1.5 is ac-
ceptable. Determine the activity of the col-
umn toward polar compounds by determining both
the asymmetry for the 1-octanol peak and the
ratio of the peak height of 1-octanol to that
of C13 alkane. The peak asymmetry is eval-
uated by drawing a perpendicular from the apex
of the peak to the baseline and measuring the
width from the front of the peak to the perpen—¦
dicular line (VL.) and from the back of the
peak to thfe perpendicular line (Wg).
AS s WB x 100
Peak asymmetries between 75 and 200 are ac-
ceptable. The ratio of peak height of the
1-octanol to that of C13 alkane should be
higher than 0.5. Determine the number of ef-
fective theoretical plates (N »-) from the
tridecane peak using the equation
where tr' is the adjusted retention time of
tridecane and W. . is the peak width at half
height. The number of effective plates of
acceptable columns must be at least 25,000.
12.1.1.2.b System Performance. Evaluate the performance
of the capillary column in the GC/MS system
each time the column is installed and each
working day prior to its use. Using split-
less injection, inject 2 Ml a test mixture
containing 20 ng each of 2,6-dimethylaniline,
2,6-dimethylphenol, DFTPP, methylstearate,
octadecene, and octadecane. Measure the pH
of the column by taking, the ratio of peak
N
eff
5.545
42
-------
heights of 2,6-dimethylaniline to that of
2,6-dimethylphenol. A pH of 0.5 to 1.5 is
acceptable. Determine the resolution of the
peaks corresponding to octadecane and octa-
decane. The peaks should be resolved with no
more than a 50% valley. Determine the asym-
metry of the methylstearate peak according to
the formula given in Section 12.1.1.2.a. If
the methylstearate peak tails, the GC/MS
transfer line is not adequately heated.
12.1.1.3 At the beginning of each day that base/neutral
analyses are to be performed, inject 100 ng
of benzidine either separately or as part of
a standard mixture that may also contain 50
ng of DFTPP. Acceptable performance is
achieved when the benzidine is identified
according to Section 13.
12.1.2 Packed Column GC/MS with a SP-2250 Column
12.1.2.1 Chromatographic Conditions
Column temperature, 60®C for 2 min, 60 to 260°C
at 80°C/min, and 260°C until after the elution
time for benz[g,h,i]perylene.
Injector temperature, 225°C
GC/MS interface temperature, 275°C
Carrier gas, helium at 30 ml/min
Injection size, 2 |Jl
An example of the separation achieved by the
column is shown in Figure 3. Relative retention
times for the base/neutral and pesticide com-
pounds on this column are listed in Table 11.
12.1.2.2 At the beginning of each day that base/neutral
analyses are to be performed, inject 100 ng of
benzidine either separately or as part of a
standard mixture that may also contain 50 ng of
DFTPP. Acceptable performance is achieved when
the benzidine is identified according to Section
13.
12.2 Acid Extracts
12.2.1 Analyze acid extracts by GC/MS using the SP-1240-DA column
described in Section 5.2.1, operated under the following
conditions.
43
-------
Column temperature, 85°C for 2 min, 85 to 185°C at 10°C/
mi n and 185"C until after the elution time for 4-nitro-
phenol.
Injector temperature, 185°C.
GC/MS surface temperature, 275°C.
Carrier gas, helium at 30 ml/min.
Injection size, 2 pi.
An example of the separation achieved by the column is
shown in Figure 4. Relative retention times for the acid
compounds are listed in Table 11.
12.2.2 At the beginning of each day that acid fraction analyses
are to be performed, inject 50 ng of pentachlorophenol
either separately or as part of a standard mixture that
may also contain DFTPP. Acceptable performance is
achieved when pentachlorophenol is identified according to
Section 13.
13. Qualitative and Quantitative Determination
13.1 Using the characteristic nuiss spectral ions listed in Tables 8 or
10 for the base/neutral and pesticide compounds and in Table 11 for
the acid compounds, plot at least three extracted ion current plots
(EICPs) for each analyte.
13.2 Identify the presence of analytes by the coincidence of peaks in
the characteristic EICPs at the appropriate retention times and
with intensities in the characteristic ratios (Tables 8 or 10 and
U).
13.3 Record the area (intensity) of the peak in the EICP for the most
intense ion for each compound identified.
14. Calculations
14.1 Determine the concentration of individual compounds in the sample.
14.1.1 If the external standard calibration procedure is used,
calculate the amount of material injected from the peak
response using the calibration curve or calibration factor
in Section 7/2.2. The concentration in the sample can be
calculated from Equation 2:
(M)(V )
Concentration, (Jg/liter * (b )(v ) ^
44
-------
where: M = Mass of material injected (ng).
Vj = Volume of extract injected ()Jl).
Vg = Volume of total extract (ml).
V = Volume of wet sludge extracted (liter)
14.1.2 If the internal standard calibration procedure was used,
calculate the concentration in the sample using Equation 3.
(A)(I )(VE)
Concentration, pg/liter = (AJS)(RRF)(Vj)(Vg) (Eq" 3)
where: A = Area of peak in sample extract.
Ajg = Area of internal standard peak in sample
extract.
Ig = Areas of internal standard injected (ng).
Vj. = Total volume of extract (ml).
Vj = Volume of extract injected (|Jl).
V = Volume of sludge extracted (liter).
s
RRF = Relative response factor.
14.2 Report results in micrograms per liter without correction for re-
covery data. When duplicate and spiked samples are analyzed, re*
port all data obtained with the sample results.
14.3 If the surrogate standard recoverues fall outside the limits in
Section 8.2, data for all parameters in that sample must be
labeled as suspect.
Method Performance
Performance data for the application of this method to both POTW and
industrial sludges are shown in Tables 13 to 15. Table 13 shows data
for B/N compounds analyzed in POTW and industrial sludges via Option A.
Table 14 shows data for B/N compounds analyzed via Option B and acidic
compounds in aliquots of the same sludges. Data for B/N compound were
analyzed via Option B and acidic compounds in sludges from 40 POTWs.
Most of these data represent results from one laboratory. Approximately
25% of the data in Table 15 was contributed by a second laboratory.
45
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16. References
1. "Carcinogens - Working With Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
2. "OSHA Safety and Health Standards, General Industry" (29CFR1910),
Occupational Safety and Health Administration, OSHA 2206 (Revised
January 1979).
3. "Safety in Academic Chemistry Laboratories," American Chemical Society-
Committee on Chemical Safety, 3rd Edition Publication (1979).
4. "Handbook of Analytical Quality Control in Water and Wastewater
Laboratories," EPA*600/4-79-019, U.S. Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
5. Grob, K., Jr., G. Grob, and K. Grob, "Comprehensive Standardized
Quality Test for Glass Capillary Columns," J. Chrom., 156» 1-20
(1978).
17. Additional Sources
1. "Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants." U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati
OH 45268, March 1977, Revised April 1977. Effluent Guidelines
Division, Washington, DC 20460.
2. "Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometry,
DPD) for Chlorine, Total Residual," Methods for Chemical Analysis
of Water and Wastes, EPA 600/4-79-020, U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory - Cincinnati
OH 45268. In preparation.
3. "Preservation and Maximum Holding Time for the Priority Pollutants,"
U.S. Environmental Protection Agency, Environmental Monitoring and
Support Laboratory, Cincinnati, OH 45268. In preparation.
4. Budde, W. L., and J. W. Eichelberger, "Performance Tests for the
Evaluation of Computerized Gas Chromatography/Mass Spectrometry
Equipment and Laboratories," EPA-600/4-80-025, U.S. Environmental
Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, OH 45268, p. 16, April 1980.
5. Kleopfer, R. D., "Priority Pollutant Methodology Quality Assurance
Review," U.S. Environmental Protection Agency, Region VII,
Kansas City, KS. Seminar for Analytical Methods for Priority
Pollutants, Norfolk, VA, January 17-18, 1980, U.S. Environmental
Protection Agency, Office of Water Programs, Effluent Guidelines
Division, Washington, DC 20460.
46
-------
TABLE 1. EXTRACTABLE ORGANIC PRIORITY POLLUTANTS
Compound
STORET No.
CAS No.
Acids
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,5-Trichlorophenol
4-Chloro-3-methylphenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
4,6-Dinitro-2-methylphenol
Benzidine
3,3'-Dichlorobenzidine
Bases
34591
34646
39032
32730
34621
34452
34586
34601
34606
34657
39210
34631
Polycyclic Aromatic Hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz[a]anthracene
Benzo"[b]fluoranthene
Benzo[k]fluoranthene
Benzo[g,h,i]perylene
Benzo[ajpyrene
Chrysene
Dibenz[a,h]anthracene
Fluoranthene
Fluorene
Indeno[1,2,3-cd]pyrene
Naphthalene
Phenanthrene
Pyrene
34205
34200
34461
34562
34242
34242
34521
34247
34562
34556
34376
34381
34403
39250
34461
34469
88-75-5
100-02-7
87-86-5
108-95-2
88-06-2
59-50-7
95-57-8
120-83-2
105-67-9
534-32-1
93-87-5
92-94-1
83-32-9
208-96-8
120-12-7
56-55-3
205-99-2
207-08-9
191-24-2
50-32-8
218-01-9
53-70-3
206-44-0
86-73-7
193-39-5
91-20-3
85-01-8
129-00-0
Phthalates
Bis(2-ethyIhexyl)phthalate
39100
Butylbenzylphthalate
34292
Diethylphthalate
34336
Dimethylphthalate
34341
Di-n-butylphthalate
39110
Di-n-octylphthalate
34596
117-81-7
85-68-7
84-66-2
131-11-3
84-74-2
117-84-0
(continued)
47
-------
TABLE 1 (continued)
Compound
STORET No.
CAS No.
Chlorinated Hydrocarbons
2-Chloronaphthalene
34581
91-58-7
1,2-Dichlorobenzene
34536
95-50-1
1,3-Dichlorobenzene
34566
541-73-1
1,4-Dichlorobenzene
34571
106-46-7
Hexachlorobenzene
39700
118-74-1
Hexachloro-1, 3-butadiene
34391
87-68-3
Hexachloroethane
34396
67-72-1
Hexachlorocyclopentadiene
34386
77-47-4
1,2,4-Trichlorobenzene
34551
129-82-1
Chloroalkyl Ethers
Bis(2-chloroethyl)ether
34273
111-44-4
Bis(2-chloroethoxy)methane
34278
111-91-1
Bis(2-chloroisopropyl)ether
34283
39638-32-9
Miscellaneous Neutrals
4-Bromophenyl phenyl ether
34636
101-55-3
4-Chlorophenyl phenyl ether
34641
7005-72-3
2,4-Dinitrotoluene
34611
121-14-2
N-Nitrosodi-n-propylamine
34428
621-64-7
N-Nitrosodimethylamine
34438
62-75-9
2,6-Dinitrotoluene
34626
606-20-2
Isophorone
34408
78-59-1
Nitrobenzene
34447
98-95-3
N-Nitrosodiphenylamine
34433
86-30-6
1,2-Diphenylhydrazine
34346
122-66-7
Pesticides
$-Endosulfan
34356
33213-65-9
o-BHC
39337
319-84-6
7-BHC
34264
58-89-9
P-BHC
39338
319-85-7
Aldrin
39330
309-00-2
Heptachlor
39410
76-44-8
Heptachlor epoxide
39420
1024-57-3
a-Endosul£an
34361
959-98-8
Dieldrin
39380
60-57-1
4,4'-DDE
39320
72-55-9
4,4'-DDD
39310
72-54-8
4,4'-DDT
39300
50-29-3
(continued)
48
-------
TABLE 1 (concluded)
Compound
STORET No.
CAS No.
Endrin
39390
72-20-8
Eadosulfan sulfate
34351
1031-07-8
6-BHC
34259
319-86-8
Chlordane
39350
57-74-9
Toxaphene
39400
8001-35-2
PCB-1242
39496
53469-21-9
PCB-1221
39504
11104-28-2
PCB-1254
39488
11097-69-1
PCB-1232
39492
11141-16-5
PCB-1248
39500
12672-29-6
PCB-1260
39508
11096-82-5
PCB-1016
34671
12674-11-2
49
-------
TABLE 2. UNSTABLE B/N COMPOUNDS
Bis (2-chloroisopropyl) ether
Nitrobenzene
N-Nitroso-di-n-propylamine
Bis(2-chloroethoxy)methane
Isophorone
2,6-Dinitrotoluene
2,4-Dinitrotoluene
1,2-Diphenylhydrazine
Benzidine
3,3'-Dichlorobenzidine
N-Nitrosodimethylamine
TABLE 3. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA
m/e
Ion abundance criteria
51
30-60% of m/e 198
68
< 2% of m/e 69
70
< 2% of m/e 69
127
40-60% of 198
197
< 1% of mass 198
198
Base peak, 100% relative abundance
199
5-9% of m/e 198
275
10-30% of m/e 198
365
1% of m/e 198
441
Present and < m/e 443
442
40% of m/e 198
443
17-23% of m/e 442
a 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).
50
-------
TABLE 4. REPRESENTATIVE EXTRACTABLE COMPOUNDS
FOR RECOVERY STUDIES
Acenaphthylene
Benzidine
Benzo[a]pyrene
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl)phthalate
Butylbenzyl phthalate
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,4-Dimethylphenol
2,6-Dinitrotoluene
Fluoranthene
Hexachloroethane
N-Nitrosodimethylamine
1,4-Dichlorobenzene
Pentachlorophenol
Phenol
Dieldrin
a-BHC
£,£'-DDE
Heptachlor
51
-------
TABLE 5. SUGGESTED SURROGATE STANDARDS
Base/neutral fraction
Acid fraction
Aniline-ds
Anthracene-d^
Benzo[a]anthracene-d12
4,4'-Dibromobiphenyl
2-Fluorophenol
Pentafluo ropheno1
Pheaol-d5
2-Perfluoromethyl phenol
4,4*-Dibromooctafluorobiphenyl
Decafluorobiphenyl
2,2'-Difluorobiphenyl
2-Fluoraniline
1-Fluoronaphthylene
2-Fluoronaphthylene
Naphthalene-d8
Nitrobenzene-ds
1,2,3,4,5-Penta fluo robiphenyl
Phenanthrene-dio
Pyridine-d5
52
-------
TARUt 6. EMIT I OH PATTERNS AW KOWKMES OF SEiKCTKO HASK/MKt ITU Alii CN^TOOMWII ON SII.ICA «Kl"
Frattiuu II Frxlion III fraction IV
Spike Fraction I IOJ dirklnrwIhiiK/ "iOX dit-hlciroawlliaiie/ arrlnm:/
level hexane hexane hcxaiic illrhloroaielliaiic
CuiiiiiI (fig) (?' *!).. _ (5®. J5® l!i Jt '.?®."!.)!
t ,4-U Wtilnrobcitzcnr 46.8 t t
llrxaililoroet hane 31.2 t
Ris(2-yl)etbcr) 49.6 *
Ris(2-rliloroclliyt)clller 31.6 <
Acenaphdiylenc 28.S *
2,6-l>iiii t rotolnrue 35.1 •
Fluoranthenc 27.0 ~
Renzi-dim; 31.0
3,3'-OichloroJienaiifine 36.4 t
n-lul)|Hienzyl|ittthal«te 45.1 4
BJs(2-ethylhexyl)|>btbalate 39.6 a
Renzo|a)pyrcnc 30.0 ~
b
«¦
-------
TANU 7.
fc MIT II IN rATTICMNK ANI> MiCUVMilKK «M- KKIJiCTKU IIASK./NKIITKAI.S IIMKUIAlmiltAI'UKII (IN MittlS!!*
traction II
f rail Inn III
Krurl iim IV
S|tihf
Frai l itHi 1
IUX diibioinMrlhaili*/
5U1 ilii liliuiNM-l liani'/
5% arrliMM'/
Twl al
Iwl
ItexaiM!
bi-aaiir
hi-xaiu*
il i i'b 1 uriMai'l liiiw
Ki'iovi-
Ci«|Niuml
(l*S>
(20 mI)
(50 Ml)
(50 ail)
(ISO Ml)
(X)
1,4"llii«loriM.>l Imm!
62.4
•I
I
i
67
Ri*(2-rtby lbe«y 1 )|ifathalale
79.2
1
92
Bengal a ||»yrcn«
60.0
~
~
• 7
a IX deactivated ftar(ail.
k Aaalyaes dome by packed calMa GC/MS.
t * indicates anrc I baa 11
recMwif ia lhal fractioa.
-------
tamj: a. emitim r*nr.Mis mw tKMiviuiies of seu:ctu> *ASE/Mt:irnui./itaiciw„s ctHuvtATomAmi) m silica cki.
wii mi r.um«m •sunt
Fraction || Fraction III Fraction IV
Fraction I IOX dirliloroaelliaae/ 50X ilii hlorrartliane/ 5% acetone/ Tola I (
ktiaw hesane krimc ilit'liliidwibiir Rrtovrry
C.»|H.Hml OOOal) (Mai) (Hal) (ISO «I) «)
Bii(2-thlorortliyl )etlier
95 1 22
1 .MNikUrotnuM
«
64 i 6
1,2-0l«hlorobcozene
~
67 i 9
Nexachloroethaac
~
73 1 14
It-nit roaodl -a-propylaaiae
*
94 1 12
Hi t robenzrue
«
*
67 t 3
Bia(2-ch1oroeIhoay)aetbane
»
66 i 5
1,2,4-Tricklorofceazene
*
70 1 17
Naphthalene
~
I
~
Hi I
Hrxar.blorolmtadieac
~
142 1 51
Ilrxachlorocyclopeatadiene
»
.100 1 55
2-Chl oronaphtlialeae
~
~
94 t 5
Acenapfctbylene
~
4
77 1 21
2,6-Oiai trotolHenc
~
9) 1 19
Acenapfcthalene
~
*
88 1 12
2,4-Diiiitrotolnene
«
95 1 14
Fluorene
t
87 t 22
4-Chloroptienyl phenyl ether
~
109 1 12
Dlclhylpbllialate
~
90 t 41
4-Rroaopheaylphcnylethcr
t
116 t 15
ttcsach 1 o rohenzene
4
¦5 i 30
Ilienaalkreiie
*
•5 1 30
Anthracene
~
•3 1 28
(continued)
-------
Ul
|l)|lrtlwlMt
lr«u| a InicM
Oibeaz|a,h|aalkrace
-------
TABLE 9. CHROMATOGRAPHIC CONDITIONS AND CHARACTERISTIC EI IONS FOR
THE BASE/NEUTRAL COMPOUND ANALYZED BY CAPILLARY COLUMN GC/MS
Compound
RRT
a,b
Characteristic EI ions
(relative intensity)
N-Nitrosodiraethylamine
Bis(2-chloroethyl)ether
1.3-Dichlorobenzene
1.4-Dichlorobenzene
1,2-Dichlorobenzene
Bis(2-chloroisopropyl)ether
Hexachloroethane
N-Nitrosodi-n-propylamine
Nitrobenzene
Isophorone
Bis(2-chloroethoxy)methane
1,2,4-Trichlo robenzene
Naphthalene
Hexachlorobutadiene
Hexachlorocyclopentadiene
2-Chloronaphthalene
Acenaphthylene
DimethyIphthalate
2,6-Dinitrotoluene
Acenaphthene
2,4-Dinitrotoluene
Fluorene
4-Chlorophenyl phenyl ether
Diethylphthalate
N-Nitrosodiphenylaming
1,2-Diphenylhydrazine
4-Bromophenyl phenyl ether
Hexachlorobenzene
Phenanthrene
Anthracene
d 1,0- Anthracene
Di-n-butyIphthalate
Fluoranthene
Pyrene
Benzidene
ButylbenzyIphthalate
Chrysene
3,3'-Dichlorobenzidene
Bis(2-ethylhexy1)phthalate
Benzo[k]fluoranthene
0.04
42 (
00),
74(88), 44(21)
0.21
93(
00),
63(99), 95(31)
0.22
146
100),
148(64), 113(12)
0.22
146
100),
148(64), 113(11)
0.25
146
100),
148(64), 113 (11)
0.29
45 (
00),
77(19), 79(12)
0.29
117
100, 199(61), 201(99)
22), 42(64), 101(12)
0.31
130
0.32
77 (
00),
123(50), 65(15)
0.36
82 (
00),
95(14), 138(18)
0.41
93 (
00),
95(32), 123(21)
0.42
74(
00),
109(80), 145(52)
0.43
128
100)
223(63), 227(65)
0.47
225
100)
223(63), 227(65)
0.60
237
100)
235(63), 272(12)
0.63
162
100)
164(32), 127(31)
0.70
152
100)
153(16), 151(17)
0.72
163
100)
164(10), 194(11)
0.72
165
100)
63(72), 121(23)
0.73
154
100)
155(95), 152(13)
0.78
165
100)
63(72), 121(23)
0.82
166
100)
165(80), 167(14)
0.84
204
100)
206(34), 141(29)
0.84
149
100)
178(25), 150(10)
0.84
169
100)
168(71), 167(50)
0.86
77(
00),
93(58), 105(28)
0.92
248
100)
250(99), 141(45)
0.93
284
100)
142(30), 249(24)
0.98
178
100)
179(16), 176(15)
0.99
178
100)
179(16), 176(15)
1.00
188
100)
94(19), 80(18)
1.14
149
100)
150(27), 104(10)
1.19
202
100)
101(23), 100(14)
1.23
202
100)
101(26), 100(17)
1.24
184
100)
92(24), 185(13)
1.40
149
100)
91(50)
1.45
228
100)
229(19), 226(23)
1.47
252
100)
254(66), 126(16)
1.52
149
100)
167(31), 279(26)
1.62
252
100)
253(23), 125(16)
(continued)
57
-------
TABLE 9 (continued)
Compound
RRTa,b
Characteristic EI ions
(relative intensity)
Di-n-octylphthalate
Benzo[a]pyrene
DibenzTa,h]anthracene
Benzo{gTjlTi]perylene
1.63
1.67
1.84
1.87
149(100), 167(29), 279(22)
252(100), 253(23), 125(21)
278(100), 139(31), 279(12)
276(100), 138(37), 277(25)
a Relative to dxo*anthracene. Retention times data were not determined
for the priority pollutant pesticides and a few base/neutral compounds.
However, their retention properties should be roughly equivalent to
those on SP-2250 (see Table 6).
b SE-54 WCOT glass capillary (15 m x 0.24 am ID), He at 10 psi, program:
50°C for 4 min, then 4°C/min to 320°C.
c Elutes as dipheaylamine.
d Elutes as azobenzene.
58
-------
TABLE 10. COMPOSITION OF CAPILLARY COLUMN PERFORMANCE
TEST MIXTURES
Test mixture
Composition
Varian
P/N 82-005049-01
(nonpolar)
Alltech
TP-5 (polar)
Analabs
Test probe LPK-013F
(general purpose)
2-octanone
1-octanol
naphthalene
2,6-dimethylphenol
2,4-dimethylaniline
Cxj-alkane
Cx3-alkane
C^-alkane
C14-alkane
Cxs'alkane
Cig-alkane
1-octanol
5-nonanone
2,6-dimethy1ani1ine
2,6-dimethylphenol
naphthalene
Cx2-acid methyl ester
Cn-acid methyl ester
Cid-acid methyl ester
C1(j-alkane
Cu-alkane
1-octanol
Nonanal
2,3-butanediol
2,6-dimethylphenol
2,6-dimethylaniline
dicyclohexylamine
2-ethylhexanoic acid
0.2 |Jg/Ml
0.2
0.2
0.2
0.2
0.2
0.2
0.1 jjg/Ml
0.1
0.1
0.1
0.5
0.3
0.4
0.4
0.5
41 ng/|Jl
41
42
28
29
36
40
53
32
32
31
38
59
-------
TABLE 11.. CHROMATOGRAPHIC CONDITIONS AND CHARACTERISTIC IONS
FOR THE BASE/NEUTRAL AND PESTICIDE COMPOUNDS ANALYZED
BY PACKED COLUMN QC/MS
. Characteristic EI ions
Compound RRx ' (relative intensity)
N-Nitrosodimethylamine 0.15
1.3-Dichlorobenzene 0.31
1.4-Dichlorobenzene 0.33
Hexachloroethane 0.35
1,2-Dichlorobenzene 0.35
Bis(2-chloroisopropyl)ether 0.37
N-Nitrosodi-n-propylamine 0.42
Nit robenzene 0.45
Isophorone 0.47
Hexachlorobutadiene 0.48
1,2,4-Trichlorobenzene 0.49
Bis(2~chloroethoxy)methane 0.50
Naphthalene 0.51
Bis(2-chloroethyl)ether 0.55
Hexachlorocyclopentadiene 0.60
2-Chloronaphthalene 0.68
Acenaphthy1ene 0.75
Acenaphthene 0.77
Dimethyl phthalate 0.78
2,6-Dinitrotoluene 0.81
Fluorene 0.85
2,4-Dinitrotoluene 0.85
4-Chlorophenyl phenyl ether 0.85
Diethyl phthalate . 0.87
1,2-Diphenylhydrazine 0.88
N-Nitrosodiphenylamine 0.89
Hexachlorobenzene 0.92
4-Bromophenyl phenyl ether 0.92
Phenanthrene 0.99
Anthracene 0.99
Deuterated anthracene (D-10) 1.00
D-n-butylphthalate 1.09
Fluoranthene 1.18
Pyrene 1.22
Benzidine 1.27
2,3,7,8-Tetrachlorodibenzo- 1.33
2"dioxin
Butylbenzylphthalate 1•34
Bis(2-ethylhexyl)phthalate 1.37
Chrysene * 1.40
42(100),
146(100)
146(100)
117(100)
146(100)
45(100),
130(22),
77(100),
82(100),
225(100)
74(100),
93(100),
128(100)
93(100),
237(100)
162(100)
152(100)
154(100)
163(100)
165(100)
166(100)
165(100)
204(100)
149(100)
77(100),
169(100)
284(100)
248(100)
178(100)
178(100)
188(100)
149(100)
202(100)
202(100)
184(100)
322(100)
149(100)
149(100)
228(100)
74(88),
, 148(64)
, 148(64)
, 199(61)
, 140(64)
77(19),
42(64),
123(50),
95(14),
, 223(63)
109(80),
95(32),
, 127(10)
63(99),
235(63)
164C32)
153(16)
153(95)
164(10)
63(72),
165(80)
63(72),
206(34)
178(25)
93(58),
168(71)
142(30)
250(99)
179(16)
179(16)
94(19),
150(27)
101(23)
101(26)
92(24),
320(90)
91(50.)
167(31)
229(19)
44(21)
, 113(12)
, 113(11)
, 201(99)
, 113(11)
79(12)
101(12)
65(15)
138(18)
227(65)
145(52)
123(21)
129(11)
95(31)
272(12)
127(31)
151(17)
152(53)
194(11)
121(23)
167(14)
121(23)
141(29)
150(10)
105(28)
167(50)
249(24)
141(45)
176(15)
176(15)
80(18)
104(10)
100(14)
100(17)
185(13)
59(95)
279(26)
226(23)
(continued)
60
-------
TABLE 11 (continued)
b Characteristic EI ions
Compound RRT ' (relative intensity)
Benz[a]anthracene
1.40
228(100)
229(19)
226(19)
Benzolb]fluoranthene
1.43
252(100)
253(23)
125(15)
Benzo[k]fluoranthene
1.43
252(100)
253(23)
125(16)
3,3'-Dichlorobenzidine
1.45
252(100)
254(66)
126(16)
Di-n-octylphthalate
1.50
149(100)
167, 279
Benzo[a]pyrene
1.50
252(100)
253(23)
125(21)
IndenoTl,2,3-cdjpyrene
1.86
276(100)
138(28)
277(27)
Benzo[g,h,i]perylene
Bis(chloromethyl) ether
1.98
276(100)
138(37)
277(25)
d
45(100),
49(14), 51(5)
0-Endosulfan
0.47
201(100)
283(48)
278(30)
a-BHC
0.94
183(100)
109(86)
181(91)
y-bhc
1.00
183(100)
109(86)
181(91)
p-BHC
1.03
181(100)
183(93)
109(62)
5-BHC
1.04
183(100)
109(86)
181(90)
Aldrin
1.05
181(100)
183(93)
109(62)
Heptachlor
1.06
183(100)
109(86)
181(90)
Heptachlor epoxide
1.13
66(100),
220(11),
263(73)
a-Endosulfan
1.14
100(100)
353(79)
351(60)
Dieldrin
1.18
201(100)
283(48)
278(30)
4,4'-DDE
1.20
79(100),
263(28),
279(22)
4,4'-DDD
1.22
246(100)
248(64)
176(65)
4,4'-DDT
1.27
235(100)
237(76)
165(93)
Endrin
1.30
81(100),
82(61), 263(70)
Endosulfan sulfate
1.30
272(100), 387(75), 422(25)
Chlordane
1.05-1.26
373(19),
375(171,
i, 235)t
377(10)
Toxaphene
1.12-1.35
(231, 23:
PCB-1242
0.86-1.14
(224, 260, 294)t
PCB-1254
1.09-1.30
(294, 330, 362)1
a 3% SP-2250 on 100/120 mesh Supelcoport in a 1.8 m x 2 mi ID glass column;
He at 30 ml/min. Program: 60°C for 2 min, then 8°C/min to 260°C and
hold for 15 min.
b Elutes as azobenzene.
c Elutes as diphenylamine.
d No data.
e These three ions are characteristic for the a and y forms of chlordane.
No stock should be set in these three for other isomers.
f These ions are listed without relative intensities since the mixtures they
represent defy characterization by three masses.
61
-------
TABLE 12. CHROMATOGRAPHIC CONDITIONS AND CHARACTERISTIC IONS
FOR THE ACID COMPOUNDS ANALYZED BY PACKED COLUMN GC/MS
Compound
RRT*'b
Chlorophenol
0.51
2-Nitrophenol
0.55
Phenol
0.61
2,4-Dimethylphenol
0.67
2,4-Dichlorophenol
0.69
2,4,6-Trichlorophenol
0.79
4-Chloro-a-cresoI
0.86
2,4-Dinitropheno1
1.04
4,6-Dinitro-o-cresol
Pentachlorophenol
1.04
1.13
4-Nitrophenol
1.63
Characteristic EI ions
(relative intensity)
128(100)
139(100)
94(100),
122(100)
162(100)
196(100)
142(100)
184(100)
198(100)
266(100)
65(100),
i 64(54),
, 65(35),
65(17),
, 107(90)
, 164(50)
, 198(92)
, 107(80)
, 63(59),
, 182(35)
, 264(62)
139(45),
130(31)
109(8)
66(19)
» 121(55)
, 98(61)
, 200(26)
> 144(32)
154(53)
» 77(28)
, 268(63)
109(72)
a Relative to djQ-anthracene.
b 1% SP-1240-DA on 100/120 Supelcoport ia a 1.2 o t 2 mo
ID glass column; He at 30 ml/min. Program: 85°C
for 2 min, then 10°C/min to 185 °C and hold for 5 min.
62
-------
TAME 13. ACCURACY AMU IWECISKM FOR lASE/NEUTRAL EXTRACT ABLE «WHANICS ANALYZE!! VIA OTION A
(SIUCA CtXCUANW, MGC/NS UETKHIIMATIOM) ID THREE ItfTW AMI TOO INDUSTRIAL SMRXjES
Three HltV alndgea _ Two Industrial sludges
Sfiiie trcowtf Spike recovery
CoajMHMMl
Dcleraia
tlnu
Spike level
•- (w/*> ....
Hinl— Han If
Mean
(R
Standard
deviation
Mean
USD lor
Tripl.
tt)
PRlrraina-
Lions
Spike level
1,4-IM ch torolwiizriie
27
400
40,000
44
25
37
IB
400
40,000
65
59
12
tteaarh 1 ororlkiM
25
400
40,000
24
17
31
U
400
40,000
55
65
55
Ria(2-€"hloroelhyl tether
27
400
40,000
110
77
54
16
400
40,000
«0
44
20
Acenaphlliylcne
27
400
40,000
110
66
26
15
400
40,000
95
27
14
2,6-Uini trotoluene
25
400
40,000
33
35
72
15
400
40,000
R9
63
42
Flwnrailthrur
24
400
40,000
140
64
25
15
400
40,000
110
42
IB
Rraxidine
It
7,900
¦0,000
31
31
49
12
780
10,000
120
96
25
3,3'-Dirhlorol>enKidine
9
402
4,130
50
7R
66
a
-
-
-
-
-
Ruty1benzy1phtha1ate
IS
4,000
40,000
140
59
!R
12
400
40,000
130
92
19
Dl-n-octylphthalate
IB
400
40,000
130
75
40
15
400
4B.BOO
1)0
71
30
Renzo|aIpyreae
21
400
40,000
no
43
24
IS
400
40,100
82
70
30
a This coapomid vaa not apiked lato the industrial alud|ea.
-------
TAME 14. ACCURACY AM* mxiSIUO HW RASC/MUITRAI. KXTRACTARI.E UHCANICS MUUKKO VIA WINI 0
(OK OKMMT, OC/MS WTIWIIHATKIH AW* ACIDIC EXTRACTARI.K MMSMIICft
NfM «* W IMNKTRIAL SMNWCS
Tbrrc rO|W ...... Two Industrial sludge*
Suite iirawri Spike rcruvnry
Mean jji'M
Spike Irvcl RSI) lac S|*ikr level Will (or
Ciii«|iiiiiiiiI
fcUniu-
Il*«a
a itrfgi...
_ Minima Mm »»w
Hcan
«>
Standard
deviating
Tripl.
<*)
Orlcraina-
lltlM
—. (»/«!_
jjinlMM Mai law*
Ifea*
. it>
Standard
deviation
/IS'
1 ,t-Wckl«iikrMU!M
If
4*
41, 400
69
28
14
IS
400
40,000
IS
14
9
fclM'kl*rwlk«M)
23
4M
44,100
40
II
10
14
400
40,000
St
31
14
Oi«( 2-«Ml by 1 tellwr
H
4M
40,100
220
190
II
14
400
40,000
120
SI
1
Ai'rnaptitliytrne
21
4M
40.000
26
9
IS
400
40,000
110
41
12
2,4-IMnil rwlolwcMe
14
4, MM
40,000
so
31
10
12
4,000
40,000
100
3S
10
F Intrant btw
24
4M
40,080
SI
2?
14
IS
400
40,000
91
22
8
kHl4iM
14
4,1)1
¦0,000
19
S9
8
14
aoo
10,000
II
41
10
3, 3' -#1 ikUnkcu MIm
1)
415
4,13*
49
40
II
3
4,000
4,000
110
13
13
hl|lktu|lrklk>lrlt
ia
4.S00
40,000
130
120
1
12
400
40,000
69
IS
9
M-n-orty IfM kilau
28
4, MM
40,000
90
II
13
12
400
4a,aoo
81
13
10
Renx»|a||»yrrnr
Ift
400
40,100
120
94
13
14
400
40,000
44
41
1
Hie Hoi
24
400
44. 300
13
24
21
14
400
40,000
12
34
26
t,<-llttkfl|kfl
M
4M
41,100
sa
42
31
12
400
40,000
110
44
23
1,4-Dicklwtfkcwl
21
399
40,000
89
32
IB
IS
400
40.000
140
94
IS
Pentachlaroplmnal
26
400
40,000
120
41
31
10
400
40,000
SO
14
28
-------
TABLE 15. ACCURACY AND PRECISION FOR BASE/NEUTRAL EXTRACTABLE ORGANICS
ANALYZED VIA OPTION B (GPC CLEANUP, GC/MS DETERMINATIONS) AND
ACIDIC EXTRACTABLE ORGANICS IN PRIMARY SLUDGES FROM 40 POTWs3
Spike recovery*3
Determina-
Mean
Standard
Mean Avg
Compound
tions
(%)
Deviation
Dev. for
1,3-Dichlorobenzene
27
86
39
11
1,2-Dichlorobenzene
24
68
25
11
Nitrobenzene
13
49
28
17
Hexachlorobutadiene
27
71
22
7
Naphthalene
27
94
37
8
2-Chio ronaphthalene
27
89
33
8
Acenaphthalene
24
79
27
8
2,6-Dinitrotoluene
23
59
38
15
Fluorene
27
94
34
10
N-Nitrosodiphenylanine
24
140
84
11
4-Bromophenylphenylether
27
80
27
5
Di-n-butylphtbalate
26
79
43
9
Fluoranthene
26
85
40
9
Pyrene
27
90
47
8
Butylbenzylphtha1ate
26
95
64
11
Bis(2-ethylhexyl)phthalate
22
65
34
8
Benzo[a]pyrene
27
85
49
11
1,4-Dichlorobenzene
27
82
34
11
Hexachloroethane
21
49
25
21
Isophorone
27
51
27
15
1,2,4-Tri chlorobenzene
27
83
32
9
Bis(2-chloroethoxy)methane
24
54
27
12
Hexa chlo ro eye1op entadiene
20
0
0
0
Acenaphthylene
19
76
24
9
Dimethylphthalate
27
50
33
20
2,4-Dinitrotoluene
26
65
50
14
Diethylphthalate
27
65
35
12
Hexachlorobenzene
27
63
21
10
Phenanthrene/anthra c ene
26
71
39
11
Chrysene/Benz[a]anthracene
27
71
27
11
BenzoIg,h,iJperylene
19
31
15
10
N-Nitrosodi^-N-propylamine
24
77
54
13
1,2-Diphenylhydrazine
23
64
30
9
Benzidine
21
8
11
15
3,3'-Dichlorobenzidine
27
56
58
14
2-Chlorophenol
27
59
16
14
2-Nitrophenol
27
46
39
17
4-Nitrophenol
25
22
23
15
Phenol
26
66
28
11
(continued)
65
-------
TABLE 15 C coa.tiau.ed)
Compound
2,4-Dimethylphenol
2,4-Dichlorophenol
2,4,6-Tri chlorophenol
1.3-Dichlorobenzene
£-Chloro-m-cresol
2.4-Dinitrophenol
4,6-Dinitro-o-cresol
Pentachlo rophenol
a-BHC
Dieldrin
4,4f-DDE
Heptaciilor
Detenaina- Mian.
Spike recovery
Standard Mean
tions
(X)
Deviation
Dev. for
27
34
39
20
27
68
25
11
27
71
25
13
27
86
39
11
22
58
32
9
24
14
27
11
26
13
24
15
27
84
43
15
27
39
32
10
27
72
30
8
27
57
19
11
26
76
35
10
a Swanson, Stephen E., T. Murry Williams, Lloyd M. Petrie, and Earl M. Hansen.
"Survey of Analysis of POTW Sludges for Priority Pollutants: Part II
Quality Assurance Data," Final Report prepared under EPA Contract No.
68-01-5915, Task 35 (1981).
b Minimum spike level 125 Mg/£; maximum spike level 1,250 pg/SL.
66
-------
Stmlga
(ao»i)
i . i
Figure 1. Scheme for analysis of extractable organics in sludge.
-------
KlKurt? 2. CIC/MS cliruaarngrna of baso/nentral compounds on a fused silica capillary column.
-------
100.0-1
BIC.
ON
vo
8622G8.
e
«
o
c
*
M
C
•
A
e
«
>*
O.
•Si
V'
CO
o
c
«
•o
c
—I—
8s29
«li
C *
« O H i
M H >\ >»
O -C C C 41
9 O « 4» 4:
h | i! £ u
tM ^ tt Ok »B
16«49
—I
25:88
33t29
—I
4ti40
TlltE
Figure 3. GC/MS chromat»*ram for the base/neutral compounds on a packed column.
-------
Figure 4. GC/MS chromatogram of the acidic conpounds.
------- |