-------
Compounds
CASNo3 3510 3520 3540/3541 3545 3550 3580
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
Hexachlorophene
Hexachloropropene
Hexamethyl phosphoramide
(HMPA)
Hydroquinone
lndeno(1,2,3-cd)pyrene
Isodrin
Isophorone
Isosafrole
Kepone
Leptophos
Malathion
Maleic anhydride
Mestranol
Methapyrilene
Methoxychlor
Methyl methanesulfonate
Methyl parathion
3-Methylcholanthrene
4,4'-Methylenebis(2-chloroaniline)
4,4'-Methylenebis(A/,A/-dimethyl-
aniline)
1 -Methylnaphthalene
2-Methylnaphthalene
2-Methylphenol (o-Cresol)
3-Methylphenol (m-Cresol)
4-Methylphenol (p-Cresol)
Mevinphos
Mexacarbate
Mi rex
Monocrotophos
Naled
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
Nicotine
5-Nitroacenaphthene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
5-Nitro-o-anisidine
Nitrobenzene (NB)
4-Nitrobiphenyl
Nitrofen
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~
~
~
-
~
~
118-74-1
~
~
~
~
~
~
87-68-3
~
~
~
~
~
~
77-47-4
¦/*
*
¦/*
¦/*
¦/*
¦/*
67-72-1
~
~
~
~
~
~
70-30-4
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Compounds
CASNo3 3510 3520 3540/3541 3545 3550 3580
2-Nitrophenol
88-75-5
~
y
y
y
y
y
4-Nitrophenol
100-02-7
*
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Compounds
CAS Noa
3510
3520
3540/3541
3545
3550
3580
2,4-Toluene diisocyanate
584-84-9
*
*
-
-
-
~
o-Toluidine
95-53-4
~
~
-
~
*
~
Toxaphene
8001-35-2
~
~
~
-
~
~
1,2,4-T richlorobenzene
120-82-1
~
~
~
~
~
~
2,4,5-T richlorophenol
95-95-4
~
~
~
~
~
~
2,4,6-T richlorophenol
88-06-2
~
~
~
~
~
~
0,0,0-Triethyl phosphorothioate
126-68-1
~
~
-
-
~
-
Trifluralin (Treflan)
1582-09-8
~
-
-
-
-
~
Trimethyl phosphate
512-56-1
*
*
-
-
-
~
2,4,5-T rimethylaniline
137-17-7
~
-
-
-
-
~
1,3,5-Trinitrobenzene (1,3,5-TNB)
99-35-4
~
~
-
~
~
~
Tris(2,3-dibromopropyl)phosphate
126-72-7
~
-
-
-
-
*
Tri-p-tolyl phosphate
78-32-0
~
-
-
-
-
~
a Chemical Abstract Service (CAS) Registry Number
b See Sec. 1.2 for other acceptable preparation methods.
cChemical name changed by Integrated Risk Information System (IRIS) on November 30, 2007
from Bis(2-chloroisopropyl)ether to Bis(2-chloro-1-methylethyl)ether (common name). This
analyte is also known as 2,2'-oxybis(1-chloropropane) (CAS index name). See the link at
http://www.epa.gov/iris/subst/0407.htm, Sec. VII for the "Revision History" and Sec. VIII for
synonyms of this chemical.
KEY TO ANALYTE LIST
S Historically, adequate recovery and precision can be obtained for this analyte by this
technique. However, actual recoveries may vary depending on the sample matrix, the number
of constituents being analyzed concurrently, analytical instrumentation, and the preparation
method used. Performance data from a large multi-site laboratory control sample (LCS) study
were used to update this table (data can be found in Reference 13 in Sec. 16 and in Table 2). If
the average % recovery (%R) fell between 50 - 150% in this study, the preparation technique
was considered adequate.
NOTE: Not every analyte has sufficient data points in the study for consideration. The S is also
used for analytes if the previous version of this method listed the preparation technique
as adequate. See Table 2 for study data. Refer to Sec. 9 for guidance on establishing
LCS acceptance criteria.
- This analyte was not determined by this preparation method.
* This analyte exhibits known difficulties with reproducibility, response, recovery,
stability, and/or chromatography that may reduce the overall quality or confidence in the result
when using this preparation method combined with analysis by Method 8270. This analyte may
require special treatment to improve extraction efficiency and analytical performance to a level
that would meet the needs of the project and, where necessary, may also require the use of
appropriate data qualification. See Sec. 1.4 for specific information regarding this analyte.
S* This analyte met the criteria for adequate performance using this preparation
technique (see definition for S). However, the analyte is known to exhibit the problems listed in
Sec. 1.4 (see definition for *).
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1.2 In addition to the sample preparation methods listed in the above analyte list, the
following methods may be used for extraction of semivolatile organic compounds provided the
method can be demonstrated to meet the needs of the project:
Air (particulates and sorbent resin)
Method 3542 Extraction of Semivolatile Analytes Collected Using Method 0010
Water (including Toxicity Characteristic Leaching procedure (TCLP) leachates)
Method 3511 Microextraction
Method 3535 Solid-Phase Extraction (SPE)
Soil. Sediment, and Waste
Method 3546 Microwave Extraction
Method 3561 Supercritical Fluid Extraction of Polynuclear Aromatic Hydrocarbons
(PAHs)
1.3 This method can be used to quantitate most neutral, acidic, and basic organic
compounds that are soluble in methylene chloride (or other suitable solvents provided that the
desired performance data can be generated) and are capable of being eluted, without
derivatization, as sharp peaks from a gas chromatographic fused-silica capillary column coated
with a slightly polar silicone. Such compounds include PAHs, chlorinated hydrocarbons,
chlorinated pesticides, phthalate esters, organophosphate esters, nitrosamines, haloethers,
aldehydes, ethers, ketones, anilines, pyridines, quinolines, aromatic nitro compounds, and
phenols (including nitrophenols). See Table 1 for a list of compounds and their characteristic
ion(s) that have been evaluated.
In most cases, this method is not appropriate for the quantitation of multicomponent
analytes (e.g., polychlorinated biphenyls (PCBs) as Aroclors, technical toxaphene, chlordane,
etc.) because of limited sensitivity for these analytes or potential for measurement bias using
gas chromatograph/mass spectrometer (GC/MS) technology. Tandem mass spectrometry
(GC/MS/MS) may provide adequate sensitivity and selectivity for performing multi-component
analyses. Individual components (e.g., a subset of PCB congeners) may be determined with
any technology provided sensitivity is sufficient for the data application and interference from
other components is minimal. When these analytes have been identified by another technique,
Method 8270 may be appropriate for confirmation of the identification of these analytes when
concentration in the extract permits. See Sec. 11.7.5 for more information.
1.4 The following compounds may require special treatment when being determined by
this method:
NOTE: Some compounds may appear in more than one paragraph.
1.4.1 Benzidine may be subject to oxidative losses during solvent
concentration.
1.4.2 Under the alkaline conditions of the extraction step from aqueous
matrices, a-BHC, y-BHC, endosulfan I and II, and endrin are subject to decomposition.
Neutral extraction should be performed if these compounds are to be reported.
1.4.3 Hexachlorocyclopentadiene is subject to thermal decomposition in the
inlet of the GC, chemical reaction in acetone solution, and photochemical
decomposition. Protecting this analyte from light during heated extraction steps in the
procedure (such as concentration) is recommended.
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1.4.4 N-Nitrosodimethylamine may be difficult to separate from the solvent
peak under the chromatographic conditions described.
1.4.5 N-Nitrosodiphenylamine decomposes in the GC inlet and cannot be
separated from diphenylamine. For this reason, it is acceptable to report the combined
result for n-nitrosodiphenylamine and diphenylamine for either of these compounds as a
combined concentration.
1.4.6 1,2-Diphenylhydrazine is unstable (even at room temperature) and readily
converts to azobenzene. Given this analyte's stability problems, it would be acceptable
to calibrate for 1,2-diphenylhydrazine using azobenzene. Under these circumstances
(poor compound separation) the results for either of these compounds should be
reported as a combined concentration.
1.4.7 Benzidine, benzyl alcohol, benzoic acid, 7,12-dimethylbenz(a)anthracene,
2,4-dinitrophenol, 4,6-dinitro-2-methylphenol, dinocap, hexachlorophene, kepone,
mathapyrilene, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 4-nitrophenol,
pentachlorophenol, 1,4-phenylenediamine, phthalic anhydride, and o-toluidine are
subject to erratic chromatographic behavior, especially if the GC system is contaminated
with high boiling material.
1.4.8 Analytes that readily ionize in solution may not recover from water
matrices unless the pH is adjusted to acidic conditions (e.g., phenols with low acid
dissociation constant (pKa)) or to basic conditions (e.g., aniline and pyridine) prior to
extraction.
1.4.9 Some analytes may perform poorly at the GC injection port temperatures
listed in this method. Lowering the injection port temperature may reduce the amount of
degradation. However, the analyst must use caution in modifying the injection port
temperature, as the performance of other analytes may be adversely affected. A
programmable temperature inlet may also be used.
1.4.10 More volatile analytes such as dichlorobenzenes, 1,4-dioxane, and
pyridine may be lost during the evaporative concentration step during sample
preparation. As a result, many of the extraction methods listed above may yield low
recoveries unless great care is exercised during the concentration steps. To better
assess the performance of these analytes, it may be appropriate to use additional
surrogates which have similar physicochemical properties such as 1,2-dichlorobenzene-
d4, 1,4-dioxane-dg, and pyridine-ds, respectively.
1.4.11 2,4-Toluene diisocyanate rapidly hydrolyzes in water (it has a half-life of
less than 30 minutes). Therefore, recoveries of this compound from aqueous matrices
should not be expected. In addition, in solid matrices, 2,4-toluene diisocyanate often
reacts with alcohols and amines to produce urethane and ureas and consequently
cannot usually coexist in a solution containing these materials.
1.4.12 The following analytes may be subject to oxidation or hydrolysis during
extraction from water matrices which may be accelerated by acidic or basic conditions
(Methods 3510 and 3520): aramite, p-benzoquinone, captafol, demeton-O, demeton-S,
2,4-diaminotoluene, dichlone, dimethoate, 1,4-dinitrobenzene, dinocap, maleic
anhydride, malathion, 4,4'-methylenebis(2-chloroaniline), mexacarbate, monocrotophos,
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phosalone, phosmet, phthalic anhydride, phthalates, phosphamidon, resorcinol, and
trimethylphosphate.
1.4.13 The following analytes may be subject to hydrolysis in water matrices
during storage (Methods 3510 and 3520): aramite, azinphos-methyl, captafol, captan,
demeton-O, dimethoate, dinocap, malathion, mexacarbate, phosalone, and phosmet.
1.4.14 The following analytes may be subject to degradation during storage: 4-
aminobiphenyl, atrazine, benzidine, benzaldehyde, 3,3'-dichlorobenzidine, 3,3'-
dimethylbenzidine, diethylstilbestrol, 7,12-dimethylbenz(a)anthracene, famfur,
hexachlorophene, kepone, 4,4'-methylenebis(2-chloroaniline), methyl methanesulfonate,
1,4-naphthoquinone, 1-naphthylamine, 2-naphthylamine, and strychnine. This
degradation may be accelerated when combined with incompatible analytes or solvents
such as in calibration standards (e.g., amines and aldehydes are incompatible).
1.4.15 The following analytes may have low response and/or low recovery: 1-
acetyl-2-thiourea, 2-cyclohexyl-4,6-dinitro-phenol, barban, diethyl sulfate, 3,3'-
dimethoxybenzidine, 4,4'-methylenebis(2-chloroaniline), octamethylpyrophosphoramide,
propylthiouracil, and tris(2,3-dibromopropyl)phosphate.
1.4.16 The following analytes are known to adhere to surfaces during extraction
and storage in water matrices (Methods 3510 and 3520): diethylstilbestrol,
hexachlorophene, and strychnine.
1.4.17 The following analytes have an unfavorable distribution coefficient when
extracting from water matrices which may be of more concern when preparing samples
using Method 3510: benzoic acid, caprolactam, 2,4-diaminotoluene, ethyl carbamate,
nicotine, 4-nitrophenol, N-nitrosodimethylamine, phenol, and resorcinol.
1.4.18 In addition, analytes in the list provided above are flagged when there
are limitations caused by sample preparation and/or chromatographic problems.
1.5 This method includes the optional use of an alternate carrier gas (hydrogen) and
GC/MS/MS. See Appendix B and Sec. 6.1.3.3.
1.6 Prior to employing this method, analysts are advised to consult the base method
for each type of procedure that may be employed in the overall analysis (e.g., Methods 3500,
3600, 5000, and 8000) for additional information on QC procedures, development of QC
acceptance criteria, calculations, and general guidance. Analysts also should consult the
disclaimer statement at the front of the SW-846 manual and the information in Chapter Two for
guidance on the intended flexibility in the choice of methods, apparatus, materials, reagents,
and supplies, and on the responsibilities of the analyst for demonstrating that the techniques
employed are appropriate for the analytes of interest, in the matrix of interest, and at the levels
of concern.
In addition, analysts and data users are advised that, except where explicitly specified in
a regulation, the use of SW-846 methods is not mandatory in response to Federal testing
requirements. The information contained in this method is provided by Environmental
Protection Agency (EPA or the Agency) as guidance to be used by the analyst and the
regulated community in making judgments necessary to generate results that meet the data
quality objectives (DQOs) for the intended application.
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1.7 Use of this method is restricted to use by, or under supervision of, personnel
appropriately experienced and trained in the use of the GC/MS and skilled in the interpretation
of mass spectra. Each analyst must demonstrate the ability to generate acceptable results with
this method.
2.0 SUMMARY OF METHOD
2.1 The samples are prepared for analysis by GC/MS using the appropriate sample
preparation (refer to Method 3500) and, if necessary, sample cleanup procedures (refer to
Method 3600).
2.2 The semivolatile compounds are introduced into the GC/MS by injecting the
sample extract into a GC equipped with a narrow-bore fused-silica capillary column. The GC
column is temperature-programmed to separate the analytes, which are then detected with an
MS connected to the GC.
2.3 Analytes eluted from the capillary column are introduced into the MS via a direct
connection. Identification of target analytes is accomplished by comparing their mass spectra
and retention times (RT) with the mass spectra and RTs of known standards for the target
compounds. Quantitation is accomplished by comparing the response of a major (quantitation)
ion relative to an internal standard (IS) using an appropriate calibration curve for the intended
application.
2.4 This method includes specific calibration and QC steps that supersede the general
recommendations provided in Method 8000.
3.0 DEFINITIONS
Refer to Chapter One and the manufacturer's instructions for definitions that may be
relevant to this procedure.
4.0 INTERFERENCES
4.1 Solvents, reagents, gases, other samples, and the environment in which the
analysis is performed may yield artifacts and/or interferences for target analytes. The sample
preparation and analysis process must be demonstrated to be free from observable
interferences by the analysis of method blanks (MBs). Refer to each method to be used for
specific guidance on QC procedures and to Chapter Four for general guidance on the cleaning
of glassware. Refer to Method 8000 for a discussion of interferences.
4.2 Raw GC/MS data from all blanks, samples, and spikes must be evaluated for
interferences. Determine if the source of interference is in the preparation and/or cleanup of the
samples and take corrective action to eliminate the problem. Subtracting blank values from
sample results is not permitted. If measured analyte concentrations are suspected of being
biased or false positive results for a sample, the laboratory should qualify the affected data or
otherwise inform the data user(s) of any suspected data quality issues.
4.3 Contamination by carryover can occur whenever high-concentration and low-
concentration samples are sequentially analyzed. To reduce carryover, the sample syringe
must be rinsed with solvent between sample injections. Some contamination may be eliminated
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by baking out the column between analyses. Whenever an unusually concentrated sample is
encountered, it should be followed by the analysis of solvent to check for cross-contamination.
Low-level samples that immediately follow high-level samples need to be inspected for possible
carryover. See Method 8000, Sec. 4.2 for further guidance.
5.0 SAFETY
This method does not address all safety issues associated with its use. The laboratory
is responsible for maintaining a safe work environment and a current awareness of
Occupational Safety and Health Administration (OSHA) regulations regarding the safe handling
of the chemicals listed in this method. A reference file of safety data sheets (SDSs) must be
available to all personnel involved in these analyses. See Appendix B, Sec. B1.4 for safety
guidance on using hydrogen carrier gas.
6.0 EQUIPMENT AND SUPPLIES
The mention of trade names or commercial products in this manual is for illustrative
purposes only and does not constitute an EPA endorsement or exclusive recommendation for
use. The products and instrument settings cited in SW-846 methods represent those products
and settings used during method development or subsequently evaluated by the Agency.
Glassware, reagents, supplies, equipment, and settings other than those listed in this manual
may be employed provided that method performance appropriate for the intended application
has been demonstrated and documented.
This section does not list common laboratory glassware (e.g., beakers and flasks).
6.1 GC/MS system
6.1.1 GC - An analytical system equipped with a temperature-programmable
GC suitable for splitless injection and all required accessories, including syringes,
analytical columns, and gases (see Appendix B for guidance on using hydrogen carrier
gas). The injection port can be split/splitless, temperature-programmable split/splitless
(programmable temperature vaporization or PTV), or on-column. The capillary column
should be directly coupled to the source. The GC should be equipped with flow
controllers such that the column flow rate will remain constant throughout temperature
program operation.
6.1.2 Column - 30 m x 0.25 mm ID (or 0.32 mm ID) 0.25, 0.5, or 1 |jm film
thickness silicone-coated fused-silica capillary column (5% phenyl-methylpolysiloxane,
5% phenyl-arylene dimethylpolysiloxane, or equivalent). The columns listed in this
section were the columns used in developing the method. The listing of these columns
in this method is not intended to exclude the use of other columns that may be
developed. Laboratories may use these columns or other capillary columns provided
that the laboratories document method performance data (e.g., chromatographic
resolution, analyte breakdown, and sensitivity) that are appropriate for the intended
application.
6.1.3 MS
6.1.3.1 Capable of acquiring mass spectra from mass/charge (m/z) 35
to 500 at a rate fast enough to acquire at least 5 (but preferably 10 or more)
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mass spectra across each chromatographic peak of interest, using 70 volts
(nominal) electron energy in the electron impact ionization mode. The MS must
be capable of producing a mass spectrum for decafluorotriphenylphosphine
(DFTPP) which meets the criteria as outlined in Sec. 11.3.1.
6.1.3.2 An ion trap MS may be used if it is capable of axial modulation
to reduce ion-molecule reactions and can produce electron impact like spectra
that match those in the EPA/National Institute of Standards and Technology
(NIST) library (or equivalent). The MS must be capable of producing a mass
spectrum for DFTPP which meets the criteria as outlined in Sec. 11.3.1.
6.1.3.3 An MS/MS detector may be used if the detector has the
necessary pumps, collision cell, collision gases, and high-vacuum system
capable of performing transitions in product ion scan mode or the selected
reaction monitoring mode (SRM) for the target analytes of interest.
Recommendations for specific precursor and product ions in SRM are available
for some target analytes from the manufacturers of the equipment. When
analysis is performed using product ions for quantitation, it is not an appropriate
verification of the system to perform DFTPP analysis and meet the criteria
outlined in Sec. 11.3.1. The system, however, must be capable of documenting
the performance of both MSs against manufacturer specifications for mass
resolution, mass assignment, and sensitivity using the internal calibrant (e.g.,
Perfluorotributylamine). The performance of the system should be checked at
least weekly, or at a frequency appropriate to meet the needs of the project. At a
minimum, the performance of the system must be checked just prior to the initial
calibration (ICAL).
6.1.3.4 Selected ion monitoring (SIM) or chemical ionization (CI) mass
spectrometry are acceptable techniques for applications requiring quantitation
limits below the normal range of electron impact mass spectrometry or to reduce
interferences from the sample matrix. DFTPP analysis is not appropriate when
CI analysis is used for quantitative purposes. See Sec. 11.3.1.
6.1.4 GC/MS interface - Any GC-to-MS interface may be used that gives
acceptable calibration points for each compound of interest and achieves acceptable
tuning performance criteria. For a narrow-bore capillary column, the interface is usually
capillary direct into the MS source.
6.1.5 Data system - A computer system that allows the continuous acquisition
and storage of all mass spectra obtained throughout the duration of the chromatographic
program must be interfaced to the MS. The computer must have software that can
search any GC/MS data file for ions of a specific mass and that can plot such ion
abundances versus time or scan number. This type of plot is defined as an Extracted
Ion Current Profile (EICP). Software should also be available that allows integrating the
abundances in any EICP between specified time or scan number limits. A recent
version of the EPA/NIST mass spectral library (or equivalent) should also be available.
6.1.6 Guard column (optional) - Between the injection port and the analytical
column, joined with column connectors or may be purchased integrated into the
analytical column.
6.2 Syringes - various
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6.3
stoppers
Volumetric flasks, Class A - Appropriate sizes equipped with ground-glass
6.4 Balance - Analytical, capable of weighing 0.0001 g
6.5 Bottles - Glass equipped with polytetrafluoroethylene (PTFE)-lined screw caps or
crimp tops
6.6 Vials - for GC autosampler
7.0 REAGENTS AND STANDARDS
7.1 Reagent-grade chemicals must be used in all tests. Unless otherwise indicated, it
is intended that all reagents conform to the specifications of the Committee on Analytical
Reagents of the American Chemical Society (ACS), where such specifications are available at:
http://pubs.acs.orq/reaqents/comminfo/techquestions.html. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination. Reagents should be stored in glass to
prevent the leaching of contaminants from plastic containers.
7.2 Organic-free reagent water - All references to water in this method refer to
organic-free reagent water.
7.3 Standard solutions
The following sections describe the preparation of stock, intermediate, and working
standards for the compounds of interest. This discussion is provided as an example. Other
approaches and concentrations of the target compounds may be used if appropriate for the
intended application. See Method 8000 for additional information on the preparation of
calibration standards. Commercially prepared stock standards may be used at any
concentration if they are certified by an accredited supplier or third party.
7.4 Stock standard solutions (1000 mg/L) - Standard solutions can be prepared from
pure standard materials or purchased as certified solutions.
7.4.1 Prepare stock standard solutions by accurately weighing about 0.0100 g
of pure material. Dissolve the material in a suitable solvent and dilute to volume in a 10-
mL volumetric flask. Larger volumes can be used at the convenience of the analyst.
When compound purity is assayed to be 96% or greater, the weight may be used without
correction to calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by the
manufacturer or by an independent source.
7.4.2 Transfer the stock standard solutions into bottles equipped with PTFE-
lined screw caps. Store the vials (protected from light) at <6 °C or as recommended by
the standard manufacturer. Stock standard solutions should be checked frequently for
signs of degradation or evaporation, especially just prior to preparing calibration
standards from them.
7.4.3 Certified solutions purchased from a vendor must be replaced per the
manufacturer's recommended expiration date. Stock standard solutions prepared in-
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house must be replaced after one year or sooner if comparison with QC check samples
indicates a problem. When solutions are mixed together, regardless of the source, they
must be replaced after the manufacturer's expiration date or one year (whichever occurs
first) or sooner if problems are indicated.
7.4.4 It is recommended that nitrosamine compounds be placed together in a
separate calibration mix and not combined with other calibration mixes. When using a
premixed certified standard, consult the manufacturer's instructions for additional
guidance.
7.4.5 Mixes with hydrochloride salts may contain hydrochloric acid, which can
cause analytical difficulties. When using a premixed certified standard, consult the
manufacturer's instructions for additional guidance.
7.5 IS solutions - The recommended ISs are: 1,4-dichlorobenzene-d4, naphthalene-dg,
acenaphthene-cf™, phenanthrene-cf™, chrysene-^, and perylene-^ (see Table 5). See Sec.
11.4.3 of Method 8000 for additional information. Other compounds may be used as ISs as long
as they have RTs similar to their target compounds, they can be unambiguously identified and
meet any applicable acceptance criteria described in Sec. 11. See Sec. 11.4.3 of Method 8000
for additional information.
7.5.1 Dissolve 0.200 g of each compound with a small volume of carbon
disulfide. Transfer to a 50-mL volumetric flask and dilute to volume with methylene
chloride so that the final solvent is approximately 20% carbon disulfide. Most of the
compounds are also soluble in small volumes of methanol, acetone, or toluene, except
for perylene-cf?2. The resulting solution will contain each standard at a concentration of
4,000 ng/|jL. Each 1-mL sample extract undergoing analysis should be spiked with 10
|jL of the IS solution, resulting in a concentration of 40 ng/|jL of each IS. Store away
from any light source at <6 °C when not in use (-10 °C is recommended). When using
premixed certified solutions, store according to the manufacturer's documented holding
time and storage temperature recommendations.
7.5.2 A more dilute internal standard solution may be employed to achieve
lower detection levels.
7.6 GC/MS tune check solution - It is recommended that DFTPP solutions are
prepared at 50 ng/|jl or less in methylene chloride. Preparation in alternate solvents may result
in degradation of DFTPP. The standard should also contain 50 ng/|jL each of
4,4'- dichlorodiphenyltrichloroethane (DDT), pentachlorophenol, and benzidine to verify injection
port inertness and GC column performance. Alternate concentrations may be used to
compensate for different injection volumes if the total amount injected is 50 ng or less. Store
away from any light source at <6 °C when not in use (-10 °C is recommended). If a more dilute
IS is employed to achieve lower quantitation levels, a more dilute tune check solution may be
necessary. When using premixed certified solutions, store according to the manufacturer's
documented holding time and storage temperature recommendations.
7.7 Calibration standards - There are two types of calibration standards used for this
method: standards made from the primary source for ICAL and continuing calibration verification
(CCV), and standards made from a second source for initial calibration verification (ICV). When
using premixed certified solutions, store according to the manufacturer's documented holding
time and storage temperature recommendations.
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7.7.1 ICAL standards must be prepared at a minimum of five different
concentrations from the secondary dilution of stock standards or from a premixed
certified solution. Include a minimum of five different concentrations in the calibration for
average response factor (RF) or linear (first-order) calibration models and six different
concentrations for a quadratic (second-order) model with the low standard at or below
the lower limit of quantitation (LLOQ) (see Sec. 9.9 and Method 8000). At least one of
the calibration standards should correspond to a sample concentration at or below that
necessary to meet the DQOs of the project. The remaining standards should
correspond to the range of concentrations found in actual samples but should not
exceed the working range of the GC/MS system. Each standard and/or series of
calibration standards prepared at a given concentration should contain all the desired
project-specific target analytes for which qualitative and quantitative results are to be
reported by this method.
7.7.2 CCV standards should be prepared at a concentration near the mid-point
of the ICAL from the same source as the ICAL or be a midlevel standard used in the
ICAL.
7.7.3 Second source standards for ICV should be prepared at a concentration
near the mid-point of the calibration range with standards from a second manufacturer or
from a manufacturer's batch prepared independently from the batch used for calibration.
A second lot number from the same manufacturer may be adequate to meet this
requirement. The standard should contain all target analytes that will be reported for
the project, if readily available. See Sees. 9.3.2 and 11.3.7 for guidance and acceptance
limits.
7.7.4 It is the intent of EPA that all target analytes for a particular analysis be
included in the calibration standard(s). These target analytes may not include the entire
list of analytes (Sec. 1.1) for which the method has been demonstrated. However, the
laboratory shall not report a quantitative result for a target analyte that was not included
in the calibration standard(s).
7.7.5 Each 1-mL aliquot of calibration standard should be spiked with 10 |jL of
the IS solution prior to analysis. All standards should be stored away from any light
source at <6 °C when not in use (-10 °C is recommended), and should be freshly
prepared once a year, or sooner if check standards indicate a problem. The ICV and
CCV standards should be prepared, as necessary, and stored at <6 °C.
7.8 Surrogate standards - The recommended surrogates are: phenol-d6, 2-
fluorophenol, 2,4,6-tribromophenol, nitrobenzene-ds, 2-fluorobiphenyl, and p-terphenyl-cf?4.
Other compounds with physicochemical properties more similar to the analyte classes of
interest may be used as surrogates (e.g., deuterated monitoring compounds in the EPA
Contract Laboratory Program's (CLP) current statement of work (SOW), which can be found in
Reference 17 in Sec. 16), provided they are not found in field samples, can be unambiguously
identified, and meet any applicable acceptance criteria described in Sec. 11 for ICAL and CCV.
See Method 3500 for instructions on preparing the surrogate solutions. See Sec. 1.4.10 for
surrogate suggestions for more volatile analytes.
NOTE: In the presence of samples containing residual chlorine, phenol-d6 has been known to
react to form chlorinated phenolic compounds. Sample preservation precautions
outlined in Chapter Four should be used when residual chlorine is known to be present
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in order to minimize degradation of deuterated phenols or any other susceptible target
analyte.
NOTE: It is a good practice to analyze surrogates spiking solutions prior to their use to verify
they are prepared at the correct concentrations. This is also recommended as a
troubleshooting step when surrogate recoveries in blanks and LCSs are problematic.
7.9 Matrix spike and LCSs - See Method 3500 for instructions on preparing the matrix
spike standard. Matrix spikes and LCSs should be prepared with target analytes from the same
source as used for the ICAL standards to restrict the influence of standard accuracy on the
determination of recovery through preparation and analysis. Matrix spike and LCS standards
should be prepared with targets representative of the compounds being investigated. It is
recommended that all reported target analytes be included in all LCS and matrix spike samples.
For some applications, a limited set of representative analytes is acceptable.
NOTE: It is a good practice to also analyze/verify target compound spiking solutions prior to use
or as a troubleshooting step when trying to determine the root cause of poor target
compound spike recoveries in the LCS.
7.10 Solvents - Acetone, hexane, methylene chloride, isooctane, carbon disulfide,
toluene, and other appropriate solvents may be used. All solvents should be pesticide quality or
equivalent. Solvents may be degassed prior to use, if necessary.
7.11 Carrier gas - Helium or hydrogen may be used. If hydrogen is used, analytical
conditions may need to be adjusted for optimum performance, and calibration and all QC tests
in Sec. 9.0 must be performed with hydrogen carrier gas. See Appendix B for guidance.
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
Sample collection, preservation and storage requirements may vary by EPA program
and may be specified in a regulation or project planning document that requires compliance
monitoring for a given contaminant. Where such requirements are specified in a regulation,
follow those requirements. In the absence of specific regulatory requirements, use the following
information as guidance in determining the sample collection, preservation and storage
requirements.
8.1 See the introductory material to Chapter Four, "Organic Analytes" for storage
conditions and holding times.
8.2 Store the sample extracts at <6 °C (protected from light) in sealed vials (e.g.,
screw-cap vials or crimp-capped vials) equipped with unpierced PTFE-lined septa.
9.0 QUALITY CONTROL
9.1 Refer to Chapter One for guidance on quality assurance (QA) and QC protocols.
When inconsistencies exist between QC guidelines, method-specific QC criteria take
precedence over both technique-specific criteria and those criteria given in Chapter One, and
technique-specific QC criteria take precedence over the criteria in Chapter One. Any effort
involving the collection of analytical data should include development of a structured and
systematic planning document, such as a quality assurance project plan (QAPP) or a sampling
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and analysis plan (SAP), which translates project objectives and specifications into directions for
those who will implement the project and assess the results. Each laboratory should maintain a
formal QA program. The laboratory should also maintain records to document the quality of the
data generated. All data sheets and QC data should be maintained for reference or inspection.
9.2 Refer to Method 8000 for specific determinative method QC procedures. Refer to
Method 3500 or 5000 for QC procedures to ensure the proper operation of the various sample
preparation techniques. If an extract cleanup procedure is performed, refer to Method 3600 for
the appropriate QC procedures. Any more specific QC procedures provided in this method will
supersede those noted in Methods 3500, 3600, 5000 or 8000.
9.3 QC procedures necessary to evaluate the GC system operation are found in
Method 8000 and include evaluation of RT windows, calibration verification and
chromatographic analysis of samples. In addition, discussions regarding the instrument QC
criteria listed below can be found in the referenced sections of this method, and a summary is
provided in Table 6. Quantitative sample analyses should not proceed for those analytes that
do not meet the QC acceptance criteria. However, analyses may continue for those analytes
that exceed the criteria with an understanding that these results could be used for screening
purposes and would be considered estimated values.
9.3.1 The GC/MS must meet DFTPP criteria prior to the ICAL. See Sees.
11.3.1 and 11.4.1 for further details. Acceptance criteria are primarily intended to verify
sensitivity, mass assignments and mass resolution under the same conditions used for
analysis.
9.3.2 There must be an ICAL of the GC/MS system as described in Sec. 11.3.
Prior to analyzing samples, verify the ICAL standards using a second source ICV
standard, if readily available (See Sees. 7.7.1 and 11.3.7).
9.3.3 The GC/MS system must meet the CCV acceptance criteria in Sec. 11.4.
9.4 Initial demonstration of proficiency (IDP)
Prior to implementation of a method, each laboratory must perform an I DP consisting of
at least four replicate reference samples spiked into a clean matrix taken through the entire
sample preparation and analysis. Whenever a significant change to instrumentation or
procedure occurs, the laboratory must demonstrate that acceptable precision and bias can still
be obtained by the changed conditions. Also, whenever new staff members are trained, each
analyst must perform an I DP for the method or portion of the method for which the analyst is
responsible. This demonstration should document that the new analyst is capable of
successfully following the SOP established by the laboratory and meeting any applicable
acceptance criteria specified therein. Refer to Sec. 9.3 of Method 8000 for more information on
how to perform an I DP.
9.5 Blanks
9.5.1 Before processing any samples, the analyst must demonstrate through
the analysis of a MB or instrument blank that equipment and reagents are free from
contaminants and interferences. If a peak is found in the blank that would prevent the
identification or bias the measurement of an analyte, the analyst should determine the
source of the contaminant peak and eliminate it, if possible. As a continuing check, each
time a batch of samples is extracted, cleaned up, and analyzed, and when there is a
change in reagents, a MB must be prepared and analyzed for the compounds of interest
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as a safeguard against chronic laboratory contamination. MBs and field blanks must be
carried through all stages of sample preparation and analysis. At least one MB or
instrument blank must be analyzed on every instrument after calibration standard(s) and
prior to the analysis of any samples.
9.5.2 Blanks are generally considered to be acceptable if target analyte
concentrations are less than one half the LLOQ or are less than project-specific
requirements. Blanks may contain analyte concentrations greater than acceptance limits
if the associated samples in the batch are unaffected (i.e., targets are not present in
samples or sample concentrations/responses are >10X the blank). Other criteria may be
used depending on the needs of the project.
9.5.3 If an analyte of interest is found in a sample in the batch near a
concentration confirmed in the blank (refer to Sec. 9.5.2), the presence and/or
concentration of that analyte should be considered suspect and may require
qualification. Contaminants in the blank should meet most or all of the qualitative
identifiers in Sec. 11.6 to be considered. Samples may require re-extraction and/or re-
analysis if the blanks do not meet laboratory-established or project-specific criteria. Re-
extraction and/or re-analysis is not necessary if the analyte concentration falls well below
the action or regulatory limit or if the analyte is deemed not important for the project.
9.5.4 When new reagents or chemicals are received, the laboratory should
monitor the blanks associated with samples for any signs of contamination. It is not
necessary to test every new batch of reagents or chemicals prior to sample preparation
if the source shows no prior problems. However, if reagents are changed during a
preparation batch, separate blanks should be prepared for each set of reagents.
9.5.5 The laboratory should not subtract the results of the MB from those of any
associated samples. Such "blank subtraction" may lead to negative sample results. If
the MB results do not meet the project-specific acceptance criteria and reanalysis is not
practical, then the data user should be provided with the sample results, the MB results,
and a discussion of the corrective actions undertaken by the laboratory.
9.6 Sample QC for preparation and analysis
The laboratory must also have procedures for documenting the effect of the matrix on
method performance (i.e., precision, bias, and method sensitivity). At a minimum, this must
include the analysis of a MB and LCS, and where practical, a matrix spike, and a duplicate in
each preparation batch, as well as monitoring the recovery of surrogates. These QC samples
should be subjected to the same analytical procedures (Sec. 11.0) as those used on field
samples.
9.6.1 Documenting the effect of the matrix should include the analysis of at
least one matrix spike and one duplicate unspiked sample or one matrix spike/matrix
spike duplicate pair. The decision on whether to prepare and analyze duplicate samples
or a matrix spike/matrix spike duplicate must be based on knowledge of the samples and
project goals and should be addressed in the project planning documents. If samples
are expected to contain target analytes, laboratories may use a matrix spike and a
duplicate analysis of an unspiked field sample. If samples are not expected to contain
target analytes, then laboratories should use a matrix spike and matrix spike duplicate
pair. Consult Method 8000 for information on developing acceptance criteria for the
matrix spike and matrix spike duplicate.
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9.6.2 An LCS must be included with each preparation batch. The LCS consists
of an aliquot of a clean (control) matrix similar to the sample matrix and of the same
weight or volume. The LCS is spiked with the same analytes at the same concentrations
as the matrix spike, when appropriate. When the results of the matrix spike analysis
indicate a potential problem due to the sample matrix itself, the LCS results are used to
verify that the laboratory can perform the analysis in a clean matrix. Consult Method
8000 for information on developing acceptance criteria for the LCS.
9.6.3 A MB or instrument blank must be included with each analytical batch.
MBs consist of an aliquot of clean (control) matrix similar to the sample and of a similar
weight or volume. Other types of blanks (e.g., equipment rinsates, storage blanks, etc.)
should be included when appropriate but they are distinct from MBs.
9.6.4 Also see Method 8000 for the details on carrying out QC procedures for
preparation and analysis. In-house method performance criteria for evaluating method
performance should be developed using the guidance found in Method 8000.
9.7 Surrogates must be added to every blank, field sample, laboratory QC, and field
QC. The laboratory should evaluate surrogate recovery data from individual samples versus the
surrogate control limits developed by the laboratory. See Method 8000 for information on
evaluating surrogate data and developing and updating surrogate limits. Procedures for
evaluating the recoveries of multiple surrogates and the associated corrective actions should be
defined in the laboratory's SOP or in an approved project plan.
9.8 Monitor IS responses to ensure sensitivity is maintained and to limit the potential
for measurement bias of associated target analyte concentrations. IS responses in field
samples are compared to responses of the same IS in the ICAL standards or CCV standards,
with suggested acceptance criteria provided in Sec. 11.5.4.1. When IS responses fall outside
the acceptance limit, further investigation is warranted and results may require qualification for
detects and non-detects.
9.9 Lower limit of quantitation (LLOQ)
General guidance for LLOQ is provided in this section and in Method 8000. The LLOQ
is the lowest concentration at which the laboratory has demonstrated target analytes can be
reliably measured and reported with a certain degree of confidence. The LLOQ must be greater
than or equal to the lowest point in the calibration curve. The laboratory shall establish the
LLOQ at concentrations where both quantitative and qualitative requirements can consistently
be met (see Sec. 11.6). The laboratory shall verify the LLOQ at least annually, and whenever
significant changes are made to the preparation and/or analytical procedure, to demonstrate
quantitation capability at lower analyte concentration levels. The verification is performed by the
extraction and/or analysis of an LCS (or matrix spike) at 0.5 - 2 times the established LLOQ.
Additional LLOQ verifications may be useful on a project-specific basis if a matrix is expected to
contain significant interferences at the LLOQ. The verification may be accomplished with either
clean control material (e.g., reagent water, solvent blank, Ottawa sand, diatomaceous earth) or
a representative sample matrix, free of target compounds. Optimally, the LLOQ should be less
than the desired decision level or regulatory action level based on the stated DQOs.
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9.9.1 LLOQ Verification
9.9.1.1 The verification of LLOQs using spiked clean control material
represents a best-case scenario because it does not evaluate the potential matrix
effects of real-world samples. For the application of LLOQs on a project-specific
basis, with established DQOs, a representative matrix-specific LLOQ verification
may provide a more reliable estimate of the lower quantitation limit capabilities.
9.9.1.2 The LLOQ verification is prepared by spiking a clean control
material with the analyte(s) of interest at 0.5 - 2 times the LLOQ concentration
level(s). Alternatively, a representative sample matrix free of targets may be
spiked with the analytes of interest at 0.5 - 2 times the LLOQ concentration
levels. The LLOQ check is carried through the same preparation and analytical
procedures as environmental samples and other QC samples. It is
recommended to analyze the LLOQ verification on every instrument where data
is reported; however, at a minimum, the lab should rotate the verification among
similar analytical instruments such that all are included within three years.
9.9.1.3 Recovery of target analytes in the LLOQ verification should be
within established in-house limits or within other such project-specific acceptance
limits to demonstrate acceptable method performance at the LLOQ. Until the
laboratory has sufficient data to determine acceptance limits, the LCS criteria ±
20% (i.e., lower limit minus 20% and upper limit plus 20%) may be used for the
LLOQ acceptance criteria. This practice acknowledges the potential for greater
uncertainty at the low end of the calibration curve. Practical, historically based
LLOQ acceptance criteria should be determined once sufficient data points have
been acquired.
9.9.2 Reporting concentrations below LLOQ - Concentrations that are below
the established LLOQ may still be reported; however, these analytes must be qualified
as estimated. The procedure for reporting analytes below the LLOQ should be
documented in the laboratory's SOP or in a project-specific plan. Analytes below the
LLOQ that are reported should meet most or all of the qualitative identification criteria in
Sec. 11.6.
9.10 It is recommended that the laboratory adopt additional QA practices for use with
this method. The specific practices that are most productive depend upon the needs of the
laboratory and the nature of the samples. Whenever possible, the laboratory should analyze
standard reference materials and participate in relevant performance evaluation studies.
10.0 CALIBRATION AND STANDARDIZATION
See Sees. 11.3 and 11.4 for information on calibration and standardization.
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11.0 PROCEDURE
11.1 Samples are normally prepared by one of the following methods prior to GC/MS
analysis:
Matrix
Methods
Air (particulates and sorbent resin)
3542
Water (including TCLP leachates)
3510, 3511,
3520,
3535
Soil/sediment
3540, 3541,
3545,
3546, 3550, 3561
Waste
3540, 3541,
3545,
3546, 3550, 3561, 3580
11.2 Extract cleanup - Cleanup procedures may not be necessary for relatively clean
sample matrices. Extracts from environmental and waste samples may require additional
cleanup steps prior to analysis. The specific cleanup procedure used will depend upon the
analytes of interest, the nature of the interferences, and the DQOs for the project. General
guidance for sample extract cleanup is provided in this section and in Method 3600.
Extracts may be cleaned up by any of the following methods prior to GC/MS analysis:
Analytes of Interest Methods
All base, neutral, and acid Priority Pollutants
3640
Aniline and aniline derivatives
3620
Chlorinated hydrocarbons
3620,
3640
Haloethers
3620,
3640
Nitroaromatics and cyclic ketones
3620,
3640
Nitrosamines
3610,
3620,
3640
Organochlorine pesticides
3610,
3620,
3630, 3640, 3660
Organophosphorus pesticides
3620,
3640
PAHs
3611,
3630,
3640
PCBs
3620,
3630,
3660, 3665
Petroleum waste
3611,
3650
Phenols
3630,
3640
Phthalate esters
3610,
3620,
3640
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11.3 Initial calibration
Establish the GC/MS operating conditions, using the following settings as guidance:
Analytes of Interest
Methods
Mass range:
Acquisition rate:
m/z 35 - 500
Sufficient to acquire at least 5 (but preferably 10 or
more) mass spectra across a peak
40 °C, hold for 4 minutes
40 - 320 °C at 10 °C/minutes
320 °C, hold until 2 min after benzo(g,h,i)perylene elutes
225 - 300 °C
250 - 300 °C
According to manufacturer's specifications
Grob-type, split/splitless
0.5-2 Mi-
Hydrogen at 50 cm/second or helium at 30 cm/second
Set axial modulation, manifold temperature, and
emission current to manufacturer's recommendations
Initial temperature:
Temperature program:
Final temperature:
Injector temperature:
Transfer line temperature:
Source temperature:
Injector:
Injection volume:
Carrier gas:
Ion trap only:
Split injection is allowed if the sensitivity of the MS is sufficient.
11.3.1 The GC/MS system must be hardware-tuned such that injecting 50 ng or
less of DFTPP meets the manufacturer's specified acceptance criteria or as listed in
Table 3. The tuning criteria as outlined in Table 3 were developed using quadrupole MS
instrumentation with helium carrier gas and it is recognized that other tuning criteria may
be more effective depending on the type of instrumentation (e.g., time-of-flight, ion trap,
etc.). In these cases, it would be appropriate to follow the manufacturer's tuning
instructions or some other consistent tuning criteria. However, no matter which tuning
criteria are selected, sample analyses must be performed under the same conditions as
the calibration standards.
Acceptable system performance may also be demonstrated by meeting
manufacturer specifications for mass resolution, mass accuracy, and sensitivity using the
internal calibrant (e.g., perfluorotributylamine, also known as PFTBA). Tuning the
instrument should only be performed prior to initial calibration. Other reference compounds
may also be appropriate for demonstrating acceptable MS performance depending on the
system or conditions used for analysis (e.g., octafluoronaphthalene for negative ion CI).
Regardless of how MS performance is evaluated, system calibration must not begin until
performance criteria are met, and calibration standards and samples must be analyzed
under the same conditions. If CI, SIM or tandem MS is used, the manufacturer's MS
tuning criteria or one of the alternative procedures listed above may be substituted for the
DFTPP tune verification requirement.
11.3.1.1 In the absence of specific recommendations on how to acquire
the mass spectrum of DFTPP from the instrument manufacturer, the following
approach should be used: Use a single spectrum at the apex of the DFTPP peak,
an average spectrum of the three highest points of the peak, or an average
spectrum across the entire peak to evaluate the performance of the system.
Background subtraction is allowed and is accomplished using a single mass
spectrum acquired within 20 seconds of the elution of DFTPP. The background
subtraction should be designed only to eliminate column bleed or instrument
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background ions. Do not subtract part of the DFTPP peak or any other discrete
peak that does not coelute with DFTPP.
11.3.1.2 Use the DFTPP mass intensity criteria in the manufacturer's
instructions as primary tuning acceptance criteria or those in Table 3 as default
tuning acceptance criteria if the primary tuning criteria are not available.
Alternatively, other documented tuning criteria may be used (e.g., CLP or Method
625), provided that method performance is not adversely affected. The analyst is
always free to choose criteria that are more stringent than those included in this
method or to use other documented criteria provided they are used consistently
throughout the ICAL, calibration verification, and sample analyses.
NOTE: All subsequent standards, field samples, and QC samples associated
with a DFTPP analysis must use identical MS instrument conditions with
the exception of SIM analysis. DFTPP may be analyzed in full scan
mode while standards, samples, and QC are analyzed in SIM. As an
alternative to DFTPP for SIM analysis, the laboratory may use an
alternate detector verification, such as PFTBA, or the manufacturer's
recommended detector check.
NOTE: DFTPP tune checks are not appropriate for CI analysis or tandem MS
analysis using SRM. However, the laboratory must demonstrate, prior to
the ICAL, that the MS system achieves mass accuracy and mass
resolution criteria specified by the instrument manufacturer for the
perfluorotributylamine (PFTBA) internal calibrant or another appropriate
chemical.
11.3.1.3 The GC/MS tune check solution should also be used to assess
the GC column performance and injection port inertness. Degradation of DDT to
dichlorodiphenyldichloroethylene (DDE) and dichlorodiphenyldichloroethane
(DDD) should not exceed 20% (See Method 8081 for the percent breakdown
calculation). Benzidine and pentachlorophenol should be present at their normal
responses, and should not exceed a tailing factor of 2 given by the following
equation:
BC
Tailing Factor = —
Ad
where the peak is defined as follows (see Figure 1 for a
full-page version of this image with additional information):
AB is the line segment from the center to point A; AC is
the width at 10% height; BC is the line segment from the
center to point C; DE is the height of peak and
B is the height at 10% of DE. This equation compares the
width of the back half of the peak to the width of the front
half of the peak at 10% of the height. (See Figure 1 for an
example tailing factor calculation.)
NOTE: Degradation and tailing factor checks are performed to verify injection
port inertness and are important when the target list includes a broad
range of analyte chemistries, especially reactive phenols and pesticides.
These checks are optional when the analytes of interest are not subject to
the same chromatography or reactivity problems (e.g., PAHs, PCBs) or
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when using alternate MS techniques where routine full scan analysis is
not performed (e.g., CI, MS/MS).
11.3.1.4 If degradation is excessive and/or poor chromatography is
noted, the injection port may require maintenance. It may also be necessary to
cut off the first six to 12 inches of the capillary column to remove high boiling
contaminants in the column. The use of a guard column (Sec. 6.1.6) between
the injection port and the analytical column may help prolong analytical column
performance life.
11.3.2 The base peak m/z of each target analyte and IS is appropriate for use
as the primary m/z for quantitation (see Table 1), but another prominent m/z in the mass
spectrum may also be used for quantitation provided it is used consistently. If
interferences are noted, use the next most intense ion as the quantitation ion (e.g., for
1,4-dichlorobenzene-d4, use m/z 152 for quantitation).
11.3.3 Analyze a consistent volume of each calibration standard (i.e., containing
the compounds for quantitation and the appropriate surrogates and ISs) and tabulate the
response of the primary ion against the concentration for each target analyte (as
indicated in Table 1). A set of at least five calibration standards must be analyzed with
the low standard at or below the LLOQ (see Sees. 7.7, 9.9 and Method 8000). Alternate
injection volumes may be used if the applicable QC requirements for using this method
are met. The injection volume must be the same for the analysis of all standards and
sample extracts. Figure 2 shows a chromatogram of a calibration standard containing
base/neutral and acid analytes.
NOTE: LLOQs should be established at concentrations where both quantitative and
qualitative requirements can be consistently and reliably met (see Sees. 9.9 and
11.6). Target analyte peaks in the calibration standard at the LLOQ should be
visually inspected to ensure that peak signal is adequately distinguishable from
background and meets the qualitative requirements outlined in 11.6.
11.3.4 Initial calibration calculations
Tabulate the response of the quantitation ions (see Table 1 for suggested ions)
against the concentration for each target analyte and each IS. Calculate RFs for each
target analyte relative to one of the ISs as follows:
... A,xCis
' AisxC,
where:
As = Peak response of the analyte or surrogate
Ais = Peak response of the IS
Cs = Concentration of the analyte or surrogate (e.g., in jjg/ml)
Cis = Concentration of the IS (e.g., in jjg/ml)
11.3.4.1 Calculate the mean RF and the relative standard deviation
(RSD) of the RFs for each target analyte using the following equations:
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II
> RF,
sn
RSD = -== x 100
RF
^P(RF, — RF)2
n
mean RF = EF = -i=3L
cn —
hJraLjt
n
n -1
where:
RFi = RF for each of the calibration standards
RF = Mean RF for each compound from the ICAL
n = Number of calibration standards (e.g., 5)
SD = Standard deviation
11.3.4.2 The RSD should be <20% for each target analyte (see Sec.
11.3.5). Table 4 contains minimum RFs that may be used as guidance in
determining if the system is behaving properly and as a check to see if calibration
standards are prepared correctly. Because the minimum RFs in Table 4 were
determined using specific ions and instrument conditions that may vary, it is
neither expected nor required that all analytes meet these minimum RFs. The
information is provided as guidance only. The laboratory should establish
procedures in its SOP (e.g., laboratory established minimum RFs, signal-to-noise
(S/N) checks, etc.) to ensure that the instrument is working properly and that
calibration standards were correctly prepared.
NOTE: For a target analyte, whose RF <0.01 (response of peak is <1/100 the
response of the IS), it is recommended that its concentration in relation to
other analytes be increased to make the response more comparable to
other analytes.
11.3.5 Linearity of target analytes - If the RSD of any target analyte is 20% or
less, then the RF is assumed to be constant over the calibration range, and the average
RF may be used for quantitation (Sec. 11.7.2). The average RF should not be used for
compounds that have an RSD greater than 20% unless the concentration is reported as
estimated.
11.3.5.1 If the RSD of any target analyte is greater than 20%, refer to
Sec. 11.5 in Method 8000 for guidance in selecting an alternate calibration
model. One of the options must be applied to GC/MS calibration in this situation,
or a new ICAL must be performed.
11.3.5.2 When the RSD exceeds 20%, the plotting and visual inspection
of a calibration curve can be a useful diagnostic tool. The inspection may
indicate analytical problems, including errors in standard preparation, the
presence of active sites in the chromatographic system, analytes that exhibit
poor chromatographic behavior, etc.
11.3.5.3 If more than 10% of the compounds included with the ICAL (or
more than 10% of those that will be reported) exceed the 20% RSD limit and do
not meet the minimum correlation criteria (r2>0.99 or relative standard error
(RSE) <20%) for alternate curve fits, then the chromatographic system is
considered too reactive for analysis to begin. Correct the source of the problem;
then repeat the calibration procedure beginning with Sec. 11.3. If compounds fail
to meet these criteria, the associated concentrations may still be determined but
they must be reported as estimated. In order to report non-detects, it must be
demonstrated that there is sufficient accuracy to detect the failed compounds at
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the applicable LLOQ (see Sees. 11.3.6 for refitting standards and 11.4.4.2 for
CCV). Refer to Method 8000 for further discussion of RSE. Example RSE
calculations can be found in Reference 19.
11.3.5.4 Due to the large number of compounds that may be analyzed
by this method, some compounds may fail to meet these criteria. For these
occasions, it is acknowledged that the failing compounds may not be critical to
the specific project. The analyst should strive to place more emphasis on
meeting the calibration criteria for those compounds that are critical project
compounds, rather than meeting the criteria for those less important compounds.
It is not necessary to meet criteria for compounds that will not be reported.
NOTE: It is considered inappropriate once the calibration models have been
finalized to select an alternate fit solely to pass the recommended QC
criteria for samples and associated QC on a case-by-case basis.
11.3.6 Calibration, especially when using linear regression models, has the
potential for a significant bias at the lower portion of the calibration curve. The lowest
calibration point should be recalculated (not reanalyzed) using the final calibration curve
in which this standard is used (i.e., re-fitting the response from the low concentration
calibration standard back into the curve). See Method 8000 for additional details. The
recalculated concentration of the low calibration point (especially where linear regression
fits are used) should be within ±50% of the standard's true concentration, and the
recalculated concentrations of any calibration standards above the LLOQ should be
within ±30%. Alternate criteria may be applied depending on the needs of the project;
however, those criteria should be clearly defined in a laboratory SOP or a project-
specific QAPP. Analytes which do not meet the re-fitting criteria should be evaluated for
corrective action. If a failure occurs in the low point and it is equivalent to the LLOQ, the
analyte should be reported as estimated near that concentration or the LLOQ should be
reestablished at a higher concentration.
11.3.7 ICV - Prior to analyzing samples, verify the ICAL using a standard
obtained from a second source to the calibration standard, if possible, such as a second
manufacturer or a manufacturer's batch prepared independently from the batch used for
calibration, if readily available. Suggested acceptance criteria for the analyte
concentrations in this standard are 70 - 130% of the expected analyte concentration(s).
Alternative criteria may be appropriate based on project-specific DQOs. Quantitative
sample analyses should not proceed for those analytes that do not meet the ICAL
verification criteria. However, analyses may continue for those analytes that do not meet
the criteria with an understanding that these results could be used for screening
purposes and would be considered estimated values.
11.3.8 Additional considerations for SIM and SRM analysis
SIM and SRM may be useful for applications requiring quantitation limits below
the normal range of electron impact quadrupole mass spectrometry, and both are
allowable options for this method. Using the primary m/z (or product ion for SRM
detectors) for quantitation and at least one secondary m/z (or product ion,) for
confirmation, set up the collection groups based on their chromatographic RTs. The
selected m/z (or product ion) values should include any mass defect noted in the target
analyte mass spectra acquired on the instrument, usually less than 0.2 amu. The dwell
time for each ion may be automatically calculated by the instrument software or may be
calculated based on the peak widths of the analytes of interest, the number of spectra
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needed to be acquired across each peak, and the number of concurrent ions that need
to be acquired in each segment. When fewer masses are monitored in each segment,
the acquisition time for each mass can be increased, thereby increasing the sensitivity of
the system. The total cycle time for the MS should be short enough that at least five but
preferably ten or more spectra are acquired per chromatographic peak.
When samples are analyzed in SIM or SRM mode (generally to achieve lower
reporting limits or reduce interferences) the following best practices are recommended:
- At least two ions should be monitored for each target analyte and use the mid-
point of the calibration curve to establish proper ion ratios for each compound.
The ratios of primary and secondary ions are the only qualitative tool available in
SIM and SRM runs (other than RT), which increases their importance in proper
identification. When interferences are expected or observed in a given matrix,
acquiring multiple secondary ions may aid in qualitative identification.
- All monitored ions must be correctly integrated in order to achieve proper ion
ratios. The primary/secondary ion ratios and the reference mass spectrum
should be updated from the mid-point ICAL standard.
Additional guidance for performing SIM analyses, in particular for PAHs and
phenol target analyte compounds, can be found in the most recent CLP
semivolatile organic methods SOW. See the SIM sections from the following
CLP SOW for further details: EPA CLP Multi-concentration Organics Analysis,
SOM01.2 SOW (Reference 12), or the current version of Method 625.
11.4 CCV - A CCV standard must be analyzed at the beginning of each 12-hour
analytical period prior to any sample analysis.
11.4.1 Daily analysis of the GC/MS tune check solution is no longer required as
part of the CCV. The analyst should, however, closely monitor chromatography as well
as target and IS responses in the CCV for deterioration in the system. See the note in
Sec. 11.4.4.2 for additional detail.
11.4.2 The ICAL (Sec. 11.3) for each compound of interest must be verified
once every 12 hours prior to sample analysis, using the introduction technique and
conditions used for analysis of ICAL standards and samples. This is accomplished by
analyzing a calibration standard (containing all the compounds that will be reported)
prepared from the same stock solutions or source materials used for the ICAL standards
at a concentration near the midpoint of the calibration range of the GC/MS. The results
must be compared against the most recent ICAL curve and should meet the verification
acceptance criteria provided in Sees. 11.4.4 through 11.4.6.
NOTE: A CCV may be omitted if samples are analyzed within 12 hours of ICAL, and the
injection of the last ICAL standard may be used as the starting time reference for
evaluation.
11.4.3 A MB or instrument blank must be analyzed after the CCV and prior to
samples in order to ensure that the total system (i.e., introduction device, transfer lines
and GC/MS system) is free of contaminants. If the MB indicates contamination, then it
may be appropriate to analyze an instrument blank to demonstrate that the
contamination is not a result of carryover from standards or samples. See Method 8000
for information regarding MB performance criteria.
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11.4.4 CCV standard criteria
11.4.4.1 The calculated concentration or amount of each analyte of
interest in the CCV standard should fall within ±20% of the expected value.
NOTE: For the RF calibration model, % difference (%D) between the calculated
RF of an analyte in the calibration verification standard and the RFavg of
that analyte from the ICAL is the same value as % drift for calculated
versus expected concentration. Refer to Method 8000 for guidance on
calculating %D and % drift.
11.4.4.2 If the %D or percent drift for a compound is <20%, then the
ICAL for that compound is assumed to be valid. Due to the large numbers of
compounds that may be analyzed by this method, it is expected that some
compounds will fail to meet the criterion. The analyst should strive to place more
emphasis on meeting the CCV criteria for those compounds that are critical to
the project. If the criterion is not met (i.e., greater than ±20%D or drift) for more
than 20% of the compounds included in the ICAL (or more than 20% of those
that will be reported), then corrective action must be taken prior to the analysis of
samples. Target analytes that do not meet the CCV criteria and are reported in
the associated samples must be qualified to indicate the reported concentrations
are potentially estimated or biased values. In cases where compounds fail low,
they may be reported as non-detects if it can be demonstrated that there was
adequate sensitivity to detect the compound at the LLOQ or project specific level
of interest (e.g., by calibrating below the established LLOQ to confirm the non-
detect, or by analyzing a standard near that level to confirm the analyte could be
qualitatively identified if it were present [See Sec. 11.7 of Method 8000]).
Alternatively, the non-detect could be qualified or the LLOQ raised to a higher
level. In cases where compounds fail high in the CCV and are not found in the
associated field samples, they may be reported without qualification.
NOTE: Daily tailing and degradation checks are good indicators of reactivity in
the system and the need for maintenance. Because these are no longer
required daily, the analyst must closely monitor responses and
chromatography in the CCV for signs that the system is too reactive for
analysis to continue (e.g., losses of reactive analytes, unusual tailing, loss
of resolution). If significant losses of target analytes/ISs occur (<50%
recovery) or if significant degradation of the chromatography occurs
(tailing factor >2), system maintenance must be performed or the analyst
must demonstrate there is adequate sensitivity at the LLOQ.
11.4.4.3 Problems similar to those listed under ICAL could affect the
ability to pass the CCV standard analysis. If the problem cannot be corrected by
other measures, a new ICAL must be generated. The CCV criteria must be met
before sample analysis begins.
11.4.5 IS RT - If the absolute RT for any IS changes by more than 30 seconds
from that in the mid-point standard level of the most recent ICAL sequence (or the most
recent CCV), then the chromatographic system must be inspected for malfunctions and
corrections must be made, as required. When corrections are made, reanalysis of
samples analyzed while the system was malfunctioning is required.
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11.4.6 IS responses - In order to demonstrate continued stability of the
measurement system after ICAL, IS responses in the CCVs must be evaluated by
comparing them to the responses of the same ISs in the ICAL standard(s). If the
response of an IS changes by more than a factor of 2 (50 - 200%) relative to the
response of that IS in the mid-point ICAL standard or the average of responses in the
suite of ICAL standards (as defined in the laboratory's SOP), then corrective actions
should be taken as needed. These corrective actions may include but are not limited to
replacing and/or reanalyzing the CCV standard or retuning the MS and re-calibrating.
When IS responses do not meet these criteria, system sensitivity may have been
compromised, and sample reanalysis is recommended, especially if any action limits for
the project are near the LLOQ.
11.5 GC/MS analysis of samples
11.5.1 It is recommended that sample extracts be screened on a GC/flame
ionization detector (FID) or GC/photo ionization detector (PID) using the same type of
capillary column used in the GC/MS system. This will minimize contamination of the
GC/MS system from unexpectedly high concentrations of organic compounds. GC/MS
calibration verification criteria must be met before analyzing samples.
11.5.2 Allow the sample extract to warm to room temperature. Prior to analysis,
add 10 |jL of the IS solution to the 1 mL of concentrated sample extract obtained from
sample preparation.
11.5.3 Inject an aliquot of the sample extract into the GC/MS system, using the
same operating conditions that were used for the calibration (Sec. 11.3). The injection
volume must be the same volume that was used for the calibration standards.
11.5.4 If the concentration for any analyte exceeds the ICAL range of the
GC/MS system, the sample extract must be diluted and reanalyzed. Additional IS
solution must be added to the diluted extract to maintain the same concentration as in
the calibration standards. Secondary ion quantitation should be used only when there
are sample interferences with the primary ion.
11.5.4.1 IS responses (area counts) and RTs must be monitored in all
samples, spikes and blanks to effectively check method performance and to
anticipate the need for system maintenance. If the response of the primary m/z
for any of the ISs in samples, spikes, and blanks changes by a factor of two (from
50% to 200%) from the responses determined in the mid-point standard level of
the most recent ICAL sequence or CCV standard (whichever was analyzed more
recently), corrective action should be taken. The samples, spikes, or blanks
should be reanalyzed or the associated data should be qualified.
11.5.4.2 When ions from a compound in the sample saturate the
detector, this analysis should be followed by the analysis of an instrument blank
consisting of clean solvent. If the blank analysis is not free of interferences, then
the system must be decontaminated. Sample analysis may not resume until the
blank analysis is demonstrated to be free of interferences. Contamination from
one sample to the next on the instrument usually takes place in the syringe. If
adequate syringe washes are employed, then carryover from high concentration
samples can usually be avoided.
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11.5.4.3 It is recommended to target the response in the mid to upper
half of calibration range for target analytes that exceeded the calibration range
and required dilution.
11.6 Analyte identification
11.6.1 Target Identification - The qualitative identification of compounds
determined by this method is based on RT and on comparison of the sample mass
spectrum, after background correction, with characteristic ions in a reference mass
spectrum. Compounds are identified when the following criteria are met.
11.6.1.1 The intensities of the characteristic ions of a compound must
maximize in the same scan or within one scan of each other.
11.6.1.2 The RT should be within ±10 seconds of the RT for this analyte
in the CCV run at the beginning of the 12-hour period (delta RT 0.17 minute) or
within ±10 seconds relative to the shift of the associated IS (delta RT of the IS ±
10 seconds). Chromatograms should be carefully inspected to minimize the
occurrence of both false positive and false negative results. If the RT for the IS
has shifted, the sample should be inspected for similar shifts for the associated
target analytes. If RT drift is significant, relative retention time (RRT) may be
used as an alternative to delta RTs. See Sec. 11.4. of Method 8000 for
additional information.
NOTE: Some analytes such as phenols may have RT shifting that is much
greater than the associated IS (greater than ± 10 seconds relative to the
IS shift) and is still the target analyte. In those cases, it may be more
useful to compare the delta RT with compounds that have similar
chemistries (e.g., phenolic surrogates) to help identify the target. Also,
dilutions or spiked samples are recommended to help minimize the
effects of matrix on the elution of the target and assist in target
identification.
11.6.1.3 The relative intensities of the qualifier ion(s) (i.e., secondary
characteristic ions, or additional monitored MS/MS transitions) should agree
within 30% of the relative intensities of these ions in the reference spectrum. For
example, for a qualifier ion with response of 50% of the quantitation ion in the
reference spectrum, the corresponding qualifier ion ratio in a sample mass
spectrum can range between 20% and 80%. The reference mass spectrum used
for this comparison should be generated by the laboratory using the conditions of
this method (typically a mid-level calibration standard). Use professional
judgment in interpretation where interferences are observed. Qualitative
identification of sample mass spectra not acquired in limited ion acquisition
modes (i.e. SIM or SRM) may also be supported by comparison to a reference
library as described in Sec. 11.6.2.
11.6.1.4 Unresolved structural isomers with similar mass spectra are
identified as isomeric pairs. Isomers are considered resolved if the peaks are at
least 50% resolved (i.e., the height of the valley between two isomer peaks is <
50% of the average of the two peak heights, or 1-[valley height]/[average peak
height] is >50%). The resolution should be verified on the mid-point
concentration of the ICAL as well as the laboratory-designated CCV level if
closely eluting isomers are to be reported (e.g., benzo(b)fluoranthene and
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benzo(k)fluoranthene). It is important to check the separation of structural
isomers in the ICV and the daily CCV check standards to verify if the instrument
performance is adequate regarding separation of compounds of interest which
are structural isomers.
11.6.1.5 Identification is hampered when sample components are not
resolved chromatographically and produce mass spectra containing ions
contributed by more than one analyte. When gas chromatographic peaks
obviously represent more than one sample component (i.e., a broadened peak
with shoulder(s) or a valley between two or more maxima), appropriate selection
of analyte spectra and background spectra is important.
11.6.1.6 Examination of extracted ion current profiles of appropriate ions
can aid in the selection of spectra and in qualitative identification of compounds.
When analytes co-elute (i.e., only one chromatographic peak is apparent), the
identification criteria may be met, but each analyte spectrum will contain
extraneous ions contributed by the co-eluting compound.
11.6.2 Tentative Identification - For samples containing components not
associated with the calibration standards, a library search may be made for the purpose
of tentative identification. The necessity to perform this type of identification will be
determined by the purpose of the analyses being conducted. For example, the
Resource Conservation and Recovery Act (RCRA) permit or waste delisting
requirements may require the reporting of non-target analytes. Data system library
search routines should not use normalization routines that would misrepresent the library
or unknown spectra when compared to each other. Only after visual comparison of
sample spectra with the library searches may the analyst assign a tentative
identification. Guidelines for tentative identification are:
(1) Major ions in the library reference spectrum (ions greater than 10% of the most
abundant ion) are present in the sample spectrum at similar relative intensities.
(2) The molecular ion in the library reference spectrum is present in the sample
spectrum. If the molecular ion is not present, carefully review library matches in
order to avoid misidentification.
(3) Major ions present in the sample spectrum but not in the reference spectrum are
reviewed to determine whether they may be contributed by co-eluting
compounds.
(4) Ions present in the reference spectrum but not in the sample mass spectra are
reviewed for unintended subtraction. Data system library reduction programs
can sometimes create these discrepancies.
(5) Mass spectral library search algorithms typically assign a match factor to the
peak identity based on comparison of an unknown mass spectrum to library
spectra. For spectra meeting the above conditions, match factors greater than
0.8 (80%) may be considered confirming evidence. Where a known limitation in
data collection is identified, e.g., the presence of an incompletely resolved
spectral interference, a lower match factor may be considered confirmatory. For
multiple library spectra with similar match factors (e.g., for hydrocarbons with low
abundance molecular ions, or structural isomers), the tentative identification
assigned to the unknown may be better represented as a more generic structure
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(e.g., unknown hydrocarbon, C4 benzene structural isomer). See Reference 18
in Sec. 16 for more information.
11.7 Quantitation
11.7.1 Once a target compound has been identified, the quantitation of that
compound will be based on the integrated abundance of the primary characteristic ion
from the EICP. The IS used should be the one nearest the RT of that of a given analyte.
11.7.1.1 It is highly recommended to use the integration produced by the
software if the integration is correct because the software should produce more
consistent integrations than an analyst will manually. However, manual
integrations may be necessary when the software does not produce proper
integrations because baseline selection is improper; the correct peak is missed; a
co-elution is integrated; the peak is partially integrated; etc. The analyst is
responsible for ensuring that the integration is correct whether performed by the
software or done manually.
11.7.1.2 Manual integrations should not be substituted for proper
maintenance of the instrument or setup of the method (e.g., RT updates,
integration parameter files, etc.). The analyst should seek to minimize manual
integration by properly maintaining the instrument, updating RTs, and configuring
peak integration parameters.
11.7.2 If the RSD is 20% or less, then the RF calibration model is acceptable for
ICAL (Sec. 11.3.4). See Method 8000 for the equations describing IS calibration and
either linear or non-linear calibrations.
11.7.3 Where applicable, the concentrations of any non-target analytes
identified in the sample (Sec. 11.6.2) may be estimated. The same formula (as in Sec.
11.3.4) should be used with the following modifications: The responses Ax and A-IS
should be from the total ion chromatograms, and the RF for the compound should be
assumed to be 1.
11.7.4 The resulting concentration should be reported indicating that the value
is an estimate. Use the nearest IS free of interferences.
11.7.5 Quantitation of multicomponent compounds to estimate total
concentrations (e.g., toxaphene, Aroclors, chlordane) is beyond the scope of Method
8270. When 8270 is used to confirm PCBs, it is primarily a mass spectral (qualitative)
confirmation of the isomer or level of chlorination where individual congeners cannot be
resolved. Normally, quantitation is performed using a GC/electron capture detector
(ECD), for example by Methods 8081 or 8082. Individual components (e.g., a subset of
PCB congeners) may be determined with this method provided sensitivity is sufficient for
the data application and interference from other components is minimal. For PCBs,
Cochran and Frame (Reference 14 in Sec. 16) provide a literature review of analytical
chemistry of PCB congeners, including identification of congeners that coelute under
different chromatographic conditions. Table 1 of Parris, et al. (1996) and Table 8 of
Kucklick, et al. (2013) (References 15 and 16 in Sec. 16) provide PCB congener lists
that might be determined by 8270 under the described conditions, along with identified
coeluting congeners. Refer to Methods 8081 and 8082 for guidance on calibration and
quantitation of multicomponent analytes such as Aroclors, toxaphene, and chlordane.
Refer to Method 680 for information related to calibration and quantitation of PCBs as
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homolog groups. Refer to Method 1668 for more information related to quantitation of
PCBs as individual congeners. Refer to Method 8276 for guidance on measurement of
toxaphene by negative ion chemical ionization GC/MS.
11.7.6 Quantitation of multicomponent parameters such as diesel range
organics (DROs) and total petroleum hydrocarbons (TPH) using the IS technique
described in this method is not recommended. Typically, quantitation for these
parameters is performed using Method 8015 with GC/FID analysis; however, it is
acceptable to use the total ion chromatogram that is generated from this method with
external standard calibration to quantitate such parameters. External standard
calibration is recommended in order to reduce the need to subtract area contributed by
multiple non-target peaks (such as the ISs) in the TPH chromatogram. See Sec. 11.4.2
in Method 8000 and Method 8015 for additional guidance.
12.0 DATA ANALYSIS AND CALCULATIONS
See Sec. 11.7 and Method 8000 for information on data analysis and calculations.
13.0 METHOD PERFORMANCE
13.1 Performance data and related information are provided in SW-846 methods only
as examples and guidance. The data do not represent required performance criteria for users
of the methods. Instead, performance criteria should be developed on a project-specific basis,
and the laboratory should establish in-house QC performance criteria for the application of this
method. These performance data are not intended to be and must not be used as absolute QC
acceptance criteria for purposes of laboratory accreditation. The performance data provided in
Reference 13 in Sec. 16 are for guidance purposes only.
13.2 Single laboratory initial demonstration of capability data were generated from five
replicate measurements using a modified continuous liquid-liquid extractor (Method 3520) with
hydrophobic membrane. In this case, only a single acid pH extraction was performed using the
CLP calibration criteria and the applicable CLP target analytes. These data are located at
https://www.epa.gov/hw-sw846/sw-846-test-method-8270e-semivolatile-organic-compounds-
qas-chromatoqraphvmass-spectrometrv. Laboratories should generate their own acceptance
criteria depending on the extraction and instrument conditions. See Method 8000 for more
detailed guidance.
13.3 Chromatograms from calibration standards analyzed with Day 0 and Day 7
samples were compared to detect possible deterioration of gas chromatographic performance.
These recoveries (using Method 3510 extraction) are located at https://www.epa.gov/hw-
sw846/sw-846-test-method-8270e-semivolatile-orqanic-compounds-qas-chromatoqraphvmass-
spectrometrv. These data are provided for guidance purposes only.
13.4 Method performance data using Method 3541 (i.e., automated Soxhlet extraction)
are located at https://www.epa.gov/hw-sw846/sw-846-test-method-8270e-semivolatile-orqanic-
compounds-gas-chromatographymass-spectrometry. Single laboratory accuracy and precision
data were obtained for semivolatile organics in a clay soil by spiking at a concentration of 6
mg/kg for each compound. The spiking solution was mixed into the soil during addition and
then allowed to equilibrate for approximately one hour prior to extraction. The spiked samples
were then extracted by Method 3541 (Automated Soxhlet). Three extractions were performed
and each extract was analyzed by GC/MS following Method 8270. The low recovery of the
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more volatile compounds is probably due to volatilization losses during equilibration. These
data as listed were taken from Reference 5 and are provided for guidance purposes only.
13.5 Surrogate precision and accuracy data are located at https://www.epa.gov/hw-
sw846/sw-846-test-method-8270e-semivolatile-organic-compounds-gas-chromatographymass-
spectrometrv from a field dynamic spiking study based on air sampling by Method 0010. The
trapping media were prepared for analysis by Method 3542 and subsequently analyzed by this
method (i.e., 8270). These data are provided for guidance purposes only.
13.6 Single-laboratory precision and bias data using Method 3545 (i.e., pressurized
fluid extraction) for semivolatile organic compounds are located at https://www.epa.gov/hw-
sw846/sw-846-test-method-8270e-semivolatile-organic-compounds-gas-chromatographymass-
spectrometrv. The samples were conditioned spiked samples prepared and certified by a
commercial supplier that contained 57 semivolatile organics at three concentrations (i.e., 250,
2500, and 12,500 jjg/kg) on three types of soil (i.e., clay, loam, and sand). Spiked samples
were extracted both by the Dionex Accelerated Solvent Extraction (ASE) system and by the
Perstorp Environmental Soxtec™ (i.e., automated Soxhlet). The data are located at
https://www.epa.gov/hw-sw846/sw-846-test-method-8270e-semivolatile-organic-compounds-
gas-chromatographymass-spectrometry represent seven replicate extractions and analyses for
each individual sample and were taken from Reference 7. The average recoveries from the
three matrices for all analytes and all replicates relative to the automated Soxhlet data are as
follows: clay 96.8%, loam 98.7% and sand 102.1%. The average recoveries from the three
concentrations also relative to the automated Soxhlet data are as follows: low - 101.2%, mid -
97.2% and high - 99.2%. These data are provided for guidance purposes only.
13.7 Single-laboratory precision and bias data using Method 3561 (i.e., supercritical
fluid extraction (SFE) extraction of PAHs with a variable restrictor and solid trapping material)
were obtained for the method analytes by the extraction of two certified reference materials (i.e.,
EC-1, a lake sediment from Environment Canada and HS-3, a marine sediment from the
National Science and Engineering Research Council of Canada, both naturally contaminated
with PAHs). The SFE instrument used for these extractions was a Hewlett-Packard Model
7680. Analysis was by GC/MS. Average recoveries from six replicate extractions ranged from
85 to 148%, with an overall average of 100%, based on the certified value (or a Soxhlet value if
a certified value was unavailable for a specific analyte) for the lake sediment. Average
recoveries from three replicate extractions ranged from 73 to 133%, with an overall average of
92%, based on the certified value for the marine sediment. The data are located at
https://www.epa.gov/hw-sw846/sw-846-test-method-8270e-semivolatile-organic-compounds-
gas-chromatographymass-spectrometry and were taken from Reference 8. These data are
provided for guidance purposes only.
13.8 Single laboratory precision and accuracy using Method 3561 (i.e., SFE extraction
of PAHs with a fixed restrictor and liquid trapping) were obtained for 12 of the method analytes
by the extraction of a certified reference material (i.e., a soil naturally contaminated with PAHs).
The SFE instrument used for these extractions was a Dionex Model 703-M. Analysis was by
GC/MS. Average recoveries from four replicate extractions ranged from 60 to 122%, with an
overall average of 89%, based on the certified value. The instrument conditions that were
utilized to extract a 3.4 g sample were as follows: Pressure - 300 atm; time - 60 min; extraction
fluid - CO2; modifier -10% 1:1 (v/v) methanol/methylene chloride; oven temperature - 80 °C;
restrictor temperature - 120 °C; and, trapping fluid - chloroform (methylene chloride has also
been used). The data are located at https://www.epa.gov/hw-sw846/sw-846-test-method-
8270e-semivolatile-organic-compounds-gas-chromatographvmass-spectrometrv and were
taken from Reference 9. These data are provided for guidance purposes only.
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13.9 Tables located at https://www.epa.gov/hw-sw846/sw-846-test-method-8270e-
semivolatile-orqanic-compounds-qas-chromatoqraphvmass-spectrometrv contain single-
laboratory precision and accuracy data for SPE of TCLP buffer solutions spiked at two levels
and extracted using Method 3535. These data are provided for guidance purposes only.
13.10 The table located at https://www.epa.gov/hw-sw846/sw-846-test-method-8270e-
semivolatile-orqanic-compounds-qas-chromatoqraphvmass-spectrometrv contains multiple-
laboratory data for SPE of spiked TCLP soil leachates extracted using Method 3535. These
data are provided for guidance purposes only.
13.11 Tables located at https://www.epa.gov/hw-sw846/sw-846-test-method-8270e-
semivolatile-organic-compounds-gas-chromatographymass-spectrometrv contain single-
laboratory PAH recovery data for microwave extraction of contaminated soils and standard
reference materials using Method 3546. These data are provided for guidance purposes only.
14.0 POLLUTION PREVENTION
14.1 Pollution prevention encompasses any technique that reduces or eliminates the
quantity and/or toxicity of waste at the point of generation. Numerous opportunities for pollution
prevention exist in laboratory operations. The EPA has established a preferred hierarchy of
environmental management techniques that places pollution prevention as the management
option of first choice. Whenever feasible, laboratory personnel should use pollution prevention
techniques to address their waste generation. When wastes cannot be feasibly reduced at the
source, the Agency recommends recycling as the next best option.
14.2 For information about pollution prevention that may be applicable to laboratories and
research institutions consult
http://www.acs.org/content/dam/acsorg/about/governance/committees/chemicalsafety/publicatio
ns/l ess-is-better.pdf.
15.0 WASTE MANAGEMENT
The EPA requires that laboratory waste management practices be conducted consistent
with all applicable rules and regulations. The Agency urges laboratories to protect the air,
water, and land by minimizing and controlling all releases from hoods and bench operations,
complying with the letter and spirit of any sewer discharge permits and regulations, and by
complying with all solid and hazardous waste regulations, particularly the hazardous waste
identification rules and land disposal restrictions. For further information on waste
management, consult The Waste Management Manual for Laboratory Personnel available at:
http://www.labsafetv.org/FreeDocs/WasteMgmt.pdf.
SW-846 Update VI
8270E - 36
Revision 6
June 2018
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16.0 REFERENCES
1. J. W. Eichelberger, L. E. Harris, and W. L. Budde, "Reference Compound to Calibrate
Ion Abundance Measurement in Gas Chromatography-Mass Spectrometry Systems,"
Analytical Chemistry, 47, 995-1000, 1975.
2. "Interlaboratory Method Study for EPA Method 625 - Base/Neutrals, Acids, and
Pesticides," Final Report for EPA Contract 68-03-3102.
3. S. V. Lucas, R. A. Kornfeld, "GC-MS Suitability Testing of RCRA Appendix VIII and
Michigan List Analytes," U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Cincinnati, OH 45268, Contract No. 68-03-3224,
February 20, 1987.
4. T. M. Engel, R. A. Kornfeld, J. S. Warner, and K. D. Andrews, "Screening of Semivolatile
Organic Compounds for Extractability and Aqueous Stability by SW-846, Method 3510,"
U.S. Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, OH 45268, Contract 68-03-3224, June 5, 1987.
5. V. Lopez-Avila (W. Beckert, Project Officer), "Development of a Soxtec Extraction
Procedure for Extraction of Organic Compounds from Soils and Sediments," U.S.
Environmental Protection Agency, Environmental Monitoring and Support Laboratory,
Las Vegas, NV, EPA 600/X-91/140, October 1991.
6. J. Bursey, R. Merrill, R. McAllister, and J. McGaughey, "Laboratory Validation of VOST
and SemiVOST for Halogenated Hydrocarbons from the Clean Air Act Amendments
List," Vol. 1 and 2, U.S. Environmental Protection Agency, EPA 600/R-93/123a and b,
(NTIS PB 93-227163 and 93-27171), Research Triangle Park, NC, July 1993.
7. B. Richter, J. Ezzell, and D. Felix, "Single Laboratory Method Validation Report:
Extraction of Target Compound List/Priority Pollutant List BNAs and Pesticides using
Accelerated Solvent Extraction (ASE) with Analytical Validation by GC/MS and
GC/ECD," Document 101124, Dionex Corporation, Salt Lake City, UT, June 16, 1994.
8. H. B. Lee, T. E. Peart, R. L. Hong-You, and D. R. Gere, "Supercritical Carbon Dioxide
Extraction of Polycyclic Aromatic Hydrocarbons from Sediments," J. Chromatography, A,
653, 83-91 (1993).
9. S. Warner, "SFE Extraction of PNAs from Solid Matrices Using the Dionex 703M SFE
Extractor and a Liquid Trap," EPA Region III, Central Regional Laboratory, 839 Bestgate
Road, Annapolis, MD 21401, December 12, 1994.
10. C. Markell, "3M Data Submission to EPA," letter to B. Lesnik, June 27, 1995.
11. U.S. EPA Method 525.3, "Determination of Semivolatile Organic Chemicals in Drinking
Water by Solid Phase Extraction and Capillary Column Gas Chromatography/Mass
Spectrometry," National Exposure Research Laboratory, Office of Research and
Development, US EPA, Cincinnati, OH, Version 1.0, February, 2012.
12. USEPA, Superfund Analytical Services/Contract Laboratory Program (CLP), Multi-
Media, Multi-Concentration Organics Analysis, SOM01.2, Exhibit D - Analytical Methods,
"Analytical Method for the Analysis of Semivolatile Organic Compounds," June, 2007.
SW-846 Update VI
8270E - 37
Revision 6
June 2018
-------
13. Data on precision and accuracy of compound recoveries was taken from an EPA
statistical analysis of LCS data from the Department of Defense (DOD) Environmental
Data Quality Workgroup (EDQW) LCS study. This study was conducted by DOD in
2012 and the raw data was shared with the EPA work group. The final DOD study was
published in 2013, after the EPA statistical analysis had been done independently.
14. J. Cochran and G. Frame, "Recent Developments in the High-Resolution Gas
Chromatography of Polychlorinated Biphenyls", Journal of Chromatography A, 843, 1-
434, May 28, 1999.
15. Parris et al., "NIST/NOAA NS&T/EPA EMAP Intercomparison Exercise Program for
Organic Contaminants in the Marine Environment: Description and Results of 1995
Organic Intercomparison Exercises", NOAA Technical Memorandum NOS ORCA 104,
1996.
16. Kucklick et al., "Persistent Organic Pollutants and Vitamins in Northern Fur Seals
(Callorhinus ursinus) Collected from St. Paul Island, Alaska as Part of the Alaska Marine
Mammal Tissue Archival Project", NISTIR 7958, August 2013.
17. EPA Contract Laboratory Organic Statement of Work (S0M02.3d), which can be found
at the website: http://www.epa.gov/sites/production/files/2015-
10/documents/som23d.pdf.
18. NIST/EPA/NIH Mass Spectral Library (NIST 14) and NIST Mass Spectral Search
Program (Version 2.2) User's Guide. National Institute of Standards and Technology,
June 2014.
19. R. Burrows, Basic RSE calculator v2 and instructions, December 2016. Available at:
http://nelac-institute.org/docs/comm/emmec/Calculating%20RSE.pdf.
17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA
The following pages contain the tables and figures referenced by this method.
SW-846 Update VI
8270E - 38
Revision 6
June 2018
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TABLE 1
CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS3
Compound15
Primary Ion
Secondary Ions
Acenanaphthene-cf™ (IS)
164
162, 160
Acenaphthene
154
153, 152
Acenaphthylene
152
151, 153
Acetophenone
105
71, 51, 120
2-Acetylaminofluorene
181
180, 223, 152
1-Acetyl-2-thiourea
118
43, 42, 76
Aldrin
66
263, 220
2-Aminoanthraquinone
223
167, 195
Aminoazobenzene
197
92, 120, 65, 77
4-Aminobiphenyl
169
168, 170, 115
Anilazine
239
241, 143, 178, 89
Aniline
93
66, 65
o-Anisidine
108
80, 123, 52
Anthracene
178
176, 179
Aramite
185
191, 319, 334, 197, 321
Atrazine
200
173, 215
Azinphos-methyl (Guthion)
160
132, 93, 104, 105
Azobenzene
182
105, 77
Barban
222
51, 87, 224, 257, 153
Benzaldehyde
77
105, 106
Benz(a)anthracene
228
229, 226
Benzidine
184
92, 185
Benzo(b)fluoranthene
252
253, 125
Benzo(k)fluoranthene
252
253, 125
Benzoic acid
122
105, 77
Benzo(g,h,i)perylene
276
138, 277
Benzo(a)pyrene
252
253, 125
Benzo(e)pyrene
252
253, 125
p-Benzoquinone
108
54, 82, 80
Benzyl alcohol
108
79, 77
a-BHC
183
181, 109
P-BHC
181
183, 109
y-BHC (Lindane)
183
181, 109
5-BHC
183
181, 109
1,1 '-Biphenyl
154
153, 76
Bis(2-chloro-1 -methylethyl)ether
45
77, 121
Bis(2-chloroethyl)ether
93
63, 95
Bis(2-chloroethoxy)methane
93
95, 123
Bis(2-ethylhexyl)phthalate
149
167, 279
Bromoxynil (Brominal)
277
279, 88, 275, 168
4-Bromophenyl phenyl ether
248
250, 141
Butyl benzyl phthalate
149
91, 206
Caprolactam
113
55, 56
Captafol
79
77, 80, 107
Captan
79
149, 77, 119, 117
Carbaryl (Sevin)
144
115, 116, 201
Carbazole
167
166, 139
SW-846 Update VI 8270E - 39 Revision 6
June 2018
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Compound15
Primary Ion Secondary Ions
Carbofuran (Furaden)
164
149, 131, 122
Carbophenothion
157
97, 121, 342, 159, 199
Chlorfenvinphos
267
269, 323, 325, 295
4-Chloroaniline
127
129, 65, 92
Chlorobenzilate
251
139, 253, 111, 141
5-Chloro-2-methylaniline
106
141, 140, 77, 89
4-Chloro-3-methylphenol
107
144, 142
1 -Chloronaphthalene
162
127, 164
2-Chloronaphthalene
162
127, 164
2-Chlorophenol
128
64, 130
4-Chlorophenyl phenyl ether
204
206, 141
4-Chloro-1,2-phenylenediamine
142
144, 80
4-Chloro-1,3-phenylenediamine
142
144, 80
Chrysene
228
226, 229
Chrysene-^ (IS)
240
120, 236
Coumaphos
362
226, 210, 364, 97, 109
p-Cresidine
122
94, 137, 77, 93
Crotoxyphos
127
105, 193, 166
2-Cyclohexyl-4,6-dinitrophenol
231
185, 41, 193, 266
4,4'-DDD
235
237, 165
4,4'-DDE
246
248, 176
4,4'-DDT
235
237, 165
Demeton-0
88
89, 60, 61, 115, 171
Demeton-S
88
60, 81, 89, 114, 115
Diallate (cis or trans)
86
234, 43, 70
2,4-Diaminotoluene
121
122, 94, 77, 104
Dibenz(a,j)acridine
279
280, 277, 250
Dibenz(a,/7)anthracene
278
139, 279
Dibenzo(a,e)pyrene
302
151, 150, 300
Dibenzofuran
168
139
1,2-Dibromo-3-chloropropane (DBCP)
75
155, 157
Di-n-butyl phthalate
149
150, 104
Dichlone
191
163, 226, 228, 135, 193
1,2-Dichlorobenzene
146
148, 111
1,3-Dichlorobenzene
146
148, 111
1,4-Dichlorobenzene
146
148, 111
1,4-Dichlorobenzene-d4 (IS)
152
150, 115
3,3'-Dichlorobenzidine
252
254, 126
2,4-Dichlorophenol
162
164, 98
2,6-Dichlorophenol
162
164, 98
Dichlorovos (DDVP, Dichlorvos)
109
185, 79, 145
Dicrotophos
127
67, 72, 109, 193, 237
Dieldrin
79
263, 279
Diethyl phthalate
149
177, 150
Diethyl sulfate
139
45, 59, 99, 111, 125
Diethylstilbestrol
268
145, 107, 239, 121, 159
Dimethoate
87
93, 125, 143, 229
3,3'-Dimethoxybenzidine
244
201, 229
Dimethyl aminoazobenzene
225
120, 77, 105, 148, 42
Dimethyl phthalate
163
194, 164
7,12-Dimethylbenz(a)anthracene
256
241, 239, 120
SW-846 Update VI 8270E - 40 Revision 6
June 2018
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Compound15
Primary Ion Secondary Ions
3,3'-Dimethylbenzidine
2,4-Dimethylphenol
a,a-Dimethylphenylamine
1.2-Dinitrobenzene
1.3-Dinitrobenzene (1,3-DNB)
1.4-Dinitrobenzene
4,6-Dinitro-2-methylphenol
2,4-Dinitrophenol
2,6-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap
Dinoseb (DNBP)
Di-n-octyl phthalate
1.4-Dioxane
5.5-Diphenylhydantoin
1,2-Diphenylhydrazine
Diphenylamine
Disulfoton
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
EPN
Ethion
Ethyl carbamate
Ethyl methanesulfonate
Famphur
Fensulfothion
Fenthion
Fluchloralin
Fluoranthene
Fluorene
2-Fluorobiphenyl (surr)
2-Fluorophenol (surr)
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
Hexachlorophene
Hexachloropropene
Hexamethylphosphoramide (HPMA)
Hydroquinone
lndeno(1,2,3-cd)pyrene
Isodrin
Isophorone
Isosafrole
SW-846 Update VI
212
106, 196, 180
122
107, 121
58
91, 65, 134, 42
168
50, 63, 74
168
76, 50, 75, 92, 122
168
75, 50, 76, 92, 122
198
51, 105
184
63, 154
162
164, 126, 98, 63
165
63, 89
165
63, 89
69
41, 39
211
163, 147, 117, 240
149
167, 43
88
43, 58
180
104, 252, 223, 209
77
105, 182
169
168, 167
88
97, 89, 142, 186
195
339, 341
337
339, 341
272
387, 422
263
82, 81
67
345, 250
317
67, 319
157
169, 185, 141, 323
231
97, 153, 125, 121
62
44, 45, 74
79
109, 9745, 65
218
125, 93, 109, 217
293
97, 308, 125, 292
278
125, 109, 169, 153
306
63, 326, 328, 264, 65
202
101, 203
166
165, 167
172
171
112
64
100
272, 274
353
355, 351
284
142, 249
225
223, 227
237
235, 272
117
201, 199
196
198, 209, 211, 406, 408
213
211, 215, 117, 106, 141
135
44, 179, 92, 42
110
81, 53, 55
276
138, 277
193
66, 195, 263, 265, 147
82
95, 138
162
131, 104, 77, 51
8270E - 41 Revision 6
June 2018
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Compound15
Primary Ion Secondary Ions
Kepone
272
274, 237, 178, 143, 270
Leptophos
171
377, 375, 77, 155, 379
Malathion
173
125, 127, 93, 158
Maleic anhydride
54
98, 53, 44
Mestranol
277
310, 174, 147, 242
Methapyrilene
97
50, 191, 71
Methoxychlor
227
228, 152, 114, 274, 212
Methyl methanesulfonate
80
79, 65, 95
Methyl parathion
109
125, 263, 79, 93
3-Methylcholanthrene
268
252, 253, 126, 134, 113
4,4'-Methylenebis(2-chloroaniline)
231
266, 268, 140, 195
4,4'-Methylenebis(N,N-dimethyl-aniline)
254
253, 134
1 -Methylnaphthalene
142
141
2-Methylnaphthalene
142
141
2-Methylphenol
107
108, 77, 79, 90
3/4-Methylphenolc
107
108, 77, 79, 90
Mevinphos
127
192, 109, 67, 164
Mexacarbate
165
150, 134, 164, 222
Mi rex
272
237, 274, 270, 239, 235
Monocrotophos
127
192, 67, 97, 109
Naled
109
145, 147, 301, 79, 189
Naphthalene
128
129, 127
Naphthalene-dg (IS)
136
68
1,4-Naphthoquinone
158
104, 102, 76, 50, 130
1-Naphthylamine
143
115, 89, 63
2-Naphthylamine
143
115, 116
Nicotine
84
133, 161, 162
5-Nitroacenaphthene
199
152, 169, 141, 115
2-Nitroaniline
65
92, 138
3-Nitroaniline
138
108, 92
4-Nitroaniline
138
65, 108, 92, 80, 39
5-Nitro-o-anisidine
168
79, 52, 138, 153, 77
Nitrobenzene
77
123, 65
Nitrobenzene-ds (surr)
82
128, 54
4-Nitrobiphenyl
199
152, 141, 169, 151
Nitrofen
283
285, 202, 139, 253
2-Nitrophenol
139
109, 65
4-Nitrophenol
139
109, 65
4-Nitroquinoline-1-oxide
174
101, 128, 75, 116
/V-Nitrosodi-n-butylamine
84
57, 41, 116, 158
/V-Nitrosodiethylamine
102
42, 57, 44, 56
N-Nitrosodimethylamine
42
74, 44
/V-Nitrosodiphenylamine
169
168, 167
/V-Nitrosodi-n-propylamine
70
42, 101, 130
N- N itrosom ethylethy lam i ne
88
42, 43, 56
N-Nitrosomorpholine
56
116, 86
/V-Nitrosopiperidine
114
42, 55, 56, 41
/V-Nitrosopyrrolidine
100
41, 42, 68, 69
5-Nitro-o-toluidine
152
106, 79
Octamethylpyrophosphoramide
135
44, 199, 286, 153, 243
4,4'-Oxydianiline
200
108, 171, 80, 65
SW-846 Update VI 8270E - 42 Revision 6
June 2018
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Compound15
Primary Ion
Secondary Ions
Parathion
109
97, 291, 139, 155
Pentachlorobenzene
250
252, 108, 248, 215, 254
Pentachloronitrobenzene
237
142, 214, 249, 295, 265
Pentachlorophenol
266
264, 268
Perylene
252
253, 125
Perylene-cf?2 (IS)
264
260, 265
Phenacetin
108
180, 179, 109, 137, 80
Phenanthrene
178
179, 176
Phenanthrene-cf™ (IS)
188
94, 80
Phenobarbital
204
117, 232, 146, 161
Phenol
94
65, 66
Phenol-d6 (surr)
99
42, 71
1,4-Phenylenediamine
108
80, 53, 54, 52
Phorate
75
121, 97, 93, 260
Phosalone
182
184, 367, 121, 379
Phosmet (Imidan)
160
77, 93, 317, 76
Phosphamidon
127
264, 72, 109, 138
Phthalic anhydride
104
76, 50, 148
2-Picoline
93
66, 92
Piperonyl sulfoxide
162
135, 105, 77
Pronamide (Kerb)
173
175, 145, 109, 147
Propylthiouracil
170
142, 114, 83
Pyrene
202
200, 203
Pyridine
79
52, 50
3-(Chloromethyl)pyridine hydrochloride
92
127, 129, 65, 39
Resorcinol
110
81, 82, 53, 69
Safrole
162
104, 77, 103, 135
Strychnine
334
334, 335, 333
Sulfallate
188
88, 72, 60, 44
T erbufos
231
57, 97, 153, 103
Terphenyl-cf?4 (surr)
244
122, 212
1,2,4,5-Tetrachlorobenzene
216
214, 179, 108, 143, 218
2,3,4,6-Tetrachlorophenol
232
131, 230, 166, 234, 168
Tetrachlorvinphos (Stirophos, Gardona)
329
109, 331, 79, 333
Tetraethyl dithiopyrophosphate
97
202, 238, 266
Tetraethyl pyrophosphate (TEPP)
99
155, 127, 81, 109
Thionazine
107
96, 97, 143, 79, 68
Thiophenol (Benzenethiol)
110
66, 109, 84
2,4-Toluene diisocyanate
174
145, 173, 146, 132, 91
o-Toluidine
106
107, 77, 51, 79
Toxaphene
159
231, 233
2,4,6-Tribromophenol (surr)
330
332, 141
1,2,4-T richlorobenzene
180
182, 145
2,4,5-T richlorophenol
196
198, 97, 132, 99
2,4,6-T richlorophenol
196
198, 200
0,0,0-Triethyl phosphorothioate
198
121, 93
Trifluralin (Treflan)
306
43, 264, 41, 290
Trimethyl phosphate
110
79, 95, 109, 140
2,4,5-T rimethylaniline
120
135, 134, 91, 77
1,3,5-T rinitrobenzene
75
74, 213, 120, 91, 63
Tris(2,3-dibromopropyl)phosphate
201
137, 119, 217, 219, 199
SW-846 Update VI 8270E - 43 Revision 6
June 2018
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Compound15
Primary Ion
Secondary Ions
Tri-p-tolyl phosphated
368
367, 107, 165, 198
IS = internal standard
surr = surrogate
a The data presented are representative of DB-5 type analytical columns.
b Aroclors, Chlordane (NOS), and PCBs (NOS) are not included in this table because the
quantitation ions vary with the individual components.
c Compounds cannot be separated for quantitation
d Substitute for the non-specific mixture, tricresyl phosphate
SW-846 Update VI
8270E - 44
Revision 6
June 2018
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TABLE 2
2012 DEPARTMENT OF DEFENSE LABORATORY CONTROL SAMPLE CONTROL
LIMIT STUDY AVERAGE % RECOVERY PER PREPARATION TECHNIQUE
Compounds
CAS No
3510
3520
3540/
3541
3545
3550
3580
Acenaphthene
83-32-9
80
83
77/89
80
76
-
Acenaphthylene
208-96-8
79
85
77/92
79
79
86
Acetophenone
98-86-2
81
77
65/61
70
73
-
2-Acetylaminofluorene
53-96-3
87
100
-/-
91
80
-
1-Acetyl-2-thiourea
591-08-2
-
-
-/-
-
-
-
Aldrin
309-00-2
95
-
-/-
-
97
-
2-Aminoanthraquinone
117-79-3
-
-
-/-
-
-
-
Aminoazobenzene
60-09-3
-
-
-/-
-
-
-
4-Aminobiphenyl
92-67-1
82
67
-/-
-
32
-
3-Amino-9-ethylcarbazole
132-32-1
-
-
-/-
-
-
-
Anilazine
101-05-3
-
-
-/-
-
-
-
Aniline
62-53-3
60
61
53/51
49
63
-
o-Anisidine
90-04-0
-
-
-/-
-
-
-
Anthracene
120-12-7
86
86
80/89
83
82
-
Aramite
140-57-8
83
90
-/-
-
71
-
Atrazine
1912-24-9
91
94
90/-
86
86
-
Azinphos-methyl (Guthion)
86-50-0
-
-
-/-
-
-
-
Azobenzene
103-33-3
83
92
-/-
-
82
-
Barban
101-27-9
-
-
-/-
-
-
-
Benzaldehyde
100-52-7
71
86
66/-
68
68
-
Benzidine
92-87-5
46
26
-/12
61
37
-
Benzo(a)anthracene
56-55-3
89
89
81/91
86
84
101
Benzo(b)fluoranthene
205-99-2
89
89
75/91
87
86
98
Benzo(k)fluoranthene
207-08-9
91
90
83/95
89
87
100
Benzoic acid
65-85-0
29
58
46/64
48
71
93
Benzo(g,h,i)perylene
191-24-2
89
90
78/98
84
86
101
Benzo(a)pyrene
50-32-8
88
87
78/95
88
84
91
Benzo(e)pyrene
192-97-2
84
-
-/-
-
77
-
p-Benzoquinone
106-51-4
-
-
-/-
-
-
-
Benzyl alcohol
100-51-6
66
80
75/82
63
74
-
a-BHC
319-84-6
95
-
-/-
-
95
-
P-BHC
319-85-7
91
-
-/-
-
95
-
5-BHC
319-86-8
96
-
-/-
-
97
-
y-BHC (Lindane)
58-89-9
94
-
-/-
-
98
-
1,1 '-Biphenyl
92-52-4
80
77
73/82
69
73
-
Bis(2-chloroethoxy) methane
111-91-1
81
83
76/89
70
75
94
Bis(2-chloroethyl)ether
111-44-4
77
79
75/88
68
71
-
Bis(2-chloro-1-methylethyl)ether
108-60-1
76
83
-/-
-
76
-
Bis(2-ethylhexyl)phthalate
117-81-7
93
94
87/94
83
90
103
4-Bromophenyl phenyl ether
101-55-3
86
89
78/91
78
82
-
Bromoxynil (Brominal)
1689-84-5
-
-
-/-
-
-
-
Butyl benzyl phthalate
85-68-7
91
94
84/95
82
88
99
Caprolactam
105-60-2
21
42
76/-
86
80
-
Captafol
2425-06-1
-
-
-/-
-
-
-
Captan
133-06-2
-
-
-/-
-
-
-
Carbaryl (Sevin)
63-25-2
-
-
-/-
-
-
-
SW-846 Update VI
8270E - 45
Revision 6
June 2018
-------
Compounds
3540/
CAS No 3510 3520 ^ J 3545 3550 3580
Cabriole
Carbofuran (Furaden)
Carbophenothion
Chlordane (NOS)*
Chlorfenvinphos
4-Chloroaniline
Chlorobenzilate
5-Chloro-2-methylaniline
4-Chloro-3-methylphenol
3-(Chloromethyl)pyridine
hydrochloride
1-Chloronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chloro-1,2-phenylenediamine
4-Chloro-1,3-phenylenediamine
4-Chlorophenyl phenyl ether
Chrysene
Coumaphos
p-Cresidine
Crotoxyphos
2-Cyclohexyl-4,6-dinitrophenol
4,4'-DDD
4,4'-DDE
4,4'-DDT
Demeton-0
Demeton-S
Diallate (cis or trans)
2,4-Diaminotoluene
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
Dibenzofuran
Dibenzo(a,e)pyrene
1,2-Dibromo-3-chloropropane
(DBCP)
Di-n-butyl phthalate
Dichlone
1.2-Dichlorobenzene
1.3-Dichlorobenzene
1.4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos (DDVP, Dichlorvos)
Dicrotophos
Dieldrin
Diethyl phthalate
Diethyl sulfate
Diethylstilbestrol
Dimethoate
SW-846 Update VI
86-74-8
89
90
75/88
84
87
-
1563-66-2
-
-
-/-
-
-
-
786-19-6
-
-
-/-
-
-
-
57-74-9
95
-
-/-
-
94
-
470-90-6
-
-
-/-
-
-
-
106-47-8
74
77
56/71
54
63
-
510-15-6
93
103
-/-
93
76
-
95-79-4
-
-
-/-
-
-
-
59-50-7
82
86
79/91
76
81
-
6959-48-4
-
-
-/-
-
-
-
90-13-1
-
83
-/-
-
80
-
91-58-7
75
78
75/85
72
75
-
95-57-8
73
77
77/87
68
74
93
95-83-0
-
-
-/-
-
-
-
5131-60-2
-
-
-/-
-
-
-
7005-72-3
84
87
79/91
76
80
-
218-01-9
89
89
82/91
87
85
100
56-72-4
-
-
-/-
-
-
-
120-71-8
-
-
-/-
-
-
-
7700-17-6
-
-
-/-
-
-
-
131-89-5
-
-
-/-
-
-
-
72-54-8
96
-
-/-
-
101
-
72-55-9
94
-
-/-
-
100
-
50-29-3
94
-
-/-
-
96
-
298-03-3
-
-
-/-
-
-
-
126-75-0
-
-
-/-
-
-
-
2303-16-4
89
93
-/-
87
79
-
95-80-7
-
-
-/-
-
-
-
224-42-0
-
-
-/-
-
89
-
53-70-3
89
90
80/97
86
87
101
132-64-9
82
86
75/92
73
80
-
192-65-4
94
-
-/-
-
93
-
96-12-8
-
-
-/-
-
-
-
84-74-2
90
93
83/93
82
87
-
117-80-6
-
-
-/-
-
-
-
95-50-1
68
69
70/86
65
72
-
541-73-1
65
67
68/84
63
69
93
106-46-7
66
69
72/85
64
70
-
91-94-1
79
75
57/83
78
73
78
120-83-2
81
82
80/91
72
77
-
87-65-0
83
81
96/84
71
78
-
62-73-7
-
-
-/-
-
-
-
141-66-2
-
-
-/-
-
-
-
60-57-1
96
-
-/-
-
98
-
84-66-2
88
91
80/93
79
84
-
64-67-5
-
-
-/-
-
-
-
56-53-1
-
-
-/-
-
-
-
60-51-5
88
108
-/-
-
80
-
8270E - 46 Revision 6
June 2018
-------
Compounds
CAS No
3510
3520
3540/
3541
3545
3550
3580
3,3'-Dimethoxybenzidine
119-90-4
-
-
-/-
-
-
-
Dimethyl aminoazobenzene
60-11-7
87
99
-/-
92
88
-
Dimethyl phthalate
131-11-3
85
90
80/93
77
83
-
7,12-Dimethylbenz(a)-anthracene
57-97-6
98
89
-/-
79
91
-
3,3'-Dimethylbenzidine
119-93-7
47
48
-/-
48
23
-
a,a-Dimethylphenethylamine
122-09-8
-
-
-/-
-
-
-
2,4-Dimethylphenol
105-67-9
75
68
54/87
71
74
95
1,2-Dinitrobenzene
528-29-0
86
77
-/-
-
80
-
1,3-Dinitrobenzene (1,3-DNB)
99-65-0
83
96
-/-
82
81
-
1,4-Dinitrobenzene
100-25-4
85
-
-/-
-
74
-
4,6-Dinitro-2-methylphenol
534-52-1
88
90
72/75
69
82
85
2,4-Dinitrophenol
51-28-5
80
82
59/63
57
74
70
2,4-Dinitrotoluene
121-14-2
90
91
84/95
81
85
98
2,6-Dinitrotoluene
606-20-2
88
90
83/94
78
82
95
Dinocap
39300-45-3
-
-
-/-
-
-
-
Dinoseb (DNBP)
88-85-7
92
95
-167
-
52
-
Di-n-octyl phthalate
117-84-0
93
94
84/96
87
89
108
1,4-Dioxane
123-91-1
41
57
49/40
48
48
-
Diphenylamine
122-39-4
82
89
-/90
-
77
-
5,5-Diphenylhydantoin
57-41-0
-
-
-/-
-
-
-
1,2-Diphenylhydrazine
122-66-7
83
85
84/88
73
82
97
Disulfoton
298-04-4
87
95
-/-
-
72
-
Endosulfan I
959-98-8
102
-
-/-
-
102
-
Endosulfan II
33213-65-9
-
-
-/-
-
-
-
Endosulfan sulfate
1031-07-8
-
-
-/-
-
-
-
Endrin
72-20-8
99
-
-/-
-
99
-
Endrin aldehyde
7421-93-4
99
-
-/-
-
100
-
Endrin ketone
53494-70-5
-
-
-/-
-
-
-
EPN
2104-64-5
-
-
-/-
-
-
-
Ethion
563-12-2
-
-
-/-
-
-
-
Ethyl carbamate
51-79-6
-
-
-/-
-
-
-
Ethyl methanesulfonate
62-50-0
87
76
-/-
64
75
-
Famphur
52-85-7
136
-
-/-
-
174
-
Fensulfothion
115-90-2
-
-
-/-
-
-
-
Fenthion
55-38-9
-
-
-/-
-
-
-
Fluchloralin
33245-39-5
-
-
-/-
-
-
-
Fluoranthene
206-44-0
89
90
82/92
87
86
100
Fluorene
86-73-7
84
86
79/90
82
80
-
Heptachlor
76-44-8
93
-
-/-
-
96
-
Heptachlor epoxide
1024-57-3
95
-
-/-
-
99
-
Hexachlorobenzene
118-74-1
86
86
79/89
78
81
-
Hexachlorobutadiene
87-68-3
68
72
73/89
70
74
-
Hexachlorocyclopentadiene
77-47-4
59
39
57/46
53
69
70
Hexachloroethane
67-72-1
64
66
72/84
64
69
-
Hexachlorophene
70-30-4
74
-
-/-
-
-
-
Hexachloropropene
1888-71-7
59
45
-/78
60
66
-
Hexamethylphosphoramide
680-31-9
-/-
(HMPA)
Hydroquinone
123-31-9
-
-
-/-
-
-
-
lndeno(1,2,3-cd)pyrene
193-39-5
89
89
81/98
85
87
102
SW-846 Update VI
8270E - 47
Revision 6
June 2018
-------
Compounds
CAS No
3510
3520
3540/
3541
3545
3550
3580
Isodrin
465-73-6
92
97
-/-
82
79
-
Isophorone
78-59-1
79
84
75/89
70
74
89
Isosafrole
120-58-1
85
78
-/-
68
78
-
Kepone
143-50-0
64
-
-/-
-
52
-
Leptophos
21609-90-5
-
-
-/-
-
-
-
Malathion
121-75-5
-
-
-/-
-
-
-
Maleic anhydride
108-31-6
-
-
-/-
-
-
-
Mestranol
72-33-3
-
-
-/-
-
-
-
Methapyrilene
91-80-5
41
-
-/-
-
-
-
Methoxychlor
72-43-5
95
-
-/-
-
94
-
Methyl methanesulfonate
66-27-3
72
69
-/-
-
73
-
Methyl parathion
298-00-0
100
109
-/-
-
73
-
3-Methylcholanthrene
56-49-5
84
91
-/-
86
82
-
4,4'-Methylenebis(2-chloroaniline)
101-14-4
-
-
-/-
-
-
-
4,4'-Methylenebis(A/,A/-dimethyl-
101-61-1
-/-
aniline)
1-Methylnaphthalene
90-12-0
76
78
78/-
78
77
-
2-Methylnaphthalene
91-57-6
75
80
75/89
77
77
-
2-Methylphenol
95-48-7
67
79
73/87
69
74
93
3-Methylphenol
108-39-4
65
81
75/91
71
77
-
4-Methylphenol
106-44-5
65
81
75/91
71
77
-
Mevinphos
7786-34-7
-
-
-/-
-
-
-
Mexacarbate
315-18-4
-
-
-/-
-
-
-
Mi rex
2385-85-5
-
-
-/-
-
-
-
Monocrotophos
6923-22-4
-
-
-/-
-
-
-
Naled
300-76-5
-
-
-/-
-
-
-
Naphthalene
91-20-3
75
77
74/89
77
74
98
1,4-Naphthoquinone
130-15-4
68
66
-/-
80
72
-
1-Naphthylamine
134-32-7
68
64
-/-
-
30
-
2-Naphthylamine
91-59-8
69
53
-/-
-
31
-
Nicotine
54-11-5
-
-
-/-
-
-
-
5-Nitroacenaphthene
602-87-9
-
-
-/-
-
-
-
2-Nitroaniline
88-74-4
88
90
79/88
78
84
91
3-Nitroaniline
99-09-2
80
87
66/78
70
76
71
4-Nitroaniline
100-01-6
91
-
-/-
-
86
-
5-Nitro-o-anisidine
99-59-2
-
-
-/-
-
-
-
Nitrobenzene
98-95-3
80
80
73/89
68
75
95
4-Nitrobiphenyl
92-93-3
-
-
-/-
-
-
-
Nitrofen
1836-75-5
-
-
-/-
-
-
-
2-Nitrophenol
88-75-5
81
82
77/89
70
76
-
4-Nitrophenol
100-02-7
38
83
70/86
74
80
94
4-Nitroquinoline-1-oxide
56-57-5
100
76
-/-
63
96
-
/V-Nitroso-di-n-butylamine
924-16-3
87
86
-/90
-
86
-
N-Nitrosodiethylamine
55-18-5
76
78
-/80
64
78
-
N-Nitrosodimethylamine
62-75-9
48
75
67/75
61
69
86
N-Nitrosodiphenylamine
86-30-6
85
81
77/91
78
80
-
N-Nitroso-di-n-propylamine
621-64-7
82
84
75/86
71
75
-
N-Nitrosomethylethylamine
10595-95-6
70
77
-HA
64
75
-
N-Nitrosomorpholine
59-89-2
80
83
-/-
73
91
-
N-Nitrosopiperidine
100-75-4
83
82
-185
-
80
-
SW-846 Update VI
8270E - 48
Revision 6
June 2018
-------
Compounds
3540/
CAS No 3510 3520 ^ J 3545 3550 3580
N-Nitrosopyrrolidine
5-Nitro-o-toluidine
Octamethyl pyrophosphoramide
4,4'-Oxydianiline
Parathion
Pentachlorobenzene
Pentachloronitrobenzene
Pentachlorophenol
Perylene
Phenacetin
Phenanthrene
Phenobarbital
Phenol
1,4-Phenylenediamine
Phorate
Phosalone
Phosmet (Imidan)
Phosphamidon
Phthalic anhydride
2-Picoline (2-Methylpyridine)
Piperonyl sulfoxide
Polychlorinated biphenyls (NOS)
Pronamide (Kerb)
Propylthiouracil
Pyrene
Pyridine
Resorcinol
Safrole
Strychnine
Sulfallate
Terbufos
1.2.4.5-T etrachlorobenzene
2.3.4.6-T etrachlorophenol
Tetrachlorvinphos (Stirophos,
Gardona)
Tetraethyl dithiopyrophosphate
Tetraethyl pyrophosphate (TEPP)
Thionazine
Thiophenol (Benzenethiol)
2,4-Toluene diisocyanate
o-Toluidine
Toxaphene
1.2.4-T richlorobenzene
2.4.5-T richlorophenol
2.4.6-T richlorophenol
0,0,0-Triethyl phosphorothioate
Trifluralin (Treflan)
Trimethyl phosphate
2,4,5-T rimethylaniline
1,3,5-T rinitrobenzene
SW-846 Update VI
930-55-2
78
81
-184
76
79
-
99-55-8
84
90
-/-
90
63
-
152-16-9
-
-
-/-
-
-
-
101-80-4
-
-
-/-
-
-
-
56-38-2
96
112
-/-
-
72
-
608-93-5
87
88
-/87
74
87
-
82-68-8
91
98
-/-
85
80
-
87-86-5
83
84
66/79
79
78
97
198-55-0
87
-
-/-
-
75
-
62-44-2
91
96
-/-
88
80
-
85-01-8
87
88
80/90
82
83
-
50-06-6
-
-
-/-
-
-
-
108-95-2
37
76
76/88
69
74
86
106-50-3
-
-
-/-
12
-
-
298-02-2
79
100
-/-
-
69
-
2310-17-0
-
-
-/-
-
-
-
732-11-6
-
-
-/-
-
-
-
13171-21-6
-
-
-/-
-
-
-
85-44-9
-
-
-/-
-
-
-
109-06-8
59
69
-/-
60
64
-
120-62-7
-
-
-/-
-
-
-
1336-36-3
-
-
-/-
-
-
-
23950-58-5
87
99
-/-
86
75
-
51-52-5
-
-
-/-
-
-
-
129-00-0
89
90
81/93
86
85
98
110-86-1
42
53
67/-
44
52
-
108-46-3
-
-
-/-
-
-
-
94-59-7
84
82
-/-
68
77
-
57-24-9
-
-
-/-
-
-
-
95-06-7
-
-
-/-
-
-
-
13071-79-9
-
-
-/-
-
-
-
95-94-3
75
84
87/85
70
76
-
58-90-2
87
89
92/83
83
80
-
961-11-5
-
-
-/-
-
-
-
3689-24-5
86
101
-/-
-
69
-
107-49-3
-
-
-/-
-
-
-
297-97-2
103
105
-/-
-
81
-
108-98-5
-
-
-/-
-
-
-
584-84-9
-
-
-/-
-
-
-
95-53-4
75
62
-/-
56
39
-
8001-35-2
100
-
-/-
-
99
-
120-82-1
68
72
74/89
68
72
-
95-95-4
85
87
80/93
76
79
98
88-06-2
84
86
80/90
74
79
98
126-68-1
87
90
-/-
-
75
-
1582-09-8
-
-
-/-
-
-
-
512-56-1
-
-
-/-
-
-
-
137-17-7
-
-
-/-
-
-
-
99-35-4
85
98
-/-
95
85
-
8270E - 49 Revision 6
June 2018
-------
Compounds
3540/
CAS No 3510 3520 ^ J 3545 3550 3580
Tris(2,3-dibromopropyl)phosphate 126-72-7 - - -/-
Tri-p-tolyl phosphate 78-32-0
* Average % recovery for Chlordane (NOS) taken from gamma-chlordane results in Department
of Defense (DOD) Study.
SW-846 Update VI
8270E - 50
Revision 6
June 2018
-------
TABLE 3
DFTPP KEY IONS AND ION ABUNDANCE CRITERIA3'15
Mass
Ion Abundance Criteria
68
<2% of m/z 69
69
Present
70
<2% of m/z 69
197
<2% of m/z 198
198
Base peak or present
199
5-9% of m/z 198
365
>1% of Base Peak
441
<150% of m/z 443
442
Base peak or present
443
15-24% of m/z 442
a The criteria are taken from Reference 11 (Method 525.3).
b The criteria in this table are intended to be used as default
criteria for quadrupole instrumentation if optimized
manufacturer's operating conditions are not available.
Alternate tuning criteria may be employed (e.g., CLP or
Method 625), provided that method performance is not
adversely affected. See Sec. 11.3.1.
SW-846 Update VI
8270E - 51
Revision 6
June 2018
-------
TABLE 4
GUIDANCE RESPONSE FACTOR CRITERIA FOR INITIAL CALIBRATION USING THE
SUGGESTED IONS FROM TABLE 1 (See Sec. 11.3.4.2)
Semivolatile Compounds
Guidance Min
Response Factor
(RF)
Acenaphthene
0.9
Acenaphthylene
0.9
Acetophenone
0.01
Anthracene
0.7
Atrazine
0.01
Benzaldehyde
0.01
Benzo(a)anthracene
0.8
Benzo(a)pyrene
0.7
Benzo(b)fluoranthene
0.7
Benzo(g,h,i)perylene
0.5
Benzo(k)fluoranthene
0.7
1,1 '-Biphenyl
0.01
Bis(2-chloroethoxy) methane
0.3
Bis(2-chloroethyl)ether
0.7
Bis-(2-ethylhexyl)phthalate
0.01
4-Bromophenyl-phenyl ether
0.1
Butyl benzyl phthalate
0.01
Caprolactam
0.01
Carbazole
0.01
4-Chloroaniline
0.01
4-Chloro-3-methylphenol
0.2
2-Chloronaphthalene
0.8
2-Chlorophenol
0.8
4-Chlorophenyl-phenyl ether
0.4
Chrysene
0.7
Dibenz(a,/7)anthracene
0.4
Dibenzofuran
0.8
Di-n-butyl phthalate
0.01
3,3'-Dichlorobenzidine
0.01
2,4-Dichlorophenol
0.2
Diethyl phthalate
0.01
Dimethyl phthalate
0.01
2,4-Dimethylphenol
0.2
4,6-Dinitro-2-methylphenol
0.01
2,4-Dinitrophenol
0.01
2,4-Dinitrotoluene
0.2
2,6-Dinitrotoluene
0.2
Di-n-octyl phthalate
0.01
Fluoranthene
0.6
Fluorene
0.9
Hexachlorobenzene
0.1
Hexachlorobutadiene
0.01
Hexachlorocyclopentadiene
0.05
Hexachloroethane
0.3
lndeno(1,2,3-cd)pyrene
0.5
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Semivolatile Compounds
Guidance Min
Response Factor
(RF)
Isophorone
0.4
2-Methylnaphthalene
0.4
2-Methylphenol
0.7
4-Methylphenol
0.6
Naphthalene
0.7
2-Nitroaniline
0.01
3-Nitroaniline
0.01
4-Nitroaniline
0.01
Nitrobenzene
0.2
2-Nitrophenol
0.1
4-Nitrophenol
0.01
/V-Nitroso-di-n-propylamine
0.5
/V-Nitrosodiphenylamine
0.01
2,2'-Oxybis-(1 -chloropropane)
0.01
Pentachlorophenol
0.05
Phenanthrene
0.7
Phenol
0.8
Pyrene
0.6
1,2,4,5-T etrachlorobenzene
0.01
2,3,4,6-T etrachlorophenol
0.01
2,4,5-T richlorophenol
0.2
2,4,6-T richlorophenol
0.2
These RFs are provided as guidance only and are not intended to be a
requirement.
See Sec. 11.3.4.2 and Appendix B for additional information.
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TABLE 5
SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION
1,4-Dichlorobenzene-d4
Naphthalene-dg
Acenaphthene-cf™
Aniline
Acetophenone
Acenaphthene
Benzaldehyde
Benzoic acid
Acenaphthylene
Benzyl alcohol
Bis(2-chloroethoxy)methane
1,1 '-Biphenyl
Bis(2-chloroethyl)ether
Caprolactam
1-Chloronaphthalene
Bis(2-chloro-1-methylethyl)ether
4-Chloroaniline
2-Chloronaphthalene
2-Chlorophenol
4-Chloro-3-methylphenol
4-Chlorophenyl phenyl
1,2-Dichlorobenzene
2,4-Dichlorophenol
ether
1,3-Dichlorobenzene
2,6-Dichlorophenol
Dibenzofuran
1,4-Dichlorobenzene
a,a-Dimethylphenethylamine
Diethyl phthalate
1,4-Dioxane
2,4-Dimethylphenol
Dimethyl phthalate
Ethyl methanesulfonate
Hexachlorobutadiene
2,4-Dinitrophenol
2-Fluorophenol (surr)
Isophorone
2,4-Dinitrotoluene
Hexachloroethane
2-Methylnaphthalene
2,6-Dinitrotoluene
Methyl methanesulfonate
1 -Methylnaphthalene
Fluorene
2-Methylphenol
Naphthalene
2-Fluorobiphenyl (surr)
4-Methylphenol
Nitrobenzene
Hexachlorocyclopentadiene
N-Nitrosodimethylamine
Nitrobenzene-dg (surr)
1-Naphthylamine
N-Nitroso-di-n-propylamine
2-Nitrophenol
2-Naphthylamine
Phenol
N-Nitrosodi-n-butylamine
2-Nitroaniline
Phenol-d6 (surr)
N-Nitrosopiperidine
3-Nitroaniline
2-Picoline
1,2,4-T richlorobenzene
4-Nitroaniline
Pyridine
4-Nitrophenol
Pentachlorobenzene
1,2,4,5-T etrachlorobenzene
2,3,4,6-T etrachlorophenol
2,4,6-Tribromophenol (surr)
2,4,6-T richlorophenol
2,4,5-T richlorophenol
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Phenanthrene-cf™
Chrysene-cf?2
Perylene-^
4-Aminobiphenyl
Anthracene
Atrazine
4-Bromophenyl phenyl ether
Carbazole
Di-n-butyl phthalate
4,6-Dinitro-2-methylphenol
Diphenylamine
Fluoranthene
Hexachlorobenzene
4-Nitroquinoline-1-oxide
/V-Nitrosodiphenylamine
Benzidine
Benzo(a)anthracene
Bis(2-ethylhexyl)phthalate
Butyl benzyl phthalate
Chrysene
3,3'-Dichlorobenzidine
Dimethyl aminoazobenzene
Di-n-octyl phthalate
Pyrene
Terphenyl-cf?4 (surr)
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzo(e)pyrene
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
7,12-
Dimethylbenz(a)anthracene
lndeno(1,2,3-cd)pyrene
3-Methylcholanthrene
Perylene
Pentachlorophenol
Pentachloronitrobenzene
Phenacetin
Phenanthrene
Pronamide
(surr) = surrogate
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TABLE 6
SUMMARY OF QC CRITERIA FOR USE WITH 8270E3
Quality
Control Type
Minimum
frequency
Specification
Suggested Acceptance
Criteria
Instrument
performance
check (Sees.
9.3.1, 11.3.1)
Prior to initial
calibration
<50 ng
Decafluorotriphenylphosphine
(DFTPP) injected
Meet ion ratio criteria for
reference compound:
DFTPP (Table 3), or
alternative documented
criteria; Tailing factor <2 and
degradation <20%
For average RF calibration
model: <20% relative
standard deviation (RSD) of
RFs
For LR or QR model:
R>0.995, R2>0.99.
Initial
calibration
(ICAL) (Sees.
9.3.2, 11.3)
Prior to
analyzing
samples, and
as needed if
continuing
performance
criteria cannot
be met
5 points minimum for
response factor (RF) and
linear regressions (LR), 6
points minimum for quadratic
regression (QR)
>90% of reported target
analytes meet ICAL criteria
Independent of calibration
model: Low standard
recalculation (refit) should be
±50% of true value; other
standards >lower limit of
quantitation (LLOQ) are
recommended to be ±30% of
true value.
Or, relative
standard error (RSE) <20%
(Refer to Method 8000 and
reference 19 for calculation).
See Method 8000 for
additional criteria.
Initial
Calibration
Verification
(ICV) (Sees.
9.3.2, 11.3.7)
After each ICAL
and prior to
analyzing
samples
Prepared from different
source of target analytes than
ICAL standards
Calculated concentrations of
target analytes are ±30% of
true value
Continuing
Calibration
Verification
(CCV) (Sees.
9.3.3, 11.4)
Once at least
every 12 hours
>80% of target analytes meet
CCV criteria
Targets are <20% difference
or drift; IS responses are
within 50% to 200% of mid-
point of ICAL or average of
ICAL ISs; and retention
times for ISs have not shifted
>30 seconds relative to ICAL
Blanks
(Sec. 9.5)
One method
blank (MB) per
preparation
NA
T arget analyte
concentrations in blanks are
<1/2 LLOQ, or <10% of
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Quality Minimum Specification Suggested Acceptance
Control Type frequency Criteria
batch of 20 or
fewer samples;
Instrument
blanks as
needed
concentration in field
samples
Laboratory
Control
Sample (LCS)
(Sec. 9.6.2)
One per
preparation
batch of 20 or
fewer samples
NA
Meets recovery criteria
Duplicates
and Matrix
Spikes
(Sec. 9.6.1)
A duplicate and
matrix spike, or
matrix
spike/matrix
spike duplicate
per preparation
of 20 or fewer
samples (not
required per
batch)
NA
Performance-based or
project-defined recovery
criteria for matrix spikes;
Relative percent difference
(RPD) criteria between
measured concentrations in
sample and laboratory
duplicate or in matrix spike
and matrix spike duplicate
Surrogates
(Sec. 9.7)
Added to each
sample
NA
Performance-based recovery
criteria established by the
laboratory or criteria chosen
for the project
Internal
Standards (IS)
(Sees. 9.8,
11.5.4)
Added to each
sample
NA
IS response is within 50-
200% of the response of the
same IS in the midpoint
ICAL standard (or average of
ICAL) or most recent CCV
Qualitative
Analyte
Identification
(Sec. 11.6.1)
Each target
analyte
NA
RT in sample is within ±10
seconds of RT in midpoint
ICAL or CCV standard) or
within ±10 seconds relative
to the shift of the associated
IS (delta RT of the IS ± 10
seconds)
Characteristic ion(s) within
±30% of expected ion ratio in
reference spectrum; or,
match to reference library
spectra >0.8 (only for full
mass range acquisition
modes)
a Default acceptance criteria; alternative criteria may be specified for a given application.
Refer to Sec. 9 for more information.
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FIGURE 1
TAILING FACTOR CALCULATION
TAILING FACTOR^ ~
Example calculation: Peak Height = DE = 100mm
10% Peak Height = BD = 10 mm
Peak Width at 10% Peak Height = AC a 23 mm
AB = 11 mm
BC = 12 mm
12
Therefore: Tailing Factor- — =1.1
11
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FIGURE 2
GAS CHROMATOGRAM OF BASE/NEUTRAL AND ACID CALIBRATION STANDARD3
1e+07 -
Jx
S 5
10.00
a Courtesy of EPA Region 6
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Appendix A: Changes to 8270E, Rev. 6 compared to 8270D, Rev. 5
1. Throughout: The term mass was replaced with the ratio of mass/charge (m/z) as that is
what is actually measured. Area or height was replaced with response.
2. Table, Sec. 1.1: Designation for appropriate preparation technique in the analyte table in
Sec. 1.1 was changed from X to S to be more intuitive. All abbreviations for problematic
compounds were removed and replaced with * (definitions and specific analytes were
added to Sec. 1.4). The analyte table in Sec. 1.1 was updated using data from an EPA
statistical analysis by preparation method of data from a DOD LCS study conducted in
2012 (which was published in 2013). If average %R fell between 50-150%, the
preparation technique was designated as adequate. If there was inadequate data in the
study, a - (dash) or S* was used {S* is for analytes listed as having adequate recovery in
previous versions). Method 3545 was added as a preparation technique. Footnote c was
updated with additional information. The key to the analyte list has new definitions for
symbols used in the table.
3. The following analytes were added to the table: atrazine, azobenzene, benzaldehyde,
benzo(e)pyrene, 1,1 '-biphenyl, caprolactam, carbazole, 1,4-dioxane, 1-methylnaphthalene,
perylene, and pyridine. The following names were updated to match the NIST database:
benzo(g,h,i)perylene, 4-nitroquinoline-1-oxide, and 2,4-toluene diisocyanate.
4. Sec. 1.2: Method 3545 was removed from Sec. 1.2 and added to the analyte table in Sec.
I.1 as it is commonly used. Method 3511 was added as an allowable preparation method.
5. Sec. 1.3: Added GC/MS/MS as technology for multi-components.
6. Sec. 1.4: Abbreviations from the analyte table in Sec. 1.1 were moved into subsections of
Sec. 1.4 (new Sees. 1.4.10 through 1.4.17). Additional analytes were added if they were
known to be problematic (Sec. 1.4.7 and 1.4.14). Sec. 1.4.8 was added regarding
adjusting pH prior to water extractions for some analytes. Surrogate compound
suggestions were added for more volatile analytes in Sec. 1.4.10.
7. Sec. 1.5: The section about LLOQ and reference to old Table 2 were removed. Language
was added discussing the use of hydrogen carrier gas and tandem mass spectrometry
instrumentation.
8. Sec. 2.3: Jet separator interface was removed.
9. Sec. 4.2: Added information about blank contamination may not be subtracted from
samples and may require sample qualification.
10. Sec. 5.0: Added reference to new Appendix B for using hydrogen carrier gas.
11. Sec. 6.1.1: Added specific GC inlet types. References to column vendors were removed.
12. Sec. 6.1.3: Changed from scan rate to minimum number of spectra per peak. Added
subsections for MS/MS (Sec. 6.1.3.3) and SIM/CI (Sec. 6.1.3.4).
13. Sec. 7.4.3: Added language regarding expiration dates of standards and when standards
must be discarded.
14. Sec. 7.5: Removed reference to Sec. 11.3.2 for IS criteria and added reference to Sec.
II.4.3 of Method 8000 (IS calibration).
15. Sec. 7.6: Added warning about preparing DFTPP in alternate solvents.
16. Sec. 7.7.1: Added language about minimum number of calibration standards for
regression curve types and low point at or below LLOQ.
17. Sec. 7.7.2: Added paragraph for CCV.
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18. Sec. 7.7.3: Added paragraph about performing ICV with second source.
19. Sec. 7.8: Added reference for additional surrogates. Reworded note about verifying
surrogate solutions.
20. Sec. 7.8.1: Removed note about surrogate requirement from Method 3561.
21. Sec. 7.9: Added recommendation to use full analyte list for LCS spike solution. Added note
about verifying solutions prior to use or for troubleshooting.
22. Sec. 7.11: Added carrier gases to Reagents and Standards section.
23. Sec. 9.3.1: Changed tune verification frequency to just prior to ICAL. Added language
regarding purpose for verification.
24. Sec. 9.3.2: Clarified when the ICV is required.
25. Sec. 9.3.4: Removed paragraph for relative retention time.
26. Sec. 9.5: Significant revisions/additions were made to blank section. Added clarifying
information about concentrations allowed in blanks (1/2 LLOQ), how blank concentration
relates to sample concentration (<1/10) and some guidance for qualifying data.
27. Sec. 9.6.3: Added paragraph requiring use of MB in each batch.
28. Sec. 9.7: Reworded to require use of surrogates.
29. Sec. 9.8: Added language for monitoring of ISs in samples.
30. Sec. 9.9: LLOQ language from Method 8000 was added. Additional information/revisions
made to LLOQ language (e.g., concentration range of 0.5 - 2X added for LLOQ
verification; frequency). Section was added for reporting concentrations below LLOQ.
31. Sec. 11.1: Method 3560 was removed. Method 3511 was added.
32. Sec. 11.2: The reference to derivatization in Method 8041 was removed. Method 3640
was added.
33. Sees. 11.3 & 11.4: Reorganized sections to place all criteria and checks for ICAL (e.g.,
curve calculations and criteria, refitting low point, and ICVs) in Sec. 11.3 and to place all
criteria and checks for CCVs in Sec. 11.4. Redundant information was removed and the
requirements were clarified.
34. Sec. 11.3: Updated GC/MS operating conditions.
35. Sec. 11.3.1.2: Updated note about performing tune verification for SIM/scan. Added note
about instrument performance check for CI or tandem MS analysis.
36. Sec. 11.3.1.3: Added tailing graphic. Added note that degradation and tailing checks are
not needed for limited analyte lists.
37. Sec. 11.3.2: Removed relative time reference for targets compared to IS (0.8-1.2)
38. Sec. 11.3.3: Added note about having adequate sensitivity at LLOQ.
39. Sec. 11.3.4.2: Added language to make minimum RFs in Table 4 guidance only. Added
suggestions for laboratories to establish procedure for checking preparation of standards.
Added a note about analytes with low responses (RF <0.01).
40. Sec. 11.3.5.1: Added note about curve fit when blank contamination is present.
41. Sec. 11.3.5.3: Added criteria for regression curves and RSE. Removed RRT language.
42. Sec. 11.3.6: Clarified language for refitting low ICAL point. Changed criteria for refitting to
±50%. [Moved from 11.4.5.6]
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43. Sec. 11.3.7: Added section about ICV requirements.
44. Sec. 11.3.8: Updated SIM and SRM guidance. [Moved from 11.5.5]
45. Sec. 11.4.1: Decreased DFTPP tune check, tailing, and breakdown frequency from every
12 hours to once prior to ICAL.
46. Sec. 11.4.2: Clarified note to allow the injection time for last ICAL standard as start of 12-
hour clock.
47. Sec. 11.4.3: Clarified that a blank is required after calibration.
48. Sec. 11.4.4: Removed requirement to check min RFs. Added allowance for single CCV
evaluation report using concentration for mixed calibration models.
49. Sec. 11.4.4.2: Added note about monitoring system performance in absence of
degradation and tailing checks.
50. Sec. 11.4.6: Clarified that monitoring of ISs in CCVs is required.
51. Sec. 11.5.4: Expanded dilution target range to include middle of curve.
52. Sec. 11.6.1: Added language requiring the evaluation of the absolute shifts of target
analytes. Added clarifying language for analytes with greater shifts. Revised RRT to be
an alternate method for evaluating RT shifts.
53. Sec. 11.6.1.4: Updated calculations for verifying peak resolution.
54. Sec. 11.6.2: Revised tentative identification interpretation language.
55. Sec. 11.7.5: Added references for performing PCB analysis as individual congeners using
low and high-resolution mass spectrometry and as homolog series.
56. Sec. 11.7.6: Clarified language forTPH (GRO and DRO). Added allowance to use GC/MS
analysis.
57. Sec. 13.0: Removed all references to tables and replaced with references to:
http://www.epa.qov/hw-sw846/validated-test-method-8270e-semivolatile-orqanic-
compounds-gas-chromatographymass-spectrometry.
58. Sec. 14 & 15: Website links to previous ACS documents were updated as the old
documents listed are no longer available. Reference was updated to
http://www.acs.org/content/dam/acsorg/about/governance/committees/chemicalsafety/publ
ications/less-is-better.pdf and http://www.labsafety.org/FreeDocs/WasteMgmt.pdf.
59. Sec. 16.0: Added reference for DOD data. Added references for PCB analysis.
60. Table 1: Added new analytes with suggested ions. Removed Aroclors.
61. Table 2: LLOQ limits removed. Replaced with 2012 DOD study data.
62. Table 3: DFTPP criteria updated with criteria from EPA Method 525.3.
63. Table 4: Min RF table renamed as guidance. Caution added below table. Compounds
were alphabetized by name.
64. Table 5: New analytes added with suggested IS. Compounds were alphabetized by
name.
65. Tables 6 - 22: Removed tables 6 - 22 from 8270D containing performance data. See web
link in Sec. 13.
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Appendix B: Guidance for Using Hydrogen Carrier Gas
B1.0 Guidance for Using Hydrogen Carrier Gas
B1.1 Hydrogen is an acceptable carrier gas to use for this analysis. However, the
following modifications may be needed to make the analysis comparable to helium carrier gas:
B1.1.1 It is recommended that the highest purity hydrogen gas (i.e., 99.999% or
better) be used, such as from a generator or from high purity cylinders that will have
minimal interferences present (e.g., hydrocarbons and water). Use of stainless steel
tubing instead of copper tubing may increase the longevity of gas lines as older copper
lines may become brittle over time with the use of hydrogen. MS ion source materials
should be designed and approved for use with hydrogen. Contact the manufacturer of
the MS to confirm the ion source is compatible.
Additionally, the pressure in the source should be reduced when hydrogen is
used to prevent chemical ionization or other detrimental reactions from occurring. This
may be done by the use of narrower bore columns (0.18 mm ID or smaller), reduction in
the flow to the MS, and/or by the use of internal MS vacuum pumps (turbo pumps) with
greater volumetric or pumping efficiency. Hydrogen may not be a suitable carrier gas for
systems that have internal diffusion pumps.
B1.1.2. Use of hydrogen will clean (scrub) the metal surfaces of the analytical
system of compounds that have adhered to the surface (generally hydrocarbons) and
increase the background presence of these interferences. A bake-out of the system
using high flows of hydrogen may decrease these interferences to a level that would not
interfere with analysis. It is also recommended new filters be installed on gas lines prior
to switching to hydrogen to prevent the scrubbing of impurities from the filters.
B1.1.3 Methylene chloride used in calibration standards and extracts may form
hydrochloric acid (HCI) in the inlet when hydrogen is used as a carrier gas. HCI may
build up overtime, creating active sites in the chromatographic system, and potentially
causing permanent damage to sensitive parts due to corrosion. Using an alternate
solvent such as ethyl acetate to prepare calibration standards should reduce the
formation of HCI. However, this would also require a solvent switch for extracts from any
associated preparation methods, as extracts are required to be in the same final solvent
as calibration standards (>80% the same). Use of the lowest practical inlet temperature
setting (e.g., 225 °C), use of split injections, and/or frequent replacement of inlet liners
may also prevent the formation of HCI if methylene chloride is used. Regular
replacement of inlet liners to mitigate performance issues related to active site and HCI
formation is recommended. Alternate injection techniques may be used as long as the
user can demonstrate adequate perform for their project needs using that introduction
method.
B1.2 Use of hydrogen as the carrier gas may also reduce the responses of target
analytes (i.e., approximately 2 - 5 times) as compared to helium. RF criteria listed in Table 4
were developed using helium carrier gas and are not appropriate for hydrogen carrier gas due
to the reduced response of some analytes. If minimum RFs are used in evaluating the
calibration, the laboratory should develop their own criteria or use published RF from the
instrument manufacturer. Reactivity of target analytes will vary with instrument conditions. As
part of the I DP process, evaluate target analytes for stability under the expected analytical
conditions.
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B1.3 As with any method modification, all QC procedures listed in Sec. 9.0 of this
method should be repeated and passed using hydrogen as the carrier gas prior to the analysis
of samples. This would include the use of alternate solvents for extracts and calibration
standards, if utilized.
B1.4 Because hydrogen gas is flammable, additional safety controls may be necessary
to prevent explosive levels of gas from forming. This may be accomplished by connecting vent
lines from the GC inlet and MS rough pump to exhaust systems in the laboratory and leak
testing all gas line connections. The flow of hydrogen should also be turned off at the source
prior to opening gas lines on the GC and prior to venting the MS (such as when maintenance is
performed). The user should consult additional guidelines for the safe use of hydrogen from the
instrument manufacturer prior to implementing its use.
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