pagel
EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
METHOD #: 525
(EPA-500 Series, Revision 2.1,1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-Solid
Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
1.0 SCOPE AND APPLICATION
1.1 This is a general purpose method that provides procedures for determination
of organic compounds in finished drinking water, raw source water, or
drinking water in any treatment stage. The method is applicable to a wide
range of organic compounds that are efficiently partitioned from the water
sample onto a CIS organic phase chemically bonded to a solid inorganic
matrix, and sufficiently volatile and thermally stable for gas
chromatography. Particulate bound organic matter will not be partitioned,
and more than trace levels of particulates in the water may disrupt the
partitioning process. Single-laboratory accuracy and precision data have
been determined at two concentrations with two instrument systems for the
following compounds:
ANALYTE:
Acenaphthylene
Alachlor
Aldrin
Anthracene
Atrazine
Benz [a] anthracene
Benzo [b] f luoranthene
Benzo [k] f luoranthene
Benzo [a] pyrene
Benzo [g,h, i] perylene
Butylbenzyl Phthalate
Alpha - chlordane
Gamma - chlordane
Trans Nonachlor
2 -Chlorobiphenyl
Chryaene
Dibenz [a,h] anthracene
Di-n-butyl Phthalate
2 , 3-Dichlorobiphenyl
Diethylphthalate
Di (2-ethylhexyl) adipate
Di (2-ethylhexyl) phthalate
Dimethyl Phthalate
Bndrin «
Pluorene
Heptachlor
Heptachlor Epoxide
2, 2 ' , 3, 3 ' , 4, 4 ' , 6 -Heptachlorobiphenyl
Hexachlorobenzene
2,2', 4, 4', 5, 6' -Hexachlorobiphenyl
Hexachlorocyc lopentadiene
Indeno [ l , 2 , 3 , c , d] pyrene
CAS #
208-96-8
15972-60-8
309-00-2
120-12-7
1912-24-9
56-55-3
205-82-3
207-08-9
50-32-8
191-24-2
85-68-7
5103-71-9
5103-74-2
39765-80-5
2051-6.0-7
218-01-9
53-70-3
84-72-2
16605-91-7
84-66-2
103-23-1
117-81-7
131-11-3
72-20-8
86-73-7
76-44-8
1024-57-3
52663-71-5
118-74-1
60145-22-4
77-47-4
193-39-5
MW<1)
152
269
362
178
215
228
252
252
252
276
312
406
406
440
188
228
278
278
222
222
370
390
194
378
166
370
386
392
282
358
270
276
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
Lindane 58-89-9 288
Methoxychior 72-43-5 344
2,2’ ,3,3’ 14,5’ ,6,6’ -Octachiorobiphenyl 40186-71-8 426
2,2’ ,3’,4,6-Pentachlorobiphenyl 60233-25-2 324
Pentachiorophenol 87-86-5 264
Phenanthrene 85-01-8 178
Pyrene 129-00-0 202
Simazine 122-34-9 201
2,2’ ,4,4’-Tetrachlorobiphenyl 2437-79-8 290
Toxaphene Mixture 8001-35-2
2,4, 5-Trichiorobiphenyl 15862-07-4 256
(1) Monoisotopic molecular weight calculated from the atomic
masses of the isotopes with the smallest masses.
INSTRUMENTATION: GC/MS
A laboratory may use this method to identify and measure additional
analytes after the laboratory obtains acceptable (defined in Sect. 10)
accuracy and precision data for each added analyte.
1.2 Method detection limit (MDL) is defined as the statistically calculated
minimum amount that can be measured with 99% confidence that the
reported value is greater than zero (1). The MDL is compound dependent
and is particularly dependent on extraction efficiency and sample matrix.
For the listed analytes, MDLs vary from 0.01 to 15 ug/L. The concentration
calibration range of this method is 0.1 ug/L to 10 ugIL.
2.0 SUMMARY OF METHOD
Organic compound analytes, internal standards, and surrogates are extracted
from a water sample by passing I liter of sample water through a cartridge
containing about I gram of a solid inorganic matrix coated with a
chemically bonded CI 8 organic phase (liquid-solid extraction, LSE). The
organic compounds are eluted from the LSE cartridge with a small quantity
of methylene chloride, and concentrated further by evaporatipn of some of
the solvent. The sample components are separated, identified, and measured
by injecting an aliquot of the concentrated methylene chloride extract into a
high resolution fused silica capillary column of a gas chromatography/mass
spectrometry (GC/MS) system. Compounds elating from the GC column are
identified by comparing their measured mass spectra and retention times to
reference spectra and retention times in a data base. Reference spectra and
retention times for analytes are obtained by the measurement of calibration
standards under the same conditions d ed for samples. The concentration of
each identified component is measured by relating the MS response of the
quantitation ion produced by that compound to the MS response of the
quantitation ion produced by a compound that is used as an internal
standard. Surrogate analytes, whose concentrations are known in eveiy
sample, arc measured with the same internal standard calibration procedure.
3.0 DEFINITIONS
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
3.1 Internal standard -- A pure analyte(s) added to a solution in known
amount(s) and used to measure the relative responses of other method
analytes and surrogates that are components of the same solution. The
internal standard must be an analyte that is not a sample component.
3.2 Surrogate analyte -- A pure analyte(s), which is extremely unlikely to be
found in any sample, and which is added to a sample aliquot in known
amount(s) before extraction and is measured with the same procedures used
to measure other sample components. The purpose of a surrogate analyte is
to monitor method performance with each sample.
3.3 Laboratory duplicates (LDI and LD2) -- Two sample aliquots taken in the
analytical laboratory and analyzed separately with identical procedures.
Analyses of LDI and LD2 give a measure of the precision associated with
laboratory procedures, but not with sample collection, preservation, or
storage procedures.
3.4 Field duplicates (FDI and FD2) -- Two separate samples collected at the
same time and place under identical circumstances and treated exactly the
same throughout field and laboratory procedures. Analyses of FDI and FD2
give a measure of the precision associated with sample collection,
preservation, and storage, as well as with laboratory procedures.
3.5 Laboratory reagent blank (LRB) -- An aliquot of reagent water that is treated
exactly as a sample including exposure to all glassware, equipment,
solvents, reagents, internal standards, and surrogates that are used with other
samples. The LRB is used to determine if method analytes or other
interferences are present in the laboratory environment, the reagents, or the
apparatus.
3.6 Field reagent blank (FRB) -- Reagent water placed in a sample container in
the laboratory and treated as a sample in all respects, including exposure to
sampling site conditions, storage, preservation, and all analytical
procedures. The purpose of the FRB is to determine if method analytes or
other interferences are present in the field environment.
3.7 Laboratory performance check solution (LPC) -- A solution of method
analytes, surrogate compounds, and internal standards used to evaluate the
performance of the instrument system with respect to a defined set of
method criteria.
3.8 Laboratory fortified blank (LFB) -- An aliquot of reagent water to which
known quantities of the method analytes are added in the laboratory. The
LFB is analyzed exactly like a sample and its purpose is to determine
whether the methodology is in control, and whether the laboratory is
capable of making accurate and precise measurements at the required
method detection limit.
3.9 Laboratory fortified sample matrix (LFM) — An aliquot of an environmental
sample to which known quantities of the method analytes are added in the
laboratory. The LFM is analyzed exactly like a sample, and its purpose is to
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
- Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
determine whether the sample matrix contributes bias to the analytical
results. The background concentrations of the analytes in the sample matrix
must be determined in a separate aliquot and the measured values in the
LFM corrected for background concentrations.
3.10 Stock standard solution --A concentrated solution containing a single
certified standard that is a method analyte, or a concentrated solution of a
single analyte prepared in the laboratory with an assayed reference
compound. Stock standard solutions are used to prepare primary dilution
standards.
3.11 Primary dilution standard solution -- A solution of several analytes prepared
in the laboratory from stock standard solutions and diluted as needed to
prepare calibration solutions and other needed analyte solutions.
3.12 Calibration standard (CAL) -- a solution prepared from the primary dilution
standard solution and stock standard solutions of the internal standards and
surrogate analytes. The CAL solutions are used to calibrate the instrument
response with respect to analyte concentration.
3.13 Quality control sample (QCS) -- a sample matrix containing method
analytes or a solution of method analytes in a water miscible solvent which
is used to fortify reagent water or environmental samples. The QCS is
obtained from a source external to the laboratory, and is used to check
laboratory performance with externally prepared test materials.
4.0 INTERFERENCES
4.1 During analysis, major contaminant sources are reagents and liquid-solid
extraction columns. Analyses of field and laboratory reagent blanks provide
information about the presence of contaminants.
4.2 Interfering contamination may occur when a sample containing low
concentrations of compounds is analyzed immediately after a sample
contnining relatively high concentrations of compounds. Syringes and
splitless injection port liners must be cleaned carefully or replaced as
needed. After analysis of a sample containing high concentrations of
compounds, a laboratory reagent blank should be analyzed to ensure that
accurate values are obtained for the next sample.
5.0 SAFETY
5.1 The toxicity or carcinogenicity of chemicals used in this method has not
been precisely defined; each chemical 4 should be treated as a potential health
hazard, and exposure to these chemicals should be minimized. Each
laboratory is responsible for maintaining awareness of OSHA regulations
regarding safe handling of chemicals used in this method. Additional
references to laboratory safety are cited (2-4).
5.2 Some method analytes have been tentatively classified as known or
suspected human or mammalian carcinogens. Pure standard materials and
stock standard solutions of these compounds should be handled with
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
suitable protection to skin, eyes, etc.
6.0 Apparatus and Equipment
6.1 All glassware must be meticulously cleaned. This may be accomplished by
washing with detergent and water, rinsing with water, distilled water, or
solvents, air-drying, and heating (where appropriate) in an oven. Volumetric
glassware is never heated.
6.2 Sample containers. 1-liter or 1-quart amber glass bottles fitted with a Teflon-
lined screw cap. (Bottles in which high purity solvents were received can be
used as sample containers without additional cleaning if they have been
handled carefully to avoid contamination during use and after use of onginal
contents.)
6.3 Separatory funnels. 2-liter and 100-mL with a Teflon stopcock.
6.4 Liquid chromatography column reservoirs. Pear-shaped 100- or 125 -rnL
vessels without a stopcock but with a ground glass outlet joint sized to fit
the liquid-solid extraction column. (Lab Glass, Inc. part no. ML-700-706S,
with a 24/40 top outer joint and a 14/3 5 bottom inner joint, or equivalent). A
14/35 outlet joint fits some commercial cartridges.
6.5 Syringe needles. No. 18 or 20 stainless steel.
6.6 Vacuum flasks. 1- or 2-liter with solid rubber stoppers.
6.7 Volumetric flasks, various sizes.
6.8 Laboratory or aspirator vacuum system. Sufficient capacity to maintain a
slight vacuum of 13 cm (5 in.) of mercury in the vacuum flask.
6.9 Micro syringes, various sizes.
6.10 Vials. Various sizes of amber vials with Teflon-lined screw caps.
6.11 Drying column. Approximately 1.2 cm x 40 cm with 10 mL graduated
collection vial.
6.12 Analytical balance. Capable of weighing 0.0001 g accurately.
6.13 Fused silica capillary gas chromatography column. Any capillary column
that provides adequate resolution, capacity, accuracy, and precision (Sect.
10) can be used. A 30 mX 0.25 mm id fused silica capillary column coated
with a 0.25 urn bonded film of polyphenyl methylsilicone is recommended
(i&W DB-5 or equivalent).
6.14 Gas chroniatograph/mass spectrometer/data
(GC/MSIDS)
6.14.1 The GC must be capable of temperature progiiir’iming and be
equipped for splitlesslsplit injection. The injection tube liner should
be quartz and about 3 mmin diameter. The injection system must
not allow the analytes to contact hot stainless steel or other metal
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I Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds in Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
surfaces that promote decomposition.
6.14.2 The GC/MS interface should allow the capillary column or transfer
line exit to be placed within a few mm of the ion source. Other
interfaces, for example the open split interface, are acceptable as
long as the system has adequate sensitivity (see Sect. 9 for
calibration requirements).
6.14.3 The mass spectrometer must be capable of electron ionization at a
nominal electron energy of 70 eV. The spectrometer must be
capable of scanning from 45 to 450 amu with a complete scan cycle
time (including scan overhead) of 1.5 sec or less. (Scan cycle time
= Total MS data acquisition time in sec divided by number of scans
in the chromatogram). The spectrometer must produce a mass
spectrum that meets all criteria in Table I when 5 ng or less of
DFTPP is introduced into the GC. An average spectrum across the
DFTPP GC peak may be used to test instrument performance.
6.14.4 An interfaced data system is required to acquire, store, reduce, and
output mass spectral data. The computer software must have the
capability of processing stored GC/MS data by recognizing a GC
peak within any given retention time window, comparing the mass
spectra from the (IC peak with spectral data in a user-created data
base, and generating a list of tentatively identified compounds with
their retention times and scan numbers. The software must also
allow integration of the ion abundance of any specific ion between
specified time or scan number limits, calculation of response factors
as defined in Sect. 9.2.6 (or construction of a second or third order
regression calibration curve), calculation of response factor
statistics (mean and standard deviation), and calculation of
concentrations of analytes using either the calibration curve or the
equation in Sect. 12.
7.0 REAGENTS AND CONSUMABLE MATERIALS
7.1 Helium carrier gas, as contaminant free as possible.
7.2 Liquid-solid extraction (LSE) cartridges. Cartridges are inert nonleaching
plastic, for example polypropylene, or glass, and must not contain
plasticizers, such as phthalate esters or adipates, that leach into inethylene
chloride. The cartridges are packed with about 1 gram of silica, or other
inert inorganic support, whose surface is modified by chemically bonded
octadecyl (C18) groups. The packing must have a narrow size distribution
and must not leach organic compounds into methylene chloride. One liter of
water should pass through the cartridge in about 2 hrs with the assistance of
a slight vacuum of about 13 cm (5 in.) of mercury. Sect. 10 provides criteria
for acceptable LSE cartridges which are available from several commercial
suppliers.
7.3 Solvents
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
7.3.1 Methylene chloride, acetone, toluene and methanol. High purity
pesticide quality or equivalent.
7.3.2 Reagent water. Water in which an interferent is not observed at the
method detection limit of the compound of interest. Prepare reagent
water by passing tap water through a filter bed containing about 0.5 kg
of activated carbon or by using a water purification system. Store in
clean, narrow-mouth bottles with Teflon-lined septa and screw caps.
7.4 Hydrochloric acid. 6N.
7.5 Sodium sulfate, anhydrous. (Soxhlet extracted with methylene chloride for a
minimum of 4 brs.)
7.6 Stock standard solutions. Individual solutions of analytes, surrogates, and
internal standards may be purchased as certified solutions or prepared from
pure materials. To prepare, add 10 mg (weighed on an analytical balance to
0.1 mg) of the pure material to 1.9 mL of methanol or acetone in a 2-niL
volumetric flask, dilute to the mark, and transfer the solution to an amber
glass vial. If the analytical standard is available only in quantities smaller
than 10 nig, reduce the volume of solvent accordingly. Some polycyclic
aromatic hydrocarbons are not soluble in methanol or acetone, and their
stock standard solutions are prepared in toluene. Methylene chloride should
be avoided as a solvent for standards because its high vapor pressure leads
to rapid evaporation and concentration changes. Methanol and acetone are
not as volatile as methylene chloride, but their solutions must also be
handled with care to avoid evaporation. Compounds 10, 11, and 35 in Table
2 are soluble in acetone. Compounds 12, 13, and 20 in Table 2 are soluble in
toluene. If compound purity is certified by the supplier at >96%, the
weighed amount can be used without correction to calculate the
concentration of the solution (5 ug/uL). Store the amber vials in a dark cool
place.
7.7 Primary dilution standard solution. The stock standard solutions are used to
prepare a primary dilution standard solution that contains zmjltiple analytes.
The recommended solvent for this dilution is acetone. Aliquots of each of
the stock standard solutions are combined to produce the primary dilution in
which the concentration of the analytes is at least equal to the concentration
of the most concentrated calibration solution, that is, 10 ng/uL. Store the
primary dilution standard solution in an amber vial in a dark cool place, and
check frequently for signs of deterioration or evaporation, especially just
before preparing calibration solutions.
7.8 Fortification solution of internal standards and surrogates. Prepare a solution
of acenaphthene-D10, phenanthrene-D10, chrysene-D12, and perylene-D12
in methanol or acetone at a concentration of 500 ug/mL of each. This
solution is used in the preparation of the calibration solutions. Dilute a
portion of this solution by 10 to 50 ug/mL and use this solution to fortify the
actual water samples (see Sect. 11.2). Other surrogates, for example,
caffeine-15N2 and pyrene-Dl0 may be included in this solution as needed (a
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TiTLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
100-uL aliquot of this 50 ug/mL solution added to 1 liter of water gives a
concentration of 5 ug/L of each internal standard or surrogate). Store this
solution in an amber vial in a dark cool place.
7.9 MS performance check solution. Prepare a 5 ng/uL solution of DFTPP in
methylene chloride. Store this solution in an amber vial in a dark cool place.
7.10 Calibration solutions (CALl through CAL6). Prepare a series of six
concentration calibration solutions in acetone which contain all analytes
except pentachiorophenol and toxaphene at concentrations of 10, 5, 2, 1,
0.5, and 0.1 ng/uL, with a constant concentration of 5 ng/uL of each
internal standard and surrogate in each CAL solution. CALl through
CAL6 are prepared by combining appropriate aliquots of the primary
dilution standard solution (7.7) and the fortification solution (500 ug/mL)
of internal standards and surrogates (7.8). Pentachiorophenol is included in
this solution at a concentration four times the other analytes. Toxaphene
CAL solutions should be prepared as separate solutions at concentrations
of 250, 200, 100, 50, 25, and 10 ng/uL. Store these solutions in amber vials
in a dark cool place. Check these solutions regularly for signs of
deterioration, for example, the appearance of anthraquinone from the
oxidation of anthracene.
7.11 Reducing agents. Sodium sulfite or sodium arsenite. Sodium thiosulfate is
not recommended as it may produce a residue of elemental sulfur that can
interfere with some analytes. -
7.12 Fortification solution for optional recovery standard. Prepare a solution of
terphenyl-D14 in methylene chloride at a concentration of 500 ugfmL. An
atiquot of this solution may be added (optional) to the extract of the LSE
cartridge to check on the recovery of the internal standards in the extraction
process.
8.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
8.1 Sample collection. When sampling from a water tap, open the tap and allow
the system to flush until the water temperature has stabilized(usually about
2-5 mm). Adjust the flow to about 500 mL/min and collect samples from the
flowing stream. Keep samples sealed from collection time until analysis.
When sampling from an open body of water, fill the sample container with
water from a representative area. Sampling equipment, including automatic
samplers, must be free of plastic tubing, gaskets, and other parts that may
leach analytes into water. Automatic samplers that composite samples over
time must use refrigerated glass sample containers.
8.2 Sample dechlorination and preservation. All samples should be iced or
refrigerated at 4 °C from the time of collection until extraction. Residual
chlorine should be reduced at the sampling site by addition of a reducing
agent. Add 40-50 mg of sodium sulfite or sodium arsenite (these may be
added as solids with stirring until dissolved) to each liter of water.
Hydrochloric acid should be used at the sampling site to retard the
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds in Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
microbiological degradation of some analytes in unchiorinated water. The
sample pH is adjusted to <2 with 6 N hydrochloric acid. This is the same pH
used in the extraction, and is required to support the recovery of
pentachlorophenoi
8.3 Holding time. Samples must be extracted within 7 days and the extracts
analyzed within 30 days of sample collection.
8.4 Field blanks.
8.4.1 Processing of a field reagent blank (FRB) is recommended along with
each sample set, which is composed of the samples collected from the
same general sample site at approximately the same time. At the
laboratory, fill a sample container with reagent water, seal, and ship to
the sampling site along with the empty sample containers. Return the
FRB to the laboratory with filled sample bottles.
8.4.2 When hydrochloric acid is added to samples, use the same procedures
to add the same amount to the FRB.
9.0 CALIBRATION
9.1 Demonstration and documentation of acceptable initial calibration is
required before any samples are analyzed and is required intermittently
throughout sample analysis as dictated by results of continuing calibration
checks. After initial calibration is successful, a continuing calibration check
is required at the beginning of each 8 hr. period during which analyses are
performed. Additional periodic calibration checks are good laboratory
practice.
9.2 Initial calibration
9.2.1 Calibrate the mass and abundance scales of the MS with calibration
compounds and procedures prescribed by the manufacturer with any
modifications necessary to meet the requirements in Sect. 9.2.2.
9.2.2 Inject into the GC a 1-uL aliquot of the 5 ng/uL DFTP solution and
acquire a mass spectrum that includes data for m/z 45-450. Use GC
conditions that produce a narrow (at least five scans per peak)
symmetrical peak. If the spectrum does not meet all criteria (Table 1),
the MS must be retuned and adjusted to meet all criteria before
proceeding with calibration. An average spectrum across the GC peak
may be used to evaluate the performance of the system.
9.2.3 Inject a 1-uL aliquot of a medium concentration calibration solution,
for exnmple 0.5-2 ug/L, and acquire and store data from rn/z 45-450
with a total cycle time (including scan overhead time) of 1.5 sec or
less. Cycle time should be adjusted to measure at least five or more
spectra during the elution of each OC peak.
9.2.3.1 Multi-ramp temperature program GC conditions. Adjust the
helium carrier gas flow rate to about 33 cm/sec. Inject at 45 .C
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TiTLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
and hold in splitless mode for 1 mm. Heat rapidly to 130 C. At
3 mm start the temperature program: 130-180 C at 12-/mm;
180-240 C at 7-/mm; 240-320 C at I 2-/mm. Start data
acquisition at 5 mm.
9.2.3.2 Single ramp linear temperature program. Adjust the helium
carrier gas flow rate to about 33 cm/sec. inject at 40 °C and
hold in splitless mode for 1 mm. Heat rapidly to 160 C. At 3
mm start the temperature program: 160-320 C at 6-/mm; hold
at 320- for 2 mm. Start data acquisition at 3 rein.
9.2.4 Performance criteria for the medium calibration. Examine the stored
GC/MS data with the data system software. Figure 1 shows an
acceptable total ion chromatogram.
9.2.4.1 GC performance. Anthracene and phenanthrene should be
separated by baseline. Benz [ a]anthracene and chrysene should
be separated by a valley whose height is less than 25% of the
average peak height of these two compounds. If the valley
between benz [ a}anthracene and chrysene exceeds 25%, the GC
column requires maintenance. See Sect. 9.3.6.
9.2.4.2 MS sensitivity. The GC/MS/DS peak identification software
should be able to recognize a OC peak in the appropriate
retention time window for each of the compounds in
calibration solution, and make correct tentative identifications.
If fewer than 99% of the compounds are recognized, system
maintenance is required. See Sect. 9.3.6.
9.2.4.3 Lack of degradation of endrin. Examine a plot of the
abundance of m/z 67 in the region of 1.05-1.3 of’ the retention
time of endrin. This is the region of elution of endrin
aldehyde, a product of the thermal isomerization of endrin.
Confirm that the abundance of m/z 67 at the retention time of
endrin aldehyde is <10% of the abundance of /z 67 produced
by endrin. if more than 10% endrin aldehyde is observed,
system maintenance is required to correct the problem. See
Sect. 9.3.6.
9.2.5 If all performance criteria are met, inject a 1-uL aliquot of each of the
other CAL solutions using the same GC/MS conditions.
9.2.6 Calculate a response factor (RF) for each analyte and surrogate for
each CAL solution using the internal standard whose retention time is
nearest the retention time of the analyte or surrogate. Table 2 contains
suggested internal standards for each analyte and surrogate, and
quantitation ions for all compounds. This calculation is supported in
acceptable GC/MS data system software (Sect. 6.14.4), and many
other software programs. RF is a unitless number, but units used to
express quantities of analyte and internal standard must be equivalent.
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
RF= [ (A(x))(Q(is))]/((A(is))(Q(x))]
where:
A(x) = integrated abundance of the quantitation ion
of the analyte.
A(is) = integrated abundance of the quantitation ion
internal standard.
Q(x) = quantity of analyte injected in ng or
concentration units.
Q(is) = quantity of internal standard injected in ng
or concentration units.
9.2.6.1 For each analyte and surrogate, calculate the mean RF from the
analyses of the six CAL solutions. Calculate the standard
deviation (SD) and the relative standard deviation (RSD) from
each mean: RSD = 100 (5 DIM). if the RSD of any analyte or
surrogate mean RF exceeds 30%, either analyze additional
aliquots of appropriate CAL solutions to obtain an acceptable
RSD of RFs over the entire concentration range, or take action
to improve GC/MS performance. See Sect. 9.2.7.
9.2.7 As an alternative to calculating mean response factors and applying
the RSD test, use the GC/MS data system software or other available
software to generate a linear, second, or third order regression
calibration curve.
9.3 Continuing calibration check. Verify the MS tune and initial calibration at
the beginning of each 8 hr. work shift during which analyses are performed
using the following procedure.
9.3.1 Inject a 1-uL aliquot of the 5ng/uL DFTPP solution and acquire a mass
spectrum that includes data for m/z 45-450. If the spectrum does not
meet all criteria (Table 1), the MS must be retuned and adjusted to
meet all criteria before proceeding with the continuing alibration
check.
9.3.2 Inject a 1-uL aliquot of a medium concentration calibration solution
and analyze with the same conditions used during the initial
calibration.
9.3.3 Demonstrate acceptable performance for the criteria shown in Sect.
9.2.4.
9.3.4 Determine that the absolute areas of the quantitation ions of the
internal standards and surrogate(s) have not decreased by more than
30-/0 from the areas measured in the most recent continuing
calibration check, or by more than 50% from the areas measured
during initial calibration, if these areas have decreased by more than
these amounts, adjustments must be made to restore system sensitivity.
These adjustments may require cleaning of the MS ion source, or other
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I Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
maintenance as indicated in Sect. 9.3.6, and recalibration. Control
charts are useful aids in documenting system sensitivity changes.
9.3.5 Calculate the RF for each analyte and surrogate from the data
measured in the continuing calibration check. The RF for each analyte
and surrogate must be Within 30% of the mean value measured in the
initial calibration. Alternatively, if a second or third order regression is
used, the point from the continuing calibration check for each analyte
and surrogate must fall, within the analyst’s judgement, on the curve
from the initial calibration. If these conditions do not exist, remedial
action must be taken which may require reinitial calibration.
9.3.6 Some possible remedial actions. Major maintenance such as cleaning
an ion source, cleaning quadrupole rods, etc. require returning to the
initial calibration step.
9.3.6.1 Check and adjust GC and/or MS operating conditions; check
the MS resolution,. and calibrate the mass scale.
9.3.6.2 Clean or replace the splitless injection liner; silanize a new
injection liner.
9.3.6.3 Flush the CC column with solvent according to
manufacturer’s instructions.
9.3.6.4 Break off a short portion (about 1 meter) of the column from
the end near the injector; or replace CC column. This action
will cause a change in retention times.
9.3.6.5 Prepare fresh CAL solutions, and repeat the initial calibration
step.
9.3.6.6 Clean the MS ion source and rods (if a quadrupole).
9.3.6.7 Replace any components that allow analytes to come into
contact with hot metal surfaces.
9.3.6.8 Replace the MS electron multiplier, or any other faulty
components.
10.0 QUALITY CONTROL
10.1 Quality control (QC) requirements are the initial demonstration of
laboratory capability followed by regular analyses of laboratory reagent
birniks, laboratory fortified blanks, and laboratory fortified matrix samples.
The laboratory must maintain records to document the quality of the data
generated. Additional quality control practices are recommended.
10.2 Initial demonstration of low system background and acceptable particle size
and packing. Before any samples are analyzed, or any time a new supply of
cartridges is received from a supplier, it must be demonstrated that a
laboratory reagent blank (LRB) is reasonably free of contamination that
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
would prevent the determination of any analyte of concern. In this same
experiment, it must be demonstrated that the particle size and packing of the
LSE cartridge are acceptable. Consistent flow rate is an indication of
acceptable particle size distribution and packing.
10.2.1 A major source of potential contamination is the liquid-solid
extraction (LSE) cartridges which very likely will contain phthalate
esters, silicon compounds, and other contaminants that could prevent
the determination of method analytes (5). Generally, phthalate esters
will be leached from the cartridges into methylene chloride and
produce a variable background that is equivalent to <2 ug/L in the
water sample. If the background contamination is sufficient to
prevent accurate and precise analyses, the condition must be
corrected before proceeding with the initial demonstration. Figure 2
shows unacceptable background contamination from a poor quality
commercial LSE cartridge. The background contamination is the
large broad peak, and the small peaks are method analyte present at a
concentration equivalent to 2 ug/L. Several sources of LSE
cartridges may be evaluated before an acceptable supply is
identified.
10.2.2 Other sources of background contamination are solvents, reagents,
and glassware. Background contamination must be reduced to an
acceptable level before proceeding with the next section. In general,
background from method analytes should be below the method
detection limit.
10.2.3 One liter of water should pass through the cartridge in about 2 hrs
with a partial vacuum of about 13 cm(5 in.) of mercury. The
extraction time should not vary unreasonably among LSE cartridges.
10.3 Initial demonstration of laboratory accuracy and precision. Analyze four to
seven replicates of a laboratory fortified blank containing each analyte of
concern at a concentration in the range of 2-5 ug/L (see regulations and
maximum contaminant levels for guidance on appropriate concentrations).
10.3.1 Prepare each replicate by adding an appropriate aliquot of the
primary dilution standard solution, or another certified quality
control sample, to reagent water. Analyze each replicate according to
the procedures described in Sect. 11 and on a schedule that results in
the analyses of all replicates over a period of several days.
10.3.2 Calculate the measured concen 1ralion of each analyte in each
replicate, the mean concentration of each analyte in all replicates,
and mean accuracy (as mean percentage of true value) for each
analyte, and the precision (as relative standard deviation, RSD) of
the measurements for each analyte. Calculate the MDL of each
analyte using the procedures described in Sect. 13.1.2(1).
10.3.3 For each analyte and surrogate, the mean accuracy, expressed as a
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I Method 525 (EPA -500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds in Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
percentage of the true value, should be 70-130% and the RSD should
be <30%. Some analytes, particularly the polycyclic aromatic
hydrocarbons with molecular weights >250, are measured at
concentrations below 2 ug/L, with a mean accuracy of 35-130% of
true value. The MDLs should be sufficient to detect analytes at the
regulatory levels, if these criteria are not met for an analyte, take
remedial action and repeat the measurements for that analyte to
demonstrate acceptable performance before samples are analyzed.
10.3.4 Develop and maintain a system of control charts to plot the precision
and accuracy of analyte and surrogate measurements as a function of
time. Charting of surrogate recoveries is an especially valuable
activity since these are present in every sample and the analytical
results will form a significant record of data quality.
10.4 Monitor the integrated areas of the quantitation ions of the internal
standards and surrogates in continuing calibration checks (see Sect. 9.3.4).
in laboratory fortified blanks or samples, the mtegrated areas of internal
standards and surrogates will not be constant because the volume of the
extract will vary (and is difficult to keep constant). But the ratios of the
areas should be reasonably constant in laboratory fortified blanks and
samples. The addition of 10 uL of the recovery standard, terphenyl-D14
(500 ug/mL), to the extract is optional, and may be used to monitor the
recovery of internal standards and surrogates in laboratory fortified blanks
and samples. Internal standard recovery should be in excess of 70%.
10.5 Laboratory reagent bbinkc. With each batch of samples processed as a
group within a work shift analyze a laboratory reagent blank to determine
the background system contamination. Any time a new batch of LSE
cartridges is received, or new supplies of other reagents are used, repeat the
demonstration of low background described in 10.2.
10.6 With each batch of samples processed as a group within a work shift,
analyze a single laboratory fortified blank (LFB) containing each analyte of
concern at a concentration as determined in 10.3. If more than 20 samples
are included in a batch, analyze a LFB for every 20 samples. Use the
procedures described in 10.3.3 to evaluate the accuracy of the
measurements, and to estimate whether the method detection limits can be
obtained. If acceptable accuracy and method detection limits cannot be
achieved, the problem must be located and corrected before further samples
are analyzed. Add these results to the on-going control charts to document
data quality.
10.7 Determine that the sample matrix does not contain materials that adversely
affect method performance. This is accomplished by analyzing replicates of
laboratory fortified matrix samples and ascertaining that the precision,
accuracy, and method detection limits of analytes are in the same range as
obtained with laboratory fortified blanks. If a variety of different sample
matrices are analyzed regularly, for example, drinking water from
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
groundwater and surface water sources, matrix independence should be
established for each. A laboratory fortified sample matrix should be
analyzed for every 20 samples processed in the same batch.
10.8 With each set of field samples a field reagent blank (FRB) should be
analyzed. The results of these analyses will help define contamination
resulting from field sampling and transportation activities.
10.9 At least quarterly, replicates of laboratory fortified blanks should be
analyzed to determine the precision of the laboratory measurements. Add
these results to the on-going control charts to document data quality (as in
Sect. 10.3).
10.10 At least quarterly, analyze a quality control sample from an external
source. If measured analyte concentrations are not of acceptable accuracy
(Sect. 10.3.3), check the entire analytical procedure to locate and correct
the problem source.
10.1 1 Numerous other quality control measures are incorporated into other parts
of this procedure, and serve to alert the analyst to potential problems.
11.0 PROCEDURE
11.1 Setup the extraction apparatus shown in Figure 3A. The reservoir is not
required, but recommended for convenient operation. Water drains from
the reservoir through the LSE cartridge and into a syringe needle which is
inserted through a rubber stopper into the suction flask. A slight vacuum of
13 cm (5 in.) of mercury is used during all operations with the apparatus.
The pressure used is critical as a vacuum> than 13 cm may result in poor
precision. About 2 hrs is required to draw a liter of water through the
system.
11.2 Pour the water sample into the 2-L separatory funnel with the stopcock
closed. Residual chlorine should not be present as a reducing agent should
have been added at the time of sampling. Also the pH of the sample should
be about 2. If residual chlorine is present and/or the pH is >2, the sample
may be invalid. Add a 100-uL aliquot of the fortification solution (50
ug/mL) for internal standards and surrogates, and mix immediately until
homogeneous. The concentration of these compounds in the water should
be 5 ug/L.
11.3 Flush each cartridge with two 10 mL aliquots of methylene chloride,
followed by two 10 mL aliquots of methanol, letting the cartridge drain dry
after each flush. These solvent flushe’s may be accomplished by adding the
solvents directly to the solvent reservoir in Figure 3A. Add 10 mL of
reagent water to the solvent reservoir, but before the reagent water level
drops below the top edge of the packing in the LSE cartridge, open the
stopcock of the separator)’ funnel and begin adding sample water to the
solvent reservoir. Close the stopcock when an adequate amount of sample
is in the reservoir.
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
11.4 Periodically open the stopcock and dram a portion of the sample water into
the solvent reservoir. The water sample will dram into the cartridge, and
from the exit into the suction flask. Maintain the packing material in the
cartridge immersed in water at all times. After all of the sample has passed
through the LSE cartridge, wash the separator)’ funnel and cartridge with
10 mL of reagent water, and draw air through the cartridge for 10 mm.
11.5 Transfer the 125-mL solvent reservoir and LSE cartridge (from Figure 3A)
to the elution apparatus (Figure 3B). The same 125-mL solvent reservoir is
used for both apparatus. Wash the 2-liter separatoly funnel with 5 mL of
methylene chloride and collect the washings. Close the stopcock on the
100-mL separatory funnel of the elution apparatus, add the washings to the
reservoir and enough additional methylene chloride to bring the volume
back up to 5 mL and elute the LSE cartridge. Elute the LSE cartridge with
an additional 5 mL of methylene chloride (10-mi. total). A small amount of
nitrogen positive pressure may be used to elute the cartridge. Small
amounts of residual water from the LSE cartridge will form an immiscible
layer with the methylene chloride in the 100-mL separatory funnel. Open
the stopcock and allow the methylene chloride to pass through the drying
column packed with anhydrous sodium sulfate (1-in) and into the
collection vial. Do not allow the water layer to enter the drying column.
Remove the 100 mL separatory funnel and wash the drying column with 2
mL of methylene chloride. Add this to the extract. Concentrate the extract
to 1 mL under a gentle stream of nitrogen. If desired, gently warm the
extract in a water bath to evaporate to between 0.5 - 1.0 mL (without gas
flow). Do not concentrate the extract to less than 0.5 mL (or dryness) as
this will result in losses of analytes. if desired, add an aliquot of the
recovery standard to the concentrated extract to check the recovery of the
internal standards (see Sect. 10.4).
11.6 Analyze a 1-2 uL aliquot with the GC/MS system under the same
conditions used for the initial and continuing calibrations (Sect. 9.2.3).
11.7 At the conclusion of data acquisition, use the same software that was used
in the calibration procedure to tentatively identify peaks in retention time
windows of interest. Use the data system software to examine the ion
abundances of components of the chromatogram. If any ion abundance
exceeds the system working range, dilute the sample aliquot and analyze
the diluted aliquot.
11.8 Identification of analytes. Identify a sample component by comparison of
its mass spectrum (after background subtraction) to a reference spectrum in
the user-created data base. The GC retention time of the sample component
should be within 10 sec of the time observed for that same compound when
a calibration solution was analyzed.
11.8.1 In general, all ions that are present above 10% relative abundance in
the mass spectnlm of the standard should be present in the mass
spectrum of the sample component and should agree within absolute
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
20%. For example, if an ion has a relative abundance of 30% in the
standard spectrum, its abundance in the sample spectrum should be in
the range of 10 to 50%. Some ions, particularly the molecular ion, are
of special importance, and should be evaluated even if they are below
10% relative abundance.
11.8.2 Identification is hampered when sample components are not resolved
chromatographically and produce mass spectra containing ions
contributed by more than one analyte. When GC peaks obviously
represent more than one sample component (i.e., broadened peak
with shoulder(s) or valley between two or more maxima), appropriate
analyte spectra and background spectra can be selected by examining
plots of characteristic ions for tentatively identified components.
When analytes coelute (i.e., only one GC peak is apparent), the
identification criteria can be met but each analyte spectrum will
contain extraneous ions contributed by the coeluting compound.
11.8.3 Structural isomers that produce very similar mass spectra can be
explicitly identified only if they have sufficiently different GC
retention times. See Sect. 9.2.4.1. Acceptable resolution is achieved if
the height of the valley between two isomer peaks is less than 25% of
the average height of the two peak heights. Otherwise, structural
isomers are identified as isomeric pairs. Benzo [ b] and
benzo [ k]fluoranthene are measured as an isomeric pair.
11.8.4 Phthalate esters and other background components appear in variable
quantities in laboratory and field reagent blanks, and generally cannot
be accurately measured at levels below about 2 ug/L. Subtraction of
the concentration in the blank from the concentration in the sample at
or below the 2 ug/L level is not recommended because the
concentration of the background in the blank is highly variable.
12.0 CALCULATIONS
12.1 Complete chromatographic resolution is not necessary for accurate and
precise measurements of analyte concentrations if unique ions with adequate
intensities are available for quanlitation. For example, although two listed
analytes, dibenz [ a,h]anthracene and indeno [ 1,2,3,c,d]pyrene, were not
resolved with the OC conditions used, and produced mass spectra
containing common ions, concentrations (Tables 3-6) were calculated by
measuring appropriate characteristic ions.
12.1.1 Calculate analyte and surrogate concentrations.
C(x) ((A(x)) (Q(is))]/(A(is)) RF. V
where:
C(x)= concentration of analyte or surrogate in ugfL
in the water sample.
A(x)= integrated abundance of the quantitation ion
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TiTLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillaty Column Gas Chromatography/Mass Spectrometry
of the analyte in the sample.
A(is) integrated abundance of the quantitation ion
of the internal standard in the sample.
Q(is)= total quantity (in micrograms) of internal
standard added to the water sample.
V = original water sample volume in liters.
RF = mean response factor of analyte from the
initial calibration.
12.1.2 Alternatively, use the GC/MS system software or other available
proven software to compute the concentrations of the analytes and
surrogates from the second or third order regression curves.
12.1.3 Calculations should utilize all available digits of precision, but final
reported concentrations should be rounded to an appropriate number
of significant figures (one digit of uncertainty). Experience indicates
that three significant figures may be used for concentrations above
99 ugIL, two significant figures for concentrations between 1-99
ug/L, and one significant figure for lower concentrations.
13.0 METHOD PERFORMANCE
13.1 Single laboratory accuracy and precision data (Tables 3-7) for each listed
analyte was obtained at two concentrations with the same extracts analyzed
on two different instrument systems. Seven 1-liter aliquots of reagent water
containing 2 ugIL of each analyte, and five to seven 1-liter aliquots of
reagent water containing 0.2 ug/L of each analyte were analyzed with this
procedure.
13.1.2 With these data, method detection limits (MDL) were calculated
using the formula:
S t(n-l,l-aipha = 0.99)
where:
t(n-l,l-alpha 0.99) = Student’s t
99% confidence level with n-i
freedom
n = number of replicates
S = standard deviation of replicate
13.2 Problem compounds
value for the
deg ees of
analyses.
13.2.1 The common phthalate and adipate esters (compounds 14, 21, and
23-26), which are widely used commercially, appear in variable
quantities in laboratory and field reagent blanks, and generally
cannot be accurately or precisely measured at levels below about 2
ug/L. Subtraction of the concentration in the blank from the
concentration in the sample at or below the 2 ug/L level is not
recommended because the concentrations of the background in
blanks is highly variable.
13.2.2 Some polycyclic aromatic hydrocarbons are rapidly oxidized and/or
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TiTLE: Determination Of Organic Compounds in Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
chlorinated in water containing residual chlorine. Therefore residual
chlorine must be reduced before analysis.
13.2.3 In water free of residual chlorine, some polycyclic aromatic
hydrocarbons (for example, compounds 9, 12, 13, 20, and 35) are
not accurately measured because of low recoveries in the extraction
process.
13.2.4 Pentachiorophenol No. 40 and hexachlorocyclopentadiene No. 34
may not be accurately measured. Pentachlorophenol is a strong acid
and elutes as a broad weak peak. Hexachiorocyclopentadiene is
susceptible to photochemical and thermal decomposition.
14.0 REFERENCES
1. Glaser, J. A., D. L. Foerst, G. D. McKee, S. A. Quave, and W. L. Budde,
“Trace Analyses for Wastewaters,” Environ. Sci, Technol. 198115, 1426-
1435.
2. “Carcinogens - Working With Carcinogens,” Department of Health,
Education, and Welfare, Public Health Service, Center for Disease Control,
National Institute for Occupational Safety and Health, Publication No. 77-
206, Aug. 1977.
3. “OSHA Safety and Health Standards, General Industry,” (29CFR1910),
Occupational Safety and Health Administration,, OSHA 2206, (Revised,
January 1976).
4. “Safety in Academic Chemistry Laboratories,” American Chemical Society
Publication, Committee on Chemical Safety, 3rd Edition, 1979.
5. Junk, G.A., M. J. Avery, J. J. Richard, “Interferences in Solid-Phase
Extraction Using C-18 Bonded Porous Silica Cartridges,” Anal. Chem. 1988,
60, 1347.
TABLES BEGIN ON NEXT PAGE
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TiTLE: Determination Of Organic Compounds in Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
TABLE 1. ION ABUNDANCE CRITERIA FOR BIB (PERPLUOROPHENYL) PRENYL
PROSPRINE (DECAFLUOROTRIPRENYIIPROSPRINE, DFTPP)
Mass
(m/z)
Relative Abundance
Criteria
Purpose of theckpoint(l)
51
10-80% of the base peak
low mass sensitivity
68
<2% of mass 69
low mass resolution
70
<2% of mass 69
low mass resolution
127
10-80% of the base peak
low-mid mass sensitivity
197
<2% of mass 198
mid-mass resolution
198
base peak or >50% of 442
mid-mass resolution and sensitivity
199
5-9% of mass 198
mid-mass resolution and isotope ratio
275
10-60% of the base peak
mid-high mass sensitivity
365
>1% of the base peak
baseline threshold
441
Present and c mass 443
high mass resolution
442
base peak or >50% of 198
high mass resolution and sensitivity
443
15-24% of mass 442
high mass resolution and isotope ratio
(1) All ions are used primarily to check the mass measuring accuracy of
the mass spectrometer and data system, and this is the most important
part of the performance test. The three resolution checks, which
include natural abundance isotope ratios, constitute the next most
important part of the performance test. The correct setting of the
baseline threshold, as indicated by the presence of low intensity
ions, is the next most important part of the performance test.
Finally, the ion abundance ranges are designed to encourage some
standardization to fragmentation patterns.
TABLE 2. RETENTION TINE DATA, QUANTITATION IONS, AND INTERNAL
STANDARD REFERENCES FOR METROD ANALYTES.
Internal
Standard C ound
Reference
C ound Retention
Number Time (mint see)
A(a) 3(b)
Quantitation
Ion (m/z)
Internal standards
acenaphthene -nO
phenanthrene -1)10
chrysene -1)12
Surrogate
perylene -1)12
Target analytes
acenaphthylene
aldrin
anthracene
atrazine
benz (a] anthracene
benzo (b] fluoranthene
benzo 1k] fluoranthene
benzo (a] pyrene
benzo (g, h, ii perylene
butylbenzylphtha late
1
4:49
7:45
164
2
8:26
11:08
l88
3
18:14
19:20
240
4
23:37
22:55
264
3
5
6
4:37
11:21
7:25
13:36
152
66
1
2
7
8:44
11:20
178
2
8
7:56
10:42
200/215
1/2
9
18:06
19:14
228
3
10
22:23
22:07
252
3
11
22:28
22:07
252
3
12
23:28
22:47
252
3
13
27:56
26:44
276
3
14
16:40
18:09
149
2/3
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EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Detennination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
TABLE 2. RETENTION TINE
DATA. QUANTITATION IONS, AND INTERNAL
STANDARD REFERENCES FOR METHOD ANALYTES. CONTINUED
Compound Retention
Internal
Nonber Time (mm: eec)
Quantitation
Standard C eund
A (a) B (b)
Ion (m/s)
Reference
Target analytee, Continued
chiordane components
a lpha-ch].ordane
15 13:44 15:42
375
2/3
garmna-ch lordane
16 13:16 15:18
375
2/3
trans nonachior
17 13:54 15:50
409
2/3
2-chiorobiphenyl
18 4:56 7:55
188
-
chrysene
19 18:24 19:23
228
3
dibenz(a,hjanthracene
20 27:15 25:57
278
3
di-n-butylphthalate
21 10:58 13:20
149
2
2,3-dichiorobiphenyl
22 7:20 10:12
222
1
diethy lphtha late
23 5:52 8:50
149
1
di (2-ethylhexyl)
phtha late
24 19:19 20:01
149
2/3
di(2-ethylhexyl)adipate
25 17:17 18:33
129
2/3
dimethy lphtha late
26 4:26 7:21
163
1
endrin
27 15:52 16:53
81
2/3
fluorene
28 6:00 8:53
166
1
heptachior
29 10:20 12:45
100/160
2
heptachior epoxide
30 12:33 14:40
81/353
2
2, 2’ , 3,3’ , 4,4’ , 6-hepta-
ch lorobipheny].
31 18:25 19:25
394/396
3
hexachlorobenzene
32 7:37 10:20
284/286
1/2
2,2’ ,4,4’,5,6’-hexa-
chiorobiphenyl
hexach].orocyclopentadiene
indenoLl,2,3,c,dJ pyrene
33 14:34 16:30
34 3:36 6:15
35 27:09 25:50
360
237
276
2
1
3
lindane
36 8:17 10:57
181/183
1/2
cuethoxychior
37 18:34 19:30
227
3
2, 2’ , 3,3’ , 4, 5’ ,6,6 ‘octa-
chiorobiphenyl
38 18:38 19:33
2,2’, 3’ ,4, 6-penta-
ch].orob].pheny].
pentachiorophenol
phenanthrene
39 12:50 15:00
40 8:11 10:51
41 8:35 11: 13
pyrene
42 13:30 15:29
simazine
43 7:47 10:35
2, 2’ ,4,4’ - tetrachioro-
biphenyl
44 11:01 13:25
292
2
toxaphene
45 11:30-23:30 13:00-21:30
159
2
2,4,5-trichlorobiphenyl
46 9:23 11:59
256
2
alachior
47 -- 13:19
160
2
(a) Single ramp linear temperature program conditions (Sect. 9.2.3.2).
(b) Multi-ramp linear temperature program conditions (Sect. 9.2.3.1).
TABLES ARE CO1*1TIRUED ON NEXT PAGE
© Genium Publishing Corporation 1996, Schenectady, NY 12304
430
326
266
178
202
201
3
2
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page 22
EPA Method 525 (EPA -500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
TABLE 3. ACCURACY AND PRECISION DATA FROM SEVEN DETERMINATIONS OF
THE METHOD ANALYTES AT 2 ugfL WITH LIQUID-SOLID
EXTRACTION AND THE ION TRAP MASS SPECTROMETER
Mean Rel. Mean Method Method
Co ound True Observed Btd. Std. Accuracy Detection
Number Cone. Cone. De,. Dev. (% of True Limit (MDL)
(Table 2) (ug/L) (ug/L) (ug/L) (%) Cone.) (ug/L)
4 5 5.0 0.3 6.0 100 a
5 2 1.9 0.2 11. 95 a
6 2 1.6 0.2 13. 80 a
7 2 1.7 0.1 5.9 85 a
8 2 2.2 0.3 14. 110 a
9 2 1.8 0.2 .11. 90 a
10 2 not separated from No. 11; measured with No. 11
11 2 4.2 0.3 7.1 105 a
12 2 0.8 0.2 25. 40 a
13 2 0.7 0.1 14. 35 a
14 2 2.0 0.3 15. 100 a
15 2 2.0 0.2 10. 100 a
16 2 2.2 0.3 14. 110 a
17 2 2.7 1.0 37. 135 a
18 2 1.9 0.1 5.2 95 a
19 2 2.2 0.1 4.5 110 a
20 2 0.3 0.3 100. 15 a
21 2 2.2 0.3 14. 110 a
22 2 2.3 0.1 4.3 115 a
23 2 2.0 0.3 15. 100 a
24 2 1.9 0.2 11. 95 a
25 2 1.6 0.3 19. 80 a
26 2 1.9 0.2 11. 95 a
27 2 1.8 0.1 5.5 90 a
28 2 2.2 0.2 9.1 110 a
29 2 2.2 0.3 14. 110 a
30 2 2.3 0.2 8.7 115 a
31 2 1.4 0.2 14. 70 a
32 2 1.7 0.2 12. 85 a
33 2 1.6 0.4 25. 80 a
34 2 1.1 0.1 9.1 55 a
35 2 0.4 0.2 50. 20 a
36 2 2.1 0.2 9.5 105
37 2 1.8 0.2 11. 90 a
38 2 1.8 0.2 11. 90 a
39 2 1.9 0.1 5.3 95 a
40 8 8.2 1.2 15. 102 a
41 2 2.4 0.1 4.2 120 a
42 2 1.9 0.1 5.3 95 a
43 2 2.1 0.2 9.5 105 a
44 2 1.5 0.1 6.7 75 a
45 25 28. 4.7 17. 112 15.
46 2 1.7 0.1 5.9’ 85 a
Mean(b) 2 1.8 0.2 15. 91 0.6
(a) See Table 4. (b)Compounds 4, 40, and 45 excluded from the means.
TABLES ARE CONTINUED ON NEXT PAGE
© Geniuni Publishing Corporation 1996, Schenectady, NY 12304
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page 23
EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Deterniination Of Organic Compounds in Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrornetry
TABLE 4. ACCURACY AND PRECISION DATA FROM FIVE TO SEVEN
DETERMINATIONS OF THE METHOD A}IALYTES AT 0.2 ug/L WITH
LIQUID-SOLID EXTRACTION AND THE ION TRAP MASS
aa a awa’aa an
Compound True
Number Cone.
(Table 2) (ugfL)
4 0.5
S 0.2
6 0.2
7 0.2
8 0.2
9 0.2
10 0.2
Mean Rel.
Observed Std. Std.
Cone. Dev. Dev.
(ug/L) (ug/L) (%)
0.45 0.6 13.
0.13 0.03 23.
0.13 0.03 23.
0.13 0.01 7.7
0.24 0.03 13.
0.14 0.01 7.1
not separated from No. 11;
Mean Method Method
Accuracy Detection
(% of True Limit (MDL)
Cone.) (ug/L)
90 0.1
65 0.1
65 0.1
65 0.04
120 0.1
70 0.04
measured with No. 11
62 0.2
15 0.04
15 0.1
160 0.3
85 0.2
95 0.1
85 0.3
95 0.1
105 0.04
150 0.1
240 0.3
100 0.1
225 0.8
195 0.6
155 0.6
105 0.04
60 0.5
105 0.2
110 0.04
95 0.2
95 0.1
80 0.1
95 0.1
20 0.03
20 0.1
110 0.1
55 0.04
95 0.2
65 0.1
97 0.3
100 0.01
90 0.02
125 0.2
70 0.1
11 0.2 0.25 0.04 16.
12 0.2 0.03 0.01 33.
13 0.2 0.03 0.02 67.
14 0.2 0.32 0.07 22.
15 0.2 0.17 0.04 24.
16 0.2 0.19 0.03 16.
17 0.2 0.17 0.08 47.
18 0.2 0.19 0.03 16.
19 0.2 0.21 0.01 4.8
20 0.2 0.03 0.02 67.
21 0.2 0.48 0.09 19.
22 0.2 0.20 0.03 15.
23 0.2 0.45 0.21 47.
24 0.2 0.39 0.16 41.
25 0.2 0.31 0.16 52.
26 0.2 0.21 0.01 4.8
27 0.2 0.12 0.12 100.
28 0.2 0.21 0.05 24.
29 0.2 0.22 0.01 4.5
30 0.2 0.19 0.04 21.
31 0.2 0.19 0.03 16.
32 0.2 0.16 0.04 25.
33 0.2 0.19 0.03 16.
34 0.2 0.04 0.01 25.
35 0.2 0.04 0.03 75.
36 0.2 0.22 0.02 9.1
37 0.2 0.11 0.01 9.1
38 0.2 0.19 0.05 26.
39 0.2 0.13 0.02 15.
40 0.8 0.78 0.08 10.
41 0.2 0.20 0.004 2.0
42 0.2 0.18 0.005 2.8
43 0.2 0.25 0.04 16.
44 0.2 0.14 0.04 29.
45 not measured at this 1e 1
46 0.2 0.13 0.02 15. 65 0.06
Mean(a) 0.2 0.18 0.04 25. 95 0.16
(a) Compounds 4, 40, and 45 excluded from the means.
© Geniuni Publishing Corporation 1996, Schenectady, NY 12304
TABLES ARE CONTINt1ED ON NEXT PAGE
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page 24
EPA Method 525 (EPA -500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectronietry
TABLE 5. ACCURACY AND PRECISION DATA PROM SEVEN DETERMINATIONS OF
THE METHOD ANALYTES AT 2 uGIL WITH LIQUID-SOLID EXTRACTION
AND A MAGNETIC SECTOR MASS SPECTROMETER
Mean Rd. Mean Method Method
Compound True Obaerved Std. Btd. Accuracy Detection
Number Conc. Conc. Dev. Dcv. (% of True Limit (MDL)
(Table 2) (ug/L} (ug/L) (ug/L) (%) Conc.) (ug/L)
4 5 5.7 0.34 6.0 114 a
5 2 1.9 0.22 12. 95 a
6 2 1.6 0.18 11. 80 a
7 2 2.2 0.67 30. 110 a
8 2 2.4 0.46 19. 120 a
9 2 2.2 0.87 40 110 a
10 2 not separated from No. 11; measured with No. 11
11 2 4.0 0.37 9.3 100 a
12 2 0.85 0.15 18. 43 a
13 2 0.69 0.12 17. 35 a
14 2 2.0 0.20 10. 100 a
15 2 2.2 0.41 19. 110 a
16 2 2.1 0.38 18. 105 a
17 2 1.9 0.10 5.2 95 a
18 2 2.0 0.29 14. 100 a
19 2 2.1 0.32 15. 105 a
20 2 0.75 0.18 24. 38 a
21 2 2.5 0.32 13. 125 a
22 2 2.0 0.23 12. 100 a
23 2 3.5 1.8 51. 175 a
24 2 2.0 0.28 14. 100 a
25 2 1.4 0.16 11. 70 a
26 2 2.9 0.70 24. 145 a
27 2 1.7 0.45 26. 85 a
28 2 2.6 1.0 38. 130 a
29 2 1.2 0.10 8.3 60 a
30 2 2.6 0.42 16. 130 a
31 2 1.5 0.19 13. 75 a
32 2 1.5 0.35 23. 75 a
33 2 1.9 0.17 8.9 95 a
34 2 0.89 0.11 12. 45 a
35 2 0.83 0.072 8.7 42 a
36 2 2.2 0.10 4.5 110
37 2 2.0 0.88 44. 100 a
38 2 1.5 0.11 7.3 75 a
39 2 1.6 0.14 8.8 80 a
40 8 12. 2.6 22. 150 a
41 2 2.3 0.18 7.8 115 a
42 2 2.0 0.26 13. 100 a
43 2 2.5 0.34 14. 125 a
44 2 1.6 0.17 11. 80 a
45 25 28. 2.7 10. 112 9.
46 2 1.9 0.073 3.8 ‘ 95 a
Mean(b) 2 1.8 0.32 16. 88 1.
(a) See Table 6. (b)Compounds 4, 40, and 45 excluded from the means.
TABLES ARE CONTINUED ON NEXT PAGE
© Geniuin Publishing Corporation 1996, Schenectady, NY 12304
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page 25
EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
TABLE 6. ACCURACY AND PRECISION DATA FROM SIX OR SEVEN
DETERMINATIONS OP THE METHOD ANALYTES AT 0.2 uG/L WITH
LIQUID-SOLID EXTRACTION AND A MAGNETIC SECTOR MASS
SPECTROMETER.
Mean Re].. Mean Method Method
Cos ound True Observed Btd. Std. Accuracy Detection
Number Cone. Conc. Dev. Dev. (% of True Limit (MDL)
(Table 2) (ug/L) (ug/L) (ug/L) (%) Cone.) (ugfL)
4 0.5 0.67 0.07 9.4 134 0.2
5 0.2 0.11 0.03 24. 55 0.1
6 0.2 0.11 0.02 21. 56 0.1
7 0.2 0.14 0.02 17. 70 0.1
8 0.2 0.26 0.08 31. 130 0.3
9 0.2 0.24 0.06 26. 120 0.2
10 0.2 not separated from No. 11; measured with No. 11
11 0.2 0.40 0.10 25. 100 0 3
12 0.2 0.08 0.02 27. 38 0.1
13 0.2 0.07 0.01 22. 33 0.1
14 0.2 0.33 0.16 48. 160 0.5
15 0.2 0.19 0.02 13. 95 0.].
16 0.2 0.17 0.08 45. 85 0.3
17 0.2 0.19 0.04 18. 95 0.1
18 0.2 0.17 0.02 13. 85 0.1
19 0.2 0.27 0.08 28. 135 0.3
20 0.2 0.09 0.01 15. 46 0.1
21 0.2 1.1 1.2 109. 550 4.
22 0.2 0.18 0.05 30. 90 0.2
23 0.2 0.29 0.17 59. 145 0.6
24 0.2 0.42 0.23 55. 210 0.8
25 0.2 0.32 0.16 50. 160 0.5
26 0.2 0.20 0.09 47. 100 0.3
27 0.2 0.53 0.30 57. 265 1.
28 0.2 0.18 0.03 15. 90 0.1
29 0.2 0.11 0.05 42. 55 0.2
30 0.2 0.33 0.08 26. 165 0.3
31 0.2 0.17 0.01 7.1 85 0.04
32 0.2 0.11 0.04 40. 55 0.2
33 0.2 0.17 0.03 15. 85 0.1
34 0.2 0.05 0.02 35. 24 0.1
35 0.2 0.08 0.06 8.1 40 .0.02
36 0.2 0.27 0.03 11. 135 0.1
37 0.2 0.24 0.09 39. 120 0.3
38 0.2 0.15 0.02 12. 75 0.1
39 0.2 0.13 0.02 13. 65 0.1
40 0.8 1.8 0.82 46. 225 3.
41 0.2 0.21 0.07 33. 105 0.2
42 0.2 0.19 0.04 23. 95 0.1
43 0.2 0.27 0.07 27. 135 0.2
44 0.2 0.13 0.03 22. 65 0.1
45 not measured at thia level’
46 0.2 0.16 0.04 23. 80 0.12
Mean(a) 0.2 0.21 0.09 28. 102 0.3
(a) Compounds 4, 40, and 45 excluded from the means.
© Genlum Publishing Corporation 1996, Schenectady, NY 12304
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page 26
EPA Method 525 (EPA-500 Series, Revision 2.1, 1988)
TITLE: Determination Of Organic Compounds In Drinking Water By Liquid-
Solid Extraction And Capillary Column Gas Chromatography/Mass Spectrometry
TABLE 7. ACCURACY AND PRECISION DATA FROM SEVEN DETERMINATIONS AT 2
ug/L WITH LIQUID-SOLID EXTRACTION AND A QUADRUPOLE MASS
SPECTROMETER
Mean Rel. Mean Method Method
Cen ound True Obeerved Std. Std. Accuracy Detection
Number Conc. Conc. Dev. Dew. (% of True Limit (NDL)
(Table 2) (ug/L) (ug/L) (ug/L) (%) Conc.) (ug/L)
47 2 2.4 0.4 16. 122 1.0
© Genium Publishing Corporation 1996, Schenectady, NY 12304
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